Electric Refractory Materials

Electric Refractory
Materials
edited by
Yukinobu Kumashiro
Yokohama National University
Hodogaya-ku, Yokohama, Japan
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Preface
This book provides a state-of-the-art overview of electric refractory materials as exotic materials
(i.e., metallic and semiconducting refractory materials) from fundamental properties to applica-
tion in a wide variety of electronics. The metallic ceramics or metalloids are the transition metal
carbides, nitrides, and diborides of groups IV and V. The refractory semiconductors are silicon
carbide, diamond, boron-based semiconductors, wide gap nitrides, and related mixed crystals.
The high melting points and high brittleness of refractory materials make it difficult to prepare
single crystals so use of these materials has been limited by hard coating and cutting tools,
regardless of their electric uses. After the crystal growth techniques—including thin film
growths—were established, such fundamental studies as electronic structures, bonding charac-
ters, and various physical properties were clarified with the development of new electric refrac-
tory materials.
Recently ‘‘hard electronics’’ was used in Japan (International Workshop on Hard Electron-
ics Abstract, 1997) and promised to bring new electronics needed in severe circumstances by
utilizing hard materials (adamantine) that were essentially hard themselves and very hard to
handle. The final goal of hard electronics involves not only high-temperature electronics, but also
various types of electronics that can operate under harsh conditions. Then ‘‘electric refractory
materials’’ would replace ‘‘hard electronic materials.’’
Consistency descriptions from preparation, characterization, properties, and electronic ap-
plications are shown on the cover, illustrating how electric refractory materials form a bridge
of knowledge from the basic sciences to electronic applications. This book emphasizes the im-
portance of refractory metalloids and semiconductors as electric materials from the standpoint
of high-temperature technology by reviewing newly developed fundamental research such as
chemical bonding, electrical, optical, and thermal properties. This book describes in detail for
the first time the most important work done in the field of refractory metalloids and semiconduc-
tors. Chapter 1 emphasizes the importance of refractory metalloids and semiconductors as elec-
tronic materials by reviewing characterization and properties of materials, and by summarizing
a wide variety of synthesis, evaluation, and measurement methods.
The transition metal carbides, nitrides, and diborides have aroused theoretical and practical
interest in such unique properties as extremely high melting point, extreme hardness, metallic
properties, and superconductivity. These unique common properties are closely connected with
electronic structures and the band structures resemble each other among the materials with the
same crystal structure. The refractory metalloids, described in Chapter 2, have become highly
clarified materials. This chapter is an introduction to Chapters 3–14.
On the other hand, the communication fields are constantly demanding higher frequencies
and power levels. Applications ranging from automobile engines to space telescopes require
device operation in harsh environments. Such issues have given rise to a new class of materials
known as wide-gap refractory semiconductors because of their potential applications in the de-
vices used for high-power, high-temperature, radiation influence; ultraviolet light influence; and
iii
iv Preface
high-frequency/high power. The major emphasis has been placed on diamond and silicon car-
bides. Silicon carbide is in a much more advanced stage of development. However, recent de-
velopment of blue light-emitting devices using GaN-based nitrides in Japan has stimulated
the study of nitride semiconductors for blue light-emitted laser, high-temperature, and high-
frequency devices.
Due to their unique mechanical, thermal, optical, chemical, and electrical properties, the
other refractory semiconductors are anticipated to find applications in thermoelectric, electro-
optic, piezoelectric, and acousto-optic devices as well as protective coating, hard coatings, and
heat sinks. The refractory semiconductors described in Chapters 15–27 are progressing year by
year and differ from material to material. These chapters cover the issues related to crystal
growth; microstructure; defects; doping; electric, thermal, and optical properties; and device
applications, while identifying common themes in heteroepitaxy and the role of defects in dop-
ing, compensation, and phase stability of unique classes of materials.
The book covers most aspects of electric refractory materials and can serve as a general
reference to this new and developing area.
I wish to thank all the authors for their contributions. A number of figures and tables have
been taken from the literature. I would like to thank the authors and publishers of these materials
for permission to reproduce them here. I am also grateful to R. Dekker, M. Ludzki, B. Wrage,
E. Stannard, and K. Baldonado, of Marcel Dekker, Inc., for their useful comments, constant
encouragement, and invaluable support throughout this project. Finally, I am indebted to Mr.
S. Chiba for his assistance in preparing the book’s index and cover art.
Yukinobu Kumashiro
Contents
Preface iii
Contributors vii
1. Importance and Research Program of Electric Refractory Materials 1

Yukinobu Kumashiro
2. Survey of Refractory Metalloids: Transition Metal Carbides, Nitrides,

and Diborides 7
Yukinobu Kumashiro
3. Bulk Crystal Growth 19

Yukinobu Kumashiro
4. Thin-Film Preparation 55
Konosuke Inagawa
5. Electronic Structure 81
Adolf Neckel
6. Lattice Vibrations, Heat Capacity, and Related Properties 153

Göran Grimvall
7. Electrical and Thermal Conductivity and Related Transport Properties

at Low Temperatures 173
Göran Grimvall
8. High-Temperature Characteristics 191

Yukinobu Kumashiro
9. Surface Electronic Structures and Surface Reactivities 223

Kazuyuki Edamoto
10. Irradiation Properties of Electric Refractory Materials 245

Naoto Kobayashi
11. Transition Metal Carbide Field Emitters 269

Yoshio Ishizawa
v
vi Contents
12. NbN Superconducting Devices 289

Masahiro Aoyagi
13. Solar Absorbers—Selective Surfaces 307

Robert Blickensderfer
14. Metalloids for Plasma-Facing Materials 321

Tatsuhiko Tanabe and Masakazu Fujitsuka
15. Synthesis of Diamond from the Gas Phase 347

Andrzej Badzian
16. The Electrical and Optical Properties of Diamond 369

Alan T. Collins
17. Semiconducting Diamond and Diamond Devices 385

Shinichi Shikata and Naoji Fujimori
18. SiC Boule Growth 409

Yuri M. Tairov
19. Epitaxial Growth, Characterization, and Properties of SiC 437

Sadafumi Yoshida
20. Silicon Carbide Power Electronic Devices 477

B. Jayant Baliga
21. Science and Technology of Boron Nitride 495

Osamu Mishima and Koh Era
22. Boron Phosphide 557

Yukinobu Kumashiro
23. Boron and Boron-Rich Compounds 589

Helmut Werheit
24. Boron Films 655

Katsumitsu Nakamura
25. Single Crystal of AlN 675

Takeshi Meguro and Katsutoshi Komeya
26. AlN Sintered Polycrystal 691

Fumio Ueno
27. GaN-AlN-InN Blue Light–Emitting Devices 715

Shuji Nakamura
Index 747
Contributors
Masahiro Aoyagi, Ph.D. Electron Devices Division, Electrotechnical Laboratory, Tsukuba,

Ibaraki, Japan
Andrzej Badzian, Ph.D., Dr.Sc. Materials Research Laboratory, The Pennsylvania State Uni-
versity, University Park, Pennsylvania
B. Jayant Baliga, Ph.D. Department of Electrical and Computer Engineering, North Carolina
State University, Raleigh, North Carolina
Robert Blickensderfer, Ph.D. Research Metallurgist, Consultant, Albany, Oregon
Alan T. Collins, Ph.D., D.Sc. Department of Physics, King’s College London, London,
England
Kazuyuki Edamoto, D.Sc. Department of Chemistry and Materials Science, Tokyo Institute
of Technology, Meguro-ku, Tokyo, Japan
Koh Era, Ph.D. Helios Optical Science Laboratory, Inc., Tsukuba, Ibaraki, Japan
Naoji Fujimori, Dr.Eng. Itami Research Laboratories, Sumitomo Electric Industries, Ltd.,
Itami, Hyogo, Japan
Masakazu Fujitsuka Department of Mechanical Properties, National Research Institute for

Metals, Tsukuba-shi, Ibaraki, Japan
Göran Grimvall, Ph.D. Department of Physics, Royal Institute of Technology, Stockholm,

Sweden
Konosuke Inagawa, Ph.D. Chiba Institute for Super Materials, ULVAC Japan, Ltd., Tsukuba,
Ibaraki, Japan
Yoshio Ishizawa, Ph.D. Department of Materials Science, Iwaki Meisei University, Iwaki,
Fukushima, Japan
Naoto Kobayashi, Ph.D. Quantum Radiation Division, Electrotechnical Laboratory, Tsukuba,

Ibaraki, Japan
vii
viii Contributors
Katsutoshi Komeya, Dr.Eng. Department of Engineering, Yokohama National University,

Yukinobu Kumashiro, Ph.D. Department of Engineering, Yokohama National University,

Takeshi Meguro, Ph.D. Department of Materials Chemistry, Yokohama National University,

Osamu Mishima National Institute for Research in Inorganic Materials, Tsukuba, Ibaraki,
Japan
Katsumitsu Nakamura, Dr.Eng. Department of Chemistry, College of Humanities and Sci-

ences, Nihon University, Setagaya-ku, Tokyo, Japan
Shuji Nakamura, Ph.D. Materials Department, University of California, Santa Barbara, Cali-
fornia
Adolf Neckel, Ph.D. Institute for Physical Chemistry, University of Vienna, Vienna, Austria
Shinichi Shikata, M.D. Itami Research Laboratories, Sumitomo Electric Industries, Ltd.,
Itami, Hyogo, Japan
Yuri M. Tairov, Ph.D. Department of Microelectronics, St. Petersburg Electrotechnical Uni-

versity, St. Petersburg, Russia
Tatsuhiko Tanabe, Dr.Eng. Department of Mechanical Properties, National Research Insti-

tute for Metals, Tsukuba-shi, Ibaraki, Japan
Fumio Ueno, Ph.D. Corporate Research and Development Center, Toshiba Corporation, Ka-
wasaki, Japan
Helmut Werheit, Prof.Dr.rer.nat. Solid State Physics Laboratory, Gerhard Mercator Univer-
sity, Duisburg, Germany
Sadafumi Yoshida, Ph.D. Department of Electrical and Electronic Systems, Saitama Univer-
sity, Urawa, Saitama, Japan
1
Importance and Research Program of
Electric Refractory Materials
Yukinobu Kumashiro
Yokohama National University, Hodogaya-ku, Yokohama, Japan
The extreme technologies involving ultrahigh temperature, ultrahigh pressure, ultralow tempera-
ture, and ultravacuum are part of advanced science and technology and important research sub-
jects. Their development and utilization reveal new materials and improve the characteristics
of conventional materials, resulting in new phenomena and developments in material science
technology. New materials with peculiar characteristics including stability under extreme condi-
tions, such as ultrahigh temperatures ⭌ 2300 K, ultralow temperatures ⬉ 4 K, ultrahigh pressures
⭌ 10 9 Pa, and low vacuum ⬉ 10 ⫺9 Pa, often form exotic materials. The following types of
exotic materials would be expected:
1. High-purity materials: Electronic and optical materials and atomic nuclear materials.
2. Perfect crystals: Bulk single crystals with few defects, ultrathin films, whiskers, and
ultrafine powders.
3. New material phases: New stoichiometry, quasi-stable amorphous phases, intermetal-
lic compounds, and superlattices.
4. Composites: New cermets, fiber-reinforced materials (FRMs), and functional gradient
materials (FGMs).
Among these, refractory materials are related to the development of materials with high
stability, a long lifetime, and high reliability at high temperatures, promising electronic devices
with high capacity and high power density for uses in harsh environments. They would also
result in increased conversion efficiency at high temperatures, simplified control systems for
apparatus, and improved new systems. Industries such as the aerospace, automotive, and petro-
leum industries have continuously provided the impetus for the development of fringe technolo-
gies that are tolerant of increasingly high temperatures and hostile environments (1).
The refractory materials in the present case are nonoxides with high melting points, strong
atomic bonding, high hardness, and high thermal shock resistance. The various functions of
refractory materials are summarized in Table 1. These functions are closely related to each other
as reflected in Fig. 1. The functions are generally influenced by such imperfect characteristics
as crystal structure, impurity, atomic vacancy, lattice defect, dislocation, crystal grain boundary,
and aggregation texture. Characterization is fundamental to the development of material science
and provides indexes for databases in material design.
In general, characterization describes those features of the composition and structure in-
1
2 Kumashiro
Table 1 Functions and Applications of Refractory Materials

Function Device Materials
Electronic function
Insulation Integrated circuit substrate AlN, SiC, diamond
Passivation film Si3N4, BN, AlN
Conduction Electrode Transition metal carbides and
nitrides
Resistor TaN, ZrN
Interconnection TiN
Superconduction Superconducting magnet NbN, NbN-NbC
Josephson device
Piezoelectricity Surface acoustic wave device
Piezoelectric filter AlN
Light guide
Acoustic emission (AE) sensor
Semiconduction Thermistor B, SiC, BP
Thermoelectric device SiC, BP, B, B4 C
Diode SiC, BP, diamond
Transistor SiC, BP
Electron emission Emitter TiC, TaC, TiB2, TiN
Thermionic generator device TiC, TaC, TaB2
Electrode for magnetohydrody- Transition metal diborides
namic generator
Optical function
Fluorescence Light-emitting diode GaN, SiC, c⋅BN
Light absorption Solar selective and absorption ZrC, HfC
films
Protective film for reflection BP
Light reflection Solar thermal concentrator TiC, TiN
Photosensitivity Photoelectrochemical cell BP
Mechanical function
High strength Turbine blade, engine Si3N4, SiC
Hardness Speaker film B
Abrasivity and cutting Abrasive polishing, whetstone Diamond, carbides
cutting tool BN, nitrides
Lubrication Solid lubricant BN
Thermal function
Refractory Refractory structural materials SiC, ZrB2
Conduction Insulating substrate Diamond, SiC, AlN
Heak sink Diamond, SiC, AlN, BP
Atomic power and nuclear fusion functions
Resistive for radiated ray Nuclear fuel coating materials C, SiC
Control rod B4C
Plasma resistance First wall of tokamak SiC, TiC, TiB2, B4C, B
Radioactivity detection α-ray detector Diamond, SiC
Neutron detector BP, B
Chemical function
Corrosion resistance Oxidation-resistant materials Diborides, SiC
Acid resistance Carbides and diborides, BP
Catalysis Control of chemical reactions Transition metal carbides and
nitrides
Importance and Research Program 3
Figure 1 The relationship between various functions in refractory materials.
cluding defects of materials that are significant for a particular preparation and study of proper-
ties or uses and suffice for the reproduction of the material (2). The assessment of the physical
and chemical perfection of crystals has come to be called characterization by crystal growers
(2). Many crystals have been characterized to the point where relationships between their proper-
ties and the concentration of their constituent atoms have been found. Most important for crys-
tal growers is to relate the growth process to control of the perfection of crystals in desired
ways (2).
The characterization does not merely examine macro- and microscopic features of materi-
als but clarifies the chemical composition and structure texture as factors reflecting material
properties and functions in relation to the history of materials, i.e., raw material → material
handling → production. The concept of characterization is illustrated in Fig. 2. The characteris-
tics change dynamically in the functional state, which corresponds to ‘‘status analysis’’ instead
of analysis in Fig. 2.
Table 2 summarizes the synthesis, evaluation, and measurement technologies for refrac-
tory materials. The development of new preparative processes such as plasma, laser, particle,
and high-speed ion-ray processes would lead to new exotic materials. In cases in which the
preparation of single crystals of refractory materials is very difficult, some film growth tech-
niques are powerful tools for clarifying the intrinsic properties of bulk crystals. Physical vapor
deposition (PVD) is supercooling process used to realize a quasi-equilibrium state that could
4 Kumashiro
Figure 2 Concept of characterization. The shaded part of the figure represents the status of characteriza-
tion.
not be attained in the bulk process. Also, status analysis of thin films including surfaces and
interfaces is very important for characterization.
The evaluation technologies are divided into three categories: microscopic, spectrographic,
and diffraction methods. Developments of microscopic evaluation technologies down to the
atomic level, such as scanning tunneling microscopy, are due to progress in techniques using
secondary electrons and iron, scattered X-rays, together with ultravacuum technology.
We could not always discriminate clearly between evaluation and measurement technolo-
gies. The Hall effect and lifetime measurements in semiconductors are frequently part of evalu-
ation technology. The measurement technologies require various sophisticated extreme tech-
nologies including pulse technology to clarify extreme characteristics. Such inconsistent
requirements as simultaneous measurements of static and dynamic properties are one of the
problems to be solved.
The refractory materials are hard and brittle with superior chemical stability, so that the
establishment of such material handling processes as cutting and abrasion, including micro-
processes for etching and patterning, is indispensable to the development of electronic device
applications of these materials.
The electric refractory materials in this book are classified into metallic ceramics (i.e.,
transition metal carbides, nitrides, and diboride) and wide-gap semiconductors (i.e., diamond,
SiC, GaN, BP, AlN, BN, and high-boron base semiconductors.
Table 2 Synthesis, Evaluation, and Measurement Technologies for Refractory Materials

Crystal growth technology
High-temperature technology
Radio-frequency induction heating, infrared heating, arc plasma heating, electron beam heating,
CO 2 laser, self-propagating high-temperature synthesis (SHS)
High-pressure technology
Gas pressure, hydrostatic pressing, hot pressing, isostatic pressing, shock wave synthesis
Ultra-vacuum technology
Evaporation-condensation, evaporation (reactive evaporation, molecular beam deposition,
sputtering), ion beam [ionized cluster beam (ICB), ion plating, electron cyclotron resonance
(ECR)]
Importance and Research Program 5
Table 2 Continued
Chemical vapor deposition (CVD)
Hydrogen reduction, chemical transport, hydrogen decomposition, metal organic CVD, plasma
CVD
Liquid growth
Liquid-phase epitaxy (LPE), flux growth
Solid growth
Recrystallization, solid-phase epitaxy (SPE)
Beam process
Radial beam, cluster beam, excimer laser
Evaluation technology
Crystal structure
X-ray diffraction, electron diffraction, neutron diffraction, field ion microscope (FIM)
Composition analysis
X-ray fluorescence spectroscopy (XRF), X-ray photoelectron spectroscopy (XPS), ultraviolet
photoelectron spectroscopy (UPS), Auger electron spectroscopy (AES), electron probe
microanalysis (EPMA), particle-induced X-ray emission (PIXE), Rutherford backscattering
spectroscopy (RBS)
Impurity analysis
Secondary ion mass spectroscopy (SIMS), induced coupled plasma mass spectroscopy (ICP-MS)
Crystal quality
Optical microscope, light scattering method, X-ray and electron diffractions, X-ray topograph
bond method, channeling, infrared (IR) spectroscopy, Raman spectroscopy
Defect and impurity analysis
Deep level transient spectroscopy (DLTS), photoacoustic spectroscopy (PAS), photoluminescence
(PL), cathodoluminescence (CL), electron spin resonance (ESR), nuclear magnetic resonance
(NMR), transmission electron microscopy (TEM), high-resolution electron microscopy (HREM)
Surface structure
Low-energy electron diffraction (LEED), reflection high-energy electron diffraction (RHEED), ion
scattering spectroscopy (ISS), impact-collision ion scattering spectroscopy (ICISS), electron
energy loss spectroscopy (EELS), scanning tunneling microscopy (STM), atomic force
microscopy (AFM), X-ray absorption near edge structure (XANES), extended X-ray absorption
fine structure (EXAFS), XPS, UPS
Measurement technology
Electronic properties
Conductivity, work function, superconducting transition temperature (Tc), superconducting critical
field (H c2), thermoelectric power, Hall effect, photoconductivity, drift mobility, lifetime,
piezoelectric constant, breakdown voltage, dielectric loss, dielectric constant
Mechanical properties
Elastic coefficient (Young’s modulus, shear modulus, Poission ratio, microhardness)
Strength (compressive, tensile, impact, fracture, fatigue)
Stress (bending, tensile, compressive)
Fracture toughness
Coefficient of friction, coefficient of abrasion
Thermal properties
Thermal expansion coefficient, heat capacity, thermal diffusivity, thermal conductivity, vapor
pressure
Optical properties
Emissivity, reflection absorption and absorption edge, refraction index, photomission, brightfringe
Chemical properties
Diffusion coefficient, oxidation rate, etching rate
6 Kumashiro
The refractory metallic ceramics are promising candidate materials for the following areas:
1. Very large scale integration (VLSI) technology and electronic devices: Carbides and
diborides as field and thermal emitters, TiN as a diffusion barrier in metallization to
Si semiconductors, resistive thermoconductive humidity sensors with TaN film, and
Josephson tunnel junctions with NbN film.
2. Energy-related materials: Solar-selective surfaces with ZrC thin films, emitters for
thermoionic generators, ZrB 2 and HfB 2 electrodes for MHD generators, and first wall
coating with TiC or TiB 2 film for tokamaks.
Refractory semiconductors are under intense study because of their potential applications
in electronic devices for high temperature, high frequency, and high power and blue light–
emitting devices (3). Electronics based on the existing semiconductor device technologies with
Si and GaAs cannot tolerate greatly elevated temperatures or chemically hostile environments
due to the uncontrolled generation of intrinsic carriers and their low resistance to caustic chemi-
cals. The wide-band-gap semiconductors SiC and GaN, and perhaps sometime in the future
diamond, with their excellent thermal conductivities, large breakdown fields, and resistance to
chemical attack, will be materials of choice for these applications (4).
Other refractory semiconductors will continue to be developed and compete for niches.
A suitable high-temperature semiconductor technology could allow bulky aircraft hydraulics
and mechanical control systems to be replaced with heat-tolerant in situ control electronics. On-
site electronics, actuators, and sensors would reduce complexity and increase reliability. Hydrau-
lic system, a fire hazard in aircraft, and heat radiators in satellites could then be greatly reduced
in size and number, yielding a considerable weight reduction (4). In addition, many wide-gap
semiconductors are anticipated to find applications in thermoelectric, electro-optic, piezoelectric,
and acousto-optic devices and heat sinks.
REFERENCES
1. JJ Gangler. NASA research on refractory compounds. High Temp High Press 3:487, 1971.
2. RA Laudise. In: R Ueda, JB Mullin, eds. Crystal Growth and Characterization. Amsterdam: North-
Holland, 1975, p 255.
3. H Morkoc, S Strite, GB Gao, ME Lim, B Sverdlov, M Burns. Large-band-gap SiC, III–V nitride,
and II–VI ZnSe-based semiconductor device technologies. J Appl Phys 76:1363, 1994.
4. Y Kumashiro. Recent developments of refractory semiconductor materials. JRCM News 20:2, 1993.
2
Survey of Refractory Metalloids: Transition
Metal Carbides, Nitrides, and Diborides
Yukinobu Kumashiro
The transition metal carbides, nitrides, and diborides of groups IV and V of the periodic table
are electronically conductive but are also very hard and have high melting points (1). These
compounds are characterized by their unique chemical bonding; metal and nonmetal bonds are
related to lattice formation, and the metallic, covalent, and ionic (about 15%) bonds contribute
simultaneously to the cohesive energy (2). The carbides and nitrides have a B1(NaCl) structure
(space group O 5h Fm3m) with wide homogeneity. They are called interstitial compounds, i.e.,
with a face-centered cubic (fcc) structure at the centers of octahedral interstitial sites or trigonal
prismatic voids of the metallic lattice. Physical properties of these compounds are similar and
depend on the composition. The cohesive energy relations for carbides and nitrides with rock-
salt structures are explained in terms of melting point and bond length (3). Cohesion is due to
electron transfer, but the values deviate from a simple exchange relation associated with limited
sd band participation in bonding.
The carbides of group IV deviate largely from the stoichiometric composition MC 1.00 , and
the homogeneity regions for group V carbides are less extended than for the carbides of group
IV (4). The VC phase in equilibrium with carbon terminates near VC0.9 rather than the perfect
lattice composition. Group V carbides form disordered lower carbides with the hexagonal close-
packed (hcp) structure of W2C (L′3) (4). Vanadium carbide exhibits an order-disorder transition
in the range of stoichiometry, that is, VC0.83 ⫽ V6C 5 (hexagonal) and VC 0.875 ⫽ V8C 7 (cubic).
The chemistry of the material does not change: with no change in the number of particles, the
vacancy in the disordered, nonstoichiometric compound becomes ordered, resulting in a different
crystal structure (5). Long-range order in these vanadium carbides was detected using nuclear
magnetic resonance (NMR) (6) and electron diffraction (ED) (7).
Neutron diffraction patterns of annealed NbC x (0.81 ⬉ x ⬉ 0.88) (4,8) and TaC x
(0.79 ⬉ x ⬉ 0.90) specimens display weak superstructure peaks along with intense structural
lines, suggesting an incommensurate ordered phase with a composition close to M 6C 5 (4).
The parameter of the fcc sublattice of metals for the ordered phase is larger than that for the
disordered carbides, indicating that the volume of the crystal varies discontinuously during
ordering (4).
The transition metal nitrides are close to carbides in structure and properties. They are
often isostructural and usually form solid solutions with each other. The electrical and thermal
conductivities; of hot-pressed stoichiometric carbonitrides appear to behave very similarly (9);
i.e., the electronic and thermal conductivities tend to increase with increasing nitrogen content
7
8 Kumashiro
Figure 1 Reflectance of stoichiometric titanium carbonitrides Ti(Cx N1⫺x)1.00 and Ti(CxN1⫺x ) 0.82 as a func-
tion of [C]/([C] ⫹ [N]) ratio. (From Ref. 9.)
in a similar fashion. The reflectance curves for the carbonitrides are shown in Fig. 1 (9). For
the nitrides, a distinct minimum in the reflectance curves in the blue region could be observed,
indicative of a yellow appearance of the nitrides. Upon the introduction of carbon, this minimum
shifts toward higher wavelengths and becomes weaker. The wavelength shift corresponds to a
conversion of the color toward violet. This color change from yellow through violet to gray is
shifted toward higher carbon contents, the higher the atomic number of the transition metal.
The substoichiometric carbonitrides show almost linear reflectance curves without a pronounced
minimum in any spectral region, which is the reason for their gray appearance.
The nitrides of group IV have a B1 (NaCl) structure. Those of group V form δ-phases—
mononitrides—with an fcc metallic sublattice, as well as ⑀-phases—stoichiometric MN1.00 ni-
tride—with an hcp structure and lower M 2N nitrides with an hcp structure (10). The nitride
systems are pressure dependent, and in carbide systems the influence of pressure can be ne-
glected. Many binary nitride phase diagrams are still inexactly known and there exists a great
deal of controversy about proposed diagrams (10). One particular problem confounding phase
diagram studies of nitrides is the sensitivity of phase stabilities to the method of preparation.
The tendency to deviate from stoichiometry causes difficulties in defining the melting points.
Loss of nitrogen at high temperatures makes the nitrides nonstoichiometric, resulting in a de-
crease of the melting temperature so that the melting points of the nitrides cannot be defined
unambiguously without defining the nitrogen pressure. The melting point of δ-TaN is expected
to take place at about 2800–3000°C and at nitrogen equilibrium a pressure of about 1000–3000
bar (10).
The transition metal hexagonal AlB 2-type structure (space group D′6h-P6/mmn) consists of
hexagonal closed-packed metal layers (A) and ‘‘graphite’’-like boron layers (H) stacked in the
simple sequence AHAHAH ⋅ ⋅ ⋅ (11). The hexagonal unit cell contains metal atoms at (0, 0, 0)
and boron atoms at (1/3, 2/3, 1/2) and (2/3, 1/3, 1/2). The bonding within the basal plane is
determined by the strong BB bonds within the boron layer, whereas the cohesive force in
the c direction is determined mainly by MB bonds (M denotes metal). Furthermore, the micro-
hardness of the VB 2 single crystal in the ⬍1000⬎ direction shows slightly higher values than
in the other directions, which would indicate strong BB bonds in the diboride structure (12).
The transition metal diborides have melting points ranging from 2000 to 3000°C and relatively
low volatility in comparison with the carbides and nitrides. All the diborides with the exception
of the niobium and tantalum diborides have a small homogeneity range (13). The boron-rich
compositions contain interstitial boron atoms at (0, 0, 1/2) rather than vacancies at the metal
position. The simultaneous occurrence of metal vacancies and interstitial boron atoms accommo-
Survey of Refractory Metalloids 9
Figure 2 Microhardness of TaB2 and NbB2 within the homogeneity ranges. (From Ref. 15.)
dated in the larger holes at (1/3, 2/3, 0) and (2/3, 1/3, 0) results in wide homogeneity ranges
in NbB2 and TaB2 (14). Microhardness values for two diborides are plotted against boron con-
tents in Fig. 2 (15). The microhardness increases with increasing boron content, consistent with
the increase in bond strength for boron-rich NbB2 and TaB2 compositions although an abrupt
increase in the hardness of the metal-rich composition of NbB2 can be seen.
Transport properties of these compounds are reviewed. The resistivity of MCx single crys-
tals except for VCx at room temperature increases with decreasing x but begins to saturate (1).
The contribution of phonon scattering for TiC was found to be 30, 20, and 10% at a composition
(C/Ti) of 0.95. 0.9, and ⬍0.8, respectively (16). Also the inverse mobility for nonstoichiometric
carbides is proportional to the vacancy concentration, showing evidence that carbon vacancies
act as scattering centers for electrons (17). This relationship can be revised to obtain the point-
defect concentration and the chemical composition of a carbide from its resistivity (18).
Nearly the entire composition range corresponds to one or the other of the ordered phases
in the vanadium-carbon system (5). Only a small region of disorder exists between the regions
of order. A single-crystal sample of V8C 7 had the lowest residual resistivity (3.17 µΩ cm) ever
measured in a nonsuperconducting group IV or V transition metal carbide. The heat capacity
of both ordered and disordered niobium carbide, NbC x, also decreases with decreasing carbon
content. An ordered niobium carbide has a higher heat capacity than a disordered carbide of
the same composition (19). The maximum value of the difference of the heat capacities of an
ordered and a disordered specimen is observed for NbC 0.83 , corresponding to the stoichiometric,
composition of an ordered Nb 6 C5 phase. Then the thermal conductivities of the ordered phases
V6C 5 and Nb 6C 5 at room temperature are attributable to a decrease in electron vacancy and
phonon vacancy scattering. As electrons suffer less scattering in the partially ordered compounds
by the Wiedemann-Franz law, K e ⫽ L 0 σT, the resulting electrical conductivity also increases
the contribution to the thermal conductivity by electrons, Ke (20).
Some transition metal carbides and nitrides show superconductivity above liquid nitrogen
temperature. Those having a Tc of 17 K or higher are NbN and compounds represented by the
general formula NbC xN 1⫺x , and most of the others have a Tc of 14 K or lower. The factors
10 Kumashiro
determining Tc are the state density of electrons at the Fermi level N(E F ), the electron-phonon
interaction parameter Vph , and the Debye temperature θ D (21). The Fermi level of group IV
carbides involves a minimum point of state density, so these materials are not superconducting.
In contrast, the group V carbides and group IV and V nitrides become superconducting because
of an increase in N(E F ) (21), corresponding to the increase in valence electron number. However,
TaN has lower than expected Tc values, which may result from the presence of vacant lattices,
since they largely comprise antibonding orbitals and are not reactive. Furthermore, VN has
relatively low Tc values for its high N(E F ) values, conceivably resulting from spin fluctuations
(21).
The high Tc values are due mainly to abnormalities of lattice vibrations (21). Phonon
abnormalities are observed with such compounds as NbC, TaC, TiN, ZrN, HfN, and NbN, which
have high Tc values, but not with carbides of group IV elements. This is explained directly by
comparing the acoustic phonon energy dispersion curves and phonon state densities of NbC
and ZrC (Fig. 3). NbC has three depressed parts at (0, 0, 0.7), (0.55, 0.55, 0), and (0.5, 0.5,
0.5) on the dispersion curve. These are referred to as phonon abnormalities, the phenomenon
stemming from the negative force constant at a point corresponding to the reciprocal lattice
vector of the depressed parts. Also, NbC has a phonon state density whose centroid greatly
deviates from that of ZrC to the low-energy side. NbN has a still larger depressed part at point
X on the dispersion curve, and its phonon state density is moved farther toward the low-energy
side. Thus, the order of magnitude of ⬍ω 2⬎, which determines the electronic phonon coupling
constant λ, is ZrC ⬎ NbC ⬎ NbN, and this order is reversed with respect to λ. NbN, with a
large λ, has a high Tc .
Next we would like to mention the mechanical properties of these compounds. The micro-
hardness anisotropy of a single crystal induces a slip system because the hardness maxima and
minima correspond to the effective resolved shear stress minima and maxima, respectively (22).
The periodicity of the hardness curve of the carbides in (100) planes and theoretical curves
given by Hannink et al. (23) and Kohlstedt (24) indicate that the primary slip system of TaC
(25–27) is {111}⬍110⬎, whereas in TiC (28), ZrC (26), and HfC (27) the {110}⬍110⬎
system is found. In the case of VC and NbC with double maxima, the slip systems are
coexistent with {111}⬍110⬎ and {110}⬍110⬎ (29,30). But the use of the Burgers vector
and transmission electron microscopy for NbC (29) single crystals identifies a slip system
of {111}⬍110⬎.
Microplasticity has been found in localized regions around hardness indentations revealed
Figure 3 Acoustic phonon dispersion curves and phonon density of states of NbC and ZrC (21). De-
pressed parts, as indicated by arrows, are formed on the dispersion curve of NbC, which moves the state
density of the compound to the low-energy side.
by slip lines, i.e., the formation of cracks and dislocation motion along the slip systems
{110}⬍110⬎ and {100}⬍110⬎. The degree of plastic deformation and the importance of the
slip system {111}⬍110⬎ increase as the C-to-Ti ratio decreases from 0.99 to 0.64 (31–33).
A new deformation mode induced during high-speed abrasive preparation of TiC single
crystals, which involves a stress-induced martensitic transformation from cubic TiC to rhombo-
hedral and hexagonal structures, has been reported (34). The new phase is designated 8H, to
reflect the height of the unit cell (eight TiC atom planes) and the hexagonal symmetry (H).
The observed martensitic transformation appears to be peculiar to dynamic deformation at high
loading rates. The transformed structure would be governed by the Ti sublattice and carbon
atoms remaining in octahedral coordination. Under certain types of loading, it might be possible
to produce similar transformations in the vicinity of crack tips or other stress concentrations.
The slip for TiN and ZrC single crystals from the slip traces produced by microhardness
indentations indicates that {111}⬍110⬎ slip is operative (35). The main slip system contributing
to the hardness anisotropy of titanium diboride single crystals is found to be (0001) ⬍1120⬎,
that of zicronium diboride is {1010} ⬍1210⬎, and that of hafnium diboride single crystals
involves both slip systems (36). NbB 2 crystals have an axial ratio (c/a ⫽ 1.06) near unity, so
NbB 2 single crystals may have another prismatic slip system {1010} [0001], as well as the two
(0001) ⬍1120⬎ and {1010} ⬍1121⬎ types (37). However, Vahldiek and Mersol (35) con-
firmed slip systems of {1010} [0001] and {1010} [1120] in as-grown diboride single crystals
by observing slip patterns on the (0001) and {1010} planes. Considering the shortest Burgers
vector of the ⬍1120⬎ directions and the closeness of lattice parameters a and c in the diborides,
⬍1120⬎ would be the primary slip direction and [0001] is also an effective slip direction (35).
Figure 4 shows hardness and composition for transition metal nitrides. The hardness de-
creases with increasing nitrogen content for the group V nitrides (38,39), which would be due
to electronically induced lattice softening as a result of the generation of antibonding states.
Antibonding states are successively occupied in fcc transition metal compounds with more than
eight valence electrons. An increasing valence electron concentration due to increasing nitrogen
Figure 4 Microhardness of δ-TiN and group V nitrides as a function of stoichiometry. (From Ref. 38,
39.)
12 Kumashiro
content would lead to a decrease in hardness when the number of valence electrons exceeds
eight. In δ-TiN 1⫺x a maximum in microhardness is found for the composition δ-TiN 0.67 , corre-
sponding to 7.3 valence electrons. For δ-HfN 1⫺x a smooth increase in microhardness with in-
creasing nitrogen content is observed, probably as a result of the difference in electronic states
due to 5f electrons.
The changes in interatomic bonding appear as changed elastic constants (40). The Black-
man diagram in Fig. 5 shows results for one particular choice of ratios: y ⫽ C 12 /C 11 and x ⫽
C 44 /C 11 represent ratios of interatomic force constants because y and x are mass-density (volume)
independent (41). Lines radiating from the upper left correspond to various Zener anisotropies,
A ⫽ 2C 44 /(C 11 ⫺ C 12), from 0.5 to 12. Curved lines correspond to various quasi-isotropic Poisson
ratio values from ⫺0.1 to 0.4. The transition metal carbides with an NaCl-type crystal structure
suggest a strong ionic bonding component. Figure 6 shows the three-dimensional surface repre-
senting the Young’s modulus of TiB 2 single crystal as a function of crystallographic direction,
indicating that the elastic constants of TiB 2 single crystals are more isotropic and stiffer than
previously considered (42).
The Young’s modulus E and hardness H of TiN films measured by a depth-sensing nanoin-
dentation technique and the shear modulus G obtained by measuring the velocity of the acoustic
surface wave by Brillouin light scattering are shown in Fig. 7 (43). For x ⫽ 0 (pure titanium)
both measured values of Young’s shear modulus agree well with the standard value for titanium,
indicating that the film quality is rather good and that the small discrepancy might also be due
to other effects, e.g., a different morphology of the films and/or texture. Both Young’s modulus
and hardness increase with increasing [N]/[Ti] ratio in a similar fashion. The plot of the hardness
versus Young’s modulus shows a linear relationship, which would be due to the fine polycrystal-
line structure.
Mutual alloying and doping improve the mechanical properties. Hardness values of the
TiC-VC system with carbon-to-metal ratios close to 0.84 obtained for various cooling rates in
a floating-zone process indicated that the variation in hardness of pure VC 0.84 obtained by chang-
Figure 5 The plot of reduced cubic-symmetry elastic stiffness shows groupings according to bonding
types (41). A, Alkali metals; B, fcc metal; C, covalent compounds; D, bcc transition metals; E, oxides;
F, alkali; G, NaCl-type carbides.
Figure 6 Three-dimensional surface representing Young’s modulus of TiB2 in different crystallographic

directions according to the elastic constants. (From Ref. 42.)
Figure 7 The shear modulus as derived from Brillouin light scattering, Young’s modulus, and the micro-
hardness obtained by ultra load indentation measurements as a function of the N/Ti ratio in TiNx films.
(From Ref. 43.)
14 Kumashiro
ing the cooling rate is related to the vacancy domain size. The observed trend in hardness of
the alloys is for higher values for TiC-rich than VC-rich alloys and higher values for both alloys
than for the parent carbides (44).
Composite materials are of interest from an engineering standpoint, with potential applica-
tions in the areas of turbine blades, ball bearings, cutting tools, etc. Directionally solidified
lamellar ZrC-ZrB 2 and Chinese-script ZrC-TiB2 eutectics with a phase spacing of 1.85 µm in
a floating-zone method exhibited superior mechanical properties compared with the individual
constituents (45). Notably high values of microhardness (24.02 GPa) and fracture toughness
(5.44 MN/m 3/2) were found for the ZrC-ZrB 2 eutectic. The fracture toughness (KIc) is an impor-
tant selection criterion for brittle materials used in engineering applications. Value of K ic ob-
tained by different techniques vary greatly. The indentation strength (IS), chevron notched beam
(CNB), and indentation fracture (IF) methods are common techniques that were compared with
the recently standardized single-edge precracked beam (SEPB) method (46). The SEPB method
was more difficult to apply, but it represents the most rigorous method for K ic determination
because it uses few assumptions and requires a direct measurement of crack length.
Transition metal nitride superlattices, including TiN/VN (47), and TiN/(V0.6 Nb0.4)N (48),
exhibit Vickers hardness values as much as 2.5 times those for homogeneous nitrides (Fig. 8).
Single-crystal superlattices eliminate possible polycrystalline film structure effects in the hard-
ness measurements. TiN/VN superlattices, with a 2.4% lattice mismatch between the layers,
exhibit pronounced peaks at Λ ⬃ 5 nm, which would be due, at least in part, to the ‘‘supermodu-
lus’’ effect, i.e., increases by a factor of 2–4 of the elastic moduli at specific values of Λ. For
TiN/(V0.6Nb 0.4)N superlattices, with lattice matching of ⬃0.2%, the hardness increase was
smaller and a pronounced peak was not observed. However, the elastic constants of C 44 for TiN/
V0.6 Nb 0.4 N and TiN/NbN superlattices from Brillouin scattering measurements (49) exhibited no
anomalies over the wavelength range investigated, so elastic anomalies are not responsible for
the large hardness enhancements in nitride superlattices. The hardness value for the TiN/
(V0.6 Nb 0.4)N lattice-matched superlattice agrees with that for TiN/VN superlattices, so coherency
strains do not play a major role in enhancing the hardness of these nitride superlattices.
Transition metal carbides and nitrides have attracted considerable attention as catalysts
because of their availability in high specific surface area form with reasonably clean surfaces
(50). They have been shown to have exceptionally high activity in reactions involving hydrogen
Figure 8 Vickers hardness of nitride superlattice structures as a function of superlattice period λ. (From
Ref. 47, 48.)
transfer, such as hydrogenation, hydrogenolysis, isomerization, hydrodesulfurization (HDS), and

hydrodenitrogenation (HDN) of hydrocarbons (50,51). They also show excellent hydrogenation
activity in the treatment of quinoline and coal-derived liquid. Their catalytic activities in hydro-
processing indicate tolerance of sulfer (51).
ACKNOWLEDGMENTS
A number of the figures have been taken from the literature. The author would like to thank
the authors and publishers of these materials for permission to reproduce them here, especially
the American Institute of Physics (Fig. 5 (Ref. 41), Fig. 6 (Ref. 42), Fig. 7 (Ref. 43), and Fig.
8 (Ref. 47 and 48)), Elsevier Science Ltd. (Fig. 1 (Ref. 9) and Fig. 2 (Ref. 15)), and John
Wiley & Sons, Ltd. (Fig. 4 (Ref. 39)).
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3
Bulk Crystal Growth
Yukinobu Kumashiro
I. INTRODUCTION
According to the classification based on the state of aggregation of the starting materials, these
compounds are obtained by liquid-phase, solid-phase, gas-phase, and solution processes and
combinations of these processes. Evaporation-condensation is a physical vapor deposition (PVD)
method in which a metal is evaporated in an atmosphere of rarefied in active gas. In chemical
vapor deposition (CVD) the types of deposits are films, whiskers, bulk crystals, and powders.
Powders are made by growth of nuclei following homogeneous nucleation, and whiskers and
bulk crystals are formed by heterogeneous nucleation on the substrate. Plasma reactants offer
potential advantages for powder preparation: a fast reaction time due to high temperatures and
rapid cooling rates leading to a high degree of supersaturation and homogeneous nucleation.
Carbide and nitride powders are conventionally prepared by the carboreduction of oxide
powder with subsequent nitridation in a nitrogen atmosphere or carborization in an inert gas.
Diboride powders are synthesized by carbothermal reduction, where boron needs to form the
boride and carbon aids in the removal of oxygen. These processes require a high temperature
and a long heating time. Fine powders of these compounds are prepared by the thermite method
by reduction with Mg.
New processes for the production of powders have been developed. Molecular precursor
methods for preparing nitrides are currently being explored. A precursor processible to metal
boride is obtained by dispersing a metal source in a boron carbide polymeric precursor. Electro-
chemically prepared polymeric precursors have been used for the formation of pure nitride and
carbide powders. Direct formation of carbides and diborides by mechanical alloying of metal
powder and carbon or boron powder is also an effective method for synthesizing nanocrystalline
powders.
Self-propagation high temperature synthesis (SHS) or combustion synthesis is of interest
for making a wide variety of powders and sintered bodies, which involves highly exothermic
chemical interactions in combustion mode. The products are generally in the form of powder
blocks or powders, which are comminuted, and the resulting powders are used in fabricating
components by conventional powder metallurgy. The ideal production process would combine
the synthesis and densification steps in a one-step process. New techniques for simultaneous
densification of products in SHS are explosive consolidation or dynamic compaction, hot forg-
ing, and shock-induced reaction synthesis.
These compounds are known to be difficult to sinter to high density because of the small
19
20 Kumashiro
diffusion coefficient of the constituent atoms. Hot pressing and hot isostatic pressing techniques
are usually essential. Additives to the specimen such as Ni, Co, and Al play an important role
in promoting densification via liquid-phase sintering.
The preparation of single crystals of these refractory compounds is fairly difficult because
of their high melting point—3000°C or above. The largest crystals were obtained by liquid-
phase and solid-phase methods; it is much more feasible to prepare larger single crystals of
carbides by these methods than by gas-phase and solution processes. Crystal growth in closed
tubes, involving chemical reactions and gas transport referred to as chemical vapor transport
(CVT), requires a temperature gradient to be described as two successive thermodynamic sys-
tems. The purest crystals (e.g., with purity of the order of 99.98 wt %) have been obtained by
the liquid-phase method and somewhat less pure ones (e.g., of 99.5 wt %) have been prepared
by the solution method, where the impurities in the crystals are the solvent metal. Large single
crystals of carbides and diborides are obtained by the radio frequency (RF) floating-zone process,
but those of nitrides are limited by sold-phase methods. Plasma-arc heating provides not only
high temperature but also the use of light element–containing gases (CO2, CH4, N2, and NH3
gas) as components of the plasma-generating gas, which serves for the compensation of carbon
and nitrogen losses in carbides and nitrides, respectively.
In this chapter, the preparation of powders, fabrication of polycrystalline specimens, and
growth of single crystals are reviewed in relation to crystal characterization.
II. POWDERS
A gas evaporation method in which a carbon rod vertically touches the top surface of a metal
block in a vacuum chamber produces ultrafine particles of various carbides (1). As the electric
current is increased until the carbon rod changes from red heat to white heat in a helium or
argon atmosphere, the metal block melts and molten metal climbs up along the surface of the
carbon rod. Spherical or trigonal smoked TiC with a diameter of about 50 nm can be most
easily obtained (1).
In the CVD process the reactants are gaseous, volatile liquids, or solids with reaction
temperature. The carbide, nitride, and diboride specimens were prepared using TiCl4, ZrCl4,
HfCl4, NbCl4, NbCl5, VCl4, CH4, C3H8, CCl4, NH3, N2, B2H6, and BCl3 at various temperatures
and gas pressures. Ultrafine nitrides such as TiN, VN (2), and NbN (3) were prepared using
MCl4-NH3-H2-N2 systems at temperatures above 800°C. The properties of NbN powders de-
pended on the reaction temperature, mixing temperature of NbCl4 and NH3, and gas composition
ratio ([NH3]/[NbCl4]). The process consisted of the initial formation of NbCl4-NH3 adduct parti-
cles (NbCl4 ⋅ nNH3) in the low temperature (⬍800°C) zone of the reactor and their subsequent
thermal decomposition to NbN particles in the high temperature zone (ⱖ800°C). The NbN
powders consisted of particles with sizes less than 50 nm and showed a superconducting transi-
tion temperature of 14.1 K. Polycrystalline TiB2 powders with 10-nm crystallites (4) and nano-
sized TiC powders (5) were synthesized by CO2 laser–induced pyrolysis of TiCl4-B2H6 and
TiCl4-hydrocarbon. The TiC nanopowder showed high reactivity on air exposure as evidenced
by the surface oxidation of the particles.
Let us consider the various plasma processes for producing powders. One process involves
the reaction between metal halides and reactive gases, which have been widely used in ordinary
CVD processes. The compositions of the products are controlled linearly by those of the re-
actants (6). Titanium diboride powder consisting of submicrometer-sized crystals of equiaxed
and tabular forms with only small amounts of crystal intergrowth was produced in an arc plasma
Bulk Crystal Growth 21
by the reaction of titanium tetrachloride and boron trichloride gases in the presence of excess
hydrogen (6).
In another process, pure metallic powders are used as starting materials. The metallic
powders are vaporized completely in a plasma region and react directly with reactive gases with
an RF plasma torch (30 kW, 4.0 MHz) (7). The compositions of the products were correlated
with the [N2]/[Ti] molar ratio. Thermodynamic equilibrium compositions for the Ti-N2-Ar sys-
tem calculated up to a temperature of 6000 K show nine gaseous species [Ar, Ar⫹, Ti(g), Ti⫹,
N2, N, N⫹, e⫺, TiN(g)] and two condensed species [Ti(c), TiN(c)] (Fig. 1). Ti(c) cannot be
present, so a low flow rate of nitrogen is sufficient to produce TiN particles from the gas mixture.
The condensation temperature of TiN(c) is 2760 K, indicating that solid particles of TiN would
grow from the vapor phase directly, because the melting temperature is about 3220 K. The mole
concentrations of N, Ti⫹, e⫺, and TiN(g) at the condensation temperature would play important
roles in determining the nucleus centers at the beginning of a homogeneous nucleation. There
exists an optimal molar ratio of [N2]/[Ti] for making stoichiometric TiN. Each particle is a
single crystal, and the preferential growth form is a cube bounded by (100) planes.
Adiabatic expansion through a converging-diverging nozzle could be used as an alternative
means to produce the high rates of temperature change required to preserve metastable products;
here the reactants are heated in a plasma and then expanded through a converging-diverging
nozzle to freeze in the desired products (8). The velocity of the gas increases continually from
the inlet in a nozzle, reaches the sonic point near the throat, and becomes supersonic in the
diverging section. The average rate of cooling in a supersonic nozzle is of the order of 107 K/s,
which allows use of TiO2 and C as reactants for the production of TiC (8).
Figure 1 Thermodynamic equilibrium diagram for the Ar-Ti-N system under 1 atm. (From Ref. 7.)
22 Kumashiro
Using liquid synthesis, Powell et al. (9) produced ultrafine powders of NbC and NbN by
conversion of an Nb-bearing spray-dried powder in hydrogen-methane and ammonia atmo-
spheres at temperatures as low as 800 and 700°C, respectively. The solution prepared by slowly
dissolving NbCl5 powder in high-purity ethanol formed a new dissolved compound
[NbCl2(OC2H5)3] and HCl gas. Conversion of the spray-dried powders to NbC was achieved at
temperatures from 800 to 1050°C in a mixed atmosphere of hydrogen and methane, and that
to the NbN was achieved at temperatures of 700–1000°C using an ammonia atmosphere. The
powder processed at 700, 800, and 850°C had the structure of δ-NbN, but it gradually converted
to the stable ⑀-NbN phase from 900 to 1000°C. The powders consisted of 5–10-µm balls subdi-
vided into 10–100-nm microcrystallites. The Tc of the NbC powder produced at 850°C was
approximately 6.8 K with a transition width of 1.5 K.
The electrochemical preparation of polymeric precursors (10–12) involves anodic dissolu-
tion of a metal electrode in a single-compartment electrochemical cell containing an electrolyte
solution consisting of liquid NH3 and NH4X (X ⫽ Br or Cl). Following evaporation of the
solvent and calcination of the resulting powder at temperatures between 375 and 1100°C, such
nitrides as NbN, TiN, VN, and ZrN were produced (12). The NbN precursor requires anodic
dissolution of the metal anode, where Nb5⫹ reacts directly with liquid NH3 by ammonolysis to
form the ceramic precursor. Precursor calcined in pure Ar at 600 and 800°C is superconducting
despite a high level of Br contamination; calcination at 1000°C removes much of the Br, but
with a reduction of Tc.
Metallic tantalum and titanium were electrochemically dissolved in an organic electrolyte
containing n-propylamine (13,14). Metal (M) is oxidized at the anode. At the cathode, NH2R
is reduced and the corresponding anion and gaseous hydrogen are formed. Part of the titanium
occurs as Ti3⫹, which might be formed either directly at the electrodes or by reduction of Ti4⫹
by hydrogen, and tantalum occurs as Ta5⫹. In the course of the electrolysis and drying, the
viscosity of the solution formed amorphous products with the empirical formulas TaC19.3H3.3N5.87
and TiC3.94H8.24N1.14. The former product calcined in anhydrous ammonia and argon at 1000°C
showed the cubic phase of TaC. Calcination of the latter precursor in an atmosphere of anhydrous
ammonia resulted in the formation of a gold-colored titanium nitride–titanium carbide solid
solution with a comparatively low carbon content, about 5%. When the calcination was carried
out in nitrogen, Ti(C,N) solid solutions containing large amounts of carbon were obtained.
Calcining at comparatively low temperatures led to products with poor crystallinity.
An alternative method for the synthesis of nitride powder at a lower reaction temperature
than 1300°C was performed using methane as a reducing agent in the nitridation of zirconia
prepared by a sol-gel technique (15). Anhydrous ammonia was used as the nitrogen source and
methane was used as the reducing agent at a reaction temperature of 1323 K.
Molecular precursor methods (16) also produce transition metal nitrides, where the conver-
sion of the pentamer [(tBuCH2)2 TaN]5 and ammonia to cubic TaN0.8 proceeds via precipitate
1/n[TaC1.41H3.90N1.90]n and amorphous TaN. Precursors other than (tBuCH2)3Ta CHtBu and
NH3, which provided [(tBuCH2)2TaN]5, such as Ta(NMe2)5 and NH3 (Me2N)3 Ta NtBu and
NH3, afforded TaN0.8 with low quality (16).
A precursor processible to a metal diboride is obtained by dispersing a metal source such
as TiO2 or ZrO2 in a boron carbide polymeric precursor, i.e., decaborane-dinitrile polymer. When
these mixtures are heated to ⬎1450°C the corresponding diborides are formed in high chemical
yields (⬎90% based on metal) (17) with very low levels of carbon, hydrogen, oxygen, and
nitrogen. The oxygen contents decrease at higher temperatures. The powders formed at lower
temperatures have a small grain size, but larger crystals with an average size of ⬃2–5 µm were
obtained upon heating at 2000°C.
Direct formation of carbides and diborides by mechanical alloying of metal powder and
carbon or boron powder produces nanocrystalline powders (18–21), where the powder particles
are repeatedly fragmented and cold welded to result in the intimate mixing of reactant particles
on the nanoscale (22). The average grain size of TiC was about 9–11 nm after 27 h of milling
(20). The large negative heat of formation of TiC not only provides a driving force to reaction
but also favors the reaction by increasing the diffusivity of C atoms. Ball milling of titanium
hydride in air for 30 h causes simultaneous dehydrogeneration and nitrogenation of the titanium
hydride to result in nearly stoichiometric TiN with good stability (23). For some highly exother-
mic reactant systems, spontaneous compound formation occurs by a mechanically induced self-
propagating reaction, the mechanism of which is analogous to that of thermally ignited self-
propagating high-temperature synthesis (SHS) (22). When mechanically activated mixtures of
Nb and C powders with 50–80 mol % C ground in a planetary ball mill were transferred into
a graphite crucible and exposed to air, they ignited spontaneously and SHS took place to produce
almost stoichiometric NbC (24).
Solid nitrogen driven by mechanical alloying is a promising method for preparing nano-
crystalline nitrides, where surface-induced dissociation of molecular nitrogen and chemisorption
of nitrogen onto clean metal surfaces created by milling play an important role (25). After 60
h of milling, the fully developed structure of TiN with a very fine grain size of 9 nm is obtained.
The grain size of as-milled ZrN powders was found to be 14 nm. Hf will behave in the same
way. However, Ta2N is the only dominant phase formed in the whole milling process (26). The
heat of formation of Ta2N (⫺271 kJ/mol) is larger than that of TiN (⫺252 kJ/mol), demonstrat-
ing that the formation of Ta2N is thermodynamically more favorable than the formation of
TaN.
A method for producing submicrometer (0.1 µm), low-oxygen-content nonagglomerated
TiC powders involved the carbothermal reduction of carbon-coated titanium diboride (TiO2)
(27), where carbothermal synthesis proceeded via the purification of titanium oxycarbide toward
pure titanium carbide. The carbon coating process provided a high contact area of the reactants
to produce a TiC powder with uniform shape by synthesis at 1550°C for 4 h.
Rapid preparation of TiN, TiC, and TiCxNy powders from mixtures of TiO2 and graphite
powders became possible with an arc imaging furnace (28). TiO2 was reduced completely and
single-phase TiN with fine grains of ⬃1 µm diameter was synthesized within 30 s. The reaction
between TiO2, carbon, and nitrogen was completed to form TiCxNy in a period of time shorter
than 30–120 s. The other transition metal (Nb, Ta, and V) nitride and carbide powders (29)
were synthesized in a short heating time (⬃30 s) using a mixture of transition metal oxides and
graphite in 1 atm of nitrogen or argon flowing gas.
Many diboride powders were prepared by a carbothermic reduction process (30). NbB2
powders with particles of size 40–50 nm with a carbon residue of 2.65% were synthesized from
fine precursor particles prepared from Nb2O5, H3BO3, and cornstarch as starting materials under
optimal conditions (31). An intermediate reaction at 1400°C produced ZrB2 powder by the reduc-
tion of ZrO2 with B4C and carbon with respect to both thermodynamical calculation and experi-
mental observation (32). Excess boron is added to compensate for the boron loss caused by the
volatile intermediate product B2O3 in order to prepare high-purity ZrB2 powder. The higher
processing temperature decreases the oxygen and carbon contents of the product powder but
increases the particle size.
Borothermic reduction was confirmed at a lower temperature, and the carbothermic reduc-
tion occurred at a higher temperature (33), which favors the production of high-purity powders.
TiB2 and ZrB2 powders were also synthesized by mechanochemical treatment of titania and
zirconia powders with amorphous boron followed by a relatively low-temperature annealing
(1100°C) (34). The occurrence of polymorphic transformations has been observed with milling
time for both systems, together with a decrease upon annealing of the temperature of the boro-
24 Kumashiro
thermic reduction reactions with increased milling time. The reaction paths are different for
TiB2 and ZrB2, with TiBO3 and Ti2O3 formed as intermediate compounds in the case of the
borothermic reduction of titania, whereas in the zirconia-boron system a direct borothermic
reduction of zirconium oxide is observed.
Mitamura and coworkers (35–41) have synthesized fine powders of carbides, nitrides, and
diborides (particle size 30–100 nm) by means of the thermite method by reduction with Mg;
metal oxides were used as a source, and CH4 gas, N2 gas, and amorphous boron were used as
light element sources. The preparative process is shown in Fig. 2. The synthesis conditions for
single-phase powders depend noticeably on the molar ratio of Mg to metal oxide, temperature,
and heating rate. The powder product was washed with (0.05–1) M HCl to remove by-product,
washed with water and ethanol, and then finally recovered centrifugally. In the case of carbide
(35–37), Mg plays the important role of continuously feeding C into the reaction group through
the Mg-Mg2C3-Mg cyclic reaction. The Mg2C3 decomposes easily so that reduction by Mg is
not inhibited, and formation and decomposition of Mg2C3 improve the carbonization of the
reduced product of metal by supplying the C source. Metal oxides are not completely reduced
in an N2 gas stream because Mg3N2 is formed by a reaction of the N2 gas and Mg (N source
and reducing metal), lessening the activity of Mg as a reducing metal. Then nitride powder
(38,39) is obtained by nitridation of metal at a temperature at which the decomposition of Mg3N2
occurs after completing the reduction of metal oxide with Mg. The reaction of Mg with amor-
phous B occurred to form MgB2, which decomposed into MgB4 and Mg (40,41). MgB2 did not
interfere with the formation of diboride because it decomposed above 750°C, but MgB4 inter-
fered with the boridation of metal above 850°C. It is most important to suppress the formation
of MgB4 by controlling the reaction temperature below 850°C.
TiN powders were also produced by reacting NaCN, sodium cyanide, at 1000°C with
several Ti compounds: TiO2 (42), TiP2O7, (TiO)2P2O7, NaTi2(PO4)3, and Na4(TiO)(PO4)2 (43).
Combustion synthesis (44) is an efficient method for making a wide variety of materials
such as carbides (45,46), borides (47), and nitrides (48,49) and is superior to conventional meth-
ods with respect to higher purity and more reactivity (Fig. 3a). When the SHS reaction is carried
out with powders containing ‘‘nonvolatile’’ contaminants, significant amounts of these impuri-
ties remain in the product (50). The initial reactant mixtures (chemical composition, shape and
size of reactant particles, and shape, size, and density of samples) and combustion conditions
(composition and pressure of the environment, initial temperature of the compact, the method
and intensity of combustion initiation, or additional external effects) determine the properties
of synthesized materials (45–49).
Three different modes of combustion behavior, steady-state burning, oscillatory burning,
and spin burning, were noted in the synthesis of various materials, and the differences in the
burning behavior were attributed to the heat losses and to the exothermicity of the reaction (44).
Combustion velocities are influenced by the theoretical maximum density and particle sizes of
Ti and C (51). Synthesis of TiC consists of an initial diffusional reaction of liquid Ti and C at
the combustion front, mainly occurring during the passage of the combustion front, and an
additional reaction leading to completion within 400 ms after melting of Ti metal, confirmed
by real-time diffraction using synchrotron radiation (52). Utilization of a very high surface area
carbon for the synthesis of TiC leads to a very low surface area carbide (53). The apparent
reactivity of titanium with graphite powder was higher than with amorphous carbon black pow-
der. The reaction between graphite and liquid titanium was accomplished mainly on the surface
of the thinly fissured layer where the carbon diffusion through TiC is the rate-controlling process.
The reaction occurring in the bulk titanium phase produces the sintered grain structure, and that
occurring in the inter- and intraparticle pores of carbon produces the agglomerated fine particles
(54). The SHS method is used with mixtures of TiO2, Mg, and C to prepare TiC powder. The
Bulk Crystal Growth
Figure 2 The preparative processes in the thermite method (35–41). (Courtesy of Prof. T. Mitamura, Saitama Institute of Technology.)
25
26
Figure 3 Schematic representation of various SHS processes including high-pressure self-combustion sintering as a combination of SHS and high-
pressure technique (79–81).
Kumashiro
TiC/MgO product is leached by hydrochloric acid to remove the MgO and to obtain TiC with
⬎99.9% purity and a uniform particle size of 0.3–0.4 µm (55).
Although SHS of diborides was performed in an argon atmosphere (56), it is possible to
initiate and sustain it in a vacuum using the plane wave propagation mode of combustion reac-
tions between particles mixed corresponding to the composition TiB2 (57). The synthesis wave
propagation underwent considerable volume expansion, so that a spongelike structure of the
reactant TiB2 was obtained. When combustion synthesis was carried out in air, some TiN forma-
tion was also observed (58).
The product of combustion of Ti under nitrogen at 1 atm is a mixture of titanium nitride
and two solid solutions of nitrogen in titanium (primarily α and β-transformed α). The relative
abundance of the latter phases depended on the degree of melting of titanium and the initial
relative density of the sample (59,60). The influence of nitrogen pressure on the combustion
wave velocity and the degree of conversion to NbN indicated that the dominant nitride phase
was Nb4N3 at low pressures (⬍2.7 atm), but at higher pressures the major phase in the surface
layer was NbN (61). The conversion increased rapidly from about 35 to 70%. Further increase
in the pressure produced a much less significant increase in conversion, approaching an asymp-
totic value of 75% at the highest experimental pressure, 13.6 atm, related to the formation of
a surface layer. The relative thickness of the surface layer continues to grow as the pressure
increases beyond this value, ultimately increasing by a factor of 3 as the pressure reaches the
maximum of 13.6 atm.
Nitrogen and Ta in the combustion wave form the intermediate product TaN with a single
phase if the process is quenched after the combustion wave has passed (44). If the sample is
heated by the combustion wave in nitrogen, repeated combustion takes place with the forma-
tion of the TaN phase. It should be noted that experiments at ambient nitrogen pressure (⬃40
atm) produce a hexagonal modification of TaN, but those at high pressures (⬃3000 atm) yield
a cubic one. The cubic modification is synthesized by the combustion of Ta in liquid nitro-
gen (44).
The TaN was also synthesized by shock compression (62). Shock compression recovery
experiments with a porous sample of tantalum nitride with a hexagonal structure were performed
in the impact velocity range up to 1.5 km s⫺1. The recovery rate of the B1-type phase increased
with increasing porosity. Almost 100% recovery was achieved for a powder of 70% porosity
on impact by a 2-mm-thick tungsten plate with velocities above 1.4 km s⫺1. The shock-synthe-
sized B1-type tantalum nitride has good stoichiometry compared with combustion-synthesized
ones.
The synthesis of refractory ceramics via rapid solid-state metathesis (SSM) reactions be-
tween solid metal halides and alkali (or alkaline earth) metal main group compounds (e.g., Li3N
or MgB2) is combustion-like synthetic technique (63). Rapid, highly exothermic reactions can
reach high temperatures (⬎1000°C) in a very short time (⬍1 s) with careful choice of the
precursors. The desired product is easily separated from the salt by-products and any unreacted
starting materials by washing with alcohol and/or water. Metal chlorides with a high oxidation
state provide sufficient volatility and reactivity to result in rapid, exothermic reactions with
lithium nitride or sodium azide. A mixture of finely divided ZrCl4 and Li3N is ignited with a
heated filament to produce superconducting ZrN in a molten LiCl flux, while the reaction front
containing reactive species moves quickly through the sample. Partial substitution of Li3N by
NaN3 reduces the amount of undernitrided material in favor of the stoichiometric cubic mononi-
tride. The reaction mode in the diborides varies with the metal halide used. An alkaline earth
boride, MgB2, is used as the boron source (64). Generally, group V chlorides lead to rapid self-
propagating reactions, whereas group IV counterparts (TiCl3, ZrCl4, and HfCl4) require pro-
longed external heating (⬎650°C) in evacuated silica tubes to produce a complete reaction.
28 Kumashiro
III. POLYCRYSTALLINE SPECIMENS
It is very difficult to obtain fully dense specimens by conventional sintering unless very fine
nanocrystalline powders (65) or ‘‘in-flight plasma powder treatment’’ is used (66). Complete
densification of a titanium diboride powder by pressureless sintering occurred when a powder
with high purity and submicrometer particle size was produced by an arc-plasma method (6).
Considerable changes of chemical composition took place during the introductory plasma treat-
ment of titanium carbide powders involving the formation of carbon site vacancies and the
dissolution of oxygen atoms on the surface of the particles, which gave rise to greater shrinkage
at the initial stage of the sintering process due to diffusional transfer of atoms through the
vacancies at temperatures lower than 1700°C. The sintering behavior is affected by the amount
of oxygen in the starting powder and the type and content of metal dopants. Additives to TiN
such as Ni or Co (67) play an important role in promoting densification and cause the precipita-
tion of a second phase at the grain boundary, resulting in a reduction of grain size in comparison
with additive-free TiN. Dense TiB2 bodies (⬎94% of theoretical density) were obtained at tem-
peratures as low as 1500°C using nickel as the sintering additive under vacuum and in an argon
atmosphere (68). The addition of carbon strongly reduced the density and oxygen content and
inhibited grain growth, so that the exaggerated grain would be enhanced by surface diffusion
in a titanium oxide–rich layer on the TiB2 grains. Dense ZrB2 has been produced from powder
mixtures of B6Si and ZrO2 or ZrSi4 by the thermal explosion mode in an SHS process through
the formation of a thin glass phase along the ZrB2 grain boundaries (69). The simultaneous
synthesis and the use of an additive to provide the liquid phase in the combustion process is
also essential to promote densification of the products. Addition of Ni to the initial Ti and C
powder mixture pellets produced a maximum density of ⬃75% of the theoretical density after
SHS reaction by filling of the pores by Ni during the SHS reaction (70).
The microwave sintering method (2.45 GHz, 6 kW) is suitable for rapid densification
above 2000°C. An enhanced sintering ‘‘microwave effect’’ occurs with 2.45-GHz processing
with an inert gas atmosphere as compared with conventional sintering, so that the microwave
sintering of TiB2 –3 wt %CrB2 occurs at lower temperatures (200°C lower) and yields material
with improved hardness, grain size, and fracture toughness (71).
Hot pressing or hot isostatic pressing techniques are usually applicable for the densification
of ceramics (72), and the synthesis and simultaneous sintering of ceramics can be accomplished
directly from the constituent elements in a period of seconds without external heating for a
longer time. The activation energy of ZrC hot pressing (73) was in better agreement with that
of carbon diffusion. Hot-pressed NbB2, fabricated without additives contains pores both at the
grain boundaries and within the grains and cracks along the grain boundaries (74). TiN additions
are effective in preventing grain growth and improve the mechanical properties by reducing
porosity and grain size. The effect of Al as an additive to TiN in hot press sintering indicated
that the formation of an intermetallic compound, TiAl3 (melting point 1340°C), was the major
factor in densification, so that densification started at 1300–1400°C (74).
A high-pressure self-combustion sintering (HPCS) process is a combination of SHS and
a high-pressure technique (Fig. 3c and d). Forced consolidation techniques that involve small
time scales, such as high-speed forging, would be preferable to techniques that require substan-
tially more time, such as hot pressing or hot isostatic pressing (HIP). A dense TiB2 compact
with a relative density of 95% and a microhardness of 20 GN/m2 is easily fabricated in a few
seconds with electric ignition at one end of a powdered mixture of the constituent elements
under 3 GPa by means of a cubic anvil press (76). High-density and high-hardness TiB2 and
TiB2-based materials are obtained by SHS under uniaxial compression (77). Miyamoto and
Koizumi (78) and Miyamoto (79) have attempted to apply gas pressure using HIP (Fig. 3d). Two
ignition electrodes were installed in the HIP equipment, and the conventional glass encapsulation
technique for HIP was adopted to prevent gas penetration into the green compact. Nearly fully
dense ceramics and ceramic composites of TiB2, TiCx, and TiC ⫹ Ni have been obtained from
their elemental powders under an Ar gas pressure of 100 MPa by the gas pressure combustion
sintering method. Some alterations in HPCS would be necessary to obtain monophase nitride
(80,81), with an Nb metal plate embedded in the combustion agent of Nb ⫹ NbN powders and
the agent burned at nitrogen pressures above 3 MPa (Fig. 3d). The Nb plate is converted to an
NbN ceramic plate by the nitriding, mainly because of the reaction heat of the combustion agent.
When the Nb metal is thin, less than 100 µm thick, the plate is completely nitrided NbN0.88 with
a Tc of 16.4 K in a few minutes. The B1 NbN is a high-temperature phase in equilibrium above
1300°C, so that the high-temperature phase is quenched by the rapid propagation of combustion.
With thick Nb metal, NbN and Nb2N layers are formed at the surface.
New techniques for simultaneous densification of the products are explosive consolidation
(82) or dynamic compaction (83–87), hot forging (88–90), and shock-induced reaction synthesis
(91,92). These techniques have been used to produce TiC and TiB2 with greater than 96–98%
of theoretical density and microhardness values equal to or greater than those of commercially
available hot-pressed materials. Their fracture properties indicate an improvement in intergrain
bonding. In the SHS/DC technique, hot and porous ceramic bodies formed during the SHS
reactions are consolidated to high density by the action of a pressure wave generated by the
detonation of a high explosive and/or the impact of an explosively driven flyer plate. Under
appropriate conditions, near fully dense TiB2, TiC (83), and HfC (84) ceramics could be pre-
pared. The effects of the powder characteristics, inert diluent, impurities, delay time, C/M ratio,
and ratio of the explosive mass to the metal driving plate mass on the synthesis and compaction
were clarified. The C/Ti ratio significantly alters the structure of the product TiC. The ideal
composition for TiC made by the SHS/DC technique has a C/Ti ratio of 0.95 to 0.90, and
sufficient density is achieved without significantly reducing the microhardness (95). TiB2 speci-
mens prepared by the SHS/DC method using boron powder containing 1–5% carbon had higher
densities and less cracking than those prepared using purer boron powder (0.2% carbon), so
less pure boron powders were employed in the production of dense TiB2 ceramics (94). The
grain boundary strength of the TiB2 and TiC prepared by the SHS/DC process was relatively
weak because of the rapid heating, compression, and cooling in the process (95). The process
of shock compression loading places a material in a highly unusual combination of states. Very
high pressures and significant increases in temperature for a few microseconds cause deforma-
tion and forced relative mass motion of individual particles, exposure of fresh surfaces, and
cleansing of existing surfaces that lead to interparticle bonding. The passage of a shock wave
triggers an exothermic, self-sustaining reaction between elemental powder mixtures of Ti and
B and of Ti and C (91) to produce compact ceramics. Almost crack-free compacts with better
than 96% density and hardness of ⬃2000 kg/mm2 have been produced (91).
The SHS process was used to produce ceramic composite materials (81) consisting of
titanium carbide (TiC) and an intermetallic alloy of the nickel-aluminum (Ni-Al) system (95).
The materials were produced by rapidly heating a mixture of elemental titanium (Ti), carbon
(C), Ni, and Al powders in a graphite die up to the ignition temperature. By applying mechanical
pressure during or immediately following the combustion reaction, products with greater than
99% of theoretical density were obtained. It is possible to synthesize simultaneously composites
composed of both TiB2 and TiN phases from elemental powders of Ti, B, and BN by SHS (96).
Both TiN and TiB2 phases had small grain sizes, less than 1µm, due to the pinning effect of
TiN grains. Boron nitrides can be used as solid nitrogen sources to fabricate desired composites,
including nitrides, where nitrogen turns into the green mixtures in the form of decomposition
compounds and makes it possible to overcome the problem of permeation while increasing the
30 Kumashiro
amount of bonded nitrogen (97). TiB2 /TiC0.5N0.5 composites were fabricated by controlling the
ratio and adjusting the combustion parameters of the initial reactants of Ti, B4C and BN.
The self-propagating reaction process is expected to be an excellent method for producing
functional gradient material (FGM) (98) whose interlayers form a compositional gradient. TiB2-
Cu composites were fabricated with stepwise compact interlayers of Ti, Cu, and B mixed pow-
ders. The maximum temperature of the product was calculated for the adiabatic reaction, and
the reaction propagating regions were obtained for Ti-2B-TiB2-Cu mixed powder.
IV. SINGLE CRYSTALS
Single-crystal whiskers of similar refractory carbides [TiC (99–105), ZrC (106), and HfC
(107,108), nitrides [TiN (109–111) and HfN (107)], and diboride [NbB2 (112) have been grown
by the CVD method. A number of authors have reported investigations of the catalystic effect
of impurities on the growth of whiskers by the vapor-liquid-solid (VLS) mechanism in high
temperature ranges. In the lower temperature region, ZrC (106) and HfC (107) whiskers are
considered to grow by the vapor-solid (VS) mechanism and NbB2 whiskers (112) by radial
growth with a comparable rate by a VS mechanism. Also, NbC whiskers were synthesized by
heating of Nb2O5 powder and carbon black in the graphite crucible at an argon atmosphere of
1 MPa to a temperature in excess of 1100°C (113). Sodium fluoride and sugar were added to
initiate the reaction and supply an active carbon source. According to the VLS mechanism, the
major factor inhibiting the growth of TiC whiskers is capture of part of the Ni-Ti-C alloy by
the growing whiskers (103). TiC whiskers could be grown by the VLS mechanism in a lower
temperature range from 1270 to 1370 K (114). In this method TiC, the product of the gaseous
reaction, is first transferred from the vapor to the liquid eutectic alloy Ni-Ti on a nickel substrate,
diffuses through the liquid toward the liquid-solid interfaces, and finally, on saturation, is precipi-
tated on the interface as whiskers. Crystal qualities of whiskers were examined by field ion
microscopy (FIM), electron diffraction and high-resolution lattice imaging, and X-ray topogra-
phy. Figure 4 shows an FIM image of an HfC whisker with twofold symmetry (107).
Transmission Berg-Barrett topographs (115) of a tapered 〈111〉 TiC whisker are shown
in Fig. 5. Several intense broad lines for grooves and faint sharp lines for edges are observed
to run along the growth axis. The image contrast of the whisker edge is considered to be formed
by the lattice distortion around the whisker edge. The whisker tips surrounded by several facets
are imaged with intense enhancement. The image contrast at the tips would be due mainly to
lattice distortion caused by segregated impurities, although an electron probe microanalysis
(EPMA) test failed to detect possible impurities because of the small content. The included
impurities at the tip are considered to take part in the whisker growth.
Kamiya et al. (116) reported on the preparation of TiN fibers (presumably polycrystalline)
by nitridation with NH3 of TiO2 fibers prepared by a sol-gel method; for a 5-h exposure to NH3,
the nitriding reaction started at 900°C and was complete at 1100°C. Microcoiled fibers of TiC
were prepared by vapor-phase metallizing of microcoiled fibers with full preservation of the
coiling morphology of the source coiled carbon fibers (117). TiC1.0 coils were obtained at 1100–
1200°C for 1.5 h. The bulk resistivity of the coiled TiC fibers sharply decreased with the bulk
density and was 10⫺2 S⫺1 cm at 1.4 g cm⫺3.
When sodium titanium bronze (STB), NaxTiO2, was reacted with NaCN formed at 1000°C,
the TiN had the morphology of needles or whiskers (118). The presence of Ti3⫹ in the bronze
enhanced the initial concentration of Ti in NaCN. The yields of TiN whiskers were always close
to 100%, so whisker formation did not involve a volatile Ti species.
Dai et al. (119) reported the synthesis of nanoscale structures based on nanotubes, in which
Figure 4 Neon field-ion micrograph of HfC whisker. The twofold symmetry of the image shows that
the growth orientation is along the 〈110〉 axis (107). (Courtesy of Dr. M. Futamoto, Central Research
Laboratory, Hitachi Ltd., Kokubunji, Tokyo.)
the tubes are converted to carbide rods by reaction with volatile oxide and/or halide species.
Transmission electron microscopy (TEM) images of the product obtained from the reaction of
TiO and carbon nanotubes at 1375°C show both straight and smoothly curved, solid rodlike
structures that are distinct from the irregularly curved and hollow carbon nanotube reactant.
The TiC nanorods were single crystals with a very low density of stacking faults. The diameters
of the rodlike products were similar to those of the carbon nanotubes, 2–30 nm, and the lengths
Figure 5 The 220 topographs of a TiC 〈111〉 direction whisker (115). (Courtesy of Prof. K. Hamamura,
Polytech College, Tokyo.)
32 Kumashiro
typically exceeded 1 µm. TEM and electron diffraction studies of stoichiometric TiC single
nanorods showed a smooth regular sawtooth with 〈110〉 axis and irregularly faceted nanorod
with 〈111〉 axis morphologies. The reaction of Nb metal and I2 with carbon nanotubes at 730°C
yields superconducting polycrystalline NbC nanorods because of the low reaction temperature.
The data can be explained in part by a mechanism involving template-mediated growth.
CVD is the most suitable technique for preparing highly dense, thick, and oriented plates.
Octahedral single crystals (⬃1.5 mm) were deposited on a graphite substrate from a vapor phase
consisting of TiCl4-CCl4-H2 in the temperature range 1200–1600°C (105). Titanium carbide
(TiCx, x ⫽ 0.6–1.0) (117), titanium diboride (121,122), and titanium nitride (TiNx, x ⫽ 0.74–
1.0) (123) plates were prepared using various gases at various deposition temperatures (Tdep)
and total gas pressures (Ptot) of 4 to 40 kPa. The Tdep was in the range 1673–1873 K for TiCx,
1323–1773 K for TiB2, and 1373–1873 K for TiNx. The preferred orientation of the plate varied
mainly with Ptot. The deposition rates showed a strong gas molar ratio and the maximum rate
was found at a certain ratio. This maximum peak shifted to a lower gas molar ratio for TiN.
The stoichiometries for TiNx and TiCx were controlled by the deposition conditions. The activa-
tion energies for the formation of plates are 41–50 kJ/mol for TiB2 and 86–95 kJ/mol for TiCx,
indicating that the diffusion of the gaseous species through the boundary layer is rate determin-
ing. The activation energy for TiNx is 80 kJ/mol in the lower temperature range, so that the
deposition reaction of NH3 gas would be associated with the rate-controlling step. However,
the diffusion process would predominate to form a large amount of powder (mainly NH4Cl) in
the gas. Nonstoichiometry may be controlled over wide ranges, and the deposition region of
nonstoichiometric TiNx becomes smaller at higher Tdep values (124). Although the calculations
and experiments have the same trend—i.e., x values increase with increasing source gas molar
ratio m N/Ti (⫽[NH3]/[TiCl4])—there is a significant discrepancy between the calculated and ex-
perimental m N/Ti values for the deposition of nonstoichiometric TiNx plates, which suggests the
formation of intermediate species (such as imides or amides) in the gas phase.
The thermodynamic approach (125) was used to calculate the gas-phase composition in
equilibrium with the solid and the theoretical efficiencies of deposition at equilibrium. The
chemical compatibility of the substrate with the gas phase in the first stages of the deposition,
to define the pressure-temperature-composition ranges of stability of various solid phases in
multicomponent gas-solid systems, are shown for TiC (Fig. 6) together with the curves obtained
for values of P 0TiCl4 equal to 10⫺2, 10⫺1, and 0.5 atm. The minimum possible value of C/Ti in-
creases when P 0TiCl4 increases, which is the complete ‘‘CVD phase diagram’’ for Ti-C solids
deposited from TiCl4-CH4-H2. Isostoichiometric curves are also reported in the deposition do-
main of the pure ZrxC1⫺x solid solution (126). For equilibrium, the deposited phase (ZrC ⫹ C,
ZrC, ZrC ⫹ Zr) and composition of the pure solid solution may be easily varied by adjusting
the input partial pressure of CH4 at a constant ZrCl4 feed. At 1900 K, the field of interest is
located in the following range (atm units): 5 ⫻ 10⫺3 ⬍ P 0CH4 ⬍ 10⫺2 and 6 ⫻ 10⫺2 ⬍ P 0ZrCl4 ⬍
10⫺1.
Both the suitability of a system for transport and the transport direction can be predicted
in the CVT method (127). Iodine was the most popular transport agent. TeCl4 was the best
transport agent (TA). In particular, TiB2 single crystals of known atomic ratio (128) were investi-
gated in relation to the influence of the transporting agent. Two groups of TAs were selected:
(a) a group with T2 ⬎ T1 (I2, BI3) in which the efficient chemical species are BX3 and TiX4 and
(b) a group with T2 ⬍ T1 (TeCl4, BBr3) in which the transport is due principally to BX3 and
TiX3. The T1 and T2 ranges were 1050–1255 K and 1105–1225 K, respectively. The transport by
TeCl4 should occur in a reverse temperature gradient (1250–1120 K). The amount of transported
diboride was three times as important as in I2 and BI3. The TiB2 crystals are well-formed hexago-
nal-based prisms well developed along the three crystallographic directions, ranging from 1 to
Figure 6 Phase fields for solid species deposited at equilibrium in the Ti-C-H-Cl system, showing the
iso-concentration curves in the titanium carbide single-phase domain. (From Ref. 125.)
3 mm in size, and the faces of these crystals have spirals typical of vapor-phase growth. The
B/Ti atomic ratio varies from 1.89 to 1.94 for I2, BBr3, and TeCl4 and increases as the atomic
ratio of boron to titanium in the gas phase increases. Correlation with the gas-phase composition
should lead to a value of about 1.96 for BBr3. Thermodynamic computations give the partial
pressures of all the gaseous compounds present in the system; the ratio of the ‘‘boron’’ partial
pressure to the ‘‘titanium’’ (combined forms) partial pressure in the gas phase in equilibrium
with the growing crystals varies when going from I2 to BBr3.
Next, we would like to introduce the flux method. Several attempts have been made to
prepare some of carbides and diboride crystals with the aid of metal flux solvents (129). Nakano
et al. (130) prepared TiB2, ZrB2, and HfB2 from molten Fe solutions. Cobalt, nickel, and alumi-
num fluxes were also used to obtain TiB2 single crystals (128,129). As for carbide crystals, the
growth of TaC (133,134) and HfC (134) from Fe solutions has been reported. Higashi et al.
(135) grew single crystals of diborides and carbides of TiB2, ZrB2, HfB2, NbB2, TaB2, TiC, and
TaC by using molten Al as a solvent to demonstrate that Al is a suitable solvent for the growth
of diborides and carbides. The molten solutions were kept at 1500–1550°C for 10 h except for
TaC, which was kept at 1300°C for 50 h. They cooled to 600°C at the rate of 10°C/h. Metals
dissolve in the Al melts at the initial stage of heating of materials and then gradually react with
B (or C) to produce powdery crystals. The crystals mostly subside to the bottom of the crucible,
34 Kumashiro
with only the very small ones dissolving in the Al melt even at the maximum temperature.
While the molten mixtures are kept at this temperature, the melt becomes supersaturated, and
they grow into crystals in the lower temperature regions of the crucible, while the powdery
products supply the solute materials for further crystal growth (135). The amounts of solvent
atoms incorporated in these crystals range from 0.02 to 0.1 wt %. As-grown crystals with well-
developed prismatic and pyramidal planes had the shape of a needle-like hexagonal prism. Many
shallow and sharp pits corresponding to local defects such as impurities are observed in the
(0001) and (101̄0) planes.
Chan and Kauzlarich (136) discovered a novel synthetic route for making TaC and NbC
single crystals in the course of studying the superconducting phase of Lu2Cl2C2⫺x. TaC and NbC
single crystals can be prepared by reacting Ta or Nb and C in an LnCl3 (Ln ⫽ Y, Lu) flux at
1000–1150°C for 14 days.
The revised eutectic temperature of 1270°C instead of 1680°C for the published phase
diagrams of the quasi-binary system TaC-Co makes it impossible to use alumina crucibles, so
TaC0.98 single crystals have been grown from a Co flux using intermittent stirring and a modified
Czochralski technique (137). The furnace unit (Fig. 7) consisted of a water-cooled aluminum
cast housing that could be evacuated to 0.4 torr. The graphite heater is surrounded by a heat
shield of graphite wool. The experiment was performed with He gas as a protective atmosphere
at a slight overpressure against atmosphere. The crucible was rotated in order to avoid concentra-
tion gradients in the melt with resulting constitutional supercooling and spurious nucleation.
After the melt was homogenized at 1600°C, it was slowly lowered to the pulling temperature.
The seed was brought near the melt surface to reach the temperature of the surroundings (⬃ 1
h). Then it was dipped in the flux and pulling began with intermittent stirring. A cooling rate
of 5°C/day produced the largest cubic TaC (⬃ 7 mm) with (100) faces.
Next, a solid-phase process for carbides and nitride will be mentioned. Good single crystals
Figure 7 Furnace unit with crystal pulling system. (From Ref. 137.)
for several carbides were obtained by Fleischer and Tobin (138,139) using liquid-state carburiza-
tion at high temperatures. Reactions of liquid Ti, Zr, Hf, V, Nb, and Ta with graphite thimbles
produce the transition metal monocarbides. Carbon gradients in the carbides produced by direct
reaction were largely eliminated by extended homogenizing anneals (⬃100 h) at temperatures
100 to 200°C below the carbide-carbon eutectic temperatures. The resulting grain structures
were fine and uniform in HfC; larger and nonuniform in TiC, ZrC, NbC, and TaC; and very
coarse and irregular in VC. The conversion of the polycrystalline carbides to single crystals and
grain size refinement were examined by uniaxial loading experiments. Sufficient strain was
developed by deforming these carbides in the temperature range 2000 to 2500°C to recrystallize
them on subsequent annealing at higher temperatures. The recrystallized grain size was a func-
tion of the amount of plastic strain. Strain levels near the critical strain encouraged very large
grains, i.e., single crystals of TiC, ZrC, HfC, NbC, and TaC without lineage structure. The main
problems would be long annealing times at very high temperatures, cracking, and difficulties
of seeding particular orientations.
Growing nitride single crystals with the δ-phase turned to be extremely difficult, because
the cubic phase can be produced only in a very narrow range of temperatures, pressures, and
concentrations. Scheerer (140) tried to prepare NbN by diffusion of N into Nb and NbN1⫺x at
temperatures higher than 2000°C, so nitriding niobium single crystals over a period of several
days by direct or indirect heating in a tungsten crucible to 1600 up to 2000°C at a nitrogen
pressure of 20 bar is a workable possibility for preparing δ-NbN0.89 single crystals with a super-
conducting transition temperature of 14.5–15 K. Christensen et al. (141) prepared single crystals
of δ-NbN by a zone annealing technique. A niobium rod of 99.99% purity was annealed in a
nitrogen atmosphere at a pressure of 2 MPa and a temperature of approximately 2100°C for
100 h to convert it to γ-NbN. Single crystals of γ-NbN with volumes of 0.5–1 cm3 were cut
from the rod and were zone annealed at 2 MPa nitrogen gas and 2300°C for 100 to 150 h to
produce δ-NbN0.93. This method was applied to prepare other transition metal nitrides. A hafnium
rod of 99.9% purity was made by zone melting in helium, and the rod was then annealed in a
nitrogen atmosphere at high pressure to give a single crystal of δ-HfN0.93 (142).
The RF floating-zone process is suitable for growing large single crystals. Packer and
Murray (143) examined zone melting of TiC, ZrC, VC, and NbC by RF heating employing an
eddy current concentrator under pressure of an argon atmosphere (Fig. 8). The concentrator
consisted of two main parts: a cylinder with a single longitudinal slit and a U-shaped insert that
is situated inside the split cylinder so as to bridge the slit halfway along its length. Currents
induced in the cylinder by the work coil must be conducted through the insert, whose thickness
is a principal factor determining the length of the molten zone. Some attention was given to
the shape of the concentrator insert to maximize the stability of the molten zone for crystal
growth. Single crystals of VC with compositions of VC0.34–0.77 and of NbC with compositions
around NbC0.84 were readily grown (144), but high pressure was necessary to obtain stoichiomet-
ric NbC and TiC single crystals. TaC has been melted, but it has not been possible to form a
stable zone in the material. This method was not widely used, but the RF floating-zone method
developed by Haggerty and Lee (145,146) became popular and was used to prepare most carbide
and diboride single crystals, 6–10 mm in diameter and 30–100 mm in length (147).
First, the conventional RF floating method will be reviewed (Fig. 9). The sintered speci-
men was heated gradually to its melting point. During solidification the specimen was pulled
up continuously at constant rate. It was rather difficult to keep the molten zone stable during
crystal growth owing to overflow of the melt and puncturing of the coils by arcing between the
coil and the melt or between one coil turn and another. An outer polycrystalline rim was observed
at both ends of the single crystals, which is attributed to the light elements being prone to diffuse
outward through molten region during crystal growth, so that the vacancies introduced into the
36 Kumashiro
Figure 8 Schematic diagram of the floating zone apparatus using an eddy current concentrator. (From
Ref. 143.)
structure coalesce to produce the clusters that form grain boundaries (148). There would exist
an optimal pressure for growing such refractory carbides, depending on the dissociation pressure
of the specimen, the viscosity of the melt, and both heat and mass losses caused by convection
(148,149). Single crystals of VC (150), NbC (151), ZrC (152), and TaC (152) were grown under
appropriate pressures of 0.3 and 1.0 MPa, respectively. Above this, both the rates of transporta-
tion of evaporated species and heat from the surface of the specimen, accompanied by convection
flow of gas, would become larger (150). An increase in density of convection flow over the
specimen surface, therefore, is found at higher gas pressure. The C/Ti ratio along the radial
direction (Fig. 10) indicated that in the case of lower ambient pressure the C/Ti ratio is constant,
corresponding to TiC1.00⫾0.02 over the whole region, compared with the case of higher ambient
pressure. Then the temperature gradient toward the inner side from the surface in the growing
specimen at 17 atm becomes larger than at 3 atm. In the phase diagram of the Ti-C system, the
carbon vacancies increase with temperature, resulting in a decrease in carbon content from S
to B in Fig. 10. The increase in carbon content from B to A is due to the diffusion of vacancies
toward region B from the inner part with constant composition. In the case of 3 atm, the tempera-
ture gradient across the specimen would be expected to be lower because of small heat loss
from its surface.
Larger etch pit densities of VC0.88 than of VC0.83 form the subgrain boundaries characterized
by the presence of substructure such as antiphase boundaries due to the formation of an ordered
compound (150). The hardness of NbC decreases with carbon content and the hardness anisot-
ropy of NbC0.8 is less pronounced than that of NbC0.9 (Fig. 11), which would be due to (a)
deviation from stoichiometry of the crystal and (b) ordering of carbon vacancies. A high-resolu-
tion electron microscopy (HREM) study gives very detailed information about defect order
Figure 9 Diagram of the zone melting arrangement. Broken lines indicate the shape of the molten zone
(148–152).
within carbides (153–158), such as conservative and/or nonconservative antiphase boundaries

(APBs), domain boundaries, and interfaces between differently ordered superstructures. A
multibeam image recorded at a relatively large thickness (⬎100 Å) of the 〈110〉 lattice of an
NbC0.88 annealed specimen (157) shows two sets of {111} face-centered cubic (fcc) planes are
resolved (d{111} ⬃ 2.58 Å). The ordering of domains along the [11̄1] and [11̄ 1̄] cubic directions
is confirmed: the superlattice fringes that appear in the precipitates correspond to a doubling of
Figure 10 C/Ti ratio determined by EPMA with scanning along the radial direction. (From Ref. 149.)
38 Kumashiro
Figure 11 Hardness anisotropy of {100} plane of NbC0.8 and NbC0.9. (From Ref. 150.)
this {111} matrix distance, that is, d1 ⫽ 5.15 Å ⫽ 2d{111} (d1 is the distance between nearest
‘‘vacancy-containing’’ carbon layers of the {111} cubic family). Matching of the experimental
HREM micrograph with images simulated by ‘‘multislice’’ calculation (Fig. 12) demonstrates
that the ordering of carbon vacancies would induce a detectable difference in intensity for white
dots, which represent the 〈110〉 carbon columns, with the atomic rows that are fully occupied
in lower contrast than those with an occupancy factor of 2/3, but the metallic sublattice is not
observed.
Crystal growth experiments with TiN and ZrN rods (159) using the floating-zone process
with a nitrogen pressure of 18.8 atm did not produce large single crystals by expansion before
melting, showing cavities and a fairly thick and powdery surface layer, while those with group
V nitrides (147,150,151) produced δ- and β-phases with lamellar structures. The transverse and
longitudinal cross sections of NbN crystals show lamellar structures caused by the eutectic of
NbN-Nb2N. These structures arise from low interfacial energy of a highly coherent interface
{111}NbN //{0001}Nb2N. The dislocation-pit arrays, arising from δ-NbN, cross over the lamellar struc-
ture in transverse cross section with a density of ⬃ 105 /cm2. A single colony eutectic structure can
be described as an eutectic ‘‘single crystal’’ that reflects the X-ray Laue pattern (150,151).
The overall chemical composition of the zone-melted specimens close to VN0.65 in zone
melting of sintered rods of δ-VN in an ambient nitrogen gas pressure of 1 MPa changed the
composition range from VN0.84 to VN1.0 in subsequent zone annealing at 2000°C and 2 MPa
(160).
The structures of vanadium and niobium diboride crystals (161) resemble those of tantalum
diboride grown by the floating-zone method (162). Widmanstätten-type precipitates found in
Figure 12 Matching the experimental HREM micrographs (top row) with simulated images (bottom
row) for both disordered (left) and ordered (right) NbC0.83 phases. Dark atoms: Nb, grey atoms: C in bottom
row. The superimposed simulation has been obtained from Nb6C5 structure at ⫺800 Å defocus and 180
Å thickness. [001]-monoclinic C ordered phase//. [110]fcc azimuth. (Courtesy of Dr. T. Epicier, Chargé de
Recherches CNNS, France.)
melt-grown group IV diboride (146) single crystals were not observed in group V diboride
single-crystal grains, indicating that the second phase, with a composition slightly different from
that of the diboride matrix, is difficult to precipitate owing to the wide homogeneity range of
the group V diboride phase. VB2 vaporizes congruently, so diboride is easy to obtain as a single
phase, whereas TaB2 and NbB2 vaporize incongruently near their melting points, so boron defi-
ciency and Ta3B4 or Nb3B4 or lower borides result instead of single phases. The periphery had
polycrystalline structures, especially in the case of niobium and tantalum diborides, where MB2
and M3B4 phases were observed; however, the inner part was single crystalline. Cracks were
observed in the single-crystal region and attributed to the thermal stresses arising from the high
temperature gradients. Lang X-ray topography of a thin section (VB2 single crystal) parallel to
the (1̄100) plane showed distinct dislocation images along the [0001] direction (Fig. 13), gener-
ated by prismatic slip caused by the high thermal stresses in the growth process. The occurrence
of straight dislocation lines would be attributed to the high Peierls potential of the dislocations.
The (0001) plane of the diborides had a high etch pit density of nearly the same order as that
of the (101̄1) plane, whereas the (101̄0) and (112̄0) planes had low etch pit densities. The etch
pit densities were much higher for basal and pyramidal planes than for prismatic planes, sug-
gesting that prismatic slip of TaB2 single crystals predominates at high temperatures.
Next we would like to discuss controlling the composition of the melt to obtain single
crystals with uniform composition. The traveling solvent float zone (TSFS) technique (163) was
applied to grow TiC (164,165), ZrC (166), HfC (167), VC (168), NbC (169), and TaC (170)
40 Kumashiro
Figure 13 Lang topography of a VB2 thin section parallel to the (1̄100) plane. The direction of the
diffraction vector (g ⫽ 112̄0) is indicated by an arrow and is 1.0 mm on the topograph. (From Ref. 161.)
single crystals. Figure 14 illustrates the TSFS technique for the growth of TiC single crystals
(165). A 〈100〉 seed crystal was set on the lower shaft. An initial molten zone was formed by
melting the seed crystal together with a carbon disk put on the crystal because the feed rod had
too low a density to initiate the melting. The carbon disk was used to control the composition
of the initial molten zone so as to produce zone leveling conditions on initial melting, C/Ti ⫽
1.3. The composition of the feed rod was controlled at C/Ti ⫽ 0.98 to compensate for the
composition change due to evaporation during a zone pass. In preparation from a commercial
Figure 14 A modified zone leveling method (164–175).

powder the growth rate was decreased to 0.5 cm/h to avoid cellular growth due to the impurity
W (0.05–0.5 wt %), which makes the growth difficult and decreases the crystal quality. The
visible misorientations between the grains were higher than 1°. The W impurity cannot be re-
moved by evaporation or zone refining because of its low vapor pressure and its distribution
coefficient (k ⬎ 1) (171). Therefore, a starting material without W impurity was prepared from
Ti metal and carbon by an SHS method (Fig. 3b) (172,173). Crystals prepared at a slow rate
were subjected to a strong thermal stress, caused by a steep temperature gradient (maximum
200°C/mm) along the crystal rod for a long time. The crystals can be prepared at a higher rate
using an SHS rod. The growth rate was 1.5 cm/h, and the feed rod was melted into the molten
zone at a rate of 3.5 cm/h to compensate for its low density (172,173). The crystal quality was
improved to such an extent that the cleavage plane was like a mirror plane without subgrain
boundaries. A crystal rod of V8C7 with a slight gradient composition was prepared around a
composition (C/V) of 0.875 (174) and had the highest residual resistance ratio, 19.4, among the
reported values. Furthermore, a microcomputer (CPU) and two digital voltmeters (DVMs) were
attached to the RF generator (200 kHz, 40 kW) for automatic growth (175) to detect the shape
of the molten zone and to provide a zone pass more stable than in the case of manual growth.
Subgrain boundaries of diboride single crystals have been removed by controlling the
molten-zone composition (Fig. 15). The growth rate of diboride crystals was determined in the
process of removing the flux at the growing interface (176–178). Single crystals of TiB2, which
evaporates at a 50 times higher rate than TiC, were prepared by increasing the growth rate up
to 9 cm/h (176). All the crystals grew almost normal to the c-axis of the hexagonal crystal
lattice. The existence of a preferential growth direction is favorable for increasing the optimal
growth rate. The molten zone had a higher boron content, B/Ti ⫽ 2.6, than a stoichiometric
composition because of violent evaporation during growth. The crystal grew by removing the
excessive boron acting as a flux at the growing interface. High-quality ZrB2 crystals that have
the same growth temperature, 3270°C, as TiB2 were obtained at a rate of 3 cm/h (177). The
molten zone had an excess of zirconium because of the evaporative loss of boron. HfB2 melts
congruently at 3380°C, the highest value among the diborides. High-quality HfB2 crystals (178)
were obtained at a rate of 2–3 cm/h, using a feed rod with B/Hf ⫽ 2.1–2.15 whose molten
Figure 15 Etching pattern of TiB2 (101̄0) single crystal (176). The diameter is 10 mm. (Courtesy of
Dr. S. Otani, National Institute for Inorganic Materials, Tsukuba, Ibaragi.)
42 Kumashiro
zone had an excess of hafnium. The differences in flux among TiB2, ZrB2, and HfB2 influence
growth rates. The growth rate of TiB2 is higher when the molten zone is controlled to have
excess boron, which has a lower mass number than metals such as Zr and Hf. The growth rate
increases with increasing growth temperature, indicating that the growth rate is determined in
the process of removing the flux at the growing interface. The high growth rate of 9 cm/h for
TiB2 crystals is due to the boron flux and high growth temperature. Furthermore, helium ambient
gas causing convection in the molten zone is useful for increasing the growth rate (176–178).
Argon ambient gas contains more inclusions, so the growth rate must be decreased compared
with that in helium gas to remove them. The heating powder of an SHS rod was several percent
less than that of a sintered rod used as the feed rod (179). This is due to low thermal conductivity
caused by the low density of the SHS rod, which is an advantage of using SHS rods. The crystal
has a stoichiometric composition.
Plasma-arc heating provides crystal growth of refractory materials. A schematic diagram
of the plasma torch method (180) is shown in Fig. 16. The growth of a single crystal starts with
fusing the end plane of a seed crystal by a plasma jet. A rod of the carbide, 3–10 mm in diameter,
is then transported from the side and fused in the plasma jet so that the drops of melt fall into
a cone-shaped void punched in a single-crystalline ingot of the tungsten bath and provide steady
feeding. If drops of carbide are added to the melt bath by means of input of the charge rod to
the plasma arc and if the velocity of lowering the tungsten substrate is properly chosen, crystalli-
zation will start at the peak of the cone to form a few crystallization centers. Competitive growth
of a restricted number of grains takes place in the cone-shaped bath so as to form a single crystal
practically throughout the volume. The technique permits us to obtain sufficiently large single
Figure 16 Schematic diagram of the plasma torch method. (From Ref. 180.)
crystals of high-melting carbides (20 mm or more in diameter): subboundaries of the first order,
with a disorientation not greater than 10, and an etch pit density of 104 –105 cm⫺2.
Czochralski growth of single crystals has been carried out using an arc-melting technique
(181) with a tri-arc Czochralski furnace (Fig. 17), which consists of an upper cathode and a
lower anode insulated from each other by glass ring. The upper body includes three ball and
socket joints for the electrodes, a central ball and socket for the water-cooled seed rod, and
three windows for observation. Arc melting on a well-cooled hearth permits Czochralski growth
without a hot crucible. The circumference of the melt is heated by three arcs, and the crystal
is pulled from the center of the melt with a water-cooled seed rod. The charge is contained in
a hollow water-cooled copper hearth fitted with a piston so that the melt can be continuously
fed. The seed is dipped into the melt and raised rapidly to form a neck in the growing crystal
in order to favor a single growth front. Tungsten studs mounted in the seed holder were used
for starting crystallization to produce a VB2 single crystal (182). After a diameter of 2–3 mm
was reached, the crystal growth proceeded constantly with a high pulling speed of about 30
mm/h.
An arc-induced floating-zone technique (Fig. 18) was adopted to grow refractory materials
(183,184). Mackie and Hinrichs (184) have successfully prepared single crystals of ZrCx up to
3 mm in diameter and 6 cm in length using a travel speed in the range of 10–30 cm/h under
the inert gas. Two pieces of sintered ZrC rod were supported vertically between two molybde-
num clamps with their free ends touching. A sharpened electrode (or stinger) made of sintered
ZrC was held in a horizontal position on a screw-driven stage that could be moved up or down.
Figure 17 Schematic drawing of a tri-arc Czochralski furnace. (From Ref. 181.)

44 Kumashiro
Figure 18 Schematic drawing of the arc-induced floating zone method used for LaB6. (From Ref. 183.)
As the stinger was brought near the sintered rods, an arc could be initiated and sustained between
the rods and the stinger. The molten zone was moved along the rod by moving the stinger stage.
A 75% Ar–25% He mixture is effective in suppressing evaporation, as argon is about ten times
as effective as helium.
A new process was developed using a well-focused RF plasma flow for the crystal growth
of nitrides in which escape of nitrogen is suppressed by the plasma gas pressure (185–188).
The characteristics of the RF plasma for the crystal growth of nitrides with high dissociation
pressures are described. The plasma generator is an annular planar jet composed of four sections
(Fig. 19). Four quadrant plasma guns [1] are combined into an annular shape, and a grounded
electrically conductive specimen [4] is set up facing the annular opening of the plasma gun with
a spacing [3] of 0.5–1.0 mm. By applying an RF potential to the electrode [5] from the RF
supply through the cooling water inlet pipe [8] an RF discharge is initiated between the tip
portion [5b] of the electrode [5] and the specimen [4]. The discharge is then pushed along by
the gas flow to establish a steady and stable plasma flow. The flow of gas between the electrode
plate [14] and the wall [2] serves to direct the plasma on both the upper and lower sides onto
the specimen [4]. The electrical behavior measured with a new ammeter is sensitive to both gas
composition and ambient pressure in Ar-N2 atmospheres.
The experiment with VN0.83 rod was performed under optimal conditions: the RF voltage
Figure 19 Sketch of the annular plasma generator: [1] plasma gun; [2] discharge chamber; [3] opening;
[4] specimen; [5] discharge electrode; [5] convex part of the discharge chamber; [7] insulating spacer;
[8,9] water inlet and outlet pipes; [10] electrode supporting plate; [11] insulating adapter; [12] RF supply;
[13] gas inlet pipe; [14] electrode plate; [15] spacer; [16] screw (185–188).
decreases with increasing RF current, the discharge changes from glow to arc, and the rod is
melted in the arc region. The current waveforms indicate that the higher the plasma impedance,
the higher the anode efficiency, with good matching between output and plasma impedances.
To compare the nitrogen content, the VN0.83 rod was also melted by RF induction heating under
nitrogen pressures of 10 atm. The RF plasma is focused onto the surface of the specimen by
the gas flow and the specimen is subsequently melted by the heat capacity of the plasma. The
composition of the crystal obtained by the plasma method is almost equivalent to that obtained
by RF induction heating at 10 atm in nitrogen, which demonstrates the utility of RF plasma
melting for nitride crystal growth.
V. CONCLUSION
In the past two decades, well-characterized crystals have been obtained by various unique meth-
ods and advanced technologies. Nanostructured powder with a high surface area would be of
interest as a material for catalysis. The heavy collision of balls in mechanical alloying proceeds
gradually during milling as the repeated fragmentation and coalescence process continuously
brings unreacted material into contact. In the case of solid-nitrogen systems, the nitrogen ab-
sorbed on the surface layer is subsequently moved by the successive collisions into deeper
surface layers (25). In the mechanically induced self-propagating reaction mode, once a portion
of the elemental powder mixture reacts during milling, the heat liberated by the exothermic
reaction propagates and ignites the unreacted portion until the bulk of the elemental powder
mixture is converted to the product (22).
The nanorod represents an important building block for nanostructures. Nanorods would
be useful as reinforcements in metal and ceramic matrix composites as well as ideal structures
with which to pin vortices in high-temperature superconductors (119). Whiskers represent attrac-
tive reinforcing additives for metal and ceramic matrix compositions to impart more strength
to the ceramic object. The superior performance of titanium carbide reinforcements is found in
two different forms, discontinuous fiber and hollow microspheres, by controlled morphology
carbide synthesis where titanium and carbon precursors combine in specially designed graphite
46 Kumashiro
(189). The process can also produce other carbides (Hf-, Ta- and Zr-). The existence of an
impurity droplet on the top of the whisker supports the VLS mechanism, which is confirmed
by X-ray topography (115).
Electrochemical methods for synthesizing nitride precursors afford a significant level of
control over characteristics of powders, i.e., high surface area, small particle sizes, and high
purity. To take full advantage of the molecular precursor method, the relationship between com-
plex and solid phases should be clarified through analysis of intermediate stages of conversion.
The key requirements of the polymer components in polymeric precursor methods are that they
are stable and processible and contain both the boron needed to form the metal boride and
carbon to aid in the removal of oxygen. The polymer precursor technique would be applicable
to nitride.
New materials such as ultrafine powders could be produced by the RF plasma process,
in which the products can be metastable with regard to stoichiometry and phase structure. The
key to the formation of these products is a rapid rate of cooling, ⬃106 K/s, which ‘‘freezes in’’
the desired stoichiometries and phases. NbN with B1 phase is in a high-temperature equilibrium
form above 1300°C and is usually not easily synthesized. The rapid cooling effects of a plasma
or combustion reaction have the effect of quenching the high-temperature phase.
The SHS method is expected to be developed as a process for producing new materials
from composite powders and solid solutions that are difficult to prepare by conventional synthe-
sis methods. By varying the combustion synthesis parameters, the properties of the product can
be tailored to meet specific application needs. The combustion-consolidation method makes it
possible to change the metal composition in the ceramic matrix because the initial arrangement
of compositional constituents of the green body remains in the product due to the rapid wave
propagation of the combustion reaction.
The cylindrical shock wave technique is unique among processes for crystal growth at
high speed from the gas phase far from equilibrium conditions at high temperatures and high
pressures (190). Because thermodynamic self-cooling takes place as a result of an adiabatic
wave front, the high-temperature ultrasupersaturated gas generated condenses within a few mi-
croseconds. Then fine crystals with various growth forms grow at high speeds from the gas
phase under extremely nonequilibrium conditions. As a result of the detonation of explosive
surrounding the steel container, shock waves generated by detonation in the gas in the container
converge on the axis of the sample. A ‘‘Mach-disk’’ region at ultrahigh pressure (⬃100 GPa)
and high temperature (⬃5000 K) is calculated.
CVD and CVT in multicomposition gas-solid systems are complex processes in which
many factors can affect the deposition mechanism and the final composition and structure of
the materials. A thermodynamic approach gives information about the optimal conditions for the
synthesis of specified solid phases, but the uncertainties of thermodynamic data and significant
departure from equilibrium should be kept in mind.
The floating-zone technique eliminates many problems of contamination arising from
holding specimens in a container and makes it possible to grow large single crystals of carbides
and diborides, but the crystals contain subgrain boundaries. The crystal quality could be im-
proved by controlling the molten-zone composition. Furthermore, the crystal purity was in-
creased by more than one order of magnitude by using a self-combustion rod. In automatic
growth, the feed rate is controlled by small changes in the zone shape to decrease variation in
the zone shape during a zone pass, which is related to growing single crystals with high quality.
Since single crystals of high chemical and known structural perfection have been available,
grain boundaries and structural defects in a grain would be eliminated and their intrinsic transport
properties would be fully clarified.
The well-characterized nitride single crystals are limited to diffusion of nitrogen to metal
single crystals at high temperatures. These crystals should serve to measure many uncertain
characteristics because it is difficult to obtain large single crystals by other methods. The diffu-
sion and layer growth behavior in the transition metal–boron system are different from those
in the corresponding carbide and nitride systems (191). Various diffusion layers are formed,
with which it would be difficult to prepare diboride single crystals.
In the plasma zone melting method it is necessary to focus the plasma flame stably, so
many sophisticated techniques are required. In addition to plasma processes, the laser technique
is a promising method for the preparation of powders and single crystals. In particular, a laser-
heated floating zone process using a CO2 laser (192) is suitable for preparing filamentary single
crystals of carbides and diborides for high-brightness electron emission sources.
ACKNOWLEDGMENTS
A number of figures have been taken from the literature. The author would like to thank the
authors and publishers of these materials for permission to reproduce them here, especially,
Kluwer Academic Publishers (Fig. 1 (Ref. 7)), The Electrochemical Society, Inc. (Fig. 6 (Ref.
125)), IOP Publishing Limited (Fig. 8 (Ref. 143)), and Elsevier Science (Fig. 4 (Ref. 107), Fig.
5 (Ref. 115), Fig. 7 (Ref. 137), Fig. 11 (Ref. 150), Fig. 13 (Ref. 161), Fig. 14 (Ref. 175), Fig.
15 (Ref. 176), Fig. 16 (Ref. 180), Fig. 17 (Ref. 181), Fig. 18 (Ref. 183), Fig. 19 (Ref. 186)).
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4
Thin-Film Preparation
Konosuke Inagawa
Chiba Institute for Super Materials, ULVAC Japan, Ltd., Tsukuba, Ibaraki, Japan
I. INTRODUCTION
In general classification, a surface treatment consists of a thin-film preparation (i.e., deposition

or coating) on a substance and a modification of a top surface thereof. The techniques involved
in the surface treatment are divided into two types, wet and dry processes. The former include
electroplating, chemical plating, anodic oxidation, and conversion coating. The latter comprise
physical vapor deposition (PVD), chemical vapor deposition (CVD), ion implantation, ion nitrid-
ing, ion carburizing, etc. Of these many processes, PVD and CVD have proved most suited to
preparation of thin films of refractory materials, i.e., ceramics such as carbides, nitrides, and
borides, because only these two methods produce films of excellent quality, sufficiently high
purity, and high density with stoichiometric composition.
PVD is a fundamental process that relies on a solid-liquid-gas or solid-gas-solid phase
transformation to deposit a very thin film with uniform thickness over a wide area. PVD technol-
ogy has progressed historically starting with vacuum evaporation, followed by sputtering to
utilize the energy of charged particles, and more recently ion plating to use the charge and
chemical activity of charged particles. In the preparation of a ceramic thin film, PVD encom-
passes many methods, including direct evaporation, reactive evaporation, reactive ion plating,
direct sputtering, reactive sputtering, and dynamic mixing.
CVD utilizes the solidification generated by a decompositive reaction from a gas phase.
Its characteristic is the low-temperature synthesis of refractory materials. The main CVD tech-
niques for depositing ceramic films are thermal CVD carried out at normal or lower pressure
and plasma CVD utilizing a discharge.
In this section, preparation and characterization of carbide, nitride, and boride films will
be described. The oxide will be discussed briefly if the occasion demands.
II. CONDITIONAL PARAMETERS FOR DEPOSITING THIN FILMS

A. General Aspects
The characteristics of the thin films deposited by PVD and CVD are greatly influenced by the
substrate temperature, deposition rate, and gas pressure. Moreover, in some cases, other condi-
tions such as plasma power play a part. The grain size and texture of a deposited film grown
with increasing substrate temperature result in good crystallinity of the film. The lower the
55
56 Inagawa
Table 1 Pressure, Substrate Temperature, and Deposition Rate in PVD and CVD Processes
Operating Ultimate Substrate Deposition
Method pressure (Pa) a pressure (Pa) temperature (°C) rate (nm/s)
PVD process
Vacuum evaporation 10 ⫺7 –10 ⫺2 10 ⫺9 –10 ⫺4 Arbitrary ⬃10 3
Sputtering 10 ⫺1 –10 10 ⫺7 –10 ⫺4 Arbitrary ⬃10
Ion plating 10 ⫺1 –5 10 ⫺5 –10 ⫺3 Arbitrary ⬃10 3
Ion beam deposition 10 ⫺6 –10 ⫺4 10 ⫺7 –10 ⫺5 Arbitrary ⬃1
CVD process
Thermal CVD 10–10 5 10 ⫺4 –10 ⫺2 ⱖReaction temperature ⬃10
Plasma CVD 1–10 10 ⫺7 –10 ⫺5 200–600 ⬃10
Laser CVD 10–10 3 10 ⫺7 –10 ⫺5 200–400 0.2–0.3
Metal organic CVD 10–10 3 10 ⫺6 –10 ⫺4 ⱖReaction temperature ⬃10
a
Pa ⫽ 7.50 ⫻ 10 ⫺3 torr.
Source: Itoh, 1986.
deposition rate and pressure, the denser the film obtained and the smoother its surface. In practi-
cal film formation, the characteristics and properties are decided by the complicated relation
among the pressure, substrate temperature, deposition rate, etc. as they occur in each applied
method.
B. Effect of Pressure on PVD and CVD Films

Table 1 gives the distinctive gas pressures, substrate temperatures, and deposition rates used in
the preparation of PVD and CVD films (1). It is clear that the ultimate pressure before deposition
and the operating pressure in PVD are lower than those in CVD. In each method, the film
characteristics such as impurities and defects are strongly influenced by the gas pressure. This
very significant factor may be called the ‘‘vacuum character.’’ The relationship of the character-
ization of thin films and the vacuum character is shown in Fig. 1 (1). Besides pressure, of course,
Figure 1 Characterization of thin-film material. (From Itoh, 1986.)

Thin-Film Preparation 57
Figure 2 Schematic representation of the influence of residual gas pressure. (From Namba, 1971.)
surface cleanness of the substrate, substrate temperature, deposition rate, exciting energy, applied
substrate voltage, etc. are important process parameters.
The effect of pressure is as follows. The lower the ultimate pressure, the higher the purity
of the deposited film, although the extent of the impurity involved differs a little according to
the method employed. Moreover, the operating pressure affects the morphology of the film.
Namba (2) showed that any vacuum-deposited film grows more densely with a smoother surface
in a lower surrounding pressure, as shown in Fig. 2. As for sputter deposition, Thornton (3)
showed the relation of the film morphology to substrate temperature and discharge gas pressure
as illustrated in Fig. 3. Wan et al. (4) evaluated the film deposited by ion plating with their
figure of merit of morphology (FOM) introduced by arranging morphologic characteristics of
the film as a function of gas pressure, ion bombardment power, deposition rate, and substrate
temperature. From these considerations, it may be postulated that a low deposition pressure in
PVD improves the film growth morphology, with a dense bulk with less defects and a smooth
surface. Similarly, in CVD a dense film with crystallinity is deposited with lower supersaturation.
III. PREPARATION OF CERAMIC FILMS

A. Direct Evaporation
Direct evaporation with a ceramic used as an evaporant material has been carried out since the
1950s. However, the technique encounters two problems. One is partial dissociation of the start-
ing ceramic, resulting in a discrepancy in the chemical composition between the deposited film
and the evaporant material. This is one of the reasons for a reduction in the quality of the film. For
instance, TiC, ZrC, TiB 2, ZrB 2, (TiC-ZrC), (TiC-TiB 2), and (TiC-TiB 2-Co) films were directly
deposited by electron beam heating using each of the ceramic materials (5). In the case of the
TiC film, a micro Vickers hardness in the range of 945 to 1615 kg/mm 2 was obtained. This
was considerably lower than that of the bulk, 3200 kg/mm 2. It is just too difficult to obtain
excellent properties with direct evaporation. Another problem is that the evaporation source
58 Inagawa
Figure 3 Microstructure zone diagram for metal films deposited by sputtering. T is the substrate tempera-
ture, and T m is the melting point of the coating material in degrees absolute. (Reprinted with permission
from J. A. Thornton, Journal of Vacuum Science & Technology A3:3059, 1986. Copyright 1986 American
Vacuum Society.)
needs to be of high power density to evaporate the ceramic because of the high melting point
involved. In some cases, safely becomes a factor in operating it for a long time. To solve these
problems, reactive evaporation, reactive ion plating, etc. were developed, as explained in the
following.
B. Reactive Evaporation
Figure 4 shows a schematic of reactive evaporation in which a metal such as Ti, Zr, Si, or Al
is evaporated using an electron beam source, a resistance heater, etc., while a reactive gas such
as C 2 H 4, C 2 H 2, N 2, or NH 3 is simultaneously introduced into the vacuum chamber, resulting in
the formation of carbide and nitride films of the metal concerned. The ultimate pressure before
introduction of the reactive gas needs to be kept sufficiently low to avoid any bad effect from
residual gas, as the operating pressure during deposition is pretty low, 4 ⫻ 10 ⫺4 to 1.3 ⫻ 10 ⫺2
Pa. At a fixed substrate temperature, when the frequency ratio of reactive gas molecules and
metal atoms incident on the substrate, Γ, attains an adequate value, Γ 0, a stoichometric composi-
tion is obtained, and there is little composition change in the range above Γ 0. Several carbides
and nitrides such as TiC, SiC, TiN, ZrN, and AlN can easily be prepared at deposition rates of
0.006 to 0.018 µm/min, which are not so large.
In this so-called reactive evaporation, the reactive gas is introduced to improve upon the
discrepancy in chemical composition in direct evaporation.
C. Reactive Ion Plating

Reactive ion plating is a deposition process in which a part of the evaporated atoms and reactive
gas is ionized and energetically neutralized by a gas discharge. These activated particles enable
the ceramic film to form on the substrate at a high deposition rate. Reactive ion plating consists
Figure 4 Schematic of reactive evaporation.
of hollow cathode discharge (HCD) ion plating, cathodic arc ion plating, activated reactive
evaporation, radio frequency (RF) ion plating, etc.
Using these methods, many ceramic films such as carbides—TiC, ZrC, HfC, VC, NbC,
TaC, WC, TiC-Ni, VC-TiC, CrC, SiC, Ti (C, N), etc.—and nitrides—TiN, Ti 2 N, ZrN, NbN,
HfN, TaN, CrN, AlN, Si 3 N 4, cBN (cubic boron nitride), (Ti, Al) N, (Ti, Zr) N, (Ti, Nb) N, (Ti,
Hf) N, etc.—have been deposited. Reactive ion plating has the desirable characteristics of a
much higher deposition rate than reactive evaporation, a high density with little porosity of the
deposited film and strong adhesion of the deposited film to the substrate. Reactive ion plating
technology is applied in the field of structural materials as a protective coating, to promote wear
resistance, heat resistance, corrosion resistance, and lubricant properties as thick films of a few
to a few tens of micrometers can be formed quickly at a high deposition rate.
Let us move on to HCD ion plating as an example of ceramic film formation. A schematic
illustration is shown in Fig. 5. A high-current electron beam attracted from a hollow cathode
strikes an evaporant in the water-cooled hearth, heating and evaporating it. Ionization occurs
as the evaporating atoms collide with the electrons. The ionization efficiency of the evaporating
atoms in the HCD process is high, 40 to 70%. In TiC film deposition, C 2 H 2 gas is introduced
into the chamber together with Ar gas to maintain an HCD discharge, and N 2 gas is introduced
in the case of TiN. Cointroduction of C 2H 2 and N 2 forms a TiC 1⫺x N x film. Because the operating
pressure is quite high, about 1.3 ⫻ 10 ⫺1 Pa, the throwing power of the deposited film on the
substrate is good. The maximum deposition rate of the film formed on a flat substrate is about
2 µm/min in a production machine.
Generally, in reactive ion plating the characteristics of the deposited film are strongly
affected by the voltage applied to the substrate because of the great quantity of ions impinging
on the substrate. Figure 6 shows the relation between the micro Vickers hardness of a TiC film
and the applied substrate bias voltage. The hardness increases rapidly with a negative bias volt-
60 Inagawa
Figure 5 Schematic of HCD ion plating.
Figure 6 Variation of micro Vickers hardness with substrate bias voltage for a TiC film deposited by
the HCD process. Inconel 625 substrate; substrate temperature 500°C; 10 µm thick; 25-g load.
Figure 7 Variation of internal stress with substrate bias voltage for TiC film.
age up to ⫺20 to ⫺50 V and decreases after reaching the maximum value at around ⫺70 V.
The maximum value of the hardness is 4000 kg/mm 2. This is larger than in the bulk. As shown
in Fig. 7, the internal stress of the deposited film, which is largely compressive, indicates the
same substrate bias dependence as the hardness. It should be pointed out that the film peels off
in some cases when the internal stress is very large, so attention must be paid to this in the
deposition of a thick film. It is therefore important to control the substrate bias voltage to accom-
modate an object that is of high hardness or requires strong adhesion. Moreover, the lattice
constant, the full width at half-maximum (FWHM), and the preferred orientation are affected
by the substrate bias voltage as shown in Figs. 8 and 9.
In RF ion plating and RF sputtering, a large change in the characteristics of the film
deposition is generated at ⫺100 to ⫺300 V, which is much higher in than HCD ion plating.
This fact suggests that the HCD process involves a larger ion quantity than that found in RF
ion plating and RF sputtering. It is considered that such changes in film characteristics are caused
by the following: (a) incorporation of gas molecules into the film, (b) incorporation of impurities,
and (c) the peening effect of ions, with their effects differing depending on the process.
Results of scratch tests to investigate the adhesion of TiN films deposited by HCD ion
plating are shown in Fig. 10 (6). The critical load at which the film peels off increases with
62 Inagawa
Figure 8 Variation of lattice constant and full width at half-maximum with substrate bias voltage for
TiC film. Determined from the 220 line.
increasing deposition temperature in each substrate of a cemented carbide (WC-Co) and a high-
speed steel (SKH 9).
D. Sputtering
Direct or reactive sputtering is employed to produce ceramic films in a sputtering process. Using
a ceramic target such as carbide, nitride, or boride, many ceramic films are deposited by direct
sputtering for practical use in industry. However, there are some problems. The first is the need
to hand manufacture the expensive ceramic target. The second is the discrepancy in chemical
composition between the film and target, a problem similar to that in direct evaporation using
a ceramic evaporant. Moreover, it is undesirable from the standpoint of industrialization that
the sputtering yield of the ceramic target is smaller by nearly one figure than that of a metal
target.
To overcome these disadvantages, reactive sputtering is applied to ceramic film deposition.
Figure 11 is a schematic of reactive sputtering. We can use most metals and semiconductors
as the reactive sputtering target and CH4, C 2 H 2, or CO as the reactive gas for carbides and N 2
or NH 3 for nitrides. The reactive gas is introduced into a discharge gas, Ar, at a rate of 1 to
50%. Carbide films of TiC, VC, TaC, WC, SiC, Fe 3C, etc. and nitride films of TiN, ZrN, NbN,
TaN, Si 3N 4, AlN, Ta 2N-TaN, (Ti, Al) N, etc. are deposited by reactive sputtering. Table 2 shows
examples of the ceramic films prepared by direct and reactive sputtering. As shown in Fig.
12, in reactive sputtering, the deposition rate decreases gradually (to about 0.09 µm/mm) with
increasing reactive gas pressure until a critical value, P C1, after which it decreases rapidly and
at higher pressures decreases only slightly (about 0.02 µm/mm). In the case of decreasing pres-
sure, the critical value P C2, that is, the pressure at which there is a rapid increase of the deposition
Figure 9 Influence of substrate bias voltage on relative intensity of X-ray diffraction line for TiC film.
rate, is lower than P C1, hence a hysteresis loop is seen. This phenomenon is attributed to the
ceramic formation, which has a low sputtering yield, on the target surface reacting with the
reactive gas. The term reactive sputtering is also used when the reactive gas is introduced to
combat a deficiency of the volatile gas composition in direct sputtering.
Magnetron sputtering is employed to increase the deposition rate above that in conven-
tional sputtering when the deposition rate is relatively low. The magnet is set behind the target
as shown in Fig. 13. The discharge plasma is confined and enhanced surrounding the magnetic
field generated on the target, resulting in an increase of the deposition rate. The deposition rate
in magnetron sputtering can be increased nearly ten fold.
E. Chemical Vapor Deposition

CVD is the deposition process in which a ceramic film is formed through the reaction of raw
gases introduced on the heated substrate. There are three main types of reaction, hydrogen
reduction, thermal decomposition and solid-phase diffusion. Some examples of ceramic films
prepared by CVD are given in Table 3. Figure 14 shows a schematic diagram of equipment
used to prepare a TiC film by thermal CVD. A TiCl 4 gas is conveyed in a carrier gas, H 2, and
after mixing with CH 4 is introduced into a deposition system. The reaction is generally carried
64 Inagawa
Figure 10 Influence of substrate temperature on critical load of TiN film deposited using HCD ion
plating. Deposition rate 0.08 µm/min; substrate bias voltage ⫺20 V; 2.1 µm thick; micro Vickers hardness
1650 kg/mm 2 under 10-g load. (From Oishi, 1990.)
Figure 11 Schematic of reactive sputtering.

Table 2 Examples of Carbide, Nitride, and

Boride Films Prepared by Direct and Reactive
Sputtering
Carbide Nitride Boride
TiC TiN TiB 2
ZrC ZrN ZrB 2
HfC HfN HfB 2
VC VN VB 2
NbC NbN NbB 2
TaC TaN TaB 2
Cr 3 C 2, Cr 7 C3 CrN WB 2
Cr 23 C 6 Fe 4N MoB 2
Fe 3C AlN
SiC Si 3 N 4
MoC 2 TiN-Ti
WC, W 2C (Ti, V)N
TiC-TiN (Ti, Al)N
TiC-VC (Ti, Cr)N
Ti-Si-C (Si, Al)N
(Fe, Mn) 3C
Figure 12 Schematic illustration of variation of deposition rate with reactive gas pressure in reactive
sputtering.
66 Inagawa
Figure 13 Schematic of magnetron sputtering cathode.
Table 3 Examples of Carbide, Nitride, and Boride Films Prepared by CVD

Synthesis
Material Deposition method Raw gas temperature (°C)
Carbide
TiC Thermal CVD TiCl 4, CH 4, H 2 950–1050
Plasma CVD TiCl 4, CH 4, H 2 400–900
Laser CVD TiCl 4, CH 4, H 2 —
SiC Thermal CVD SiCl 4, C 3H 8, H 2 1200–1500
Thermal CVD SiH 4, CH 4 1300
Thermal CVD CH 3 SiCl 3 1300–1400
Thermal CVD (CH 3) 2 SiCl 2 1100–1365
Plasma CVD SiF 4, CF 4, H 2 140–600
Plasma CVD Si(CH 3) 4 140–600
Plasma CVD SiH 4, CnHm 140–600
Nitride
TiN Thermal CVD TiCl 4, N 2, H 2 850–1050
Plasma CVD TiCl 4, N 2, (NH 3) 250–1000
Si 3N 4 Thermal CVD SiCl 4, NH 3, H 2 850–1050
(Si-N) Plasma CVD SiH 4, N 2, (He, Ar) 25–500
Plasma CVD SiH 4, NH 3, (He, H 2) 25–500
AlN Thermal CVD AlCl 3, N 2, H 2 900–1000
Plasma CVD AlCl 3, N 2, H 2 ⬃1000
BN Thermal CVD BCl 3, NH 3, (NH 4Cl), H 2 1000–1400
Thermal CVD B 2 H 6,NH 3 700–1250
Plasma CVD BCl 3, NH 3, (Ar) 300–700
Plasma CVD B 3N 3 H6 300–700
Boride
TiB 2 Thermal CVD TiCl 4, BCl 3, H 2 850–1100
NbB2 Plasma CVD TiCl 4, BCl 3, H 2 480–650
Thermal CVD NbBr 5, BBr 3, H 2 1500
TaB2 Thermal CVD TaBr 5, BBr 3, H 2 1500
SiB14 Thermal CVD SiBr 4, BBr 3, H 2 927–1327
Figure 14 Schematic representation of thermal CVD for depositing a TiC film.
out at normal pressure or at a reduced pressure of (6.6–13) ⫻ 10 3 Pa. To achieve uniform

thickness and good microstructure in any part of the furnace, reduced pressure is more desirable
than normal pressure. The TiC film is prepared at a substrate temperature of 950 to 1050°C
according to the following reaction:
TiCl 4 ⫹ CH 4 → TiC ⫹ 4HCl
The deposition rate is about 0.033 µm/min.
The merits of film deposition by the thermal CVD process are as follows: (a) the film has
good crystallinity because of the reaction at high temperature, (b) the film adheres strongly to
the substrate owing to interdiffusion, and (c) it is possible to form a film even on a substrate
of complicated shape. In thermal CVD, however, the types of substrates are generally restricted
to those whose mechanical strengths are maintained despite the high temperature of 800 to
1500°C. But a reheat treatment after deposition at high temperature spreads the substrate material
to be used in thermal CVD.
In plasma CVD, the film is deposited by utilizing an excited reactive species in a thermally
nonequilibrium state. This species is generated by electron collision with gas molecules in a
discharge plasma. The reaction is accelerated even more at a lower substrate temperature because
of the presence of excited atoms and molecules, radicals, ions, etc. The reaction temperature
in plasma CVD is much lower than in thermal CVD, as seen in Table 3. The substrate tempera-
ture of TiC deposition can be decreased to less than 500°C, at which the deposition rate is about
0.045 µm/min. Carbide films of TiC, ZrC, HfC, TaC, WC, W 2C, SiC, B 4C, etc.; nitride films
of TiN, HfN, AlN, Si 3 N 4, BN, etc.; and boride films of TiB 2, NbB 2, TaB 2, SiB 4, etc. are deposited
by the two CVD processes.
68 Inagawa
Figure 15 Schematic of dynamic mixing for TiN film formation.
F. Dynamic Mixing
Recently, dynamic mixing, which is a combination of ion implantation and vacuum evaporation,
has been applied for the preparation of ceramic films. Ion implantation is advantageous for
surface modification of the material, in addition to its use in semiconductor processes in which
ions such as B, P, and As are implanted into Si and GaAs in impurity doping. It takes about
100 times the quantity of ions used in a doping process to perform a surface modification.
Therefore, in many cases a large quantity of ions are implanted into a substrate with a large
surface without mass separation generated in an ion source.
Figure 15 depicts schematically a process for depositing a TiN film using dynamic mixing,
carried out by a simultaneous operation of Ti evaporation and nitrogen ion implantation. The
ceramic film deposited by dynamic mixing shows excellent adhesion because of the presence
of a mixed layer formed between the film and substrate. Ceramic films such as TiN, ZrN, AlN,
(Ti, Al) N, cBN, and TiC are prepared by this method.
IV. CHARACTERISTICS AND APPLICATIONS OF CERAMIC FILMS
The ceramic films prepared by PVD and CVD are applied in two fields in accordance with their
characteristics. One is surface treatment (or surface modification), in which the mechanical,
chemical, and decorative characteristics of ceramic films are utilized for protective coatings in
the field of structural materials. The other utilizes the functional characteristics such as the
electrical and optical properties of ceramic films. In this section, all of the carbide, nitride, and
boride films mentioned above except for oxide films, which are largely applied in the optical
field, are discussed.
A. Wear-Resistant Films
1. Wear Property of Ceramic Films
Hard coated films are available that resist abrasive wear because of their high hardness and
resistance to plastic deformation. Moreover, if a film is chemically stable, it is durable to both
adhesive and corrosive wear. In addition to the preceding properties, a lowering of friction with
any sliding material and chemical stability at high temperature are important conditions in the
selection of a wear-resistant film. Ceramics satisfy these requirements to a certain extent.
In high-speed cutting under severe load, the temperature of the cutting edge of the tool
becomes high due to friction with the workpiece, diffusion and oxidation, etc. This results in
serious wear. It is necessary that a wear-resistant film be coated so that it will not diffuse with
atoms of the work material or oxidize but will be chemically stable. Figure 16 shows a diagram
of the free energy of formation of ceramic materials, which represent values of the chemical
stability (7). The smaller the free energy of formation, the more chemically stable the ceramic
material is. Generally, the free energy of formation becomes small with enhanced thermal stabil-
Figure 16 Free energy of formation for ceramics. (From Kikuchi, 1981.)

70 Inagawa
ity in the order carbide, nitride, and oxide. Because hardness is an important factor in resistance
to abrasive wear, it is necessary that hardness be maintained when the temperature of the film
substance is high. Microhardness values for ceramic materials at elevated temperatures are
shown in Fig. 17 (8). In terms of both the free energy of formation and the hardness at elevated
temperature, HfN is considered to be the most excellent wear-resistant material. In practical
cutting, it has been shown that HfN films are superior to TiN films, which are mostly used now
(8). For wear-resistant films, TiC, TiN, Ti(C, N), (Ti, Al)N, and Al 2O 3 are mainly used, with
TiN being the most common. The endurance of these films against abrasive wear is high, in
the order of TiC, Ti(C, N), TiN, and Al 2 O 3, whereas against adhesive wear it is in the reverse
order. For instance, a comparison of the tool life of cemented carbide inserts coated with TiC
and Al 2O 3 films produced by thermal CVD is shown in Fig. 18 (9). In low-speed cutting, the
life of a TiC-coated tool is longer than that of an Al 2 O 3-coated one, whereas the Al 2 O 3 film
shows excellent wear resistance in high-speed cutting, in which the tool is subject to a higher
temperature. Figure 19 shows the cutting performance of cemented carbide inserts coated with
various nitride films (10). The best performance is seen with the (Ti, Al)N film–coated insert.
2. Practical Application
Table 4 shows the general application of PVD and CVD ceramic films in the field of structural
materials, including their wear resistances (11). As an application of PVD, reactive ion plating
Figure 17 Hardness at elevated temperature for ceramics. (From Leverenz, 1977.)

Figure 18 Tool life of cemented carbide insert coated with ceramic film using thermal CVD. (From
Takatsu, 1983.)
has been employed to prepare TiN, TiC, Ti(C, N), and (Ti, Al)N films a few micrometers thick
on cutting tools made of high-speed steel for such uses as end milling, hobbing, and drilling.
Use of these materials dates back to 1977 except for (Ti, Al)N, which came 10 years later. More
recently, cemented carbide has found use as a substrate. The life of a ceramic film–coated cutting
tool is two to five times that of an uncoated one. The application of thermal CVD for TiC
coating on cemented carbide tools began in 1969. Now, the utilization of a single layer of TiC,
TiN, and Al 2 O 3 is decreasing slowly, while mulilayering is increasing. Two-layer coatings of
Figure 19 Flank wear versus cutting time of cemented carbide insert coated with ceramic film using
cathodic ion plating. Work material low-carbon steel S 50C; cutting speed 170 m/min; feed 0.25 mm/
rev; depth of cut 0.1 mm; dry cutting. (From Ikeda and Satoh, 1993.)
72
Table 4 Ceramic Films Prepared by PVD and CVD That Are Applicable in the Field of Structural Materials
Property Application Film Substrate
Wear resistance Cutting tools, machine parts TiC, TiN, Ti(C, N), (Ti, Al)N Cemented carbide
Electric parts, optical parts CrN, Cr 7 C 3, Al 2 O 3, SiO 2 Quenched and tempered steel, stain-
W 2 C, TiB 2, diamond less steel, Ti alloy, Al alloy,
Diamond-like carbon PET film
Plastic lens
Wear resistance Mold TiC, TiN, Ti(C, N) Cemented carbide
Seizure resistance (Ti, Al)N, W 2 C Quenched and tempered steel
Corrosion resistance
Oxidation resistance Semiconductor parts SiC, Si 3 N 4, Al 2 O 3, MoSi 2 Carbon, quenched and tempered
Die for high temperature steel, sintered Si 3 N 4, sintered
Structural material SiC
Corrosion resistance Hearth BN, Si 3 N 4 Carbon, SiO 2
High strength Composite material SiC Carbon fiber
Oxidation resistance
Corrosion resistance
Low outgassing Vacuum equipment and parts TiN, TiC, CrN, BN Stainless steel, Al alloy
Wear resistance
Low atomic number Nuclear reactor TiC Mo, Inconel
Plasma erosion resistance
Radiation resistance Nuclear fuel C UO 2
Color, wear resistance Personal ornaments TiN, Ti(C, N, O), (Ti, AL)N Cemented carbide
Corrosion resistance Daily commodities ZrN, CrN, Cr(N, C, O) Quenched and tempered steel, stain-
DLC less steel, Ti alloy
Acoustic property Oscillation plate Diamond, DLC Al 2 O 3 plate, Ti plate
Gas barrier Packaging material SiO x, Al 2 O 3 PET film
Transparency
Source: Inagawa, 1993.

Inagawa
Ti(C, N)/TiC/substrate (henceforth substrate details are omitted), TiN/TiC, and Al 2 O3 /TiC and
three-layer coatings of TiN/Ti(C, N)/TiC and TiN/Al 2 O 3 /TiC are widely used. In special cases
more than 10 layers can be coated. The total film thickness, for instance, of four layers of the
TiN/Al 2 O 3 /TiC/Ti compound is 8 to 10 µm.
In addition to cutting tools, the sliding parts of many components of various machines
are coated with wear-resistant ceramic films. Also, hard ceramic films are utilized in many kind
of molds for such applications as sheet metal forming, cold forming, powder forming, die cast-
ing, and injection molding because of their good release properties and to assist maintenance
of specular surfaces. TiN films prepared by reactive ion plating; (Ti, Al)N films prepared by
reactive sputtering; TiC, Ti(C, N), and TiN/Ti(C, N)/TiC films prepared by thermal CVD; W 2C
films made by low-temperature CVD at 300 to 500°C; and TiN, TiC, and Ti(C, N) films made
by plasma CVD are all applied to the surfaces of molds.
3. Emerging Materials for High Hardness

Cubic boron nitride (cBN) is a very promising material that, after diamond, displays the highest
hardness, excellent thermal conductivity, and important characteristic properties such as high
electrical insulation and chemical and thermal stability. The cBN film can be deposited on a
cemented carbide insert using activated reactive evaporation with a gas activation nozzle. Figure
20 shows the relation between the micro Vickers hardness (10 g load) of a BN film and its
Figure 20 Micro Vickers hardness of BN film deposited using activated reactive evaporation with a
gas activation nozzle. Load 10 g. (Reprinted from Ref. 12 with permission from Elsevier Science.)
74 Inagawa
chemical composition ratio N/B (12). The hardness of a cBN film about 1.5 µm thick is very
high, 5500–6300 kg/mm 2, as high as that of converted compact cBN. For practical uses, it is
necessary to establish much stronger adhesion of the cBN film to the substrate.
An interesting mechanical characteristic has also been obtained in a superlattice film and
in a multilayer coating. Figure 21 shows the relation between the Knoop hardness and the lamina-
tion period, λ, of a TiN/AlN superlattice film deposited on cemented carbide using cathodic
arc ion plating to a total thickness of more than 1.3 µm (13). The hardness depends a great deal
on the period and at λ ⫽ 2.5 nm has a maximum value about 1.6 times that of TiN film. This
tendency is similar to that of a TiN/VN epitaxial superlattice film, whose micro Vickers hardness
has a maximum value of 5560 kg/mm 2 (14). A TiN/AlN superlattice film–coated cemented
carbide end mill and insert display excellent performance in high-speed cutting. Also, a
multilayer film such as TiC/TiB 2 and TiN/TiC, for instance, of 1000 layers with a total thickness
of 5 µm, deposited using magnetron sputtering, shows a distinct improvement in mechanical
properties such as hardness, friction coefficient, and wear resistace (15).
A superhard Ti-B-C film with a micro Vickers hardness of 7200 kg/mm 2 was obtained
by reactive DC magnetron sputtering with a TiB 2 target and CH 4 gas introduced (16). The
implication of the very high hardness is that carbon atoms are included interstitially in the TiB 2
lattice.
The latest exciting development in hard coating is the synthesis of β-C 3 N 4 a new material
with the same structure as the well-known β-Si 3 N 4. Theoretical calculations suggest that β-C 3 N 4
has extremely high hardness (comparable to or greater than that of a diamond of 10,000 kg/
mm 2) and a low friction coefficient (17,18). Preparations of β-C 3 N 4 films are being attempted
employing a wide variety of methods such as magnetron sputtering (19), cathodic arc ion plating
(20), ion beam–assisted sputtering (21), ion implantation (22), laser ablation (23), and plasma
Figure 21 Variation of Knoop hardness with lamination period for TiN/AlN superlattice film prepared
using cathodic arc ion plating. Load 50 g. (From Nakayama, Stetoyama, and Yoshioka, 1994.)
CVD (24). Results so far have not shown the anticipated hardness. Active investigation will no
doubt continue toward realizing the potential of β-C 3 N 4.
B. Oxidation- and Corrosion-Resistant Films

The behavior of ceramics with good oxidation and corrosion resistance has been studied by
exposing the films in air to elevated temperatures and dipping them into acid solution, respec-
tively. Figure 22 shows a comparison of the weight gain, i.e., the oxidation rate, of TiC, TiN,
(Ti, Zr, Al)N, (Ti, Al)N films in hot air (25). The ceramic films were deposited on stainless
steel substrates using reactive magnetron sputtering. The (Ti, Al)N film showed the best oxida-
tion resistance, beginning to oxidize at a temperature of 700 to 750°C, nearly 200°C higher
than TiN film. A protective layer of amorphous Al 2 O 3 formed at the top surface of the (Ti,
Al)N film, preventing further oxidation of the sample.
Next, Fig. 23 shows the weight reduction of TiN and CrN films dipped in a 10% hydrochlo-
ric acid solution (26). The films were deposited on stainless steel substrates using cathodic arc
ion plating. The weight loss of the coated samples is smaller than that of the uncoated sample.
In particular, the corrosion resistance of the CrN film is noted to be superior to that of the TiN
film, as a Cr 2 O 3 layer is more stable than a TiO 2 one in regard to each protective layer formed
in a corrosive solution.
C. Decorative Film
Most metals, with the exception of Au and Cu, are colorless, whereas ceramics exhibit various
colors. TiN, ZrN, HfN, and TaC are all gold with small differences in color tone, Be 2C is red,
NbN is bright brown, WN is brown, and MnN is black. Reflectance spectra of materials having
a gold color are shown in Fig. 24 (27). The TiN x film was prepared using reactive ion plating.
The reflectance curve of the sample with an about 0.1-µm-thick Au coating to raises the bright-
Figure 22 Oxidation property of ceramic film deposited using reactive magnetron sputtering. (Adapted
with permission from W. D. Münz, Journal of Vacuum Science & Technology A4:2717, 1986. Copyright
1986, American Vacuum Society.)
76 Inagawa
Figure 23 Corrosion property of stainless steel SUS 304 coated with TiN and CrN films using cathodic
arc ion plating. (From Kohno, Ikenaga, and Ichimura, 1993.)
ness, after TiN x deposition is similar to that of an electroplated Au alloy. Other colors such as
whitish gold, pinkish gold, brown gold, and gray are realized by the simultaneous introduction
of H 2, O 2, C 2 H 2, etc. in addition to the reactive gas N 2. As a decorative film with wear and
corrosion resistance, the TiN-based one is utilized for personal ornament; in stationery; and in
commodities such as watch cases and bands, spectacle frames, scissors, shaving edges, and
cooking knives.
Also, CrN (gray) and Cr 2 N (white) films deposited using reactive ion plating and (Ti,
Al)N films (brown) prepared by reactive magnetron sputtering have found practical use.
Figure 24 Reflection spectrum of TiN group film showing gold deposited using reactive ion plating.
(From Yamazaki, 1986.)
D. Electrical Applications
1. Resistance Film
For ceramic resistor use, cermet and Ta 2N films have been used since the time of the early
hybrid integrated circuits (ICs). A cermet film is produced by mixing a metal and ceramic, for
instance, Cr-SiO, Cr-MgF 2, and Au-SiO. The Cr-SiO (SiO 25–90%) film is generally used
because of its stable properties and its specific resistance of 3.1 ⫻ 10 ⫺4 to 4.3 ⫻ 10 ⫺3 Ω cm.
Ta 2N resistance film is prepared using reactive sputtering. Figure 25 shows the relation
of the N 2 partial pressure and crystal structure, specific resistance, and temperature coefficient
of resistance (TCR) (28). Under general sputtering conditions, a Ta film shows a β-phase (tetra-
gonal structure); however, an α-phase (body-centered cubic) forms at a high substrate tempera-
ture and in the low gas pressure of a discharge. A film involving a Ta 2N phase is appropriate
for a resistor, because its specific resistance is large and its TCR is close to zero. The properties
of little scatter and only a small variation over time are beneficial. In addition to Ta 2N, the
electrical properties of (Ti, Al)N, (Ta, Al)N, (Ti, Si)N, Ta(N, O), AlN, TiN, and ZrN have been
investigated and some of these are applied to thin-film resistors and heaters.
2. Diffusion Barrier and Insulation Films

Many oxide films are utilized in semiconductor ICs, along with a few nitrides. TiN film is
prepared by sputtering and CVD for use as a diffusion barrier in metallization. A CVD Si 3 N 4
film is used for an insulator in dynamic random-access memory (DRAM). Si 3 N 4 film is largely
applied in gate insulators for metal-oxide-semiconductor (MOS) transistors, insulators for capac-
itors, interlayer insulators between interconnecting materials, surface passivation uses, etc.
3. Surface Accoustic Wave Devices

Oxides such as LiNbO 3, SiO 2, and especially ZnO film are usually used for surface accoustic
wave devices that operate utilizing the piezoelectric effect. Also, AlN films are applied in these
devices. These films are generally formed using RF magnetron sputtering.
Figure 25 Variation of specific resistance and temperature coefficient of resistance with N 2 partial pres-
sure for TiN film deposited using reactive sputtering. (From Kinbara, 1984.)
78 Inagawa
4. Superconducting Films
Preparing superconducting films is a fundamental technique for creating electronic devices based
on the Josephson effect, such as switching devices and magnetic and optical sensors. As a
superconductor has perfect diamagnetism, a superconducting current will flow through a surface
layer 30 to 200 nm thick, i.e., the magnetic penetration depth. It is therefore sufficient for utiliza-
tion to ensure about the same thickness, and a thin film proves to be the most suitable form.
Ceramic superconducting films are divided into three classes, B1-type compounds, ternary
compounds, and high-temperature oxide superconductors. The B1-type (NaCl-type structure)
compound superconductors consist of nitrides and carbides with 5A, 6A, and 7A transition
metals, such as TiN, ZrN, HfN, VN, NbN TaN, MoN, WN, TiC, ZrC, HfC, VC, NbC, TaC,
MoC, WC, NbN 1⫺x C x , hex-MoN, and hex-MoC. Regarding the thin-film material, it is notable
that NbN and NbN 1⫺x C x (x ⫽ 0.08 and 0.15) have superconducting critical temperature, T c ,
values of 17.3 and 17.8 K, respectively. The deposition method used is almost always sputtering
or CVD. The properties of films deposited by the former method are superior. A highly reliable
Josephson device was realized with an NbN film.
Ternary compound superconductor films such as BaPb 1⫺x Bi x O 3, Ba 1⫺xK x BiO 3, and Ba 1⫺x-
Rh x BiO were prepared using sputtering, molecular beam epitaxy (MBE), and laser ablation, and
a maximum T c of 25 K was achieved. Since the high-temperature oxide superconductor was
discovered in 1986, research and development on it have been largely carried out with the aim of
finding the highest critical temperature, critical magnetic field, and critical current. YBa 2 Cu 3 O 7,
Bi 2 Sr 2 CaCu 2 O 8, Bi 2 Sr 2 Ca 2 Cu 3 O 10, HgBa 2 CaCu 2 O 10, and Tl 2 Ba 2 Ca 2 Cu 3 O 10 films were depos-
ited by various methods such as vacuum evaporation, sputtering, laser ablation, ionized cluster
beam (ICB) and CVD, with a maximum T c of 122 K being obtained.
E. Miscellaneous
A TiN film formed by reactive ion plating is used to produce low outgassing of the inner walls
of vacuum chambers and parts for vacuum equipment. It is considered that two functions contrib-
ute to the low outgassing rate of TiN film. One is the barrier effect against H 2 gas dissolved in
the wall material. The other is the low adsorption and/or desorption of each gas component in
air.
In magneto-optical disks, Si 3 N 4 and AlN films produced by sputtering are applied to pro-
tect against oxidation of the magnetic layer and enhance the magnetic Kerr rotation angle.
In the medical field, for dental restoration, TiN films produced by reactive ion plating are
serving in pratical applications to prevent wear and corrosion.
REFERENCES
1. Itoh A. Characterization and evaluation of ceramic coatings. Bull Ceram Soc Jpn 21:502, 1986.
2. Namba Y. Growth of evaporated Bi film and its cross-sectional structure. Oyo Buturi (Appl Phys)
40:639, 1971.
3. Thornton JA. The microstructure of sputter-deposited coatings. J Vac Sci Technol A4:3059, 1986.
4. Wan CT, Chambers DL, Carmichael DC. Effect of processing conditions on characteristics of coat-
ings vacuum deposited by ion plating, Proceedings of 4th International Conference on Vacuum Met-
allurgy, 1974, pp 231–237.
5. Bunshah RF, Nimmagadda R, Dunford W, Movchan BA, Demchishin AV, Chursanov NA. Structure
and properties of refractory compounds deposited by electron beam evaporation. Thin Solid Films
54:85, 1978.
6. Oishi M. On the preparation of wear resistance hard films by physical vapor deposition. J Surf Fin
Soc Jpn 41:1125, 1990.
7. Kikuchi N, Itaba S. Application of ceramic coatings for cutting tool. Bull Ceram Soc Jpn 16:170,
1981.
8. Leverenz RV. Hafnium nitride coating for cutting tools, Proceedings of Symposium on New Develop-
ments in Tool Materials, Chicago, 1977, pp 1–5.
9. Takatsu S. CVD on tool materials. Zairyo Gijutsu (Mater Technol) 1:78, 1983.
10. Ikeda T, Satoh H. High-temperature oxidation and wear resistance of Ti-Al-N hard coating formed
by PVD method. J Jpn Inst Met 57:917, 1993.
11. Inagawa K. Recent development in preparation and applications of super hard films. J Jpn Soc Prec
Eng 59:373, 1993.
12. Inagawa K, Watanabe K, Saitoh K, Yuchi Y, Itoh A. Structure and properties of c-BN film deposited
by activated reactive evaporation with a gas activation nozzle. Surf Coat Technol 39/40:253, 1989.
13. Nakayama A, Setoyama M, Yoshioka T. Preparations and evaluations of TiN/AlN superlattices by
arc ion plating. J Vac Soc Jpn 37:929, 1994.
14. Helmersson U, Todorova S, Bernett SA, Sundgren J-E, Markert LC, Grren JE. Growth of single-
crystal TiN/VN strained-layer superlattices with extremely high mechanical hardness. J Appl Phys
62:481, 1987.
15. Holleck H, Schier V. Multilayer PVD coatings for wear protection. Surf Coat Technol 76–77:328,
1995.
16. Knotek O, Breidenbach R, Jungbut F, Loffer F. Surf Coat Technol 43/44:107, 1990.
17. Liu AY, Cohen ML. Prediction of new low compressibility solids. Science 245:841, 1989.
18. Liu AY, Cohen ML. Structural properties and electronic structure of low-compressibility materials:
β-Si 3 N 4 and hypothetical β-C 3N 4. Phys Rev B 41:10727, 1990.
19. Marumo Y, Yang Z, Chung YW. Optimization of properties of carbon nitride and CN x /TiN coatings
prepared by single-cathode magnetron sputtering. Surf Coat Technol 86–87:586, 1996.
20. Chhowalla M, Alexandrou I, Kiely C, Amaratunga GAJ, Aharonov R, Fontana RF. Investigation of
carbon nitride films by cathodic arc evaporation. Thin Solid Films 290–291:103, 1996.
21. Hammer P, Baker MA, Lenardi C, Gissler W. Ion beam deposited carbon nitride films: Characteriza-
tion and identification of chemical sputtering. Thin Solid Films 290–291:107, 1996.
22. Xie EQ, Jin YF, Wan ZG, He DY. Formation of C-N compounds by N-implantation into diamond
films. Nucl Instrum Methods B 135:224, 1998.
23. Soto R, González P, Redondas X, Parada EG, Pou J, León B, Pérez-Amor M, da Silva MF, Soares
JC. Growth and characterization of carbon nitride films prepared by laser ablation. Nucl Instrum
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24. Dekempeneer EHA, Meneve J, Smeets J, Kuypers S, Eesels L, Jacobs R. Structural, mechanical and
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Surf Coat Technol 68/69:621, 1994.
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A4:2717, 1986.
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Surf Fin Soc Jpn 44:708, 1993.
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210.
5
Electronic Structure
Adolf Neckel
Institute for Physical Chemistry, University of Vienna, Vienna, Austria
I. INTRODUCTION
The high interest in the electronic structure of the refractory hard metals, among which primarily
the monocarbides, mononitrides, and diborides of the transition metals of the fourth and fifth
groups of the periodic table are understood, arises from the unusual combination of properties
that characterizes these compounds. Because of its very similar properties, tungsten monocar-
bide, WC, has also been included in this review. These substances exhibit, on the one hand,
ultrahardness and high melting points, characteristics typical of covalently bonded compounds.
On the other hand, they also display metallic properties, such as high electric and thermal con-
ductivity. Some of the compounds of this class of substances are superconductors with transition
temperatures as high as 18 K (niobium nitride, 17.3 K; niobium carbonitride, NbC 0.3 N 0.7, 18
K). The monocarbides and mononitrides of the elements Ti, V, Zr, Nb, Hf, and Ta* crystallize
in the sodium chloride (B1 type) structure, which is found mostly with ionic compounds. For
WC the hexagonal form (α-WC) is the stable modification, whereas WC crystallizing in the B1
structure (β-WC) is a metastable form. Transition metal monocarbides and mononitrides will
be designated by the formula MX. The transition metal diborides (MB2) crystallize in the AlB2
structure (C32 type), in which hexagonal-close-packed M layers alternate with graphite-like B
layers.
The transition metal monocarbides and mononitrides typically exhibit wide homogeneity
regions, caused by the formation of vacancies, mainly on the nonmetal sites and, to a much
lesser extent, also on the metal sites. Because the vacancies have a strong influence on the
physical and chemical properties of the substances, a large number of theoretical and experi-
mental investigations have been devoted to the study of the electronic structure of vacancy-
containing transition metal carbides and nitrides.
The aim of this chapter is to present a short overview of the electronic structure—mainly
based on theoretical approaches—of the foregoing classes of substances. However, it must be
clearly stated that numerous experimental methods have produced significant findings about the
electronic structure. Only the mutual supplementing and cross-checking of theory and experi-
ment can provide an in-depth understanding of electronic structure. Both tools are equally impor-
tant. A heightened interest, awakened especially by the properties of the transition metal carbides
* TaN crystallizing in the sodium chloride structure is a metastable phase.

81
82 Neckel
and nitrides and the great number of investigations dedicated to the elucidation of the electronic
structure and the bonding mechanism of this class of substances, has led to several review
articles (1–6). The book by Gubanov et al. (7) and Johansson’s comprehensive review article
(8) on the electronic and structural properties of transition metal carbide and nitride surfaces
deserve special mention. The relations between electronic structure and cohesive properties will
be dealt with in Chap. 6.
It is impossible to present the whole field and its related literature in this chapter. Rather,
typical results and characteristics will be discussed for representative examples. A comprehen-
sive bibliography can be found in the book by Gubanov et al. (7).
II. ELECTRONIC STRUCTURE OF STOICHIOMETRIC TRANSITION METAL

MONOCARBIDES AND MONONITRIDES
Most calculations have been performed for stoichiometric phases MX, which constitute model
compounds. The real crystals used for the experimental investigations, however, almost always
show deviations from ideal stoichiometry and crystal defects.
A. Electronic Structure and Bonding Mechanisms: Early Ideas and

Calculations
The unusual combination of properties gave rise to early speculations about the bonding mecha-
nism in these substances. Hägg (9) studied compounds of the transition metals with the elements
H, C, N, and O from a crystallographic point of view as early as 1931. He found a relationship
between the ratio (r X /r M ), where r X is the radius of the nonmetal atom X and r M the radius of
the metal atom M, and the crystal structure of the compound. He observed that compounds for
which the ratio (r X /r M ) is smaller than 0.59 frequently crystallize in a structure having the same
metal sublattice as the corresponding pure metal and that the MM distances are only slightly
larger than those in the pure metal. Hägg concluded from these findings that the nonmetal atoms
occupy only the voids in the metal lattice and do not contribute to the stability of the compounds.
He coined the name ‘‘interstitial compounds’’ for this class of substances, which is still in use.
Consequently, he assumed that only the MM bonds are essential for the stability of these
compounds.
Rundle (10) revised this view and inferred a weakening of the MM bonds from the
slight increase of the MM distances in the compounds compared with the MM distances
in the corresponding pure metals. He assumed that MX bonds are also formed and that these
are responsible for the hardness and brittleness of these substances.
The importance of π bonds between nonmetal p orbitals and metal d orbitals (of t 2g symme-
try) was stressed by Krebs (11).
Pauling (12) held the view that the octahedral coordination of six metal atoms about each
carbon or nitrogen atom involves resonance among six positions, because a carbon or nitrogen
atom can form only a maximum of four covalent bonds.
The first band structure calculation for TiC, TiN, and TiO was performed by Bilz (13).
He used a simplified linear combination of atomic orbitals (LCAO) method and considered only
the MX bonds as the important ones. From his results he inferred a charge transfer from the
metal to the nonmetal atom. A completely opposite point of view was adopted by Costa and
Conte (14). These authors ignored the MX bonds and considered only the MM bonds.
According to their calculations, a transfer of electronic charge from the nonmetal to the metal
atom should occur. Lye and Logothetis (15), using optical data to adjust the parameters in their
Electronic Structure 83
semiempirical LCAO band structure calculation for TiC, came to similar conclusions. These
authors considered both TiC and TiTi bonds. Their results, however, could not be con-
firmed by later calculations or experiments. Ern and Switendick (16) performed the first ab initio
band structure calculation for TiC, TiN, and TiO using the augmented plane wave (APW)
method. Their calculation was based on a crystal potential that was derived from a superposition
of atomic or ionic electron densities. Because the authors did not carry their calculations to self-
consistency, their results depended on the assumed atomic configuration. Later, however, Neckel
et al. (17–19) showed that the main features of the findings of Ern and Switendick agreed with
those obtained by the self-consistent APW method.
B. Electronic Structure: Computational Methods

A great number of electronic structure calculations have been performed since the early band
structure calculations, mentioned in Sect. II.A. In principle, two different groups of methods
have been applied: cluster methods and band structure methods.
In the cluster approach only a small part of the crystal, a cluster, is considered. Quantum
chemical methods developed for the study of molecules or complexes are used to compute the
electronic structure of the cluster. The crystalline surrounding of the cluster can also be taken
into account by using an embedded cluster scheme. The main advantage of the cluster methods
is their simplicity. They are, by their nature, particularly appropriate for calculating properties
caused by the interaction between nearest-neighbor atoms. The limited size of the cluster can
sometimes lead to unrealistic results (‘‘cluster effects’’). Within the range of their applicability,
however, cluster methods frequently provide results that are in good agreement with band struc-
ture calculations or the experiment. A description of the methods for calculating the electronic
structure of clusters and for computing properties of solids on the basis of cluster models can
be found in Ref. 7 and in the literature cited therein.
The band structure methods are based on the concept of an infinite, ideal crystal. A band
structure represents the electron states as a function of energy and wave vector. Band structure
methods implicitly take into account the translational symmetry of the crystal. Therefore, they
can also be applied for the calculation of properties that cannot properly be obtained by means
of cluster methods. Extreme examples are the topology of the Fermi surface and the dispersion
of the energy bands, i.e., the dependence of the energy of the electron states on the wave vector
k. In general, band structure calculations require more computational effort than cluster methods.
Furthermore, one has to bear in mind that in band structure methods several approximations
are also used. One of the most important features is the fact that band theory is a one-electron
approach. The basis of the one-electron treatment of ground state properties forms the density
functional theory (DFT) of Hohenberg and Kohn (20) and Kohn and Sham (21) and the local
density approximation (LDA) (21,22). Essential for the quality of the results is the self-consis-
tency (SC) of a band structure calculation. Starting from an assumed electron density, which is
usually obtained by superposition of the electron densities of the constituent atoms, the Coulomb
potential is computed by solving Poisson’s equation. The exchange-correlation potential, which
is essential in a one-electron band structure method and which includes all many-body effects
on the ground state properties, can also be computed from the electron density. The one-electron
Schrödinger equation is solved for the sum of these two potentials using one of the many avail-
able schemes. The solutions of the Schrödinger equation yield the energy eigenvalues of the
electron states for special wave vectors k and the corresponding wave functions. By summing
the squares of the wave functions of the occupied electron states a new electron density is
obtained, which forms the basis of a new iteration. This procedure is repeated until certain
convergence criteria are fulfilled. Reliable values for the amount of s-, p-, and d-like character
84 Neckel
of the wave functions and consequently for the configuration of each atom in the compound
can be derived only from self-consistent band structure calculations. Self-consistency is also an
inevitable prerequisite for the calculation of the charge transfer between the constituent atoms
of the compound.
Various methods for the calculation of band structures have been devised. The augmented
plane wave (APW) method (23,24) and the Green’s function (GF) method of Korringa, Kohn,
and Rostocker (KKR) (25–28) were used for most of the early calculations of the band structures
of transition metal compounds. A common approximation in both methods is the use of the so-
called muffin tin potential. In this approximation it is assumed that the crystal potential is spheri-
cally symmetric within nonoverlapping spheres around the atomic sites and constant in the
region between the atomic spheres.
Various forms of the exchange-correlation potential have been proposed in the literature
(29–35). Fortunately, the results of band structure calculations frequently do not depend much
on the choice of the exchange-correlation potential. However, differences up to about 25 mRyd
can occur when different exchange-correlation potentials are applied.
Linearized band structure methods were developed in the 1970s: the linearized augmented
plane wave (LAPW) method (36), the linear combination of muffin-tin orbitals (LMTO) method
(37), the augmented spherical wave (ASW) method (38), and some others. In the LAPW method
a warped muffin tin potential is frequently used, in which the real shape of the crystal potential
in the interstitial region between the atomic spheres is taken into account. In the LMTO and
ASW approaches the atomic sphere approximation (ASA) is frequently applied, in which—
contrary to the muffin-tin approximation—overlapping atomic spheres are used. The crystal
potential in the spheres is again assumed to be spherically symmetric. The sum of the atomic
sphere volumes must be equal to the total volume of the unit cell. No interstitial space remains.
The main advantage of the linearized methods is a considerable reduction is computing
time. This reduction is achieved by the introduction of further approximations, which, however,
influence the quality of the results only slightly in most cases. The introduction of these tech-
niques has extended the applicability of band structure methods to considerably more complex
crystal structures. A detailed description of the linearized methods can be found in the articles
by Andersen et al. (39), Andersen (40), Skriver (41), and Nemoshkalenko and Antonov (42).
In the 1980s, methods were introduced that permit dealing with a crystal potential of
completely general shape (‘‘full-potential’’ methods). The full-potential linearized augmented
plane wave (FLAPW) method was developed by Wimmer et al. (43) in 1981. Another version
of the FLAPW method was elaborated by Blaha et al. (44,45). A full-potential linear muffin
tin orbital method has also been introduced (46,47).
Relativistic effects have to be taken into account for compounds containing transition
elements with higher atomic numbers; the 5d transition elements (Hf, Ta, W) are of particular
concern in the present review. A fully relativistic treatment requires the solution of the Dirac
equation instead of the Schrödinger equation. However, in many cases, it is sufficient to use a
scalar relativistic scheme (48) as an approximation. In this technique, the mass-velocity term
and the Darwin s-shift are considered. The spin-orbit splitting, however, is neglected. In this
approximation a different procedure must be used to calculate the radial wave functions, but
the nonrelativistic formalism, which is computationally much simpler than solving Dirac’s equa-
tion, is retained.
Only the most important band structure methods have been mentioned in this section. The
repertoire of techniques is by no means exhausted by the present description; for example,
reference should be made to the pseudopotential methods (49–51).
Angle-integrated and angle-resolved photoemission experiments provide an efficient
source for the experimental elucidation of band structures. Angle-integrated photoemission in-
vestigations primarily permit the determination of the relative positions of the energy bands
and the approximate shape of the density of states. From angle-resolved photoemission (ARP)
experiments, however, detailed information about a band structure can be extracted. ARP studies
facilitate the exact determination of the position and the dispersion of energy bands. In connec-
tion with the evaluation and interpretation of ARP spectra, numerous band structure calculations,
frequently to high energies, have been performed. These calculations will not be covered in this
chapter, as they are included in the article by Johansson (See Ref. 8, and references therein).
C. Band Structures of the Stoichiometric Monocarbides and

Mononitrides of Ti, V, Zr, and Nb
The graph of the energy E of the electron states as a function of the wave vector k along a
certain path in the first Brillouin zone (BZ) represents an energy band. E(k) is a multivalued
function of k, the branches being numbered by a band index in order of increasing energy. A
branch of E(k) corresponding to a certain band index represents a band of closely spaced energy
levels. The form of E(k) throughout all branches (bands) is called the band structure of the
crystal. As already mentioned, the transition metal monocarbides and mononitrides crystallize
in the sodium chloride (B1 type) structure (Fig. 1). The first BZ for a face-centered cubic (fcc)
lattice, the translational lattice for the B1 structure, is displayed in Fig. 2. The labeling of symme-
try points in the BZ normally follows the notation (Γ, ∆, X, . . . .), introduced by Bouckaert
et al. (52).
The electron states in the compounds can be classified as follows:
1. Core states, which lie energetically deep and are not directly involved in the bonding.
They can be treated as atomic-like and calculated using the self-consistent crystal
potential. They show no dispersion of the energy in k space.
2. Semicore states, with relatively low energies, which show only a slight energy disper-
sion in k space. They are usually not displayed in the band structure.
3. Valence states, which show a strong energy dispersion in k space and are displayed
in the band structure.
Various band structure calculations for the title compounds have been performed (see Ref.
7). The present discussion is based mainly on the results obtained by means of the SC APW
method by Neckel et al. (17–19) for TiC, TiN, VC, and VN; Schwarz et al. (53) for VC; Schwarz
et al. (54) for ZrC and ZrN; and Schwarz (55,56) for NbC and NbN and on the results of
Figure 1 Cubic unit cell of the B1 type structure (sodium chloride structure).
86 Neckel
Figure 2 First Brillouin zone (BZ) for a face-centered cubic (fcc) translational lattice.
additional calculations for TiC and TiN by Schwarz and Blaha (22,57) using the SC LAPW
method and by Herzig et al. (58), who applied the SC FLAPW method.
Blaha and Schwarz (59) also performed a band structure calculation for VN by means of
the full-potential LAPW method. The authors compared the band structures, densities of states,
and partial charges obtained by this method with the results of the earlier APW calculations
(17,19), in which the muffin-tin approximation was used. The main differences between the two
methods were outlined. It was found that the non-muffin-tin effects in this highly coordinated
compound are very small.
Price and Cooper (60) calculated the electronic structure, total energies, and equilibrium
lattice constants for TiC with B1 structure and for various prototype superlattice structures by
means of the full-potential LMTO method (37).
The band structures of this class of compounds show great similarities. The main features
will be discussed on the basis of band structures of TiC and TiN (Figs. 3 and 4), but the argu-
ments apply equally to the band structures of the other compounds.
1. The band structures are characterized by an energetically low-lying band, which is
derived from the nonmetal 2s state. The wave functions of the states of this band
display almost exclusively s symmetry. This band will be designated the ‘‘s band.’’
2. Separated by an energy gap from the s band, three overlapping bands occur, which are
derived from the nonmetal 2p states. These three bands originate from the threefold
degenerate state at the k point Γ labeled Γ15. The wave functions of the states of these
bands are primarily characterized by p symmetry, but they also contain a significant
contribution from d symmetry, due to the interactions of the nonmetal 2p orbitals
with the transition metal nd orbitals. The amount of d character generally decreases
from the carbide to the nitride. These three overlapping bands will be denoted ‘‘p
bands.’’
3. Progressing to higher energies, five overlapping bands are found that originate from
the states Γ′25 and Γ12 . These bands are mainly derived from the transition metal nd
states but also exhibit some p character. These bands will be called ‘‘d bands.’’ In the
lower energy range the d bands overlap the p bands. The upper limit of the p bands can
be defined in such a way that they contain exactly six electrons per unit cell.
Figure 3 Band structure of TiC, calculated by means of the full-potential LAPW method. The energy
(Ryd) refers to the mean value of the potential in the region between the atomic spheres as energy zero.
The Fermi energy, indicated by a horizontal line, is at 0.64172 Ryd. (From Ref. 58.)
4. The next band above the d bands originating from the state Γ1 can be derived from
the transition metal (n ⫹ 1)s state. This band is characterized by highly delocalized
states with prevailing s and p symmetry and will be denoted the M-s band. Contrary
to the situation in the pure transition metals, where the broad (n ⫹ 1)s band overlaps
the narrow nd bands, in the carbides and nitrides the (n ⫹ 1)s band is shifted to higher
energies above the Fermi energy due to the repulsive interaction with the nonmetal
s band. Passing from the carbides to the nitrides, the nonmetal s band is lowered in
energy and increasingly localized. Because of these effects, the repulsion between the
nonmetal s and the transition metal (n ⫹ 1)s band (M-s band) is reduced and, conse-
quently, the M-s band, particularly the state Γ1, is shifted to lower energies.
The band structures of the four compounds ZrC, ZrN (54), NbC, and NbN (55,56) were
calculated using the nonrelativistic SC APW method. Weinberger (61) has proved that the ne-
glect of relativistic effects for the 3d and, to a lesser extent, the 4d transition metal carbides
(and nitrides) is essentially justified. This author calculated relativistic energy bands along the
[100], and [110], and [111] directions in the BZ for VC and NbC. The calculations were based
on self-consistent nonrelativistic APW crystal potentials and were performed by means of the
relativistic KKR method (27,28). These calculations show that, in taking into account relativistic
effects, only small changes occur. Some degeneracies are lifted by the spin-orbit splitting, which
is found to be of the order of 5 mRyd in the case of VC and of the order of 10 to 20 mRyd in
the case of NbC.
88 Neckel
Figure 4 Band structure of TiN, calculated by means of the full-potential LAPW method. The energy
(Ryd) refers to the mean value of the potential in the region between the atomic spheres as energy zero.
The Fermi energy, indicated by a horizontal line, is at 0.77582 Ryd. (From Ref. 58.)
Figures 5 and 6 show the band structures of ZrC and ZrN, respectively. The band structures
are similar to those of TiC and TiN. One can recognize the s band (originating from the state
Γ1), the p bands (originating from the state Γ15), and the d bands (originating from the states
Γ′25 and Γ12). The M-s band, which lies above the d bands in the 3d compounds, is found to
lie in ZrC and ZrN at much lower energies. The states of the bands at higher energies are highly
delocalized and represent a mixture of different symmetries.
In addition to the band structure calculations for NbC and NbN already mentioned, LMTO-
ASA band structure calculations for NbC are available from Rajagopalan et al. (62) and for
NbN from Palanivel et al. (63). The electronic structure and other electronic properties, such
as the superconducting transition temperature, of NbN (and also VN, TaN, CrN, MoN, and WN)
were calculated by Papaconstantopoulos et al. (64). The band structures of NbC and NbN are
principally analogous to the structures of the monocarbides and mononitrides discussed previ-
ously. The band structure of NbN for two different crystal structures, namely the hexagonal
and the NaCl structure, was calculated by Alekseev and Tatarchenko (65) using the LMTO
method. From their calculations it follows that NbN in the hexagonal structure has semimetallic
properties, whereas in the NaCl type structure it has metallic ones.
D. Densities of States and Partial l-like Densities of States for the

Stoichiometric Monocarbides and Mononitrides of Ti, V, Zr, and Nb
The density of states (DOS) is defined as the number of electron states in a unit interval of
energy per unit cell and can be computed by a simple histogram technique. As this procedure
Figure 5 Band structure and density of states, N(E ), of ZrC. The energy scale is shown twice: to the
left in Ryd with respect to the muffin-tin zero V 0, to the right in eV with respect to the Fermi energy E F.
N(E ) is given in states of both spin directions per Ryd and unit cell. (From Ref. 54. Reproduced with the
permission of the Springer Verlag,  Springer Verlag.)
Figure 6 Band structure and density of states, N(E ), of ZrN. The energy scale is shown twice: to the
left in Ryd with respect to the muffin-tin zero V 0, to the right in eV with respect to the Fermi energy E F.
N(E ) is given in states of both spin directions per Ryd and unit cell. (From Ref. 54. Reproduced with the
permission of the Springer Verlag,  Springer Verlag.)
90 Neckel
requires the calculation of the energy eigenvalues for a great number of k points, more efficient
techniques have been devised, such as schemes involving gradients (66) or the more commonly
used tetrahedron method (67). An LCAO interpolation scheme, following Slater and Koster
(68), was applied because in the early APW calculations for TiC, TiN, VC, and VN (17–19)
and for NbC and NbN (55,56) the energy eigenvalues could be calculated for only a limited
number of k points. Starting from the X-s, X-p, and M-d orbitals as basis functions, the necessary
interaction integrals in the LCAO scheme were determined by a nonlinear least squares fit to
APW energies. Having determined the LCAO interaction integrals, the energy eigenvalues for
the states being derived from the corresponding basis functions for a great number of k points
can be computed. Later (69,70), the basis of the LCAO interpolation scheme was extended to
include M-s and M-p functions and applied to ScN, ScP, TiN, and ZrN. Klein et al. (71) also
used an LCAO interpolation scheme with an extended basis set to calculate energy eigenvalues
for NbC, HfC, and TaC.
With the advent of the computationally much faster linearized methods, the computation
of reliable densities of states has become much easier. These techniques allow the calculation
of energies for a great number of k points in an energy band. The DOS is then obtained by
means of the tetrahedron method (67).
Examples for DOSs are given in Figs. 5 and 6, which display the band structures of ZrC
and ZrN, together with the corresponding DOSs, calculated on the basis of LAPW results (54)
by means of the tetrahedron method (67). The band structure is reflected in the DOS. Typical
for this class of compounds is the minimum in the DOS at the energy where the number of
valence electrons per unit cell equals eight. Therefore, the Fermi energy, E F, for ZrC, which
has eight valence electrons per unit cell, lies at this minimum, whereas for ZrN, which has one
more valence electron, E F lies in the lower part of the Zr-d bands.
For the discussion of the chemical bonding or for the interpretation of experimental results,
e.g., X-ray emission or photoelectron spectra, partitioning the DOS into its components, corre-
sponding to different angular momentum quantum numbers l, is very useful. Although in the
LCAO interpolation scheme no wave functions appear, because only the interaction integrals
are fitted, the modulus of each LCAO eigenvector component determines the weight with which
the corresponding orbital contributes to the wave function of a given state. The partial l-like
DOS can be obtained by weighting every state with the square of the modulus of the correspond-
ing LCAO eigenvector component. In this way the DOS can be divided into partial l-like densi-
ties of state, g lt (E ). (The superscript t refers to the atom t on which the corresponding orbital
is centered). The partial l-like density of states specifies the number of electron states correspond-
ing to the angular momentum quantum number l per unit energy interval and unit cell.
In the band structure methods that use the concept of an atomic sphere (muffin-tin sphere),
a wave function in an atomic sphere is represented by the product of a radial function and an
angle-dependent function Y ml (spherical harmonic). By weighting the total DOS by the square
of the contribution of the partial functions with a specific l value to the total wave function of
each state, a local (site projected) l-like partial DOS is obtained. The total DOS, g(E ), is thus
spatially divided according to
g(E ) ⫽ gout (E ) ⫹ 冱 g (E )
t, l
t
l (1)
into local partial l-like DOSs, g tl (E ), corresponding to the atomic sphere t. The g out (E ) is the
contribution of the interstitial space between the muffin-tin spheres. If a transition metal is
octahedrally coordinated by the ligands (nonmetal atoms) X, the d electron states of the transition
metal atom are split into orbitals (dxy, dxz, d yz) of t2g symmetry and orbitals (d z2 , d x2⫺y 2) of eg
symmetry. Correspondingly, the partial d-like DOS can be split into a t2g and an eg component.
The partial t2g- and eg-like DOSs are valuable for a discussion of the chemical bonding.
The LCAO partial l-like DOSs for the compounds TiC, TiN, VC, and VN are displayed
in Figs. 7 and 8. From these diagrams it can be gathered—as already discussed in the context
of the band structures—that the energetically low-lying X-s band exhibits nonmetal s character.
In passing from the carbides to the nitrides, this band is energetically lowered and becomes
noticeably narrower, indicating an increased localization of the wave functions of these states
at the nonmetal atom site. Separated from the X-s band by an energy gap and extending to the
minimum of the DOS, the X-p bands follow. As can be seen from the partial l-like DOSs, the
crystal wave functions of the states of the X-p bands exhibit not only X( p) symmetry but also
M(d ) symmetry. This is demonstrated by the strong contribution of a partial d-like DOS. Above
the minimum of the DOS the M-d bands are found, in which the M(d )-like DOS is predominant
but which also contain a small contribution of X( p)-like DOS. Figures 9 and 10 exemplify the
partition of the LCAO partial d-like DOS into its components of t 2g and eg symmetry. In the
X-p bands of TiC, VC, and VN the eg component is somewhat smaller than the t2g component,
whereas in TiN the opposite behavior is found. In the M-d bands the t 2g component predominates
in all compounds. With increasing number of valence electrons in the sequence TiC–TiN, VC–
VN the Fermi energy is shifted to higher energies in the M-d bands. The partial l-like DOSs
of the M-4s band are not included in these figures.
A similar situation is encountered for NbC and NbN. The LCAO partial l-like DOSs,
shown in Fig. 11, for these two compounds were calculated by Schwarz (55,56). The X-s band
is lowered in energy going from the carbide to the nitride. In the X-p bands (between 0.25 and
0.65 Ryd), in which the X( p)-like DOS prevails, a considerable contribution of Nb(d )-like DOS
is found for NbC, which is significantly reduced in NbN. At higher energies the Nb(d )-like
DOS predominates.
The LAPW total and local partial l-like DOSs for TiC and TiN are displayed in Figs. 12
and 13. Figure 14 shows the partition of the LAPW local partial d-like DOSs of TiC and TiN
into the t2g and eg manifolds, respectively (4,72). There exist some differences between the
Figure 7 LCAO partial l-like densities of states, g tl (E ), in units of states of both spin directions per Ryd
and unit cell for TiC (top) and TiN (bottom). The energy (Ryd) refers to the muffin-tin zero V 0 of the APW
calculation. Dotted curves, g Xs (E ); broken curves, g pX(E) (with X ⫽ C, N); full curves, g Tid (E ). (From Refs.
17 and 18. Reproduced with the permission of the Institute of Physics Publ.,  Institute of Physics Publ.)
92 Neckel
Figure 8 LCAO partial l-like densities of states, g tl (E ), in units of states of both spin directions per Ryd
and unit cell for VC (top) and VN (bottom). The energy (Ryd) refers to the muffin-tin zero V 0 of the APW
calculation. Dotted curves, g Xs (E ); broken curves, g Xp (E ) (with X ⫽ C, N); full curves, g Vd (E ). (From Refs.
17 and 18. Reproduced with the permission of the Institute of Physics Publ.,  Institute of Physics Publ.)
Figure 9 Partition of the LCAO partial d-like DOS, g Tid (E ), into the components with t 2g (full curves)
and e g (broken curves) symmetry for TiC (top) and TiN (bottom) in units of states of both spin directions
per Ryd and unit cell. (From Refs. 17 and 18. Reproduced with the permission of the Institute of Physics
Publ.,  Institute of Physics Publ.)
Figure 10 Partition of the LCAO partial d-like DOS, g Vd (E ), into the components with t 2g (full curves)
and e g (broken curves) symmetry for VC (top) and VN (bottom) in units of states of both spin directions
per Ryd and unit cell. (From Refs. 17 and 18. Reproduced with the permission of the Institute of Physics
Publ.,  Institute of Physics Publ.)
Figure 11 LCAO partial l-like DOS, g tl (E ), in units of states of one spin direction per Ryd and unit
cell for NbC (top) and NbN (bottom). Dotted curves, g Xs (E ); broken curves, g Xp (E ) (with X ⫽ C, N); full
curves, g Nb
d (E ). The energy (Ryd) refers to the muffin-tin zero of the original APW calculation. (From
Ref. 56. Reproduced with the permission of the Institute of Physics Publ.,  Institute of Physics Publ.)
94 Neckel
Figure 12 LAPW total, g(E ), and local partial l-like densities of states, g tl (E ), for TiC in units of states
of both spin directions per Ryd and unit cell, calculated by means of the full-potential LAPW method.
g(E ),———; g Cs (E ),⋅ ⋅ ⋅ ⋅; g Cp (E ),---; g Tid (E ),-⋅-⋅-.(From Ref. 58.)
Figure 13 LAPW total, g(E ), and local partial l-like densities of states, g tl (E ), for TiN in units of states
of both spin directions per Ryd and unit cell, calculated by means of the full-potential LAPW method.
g(E ),———; g Ns (E ),⋅ ⋅ ⋅ ⋅; g Np (E ),---; g Tid (E ),-⋅-⋅-.(From Ref. 58.)
Figure 14 Partition of the LAPW local partial d-like DOS, g Tid (E ), into the components with t 2g (full
curves) and e g (broken curves) symmetry for TiC (top) and TiN (bottom) in units of states of both spin
directions per Ryd and unit cell. (From Ref. 72. Reproduced with the permission of Prof. P. Blaha, Techn.
University of Vienna.)
LCAO partial l-like DOSs and the LAPW local partial l-like DOSs (4), because the LCAO
partial l-like DOSs refer to the whole unit cell, whereas the LAPW local partial l-like DOSs
refer to specific muffin-tin spheres. As an example of this difference, the partition of the d-like
DOS of TiC in the range of the p bands may be mentioned. According to the LCAO calculation
the t 2g component of the partial d-like DOS is higher than the eg component, as can be inferred
from Fig. 9. However, the local partial t 2g-like DOS obtained by means of the LAPW method
is smaller than the eg component, as can be gathered from Fig. 14.
E. Bonding Mechanisms for the Stoichiometric Monocarbides and

Mononitrides of Ti, V, Zr, and Nb
The exceptional combination of properties that is a characteristic feature of this class of com-
pounds has its root in the bonding mechanism. The electronic structure calculations reveal that
all three main types of chemical bonding (ionic, covalent, and metallic) occur in these sub-
stances.
1. Charge Distribution
From band structure calculations utilizing the muffin-tin approximation, the distribution of the
charges of the valence electrons over the muffin-tin spheres and the interstitial region between
the spheres can be calculated: qout is the charge in the interstitial region, q tot
t
the total charge
t
residing in the muffin-tin sphere t, and the partition of q tot yields the local (inside muffin-tin
96 Neckel
sphere t) partial (l-like) charges q lt. The partial charges thus defined satisfy the following equa-
tion:
N val ⫽ q out ⫹ 冱q t
t
tot ⫽ q out ⫹ 冱冱q t l
t
l (2)
where N val is the total number of valence electrons. A systematic comparison in terms of the
valence electron charge distribution for the eight compounds ZrC, ZrN, NbC, NbN, TiC, TiN,
VC, VN was performed by Schwarz et al. (54) and is presented in Tables 1 and 2. Such a
comparison provides insight into the charge transfer and, consequently, into the ionic bonding
component. Each type of the considered energy bands contains N b electrons: the X-s bands 2,
the X-p bands 6, and the M-d bands (N val ⫺ 8) electrons. To establish a common basis for the
comparison, all partial charges have been normalized, according to
q̄ lt ⫽ q lt /N b (3)
where q̄ t represents the charge contribution corresponding to one electron in that band. For the
X-s band the values of the total charges q̄ t, and for the X-p and the M-d bands, only the values
of q̄ tl for the most important components are listed. The lattice constants decrease monotonically
in the sequence of the compounds in Table 1, and, as a consequence, there is a great variation
in the unit cell volume, Ω, and in the volumes of the three different regions of the unit cell, as
listed at the bottom of Table 1. To account for these variations a mean l-like valence electron
density, f lt, per valence band and valence electron has been defined
f lt ⫽ q̄ lt /Ω t (4)
Table 1 Local Partial APW Charges, q̄ tl , According to Eqs. (2) and (3) in Percent a
M(4d )X M(3d )X
ZrC ZrN NbC NbN TiC TiN VC VN
Compound
N val 8 9 9 10 8 9 9 10
M
d-bands q̄
d (39) 41 41 48 60 62 68
X
q̄p (27) 23 27 23 14 17 13
out
q̄ (28) 30 25 24 22 17 16
p-bands q̄ dM 23 16 28 21 26 17 32 20
q̄ pX 39 50 33 46 40 53 35 50
q̄ out 31 26 31 27 28 24 27 24
M
s-band q̄ tot 14 11 15 11 12 9 13 8
X
q̄ tot 65 75 62 73 65 76 62 75
q̄ out 21 14 23 16 23 15 25 17
a(Å) 4.685 4.585 4.471 4.400 4.328 4.242 4.182 4.140
Ω M(a3 0) 61.8 60.2 52.6 52.0 41.3 40.4 37.8 37.3
ΩX 32.3 28.8 28.8 26.2 30.8 27.8 27.4 26.2
Ω out 79.6 73.6 69.4 65.5 64.7 60.5 58.2 56.5
Ω 173.7 162.6 150.8 143.7 136.8 128.7 123.4 120.0
a
N val , number of valence electrons in the respective band; a, lattice constant (in Å); Ω, volume of the unit cell and its
partition into the volumes of the metal sphere, Ω M, the nonmetal sphere, Ω X, and the region outside the spheres, Ω out.
All volumes in atomic units (a 0)3.
Source: From Ref. 54. Reproduced with the permission of the Springer Verlag,  Springer Verlag.
Table 2 Local Partial APW Electron Densities, f tl , According to Eq. (4) in Units of 10⫺4 Electrons
per Atomic Unit (a 0) 3
M(4d )X M(3d )X
ZrC ZrN NbC NbN TiC TiN VC VN
Compound
N val 8 9 9 10 8 9 9 10
M
d-bands fd (63) 68 78 92 148 164 182
X
f p (84) 80 94 88 50 62 50
out
f (35) 41 36 37 36 29 28
p-bands f dM 37 27 53 40 63 42 85 54
f pX 121 174 115 176 130 191 128 191
f out 39 35 45 41 43 40 46 42
M
s-band f tot 23 18 29 21 30 22 34 21
X
f tot 201 260 215 279 211 273 226 286
out
f 26 19 33 24 36 25 43 30
a(Å) 4.685 4.585 4.471 4.400 4.328 4.242 4.182 4.140
Source: From Ref. 54. Reproduced with the permission of the Springer Verlag,  Springer Verlag.
In order to reveal the main trends in the chemical bonding from Tables 1 and 2, the figures
in these tables have been analyzed (54) according to three points of view:
1. Changes in passing from the carbide MC to the nitride MN. In the nonmetal sphere,
the charges q̄ Xtot in the X-s band as well as the charges q̄ Xp in the X-p bands increase,
whereas the charges q̄ dM and q̄ out in the X-p bands decrease. This behavior indicates
a higher degree of localization and a reduced interaction between the X-p and M-d
states within the N sphere. In the M-d bands the opposite effect is observed: the
charges q̄ Xp are diminished, whereas the charges q̄ dM are slightly increased, indicating
a reduction of the X( p)-M(d ) interaction.
2. Changes in passing from M(n,d)X to M(n,d ⫹ 1)X (both metals in the same period
of the periodic table). The charges q̄ dM in the X-p and M-d bands increase only slightly.
Because the volumes Ω M decrease, the mean electron densities f dM increase more
strongly. This effect reflects the stronger localization of the M(n,d ⫹ 1) wave func-
tions. The values for the charges q̄ pM remain almost constant in the M-d bands, whereas
they decrease in the X-p bands. This decrease goes parallel with the reduction of the
volumes Ω X, yielding nearly constant values for f Xp.
3. Changes in passing from M(3d)X to M(4d)X. The most pronounced changes are ob-
served in the M-d bands. The charges q̄ dM and—to a much higher extent due to the
larger volumes Ω M —the mean electron densities f Md decrease. This effect is caused
by the greater delocalization of the 4d wave functions compared with the 3d wave
functions. Furthermore, a stronger M(d )-X( p) interaction can be inferred from the
fact that the corresponding q̄ Md and q̄ Xp (or f Md and f Xp values) are more similar in the
case of the M(4d ) than of the M(3d ) compounds.
2. Radial Charge Densities: Charge Transfer

An ionic contribution to the binding mechanism is caused by the transfer of electronic charge
from one atom (muffin-tin sphere) to another one, resulting in an electrostatic contribution to
the binding energy. A charge transfer can be defined only with respect to a suitable chosen
98 Neckel
reference state. Frequently, the spherically averaged radial electron density σ tsuperposed (r), obtained
by the superposition of the atomic electron densities of the corresponding neutral atoms, placed
on the positions of the atoms, is chosen as reference state. (σ tsuperposed (r) ⫽ 4πr 2 ρ̄(r), where r is
the distance from the center of atomic sphere t and ρ̄(r) the spherically averaged electron den-
sity). σ superposed
t
(r) is often used as the initial density in an SC band structure calculation. The
charge transfer density ∆σ t (r) is defined as the difference between the radial electron density,
σ crystal
t
(r), obtained from a self-consistent band structure calculation, and the superposed atomic
radial electron density, σ superposed
t
(r),
∆σ t (r) ⫽ σ crystal
t
(r) ⫺ σ superposed
t
(r) (5)
In Fig. 15 the difference ∆σ t(r) is plotted versus the distance r from the center of the atomic
sphere t for TiC, TiN, VC, and VN. R X and R M are the radii of the atomic spheres around the
nonmetal X site and the metal M site, respectively. ∆σ t(r) is positive (except for a very small
region near the atomic nucleus) in the nonmetal sphere, indicating an increase in electronic
charge in this region of the crystal compared with the electronic charge in a hypothetical crystal
of noninteracting neutral atoms, and negative in the metal sphere. The total amount of transferred
electronic charge, ∆Q t , obtained by integrating ∆σ t(r) over the respective atomic sphere t ac-
cording to Eq. [6] depends on the atomic sphere radius Rt, which is not uniquely defined.
冮
R
t
∆Q t ⫽ ∆σ t(r′) dr′ (6)
O
However, as can be gathered from Fig. 15, for a different choice of the atomic sphere
radii, R t, there will always be an increase of electronic charge within the nonmetal sphere and
Figure 15 The difference, ∆σ t (r), between the radial charge density of the crystal, σ tcrystal (r), and the
superposed atomic radial charge density, σ tsuperposed (r), in the muffin-tin sphere t plotted versus the distance
r from the center of the muffin-tin sphere t in atomic units [see Eq. (5)]. Full curves, nonmetal sphere;
broken curves, metal sphere. R X and R M are the radii of the respective muffin-tin spheres around the non-
metal atom X (X ⫽ C, N) and around the metal atom M (M ⫽ T, V), respectively. (From Refs. 18 and
19. Reproduced with the permission of the Berichte der Bunsen-Gesellschaft,  Berichte der Bunsen-
Gesellschaft.)
a decrease within the metal sphere, compared with the hypothetical crystal of noninteracting
neutral atoms. Values for the charge transfer ∆Q t (in electrons per atomic sphere) based on the
atomic sphere radii used by Neckel et al. (17,18) and Schwarz (55) are listed in Table 3. The
charge transfer is about the same for all compounds of the group of substances considered and
does not follow the simple electronegativity rules, from which a higher charge transfer, ∆Q t,
in the nitrides MN than in the carbides MC would be expected. However, a complex mechanism
is responsible for the actual charge transfer. The higher electronegativity of the nitrogen atom
causes a stronger localization of the 2p states of the nitrogen atom. This effect should cause an
increase of charge in the nitrogen sphere. In the metal sphere two opposite effects occur: the
Fermi energy is shifted to higher energies in the range of the d bands on passing from the
carbide MC to the nitride MN. Therefore, the additional electron of the nitrogen atom occupies
states in the d bands, whose wave functions are localized predominantly in the metal sphere,
leading to an increase of charge, q Md,d bands , in the metal sphere in the range of the d bands. On
the other hand—due the lower energy and to the higher localization of the 2p states of the
nitrogen atom—the N( p)-M(d ) interaction is reduced, resulting in a decrease of the charge,
M
q d,p bands , in the metal sphere in the range of the p bands. This complex mechanism results in the
charge transfer ∆Qt being about the same in the carbides and nitrides.
3. Valence Electron Densities

Calculations of the valence electron densities (VEDs) by means of the LAPW method for TiC,
TiN, and TiO (57), for TiC (73), and for VN (59,74), as well as by means of the FLAPW
method for TiC and TiN (58), form the basis for an extensive discussion of the mechanism of
chemical bonding in these substances. The theoretical electron densities (EDs) were compared
Table 3 Charges and Charge Transfer in Different Regions of the Crystal for TiC, TiN, VC, VN,
NbC, and NbN a
Substance TiC TiN VC VN NbC NbN
Metal sphere M Ti Ti V V Nb Nb
Metal sphere radius R M 2.1444 2.1290 2.0807 2.0722 2.3244 2.3146
Total APW charge Q Mcrystal 19.8589 19.8540 20.9246 20.8705 38.846 38.499
Atomic superposed charge Q Mat 20.2164 20.1782 21.2137 21.1482 39.125 39.075
∆Q M ⫽ Q Mcrystal ⫺ Q Mat ⫺0.3575 ⫺0.3242 ⫺0.2891 ⫺0.2777 ⫺0.639 ⫺0.576
Nonmetal sphere X C N C N C N
Nonmetal sphere radius R X 1.9449 1.8789 1.8706 1.8394 1.9001 1.8428
Total APW charge Q Xcrystal 5.8448 6.9803 5.6544 6.8779 5.680 6.834
Atomic superposed charge Q Xat 5.4118 6.5235 5.3018 6.4718 5.240 6.268
∆Q X ⫽ Q Xcrystal ⫺ Q Xat 0.4330 0.4568 0.3526 0.4061 0.440 0.566
Region between the atomic
spheres
Total APW charge q out crystal 2.2963 2.1657 2.4210 2.2516 2.834 2.667
Atomic superposed charge q atout 2.3718 2.2983 2.4845 2.3800 2.635 2.657
∆q out ⫽ q out
crystal ⫺ q at
out
⫺0.0755 ⫺0.1326 ⫺0.0635 ⫺0.1284 0.199 0.010
a
Q tcrystal, q out
crystal , charge (number of electrons) in the muffin-tin sphere t and the region outside the muffin-tin spheres,
respectively, in the crystal; Q tat , q out at , charge (number of electrons) in the muffin-tin sphere t and in the region outside
the muffin-tin spheres, respectively, of a lattice with superposed, noninteracting neutral atoms; ∆Qt, charge transfer
(number of electrons) in sphere t with respect to the superposed atomic charges (∆Q t ⫽ Q tcrystal ⫺ Q tat); ∆qout , charge
transfer (number of electrons) in the region outside the atomic spheres with respect to the superposed atomic charges
(∆qout ⫽ q out crystal ⫺ qat ); R t , radius of the muffin-tin sphere t (au).
out
Source: Data from Refs. 17, 18, and 55. Reproduced with the permission of the Institute of Physics Publ.
100 Neckel
Figure 16 Valence electron densities (VEDs) of TiC, TiN, and VN in the (110) plane. (a) Theoretical
VEDs; (b) experimental VEDs. Contour intervals 0.2 electron/Å3. Labeled contour lines must be divided
by 10 to obtain electrons per cubic angstrom. The end points of the plots correspond to 0, 0, 0; 0.5, 0.5, 0;
and 0, 0, 1. (From Ref. 74. Reproduced with the permission of Academic Press, Inc.,  Academic Press, Inc.)
with experimental ones for TiC and TiN (75) and VN (76), obtained from X-ray diffraction
measurements. For this comparison, however, the experimental data had to be refined. The
sample of titanium carbide investigated had the composition TiC 0.94 with 6% vacancies. Further-
more, a static displacement of the Ti atoms adjacent to the vacancies by about 0.1 Å had to be
considered. Dunand et al. (75) and Kubel et al. (76) developed a model that takes into account
various factors and permits an extrapolation of the raw X-ray data to those of an ideal crystal.
Good agreement between the theoretical and the extrapolated VED has been found in general.
In particular, the nonspherical electron density distribution around the metal sites and the density
distribution around the nonmetal sites agree well, whereas the magnitudes of the 3d maxima
Figure 17 VEDs in the (100) plane for TiC (left) and TiN (right). For the contour lines a logarithmic
grid has been used. x i ⫽ x 02i/3, x 0 ⫽ 0.2 e/Å3. (From Ref. 58.)
were found to be higher in the experiment. A comparison between theoretical and (extrapolated)
experimental VEDs of TiC, TiN, and VN in the (110) plane is presented in Fig. 16.
It should be mentioned here that theoretical EDs provide much more information and
therefore have an important advantage over experimentally determined EDs. Only the total ED
is experimentally available, whereas through theory the total ED can be partitioned into the
contributions from respective energy bands.
The results obtained in these investigations for the VEDs of TiC, TiN, TiO, and VN are
visualized in Figs. 17 and 18 and can be summarized as follows:
1. The VED around the nonmetal sites is essentially spherically symmetric, as expected
for p states in an octahedral crystal field, which does not lift the degeneracy of the
Figure 18 (Left) VED of TiO in the (100) plane. Contour intervals 0.1 e/Å ⫺3 (numbers are in these
units). Note the cutoff for the VED of the O atom at 1.7 e/Å 3. (From Ref. 57. Reproduced with the
permission of John Wiley & Sons, Inc.,  John Wiley & Sons, Inc.) (Right) VED of VN in the (100)
plane. Contour intervals 0.2 e/Å 3. Labeled contours must be divided by 10 to obtain electrons per cubic
angstrom. Note the cutoff for the VED of the N atom at 3.0 e/Å 3. (From Ref. 59. Reproduced with the
permission of the American Physical Society,  American Physical Society.)
102 Neckel
p states. The three 2p orbitals ( px , py, pz ) are equally occupied. The VED increases
from the carbide to the nitrides. (Note the cutoff of the VEDs for the O and N atom
in Fig. 18.) The VED around the metal atom site remains about constant in the cases
of TiC and TiN but increases in VN.
2. The octahedral crystal field at the metal site splits the d orbitals into t 2g- and e g-type
orbitals. Therefore, the contribution to the VED caused by the d orbitals can also be
partitioned into a t 2g- and e g-like component. The t 2g (dxy, d xz, d yz) orbital lobes point
toward the nearest metal atoms and consequently the t 2g-like VED shows maxima in
these directions in the vicinity of the atomic position. The e g (d x2⫺y2 , dz2) orbital lobes
point toward the nearest nonmetal neighbours, causing maxima in the e g-like VED
in the directions to nearest nonmetal atoms.
The VED around the metal sites deviates from spherical symmetry. Most re-
markable is the change in the symmetry of the nonspherical component in the series
TiC, TiN, TiO, VN (TiO is included here in the discussion, because it allows a clear
recognition of the trend caused by changing the nonmetal atom). As can be gathered
from Figs. 17 and 18, which present the VEDs in the (100) plane, the e g-like VED
prevails in TiC. In TiN a slight excess of t 2g-like VED can already be observed,
whereas in VN, as well as in TiO, the t 2g-like component predominates.
The VEDs for the four compounds MX (with M ⫽ Zr, Nb and X ⫽ C, N) have been
calculated by Schwarz (4), again using the LAPW method. The main difference between the
4d metals (Zr, Nb) and the 3d metals (Ti, V) is the existence of an additional nodal surface in
the VED of the former, leading to a spatially more diffuse electron density distribution.
The VED in the interstitial region in the crystal is relatively high, as can be seen from
Fig. 19, where the valence electron density ρ(r) for TiC, ZrC, and NbC (4) is plotted along the
[100] direction (the direction between next-nearest neighbors) and the [110] direction (the direc-
tion between nearest atoms of the same kind). The additional node in the radial wave function
in the case of the 4d metals (Zr,Nb), compared with the 3d metals, can be clearly seen. Other-
wise, the VEC in the interstitial region is nearly the same. From this fact and the nonvanishing
DOS at the Fermi energy (see Sec. II.D), the presence of a metallic bonding component can be
inferred.
4. Covalent Bonding
The covalent bonding component is of essential importance for the understanding of the bonding
mechanism. The local partial l-like charges and the partial l-like DOSs allow only a rough
estimate of this bonding component. Much more detailed information can be obtained from
valence electron densities (VEDs) and the VEDs of special states.
The simple molecular orbital (MO) concept for diatomic molecules can be applied to
describe the covalent bonds between adjacent atoms in the crystal. By a linear combination of
atomic orbitals (LCAO) on neighboring atoms, bonding or antibonding MOs can be constructed.
Applying this description to the case of the transition metal carbides and nitrides, several types
of covalent bonds can be formed. The transition metal atoms participate in covalent bonds mainly
by their d electrons, which are split by the octahedral crystal field, generated by the nearest
nonmetal neighbours, into the t 2g and the eg manifold.
To illustrate the various types of covalent bonds occuring in transition metal carbides and
nitrides, Herzig et al. (58) selected, in the band structures of TiC and TiN, representative k
points that are characterized by a particular type of covalent interaction in more or less pure
form. For the selected states, VEDs were computed using the results of full-potential LAPW
band structure calculations. Each of Figs. 20–26 shows, in the top panel, a schematic representa-
tion of a special bond type and, in the bottom panel, the VED in a definite crystal plane for a
Figure 19 Total valence electron density, ρ(r), in the [100] direction from the carbon atom C to the
metal atom M (M ⫽ Ti, Zr, Nb) and in the [110] direction between the metal atoms (full curves) and the
carbon atoms (broken curves). (From Ref. 4. Reproduced with the permission of Critical Reviews in Solid
State and Materials Sciences, CRC Press LLC.,  Critical Reviews in Solid State and Materials Sciences,
CRC Press LLC.)
selected state that contains this particular type of bond. [The states are characterized by their
energy and their main components of the local partial l-like charges, q t l, in the respective atomic
spheres, t, in percent. For the contour lines in the VED plots a logarithmic grid is used. Each third
contour line corresponds to a doubling of the electron density. In the schematic representation of
the atomic orbitals positive and negative regions of the orbitals are distinguished by their tint.
Figures 20–26 are taken from Herzig et al. (58).]
In order to obtain the required cubic symmetry of the VED the sum over the star of k
has to be formed. It cannot be avoided that some of the chosen k points also contain other types
of covalent bonds besides the considered one. To reduce this ‘‘mixing’’ of bond types as far
as possible, in some cases the cubic crystal has been considered as artificially tetragonal to
separate orbitals in the xy plane from those in the xz and yz planes. (The legends to the figures for
the VEDs indicate whether the crystal has been considered as cubic or as artificially tetragonal.)
As already discussed by Neckel et al. (19), three main types of covalent bonds can be
distinguished in the transition metal monocarbides and mononitrides.
The orbital lobes of the transition metal e g orbitals (d x2⫺y2 , dz2) point toward the neighboring
nonmetal atoms. These orbitals can form pd σ bonds with 2p orbitals of the neighboring nonmetal
atoms. This bond type is depicted in Fig. 20, which shows the interaction of a metal d x2⫺y2 orbital
(center) with px and py orbitals, respectively, of neighboring nonmetal atoms.
The orbital lobes of the t 2g orbitals (dxy, d xz, d yz) extend toward the neighboring metal
atoms. These orbitals can form pd π bonds with 2p orbitals of neighboring nonmetal atoms.
Figure 21 shows the interaction of a metal d xy orbital (center) with px and py orbitals of neigh-
boring nonmetal atoms.
104 Neckel
Figure 20 (Top) Schematic representation of the formation of pd σ bonds in the (001) plane by the
interaction of a transition metal d x 2⫺y 2 orbital (center) with px and py orbitals of neighboring nonmetal atoms.
(Bottom) VED for the state N (tetragonal description, corresponds to L′ 3 in cubic description), at 0.42722
Ryd (occupied), in the (001) plane of TiC. q tl: 37.9% C( p), 36.4% Ti(d ). (From Ref. 58.)
The t 2g orbitals can also form dd σ bonds with the t 2g orbitals of the nearest metal atoms.
This bond type is represented in Fig. 22, which shows metal (d xy)–metal (d xy) σ bonds.
A similar illustration of the three main types of covalent bonds by VED plots has been
given by Schwarz and Blaha (22).
Besides these main types of covalent bonds, other covalent interactions can occur, which
probably play a minor role. Some of the possible types are mentioned in the following.
Inspection of the local partial l-like DOSs shows that in the nonmetal s band states occur
that have simultaneously nonmetal s and a small amount of metal e g (d x2⫺y2 , d z2) character. From
this fact it can be concluded that in the energy range of the nonmetal s band sdσ bonds occur.
To illustrate this type of interaction, in Fig. 23 sd σ bonds between a metal d x2⫺y2 orbital (center)
and the s orbitals of neighboring nonmetal atoms are shown.
The d orbitals of the transition metal atoms can participate in different types of metal-
Figure 21 (Top) Schematic representation of the formation of pd π bonds in the (001) plane by the
interaction of a transition metal d xy orbital (center) with p x and p y orbitals of neighboring nonmetal atoms.
(Bottom) VED for the state ⌺ 3 (cubic description), at 0.55980 Ryd (occupied), in the (001) plane of TiC.
q tl : 25.2% C( p), 1.4% C(d ), 1.7% Ti( p), 38.1% Ti(d ). (From Ref. 58.)
metal bonds. The d z2 orbital of a metal atom can interact with the d z2 orbitals of neighboring
metal atoms in the (110) and (110) planes, respectively, to form metal (d z2)–metal (d z2) σ bonds
as shown in Fig. 24. Also metal-metal π bonds can be formed. Figure 25 shows the interaction
of d x2⫺y2 orbitals of neighboring metal atoms in the (001) plane leading to metal (d x2⫺y2)–metal
(d x2⫺y2) π bonds. In a similar way the d z2 orbitals of neighboring metal atoms in the (100) and
(010) planes can interact forming π-like bonds as depicted in Fig. 26.
Other types of covalent bonds, e.g., δ bonds, and bonds involving metal s and p orbitals,
can also be imagined. Not all of the bond types mentioned are found in the occupied energy
range.
5. Discussion of the Bonding Mechanism
The discussion of the bonding mechanism in this section is based on TiC, TiN, TiO, and VN
as representative examples. Inspection of the partial l-like DOSs and of the partition of the
106 Neckel
Figure 22 (Top) Schematic representation of the formation of dd σ bonds in the (001) plane by the
interaction of a transition metal d xy orbital with d xy orbitals of neighboring transition metal atoms. (Bottom)
VED for the state Γ′25 (tetragonal description, corresponds to Γ′25 in cubic description) at 0.72835 Ryd
(occupied), in the (001) plane of TiN. q tl: 2.3% N(d ), 71.9% Ti(d ). (From Ref. 58.)
partial l-like charges into the contributions of the respective energy bands shows that, in the p
bands, the X( p)-like charge prevails and the M(d )-like charge is the minor component. In the
d bands the opposite situation is encountered. Such behavior is to be expected when a covalent
X( p)-M(d ) interaction is present.
In the simple MO description of heteronuclear diatomic molecules MX two atomic orbitals
of appropriate symmetry form a bonding and an antibonding MO. The bonding orbital tends to
concentrate on the atom with the lower energy orbital, in the present case the X-2p orbital. The
antibonding MO tends to resemble the higher energy atomic orbital, in the present case the M-
3d orbital. The energy separation between the M-3d orbital and the X-2p orbital increases in
the sequence X ⫽ C, N, O (keeping M constant), leading to a diminishing M(d )-X( p) interaction
and consequently to an increase of the X-2p character [X(2p)-like charge] and to a decrease of
the M-3d character [M(3d )-like charge] in the bonding MO. In the antibonding MO the opposite
Figure 23 (Top) Schematic representation of the formation of sd σ bonds in the (001) plane by the
interaction of a transition metal d x 2⫺y 2 orbital (center) with s orbitals of neighboring nonmetal atoms. (Bot-
tom) VED for the state X (tetragonal description, corresponds to X 1 in cubic description) at ⫺0.08921
Ryd (occupied), in the (001) plane of TiC. q tl : 60.3% C(s), 1.2% Ti(s), 12.4% Ti(d ). (From Ref. 58.)
behavior is observed. From this point of view, the characteristic minimum in the DOS, which
always occurs at approximately eight valence electrons, could be regarded as separating the
bonding from the antibonding X( p)-M(d ) interactions. The strongest X( p)-M(d ) interactions
are found in TiC, because the atomic orbitals involved have nearly equal energies and the wave
functions overlap effectively. The X( p)-M(d ) interactions decrease passing to TiN and further
to TiO. In VN these interactions are slightly stronger than in TiN. This behavior can be under-
stood if one takes into account that the V-3d orbitals lie about 0.8 eV lower than the Ti-3d
orbitals and are therefore energetically nearer to the N-2p orbitals.
For a closer examination of the types of covalent bonds occurring in the p and d bands,
respectively, not only the partition of the partial d-like DOS into the e g and t 2g components but
also the partial l-like charges as well as the VEDs have to be considered.
108 Neckel
Figure 24 (Top) Schematic representation of the formation of dd σ bonds in the (110) plane by the
interaction of a transition metal d z2 orbital with d z2 orbitals of neighboring transition metal atoms in the
same (001) plane. (Bottom) VED for the state Γ 12 (tetragonal description, corresponds to Γ 12 in cubic
description) at 0.81497 Ryd (0.03915 Ryd above E F ) in the (110) plane of TiN. q lt: 3.8% N(d ), 81.4%
Ti(d ). (From Ref. 58.)
In TiC only the p bands are occupied and the p- and the d-like DOSs are of comparable
size. Both the LCAO partial d-like DOSs (Fig. 9) and the LAPW local partial d-like DOSs
(Fig. 14) show that the e g and the t 2g components are of almost equal magnitude (although
the two schemes lead to somewhat different results, as mentioned in Sec. II.D). As can be
gathered from Fig. 17, the maxima in the VED near the Ti atoms point toward the next nearest
C neighbors, indicating the predominance of e g orbitals. From the partial e g-like DOS and from
the clear e g-like VED it can be concluded that pd σ bonds prevail. In TiC only the states that
correspond to bonding pd σ bonds are occupied, whereas all antibonding pd σ states remain empty.
The occurrence of the t 2g component leads to the assumption that pd π and some dd σ bonds are
also present.
In the p bands of TiN the partial d-like DOS is reduced compared with TiC. The e g
component is somewhat higher than the t 2g component. The occurrence of pd σ bonds has, there-
fore, to be assumed. The t 2g states will form predominantly pd π bonds because many N-2p states
are available in the p bands. In the occupied range of the d bands the partial d-like DOS has
exclusively t 2g character. Because the number of N-2p states is small in this energy range, mainly
Figure 25 (Top) Schematic representation of the formation of dd π bonds in the (001) plane by the
interaction of a transition metal d x2⫺y2 orbital with d x2⫺y2 orbitals of neighboring transition metal atoms.
(Bottom) VED for the state X (tetragonal description, corresponds to X 5 in cubic description) at 0.89386
Ryd (unoccupied), in the (001) plane of TiN. q tl: 3.1% N(d ), 87.4% Ti(d ). (From Ref. 58.)
dd σ bonds will be formed. The results of these considerations are confirmed by the VED of TiN
(Fig. 17), which shows a slight excess of the t 2g-like component.
In the p bands of TiO the admixture of partial d-like DOS is small, so very little pd
bonding occurs. The main covalent bonding contribution is brought about by the dd σ bonds in
the occupied range of the d bands. In the titanium compounds considered, the covalency de-
creases from the carbide to the oxide. The ionicity—actually the localization of the charge on
the nonmetal atom—increases in that direction, whereby the charge transfer remains almost
constant, as already discussed in Sec. II.E.2.
The behavior of VN lies between that of TiC and that of TiN. A charge analysis (59)
reveals that in the p bands 2.88 electrons with p symmetry are found in the N sphere and 1.30
electrons with d symmetry in the V sphere. From the latter 0.74 electrons exhibit e g character.
110 Neckel
Figure 26 (Top) Schematic representation of the formation of π-like transition metal (d z 2)–transition
metal (d z 2) bonds by the interaction of transition metal d z 2 orbitals in the (100) plane. (Bottom) VED for
the state Γ 12 (tetragonal description, corresponds to Γ 12 in cubic description) at 0.81497 Ryd (0.03915 Ryd
above E F ) in the (100) plane of TiN. q tl:3.8% N(d ), 81.4% Ti(d ). (From Ref. 58.)
Accordingly, the e g component of the local partial d-like DOS predominates the t 2g component.
From these facts the presence of pd σ bonds in the range of the p bands can be inferred. A small
amount of pdπ bonding may also be present.
In the occupied part of the d bands the local partial p-like DOS is small (0.24 p electrons
in the N sphere). Only about 8% of the d electrons (1.35 d electrons in the V sphere) possess
e g symmetry. This situation leads to the prevailing formation of dd σ bonds. In the total VED
the contribution of the d bands predominates, so that the total VED has t 2g character, as can be
seen from the VEDs in the (110) plane (Fig. 16) and in the (100) plane (Fig. 18). These conclu-
sions concerning the bonding in VN are corroborated by an analysis of the VED (74). In Fig.
27 the total VED of VN is split into the contributions of the (s ⫹ p) bands (eight electrons)
and the occupied part of the d bands (two electrons). In the (s ⫹ p) bands the VED has e g
character (Fig. 27, bottom). The maxima near the V atom point toward the neighboring N
Figure 27 VEDs in the (100) plane of VN. (Note the cutoff of the VED for the N atom at 3.0 e/Å ⫺3.
(Top) Total VED; (middle) contribution of the occupied part of the d bands (two electrons); (bottom)
contribution of the s and p bands (eight electrons). (From Ref. 74. Reproduced with the permission of
Academic Press, Inc.,  Academic Press, Inc.)
atoms, indicating the presence of pd σ bonds. In the d bands (Fig. 27, middle), however,
the maxima near the V atoms point toward the neighboring V atoms, indicating the presence
of dd σ bonds.
For the compounds ZrC, ZrN, NbC, and NbN a bonding situation qualitatively similar to
that of the corresponding compounds with the 3d metals Ti and V can be expected for the p
bands as judged by the partial charges (Table 1). This view is also supported by the calculated
VEDs (4). Because the M-4d wave functions are more diffuse than the M-3d wave functions,
the overlap with the X-2p wave functions will be more efficient and a stronger bonding M(d )-
X( p) interaction will result. In the d bands, however, the situation seems to differ from that
with the M-3d compounds. The partial p-like charges q̄ Xp , and particularly the f Xp values (Tables
1 and 2), in the d bands are higher for the M-4d compounds, which leads to the assumption
that the M(d )-X( p) interactions are stronger.
112 Neckel
6. Metallic Bonding Component

From the nonvanishing DOS at the Fermi energy and from the relatively high electron density
in the interstitial region between the muffin-tin spheres (see Sec. II.E.3), metallic behavior can
be expected.
F. Electronic Structure of the Stoichiometric Monocarbides and

Mononitrides of Hf and Ta
1. Band Structures: Densities of States
For the band structure calculations for the monocarbides and mononitrides of the transition
elements Hf and Ta the application of relativistic methods is necessary, as demonstrated by
Weinberger et al. (77,78). These authors used the self-consistent relativistic KKR method (27,28)
to calculate the band structures of HfC and TaC (77) as well as those of HfN and TaN (78).
Further band structure calculations for HfC and TaC (71,79) and TaN (64,80) have been reported
in the literature.
Total and local partial l-like DOSs for HfC and HfN were calculated by Schadler and
Monnier (81) by means of the relativistic KKR-GF method. The same approach was used by
Schadler et al. (82) to calculate the total and local partial l-like DOSs for TaC.
As an example, the energy bands of HfC, obtained by Weinberger et al. (77), for the
directions [111] (Γ-Λ-L), [100] (Γ-∆-X ), and [110] (Γ-⌺-K ) in the first BZ are displayed in Fig.
28. Also shown in this figure are the nonrelativistic bands in the direction [100] (Γ-∆-X ). In
the following the notation l j (l, angular momentum quantum number; j, total angular momentum
quantum number) is used, instead of the relativistic quantum number κ, to characterize an elec-
tron state. If both values of j, namely j ⫽ 1 ⫾ 1/2 , apply, the superscript in the symbol l j is
dropped. The relativistic band structure of HfC is characterized by the following bands: a broad
C-2s band, originating at the state Γ ⫹6 (⫺0.1496 Ryd); broad C-2p bands, originating at the
states Γ 6⫺ (0.8533 Ryd); and Γ ⫺8 (0.8640 Ryd). The states of the C-2p bands contain, besides p
character, an appreciable amount of d character (up to 20% of the charge of a state) due to the
interaction between the C-2p and the Hf-5d orbitals. Originating at the states Γ ⫹8 (0.9892 Ryd),
Γ 7⫹ (1.0083 Ryd), and Γ 8⫹ (1.2048 Ryd), the very broad Hf-5d bands follow. Most interesting
is the fact that the Hf-4f 7/2 bands, originating at the states Γ ⫺6 (0.3852 Ryd), Γ ⫺7 (0.4010 Ryd),
and Γ 8⫺ (0.4017 Ryd), cut through the C-2p bands in the [111] direction. The Hf-4f 5/2 bands,
originating at the states Γ 8⫺ (0.2708 Ryd) and Γ 7⫺ (0.2721 Ryd), lie about 0.13 Ryd below the
Hf-4f 7/2 bands. The Fermi energy lies at 0.8165 Ryd. A comparison of the relativistic and nonrel-
ativistic band structures reveals that the relativistic C-2s and C-2p bands are much broader than
the nonrelativistic ones. The relativistic Hf-4f 5/2 and Hf-4f 7/2 bands are split. The mean value
of the f-like Γ 7⫺ states lies 0.149 Ryd below the energy of the corresponding nonrelativistic
Γ 2⫺ state.
The relativistic band structure of HfN (78) is characterized by a N-2s 1/2 band at the bottom
of the valence band region. This band lies well below the very narrow Hf-4f bands. Above the
Hf-4f bands, and nearly touching the Hf-4f 7/2 band, the N-2p bands are found. They are separated
by a small indirect gap from the Hf-5d,6s band complex. The Fermi energy cuts through the
Hf-5d bands.
The relativistic band structure of TaC (77) is characterized by overlapping C-2p and Ta-
5d bands. The Ta-4f bands lie well below the C-2s band (Fig. 29). For TaN one has to bear in
mind that the modification crystallizing in the NaCl structure is a metastable phase. In the phase
diagram of the Ta-N system, two hexagonal phases exist near the equiatomic composition:
⑀-TaN, crystallizing with the CoSn structure, and δ-TaN, crystallizing with the WC structure.
Figure 28 Self-consistent relativistic energy bands for HfC along the [111], [100], and [110] directions
and nonrelativistic energy bands along the [100] direction in the first Brillouin zone. Fermi energy at
0.8165 Ryd. (From Ref. 77. Reproduced with the permission of the Institute of Physics Publ.,  Institute
of Physics Publ.)
⑀-TaN has the stoichiometric composition and no range of homogeneity, and δ-TaN exists in
the composition range from TaN 0.8 to TaN 0.9 . The most significant feature of the relativistic band
structure of B1 TaN is the overlap of the N-2s 1/2 band with the Ta-4f 5/2 band in the [111] and
[110] directions of the first BZ. In this energy range there are states that exhibit s-like character
in the N sphere and f 5/2-like character in the Ta sphere, indicating an interaction between the
corresponding orbitals. At higher energies the N-2p bands are found, which touch a Ta-5d band
at the X point. The Fermi energy lies slightly above the lowest states of the Ta-6s 1/2 band.
2. Radial Charge Densities: Charge Transfer

Weinberger et al. (77) computed for HfC and TaC as well as for HfN and B1 TaN (78) the
following quantities by means of the self-consistent, relativistic KKR method: (a) partial l j-like
charges in a special atomic sphere P for selected electron states; (b) partial l j-like charges in a
special atomic sphere P corresponding to the occupied region of the valence bands; (c) l j-like
radial charge densities in a special atomic sphere P.
From the large amount of information obtained in these calculations only a few points
that are of special interest for the understanding of the bonding mechanism can be mentioned.
From the listed partial l j-like charges of special states it can be seen that in HfC there is an
f 5/2-like state with a significant s 1/2-like partial charge in the carbon sphere. Also, f 7/2-like states
with some p-like partial charge in the carbon sphere can be found. From this fact it can be
114 Neckel
Figure 29 Self-consistent relativistic energy bands for TaC along the [111], [100], and [110] directions
and nonrelativistic energy bands along the [100] direction in the first Brillouin zone. Fermi energy at
0.8749 Ryd. (From Ref. 77. Reproduced with the permission of the Institute of Physics Publ.,  Institute
of Physics Publ.)
concluded that f electrons take part, at least to a minor extent, in the chemical bonding. The l j-
like radial charge densities, σ Pl j (r), in the metal and nonmetal spheres are displayed in Fig. 30
for HfC and in Fig. 31 for TaC. Furthermore, the difference between the self-consistent radial
crystal charge density, σ P(r), and the relativistic radial charge density, σ Psuperposed (r), obtained by
the superposition of the charges of the constituent atoms has been calculated and is displayed
for HfC in Fig. 32 and for TaC in Fig. 33. By comparing Fig. 32 with Fig. 30 it can be seen
that, in the Hf sphere of HfC, there is an increase of electronic charge, relative to the radial
charge density of the superposed atoms, which is caused by Hf(s 1/2)-, Hf( p 1/2)-, and Hf( p 3/2)-
like charge densities. Charge is lost in the region where the d-like charges prevail. In total, these
two contributions compensate each other so that the total charge in the Hf sphere remains almost
constant. The charge in the C sphere of HfC increases by about 0.5 electrons. A similar situation
is encountered in TaC, where only a small amount of charge (about 0.2 electrons) is lost in the
Ta sphere and about 0.55 electrons are gained in the C sphere. The corresponding calculations
for HfN and TaN yield similar results. The charge in the metal spheres remains almost constant
compared with the charge obtained by the superposition of the charges of the neutral atoms,
whereas the charge in the N sphere of HfN increases by about 0.52 electrons and in the N sphere
Figure 30 l j-like radial charge densities, σ lPj (r), for HfC within the Hf sphere (a, b) and the C sphere
(c) plotted versus the distance r from the center of the respective muffin-tin sphere. RHf and RC are the
atomic sphere radii of the Hf and the C sphere, respectively. The quantum number κ is replaced by the
more familiar notation l j . (From Ref. 77. Reproduced with the permission of the Institute of Physics Publ.,
 Institute of Physics Publ.)
Figure 31 l j-like radial charge densities, σ lPj (r), for TaC within the Ta sphere (a, b) and the C sphere
(c) plotted versus the distance r from the center of the respective muffin-tin sphere. R Ta and R C are the
atomic sphere radii of the Ta and the C sphere, respectively. The quantum number κ is replaced by the
more familiar notation l j . (From Ref. 77. Reproduced with the permission of the Institute of Physics Publ.,
116 Neckel
Figure 32 Differences between the total radial charge density, σ P (r), and the superposed relativistic
atomic radial charge density, σ superposed
P
(r), within the Hf sphere (curve A) and the C sphere (curve B) for
HfC plotted versus the distance r from the center of the respective sphere. (From Ref. 77. Reproduced
with the permission of the Institute of Physics Publ.,  Institute of Physics Publ.)
Figure 33 Differences between the total radial charge density, σ P(r), and the superposed relativistic
atomic radial charge density, σ superposed
P
(r), within the Ta sphere (curve A) and the C sphere (curve B) for
TaC plotted versus the distance r from the center of the respective sphere. (From Ref. 77. Reproduced
with the permission of the Institute of Physics Publ.,  Institute of Physics Publ.)
of TaN by about 0.43 electrons. This insignificant loss of charge in the metal spheres is in
contrast to the behavior of the first-row transition metal carbides and nitrides, where a larger
loss of electronic charge is observed.
The main contribution to the chemical bonding is provided by the nonmetal (2p)–metal
(5d ) interaction in the range of the nonmetal p bands. Also, metal (5d )–metal (5d ) interaction
can be expected, particularly in the Ta compounds. In addition to the binding components already
mentioned, contributions to the chemical bonding result—particularly in the case of TaC—
from interactions between nonmetal s states and metal s, p, and d states.
G. Electronic Structure of Tungsten Monocarbide WC

Tungsten monocarbide has been included in the present overview because its properties greatly
resemble those of the fourth and fifth group transition metal monocarbides. Whereas the fourth
and fifth group transition metal monocarbides (TiC, ZrC, HfC and VC, NbC, TaC) crystallize
in the B1 structure, the monocarbides of the transition elements of the sixth group (Cr, Mo, and
W) with B1 structure are scarcely stable. CrC does not exist. This fact was qualitatively ex-
plained by Zhukov et al. (6) and also follows from the analysis of thermodynamic parameters
of metastable carbides by Guillermet and Grimvall (83). A molybdenum carbide phase (α-
MoC 1⫺x) with B1 structure shows a homogeneity range, large carbon deficiency (composition
about MoC 0.7), and is stable only at temperatures above 1960°C.
Tungsten monocarbide with B1 structure (β-WC) exists only at temperatures above about
2525°C and also exhibits substoichiometry.
The stable modification of tungsten monocarbide, WC, at room temperature crystallizes
l
in a hexagonal structure (α-WC) with the space group symmetry D 3h (P6m2). This structure
consists of alternating simple hexagonal layers of W and C atoms with the stacking sequence
ABAB. . . . The nearest neighbor coordination of both the W and the C atom is trigonal prismatic,
in contrast to the B1 structure, where each site is octahedrally coordinated. The structures of
hexagonal WC and its first BZ are displayed in Fig. 34. Of special importance is the high
catalytic activity of hexagonal WC for the chemical reactions that are usually catalyzed by Pt
or Pd (84,85).
Self-consistent, scalar relativistic energy band calculations for hexagonal WC in bulk and
thin-film forms were performed by Mattheiss and Hamann (86) by means of the LAPW method.
Figure 34 (a) Crystal structure of hexagonal WC. (b) First Brillouin zone for the hexagonal translational
lattice corresponding to the hexagonal WC structure. (From Ref. 91. Reproduced with the permission of
the American Physical Society,  American Physical Society.)
118 Neckel
The band structure results for WC obtained by these authors agree qualitatively with those of
previous studies (87,88). Zhukov and Gubanov (89) used the LMTO-ASA method, including
the most important relativistic corrections, i.e., the Darvin and mass-velocity terms, to calculate
the electronic structure of B1 and hexagonal WC [as well as of body-centered cubic (bcc) W
and W 2 C]. Scalar-relativistic pseudopotential local orbital calculations (49,50) for cubic WC
were carried out by Liu and Cohen (90) and for hexagonal WC by Liu et al. (91). The electronic
structure of cubic and hexagonal WC was also investigated by Price and Cooper (60). These
authors also performed similar calculations for TiC, crystallizing in the B1 structure, in the
hexagonal WC structure, and in other prototype superlattice structures. The electronic structures
of TiC and WC crystallizing in the cubic and the hexagonal modifications were compared. The
main goal of these studies was to elucidate the role played by the two additional valence electrons
of tungsten compared with titanium in stabilizing the different crystal structures. From the work
of Zhukov and Gubanov (89) and Price and Cooper (60) it follows that the band structure of
cubic WC shows the typical features of the band structures of the fourth and fifth group transition
metal monocarbides. For cubic WC the Fermi energy is located in a region of the d bands, where
antibonding C(2p)-W(5d ) states or W(5d )-W(5d ) bonds with either nonbonding or antibonding
character prevail, tending to destabilize the B1 structure. Liu and Cohen (90) show that the insta-
bility of cubic WC arises from the occupation of antibonding states in the region of the d bands.
The electronic structure of hexagonal WC shows a different behavior, as can be seen from
the total DOS and the partial l-like DOSs (Fig. 35). The C-2s band (between ⫺14 eV and ⫺10
eV in Fig. 35) has preserved its shape and character. In the following peaks, up to about 2 eV
below the Fermi level, the contributions from the C-2p and W-5d states are almost equal. In
the next two peaks just below and above the Fermi energy the W-5d character predominates.
Figure 35 Total density of states of WC and the partial contributions to the density of states from orbitals
of different angular symmetry centered on C and W sites (partial l-like DOSs). Energies are measured
relative to the Fermi level, which is indicated by the dashed line. (From Ref. 91. Reproduced with the
permission of the American Physical Society,  American Physical Society.)
Most remarkable is the shift of some states from the d bands to lower energies. The eight C-
2p and W-5d bands are apparently split symmetrically in a bonding and an antibonding manifold.
The Fermi energy lies at the minimum of the DOS, where eight valence electrons occupy the
bonding states leaving the antibonding states unoccupied. The bonding states represent a mixture
of states with C-2p and W-5d character, as can be concluded from the partial l-like DOSs (see
Fig. 35). About half the energy bands at or below the Fermi energy have predominantly C-2p
and W-5d character, respectively. This means that the valence charge is nearly equally distrib-
uted between the C and the W atom, leading to a net charge transfer from W to C, which,
according to Liu et al. (91), amounts to about 1.4 electrons. In contrast to the transition metal
monocarbides with B1 structure, where the bonding-antibonding C( p)-M(d ) bands are distrib-
uted in almost the same ratio (3 :5) as the atomic p and d states, the ratio of the bonding to the
antibonding bands is 4 :4 in the case of hexagonal WC. In spite of the fact that the environment
of a C or W atom is no longer octahedral in the hexagonal form, the C( p)-W(d ) interaction
still persists. It can be assumed therefore that the strength and stability of hexagonal WC can
also be attributed to the formation of strong CW bonds. Calculations of the VED (86,91)
prove the existence of nearest neighbor CW bonds. The VEDs in the W and C planes do not
indicate pronounced interplanar directional bonds but show a large background charge, espe-
cially in the W planes. Liu et al. (91) explained the bonding in hexagonal WC by stating that
the addition of C atoms to bcc W generates strong WC bonds while leaving some metallic
W bonding intact.
The Fermi surface of hexagonal WC is that of a semimetal, consisting of small pockets
of electrons and holes (86).
III. ELECTRONIC STRUCTURE OF NONSTOICHIOMETRIC TRANSITION

METAL CARBIDES AND NITRIDES OF THE FOURTH AND FIFTH
GROUPS OF THE PERIODIC TABLE WITH B1 STRUCTURE
A. Introduction
The cubic transition metal monocarbides and mononitrides exhibit wide homogeneity ranges
corresponding to the composition MX x , where, for example in titanium monocarbide, x ranges
from about 0.48 to about 0.99 depending on the temperature (92). Substoichiometry (x ⬍ 1) of
these phases is caused by vacancies at the nonmetal subattice sites. Mononitrides may also
contain several percent metal vacancies, e.g., TiN x , whose composition range extends from
TiN 0.41 to TiN 1.08. For some nitrides vacancies exist on both sublattices (metal and nitrogen)
even at the stoichiometric composition MN. The vacancies may be randomly distributed over
the nonmetal sites of the B1 structure. Frequently, some short-range order between the nonmetal
atoms and the vacancies occurs. However, one also encounters long-range-ordered vacancies
forming a superlattice, e.g., V8 C 7 , Nb 6 C 5. A general overview of the defect structures and order-
disorder transformations in transition metal carbides and nitrides can be found in the review
articles by de Novion et al. (93), de Novion and Landesman (94,95) and Gusev and Rempel
(96). The vacancies affect the properties of the nonstoichiometric monocarbides and mono-
nitrides (97) significantly.
A remarkable feature of the defect structures is the occurrence of static displacements of
the metal atoms adjacent to a nonmetal vacancy. Various experimental studies of these com-
pounds, such as measurements of the Debye-Waller factors (98), elastic diffuse neutron scatter-
ing (93,99,100), ion channeling (101), extended X-ray absorption fine structure (EXAFS) (102),
and X-ray diffraction measurements (75,103,104), have proved the existence of atomic static
displacements. It has been found that the main displacement is always a shift of the neighboring
metal atoms away from the vacancy by, typically, 0.05 Å.
120 Neckel
B. Theoretical Methods Applied for the Investigation of the Influence of

Vacancies on the Electronic Structure of Transition Metal Carbides
and Nitrides with B1 Structure
The remarkable effects caused by vacancies on the properties of carbides and nitrides have given
rise to numerous experimental and theoretical studies. In the present overview we will concen-
trate on theoretical approaches only, although experimental results are imperative as a basis
for testing theoretical models and methods. A complete list of references of computations on
nonstoichiometric carbides and nitrides can be found in the book of Gubanov et al. (7). An
essential problem in the theoretical investigations of the electronic structure of the substoichio-
metric materials is a proper description of the vacancy-containing phases. Various concepts
and models have been devised to treat the vacancy problem. Essentially four different types of
approaches can be distinguished.
The influence of the vacancies on the electronic structure can be studied by means of
cluster models, with vacancies replacing the central atom and/or ligand atoms. Because the
metal-nonmetal interaction furnishes an essential contribution to the chemical bonding in the
transition metal monocarbides and mononitrides, the occurrence of vacancies will affect mostly
the electronic structure of the atoms that surround the vacancy. Cluster surface effects can be
minimized by choosing the cluster size relatively large and by applying suitable boundary condi-
tions (105–108).
The cluster approach, in combination with the scattered wave Xα method, was used as
early as 1976 by Schwarz and Rösch (109) to study the electronic structure of NbC x . These
authors chose a 䊐 C Nb 6 V12 Nb 8 cluster (䊐 C is the carbon vacancy) to model the effect of vacan-
cies in NbC x. This cluster represents the first three coordination shells around a vacancy. Ries
and Winter (110) applied a modification of the self-consistent multiple scattering Xα method
to investigate the electronic structure of a nonmetal vacancy in NbC x and VN x . As a first step
the electron density and the potential of a cluster having perfect order and consisting of 53
atoms with a nonmetal atom at its center were computed. The calculation was repeated for a
cluster with a vacancy at the position of the central atom. By use of group theoretical means,
these authors were able to treat clusters up to 200 atoms. The influence of vacancies in the
nonmetal and in the metal sublattice on the electronic structure of TiC x and TiO x was studied
by Gubanov et al. (111) by applying the discrete variational (DV) method (112) in the ‘‘embed-
ded cluster’’ scheme (105,106). In these calculations the effect of a C vacancy was modeled
by the cluster 䊐 C Ti 6 C 12 Ti 8 and that of a Ti vacancy in TiCx by the cluster 䊐 Ti C 6 Ti 12 C 8. The
same approach was also used by Novikov et al. (113) to study the influence of various shifts
of the Nb atoms surrounding the vacancy in a 䊐 C Nb 6 C 18 cluster. Kucherenko et al. (108) calcu-
lated the electronic structure of a 䊐 N Ti 6 N 12 cluster by means of the self-consistent scattered
wave Xα-method. Cluster calculations taking into account the static displacements of the metal
atoms surrounding the vacancy applying the ‘‘Complete Neglect of Differential Overlap, Ver-
sion 2’’ (CNDO/2) method were performed for VN x by Skála and Čapková (114) and for TiC x
and TiN x by Čapková and Skála (115). The main drawback of the cluster approach is its inability
to yield well-defined valence bands. Calculations for smaller clusters may not be entirely free
from cluster-surface effects, and the results for a system with only one vacancy may not be
valid for substoichiometric compounds with many vacancies.
The second approach involves conventional band structure calculation methods, assuming
an ordered array of vacancies. Such calculations, which are based on extended unit cells con-
taining one or more vacancies, allow the investigation of compounds with higher vacancy con-
centrations. Furthermore, the changes in interatomic interactions caused by the vacancies can
be taken into account by the self-consistency process. From band structure calculations, valence
electron densities, for example, can be derived, which provide insight into the bonding situation.
An obvious disadvantage of the method is that only compounds with special compositions (e.g.,
25% ordered vacancies) can be treated.
Redinger et al. (116,117) as well as Herzig et al. (118) performed self-consistent APW
band structure calculations for a model substance Ti 3[4]Ti [6]X3 䊐X , X being C (116,117) and N
(118), respectively. The hypothetical ordered structure corresponds to the composition TiX 0.75.
The chosen model structure (Fig. 36) is derived from the cubic unit cell of the B1 structure
containing four formula units TiX by replacing the nonmetal atom at the center of the unit cell
by a vacancy 䊐 X . Due to the existence of the vacancy two different types of Ti atoms occur,
which are designated by their respective number of coordinating nonmetal atoms. The Ti [6] atoms
at the corners of the unit cell are octahedrally coordinated by six nonmetal atoms as in the
stoichiometric compound TiX. The second type of Ti atoms, designated by Ti [4], occupy the
centers of the cube faces. They are quadratically surrounded by four X atoms. Based on this
model structure, band structures, DOSs, local partial l-like DOSs, and VEDs in special crystallo-
graphic planes were calculated for TiC 0.75 (116,117) and TiN 0.75 (118). The same model structure
was also employed by Benco (119), who performed band structure calculations for VN 0.75 (and
VN) by means of the extended Hückel method. This author also performed a molecular orbital
calculation for the cluster V14N 12 䊐 N .
The LMTO method was used by Zhukov and Gubanov (120) and Zhukov et al. (121) to
calculate the band structures and some characteristics of the ground state of TiC 0.75, VC 0.75 (120)
and TiN 0.75, VN 0.75 (121). These authors also estimated the lattice constants, bulk moduli and
cohesive energies, and the energies of vacancy formation. The results of the APW and LMTO
calculations, which will be discussed in Sec. III.D, show great similarities to each other. The
assumed periodic long-range order of the vacancies leads to sharp structures in the DOSs, which
are probably not realistic.
The third group of methods starts from an alloy problem. This approach is based on the
assumption that the vacancies are randomly distributed over the nonmetal lattice sites, leading
to a loss of translational symmetry. If one also wants to apply a conventional band structure
calculation method in such a case, some sort of averaging has to be carried out in order to retain
the translational symmetry for the non-long-range-ordered crystal.
The first calculations along this line were performed for VC x by Zbasnik and Toth (122)
and Neckel et al. (123) and for VC x , ZrC x, and NbC x by Ihara (124), using a special version
of the so-called virtual crystal approximation (VCA). If, for the band structure calculations, the
Figure 36 Cubic unit cell for the TiX 0.75 model structure. (䊉) X atoms (X ⫽ C, N); (䊊) vacancy; ( )
Ti [4] atoms; ( ) Ti [6] atoms; (---) (100) plane, section 1; (⋅ ⋅ ⋅) (100) plane, section 2; (-⋅-⋅-) (110) plane;
(———) (111) plane. (From Ref. 117. Reproduced with the permission from Elsevier Science,  Elsevier
Science.)
122 Neckel
APW method is used, the averaging is achieved by replacing the logarithmic derivative of the
nonmetal wave function at the nonmetal muffin-tin radius in the Hamiltonian matrix elements
for the stoichiometric compound by the average of the logarithmic derivatives of the nonmetal
and the vacancy wave functions in the case of the substoichiometric phases. However, these
calculations proved to be unsatisfactory in many respects, mainly because they did not take into
account the changes in the local symmetry of the metal atoms adjacent to the vacancy.
Another possible method for solving the true alloy problem and calculating the electronic
structure of substoichiometric compounds is the ‘‘tight binding coherent potential approxima-
tion’’ (TB-CPA) method, which was used by Klima for TiC x (125) and TiN x (126) and by Klein
et al. (71) for NbC x , TaC x , and HfC x . In this method the tight-binding Hamiltonian for the
stoichiometric compound is replaced by a translationally symmetric effective Hamiltonian with
complex eigenvalues and average scattering properties for the substoichiometric crystal. The
average scattering amplitudes for the valence electrons at the nonmetal sublattice sites are deter-
mined self-consistently assuming random distribution of the vacancies over the nonmetal sites.
However, these calculations (125,126,71) failed to yield ‘‘vacancy states’’ or a ‘‘vacancy band,’’
a point that will be discussed later. This failure is probably due to the assumption that the
potential in a vacancy sphere tends to infinity. Also, the DOS and its dependence on the vacancy
concentration in the region in the neighborhood of the Fermi energy is probably wrong because
the vacancy-induced states are not properly accounted for.
If the effective scattering amplitudes at the nonmetal sublattice sites are not determined
self-consistently but set equal to the arithmetic mean of the nonmetal and the vacancy t-matrix,
the ‘‘average T-matrix approximation’’ (ATA) follows. This approximation, combined with the
Korringa-Kohn-Rostocker (KKR) method, was used by Huisman et al. (127) to study the mecha-
nism of the vacancy stabilization in titanium carbide and titanium oxide. According to the calcu-
lations of these authors, stabilizing vacancy states occur in the minimum of the DOS between
the nonmetal p and the metal d bands, increasing the DOS in this energy range.
Klima et al. (128) applied the KKR coherent potential approximation (CPA) and the KKR–
Green’s function (GF) method to study the electronic structure of substoichiometric phases. The
KKR-CPA treats the case of completely randomly arranged vacancies and avoids some of the
deficiencies occurring in the TB-CPA calculations of Klima (125,126) and Klein et al. (71). In
this approach the physical properties of an alloy are derived from the effective Green’s function
Ĝ c (E ). The CPA-GF corresponds to an ordered lattice of complex, energy-dependent, effective
potentials replacing the varying potentials in the alloy. In the KKR-CPA the effective Green’s
function Ĝ c (E ) is defined by
Ĝ c (E ) ⫽ xĜ Ac ⫹ (1 ⫺ x)Ĝ Bc (7)
where, in the single-site approximation, the GFs Ĝ Ac and Ĝ Bc describe a single impurity atom A
and B, respectively, in an otherwise perfect effective lattice, and x stands for the concentration
of atoms A in a binary alloy A x B 1⫺x . A detailed description of this technique can be found in
the paper by Klima et al. (128). The KKR-CPA has the advantage of treating as special cases
all interesting systems: the stoichiometric crystal MX, a single vacancy in an otherwise perfect
crystal MX, and the alloy MX x . By this approach the electronic structures of TiN x (128) of
TiC x , TiN x , VC x, and VN x (129) and of ZrC x, ZrN x , NbC x , and NbN x (130) were studied.
Several calculations were devoted to the study of the influence of a single, isolated vacancy
on the electronic structure of an otherwise perfect crystal. It is assumed that the results obtained
by investigating a single vacancy are also characteristic for crystals with somewhat higher va-
cancy concentrations. Ivanovsky et al. (131) considered an isolated vacancy as an impurity and
proposed a self-consistent solution for this problem. These authors started from the LMTO
procedure and the KKR-GF equations and developed an LMTO-GF method, which they applied
to the calculation of the electronic structure of TiC, TiN, TiO, VC, VN, and VO containing
isolated vacancies in both the nonmetal and the metal sublattice. They supplemented their inves-
tigations by cluster Xα discrete variation (DV) calculations. A TB calculation for a single carbon
vacancy in NbC was performed by Pecheur et al. (132). The perturbation caused by the vacancy
was introduced by the Green’s function method. The changes in the overlaps of the metal and
nonmetal wave functions caused by the vacancy were taken into account. A resonant peak associ-
ated with the vacancy appears in the DOS minimum between the C-2p and the Nb-4d bands lying
1.5 eV below E F. It is assumed that this peak will also persist at higher vacancy concentrations.
The electronic structure of an isolated carbon vacancy in NbC was also investigated by
Pickett et al. (133) using the SC muffin-tin Green’s function method. These authors found an
s-like vacancy induced peak in the DOS 2.6 eV below E F and a weaker p-like peak at 1.74 eV
below E F.
C. Band Structures of Substoichiometric Transition Metal Carbides and

Nitrides MXx (x ⬍ 1)
In the case of long-range-ordered vacancies, the translational symmetry of the crystal is retained
and, therefore, a conventional band structure calculation can be performed. As a typical example,
the band structure of the ordered model substance TiC 0.75 (Ti 3[4]Ti [6]C 3䊐 C ), whose unit cell is
depicted in Fig. 36, will be discussed. The band structure of this model substance was calculated
by Redinger et al. (116), using the SC APW method. In Fig. 37 the band structure of ordered
TiC 0.75 (Fig. 37b) is compared with the band structure of stoichiometric TiC (Fig. 37a). In order
to facilitate comparison, the band structure of TiC is drawn for a cubic unit cell containing four
formula units, but it is otherwise entirely equivalent to the band structure of TiC displayed in
Ref. 17. The larger real space unit cell for Ti 4 C 4 corresponds to a smaller BZ, having only one-
quarter of the volume of the BZ for the ordinary fcc unit cell containing one formula unit. The
energy bands of TiC are backfolded into this smaller BZ and a complex-looking band structure
with 4 C-2s (instead of 1) and 12 C-2p (instead of 3) valence bands results. Many of the energy
states are degenerate in the symmetry directions displayed in Fig. 37a. Because of the lower
symmetry of the model compound Ti 3[4] Ti [6] C 3 䊐 C , some of these degeneracies are lifted. Instead
of only 3 C-2s and 9 occupied C-2p bands—which one would expect because a formula unit
contains three carbon atoms—13 or even 14 energy bands appear below the Fermi energy.
Inspection of the partial charges of some of the additional energy states near the Fermi level
reveals that they are mainly formed by Ti [4]-3d z 2 orbitals. (For the designation of the orbitals of
the Ti [4] atoms a local coordinate system has been used, which is oriented in such a way that
the z-axis points from the Ti [4] atom toward the vacancy and the x- and y-axes toward the neigh-
boring C atoms.) The additional states also exhibit a remarkable amount of charge (about 20%)
in the vacancy sphere. These ‘‘vacancy states,’’ as they are called, are marked in Fig. 37b by
small circles. If the carbon atom at the (1/2 , 1/2 , 1/2 ) lattice site of the cubic unit cell is missing,
the Ti [4]-3d z2 (Ti [4]-3d xz, 3d yz) orbitals cannot form dpσ (dp π) bonds. This situation leads to ‘‘dan-
gling’’ d bonds. The overlap of these Ti [4]-3d orbitals in the region of the vacancy sphere results
in a certain amount of charge in the vacancy sphere. The ‘‘vacancy band’’ can therefore be
better understood as a metal d band that is lowered in energy to the region of the Fermi level.
The lowering of d bands by the introduction of a nonmetal atom vacancy at the site (1/2 ,
1/2 , 1/2 ) of the cubic unit cell can be explained by simple electrostatic crystal field arguments.
As is well known (see also Secs. II.E.3 and II.E.4), the five d orbitals of a transition metal atom
are split in an octahedral crystal field into the three energetically lower lying t 2g orbitals and the
two energetically higher e g orbitals. Because the e g orbitals point directly toward the (negatively
charged) ligands, the electrons in these orbitals are more strongly repelled than the electrons in
the t 2g orbitals, which point along the bisectors of the angles between the directions toward the
ligands. This situation still holds for the Ti [6] atoms in the model structure. However, the Ti [4]
124
Figure 37 Band structure of stoichiometric TiC (a) and ordered TiC 0.75 (b). The energy (Ryd) refers to the constant muffin-tin potential between
the muffin-tin spheres. The band structure of TiC(17) has been backfolded into the smaller Brillouin zone corresponding to the cubic real space
unit cell shown in Fig. 1. So-called vacancy states are circled in (b). (From Ref. 116. Reproduced with the permission from Elsevier Science,
Neckel
 Elsevier Science.)
Figure 38 Energetic splitting of the d levels in electrostatic fields of Oh and D4h symmetry. (From Ref.
117. Reproduced with the permission from Elsevier Science,  Elsevier Science.)
atoms in the model structure are surrounded quadratically by only four nonmetal atoms and
therefore experience a crystal field of D 4h symmetry. The five d states are now split into orbitals
of symmetry a 1g (d z2), e g (d xz, d yz), b 2g (d xy), and b1g (d x2⫺y 2). The pattern of the orbital splitting
in a quadratic crystal field is displayed in Fig. 38. In this case we can also attribute the energetic
sequence of the orbitals to the different degrees of repulsion that the electrons occupying these
orbitals experience by the ligands. For the electrons in the d z2 orbital, which points directly
toward the neighboring vacancies, this repulsion is greatly reduced compared with the octahedral
enviroment. To a lesser extent this situation also holds for the electrons in the d xz and d yz orbitals.
Therefore these electronic states are lowered in energy with respect to the corresponding states
in an octahedral crystal field. This mechanism leads to an energetic lowering of d bands with
appropriate symmetry into the region at the top of the p bands and the bottom of the d bands.
However, one also has to take into consideration that in a molecular orbital description
the number of Ti(3d z 2)-C(2p) σ bonds and Ti(3d xz , 3d yz)-C(2p) π bonds between the respective
Ti [4]-3d and C-2p states is reduced due to the missing carbon atoms. The Ti [4]-3d orbitals not
participating in bonds are destabilized and shifted from the region of the p bands to a position
just below or at the bottom of the d bands. On the other hand, the loss of carbon partners
will shift Ti-3d states involved in antibonding Ti(3d )-C(2p) interactions in the stoichiometric
compound downward, leading qualitatively to the same result as the crystal field description.
A similar calculation as for ordered TiC 0.75 was performed for ordered TiN 0.75 (Ti 3[4]-
Ti [6]N 3 䊐 N ) by Herzig et al. (118). In this case again, energy bands containing vacancy states
appear in the region of the minimum of the DOS between the p and d bands of the stoichiometric
compound.
D. Total Densities of States and Local Partial l -like Densities of States of

Substoichiometric Transition Metal Carbides and Nitrides MXx (x ⬍ 1)
The effect of the introduction of vacancies on the DOS can be seen from Fig. 39, which shows
a comparison of the DOSs of stoichiometric TiC and ordered TiC 0.75 (Ti 3[4] Ti [6] C 3 䊐 C ) calculated
126 Neckel
Figure 39 Total DOS (———), local interstitial DOS (---), and local vacancy DOS (⋅ ⋅ ⋅) for stoichio-
metric TiC and ordered TiC 0.75 in units of states per Rydberg, per spin, and cubic unit cell. (The cubic
unit cell for TiC contains four formula units.) The curves are adjusted to coincide in the bottom of the
C-2s band. The Fermi level of TiC 0.75 is chosen as energy zero. (From Ref. 116. Reproduced with the
permission from Elsevier Science,  Elsevier Science.)
by means of the SC APW method. The main components of the local partial l-like DOSs (Ti[4]-
and Ti [6]-3d, C-2p, and C-2s) are displayed in Fig. 40. [The presence of three equivalent Ti[4]
atoms and only one Ti [6] atom in the unit cell of Ti 3[4] Ti [6]C 3 䊐 C causes the statistical weight of
the local partial Ti[4](3d )-like DOS to be three times larger than that of the local partial Ti [6](3d )-
like DOS.] Inspection of Figs. 39 and 40 reveals that the reduced number of C-2s and C-2p
states in the substoichiometric compound, leading to a reduction of possible interactions with
Ti-3d states, results in a clearly recognizable decrease of the local partial Ti [4](3d )-like DOS in
the range of the p bands where the Ti(3d )-C(2p) interactions mainly occur. The lower number
of Ti(3d )-C(2p) and Ti(3d )-C(2s) bonds causes a narrowing of the corresponding bands by
approximately 0.03 Ryd. The most remarkable feature in the DOS of Ti 3[4]Ti [6]C 3 䊐 C is, however,
the appearance of two additional narrow peaks in the region of the minimum of the DOS between
the p and d bands of the stoichiometric compound. These two peaks are mostly formed by Ti [4]-
3d states but also contain a noticeable contribution of the vacancies. The vacancy partial l-like
DOS in the peak just below E F exhibits predominantly s symmetry, whereas the vacancy partial
l-like DOS in the peak above E F shows mainly p symmetry with respect to the center of the
vacancy sphere. Figure 41 displays the local vacancy DOS for TiC 0.75 with its s and p com-
ponents. The charge in the vacancy sphere is caused by the tails of the 3dz2 wave functions of
the surrounding six Ti [4] atoms, which reach into the vacancy sphere. The s or p symmetry re-
Figure 40 Main local partial l-like DOSs, g tl(E ), for stoichiometric TiC and ordered TiC 0.75. The same
units and conventions as for Fig. 39 are employed. (-⋅-) C(2s)-like DOS; (⋅ ⋅ ⋅) C(2p)-like DOS; (———)
Ti(3d )- and Ti [6] (3d )-like DOS; (---) Ti [4] (3d )-like DOS. (From Ref. 116. Reproduced with the permission
from Elsevier Science,  Elsevier Science.)
Figure 41 Local partial l-like DOSs, g tl (E ), in the vacancy sphere of ordered TiC 0.75 in units of states
per Rydberg, per spin, and cubic unit cell. (———) Total local vacancy DOS; (⋅ ⋅ ⋅) vacancy s-like
DOS; (---) vacancy p-like DOS. (From Ref. 116. Reproduced with the permission from Elsevier Science,
 Elsevier Science.)
128 Neckel
sults by viewing the wave functions from the center of the vacancy sphere. The s symmetry
of the wave functions can be considered as resulting from Ti [4] (3d z 2)-Ti [4](3d z 2) bonding and
the p symmetry as resulting from Ti [4](3d z 2)-Ti [4] (3d z 2) antibonding interactions across the va-
cancy.
A similar situation is found for ordered TiN 0.75 (Ti [6]Ti 3[4]N 3 䊐 N ). In Fig. 42 the total DOSs
for stoichiometric TiN and ordered TiN 0.75 are compared. The first and the second peak in the
total DOS, formed mainly by N-2s states (s band) and N-2p states ( p bands), respectively, show
reduced width and reduced magnitude in the substoichiometric compound because a smaller
number of N-2s and N-2p states is available. Most remarkable is the appearance of two peaks
(‘‘vacancy peaks’’) in the lower part of the d bands of the substoichiometric compound, which
are formed predominantly by Ti [4]-3d states of d z 2 and d xz, d yz symmetry. The energetically lower
peak is situated below E F, the higher one exactly at E F. Both peaks contain an appreciable
amount of vacancy partial l-like DOS. As in the substoichiometric carbide, the vacancy partial
l-like DOS exhibits s symmetry in the lower peak and p symmetry in the higher peak (compare
Fig. 47). In Fig. 43 the local partial N(2s)-, N(2p)-, Ti [6](3d )-, and Ti [4] (3d )-like DOSs of TiN 0.75
are displayed. In the p bands not only the N(2p)-like but also the Ti [4] (3d )-like DOS is greatly
reduced, indicating less N(2p)-Ti(3d ) bonding in the substoichiometric nitride.
The LMTO-ASA method was applied by Zhukov and Gubanov (120) and Zhukov et al.
(121) to calculating the band structures and total and local partial DOSs of TiC 0.75, TiN 0.75, VC 0.75,
Figure 42 Total DOS, g(E ), for stoichiometric TiN and ordered TiN 0.75 in units of states per Rydberg,
per spin, and cubic unit cell. (The cubic unit cell contains four formula units.) The curves are adjusted to
coincide in the bottom of the N-2s band. The Fermi level of TiN 0.75 is chosen as energy zero. (From Ref.
118. Reproduced with the permission of Academic Press, Inc.,  Academic Press, Inc.)
Figure 43 Main local partial l-like DOSs, g tl (E ), for ordered TiN 0.75. The same units as for Fig. 42 are
used. The Fermi energy is chosen as energy zero. (---) N(2s)-like DOS; (-⋅-) N(2p)-like DOS; (⋅ ⋅ ⋅)
Ti [6] (3d )-like DOS; (———) Ti [4] (3d )-like DOS. (From Ref. 118. Reproduced with the permission of
Academic Press, Inc.,  Academic Press, Inc.)
and VN 0.75 using the same supercell model as was employed for the APW calculations (116–
118). These investigations also show the appearance of vacancy-induced states in the substoichi-
ometric compounds in the region of the minimum of the DOS of the stoichiometric compounds.
As an example, the total DOS of ordered VC 0.75 is displayed in Fig. 44. The two additional
peaks in the DOS of VC 0.75 just below E F are induced by the vacancy states. The local partial
l-like DOS of these two peaks has mainly V-3d character in the V [4] spheres. In the vacancy
sphere, however, the local partial l-like DOS exhibits s character in the lower peak and p charac-
ter in the higher peak. Both peaks lie below E F and are therefore occupied. The number of
Figure 44 Total densities of states, N(E ), for (a) stoichiometric VC and (b) ordered VC 0.75, calculated
by the LMTO method. (From Ref. 7, page 102. Reproduced with the permission of Cambridge University
Press,  Cambridge University Press.)
130 Neckel
Figure 45 Total densities of states g(E ), of TiC x phases calculated by the KKR-CPA method. The
concentrations x are indicated in the figures. (Adapted from Ref. 129. Reproduced with the permission of
the American Physical Society,  American Physical Society.)
electrons in the vacancy states of VC 0.75 (8.78 electrons per unit cell) is significantly greater
than the corresponding number (1.78 electrons per unit cell) for TiC 0.75. From this effect the
authors (120) conclude that the stability of the vacancies in VC 0.75 is higher than in TiC 0.75.
Calculations of the DOSs based on the assumption of a random distribution of vacancies
and nonmetal atoms over the nonmetal atom sublattice sites of the B1 structure were performed
for TiN x by Klima et al. (128); for TiC x , TiN x , VC x , and VN x by Marksteiner et al. (129); and
for ZrC x , ZrN x , NbC x by Marksteiner et al. (130) using the KKR-CPA method. In these calcula-
tions the total DOSs and the main contributions to the local partial l-like DOSs [metal t 2g , metal
e g , non metal t 1u ( p-like), vacancy a 1 (s-like), and vacancy t 1u ( p-like) DOS] were calculated for
many vacancy concentrations, covering the whole range of existence of these phases. As typical
examples the KKR-CPA DOSs for TiC x (x ⫽ 1.00, 0.94, 0.875, 0.76) are displayed in Fig. 45.
The DOSs derived from the KKR-CPA calculations correspond well to the DOSs obtained by
the SC APW method (118) as can be gathered from Fig. 46, in which the total DOS for ordered
TiN 0.75 is compared with the total DOS from the KKR-CPA calculation. The sharp peaks ob-
tained for the ordered structure are smoothed in the case of the random distribution of the
vacancies. The very sharp peak at E F with a high DOS is probably an artifact due to the highly
symmetric long-range-ordered model structure. In Fig. 47 the local partial l-like DOSs in the
vacancy sphere of ordered TiN 0.75 are compared with those obtained by the KKR-CPA method.
As with the total DOS (Fig. 46), the KKR-CPA DOS, particularly the peak at E F, is much more
diffuse than the DOS for the ordered structure. (The greater intensity of the KKR-CPA DOS
peaks is caused by the fact that the DOS curves for the vacancy do not refer to the corresponding
APW atomic sphere but to a larger volume.) For both calculations the first vacancy peak is
almost exclusively formed by vacancy s states, whereas the second one contains an appreciable
number of p states.
The general trends of the KKR-CPA DOSs for the preceding substoichiometric phases
MX x can be summarized as follows:
1. All sharp peaks are smoothed compared with the ordered compounds and the DOSs
become less structured with increasing vacancy concentration.
Figure 46 Total density of states, g(E ), for ordered TiN 0.75 (118) calculated by the SC APW method
(———) compared with the total density of states for TiN 0.75 (128, 129) calculated by the KKR-CPA
method (---). The same units as for Fig. 42 are used. (From Ref. 118. Reproduced with the permission
of Academic Press, Inc.,  Academic Press, Inc.)
Figure 47 Total vacancy density of states and vacancy l-like densities of states, g l䊐, for ordered TiN 0.75
calculated by the SC APW method (a) and for TiN 0.75 calculated by the KKR-CPA method (b). The same
units as for Fig. 42 are used. (———) Total vacancy DOS; (⋅ ⋅ ⋅) vacancy s-like DOS; (---) vacancy p-
like DOS. (From Ref. 118. Reproduced with the permission of Academic Press, Inc.,  Academic Press,
Inc.)
132 Neckel
2. The DOS peaks originating mainly from nonmetal 2s and 2p states lose intensity.
This effect is not surprising because there are fewer nonmetal electrons present.
3. Additional peaks (vacancy peaks) appear near the minimum of the DOS of the stoi-
chiometric compound (except for ZrCx).
4. The peaks above E F with mainly metal d character are not strongly affected by the
introduction of vacancies.
5. The Fermi energy with respect to the muffin-tin zero is generally lowered with increas-
ing vacancy concentration (except for ZrC x).
The relativistic KKR-CPA method was also employed to study the electronic structure of
substoichiometric HfC x and HfN x (81) and TaC x (82). The main difference in the electronic
structure of the substoichiometric phases HfC x and TaC x compared with the stoichiometric com-
pounds HfC and TaC is a backflow of charge from the carbon atoms to the hafnium and tantalum
atoms, respectively, with increasing vacancy concentration. This finding is in agreement with
an earlier observation following from a TB CPA calculation (71) in which the DOSs and the
Bloch spectral functions of NbC x , HfC x, and TaC x (0.7 ⱕ x ⱕ 1.0) were determined. In contrast
to the behavior of HfC x and TaC x , in substoichiometric HfN x both the hafnium and the nitrogen
atom lose electrons to the vacancy. A remarkable further result is that no significant vacancy
contribution to the DOS of TaC x is found.
The existence of vacancy-induced states in substoichiometric transition metal carbides
and nitrides was confirmed experimentally by various methods. Höchst et al. (134) were the
first to observe a structure in the X-ray photoelectron spectroscopy (XPS) valence band spectrum
of NbC 0.85, which they attributed to vacancy-induced states. Several investigations were devoted
to the study of the influence of vacancies on X-ray photoelectron spectra (135–139) and ultravio-
let photoelectron spectra (138,140,141). A comprehensive discussion of this subject, including
angle-resolved photoemission spectra, can be found in the review article by Johansson (8). X-
ray emission spectroscopy (107,108,142–144), X-ray absorption spectroscopy (102), and optical
spectroscopy (145,146) were employed to investigate vacancy-induced electronic states.
Changes of the DOS in the unoccupied energy region were observed by energy loss spectroscopy
(147–149).
E. Bonding Mechanisms in Substoichiometric Transition Metal Carbides

and Nitrides MXx (x ⬍ 1)
The bonding mechanisms can be best derived from valence electron density and difference
electron density plots. The ordered model compounds TiC 0.75 and TiN 0.75 (Ti [6] Ti 3[4] X 3 䊐 x) may
serve as representative examples. The three main types of covalent bonding ( pd σ, pd π, and dd σ)
known from the stoichiometric compounds also occur in the ordered phases TiC 0.75 and TiN 0.75
but with distinct modifications. In addition, new types of interaction appear.
As already mentioned, the d z 2 and d x 2⫺y 2 orbitals of the Ti [4] atoms are no longer equivalent
in the square crystal field of the four nonmetal atom neighbors. The Ti [4]-3d z 2 orbitals extend
toward the vacancy and cannot form pd σ bonds with the X-2p orbitals. Therefore, the number
of pd σ bonds is reduced compared with the stoichiometric compounds. More information can
be gained from Tables 4 and 5, which list the splitting of the Ti(3d )-like charge into its compo-
nents. The Ti [4]-3d z 2 and Ti[4]-3d xz, 3d yz components are greatly reduced in the p bands of the
substoichiometric compounds but furnish the biggest contributions to the DOS in the vacancy
band. From the reduction of the number of Ti [4]-3d z 2 states in the p bands of the substoichiometric
compounds it can be concluded that the number of pd σ bonds is reduced. In a similar way, the
Table 4 Partition of the Ti(3d )-like Charge in TiC and Ordered TiC 0.75 (All Charges Are Given in
Electrons per Atomic Sphere)
TiC 0.75 TiC
Ti [4] Ti [6] Ti
Bands d z2 d x2⫺y2 d xy (d xz ,d yz ) eg t 2g eg t 2g
p 0.09 0.39 0.21 0.26 0.80 0.69 0.84 0.78
Vacancy 0.22 0.01 0.03 0.31 – 0.07
Occupied valence 0.33 0.44 0.24 0.57 0.89 0.76 0.94 0.78
Source: From Ref. 116. Reproduced with the permission from Elsevier Science,  Elsevier Science.
decrease of Ti [4]-3d xz, 3d yz states indicates a reduction of pd π bonds. The pd σ and pd π bonds in
which Ti [6] atoms take part are not significantly altered by the introduction of vacancies.
Whereas the number of titanium-nonmetal bonds is diminished in the substoichiometric
compounds, the Ti(3d )-Ti(3d ) bonds gain importance.
Three types of Ti(3d )-Ti(3d ) interactions can be distinguished in the model compounds:
1. The introduction of vacancies leads to a new type of Ti(3d )-Ti(3d ) interaction. Inspec-
tion of the VED in the (100) plane of three typical vacancy states of ordered TiN 0.75,
displayed in Fig. 48, reveals that there is a distortion of the VED around the Ti [4]
atoms toward the vacancy. The increase of VED in the direction from the Ti [4] atoms
toward the vacancy can be considered as an indication of the formation of a weak
bonding interaction of s symmetry viewed from the vacancy sphere (bonding
d z2-䊐 x-d z2 interaction). Energetically these states lie in the first ‘‘vacancy peak’’ of
the DOS. The corresponding antibonding states (of p symmetry in the vacancy sphere)
are found in the second vacancy peak. These states are partly occupied in the nitride
but not in the carbide. Interactions via the vacancy can also occur between two
Ti [4]-3d z 2 orbitals oriented at right angles to each other.
2. The second type of covalent Ti(3d )-Ti(3d ) bonds is formed between Ti [4] -3d xz , 3d yz
orbitals of Ti [4] atoms surrounding a vacancy. Because the number of pd π bonds in
which Ti [4]-3d xz, 3d yz orbitals are involved is reduced in the substoichiometric com-
pounds, the Ti [4]-3d xz and 3d yz orbitals can form better overlapping (stronger) Ti [4]-
Ti [4] dd σ bonds. These bonds are oriented along the edges of the octahedra formed
by the Ti [4] atoms surrounding a vacancy (‘‘octahedral bonds’’). This type of bond
Table 5 Partition of the Ti(3d )-like Charge in TiN and Ordered TiN 0.75 (All Charges Are Given in
Electrons per Atomic Sphere)
TiN 0.75 TiN
[4] [6]
Ti Ti Ti
Bands d z2 d x2⫺y2 d xy (d xz ,d yz) eg t 2g eg t 2g
p 0.04 0.24 0.10 0.13 0.55 0.38 0.58 0.46
d ⫹ vacancy 0.33 0.01 0.09 0.51 0.01 0.41 0.01 0.58
Occupied valence 0.38 0.27 0.19 0.64 0.61 0.79 0.65 1.05
Source: From Ref. 118. Reproduced with the permission of Academic Press, Inc.,  Academic Press, Inc.
134 Neckel
Figure 48 Valence electron densities for the ‘‘vacancy band’’ states Γ 1, ∆ 1, and X l in the (100) plane,
section 2 (see Fig. 36) of ordered TiN 0.75 in units of 10 ⫺2 e/Å 3. (From Ref. 118. Reproduced with the
permission of Academic Press, Inc.,  Academic Press, Inc.)
can be realized from the electron density plot for a special state (X 3 symmetry) in
the (111) plane of ordered TiN 0.75 (Fig. 49). In the substoichiometric nitride more
bonding states forming octahedral bonds are to be found than in the corresponding
carbide, because in TiC 0.75 these states lie partly above the Fermi level. Therefore,
the stabilization of the Ti [4] octahedra is more pronounced for the substoichiometric
nitride than for the substoichiometric carbide.
3. The interaction between the Ti [4] and Ti [6] atoms also changes on passing from the
stoichiometric to the substoichiometric compounds. The Ti [4]-3d xy orbitals can form
dd σ bonds with Ti [6]-t 2g orbitals, entirely analogous to the dd σ bonds in the stoichiomet-
ric compounds. Inspection of the difference of the VED between the ordered substoi-
chiometric and the stoichiometric compounds reveals that the VED in the Ti [6]-Ti [4]
direction increases in the case of the carbide but decreases in the case of the nitride.
Therefore, it can be assumed that the Ti [6]-Ti [4] dd σ bonds are strengthened in the
carbide and weakened in the nitride.
Figure 49 Valence electron density for the state X 3 of ordered TiN 0.75 in the (111) plane (see Fig. 36)
in units of 10 ⫺2 e/Å 3. (From Ref. 118. Reproduced with the permission of Academic Press, Inc.,  Aca-
demic Press, Inc.)
The preceding conclusions about the chemical bonding are mainly based on the results
obtained for a hypothetical model structure. From the fact that both the long-range order and
the random distribution of the vacancies yield similar DOSs, it can be assumed that the general
description of the electronic structure of the substoichiometric phases is essentially correct.
F. Metal-Deficient Transition Metal Carbides and Nitrides of the Fourth

and Fifth Groups of the Periodic Table with B1 Structure M y X ( y ⬍ 1)
Metal vacancies occur almost exclusively in transition metal nitrides. Gubanov et al. (111) stud-
ied the electronic states of a Ti vacancy in TiC by means of the cluster Xα DV method. Local
DOSs of a single vacancy in TiC, VC, ZrC, TiN, and VN were calculated by Ivanovsky et al.
(131). The influence of metal vacancies on the electronic structure of zirconium nitride (Zr 0.75N
and Zr 0.8 N 0.8) was studied by Marksteiner et al. (150) using the KKR-CPA method. The DOSs
of the metal-deficient nitrides Ti 0.75N, Zr 0.75N, and Hf 0.75N, assuming a model structure that can
be described by the formula M 3 䊐 MN [6] N 3[4] (M ⫽ Ti, Zr, and Hf), were calculated by Schwarz
et al. (151,152) using the ASW method. The calculations yield a slight overlap between the N-
2p bands and the Zr-4d bands indicating metallic behavior of Zr 3N 4 whereas experimentally
(153) it is found that Zr 3N 4 is an insulator. If neon is implanted in the vacancy, the resulting
insulator NeZr 3N 4 has a lattice spacing that perfectly matches that of the superconductor ZrN.
A Josephson junction constructed from these two isostructural and isochemical substances
should have a perfect match at the interface.
IV. ELECTRONIC STRUCTURE OF TRANSITION METAL CARBONITRIDES

OF THE FOURTH AND FIFTH GROUPS OF THE PERIODIC TABLE
Transition metal monocarbides MC and mononitrides MN form solid solutions MC x N 1⫺x . Some
of them are of great technical importance, e.g., as hard coatings. Weinberger (154–156) em-
ployed the relativistic KKR-ATA method to study the electronic structure of TiC xN 1⫺x , TiC x O 1⫺x ,
TiN x O 1⫺x , and HfCxN 1⫺x . Petru and Klima (157) used the KKR-CPA method to investigate the
electronic states in TiC xN 1⫺x (x ⫽ 0.4 and 0.6). The DOSs of the solid solutions NbC x N 1⫺x (x
⫽ 1.0, 0.75, 0.5, 0.25, 0.12, and 0) were calculated by Nikiforov and Kolpachev (158) using
the cluster version of the local coherent potential approximation. The calculated DOS at the
Fermi level correlates with the dependence of the superconducting transition temperature on
the carbon concentration x. (In the solid solutions NbC x N 1⫺x the highest value, about 18 K, of
the superconducting transition temperature for transition metal carbides and nitrides is found.)
The band structures and cohesive energies of titanium carbonitrides Ti 4C 4⫺nN n , with n ⫽ 0, 1,
2, 3, and 4 (corresponding to TiC xN 1⫺x , x ⫽ 1, 0.75, 0.5, 0.25, and 1) were calculated by Zhukov
et al. (159) employing the SC LMTO ASA method. The results were used to analyze available
electromagnetic, thermodynamic, and elastic properties of the compounds.
Gustenau-Michalek et al. (160) performed SC LAPW calculations for the three ordered
model structures Ti 4C 3N (TiC 0.75N 0.25), Ti 2CN (TiC 0.5N 0.5), and Ti 4CN 3 (TiC 0.25N 0.75). The total
DOSs for these three ordered compounds are displayed in Fig. 50. The lowest lying valence
band is formed by N-2s states (‘‘N-2s band’’). After a gap of about 0.2 Ryd the corresponding
‘‘C-2s band’’ follows. A further gap separates the ‘‘N-2p bands,’’ which overlap the slightly
higher lying ‘‘C-2p bands.’’ After a minimum in the DOS the ‘‘Ti-3d bands’’ follow. The VEDs
in the (100) plane for the three model structures together with the VEDs of the pure compounds
TiC and TiN are displayed in Fig. 51. The maxima of the VED in the Ti spheres are much
more pronounced in the directions toward the carbon atoms than toward the nitrogen atoms,
indicating that the covalent TiC bonds are stronger than the TiN bonds. The successive
Figure 50 Total densities of states, DOS, for Ti 4C 3N (left), Ti 2CN (middle), and Ti 4CN 3 (right) in units of states per Rydberg and unit cell. The Fermi energies are
indicated by vertical lines. (From Ref. 160. Reproduced with the permission from Elsevier Science,  Elsevier Science.)
Figure 51 Valence electron densities in the (100) plane of TiC, Ti 4C 3N, Ti 2CN, Ti 4CN 3, and TiN (from left to right) in units of 10 ⫺1 e/Å 3. The atom in the center
is Ti in all cases. The number of C atom neighbors of a Ti atom is indicated in the square bracket of the superscript of the respective Ti atom. (From Ref. 160. Reproduced
with the permission from Elsevier Science,  Elsevier Science.)
138 Neckel
replacement of C atoms by N atoms leads to a weakening of the covalent titanium-nonmetal

bonds and an increased ionicity of the bonds. At the same time the TiTi dd σ bonds are
strengthened. In pure TiN the maxima of the VED around the Ti atoms are directed toward the
neighboring Ti atoms (t 2g-like VED). If the TiC and TiN bonds are considered separately,
almost no influence of the C/N ratio on the strength of the particular titanium-nonmetal bonds
is found.
Schadler and Monnier (81) considered not only the effect of the nonmetal atom substitution
but also the presence of vacancies in the solid solutions Hf(C xN 1⫺x)y . To handle this problem
in the frame of the relativistic KKR approach for y ⬍ 1, a three-component CPA method had
to be developed. Total and local DOSs for HfC 0.8, Hf 0.9 C 0.37 N 0.53, HfC 0.42 N 0.58, and HfN 0.8 were
calculated.
V. ELECTRONIC STRUCTURE OF M 2X PHASES
In the phase diagrams of the fifth and sixth group transition metals with carbon subcarbides
M 2C (V 2C, Nb 2C, Ta 2C, Mo 2C, W 2C) appear. In the metal sublattice of these compounds there
is one octahedral interstitial site per metal atom. One half of the interstitial sites is occupied by
carbon atoms, the other half of the interstitials is vacant. The stable high-temperature modifica-
tion is the L′3 type structure with a random distribution of carbon atoms in half of the octahedral
interstitial sites. An exception is β-W 2C which crystallizes in the orthorhombic ξ-Fe 2N structure.
At lower temperatures ordering of the carbon atoms occurs, partly associated with a distortion
of the metal sublattice. Ivanovsky et al. (161) performed LCAO MO calculations for clusters
of the type MX 3M 12 (M ⫽ V, Nb; X ⫽ C, N) to study the electronic structure of V 2X and
Nb 2X. A remarkable finding is that in these compounds not only metal-carbon bonds but also
metal-metal bonds form the main covalent bonding components. In contrast, in the monocarbides
mostly covalent metal-carbon bonds are found in the occupied energy region.
In the TiN system two phases with a composition near TiN 0.5 are found, δ′-Ti 2N and
ε-Ti 2N. δ′-Ti 2N has a long-range-ordered defect structure. This structure can be derived from
the sodium chloride (B1) structure by assuming a long-range order of the vacancies on the
nitrogen sublattice and by shifting the titanium atoms (by about 0.123 Å) along the fourfold
tetragonal axis away from the adjacent vacancy in this axis (space group I4 1 /amd). The tetrago-
nal unit cell of δ′-Ti 2N is displayed in Fig. 52. δ′-Ti 2N is a metastable phase and transforms
into the stable, tetragonal ε-Ti 2N phase, which crystallizes in the antirutile structure (space group
P4 2 /mnm) displayed in Fig. 53. As can be seen from Figs. 52 and 53, in both δ′- and ε-Ti 2N
each N atom is surrounded by a slightly distorted octahedron of Ti atoms. Band structures, total
DOSs, local partial l-like DOSs, and VEDs for these two phases were calculated by Eibler (162)
by means of the SC LAPW method. The total DOSs for both ε- and δ′-Ti 2N are shown in Fig.
54. For both structures the energetically lowest lying peak is formed by N-2s states (‘‘N-2s
band’’). Separated by an energy gap of about 0.6 Ryd, the six ‘‘N-2p bands’’ follow. These
bands originate predominantly from N-2p states but also contain a contribution of Ti-3d states.
The N-2p bands overlap only slightly with the lowest ‘‘Ti-3d band.’’ A pronounced minimum
in the DOS (at about ⫺0.24 Ryd for ε-Ti 2N and ⫺0.22 Ryd below E F for δ′-Ti 2N) separates
the ‘‘N-2p bands’’ from the ‘‘Ti-3d bands.’’ The main difference in the DOSs between ε- and
δ′-Ti 2N is found at the bottom of the Ti-3d bands. Two peaks, d 1 and d 2, separated by a sharp
minimum at ⫺0.11 Ryd below E F, characterize the DOS of the lower part of the Ti-3d bands
of ε-Ti 2N. In δ′-Ti 2N, however, only one peak at about ⫺0.1 Ryd appears at the bottom of the
Ti-3d bands. The Fermi level for ε-Ti 2N is located in the DOS minimum above the peak d 2,
and the Fermi level for δ′-Ti 2N lies in the ascent of the main peak of the Ti-3d bands just above
a minimum in the DOS. A shift of the Fermi level to this minimum and assuming a rigid band
Figure 52 Tetragonal unit cell of δ′-Ti 2N with crystallographic axes X, Y, and Z. Empty circles, Ti
atoms; full circles, N atoms; squares, N vacancies. The shift of the Ti atoms adjacent to a vacancy is
indicated by arrows. (From Ref. 162. Reproduced with the permission of the Institute of Physics Publ.,
model would lead to a titanium nitride with the composition Ti 2N 0.98, very close to the composi-
tion Ti 2N.
A thorough discussion of the results obtained furnishes a qualitative explanation for both
the occurrence of the metastable δ′-Ti 2N structure and the stability of the ε-Ti 2N phase. In δ′-
Ti 2N the t 2g orbitals of the Ti atoms surrounding a vacancy can form octahedral dd σ bonds, as
discussed in the context of the electronic structure of ordered TiN 0.75. The t 2g states involved in
octahedral bonding are lowered in energy and form the peak in the DOS at the bottom of the
Ti-3d bands. This peak is separated from the remaining part of the Ti-3d bands. In contrast to
the results for the ordered model structure of TiN 0.75, the tails of the Ti-e g orbitals (Ti-3d z 2 orbitals
in the model structure for TiN 0.75) reaching into the vacancy overlap only very slightly. There-
fore, no significant Ti(d )-Ti(d ) interaction across the vacancy occurs. This behavior may be
due to the shift of the Ti atoms away from the vacancy, thus reducing the overlap and the
amount of charge in the vacancy.
The VED plot of ε-Ti 2N in the (001) plane shows the presence of strong pd σ bonds between
Figure 53 Unit cell of ε-Ti 2N with crystallographic axes X, Y, and Z. Empty circles, Ti atoms; full
circles, N atoms (From Ref. 162. Reproduced with the permission of the Institute of Physics Publ.,  In-
stitute of Physics Publ.)
140 Neckel
Figure 54 Densities of states of (a) ε- and (b) δ′-Ti 2N in states of one spin direction per Rydberg and
unit cell. For δ′-Ti 2N the local vacancy DOS is indicated by the dash-dotted curve. (From Ref. 162. Repro-
duced with the permission of the Institute of Physics Publ.,  Institute of Physics Publ.)
each N atom and its two nearest (apical) Ti atoms (Fig. 55). The Ti 2N units are aligned in the
[110] direction in the basal plane. Adjacent, parallel Ti 2N units only interact in the [110] direc-
tion at right angles to the orientation of the Ti 2N units via weak TiTi dd σ bonds formed by
Ti-e g states. The VED plot of δ′-Ti 2N in the (001) plane is displayed in Fig. 56. As can be seen
from this figure, the N atoms form pd σ bonds with the four Ti atoms surrounding each N atom
in the (001) plane. (Note that the Ti atoms are shifted by ⫾ 0.123 Å out of the (001) plane.)
The transformation of δ′-Ti 2N into ε-Ti 2N allows the Ti-e g orbitals to form not only strong
Figure 55 Valence electron density in the (001) plane of ε-Ti 2N. Contour lines on a linear mesh in units
of 10⫺1 e/Å3. (From Ref. 162. Reproduced with the permission of the Institute of Physics Publ.,  Institute
of Physics Publ.)
Figure 56 Valence electron density in the (001) plane of δ′-Ti 2N. Contour lines on a linear mesh
in units of 10 ⫺1 e/Å 3. (From Ref. 162. Reproduced with the permission of the Institute of Physics Publ.,
NTi pd σ bonds but also TiTi dd σ bonds in the basal plane between the strongly bound
‘‘molecular’’ Ti 2N units. The corresponding states are stabilized and form the subband d 1 at
the bottom of the Ti-3d bands. This effect is presumably the main reason for the stabilization
of the ε-Ti 2N structure with respect to the δ′-Ti 2N structure.
A quantitative confirmation of the higher stability of the ε-phase was furnished by Eibler
(163), who calculated the total energies of ε- and δ′-Ti 2N by volume minimization using the
FLAPW method (43). Figure 57 shows the total energies of ε- and δ′-Ti 2N plotted as a function
of the volume of the unit cell. At 0 K, the ε-phase is found to be more stable than the δ′-phase
by 9.35 kJ/mol and has a 2% smaller equilibrium volume, indicating stronger bonding. The
experimental volumes are higher by 1.8% for both phases. This deviation is characteristic for
all band structure calculations based on the local density approximation (LDA).
Figure 57 Total energies of δ′- and ε-Ti 2N plotted versus the volume of the respective unit cell. (From
142 Neckel
VI. ELECTRONIC STRUCTURE OF TRANSITION METAL DIBORIDES MB 2

OF THE FOURTH AND FIFTH GROUPS OF THE PERIODIC TABLE
Many transition metal diborides MB 2 (M ⫽ Sc, Ti, V, Cr, Mn, Y, Zr, Nb, Mo, Hf, Ta) crystallize
in the C 32 (AlB 2) structure with the space group P6/mmm. The translational lattice of this
structure is a simple hexagonal lattice. The boron atoms form graphite-like layers that are sepa-
rated by hexagonal closed-packed metal layers. The center of a hexagonal boron ring lies both
directly above and below each metal atom. The structure is displayed in Fig. 58. The unit cell
contains one metal and two boron atoms.
The properties of the transition metal diborides with C 32 structure resemble those of the
transition metal monocarbides and mononitrides. The diborides also have high melting points,
hardness, chemical stability, and metallic conductivity.
Perkins and Sweeney (165) performed an LCAO-TB calculation for TiB 2. A remarkable
result is the close grouping of the Ti-3d bands. The Fermi level lies within this group of Ti-3d
states and splits the Ti-3d bands into lower (bonding) and upper (antibonding) states. Also,
graphite-like features are found in the band structure. The band structure and the total DOS of
ZrB 2 was calculated by Ihara et al. (166) using the APW method. According to these authors,
the bonding mechanism in ZrB 2 can be explained as a combination of the graphitic bonding
model of boron network and the hcp-metal bonding model of zirconium. Similar results have
been obtained by Johnson et al. (167), who employed the KKR method to study the electronic
structure of ZrB 2. Armstrong (168) used the LCAO MO method to calculate the band structures
and total DOSs for the transition metal diborides MB 2 (M ⫽ Sc, Ti, V, Cr, and Mn). Trends
in the electrical conductivity and spin susceptibility were evaluated. The solid-state calculational
procedure was supplemented by cluster calculations using a cluster (M 18B 36) comprising 54
atoms. These investigations led to the following trends: The metal-metal bonding in the metal
Figure 58 Two projections of the AlB 2-type structure. The top view is down the z-axis with the metal
atoms at z ⫽ 0 and the boron atoms at z ⫽ 1/2. The bottom view is a projection of the x ⫺ z plane with
the metal atoms at y ⫽ 0 and the positions of the two boron atoms at y ⫽ 1/3 and 2/3. a 0, c 0, lattice
constants. (From Ref. 164. Reproduced with the permission from Elsevier Science,  Elsevier Science.)
plane reaches a maximum at VB 2. The interlayer metal-metal bonding is small for ScB 2 and
TiB 2 but reaches large values for VB 2, CrB 2, and MnB 2, corresponding to the enhanced 3d
orbital population. Metal-boron bonding increases along the series from ScB 2 to MnB 2. The
boron-boron bonding in the hexagonal boron plane, however, is strongest for ScB 2 and decreases
gradually from ScB 2 to MnB 2. The bonding between the boron layers is weak.
The electronic structure of the transition metal diborides MB 2 (M ⫽ Sc, Ti, V, Cr, and
Mn) was also investigated by Burdett et al. (169) employing band structure calculations of the
extended Hückel type. The bonding mechanism was discussed, and it was concluded that the
interactions of the metal orbitals with those of the planar, graphite-like net of boron atoms and
with those of other metal atoms are both important in influencing the properties of the diborides.
The authors offer an explanation for the experimentally observed variation in the heat of forma-
tion of the diborides, which depends, according to their calculations, on the extent of occupation
of the metal-boron orbitals.
The SC LMTO ASA method was used by De-Cheng Tian and Xiao-Bing Wang (170) to
calculate the band structure and total and partial l-like DOSs for TiB 2. Figure 59 shows the
total DOS of TiB 2. The peak A arises from the B-2s states, and the broad peak B originates
from the B-2p and Ti-3d states, which overlap strongly. The Fermi level lies exactly in a pro-
nounced minimum (pseudogap) of the DOS. [A similar minimum at the Fermi level was also
found by Ihara et al. (166) for ZrB 2.] The authors regard this minimum as caused by a competing
effect of a Ti-3d resonance and the strong bonding interaction between the B-2p and Ti-3d
states. The DOS above the Fermi level (peak C) can be put down to nonbonding Ti-3d states.
The authors stress that the covalent metal-boron bonding is a least as important as other types
of bonding. The fact that the Ti-3d and the B-2p states belong to different layers proves the
importance of the interlayer bonding. Therefore, TiB 2 cannot be regarded as a true interlayer
compound, because there is a strong interaction between the metal and the boron layers. The
calculations of De-Cheng Tian and Xiao-Bing Wang (170) were extended by Xiao-Bing Wang
et al. (171) to a series of transition metal diborides MB 2 (M ⫽ Sc, Ti, V, Cr, Mn, Y, Zr, Nb,
Mo, Hf, and Ta) using the same computational approach. The total DOSs for VB 2, ZrB 2, NbB 2,
HfB 2, and TaB 2 are displayed in Fig. 60. The DOS curves for the different compounds show
great similarity. (Also compare the DOS of TiB 2, Fig. 59.) The boron sublattice, which has the
planar graphite-like structure, is reflected in the DOS by the lowest lying peak (peak A). All
diborides are characterized by a pronounced minimum (pseudogap) of the DOS. The broad peak
Figure 59 Total density of states, TDOS, (left scale) and integrated density of states, IDOS, (right scale)
of TiB 2. Fermi energy at 0.04 rydberg. The Fermi energy is indicated by a vertical dashed line. (From
144 Neckel
Figure 60 Total densities of states, DOS, of VB 2, ZrB 2, NbB 2, HfB 2, and TaB 2 in units of states per
Rydberg and unit cell. The Fermi energies are at 0.08 Ryd (VB 2), 0.04 Ryd (ZrB 2), 0.14 Ryd (NbB 2),
0.04 Ryd (HfB 2), and 0.16 Ryd (TaB 2. (From Ref. 171. Reproduced with the permission of the Institute
of Physics Publ.,  Institute of Physics Publ.)
below the minimum (peak B) is caused by the overlapping transition metal d and the boron
2p orbitals, leading to strong covalent transition metal(d )–boron(2p) bonds. The DOSs have
nonvanishing values at E F, indicating that the diborides possess metallic properties. The peak
above the minimum of the DOS (peak C) originates from nonbonding transition metal d states.
The authors stressed that, besides the interaction of the transition metal d orbitals with the boron
2p orbitals and the interactions between the transition metal orbitals, the boron-boron interaction
is also of importance. Furthermore, the variation of the chemical stabilities of the investigated
transition metal diborides was analyzed and it was found that the observed trends can be under-
stood in terms of a band-filling concept of the bonding states.
The electric field gradients at the boron and metal sites for various transition metal dibor-
ides MB 2 (M ⫽ Ti, V, Cr, Zr, Nb, Mo, and Ta) were calculated by Schwarz et al. (172) by
means of the full-potential LAPW method as embodied in the Wien 95 code (45) in a scalar
relativistic version.
ACKNOWLEDGMENTS
Figures and tables in this article are reproduced with permission from the authors of the corre-
sponding papers and from the following publishers who own the copyright on the respective
figures and tables: Academic Press Inc., American Physical Society, Berichte der Bunsen-Gesell-
schaft, Cambridge University Press, Critical Reviews in Solid State and Materials Sciences
(CRC Press LLC), Elsevier Science, Institute of Physics Publ., Springer Verlag, and John Wi-
ley & Sons, Inc. This assistance is gratefully acknowledged.
The author would like to express his thanks to Prof. Peter Herzig for many valuable discus-
sions.
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6
Lattice Vibrations, Heat Capacity, and
Related Properties
Göran Grimvall
Royal Institute of Technology, Stockholm, Sweden
I. INTRODUCTION
The discussions in this chapter will pay particular attention to relations that are relevant for
diatomic solids in either the NaCl-type crystal structure, as exemplified by TiC and TiN, or in
the AlB 2-type crystal structure, as exemplified by TiB 2.
A nonmagnetic metal has contributions to its heat capacity C p from the excitation of lattice
vibrations (phonons) and conduction electrons. The vibrational part C vib can be expressed in the
phonon density of states F(ω). Similarly, the vibrational entropy S vib , the corresponding Helm-
holtz energy Fvib ⫽ Uvib ⫺ TSvib , etc. are expressed in F(ω). The low-frequency part of F(ω) is
uniquely given by the single-crystal elastic coefficients cij, for instance, by the three quantities
c11 , c12 , and c44 for a solid with cubic lattice symmetry. The elastic coefficients c ij, when properly
averaged, yield the engineering elastic constants of a polycrystalline material, i.e., the bulk
modulus K, the shear modulus G, and Young’s modulus E. The phonon density of states also
yields other quantities, such as the vibrational displacement that enters the Debye-Waller factor.
Because the forces that determine the phonon frequencies ω are related to the bonding in the
solid, there are connections between the properties just mentioned and other cohesion-related
quantities, such as the cohesive energy and the melting temperature. This chapter briefly outlines
the theoretical connection between these properties and then gives an application to refractory
transition metal carbides, nitrides, and borides. The role of electronic excitations is also briefly
exposed. Most of the general relations in the following sections are well known and can be
found in a monograph by the present author (1) and in many textbooks. Therefore they are
usually given without references to original work.
II. THE DEBYE AND SOMMERFELD MODELS OF THE HEAT CAPACITY
Often the vibrational heat capacity Cvib of a solid is described by the Debye model, with a Debye
temperature θ D. The electronic part Cel is usually described by the Sommerfeld model in which
the heat capacity is linear in the temperature T. Thus,
Cp ⫽ Cvib ⫹ Cel ⫽ CD (T/θ D) ⫹ γT (1)
153
154 Grimvall
In the low-temperature limit, C vib varies as T 3, and the Debye-model heat capacity per mole
takes the form
冢冣
3
12π 4 T
CD ⫽ rLk B (2)
5 θD
Here r is the number of atoms per formula unit (i.e., r ⫽ 2 for TiC and r ⫽ 3 for TiB 2), L
is Avogadro’s number, and k B is Boltzmann’s constant. In the electronic contribution at low
temperatures, and per mole,
2π 2 2
γ⫽ k BN(E F ) (1 ⫹ λ el-ph ) (3)
3
where N(E F ) is the electron density of states at the Fermi level E F, per spin and mole. [Many
sources let N(E F) refer to both electron spin directions. Then the prefactor 2 in Eq. (3) should
be absent.] In Sommerfeld’s original theory, the so-called enhancement factor 1 ⫹ λ el-ph was
not included. It is caused by many-body electron-phonon interactions, and its existence was not
fully understood until the 1960s. The magnitude of λ el-ph typically varies between 0.2 and 1.5,
with no simple correlation with the chemical composition of the solid. For transition metals and
their compounds λ el-ph is often between 0.4 and 1.0, and λ el-ph ⬇ 0.9 may be a good estimate for
several of the materials of interest here (2). Thin films often have a larger λ el-ph ; for example,
λ el-ph ⬇ 1.46 ⫾ 0.10 was reported for NbN films by Kihlstrom et al. (3). In Eq. (3) a further
enhancement due to interactions with spin fluctuations may be present in nearly magnetic solids;
see Rietschel (4) for VN.
Some data on θ D and another Debye temperature θ S, to be defined later, are given in
Tables 2 and 5. Figure 1 gives the coefficient γ in Eq. (3) but without the enhancement factor
(1 ⫹ λ el-ph ); i.e., it shows the ‘‘band structure’’ γ that is obtained from N(E ) in electron band
structure calculations.
III. LOW-FREQUENCY PART OF THE PHONON DENSITY OF STATES

A. Sound Velocity and Debye Temperature
The Debye temperature θ D to be used in the low-temperature limit of the heat capacity is related
to the average sound velocity Cav as
冢冣
1/3
6π 2 rL
θD ⫽ Cav (4)
kB V
Cav is averaged over the longitudinal (s ⫽ 1) and the two transverse (s ⫽ 2, 3) sound velocities
Cs(θ,φ) in directions given by the angles θ, φ in the single crystal (dΩ ⫽ sin θ dθ dφ):
3
冱冮 C (θ,φ) 4π
3 1 dΩ
⫽ (5)
C 3av s⫽1
3
s
The sound velocities Cs (θ,φ) are uniquely related to the single-crystal elastic constants c ij. In
the special case that the single crystal is elastically isotropic we get
3 1 2
⫽ ⫹ (6)
C 3av C 3L C 3T
Lattice Vibrations and Heat Capacity 155
Figure 1 The coefficient γ in the electronic heat capacity C el ⫽ γT plotted versus the average number
of valence electrons per atom for some refractory compounds. γ is obtained through Eq. (3) from the
electron density of states N(E ) in ab initio electron structure calculations for 3d metal compounds (5) and
for NbN and TaN (2) i.e., without the enhancement factor (1 ⫹ λ el-ph) that is present only at low temperatures
(approximately for T ⬍ θ D /3).
The longitudinal (L) and the transverse (T) sound velocities are expressed in the bulk modulus
K and the shear modulus G as
4
ρC 2L ⫽ K ⫹ G (7)
3
and
ρC 2T ⫽ G (8)
where ρ is the mass density of the solid.
B. Elastic Properties of Polycrystalline Materials

A polycrystalline material without texture (i.e., without preferred crystal grain orientations) is
elastically isotropic, in an average sense. Then the longitudinal and transverse sound velocities
are still exactly given by Eqs. (7) and (8), even if the single crystal is not elastically isotropic.
Because the number of independent elastic coefficients c ij is at least three, while Eqs. (7) and
(8) contain only two elastic parameters K and G, there can be no general and exact algebraic
relation between c ij and both of K and G. In fact, there is such an exact relation for K and cubic
lattice symmetry only. It takes the form
c 11 ⫹ 2c 12
K⫽ (9)
3
156 Grimvall
The shear modulus G is limited by upper and lower bounds, G V ⱖ G ⱖ G R , often referred to
as the Voigt (V) and Reuss (R) bounds. Then (1)
G V ⫽ (c 11 ⫺ c 12 ⫹ 3c 44)/5 (10)
G R ⫽ 5(c 11 ⫺ c 12)c 44 /[4c 44 ⫹ 3(c 11 ⫺ c 12)] (11)
In the case of hexagonal lattice symmetry (such as for TiB 2) there are five independent elastic
coefficients, c 11, c 12 , c 13 , c 33 , and c 44 . Then the polycrystal bulk modulus and shear modulus are
bounded by K V ⱖ K ⱖ K R and G V ⱖ G ⱖ G R , with (see, e.g., Ref. 1)
1
KV ⫽ [2(c 11 ⫹ c 12) ⫹ c 33 ⫹ 4c 13] (12)
9
K R ⫽ C 2 /M (13)
1
GV ⫽ [12c 66 ⫹ 12c 44 ⫹ M] (14)
30
GR ⫽
5
冤 c 44 c 66 C 2
2 (c 44 ⫹ c 66) C 2 ⫹ 3K V c 44c 66 冥 (15)
where
C 2 ⫽ (c 11 ⫹ c 12 )c 33 ⫺ 2c 213 (16)
M ⫽ c 11 ⫹ c 12 ⫹ 2c 33 ⫺ 4c 13 (17)
c 66 ⫽ (c 11 ⫺ c 12 )/2 (18)
Under certain conditions on overall isotropy, there are narrower but algebraically more compli-
cated bounds usually referred to as the Hashin-Shtrikman bounds (see, e.g., Ref. 1). However,
for not too elastically anisotropic single crystals, one is usually satisfied with bulk and shear
moduli given by the Voigt-Reuss-Hill approximation, which has the forms
K ⬇ KVRH ⫽ (KV ⫹ K R)/2 (19)
G ⬇ G VRH ⫽ (G V ⫹ G R)/2 (20)
We shall see that this is an excellent approximation for the refractory compounds considered
in this chapter.
Young’s modulus for a polycrystalline material without texture, and expressed in K and
G, is exactly given by
9KG
E⫽ (21)
3K ⫹ G
and Poisson’s number ν is exactly given by
3K ⫺ 2G
ν⫽ (22)
2(3K ⫹ G)
Hence one can choose any two of the four elastic parameters K, G, E, and ν to specify uniquely
the other two engineering elastic constants. Because K and G are bounded as shown before, E
is also bounded, E V ⱖ E ⱖ E R, by expressions obtained from Eqs. (12)–(15) and (21). There
is no analogous bound to ν.
Table 1 Elastic Engineering Constants K, G, and E (in GPa) and Poisson’s Number v, as Calculated
from the Cited (7) Experimental c ij (in GPa) a
Compound c 11 c 12 c 44 K G E ν
TiC 513 106 178 242 188 ⫾ 1 448 0.19
ZrC 441 60 151 187 166 ⫾ 1 384 0.16
VC 0.83 366 110 192 195 163 ⫾ 3 382 0.17
NbC 0.9 413 111 206 212 182 ⫾ 2 425 0.17
TaC 0.9 505 73 79 217 120 ⫾ 14 304 0.27
a
The upper and lower limits given for G refer to the upper (Voigt) bound G V and the lower (Reuss) bound G R . G of
TaC 0.9 is discussed in the text.
Table 1 gives experimentally determined elastic coefficients c ij and the corresponding

engineering elastic constants K from Eq. (9), G ⫽ G VRH from Eq. (20), E from Eq. (21), and ν
from Eq. (22). The uncertainties in c ij, and hence in the resulting engineering elastic constants,
may be large (see comment later on TaC). Kosolapova (6) cites experimentally determined
Young’s moduli E for a large number of refractory compounds. For the compounds considered
here, the values given by Kosolapova often differ much (⬎20%) among themselves and also
differ from the E values in Table 1. However, the table also serves the purpose of showing how
K, G, E, and ν can be obtained from c ij.
We next exemplify how the elastic constants are related to the conventional Debye temper-
ature θ D from the low-temperature heat capacity [i.e., θ D(⫺3) in Table 4]. The detailed numerical
integration in Eq. (5) yields θ D as shown in the first row of Table 2, using c ij from Table 1 and
mass densities ρ calculated from the atomic volumes Ω a [⫽V/(rL)] in Table 5. As an illustration
we shall also apply Eqs. (6)–(8) together with Eqs. (19) and (20), which allow a simple calcula-
tion of θ D. Anderson (8) suggests that such an approach, with K and G estimated by the Voigt-
Reuss-Hill approximation, gives θ D to within about 2% when A H ⬍ 0.2. Here A H ⫽ (G V ⫺ G R)/
(G V ⫹ G R ) is a measure of the elastic anisotropy. Table 2 summarizes the results for θ D.
The results for TaC in Table 1 and 2 motivate a comment. Poisson’s number of TaC
differs significantly from that of TiC, ZrC, VC, and NbC. This is in contrast to the regularities
these compounds show in the atomic volume Ω a , the entropy Debye temperature θ S, and the
related quantity E S (Table 5, Figs. 7–9). Tables 2 and 5 give θ D /θ S ⫽ 1.12 ⫾ 0.05 for TiC,
ZrC, VC, and NbC, whereas θ D /θ S ⫽ 0.76 for TaC, which suggests that θ D for TaC obtained
here from cij is too low. Comparison with θ D from low-temperature heat capacity measurements
could show whether θ D calculated for TaC from c ij is correct, because the two Debye tempera-
tures should be equal. The θ D values reported by Kosolapova (6) are too uncertain to settle the
problem. However, θ D from heat capacity data in Roedhammer et al. (9), together with our θ S ,
gives θ D /θ S ⫽ 1.05 ⫾ 0.09 for TiC, ZrC, VC, and NbC and 1.06 for TaC 0.9. This is strong
evidence that the actual c 44 of TaC 0.9 lies outside the experimental uncertainty suggested in the
Table 2 Debye Temperatures θ D Calculated Accurately from c ij in Table 1 (First

Line) and Calculated Approximately from K and G (Second Line) a
TiC ZrC VC 0.83 NbC 0.9 TaC 0.9
θ D (K) 938 697 847 710 418
θ D (K) 940 699 851 713 430
AH 0.005 0.006 0.018 0.011 0.12
a
The parameter A H measures the elastic anisotropy.
158 Grimvall
experimental work (10). Suppose that G in Table 1 is too low. Assuming that ν ⫽ 0.17 and an
unchanged K ⫽ 217 GPa yields G ⫽ 184 GPa, from which θ D ⫽ 512 K and θ D /θ S ⫽ 0.93.
Even that is a bit low and also suggests a larger K. We note that θ D in Table 2 was calculated
here with the correct mass density and crystal volume for the nonstoichiometric compounds,
but with a normalization of the Debye spectrum assuming stoichiometry (r ⫽ 2). A correct
normalization for a compound MX y would reduce θ D by a factor [(1 ⫹ y)/2] 1/3 , that is, by ⬍2%
for TaC 0.9, which is negligible in the context of the present discussion. We also note that the
heat capacity may be affected by order-disorder effects in nonstoichiometric carbides (11), but
not enough to change our conclusions.
Very little is known about the single-crystal elastic coefficients c ij for the noncubic refrac-
tory diborides. For TiB 2 experimental results are available (7) for c 11 ⫽ 690 GPa, c 33 ⫽ 440
GPa, c 44 ⫽ 250 GPa, and c 12 ⫽ 410 GPa. The value c 13 ⫽ 320 GPa is estimated (7). With these
c ij, Eqs. (12)–(18) give K ⫽ 412 ⫾ 24 GPa and G ⫽ 169 ⫾ 11 GPa, where the limits refer to
the Voigt and Reuss bounds. Then θ D ⫽ 1000 K, to be compared with our θ S ⫽ 972 K. Low-
temperature heat capacity data (12) give θ D ⫽ 1182 K, after multiplication by 3 1/3 to get the
normalization used here. The lack of agreement is typical of the difficulties in determining θ D
from experiments on elastic constants or heat capacities.
C. Effect of Porosity
Many refractory compounds are obtained through sintering, which may give a material with a
certain porosity. As an illustration, we assume that the pores are spherical and with a radius
that is much larger than the size of an atom; i.e., the pores are macroscopic. Let a volume
fraction p of a material be made up of pores, so that the mass density is 1 ⫺ p of the ideal
density. The elastic properties of such a material, in the dilute limit that p ⬍⬍ 1, are given by
(subscript e refers to the effective properties of the porous material and quantities without sub-
scripts refer to the nonporous material)
冤
Ke ⬇ K 1 ⫺ p
3K ⫹ 4G
4G 冥 (23)
冤
Ge ⬇ G 1 ⫺ p
5(3K ⫹ 4G)
9K ⫹ 8G 冥 (24)
The effective Young’s modulus E e follows from Eq. (21), that is, E e ⫽ 9K e G e /(3Ke ⫹ G e ).
As the pores are assumed to be macroscopic, the heat capacity and its directly related
properties are not affected. A certain mass of the compound has the same heat capacity, irrespec-
tive of the presence of pores. The engineering elastic constants Ke and G e give the sound veloci-
ties according to Eqs. (7) and (8), but obviously those sound velocities for porous materials are
not to be used in the calculation of a Debye temperature. It is sometimes unclear how well
measured elastic constants have been corrected for porosity. Therefore one must be cautious
when Debye temperatures of refractory compounds calculated from elastic parameters are com-
pared with Debye temperatures obtained from a fit to low-temperature heat capacity data. Figure
2 shows measured moduli G e and E e for NbC, as given by Toth (13). It also gives the theoretical
E e , G e , and Ke that follow from Eqs. (23) and (24), i.e., from an extrapolation of the low-porosity
limit for spherical pores, and using the experimental values of Fig. 2 for G and E at zero porosity.
Nonspherical pores would give lower values of E e , G e, and K e .
Figure 2 Experimental data (symbols, from Ref. 13) for the shear modulus G e and Young’s modulus
E e as a function of the porosity. Solid lines give theoretical estimates for G e , E e , and the bulk modulus
K e obtained in a model with spherical pores, Eqs. (23) and (24).
IV. PHONON DENSITY OF STATES AND DEBYE TEMPERATURES

A. General Expressions for Thermodynamic Quantities
The lattice vibrations of a solid are often described by citing a Debye temperature. However,
the Debye temperature varies with the physical property one considers and with the temperature
at which this property is described. Therefore tables with Debye temperatures must always be
considered with caution. In the case of solids in which the constituent atoms have a large mass
ratio, as is the case in many refractory compounds, it is particularly important to be aware of
how different Debye temperatures are defined and used. We therefore give the theoretical back-
ground in some detail.
Thermodynamic quantities of harmonic lattice vibrations, such as the energy U, heat ca-
pacity C, and entropy S, can be expressed in the phonon density of states F(ω), normalized to
three per atom, where hω is the energy of a phonon. One has, per mole,
冮
max
U(T ) ⫽ rL UE (T;ω) F(ω) dω (25)
0
冮
max
C(T ) ⫽ rL CE (T;ω) F(ω) dω (26)
0
冮
max
S(T ) ⫽ rL S E(T;ω) F(ω)dω (27)
0
160 Grimvall
where U E , C E, and SE are the expressions for an Einstein model of the lattice vibrations, i.e.,
for a single oscillator. One has
U E(T;ω) ⫽ hω 冤exp(hω/k1 T) ⫺ 1 ⫹ 21冥 B

(28)
冢冣
2
hω exp(hω/k B T)
CE(T;ω) ⫽ k B (29)
kBT [exp(hω/k B T) ⫺ 1] 2
S E(T;ω) ⫽ k B 冤2khωT coth冢khωT冣 ⫺ ln 冢2 sinh冢2kh ωT冣冣冥

B B B
(30)
Two high-temperature expansions will be of particular interest, namely

ω
冮
max
C(T) ⫽ rLk B [1 ⫺ (1/12) (hω/k B T) 2 ⫹ (1/240) (hω/k B T) 4 ⫹ ⋅ ⋅ ⋅] F(ω)dω (31)
0
冮
max
S(T ) ⫽ rLk B [1 ⫹ ln(k B T/hω) ⫹ ⋅ ⋅ ⋅ (1/24) (hω/k B T ) 2 ⫹ ⋅ ⋅ ⋅] F(ω)dω (32)
0
The vibrational displacement of atoms will be illustrated here with a solid such as TiC, whose
primitive crystallographic cell contains two atoms (labeled 1 and 2), having masses M 1 and M 2
and displacements u 1 and u 2 . Then (1)
ω
冮
max
M 1 〈u 21〉 ⫹ M 2 〈u 22 〉 ⫽ 2 [U E(ω;T) /ω 2 ] F(ω)dω (33)
0
Brackets 〈 〉 denote a thermal average. At high temperatures UE ⬇ k B T, and

ω
冮
max
M 1 〈u 21 〉 ⫹ M 2 〈u 22 〉 ⬇ 2k B T ω ⫺2 F(ω)dω (34)
0
An interesting case is that the interatomic forces act only between nearest neighbors, in cubic
structures, and at high temperatures (i.e., T ⬎ θ D). Then the two displacements are equal and
hence independent of the mass ratio M 1 /M 2 (1,14). This counterintuitive result, with equal ther-
mal displacements of the light nonmetal and heavy metal atoms in NaCl crystal–type refractory
carbides and nitrides, seems to hold approximately even though the condition on the interatomic
forces is not strictly obeyed. This is illustrated in Table 3, which gives the Debye parameter B
Table 3 Displacements of Metal and Nonmetal Atoms at Room

Temperature, as Given by the Debye Parameter B, Based on
Experiments and from an Unpublished Compilation
Compound B metal (10 ⫺20 m 2 ) B nonmetal (10 ⫺20 m 2)
TiC 0.15 ⫾ 0.02 0.15 ⫾ 0.02
ZrC 0.21 ⫾ 0.02 0.21 ⫾ 0.02
NbC 0.19 ⫾ 0.02 0.18 ⫾ 0.02
TiN 0.18 ⫾ 0.02 0.17 ⫾ 0.02
ZrN 0.23 0.16
NbN 0.36 0.26
Source: From Ref. 15.
that enters the conventional Debye-Waller factor exp(⫺M ). Here M ⫽ B sin 2 θ/λ 2 and
B ⫽ 8π 2 〈u 2i 〉 with i referring to the metal and nonmetal atom, respectively. Data, based on
experiments, are from Ref. 15.
B. Frequency Moments
We define frequency moments ω(n) of the phonon density of states F(ω) as
ω
冮
max
ω n F(ω)dω
0
[ω(n)] ⫽ n
ω
(35)
冮
max
F(ω) dω
0
when n ⬎ ⫺3 and n ≠ 0. For n ⫽ 0, ω(0) is defined as

ω
冮
max
ln ω F(ω)dω
0
ln ω(0) ⫽ ω
(36)
冮
max
F(ω)dω
0
Equation (31) now implies that to leading order in the temperature dependence, the high-temper-
ature heat capacity of harmonic lattice vibrations depends only on the frequency moment ω(2).
From Eq. (32) we see that the high-temperature vibrational entropy depends only on the moment
ω(0). A certain combination [see Eq. (34)] of the thermal atomic displacements at high tempera-
tures depends on ω(⫺2). Table 4 summarizes these results, together with the case of very low
temperatures, which will be discussed in the following section.
In the preceding discussions, the phonons were described by their angular frequencies ω.
Many works on lattice dynamics instead use the frequency ν ⫽ ω/2π, that is, hν ⫽ hω in our
notation.
C. Debye Model for the Phonon Spectrum

It is common practice to approximate the true density of states F(ω) with the Debye model
density of states FD(ω), which has an upper cutoff frequency ω D
FD (ω) ⫽ 9ω 2 /ω 3D (37)
Table 4 In the Limit of Low or High Temperatures, Some

Important Thermodynamic Quantities Depend Only on a Single
Frequency Moment ω(n) or Equivalently on a Single Debye
Temperature θ D (n)
Thermodynamic Value of n in
quantity Temperature ω(n), θ D (n)
C vib T→0 ⫺3
S vib T→0 ⫺3
C vib High T (T ⬎ θ D) 2
S vib High T (T ⬎ θ D) 0
M 1 〈u 21 〉 ⫹ M 2 〈u 22〉 High T (T ⬎ θ D) ⫺2
162 Grimvall
Here FD (ω) has been normalized to three per atom. A Debye temperature θ D can be defined
through
k B θ D ⫽ hω D ⫽ hν D (38)
If FD (ω) replaces F(ω) in Eqs. (25)–(27) we get the Debye model expression for the heat capac-
ity, C D (T; θ D ), for the entropy, S D (T; θ D ), etc. We next require that a physical property for an
actual phonon density of states F(ω) is represented by a Debye model spectrum. For instance,
we can let the actual entropy S(T ) be described by S D (T; θ D ) and write
S(T ) ⫽ S D (T;θ D ) (39)
The S(T ) on the left-hand side of Eq. (39) could be an entropy S vib,exp (T ) determined from
experiments or it could be the result of a detailed model calculation based on a certain F(ω)
in Eq. (27). There is a solution θ D to Eq. (39) for each temperature T. We shall call that θ D a
‘‘Debye temperature.’’ Because we represent the property of a system that has 3rL degrees of
freedom with a single parameter θ D, it is obvious that we have to pay a price. In this case, the
price is that θ D varies with T and also with the physical property that is modeled. (Here θ D
refers to the entropy.) One may therefore introduce one Debye temperature θ S that describes
the vibrational entropy, another Debye temperature θ C that describes the vibrational heat capac-
ity, etc. The heat capacity Debye temperature θ C would be the solution to
C(T ) ⫽ C D(T;θ C) (40)
where C(T ) is the actual heat capacity of a system.
We can also define Debye temperatures θ D (n) such that they correctly reproduce the fre-
quency moment ω(n) of a certain density of states F(ω). One finds that
冢冣
1/n
n⫹3
k B θ(n) ⫽ hω(n) (41)
3
when n ⬎ ⫺3 and n ≠ 0. For n ⫽ 0, one has k B θ(0) ⫽ exp(1/3) hω(0). Most tables listing Debye
temperatures take θ D from a description of the heat capacity in the limit of low temperatures. One
can show that this corresponds to the limit n → ⫺3, so that the Debye temperature θ(⫺3) ⫽
θ C (T → 0). This quantity can be defined only through the mathematical limit of T → 0 in Eq.
(26), as ω(n) is defined only for n ⬎ ⫺3. The low-temperature limit of the vibrational heat
capacity (and the thermal energy and the entropy) only ‘‘probes’’ the low-frequency limit of
F(ω), i.e., the long-wavelength limit of the acoustic phonon branches. That part is also given
uniquely by the elastic constants, as mentioned before, and we can define an ‘‘elastic limit’’
Debye temperature θ E that also equals θ(⫺3). Debye temperatures obtained from the low-tem-
perature heat capacity and from the elastic constants should thus be equal, but only if the elastic
constants are also measured at very low temperatures. Normally, they are measured at room
temperature and are somewhat lower than the values at 0 K because of anharmonic effects.
Therefore θ E based on room-temperature elastic constants is usually somewhat lower than θ C
(T → 0). [One may note that c 12 increases slightly with T from 0 K to 300 K for TiC, VC 0.83 ,
and NbC 0.83 but c 11 and c 44 decrease; see Kumashiro et al. (16) and Every and McCurdy (7).]
The expression (31) for the heat capacity can never exceed the value 3k B per atom because
it assumes strictly harmonic vibrations. In contrast, real systems are anharmonic and usually
the heat capacity increases with T above the value 3k B . Then Eq. (40) has no physical solution
θ D. When the measured C(T ) approaches 3k B per atom, small errors in C(T ) give rise to a large
uncertainty in θ C . Therefore the heat capacity Debye temperature θ C (T ) of a real system is
meaningful only for, say, T ⬍ θ D. The case of the entropy is different. There is no upper limit
for the vibrational entropy, and the equation S vib (T ) ⫽ S D(T;θ S) always has a solution θ S(T ).
Further, when anharmonic effects enter S vib they are correctly accounted for, to low order in
quantum mechanical perturbation theory, by anharmonic shifts in θ S(T ) (1). Finally, as we shall
return to later, the atomic masses enter θ S in a simple multiplicative way.
Figure 3 shows the gross features of the phonon density of states F(ν) for TiC, as obtained
by Pintschovius et al. (17) from a fit to their experiments using inelastic neutron scattering. (The
actual measurements were performed on crystals having the compositions TiC 0.95 and TiC 0.89. We
treat the data as if they refer to stoichiometric TiC.) The two more thinly drawn parabolic curves
in Fig. 3 are Debye densities of states. These Debye models have cutoff frequencies ν D and
corresponding Debye temperatures θ D ⫽ hν/k B. The one with the higher ν D encloses the same
area as the experimental F(ν). The parabolic curve with the lower ν D has half of that area, i.e.,
ν D is smaller by a factor 2⫺1/3 , and it would correspond to a θ D that is also smaller by the same
factor. At very low temperatures, the optical branch of the phonon spectrum is not excited. The
heat capacity then depends only on the acoustic vibrations, i.e., on the low-frequency part of
F(ω). One may then take r ⫽ 1 in Eq. (2) and ignore the carbon or nitrogen atoms (although
the mass density ρ must also include the nonmetal atoms) or take r ⫽ 2 and normalize F D and
θ D accordingly. Both approaches give the same heat capacity at very low T, but because only
a description with r ⫽ 2 is relevant at intermediate and high temperatures, we will adopt the
latter definition in this chapter. The two possibilities are mentioned here for the reason that the
convention r ⫽ 1 has been used in publications on the thermal properties of refractory carbides
and nitrides (9,11,12).
Figure 4 shows the solutions θ S (T ) and θ C (T ) to Eqs. (39) and (40) for TiC when the heat
capacity and the entropy are taken from recommended experimental data in the JANAF tables
(18) of thermodynamic functions. Because the experiments give the sum of vibrational and
electronic contributions, an electronic part has been subtracted assuming that γ ⫽ 0.5 mJ/(mol ⋅ K 2)
at all T and (for simplicity) without correction for the electron-phonon enhancement. In fact,
the enhancement goes to zero with increasing temperature and can be ignored when T ⬎ θ D /
3. [A table with data for TiC at a more dense set of temperatures than in the printed JANAF
Figure 3 The phonon density of states F(ν) for TiC (17), based on neutron scattering data. The two
thinly drawn parabolas give Debye model spectra normalized to one and two atoms per formula unit,
respectively (see text).
164 Grimvall
Figure 4 The entropy Debye temperature θ S(T ) and the heat capacity Debye temperature θ C(T ) for TiC,
as obtained from recommended thermodynamic data (18), using Eqs. (39) and (40).
version was obtained from Dr. Malcolm Chase at the National Institute of Standards and Tech-
nology (NIST).] At high temperatures (T ⬎ 300 K) the value of θ C becomes physically meaning-
less, for reasons discussed earlier.
Figure 5 shows the entropy Debye temperature θ S (T ) obtained as in Fig. 4 but plotted
here up to the melting temperature of TiC. The rather strong temperature dependence of θ S(T )
below about 300 K is due to the fact that we model the vibrational entropy of a complex phonon
spectrum by a function of a single parameter (i.e., θ S). At high T and if the vibrations were
strictly harmonic, θ S(T ) would asymptotically approach the value θ S ⫽ θ(0). However, anhar-
monic effects usually cause the vibrational frequencies to decrease with T. This is the reason
Figure 5 The entropy Debye temperature θ S (T ) for TiC, as in Fig. 4 but extended to the melting tempera-
ture.
for the decrease in θ S(T ) that is seen in Fig. 5 above about 400 K. To low order in quantum
mechanical perturbation theory, this decrease is linear in T. At very high temperatures there are
higher order anharmonic effects that give rise to a faster temperature dependence. We finally
remark that part of the strong decrease in θ C (T ) above 300 K would be suppressed if we had
fitted the Debye model to the heat capacity at constant volume, C V(T ), instead of the fit to the
experimental C p(T ), which is measured at constant pressure. It is a common misunderstanding
that the vibrational heat capacity C V has all anharmonicity suppressed and hence tends to 3k B
per atom at high T. This is not true, because there remain the anharmonic effects due to increased
vibrational atomic displacements, even when the total volume is kept fixed. Therefore θ C(T )
may not be a well-behaved quantity at very high T, even when it is calculated from CV data.
V. QUANTITIES RELATED TO THE BONDING IN THE SOLID
There are several, more or less well defined, quantities that can be taken as measures of the
strength of the bonding in a solid. Refractory transition metal carbides, nitrides, and borides
are characterized by a high hardness and a high melting temperature T m. The hardness is a
property that in practice depends in a complex way on defect structures and other characteristics
of the specific test sample. Therefore hardness is not a quantity that can be uniquely related to
a fundamental description of the electronic structure. The melting temperature, on the other
hand, is in principle determined only by the electronic structure of the solid and liquid phases,
but since the thermodynamic properties of the liquid are so difficult to account for accurately,
one cannot reliably calculate Tm from first-principles considerations. This can be contrasted with
the cohesive energy E coh and the enthalpy of formation ∆H. Modern first-principles electronic
structure calculations (at 0 K) are so advanced that E coh and ∆H, within a not too distant future,
can be obtained with an accuracy that matches that of experiments. Already today, they accu-
rately give the trends when chemically similar compounds are compared, for instance, by varying
the constituent atoms horizontally or vertically in the periodic table. Such theoretically estab-
lished trends may predict unknown quantities when there are experimentally determined data
for a few compounds that can be used for ‘‘calibration’’ (5,19–21). The electronic structure of
refractory compounds is considered elsewhere in this book. In this chapter we shall relate the
bonding strength to the lattice vibrations and introduce an entropy-related quantity E S that has
the dimension of energy and correlates well with other measures of the bonding strength.
The phonon spectrum of a solid depends on the interatomic forces as well as on the atomic
masses. For an element, the mass dependence is trivial. All phonon frequencies, and hence also
all frequency moments ω(n), vary with the atomic mass M as M ⫺1/2. In a compound with two
or several different atomic masses, the vibrational frequencies depend on the interatomic forces
and on the masses in a complex way, with two exceptions. In the low-frequency part of the
phonon density of states, which is uniquely given by the sound velocities, the vibrational fre-
quencies vary as ρ ⫺1/2 , where ρ is the mass density of the solid. It follows that θ C (⫽ θ S) in
the limit of low temperatures has interatomic forces and atomic masses separated in the form
of two multiplicative factors. The force-constant part is directly related to the elastic coefficients
c ij. Hence the low-temperature limit of the Debye temperature gives a certain average over the
interatomic forces, as it is reflected in the sound waves. We shall now introduce another average
over the interatomic forces, uniquely related to the entire phonon spectrum.
It has been shown (22) that in the logarithmic average ω(0) of the phonon spectrum, the
atomic masses enter only as a multiplicative factor (M log ) ⫺1/2. We noted earlier that k B θ S ⬇
hω(0) exp(1/3) at high temperatures. Then one can write
k B θ S ⫽ √k S /M log (42)
166 Grimvall
Here k S has the dimension of a force constant and is a certain (complicated) average over all
the interatomic forces in the solid, and M log is the logarithmic average of the atomic masses.
For instance, M log ⫽ (M TiM C)1/2 in TiC and M log ⫽ (M TiM 2B) 1/3 in TiB 2.
Equation (42), with θ S determined from experiments, thus allows us to obtain an ‘‘experi-
mental’’ value for k S . A practical difficulty is that θ S(T ) varies with T. One unique prescription
for evaluating k S would be to base it on the value of θ S(T ) taken at T ⫽ θ S. Then the temperature
is still low enough that anharmonic effects are moderate, but the temperature is also high enough
that the variations of θ S(T ) caused by the precise shape of F(ω) are small. This definition is
adopted in most of this chapter. However, in some cases the only entropy information available
refers to the standard entropy S°(298.15 K). Taking the corresponding θ S (298.15 K) is also
reasonable in a calculation of k S. We see from Figs. 4 and 5 that θ S(T ) is slowly varying over
a wide temperature range at intermediate temperatures and therefore gives only a small variation
in the corresponding force constant k S .
The quantities E coh , ∆H, and k B Tm are three measures of the bonding strength that all have
the physical dimension of energy. To enable a comparison with bonding strengths extracted
from θ S, we multiply k S by a length squared. One could define such a length in different ways.
Here it will be obtained as Ω 1/3 a , where Ω a is the average volume per atom in the compound,
i.e., the total volume of a crystallographic unit cell divided by the number of atoms in that cell
[Ω a ⫽ V/(Lr) in Eq. (4)]. This definition has the advantage that it makes no explicit reference
to the crystal structure. Now a cohesion-related quantity E S can be defined as
E S ⫽ k S Ω a2/3 (43)
The E S has several attractive features. It is uniquely related to the vibrational entropy at high
temperatures but still does not depend on atomic masses. Hence E S depends only on the elec-
tronic structure in the solid. Further, E S behaves in a regular way and is often approximately
constant when chemically similar compounds are compared. The standard entropy S° of a com-
pound is often better known than other thermodynamic quantities, which makes E S a readily
available quantity. Extrapolations or interpolations of experimentally determined E S may provide
an accurate way to obtain otherwise unknown Debye temperatures and gives a link (although
approximate) to elastic parameters.
VI. COMPARISON OF BONDING-RELATED QUANTITIES
In this section we compare several of the bonding-related quantities we have introduced, with
particular attention to trends in the periodic table. Table 5 summarizes some important data.
Debye temperatures depend on the atomic masses as well on the electronic structure, as the
latter is reflected in the interatomic forces. In addition to considering trends in the entropy Debye
temperature θ S (determined at T ⬇ θ S ), we consider trends in the related quantity E S, which is
not affected by the atomic masses. We will also consider the cohesive energy E coh (per atom)
for a compound AX, defined by
1
E coh ⫽ ⫺ (E AX,cryst ⫺ E A,atom ⫺ E X,atom) (44)
2
where E AX,cryst is the total energy of the compound AX, and E A,atom and E X,atom are the total energies
of atoms of the elements A and X. Hence E coh is the energy required to separate the solid AX
into atoms A and X.
We shall now demonstrate, in a number of figures, how various bonding-related quantities
covary and show regular behavior with the position of the chemical elements in the periodic
table. Figure 6 shows how the entropy Debye temperature θ S varies with the transition metal
Table 5 The Entropy-Related Debye Temperature θ S , the

Corresponding Force Constant k S and Energy E S , Average Volume per
Atom Ω a , and Cohesive Energy E coh
kS Ωa ES
Compound θ S (K) (N/m) (10 ⫺30 m 3 ) (Ry) a
ScC 654 283 13.144 7.23
TiC 805 442 10.110 9.48
VC 745 391 9.058 7.79
CrC 664 314 8.700 6.09
ScN 755 407 11.429 9.47
TiN 710 372 9.521 7.67
VN 631 303 8.869 5.96
CrN 535 220 8.921 4.34
ZrC 650 398 12.962 10.07
HfC 581 445 12.494 10.99
NbC 634 382 11.164 8.75
TaC 551 403 11.064 9.18
ZrN 582 345 11.958 8.28
HfN 521 386 11.529 9.04
NbN 539 298 10.591 6.59
TaN 489 343 10.217 7.41
TiB2 972 477 8.566 9.16
ZrB2 834 436 10.234 9.43
HfB2 741 426 9.883 9.00
a
1 Ry ⫽ 2.18 ⫻ 10⫺18 J.
Source: Data from Refs. 5, 19, 20, and 23.
Figure 6 The entropy Debye temperature θ S (from Refs. 5, 19, 20, and 23; see Table 5) for transition
metal carbides, nitrides, and oxides.
168 Grimvall
Figure 7 The entropy-related quantity E S , the cohesive energy E S , and the melting temperature T m for
transition metal carbides (filled symbols) and nitrides (unfilled symbols) in the NaCl-type crystal structure.
Data as in Figs. 8–10.
for carbides, nitrides, and oxides in the NaCl-type structure. Figure 7 gives a similar plot for
the cohesive energy E coh, the quantity E S, and the melting temperature T m, for some carbides
(filled symbols) and nitrides (open symbols). Figure 8 shows that E S varies with the metallic
element for carbides, nitrides, and oxides in a regular way, when plotted as a function of the
average number of valence electrons n e per atom in the compound. E S is a measure of the
bonding strength and may correlate well with the melting temperature, as shown in Fig. 9. The
origin of this relation is analogous to that of the well-known Lindemann melting rule. As in
the latter case, one does not expect a universally obeyed relation between E S and Tm. It works
best for elements and binary compounds, where the interatomic forces can be well described
by simple nearest-neighbor interactions. Figure 10 shows a similar plot for the correlation be-
tween E S and E coh. It is not as good as that between E S and Tm. This is not unexpected because
E S and T m depend on the interatomic forces characteristic of the condensed compound AX and
E coh measures the forces when AX is taken all the way from the condensed phase to separated
atoms. Further plots relating E S , E coh , Tm, and other cohesion-related quantities have been pub-
lished for 3d, 4d, and 5d transition metal carbides and nitrides (5,19–21,23–26) and AlB 2 struc-
ture–type transition metal diborides (27,28).
The parameter γ in Fig. 1 is directly proportional to N(E ). Thus, with reference to a rigid-
band electron structure, Fig. 1 can also be viewed as giving an approximate variation of N(E )
with the electron energy E. TiC and ScN have a Fermi level falling at a minium in N(E ) that
separates the lower lying bonding electron states from antibonding states of higher energy. The
high cohesive strength of these compounds is thus explained by the full utilization of the bonding
electron states (21). The decreases in θ S and E S seen for ScC in Figs. 6–8 are immediately
explained by the fact that the bonding electron states are not completely filled for ScC.
Figure 8 The phonon-related energy E S , for solids in the NaCl-type crystal structure, and in energy
units of Ry (1 Ry ⫽ 2.18 ⫻ 10⫺18J), plotted versus the average number n e of valence electrons per atom
in the compound (n e ⫽ 4 for pure C; 5 for N; 3 for Ti, Zr, Hf; 4 for V, Nb, Ta, etc.). Data from Refs. 5,
19, 20, and 23; see Table 5.
Figure 11 correlates the entropy-related force constant k S with the hardness of some refrac-
tory compounds. Because the hardness is measured in the unit of pressure (i.e., having the
dimension of force constant per length), we correlate hardness with k S /a, where a is the measured
lattice parameter.
VII. CONCLUSIONS
This chapter has focused on properties related to the interatomic forces in solids, in particular
as they are reflected in the phonon spectrum and in the elastic constants. A phonon spectrum
is often crudely characterized by a Debye temperature. The concept of a Debye temperature
may give a convenient and accurate description of the vibrational spectrum, provided that the
Debye temperature is properly defined. Different physical phenomena depend on different aver-
ages over the phonon spectrum and hence cannot be described by the same Debye temperature.
170 Grimvall
Figure 9 The melting temperature T m plotted versus the phonon-related energy E S for solids in the NaCl-
type crystal structure. Unfilled symbols refer to compounds that decompose or change crystal structure
before melting. Melting points are from Ref. 18 or, if not given there, from Ref. 29 or 6. T m for TaC is
exceptionally uncertain.
Figure 10 The experimental cohesive energy E coh (data from Refs. 5, 19, and 20; see Table 5) plotted
versus the phonon-related energy E S for solids in the NaCl-type crystal structure and in energy units of
Ry (1 Ry ⫽ 2.18 ⫻ 10⫺18 J). The straight lines are only guides for the eye. They refer to 4d and 5d
transition metals from groups IV (Zr, Hf) and V (Nb, Ta) in the periodic table, respectively, and 3d elements
from group V (V) and from group IV (Ti) plus Sc from group II and Cr from group V.
Figure 11 The hardness of some refractory compounds plotted versus k S /a, where k S is the force constant
obtained from θ S through experimental vibrational entropy data. Adopted from Ref. 30.
We have paid particular attention to the entropy Debye temperature θ S, not only because it is
the relevant parameter to represent the entropy (and hence the Gibbs energy) but mainly because
it is physically well defined, often readily available from thermodynamic data, smoothly varying
with temperature and chemical composition, and has a simple dependence on the atomic masses
and the electronic structure of the solid. In this chapter we have also considered in some detail
the elastic properties, in particular the relation between the elastic coefficients c ij describing a
single crystal and the engineering elastic constants describing a polycrystalline material, i.e.,
Young’s modulus E, the shear modulus G, the bulk modulus K, and Poisson’s number v. The
effect of porosity and nonstoichiometry is also dealt with.
In addition to a general theoretical treatment of properties related to lattice vibrations, this
chapter gives some experimental data for refractory materials. Much of the available experimen-
tal information is uncertain, with conflicting results reported by different research groups and
using different experimental techniques. In assessments of such experimental information for
a particular material, it may be helpful to employ the theoretically and empirically well-founded
correlations that have been discussed here. This was exemplified is some detail for TaC, sug-
gesting a new value for the shear modulus G.
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2. DA Papaconstantopoluos, WE Pickett, BM Klein, LL Boyer. Electronic properties of transition-metal
nitrides: The group-V and group-VI nitrides VN, NbN, TaN, CrN, MoN, and WN. Phys Rev B31:
752, 1985.
3. KE Kihlstrom, RW Simon, SA Wolf. Tunneling α 2 F(ω) from sputtered thin-film NbN. Phys Rev
B32:1843, 1985.
4. H Rietschel. Importance of spin fluctuations for the thermodynamic properties of superconducting
V and VN. Phys Rev B24:155, 1981.
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of 3d-transition metal carbides and nitrides with the NaCl-type structure. Phys Rev B43:14400, 1991.
6. TY Kosolapova, ed. Handbook of High-Temperature Compounds: Properties, Production, Applica-
tions. New York: Hemisphere, 1990.
172 Grimvall
7. AG Every, AK McCurdy. Second and higher order elastic constants. In: Landolt-Börnstein New
Series. Vol 29a. Berlin: Springer-Verlag, 1992.
8. OL Anderson. A simplified method for calculating the Debye temperature from elastic constants. J
Phys Chem Solids 24:909, 1963.
9. P Roedhammer, W Weber, E Gmelin, KH Rieder. Low temperature specific heat and phonon anoma-
lies in transition metal compounds. J Chem Phys 64:581, 1976.
10. RW Bartlett, CW Smith. Elastic constants of tantalum monocarbide, TaC 0.90 . J Appl Phys 38:5428,
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11. AI Gusev, AA Rempel, VN Lipatnikov. Heat capacity of niobium and tantalum carbides NbCy and
TaC y in disordered and ordered states below 300 K. Phys Status Solidi (b) 194:467, 1996.
12. BD Hanson, M Mahnig, LE Toth. Low temperature heat capacities of transition metal borides. Z
Naturforsch 26a:739, 1971.
14. C Huiszoon, PPM Groenewegen. Irrelevance of atomic masses for Debye-Waller B values in the
limit of high temperatures. Acta Crystallogr A28:170, 1972.
15. G Grimvall, J Rundgren. Unpublished.
16. Y Kumashiro, H Tokumoto, E Sakumura, A Itoh. The elastic constants of TiC, VC, and NbC single
crystals. In: RR Haseguti, N Mikoshiba, eds. Internal Friction and Ultrasonic Attenuation in Solids,
Proceedings of the 6th International Conference. Tokyo: Tokyo University Press, 1977, p 295.
17. L Pintschovius, W Reichhardt, B Scheerer. Lattice dynamics of TiC. J Phys C 11:1557, 1978.
18. MW Chase, CA Davies, JR Downey, DJ Frurip, RA McDonald, AN Syverud, eds. JANAF Thermo-
chemical Tables. 3rd. ed. J Phys Chem Ref Data 14(suppl. 1), 1985.
19. A Fernández Guillermet, J Häglund, G Grimvall. Cohesive properties of 4d-transition-metal carbides
and nitrides in the NaCl-type structure. Phys Rev B45:11557, 1992.
20. A Fernández Guillermet, J Häglund, G Grimvall. Cohesive properties and electronic structure of 5d-
transition-metal carbides and nitrides in the NaCl structure. Phys Rev B48:11673, 1993.
21. J Häglund, A Fernández Guillermet, G Grimvall, M Körling. Theory of bonding in transition-metal
carbides and nitrides. Phys Rev B48:11685, 1993.
22. G Grimvall, J Rosén. Vibrational entropy of polyatomic solids: Metal carbides, metal borides, and
alkali halides. Int J Thermophys 4:139, 1983.
23. A Fernández Guillermet, G Grimvall. Cohesive properties and vibrational entropy of 3d transition-
metal compounds: MX(NaCl) compounds (X ⫽ C, N, O, S), complex carbides, and nitrides. Phys
Rev B40:10582, 1989.
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75:61, 1986, (2nd International Conference on Science of Hard Materials, Rhodes, 1986).
7
Electrical and Thermal Conductivity and
Related Transport Properties at Low
Temperatures
Göran Grimvall
Royal Institute of Technology, Stockholm, Sweden
I. INTRODUCTION
This review deals mainly with the electrical and thermal conductivities at temperatures T from
0 K to room temperature. It is the region where the lattice vibrations must be described by
quantum mechanics, and the phonon spectrum determines much of the temperature dependence
of the transport properties. The absolute magnitudes of the electrical and thermal conductivties
depend crucially on a consideration of the quantum mechanical matrix elements for the scattering
of electrons and phonons. They are difficult to calculate, not only for the refractory systems of
interest here but for most solids. Theories of conduction properties therefore contain parameters,
some of which are fairly well known while others are quite uncertain.
An additional difficulty in the present chapter is the lack of extensive and accurate experi-
mental data on well-defined specimens for many of the compounds of interest. Williams (1)
reviewed electrical conduction in the solids treated here, with an account of how the accuracy
and relevance of experimental data have gradually been improved. He also gave references to
many early reviews of transition metal carbides, nitrides, and borides. Another review of the
electrical properties of these and related systems is that of Wang et al. (2).
The present work presents standard theories of transport properties, and as we proceed
connection is made mainly to carbides, nitrides, and borides of the transition metals of group
IV (Ti, Zr, Hf) and group V (V, Nb, Ta) in the periodic table. In particular, we shall discuss
the extent to which the simple textbook relations may have to be modified in order to describe,
e.g., refractory compounds. The theoretical arguments leading to many of the general results
cited in this chapter are discussed in more detail, e.g., in two monographs by the present author
(3,4). References to such well-known relations will usually not be explicitly given but can be
found in these two books and in many of the papers referred to in the chapter. Those papers
also give more experimental information. Some additional experimental data on the systems of
interest, and on many related systems, are found in the compilation by Kosolapova (5).
173
174 Grimvall
II. ELECTRICAL CONDUCTION

A. Ideal Resistivity
A standard textbook result for the electrical conductivity is
σ ⫽ ne 2 τ el /m (1)
where n is the number of conduction electrons (charge carriers) per volume, e is the electron
charge, m is an effective electron mass, and τ el is the average electron lifetime between scattering
events. The important part of this relation is the lifetime. In a pure and defect-free crystalline
material, τ el is limited by the thermal motion of the atoms, i.e., by the electron-phonon interac-
tion. The corresponding resistivity ρ (⫽1/σ) is sometimes called the ideal resistivity, and we
shall denote it ρ el-ph . (There is also an electron-electron scattering term, which in most cases is
negligible, and in systems with magnetic moments there is an additional contribution to the
electrical resistivity.)
At high enough temperatures (T ⬎ θ D , where θ D is a Debye temperature), and according
to a simple model, the resistivity ρel-ph increases linearly with T,
ρel-ph ⫽ αT (2)
Here we are mainly interested in temperatures T ⬍ θ D . For more than half a century, the Bloch-
Grüneisen (BG) formula has been used frequently to describe ρ el-ph (T ) at intermediate and low
temperatures. It is often given in the form
冮
q
C1 D q 5 dq
ρ BG ⫽ (3)
T 0 [exp(hCq/k BT) ⫺ 1] [1 ⫺ exp(⫺hCq/k BT)]
where C 1 is a constant, specific for the metal under consideration, C is the sound velocity, q is
a phonon wave number lying between 0 and the Debye cutoff value q D, hCq is a corresponding
phonon energy, and kB is Boltzmann’s constant. With z ⫽ hCq/k B T and hCqD ⫽ kBθ D , we rewrite
(3) as
冢冣冮冢冣冢冣
5 θ 5
C2 T D/T z 5 dz C T θD
ρBG ⫽ ⫽ 2 J5 (4)
θD θD 0 (e ⫺ 1) (1 ⫺ e ⫺z ) θ D θ D
z
T
where C 2 is another constant and J5 is the ‘‘transport integral of order 5.’’ At low temperatures
we need J5 (∞) ⫽ 124.4. At high temperatures (T ⬎ θ D) we have J 5 ⬇ (1/4) (θ D /T) 4. These two
limits imply that ρ BG ⬃ T at high T and ρ BG ⬃ T 5 at low T.
The Bloch-Grüneisen formula is a special case of a more general expression. Within a
variational solution of the Boltzmann equation we can, to a good approximation, write the resisti-
vity ρ el-ph that is limited by the scattering of conduction electrons by phonons as
冢冣冮
2 ω
4π max (hω/kB T) α 2tr F(ω)dω
ρ el-ph ⫽ (5)
ω pl 0 [exp(hω/kB T ) ⫺1] [1 ⫺ exp(⫺hω/kB T )]
The plasma frequency ω pl has the form (ω pl) 2 ⫽ 4πne 2 /m for a free electron gas, and it can be
rigorously generalized to account for a complicated electron band structure. The function
α 2tr F(ω) can, somewhat loosely, be regarded as the product of an electron-phonon interaction
α 2tr (essentially quantum mechanical matrix elements squared) and a phonon density of states
F(ω). The index tr stands for transport property. [There is another electron-phonon coupling
Electrical and Thermal Conductivity 175
α 2 F(ω) that enters the theory of superconductivity and the electron-phonon enhancement of the
electronic heat capacity at low T; see Eq. (25).] The maximum phonon frequency is ω max.
Let us model α 2tr F(ω) with a power-law expression in ω:
α 2tr F(ω) ⫽ C0 ω n 0 ⬍ ω ⬍ ω max (6)
where C 0 is a constant that depends on the considered material. The Bloch-Grüneisen formula
(4), with a T 5 behavior at low T, is obtained with n ⫽ 4 in Eq. (6). The orginal motivation of
ρ BG was based on several simplifying assumptions. When interpreted in terms of the modern
formulation in Eq. (5), they can be stated as follows: take a Debye model for the phonon density
of states F(ω), let α 2tr refer only to coupling between electrons and longitudinal phonons, and
ignore Umklapp processes. However, we prefer to view the Bloch-Grüneisen formula, and its
generalizations for n ≠ 4, as models in which the true α 2tr F(ω), including all its complications,
is described by Eq. (6). We see that at high T (i.e., when kBT ⬎ hω) any form of α 2tr F(ω) yields
ρ ⬃ T, in accord with Eq. (2). At low T we get ρ ⬃ T n⫹1 if, in the low-frequency limit,
α 2tr F(ω) ⬃ ω n .
It is useful to define a quantity
冮 α 2tr F(ω)
max
λ tr ⫽ 2 dω (7)
0 ω
Here λ tr is a ‘‘transport’’ electron-phonon coupling parameter. It is a number, typically 0.5–1
for many transition metals, and is closely related to the electron-phonon coupling parameter λ el-ph
that appears in the theory of superconductivity; see Eqs. (25) and (26). The high-temperature
version of Eq. (5) can then be written
冢冣
2
4π kB
ρ el-ph (T ) ⫽ λ trT (8)
ω pl 2h
where we again recover the general result of Eq. (2). However, most materials show deviations
from linearity in T at high temperatures. The coupling constant λ tr depends on ⬍ω ⫺2⬎, where
⬍ ⬎ denotes a weighted average of the phonon frequencies ω. Because anharmonic effects
usually lead to a ‘‘softening’’ of the lattice vibrations, i.e., a decrease in ω, the term ⬍ω ⫺2⬎
will cause λ tr to increase with T. The result is that ρ el-ph(T ) increases more rapidly than linearly
in T. Another effect, resistivity saturation, gives a temperature dependence with opposite trend.
It is considered in Sec. II.C.
The quantity α 2tr F(ω) cannot be obtained directly from experiment, but in superconductors
(see Sec. V) a closely related quantity α 2 F(ω) can be measured in tunneling experiments. Trals-
hawala et al. (6) found that their measured α 2F(ω) in superconducting VN, when inserted for
α 2tr F(ω) in Eq. (5), accurately accounted for the temperature dependence of their measured elec-
trical resistivity of VN between 10 and 300 K. Suppose that we want to model α 2tr F(ω) with
α 2 F(ω) of Tralshawala et al. (6) with C0 ω n as in Eq. (6). There are three parameters, C 0, n, and
the cutoff frequency ω max . We then require that our model α 2tr F(ω) has the same λ tr [see Eq.
(7)] as the λ exp that was measured, i.e., C0 ⫽ nλ exp /(2ω nmax). It still leaves us with two fitting
parameters, n and ω max . Figure 1 shows a possible model, here with n ⫽ 3. We note that ω max
is not necessarily to be identified with the highest frequency in the actual phonon spectrum.
The experimental α 2 F(ω) and the generalized Bloch-Grüneisen α 2 F(ω) in Fig. 1 obviously are
quite different, but when inserted in Eq. (5) they both yield the same high-temperature ρ el-ph (T ).
Moreover, the same ρ el-ph at high T would result with another n, provided that ω max and C0 were
also changed accordingly. It is clear that a property such as the electrical resistivity, which is
176 Grimvall
Figure 1 The electron-phonon coupling function α 2tr F(ω) derived from experiments on VN (6) (thin
lines) and a possible representation of α 2tr F(ω) through a generalized Debye-type phonon spectrum, as in
Eq. (6) (thick lines).
an integrated quantity over the phonon spectrum, does not depend much on fine structure in
that spectrum. This fact is the basis for the ability of Bloch-Grüneisen type formulas to account
for ρ el-ph (T ).
Sometimes a kind of ‘‘Debye temperature’’ θ R is derived from resistivity data through
hω max ⫽ kB θ R in Eq. (6). The temperature dependence of other physical properties is also often
described in terms of a Debye temperature (see Chap. 6). However, this means that one uses
a model with a single parameter (i.e., θ) to describe a temperature dependence that is a function
of the entire phonon spectrum and usually also involves other complications related to, e.g., the
electronic states. It is obvious that such Debye temperatures should not be equal. They give
information only about the magnitude of characteristic phonon frequencies, for a given material
and for a certain weighting of its various frequency parts. In the case of θ R, one varies not only
θ R but also n, in a fit to experiments. Nevertheless, a quantity θ R is often extracted from ρ(T ).
Table 1 gives some θ R values obtained in this way and θ S derived from heat capacity data, so
that θ S (see Chap. 6) reproduces the vibrational entropy (10) at T ⬇ θ S.
Table 1 A ‘‘Debye Temperature’’ θ R Obtained by Fitting a Generalized Bloch-

Grüneisen Expression to the Measured Resistivity at Low and Intermediate
Temperatures and an ‘‘Entropy Debye Temperature’’ θ S That Reproduces the
Experimental High-Temperature Vibrational Entropy a
TiC ZrC VC NbC TaC TiB 2
θ R (K) 719 b
570 c
587 c
431 c
272 c
720 d
θ S (K) 805 650 745 634 551 972
a
See Chapt. 6
b
Modine et al. (7) for TiC 0.95.
c
Allison et al. (8) for ZrC 0.93, VC 0.88, NbC 0.95, and TaC 0.99.
d
Williams et al. (9).
It is interesting to note that in an Einstein model for the phonon spectrum, i.e., when
α 2tr F(ω) ⬃ δ(ω ⫺ ω e), ρ/T from Eq. (5) has exactly the same temperature dependence as the
phonon heat capacity. In Fig. 2 we illustrate to what extent ρ el-ph /T covaries with the heat capacity
C p for TaC. For ρ el-ph Allison et al. (8) found that a generalized Bloch-Grüneisen formula with
n ⫽ 2 in Eq. (6), i.e., involving the transport integral J3 and hence a T 3 behavior at low T, gives
a good fit to their experiments on TaC between 10 and 350 K. We normalize their ρ/T to 1 at
high T in Fig. 2 and compare with the experimental heat capacity Cp (10), normalized to the
value 3kB per atom that holds for harmonic lattice vibrations at high T. Although the general
shapes of the two curves in Fig. 2 are similar, they are obviously governed by different character-
istic temperature scales. The resistivity in this case depends to a large extent on the low-fre-
quency part of the phonon spectrum. This is in line with the difference between the Debye
temperatures θ R and θ S for TaC given in Table 1, and the other compounds listed there give a
closer agreement between ρ(T )/T and C p (T ).
Figure 2 The phonon-limited electrical resistivity plotted as ρ el-ph (T )/T of TaC, based on experiments
by Allison et al. (8) and normalized to 1 at high temperatures, and the heat capacity C p (10), normalized
as C/3k B per atom.
178 Grimvall
B. Matthiessen’s Rule
Matthiessen’s rule gives the total electrical resistivity ρ tot of (dilute) alloys as
ρ tot ⫽ ρ 0 ⫹ 冱cρ
i
i
imp
i ⫹ 冱c ρ
j
j
def
j (9)
where ρ 0 is the resistivity of the pure and defect-free host (i.e., ρ 0 ⫽ ρ el-ph in most cases), c i is
the concentration (e.g., in atomic percent) of the alloying element i, and ρ imp i ⫽ dρ tot /dc i is the
corresponding resistivity per impurity concentration. The terms in the last sum refer to static
lattice defects j such as grain boundaries, dislocations, and vacancies, and c j measures the
amounts of those defects. Typical values for ρ imp i in transition metals fall in the range 1–5
µΩ ⋅ cm/at. % (11). Most of the refractory compounds of interest here are nonstoichiometric,
with vacancies on some of the nonmetal lattice sites. These vacancies strongly scatter electrons
and can give a dominating contribution to ρ tot , as shown in Fig. 3 for TiCx , ZrCx, VCx, and
TaCx . We note that the additional resistivity per atomic % vacant sites is larger than for typical
impurities in transition metals. In some cases, the vacancies can form an ordered lattice structure.
Shacklette and Williams (12,13) and Otani (14) showed that the ordered compounds V6 C5 and
V8 C7 have resistivities that are much lower than in the compounds with the same composition
but disordered vacancies; see Fig. 3. Similar work has been done on Nb6 C5 by Dy and Williams
(15) and by Lorenzelli et al. (16) on Ti8 C5 . Dy and Williams (15) also studied the effect of
hydrogen impurities on the resistivity of NbCx.
C. Resistivity Saturation
If the electron scattering is caused by independent scattering mechanisms, e.g., scattering by
phonons, by atomic impurities i (alloying elements or vacancies), and by defects j, the scattering-
time approximation gives
Figure 3 The resistivity ρ of compounds TiC x (16), ZrC x (7), VC x (13,14), and TaC x (17), as a function
of x, when the vacant carbon sites are disordered, and the lower ρ as a result of ordering in V6 C5 and
V8 C7 (13,14). The curve for disordered VC x is a tentative extrapolation. Data refer to very low temperatures
(residual resistivity), except for TaC x , which refers to ⫺196° C.
冱τ ⫹ 冱τ
1 1 1 1
⫽ ⫹ (10)
τ el τ el-ph i i j j
We see that taking this τ el in (1) gives an expression equivalent to Matthiessen’s rule as in (9).
It is instructive to express the electron scattering rate not in terms of scattering times τ but in
the corresponding mean free paths ᐉ ⫽ vτ, where v is some properly defined electron velocity
at the Fermi energy. (In a model with a spherical Fermi surface, v is the Fermi velocity v F.)
Then the equivalent of Eq. (10) is
冱ᐉ ⫹ 冱ᐉ
1 1 1 1
⫽ ⫹ (11)
ᐉel ᐉel-ph i i j j
In this picture, a conduction electron travels a distance ᐉ el between two successive scattering
events. At low temperatures, and for defect-free and dilute alloys, ᐉ el is much larger than a
typical distance between neighboring atoms. If the temperature is increased, the electron-phonon
scattering becomes more important and ᐉ el-ph decreases correspondingly. Similarly, if we increase
the concentration of alloying atoms in solid solution, ᐉ i will be shorter. But it is obvious that
ᐉ el cannot decrease indefinitely, i.e., ρ el cannot be made arbitrarily large, while still maintaining
the picture with charge carriers that move between scattering centers. For instance, it would be
meaningless to have ᐉ el less than a typical distance a between nearest-neighbor atoms. In fact,
ᐉ el must be large compared with the de Broglie wavelength λ associated with a conduction
electron for our picture to be valid. For the electrons near the Fermi level, which are respon-
sible for the conduction, λ ⫽ λ F ⬃ 1/a. Using the free electron model, where v ⫽ v F ⫽ (h /m)
(3π 2 n) 1/3 , with ᐉ el ⫽ 1/a and n ⫽ 1/a 3 (a typical value), we get σ ⫽ ne 2 ᐉ el /(mvF ) ⫽ e 2 a ⫺2 /
h(3π 2 a ⫺3 ) 1/3 ⫽ (3π 2 ) 1/3 e 2 /(ha). This suggests a universal maximum resistivity of the order of
ha/e 2 ⬃ 10 2 µΩ ⋅ cm for conduction described by the scattering of electrons (i.e., by the Boltz-
mann equation). A value of this order of magnitude crudely distinguishes between insulators,
where the electrons are localized at a specific atom, and metals, where there are mobile electrons.
In nontransition metals and alloys the electron mean free path is usually so large that the
standard Boltzmann equation suffices to describe the electrical resistivity. However, both pure
transition metals and their alloys and compounds often show a ‘‘saturation’’ of the resistivity
when the mean free path becomes short. A further increase in the lattice disorder through more
alloying atoms, more static defects, or larger atomic vibrations caused by increased temperature
will not have a significant effect on the total resistivity. The temperature dependence of the
resistivity ρ in such a material approaching resistivity saturation is sometimes well described
by the empirical ‘‘parallel resistor’’ formula due to Wiesmann et al. (18):
1 1 1
⫽ ⫹ (12)
ρ(T ) ρ ideal(T ) ρ max
Here ρideal (T ) is the resistivity without saturation, e.g., described as in Eq. (1), and ρ max is the
limiting value to which the resistivity of a particular material saturates in the extrapolated limit
that ρideal(T ) ⬎⬎ ρmax. Resistivity saturation was highlighted in a seminal paper by Mooij (19)
in 1973. After several decades, the phenomenon is still poorly understood; see, e.g., work by
Nath and Majumdar (20) on transition metal alloys and references therein. Although it may be
difficult to notice a correction due to resistivity saturation in data taken for refractory compounds
at low temperature, high-temperature measurements clearly reveal its existence. For example,
for VN experiments (6) show the effect even below room temperature.
180 Grimvall
III. THERMAL CONDUCTION

A. The Wiedemann-Franz Law
The Wiedemann-Franz law, relating the electrical conductivity σ to the electronic contribution
κ el to the thermal conductivity in metals, reads
κ el ⫽ LTσ ⫽ LT/ρ (13)

where L is the Lorenz number. Under certain simplifying conditions L is a universal constant,
L ⫽ L 0 ⫽ (π 2 /3) (k B /e) 2 ⫽ 2.44 ⫻ 10 ⫺8 WΩK ⫺2. Deviations from the value L ⬇ L 0 may occur
as a result of electron band structure effects and, at intermediate and low temperatures, of the
inelastic nature of the electron scattering by phonons. At very low temperatures, where impurity
scattering dominates, it is often a good approximation to let L ⫽ L 0. As an example, Fig. 4
shows L(T ) for iron, based on an analysis of experimental electrical resistivity and thermal
conductivity data (21), with a tentative extrapolation to T ⫽ 0 K assuming that L(0) ⫽ L 0.
In order to illustrate further when the Wiedemann-Franz law is valid, we express the
thermal conductivity κ el on a form analogous to Eq. (5) for electrical conduction (3,4):
冢冣冮
2 ω
1 1 4π max (hω/kBT)
⫽
κ el L 0T ω pl 0 0 [exp(hω/k BT) ⫺ 1] [1 ⫺ exp(⫺hω/kB T)]
(14)
冦冤冢冣冥冢冣冧
2 2
1 hω 3 hω
⫻ 1⫺ 2 α F(ω) ⫹ 2
2
tr α F(ω) dω
2
2π kBT 2π kB T
Figure 4 The Lorenz number L(T ) as a function of T for Fe, after Ref. 21 (thick line), and with a
tentative extrapolation to L ⫽ L 0 at low T (thin line), where impurity scattering dominates.
Here α 2 F(ω) is an electron-phonon coupling introduced later (Sec. V). It is the inelastic nature
of the scattering of electrons by phonons that affects the electrical and thermal conductivities
differently, and therefore is one reason why in pure specimens L ≠ L 0 at temperatures T ⬍ θ D ,
where θ D is a characteristic Debye temperature for the solid considered. We see that the Wiede-
mann-Franz law is valid if we can neglect at term
冢冣
2
1 hω
[3α 2 F(ω) ⫺ α 2tr F(ω)] (15)
2π 2 kB T
in the integrand of (14). That is a very good approximation when T ⬎ θ D. When T ⬍⬍ θ D,

electron scattering by impurities may dominate the electron-phonon scattering. Then τ el ⫽ τ imp,
and L ⬇ L 0 is often a good approximation; see Fig. 4. There are also corrections to the ideal
Wiedemann-Franz law caused by electron band structure effects and by a term related to the
thermoelectric power, but we refrain from further comments on them in this chapter.
B. Phonon Contribution to the Thermal Conductivity

In metals the major contribution to the thermal conductivity comes from the conduction elec-
trons. But it is an insulator, diamond, that has by far the highest thermal conductivity at room
temperature, showing that conduction through phonons is not always small. The total thermal
conductivity κ tot is the sum of an electronic part κ el and a phonon (lattice) part κ lat :
κ tot ⫽ κ el ⫹ κ lat (16)
The electronic part was dealt with in the previous subsection. The phonon part is very difficult
to model accurately. In a standard textbook model, taken from the theory of thermal conduction
in gases, one can formally write
1 1
κ lat ⫽ Clat C 2 τ lat ⫽ Clat Cᐉ lat (17)
3 3
where Clat is the phonon (lattice) heat capacity, C is an average sound velocity, τ lat is an average
phonon lifetime, and ᐉ lat ⫽ Cτ lat is the corresponding mean free path. In analogy to the scattering
of electrons by independent mechanisms, leading to Eq. (10), we can distinguish between various
contributions to τ lat :
1 1 1 1 1
⫽ ⫹ ⫹ ⫹ (18)
τ lat τ size τ def τ ph-ph τ ph-el
In small and pure systems, and at low temperature, the mean free path of the phonons may
approach a characteristic dimension (size) of the specimen. That limits a further increase in τ lat ,
through the term τ size . Impurities and other lattice defects give a contribution τ def. Both τ size and
τ def are temperature independent. The phonon-phonon interaction gives a temperature-dependent
τ ph-ph , which at high T and in a simple model varies inversely with the number of excited phonons,
i.e., as 1/T. At these temperatures, the heat capacity C lat has approximately the classical Dulong-
Petit value of 3k B per atom. If then τ ph-ph gives the most important contribution to τ lat , Eq. (17)
implies that the lattice contribution to the thermal conductivity varies as τ ph-ph , that is, as 1/T.
With decreasing T, typically below θ D /2, τ ph-ph increases exponentially in 1/T, which leads to a
rapidly increasing κ ph-ph . Eventually τ ph-ph will be so large that τ def or τ size , which are both indepen-
dent of T, dominates τ lat . Then κ lat has the same temperature dependence as the heat capacity
C lat(T ), i.e., varying as T 3 at very low temperatures. This would be the description of κ lat in
182 Grimvall
insulators. In metals we must also consider the scattering of phonons by conduction electrons,
described by τ ph-el in Eq. (18).
Relations (17) and (18) are deceptively simple but present enormous difficulties if one
wants more than a crude numerical estimate. A major root of the difficulty is that τ ph-ph requires
an average over terms involving the anharmonic phonon-phonon interaction. In fact, attempts
at accurate such calculations have been made for only a few solids, mainly alkali halides and
solid noble gases. Also, the phonon-electron term τ ph-el is difficult to calculate. Little is therefore
known through direct calculation about the magnitude of κ lat in metallic systems. Instead, κ lat
is often inferred from measurements of the total thermal conductivity, after subtraction of an
electronic part κ el that is obtained from the experimental electrical conductivity and the applica-
tion of the Wiedemann-Franz law with L ⫽ L o . It is believed that in many transition metals κ lat
makes an almost negligible contribution to κ tot, say κ lat ⬇ 0.1 κ el at room temperature. But the
refractory compounds dealt with here show a behavior quite different from that of normal transi-
tion metals. For instance, measurements by Morelli (22) on TiC 0.95 suggest that the thermal
conductivity is dominated by the lattice part, κ el being about 25% of κ tot at 300 K and only
about 5% at 100 K; see Fig. 5. Those thermal conductivity data essentially agree with earlier
measurements by Radosevich and Williams (23).
Some unexpected features arise from the studies of Morelli (22) and Radosevich and
Williams (23). The thermal conductivity of TiCx at low T increases with increasing x, i.e., with
more vacant carbon sites. This fact shows that phonon scattering by vacancies is rather unimport-
ant, contrary to the case of electron scattering in the electrical conductivity. Instead, the vacan-
cies affect the electron structure through τ ph-el . This is important because τ lat at low T is strongly
limited by τ ph-el in TiC.
An account of κ lat through a fitting of parameters that describe the various contributions
to τ lat in Eq. (18) leaves many uncertainties, not only because of the large number of fitting
Figure 5 The lattice contribution κ lat to the thermal conductivity of TiC 0.93 and the total thermal conduc-
tivity κ tot ⫽ κ lat ⫹ κ el . The lattice part κ lat is deduced from the measured total thermal conductivity κ tot by
subtracting an electronic part κ el that is calculated from the measured electrical resistivity and assuming
the Wiedemann-Franz law with L ⫽ L 0. After experiments by Morelli (22).
parameters but primarily because we have no universally valid and simple theoretical expres-
sions to fit to. Work by Radosevich and Williams (23) illustrates well the difficulties one encoun-
ters. Finally, we note that in analogy to the electrical resistivity saturation in systems with strong
electron scattering, a saturation may also take place in κ lat when ᐉ lat becomes of the order of
the interatomic distance a.
There are few measurements of the thermal conductivity of refractory compounds. Wil-
liams et al. (24) measured κ(T ) in TiB 2. Radosevich and Williams (25) [see also Williams (26)]
measured κ in normal and superconducting NbC. In a conventional superconductor, the thermal
conductivity decreases on the transition to the superconducting state. The reason is that the
electrons in the superconductor cannot transport heat because they would fall into the forbidden
energy gap if they lost energy. (A superconductor is not a ‘‘thermal superconductor,’’ and the
Wiedemann-Franz law is not valid.) Contrary to this behavior, κ tot in NbC increased as one
passed below Tc . This can be understood from the dominating role of κ lat, which is limited by
τ ph-el . In the superconducting NbC the phonon-electron interaction becomes weaker and hence
κ lat increases.
IV. CONDUCTION IN INHOMOGENEOUS MATERIALS

A. Two-Phase Materials
Many materials of practical interest consist of two or several phases. An important special case
is a porous material, in which the voids can be regarded as a separate phase. The mathematical
results given in this section, and in the following section on anisotropic materials, hold equally
well for the thermal conductivity κ and the electrical conductivity σ.
Suppose that we know the conductivities κ i of each phase i and their volume fractions f i
with ∑ f i ⫽ 1. Further, neglect any grain boundary effects. The overall conductivity κ eff is always
bounded from above and below by the conductivities of a corresponding material in which the
same amounts of the phases are arranged in a series or parallel coupling, as in lamellar or fiber
composites. Another, and nontrivial, geometry is one in which the phases are distributed so as
to make κ eff isotropic, in a statistical sense. This would be the case in a random distribution of
inclusions in a matrix. Then κ eff is bounded from above and below by the Hashin-Shtrikman
(27) bounds κ HS⫹ and κ HS⫺. With two phases, i ⫽ 1 and 2, one has
f2
κ HS⫺ ⫽ κ 1 ⫹ (19)
1/(κ 2 ⫺ κ 1) ⫹ f1 /(3 κ 1)
Here labels 1 and 2 are chosen so that κ 2 ⬎ κ 1 , and both phases are assumed to have isotropic
κ. The upper bound κ HS⫹ is obtained by interchanging the labels 1 and 2 in Eq. (19).
One may also try to get a direct estimate κ* of κ eff , rather than limiting κ eff by bounds.
There are several schemes to accomplish this. We shall exemplify them with one version of
what is called an effective medium theory. In its simplest form it assumes that each individual
grain of a phase does not deviate systematically from a spherical shape. Then κ* is the solution
to the equation
冢 κ 1 ⫺ κ*
κ 1 ⫹ 2κ* 冣冢
f1 ⫽
κ* ⫺ κ 2
κ 2 ⫹ 2κ*
f2
冣 (20)
In the ‘‘dilute limit,’’ i.e., when the volume fraction of the inclusions in a matrix is so low that
one may neglect the mutual influence of two neighboring inclusions on the overall properties,
184 Grimvall
exact results can be obtained for ellipsoidal inclusions. In the special case of spherical inclusions
(phase i) in a matrix (phase m) one has
冤
κ eff ⬇ κ m 1 ⫺ fi
2κ m ⫹ κ i 冥
3(κ m ⫺ κ i )
(21)
For pores, corresponding to κ i ⫽ 0, Eq. (21) reduces to

3
κ eff ⫽ κ m [1 ⫺ fi] (22)
2
which coincides with the upper Hashin-Shtrikman bound for fi ⬍⬍ 1.
There are many, more or less fundamental, relations aiming at a description of conduction
in inhomogeneous materials. They come under various names, and some of them are in fact
identical, although that may not be immediately apparent. For instance, the Maxwell-Eucken
relation cited by Williams et al. (9) and used by them to correct for the presence of Ti 2 O 3 in
TiB 2 is identical to the upper Hashin-Shtrikman bound. Generalizations of such relations to
three or more phases, to ellipsoidal inclusions, etc. are reviewed in Ref. 3.
Relations such as (19) and (20) assume that one can ignore grain boundary effects. That
is usually a good approximation, because the region of a grain boundary, where the atomic
arrangement and composition differ from those of the bulk phases, has a width of only a few
atomic diameters. It could then be viewed as another phase, occupying a very small volume
fraction of the composite material, and methods of the type discussed in this section could be
applied. However, there are cases in which complications arise, as will be now be exemplified.
Both TiB 2 and SiC have thermal conductivities more than five times higher than that of cold-
pressed titanium. In an experiment (28) particulate composites were made by cold-pressing Ti
powder with either TiB 2 or SiC particles, followed by a heat treatment and extrusion. For Ti-
TiB 2 the thermal conductivity of the composite was higher than that of the matrix Ti material,
as expected, but in the case of Ti-SiC the conductivity was lower. This result was explained
by reactions at the interface between Ti and SiC. The reaction products caused a large (4.6%)
volume expansion in the reaction zone, leading to interfacial cracking and poor thermal contact.
B. Average Conductivity in Noncubic Lattice Structures

In a lattice with cubic symmetry the single-crystal conductivity is isotropic. Hence it is also
isotropic in a polycrystal, irrespective of the geometric arrangement of the individual grains. This
is the case, e.g., for TiC that has an NaCl-type lattice structure. TiB 2 has hexagonal structure, and
its single-crystal conductivity is characterized by the conductivities κ c (along the crystallo-
graphic c-axis) and κ a (in the plane perpendicular to the c-axis). The effective conductivity κ eff
of a polycrystal, of course, must lie between the values κ c and κ a that will be attained when all
the single crystals in a specimen have aligned crystallographic c-axes. If the arrangement of
grains is such that the conductivity of the specimen is isotropic, κ eff always lies between the
bounds
⫺1
3
冢
2
⫹
1
κa κc 冣 ⱕ κ eff ⱕ
1
3
(2κ a ⫹ κ c) (23)
For a polycrystal in which the individual grains are more or less spherical and with random
crystallographic orientation, the effective conductivity is isotropic. It can be approximated by
an effective-medium result κ* (29) that, for hexagonal symmetry, has the form
1
κ* ⫽ [κ a ⫹ (κ 2a ⫹ 8κ a κ c) 1/2 ] (24)
4
The anisotropies κ c /κ a and σ c /σ a for the thermal and electrical conductivities in TiB 2 and related
noncubic compounds seem not to be known but are thought to be weak. As a numerical illustra-
tion, let us assume that κ c /κ a ⫽ 1.1. Then, from Eq. (23), 1.03125κ a ⱕ κ eff ⱕ 1.03333κ a, while
Eq. (24) gives κ* ⫽ 1.03262κ a . Correspondingly, with κ c /κ a ⫽ 1.3 we get 1.08333κ a ⱕ κ eff ⱕ
1.11000κ a and κ* ⫽ 1.09410κ a .
V. SUPERCONDUCTIVITY
The transition temperature Tc of the traditional superconductors of interest here (as opposed to
the more recently discovered high-temperature superconductors) depends on the strength of the
electron-phonon interaction parameter λ el-ph . It can be written in the form
冮 α 2 F(ω)
max
λ el-ph ⫽ 2 dω (25)
0 ω
We immediately see the similarity to the parameter λ tr of Eq. (7). The electron-phonon coupling
function α 2 F(ω) essentially differs from α 2tr F(ω) in that the latter function contains an average
over a geometric factor 1 ⫺ cos θ, where θ is the angle between the wave vectors of the initial
and final states of an electron in a scattering event. Since the average of 1 ⫺ cos θ is rather
close to 1, it may be a good approximation to take λ tr ⬇ λ el-ph . The function α2F(ω) can be
measured by tunneling in superconductors; see Tralshawala et al. (6) and Fig. 1 for VN and
Kihlstrom et al. (30) for NbN.
The quantity λ el-ph enters two important physical relations. It gives the electron-phonon
enhancement of the low-temperature electronic heat capacity as Cel ⫽ γT ⫽ γ bandT(1 ⫹ λ el-ph),
where γ band T is the heat capacity obtained from the electron band structure without regard to
the electron-phonon interaction. The other important relation, of particular interest here, is the
connection between λ el-ph and the transition temperature T c. An accurate calculation of T c requires
the solution of the Eliashberg equations, which explicitly take into account the shape of α 2 F(ω).
In many practical applications one instead obtains Tc from a semiempirical relation containing
α 2 F(ω) in the form of the average λ el-ph , Eq. (25). The most frequently used such relation is
that due to McMillan (31). It reads
Tc ⫽
θD
1.45
exp 冤
⫺1.04(1 ⫹ λ el-ph )
λ el-ph ⫺ µ*(1 ⫹ 0.62λ el-ph ) 冥 (26)
Here θ D is a Debye temperature and µ* is a parameter measuring the strength of the electron-
electron interaction. The latter is not very accurately known. For many systems, including transi-
tion metals, it is usually assumed that µ* lies in the interval 0.10–0.13. Equation (26) is often
used to derive λ el-ph from a known Tc . It could also be used in the reverse direction, to estimate
Tc from a λ el-ph that is theoretically calculated or inferred from, e.g., λ tr and resistivity data. The
parameters θ D , λ el-ph , and µ* in Eq. (26) that determine Tc do not depend sensitively on lattice
defects, but with the large variations in vacancy concentration and specimen state encountered
for the compounds reviewed here, there are significant variations in Tc ; see Table 2.
186 Grimvall
Table 2 Exemplifying That the Transition Temperature Tc to Superconductivity

Depends on the Composition x a
Compound x Tc (K) Reference
NbC 0.96 10 Shacklette et al.(32)
NbC x 0.92–0.98 6–10 Storms et al. (33)
NbC x 0.83–0.97 2–10 Dy and Williams (15)
TaC x 0.98 10 Dy and Williams (15)
TiN 6 Wokulski and Sulkowski (34)
ZrN x 0.98 10 Storms et al. (33)
VN 9 Zasadzinski et al. (35)
VN x 0.70–0.98 4–9 Chen et al. (36)
VN x 0.64–0.99 4–9 Zhao et al. (37)
VN x 0.75–1 2–8 Ajami and MacCrone (38)
NbN 16 Gray et al. (39)
NbN x 0.82–0.95 14–16 Chen et al. (36)
TaN x 0.95 8 Chen et al. (36)
a
Tc also depends on the state of the specimen (mode of preparation).
VI. TRANSPORT PROPERTIES RELATED TO MAGNETISM
We shall consider two refractory compounds in which electron scattering due to magnetic effects
may appear: TiB 2, which shows a resistivity minimum at low temperatures that has been attrib-
uted to the Kondo effects, and VN, in which spin fluctuations have been suggested to affect
the resistivity.
Measurements of ρ(T ) for TiB 2 by Williams et al. (9) from 4.2 to 300 K showed a resisti-
vity minimum in the range 34–47 K. A normal resistivity term ρ el-ph (T ) could be extracted. It
was well described by a Bloch-Grüneisen expression varying as T 5 at low T and with θ R ⫽ 720
K. The latter value seems reasonable, when compared with θ S; see Table 1. The Kondo effect
is caused by a spin-flip interaction between conduction electrons and localized magnetic mo-
ments of impurity atoms. Ni impurities are essential, but there are still several unsolved problems
in the interpretation of the Kondo minimum in TiB 2.
It has generally been assumed that spin fluctuations in strongly paramagnetic systems
contribute a term to the electrical resistivity, as well as a related enhancement of the electronic
heat capacity, with a characteristic coupling parameter λ sp in analogy to the quantity λ el-ph intro-
duced in Sec. V. There is not yet a theoretical description that can give a good numerical estimate
of the magnitude of the effect. It has sometimes been regarded as an explanation for an extra
term, beyond standard descriptions, that has seemed necessary to account for experimental re-
sults, e.g., in VN; see Refs. 35, 37, 38, 40 and 41.
The Hall coefficient has been studied for a few of the compounds reviewed here. It has
helped to distinguish between effects due to changes in the carrier density and effects due to
defect scattering in nonstoichiometric compounds; see Modine et al. (7,42) for work on TiC,
ZrC, and HfC with varying vacancy concentration; Santoro and Dolloff (17) for similar work
on TaC; and Shacklette and Ashworth (43) for the effect of vacancy ordering in VC.
VII. EXPERIMENTS ON TRANSPORT IN CARBIDES, NITRIDES, AND

BORIDES
We end this review by giving references in Tables 3 and 4 to experiments on transport properties
in some carbides, nitrides, and borides formed by group IV and V transition metals. The list is
Table 3 Some References to Transport Properties of Transition Metal Carbides:

Electrical Resistivity (ρ) and Thermal Conductivity (κ)
Compound References Property
TiC Modine et al. (7) ρ, Hall coefficient
Shacklette and Williams (12,13) ρ
Otani et al. (14) ρ
Lorenzelli et al. (16) ρ
Lei et al. (44) ρ
Wokulski and Sulkowski (34) ρ, Ti(C,N)
Radosevich and Williams (23) κ
Morelli (22) κ, thermoelectricity
ZrC Modine et al. (7,42) ρ, Hall coefficient
Allison et al. (8) ρ
Lei et al. (44) ρ
Radosevich and Williams (23) κ
HfC Modine et al. (7) ρ, Hall coefficient
Lei et al. (44) ρ
Dy and Williams (15) ρ
VC Allison et al. (8) ρ
Otani et al. (14) ρ
Shacklette and Ashworth (43) κ, Hall coefficient
NbC Shacklette et al. (32) κ (T ⬎ Tc ; T ⬍ Tc)
Radosevich and Williams (25) κ (T ⬎ Tc ; T ⬍ Tc)
Williams (26) κ (T ⬎ Tc ; T ⬍ Tc)
TaC Santoro and Dolloff (17) ρ, Hall coefficient
Allison et al. (8) ρ
Cooper and Hansler (45) ρ
Table 4 Some References to Transport Properties of Transition Metal Nitrides

and Borides: Electrical Resistivity (ρ) and Thermal Conductivity (κ)
Compound References Property
TiN Lei et al. (44) ρ
ZrN Lei et al. (44) ρ
HfN Lei et al. (44) ρ
VN Tralshawala et al. (6) ρ
Zasadzinski et al. (35) ρ
Zhao et al. (37) ρ
Ajami and MacCrone (38) ρ
NbN Gray et al. (39) ρ
Nigro et al. (46) ρ
TiB 2 Williams et al (9) ρ, Kondo effect
Williams (26) ρ, κ, Seebeck coefficient
McLeod et al. (47) ρ
Rahman et al. (48) ρ
Choi et al. (49) ρ
ZrB 2 Rahman et al. (48) ρ
188 Grimvall
not complete. In particular, many old references have been left out, often because the data were
obtained with poorly characterized specimens. Many of the experiments cited refer to thin films.
They usually contain lattice defects that strongly affect the transport properties and hence may
not reflect the properties of bulk specimens.
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9. RK Williams, PF Becher, CB Finch. Study of the Kondo effect and intrinsic electrical conduction
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8
High-Temperature Characteristics
Yukinobu Kumashiro
I. INTRODUCTION
These refractory metalloids are frequently considered for employment whenever extreme envi-
ronments are to be encountered. The meaning of ‘‘high temperature’’ and the value assigned
to it vary among industries and disciplines. Melting point is the most important criterion in the
selection of materials for high-temperature applications.
Interest in the carbides and diborides as cathodes in Hall-Heroult cells has a long history,
which is due to good corrosion resistance in the use environment, high electrical conductivity,
and good wettability by molten aluminum. There is some industrial production of crucibles of
titanium diboride for vaporization of metals in high vacuum and at high temperature. High-
thermal-conductivity TiB2 and ZrB2 are used for thermocouple protection and tubes in steel
baths and in aluminum. Diboride would be desirable for application in rocket nozzles, combus-
tion chambers, and jet engine turbines. Titanium carbide and diborides are materials for a possi-
ble first-wall fusion reactor because of their low atomic numbers. When designing new materials
for high-temperature structural ceramics, constituents with similar thermal expansion coeffi-
cients must be chosen, because large differences in the expansion coefficients would create large
stress in the materials.
For the various high-temperature applications mentioned above it is necessary to clarify
high-temperature electrical, thermal, and mechanical properties using well-characterized speci-
mens.
Applications for carbides and diborides would include cathodes for advanced thermionic
energy conversion, high-current-density field emission cathodes. These require spectral emit-
tance data, which are also related to measuring accurate high temperatures.
High-temperature vaporization behaviors that yield high-temperature thermodynamic data
such as activity and enthalpy are necessary for uses as nuclear reactor and fusion materials.
High-temperature activity measurements make it possible to determine the Gibbs free energy
of formation of compounds from the elements. Accurate high-temperature thermodynamic data
serve to establish temperature-composition phase diagrams, i.e., limits for the formation of bi-
nary phases.
Self-diffusion processes play major roles at high temperatures in the relief of residual
stresses and plastic deformation, sintering, homogenization, and grain growth.
In this chapter emissivity measurement; vaporization behavior; diffusion studies; and elec-
trical, thermal, and mechanical properties at high temperatures will be discussed.
191
192 Kumashiro
II. EMITTANCE
The spectral emittance is defined as the ratio of the radiant power per unit area leaving the
surface of a body at some given wavelength to that leaving a blackbody at the same temperature.
The spectral emittance can be determined practically by comparing the observed or apparent
surface temperature of a material with that of a blackbody cavity existing in the same material.
The normal spectral emittance is a special case in which the viewing direction is normal to the
smooth, opaque surface of the crystalline material. Emissivity is a property of the surface of
real specimens.
Emittance was calculated from
⑀ 2 (T ) ⫽ exp[C/λ(1/αTBB ⫺ 1/αTsurf )] (1)
where TBB is the pyrometer temperature in K shown by the blackbody cavity, Tsurf is the pyrometer
temperature in K measured on and in a direction normal to the surface of the specimen, C is a
constant (C ⫽ hc/k ⫽ 14388 µm-K), and λ is the wavelength of the light detected. The emittance
measurements were taken at the commonly used pyrometer wavelength of 0.65 µm. The α is
a correction for the brightness lost in transmission through the Pyrex viewpoint.
The normal spectral emittance of crystalline carbides by floating-zone arc refinement were
measured in vacuum (10 ⫺8 or low 10 ⫺7 torr) in the temperature range 1200 ⬍ T ⬍ 2400 K (1).
Reproducible results within the errors were obtained after thermally cleaning these carbides,
despite variations in surface roughness or the type of pyrometer used for the temperature mea-
surements. The values for emittance are for samples that were clean as determined by Auger
analysis. The emittance of HfC0.86 tends to increase slightly with temperature, whereas those of
NbC0.83, TaC0.79 , TiC0.98 and ZrC0.92 decrease
⑀ HfC ⫽ 0.4322 ⫹ 1.065 ⫻ 10 ⫺6 T

⑀ NbC ⫽ 0.4913 ⫺ 6.6 ⫻ 10 ⫺5 T
⑀ TaC ⫽ 0.4662 ⫺ 5.084 ⫻ 10 ⫺5 T
⑀ TiC ⫽ 0.8192 ⫺ 1.66 ⫻ 10 ⫺4 T
⑀ ZrC ⫽ 0.715 ⫺ 1.174 ⫻ 10 ⫺4 T
III. VAPORIZATION BEHAVIORS
High-temperature activity measurements for carbide as a function of composition and tempera-

ture were performed by using knundsen effusion in a mass spectrometer (2–4). A Langmuir
measurement at the congruently vaporizing composition (CVC) was made, from which absolute
pressures were obtained. These data give heat and entropy of vaporization and total vaporization
energy, defined as the heat needed to produce 1 mole of vapor having the composition of the
solid.
Activities at 2300 and 2500 K for NbC are plotted as a function of composition in Fig.
1. From a smooth curve through these points, the activity of carbon was calculated by a Gibbs-
Duhem integration. Compositions at the low-carbon boundary of NbC were obtained at 2300
and 2500 K from the intersection between the horizontal line that represents the activity in the
two-phase region, Nb2 C ⫹ NbC, and the curve through the single-phase points in Fig. 1. The
heat formation and the entropy tend to show an increasing deviation from other measurements
as the NbC phase becomes more defective. This discrepancy is reduced considerably if only
High-Temperature Characteristics 193
Figure 1 Activities of niobium and carbon at 1700 and 2000 K as a function of composition. (From
Ref. 2.)
Figure 2 Activities of vanadium and carbon at 1700 and 2000 K as a function of composition. (From
Ref. 3.)
part of the randomization entropy is added to the measured entropy so that the material used
for the heat capacity and heat content measurements was partially ordered.
The activity of vanadium at 1700 and 2000 K is shown as a function of composition in
Fig. 2. The phase boundaries at 1700 and 2000 K for V2 C and VC were obtained from Fig. 2
by noting where the curve through the single-phase regions intersected the horizontal line
through the two-phase regions. There is an indication of a break in the 1700 K activity curve
near VC0.66, which might be due to the presence of ζ phase. This effect is gone at 2000 K. The
activity measurements place the upper V2C boundary at VC0.58 and 1700 K with a slight trend
to higher compositions as the temperature is increased. VC exists between VC0.74 and VC0.91 at
1700 K. At the upper composition, the vacancy order at 1403 K give V8C7 and graphite. A
stable phase exists between V2C and VC below approximately 1800 K that has a stoichiometry
of V3 C 2 . V2 C extends from VC0.45 to VC0.56 at 1700 K. The failure to observe the upper composi-
194 Kumashiro
tion in quenched material would be attributed to rapid precipitation of VC at the order-disorder

transition in V2C.
The zirconium activity for each composition (Fig. 3) accounts well for results calculated by
Guillermet (5) using phenomenological models for the Gibbs energy function, i.e., the compound
energy model (CEM). The lower phase boundary at 2100 K was placed at ZrC0.565 . The behavior
of the partial enthalpy indicates that this boundary will move only slightly to higher compositions
as the temperature decreases. The upper boundary at 2100 K is at ZiC1.0 and moves to lower
compositions as the temperature is increased. ZiC0.975 will contain two phases above 2603 K,
so compositions near ZrC0.96 commonly occur because the material is in equilibrium with carbon
at some very high temperature, suggesting that the stoichiometry of ZrC may actually exceed
unity below 2100 K. The change in zirconium activity with the carbon content of the ZiC phase
is most rapid in the high-carbon region. Near ZrC0.8 the rate becomes much lower and remains
constant down to the low-carbon boundary. The partial molar heat of vaporization also shows
two regions with a transition near ZrC0.8 . The composition of the upper phase boundary at 2100
K is ZrC1.0 , and this changes to lower compositions as the temperature is increased. The low-
carbon boundary moves slightly to higher compositions as the temperature is reduced.
ZiC2 has been found over ZrC ⫹ C at 2660 K with a ZrC2 /Zr ratio of 0.06. This compares
with 0.04 for NbC2 /Nb, 0.005 for TiC2 /Ti, and 0.003 for VC2 /V at the same temperatures corre-
sponding to the ionic bond in the solid; i.e., the more ionic the bond in the solid, the more stable
the MC2 vapor in the gas.
During vaporization of carbides (MC) the surface composition changes with time due to
Figure 3 Zirconium and carbon activities at 2100 K for various compositions. (From Ref. 4.)
incongruent loss of metal (M) and carbon (C) atoms, eventually approaching a CVC (6), where
M and C atoms are removed in a ratio equal to that present on the solid surface. The temperature
dependence of a M and a C and the molar vaporization rate of M and C estimated by Langmuir’s
model determine CVC. Calculated CVC values in NbC are in excellent agreement with the
observed value above 2600 K. The experimental compositions for ZrC are ⬇ 2% smaller than
the calculated value, and those for HfC are ⬇ 12% greater than the calculated values. The
calculated values for VC are larger than the values for the carbon-rich phase boundary in the
VC phase, suggesting that VC vaporizes incongruently to C. TiC also vaporizes incongruently
to C below 2700 K. The surface composition determines the equilibrium vapor pressure of metal
and carbon atoms and influences the overall loss of carbide, which is determined in large part
by solid-state diffusion of C. Figure 4 summarizes the congruent mass vaporization rates for
graphite, TiC, ZrC, HfC, NbC, and VC (6).
In laser diagnostic methods developed to study the vaporization behavior of ZrC (7), a
vapor phase was produced by laser ablation of a ZrC target. The temperatures of the plasmas
are estimated to be between 9000 and 12,000 K. Thermodynamic calculations for 9000 K predict
that C 3 has the highest partial pressure, followed by C2 and C5. Zirconium has the lowest calcu-
lated partial pressure. The dominant neutral gas species of an expanding plasma plume are
predicted to be Zr and C followed by, in decreasing order of importance, C2 , C3 , C4 , and C5 .
The optical emission spectra of the ablated ZrC from 200 to 500 nm at delay times from 10 µs
to 1 ms (Fig. 5) contain lines only for excited Zr. Emission peaks from C, C2 , and C3 were
absent from the spectra, apparently because of the inherently low emission intensities of these
species compared with that of Zr, which has a very strong spectrum in the ultraviolet frequency
range.
On the contrary, the experimental partial pressures of N2 , p(N2), as a function of composi-
tion over ZrN in the literature show significant scatter, which would be largely due to the wide
homogeneity range of the nitride and the preferential loss of nitrogen from the sample surface:
Fig. 6 shows the Zr activity a(Zr) and p(N2) in the face-centered cubic (fcc) phase at 2000 K
(8). The activity coefficient of Zr decreases with increasing nitrogen constant, indicating that
Zr is stabilized with increasing nitrogen content. At the same time p(N2) increases progressively
with increasing nitrogen content.
Figure 4 Congruent mass vaporization rate for carbides. (From Ref. 6.)
196 Kumashiro
Figure 5 ZrC ablation plume emission spectrum at 10 µs delay. (From Ref. 7.)
Figure 6 Component activities at 2000 K as a function of nitrogen content. Calculated (solid curve)
and experimental (circles) results are shown. (From Ref. 8.)
IV. DIFFUSION STUDIES
The most commonly defined diffusion coefficients are the chemical or interdiffusion, intrinsic
diffusion, and tracer or self-diffusion coefficients. The relevant coefficient depends on the driv-
ing force. The diffusion coefficient exhibits Arrhenius behavior, according to the relationship
D ⫽ D0 exp(⫺Q/RT), where D 0 is the preexponential factor and Q is the activation energy. The
activation energy involves the activation enthalpy and entropy value. The entropy values are
consistent with Zener’s theories of volume diffusion. A driving force for diffusion includes any
influence that increases the jump frequency. Examples of driving forces include chemical poten-
tial, thermal, and stress gradients. The use of single-crystal or well-characterized specimens is
important for accurate data and interpretation. Diffusion along grain boundaries in polycrystal-
line specimens tends to lower both D 0 and Q.
Because very little is known about diffusion in diboride, this discussion is restricted to
carbides and nitrides. The mechanism of diffusion in transition metal carbides and nitrides differs
for metal and nonmetal sublattices. The nonmetal diffusion proceeds via a vacancy mechanism
in the nonmetal sublattice because the vacancy concentration is a function of composition within
the homogeneity range of fcc phases (9,10).
The self-diffusivity of the transition metal in carbides is composition independent, and
that of carbon is greater than that for the metal atom by several factors of 10. For metal atom
diffusion, formation and migration terms are needed in the diffusion equation. In the metal
sublattice, vacancies are formed thermally by Schottky disorder, and these concentrations may
be assumed to be independent of the composition, as confirmed by the experimental data (10).
Sarian (11–14) and Yu and Davis (15,16) studied systematic variation of the composition for
carbides to propose a common diffusion mechanism. Table 1 lists D 0 and Q for various transition
metal carbides. The experimental temperatures were high enough that any residual order and
hence nonrandom vacancy distribution would be assumed to have no influence on matter trans-
port processes.
Sarian (14) pointed out that the activation entropy and enthalpy for carbon migration in
VC, TiC, and ZrC are proportional to the melting points and concluded that the geometry of
the diffusion path, as well as that of the vacancy distribution, is common to all three compounds.
The results are in substantive agreement with the Zener model for the diffusion of interstitials.
Yu and Davis (15,16) have argued that, at least for NbCx , the exact diffusion path for carbon
may change as a function of composition. The notable difference in the D 0 and Q values between
the higher C content crystals (NbC0.87 and NbC0.84) and the lower C content crystal (NbC0.766)
was caused by the presence of two diffusion mechanisms. In the former two materials, the
Table 1 Arrhenius Coefficients for Carbon-14 Self-Diffusion in Transition Metal Carbides
Temp.
Composition D0 (cm2 /s) Q (kcal/mol) range (°C) Reference
TiC 0.97 6.98 95.3 1475–2720 11
TiC 0.89 45.44 106.8 1450–2280 11
TiC 0.67 1.14 ⫻ 102 109.9 1745–2080 12
TiC 0.67 2.85 ⫻ 10⫺4 49.6 2080–2720 12
ZrC 0.97 1.32 ⫻ 102 113.2 1350–2150 13
VC 0.84 2.65 85.0 1700–2200 14
NbC 0.87 2.59 100.4 1630–2040 15
NbC 0.84 7.44 105.0 1630–2040 15
NbC 0.76 2.22 ⫻ 10⫺2 76.0 1630–2040 15
198 Kumashiro
dominant mechanism of 14C transport would be the movement of these species from an occupied
octahedral site to a similar vacant octahedral site via a neighboring tetrahedal position (O-T-O
mechanism) with an effective jump distance a 0 /√2 and shorter ⬍111⬎ jump. Two jumps are
involved in going to and from the tetrahedral site. In NbC0.766 , however, 14 C is thought to move
to the vacant octahedral site via an Nb vacancy. The latter process necessitates the formation
of a transient ‘‘divacancy’’ between the vacant C and Nb sites in which the diffusing 14 C atom
only momentarily resides in the Nb vacancy. The presence of a large number of structural C
vacancies in all compositions would indicate that the activation energy for the (O-T-O) and
transient divacancy mechanisms would consist essentially of the C migration energy in the
former and the energy of Nb vacancy formation in the latter transport path.
The Nb vacancy formation energy for NbC0.750 is 60.49 kcal/mol according to the vapor
pressure data (2), which is in line with the 76.0 kcal/mol Q value found in NbC0.766 . The Nb
self-diffusion coefficients for NbC0.868 . NbC0.834 , and NbC0.766 are essentially independent of the
C/Nb ratio in the temperature range 2370–2660 K and are expressed as
冢
D *Nb ⫽ 4.54
⫹2.85
⫺1.75 冣
exp[⫺(140.0 ⫾ 2.4 kcal/mol)/RT ] cm 2 /s (2)
The 95 Nb migration energy depends on the size of the relevant gap in each mechanism through
which the Nb atoms must pass to reach the analogous vacancy. Then Nb atoms diffuse by the
(O-O) mechanism, just as a pure metal diffuses in an fcc lattice, in which the atom migrates
from its lattice position directly to an analogous vacant site. The activation energy, Q, for self-
diffusion in fcc metals is given by Q/Tm ≅36 cal/K. Using Tm ⫽ 3873 K for niobium carbide,
the Q is found to be 139.4 kcal/mol, which is in excellent agreement with the experimental
value of ≅ 140 kcal/mol.
Modeling the diffusion-coupled vaporization process associated with nonstoichiometric
carbides requires the use of the chemical diffusion coefficient to calculate the temporal concen-
tration (6,17). The chemical diffusion coefficient has a strong concentration dependence and
has been determined mainly by layer growth, where a diffusion couple consisting of C and M
is held at a temperature for varying times. The activation energy for chemical diffusion is smaller
than that for self-diffusion in a single crystal. However, there is one report on chemical diffusion
using a TiC single crystal (18). The diffusion of carbon was allowed to proceed in a chemical
gradient to induce the following expression:
D ⫽ 220 exp[⫺(97.7 kcal/mol)/RT] cm 2 /s (3)
Good agreement between self-diffusion and chemical diffusion was obtained. A smaller activa-
tion energy in chemical diffusion would be short-circuited by a grain boundary referring to grain
boundary diffusion (19) rather than volume diffusion. Then the data on chemical diffusion for
various carbides should be revised by using single crystals.
In transition metal nitrides, nitrogen diffusivity is studied mainly by phase-band growth
as a function of time and temperature under the assumption that nitrogen is the only diffusing
species (20). Table 2 summarizes the diffusion data for nitrides obtained from nitridation kinetics
at high temperatures.
Although the metal diffusivity in transition metal nitrides has not yet been investigated
in detail, the activation energy of that process is probably much higher than that of nitrogen
diffusivity by two to three times (26). Data referring to chemical diffusion obtained from nitrida-
tion kinetics at relatively high temperatures, i.e., values of D 0 and Q obtained at T ⬍ 1200°C
Table 2 Collected Diffusion Data for Nitrides with NaCl-Type Structure

Temp.
Materials D0 (cm2 /s) Q (kcal/mol) range (°C) Reference
δ-TiN 2.3 ⫻ 10⫺3 50.2 1300–1600 21
δ-ZrN 6.0 ⫻ 10⫺2 59.8 1250–1700 22
1.7 ⫻ 10⫺2 53.6 1260–1720 22
3.12 79.0 1200–1500 22
δ-ZrN 0.76 0.75 78.1 1600–2200 22
δ-HfN 0.02 62.9 1160–1800 23
δ-VN1⫺x 2.60 62.3 1100–1700 20
δ-VN1⫺x 12.7 67.1 1100–1700 24
δ-NbN1⫺x 3.27 76.0 1400–1900 25
on polycrystalline samples, are actually typical of nitrogen transport associated with a short-
circuit diffusion mechanism (22). However, considering the very limited diffusion data, the
mechanism of nitrogen diffusion in single crystals is still an open problem.
V. ELECTRICAL PROPERTIES
The transition metal carbides, nitrides, and diborides show metallic conductivity with a resisti-
vity of 7–250 µΩ ⋅ cm and have a negative Hall coefficient. Also, the higher carrier concentration
of 10 22 /cm 3 and lower thermoelectric power of several µV/K indicate that the electron gas in
the specimen could be regarded as strongly degenerate (28). These facts are reflected in Fig. 7,
i.e., temperature dependences of resistivity (ρ), thermoelectric power (S), Hall coefficient (RH ),
and mobility (µ H) of TiC1.0 single crystals (29). Both RH and S are negative in sign over the entire
temperature range, indicating that the predominant charge carriers are electrons. The mobility µ H
decreases with temperature and up to about 600°C conduction is performed by vacancy scatter-
Figure 7 Temperature dependences of resistivity (ρ), thermoelectric power (S), Hall coefficient (R H ),
and Hall mobility (µ H ) of TiC1.0 single crystal. (From Ref. 29.)
200 Kumashiro
ing; above 650°C, it is due to the scattering of lattice vibrations as in semiconductors, which
is confirmed by plotting the relationship between log µ H and 1/T (µ ⬀H T ⫺3/2 ).
The metallic nature of TiB 2 (30) also leads to a resistance that increases linearly with
temperature (Fig.8). The resistivity of the bicrystal, single crystal (sample 1), is greater than
that of the two single crystals (samples 2 and 3). The increase of resistivity of the bicrystal
could be due to the presence of the grain boundary. The average coefficient of resistivity,
α ⫽ m/ρ298 would represent intrinsic electrical behavior of a metal-like material (30) and the
value of α for TiB2 with a similar type and level of impurites is practically constant and indepen-
dent of the physical state of aggregation, i.e., monocrystalline or polycrystalline. The coefficient
α is not influenced by the presence of pores, grain boundaries, and cracks in the materials.
The temperature dependence of the electrical resistivity of the TiB2-ZrB2 system as a
function of temperature (31) obeys the same behavior as TiB2 . The ρ298 (µΩ ⋅ cm) and m (µΩ
⋅ cm/K) values for ZrB2 were determined to be 7.8 and 10, both of which increase with TiB2
content. These values for TiB2 were determined to be 20.4 and 36, respectively. Electrical con-
duction in the diborides of intermediate compositions may be primarily via the zirconium-rich
Figure 8 Resistivity of TiB2 polycrystals and single crystals up to high temperatures. (From Ref. 30.)
solid-solution phases, indicating that α values for the intermediate compositions are only slightly
higher than that of ZrB2 and, essentially, remain constant regardless of an increasing amount
of titanium-rich phase in the system.
Williams et al. (32) measured resistivity up to 1800 K using high-purity polycrystalline
TiB2 to deduce the ideal resistivity from the Debye temperature, Grüneisen parameter, and ther-
mal expansion coefficient. They induced the ideal resistivity ρi(µΩ ⋅ cm) at high temperatures
as follows:
ρi ⫽ 0.03T ⫹ 0.23 ⫻ 10 ⫺5 T 2 (4)
The resistivity of single-crystal ZrC0.93 in the temperature range 1000–3000 K was mea-
sured for the first time by Hinrichs et al. (33). All measurements were made in argon at 1 atm
pressure to reduce evaporation to a tolerable level over the time required to make the measure-
ments. Temperatures were corrected by emissivity (1). The resistivity data in Fig. 9 fit the
following formula well:
ρ ⫽ 176.5 ⫹ 0.0552T ⫺ 650 exp(⫺6900/T ) (5)
The observed temperature dependence of the resistivity can be explained by a combination of
phonon-induced interband scattering of electrons and a temperature-dependent Fermi energy.
Williams et al. (34–36) studied the electrical resistivity of these VC and NbC phases and
the influence of defect scattering on the temperature dependence of the resistivity. They found
a discontinuity in the electrical resistivity of 5 to 10% at the transformation temperature and a
virtual disappearance of the large residual resistivity normally associated with these nonstoichio-
metric compounds. This result confirmed the interpretation attributing the residual resistivity to
strong scattering of electrons by randomly arranged and abundant carbon vacancies. The behav-
ior of the resistivity around the critical point in V6 C5 is presented in Fig. 10. The change in the
resistivity of V6 C5 at its critical point was found to be 5.4 ⫾ 0.3 µΩ ⋅ cm or (3.6 ⫾ 0.2)% of
the total resistivity of the disordered solid. The order parameter was computed in the Bragg-
Williams approximation for a hypothetical A 5B alloy having an fcc lattice, where A was identi-
fied with carbon atoms and B with vacancies. This calculation predicts that the order-disorder
Figure 9 Resistivity of ZrC single crystal as a function of temperature. (From Ref. 33.)
202 Kumashiro
Figure 10 Temperature dependences of well-annealed samples of V6 C5 and V8 C7 prepared by annealing

V6 C5 in VC0.875 powder. (From Ref. 35.)
transition in V6C5 will be of first order, as evidenced by the discontinuous jump in the order
parameter at Tc.
The temperature dependence of the resistivity of a well-annealed sample of V8 C7 also
shows a discontinuity at the critical point, indicating a first-order transformation (Fig. 10). The
region of metastability (TeH ⫺ TeL) in the V8 C7 transformation is more than three times larger
than the corresponding region in V6 C5 . The corresponding change found for V8C7 was 20.1 ⫾
1.4 µΩ cm or (14.7 ⫾ 1.0)%. The critical temperatures for disordering in the two ordered phases
were determined to be (1275 ⫾ 8)°C for V6 C5 and (1124 ⫾ 15)°C for V8 C7 . The vanadium-
carbon system (VCx) has a strong preference for one or the other of the ordered phases for
nearly all compositions in the range 0.83 ⱕ X ⱕ 0.90. These temperatures are composition
dependent and tend to reach maxima at the ideal compositions VC0.833 and VC0.875 . The resistivi-
ties of the ordered phases of vanadium carbide, V6 C7 and V8 C7 , indicate that the scattering of
electrons by vacancies makes the dominant contribution to the low-temperature resistivity and,
therefore, support conclusions regarding the role of vacancies becoming of less importance as
the temperature increases. The decline in the vacancy contribution with increasing temperature
is most likely produced by a decrease in the Hall coefficient and/or the effective mass, since
such behavior is common in the transition metal carbides. Thus the simple form of Matthiessen’s
rule, ρtotal ⫽ ρdefect ⫹ ρ(T ) phonon, which takes the defect resistivity to be temperature independent,
does not hold here.
The temperature dependence of the resistivity of Nb6 C5 (36) shows the peculiar curvature
in ρ(T ) characteristic of the superconducting compounds, which is usually fitted with the empiri-
cal expression
ρ(T ) ⫽ ρideal ⫹ a exp(b/T ) ⫽ 61.6 ⫹ 0.0145T ⫹ 61.6 exp(355/T ) (6)
VI. THERMAL PROPERTIES
The vacancies in transition metal carbides and nitrides induce lattice distortions in their neigh-
borhood and the thermal motion of metal atoms adjacent to the vacancies become asymmetric
and anharmonic. Temperature-dependent X-ray diffraction experiments yield reliable informa-
tion about the thermal vibrations under the assumption that the static part of the Debye-Waller
(D-W) factor is temperature independent—i.e., the concentrations of vacancies and lattice distor-
tions remain constant within the given temperature range—but it is very sensitive to the local
atomic arrangement. The mean value of the Debye temperature averaged over the temperature
range 623 to 1273 K is θ M ⫽ 498 ⫾ 9 K (37), so that the thermal vibrations in ZrC0.98 can be
described by the quasi-harmonic one-point potential (OPP) mode in the temperature range 295
to 1273 K. The very weak variation with temperature of the Debye temperature indicates that
the potential parameters are temperature independent.
Anharmonicity due to the presence of the N vacancies was not observed in VN and was
found to be independent of the Debye temperature of (412 ⫾ 12) K within experimental error
in the temperature range 293 to 500 K (38). For small relative concentrations of carbon vacancies
in nonstoichiometric titanium carbide (39) a large contribution of static displacements to the
D-W factor indicates that the static displacements of atoms with point defects must be taken
into account in determining vibrational characteristics from the D-W factor. The static D-W
factor for TiC0.967 is independent of temperature in the range 293 to 700 K but rapidly increases
at temperature T ⬎ 700 K (39), which includes static displacements and changes of thermal
vibrations due to the presence of vacancies. Using the quasi-harmonic approximation, the experi-
mental data for the temperature range 293 to 700 K indicate temperature dependence of the
Debye temperature.
The thermal expansion of a crystal is mainly determined by the amplitude of the atomic
vibrations about the mean positions. The repulsion energy increases more rapidly with atomic
separation than does the attraction energy, resulting in a nonsymmetrical energy minimum. Con-
sequently, as the temperature is raised, the anharmonicity of the atomic vibrations will result
in a larger time-averaged distance between the atoms, corresponding to lattice expansion (40).
The linear thermal expansion coefficient α is calculated from
d(ln a)
α⫽ (7)
dT
To a very good approximation α is given by
1 da
α⫽ (8)
a0 dT
where a is a lattice constant and is a 0 at room temperature. In cubic crystals α is a scalar,

independent of direction, and in the diboride hexagonal crystal the principal values of α are
those parallel and perpendicular to the c axis, i.e., α c and α a. The measured linear expansion
204 Kumashiro
coefficient α is the directionally averaged value, which is just one-third of the volume expansion
coefficient. Thus,
1
ᾱ ⫽ (α c ⫹ 2α a ) (9)
3
The high-temperature thermal expansion data for transition metal nitrides (41) are summarized
in Fig. 11. The thermal expansion values of Ti(CxN1⫺x), Zr(Cx N1⫺x ), and Hf(Cx N1⫺x ) with [C ⫹
N]/[Me] ⬃ 1 and TiN1⫺x with [N]/[Ti] ⫽ 1.0 to 0.67 were determined from lattice prameter
measurements made with high-temperature X-ray diffraction in the temperature range of 298–
1473 K (42). The variation in the lattice parameters with temperature is given in Table 3. Tita-
nium carbonitrides, zirconium carbonitrides, and hafnium carbonitrides obey Vegard’s rule quite
well up to 1473 K. The linear thermal expansion coefficient and the average thermal expansion
coefficient are also given in Table 4. For titanium nitride, the thermal expansion decreases with
decreasing nitrogen/titanium ratio. The decreases in the thermal expansion coefficients of the
nitrides are always greater than those of the carbides. For titanium carbonitride and hafnium
carbonitride, the function expansion versus composition is almost linear, whereas the expansion
of the zirconium carbonitrides shows a slight maximum.
Lattice parameters of carbides and nitrides were estimated up to 2400 K using an empirical
approach (43) that was developed for the estimation of high-temperature lattice parameters and
relevant structural and bonding parameters. The equation is as follows:
ra ⫹ rc
a T ⫽ a 298 ⫹ 1.2 ⫻ 10 ⫺4 (T ⫺ 298) (10)
za ⫹ zc
where a T and a 298 are the lattice parameters at high temperature T and 298 K, ra and rc are atomic
radii of the constituents, and z a and z c are the anion and cation valences. Good agreement
Figure 11 High-temperature thermal expansion of various transition nitrides. (From Ref. 41.)
Table 3 Variation of Lattice Parameter a (Å) of Carbide, Nitride, and

Carbonitrides with Temperature T (K)
Compound Equations
Ti(CxN1⫺x) a(x,T ) ⫽ 4.2313 ⫹ 0.088x ⫹ (2.338 ⫺ 0.122x) ⫻ 10⫺5 T
⫹ (1.0717 ⫺ 0.2258x) ⫻ 10 ⫺8 T 2 ⫾ 0.002
Zr(CxN1⫺x) a(x,T ) ⫽ 4.5718 ⫹ 0.1178x ⫹ (2.107 ⫹ 0.0098x) ⫻ 10 ⫺5 T
⫹ (8.253 ⫺ 0.006x) ⫻ 10 ⫺9 T 2 ⫾ 0.002
ZrC0.98 [37] a(T ) ⫽ 4.69309 ⫺ 1.0170 ⫻ 10 ⫺5 T ⫹ 4.9767 ⫻ 10 ⫺8 T 2
⫺ 1.376 ⫻ 10 ⫺11 T 3
Hf(Cx N1⫺x) a(x,T ) ⫽ 4.5173 ⫹ 0.115x ⫹ (1.9916 ⫹ 0.2875x) ⫻ 10 ⫺5 T
⫹ (1.124 ⫺ 0.877x) ⫻ 10 ⫺8 T 2 ⫾ 0.002
TiNx a(x,T ) ⫽ 4.1823 ⫹ 0.0530x ⫹ (1.2206 ⫹ 0.8348x) ⫻ 10 ⫺5 T
⫹ (1.3485 ⫺ 0.1128x) ⫻ 10 ⫺8 T 2 ⫾ 0.002
(⫾0.5%) between the literature and computed lattice parameters has been confirmed. This
method could be used to estimate the thermal expansion behavior.
The variation in the lattice parameters of the group IV—VII transition metal diborides
with temperature is given in Table 5. All the diborides display similar lattice parameter versus
temperature dependences. The equations given in Table 6 were calculated by inserting the equa-
tions in Table 5 into Eq. (8). A larger expansion coefficient along the axis is obtained for NbB2
than for TaB2 (44). The experimental data agree fairly well with those reported for similar lattice
parameter versus temperature dependences. The equations given in the literature (45–47), that
is, ᾱ a ⫽ 7.25 ⫻ 10 ⫺6 /K and ᾱ c ⫽ 10.20 ⫻ 10 ⫺5 /K for TiB2 , and ᾱ ⫽ 8.27 ⫻ 10 ⫺6 /K and 8.8 ⫻
10⫺6 /K (45) for TiB2 sintered specimens.
The coefficients are larger in the c direction than in the a direction, which is due to the
anisotropy in the bond strength between the two directions. The bonding strength in the basal
plane is determined mainly by the strong covalent BB bonds within the boron layer, while
the MB bond strength plays the dominant role in determining the cohesion in the c direction.
In the diborides of the larger metal atoms, zirconium and hafnium, the a axis is determined by
MM contacts. The BB bonds are therefore streched and the BB bond strength is probably
slightly lowered. However, the MB and MM bond strengths increase at the same time,
compensating for the decrease in BB bond strength, leading to a decrease in ᾱ c . The anisot-
Table 4 Linear Thermal Expansion Coefficient α (K⫺1) and Average Thermal Expansion Coefficient
αav (K⫺1) of Nitride and Carbonitrides in the Temperature Range 298–1473 K
Compound Equation α(x, T) (K ⫺1 ) Equation α av (K ⫺1 )
Ti(CxN1⫺x) α(x,T ) ⫽ [(2.338 ⫺ 0.122x) ⫻ 10⫺6 ⫹ αav(x) ⫽ (9.9 ⫺ 1.4x) ⫻ 10⫺6
(2.143 ⫹ 0.451x) ⫻ 10⫺9 T ]/a(x,T )
Zr(CxN1⫺x) α(x,T ) ⫽ [(2.107 ⫹ 0.0098x) ⫻ 10⫺6 ⫹ (1.650 αav(x) ⫽ (7.8 ⫹ 0.3x ⫺ 0.6x 2) ⫻ 10⫺6
⫹ 0.0012x) ⫻ 10⫺9 T ]/a(x,T )
Hf(CxN1⫺x) α(x,T ) ⫽ [(1.9916 ⫹ 0.2875x) ⫻ 10⫺6 ⫹ αav(x) ⫽ (8.5 ⫺ 2.4x) ⫻ 10⫺6
(2.248 ⫺ 1.754x) ⫻ 10⫺9T ]/a(x,T )
TiNx α(x,T ) ⫽ [(1.2206 ⫹ 0.8348x) ⫻ 10⫺6 αav(x) ⫽ (7.0 ⫹ 1.9x) ⫻ 10⫺6
⫹ (2.697 ⫺ 0.2256x) ⫻ 10⫺9T ]/a(x,T )
206 Kumashiro
Table 5 Variation of the Lattice Parameters a and c (Å) with

Temperature T (K)
Compound Equations
TiB2 a ⫽ 3.0244 ⫹ 1.447 ⫻ 10⫺5T ⫹ 5.853 ⫻ 10⫺9 T 2
c ⫽ 3.2213 ⫹ 2.348 ⫻ 10⫺5T ⫹ 6.628 ⫻ 10⫺9 T 2
ZrB2 a ⫽ 3.1637 ⫹ 1.391 ⫻ 10⫺5T ⫹ 7.109 ⫻ 10⫺9 T 2
c ⫽ 3.5259 ⫹ 1.651 ⫻ 10⫺5T ⫹ 7.386 ⫻ 10⫺9 T 2
HfB2 a ⫽ 3.1380 ⫹ 1.168 ⫻ 10⫺5T ⫹ 7.876 ⫻ 10⫺9 T 2
c ⫽ 3.4716 ⫹ 1.726 ⫻ 10⫺5T ⫹ 6.208 ⫻ 10⫺9 T 2
VB2 a ⫽ 2.9930 ⫹ 9.703 ⫻ 10⫺6T ⫹ 7.497 ⫻ 10⫺9 T 2
c ⫽ 3.0432 ⫹ 3.946 ⫻ 10⫺5T ⫹ 6.389 ⫻ 10⫺9 T 2
NbB2 a ⫽ 3.1052 ⫹ 1.421 ⫻ 10⫺5T ⫹ 5.759 ⫻ 10⫺9 T 2
c ⫽ 3.2599 ⫹ 2.295 ⫻ 10⫺5T ⫹ 7.842 ⫻ 10⫺9 T 2
TaB2 a ⫽ 3.0924 ⫹ 1.276 ⫻ 10⫺5T ⫹ 6.991 ⫻ 10⫺9 T 2
c ⫽ 3.2204 ⫹ 1.389 ⫻ 10⫺5T ⫹ 1.111 ⫻ 10⫺8 T 2
ropy in bond strength can also be seen from the variation in the c/a value with metal radius.
The lattice is prevented by the boron layer from expanding in the a direction but is allowed to
expand more easily in the c direction, giving an increase in the c/a value with increasing metal
radius (40). The difference in the magnitude of ᾱ c among the various diborides is substantially
larger than the corresponding difference in the magnitude of ᾱ a , indicating that the anisotropy
decreases with increasing radius of the metal atom. The ᾱ a is slightly smaller for diborides having
large ᾱ c values, which might be due to a Poisson contraction; i.e., the very large expansion along
the c axis leads to a contraction of the lattice in the perpendicular direction. The thermal expan-
sion coefficient in the a direction changes very little with the metal radius, owing to the fact
that the bonding strength in the basal plane is determined by the strong BB bonds within the
boron layer. A change in the type of metal atom has a larger influence on the thermal expansion
coefficient than does a change in the boron composition of the diboride.
Table 6 Variation in the Linear Thermal Expansion

Coefficients ᾱ a and ᾱ c (K ⫺1) with Temperature T (K)
Compound Equations
TiB2 ᾱ a ⫽ 5.351 ⫻ 10⫺6 ⫹ 1.933 ⫻ 10⫺9 T
ᾱ c ⫽ 7.884 ⫻ 10⫺6 ⫹ 2.051 ⫻ 10⫺9 T
ZrB2 ᾱ a ⫽ 5.061 ⫻ 10⫺6 ⫹ 2.243 ⫻ 10⫺9 T
ᾱ c ⫽ 5.298 ⫻ 10⫺6 ⫹ 2.091 ⫻ 10⫺9 T
HfB2 ᾱ a ⫽ 4.465 ⫻ 10⫺6 ⫹ 2.506 ⫻ 10⫺9 T
ᾱ c ⫽ 5.501 ⫻ 10⫺6 ⫹ 1.784 ⫻ 10⫺9 T
VB2 ᾱ a ⫽ 3.984 ⫻ 10⫺6 ⫹ 2.502 ⫻ 10⫺9 T
ᾱ c ⫽ 13.267 ⫻ 10⫺6 ⫹ 2.353 ⫻ 10⫺9 T
NbB2 ᾱ a ⫽ 6.047 ⫻ 10⫺6 ⫹ 1.851 ⫻ 10⫺9 T
ᾱ c ⫽ 7.740 ⫻ 10⫺6 ⫹ 2.400 ⫻ 10⫺9 T
TaB2 ᾱ a ⫽ 4.793 ⫻ 10⫺6 ⫹ 2.259 ⫻ 10⫺9 T
ᾱ c ⫽ 5.531 ⫻ 10⫺6 ⫹ 3.443 ⫻ 10⫺9 T
Figure 12 Heat capacities of titanium carbides and nitrides as a function of temperature. (From Ref.
48.)
The molar heat capacities (C p) of TiC and TiN are shown in Fig. 12. Generally, with
increasing temperature the molar heat approaches the theoretical value of 52 J mol ⫺1 (Dulong-
Petit rule) or even exceeds it. Nitrides have a larger heat capacity than carbides (48). The heat
capacities of the corresponding stoichiometric carbonitrides as a function of temperature were
found to lie in between the two curves, i.e., with a linear dependence on the [C]/([C] ⫹ [N])
ratio. An interesting C p versus T behavior was observed for the Ti(Cx N1⫺x ) series. A distinct
endothermic C p discontinuity could be detected, 1068 K for TiC0.82 and 973 K for TiN0.82, which
is also present in the binary compounds TiN and TiC upon heating. Upon cooling, reversible
C p behavior was observed but shifted toward slightly lower temperatures, which is evidence of
a phase transition. The transition temperature increases with increasing nitrogen content. But
X-ray powder diffraction measurements of samples quenched or cooled from temperatures both
above and below the C p discontinuity did not reveal any deviations with respect to the line pattern
or the lattice parameters. The discontinuity at around 1000 K observed for the substoichiometric
titanium carbonitrides in thermal conductivity is an intrinsic property due to a phase transforma-
tion. The transition metal carbides and nitrides do not show the expected decrease in heat conduc-
tivities with temperature (Fig. 13) but instead show an increase, which was interpreted as re-
sulting from the strong scattering of electrons by vacancies and polar optical phonons from the
strong scattering of phonons by vacancies and conduction electrons (49). An ambipolar diffusion
to thermal conductivity was suggested for TiC. Replacement of nitrogen by carbon in group IV
transition metal nitrides significantly reduces the heat conductivities (41). In the case of diborides
(50), the thermal conductivities decrease with temperature, although those for TiB2 and HfB2
show a gradual decrease in conductivity (Fig. 14).
VII. MECHANICAL PROPERTIES
The internal friction peaks in carbides are sufficiently small up to 1000°C that the dynamic
modulus can be taken as equal to the unrelaxed or Hookean modulus. Above room temperature
208 Kumashiro
Figure 13 Thermal conductivities of carbides, nitrides, and carbonitrides as a function of temperature.

(From Ref. 41.)
Figure 14 Thermal conductivity of the diborides as a function of temperature. (From Ref. 50.)
Figure 15 Plots of log H against T/Tm of various carbides measured along the ⬍001⬎ direction in the
(100) plane. The loading time was chosen as 10 s. (From Ref. 29.)
Young’s modulus is linearly related to the temperature coefficient of ⫺1 ⫻ 10 ⫺4 K ⫺1 in TiC

and VC (51). Departures from linearity occur in the temperature range 850 to 1050°C for these
carbides, depending on nonstoichimetry. The empirical equation is
E ⫽ E 0 ⫺ BT exp(⫺T0 /T ) (11)
where E 0 is Young’s modulus at 0 K and B and T0 are constants; B has been determined for
TiC as 4.3 ⫻ 10 8 dyn/cm 2 ⋅ K, and T0 is given better by T0 ⬃ (θ D /3).
High-temperature indentation hardness can be used as a suitable measure of the plastic
properties. However, in indentation experiments above 1000°C, it is not considered easy to
obtain reliable data (52). A Nikon high-temperature microhardness tester model QM is designed
so that both indenter and specimen can be heated and controlled automatically at the same
temperature within an accuracy of ⫾10°C at 1500°C in a separate furnace (53). Cracks observed
at each corner at room temperature diminish at high temperatures in TiC (53), VC0.88, and NbC0.80
(54), causing slip traces of the {111} ⬍110⬎ system. These are explained in terms of the
dislocation mobility corresponding to the neck in a logarithmic plot of hardness versus homolo-
gous temperature T/Tm represented in Fig. 15. In the case of VC0.88, an additional neck caused
by the order-disorder transition of vacancies exists (54). Data for Cu and Si (55) are shown for
comparison. Unlike that of most metals, the hardness of carbides fall rapidly between 0.2 and
0.4 Tm, which is due to the slip system. The mechanical characteristics are closely related to
210 Kumashiro
Table 7 Values of Constant m and Activation Energy Q

Q (kcal/mol)
From indentation
Carbide Plane Direction m hardness From diffusion data
TiC 1.0 (100) ⬍001⬎ 3.85 80.4 (53) 91.3 (18); 95.3 (18)
(110) ⬍001⬎ 4.05 81.2 (53)
(111) ⬍110⬎ 3.73 77.0 (53)
ZrC 0.9 (100) ⬍001⬎ 3.80 73.4 (59) 90.0 a ; 113.2 (15)
(110) ⬍001⬎ 3.77 73.7 (59)
(111) ⬍110⬎ 4.09 79.2 (59)
VC 0.88 (100) ⬍001⬎ 4.27 85.6 (54) 85 (13)
(110) ⬍001⬎ 4.07 83.2 (54)
(111) ⬍110⬎ 3.79 79.8 (54)
NbC 0.8 (100) ⬍001⬎ 3.91 90.4 (54) 105 (15)
NbC 0.9 (100) ⬍001⬎ 3.23 77.1 (59) 100.4 (15)
(110) ⬍001⬎ 3.70 87.6 (59)
(111) ⬍110⬎ 4.74 99.9 (59)
TaC 0.83 (100) ⬍001⬎ 4.26 111.4 (59) 124.0 (14)
a
Short circuit–enhanced diffusion by grain boundaries.
the bonding state. The change from covalent to metallic-like hardness suggests a change in
predominant bonding from covalent to metallic cohesion as the temperature is raised (53–59),
which produces the change in the slip system from {110} ⬍110⬎ to {110} ⬍110⬎.
Plots of log H and T ⫺1 are characterized by two linear regions, suggesting that there are
two thermally activated process corresponding to an elastic and a plastic region. Their changes in
slope near the ductile-brittle (D-T) transition suggest a corresponding change in the mechanism
controlling the dislocation dynamics. The critical homologous temperature of carbides is the
same as that of other rock salt–type crystals of NaCl, LiF, and MgO.
ZrC is the softest at high temperatures with the highest thermal softening coefficient (59),
related to the lattice vibration of carbides. The hardnesses of carbides tend to decrease with
increasing lattice constant, reflecting the strength of the chemical bond. The lattice constant
for ZrC is the largest among the carbides, and hence atomic bonds would weaken with raised
temperature, enhancing the softing of the material. The gradual decrease in hardness of TaC0.83
is characteristic (59), whereas other carbides show about a 10-fold drop in hardness in the same
temperature range. In contrast to the other carbides, TaC0.83 has the {111} ⬍110⬎ slip system
over the entire temperature range and its temperature dependence is similar to that in other fcc
metals (Cu) and covalent semiconductors (Si) with a slip system of {111} ⬍110⬎. The high-
temperature hardness of TaC is probably due to the presence of widely dissociated dislocations
resulting in extended stacking faults, i.e., Suzuki hardening (60) limited by carbon diffusion.
The Suzuki interaction results from the difference in composition in the fault compared with
the bulk observed in TaC using qualitative electron energy loss spectroscopy (61).
The indentation hardness decreases with increasing loading time (1 to 100 s) at constant
temperature (⬎.3Tm) in the plastic region. A series of straight lines were obtained. The activation
energy, Q, for creep and the constant, m, expressed by the following equations are calculated
for various carbides (see Table 7):
H ⫽ A exp(⫺BT ) (12)
and
B/t ⫽ H m exp(⫺Q/RT ) (13)
The activation energies of the self-diffusion of carbon from tracer experiments are also indicated.
No data are available for the diffusion of TaC single crystals, so the activation energy was
estimated by (29 to 33)Tm (14), a good average, for VC, TiC, and ZrC. The lower activation
energy for ZrC would be explained by enhanced diffusion along subgrain boundaries and viscous
glide. The mechanism of the slip phenomena in carbides will be governed by carbon diffusion
and dislocation climb.
Next, the high-temperature indentation hardness of diboride will be shown. The hardness
in each plane for ZrB2 crystals (62) decreases monotonously through all the testing temperatures
(Fig. 16), maintaining the following relationship: H ⬍1010⬎(0001) ⬎ H ⬍1210⬎(0001), H ⬍1210⬎{1010} ⬎
H [0001]{10110} , H ⬍1100⬎{1120} ⬎ H [0001]{1120}, where the two subscripts of H represent the direction of
the long axis of the Knoop indenter and the indentation plane, respectively. In the case of HfB2
crystals, similar temperature dependences are observed except at room temperature. Then the
main slip system contributing to the hardness anisotropy of ZrB2 and HfB2 single crystals is
{1010} ⬍1210⬎ over the entire temperature range, except that of HfB2 near room temperature.
However, in the case of TiB2 single crystals (63), the main slip system changes from (0001)
⬍1120⬎ to {1010} ⬍1210⬎ near 250°C. The high-temperature Knoop hardnesses, of NbB2
and TaB2 single crystals up to 1100°C (64) on the (0001) plane in the ⬍1010⬎ and ⬍1120⬎
indentation directions and on the {1010} plane in the ⬍1210⬎ and [0001] directions indicate
the inequalities H ⬍1010⬎(0001) ⬎ H ⬍1120⬎(0001) and H ⬍1210⬎{1010} ⬎ H [0001]{1010} for the entire temperature
ranges, showing that slip was mainly on the prismatic {1010} ⬍1210⬎ system. This was also
confirmed by slip line observations.
High-temperature friction and wear of TiC-TiB2 alloys (65) indicate that the crystal distor-
tion (∆a/a) increases with increasing temperature at high temperatures. The plastic deformation
of friction layers in the TiC-TiB2 system at high temperature would increase (∆a/a) for the TiC
component, so the TiB2 phase would play the main role in forming working layers of the TiC-
TiB2 alloys for a wide range of structural component concentrations.
Uniaxal compression loading induces deformation directly. Haggerty and Lee (66) studied
the plastic deformation of ZrB2 single crystals and showed that the oriented lamellar precipitates
controlled the deformation. Stress-strain (crosshead displacement) behavior at 2125°C for ZrB2
single crystals containing Widemanstaetten precipitates is shown in Fig. 17. The important char-
acteristic features are (a) ⬇ 37% yield drop, (b) a short easy-glide region, and (c) the beginning
of work hardening. The upper yield point occurred at ⬇ 10.6 kg/mm 2 and the easy-glide region
at 6.7 kg/mm 2. The crystal deformed ⬇ 1.2% before beginning to work harden. They attributed
the material’s resistance to plastic flow to the presence of lamellar or plate-shaped precipitates
lying on the basal and prismatic planes of the hexagonal ZrB2 crystal.
Ramberg and Williams (67) reported on the resistance to plastic flow of a polycrystalline
TiB2 specimen when subjected to an applied stress of 900 MPa at a temperature of some 2000°C.
In the temperature regime 1700 to 2000°C, the yield stress of the polycrystalline TiB2 specimen
was found to decrease from 100 kg mm ⫺2 (980 MPa) to 28 kg mm ⫺2 (270 MPa). The TiB2 of
23 µm mean grain size proved to be more deformation resistant below 1750°C than samples
with grains averaging 12 µm. The decrease in yield stress with increasing temperature was
exponential, with an apparent activation energy ranging between 0.7 and 1.3 eV atom ⫺1 as
calculated by taking the slope of log yield stress versus 1/T. Figure 18 illustrates the applicability
of the Hall-Petch relation [Eq. (14)] to the high-temperature plastic deformation of TiB2. The
relation illustrates that grain boundaries act as barriers to glissile dislocations.
212
Figure 16 Log H versus T for typical examples of diboride single crystals. (From Refs. 62 and 63.)
Kumashiro
Figure 17 Stress-crosshead displacement behavior of ZrB2 single crystal deformed at 2125°C. (From
Ref. 66.)
Figure 18 Hall-Petch form of the yield stress data (open polygons) and the revised Hall-Petch analysis
(shaded polygons) based on best fit to lines of constant activation energy. (From Ref. 67.)
214 Kumashiro
Figure 19 Temperature dependence of the yielding behavior for pure TiC0.95 and (TiMo)C solid solutions
compressed at a strain rate of 6 ⫻ 10 ⫺4 s ⫺1. (From Refs. 71 and 72.)
σ y ⫽ σ 0 ⫹ kd ⫺1/2 (14)
Here σ0 represents the single-crystal yield strength and k its dependence on the reciprocal square
root of the mean grain size. The importance of the implied dislocation grain-boundary interac-
tions will motivate further study of this system.
The mechanical properties of fine-grained polycrystalline TiC from both four-point bend-
ing and compression tests showed that the D-B transition temperature in compression was ⬇
800°C and depended on grain size and test temperature (68). The yield stress as a function of
grain size can be described by a Hall-Petch type of relation. High-temperature vacuum treatment
of as-hot-pressed TiC significantly reduced the levels of impurities at grain boundaries, which
caused a dramatic improvement in high-temperature strength (69).
Work softening was not observed in the carbides before 1982. The phenomenon was
reported only for arc-melted ZrC0.94 polycrystals (70) and under very limited testing conditions.
Yield drops were observed with plastic strain rates greater than 3 ⫻ 10 ⫺3 s ⫺1 but not with lower
strain rates. Das et al. (68) observed yield-point behavior in TiC polycrystals deformed at
1000°C, which was followed by a yield-elongation zone where deformation took place at an
approximately constant stress. At the end of the yield-elongation zone, work hardening was
observed in the stress-strain curve. The development of high rigidity and responsity of the ma-
chine produced success in finding a work softening phenomenon in carbide (71).
Figure 19 shows stress-strain curves for TiC0.95 single crystals deformed at various temper-
atures from 1280 to 2273 K at a strain rate of 1.6 ⫻ 10 ⫺3 s ⫺1. A marked yield drop occurs over
a wide temperature range. After the softening, work hardening is observed. In the curves for
1280 and 1400 K, the hardening is almost linear after a narrow transient region. The rate of
work hardening after the softening decreases as the temperatures increases above 1400 K, indi-
cating that recovery due to dislocation climb occurs during deformation at these high tempera-
tures.
From the temperature and strain-rate dependence of the critical resolved shear stress, τ0.2 ,
corresponding to 0.2% proof stress, the plastic shear-strain rate, γ, is expressed as a function
of τ0.2 and absolute temperature T as follows:
γ ⫽ A(τ0.2 /G ) m exp(⫺Q/RT ) (15)

where A is a constant, m the stress exponent, Q the activation energy for deformation, G the
shear modulus, and R the gas constant. The stress exponent m is obtained as the reciprocal of
the slope of the strain-rate dependence. The values of m and Q in low- and high-temperature
ranges I and II, respectively, are shown in Table 8. The large m value in TiC would explain
the difficulty in observing the work softening phenomenon in the carbide. A mechanical equation
of state has been reported for yield stress in sintered tantalum carbide (grain size, 13µm) (73)
and for the steady-state creep of sintered titanium carbide (grain size, 7 µm;porosity, 3.3%)
(74), ZrC single crystal (75), NbC single crystal (76), and sintered NbC0.74 (density of 99.7%)
(77). In Ref. 73, m ⫽ 13.3, Q ⫽ 89.8 kcal/mol in the low-temperature range and m ⫽ 4.5, Q
⫽ 95.7 kcal/mol in high-temperature range; in Ref. 74, m ⫽ 2.7, Q ⫽ 90.7 kcal/mol in the
low-temperature range and m ⫽ 3.5, Q ⫽ 155 kcal/mol in the high-temperature range; in Ref.
75, m ⫽ 5, Q ⫽ 110 kcal/mol in the high-temperature range; in Ref. 76, m ⫽ 3.3, Q ⫽ 85
kcal/mol; and in Ref. 77, m ⫽ 2.0–3.2, Q ⫽ 51.1–111.9 kcal/mol. The Q value for TiC single
crystals in the low-temperature range is the activation energy required for a dislocation to over-
come a high Peierls barrier, and that in the high-temperature range is close to that for carbon
diffusion, suggesting that carbon diffusion may control the dislocation motion. The carbon atoms
occupying octahedral interstitial sites in the fcc titanium sublattice act as a barrier to dislocation
motion, and hence the deformation is controlled by their diffusion.
Similar high-temperature experiments on TiC x single crystals (0.6 ⬉ x ⬉ 0.95) in the
temperature range 1180 ⬉ T ⬉ 2270 K (78) showed that Q was lower than the self-diffusion
data for carbon, except for x ⫽ 0.75. At this concentration a peak in the Q value, 133.3 kcal/mol,
about 75% of that for lattice self-diffusion of Ti in TiC, indicated that the diffusion processes of
carbon and titanium were coupled in plastic deformation.
Figure 19 also shows the curves around the yield points of solid solutions of (Ti, Mo)C
at various temperatures (72). The deformation behavior in the solid solutions is different in three
temperature ranges. In the low-temperature range (I), a yield drop is observed and the work
hardening after the drop is high. In the intermediate-temperature range, no yield drop occurs,
and from the beginning work hardening is high. In the high-temperature range (II), a yield drop
occurs again and thereafter the deformation proceeds with almost a constant flow stress. (Ti0.743
Mo0.257 )C0.955 fractured in the low-temperature range without any appreciable plastic deformation
and the expected work softening could not be observed. The D-B transition temperature of
(Ti0.743 Mo0.257)C0.955 solid solution is higher than that of pure TiC. At 2070 K, where it shows good
ductility, a yield point phenomenon is observed. Slip bands are fairly coarse in the intermediate-
temperature range (1770 K) compared with those in the low-temperature (1370 K) and high-
temperature (2270 K) ranges. Solution softening occurs on the lower side of the Mo concentra-
tion, but solution hardening occurs on the higher side. The boundary concentration is about 5
mol %. The deformation in the low-temperature range (I) is considered to be controlled by the
Peierls mechanism and in the intermediate-temperature range is considered to be controlled by
Table 8 Values of m and Q in the Low- and High-Temperature Regions, I and II

Region I Region II
Composition m Q (kcal/mol) m Q(kcal/mol)
TiC 0.95 10.1 ⫾ 0.4 57.1 5.3 ⫾ 0.3 111.9
(Ti 0.955 Mo 0.045)C 0.946 14.7 50.0 5.7 ⫾ 0.3 135.7
(Ti 0.886 Mo 0.114)C 0.936 13.2 47.6 5.2 ⫾ 0.4 142.9
(Ti 0.743 Mo 0.257)C 0.955 — — 5.4 ⫾ 0.3 150.0
Source: From Refs. 71 and 72.
216 Kumashiro
so-called dynamic strain aging (Table 8). In the high-temperature range, another kind of yield
point phenomenon occurs and the work-hardening rate after the stress drop is very low. The
slip bands are very fine. Therefore deformation in (Ti, Mo) C solid solution is considered to
be controlled by a solute-atmosphere-drag mechanism.
On the other hand, hypo Mo-10TiC has unlimited compressive ductility at and above 1270
K and hyper Mo-40TiC has unlimited compressive ductility at and above 1470 K (79). In Mo-
10TiC, the stress exponent, m, is 36 at 1870 K and 13 at 2070 K, and Mo-40TiC, m ⫽ 6.5 at
1870 K and m ⫽ 5.6 at 2070 K. The temperature and strain-rate dependences of yield stress
at high temperatures are larger than in Mo-40TiC. The difference between the calculated and
experimental curves of yield stress versus temperature is much smaller in the hypoeutectic Mo-
10TiC than in the hypoeutectic Mo-40TiC, which would arise from the difference in the internal
stress induced by the plastic strain of 0.2% and the difference in the volume fraction of the
eutectic structure region between the two composites. The smaller volume fraction means a
smaller interfacial area between the two components per unit volume, and the effects of boundary
sliding and recovery become smaller in Mo-10TiC than in Mo-40TiC.
Sufficiently pure titanium diboride (grain size ⱕ 4 µm) densified from plasma-process
powder (80) does not exhibit intrinsic slow crack growth at temperatures up to 1400°C. Dynamic
fatigue strength tests were performed at 1000 to 1400°C in argon to evaluate the intrinsic (envi-
ronment-independent) tendency for slow crack growth. The resultant bend strengths are pre-
sented in Fig. 20, which shows that strengths generated at the lower stress rate are consistently
greater than those obtained at a higher rate. Linear regression analysis was used to fit the
strengths to the equation
ln S f ⫽ ln XHR/(N ⫹ 1) ⫹ K (16)
where S f is fracture strength, XHR is machine crosshead rate, N is a slow crack growth exponent,
and K is a constant. Slow crack growth exponents for the data for 1000, 1250, and 1400°C were
found to be ⫺53.2, ⫺61.4, and ⫺62.2, respectively, using Eq. (16). A negative exponent is
incompatible with slow crack growth and implies the presence of a low-strain rate–strengthening
effect. The stress-strengthening mechanism operates by blunting flaw tips.
Furthermore, mechanical properties in an aluminum environment at 960 to 1000°C were
studied by strength versus stress rate and K Ic tests (81). According to dynamic fatigue tests on
Figure 20 Three-point bend strength as a function of stressing rate crosshead rates of 8.5 ⫻ 10 ⫺7 and
8.5 ⫻ 10 ⫺5 m/s for powder sintered at 2100°C, n (number of specimens) ⫽ 5, bars ⫽ ⫾1 standard deviation.
(From Ref. 80.)
high-purity titanium diborides in a liquid-aluminum environment, the two smallest grain size
materials (grain size ⱕ 3 µm) exhibited negative slow crack growth exponents that were the
result of stress strengthening and inconsistent with slow crack growth, and the two larger grain
size materials (grain size ⱕ 10 µm) exhibited positive slow crack growth exponents. The expo-
nents indicated an increasing tendency for slow crack growth with increasing grain size. The
dynamic fatigue results are shown in Fig. 21. The inner bars had a mean strength of 327 MPa
(XHR ⫽ 4.2 ⫻ 10 ⫺5 m/s; standard deviation ⫽ 75 MPa; n ⫽ 6). The mechanical behavior of
the cell-tested material in either an argon or an aluminum environment is changed little from
that of similar, unpenetrated material in a corresponding environment. The trend of the exponents
versus grain size suggests the presence of two opposing mechanisms that affect crack extension,
at least one of which is grain size dependent. One mechanism is predominant in larger grained
material weakening; the other predominates in finer grained materials and leads to material
strengthening. Material strength reductions resulting from the slow crack growth mechanism
are superimposed on other strength losses arising from loss of toughness in the presence of
aluminum; K Ic is reduced whether or not slow crack growth occurs. The reduction of K Ic in the
presence of aluminum corresponds to a decrease in the effective fracture energy from 31 to 24
J/m 2 (from K Ic ⫽ (2 Eγ) 1/2, E ⫽ 400 GPa). Then the reduction of K Ic appears to be due to the
phenomenon of liquid-metal embrittlement characterized by the chemisorption of metal impurity
atoms at the crack tip so that the new chemical bond formation reduces the stability of the bonds
between atoms of the material being embrittled. The lowered energy of matrix cohesion results
in a lower energy for crack propagation.
High strain rate superplasticity (HSRS) would be an efficiently near-net shape forming
and forging process for ceramic whisker– or particle-reinforced aluminum alloy composites.
The HSRS of TiB2 particle-reinforced aluminum alloy composites (82) was reported to show
superplastic characteristics (Fig. 22). The TiB2 f/2014 Al composite has an m value of about
0.25 and total elongation of less than 150% in the strain rate region between 0.08 and 1.0 s ⫺1,
and TiB2 f/6061 Al composite exhibits an m value of 0.26 and total elongation of 150–200%
in the strain rate region from 0.07 to 1.3 s ⫺1. These composites were deformed superplastically
above the solidus temperature of 2014 and 6061 Al alloy, so the matrix and the matrix-reinforce-
ment interface were partially liquid during deformation. Then the main superplastic deformation
mechanisms are fine grain boundary sliding and interfacial sliding involving a semiliquid phase.
Cermets consisting of two mutually penetrating frames of metal and refractory phases are
more promising for high-temperature applications than cermets consisting of a metal matrix
Figure 21 Dynamic fatigue data for sintered at 2100°C, tested at 960°C in Al over long periods of time.
(From Ref. 81.)
218 Kumashiro
Figure 22 Superplastic characteristics of (䊊) TiB2f/2014 and (䊉) TiB2f/6061 aluminium alloy compos-
ites. (a) (䊊) Rolling temperature 818 K, testing temperature 833 K, m ⫽ 0.25; (䊉) rolling temperature
833 K, testing temperature 873 K, m ⫽ 0.26 and (b) (䊊) rolling temperature 833 K, testing temperature
873 K. (From Ref. 82.)
with a uniform distribution of refractory particles. New possibilities in the design of plastic
frames can be achieved by changing the chemical composition and microstructure type of the
refractory compound in TiCx-nickel–based superalloy (83). The cermets based on the stoichio-
metric TiC provided high strength at high temperatures-above 950°C, because the D-B transition
temperature was achieved.
VIII. CONCLUSION
At present we can obtain well-characterized specimens, so it should be possible to clarify charac-

teristics at higher temperatures, above 2000°C. Measurements up to higher temperatures require
sophisticated knowledge of instrumentation to provide reliable data. For these purposes accurate
measurements of temperature and emissivity should be established. Transition metal diborides
are promising electrode materials for magnetohydrodynamic (MHD) generators, so their spectral
emittance data would be necessary. The very high melting point of carbides, low diffusion rate
of carbon, and good nuclear properties make them attractive for use in high-temperature nuclear
reactors, and knowledge of thermodynamic properties is indispensable for understanding the
vaporization behavior. The environment in the core of a rocket in the space is extremely harsh,
so many common diagnostic instruments cannot easily be used. Laser diagnostic methods (7)
provide some unique advantages over other diagnostic techniques, i.e., imaging ability and excel-
lent temporal and spatial resolution. They are also specific to certain corrosion production when
probing a rocket’s exhaust and supply information on local gas stream concentrations and tem-
peratures.
High-temperature equilibrium experiments have produced thermodynamic value or limits
for the formation of the binary phases. Experimental information on thermochemical properties
and phase equilibria in the Zr-C system (5) has been analyzed using phenomenological methods
for Gibbs energy. The parameters in the models are determined by computerized optimization
of selected experimental data. But some significant discrepancies are found between experiments
and model calculations. The thermodynamics of the liquid solution phase could solve the prob-
lem related to M-B systems. Accurate thermodynamic data are lacking for M-B systems, (84),
so that the consistency of the thermodynamic data for the binary phases with temperature-com-
position phase diagrams could not be tested. Experimental partial pressures over nitride show
significant scatter (8), which should be clarified using well-characterized specimens. The experi-
mental information on the phase equilibria in the ternary carbonitride systems was restricted
mainly to the quasi-binary MC-MN systems, where complete miscibilities were observed, but
isothermal sections of the phase equilibria in the systems Ti-C-N, Zr-C-N, and Hf-C-N have
been investigated to clarify the formation regions of δ-carbonitride phases in relation to composi-
tions (85).
High-temperature thermodynamic data also give information about optimal preparative
conditions in multicomponent gas-solid systems by chemical vapor deposition of the product
and optimal molar ratios for making stoichiometric compositions by plasma flame synthesis.
The diffusion coefficients are necessary for studying the reaction mechanism including self-
propagating high-temperature synthesis. Diffusion studies using single crystals for nitride should
be performed to clarify a common diffusion mechanism. Also, chemical diffusion for carbides
using single crystals should be clarified.
The diffusion coefficients are needed to study the reaction mechanism, including self-
propagation high-temperature synthesis. Hot-pressing sintering mechanisms are correlated with
self-diffusion creep theory and deformation mechanisms at high temperatures. High-temperature
mechanical properties of composites would be useful for applications as high-temperature engi-
neering components.
ACKNOWLEDGMENTS
A number of figures and tables have been taken from the literature. The author would like to
thank the authors and publishers of these materials for permission to reproduce them here, espe-
cially the American Physical Society (Fig. 10 (Ref. 35)), the American Institute of Physics
(Fig. 9 (Ref. 33) and Fig. 14 (Ref. 50)), the American Ceramic Society (Fig. 5 (Ref. 7), Fig. 8
(Ref. 30), Fig. 17 (Ref. 66), Fig. 20 (Ref. 80) and Fig. 21 (Ref. 81)), Elsevier Science Ltd.
(Tables 5 and 6 (Ref. 40), Fig. 6 (Ref. 8), Fig. 12 (Ref. 48) and Fig. 16 (Ref. 62)), John Wiley &
Sons, Ltd (Figs. 11 and 13 (Ref. 41)), and Kluwer Academic Publishers (Fig. 18 (Ref. 67) and
Fig. 22 (Ref. 82)).
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9
Surface Electronic Structures and Surface
Reactivities
Kazuyuki Edamoto
Tokyo Institute of Technology, Meguro-ku, Tokyo, Japan
I. INTRODUCTION
The group IV and V transition metal carbides (TMCs) are of considerable interest because of
an interesting combination of physical properties and a number of useful applications. They
exhibit ultrahigh hardness, a high melting point, and metallic conductivity, and some of them
are superconductors at fairly high temperatures. From a practical point of view, they have been
used as very stable field and thermal electron emitters, coating materials, wall materials for
nuclear reactors, etc. Because the surface properties play an essential role in all these applica-
tions, it has become important to investigate the atomic structures and electronic structures of
TMC surfaces. From a chemical point of view, it has been suggested that they are useful as
catalytic materials for the hydrogenation of benzene, ethylene, and carbon monoxide, the decom-
position of methanol, etc. (1); thus their surface reactivities are also of much interest. However,
in contrast to the substantial accumulation of data on elemental metal and semiconductor sur-
faces, limited information has been available on the physical and chemical properties of the
well-defined surfaces of TMCs. This is mainly because the high melting point of the material
makes it difficult to prepare a single crystal of good quality. Preparation techniques for TMC
single crystals have been developed dramatically, and single crystals of excellent quality have
become available by use of the floating-zone method (2). This has made it possible to prepare
well-defined surfaces of TMCs, which has stimulated the development of a variety of analyses
of the TMC surfaces. In this chapter, I review the developments in studies of the electronic
structures and reactivities of well-defined TMC surfaces.
First, I briefly discuss the atomic structure of TMC surfaces. The TMCs crystallize in a
rock salt structure, and studies of the surface atomic structure have been concentrated on the
three typical low-index surfaces, the (100), (110), and (111) faces. The geometries of ideal
(100), (110), and (111) surfaces are shown schematically in Fig. 1.
The (100) surface of a TMC is a neutral surface composed of equal numbers of metal
and carbon atoms (Fig. 1). All the TMC(100) clean surfaces prepared in ultrahigh vacuum
conditions show (1 ⫻ 1) low-energy electron diffraction (LEED) patterns, and no lateral recon-
struction has been found. However, LEED I–V analysis studies of the TaC(100) (3,4) and
HfC(100) (3) surfaces have revealed that rippled reconstructions are brought about on these
surfaces. The rippled reconstruction includes displacements of surface atoms vertical to the
surface; the metal atoms and carbon atoms are uniformly displaced inward and outward, respec-
223
224 Edamoto
Figure 1 Surface structures (top view) of TMC(100), (110), and (111).
tively, by a few percent of the lattice constants (Fig. 2), which maintains the (1 ⫻ 1) periodicity
of the surface. A similar rippled reconstruction has been found for the neutral surfaces of ionic
crystals such as alkali halides or metal oxides (5,6). The origin of the rippled reconstruction
can be explained by the electrostatic effect characteristic of the ionic crystal surface. At the
ionic crystal surface, the electrostatic forces felt by the anion and cation atoms are different
from each other; both the anion and cation atoms at the surface feel the electrostatic force
directed to the bulk inside because of the lack of countercoordinated ions in the vacuum side;
however, the anion and cation atoms usually have different sizes and polarizabilities, which
results in a difference in the electrostatic forces working on the surface anion and cation atoms.
Thus the rippled reconstruction for the TMC(100) surface can be ascribed to the ionicity of the
crystal. It is known that a completely stoichiometric TMC crystal is thermodynamically unstable,
and a real crystal should contain some vacancies on the carbon sites forming an MC x (x ⬍ 1)
crystal. An impact-collision ion scattering spectroscopy (ICISS) study has shown that the density
of the carbon vacancies on the TMC(100) surface depends on the preparation condition of the
surface and that a stoichiometric surface with no carbon vacancies can be obtained by flashing
the sample to a high temperature (⬎1500°C) (7).
Figure 2 Side view of the rippled TMC(100) surface.

Surface Electronic Structures and Reactivities 225
The (111) surface of TMC is a polar surface; hexagonal carbon layers and metal layers
are piled alternately along the ⬍111⬎ direction to form a rock salt type of crystal (Fig. 1),
meaning that the first layer of the ideal (111) surface should be a carbon layer or metal layer.
Such a polar surface is usually unstable because of its large electrostatic potential, which usually
induces surface reconstructions or facetings. However, every TMC(111) surface carefully pre-
pared under ultrahigh vacuum conditions shows a sharp (1 ⫻ 1) LEED pattern and no lateral
reconstruction has been found [the exception is found only for VC(111) (8,9)], suggesting that
some unique stabilization mechanism should be operative in the TMC(111) surface. As dis-
cussed later, the (1 ⫻ 1) structure is stabilized through a charge redistribution around the surface
to screen the long-range electric field, and the charge redistribution modifies the electronic struc-
ture in the surface region largely to form surface states characteristic of the TMC(111) surface.
The atomic structure of the TMC(111) surface has been extensively studied by use of the
ICISS technique. Investigations have been made for TiC(111) (10,11), HfC(111) (12), TaC(111)
(13), and NbC(111) (14), and it has been established that the first layers should be metal layers
on these surfaces. The ICISS studies have also revealed that, although TMC(111) surfaces show
no lateral reconstruction, some surface relaxation, which means a change in interlayer spacings
in the surface region from that in the bulk (Fig. 3), is brought about (10,12,14). The surface
relaxation is caused by the lack of coodinated carbon atoms in the vacuum side of the first metal
layer, which results in an attractive force only toward the bulk inside. Thus, the relaxation in
this case means shortening of the interlayer spacing between the first and second layers relative
to that in the bulk. The contraction of interlayer spacing at the surface is estimated to be 30%
of the interlayer spacing in the bulk for TiC(111) (11), 13.4% for HfC(111) (12), and 15.5%
for NbC(111) (14).
Among the group IV and V TMC(111) surfaces, only the VC(111) surface has been found
to be reconstructed. Scanning tunneling microscopy (STM) and LEED studies have shown that
the VC(111) surface is composed of a mixture of (8 ⫻ 1) and (√3 ⫻ √3)R30° reconstructed
areas (8,9). Structural analyses have shown that the atomic concentration is reduced in these
areas compared with ideal (111) surfaces (8,9). Because the cohesive energy of the VC crystal
Figure 3 Side views of the ideal (a) and relaxed (b) TMC(111) surface.
226 Edamoto
Figure 4 Side view of the TaC(110) surface.
is relatively small among the group IV and V TMCs, it has been proposed that the surface
reconstruction occurs because the reduced atomic concentration is energetically favored on the
VC(111) surface (8,9).
In contrast to the accumulation of data on the (100) and (111) surfaces of TMCs, limited
information is available at this point for the (110) surface. The ideal (110) surface should be
composed of equal numbers of carbon and metal atoms that form alternating carbon and metal
rows along the ⬍110⬎ direction (Fig. 1). The TMC(110) surface has been studied for TiC(110)
(11), TaC(110) (15,16), and NbC(110) (17), and these studies have concluded that the (110)
surfaces are reconstructed. The most extensive studies of the surface atomic structure were
made on the TaC(110) surface, which was found to consist of alternate (010) and (100) facets
periodically propagating along the ⬍011⬎ direction as in a ridge-and-valley grating with an
average period of about six lattice spacings (Fig. 4) (15,16). The atomic structure of the TiC(110)
surface was also studied, and it was found that the surface is covered with (310) facets that
consist of (100) terraces and (010) steps (11). The NbC(110) surface shows a c(2 ⫻ 2) LEED
pattern, indicating some surface reconstruction, although the detailed atomic configuration is
still unknown (17). These studies suggest that the ideal TMC(110) surface is unstable, and the
general tendency of the reconstruction seems to be to make (100) facets.
In the following sections, progress in studies of the electronic structure of TMC(100),
(110), and (111) surfaces by the application of angle-resolved photoemission spectroscopy
(ARPES) will be reviewed. Adsorption of oxygen and alkali metal on the TMC(100) and (111)
surfaces will also be reviewed as an example of progress in the surface chemistry of TMCs.
II. SURFACE ELECTRONIC STRUCTURE
In the TMC crystals, ionic, covalent, and metallic bonding components all contribute to the
atom-atom bonding to form the crystal. Details of the bonding character of TMC crystals are
covered in other parts of this monograph. The surface of the TMC is made by breaking such
unique bonding. The electronic structure of the TMC surface thus made is of interest from a
physical point of view for the following reasons.
First, the electronic structure of the TMC surface is expected to be modified from that in
the bulk because of the change of the potential felt by electrons in the surface region. The change
of the potential is thought to be mainly due to the ionicity of the TMC crystal. In the crystal,
each metal (carbon) atom is surrounded by six carbon (metal) atoms. Because the metal and
carbon atoms are positively and negatively charged respectively, in the TMC crystal, the elec-
trons are located in a sort of octahedral crystal field at each atom site in the bulk. However, at
the surface, the number of coordinated atoms is decreased by one, two, and three for the (100),
(110), and (111) ideal surfaces, respectively. The decrease of coordinated atoms should induce
considerable modification of the potential at each atom site on the surface compared with that
in the bulk. Similar potential modification should occur on the surfaces of essentially all the
compound crystals where the component atoms should have more or less different electronega-
tivities. However, few systematic studies of the electronic structure of these surfaces have been
made. This is because most of the compound crystals having ionicity strong enough to have
ionic effects on the surface electronic structure are insulators, which are not suited for electron
spectroscopic studies. As for TMC, the crystal is characterized by its metallic conductivity, and
the two typical low-index surfaces, (100) and (111), can be prepared as almost ideal surfaces
[except for VC(111)], which enables systematic studies of surface electronic structures. In this
sense, the TMC surfaces can be viewed as a model of compound crystal surfaces.
The second point is that the metallic character of the bond makes it possible to redistribute
electronic charge easily around the surface to compensate for the potential change. This effect
may induce substantial modification of surface electronic structure compared with that in the
bulk, which also makes the electronic structure of TMC surfaces a very interesting field from
a physical viewpoint.
Before discussing the surface electronic structures, I briefly review the bulk electronic
structure of TMC to make the latter discussion clearer. Figure 5 shows an example of an angle-
integrated soft X-ray photoemission spectrum taken for the NbC(100) surface. In this experimen-
tal condition, the spectrum includes overall features of the bulk density of states (DOS) of the
valence band and the inner-valence core levels for the TMCs. The band at 0–7 eV is the emission
from the valence band composed of Nb 4d and C 2p orbitals, which are hybridized to form a
metal-carbon bond. All of the group IV and V TMC valence bands are formed through hybridiza-
tion between the metal nd and carbon 2p orbitals. It is noted that the DOS around the Fermi
level (E F) is relatively small, which is common to all the DOSs of TMCs. The band at 12 eV
is the emission from the C 2s band. It is clear that the C 2s band is split from the above valence
band, and thus the C 2s orbital makes little contribution to the metal-carbon bond. The Nb
4p3/2 , 4p1/2 , and 4s states are observed at 32.0, 34.2, and 57.5 eV, respectively (Fig. 5). These
binding energies are higher than those for pure Nb metal (30.8, 32.6, and 56.4 eV, respectively).
Figure 5 Angle-integrated soft X-ray photoemission spectrum of NbC(100).

228 Edamoto
This reflects the ionicity of the NbC crystal; the charge is transferred from Nb to C, which
should result in a smaller relaxation effect on the final state of the core-level photoemission
process at the Nb atom in the NbC crystal.
A. (100) Surface
The electronic structure of the TMC(100) surface has been studied most extensively among
the low-index TMC surfaces. It is well known that the use of angle-resolved photoemission
spectroscopy (ARPES) can give direct information about the valence band structure around the
surface (18,19), and extensive ARPES studies have been performed on the valence band struc-
ture of TMC(100) surfaces such as TiC(100) (20,21), ZrC(100) (22,23), VC(100) (24–27),
NbC(100) (28–31), and TaC(100) (32,33). These studies have shown that most of the features
in ARPE spectra can be understood as emissions from the bulk bands, and thus the electronic
structures of TMC(100) are well regarded as the cross sections of the bulk electronic states.
However, in some systems, surface induced electronic states have been identified as described
in the following.
An electronic state localized to a surface, called a surface state, has been found on a
variety of solid surfaces (18,19). The surface states are considered to play an important role in
almost all the physical phenomena on solid surfaces, such as atomic reconstruction, adsorption,
and surface magnetism (34), and thus the surface state has become the subject of many experi-
mental (18,19) and theoretical (34,35) investigations. The surface states are categorized on the
basis of their origin into two types: the Shockley state and the Tamm state. The former is the
state mainly formed through breaking of the three-dimensional periodic boundary condition at
the surface; an electronic state whose wave function decays with propagation is forbidden in
the bulk, but at the surface, a state having an exponentially decaying wave function in both
directions, into the bulk and into the vacuum, can exist. Such a state should exist in a bulk band
gap and should be substantially localized to the surface. The latter state is mainly caused by
the modification of the potential felt by electrons in the surface region, which may induce a
wave function different from that in the bulk. The state is also localized to the surface when
the potential modification is large enough. These surface states are essentially two-dimensional
electronic states, and thus the wave vector component normal to the surface (k ⊥ ) is not a quantum
number for these states. In an ARPES study, we can select the k ⊥ of the initial state by selecting
the photon energy (hν), which enables us to map the k ⊥-dependent band dispersion of the bulk
state. The surface state should not have k ⊥-dependent band dispersion, which means that the
binding energy of the peak emitted from a surface state should be independent of the photon
energy. This is one of the criteria used to identify the surface state in ARPES spectra. In addition,
surface states are substantially sensitive to surface conditions, particularly to surface contamina-
tion, which enables us to identify the surface state in ARPES spectra by gas adsorption studies.
Figure 6 shows an example from an ARPES study conducted to identify surface states
on the NbC(100) surface. Figure 6 shows the effect of a small amount of oxygen exposure on
the NbC(100) surface for the normal emission spectra where the 1 L exposure is defined as 1
⫻ 10 ⫺6 torr sec. The peaks labeled B1 and B2 are the emissions from the ∆5 and ∆1 bulk bands
along the Γ-Χ direction, respectively (31), which are almost unaffected by a small amount of
oxygen exposure. However, the peak labeled S is removed sensitively by small amount of oxy-
gen exposure, meaning that the initial state of peak S is very sensitive to surface contamination.
It was also confirmed that the binding energy of peak S (1.2 eV) is independent of the photon
energy. These results show that peak S can be ascribed to the emission from a surface state.
The state can be ascribed to a Tamm surface state pulled from the ∆5 bulk band (B 1 peak) (31).
The appearance of the Tamm surface state on the NbC(100) surface can be explained by
Figure 6 Change in the normal emission spectrum of the NbC(100) surface as a function of oxygen
exposure.
the ionicity of the crystal. In the NbC crystal, each Nb(C) atom is surrounded by six C(Nb)
atoms, and electrons would feel a sort of octahedral crystal field at each atom site. However,
on the (100) surface, each surface atom loses one coordinated atom on the vacuum side, which
results in considerable modulation of the electrostatic potential in the surface region. The modu-
lation of the potential may induce energy shifts of levels in the surface region to form new
levels localized to the surface. Such a state is a typical Tamm surface state and can be resolved
from the bulk bands in photoemission spectra when the energy shift is large enough. An upward
shift of the state is expected at the carbon site on the NbC(100) surface because the lack of a
coordinated Nb atom that is positively charged should enhance the negative potential at the
surface C atom. The ∆5 bulk band observed as peak B1 is mainly composed of C 2px,y orbitals
(31); thus the state observed as peak S can be ascribed to a Tamm surface state pulled off from
the ∆5 bulk band in the carbon site. Similar modulation of the electrostatic potential is more
or less expected for the surface of every compound crystal; thus the surface state labeled S can
be regarded as the state characteristic of compound crystal surfaces.
As described before, a Tamm surface state is observed in ARPE spectra for the NbC(100)
surface. However, the Tamm surface state has not always been observed on compound crystal
surfaces because the degree of the modification of the electrostatic potential at the surface is
dependent on several factors, such as the degree of charge transfer and surface relaxation. As
for the transition metal nitride and carbide (100) surfaces, similar surface states have been found
only for TiN(100) (36), ZrC(100) (36,37), and VC(100) (26) in addition to NbC(100) (28–31).
B. (110) Surface
In contrast to the accumulation of data on (100) and (111) surfaces of TMCs, very limited
information is available for the TMC(110) surface. The ideal (100) surface should be composed
of equal numbers of metal and carbon rows and each surface atom loses two coordinated atoms
230 Edamoto
Figure 7 Change in the normal emission spectrum of the NbC(110) surface as a function of oxygen
exposure.
in the vacuum side; however, all the TMC(110) surfaces previously studied have been proved
to be reconstructed [TiC (11), TaC (15,16), and NbC (17)].
The electronic structure of TMC(110) has been studied in terms of the NbC(110) surface
using ARPES (17). Figure 7 shows an example of an ARPES study to identify a surface state
in the valence band region. Figure 7 shows normal emission spectra for an NbC(110) clean
surface and for a surface exposed to a small amount of oxygen (⬉1 L). It is seen in Fig. 7 that
a peak at 1.7 eV (peak S) is very sensitive to surface contamination; the peak is almost removed
by a small amount of oxygen exposure (0.1 L) while the other peaks are almost unaffected. It
is also confirmed that the binding energy of peak S is independent of the exciting photon energy;
that is the state has no dispersion along the surface normal direction. Thus, the peak at 1.7 eV
is well ascribed to emission from a surface state. Further analysis of ARPE spectra has proved
that the state is a Tamm surface state pulled off from the ⌺3 bulk band mostly at the surface
carbon site where the lack of coodinated Nb atoms in the vacuum side should shift the bulk
state toward the lower binding energy side (17). The peaks in the ARPE spectra (Fig. 7) other
than that at 1.7 eV are well ascribed to emissions from the Nb 4d–C 2p bulk bands.
C. (111) Surface
The (111) surface of TMCs is a polar surface, and the surface atom loses three coordinated atoms
in the vacuum side. As mentioned in Sec. I, all the TMC(111) surfaces [except for VC(111)] are
covered with metal layers. The polar surface is usually unstable because of its large electrostatic
potential at the surface, which usually induces surface reconstructions or facetings. However,
no reconstruction of TMC(111) has been found except for the VC(111) surface (8,9), suggesting
that some unique stabilization mechanism should be operative in these surfaces. Such a stabiliza-
tion mechanism should have considerable influence on the surface electronic structure; thus the
electronic structure of the TMC(111) surface is of particular interest. The electronic structure
of TMC(111) has been studied with ARPES for the TiC(111) (20,21,38,39), ZrC(111) (40),
NbC(111) (41,42), and TaC(111) (43) surfaces, and these studies have shown that the electronic
structure of the TMC(111) surface is much different from those of the (100) and (110) neutral
surfaces; surface states derived from the nd orbitals of the surface metal atoms are formed around
the Fermi level. The states give main features in the normal emission ARPE spectra in the case
of the TMC(111) surface.
An example of ARPE spectra of the TMC(111) surface is given in Fig. 8. Figure 8 shows
normal emission spectra for the TaC(111) surface taken at various excitation photon energies
(14 ⬉ hν ⬉ 32 eV). A prominent peak is observed just below the Fermi level in the normal
emission spectra (Fig. 8). This spectral feature is characteristic of all the observed normal emis-
sion spectra of TMC(111) surfaces (20,21,38–43). The binding energy region around the Fermi
level is the region where the bulk valence DOS is relatively small (Fig. 5), and the spectra of
the (100) and (110) surfaces do not show such a prominent peak around the Fermi level (Figs.
6 and 7). The peak just below the Fermi level is observed at 0.7 eV independently of the exciting
photon energy, indicating that the initial state has no dispersion as a function of k ⊥ . Figure 9
shows normal emission spectra for the TaC(111) surface and for the surface exposed to a small
amount of oxygen (1.5 L). The gas adsorption study shows that the prominent peak just below
the Fermi level is sensitively attenuated by surface contamination. These features are characteris-
tic of the emission from a surface state, and the peak can be well ascribed to the emission from
a surface state.
Figure 8 Normal emission spectra of the TaC(111) surface as a function of photon energy.
232 Edamoto
Figure 9 Normal emission spectrum for the TaC(111) surface exposed to 1.5 L of oxygen together with
that of the clean surface.
Some theoretical studies have been performed on the electronic structures of TMC(111)
surfaces such as TiC(111) (44–47), ZrC(111) (47), and NbC(111) (47). These studies have
shown that the (1 ⫻ 1) surfaces are stabilized through charge redistribution around the surfaces;
the electron density at the first metal layers is increased to screen the long-range electrostatic
field at the surface. These studies have also shown that the charge redistribution should be
accompanied by the appearance of surface states derived from the metal nd orbitals (3d for TiC
and 4d for ZrC, NbC) in the first metal layers. The states are expected to be formed around the
Fermi level (44–47) which is in good agreement with ARPES studies (20,38–43).
Resonant photoemission spectroscopy can give valuable information about the atomic
orbital component of the state in the spectra. Figure 10 shows a plot of area intensities of the
surface state induced peak for TaC(111) as a function of the exciting photon energy. In Fig.
10, a cross section of the Ta 5d band observed in the photoemission spectra for poly-Ta (48)
is also shown. The photoionization cross section for the surface state on TaC(111) is resonantly
enhanced at hν of ⬃40 and ⬃50 eV, as in the case for the Ta 5d band in poly-Ta. These
enhancements of the cross section are well explained by the resonance process that proceeds
via photon-induced excitation,
Ta 5p 6 5d n ⫹ hν → Ta 5p 5 5d n⫹1
followed by the emission of a Ta 5d electron known as a super-Coster-Kronig decay,
Ta 5p 5 5d n⫹1 → Ta 5p 6 5d n⫺1 ⫹ e ⫺
Figure 10 Intensities of the surface state induced peak in the normal emission spectra of TaC(111) as
a function of photon energy. Intensities of the Ta 5d band in the photoemission spectra for poly-Ta (48)
are also plotted.
Because the Ta 5p orbitals split into two levels due to the spin-orbit coupling (5p 1/2 ⫽ 42.2 eV,
5p 3/2 ⫽ 32.7 eV), there are two maxima separated by ⬃10 eV in the plot. As a conclusion, the
cross section of the surface state has the hν dependence characteristic of Ta 5d photoemission,
and the state is formed through recombination of the dangling bond–like Ta 5d orbitals, as
expected from theoretical studies (44–47). Previous resonant photoemission studies of TiC(111)
(39) and NbC(111) (42) have also shown that the surface states have resonances near the 3p-
3d and 4p-4d photoexcitation thresholds, respectively.
According to the theoretical studies, the electron density at the first layer of the (111)
surface is increased relative to that at the metal layer in the bulk. In other words, the chemical
environment of a metal atom in the first layer is different from that in the bulk. It is known
that core-level binding energies in photoemission spectra are very sensitive to the chemical
environment of atoms. Figure 11 shows Ta 4f core-level spectra for clean and oxygen-adsorbed
TaC(111) surfaces. For the clean surface, two pairs of doublet peaks are observed in the Ta 4f
region. One of the pairs at 25.4 and 24.9 eV represents the emission from 4f5/2 orbitals and the
other pair at 23.5 and 22.9 eV the emission from 4f7/2 orbitals. In the spectrum for the oxygen-
adsorbed surface, one of the components of each doublet observed at the lower binding energy
side (24.9 and 22.9 eV) is not observed. As the oxygen adsorption should have a significant
effect on the surface Ta, this result indicates that the lower binding energy components of pairs
are due to the emission from the surface core-level components of Ta 4f5/2 and 4f7/2, respectively.
Furthermore, the core-level photoemission spectra show that the kinetic energy of the photoelec-
trons emitted from the 4f levels of surface Ta atoms is greater than that of electrons emitted
from bulk Ta atoms. This result is compatible with a charge redistribution model, because the
model predicts an increase of electron density at the first Ta layer that results in more effective
screening of the core-hole final state at the surface to increase the kinetic energy of photoelec-
trons from the core level.
234 Edamoto
Figure 11 Ta 4f core-level spectra for a TaC(111) clean surface and a surface exposed to 10 L of oxygen.
As just described, characteristic surface states are formed on the TMC(111) surfaces. The
states are derived through charge redistribution around the surface to screen the long-range
electric field arising from the polar structure of the surface; thus the state should be characteristic
of the ideal (nonreconstructed) polar surface. However, polar surfaces of ionic crystals are gener-
ally unstable and stabilized through atomic rearrangements such as reconstruction or facetting
rather than electronic redistributions. As for the TMC(111) surface, the ideal (1 ⫻ 1) surface
is maintained [except for the VC(111) surface], probably for the following reasons: (a) atomic
rearrangement is restrained in the TMC crystal because the metal-carbon bond in the crystal
includes considerable contribution of the covalent bond, which has strong directivity and, (b)
the TMC crystal has metallic conductivity so the charge can be redistributed with ease. As
described before, it can be concluded that the surface state on the (111) surface is characteristic
of the polar surface formed by breaking of bonds that contain ionic, covalent, and metallic bond
contributions.
The two-dimensional band structure in the surface Brillouin zone (SBZ) of surface states
can be determined from measurements of the off-normal-emission ARPE spectra. Figure 12
shows off-normal emission spectra for the (111) surface of TaC. The spectra are taken at various
detection angles (θ d ) along the ⬍211⬎ direction. The detection angles are given relative to the
surface normal direction. The surface parallel component of the wave vector (k 储) of electrons
is well approximated as conserved in the photoemission process if the surface is periodic and
the exciting photon energy is in the ultraviolet region. Thus, k 储 of the initial state of the peak
in ARPE spectra can be evaluated from
k 储 ⫽ [(2m/h 2) (hν ⫺ E B ⫺ eφ)] 1/2 sin ␪ d
where hν is the excitation photon energy, E B is the binding energy of the peak, and eφ is the
work function of the surface. Figure 12 shows that the surface state observed in normal emission
spectra (S 1) disperses toward the Fermi level with increasing θ d (i.e., with increasing k 储) and
Figure 12 Off-normal emission spectra of the TaC(111) surface as a function of detection angle. The
detection plane is parallel to the ⬍21 1⬎ direction.
crosses the Fermi level at θ d ⬃ 20°. Another surface state (S 2) appears at θ d ⬎ 10°. The two-
dimensional band structure in the SBZ can be mapped using the preceding equation. The SBZ
of the TMC(111) surface is shown in Fig. 13. The band structure of the surface states on
TaC(111) is summarized in Fig. 14.
Our systematic studies of the surface electronic structure of TMC(111) have revealed that
Figure 13 Real space atomic geometry and surface Brillouin zone for the TaC(111) surface.
236 Edamoto
Figure 14 Measured dispersion of the surface states on the TaC(111) surface.
the band structures of the surface states on group IV and V TMC(111) are rather different from
each other; the surface states on group V TMC(111) show substantial dispersion, as shown in
Fig. 14 (41–43), whereas those on group IV TMC(111) show little dispersion (39,40). This
difference cannot be explained by the simple rigid band model, and a careful theoretical study
that treats the effect of surface relaxation, the many-body effect, etc. would be needed to explain
fully the band structures of the surface states on TMC(111) surfaces.
ARPES studies performed on TMC surfaces are summarized in Table 1.
III. SURFACE REACTIVITY
The surface reactivity of TMCs has attracted considerable attention because of their use as
catalytic materials for the hydrogenation of benzene, ethylene, and carbon monoxide; the decom-
position of methanol; etc. (1). Studies of gas adsorption on well-defined surfaces of TMCs have
been performed for some systems, and it has been found that the surface reactivity of TMCs
shows considerable face dependence; the surface reactivity toward gas adsorption of (111) is
much higher than that of (100). For example, oxygen adsorption studies of TiC(100) and (111)
surfaces have shown that the sticking probability of oxygen on (111) is two orders of magnitude
Table 1 Summary of Published ARPES Studies of TMCs

Compound (100) (110) (111)
TiC (20,21) (21) (20,21,38,39)
ZrC (22,23) (40)
VC (24–27)
NbC (28–31) (17) (41,42)
TaC (32,33) (43)
larger than that on (100) (11,49). Adsorption states of CO and CH 3OH have been studied on
the NbC(100) and (111) surfaces, and it has been found that at room temperature CO adsorbs
on the (111) surface but not on the (100) surface, and CH 3OH adsorbs dissociatively to form
CH 3O and H species on the (111) surface but CH 3OH adsorbs molecularly on the (100) surface
(50). The face dependence of the reactivity described here is also predicted from theoretical
analysis using extended Hückel tight binding calculations (51). From a scientific point of view,
the face dependence of reactivity is of interest because it is considered to be due to a pure
surface effect; differences in the surface electronic structure should be responsible for the reactiv-
ity difference. As discussed in the previous section, the electronic structure of the (111) surface
is characterized by the presence of surface states formed around the Fermi level, which should
act as so-called frontier orbitals for gas-surface interaction. The lack of such states may make
the (100) surface rather inert. In this section, comparative studies of oxygen adsorption on
TiC(100) and (111) surfaces are reviewed.
Adsorption of oxygen on TiC surfaces is the most extensively studied system in the field
of surface chemistry of TMCs. Several oxygen adsorption studies have been performed on
TiC(100) (7,49,52–54) and TiC(111) (11,49,55,56) to elucidate chemisorption sites or electronic
bonding levels of chemisorption. Figure 15 shows the change in the normal emission ARPE
spectra for the TiC(100) (a) and TiC(111) (b) surfaces as a function of oxygen exposure at room
temperature. On both surfaces, oxygen is adsorbed dissociatively, forming (1 ⫻ 1) overlayers
at saturation [the (1 ⫻ 1) overlayer means that the adsorbed oxygen atoms form a two-dimen-
sional lattice whose periodicity is the same as that of the substrate surface atoms]. For the (100)
surface, chemisorption bonding states are formed at 4.1 and 5.9 eV below the Fermi level (Fig.
15a). Polarization-dependent analysis by the use of symmetry selection rules (18) has proved
that the states found at 4.1 and 5.9 eV in the normal emission spectra are oxygen 2p x,y and 2p z
Figure 15 Change in the normal emission spectra of TiC(100) (a) and TiC(111) (b) as a function of
oxygen exposure.
238 Edamoto
derived chemisorption states, respectively (54). For the (111) surface, chemisorption bonding
states are found as a single peak at ⬃6 eV (Fig. 15b); however, the polarization-dependent
analysis by the use of symmetry selection rules has proved that the peak has two components:
oxygen 2px,y and 2pz derived states, and the former is formed at a slightly higher binding energy
side (56). The adsorption is saturated at exposure to 2000 L and 5 L (1 L ⫽ 1 ⫻ 10 ⫺6 torr s)
for the TiC(100) and (111) surfaces, respectively. It was confirmed that the (1 ⫻ 1) overlayers
are nearly complete on both surfaces at saturation, so that the densities of oxygen atoms can
be estimated to be 1.08 ⫻ 10 15 and 1.25 ⫻ 10 15 per cm 2 for the oxygen-saturated TiC(100) and
(111) surfaces, respectively. Thus, it is concluded that the sticking probability of oxygen on the
(111) surface is about two orders of magnitude larger than that on the (100) surface on average.
Nearly the same conclusion was obtained from the O 1s uptake measurements with X-ray photo-
electron spectroscopy (XPS) (11,49).
It is well known that the study of the photoionization cross section of the adsorbate-
induced state can give valuable information about orbital components of chemisorption bonding
states. Figure 16 shows a plot of area intensities of O 2p–derived states for the TiC(100)-(1 ⫻
1)O and TiC(111)-(1 ⫻ 1)O systems as a function of excitation photon energy. Figure 16 shows
that the cross section for the TiC(111)-(1 ⫻ 1)O system has a large maximum in the energy
range of the Ti 3p-3d photoexcitation threshold (45–50 eV). The cross section of O 2p orbitals
does not have a resonance in this energy region, and the resonance is ascribed to the photon-
induced Ti 3p → 3d excitation followed by deexcitation through the emission of O 2p electrons
mediated by interatomic energy transfer (54). This process is expected to proceed when strong
Ti 3d–O 2p hybridization is formed. Thus the existence of the resonance is reasonable, since
the first layer of TiC(111) is composed of only Ti atoms, and the adsorbed oxygen atoms should
form strong chemisorption bonds with the surface Ti atoms. On the other hand, in the case of
the TiC(100)-(1 ⫻ 1)O system, the cross section of the O 2p derived band has a much weaker
resonance in the Ti 3p-3d photoexcitation threshold region (Fig. 16). This indicates that the
Figure 16 Intensities of the total O 2p band emission for the TiC(111)-(1 ⫻ 1)O and TiC(100)-
(1 ⫻ 1)O systems as a function of photon energy.
hybridization between the Ti 3d and O 2p levels is less important for chemisorption bonding
on the TiC(100) surface. The (100) surface is composed of equal numbers of Ti and C atoms
(Fig. 1), and the result shown in Fig. 16 is compatible with an adsorption model in which oxygen
atoms are adsorbed on the carbon on-top sites on the TiC(100) surface to form chemisorption
bonds mostly with carbon atoms. This interesting adsorption model has also been proposed in
an ICISS study (52) and a theoretical study using extended Hückel tight binding calculations
(51).
Because the adsorbed oxygen atoms form periodic (1 ⫻ 1) overlayers on both TiC(100)
and (111) surfaces, it is expected that the O 2p–derived states should have two-dimensional
band dispersions due to the lateral interaction between bonding orbitals. The two-dimensional
band structure of the chemisorption bonding state can give valuable information about the nature
of the chemisorption bond. The two-dimensional band structure is deduced from off-normal
emission ARPES measurements, as discussed in the previous section. The results for the O 2p–
derived states for the TiC(111)-(1 ⫻ 1)O system are summarized in Fig. 17. In this plot, the
coordinate system is chosen such that the z axis is normal to the surface and the x and y axes
coincide with the crystallographic ⬍011⬎ and ⬍211⬎ directions, respectively. The 2p z and
2p x,y –derived states are nearly degenerate around the Γ point and cannot be resolved in the
spectra in this region. The dispersive features for the O 2p derived states are qualitatively repro-
duced by the theoretical band structure calculated by a tight binding method for an unsupported
two-dimensional hexagonal oxygen layer (57).
Figure 17 Measured dispersion of the O 2p–derived states for the TiC(111)-(1 ⫻ 1)O system. The
surface Brillouin zone is shown in the inset.
240 Edamoto
The experimental band structure of the O 2p–derived states is characterized by stabiliza-

tion of the energy levels of 2px and 2py –derived states relative to that of the 2pz derived state.
This is not expected from the calculated band structure for an unsupported oxygen layer (57), and
thus it should reflect bonding characteristics of oxygen on the TiC(111) surface. The selective
stabilization of 2px and 2py –derived states means that the O 2px,y orbitals are more important for
chemisorption bonding than the 2pz orbital on the TiC(111) surface, i.e., are stabilized through
hybridization with Ti orbitals more effectively. According to the adsorption model proposed in
the ICISS investigation (55), the oxygen atom is adsorbed on the threefold hollow site (fcc
site) on the TiC(111) surface. In this case, the adsorbed oxygen interacts dominantly with the
surrounding three surface Ti atoms; the vertical interaction with the underlying Ti atom just
below the O atom is expected to be small because the bulk Ti atom in the TiC crystal should
already have completed covalent bonds with surrounding C atoms and is more inert than the
surface Ti atoms. Thus the lateral bonding caused by the hybridization of the O 2px,y with sur-
rounding orbitals of surface Ti is considered to be important for chemisorption on this site,
which is confirmed by the two-dimensional dispersive feature of chemisorption bonding states
shown in Fig. 17.
Figure 18 shows a plot of band dispersions of O 2p–derived states for the TiC(100)-
(1 ⫻ 1)O system, measured along the ⬍100⬎ direction. In contrast to the case of the TiC(111)-
O system, the bonding state derived from the O 2pz level is observed on the higher binding
energy side relative to the 2px,y-derived states. This result indicates that, for the TiC(100)-O
system, the oxygen-surface interaction vertical to the surface is more important for the chemi-
sorption bonding; the 2pz orbital is stabilized through hybridization with surface orbitals more
effectively. The vertical interaction is expected to be important when the oygen atom is adsorbed
Figure 18 Measured dispersion of the O 2p–derived states for the TiC(100)-(1 ⫻ 1)O system. The
surface Brillouin zone is shown in the inset.
Figure 19 Schematic views of the TiC(100)-(1 ⫻ 1)O and TiC(111)-(1 ⫻ 1)O systems.
just above the surface atom (on-top site). Thus, the two-dimensional band structure shown in
Fig. 18 is compatible with the adsorption model; an oxygen atom is adsorbed on the carbon
atom on the TiC(100) surface (52). Adsorption models for the TiC(100)-(1 ⫻ 1)O and TiC(111)-
(1 ⫻ 1)O systems are shown schematically in Fig. 19.
Another interesting example of the face dependence of surface reactivity of TMCs has
been found for alkali metal adsorption systems. Alkali metal adsorption has been studied on
NbC(100) (58) and NbC(111) (59,60), on which the mechanisms of adsorption of alkali metal
have been found to be different. For the K/NbC(111) system, the 4s level of the K atom strongly
interacts with the surface states characteristic of the (111) surface formed around the Fermi
level, which results in strong polarization of adsorbed K in the initial stage of adsorption (59,60).
Adsorbed K atoms are dipersive on the surface due to the Coulomb repulsion in the initial stage.
With increasing K coverage, adsorbed K atoms are depolarized to form a metallic K overlayer
at high coverages (59,60). The adsorption mechanism of K on the NbC(111) surface is character-
ized by a polarization-depolarization transition that is directly evidenced by ARPES measure-
ments (60). On the other hand, the surface state of high density of state formed around the
Fermi level is lacking on the NbC(100) surface, which results in weak interactions between
adsorbed K atoms and the surface. On the NbC(100) surface, it has been proposed that adsorbed
K atoms form islands from the very initial stage of adsorption and the adsorption proceeds
through the growth of islands (58). The island formation is proposed to be possible because the
polarization of adsorbed K is relatively weak due to the weak interaction with the (100) surface
even in the initial stage of adsorption. Thus the face dependence of the K adsorption process may
be ascribed to the difference in surface electronic structures of TMC(100) and (111) surfaces.
IV. SUMMARY
In this part, ARPES studies of the electronic structure and reactivity of the three typical low-
index surfaces of TMCs, (100), (110), and (111), are reviewed. For the neutral (100) and (110)
surfaces, most of the features in the ARPE spectra can be understood as the emissions from
242 Edamoto
bulk bands; thus the surface electronic structures are mostly viewed as the cross sections of
bulk bands. However, surface states derived from the potential modification at the surface due
to the lack of coordinated atoms in the vacuum side are found on some surfaces. For the polar
(111) surface [except for VC(111)], characteristic surface states composed of d orbitals of the
surface metal atoms are formed around the Fermi level, where the DOSs of neutral surfaces are
rather small. The surface states are formed through charge redistribution around the surface to
stabilize the polar structure of the surface. Because of the difference in electronic structure
between the neutral and polar surfaces, in particular in the region around the Fermi level, reactiv-
ities of these surfaces are quite different from each other; the (111) surface is more active toward
gas adsorption than the neutral surfaces. Adsorption processes for an alkali metal (K) are also
found to be different; on the NbC(111) surface, the 4s orbital of adsorbed K is strongly hybrid-
ized with the surface states to form a highly polarized state in the initial state, but the K-surface
interaction is weak and adsorbed K atoms form islands even in the very initial stage on the
NbC(100) surface.
It is evident from this review that TMC surfaces are interesting subjects of both experimen-
tal and theoretical investigations. However, at this point, information on TMC surfaces is limited
compared with the substantial accumulation of data on elemental metal and semiconductor sur-
faces. There remain many unsolved elemental problems for the TMC surfaces. For example,
the surface states on the group V TMC(111) have substantial dispersion, whereas those the
group IV TMC(111) have little dispersion, which cannot be explained by a simple rigid band
model. The TMC crystals inevitably include vacancies on the carbon site, which should have
considerable effects on the surface electronic structure, although systematic studies of this point
have not yet been performed. Parallel extensive studies, both theoretical and experimental, are
needed for further progress in the surface chemistry and physics of TMCs.
ACKNOWLEDGMENTS
I am pleased to thank the staff of Photon Factory, National Laboratory for High Energy Physics,
particularly Dr. H. Kato, for their excellent support. I am also pleased to thank Dr. S. Otani of
the National Institute for Research in Inorganic Materials for providing the single-crystal TMC
samples.
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10
Irradiation Properties of Electric Refractory
Materials
Naoto Kobayashi
Electrotechnical Laboratory, Tsukuba, Ibaraki, Japan
I. INTRODUCTION
Refractory transition metal carbides and nitrides have been explored extensively in experiment
and theory because of their attractive physical and chemical properties. These compounds are
characterized by extreme hardness and high melting points due to strong covalent bonding as
in nonmetallic materials. They have high electrical conductivity, and some of them are supercon-
ductors with superconducting transition temperatures Tc around 10 K. Most of the compounds
have a simple B1 (NaCl) structure, but the physical properties including Tc are strongly affected
by any deviation from stoichiometric composition (1). A characteristic property of B1-phase
compounds is that Tc shows far less susceptibility to disorder than in other high-Tc materials
such as A15, cluster compounds, or oxide compounds (2–4). These materials are also used in
semiconductor technology for good contact or a diffusion barrier. This suggests many potential
applications of these compounds in environments subject to irradiation. NbC, ZrN, and HfN
are included in these compounds and have attractive properties not only for superconducting
materials but also for electric materials.
NbC is a B1-phase compound with a superconducting Tc above 11 K and a stable B1
structure over a wide range of vacancy concentrations. Structural investigations of NbC have
been performed in various experiments. Short-range ordering in NbC was detected by electron
diffraction experiments (5,6) and elastic diffuse neutron scattering experiments (7). Local atomic
displacements around isolated C vacancies were investigated by X-ray diffraction experiments
(8) and channeling experiments (9). Theoretical investigations of the Tc depressions in NbC due
to deviations from the stoichiometry by existing C vacancies have been performed using cluster
calculations (10,11) and with the LCAO-CPA (linear combination of atomic orbitals–coherent
potential approximation) approach (12). The Tc depressions due to disorder are, however, gov-
erned not only by vacancies but also by other defects (lattice distortion, substitution, etc.), which
influence Tc through changes in the electronic and phonon structure, and an exact knowledge
of structural disorder is necessary in order to explain the variation of superconducting properties.
In addition to the fact that ZrN and HfN are similar in physical and chemical nature to NbC
as B1-phase compounds, they are found to have an attractive insulating phase in the higher
nitride state. Zr 3 N 4 and Hf 3 N 4 have been found to produce an insulating phase, and applications
of these compounds to cryoelectronic devices were suggested (13). This chapter discusses some
typical aspects of ion beam irradiation and ion implantation of these materials.
245
246 Kobayashi
On the other hand, refractory semiconductors can have many uses as wide–bandgap semi-
conductors. BP is a III-V compound semiconductor with a band gap of 2.1 eV. This compound
semiconductor is also characterized by several outstanding properties, such as a high melting
point above 3000°C, a high decomposition temperature of about 1130°C under 1 atm, extreme
hardness, excellent stability, and high oxidation resistance at high temperatures (14). This mate-
rial therefore has potential for application for electronic devices in extreme conditions such as
high-temperature and high-radiative conditions. This chapter also gives typical results for high-
energy ion beam irradiation, ion beam–induced reaction for metal thin films and BP, and ion
beam–induced epitaxial crystallization (IBIEC) for preamorphized BP.
II. ION BEAM IRRADIATION EFFECTS ON NbC

A. Lattice Parameter and Static Atomic Displacements
X-ray diffraction experiments on polycrystalline NbC thin films irradiated with energetic ions
at room temperature (RT) revealed appreciable changes of the lattice parameter a0 with the
preservation of the B1 structure, line broadening, and intensity weakening of the Bragg peaks.
Figure 1 shows the variation of the lattice parameter a 0 of NbC thin films as a function of He ⫹
(200 keV) and Ar 2⫹ (600 keV) fluences and the corresponding value of energy deposited into
nuclear collisions Q (eV/atom) calculated by the TRIM code (15). The samples were near-
stoichiometric NbC thin films with thicknesses of about 200 nm prepared by reactive radio
frequency (RF) sputtering using CH 4 gas. The highest Tc was 11.7 K with a transition width of
0.3 K and the lattice parameter a 0 was 4.475 Å. The values of the residual resistivity ranged
from 15 to 100 µΩ cm. The energy losses due to nuclear collisions were in the range 2.4 to
4.6 eV/nm for 200-keV He and from 350 to 500 eV/nm for 600-keV Ar, respectively, between
Figure 1 The lattice parameter a 0 of ion-irradiated NbC thin films as a function of the fluences of 200-
keV He ⫹ and 600-keV Ar 2⫹ and the corresponding deposited energy value. The lattice parameter of the
bulk sample is indicated by an arrow.
Irradiation Properties 247
the surface and a depth of 200 nm. The fluence necessary to reach a certain value of deposited
energy Q is almost two orders of magnitude larger for He irradiation than for Ar irradiation.
For both He- and Ar-irradiated samples, a 0 increases and reaches a maximum value that
is greater than the initial a 0 value by 0.4% and decreases down to a value 0.5% smaller than
the initial a 0 value. Variations of a 0 on irradiation by both ion species agree on a fluence scale
corresponding to the same deposited energy. Furthermore, a 0 shows saturation at higher fluences
for Ar-irradiated samples. Because the atomic scattering factor of the C atom, fC , is much smaller
than that of Nb, fNb , X-ray scattering by Nb atoms contributes dominantly to the line intensities.
Information about static atomic displacements can be obtained from the analysis of the Debye-
Waller factor (16). In this analysis the natural logarithm of the X-ray intensity ratio ln (I/I0 ) is
plotted as a function of sin 2 θ/λ 2 where I denotes the intensity of a line after irradiation, I0 is
the intensity of the same line prior to the irradiation, θ is the diffraction angle, and λ is the X-
ray wavelength (modified Wilson plot). The relation is expressed by
ln(I/I0 ) ⫽ ⫺2B(sin 2 θ/λ 2 ) ⫹ ln C (1)
where B is a irradiation-induced static Debye-Waller factor that is equal to 8π ⬍u ⬎, where
2 2
⬍u 2⬎ is the mean square displacement amplitude of the atoms perpendicular to the reflection
planes and C is a constant that indicates the ratio of the material volume contributing to the
crystalline diffraction after and before irradiation. When ln(I/I0 ) is plotted as a function of sin 2 θ/
λ 2 , the slope of a least-squares-fit line through the data points gives the value B, from which
⬍u 2⬎ values can be calculated, and C is obtained from the axial section value on the ordinate.
Under the assumption that the dynamical behavior of the lattice atoms is not much influenced
by the irradiation, ⬍u 2⬎ corresponds to a value of average static displacements of the lattice
atoms, especially Nb atoms.
In Fig. 2, the one-dimensional static atomic displacement amplitudes of the lattice atoms
⬍u 2⬎ 1/2 are plotted as a function of He and Ar fluence and the corresponding deposited energy.
Figure 2 One-dimensional static atomic displacements ⬍u 2⬎ 1/2 of He- and Ar-irradiated NbC thin films
as a function of the ion fluences and the corresponding deposited energy.
248 Kobayashi
One can see a distinct variation of ⬍u 2⬎ 1/2 on irradiation by both ion species and an overall
behavior similar to the variation of a 0 in spite of large uncertainties. The displacements have
a maximum value of 0.08 ⫾ 0.02 Å at irradiation state Φ 1 , where the maximum a 0 was observed,
and decrease with subsequent irradiation. Saturation was also observed for the Ar-irradiated
sample at higher fluences. The material volume contributing to the crystalline diffraction was
found to decrease with increasing fluence. This concentration amounts to about 10% at state
Φ 1 and to about 20% at state Φ 2 for samples irradiated by both ions.
B. Channeling Experiments
Rutherford backscattering spectrometry (RBS) channeling experiments with 2-MeV He ions
backscattered from an NbC single crystal have revealed the structural disorder induced by 200-
keV He irradiation at state Φ 1 (4 ⫻ 10 16 He/cm 2), where the maximum a 0 in thin films was
observed. NbC 0.98 single crystals with ⬍110⬎ crystalline direction prepared by RF zone melting
were used because the Nb and C atoms are arranged in separate chains in this direction. The
Tc value of the sample obtained by this treatment was 11.2 K (9). The aligned spectrum for the
ion-irradiated sample reflects the damage distribution, with a deep large peak that shows typical
features found in materials in which covalent bonding prevails. In the transmission region of
thin films up to 200 nm, a small increase in the dechanneling yield is observed. Angular tilt
measurements performed in the region close to the surface prior to and after the irradiation with
the window at a depth region between 20 and 80 nm from the surface have shown the angular
scans of the He ion yield backscattered by Nb atoms in the irradiated sample with a narrowing
of the critical angle ψ1/2 (half-angular width at half-height between the minimum yield and the
yield for the random direction) and a slight increase of χ min (minimum yield normalized to the
random yield). After the measurements of angular scans with some typical tilt planes in the
present experiments, the increase of the total displacements of Nb atoms ∆u tot induced by irradia-
tion can be obtained by comparison with the calculated values (9). The total displacements after
the irradiation are
⬍u 2tot⬎ ⫽ ⬍u 2th⬎ ⫹ ⬍u 2st,0⬎ ⫹ ⬍u 2st,i⬎ (2)
where uth are the thermal displacements, u st,0 are the static displacements of the virgin crystal,
and u st,i are the static displacements induced by the irradiation, respectively. If no interaction
between these displacements and no change in u th on irradiation are assumed, ∆⬍u 2tot⬎ corre-
sponds to ⬍u 2st,i⬎. The value of ⬍u 2st,i⬎ 1/2 thus obtained is 0.05 Å. This value is slightly smaller
than the displacement value obtained in the X-ray experiments, mainly because channeling ex-
periments give information for a shallower region of the sample than the X-ray experiments.
The angular tilt curves obtained from the 12 C(d,p) 13C nuclear reaction as well as from
elastic scattering of the deuterons by Nb atoms are shown in Fig. 3. The window settings for
both the reaction part and the elastic scattering part range from the surface to 200 nm. Although
the Nb(d,d )Nb angular scan shows a similar small disorder in Nb sublattice as observed with
He ions, the tilt curve of the reaction part (C sublattice) reflects the feature of a highly disordered
C-sublattice. The values Ψ1/2 ⫽ 0.38 and 0.33 and χ min ⫽ 0.21 and 0.73 are observed prior to
and after the irradiation, respectively. The analysis of defects in NbC by Monte Carlo calcula-
tions (17) has revealed quite different contributions of randomly displaced C atoms and stacking
faults to the dechanneling yield in the Nb sublattice and has reproduced well the experimental
results for C-implanted NbC. On introducing stacking faults, the Nb dechanneling yield revealed
a considerable enhancement, whereas randomly displaced C atoms only slightly contributed to
the dechanneling yield in the Nb sublattice. Because the present results reflect the latter case,
the type of defects is different from stacking faults. Instead, C interstitial clusters could be
Figure 3 Angular scans of p yield produced by the 12C(d,p) 13C nuclear reaction and d yield by the Nb
(d,d )Nb elastic scattering through the ⬍110⬎ direction of an NbC 0.98 single crystal prior to and after 4
⫻ 10 16 He/cm 2 irradiation.
predominant because isolated C interstitials hardly exist after irradiation at RT. Channeling
experiments on the He-irradiated sample were performed after the same annealing processes up
to 250°C. The observed values of Ψ1/2 and χ min in the C sublattice are 0.32 and 0.74. The Ψ1/2
value shows a small decrease after 250°C and χ min increases, indicating defect redistribution.
A striking feature is the change in the dependence of the dechanneling rate on the analyzing
beam energy. The difference in the dechanneling rates after the annealing processes up to 250°C
is nearly independent of the energy, which implies the formation of stacking faults, because
such a constant dependence on energy on introducing stacking faults with partial dislocations
has also been confirmed in the Monte Carlo calculations. The enhancement of χ min is due to the
fact that the dechanneling contribution is significantly greater for stacking faults than for isolated
interstitials (18). On the other hand, Ψ1/2 and χ min of the C sublattice show almost no change
after the annealing processes, which indicates the high stability of defects in the C sublattice.
C. Properties of Structural Disorder

In the fluence range at the irradiation state Φ 1 where the lattice parameter a 0 of the thin films
has a maximum value, the irradiation-induced defects could have the same characteristics in
He- and Ar-irradiated samples because a 0 , static displacements, Tc , and resistivities revealed
almost the same variations at the same deposited energy values and showed the same annealing
behavior, as will be described later. The structural disorder is composed of defects that cause
small Nb displacements and highly displaced C defects. The observed average static displace-
ments of the Nb atoms, whose value is 0.08 Å from X-ray diffraction experiments and 0.05 Å
from channeling experiments, are correlated with the existence of point defects such as intersti-
tial Nb atoms, including antisite defects or very small Nb clusters as suggested by channeling
experiments. In irradiation experiments of TaC0.99 with high-energy electrons (19), all C defects
250 Kobayashi
(interstitials) have been annealed out below 380 K and part of the Ta defects (30%) remained
after annealing at 380 K. The same annealing behavior was also observed in TiC0.97 (20). Judging
from these results for other carbides, isolated C interstitials should have been already annealed
out and the rest could be stabilized in form of clusters in NbC by the irradiation at RT, whereas
part of the isolated Nb interstitials should remain even at RT. Although the large difference in
atomic scattering factors of Nb and C atoms makes it difficult to distinguish small amounts of
antisite defects in X-ray diffraction experiments, part of the Nb atoms that undergo displace-
ments in this fluence region can occupy the sites of C vacancies produced by the irradiation.
The increase of a 0 at state Φ 1 can therefore be attributed to Nb interstitials including antisite
defects. These defects will produce a large strain field and will cause a lattice expansion by
overcompensating the effects of vacancies that cause the lattice contraction (21). On the other
hand, the highly disordered C sublattice observed in the channeling experiments indicates the
presence of C interstitial clusters that survive at RT. Partial recovery of a 0 after the annealing
process up to 250°C was observed, as shown later, and this correlated with the formation of
extended defects such as stacking faults with partial dislocations as inferred from the energy-
dependent dechanneling analysis. Interstitial Nb clustering into faulted loops will make such
stacking faults (extrinsic stacking faults). The clustering of Nb interstitials will reduce the strain
field and cause the partial a 0 recovery.
For the samples after high-fluence irradiation (state Φ 2 ), the nature of the defects is differ-
ent in He- and Ar-irradiated samples because Tc and resistivities showed different behavior in
spite of the close agreement of the a 0 variations. However, the main origin of the a0 decrease
is the same in both samples and is thought to be due to vacancies that did not recombine with
Nb interstitials because these agglomerate into clusters or precipitates. This is suggested because
of the continuous increase of the concentration of off-lattice-site Nb atoms in spite of an a 0
decrease during the irradiation up to this irradiation state.
D. Superconducting Transition Temperatures and Resistivities

Tc decreases continuously with increasing irradiation fluence for both He- and Ar-irradiated thin-
film samples. The Tc values determined by resistive and inductive methods are shown in Fig.
4. The widths of the transition ∆Tc are also indicated by vertical bars for inductively determined
values, whereas the widths of the resistively determined values are less than 0.4 K. Agreement
of the Tc variations between He- and Ar-irradiated samples is observed except for higher flu-
ences, where Tc shows slight deviations. For He-irradiated samples Tc decreases down to a
minimum value of 3.4 K at state Φ 2 , and for Ar-irradiated samples Tc decreases down to 4.1
K at this state and shows saturation in the fluence range where the lattice parameter a 0 has
saturated.
Irradiation-induced changes of the residual resistivity at 12 K, ∆ρ0 , the thermal part of
the resistivity ρth (⫽ρRT ⫺ ρ0, where ρRT and ρ0 are resistivities at RT and 12 K, respectively),
and the residual resistivity ratio RRR (⫽ρRT /ρ0 ) of He- and Ar-irradiated samples are observed.
In contrast to the variations of a 0 and Tc , which depended only on the total energy deposited
into nuclear collisions irrespective of the impinging ion species, the behavior of the resistivities
depends on the irradiating ions. In the fluence range above Φ 1 , ρ 0 shows a continuous increase
up to 340 µΩcm and a saturation for He-irradiated samples, while it reaches a maximum value
of 190 µΩ cm and then decreases down to a value of about 110 µΩ cm for the Ar-irradiated
sample. The residual resistivity ratio RRR decreases continuously for irradiations by both ion
species but a difference is also found in the variations of ρth. The value of Ar-irradiated samples
decreases after a slight constant region and remains positive, whereas ρth of the He-irradiated
samples decreases down to negative values. The different dependence of ρ0 and ρth on fluence
Figure 4 The superconducting transition temperature T c of He- and Ar-irradiated NbC thin films, deter-
mined by the resistive and inductive methods, respectively. Transition widths in the inductive measure-
ments are indicated by vertical bars; those in resistive measurements are less than 0.4 K.
in the He- and Ar-irradiated samples is probably due to the difference of the deposited energy
density in the displacement cascades and its influence on the structure, size, and distribution of
defects. This difference apparently has no significant influence on the a 0 and Tc variations as
can be seen in Figs. 1 and 4. The decrease of ∆ρ 0 in Ar-irradiated samples will be associated
with defect recombination phenomena in the cascades. Such an effect would be feeble in dilute
cascades in the He-irradiated samples. A negative ρth has sometimes been observed in A15
compounds or cluster compounds (22). Nevertheless, up to the critical fluence of state Φ 1 at
which the maximum a 0 is observed, the agreements of resistivities are fairly good for irradiations
by both ion species and the type of defects induced should be similar in He- and Ar-irradiated
samples.
E. Annealing Experiments on Thin Films

Isochronal annealing processes were performed for Ar-irradiated thin-film samples irradiated at
state Φ 1 (4 ⫻ 10 14 Ar/cm 2) and at state Φ 2 (10 16 Ar/cm 2 ). The annealing was performed in the
temperature range between 50 and 900°C in steps of 50 K with an annealing period of 30 min
at each temperature. The results for the Tc and a 0 recoveries in the first case (state Φ 1 ) are shown
in Fig. 5, where a 0 and Tc are plotted as a function of the annealing temperature TA. The a 0 and
Tc show a few recovery stages. One can see close agreement between the recoveries of a 0 and
Tc at temperatures around 250°C and from 650 to 800°C. This means that the defects that cause
the lattice parameter increase are also responsible for the Tc depression. However, Tc shows no
change at the recovery stage of a 0 around 450°C. By the annealing processes up to 850°C, a0
has recovered to its initial value, whereas Tc has not yet reached its initial value but has begun
to decrease again. This decrease could be due to beginning of diffusion of C atoms to grain
boundaries. Defects that could be annealed above 700°C are correlated with the displacements
252 Kobayashi
Figure 5 The superconducting transition temperature T c and the lattice parameter a 0 as a function of
the temperature T A in the isochronal annealing process for the NbC thin film with the maximum a 0 after
4 ⫻ 10 14 Ar/cm 2 irradiation. a 0,i, T c,i (R), and T c,i (I) denote the initial values of a 0, resistively determined
T c , and inductively determined T c , respectively.
of Nb atoms. This is evident from the fact that the recovery stage of the static displacements
of Nb atoms coincided well with the recovery stage of a 0 . The averaged one-dimensional static
displacements ⬍u 2⬎ 1/2 of Nb atoms decrease down to about 0.03 Å above 700°C. This recovery
of the Nb displacements could be associated with the dissociation of vacancy clusters, which
are produced by ion irradiation and partly in the subsequent annealing process. These vacancy
clusters could be dissociated at temperatures in the range from 650 to 850°C and then vacancies
could be annihilated by recombination with Nb interstitial clusters (stage V). It is commonly
assumed that self-diffusion occurs through vacancy formation and migration and that the energ-
ies of vacancy formation and migration are comparable; therefore the explanation of vacancy
cluster dissociation and migration from 650 to 850°C appears plausible. The release of strain
fields due to annihilation of Nb interstitial clusters thus induces lattice relaxation and reduction
of Nb displacements.
Variations of the resistivities of the same sample (state Φ 1 ) during the annealing processes
were investigated as a function of the annealing temperature TA . One can see some recovery
stages of the residual resistivity change ∆ρ 0 . However, these stages are at lower temperatures
than the recovery stages of a 0 and Tc . The decrease of ∆ρ 0 at 150°C preceding a 0 and Tc recover-
ies could be due to defect recombination effects and the decrease from 550 to 850°C to defect
dissociation effects. RRR increased gradually in the course of the annealing processes. The same
annealing behavior of a 0 , Tc , and resistivities has been found for the He-irradiated sample up
to 250°C, and this again reflects the existence of the same type of defects in both He- and Ar-
irradiated samples.
As for the recoveries of a 0 and Tc of the Ar-irradiated sample at state Φ 2, a 0 shows a
gradual increase above 600°C but does not reach the initial value up to 900°C. Also, Tc shows
a gradual increase above 500°C, but some inhomogeneous redistribution of defects is induced
above 600°C as inferred from the increase in the transition width ∆Tc . Complete annealing is
also not yet obtained at 900°C. The residual resistivity showed first a small increase and subse-
quently a gradual decrease during the annealing process. The broad recovery behavior above
500°C is in agreement with that of the sample irradiated at state Φ 1 , which also suggests dissocia-
tion of defect clusters.
F. Superconducting Properties
The results of the channeling experiments show that the C sublattice is highly disordered and
certain amounts of C vacancies exist in the irradiated sample. The increase of C vacancy concen-
tration in NbC is a reason for Tc depression (21,23). Cluster calculations (11) have demonstrated
that the partial local atomic density of states is heavily affected by the C vacancy concentration,
and a reduction of the electron-phonon coupling parameter λ is found to be due mainly to its
electronic part rather than to the phonon part. Calculations based on the LCAO-PA approach
have revealed that the total density of states N(0) at the Fermi energy E F increases with the
vacancy concentration (12). They have suggested other reasons for the Tc depression of NbC,
such as lifetime effects. However, the Tc depressions are not only due to C vacancies but also
have other origins such as Nb vacancies and lattice distortions. Nb vacancies heavily affect Tc
as well as C vacancies because the continuous depressions of Tc are correlated with a continuous
increase of off-lattice-site Nb atoms. The band structure calculation for NbO will give a good
inference. NbO is a compound with B1 structure usually with ordered vacancies on both metal
and nonmetal sublattices and is not superconducting above 1.2 K (24). According to the self-
consistent energy band structure calculations (25) for Nb 0.75 O 0.75 , where 25% of Nb and O
vacancies are ordered, there arise additional band structures that are related to Nb and O vacanc-
ies, and these lead to variations of the density of states at E F. Although the total density of
states N(0) at E F shows a small decrease, the partial density of states of the O-p band shows a
large decrease in comparison with those of ordered and stoichiometric B1 NbO. By this analogy,
the partial density of states of the C-p band in NbC would be heavily changed and would affect
Tc through the electronic part of λ in ion-irradiated NbC, where Nb and C vacancies coexist.
Furthermore, the phonon anomalies that are crucial for high Tc in NbC (26) could also be fairly
affected by a change in the partial density of states of the C-p band, because nonmetal-p and
metal-d scattering is important for phonon anomalies (10).
It was predicted that lattice distortions have little influence on the results of the Tc calcula-
tions in the cluster calculations, and the present results also support this idea because no direct
correlation of the variation of Tc with the variations of a 0 and static displacements was observed
in the course of the irradiation (11). The agreement between the recovery stages of a 0 and Tc
around 250°C (Fig. 5) indicates, however, that a small amount of Tc depression still depends
on the lattice distortion, because it is thought that Nb interstitial clustering has occurred at this
temperature and the strain field is released by this effect and not by vacancy annihilation. As
one can see from Fig. 5, the recovery of Tc at this temperature is much smaller than the recovery
in the temperature range from 650 to 850°C, where vacancy annihilation is thought to be predom-
inant.
III. ION BEAM IRRADIATION AND ION IMPLANTATION ON

REFRACTORY METAL NITRIDES
A. Ion Beam Irradiation Effects on ZrN and HfN
Remarkable changes in the lattice parameters (a 0 ) with preservation of the B1 structure, intensity
weakening, and line broadening of the Bragg peaks were also observed in both ZrN and HfN
254 Kobayashi
films that were ion irradiated at RT. Samples used in these ion beam irradiation experiments
are stoichiometric thin films of ZrN with thicknesses of about 170 nm and HfN with thicknesses
of about 600 nm deposited on sapphire substrates by RF sputtering using N 2 gas at around
1000°C. These samples have lattice parameters (a 0 ) around 4.573 Å for ZrN and around 4.522
Å for HfN and Tc values around 9.2 K for ZrN and around 8.3 K for HfN, respectively. Figure
6 shows the variations of the lattice parameter as a function of ion fluences (200-ke V He ⫹ ions
and 600-keV Ar 2⫹ ions for ZrN and 400-keV He ⫹ ions for HfN) and the corresponding values
of energy deposited into nuclear collisions Q (eV/atom) for ZrN and HfN films. The fluence
necessary to reach a certain value of deposited energy Q is almost 150 times larger for the He
irradiation than for the Ar irradiation of ZrN. The agreement between a 0 variations due to He
and Ar ion irradiations of ZrN samples on a fluence scale corresponding to the same deposited
energy indicates that the residual ions in thin films have little influence and displacements by
Figure 6 The lattice parameter a 0 of ion-irradiated ZrN and HfN thin films as a function of the fluences
of 200-keV He, 600-KeV Ar, or 400-keV He and the corresponding value of the deposited energy. Z28
and Z30 denote sample names of ZrN films. H45 and H46 denote sample names of HfN films.
nuclear collisions are the major origin of the variation in the lattice parameter. The deposited
energy Q values that give the maximum a 0 values are shifted to higher values in both nitride
films and the relative a 0 increases are smaller than for NbC (∆a 0 /a 0 ⫽ 0.3% in ZrN and ∆a 0 /
a 0 ⫽ 0.2% in HfN). The subsequent lattice contractions of ZrN and HfN are smaller than in
NbC at the same deposited energy values. In contrast to NbC films, where a large amount of
lattice contraction is observed, a 0 values reach to the initial values for both ZrN and HfN sam-
ples. For the one-dimensional static atomic displacement amplitudes of the lattice atoms, one
can see a variation of static atomic displacements similar to that of the lattice parameter for
ZrN as for NbC, whereas the displacements in HfN increase continuously during the irradiations.
The increases of the lattice parameter in both ZrN and HfN thin films at the first stage
of the irradiations could be attributed to the same origin as in the case of NbC. Isolated nonmetal
interstitials should already have been annealed out and the rest could be stabilized in the form
of clusters by the irradiation at RT, whereas isolated metal interstitials, some of which can
occupy the vacancy sites of nonmetal atoms (antisite defects), should remain even at RT. These
metal defects can produce a large strain field and also cause a lattice expansion in these nitrides.
The subsequent decrease in the lattice parameter could be due to precipitation of metal atoms,
which results in release of the strain in the regular lattice sites. Agreement between the variation
of the lattice parameter and that of the static atomic displacements in ZrN supports this idea,
because static displacements would become small after the strain release by precipitation. Never-
theless, the continuous increase in the static displacements observed in HfN indicates another
mechanism such as stacking fault formation, because a strain field still remains during the de-
crease of the lattice parameter. The variations of the lattice parameter with composition in ZrN
and HfN show unusual behaviors. They have stable phases on both the metal atom–rich side
and the nonmetal atom–rich side (1) In both ZrN and HfN, the lattice parameters show slight
increases when the nonmetal atom sublattices are defective, whereas they show decreases when
the metal atom sublattices are defective (27). This unusual variation is very different from the
case of NbC, where no stable B1 phase exists on the nonmetal atom–rich side and nonmetal
atom vacancies lead to lattice contraction (21). In the present nitride compounds, the small
decrease in the lattice parameter at high irradiation fluence could be attributed to the coexistence
of vacancies in both sublattices, because the vacancies in both sublattices have opposite influ-
ences on the lattice parameter.
The Tc values of the Ar-irradiated ZrN film and the He-irradiated HfN film are shown as
a function of the irradiation fluence and the deposited energy in Fig. 7. They decrease continu-
ously with increasing irradiation fluence from 9.2 K down to 3.8 K for ZrN and from 8.3 K
down to 3.0 K for HfN. The widths of the transition temperature (temperature difference between
10% and 90% drops in the resistivity) were maintained within 0.4 K during the irradiations.
The residual resistivities at 11 K (ρ 0) and the residual resistivity ratios (RRR ⫽ ρ RT /ρ 0) were
measured before and after the irradiation procedures. The residual resistivities increase continu-
ously from the initial value of ρ 0 ⫽ 30 µΩ cm to 200 µΩ cm in ZrN and from the initial value
of ρ 0 ⫽ 230 µΩ cm to 490 µΩ cm in HfN. The residual resistivity ratios decrease continuously
from the initial value of RRR ⫽ 3.0 to 1.15 in ZrN and from the initial value of RRR ⫽ 1.15
to 1.05 in HfN.
The continuous decreases in Tc during the irradiations in ZrN and HfN should be relevant
to the vacancies, because no direct correlation between the variations of Tc and those of the
lattice parameter suggests little influence by the lattice distortion. Because in substoichiometric
phases of HfN, Tc remains constant on the metal atom–rich side and shows a decrease with the
content of nonmetal atoms on the nonmetal atom–rich side (27), metal vacancies might be
mainly responsible for the Tc depression in HfN.
256 Kobayashi
Figure 7 The superconducting transition temperature T c of Ar-irradiated ZrN thin film and He-irradiated
HfN thin film as a function of the ion fluences and the deposited energy. Transition widths are less than
0.4 K.
B. Ion Implantation into ZrN

1. Structural Properties
ZrN and HfN have attracted interest because of the insulating property of the metastable higher
nitride state. Johansson et al. (28) have investigated the structural and electrical properties of
the phase Z r3 N 4 synthesized with dual ion beam deposition. Schwarz et al. (13) have calculated
the electron energy band structure of this new phase and have proposed this material as an ideal
material for building Josephson junction devices.
Experiments on N ion implantation in ZrN thin films were performed in order to investi-
gate the process of N atom incorporation in this material and its influence on the structure,
electrical resistivity, and superconductivity. Polycrystalline stoichiometric thin films of ZrN with
thicknesses of about 250 nm deposited on single-crystal sapphire substrates by RF sputtering
using Ar and N 2 gas were used for the implantation samples. The partial pressure was 2 ⫻ 10 ⫺2
torr for Ar gas and in the range 1.7 to 8 ⫻ 10 ⫺3 torr for N 2 gas, and the substrate temperature
was maintained at 1000°C during the deposition. Samples had a well-developed polycrystalline
structure and had values of the lattice parameter (a 0 ) around 4.572 Å, Tc around 9.5 K, and
residual resistivity (at 11 K) around 30 µΩ cm.
Nitrogen ions were implanted at RT and at 380°C (high temperature, HT) up to the fluence
corresponding to the composition with Zr 3 N 4 (x ⫽ 0.33 in ZrN 1⫹x). Multiple-energy implantation
with a suitable fluence ratio was employed in order to achieve homogeneous doping of the films
throughout the depth. In a typical case of a sample of thickness 250 nm, N implantation was
performed at energies of 40, 90, and 200 keV with a fluence ratio of 1:2.1:6. In this case, doping
of 1% of the existing N concentration (x ⫽ 0.01 in ZrN 1⫹x) requires a total fluence of 1.49 ⫻
10 16 N/cm 2 .
Throughout the whole implantation process at both RT and HT, the B1 structure was
preserved and no other phase was observed. An initial increase followed by a decrease in the
lattice parameter was observed for the low-dose implantation such as in Ar (600 keV)–irradiated
samples. In the Ar irradiation experiments, the range of the Ar ions was beyond the film thick-
ness. The agreement of the lattice parameter variations between the N-implanted and the Ar-
irradiated samples in the low-fluence region could imply a major influence of defects (displaced
atoms, vacancies, and their clusters) induced by the implantation and a minor influence of im-
planted N atoms on the lattice expansion and contraction, because of the much smaller concentra-
tion of the residual irradiated atoms throughout the film thickness in the Ar-irradiated samples.
However, the observed reincrease in the lattice parameters in N-implanted samples at RT in the
high-fluence region reflects the influence of the implanted N atoms on the lattice expansion.
In Fig. 8, lattice parameters in the ZrN films implanted with N ions to higher fluences at
RT and at HT are shown as a function of the implanted N atom concentration x. Here the lattice
parameter decreases monotonically at HT and increases monotonically at RT. The color of the
samples implanted at both RT and HT changed from shiny gold to dark brown during the implan-
tation processes below x ⫽ 0.25 and showed an obscure transparency with a dark green color
at the composition with x ⫽ 0.33. Values of atomic displacements for both RT implantation
and HT implantation increased with the concentration of implanted N atoms. Nevertheless, dis-
placement values for RT implantation exceed those for HT implantation by 50 to 100% reflecting
the nature of the highly distorted structure.
As stated, the lattice parameter in ZrN shows an unusual dependence on the composition.
It shows a decrease in the N-rich side and remains constant in the Zr-rich side (1). The augmented
spherical wave (ASW) calculations of Schwarz et al. show the lattice parameter around 4.52 Å
in Zr 3 N4 , where 25% of Zr sites are left vacant (13). The progressive decrease of the lattice
parameter down to 4.556 Å in the N-implanted ZrN films at HT, therefore, suggests incorpora-
tion of most of the implanted N atoms in the substitutional sites, leaving vacancies at Zr sites,
whereas the increase of the lattice parameter in the samples implanted at RT could be due to
Figure 8 The lattice parameter a 0 of N-implanted ZrN films for RT implantation and HT (at 380°C)
implantation as a function of the implanted N atom concentration x in the high-fluence region.
258 Kobayashi
an increase of the strain field in the host lattice with incorporated extra N atoms mainly in the
interstitial sites. The larger static atomic displacements in the host lattice in the samples im-
planted at RT than in the samples implanted at HT also suggest high lattice distortion in the
implanted samples at RT.
2. Electrical Resistivity and Superconducting Transition Temperature

Increases in the electrical resistivities at RT (ρ RT ) and 11 K (ρ 0 ) in N-implanted ZrN films at
both RT and HT are shown in Fig. 9 as a function of the implanted N atom concentration.
Although we can see higher resistivities with an increasing N atom concentration, full insulating
properties were not reached even up to the final implantation concentration of x ⫽ 0.33 with
both RT and HT implantations. Resistivities in the samples implanted at HT exceed considerably
those in the samples for RT implantation in the initial implantation processes. They showed,
however, rather constant values at x ⫽ 0.22 and smaller values than those for RT implantation
at the final implantation step with x ⫽ 0.33. Semiconducting behavior in resistivities where the
ρ 0 is in excess of ρ RT was observed beyond x ⫽ 0.25 for RT implantation and beyond x ⫽ 0.15
for HT implantation.
The Tc in the samples implanted at RT first shows a prominent decrease down to 3.5 K
at x ⫽ 0.02 followed by a constant region and degradation below 1.3 K. In the range between
x ⫽ 0 and x ⫽ 0.02 for RT implantation, Tc decreases exponentially as a function of the total
implanted fluence. The Tc for HT implantation showed a decrease down to 5 K at x ⫽ 0.05
followed by a gradual decrease to 3.1 K at x ⫽ 0.33. The superconducting transition width was
maintained within 0.2 K for HT implantation but increased gradually for RT implantation.
The increase in the electrical resistivities with implanted N atom concentration could have
two origins. One is the localization effects (Anderson localization) due to implantation-induced
disorder (29). The other is the change in the electronic band structure due to the occurrence of
Figure 9 Resistivities at RT and at 11 K in N-implanted ZrN thin films for RT implantation and for
HT (at 380°C) implantation as a function of the implanted N atom concentration x.
another phase. Electron energy band calculations based on a simple defect structure indicate
that Zr 3 N 4 with 25% Zr vacancies on the B1 lattice has a low density of states at the Fermi
energy and suggest that Zr 3 N 4 is almost an insulator (13). The influence of the localization
effects could be smaller in the samples implanted at HT rather than RT, because less disorder
has been introduced at HT than at RT. Therefore, the larger resistivities in the samples at HT
are thought to be due mainly to the change in the electronic band structure as a result of the
higher nitride state formation. On the other hand, the change in the increasing behavior of
resistivity in the high N concentration region (x ⱖ 0.28) in the samples implanted at HT may
imply a change in the mechanism of the direct incorporation of N atoms into the substitutional
N sites.
The metastable phase of Zr 3 N 4 with 25% vacancies in Zr lattice sites is not known from
the equilibrium phase diagram and is based on the model proposed by Johansson et al. (28).
They showed experimental results with incorporation of large amounts of noble gas atoms (Ne,
Ar, or Xe) into Zr 3 N 4 . This can support the picture of the structure with vacant Zr sites, because
all these noble gas atoms are considerably larger than the N atoms and it is impossible for the
gas atoms to occupy the N lattice sites. Higher nitride states could be produced especially with
the HT implantation, as discussed earlier.
IV. ION BEAM IRRADIATION EFFECTS ON BP

A. Ion Beam Irradiation Effects on BP
In contrast to that of Si or GaAs, the study of ion beam irradiation effects on BP is very limited.
There has been little knowledge of the nature of defects induced by irradiation or implantation
for BP (30). It is of interest to investigate the basic properties of defects in ion-implanted BP
and the potential of BP in radiation environments, which can extend its applications in a new
field. For these purposes, knowledge of the structural disorder induced by irradiations with MeV
ions in this material is important. Figure 10 shows RBS-channeling spectra (P yield) for a single-
crystalline BP sample observed with 2-MeV He ions at 135° to the beam incidence direction
Figure 10 RBS-channeling spectra (P yield) for a CVD-grown BP sample observed with 2-MeV He
ions at 135° to the beam incidence direction. Spectra are shown for the random and the aligned incidences
before and after 1-MeV Ar irradiations with fluences up to 3.0 ⫻ 10 14 Ar/cm 2.
260 Kobayashi
(31). The BP samples were prepared by thermal decomposition of B 2 H 6 and PH 3 on Si(100)

(14). Spectra are shown for the random and the aligned incidences before and after 1-MeV Ar
irradiations with fluences up to 3.0 ⫻ 10 14 He/cm 2 at RT. The calculated range of 1-MeV Ar
in BP is nearly 790 nm with straggling of 105 nm. After the irradiation with 3.0 ⫻ 10 14 Ar/
cm 2 , the maximum aligned yield reached the random yield and a broad peak of dechanneling
yield in the depth direction was observed. The structure that exhibits the broad disordered region
in depth is similar to that in GaAs and a feature of compound semiconductors. Full amorphiza-
tion was observed after 1.4 ⫻ 10 15 Ar/cm 2 irradiation. For the Ar-irradiated sample, Fig. 11
shows angular scans of the He ion yield backscattered by P atoms and α yield by the 11B( p,α) 8 Be
nuclear reaction of a BP sample before and after 1-MeV Ar irradiations. The interferences be-
tween sublattices should be taken into account in the dechanneling by the individual sublattices
because displacements of atoms in the heavier sublattice could have a large influence on the
dechanneling yield in the lighter sublattice. Atomic displacements in the P sublattice could affect
the dechanneling by steering the incident ions that make close collisions with atoms in the B
sublattice for BP. Even when this effect is taken into account, the increase of the dechanneling
yield for the B sublattice is still larger than when the same amounts of displacement are assumed
(32). Therefore, the B sublattice shows a large susceptibility to irradiation, and this might be
due to the difference between values of the displacement energy (E d ) for B atoms and P atoms.
With the investigation of the dependence of the dechanneling rate dχ/dz (the variation of
dechanneling yield χ as a function of depth z) on the analyzing ion beam energy and the relation
that expresses the product of the dechanneling cross section σ D and the defect concentration N s
as σ D Ns ⫽ ∆(dχ/dz) (1 ⫺ χ min) ⫺1, where χ min is the minimum dechanneling yield, one can extract
some features of defects in ion-irradiated BP (33,34). This analysis revealed that a stacking
fault seems predominant in Ar-irradiated BP. On the other hand, for light ion irradiation (2-
MeV He) where the defect region is very broad in depth and does not show any defect peak,
the dependence of the value of σ D N s has revealed that sparse amorphous clusters or lattice
distortions with small static displacements mainly induced by antisite defects are the major
Figure 11 Angular scans of the He ion yield backscattered by P atoms and α yield by the 11B( p,α) 8Be
nuclear reaction of a BP sample before and after 1-MeV Ar irradiations. The angle φ indicates the orienta-
tion of the tilt plane relative to the {110} crystal plane.
defect features for He-irradiated BP samples that have the same level of increase of the dechan-
neling yield. In this case, however, similar large susceptibilities for the B sublattice have also
been observed. The difference in the defect structure between light and heavy ion irradiations
can be attributed to the difference in the deposited energy density in the collision cascades.
B. Ion Beam–Induced Reactions of Metal Thin Films and BP

The reactions of metal films with BP substrate are useful from the viewpoint of device applica-
tion of this compound. For Ni on BP(100), the thermal reaction processes were observed to
start between 350 and 400°C. Transient metastable phases were formed at a temperature between
400 and 450°C. Formation of the crystalline phase corresponding to a mixed binary phase (NiB
⫹ Ni 3 P) was observed at 450°C. A second phase with less Ni content was observed to be formed
beyond 600°C (35,36). On the other hand, the solid-phase reactions of Ni thin films with BP(100)
by the ion bombardment process have also been investigated from the viewpoints of advantage
in ion process for local process capability and low-temperature process possibility. Figure 12
shows RBS spectra of the reacted layer of Ni on BP with ion bombardments at various tempera-
tures. BP samples with a 50-nm-thick Ni thin film were bombarded with 600-keV Xe 2⫹ ions at
liquid nitrogen (LN 2 ) temperature, RT, and 200°C. The feature of inhomogeneous reaction was
observed for the samples bombarded at LN 2 . The reaction induced at RT shows partly reacted
Figure 12 RBS spectra of Ni thin film (50 nm) on BP(100) bombarded with 600-keV Xe 2⫹ at various
substrate temperatures to a constant fluence of 5 ⫻ 10 15 Xe/cm 2.
262 Kobayashi
behavior of the Ni layer and the reacted layer has the same composition as that induced at
200°C. The fully reacted layer with ion beam bombardments at 200°C has revealed a crystalline
phase that is the same as that of the thermally induced first phase, whereas the reacted layer
induced at LN 2 and RT shows an amorphous phase.
The progress of the reacted layer thickness as a function of the fluence of 600-keV Xe 2⫹
ions was observed in the fluence range from 1 ⫻ 10 14 to 8 ⫻ 10 15 Xe/cm 2 at various substrate
temperatures. The full reaction (50 nm) was observed with bombardments to 7 ⫻ 10 14 Xe/cm 2
at 200°C. The results reflect the progress of the reaction depending linearly on the ion fluence.
The dependence of the reaction progress in the thermal process examined at temperatures be-
tween 350 and 475°C has shown approximately linear dependence of the reaction on the duration
of the annealing time. In the ion beam–induced process, an overall linear dependence of the
reacted layer on the ion fluence in the temperature range between RT and 300°C was observed,
and the reaction had a small temperature dependence below RT and a strong temperature depen-
dence above RT. Although the activation energy for the reaction in the thermal reaction process
was observed to be 1.3 ⫾ 0.3 eV, an activation energy of 0.31 ⫾ 0.06 eV was obtained for
the ion beam–induced process at elevated temperatures above 100°C. The strong temperature
dependence of the ion beam–induced reaction process above 100°C could reflect the feature of
radiation-enhanced reaction. Intracascade effects that lead to the collapse of point defects into
dislocation loops could be responsible for the reaction, and these intracascade effects should
also be taken into account in the present Ni-BP system, where the activation energy is relatively
low. The reaction at temperatures lower than RT could be attributed to the cascade mixing
mechanism, which dominates at lower temperatures and is relatively insensitive to temperature.
Linear dependence of the reaction on bombarding ion fluence is a feature of the reaction
of the system of Ni on BP. In silicide formation in some metal-Si systems linear dependence
of the reaction progress on the ion fluence was observed in the ion beam–induced reaction (37).
This is thought to be due not to a simple diffusion process but mainly to the nonequilibrium
nature of the reaction process. In the Ni-BP system, amorphous phase formation at RT and
metastable phase formation in the thermal process suggest a complex mechanism of nonequilib-
rium reaction. As an example of the reaction of metal films on a refractory compound semicon-
ductor, a thermal reaction process (38,39) and ion beam– and laser-induced processes were
reported for Ni on SiC (40). In these cases, the first reacted phase was induced around 500°C
and was found to be a binary phase (Ni 31 Si 12 or Ni 2 Si); no reaction of Ni with C atoms was
observed. In contrast to the case of SiC, the reaction in the Ni-BP system was induced at lower
temperatures and the mixed binary phase of NiB ⫹ Ni 3P was the first phase of the Ni thin film
on BP. The preceding metastable phase below 450°C in the thermal reaction process before
formation of the first stable phase could be due to competing Ni-B and Ni-P reactions. The
dominant moving species in the reaction of Ni on BP is thought to be Ni from the results for
oxygen accumulation between the reacted layer and the nonreacted layer (35,36).
C. Ion Beam–Induced Crystallization for Preamorphized BP

Ion beam–induced epitaxial crystallization (IBIEC) has attractive features from the viewpoint of
beam-solid interactions especially in semiconductors. Specific properties and phenomenological
understandings of IBIEC in Si have been hitherto obtained on the basis of extensive investiga-
tions (41–45). The features of the process have provided not only a new field of investigation
of beam-solid interactions but also a possibility of process application of Si because of its advan-
tages, such as processing at low temperatures, local process capability, and metastable phase
formation by impurity atom incorporation at a nonthermal equilibrium concentration.
Crystalline growth properties of IBIEC in III-V compound semiconductors are, however,
less well known than in Si (46). In the refractory material BP, IBIEC was observed at extremely
lower temperatures than those expected from the high melting point (47,48). For the IBIEC
experiments, a 90-nm-thick amorphous surface layer on CVD-grown BP(100) was formed by
100-keV As implantation to a dose of 6 ⫻ 10 14 As/cm 2 at RT. The samples were preannealed
at 450°C for 15 min to provide an abrupt crystalline-amorphous (c/a) interface. The amorphized
samples were then bombarded with 400-keV Ar and Kr ions at 350°C. The current density was
changed from 0.06 to 4 µA/cm 2. Calculated values of nuclear energy deposition ν n (E ) at the
initial c/a interface are 0.45 and 1.9 keV/nm per ion for 400-keV Ar and 400-keV Kr, respec-
tively. The beam incidence direction for implantation and IBIEC was set to 7° with respect to
the sample surface normal. Analyses of the crystalline growth and structural properties of the
grown layers were performed by the RBS-channeling technique using 2-MeV He ⫹ ions. The
scattering angle used was 105° to the beam incidence direction.
RBS-channeling spectra (P yield) representing IBIEC in the P sublattice of BP by 400-
KeV Ar bombardments at 350°C are shown in Fig. 13, where planar growth up to the surface
is demonstrated. Nevertheless, a deviation from the stoichiometric composition (decrease of P
concentration) was observed in the last stage of crystalline growth. Recovery in the B sublattice
could also be observed in the lower energy region in RBS spectra, but the large dechanneling
yield near the end of the range of bombarding ions affects precise analyses of the growth in
the B sublattice. It is noted that IBIEC for BP was induced at such a low temperature in spite
of the high critical temperature for Solid Phase Epitaxial Growth (SPEG) (above 800°C), which
was confirmed in the separate experiments. Overall linear dependences on the ion dose in the
initial bombardment stages (⬍1.5 ⫻ 10 15 Ar/cm 2) could be seen at 250–400°C, whereas growth
thicknesses show deviations from linear growth at higher doses. As shown in Fig. 13, fairly
high doses of Ar ions were required to attain the final crystallization up to the surface. This
Figure 13 Random and ⬍100⬎-aligned RBS spectra representing crystalline growth of a-BP by IBIEC
with 400-keV Ar at 350°C (P yield). The initial amorphous layer was obtained by 100-keV As implantation
to a dose of 6 ⫻ 10 14 As/cm 2 at RT.
264 Kobayashi
feature is different from the IBIEC in GaAs. A weak dependence of the crystalline growth rate
on the ion species used for preamorphization (Ar, As, and P) was also observed in BP (47).
Figure 14 shows crystalline growth rate versus nuclear energy deposition density at 350°C
in a-BP (amorphous-BP) as a function of nuclear energy deposition density rate and correspond-
ing ion current density (dose rate) for 400-keV Ar and Kr bombardments. The results also reflect
the large dependence of growth rate on ion dose rate in BP, although the growth rate with Kr
is larger than with Ar at the lowest dose rate. The large dependence of the growth rate on the
dose rate implies that the dynamic behavior of the defect motion is also responsible for the
IBIEC process in BP.
In the same nuclear energy deposition regime, heavy ions produce a low density of colli-
sion cascades with a large cascade volume, whereas light ions produce a high density of collision
cascades with a small cascade volume. The interaction among collision cascades becomes promi-
nent in the higher dose rate region for heavy ion bombardments because of the large volume
of the collision cascade and this can prohibit effective migration of defects to the c/a interface
or rearrangements of atoms at the interface, resulting in the decrease in growth rate in IBIEC.
On the other hand, in the lower dose rate region, where interactions between collision cascades
are small, the interaction between defects in a cascade that forms some type of defect complex
Figure 14 Crystalline growth rate per nuclear energy deposition density at 350°C for BP preamorphized
by 100-keV As implantation as a function of ion current density of 400-keV Ar and 400-keV Kr and
corresponding nuclear energy deposition density rate.
could have a crucial role. Characterization for amorphous silicon (a-Si) by positron annihilation
experiments has revealed that small vacancies (trivacancies and/or quadrivacancies) exist in the
IBIEC-grown Si layer (49) and some of the dangling bonds are located at small vacancy-type
defects in a-Si (50). If the dangling bond is responsible for IBIEC, the small vacancies formed
by ion bombardments in the amorphous layer could have a crucial role. The reason that Kr-
induced IBIEC has shown a higher growth rate per nuclear energy deposition density (nuclearly
normalized growth rate, NNGR) than Ar-induced IBIEC in BP in the lowest dose region (Fig.
14) might be that highly efficient small vacancy cluster formation is caused by high-density
defect formation in a collision cascade by heavier ion bombardments. Therefore the dependence
of NNGR on ion species is thought to be a result of the competitive process between the interac-
tion of collision cascades and the interaction of defects in a cascade.
V. CONCLUSIONS
Ion beam irradiation–induced changes in structure and superconducting properties were investi-
gated for refractory metal carbides and nitrides. Structural disorder in He- and Ar-irradiated
thin films of NbC, ZrN, and HfN and single crystals of NbC has been investigated by X-ray
diffraction and channeling experiments, respectively. An appreciable change of the lattice pa-
rameter with the preservation of B1 structure and a continuous Tc depression down to around
3–4 K during the irradiation have been observed. The influences of He and Ar irradiations on
both the lattice parameter and Tc are nearly the same at a given deposited energy value. The
increase of the lattice parameter in the low-fluence range is attributed to interstitial metal defects
including antisite defects, and the subsequent decrease of the lattice parameter is attributed to
the clustering or precipitation of metal atoms. The Tc depression would be due mainly to both
metal and nonmetal vacancies.
Examples of incorporation of implanted N atoms in ZrN thin films are presented with RT
implantation and with HT implantation. X-ray diffraction experiments showed the B1 structure
to be stable throughout the implantation. The N atoms are thought to be incorporated mainly
in interstitial sites with RT implantation and in substitutional sites with HT implantation. The
increase in the resistivity in the samples implanted at RT should be due mainly to localization
effects, and that in the samples implanted at HT should be due to the change in the electronic
band structure. Although full insulating properties due to Zr 3 N 4 phase formation could not be
obtained and Tc remained at 3.1 K in the HT implantation experiments, fairly large amounts of
implanted N atoms are thought to be incorporated in the substitutional sites with HT implanta-
tion. This emphasizes the usefulness of the ion implantation technique in the modification of
B1 phase compounds.
Reactions were induced by energetic heavy ion bombardments from LN 2 temperature to
300°C. A metal-rich mixed binary phase was also formed in the ion beam–induced reactions
at 200°C, whereas an amorphous layer with the same composition was formed by the bombard-
ments at RT. The crystalline phase has the same compositions and X-ray diffraction patterns for
thermal and ion beam–induced reactions. The reaction progress in the thermal process depends
approximately linearly on the duration of the annealing time with an activation energy E a ⫽
1.3 ⫾ 0.3 eV. A linear dependence of the reacted thickness on the ion fluence was observed
between RT and 300°C. An activation energy of E a ⫽ 0.31 ⫾ 0.06 eV was observed in the ion
beam–induced process above 100°C.
In addition to the high-energy ion irradiation properties where large susceptibility of the
B-sublattice was observed, IBIEC in BP has revealed crystallization up to the sample surface.
A large dependence of the growth rate especially with heavy ions on the ion dose rate was
266 Kobayashi
observed for BP. This is thought to reflect a crucial role of interactions between collision cas-
cades and between defects in a collision cascade. The IBIEC experiments performed for BP
have shown a novel feature of the epitaxial growth at lower temperatures for compound semicon-
ductors.
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11
Transition Metal Carbide Field Emitters
Yoshio Ishizawa
Iwaki Meisei University, Iwaki, Fukushima, Japan
I. INTRODUCTION
The phenomenon that electrons are emitted from a metal surface or a semiconductor surface in
the presence of a strong electric field is called field emission (FE). The emission mechanism
has been well understood as electron tunneling through the surface potential barrier (1). Features
of field emission are high brightness and coherence and its small source size. Cold field emission
sources that operate at room temperature have attracted much attention in the fields of high-
brightness cathodes and vacuum microelectronics (2). Investigations (3–8) of field emission
characteristics from atomic sources constitute a new field in cold field emission. Among conven-
tional cathode materials, the present field emission source is a tungsten single crystal. However,
the field emission current from a tungsten source is not very stable and a more stable field
emission source is expected to be developed for wide use. The transition metal carbide emitters
are promising field emission sources that produces highly stable emission currents (9,10).
The transition metal carbides (TMCs) with an NaCl-type structure such as TiC and NbC
have strong advantages as field electron emitters. These carbides have high melting temperatures
of around 3000–4000°C and form some of the most stable materials (11,12). Important features
of TMCs are high mechanical strength, low ion-sputtering rate, low electrical resistivity, high
chemical inertness, and low work function. The main bonding is strong covalency between metal
d and carbon p states. The group IV carbides are semimetals, and the group V carbides are
typically metals from standard band theory. Wide nonstoichiometry is another feature of car-
bides, indicating that there are carbon-deficient carbides without metal deficiencies. Many prop-
erties depend largely on the carbon vacancy concentration. Therefore the exact chemical compo-
sition is quite important for carbides. In the case of TiC x, the NaCl structure exists in the
composition range of x from 0.55 to 0.97. In Table 1, several properties of TMCs with the
NaCl-type structure are collected and compared with each other.
In this chapter, we focus on FE characteristics of TMC emitters using ⬍110⬎-oriented
tips that show highly stable emission at room temperature because of the appropriate surface
processing (9,10). That is, emission currents from the graphite-covered surface on carbides are
highly stable because of the surface processing.
In the case of the TiC FE source. FE properties of clean surface tips were studied by several
investigators (13–17). Emission current instabilities such as step- and spikelike fluctuations were
found as a feature of the TiC FE source. In some cases, stable emission currents were observed
269
270 Ishizawa
Table 1 Features of Transition Metal Carbides with the NaCl-Type Structure a,b
Property TiC ZrC HfC NbC TaC
Melting Point b(K) 3340 3693 4201 3873 4256
Microhardness (kg/mm 2) 2900 2700 2300 2400 1600
Electrical resistivity (µΩ cm) 130 40 34 32 18
Work function c (eV) 3.8 4.0 4.5 4.2 4.3
Nonstoichiometry (C/M) 0.55–0.97 0.60–0.99 0.60–0.98 0.72–0.98 0.75–0.99
a
Properties of the TMC with nearly stoichiometric composition at room temperature.
b
Highest melting point temperatures at the relevant composition.
c
The value for the (100) clean surface (44,46).
with appropriate flashing temperatures. However, it is difficult to obtain stable emission currents
with good reproducibility. The surface-processed tip overcame obstacles of emission instability
(18,19). It was also found that emission currents from graphite-covered surfaces of NbC tips
are highly stable (20). These excellent FE properties are common features among the group IV
and group V carbides.
II. FIELD EMISSION PROPERTIES OF TRANSITION METAL CARBIDE

EMITTERS
A. Field Emission Patterns and Emission Characteristics of Transition
Metal Carbide Emitters
1. Single-Crystal Tips
There have been several investigations of the FE properties of the TMCs. The FE properties
of TiC were first reported by Senzaki and Kumashiro (13) in 1974. Since then, many papers have
been published on TiC (14–17,21–27), ZrC (17,24), HfC (17), NbC (20), and TaC (23,28,29). Of
these TMCs, we focus on TiC as a typical case of the group IV carbides and NbC as a typical
case of the group V carbides and compare TiC with NbC.
TiC x and NbC x single crystals with nearly stoichiometric (x ⫽ 0.96) and highly uniform
composition were grown by the zone leveling–floating zone technique (30,31). Single-crystal
rods with approximate dimensions of 0.2 ⫻ 0.2 ⫻ 3 mm were cut from a single crystal with
a spark-erosion machine. The rod axis was selected along the ⬍100⬎, ⬍111⬎, or ⬍110⬎
direction. Then the rod was spot welded at a tantalum hairpin wire and electrolytically sharpened
to a tip with a radius of about 0.1 µm. An expanded view of the carbide single-crystal tip is
shown in Fig. 1. The single-crystal tip was then set in the ultrahigh vacuum system. In this
experiment, the carbide tips were operated at room temperature, and the FE patterns and emission
currents were studied to clarify emission characteristics of TMC emitters.
2. Field Emission Patterns

In order to get the FE pattern from a clean surface, the single-crystal tips of TiC⬍100⬎ and
⬍110⬎ emitters were flash heated up to 1500–1600°C in a high-vacuum system. Figure 2a and
c show typical FE patterns from clean surfaces of these tips (9). The FE patterns changed from
asymmetrical patterns to symmetrical patterns through several flash-heating procedures. The
⬍100⬎ tip shows a fourfold symmetrical pattern, and the ⬍110⬎ tip shows a twofold symmetri-
cal pattern. The ⬍111⬎ tip also shows a threefold symmetrical pattern, which is not shown in
Field Emitters 271
Figure 1 Expanded view of carbide ⬍110⬎ field emitter tip. (From Ref. 18.)
Fig. 2. It was clarified experimentally that these emission patterns do not change even on expo-
sure to a gas such as oxygen up to 2000 L (Langumuir; 1 L ⫽ 1.33 ⫻ 10 ⫺4 Pa s). This property
of the FE pattern is much different from that of a tungsten tip.
The FE patterns can be interpreted as follows. In TiC, the lowest work function of about
3.7 eV appears in the (100), (110), (210), and (310) planes and the highest value of 4.7 eV is
in the (111) plane (32). It is easily predicted from this knowledge that a ⬍100⬎-oriented tip
should show an FE electron beam at the center if the electrons are emitted from a plane with
a low work function. The experiment does not show the predicted pattern. There is no electron
beam at the center as shown in Fig. 2a.
The FE patterns are related to the tip shape change. The tip shape becomes a polyhedron
composed of the (100) and (111) planes after flash heating above 1500° C, because the surface
energy of the (100) and (111) planes in TiC is relatively low compared with those of other
crystal planes (32). The polyhedral shape of the tip was directly confirmed by field ion micros-
copy (FIM) studies of a TiC single crystal (14). The tip has several sharp points on the top,
which are indicated by letters A and B in Fig. 2b and d. Points A and B correspond to bright
spots of emission patterns. Therefore, observed emission patterns can be interpreted in terms
of emissions from strong electric field portions of the tip. This interpretation is consistent with
the insensitivity of the FE patterns to exposures such as oxygen as explained earlier.
The TiC⬍110⬎ tip has an electron beam on the center as shown in Fig. 2c. Therefore,
the TiC⬍110⬎ tip is important from an application point of view. There are no differences in
current stability between the ⬍100⬎ tip, the ⬍111⬎ tip, and the ⬍110⬎ tip as shown later,
so most data are taken for the carbide ⬍110⬎ tip.
In the case of NbC tips, the same FE patterns as for TiC tips have been observed (10).
In order to get the FE pattern for a clean surface, NbC⬍110⬎ tips were flash heated at 1600°C
at a pressure of 10 ⫺8 Pa. As in the case of the TiC⬍110⬎ tip, emitted electrons hit the central
part of the fluorescent screen as shown in Fig. 2c. This means that electrons are emitted parallel
to the tip axis. Therefore, the NbC⬍110⬎ tip is important for applications. Other NbC tips such
as the ⬍100⬎ and ⬍111⬎ tips show a fourfold or threefold symmetrical patterns, respectively,
the same as for TiC tips.
272 Ishizawa
Figure 2 Field emission patterns and tip shape models of TiC⬍100⬎ and ⬍110⬎ tips. (From Ref. 9.)
3. Emission Currents
The following data on emission currents from carbide tips were obtained at room temperature
immediately after flash heating a tip. As it has been found that the stability of the total field
emission currents is almost equivalent to that of the local emission currents, measured emission
currents are usually the total field emission if there is no indication in the text.
The most important thing in evaluating cathode materials is to do the emission experiment
under no degassing environment from the anode surface. In order to achieve such a condition,
it is necessary to use small currents for the evaluation. Figure 3 shows the applied voltage versus
flashing temperature relation for a TiC⬍100⬎ tip while the total emission current is kept con-
stant at 25 nA (16). The TiC tip was first flashed at 1850°C to obtain a clean surface, then
exposed to air. The applied voltage was measured at room temperature at a pressure of 1 ⫻
10 ⫺8 Pa after each flashing temperature.
Emission properties of the TiC⬍100⬎ tip are characterized by three temperature regions
as shown in Fig. 3. Emission currents are stable in low-temperature region 1 (1300°C ⱕ T ⱕ
1450°C) and high-temperature region 3 (T ⱖ 1700°C) and unstable in temperature region 2
(1450°C ⱕ T ⱕ 1700°C). The total field emission currents with time in temperature regions 1
Field Emitters 273
Figure 3 Applied voltage versus flashing temperature relation of TiC⬍100⬎ tip at P ⫽ 7.5 ⫻ 10 ⫺9 Pa.
(From Ref. 16.)
and 3 are shown in Fig. 4 (17). The current fluctuation is below 0.2%, and the current drift is
quite small, below ⫺0.5%/h. However, it was also confirmed that higher currents result in larger
fluctuation and drift than in Fig. 4. The current fluctuations are composed of steplike and spike-
like fluctuations which are characteristic properties of emission currents from a TiC tip. Figure 5
shows emission currents in temperature region 2 (17). Typical steplike and spikelike fluctuations
Figure 4 Field emission currents with time of TiC⬍100⬎ tip in flashing-temperature regions 1 and 3.
P ⫽ 7.5 ⫻ 10 ⫺9 Pa. (From Ref. 17.)
274 Ishizawa
Figure 5 Field emission currents with time of TiC⬍100⬎ tip in flashing-temperature region 2. P ⫽
7.5 ⫻ 10 ⫺9 Pa. (From Ref. 17.)
instead of 1/f noise as usually seen in W and metal emitters are seen in the figure. This current
fluctuation in TiC is very similar to that in a glassy carbon emitter (33,34).
It has also been established that the current stability of TiC tips is independent of the tip
axis. Emission currents of the TiC⬍110⬎ tip (18–20) at 1600°C (temperature region 2), which
are very important for applications are shown in Fig. 6 (18). The steplike and spikelike fluctua-
tions peculiar to carbide tips are seen. As emission currents are relatively large, the stable temper-
ature regions 1 and 3 cannot be defined in this experiment. Also, the TiC⬍111⬎ tip (24) has
the same current feature as ⬍100⬎ and ⬍110⬎ tips.
As for the mechanism for noise generation, it is useful to note the noise frequencies. It
has been found that the number of steps and spikes of the TiC⬍100⬎ tip is nearly proportional
to the product of the current and residual pressure (15). In this case, the number of steps and
spikes per 20 min was plotted against the product of total emission currents and the vacuum
pressure as shown in Fig. 7 (15). This type of fluctuation is considered to be caused by ionic
collision of the residual gas at the tip surface (35). As seen in the figure, the generation frequen-
cies of the steps and spikes are large at 1600°C (region 2) but on heating the tip at 1950°C
(region 3) decrease to about 1/40 of that.
Here, some speculation is presented to explain the existence of the three temperature
regions of current stability. The boundary temperature of 1450°C between regions 1 and 2 is
clearly that for making the clean surface. The tip in region 1 is composed of the adsorbed
surfaces. Therefore the tip in regions 2 and 3 corresponds to the clean surface and produces
almost the same symmetrical FE pattern. The boundary temperature of regions 2 and 3 is relevant
to the surface composition.
The carbon vacancy at the TiC(100) surface was investigated by impact collision ion
scattering spectroscopy (36). This experiment suggests that the observed carbon vacancies al-
Field Emitters 275
Figure 6 Field emission currents with time of TiC⬍110⬎ tip in flashing-temperature region 2. P ⫽
3.2 ⫻ 10 ⫺8 Pa. (From Ref. 18.)
Figure 7 Number of steps and spikes per 20 minutes observed in the emission currents from a
TiC⬍100⬎ tip with the product of total emission currents (I ) and the background pressure (P). The upper
line corresponds to a flashing temperature of 1600°C and the lower line to 1950°C. P ⫽ 1.5 ⫻ 10 ⫺8 Pa.
(From Ref. 15.)
276 Ishizawa
Figure 8 Field emission currents with time of NbC⬍110⬎ tip at a flashing temperature of 1900°C.
P ⫽ 1.5 ⫻ 10 ⫺8 Pa. (From Ref. 10.)
most disappear on heating the tip in temperature region 3. That is, the surface composition in
region 3 is nearly stoichiometric, whereas the surface in region 2 includes some carbon vacancies
produced by the ion sputtering and desorption processes of adsorbed oxygen in addition to the
intrinsic vacancies. At the surface with carbon vacancies, the activation energy of atom migration
around the vacancies decreases and the atoms near the vacancies are easy to move by thermal
excitation and ion bombardment. Moreover, reactivity with residual gases increases more on a
surface without vacancies. This difference in the surface properties produces the different emis-
sion stability.
Emission characteristics of the TiC tip with flash heating in region 3 are quite good, but
a higher current produces higher fluctuations, and the tip shape changes after many flashings,
which causes a drastic change in the FE pattern. Moreover, it is quite difficult to get to the
stable state in region 3. An easier way to get more stable emission was investigated starting
with the emission from the adsorbed surfaces, and finally a graphite-covered TiC⬍110⬎ tip
was found to be a highly stable field emitter (9,10,18–20).
As an important TMC emitter, the NbC⬍110⬎ tip among the group V carbides was
selected and investigated. Emission currents from the clean surface of an NbC⬍110⬎ tip (10)
are shown in Fig. 8. Step- and spikelike fluctuations superposed on current decrease with time are
observed under the ultrahigh vacuum condition. Higher evacuation does not reduce the current
fluctuations. The graphite-covered NbC⬍110⬎ tip has been found to be a highly stable emitter
(10,20). The next section discusses how they were developed and their highly stable emission.
III. FIELD EMISSION PROPERTIES OF MONOLAYER GRAPHITE/TMC

EMITTERS
A. Forming and Evaluating a Monolayer Graphite on TMC
It has been established that TiC⬍110⬎ and NbC⬍110⬎ tips produce highly stable emission
currents after optimal surface processing (9,10). Investigations of HfC indicate similar FE prop-
erties (37,38). The present surface processing of the tips is carried out in the following two
Field Emitters 277
Table 2 Forming Conditions and Lattice Constants of Monolayer

Graphite on Transition Metal Carbide Surfaces
Forming condition Lattice constant
Substrate (°C, L) (nm)
TiC(001) 1250, 7 ⫻ 10 5 0.247
W/TiC(001) 1100, 30,000 0.245
TiC(111) 1100, 200 0.250
ZrC(001) 1100, 1 ⫻ 10 6 0.247
ZrC(111) 1050, 300 0.250
HfC(001) 1500, 1 ⫻ 10 6
HfC(111) 1050, 200 0.249
NbC(001) 1250, 50,000 0.247
NbC(111) 1100, 300 0.252
TaC(001) 1500, 50,000 0.246
TaC(111) 1100, 200 0.253
Source: Refs. 40–46.
steps. First, the clean surface tips are heated at 1000–1100°C with the voltage off in a gas such
as ethylene (C 2 H 4 ) for a suitable exposure time. Ethylene is a typical reaction gas in hydrocarbon
systems. Second, the total field emission of 10–20 µA is extracted at room temperature after
evacuation into the ultrahigh vacuum and maintained at least for 30 min.
After this procedure, the effects of the surface processing appear. The first effect is a
change in the FE pattern, the second is an increase in the emission currents under the constant-
voltage condition, and the third is stabilization of the emission currents. These effects are always
reproduced by the same procedure. This is a general phenomenon among transition metal car-
bides.
It has to be noted that monolayer graphite (MLG) can be synthesized on the tip surface
due to the surface processing using ethylene. This was confirmed by forming monolayer graphite
on the surfaces of carbide single-crystal disks under the same condition as the surface processing
of the tip (39–41).
Monolayer graphite can be formed on the flat surfaces by heating the single-crystal carbide
disks in an ethylene atmosphere. It has been found that the (111) surface is much more reactive
than the (001) surface. The forming conditions on carbide surfaces (40–46) are summarized in
Table 2. In the case of the TiC(111) surface, minimal ethylene exposure is 100–200 L at 1100°C.
It is very difficult to form MLG on a TiC(001) surface, indicating that exposures over 1 million
L using ethylene gas are needed (45). In the case of the NbC(111) surface, minimal ethylene
exposure is 100 L at 1000–1100°C, and more than about 25,000 L exposure at 1100–1250°C
is needed to form graphite on an NbC(100) substrate.
Forming graphite on carbide surfaces can be characterized and confirmed by low-energy
electron diffraction (LEED), Auger electron spectroscopy (AES), high-resolution electron en-
ergy loss spectroscopy, and ultraviolet photoelectron spectroscopy. Figure 9a shows a LEED
pattern of a graphite overlayer on NbC(111) (41) after 300 L exposure at 1100°C: six fundamen-
tal spots of the graphite overlayer in addition to fundamental substrate spots with satellite spots.
The satellite spots are attributable to multiple diffraction. The lattice constant of the graphite
overlayer is estimated to be 0.252 ⫾ 0.002 nm. This is about 2% larger than that of pristine
graphite. A LEED pattern of the graphite overlayer on NbC(100) after 50,000 L exposure at
1250°C shows a ring pattern with 12 spots on it and fundamental substrate spots as shown in
278 Ishizawa
Figure 9 LEED pattern of monolayer graphite on NbC single-crystal surfaces. (a) Monolayer graphite
on the NbC(111) surface, E ⫽ 117.3 eV. (b) Monolayer graphite on the NbC(100) surface, E ⫽ 170.1
eV. (From Ref. 41.)
Fig. 9b. The former shows a randomly oriented graphite layer and two-domain epitaxial parts.
The estimated lattice constant is 0.247 ⫾ 0.001 nm, which is the same as that for pristine
graphite.
A more powerful technique for identifying the graphite overlayer is high-resolution elec-
tron energy loss spectroscopy. Figure 10a and b are phonon dispersion relations of the graphite
overlayer on NbC(100) and NbC(111) surfaces, respectively (10,41). The phonon wave number
parallel to the surface is obtained from the electron energy and the scattering geometry according
to the momentum conservation law (40). The phonon dispersion relation also indicates that the
Field Emitters 279
Figure 10 Phonon dispersion relations of monolayer graphite on NbC single-crystal surfaces. (a) Mono-
layer graphite on the NbC(100) surface. (b) Monolayer graphite on the NbC(111) surface. (From Ref. 10
and 41.)
overlayer is graphite and the six branches of the phonon indicate that the graphite overlayer
consists of a single layer. This is monolayer graphite, which is also confirmed by other data
such as LEED intensity, AES intensity, and the π band dispersion relation (42,44,45,47–49).
It is evident from Fig. 10 that there are six distinct phonon modes in the monolayer graph-
ite. The LO branch is a longitudinal optical mode. The LA branch is a longitudinal acoustic-
like mode. The ZO branch is a vertically vibrating transverse optical mode. The ZA branch is
a vertically vibrating acoustic-like mode. The SHO branch is a shear horizontal optical mode.
The SHA is a shear horizontal acoustic-like mode. The last two SH modes appear because of
the lack of mirror symmetry in these experiments (39).
The phonon dispersion relation of the monolayer graphite on the NbC(001) surface is
almost same as that of pristine graphite, whereas that of monolayer graphite on NbC(111) shows
large softening as shown in Fig. 10. This tendency is observed in other TMCs, indicating that
280 Ishizawa
the monolayer graphite is softened on the ‘‘metallic’’ (111) surfaces but not on the ‘‘carbidic’’
(001) surfaces (44). This behavior has been discussed in detail based on the covalent bond
formation between the π orbitals of the graphite and the d orbitals of the substrate (44,45,48).
B. Field Emission Characteristics of Monolayer Graphite/TMC Emitters

1. Field Emission Patterns
The first effect of the surface processing is a change in the FE pattern. Figure 11a shows the
FE pattern of the ethylene-processed TiC⬍110⬎ tip (9). The central beam is strongly enhanced
compared with the clean FE pattern. Finally, only a central beam remains in the FE pattern. A
similar FE change occurs at the NbC⬍110⬎ tip (10) as shown in Fig. 11b. These pattern changes
are interpreted by sharpening the central portion of the tip whose model is shown in Fig. 11c.
The tip shape change is considered to be caused by transfer of carbon atoms due to the strong
field.
2. Increase in the Emission Currents

The second effect of the surface processing for TMC⬍110⬎ tips is that the emission currents
increase under constant-voltage conditions. A typical ethylene exposure dependence (10) of the
Figure 11 Field emission patterns and tip shapes of surface-processed TMC⬍110⬎ tips. (a) Surface-
processed TiC ⬍110⬎ tip; (b) surface-processed NbC⬍110⬎ tip; (c) the tip shape. (From Ref. 9 and 10.)
Field Emitters 281
Figure 12 Ethylene exposure dependence of the applied voltage of the NbC⬍110⬎ tip under constant-
current condition (10 hA). (a) Applied voltages just after the first step of the surface processing. (b) Applied
voltages after continuous emission of 20 µA for 30 min. (From Ref. 10.)
applied voltage for the NbC⬍110⬎ tip is shown in Fig. 12. These data were obtained under a
constant-current condition (10 nA). The open circles represent the applied voltages just after
the first step of the surface processing. In this step, a pattern change does not occur yet. The
applied voltages increase a little with the exposure owing to an increase in the work function.
The solid circles represent the applied voltages after continuous emissions of 20 µA for 30 min,
which is the second step of the processing. The applied voltages decrease rapidly over 100 L
exposure. The FE pattern also changes according to the rapid decreases of the applied voltages
over 100 L exposure. Therefore the emission current increase under constant-voltage conditions
is due to the tip sharpening.
Fowler-Nordheim plots of the TMC⬍110⬎ tip also support the tip sharpening. Fowler-
Nordheim plots of the TiC⬍110⬎ tip (9) are shown in Fig. 13. In this case, the surface pro-
cessing was done with 500 L ethylene exposure at 1000°C. Open circles (a) are the Fowler-
Nordheim plot of the clean surface tip flashing at 1600°C. Open and solid squares (b) and (c)
are data for the surface-processed tip flashing at 950 and 1150°C, respectively. The slope for
the surface-processed tip is clearly smaller than that for the clean surface tip. The ratio of the
slope for the surface-processed tip to that for the clean surface tip is about 0.4 in this case.
When we flashed the surface-processed tip at 1200°C, experimental points, solid circles (d),
returned to the state of the clean surface tip. The FE pattern also returned to that of the clean
surface tip. This indicates that the surface state of the surface-processed tip changes back to
that of the clean surface tip on flashing above 1200°C. This is due to the diffusion into the bulk
282 Ishizawa
Figure 13 Fowler-Nordheim plots of the TiC⬍110⬎ tip. The surface processing was done with 500 L
ethylene exposure at 1000°C. (a) Flashing temperature (Tf ) ⫽ 1600°C (the clean surface tip); (b) Tf ⫽
950°C; (c) Tf ⫽ 1150°C; (d) Tf ⫽ 1200°C. (From Ref. 9.)
from the graphite overlayer that is formed by the surface processing. The NbC⬍110⬎ tip also
shows the same behavior, and the ratio of the slopes of the surface-processed tip to clean surface
tip is about 0.3 in this case (10).
The slope of the Fowler-Nordheim plot is approximately proportional to rφ 3/2 , where r
and φ are the tip radius and the work function, respectively (1). After the surface processing,
the value of the r s φ s3/2 /rc φ c 3/2 ratio in the Fowler-Nordheim plots becomes about 1/3, where the
suffixes s and c corresponding to the surface-processed tip and the clean surface tip, respectively.
Because the work function does not change much after the surface processing, as shown in
Table 3, the rs /rc ratio becomes almost the same as the slope ratio of about 1/3. Therefore, the
change in the slope indicates the smaller tip radius. That is, sharpening of the tip happens at
the surface-processed tip. This is probably due to mass transfer caused by the high electric field
effect.
Table 3 Work Function of the Clean Surfaces and

Graphite-Covered Surfaces of Transition Metal Carbides
Work function (eV)
Graphite-covered
Substrate Clean surface surface
TiC(111) 4.7 4.4
TiC(001) 3.8 4.5
ZrC(111) 4.7 4.3
ZrC(001) 4.0 4.2
HfC(111) 4.9 3.7
HfC(001) 4.5 4.3
NbC(111) 5.0 3.8
NbC(001) 4.2 4.2
TaC(111) 4.7 3.5
TaC(001) 4.3 3.9
Source: Refs. 42, 44–46, 48.
Field Emitters 283
Figure 14 Field emission currents with time after flashing the surface-processed TMC⬍110⬎ tips. (a)
NbC⬍110⬎ tip; P ⫽ 2.1 ⫻ 10 ⫺8 Pa. The surface processing was done with 25,000 L ethylene exposure
at 1000°C. (b) TiC⬍110⬎ tip; P ⫽ 2.0 ⫻ 10 ⫺8 Pa. The surface processing was done with 100 L ethylene
exposure at 1100°C. (From Ref. 9 and 10.)
3. Emission Current Stabilization

The most striking effect of the surface processing is stabilization of the emission currents. It
has been found that the surface processing forms monolayer graphite on the surfaces of transition
metal carbides and the existence of the monolayer graphite is deeply related to current stabiliza-
tion. Figure 14 shows emission currents with time for the TiC⬍110⬎ and NbC⬍110⬎ tips
after the surface processing (9,10,18). The step- and spikelike fluctuations of the emission cur-
rents from the clean surfaces of TiC⬍110⬎ and NbC⬍110⬎ tips can be greatly reduced by
surface processing. In the most stable emission, the step- and spikelike fluctuations are less than
0.2% and the current decrease with time is less than 0.1% per hour.
The surface-processed tip shows highly stable emission compared with a W tip. Therefore
the usual evaluation of current fluctuations is not adequate. Here we define a new term, ‘‘stable
emission current’’ (9). This is the maximum current whose fluctuation amplitude is less than
1% in the initial 20 min after applying the voltage. In contrast to the surface-processed
TiC⬍110⬎ tip, the emission stability of the NbC⬍110⬎ tip depends on the ethylene exposure
(10). These experimental data are shown in Fig. 15. The ordinate is stable emission current (I )
times the environmental pressure (P), which means the degree of the stability. The stability of
Figure 15 Ethylene exposure dependence of the emission stability of the surface-processed NbC⬍110⬎
tip. The surface processing was done at 1000°C. (From Ref. 10.)
284 Ishizawa
the 25,000 L tip is better than that of 100–500 L tips. This difference can be explained by the
existence of monolayer graphite on the carbide surfaces of the emission area. Monolayer graphite
is formed on the NbC(111) surface at an exposure over 100 L, and at least 25,000 L exposure
is needed to form on the NbC(100) surface. The different conditions for forming monolayer
graphite on the (111) and (100) surfaces are deeply related to the degree of emission stability
of the NbC⬍110⬎ tip.
Figure 16 shows the stable emission current versus pressure relation for the surface-pro-
cessed TiC⬍110⬎ and NbC⬍110⬎ tips (10). Data represented by open circles (a) are for the
TiC⬍110⬎ tip and data shown by full circles (b) and a solid line (c) are for the NbC⬍110⬎
tips. The data of (a) and (b) show that log I is proportional to ⫺log P. The current fluctuations
are proportional to the product of I and P. The solid line in Fig. 16c is a calculated stable
emission current for the 25,000 L ethylene-processed NbC⬍110⬎ tip using data for the stable
emission current of 24 µA at 2.1 ⫻ 10 ⫺8 Pa. The stable emission current of the 25,000 L ethylene-
processed NbC⬍110⬎ tip is about 50 µA at 1 ⫻ 10 ⫺8 Pa. Figure 16 indicates that the stable
emission current for the ethylene-processed NbC⬍110⬎ tip is larger than that for the ethylene-
processed TiC⬍110⬎ tip. That is, the NbC tip is more stable than the TiC tip. This difference
in emission stability is attributable to lack or existence of monolayer graphite on the (100)
surface. Monolayer graphite can be formed on the NbC(100) surface over 25,000 L ethylene
exposure, but it is quite difficult to form monolayer graphite on the TiC(100) surface.
It is quite important to identify the built-up region of the surface-processed carbide tip.
It is mainly composed of graphite because the same phenomenon was not observed for the clean
carbide tip, but experimental identification remains for future work. Moreover, it is noted that
the monolayer graphite on the carbide surfaces is chemically inert. Oxygen and hydrogen atoms
could not be detected on monolayer graphite at room temperature even on oxygen and hydrogen
Figure 16 ‘‘Stable emission currents’’ versus pressure relation of the surface-processed TiC⬍110⬎ and
NbC⬍110⬎ tips. (a) TiC⬍110⬎ tip; the surface processing was done with 100 L ethylene exposure at
1100°C. (b) NbC⬍110⬎ tip; the surface processing was done with 100 L ethylene exposure at 1000°C.
(c) NbC⬍110⬎ tip; the surface processing was done with 25,000 L ethylene exposure at 1100°C. (From
Ref. 10.)
Field Emitters 285
gas exposure (46). This inertness of the monolayer graphite is greatly related to stabilization
of the emission currents.
IV. SUMMARY
Surface-processed TMC⬍110⬎ tips have been developed as cold field emission sources. The
surface processing consists of heating the tip at about 1000°C in an ethylene atmosphere and
subsequent continuous emission of 10–20 µA for more than 30 min. Emission current instability
is less than 0.2% with optimal surface processing. Monolayer graphite has been found on
TMC(111) and (100) surfaces using ethylene exposure conditions similar to those for surface
processing. It is concluded that the monolayer graphite formed on the tip after surface processing
is greatly related to stabilization of the emission currents.
ACKNOWLEDGMENTS
The author would like to thank Dr. Takashi Aizawa for numerous helpful discussions and for
supplying phonon dispersion figures for monolayer graphite and photographs of their LEED
patterns.
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12
NbN Superconducting Devices
Masahiro Aoyagi
Electrotechnical Laboratory, Tsukuba, Ibaraki, Japan
I. INTRODUCTION: HISTORY OF NbN SUPERCONDUCTING DEVICES
A superconductor shows specific characteristics such as no resistance, gap voltages, a Josephson

effect, and a Meissner effect. These characteristics are utilized for to realize an electron device.
An ultralow loss transmission line can be realized by using a superconducting electrode. A high-
speed switching device and memory device, high-frequency mixing device, and voltage standard
device can be realized by using a Josephson tunnel junction.
The initial research on superconducting devices was done using soft and fragile metals
such as Pb and Sn. The superconducting devices made with soft metals deteriorated easily with
a thermal cycle between room temperature and liquid He temperature.
The introduction of hard and refractory materials such as Nb and NbN into Josephson
junctions improved the durability in thermal cycles. This improvement has promoted rapid de-
velopment of superconducting devices.
Nb/oxide/Nb, Nb/a-Si/Nb, and NbN/oxide/NbN junction processes were proposed by
IBM (1), Sperry (2), and ETL (3), respectively. Some preliminary work on an integrated device
succeeded with these processes. After that, an Nb/AlO x /Nb junction process was proposed by
AT&T (4). This process is widely used in the field of superconducting electronics. Many re-
searchers have obtained fine results in application work on a superconducting device.
In some application fields of superconducting devices, the Nb junction is not sufficient.
Nb compounds such as NbN, Nb 3 Al, Nb 3Sn, and Nb 3Ge were studied for this purpose. Only
NbN has been continuously studied for superconducting devices. Concerning the other materials,
no one has succeeded in developing a method of making a high-quality superconducting device.
Today, oxide superconducting materials are widely studied but have problems of reliability and
reproducibility.
Niobium nitride (NbN) of B1 crystal structure has attractive characteristics, such as a
higher superconducting transition temperature of ⬃15 K, a larger superconducting gap energy
of ⬃2.5 eV, and higher chemical and thermal stability, compared with Nb. The high transition
temperature of NbN makes it possible to realize a higher temperature operation than with Nb
devices and improves the durability against temperature variation. The large gap energy of NbN
produces a higher frequency response. This property is very important for mixing devices and
microwave devices. NbN can be stored for a long time in the air at room temperature. Moreover,
NbN is stable even in the vacuum annealing process at 800°C. Nb is oxidized even in air at
room temperature.
289
290 Aoyagi
II. NbN THIN FILMS

A. Fabrication
1. Chemical Vapor Deposition
In the chemical vapor deposition (CVD) method, NbN films are fabricated by decomposing
NbCl 5 gas in NH 3 and H 2 gases at a high temperature, about 1000°C. When MgO single crystal
is used as a substrate, single-crystal NbN film can be grown (5).
2. RF Sputtering
In the radio frequency (RF) sputtering method, NbN films are fabricated by reactive sputtering
in an RF glow discharge with an Nb target in Ar and N 2 gases (6–16). A typical sputtering
system is shown in Fig. 1. To obtain highly uniform properties of NbN films, rotation of the
substrate is necessary. High-Tc NbN films, which have a Tc of over 15 K, are normally obtained
by heating a substrate at over 500°C. To make a Josephson junction, decreasing the substrate
temperature is required. We can obtain a high-Tc NbN film by adding a carbon source such as
CH 4 or C 2 H 2 gas without substrate heating (9,14). When an MgO or SiC single crystal is used
as a substrate, single-crystal NbN film can be grown by heating the substrate at over 300°C
(15,16).
3. DC Sputtering
In the DC sputtering method, NbN films are fabricated by reactive sputtering in the DC glow
discharge with an Nb target in a mixture of Ar gas and N 2 gas (17–20). For making a Josephson
junction, RF sputtering is more suitable than DC sputtering. The grain sizes of the fabricated
films are smaller than that of the films fabricated in DC sputtering. The film surface is smoother
than that of the films fabricated in DC sputtering.
4. Ion Beam Sputtering

NbN film fabrication has been reported (21). Low deposition rate is a serious problem. Junction
fabrication has never been reported.
Figure 1 Schematic diagram of RF sputtering system for NbN films.

NbN Superconducting Devices 291
5. Pulsed Laser Deposition

This method has been developed recently. We can make a film of a material with a high melting
point by this method. NbN film fabrication has been reported. A high deposition rate is easily
realized in this method (22,23). Junction fabrication has never been reported.
B. Properties of NbN Films

1. Superconducting Transition Temperature
The superconducting transition temperature Tc of an NbN film fabricated by the RF sputtering
method is as shown in Fig. 2. The Tc of the fabricated NbN film is varied with the nitrogen
content and methane content of the sputtering gas.
After annealing in a vacuum at about 800°C, the Tc of the NbN film does not change.
The NbN film is very stable against high-temperature treatment (24).
2. Magnetic Penetration Depth

In a superconductor, magnetic field penetrates to penetration depth λ, called the magnetic pene-
tration depth. Generally speaking, λ of NbN is thought to be larger than that of other supercon-
ducting materials. This is a problem for integrated circuit applications. Large λ requires a thick
film for a wiring layer in an integrated circuit. A film thickness of 1.5λ is needed to avoid
adding extra inductance. Measured values of λ in NbN films have been reported (14,25). For
a polycrystalline film fabricated by RF sputtering, the value of λ is from 300 to 400 nm. When
the value increases, the film thickness decreases. The reason is thought to be that the grain size
of the film decreases with decreasing film thickness. For a single-crystal film fabricated by RF
sputtering, the value of λ is about 200 nm. The value is independent of the film thickness. This
is thought to be acceptable for integrated circuit applications.
Figure 2 (a) Superconducting transition temperature Tc of the NbN film with changing ratio of N 2 gas
partial pressure. (b) Superconducting transition temperature Tc of the NbN film with changing ratio of CH 4
gas pertial pressure (N 2 gas, 6.7 %).
292 Aoyagi
3. Grain Size and Morphology

In an NbN polycrystalline film fabricated by RF sputtering, a columnar structure has grown
perpendicular to the substrate. The columnar grain diameter in a 200-nm-thick film was mea-
sured in the range from 20 to 50 nm (26).
III. NbN JOSEPHSON JUNCTIONS
Josephson junctions using NbN as electrodes have been developed in several institutes. Amor-
phous silicon (α-Si), niobium oxide (NbO x ), magnesium oxide (MgO), aluminum oxide (AlO x),
and aluminum nitride (AlN) have been investigated as tunnel barriers for all NbN junctions.
NbN base junctions were studied in the beginning stage of junction development (27,28).
Today, these are not investigated because of poor reliability.
A. ␣-Si Tunnel Barrier

α-Si was first investigated as a tunnel barrier in NbN junction development (29–33). It has the
attractive characteristic of a low dielectric constant (⑀ r ⬃ 10), which produces a low junction
capacitance. The α-Si tunnel barrier is made by glow discharge (29–31). This method has a
problem with the controllability of the thickness. The α-Si barrier is also made by RF sputtering
(32). The controllability of the thickness is improved by this method. Hydrogenation of the
barrier improves the subgap leakage current (33).
B. NbO x Tunnel Barrier

NbO x was also investigated as a tunnel barrier in NbN junction development (3,26,34,35). The
NbO x tunnel barrier is easy to make from NbN by plasma oxidation. The plasma oxidation can
be controlled precisely. After the oxidation, Ar sputter etching with a low bias voltage of about
30 V improves the subgap leakage current. Thus, both reproducibility and uniformity have
reached an acceptable level for an integrated circuit. Some integrated circuits using such a junc-
tion were developed successfully. The junction is stable even in the vacuum annealing process
at about 300°C. But the junction has a high dielectric constant (⑀ r ⬃ 30), which produces a high
junction capacitance. This is a disadvantage for high-speed operation.
C. AlO x Tunnel Barrier

AlO x was also investigated as a tunnel barrier in NbN junction development (36–39). It has the
attractive characteristic of a low dielectric constant (⑀ r ⬃ 8), which produces a low junction
capacitance. The AlO x tunnel barrier is the most successful one in Nb junction development,
but a high-quality NbN junction with an AlO x tunnel barrier has not yet been obtained.
D. MgO Tunnel Barrier

Moreover, MgO was investigated as a tunnel barrier in NbN junction development (40–53).
The MgO tunnel barrier is normally made by RF sputtering in Ar gas with an MgO target (40).
The use of an Mg target does not produce a better subgap characteristic than that of an MgO
target. Sputtering with an MgO target is the best way to make an MgO tunnel barrier. The
thickness of the MgO barrier is controlled precisely. Thus, both reproducibility and uniformity
have reached an acceptable level for an integrated circuit (50). Figure 3 shows typical I–V
characteristics of NbN/MgO/NbN junctions. Figure 4 shows the dependence of the Josephson
critical current density on the thickness of the MgO tunnel barrier. The junction has attractive
characteristics for integrated circuits, because it has a larger gap voltage (about 5 mV) than the
other junctions. The junction is stable even in the annealing process at about 350°C. MgO is
Figure 3 Typical I-V characteristics of NbN/MgO/NbN junctions. (a) J c , 200 A/cm 2. (b) J c , 30 kA/cm 2.
294 Aoyagi
Figure 4 Dependence of Josephson critical current density J c on the thickness of the MgO tunnel barrier.
the most promising material as a tunnel barrier for NbN electrode junctions. It has, however,
a relatively high dielectric constant (⑀ r ⬃ 10), which produces a high junction capacitance. This
is a disadvantage for high-speed operation.
E. AlN Tunnel Barrier

AlN was also investigated in NbN junction development (54–57). The AlN tunnel barrier is
normally made by sputtering with an Al target in an Ar ⫹ N2 gas mixture (54) or N 2 gas (55). It
has the attractive characteristic of a relatively low dielectric constant (⑀ r ⬃ 8.5), which produces a
low junction capacitance. AlN is one of the promising materials as a tunnel barrier for NbN
electrode junctions.
IV. APPLICATIONS OF NbN JUNCTIONS

A. Digital Circuits
Fabrication processes for integrated circuits using NbN junctions have been reported (58–76).
A fabrication process for an integrated circuit using NbN junctions (66,69,72,74) is described
as follows. Figure 5 shows the process flow. Table 1 shows a list of layers in the NbN integrated
circuit.
(1) An Nb film is deposited by DC sputtering. A resist pattern for the ground plane is
formed by ultraviolet (UV) lithography. Part of the Nb film is etched by reactive ion etching
(RIE). Then an SiO film is deposited by evaporation and lifted off. (2) A resist pattern for the
ground plane contact hole is formed by UV lithography. The surface of the Nb ground plane
is anodized. Then an SiO film and an MgO film are deposited and lifted off. (3) The surface
of the Nb ground plane contact is cleaned by Ar plasma etching. An Nb film and an NbN/
MgO/NbN trilayer film are deposited by RF sputtering. (4) A resist pattern for the base electrode
is formed by UV lithography. Part of the trilayer film is etched by RIE. (5) A resist pattern for
the small Josephson junctions is formed by UV or electron beam (EB) lithography. The upper
NbN layer is etched by RIE. Then an SiO film is deposited by evaporation and lifted off. (6)
Figure 5 Process flow of integrated circuits using NbN/MgO/NbN junctions (figure continues).
A resist pattern of the base contact hole is formed by UV lithography. Part of the SiO layer is
etched by RIE. (7) A resist pattern of the resistor is formed by UV lithography. A Pd film is
deposited by EB evaporation and lifted off. (8) A resist pattern of the wiring is formed by UV
lithography. A Pb-In film is deposited by evaporation and lifted off.
In the other processes, an Mo film deposited by sputtering is used as a resistor layer
(61,68,73). An SiO 2 film deposited by sputtering (67,73) or CVD (63,68) is used as an insulation
layer. An Si film deposited by evaporation is also used as an insulation layer. An Nb film
deposited by sputtering is used as a wiring layer (61). An NbN film deposited by sputtering is
used as a wiring layer (67,68,73) for high-temperature operation at about 10 K.
Active areas of Josephson junctions must be controlled with very high precision. A high-
resolution lithography system is required to get a wide operating margin for a circuit with a
small spread of the junction critical current.
Some logic gates such as four-junction logic (4JL) (59,60) and modified variable threshold
logic (MVTL) (73,75,76) have been fabricated using NbN junctions. The smallest logic delay
296 Aoyagi
Figure 5 Continued.
of 3.0 ps/gate has been demonstrated using 4JL gates (74). This value is still larger than that
of the gates using Nb junctions because of the large capacitance of NbN junctions.
Many integrated circuits have been demonstrated using NbN junctions. Details are shown
in Table 2. NbN/NbO x /NbN junctions were mainly used in the integrated circuits until the end
of the 1980s. After that, only NbN/MgO/NbN junctions were used. In the United States, high-
temperature (9–10 K) operation of integrated circuits has been investigated (67,75). The largest
circuit, fabricated and tested experimentally, was a 1280-bit ROM unit using NbN/MgO/
Table 1 Layers in NbN Integrated Circuits

Layer Material Thickness (nm)
Ground plane Nb 400
Planarization insulation SiO 250
Ground plane insulation Nb 2O 5 /SiO/MgO 40/200/20
Base electrode Nb/NbN 100/100
Tunnel barrier MgO 0.7
Counter electrode NbN 150
Junction insulation SiO 320
Resistor Pd 40
Wiring Pb/In 900/100
NbN junctions. Figure 6 shows a chip photograph of the NbN ROM unit. The size is 5 mm ⫻
3.45 mm.
B. SIS Mixing Devices

For 10 years, heterodyne receivers using superconductor-insulator-superconductor (SIS) tunnel
junctions as mixer elements have been used in radiotelescopes in the frequency range from 100
to about 350 GHz. A few receivers working at even higher frequencies have been developed,
and there is much interest in SIS receivers that can be operated up to 1 THz. The upper frequency
limit of the SIS quasi-particle mixer is related to the energy gap ∆ of the superconductors in
the mixer circuit. It is predicted theoretically that the tunnel junction itself should work at up
to twice the gap frequency, that is, 4∆/h. It has, however, been suggested that RF losses in the
junction electrodes and in the superconducting embedding circuit of the mixer can conflict with
optimal performance when the operating frequency approaches or exceeds the gap frequency
2∆/h. NbN is an interesting material for the development of submillimeter SIS mixers that can
be operated even above 1 THz. It has a higher gap frequency of about 1.2 THz.
The upper frequency limit of Nb SIS devices, about 700 GHz, is set by the increase in
the loss above the Nb gap frequency. Further progress in the frequency of SIS devices has been
related to NbN junctions with a highest gap frequency of about 1200 GHz. An experimental
study was performed in the millimeter band with a full NbN SIS mixer (71–76). The lowest
double sideband (DSB) receiver noise temperature is about 65 K at 160 GHz and approaches
the Nb SIS mixer performance in the millimeter band. The NbN SIS junctions can be operated
at temperature of 5.4 K, which is unacceptable with the Nb devices. This means that the introduc-
tion of low-noise NbN mixers may simplify closed-cycle refrigerators.
C. Josephson Mixing Devices

Josephson tunnel junctions have harmonic generating and mixing properties due to their highly
nonlinear current-voltage (I–V ) characteristic (83–85). Josephson junctions are able to generate
high harmonics of an externally applied frequency. Constant-voltage (Shapiro) steps on the
junction I–V characteristic are observed when the junction is irradiated with microwaves. The
steps, occurring at voltages corresponding to harmonics of the incident frequency, are at integer
multiples of hf/(2e), where f is the frequency of the incident microwaves. This feature can be
used in the direct measurement of the frequency of far infrared laser lines.
A mixing experiment at 4.25 THz has been done using Nb point-contact devices. A mixing
298
Table 2 List of Fabricated Integrated Circuits
Integrated circuits Junctions Institutes Tested parts Performances Year Reference

Logic gate chain NbN/NbOx /NbN ETL 14 gates 18 ps/gate (logic delay) 1983 59
Logic gate chain NbN/a-Si/NbN ETL 14 gates 9 ps/gate (logic delay) 1984 60
8-bit ripple carry adder NbN/NbOx /NbN ETL 364 gates Functions and 0.8 ns (critical path) 1985 61
4⫻4-bit parallel multiplier NbN/NbOx /NbN ETL 652 gates Functions and 1.0 ns (critical path) 1985 61
1K-bit SFQ memory NbN/NbOx /NbN ETL Decoder, driver Functions 1985 62
3K gate array NbN/NbOx /Pb-In-Au Hitachi 419 gates 21 ps/gate (logic delay) 1987 64
348 gates 37 ps/gate (logic delay) 1987 64
Address control unit for NbN/NbOx /NbN ETL 593 gates Functions and 345 ps (critical path) 1989 65
4-bit microcomputer
Time domain reflectrometer NbN/MgO/NbN Hypres 16 junctions and 2 Functions at 9 K 1989 67
DC-SQUID
1280-bit ROM unit NbN/MgO/NbN ETL 789 gates and 1280 Functions and 710 ps (access time) 1991 69
cells
8-bit SFQ counter NbN/MgO/NbN Hughes 16 gates Functions and 60-Ghz operation 1991 70
Logic gate chain NbN/MgO/NbN ETL 53 gates 3.6 ps/gate (logic delay) 1992 72
Logic gate chain NbN/MgO/NbN ETL 53 gates 3.0 ps/gate (logic delay) 1993 74
Shift register NbN/MgO/NbN TRW 384 gates Functions at 10 K 1993 75
Aoyagi
Figure 6 Chip photograph of a 1280-bit ROM unit containing NbN/MgO/NbN junctions.
experiment at 10 THz should be possible with NbN devices because they have about double
the energy gap of Nb. The maximum operating frequency of a Josephson mixer is proportional
to the energy gap of the superconductor used. Mixing experiment using NbN/MgO/NbN junc-
tions have already been achieved up to 3.1 THz (84).
D. X-Ray Detector
Superconducting tunnel junctions have become promising devices for X-ray detection with high
energy resolution, as an energy resolution of 37 eV at 6 keV was achieved using an Sn junction
(86). However, the Sn junction did not thermally cycle well, so there was a shift to fabricating
Nb junctions. The current record for energy resolution for Nb junctions is 36 eV at 6 keV (87).
There are two reasons for investigating NbN junctions for X-ray detection (88–90). The
first is the possibility of operating at higher temperatures than with Nb-based devices (88,89).
The second is making junctions with ‘‘trapping layers.’’
In order to suppress the thermal quasi-particle current to levels that allow high energy
resolution, it is necessary to operate the junction at a temperature 0.1 Tc. NbN has a Tc of 15
K, which would require an operating temperature of 1.5 K. This temperature is very convenient
compared with the 0.9 K of Nb junctions. In particular, in a space application the NbN junctions
are suitable for a space qualified cryostat. For the NbN junctions, we expect that they have
fewer losses and therefore higher energy resolution.
On the other hand, a thick NbN overlayer was used as a wiring and radiation absorber
for Nb/AlOx /Nb Josephson junctions (90). The NbN/Nb bilayer is also an interesting candidate
for quasi-particle trapping, because it has the best scattering rate, which enhances the trapping
process. The scattering time is strongly dependent on the quasi-particle energy and on the mate-
rial characteristic time τ 0 .
We can reduce loss of excitations and obtain enhancement of the quantum efficiency of
the detector, employing quasi-particle trapping. The Nb layer in an Nb/AlOx /Nb junction can
300 Aoyagi
act as an effective trapping layer when an NbN overlayer with a higher energy gap than Nb is
used.
E. Bolometer Mixing Devices

Nb SIS junctions are very sensitive mixer devices, but only for frequencies below the gap energy
of Nb(⬃700 GHz). Superconducting hot electron bolometers (HEBs) use the electron tempera-
ture-dependent resistance in superconducting narrow film strips. The mixer performance of the
Nb HEB mixer is promising but the bandwidth, determined by the electron-phonon interaction
time, is very narrow (⬃90 MHz). NbN has a short electron-phonon interaction time, so it is
possible to obtain a larger bandwidth of 1 GHz. NbN has a larger gap energy than Nb, so the
NbN HEB mixer can be operated over 1 THz. In some studies, preliminary experimental results
were achieved (91–94).
F. SQUID
Integrated DC superconducting quantum interference device (DC-SQUID) magnetometers were
fabricated using NbN/NbO x /NbN or NbN/MgO/NbN junctions (95–97). By using NbN/MgO/
NbN junctions, 10 K operation was achieved (96).
G. Microwave Devices
Some microwave devices have been reported (96–102). A tunable superconducting phase shifter
has been demonstrated using NbN microstrips (99). The tuning mechanism is based on induc-
tance modulation by injecting excess quasi-particles into the NbN microstrips. Flux-flow oscilla-
tors have been demonstrated using NbCN/MgO/NbCN junctions (101). Radiation in a frequency
range from 580 to 710 GHz was confirmed experimentally.
H. Others
Large series arrays for Josephson voltage standards were demonstrated using NbN/MgO/NbN
junctions (103). In the voltage standards, we use constant voltage steps which appear in the I–
V characteristic of the junction at Vn ⫽ n(h/2e)fc (n ⫽ 0,1,2, . . .) under microwave irradiation.
In the large series arrays, the voltage steps are multiplied by the number of junctions. A 1-V
step has been demonstrated under microwave irradiation at 69 GHz.
A study of using an NbN gate electrode in a semiconductor MOS device has been reported
(24). NbN is suitable for high-temperature (800–900°C) annealing in the self-aligned MOS gate
process. Superconducting wiring should be realized in a low-temperature (4.2–10 K) operation.
V. SUMMARY
Fabrication processes for NbN Josephson tunnel junctions have been developed successfully.
Many application works are in progress. In particular, high-frequency devices such as an SIS
mixer and a Josephson mixer have been fabricated and tested with practical performance. NbN
integrated circuits have also been fabricated and tested. Reproducibility and uniformity of the
NbN integrated circuit process are still worse than those of the Nb integrated circuit process.
The integration level is still less than the large-scale integration (LSI) level. The performance
has not yet reached GHz clock operation. Further investigations will be required. High-tempera-
ture (9–10 K) operation is promising for satellite and mobile applications.
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13
Solar Absorbers—Selective Surfaces
Robert Blickensderfer
Research Metallurgist, Consultant, Albany, Oregon
I. INTRODUCTION
Thin films of the carbides and nitrides of Ti and Zr have shown promise as solar absorbers.
Such films can absorb a high percentage of the incident solar radiation while reradiating only
a small percentage of the thermal energy. The net thermal energy can thus be withdrawn for
use. A surface that has the ability to absorb solar energy effectively while limiting the energy
it reradiates, or emits, is spectrally selective. For applications such as solar-thermal power plants,
high operating temperatures are desirable to provide high thermal efficiency of the heat cycle,
but the convection, conduction, and radiation losses must be minimized. Conduction and convec-
tion can be nearly eliminated by operating in vacuum, and radiation losses can be reduced by
utilizing a spectrally selective surface. Because radiation losses increase with the fourth power
of temperature, the need for spectral selectivity becomes imperative for solar-thermal collectors
operating at elevated temperatures in vacuum.
II. BACKGROUND
A. The Idealized Spectrally Selective Solar Absorber
Most of the solar radiation falling on the earth is in the wavelength range below 2 µm. For
surfaces at any temperature up to about 1000 K, most of the emitted energy is at a wavelength
greater than 2 µm. Therefore, spectral selectivity of a surface will occur in a desirable way for
solar-thermal conversion when the absorptance at wavelengths below 2 µm is greater than the
emittance at wavelengths above 2 µm.
The solar radiation leaving the sun is mainly within the wavelength range 0.3 to 2.5 µm.
The distribution of solar energy is close to the Planck blackbody distribution corresponding to
a temperature of 5500 K and with a maximum flux at a wavelength of 0.55 µm. The earth’s
atmosphere absorbs some of the solar energy but not uniformly over wavelength. Absorption
is strongly dependent on interactions with the molecules of water, carbon dioxide, ozone, and
to a lesser degree nitrogen oxides and hydrocarbons. Several strong absorption bands occur in
the solar infrared region of the spectrum between 0.7 and 2 µm. Figure 1 shows the spectral
flux (energy distribution) for solar energy arriving at the surface of the earth after passing through
an average atmosphere. This is based on average atmospheric pressure, temperature, and relative
humidity and is for air mass 2. Air mass 1 corresponds to absorption at sea level of the sun’s
307
308 Blickensderfer
Figure 1 Spectral flux distribution of sunlight and blackbodies.
rays arriving from the zenith. Air mass 2 (AM2) allows double the absorptance and is close to
the average energy distribution received from 1 h after sunrise to 1 h before sunset in the midlati-
tudes. The total solar flux for AM2 is approximately 800 W/m 2.
Thermal emittance from the surface of most solids approximates some fraction of the
theoretical Planck blackbody distribution. The maximum of the distribution is temperature de-
pendent according to Wien’s law, shifting to shorter wavelengths and increasing in magnitude
as the temperature increases. The blackbody emittance distributions for two temperatures are
included in Fig. 1. For a temperature a little above the boiling point of water, such as 400 K,
the maximum flux is at about 7 µm wavelength, with almost no flux below 3 µm; but at 600
K the maximum flux is at about 5 µm with a small amount emitted below 2 µm.
An ideal solar-thermal surface would absorb all solar radiation up to a certain cutoff wave-
length, λc . At all wavelengths greater than λ c , the emittance would be zero. The ideal cutoff
wavelength varies slightly depending on the temperature and, thus, the shape of the emittance
curve. However, a value usually taken for the cutoff is 2 µm. The spectral absorptance of the
ideal solar-thermal surface with a 2-µm cutoff would look like that of Fig. 2, where absorptance
(α) is 1 for λ ⬍ 2 µm and emittance (ε) is 0 for λ ⬎ 2 µm.
Unfortunately, surfaces with more than slight spectral selectivity do not exist in nature.
But because of the vast differences in electro-optic properties among materials, opportunities
exist for combining materials into a system that approaches the ideal spectrally selectivity ab-
sorber.
B. Definitions and Equations

At a given wavelength λ, absorptance equals emittance:
α(λ) ⫽ ε(λ) (1)
Absorptance plus reflectance plus transmittance equals unity. Therefore, for an opaque solid
with no transmittance, the relation between reflectance, r, and absorptance, at wavelength λ, is
given by
α(λ) ⫽ 1 ⫺ r(λ) (2)
Solar Absorbers—Selective Surfaces 309
Figure 2 Spectral absorptance of an ideal solar absorber. Transition from total to zero absorptance is
at 2 µm wavelength.
The solar absorptance a(s) is the fraction of the incident solar energy absorbed by the surface:
∫ φ(λ)α(λ)dλ
a(s) ⫽ (3)
∫ φ(λ) dλ
where
λ ⫽ wavelength
φ(λ) ⫽ solar flux as a function of λ, left curve of Fig. 1
α(λ) ⫽ spectral absorptance of the surface as function of λ
The thermal emittance (e T) at temperature T is calculated from

∫ b T (λ)ε T (λ) dλ
eT ⫽ (4)
∫ε T (λ)dλ
where
b T (λ) ⫽ flux of blackbody radiation at temperature T, as given by a curve similar to

those on the right of Fig. 1
ε T (λ) ⫽ spectral hemispherical emittance at temperature T.
Because the functions φ(λ), α(λ), and ε T (λ) are not simple, the integration is made numerically.
The stagnation temperature (T s) is the maximum temperature reached by a surface exposed
to sunlight. It is reached when the losses from thermal radiation, convection, and conduction
equal the solar input. Under vacuum conditions, convection losses are eliminated, conduction
losses can be negligible, and the stagnation temperature is given by
冤冥
1/4
a(s)φ ⫹ T 04
Ts ⫽ (5)
KεTs
310 Blickensderfer
where
φ ⫽ solar flux, taken as 800 W/m 2

T0 ⫽ ambient temperature, taken as 273 K
K ⫽ Stefan-Boltzmann constant, 5.673 ⫻ 10⫺8 W/m 2 K4
εTs ⫽ total hemispherical emittance at temperature T s
The conversion efficiency, CE, is a good criterion for evaluating a solar surface for both selectiv-
ity and absorbing effectiveness. It indicates the amount of heat that can be withdrawn at the
operating temperature:
Q a ⫺ Q e ∫ φ(λ)α(λ) dλ ⫺ ∫ b T (λ)e T (λ)dλ
CE ⫽ ⫽ (6)
Qs ∫ φ(λ) dλ
where Q a is the absorbed solar flux, Q e the emitted flux, and Q s the incoming solar flux. If the
solar flux is concentrated by some means, the concentration factor must be multiplied into the
Q a and Q s terms, and the equation then gives the Nettogutezahl number (N). Concentration of
the solar flux will increase Q a and Q s and hence will increase the CE.
C. Criteria for Evaluating Solar-Thermal Spectral Selectivity

1. Absorptance and Emittance
The spectral selectivity of a solar absorber can be judged by comparing its solar absorptance
and thermal emittance with the ideal values. Because of the overlap of the solar and thermal
spectra, as seen in Fig. 1, the solar absorptance of the ideal surface is limited to a maximum
of about 0.99 and the total emittance (600 K) is limited to a minimum of about 0.01.
2. Ratio of a/e
The ratio of a(s) to e T is useful for comparing the degree of spectral selectivity among various
surfaces. For a surface with no spectral selectivity, such as black paint, a/e ⫽ 1. For the idealized
surface of Fig. 2 at 600 K, the a/e ratio is approximately 0.99/0.01 or 99. The maximum a/e
ratio will decrease with increasing temperature as the radiation distribution shifts to shorter
wavelengths. In practice, it is difficult to achieve an a/e ratio greater than 10.
3. Stagnation Temperature
A high stagnation temperature is desirable because it defines the upper limit at which heat may
be extracted from a solar absorber. The stagnation temperature increases with increasing solar
absorptance and decreasing thermal emittance; therefore it is closely related to the a/e ratio.
4. Conversion Efficiency
The conversion efficiency is probably the best single indicator of the potential usefulness of a
selective solar absorber. The conversion efficiency is dependent on both the solar absorptance
and the thermal emittance. For the ideal surface mentioned before, operating at 600 K, CE ⫽
0.98. Only a few absorbers have been developed that give a CE(600 K) greater than 0.3 without
resorting to solar concentration. Many of the known selective surfaces are unable to give a
CE(600 K) greater than 0.
D. Measurements of Solar Absorptance and Thermal Emittance

Several methods are used to determine solar absorptance and thermal emittance. Measurement
of spectral reflectance is the easiest and most commonly used. This indirect method and three
direct methods of measurement (1) are briefly discussed.
1. Spectral Reflectance
Normal spectral reflectance data are obtained by scanning the surface with spectrophotometers
over the wavelength range 0.3 to 40 µm. Using Eqs. (1) and (2), the reflectance data are converted
numerically to absorptance and emittance data. The integrations of Eqs. (3) and (4) are then
carried out by numerical methods using φ(λ) for AM2 and e T (λ) for the desired temperature.
Such calculated values have agreed well with the direct measurement methods mentioned in
the following.
2. Normal Emittance
A detector that absorbs the total radiation within the range 1 to 40 µm is used to determine the
normal total emittance of a heated specimen. A typical detector uses a thin-film thermopile that
accepts a known solid angle of radiation from the specimen.
3. Heating and Cooling Rates

A laboratory light source that approximates the solar energy spectral distribution at the earth’s
surface is used to irradiate a specimen in vacuum. Knowing the specific heat of the specimen,
the initial rate of temperature rise is used to determine the solar absorptance. After reaching
T s , where the temperature stabilizes because the thermal emittance of energy equals the solar
absorptance, the light source is turned off and the initial cooling rate determines the total hemi-
spherical emittance at T s . The stagnation temperature, in addition, gives a direct measurement
of the a/e ratio at T s .
4. Microcalorimetry
A specimen is heated by electrical self-resistance in vacuum. Total hemispherical emittance is
determined from the Stefan-Boltzmann law of radiation, knowing the power input, the total
surface area, and the temperature. By using a solar simulator, as in method 3, the difference in
electric power required to maintain a given temperature with the solar simulator on and off
determines the solar absorptance.
5. Comparisons
For the Zr and Ti type of absorbers the calculated values of solar absorptance and emittance
based on reflectance data agree within a half percent of the direct measurements made with a
solar simulator at a temperature of 400 K. At 600 K, the direct measurements gave a solar
absorptance 1% greater than the calculated values and gave a total hemispherical emittance
ranging from 0 to 20% lower than the calculated values. The lower measured emittance is a
result of the angular dependence of emittance—it decreases with increasing angle from the
normal; thus actual emittance is lower than calculated values, which are based on normal reflec-
tance data. In summary, under experimental conditions at elevated temperature, the solar absorp-
tance is desirably increased and the thermal emittance is desirably decreased compared with
calculations based on room temperature reflectance data. Therefore, use of room temperature
reflectance data is conservative.
312 Blickensderfer
E. Types of Spectrally Selective Surfaces

The basic approach to design of selective surfaces has been to provide a thin surface layer of
particles or films that absorb the solar radiation but are transparent to the longer wavelength
thermal radiation. The layer is placed on a highly reflective base, which then limits the emission
of thermal radiation. A number of mechanisms operate simultaneously to produce spectral selec-
tivity, namely texture effects, resonant scattering, interband transitions, free electron interac-
tions, and interference effects. Types of spectrally selective surfaces, as reviewed in Ref. 2, are
categorized into four general types:
1. Microrough Surfaces
A metallic surface with a dendritic structure or covered with small particles or whiskers or
otherwise roughened at a size of about 1 µm will exhibit spectral selectivity. The solar radiation
becomes absorbed while making multiple reflections among the particles, because each reflection
results in partial absorption. The longer thermal wavelengths are relatively unaffected by the
small particles, and therefore emission is only slightly higher than that of the bulk metal. Exam-
ples of a microrough surface include dendritic tungsten prepared by chemical vapor deposition
(3) and surfaces of copper, nickel, and stainless steel made by sputter etching (4). Such surfaces
typically have high solar absorptance, a ⫽ 0.9, and moderately low emittance, e ⫽ 0.2.
2. Metal Particles in a Dielectric Film

Coatings consisting of small metallic particles within a dielectric film, or layers of metal particles
between dielectric layers that are deposited on a reflective surface, have proved very selective.
The small particles absorb short waves preferentially, while the dielectric is transparent (non-
emitting) to long waves. The system offers many choices regarding particle size, shape, orienta-
tion, spacing, film thickness, and composition. Two of the best known surfaces are black chrome
(5,6) and black nickel (6,7). These surfaces are produced by electroplating and consist of small
metal particles in an oxide phase. Typical solar absorptance ranges from 0.90 to 0.95, and
thermal emittance (400 K) is typically in the range of 0.07 to 0.20. Chemical vapor deposition
has been used to make black molybdenum films consisting of small MoO 2 particles with small
Mo inclusions (8). Metals and dielectrics have been codeposited by evaporation and sputtering.
For example, a system of cobalt particles in an alumina film was optimized to give a solar
absorptance of about 0.9 and thermal emittance of 0.08 (400 K) (9). Alternate thin films of
MoSi 2 and alumina and multiple layers of Pt and alumina deposited by sputtering produced
good spectral selectivity (10). Ion implantation of surfaces of vanadium and zirconium has
produced moderate spectral selectivity by formation of nitrides and surface roughness (11).
3. Semiconductor Films
Semiconductor films on metal can absorb solar radiation if the band gap energy is about 0.6
eV. Most photons in the solar spectrum have more than 0.6 eV energy and therefore are captured
in the semiconductor. The semiconductor does not emit the longer wavelength thermal radiation.
Silicon films produced by chemical vapor deposition on silver have proved the most promising
(12,13). Solar absorptance is not particularly high because of the high reflective losses of incident
waves at the silicon outer surface. Application of an antireflection coating raises the absorptance
to 0.76.
Figure 3 Model of surface of TiN xO y proposed by Lazarov et al. (16).
4. Interference-Absorbing Films
Absorbers of this type depend primarily on photon interference within the film to produce a
sharp transition at 2 µm wavelength. The film must be relatively transparent at wavelengths
greater than about 1 µm in order to provide the necessary interference between the surface and
the reflective base metal. If a transparent film is the appropriate thickness to give the first interfer-
ence minimum at about 1 µm wavelength, no interference occurs at longer wavelengths and
the reflectance is high. However, in the shortwave region, the first interference maximum will
occur near 0.5 µm, which results in poor solar absorptance. It is necessary, therefore, for the
film to absorb radiation in the shortwave region, from about 0.3 to 0.8 µm. Zirconium and
titanium nitrides, carbides, and suboxide films have the ability to absorb a large part of this
shortwave radiation while being highly transparent to longer waves (1,14,15).
A partial explanation for the short-wavelength absorptance is found in the structure pro-
posed by Lazarov et al. (18) for TiN xO y coatings. As shown in Fig. 3, the structure consists of
columnar TiN and TiO covered by a thin TiO 2 film. The voids between the columns tend to
entrap the shortwave radiation. It is believed that interband transitions and resonant scattering
in the film also contribute to the solar absorptance.
III. TITANIUM AND ZIRCONIUM INTERFERENCE ABSORBERS

A. Procedures for Making the Absorbers
The reflective substrate on which the absorber films are subsequently deposited is usually silver
or aluminum. Either one is easily deposited by radio frequency (RF) sputtering methods. Silver
is preferred because of its greater stability when the absorber is used at elevated temperatures.
After depositing the silver, titanium or zirconium is sputter deposited in the presence of a partial
pressure of nitrogen and an inert gas such as argon. During sputtering, the metal atoms react
314 Blickensderfer
Figure 4 Spectral reflectance of the ideal solar absorber and of silver.
with the nitrogen to form a film of TiN or ZrN. To produce a titanium or zirconium carbide,
a TiC or ZrC source is used for sputtering. By introducing nitrogen at a low partial pressure
during sputtering, a TiC xN y or ZrC xN y film can be deposited. The subscripts x and y are not
known, but their sum is probably about 1 because the two compounds are isomorphic. Similarly,
by introducing various partial pressures of nitrogen and oxygen into the sputtering chamber,
films of TiC xN yO z or ZrC xN yO z can be synthesized. Absorber films are also prepared simply by
heating Zr-Ag sputter-deposited films in air. As both nitrogen and oxygen diffuse into the zirco-
nium, the spectral selectivity increases. Ihara et al. (15) produced ZrC x films by sputtering Zr
in a mixture of methane and argon. In this case, x ranged from 0.8 to 8. The optimal film was
ZrC 6 and consisted of ZrC and graphite.
B. Spectral Reflectance
The spectral reflectance curve of a surface can readily be compared with the ideal curve to give
a visual indication of spectral selectivity. Figure 4 shows the the reflectance of the ideal solar
photothermal absorber with the transition at 2 µm. The reflectance curve for silver is also in-
cluded. Silver reaches a maximum reflectance of about 0.985 in the long-wavelength region,
thus placing a practical limit on longwave reflectance of a solar absorber.
The spectral reflectance of two titanium and zirconium nitride films of 0.16 µm thickness
on a silver substrate are shown in Fig. 5. Both films show relatively low reflectance in the solar
spectrum with interference minima around 1 µm. The transition from low to high reflectance
is fairly sharp near the ideal wavelength of 2 µm. At increasing wavelengths, the reflectance
rapidly approaches that of silver, indicating that the absorptive film is highly transparent to long
waves.
Zirconium carbide and zirconium carbide-nitride films on silver (ZrC–Ag and
Figure 5 Normal spectral reflectance of TiN x-Ag and ZrN x-Ag coatings.
Figure 6 Normal spectral reflectance of ZrC-Ag and ZrC xN y-Ag coatings.
ZrC xN y Ag), Fig. 6, provide spectral characteristics similar to those of the TiN and ZrN films.
The ZrC 6 film of Ihara et al. (15) has the lowest shortwave reflectance, but the transition from
low to high reflectance is not as sharp as the others. The longwave reflectance of the ZrC films,
especially the ZrC 6 film, is not as high as that of the nitride-type films.
The transition wavelength between low and high reflectance depends on the film thickness,
as shown in Fig. 7 for ZrN films on silver. Film thickness is easily controlled, being proportional
to sputtering time. The thinnest film results in a transition wavelength at about 1.4 µm, which
is too short, and insufficient solar absorption is indicated by the relatively high interference
maxima near 0.4 µm. The thickest film has a transition wavelength too far into the long wave-
lengths. The intermediate film, 0.16 µm thick, appears to be near the optimum. The transition
is near the desired 2 µm wavelength, and fairly good solar absorptance and low thermal emit-
tance are indicated.
Figure 7 Effect of absorber film thickness on reflectance of ZrN x-Ag coatings. Zr sputtered in nitrogen
at pressure of 0.16 Pa.
Absorbers made by air oxidation on zirconium films also showed good spectral selectivity.
The normal spectral reflectances of two such films are shown in Fig. 8. Unoxidized ‘‘pure’’
zirconium, shown for comparison, possesses a slight intrinsic spectral selectivity as seen in the
upper curve. This may be attributed in part to the existence of the thin film of stable ZrO 2 that
forms on zirconium at room temperature. The 4-h oxidation time greatly decreases the shortwave
reflectance while also increasing the longwave reflectance. After further heating (20 h total),
the reflectance curve is less desirable. Increased reaction with air makes the film more transparent
to both short and long waves, as indicated by the development of the interference pattern below
2 µm and the increased reflectance beyond 4 µm. The transition from low to high reflectance
of the best air-oxidized specimen is not as sharp as in the reactively sputtered specimens. This
is probably due to the composition gradient resulting from the diffusion gradient of oxygen and
nitrogen into the zirconium film. The surface composition approaches that of ZrO 2 , which is
quite transparent.
316 Blickensderfer
Figure 8 Spectral selectivity produced by air oxidation of a Zr film on Ag. The Zr film was 2.4 µm
thick, heated in air at 473 K for the times shown.
For specimens prepared by sputtering in a partial pressure of oxygen, reflectance curves

are similar to the preceding ones. At low levels of oxygen the reflectance curves display the
spectral selectivity typical of those in Figs. 5 and 6. As the oxygen content increases, the surfaces
become increasingly transparent to short wavelengths, as indicated by increasing reflectance
and interference effects, with a net increase in shortwave reflectance, similar to that of the air-
oxidized specimens.
C. Performance and Comparison of Solar Absorbers

Performances of six typical Ti- and Zr-type selective absorbers are compared in Table 1. Six
other representative types of absorbers are included for comparison. Most of the absorptance
and emittance data were calculated from normal spectral reflectance. Emittance calculations
were based on a temperature of 600 K for all specimens.
Table 1 Performance of Several Solar Absorbersa

Conversion efficiency,
Solar Thermal Ratio
Stagnation CE, at 600 K
absorp. emitt. a(s)/
Absorber Source a(s) e(600 K) e(600 K) e Tsb T s (K) 1 ⫻ conc. 3 ⫻ conc.
TiN x Ag Fig. 5 0.88 0.065 14 0.073 650 0.31 0.69
ZrN x Ag Fig. 5 0.86 0.039 22 0.041 740 0.52 0.75
ZrCAg Fig. 6 0.81 0.075 11 0.080 620 0.15 0.59
ZrC 6 SS Fig. 6 0.87c 0.123c 7 0.116 580 0 0.51
ZrC x N y Ag Fig. 6 0.88 0.052 17 0.055 690 0.42 0.73
ZrO x N y Ag Ref. 14 0.88 0.084 10 0.088 620 0.14 0.63
SiliconAg Ref. 11 0.76 0.05 15 0.050 680 0.32 0.61
PtAl 2O 3 Pt Ref. 9 0.92d 0.126d 7 0.122 580 0 0.55
Black nickel 0.94e 0.09e 10 0.095 620 0.15 0.68
Black chromium 0.96e 0.15e 6 0.136 570 0 0.52
Dendritic tungsten Ref. 2 0.96 0.26 4 0.26 490 0 0.20
Black Paint 0.98 0.98 1 0.98 374 0 0
a
Most a(s) and e(600 K) values were calculated from normal spectral reflectance data. Solar flux, φ(λ), is for AM2.
Total solar flux of 800 W/m 2 used for calculating stagnation temperature and conversion efficiency.
b
Approximate emittance values; interpolated or extrapolated at stagnation temperature, T s .
c
Calculated by Blickensderfer from Ihara’s reflectance data.
d
Calculated by Blickensderfer from Schon’s reflectance data.
e
Typical of best values in the literature.
1. Solar Absorptance
All of the TiN x , ZrC xN y , and ZrO xN y films provide solar absorptance of 0.86 to 0.88 except the
ZrC, which has an absorptance of 0.81. Direct measurements of solar absorptance give values
about 1% higher. Other absorbers in Table 1 show absorptance above 0.92, except silicon, whose
absorptance is 0.76.
2. Thermal Emittance
The thermal emittance (600 K) of the ZrN x film is a very low 0.039. The TiN x and ZrC xN y films
show an emittance of about 0.05, which is similar to that of the best silicon film. The other Ti-
and Zr-type films all have an emittance less than 0.1, except ZrC 6 , which has 0.123. It is believed
that the emittance of the ZrC 6 film could be reduced by deposition of a silver film between it
and the stainless steel substrate, as used for the other Zr absorbers. The other types of absorbers
shown in Table 1 have emittances of 0.09 or higher.
3. Ratio of a(s)/e (600 K)

All but one of the Ti- and Zr-type films show a/e ratios greater than 10. The ZrN x film provides
the highest a/e ratio, namely 22, which is considered very high. The ZrC xN y film is also very
good, with an a/e of 17. The lower a/e ratio of 7 for the ZrC 6 film is again attributed to its higher
emittance than the others. The silicon film has an a/e ratio of 15 even though its absorptance is
rather low. The other selective absorbers listed show a/e ratios of 10 for black nickel down to
4 for dendritic tungsten.
4. Stagnation Temperature
The ZrN x film has the highest stagnation temperature, namely 740 K. The other Ti- and Zr-type
films have a stagnation temperature above 600 K except for ZrC 6 , which stagnates at 580 K.
The other surfaces stagnate at temperatures from 680 K for silicon down to 374 K for nonselec-
tive black paint.
5. Conversion Efficiency
The conversion efficiencies of the absorbers operating at a temperature of 600 K and with a
solar input of 800 W/m 2 are listed in Table 1. Without concentration (1⫻), the ZrN x-Ag absorber
with a CE of 0.52, or 52%, is the highest. The CEs of the other absorbers range from 0.14 to
0.42 except for the five surfaces with zero conversion, because their stagnation temperature is
below 600 K. By concentrating the solar input three times (3⫻), the conversion efficiency of
the surfaces increases, with the Ti and Zr type ranging from 0.51 to 0.75. The silicon and
black nickel have values of 0.61 and 0.68, respectively. Only black paint still has a stagnation
temperature below 600 K and therefore, has no conversion.
D. Thermal Stability
Good stability of a solar absorber over an economical lifetime at operating temperatures is
important. The Ti- and Zr-type films show no change in their optical properties after several
years in an industrially polluted atmosphere at ambient temperatures. At elevated temperatures,
changes in optical properties result from two causes; oxidation of the absorptive film and deterio-
ration of the silver film (17). Oxidation of the absorptive film causes it to approach the composi-
tion of the stable oxide TiO 2 or ZrO 2 . Because these oxides are relatively transparent to solar
318 Blickensderfer
radiation, oxidation of the absorptive film decreases the solar absorptance. Exposure to air at
400 K for 300 h reduces the solar absorptance 10 to 50%. The resistance to oxidation is greatly
increased by coating the TiN and ZrN films with a very thin film of a stable oxide. Such films
show no change in optical properties after heating in air at 450 K for 300 h and almost no
change after an additional 300 h at 500 K. Under vacuum, absorptive films are stable when
heated for 500 h at 1000 K.
The second cause of changes in optical properties, deterioration of the silver film, occurs
above 600 to 650 K. The deterioration occurs in air or vacuum as a result of agglomeration of
the silver film or diffusion of the silver into the substrate. The problem has been partially resolved
on silicon-silver absorbers (12,13) by applying a thin film of a stabilizing chromium oxide
between the silver and substrate. Oxidized films of Cr, Ti, and Zr of 0.02 µm thickness on the
substrate can stabilize the silver film to temperatures of 773 K in vacuum (17). Another method
for stabilizing the silver film is by oxidizing a stainless steel substrate for 10 min in air at 773
K to form an FeO film (17). A specimen prepared in this manner with a ZrC xN y film showed
only small changes in optical properties after 500-h exposures at 773 and 873 K in vacuum.
IV. SUMMARY
Thin films of titanium and zirconium subnitrides, carbides, and oxides deposited on a thin film
of silver provide some of the greatest spectral selectivity for solar energy absorbers of any
known. Solar absorptance ranges from 0.81 to 0.88 and thermal emittance at 600 K is below
0.1 and as low as 0.039. The a(s)/e T ratios at 600 K range from 7 to 22. This high degree of
spectral selectivity allows a significant amount of heat energy to be extracted from the absorber
while operating at relatively high temperature. For example, the ZrN x Ag absorber operating
at 600 K in vacuum will allow 52% of the incoming solar energy to be extracted as heat without
requiring concentration of the sunlight. Black chromium and other less selective surfaces, on
the other hand, cannot reach 600 K because the radiant heat losses equal the solar input at a
temperature below 600 K, whence it stagnates.
The Ti- and Zr-type films are stable in vacuum to temperatures above 600 K and possibly
to 1000 K. The silver film, which tends to agglomerate at temperatures above 600 K, can be
stabilized to a temperature of 773 K or higher by application of a very thin film of a stable
oxide between it and the substrate.
The Ti- and Zr-type solar absorbers show promise in applications for large-scale photother-
mal power plants operating at temperatures up to 600 K without requiring optical concentration
of sunlight. Higher operating temperatures or higher conversion efficiencies may be expected
with concentration of the sunlight.
REFERENCES
1. R Blickensderfer, RL Lincoln, DK Deardorff. Reflectance and emittance of spectrally selective tita-

nium and zirconium nitrides. Bureau of Mines RI8167, U.S. Department of Interior, 1976.
2. DG Granqvist. Spectrally selective surfaces for heating and cooling applications. J Phys Tech Solar
Energy 2:191, 1987.
3. JJ Cuomo, JF Ziegler, JM Woodall. New concept for solar-thermal energy conversion. Appl Phys
Lett 26:557, 1975.
4. GL Harding, MR Lake. Sputter etched metal solar selective absorbing surfaces for high temperature
thermal collectors. Solar Energy Mater 5:445, 1981.
5. PM Driver. An electrochemical approach to the characterisation of black chrome selective surfaces.

Solar Energy Mater 4:179, 1981.
6. HYB Mar, RE Peterson, PB Zimmer. Low cost coatings for flat plate solar collectors. Thin Solid
Films 39:95, 1976.
7. PK Gogna, KL Chopra. Structure-dependent thermal and optical properties of black nickel coatings.
Thin Solid Films 57:299, 1979.
8. EE Chain, K Seshan, BO Seraphin. Optical and structural properties of black molybdenum photother-
mal converter layers deposited by the pyrolysis of Mo (CO) 6 . J Appl Phys 52:1536, 1981.
9. GA Niklasson, CG Granqvist. Ultrta fine chromium particles for photothermal conversion of solar
energy. J Appl Phys 55:3382, 1984.
10. JH Schon, G Binder, E Bucher. Performance and stability of some new high-temperature selective
absorber systems based on metal/dielectric multilayers, Solar Energy Mater Solar Cells 33:403, 1994.
11. JS Liu, A Ignatiev. Optical tailoring of solar absorbers by ion implantation. Solar Energy Mater 13:
399, 1986.
12. M Janai, DD Allred, DC Booth, BO Seraphin. Optical properties and structure of amorphous silicon
films prepared by CVD. Solar Energy Mater 1:11, 1979.
13. DC Booth, DD Allred, BO Seraphin. Stabilized CVD amorphous silicon for high temperature photo-
thermal solar energy conversion. Solar Energy Mater 2:107, 1979.
14. R Blickensderfer, DK Deardorff, RL Lincoln. Spectral reflectance of TiN x and ZrN x films as solar
absorbers. Solar Energy 19:429, 1977.
15. H Ihara, S Ebisawa, A Itch. Solar-selective surface of zirconium carbide film. Proceedings of Interna-
tional Vacuum Congress and 3rd International Conference on Solid Surfaces, Vienna, 1977, pp 1813–
1816.
16. M Lazarov, P Raths, H Metzger, W Spirkl. Optical constants and film density of TiN xO y solar selec-
tive absorbers. J Appl Phys 77:2133, 1995.
17. FW Wood, R Blickensderfer. Stabilization of absorber stacks containing Zr or Ti compounds on Ag.
14
Metalloids for Plasma-Facing Materials
Tatsuhiko Tanabe and Masakazu Fujitsuka
National Research Institute for Metals, Tsukuba-shi, Ibaraki, Japan
I. INTRODUCTION
The constituent elements of the plasma-facing components of fusion reactors often intrude into
plasma as impurities due to sputtering, erosion, sublimation, and so on. Plasma impurities result
in plasma cooling by line radiation, prevent neutral beam penetration into the plasma core,
initiate runaway electrons, and possibly affect sputtering arcing erosion rates (1). As the radiative
losses due to impurity ions increases abruptly with increasing atomic number of the impurities,
the plasma-facing materials of fusion reactors, at least their surface, should be composed of
low-atomic-weight materials (low-Z materials). Further, the materials should be resistant to ther-
mal shock and should have good properties in their interaction with plasma.
The substantial property needed for the plasma-facing materials is a high melting point.
Many high-melting-point materials such as W and Mo have high Z. Therefore, low-Z bulk
materials as well as low-Z materials coated onto the high-melting-point materials are candidates
for the first wall of fusion reactors (1,2).
The merits of using coated materials are as follows:
1. Alteration of the surface films can be performed easily and cheaply. This enables us to
provide for the evaluation tests of various coated films in the experimental equipment.
2. Substrates can be selected from the standpoint of structural materials and the surface
films can be selected from the standpoint of surface functional materials, with the
result that a broad choice of the materials is possible.
3. The thermal and mechanical properties of the coated materials can be assumed in the
structural design to be the same as those of the substrates when the films are thin.
With this, safety and reliability of the structures can easily be achieved.
4. The microstructures of the films can be so easily controlled that the freedom of the
material design increases.
In addition, they have some demerits:
1. Surface films exfoliate easily.
2. Thick films would be needed because of the increasing wastage of surface films when
the particle load against the first wall of the reactors increase with the enlargement
of fusion reactors. This leads to easy fracture and exfoliation of the films.
3. The chemical interactions between coated films and substrates at high temperatures
often cause deterioration of the films.
321
322 Tanabe and Fujitsuka
4. Degradation of the substrates occurs because of the existence of surface films.

In developing low-Z coated materials, these demerits should be surmounted.
It is natural to select low-Z, high-melting-point materials as the coating materials. The
selected low-Z, high-melting-point materials are TiC (m.p. 3340 K), TiB 2 (m.p. 3190 K), and
graphite (m.p. 4020 K). Among the low-Z coatings, TiC is considered one of the most promising
materials because of its low chemical sputtering yield and high melting point (3). On the other
hand, TiB 2 coating has a distinct advantage over TiC coating; i.e., hydrogen isotope retention
in TiB 2 is less than that in TiC, especially at elevated temperatures (4,5). Therefore, it would
be possible to get better characteristics by fabricating the bulk mixtures of TiC and TiB 2 rather
than the individual compound.
From these standpoints, the formation of TiC and TiB 2 coatings onto the high-melting-
point materials and of mixtures of TiC and TiB 2, the thermal stability of the coated materials,
and thermal shock test results for both materials are mentioned in this chapter. All the data
shown here were derived at the National Research Institute for Metals (NRIM), Japan.
II. THE RESEARCH AND DEVELOPMENT ON LOW-Z COATING

MATERIALS
There are many low-Z coating methods, such as the chemical vapor deposition (CVD), radio
frequency (RF)–reactive ion plating, the magnetron sputtering, solid reaction bonding, and vac-
uum arc deposition methods. As the properties of the coated materials depend on the coating
methods and fabricating conditions, it is important to control the conditions for each method
to get heat-resistant coated materials. Here, the RF–reactive ion plating method and magnetron
sputtering method are mentioned.
A. TiC Formation by the Ion Plating Method

Figure 1 shows a schematic representation of ion plating equipment. With this equipment, the
films could be deposited both by modified Activated Reactive Evaporation (ARE) (DC discharge
method) and by ion plating using RF electrodes (RF discharge method). The raw materials are
evaporated by the electron beam and ionized with the reactive gases in the plasma through DC
or RF glow discharge. The films are formed when the ions are accelerated by the bias voltage
and impinge on the substrate with high energy.
The formation of TiC films on Mo plate was performed by the ion plating method, whereby
the temperature of the substrate was controlled according to a program. Figure 2 shows the
principle. As the deposition rate of carbon is rate controlled through the pyrolitic reaction of
acetylene, the rate increases with increasing substrate temperature. When the deposition of the
films is done according to the heating and cooling program shown in the figure, a continuous
concentration gradient of carbon is formed at the interface. This leads to relaxation of thermal
stress, with the result that their adherence is improved.
The properties of the films are dependent on the activation rate of the plasma in the ion
plating methods. Here, two activation methods were compared. One is the RF discharge method
and the other is the ARE method. As shown in Fig. 1, RF coil was used in the former case,
and a direct current of about 20 A with 50–60 V between the Mo probe and evaporation sub-
stances was supplied in the latter case. Measurement of the specimen current revealed that the
ionization efficiency in the latter case is several times larger than in the former.
The relation between the composition ratio of Ti and C and the ratio of impinging acetylene
Metalloids for Plasma-Facing Materials 323
Figure 1 Schematic representation of an ion plating apparatus.
molecules and titanium atoms on the substrate is shown in Fig. 3. In the DC method, the C /
Ti compositional ratio becomes 1 when the acetylene/titanium ratio is larger than 40, whereas
in the RF method, the compositional ratio varies widely depending on the acetylene/titanium
ratio. This is reduced to easy decomposition and ionization of acetylene gas during the RF
discharge. In this case, the released carbons are accommodated easily in the films. (6,7)
B. TiC Formation by Magnetron Sputtering Method

Among the various coating methods, the magnetron sputtering process has the characteristics
that coating of large substrate materials is easy and coating at low temperature is possible. The
equipment for the magnetron sputtering method is shown in Fig. 4. This is a conventional RF-
type planar magnetron sputter coating device. Sintered TiC 6 inches in diameter and 1/4 inch
thick was used as a target and the supplied RF power was 3 kW with a frequency of 13.56
MHz. The substrate can be heated up to 973 K by the heater. A quadrupole mass spectrometer
was used for the analysis of the composition of the working gas during the sputtering.
TiC films were deposited on an Mo substrate with an area of 5 ⫻ 10 mm 2 at 870 K in a
discharged Ar environment by the magnetron sputtering method. The relations between the film
properties and the sputtering conditions are shown in Table 1. When titanium flakes lie on the
TiC target during sputtering, the Ti/C ratio increases accompanying a decrease in the lattice
parameter. The degree of crystallization becomes worse with decreasing substrate temperatures
if evaluated from the half-width of the X-ray diffraction line. If the substrate is highly RF biased,
the concentration of Ar accommodated in the film and the lattice parameter increase. This means
Figure 2 Improvement of adhesion between TiC film and the Mo substrate through control of the sub-
strate temperature (pressure of C 2H 2 , 1.5 ⫻ 10 ⫺2 torr).
a decrease in the degree of crystallization. Lower working gas pressure during sputtering leads
to the same result.
The Ti/C compositional ratio can easily be changed with the magnetron sputtering method
by placing Ti flakes or graphite flakes on the TiC target. TiC films were deposited on Mo
substrates with an area of 10 ⫻ 10 mm 2 heated to 870 K in a 5 ⫻ 10 ⫺1 Pa Ar environment by
applying 1 kW of RF power to the TiC target. The result is shown in Fig. 5. X-ray diffraction
revealed that the preferred plane is (111) for C-rich TiC films and (200) for Ti- rich TiC films.
No preferred texture was observed in the films that had a concentration near stoichiometry.
Figure 5 also shows the relation between the Ti/C ratio and the lattice parameter. The lattice
parameter increases with increasing C content. The internal stress in the films, estimated by using
the curvature radius of the substrate, and the Ar content in the films increased with increasing C
content. From these results, the cause of internal stress would be that in the C-rich films the
vacancy concentration of Ti becomes large and Ar gas can be accommodated in the vacancies.
Figure 6 shows the relation between the density and the compositional ratio of the films.
The figure indicates that about one-half of the extra C atoms become interstitial and one-half
of the deficient Ti atoms become vacancies. (8–11)
C. TiB 2 Formation by the Magnetron Sputtering Method

The same equipment was used to obtain TiB 2 films on an Mo substrate. The sputter working
gas was 5 ⫻ 10 ⫺1 Pa Ar. A 99.98 wt % Ti disk with a diameter of 150 mm was used as a
Figure 3 Relation between compositional ratio in TiC and the ratio of injected acetylene (C 2H 2) to Ti.
Figure 4 Schematic representation of magnetron sputtering apparatus.

Table 1 Relation Between Characteristics of TiC Films and Sputtering Conditions a

Half-width
Ti/C Ar Lattice of X-ray
Condition ratio content parameter diffraction peak
Existence of Ti on the target ⫹⫹ ⫺ ⫺⫺ ⫺
Substrate temperature ⫹⫺ ⫺ ⫹ ⫺⫺
Substrate bias voltage ⫺ ⫹⫹ ⫹⫹ ⫹⫹
Gas pressure at sputtering ⫺ ⫺⫺ ⫺⫺ ⫹⫺
a
⫹⫹, strong positive relation; ⫹, positive relation; ⫹⫺, no relation; ⫺, negative relation; ⫺⫺, strong
negative relation.
sputter target. The RF power applied to the target was 1 kW. A suitable amount of single-crystal
99.9 wt % B particles about 5 mm in size was placed on the target. In order to control the
chemical composition of the deposited film, the amount of B particles was changed. The distance
between the target and the Mo substrate was 80 mm. The deposition temperature was 870 K.
Figure 7 shows the deposition rate of Ti 1⫺xBx measured by gravimetry as a function of
the amount of B placed on the titanium target. The deposition rate was independent of an amount
of B less than 15 g and was estimated to be about 15 µg min ⫺1 cm ⫺2 . For an amount of B in
the range 15–20 g, the deposition rate decreased with increasing amount of B to 7–8 µg min ⫺1
cm ⫺2 . The deposition rate seems to be independent of the amount of B with an increase in the
amount of boron of more than 20 g.
Figure 8 represents the relation between the chemical composition of the deposited films
and the amount of B placed on the Ti target. Electron probe microanalysis (EPMA) did not
reveal any evidence of Ar atoms in the deposited Ti 1⫺xB x films. This is in contrast to the case
of Ti xC 1⫺x deposition just mentioned. The B content in the films increased with increasing
amount of B. In the range of 15–20 g of B, the B content in the deposited films increased
abruptly. In this region, a nearly stoichiometric composition of TiB 2 can be obtained. The phe-
Figure 5 Relation between lattice parameter of TiC and the compositional ratio (Ti/C).
Figure 6 Relation between density of Ti xC 1⫺x coating on Mo substrate and chemical composition. Curve
a, excess C atoms exist as interstitials; curve b, deficient Ti atoms exist as vacancies; curve c, half of the
excess C atoms and half of the deficient Ti atoms exist as interstitials and vacancies, respectively; curve
d, excess C atoms exist as graphite.
Figure 7 Deposition rate of Ti 1⫺xB x as a function of the amount of boron on 150 mmφ Ti target.
Figure 8 Chemical composition of deposited films as a function of the amount of boron on 150 mmφ
Ti target.
nomena (drop in deposition rate, abrupt change in chemical composition of deposited films, and
formation of stoichiometric products) are similar to those observed with the reactive sputtering
technique (14).
Figure 9 shows the results of microhardness measurements on the deposited Ti 1⫺xB x films
with a 25 gf load. Among the films, stoichiometric TiB 2 had the highest microhardness of about
3000 kgf cm ⫺2 , which is nearly equal to that of sintered TiB 2 .
In spite of this, the intensities of the TiB 2 diffraction peaks from the stoichiometric films
were very weak when the films were deposited without a bias voltage applied to the molybdenum
substrate. Strong intensities of the hexagonal TiB 2 diffraction peaks were obtained when the
stoichiometric films were deposited with a negative bias voltage. These results are shown in
Fig. 10. The application of a negative bias voltage does not affect the results of the microhardness
measurements.
The results of X-ray diffractometry suggest that crystallization is imperfect in the stoichio-
metric TiB 2 films deposited without a negative bias voltage and that the application of a bias
voltage to the substrate enhances the crystallization of TiB 2 .
In the X-ray diffraction analysis, the 00n diffraction peaks of the hexagonal TiB 2 had the
strongest intensity, while the intensities of 101 and 102 were weak. These results indicate that
the deposited TiB 2 films have a strong preferred (001) orientation.
Figure 11 represents the lattice parameters c and a of the deposited hexagonal TiB 2 as a
function of the applied bias voltage. Increasing the applied bias voltage slightly changed the
lattice parameter c of TiB 2 from 3.18 to 3.25 Å, although the reported value is 3.22 Å (15).
The lattice parameter a is estimated to be about 3.05 Å which is slightly larger than the reported
value of 3.02 Å. It can be said that the two estimated lattice parameters coincide well with the
reported values. (12,13)
Figure 9 Change in microhardness of Ti 1⫺xB x as a function of chemical composition x.
Figure 10 Diffraction patterns of TiB 2: (a) TiB 2 deposited without a negative bias voltage. (b) TiB 2
deposited with a ⫺50 V bias voltage.
Figure 11 Lattice parameters, a and c, of TiB 2 as a function of applied bias voltage.
III. THERMAL STABILITY OF THE COATED METALLOID FILMS
It is important to examine the thermal stability of the formed metalloid films, because when
the operating temperature is high, the formed metalloid may decompose and diffuse into the
substrate or the substrate elements intrude into the metalloid films, both of which cause deteriora-
tion of the metalloid films.
A. Thermal Stability of TiC Films Coated by Ion Plating Method

A comparison was made of the thermal stabilities of the TiC films on Mo substrates formed by
the ion plating method with and without controlling the substrate temperature. The specimens
with TiC films were heated at 2073 K in a vacuum of 5 ⫻ 10 ⫺6 torr for 40 min. Figure 12 gives
the compositional analysis by EPMA from the film surface to the substrate. The specimen,
whose substrate temperature was controlled, had a layer in which the carbon contents changed
continuously. In this specimen, there was a thick diffusion layer at the interface between the
film and the substrate. Scanning electron microscopy showed that TiC precipitated like a wedge
in the Mo substrate near the interface. The films did not exfoliate because of the thick diffusion
layer and the anchoring effect of the precipitates.
The effect of compositional ratio of TiC x on the evaporation rate of the films on the Mo
substrate was examined by heating for 40 min in the temperature range 1873–2273 K in a
vacuum of 5 ⫻ 10 ⫺6 torr. The compositional ratio, x ⫽ C/Ti, was determined from the EPMA
measurement. The results are shown in Fig. 13, where TiC films on graphites formed by the CVD
process were taken as a reference. The weight loss of the films became larger with deviation of
the compositional ratio from stoichiometry. From X-ray photoelectron spectroscopy (XPS), the
existence of free Ti was recognized in the films whose composition deviated from stoichiometry.
Figure 12 Compositional changes of TiC films on Mo substrates after heat treatment. (a) Coated material
with continuously varying content of C formed by the substrate temperature controlling method; (b) coated
material produced by normal method (substrate temperature was kept constant).
This is assumed to be the main cause of weight loss due to evaporation. The effect of temperature
on the evaporation rate of TiC films is shown in Fig. 14. The evaporation rate of TiC on Mo
increased gradually with increasing temperature from 2073 K, whereas that of TiC on graphite
was almost null. After heating to 2273 K, the surface of TiC on Mo became spongelike; however,
that on graphite did not change. X-ray diffraction revealed that after the heating, Mo 2C was
recognized on the surface of TiC on Mo. This means that free Ti appears because of the forma-
tion of Mo 2C. The formation of Mo 2C is energetically preferred to that of TiC at temperatures
higher than 1973 K from the standard free energy of formation. (3,7)
B. Thermal Stability of TiC Films Coated by the Magnetron Sputtering

Method
The effect of the amount of Ar atoms incorporated in the TiC films on the thermal stability of
the films was examined. TiC films were deposited onto Mo substrates at 870 K in a 5 ⫻ 10 ⫺1
Pa discharged Ar environment by RF planar magnetron sputter coating with a deposition rate
of about 2.5 mg/m 2 s and a deposition duration of 6 h. Some of the deposited TiC films were
heat treated at 1100–2300 K in a vacuum of about 1 ⫻ 10 ⫺4 Pa for 5 h in order to examine
Figure 13 Relation between the compositional ratio X(C/Ti) of TiC x film and the evaporation rate for
heating tests under vacuum.
their thermal stability. The deposited films had the chemical composition Ti 0.6C 0.4 (in atomic
ratio) with an NaCl-type structure, regardless of the applied voltage Va . The deposition rate,
thickness of the deposited films, Ar content, and lattice constant as a function of V a are shown in
Table 2. The deposition rate decreased with decreasing V a . The amount of Ar atoms incorporated
increased appreciably with decreasing V a as indicated in Table 2. The lattice constant of matrix
TiC increased with an increase of incorporated Ar. This suggests that the incorporated Ar exists
as a solute in the TiC matrix in the as-deposited condition.
When the deposited TiC films containing Ar atoms were heat treated, the lattice constant
Figure 14 Temperature dependence of evaporation rate of TiC coatings on Mo and POCO gra-
phite substrates. Solid line, IP-TiC/Mo and CVD-TiC/Mo; dotted line, IP-TiC/POCO G and CVD-TiC/
POCO G.
Table 2 Characteristics of Deposited TiC Films Produced by the Magnetron Sputtering

Method
Bias voltage (V)
Characteristic ⫹30 ⫺70 ⫺170 ⫺220
Deposition rate (mg/m 2 s) 2.785 2.622 2.267 2.080
Thickness (µm) a 12.26 11.31 9.98 9.15
Ar content (wt%) 0 ⬃ 0.3 3⬃8 8 ⬃ 15 9 ⬃ 15
Half-width of (200) X-ray diffraction ⬃0.4 ⬃0.6 ⬃1.0 ⬃1.1
peak
Lattice constant (Å) 4.31 4.35 4.38 4.40
∑(hkl) (au) b ⬃70 ⬃80 ⬃80 ⬃50
a
Density is assumed to be 4.91 g/cm 3.
b
au, arbitrary unit.
began to decrease at about 1100 K as shown in Fig. 15, indicating that the solutes (Ar atoms)
become mobile and begin to segregate at this temperature.
Observation of the surface morphology of as-deposited and heat-treated TiC films revealed
that faceting occurred at temperatures higher than 1500 K, indicating that the evaporation was
appreciable from this temperature. The faceting temperature rose with decreasing V a . This means
that films deposited with a higher negative bias voltage V a are more stable and resistant to
thermal evaporation.
At higher temperatures, blisters formed on films containing more than a few wt % Ar.
Depending on the Ar content, the temperature at which blisters started to form during 5 h of
heat treatment varied, from 2100 K with 3 wt % Ar to about 1300 K with 12 w % Ar. The
measured blister density was independent of the heat treatment temperatures and was propor-
tional to the Ar content. From 100 to 150 µm was a typical diameter of a blister with a density
of about 20 mm ⫺2 at 1800 K, with 12 wt % Ar. The measured thickness of the erupted blister
skin was about 7–10 µm, nearly equal to the film thickness. This means that blisters could be
Figure 15 Relation between lattice parameter of TiC films and heat treatment temperature.
formed within the film if the films were thicker than, say, 20 µm. The blister morphology
changed from flat-shaped to high-roof and dome shaped as the negative bias voltage V a increased.
The film began to exfoliate after blisters grew and erupted with increasing heat treatment temper-
ature. The growth of the blisters was as follows. The flat blisters grew by increasing their diame-
ter without appreciable increase in their roof height, and the high-roof and dome-shaped blisters
grew by increasing their roof height without appreciable increase in their diameter.
These morphological differences in the blisters could be attributed to the difference in the
adhesive strength of the deposited film. Because the film deposited with low bias voltage, V a ,
was considered to have weak adhesive strength, the blisters formed at the interface between the
film and its substrate could accommodate the rising internal pressure through expanding the
volume by debonding the film interface; that is, the blisters grew along the film interface without
appreciable increase of their heights. Meanwhile, the film deposited with higher negative bias
voltage, V a , would have higher adhesive strength, with the result that the increasing internal
pressure could not debond the adhesive interface but would exceed the fracture strength of blister
skin and would finally cause the skin to erupt.
After the blisters erupted, the film commenced to exfoliate. The TiC films with more than
15 wt % incorporated Ar did not form blisters. Instead, many small pits were formed at tempera-
tures above 1300 K. In this case, exfoliation of the films occurred substantially at above 1500 K.
Figure 16 shows a schematic representation of the behavior of deposited TiC films at ele-
vated temperatures as a function of the bias voltage, V a , or as a function of their Ar content. (10)
C. Thermal Stability of TiB 2 Films Coated by the Magnetron Sputtering

Method
TiB 2 films with a thickness of 6 µm were deposited on an Mo substrate at 870 K by the cosputter
coating method using a conventional RF-type planar magnetron sputtering coating device. The
sputter working gas was 5 ⫻ 10 ⫺1 Pa Ar and the sputter target was a Ti disk with a diameter
of 150 mm. To control the ratio of Ti and B in the films, a suitable amount of boron particles
was placed on the Ti disk. In order to examine the thermal stability of TiB 2 films, the coated
specimens were heated in a vacuum of 1 ⫻ 10 ⫺4 Pa for 5 h in the temperature range 1270–
1670 K and for 0.33 h at 2273 K.
Table 3 shows the results of thermal stability tests of deposited TiB 2 . Evaporation in Ti-
rich films (Ti 1⫺xB x; x ⬍ 0.67) occurred easily at relatively low temperatures. Ar gas incorporation
was not observed in the films. In spite of this fact, some blister formation was observed on the
Ti-rich specimens. The stoichiometric and B-rich films possessed good resistance to evaporation.
However, they showed weak adherence to Mo substrates when they were deposited without the
application of a negative bias voltage to the Mo substrates. The adherence of TiB 2 films to their
Mo substrate was improved by application of a negative bias voltage. The TiB 2 films deposited
with a negative bias voltage larger than ⫺50 V exhibited excellent thermal stability even at the
highest temperature, 2273 K. (12)
D. Improvement of TiC Films Coated on Molybdenum Substrate

In the foregoing section, it was shown that the thermal stability of TiC coated on an Mo substrate
degraded in vacuum at temperatures higher than 2073 K because of the formation of (Ti,-
Mo) xC 1⫺x and Mo 2C layers at the interface of the TiC film and Mo substrate. To prevent the
reaction, it is supposed to be effective to ensure an intermediate layer between TiC and the
substrate. From the standpoint of the high-temperature chemical reactions between Mo and
Figure 16 Stability diagram of TiC films containing Ar gas as a function of bias voltage.
Table 3 Appearance of Ti 1⫺xB x Films After Heat Treatment a

1273 K, 1473 K, 1673 2273 K,
Specimen 5h 5h K, 5 h 20 min
Ti 0.5B 0.5 G B (Ev) B (Ev) Ev
Ti 0.4B 0.6 G B B (Ev) Ev
Ti 0.33B 0.67 G B (Ex) B (Ex) (Ev) Ev
Ti 0.23B 0.77 Ex Ex Ex
Ti 0.33B 0.67(bias, ⫺50 V) G G G Ev
a
G, good; B, blistering; Ev, evaporation; Ex, exfoliation.
Figure 17 Effect of an intermediate W layer on the thermal stability of TiC coatings on Mo substrates.
materials with a high melting point and from a comparison of the standard free energies of
formation in several carbides, tungsten (W) was selected as an intermediate layer.
As an intermediate layer, W films with a thickness of 5 µm were coated on an Mo substrate
by the magnetron sputtering method under the following conditions: substrate temperature, 873
K; pressure of Ar, 6.7 Pa; RF power, 500 W. It is well known that Ar incorporation occurs
during the formation of W by sputtering. In order to lower the Ar content to a level at which
blisters do not form on heating in vacuum at high temperature, an additional heat treatment in
a vacuum lower than 10 ⫺3 Pa was needed.
The TiC films were formed on W layers on an Mo substrate by the RF–reactive ion plating
method mentioned in the previous section.
The thermal stability of TiC films was examined by heating in vacuum at temperatures
ranging from 1873 to 2273 K for 15–30 min. Figure 17 shows the effect of the W intermediate
layer on the film thickness. Little charge in the film thickness of the TiC-coated materials with
a W intermediate layer occurred after heat treatment at 2273 K. Characteristic X-ray images of
elements along the cross section of the specimen after heating at 2273 K reveal that an Mo 2C
phase was not formed and only a small amount of W existed in the TiC films coated on a W
intermediate layer. (16,17)
IV. FORMATION OF BULK CARBON MATERIALS CONTAINING TiC

AND TiB 2
Carbon materials such as graphite and C/C composites have high melting points and high ther-
mal conductivities. Furthermore, carbon is a typical low-atomic-number element. Because of
these characteristics, the materials are used for components subjected to a high heat load and
high particle fluxes of the plasma in nuclear fusion reactors. However, they also have distinct
disadvantages as plasma-facing materials, namely radiation-enhanced sublimation (21), high
retention of hydrogen isotopes, high sublimation at elevated temperatures, and radiation-induced
degradation of thermal conductivity (22). As these disadvantages will be key issues in the next-
Table 4 Results of X-Ray Diffraction Analysis in C-B-Ti Compounds

Composition of raw material Relative X-ray intensity ratio (TiB 2 (101)
(at %) as standard)
C B Ti TiB 2(101) TiC(200) Graphite(002)
50 30 20 1 0.13 0.15
45 35 20 1 0.10 0.19
42.5 42.5 15 1 0.04 0.26
40 40 20 1 0.09 0.13
37.5 37.5 25 1 0.06 0.08
35 45 20 1 0.11 0.16
35 35 30 1 0.29 0.08
35.4 13.1 51.5 1 5.6 0
33.5 37.2 29.3 1 0.36 0.87
31.3 34.7 34 1 1.63 0
30 50 20 1 1.07 0.26
25.9 28.8 45.3 1 0.89 0
24 26 50 1 3.03 0
12 38 50 1 1.43 0
generation fusion devices, many attempts are being made to improve graphites. One such exam-
ple is boronized carbon. In this material, radiation-enhanced sublimation is suppressed (23), and
the plasma performance will be highly improved because of the reduction of oxygen impurity
levels in the plasma with the addition of boron (24).
It is clear from the phase diagram that the melting point of the carbon-boron system is
much lower than that of graphite, and this is the disadvantage of the system. But if we could
add titanium to the system, the material obtained would contain TiC, TiB 2 , and carbon. As both
of the former compounds have relatively higher melting points (higher than 3173 K) than boron
carbides, the drop in the melting point due to boronizing would be avoided. Furthermore, the
radiation-induced sublimation of TiC is smaller than that of graphite (25), and also the retention
of hydrogen isotopes of TiB 2 is lower than that of graphite (4). These will make the mixed
compounds superior to graphite as plasma-facing materials.
For the preceding reasons, carbon-boron-titanium compounds were fabricated by the fol-
lowing methods. Powders of graphite (10 µm), boron (0.15 µm), and titanium (30 µm) were
dry blended and hot pressed to disk-shaped compacts at 1073 K for 5 min under a uniaxial
stress of 30 MPa in a vacuum of 1 ⫻ 10 ⫺3 Pa. The diameter of the compacts was about 30 mm
and their thicknesses were 3–10 mm. The compacts were then sintered gradually from 1473 to
1773 K and finally at 2273 K for 30 min. Some of the compacts were Hot Isostatic Pressing
(HIP) treated at 2273 K under a pressure of 2000 atm for 30 min after the hot pressing.
Table 4 shows the atomic compositions of carbon, boron and titanium in raw materials
and the relative existence ratios of TiC, TiB 2 , and graphite obtained after sintering in terms of
X-ray diffraction intensity ratios using TiB2 (101) as a standard. As can be seen in the table,
TiC, TiB 2 , and graphite are formed by the production method mentioned before. (18–20)
V. THERMAL SHOCK RESISTANCE OF METALLOIDS
In fusion reactors, heat load on their first wall often reaches 5–10 kW/cm 2 for several reasons,
such as the existence of abnormally accelerated runaway electrons, arcing between plasma and
the first wall, and plasma disruption due to sudden break of a stable plasma discharge. The first-
wall materials are damaged by such high heat loads.
At NRIM, a convenient electron beam high-heat-flux test apparatus with a hot hollow
cathode discharge gun (HCD gun) was designed to modify high heat loads attacking the first
walls of fusion reactors (26,27). Figure 18 shows a schematic representation of the apparatus.
This type of electron gun provides a low-energy (40–50 eV) and high-current (100–200 A)
electron beam; thus the surface heating is similar to that which occurs by plasma ion bombard-
ment. The beam was focused by a solenoid and passed through an Mo aperture (22 mm diame-
ter). The center of a specimen that was mounted on a cooled copper holder was irradiated. The
beam diameter was 13 mm and the average heat flux was estimated from the following relation:
Φ ⫽ I a xV c
where I s is the electron beam current to the specimen and V c is the voltage between the electron
beam gun and the specimen. In order to analyze the phenomena, including erosion and vaporiza-
tion, the specimen current was continuously monitored during the test. Typical current changes
during the thermal shock tests are shown in Fig. 19. At the onset of erosion, the current abruptly
rose and was almost constant until the end of the test. Therefore, the incubation time for erosion
could easily be determined from the specimen current-time relation chart.
A. Thermal Shock Resistance of TiC-Coated Molybdenum

Three kinds of TiC-coated Mo specimens were tested using the thermal shock test apparatus
just mentioned, namely TiC directly coated Mo (TiC/Mo), TiC-coated Mo precoated with a
thin W layer (TiC/W/Mo), and TiC-coated vacuum-heat-treated Mo with a W intermediate layer
(TiC/HT-W/Mo). High heat flux was 5.3 kW/cm 2 and the heat duration was 1.5 s.
The surface morphology was observed after the tests. In the case of TiC/Mo, there was
Figure 18 Schematic representation of pulsed electron beam heating apparatus.

Figure 19 Typical examples of change in specimen current with exposure time during pulsed electron
beam heating tests: (a) in the case of specimen fracturing; (b) in the case of specimen melting.
a melted area corresponding to the beam spot and bare Mo substrate was observed. In the case
of TiC/W/Mo, a color change of TiC was observed in the beam-heated area and there was a
melted area in its center with a diameter of 1 mm Φ. In the case of TiC/HT-W/Mo, a small
change of the color in the heated region was recognized. Therefore TiC/HT-W/Mo has adequate
thermal shock resistance.
Figure 20 shows times to surface melt of bare Mo, of TiC/Mo, and of TiC/HT-W/Mo at
a heat flux of 5.3 kW/cm 2 . It should be noted that TiC/Mo has a much shorter time to melt
than bare Mo. This indicates that compounds with low melting points would be formed at the
interface between TiC and Mo. Here also the superiority of TiC/HT-W/Mo is recognized. (17)
B. Thermal Shock Resistance of Graphite and Carbon Materials

Containing TiC and TiB 2
Fracture and/or erosion appears in specimens heated by the electron beam from the thermal
shock testing apparatus. When the specimen is thin (⬉1 mm), fracture often occurs within 1 s
of heating. When the specimen is thick (⬃10 mm), erosion occurs. The extent of erosion and
the thickness of the specimen at which fracture occurs, say just after 1 s of heating, depend on
the heat flux and the material properties.
1. Fracture of Graphite
Various kinds of isotropic and anisotropic graphites were exposed to the electron beam, whose
diameter was 13 mm. Table 5 shows the experimental results. All the specimens fractured within
1 s of the heat load. In this table, W denotes the heat flux when the specimen fractures with 1
s of heat load duration. These values were evaluated from the experimental results using an
empirical relation that the time to fracture is inversely proportional to the third power of the
incident flux. The relation was confirmed by both experiments and computer simulation. From
Figure 20 Time to surface melting in electron beam heating tests as a function of number of heating.
The heat flux was 5.3 kW/cm 2 . (a) Bare Mo substrate; (b) TiC/Mo; (c) TiC/HT-W/Mo.
Table 5 Properties of Graphite Samples and Results of High-Heat-Flux Tests
Thermal Thermal Elastic Tensile Pore

conductivity expansion modulus strength size Heat flux Fracture W
Specimen (kcal/mhK) (10 ⫺6 /K) (kg/mm 2) (kg/mm 2) (µm) (kW/cm 2) time (S) (kW/cm 2)
ISO-880U 73 6.5 1300 7.0 0.4 1.31 0.6 1.0
IG-110U 100 4.6 1000 2.5 3 1.31 1.0 1.1
ETP-10 90 3.8 1100 3.5 2 1.42 0.65 1.3
G1950S (储 ) 90 4.5 1225 3.0 ⬍0.5 1.49 0.75 1.5
(⊥) 50 5.6 850
AX650K 90 4.8 1180 3.1 2 1.24 1.0 1.4
YPD-K ( 储 ) 220 1-2 1450 0.7 2.10 1.0 2.0
(⊥) 60 12–13 470
the W values, one can see that YPD-K endures the high heat flux about twice as long as the
other samples without fracture. Also, anisotropic G1950S has the second best W value. These
two anisotropic samples have higher thermal conductivity, lower thermal expansion, and higher
elastic modulus in the direction parallel to the specimen surface than in the thickness direction.
The well-known thermal shock parameter of the material is defined as
R ⫽ σ t(1 ⫺ ν)K/(Eα)
where σ t is the fracture strength, K the thermal expansion coefficient, E Young’s modulus, and
α thermal conductivity. The lower the value of R, the lower the thermal shock to the material
becomes. If fracture stress and Poisson’s ratio do not change greatly in the present graphite mate-
rials, the graphites with higher thermal conductivity, lower thermal expansion coefficient, and
higher Young’s modulus suffer lower thermal shock, as in the case of anisotropic graphites. (27)
2. Erosion of Graphites and C/C Composite

Heat load tests were performed on isotropic graphites, pyrolytic coated graphites with a coating
thickness of 5–30 µm, and a C/C composite (felt type). The sample sizes were 25 ⫻ 25 ⫻ 3–
10 mm, the beam diameter was 12.7 mm, and the heat load duration was 5 s. The results are
shown in Table 6. Severe erosion was observed on the surface of most specimens. The erosion
mechanism may be vaporization and ejection of small carbon particles from the surface due to
thermal stress. The incubation time to erosion increased in all cases with sample thickness. This
means that the erosion process is controlled by the surface temperature, because increasing rate
of the surface temperature decreases with increasing of thickness.
In the case of pyrolytic coated graphites, the incubation time to erosion decreased with
increasing coating thickness. Also, the damaged region of pyrolytic coated graphites increased
with increasing coating thickness. This increase may be attributed to the difference in thermal
and mechanical properties between the coating and the substrate.
The damaged region of the C/C composite was larger than those of isotropic graphites
Table 6 Erosion Data of Carbon Materials
Diameter Area of
Sample Coating Heat flux Incubation of eroded eroded Erosion
thickness thickness density time of region region depth
Material (mm) (µm) (kW/cm 2) erosion (s) (mm) (cm 2) (µm)
ATX-20U 3 2.27 1.8 (fracture)
5 2.5 2.85 5.6 0.25 135
10 2.61 No erosion
ATX-30U 3 2.39 2.3 6.2 0.30 195
5 2.39 4.6 4.2 0.14 20
10 3.3 4.5 3.6 0.10 20
PyC-coated IG110-U 3 5 2.3 1.65 6.4 0.32 225
3 10 2.17 1.65 6.8 0.36 235
3 30 2.22 1.1 6.8 0.36 240
PyC-coated ETP-10 3 5 2.74 1.3 6.4 0.32 230
3 10 2.76 1.2 4.9 0.188 60
3 30 2.88 0.95 6.8 0.36 265
C/C composite (felt type) 3 2.65 1.1 6.8 0.36 310
5 2.55 3.9 5 0.196 75
under nearly the same conditions. Nevertheless, the C/C composite is superior as a plasma-
facing materials to graphites in the sense that the former did not fracture in this experiment.
SEM observation after the test revealed that erosion of the matrix was faster than that of carbon
fibers. (19,28)
3. Fracture of Graphite Containing TiC and TiB 2

Table 7 shows the results of the thermal shock test of carbon-boron-titanium materials. Resis-
tance to thermal shock fracture decreased with increasing titanium content. As shown in Table
4, the relative X-ray intensity of graphite decreased with increasing titanium content. This sug-
gests that the resistance to thermal shock fracture increases with increasing relative amount of
graphite. During the thermal shock tests, samples with a high titanium content fractured into
many pieces. The cracks originated at the center of the sample surface and propagated radially.
These cracks were probably caused by shear stresses at the central surface region, where strong
compressive stresses were induced by thermal expansion. Samples with a high graphite content
did not fracture; however, central regions of the sample surfaces were severely eroded. Micro-
cracks were observed around the eroded regions
From these results, it seems that there exists an appropriate content range of graphite,
titanium, and boron for which the sample does not fracture and suffers only slight erosion. It
is difficult, however, to clarify the role of TiC and/or TiB 2 in the thermal shock resistance from
these results. (18,20,29)
4. Thermal Shock Resistance of Mixtures of TiC and TiB 2

The fabrication method mentioned in Sec. IV also provides a TiC and TiB 2 mixture from mixed
powders of titanium, boron, and graphite. The mixtures obtained are shown in Table 8. Thermal
shock resistance of the mixtures is also shown as the heat load of crack initiation. Here, the
heat load of crack initiation is defined as the heat flux that causes catastrophic fracture of a
specimen 30 mm in diameter and 3 mm thick. It is clear that mixture No. 4, whose molar ratio
TiB 2 /TiC equals nearly 1, showed the best thermal shock property. This may be attributed to
the superiority of thermal diffusivity in No. 3 compared with the others, as shown in Table 8.
Table 7 Thermal Shock Test Data of C-B-Ti Materials

Composition of raw
material (at %)
Heat flux Duration Thermal Surface
C B Ti (kW/cm 2) (s) shock fracture erosion
95 5 0 2.3 5 Not fractured Severe
85 15 0 2.8 5 Fractured Severe
a a
50 50 0 Not fractured Severe
a a
50 40 10 Not fractured Severe
35 13 52 1.4 1 Fractured Little
a
Heat flux could not be estimated because specimen current was unstable.
Table 8 Chemical Composition, Molar Fraction of TiB 2, Heat Load of Crack Initiation, Thermal
Diffusivity of the Compounds
Heat load
Composition
Molar fraction of crack Thermal diffusivity
(at %)
of TiB 2, TiB 2 / initiation at room temperature
Specimen C B Ti (TiC ⫹ TiB 2) (kW/cm 2) (10⫺6 m 2 /s)
1 35 13 52 0.15 ⬍1.7 4.4
2 24 26 50 0.30 ⬍1.4 5.6
3 26 29 45 0.36 ⬍2.3 8.7
4 12 38 50 0.45 ⬍3.8 15.0
5 35 35 30 0.55 a ⬍3.0 8.7
a
A slight graphite phase coexisted (see Table 4).
As the maximum heat power density obtained, 3.8 kW/cm 2, is much lower than that in the case
of TiC/HT-W/Mo, further improvement of these materials is needed. (20,29,30)
VI. CONCLUSION
As possible candidates for the plasma-facing materials of fusion reactors, TiC and TiB 2 coatings
on high-melting-point materials and bulk mixtures of TiC and TiB 2 were manufactured by vari-
ous methods and their stabilities at elevated temperatures or their thermal shock resistances were
examined. The results obtained were as follows:
1. An appreciable improvement in the adhesion of TiC coatings on Mo prepared by
controlling the substrate temperature during the ion plating process was achieved.
2. Efficient ionization of the vapor species was achieved in the DC discharge method
during the ion plating process; however, careful optimization of the deposition condi-
tions was needed in the RF discharge method during the process. Stoichiometric
TiC deposits could easily be obtained by the former method, but the formation of
carbon-excess TiC films was characteristic of the latter method.
3. TiC films containing large amount of Ar were deposited on an Mo substrate by RF
magnetron sputtering when the substrate RF bias was high or the working gas pres-
sure was low. These films had large compressive internal stresses. Without Ti addi-
tion, the deposited films were excessively rich in carbon.
4. Carbon-excess Ti xC 1⫺x deposits showed a strongly preferred orientation and a much
higher hardness than nearly stoichiometric deposits.
5. Stoichiometric TiB 2 films on Mo substrates can be deposited by cosputtering Ti and
B without applying a negative bias voltage to the substrates; however, they had a
poorly crystallized structure. The application of a small negative bias voltage en-
hanced the crystallization of the films.
6. Thermal stability of the TiC films deposited by the ion plating method depended
strongly on the stoichiometry. The TiC coatings on Mo showed a large degree of
vaporization above 2073 K. Interactions between the coating and the Mo substrate
at elevated temperatures became another cause of degradation of the film.
7. The study of the behavior of TiC films deposited on Mo substrates by magnetron
sputtering in a discharged Ar environment revealed that the film deposited with a
lower bias voltage contained fewer Ar atoms but was easy to evaporate and had
weaker adhesive strength. The Tic films deposited with a higher negative bias voltage
resisted thermal evaporation and had better adhesive strength but contained more
Ar atoms and formed many blisters at elevated temperatures. The blister formation
caused film exfoliation.
8. The TiB 2 films deposited on an Mo substrate by magnetron cosputtering without a
negative bias voltage showed good thermal stability but exfoliated easily at elevated
temperatures. The most prominent effect of the application of a negative bias voltage
is improvement of the adherence of the deposited films.
9. TiC coatings prepared on vacuum heat-treated Mo with a W intermediate layer
showed good high-temperature stability and survived 2.0 pulses of heating at a power
density as high as 5.3 kW/cm 2 .
10. Among the commercial-grade graphites, the most anisotropic sample had the highest
thermal shock resistance. Although the damaged regions of C/C composites ob-
served after the thermal shock test were larger than those of graphites, C/C compos-
ites are superior to graphites as plasma-facing materials because they did not fracture
in the experiments.
11. Bulk mixtures of TiC, TiB 2 , and graphite can be manufactured from powders of Ti,
B, and graphite by powder metallurgy. In bulk mixtures of TiC, TiB 2 , and graphite,
the mixture with the molar ratio TiC/TiB 2 ⫽ 1 exhibited the best thermal shock
resistance, but it fractured at a power density of 3.8 kW/cm 2 , which is lower than
that in the case of TiC/HT-W/Mo. Further improvement of these materials is needed.
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15
Synthesis of Diamond from the Gas Phase
Andrzej Badzian
Materials Research Laboratory, The Pennsylvania State University, University Park, Pennsylvania
I. INTRODUCTION
This chapter reviews the status of chemical vapor deposition (CVD) of diamonds as electronic
materials. The CVD process was confirmed in 1952 (1). In the same year a discovery was made
that some rare bluish, boron-doped natural diamond crystals, known as type IIb, behave as
semiconductors (2). High pressure/high temperature (HP/HT) synthesis, which appeared just
after these events, allowed doping of diamonds with boron. The small size of HP/HT crystals
and limited control over doping level posed difficulties in electronic applications. In contrast,
CVD techniques introduced thin-film deposition, suitable for fabrication of devices and large
substrates for packaging. It was CVD that opened the way to diamond electronics. In the past
decade great progress has been made; however, many setbacks accompanied this success.
Diamond is considered a new electronic material because of its applications, which are
currently in the developmental stage.
Semiconductor devices such as transistors, diodes, and sensors
Single-crystal films, for device fabrication, have an advantage over polycrystalline films
because, among others, they have low levels of carrier scattering, facilitate unifor-
mity of doping, and control contact characteristics.
Heat sinks (heat spreaders) as substrates for packaging of electronic devices
Diamond has superior thermal conductivity, five times higher than that of pure copper at
room temperature. Heat sinks are currently available on the market. The other prod-
ucts are infrared (IR) windows, cutting tools, and surface acoustic wave filters.
Electron field emitters
This is a new anticipated area of diamond application. A variety of diamond materials
are being studied, including highly disordered diamonds.
II. CHEMICAL VAPOR DEPOSITION OF DIAMOND

A. Pyrolysis of Hydrocarbons
Pyrolysis of CH 4 over a diamond surface was the first extensively studied process in which
synthesis of diamond was documented in the laboratory (3,4). Molecules of CH 4 at low pressure
(⬃0.1 torr) undergo decomposition on the hot (e.g., 1000°C) diamond surface. Carbon atoms
are bonded to the surface and hydrogen atoms return to the gas phase after an abstraction process.
347
348 Badzian
This method, because of surface forces, allows diamond to start growing epitaxially; that is,
its atomic structure is replicated. Unfortunately, graphite nucleates simultaneously, making the
process of pyrolysis unpractical. Progress in the gas-phase approach to diamond synthesis was
achieved when graphite conucleation was stopped by increased concentrations of atomic hydro-
gen (H°) in the gas phase. This was achieved when a plasma was introduced into the CVD
reactor to enhance the process. Because of the higher excitation of the plasma, more H° was
involved in abstraction of hydrogen atoms from hydrocarbon radicals chemisorbed on the dia-
mond surface. Higher growth rates followed an increase of plasma excitation.
B. Plasma-Enhanced CVD
There are two main groups of CVD methods. One group has its origin in thermal CVD as
mentioned earlier. Different means have been taken to enhance the CVD process: hot filament
(5), microwave plasma (6) (Fig. 1), electrical discharges developed as plasma jets, radio fre-
quency plasma, and oxyacetylene flame (7). The basic gas composition is C and H, but ternary
gas systems such as CHO (8), CHN, CHAr, and CH-metal have also been
studied. Process parameters are as follows:
Power. Gas activation depends on the power consumed to excite the plasma. At a power
density of 30 W/cm3, 50% of hydrogen was detected as H°. High concentrations of
H° are essential to reach high growth rates of diamond.
The CH 4 concentration in H 2 is preferentially 1% but depends on the plasma temperature
and pressure. Diamond is grown in wide concentration ranges of CH 4, 0.2–100%.
The temperature of the substrate is usually in the range 700–1000°C, but diamonds can
be grown in the range 300–1800°C. It is difficult to establish the low-temperature
limit because of problematic surface temperature measurements.
Pressure is usually in the 20–80 torr range but the growth process runs in the 0.1 torr–
1 atm range.
C. Chemical Transport Reactions

The second group of methods evolved from a solid source of hydrocarbon species formed during
etching of graphite by hydrogen; see Fig. 2. Using this method, homoepitaxial, doped films
have been obtained to demonstrate that semiconductor diamond films can be grown from the
Figure 1 Schematic of tubular reactor inside resonant microwave cavity (3). The substrate is heated by
plasma; 3000°C can be reached on graphite.
Synthesis of Diamond from the Gas Phase 349
Figure 2 Chemical transport reaction apparatus. The distance between graphite and diamond substrate
is in the range 0.1–1 mm.
gas phase (9). The etching-deposition process can also be performed in different ways, as shown
in Fig. 3. In a short distance between the etched graphite and the growing diamond, growth
rates of 10 µm/h were observed. A microscale version of this experiment, which involves a
mixture of graphite powder and diamond or metal powders, has been studied (10).
III. PHASE STABILITY VERSUS GROWTH MECHANISMS

A. Phase Diagram of Carbon
New developments in diamond synthesis demonstrate the diversity of pressures, temperatures,
and chemical compositions under which diamond can be grown. For a long time, common
opinion cast doubt on the feasibility of diamond growth outside its stability region in the p, T
phase diagram of carbon. It has been known since the beginning of high pressure/high tempera-
ture synthesis that crystallization of graphite takes place simultaneously with the crystallization
of diamond in some metals or alloys (11). This means that graphite was grown in the region
Figure 3 Etching-deposition experiment in a microwave plasma conducted in the system shown in Fig. 1.
350 Badzian
of its thermodynamic metastability. It was widely held true that the solvent-catalyst process
cannot be extended below the borderline of diamond-graphite stability regions. This assumption
was abolished, and it is an important contribution to clarification of the understanding of dia-
mond synthesis. This new finding states that when glassy carbon was used as a source of carbon,
crystallization of diamond was possible below the borderline (12). At a temperature of 1700°C,
the pressure was 3.8 GPa, whereas the pressure is 6.1 GPa on the borderline. Glassy carbon is
fabricated by thermal treatment of phenol formaldehyde resins and contains some H and O.
These experiments were reproduced, and a further decrease of pressure was possible down to
3.1 GPa at 1200°C (13) (Fig. 4).
Justification for these spectacular results is rather simple. The growth process of diamond
is not directly related to the p, T phase stability diagram of carbon because diamond-graphite
growth takes place in particular chemical environments: metal solvents, hydrogen, oxygen, etc.
Diamond crystallization under HP/HT conditions is related to growth mechanisms that depend
in part on the particular metal solvent. These growth mechanisms and p, T conditions will be
different in different chemical environments, such as with the addition of H and/or O.
In a similar way, CVD techniques allow growth of diamond and graphite simultaneously.
Let us consider two substrates placed close to one another and immersed in a microwave plasma
as in Fig. 1. On the Si substrate, diamond was nucleated and grew. However, on the Fe substrate,
graphite fibers were nucleated and grew at the same atomic hydrogen (H°) concentration. This
means that the concentration of H°, which preserved diamond growth, was not enough to stop
Figure 4 A part of carbon phase diagram: 1, a triple point; 2, melting of graphite; 3, diamond → graphite
transformation; 4, Liepunski’s prediction for indirect conversion (FeC); 5, Bundy’s minimum for dia-
mond formation from FeC; 6, synthesis of diamond from glassy carbon (12); 7, the same according to
Ref. 13.
graphite formation. Graphite growth proceeds by a mechanism involving Fe participation in the

building of carbon fibers.
In another type of experiment, at a particular CH 4 concentration in H 2, it was possible to
grow oriented inclusions of graphite in a diamond crystal matrix. Heteroepitaxial relationships
between (111) diamond planes and (0001) graphite planes were observed (14).
CVD diamonds were synthesized using gas mixtures of different compositions, e.g., hy-
drocarbons-H 2, COH 2, CH 3OHAr(He), and flame of C 2H 2 O 2. It is reasonable to assume
that growth mechanisms are different in these cases.
B. Active Surface Process

This discussion formulates what we understand about the diamond growth mechanism. The
growth mechanism is related to surface processes that are difficult to describe on the atomic
scale because of their complexity and the lack of adequate tools for in situ observation and
measurements. In this case, modeling of the growth process is required to fill the gap in experi-
mental data. We refer to the diamond growth process as an active surface CVD because of the
importance of surface processes. This requires consideration of the following issues:
Activation of gas phase, e.g., formation of CH 3, C 2H 2.

Transport of carbon from gas phase to the growing surface of diamond by means of surface
reactions under bombardment of the surface by H°.
In the case of microwave plasma, there is an additional interaction of the microwave field
with the species on the surface.
Thermodynamics and chemical kinetics of possible chemical surface reactions.
Atomic structure of growing surface.
Eventual modification of crystal structure due to surface reactions. In the case of diamond,
stacking faults and/or twinning can be introduced.
Growth mechanisms link together activated gas phase, surface processes, and the resulting
crystal.
C. Novel Approaches
There are no obstacles in searching for novel approaches to diamond synthesis by studying
new growth processes: electrolysis, hydrothermal (15) and laser assisted. Graphite has been
transformed to diamond by laser process (16,17) and some laser assisted CVD processes were
successful (18).
A new discovery exploits a set of multiplexed pulsed lasers applied for the first time to
solids in general, and specifically to film deposition. The process utilizes excimer, YAG :Nd
and CO 2 lasers focused on WC/Co substrate in ambient with CO 2 and N 2 as shrouding gases
(19,20).
Hydrogen-driven CVD processes are not necessarily the only type. In a nitrogen environ-
ment, diamonds are also formed (21). Supposition that diamond can be synthesized only under
conditions of its thermodynamic stability is an old concept that has passed away. The diamond-
graphite borderline, known as Berman-Simon extrapolation, is not an exclusion to growth of
diamond at lower pressures.
352 Badzian
IV. NEARLY PERFECT CRYSTALS OF DIAMOND

A. Growth Sectors
After nucleation, diamond crystals start to grow. The growth proceeds in different crystallo-
graphic directions. Most frequently, separate diamond crystals develop cubooctahedral morphol-
ogy (Fig. 5). Such crystals are built from two types of growth sectors. One growth sector is
related to the 〈001〉 growth direction and the other to the 〈111〉 direction. The 〈110〉 growth
sectors disappear because of the particular ratio of growth rates in the 〈111〉 and 〈001〉 directions.
The change in morphology of diamond crystals from cube to octahedron involves intermediary
forms such as a cubooctahedron. The growth rates depend on growth mechanisms, which are
different for different crystallographic directions. One can change morphology by the addition
of small amounts of nitrogen or by a change of temperature.
Transmission electron microscopy, electron diffraction, and Raman spectroscopy indicated
that the 〈001〉 growth sector has less defects, whereas the 〈111〉 sector shows many stacking
faults and twins. Epitaxy on the (001) surface of diamond was the first choice in searching for
electronic quality films.
Growth in the 〈110〉 direction is the fastest. Single crystals of 0.25 carat have been grown
using a microwave plasma at Raytheon Company (Fig. 6a and b). A single crystal prism of 1.2
mm height and 0.17 carat also grown by microwave plasma CVD on the (110) substrate was
assessed as gem quality diamond (22). Growth in the 〈110〉 direction has a useful feature: it
allows preparation of epitaxial films at 1300°C with no secondary nucleation and with a smooth
surface probably due to surface diffusion.
CVD single crystals are small in comparison with HP/HT ones. Record size crystals were
grown at Sumitomo Electric, De Beers, and General Electric Companies. Sumitomo single crys-
tals reach 12 mm in linear dimension. The largest De Beers crystal weights 34 carats and is
approximately 15 mm in linear dimension. Also at De Beers, a regular octahedron with an edge
length of about 1 cm was grown. Narrow [110] corrugated faces appeared at the octahedron
edges. Experiments on thermal conductivity of synthetic diamond crystals were conducted at
General Electric. Record high thermal conductivities, 50% higher than that of the best natural
crystals, have been measured for isotopically pure crystals grown by the HP/HT method. These
Figure 5 Growth sectors of a diamond crystal. Normalized growth rates ν are indicated.
Figure 6 Single crystals grown by microwave plasma–assisted CVD. (a) Crystal grown on a (110) seed
that was 1 mm in diameter ⫻ 200 µm thick. (b) Crystal grown on a (001) seed. The center is water clear.
The crystals were grown in a 5-kW reactor. Both crystals are about 2 mm thick. (Courtesy of Thomas
Hartnett, Raytheon Co.) (c) Cross-Polarized transmission photographs along the 〈001〉 direction of water-
clear 60-µm-thick film on 250-µm-thick type IIa natural crystal. The longer edge is 2 mm long. The crystal
was grown in the system shown in Fig. 1 at 875°C and 1% CH 4 in H 2. Stresses at the growth sectors
boundaries are visible.
354 Badzian
crystals were synthesized using 12C polycrystalline CVD diamond material as the carbon source
(23). Also, 12C and 13C crystals and their solid solutions were successfully prepared.
B. Characterization of Single Crystal

A semiconductor material, in an ideal situation, should be a single crystal with a strictly periodic
lattice. Electrons or holes travel easily in such a crystal, suffering only from phonon scattering.
In a periodic potential field, electron-hole propagation takes place as nearly loss-free transport.
In a similar way, heat transport in diamond is conducted by thermal waves. The waves are least
scattered when the crystal lattice is periodic. Vibrating atoms in a crystal have potential wells
prescribed to them and the minima of these wells form a three-dimensional crystal lattice.
Lattice periodicity of CVD diamond single crystals can be evaluated by X-ray diffraction
methods and by measurements of thermal conductivity. When the lattice is strictly periodic,
diffraction patterns are composed only of Bragg peaks at the reciprocal lattice points. If lattice
periodicity is disturbed by a ‘‘defect,’’ the sharp Bragg peaks can be broadened and additional
scattering between reciprocal lattice points appears. This is so-called diffuse scattering. When
atoms are shifted from their equilibrium positions by thermal vibrations, diffuse scattering arises,
but Bragg peaks do not broaden. In the case of diamond, thermal diffuse scattering is weak.
Static defects in CVD diamonds such as stacking faults, dislocations, twinning, hydrogen,
and other impurity atoms introduce displacement disorder of the carbon atoms. They cause shifts
of atoms from the equilibrium positions. Static disturbances of lattice periodicity are the cause
of X-ray or electron diffuse scattering. The intensity of diffuse scattering is a direct measure
of the departure from the periodic network. The diffuse scattering around the 111 reciprocal
lattice point is a very sensitive test for lattice periodicity of a CVD single crystal.
Natural and HP/HT crystals also show diffuse scattering associated with the 111 Bragg
reflection.
Despite the fact that CVD crystals and films produce diffuse scattering, we can consider
some of them as nearly perfect crystals. The following data support this statement:
X-ray diffraction patterns consist of sharp Bragg peaks and some diffuse scattering. Rock-
ing curves, measured for the 004 Bragg reflection, from homoepitaxial films grown
on HP/HT Sumitomo crystals are only slightly broader when compared with the
substrate curves. Some of the type Ib Sumitomo crystals have a rocking curve full
width at half-maximum (FWHM) as small as 5–6 arc sec. The best homoepitaxial
films have FWHM equal to 8 arc sec and are comparable to the best type Ia natural
crystals (24). Such rocking curves demonstrate perfect long-range order of CVD
homoepitaxial films.
The narrowest Raman 1332 cm⫺1 peak for a CVD crystal is sharp as the narrowest peak
measured for type IIa natural diamond. The FWHM is 1.6 cm⫺1. The narrow peak is
an indication of perfect long-range order. A sharp Raman peak and low background
scattering are necessary but not sufficient proof of high-quality films. Type IIa dia-
mond crystals have a mosaic structure with mosaic block spreads of arc minutes or
even higher. This orientation effect is not directly measured by Raman spectroscopy.
If some parts of the crystal are not Raman active, they will not contribute to the
Raman spectrum, and information about these regions will be lost. For this reason
it is necessary to correlate the Raman spectrum with diffraction studies.
Thermal conductivity measured for isotopically pure, 12C homoepitaxial films was higher
than for perfect natural diamonds.
The hole mobility of the (001) homoepitaxial films doped with boron reached 1580 cm2 /V⋅s
at carrier concentrations of 1017 cm⫺3. High mobility of carriers indicates perfect

lattice periodicity (25).
The preceding measurements allow cautious optimism for the development of single-crys-
tal films for electronic applications.
C. Homoepitaxy
Perfect epitaxy is difficult to achieve.
The first obstacle is seen in diamond substrate crystals. Micrometer-size defects on the
diamond surface initiated by inclusions and other bulk defects of natural crystals
and enhanced by cutting and polishing contribute to nucleation of diamond grains
with crystallographic orientations different from those of epitaxial films. Hillocks
frequently originate at such spots and many microtwins, with 〈111〉 growth sectors,
are developed in the craters. Sometimes these craters represent such disordered dia-
mond that even the 1332 cm⫺1 signature disappears from Raman spectrum. During
boron doping these 〈111〉 microsectors accommodate more B atoms than a (001)
homoepitaxial film. Hence, they are much more conductive than a homoepitaxial
film. When a transistor is fabricated, a micro short circuit, at hillock spots, disturbs
the transistor’s performance by contributing to leakage current. Elimination of hill-
ocks is the issue of primary importance. Perfect substrates should be used, such as
Sumitomo HP/HT crystals or selected type IIa natural crystals.
Growth processes should be conducted in chemically clean environments. There should
be no interaction of the plasma with any element of the reactor, because the plasma
can etch materials and transport them to the growing substrate. In general, any etch-
ing should be eliminated, and only diamond growth should occur. Hot filaments
are not advised for homoepitaxial growth, due to contamination of the diamond by
materials from the filament. Dust particles originating inside the system should be
eliminated because they can provide secondary nucleation sites.
Stable growth conditions are also an important factor in growth of nearly perfect crystals.
Substrate temperature, pressure, and gas flow should be kept constant during the
process.
How can we improve the growth of nearly perfect crystals of diamond? Two approaches
are anticipated. One is to use C-H gas systems with no additives and impose step flow growth
on a misoriented (001) surface to avoid hillock formation. There are data supporting this ap-
proach. The second possibility is the addition to the gas phase of gases such as O 2 and N 2 and
molecules such as Ni x C yH z. These gases and their derivatives participate in growth process by
influencing step formation and elimination of twinning. Smooth surfaces have been obtained in
such processes. It is not clear, at this moment, which process parameters and gas concentrations
these observations validate.
Parametric study of the growth of homoepitaxial films is not complete. It is possible to
grow smooth diamond surfaces for certain sets of process parameters, but this does not mean
that bulk diamond will be crystallographically perfect.
1. Step Flow Growth

We have mentioned that hillocks, originating from the interface, disturb epitaxial growth. Hill-
ocks are also developed when the top surface is almost parallel to the (001) plane. There are
large (extensive) terraces on such surfaces and island growth proceeds on them. These islands
356 Badzian
have square shapes with 〈110〉 edges. When hillocks are developed, their side surfaces have
vicinal planes, (11ᏸ), where ᏸ is a number larger than 10, according to atomic force microscopy
measurements. Hillocks can interact during the growth and some twins may be formed.
Step flow growth is a new concept for diamond growth that has been adopted from Si
and SiC epitaxy (26–29). This type of growth takes place on misoriented surfaces, preferably
when the top surface is inclined along the 〈110〉 direction (Fig. 7). Step flow means that growth
proceeds through the addition of atoms to the edges of the steps. When angle γ is 3–4°, flat
surfaces free from hillocks have been grown (30). Why this value of angle γ awaits explanation.
Probably it is related to compatibility between diffusion length, step width, and CH 4 concentra-
tion. For 11° the surface morphology consists of macrosteps and the surface is rough.
What is the microstep height in the case of flat surfaces? When we look into a diamond
structure in the 〈110〉 direction, we see rows of tetrahedra. They form an orthogonal pattern of
rows. The height of the tetrahedron row is 1.78 Å, half of the unit cell edge of diamond. Inside
the tetrahedron there are carbon atoms of height 0.89 Å. The atoms on this height are involved
in single-layer growth. We call this a single atomic step. In the case of a tetrahedron we call
it a double atomic step. This is a crude simplification based on the bulk atomic structure. In
reality, the surface is reconstructed and hydrogen atoms are chemisorbed. Hydrogen atoms form
a monohydride structure, which means that one hydrogen atom is bonded to a carbon atom.
Carbon atoms are shifted from their face-centered cubic (fcc) lattice positions in such a way
that dimers are formed. The dimer row has 5 Å width and has 2 ⫻ 1 surface lattice symmetry
(31). The dimer rows reflect the positions of the rows of tetrahedra beneath them.
This is stable structure, but it has atoms at positions different from those in the bulk
diamond lattice. For example, the distance between carbon atoms in the dimer is 1.63 Å, com-
pared with 2.5 Å in the bulk diamond. The bulk structure is thermodynamically metastable
according to the phase diagram (Fig. 4), but near-surface structure is stable and growth of dia-
mond proceeds with the stable structure at the surface.
Determination of how the dimer rows are oriented on terraces with respect to the terrace
edge was facilitated by scanning tunneling microscopy (STM) (32). Dimer rows run in two
orthogonal directions. They form 2 ⫻ 1 and 1 ⫻ 2 domains. The ratio of these domains can
be determined by reflection high-energy electron diffraction (RHEED) and low-energy electron
diffraction (LEED).
These methods are used to search for a 2 ⫻ 1 single domain surface. Analysis of different
step structures suggests that the single domain step structure known in Si terminology as a D B –
double atomic step should have the lowest formation energy (33). According to Figs. 8 and 9,
Figure 7 Schematic of step flow growth on a misoriented surface.

Figure 8 Double atomic layer step flow growth. Dimers and dimer rows conversion on consecutive
terraces are shown.
growth proceeds along dimer rows. It is anticipated that step flow should prevent defect forma-
tion under special growth conditions. This issue is presently under study to reveal the crystallo-
graphic perfection of 3° misoriented films. The morphology of the top surface does not change
during growth of thicker films; the films stay smooth.
2. Antiphase Domains
By analogy with Si (001) epitaxy we can expect formation of antiphase domains. A diamond
structure reconstructed to a 2 ⫻ 1 dimer structure allows two positions for new dimer nucleation
(34). If, after nucleation, two islands grow and interact, there is a 50% probability that they will
have opposite phases. At the intersection, two kinds of antiphase boundaries exist (34). Such
boundaries have been revealed on hydrogen-etched CVD diamond surfaces by STM. In Fig. 10
we see an orthogonal network of dimer rows. The distance between rows is 5 Å. In addition
to antiphase boundaries, there are narrower rows that correspond to 3 ⫻ 1 reconstruction. In
such reconstruction we have one dihydride row (35).
Figure 9 Model of double atomic layer step D B. Open and closed circles denote carbon and H atoms,
respectively. Larger circles are used for upper-terrace atoms. The dimerization direction of surface carbon
atoms is along 〈110〉.
358 Badzian
Figure 10 An STM image of a hydrogen plasma annealed (001) CVD diamond surface. Two types of
antiphase boundaries are labeled AP1 and AP2. The 3 ⫻ 1 configurations are marked L. The distance
between dimer rows is 5 Å. The compression of images is caused by instrumental calibration. (From
Ref. 35.)
3. Modeling
An in-depth understanding of diamond growth includes knowledge of atomistic surface reaction
mechanisms. The first task is to establish surface morphology. Determination of step width,
height, and dimer orientation is an important start for the modeling of chemical reactions at the
step edges, to show how dimer rows propagate. Such modeling should include the complicated
situations of single and double atomic steps. Attempts to model growth mechanisms have already
started. Modeling has filled the gap created by nonaccessibility of processes by in situ measure-
ments. Understanding how diamond structures propagate during crystal growth is a basic scien-
tific task. The reader is referred to refs. 36–40 for a more complete account of modeling.
Diamond synthesis was developed with limited scientific understanding of the growth
processes. Despite this, scientists had the courage to put forth risky hypotheses and work with
them. In this way, enormous progress has been made in controlling diamond growth processes
as well as developing a comprehensive picture of associated phenomena.
V. DEFECTS
Graphite codeposition was the main concern at the beginning of the CVD method because of
an insufficient concentration of H° in deposition reactors. The sp2 component is of negligible
importance for crystals grown in an H°-rich environment when compared with stacking faults
and twinning. These planar defects disturb the diamond lattice predominantly in the 〈111〉 growth
sectors (41–43).
Planar defects cause deformation of regular tetrahedra. Deformation of tetrahedra takes
place when the stacking sequence departs from a cubic ABCABC type of stacking. Hexagonal
diamond, obtained under static high pressure, is composed of deformed tetrahedra because c/
a ⫽ 1.66, instead of 1.63 for a regular tetrahedron. It implicates elongation of the tetrahedron
by 0.025 Å. The departure from the cubic diamond structure in some CVD films was established
by X-ray diffraction. X-ray measurements indicate the existence of displacement disorder of
atoms from the lattice positions in CVD films with defects. Stacking faults and microtwinning
imply breaking of the symmetry of the cubic diamond lattice and have the general implication
for semiconductor crystals of introducing extra electronic levels in the band gap. In the case of
diamond, it is a subject of speculation how complicated and nontypical luminescence spectra
can be explained on the basis of new electronic states in the band gap and how new vibrational
states result from breaking of the symmetry.
Neutral vacancies formed during the growth are rarely observed in CVD crystals. Instead,
vacancies appear as silicon (or silicon pair)–vacancy complexes. This defect is frequently ob-
served in diamond crystals grown on Si. Growth sector 〈111〉 can be doped with Si to levels
above 1 at%. This doping level introduces displacement disorder of atoms in the diamond lattice
to such an extent that the 1332 cm⫺1 Raman peak almost disappears. This means that the vibra-
tion mode related to the optical phonon becomes weak in such a distorted lattice.
VI. DOPING
Doping of diamond is approached in several ways: doping during the growth, implantation,
forced diffusion, and neutron transmutation. Doping during the growth was successful with
boron, as it is in nature. High-temperature Schottky diodes and transistors were fabricated on
boron-doped films. Doping with N and P has not been fully evaluated. Experiments with Li
and Na doping during the growth were not successful. The electrical behavior of diamond with
Si and other metal dopants is not known. Inconvenient complications connected with doping
during the growth are related to the creation of defects in doped diamond. Experimenting with
P doping showed that when high concentrations of PH 3 were introduced in the CH 4 /H 2 plasma
the diamond structure was distorted. The X-ray diffraction pattern of this material is composed
of broad lines and is interpreted as disordered tetrahedral carbon. Raman peaks disappeared, as
in the case of doping with P. When doping levels are as low as 1017 cm⫺3, the resistivity of
diamond is too high for device fabrication. This can be caused by lattice defects. Are these
defects electrically active? The answer is not yet known. Nevertheless, n-type doping by P was
confirmed by Hall measurement (44).
VII. POLYCRYSTALLINE PLATES
When the first diamond polycrystalline films, a few µm thick, were grown on silicon wafers,
it was easy to etch off the Si from the back side and obtain translucent freestanding diamond
windows. Large windows fabricated in this way were considered for high-resolution X-ray li-
thography. Enormous progress has been made in several companies since this time. Now large,
water-clear windows are available. Transparencies vary, but plates as thick as 2 mm and linear
sizes of 10 cm and larger are being fabricated.
Scaling up the growth process required, at first, increasing the growth rate above 10 µm/
h. This was achieved by careful parametric studies and by creating high-temperature plasmas.
Record power for a microwave system is 75 kW and for a DC plasma torch is 100 kW.
Large area depositions are relatively easy to achieve with tungsten filament systems; how-
ever, it was difficult to reach growth rates higher than 4 µm/h even with biasing. Other tech-
360 Badzian
Figure 11 Photograph of multichip module substrates (MCMs) 7.5 ⫻ 7.5 cm cut from 15-cm plates
grown in a 915-MHz, 50-kW reactor. Plates 2 mm thick were grown. (Courtesy of Thomas Hartnett,
Raytheon Co.)
niques have problems with uniformity of plate thickness. In the case of microwave, the process
depends on the size of plasma ball suspended over the substrate. The size can be increased by
increasing the power or by decreasing the microwave frequency. Large plates are manufactured
by DC jets. The uniformity in thickness reduces the cost of polishing. New inventions in diamond
polishing are necessary to bring the cost of diamond plates down. Ideally, $1 per carat would
contribute to CVD diamond commercialization, and even $5 per carat is acceptable. Currently,
a 1-carat CVD diamond with a 1-mm-thick plate can cost hundreds of dollars.
Despite cost problems, characteristics of diamond substrates are impressive. Figure 11
shows substrates for electronic packaging. Transmission in the visible and IR spectrum is almost
identical to that of type IIa natural diamond; the only problem is light scattering at grain bound-
aries. Microstucture improvement is essential to reduce internal stresses and produce atomic
bonding between grains.
VIII. HETEROEPITAXY
A common opinion is that diamond heteroepitaxy is a necessary step in developing active dia-
mond electronics. This has not materialized yet, and we are waiting for innovative ideas to
revolutionize the agenda.
The definition of heteroepitaxy is based on the practice of semiconductor technology.
Heteroepitaxial growth means that on the surface of a single crystal A (over a macroscopic
area) another crystal B starts to nucleate and grows with a specific crystallographic orientation
relationship between A and B, which corresponds to some kind of lattice matching. Lack of
perfect matching at the interface introduces strain between these semicrystals. The strain is
released in specific ways, for example, by misfit dislocations. This formulation of heteroepitaxy
does not consider any transition interlayer between A and B; instead, direct chemical bonds are
formed between atoms of crystals A and B (45).
This definition can be applied to heteroepitaxy of diamond on cubic BN. A sharp interface
was found by cross-sectional TEM (46). Diamond crystals stick to cubic BN with no interlayer.
The two lattices fit together almost perfectly with the exception of misfit dislocations. The
growth on the (111) boron-terminated face of a single crystal of cBN (250 µm linear dimension)
provided the most perfect heteroepitaxy. Macrosteps on the surface of cBN were replicated
during diamond growth when B 2 H 6 was added for doping. Addition of B 2 H 6 seems to be benefi-
cial for the two-dimensional nucleation of diamond. Usually, diamond nucleation has a three-
dimensional character and separate microcrystals coalesce during the growth. This is an example
of perfectly oriented growth (47).
A very interesting phenomenon takes place on the nitrogen-terminated (111) face. The
nucleation density is very low, a few orders of magnitude lower than on the boron-terminated
(111) face. Oriented diamond crystals nucleate along ledges on the surface. The difficulty in
nucleation has a connection with the formation of CN bonds. The CN bonds are formed
with great difficulty on the diamond surface. Probably for this reason the sp 3 analog of a CN
compound was not synthesized. Both CN and BN bonds should be formed simultaneously
at the cBN-diamond interface to ensure charge neutrality. Such neutrality exists in the lattice
of cBN-diamond solid solutions where CC atom pairs are substituted by BN pairs.
The BP a AIIIBV compound shows a 〈111〉 polar axis just as cBN does. One would expect
epitaxy to appear on the B-terminated surface and low nucleation density to be observed on the
P-terminated (111) surface. Heteroepitaxy on cBN had a limited impact because substrate crys-
tals are not easily available. The cBN and BP single crystals were synthesized by HP/HT pro-
cesses. The largest cBN crystal has a linear dimension of 3 mm. The BP crystals grown from
B solution in liquid P at 1.5 GPa have a dimension of about 1 mm.
Ni and Cu single crystals were considered as substrates because of their fcc structure and
good lattice matching to diamond. However, heteroepitaxy was not achieved on these substrates;
only isolated oriented diamond particles were grown on Ni (48). Some improvement was re-
ported for Ni (49) and Pt (50) oriented growth. Similar efforts were undertaken on the Si (001)
surface. The distance between Si atoms along the 〈110〉 direction is 3.6 Å, which fits well the
〈001〉 direction in diamond structure with a distance of 3.56 Å. Diamond growth on Si did not
follow this matching.
These examples indicate a limitation of the geometrical aspect of heteroepitaxy definition.
The chemical interaction between two different crystal phases and the surface energy at the
interface should be taken into account. Diamond has an interface energy higher than other mate-
rials. Diamond nucleates on small spots on the foreign substrate’s surface. Figure 12 illustrates
nucleation on a scratched Si surface and shows 0.2-µm spots. More precise insight into such
spots by TEM gives a spot size of about 200 Å (51). It is unknown why diamond nucleates on
such a small area.
During initiation of diamond nucleation, the substrate surface interacts chemically with
the hydrocarbon-hydrogen plasma. Both carbon and hydrogen atoms penetrate the substrate.
Metals form carbohydrides before diamond nucleation starts. Nucleation is initiated on such
chemically modified surfaces.
Heteroepitaxy can be disturbed by the formation of disordered carbon on the surface,
creating nucleation sites for diamond. Diamond grains nucleated on carbon have a random orien-
tation.
In summary, similarity to semiconductor heteroepitaxy has a limited application to dia-
362 Badzian
Figure 12 Secondary electron image of the back side of a diamond film nucleated on a scratched Si
wafer. Bar corresponds to 5 µm.
mond because of its high interface energy. The solution to a task as challenging as making
diamond heteroepitaxy a practical process requires a nontraditional approach. Such innovative
thinking was involved in oriented growth on Si. However the films grown in this manner are
not heteroepitaxial in on the macroscale; nevertheless, their characteristics are in between those
of polycrystalline films and homoepitaxial ones.
IX. ORIENTED GROWTH
The most popular procedure enhancing nucleation on Si is scratching the wafer surface, prefera-
bly with diamond powder. From a practical point of view, let us distinguish between nucleation
and growth. Nucleation requires different process parameters than growth. For example, nucle-
ation requires a higher CH 4 concentration and lower temperature than growth. Systematic para-
metric studies showed how much morphology depends on process conditions. Figure 13 is an
illustration of columnar growth. The columns are perpendicular (with some axial tilt distribution)
to the wafer surface, but they have a random azimuthal orientation as shown in Fig. 14.
Columnar texture is a general rule for film growth. Films develop this microstructure
Figure 13 Columnar growth of diamond at 4% CH 4 in H 2, 850°C and 40 torr (5.2 kPa). Bar corresponds
to 3.27 µm. (Courtesy of Yoichiro Sato, NIRIM.)
Figure 14 Top view of film shown in Fig. 13.
because of growth competition between grains (52). Textured diamond films with 〈001〉, 〈110〉,
and 〈111〉 have been grown with specific growth conditions. The next step in controlling nucle-
ation on the surface was to find means that allow all nuclei to have the same crystallographic
orientation. According to one trial, nucleation was organized with the help of lithography to
get a patterning of the substrate and passivate some areas with Ar ion bombardment. Diamond
crystals formed a square network but they had a random orientation (53).
The second trial was based on crystallographically selective etching of a (001) Si wafer.
Diamond-type structure materials behave anisotropically when they are processed by etching;
for example, (001) faces disappear but (111) faces stay, resulting in the formation of specially
shaped holes. In this case the holes have a half octahedron, pyramid shape. Whole surfaces of
Si wafers can be covered by a regular square array of holes when a lithographic technique is
used.
In the next step, synthetic diamond octahedral crystals, 100 µm in size, are placed in these
holes. Diamond growth was conducted on these arrays of seeds. Continuous films were obtained
in this way. They have a mosaic structure, but secondary nucleation disturbs the local orientation
of the film. The difficulty with this approach is related to growth sectors. The growth starts on
mostly octahedral crystals with cubic face truncation. With this type of seed the process parame-
ters should be changed during the growth to enhance growth in the 〈111〉 directions in such a
way that only 〈001〉 growth sectors survive (54).
A new era started with the concept of biasing the substrate during the nucleation procedure
(55). This procedure revolutionized the nucleation of diamond, giving more control over the
process. Negative biasing has been applied to mirror-polished Si substrates and the concentration
of CH 4 in the plasma was substantially increased. Nucleation densities reached ⬎10 10cm⫺2. This
process leaves flexibility in the choice of energy of bombarding ions, time, CH 4 concentration,
and substrate temperature. Careful parametric studies were very successful in finding the right
conditions for azimuthal orientation of diamond grains on the (001) nontreated surface of Si
(Fig. 15). Such organized nucleation was achieved first on epitaxial β-SiC films grown on Si.
Let us compare the morphology of a random azimutal orientation shown in Fig. 14 with the
image shown in Fig. 15.
The last figure shows impressive improvement in the azimuthal orientation, but we still
have some small-angle boundaries in this material. This process was reproduced in many labora-
tories around the world. We will call these films highly oriented films.
Highly oriented films presumably have a columnar structure as shown in Fig. 13; however,
such cross-sectional etching images were not published for the bias nucleated films. The 〈001〉
364 Badzian
Figure 15 Top view of highly oriented diamond film grown on (001) Si. This photograph was presented
in 1992 by X. Jiang and C.P. Klages, Fraunhofer Institut, Hamburg, Germany. Bar corresponds to 1 µm.
columns are randomly tilted with respect to the (001) Si substrate. The angular distribution of
tilts has been measured by X-ray diffraction pole figures, giving a Gaussian function with an
FWHM around 10°. This is a substantial disturbance of the columns’ orientation. The angular
distributions of tilts are also anisotropic. Usually 80–90% of grains have the 〈001〉 orientation
and the rest have a random orientation. Bias-enhanced nucleation has been studied from different
points of view, but research has not reached a stage of comprehension. Possible explanations
are subplantation of ions, chemical reactions at the surface with impinging ions, and surface
diffusion.
When nucleation is complete (for example, after 20 min), the bias of the substrate is turned
off and process parameters are adjusted to the growth. The choice of new conditions is very
important; they should increase the growth of the 〈001〉 columns. For this purpose, temperature–
CH 4 concentration diagrams were established to identify conditions for the 〈001〉 and 〈110〉
textures. A series of experiments with continuously changing parameters imposed changes in
the ratio of growth rates in the 〈111〉 and 〈001〉 directions. Modeling of columnar morphology
was conducted, including (111) twin formation. This simulation allowed the prediction of when
(111) twins would disappear (56).
Following the proper choice of process parameters, films were grown with column tilts
having an FWHM of ⬃10° and a few degree azimuthal grain boundaries. The films contain
misoriented crystal grains. The top surface is rough and grooves appear at the grain boundaries.
The next stage of oriented film development will consider growth of a smooth top surface.
Smooth films over an area of 3 ⫻ 2 mm have already been grown on (001) β-SiC substrates
(57). Enhancement of the 〈001〉 and 〈111〉 growth rates was controlled by the gas-phase composi-
tion. Three gases were mixed: CH 4, CO, and H 2. The surfaces of these films were studied by
RHEED. A single-crystal type of pattern was obtained from a selected crystal grain on the
oriented film before the smoothing procedure. After the smooth growth is complete, the surface
is no longer crystallographically perfect. The Bragg reflections are very broad.
A similar approach to controlling growth rates in the 〈001〉 and 〈111〉 directions and intro-
ducing etching in the 〈110〉 steps was also successful in smoothing the surface (57).
The oriented diamond films achieved spectacular progress. Boron-doped oriented films
demonstrated much higher mobility with a record 280 cm2 /V⋅s and good transistor perfor-
mance (25).
During the study of oriented growth, several problems have been addressed:
Nonuniformity of the interface. There is structural and compositional nonuniformity at the
interface. X-ray photoelectron spectroscopy (XPS) indicated the formation of β-SiC,

HRTEM demonstrated direct contact between Si and diamond lattices as well as
formation of an amorphous layer. Ellipsometry and Raman spectroscopy found the
formation of sp2-type carbon. Direct contact between diamond and Si lattices appears
only in a limited area. The ratio of lattice parameters for Si and diamond approaches
3:2. The 3:2 registry has been observed with HRTEM images showing rows corre-
sponding to the (111) Si and diamond planes almost parallel in one case and with
a tilt in others. Does this mean that diamond nucleates by different means? All of
these data should be analyzed together, seeking a comprehensive picture of the inter-
face and nucleation. It seems that nucleation on scratched surfaces takes place on
an area of about 200 Å2, whereas bias-enhanced nucleation expands over 1000 Å.
How much of this microheteroepitaxy can be extended?
Orientation of columns. Strain energy of the interface is relaxed by the formation of dislo-
cations and the tilt of lattice planes of diamond grains at the contact with the Si
lattice. As a result, the columns are randomly tilted. Does any remedy exist to im-
prove the situation?
Misoriented grains. Misoriented grains usually disappear during the growth of thicker
films, but twinning can still disturb oriented films.
Structure of the top surface. The top surface of the oriented films, as in Fig. 15, is rough
due to the misorientation of columns. The (001) top facets follow this misorientation.
When the smoothing procedure is applied to such a rough surface, a question arises
about how to describe the surface crystallographically. Is the surface composed of
microvicinal planes? Vicinal planes in this case can have Miller indices of (11ᏸ),
where ᏸ is a number larger than 10. Smooth surface films are not necessarily crystal-
lographically perfect films.
X. CONCLUSIONS
If one calls how much disbelief and discouragement was associated with the CVD process at
the beginning of its development, because of a common opinion that diamond cannot grow
under the condition of its ‘‘metastability,’’ we can now say that enormous progress has been
made in the confirmation of CVD diamond as an electronic material. When CVD diamond was
accepted, feelings of euphoria were followed by exorbitant promises that soon a new technology
would be created having an impact on everyday life. The dreams and promises have not material-
ized and have turned into disappointment.
The current high cost per carat has prevented diamond from being chosen over inexpensive
materials. Diamond possesses the strongest covalent bonding, in some sense this seems to be
a luxury property, which implies there is a high cost of bringing carbon atoms together. Someone
needs to pay the price for the consumption of energy during diamond synthesis and for control
over crystallization.
Nevertheless, scaling up of CVD plasma processes has been successful with the fabrication
of 27 cm diameter plates and almost water–clear diamond windows of 10 cm in diameter.
Passive electronic applications in packaging are now in the marketplace.
Active diamond electronics has not successfully developed. After the demonstration of
rudimentary high temperature Schottky diodes and transistors, problems with the deposition of
semiconductor quality thin diamond films has limited further development. Imposing step flow
growth on homoepitaxial growth requires very expensive synthetic HP/HT diamond crystals
cut under a specific angle.
366 Badzian
Very limited success with oriented growth on Si can be attributed to a combination of

nucleation and growth difficulties. Nucleation leads to a Gaussian distribution of crystal columns
orientation. Growth on the top surface, which is the crystallographic plane (001), reveals unex-
pected defects and undesirable doping with Si.
It took 10 years to develop high frequency surface acoustic filters on polycrystalline dia-
mond bases at Sumitomo Electric in Japan. It is an exeptional achievement for CVD diamonds.
Diamond possesses such exceptional physical properties that it deserves support for re-
search on its synthesis to allow diamond growth development to reach its maturity. Hydrogen-
driven CVD processes are at an advanced stage of development; however, novel processes are
at an incubation phase, opening new expectations for the future.
ACKNOWLEDGMENTS
This work was supported by the National Science Foundation under grant DMR9522566 and
by the Office of Naval Research under grant N00014-91-J-4023. The author extends thanks to
T Badzian, B Weiss, and N Lee for their help in preparation of the manuscript.
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16
The Electrical and Optical Properties of
Diamond
Alan T. Collins
King’s College London, London, England
I. INTRODUCTION
Diamond is a wide-band gap semiconductor. At room temperature the electron and hole mobili-
ties can both be as high as 1800 cm 2 V⫺1 s⫺1 in high-quality specimens, and the thermal conduc-
tivity is about five times higher than that of copper. The breakdown field and the saturated
electron velocity are higher than for any other semiconductor. The material is very hard and
abrasion resistant, is relatively inert in a range of corrosive atmospheres, and will withstand
temperatures up to 500°C. When excited with a beam of electrons, many diamonds can exhibit
blue, green, or red cathodoluminescence, depending on the optical centers that are present. In
the late 1980s there was therefore considerable speculation (1–5) that diamond produced by
chemical vapor deposition (CVD) exhibits considerable potential for high-power, high-tempera-
ture active electronic devices and for optoelectronic applications.
Natural semiconducting diamond (type IIb diamond) was discovered in 1952 (6), and the
first diamond electronic device was a point contact diode made a few years later by Dyer and
Wedepohl (7). This worked not only at room temperature but also at 300°C. Natural type IIb
diamond was subsequently used to make a number of prototype devices. Rodgers and Raal (8)
made a sensitive high-temperature thermistor. Vermeulen and Harris (9) developed a light-sensi-
tive switch and an optical radiation detector (10). Young et al. (11) used type IIb diamond to
produce an ultrafast infrared detector, and Ho and Lee (12) also demonstrated the capability of
using semiconducting diamond as an optoelectronic switch. Prins (13) first demonstrated transis-
tor action in diamond using natural crystals, and Tzeng et al. (14) have reported using this
material to produce diodes and transistors.
General Electric (GE) announced the first manufacture of semiconducting diamond abra-
sive grit in 1962 (15), and later they demonstrated the ability to make large semiconducting
diamonds by the temperature-gradient method (16). Using GE diamonds of this type, Glover
(17) fabricated Schottky diodes and Geis et al. (18) constructed a Schottky diode rectifier that
operated at 700°C and a point-contact transistor that exhibited power gain at 510°C.
Encouraged by the results on prototype devices summarized in the previous paragraphs,
research groups around the world have been attempting, during the past 8 years or so, to exploit
the apparent potential that diamond possesses for these applications. However, the present author
has maintained on a number of occasions (19–22) that the predictions of what may be achieved
with diamond are overoptimistic and are based on an incomplete understanding of the electrical
369
370 Collins
and optical properties of this unique material. In this chapter we will review the electronic
properties of diamond that have been established experimentally for natural, high-pressure syn-
thetic, and CVD semiconducting diamond. A full treatment of the optical properties of diamond
would require a complete book, and here we will concentrate on some of the optical properties
of semiconducting diamond. Having reviewed these electronic and optical properties, the impli-
cations for diamond-based semiconducting devices will be briefly reiterated.
II. ELECTRICAL PROPERTIES
Electrical transport measurements have established that semiconducting diamond, whether of

natural origin or made by high-pressure synthesis, is a partially compensated p-type semiconduc-
tor (for a review see Ref. 23). With certain exceptions, the electronic properties of CVD diamond
can be understood using data established for bulk diamond. The major differences occur with
polycrystalline CVD diamond, in which scattering at the grain boundaries drastically reduces
the carrier mobilities and, at low doping levels, electronic surface states at the grain boundaries
act as donors that compensate p-type acceptors. We will begin by reviewing work carried out
on bulk diamond to see how this relates to CVD diamond.
A. Acceptors and Donors in Diamond

Nitrogen and boron are the only elements that significantly affect the bulk electrical conductivity
of diamond; in addition, a hydrogen-terminated surface gives rise to p-type conduction (24,25).
Nitrogen is the dominant impurity in the majority of diamonds. Most diamonds produced
commercially by high-pressure synthesis (referred to hereafter as ‘‘synthetic diamond’’) and a
small fraction (about 0.1%) of natural diamonds are type Ib, meaning that the nitrogen is present
in isolated substitutional form; typical concentrations are 40 ppm for natural type Ib diamonds
and a few hundred ppm for standard synthetic diamonds. Almost all natural diamonds are pre-
dominantly type IaA, meaning that the nitrogen is present as nearest neighbor pairs; here the
nitrogen concentration can be as high as 3000 ppm. For the rare type IIa natural diamonds the
nitrogen concentration is less than about 10 ppm. Isolated substitutional nitrogen is generally
present as a trace impurity in CVD diamond, although in the highest quality undoped material
the concentration may be no more than 0.01 ppm.
The isolated nitrogen and the A form of nitrogen both behave as donors; however, the
ionization energies are high—around 1.7 eV and 4.0 eV, respectively. Nitrogen-containing dia-
monds are therefore good electrical insulators at room temperature. At higher temperatures
(⬎ 200°C) conductivity associated with the 1.7-eV donor leads to a deterioration of the insulat-
ing properties of diamond compared, for example, with sapphire (26).
Among natural diamonds significant electrical conductivity at room temperature occurs
only for the very rare type IIb diamonds, in which boron is the major impurity. These diamonds
are p-type semiconductors with typical boron concentrations rather less than 1 ppm and an
acceptor ionization energy of 0.37 eV. Synthetic diamond containing up to 1000 ppm of uncom-
pensated boron can be produced by removing nitrogen from the growth capsule and adding
boron. Boron-doped CVD diamond, again with boron concentrations much higher than those
found in natural type IIb diamonds, is readily grown by adding a gaseous compound of boron
to the plasma.
B. p-Type Conductivity
For a partially compensated p-type semiconductor, with an acceptor concentration sufficiently
small that there is no degeneracy, the hole concentration at temperature T may be written as (27)
Electrical and Optical Properties of Diamond 371
p(p ⫹ N D)/(N A ⫺ N D ⫺ p) ⫽ (2/g a )(2πm*kT/h 2 )3/2 exp(⫺E A /kT ) (1)
where N A and N D are the acceptor and donor concentrations, g a is the ground state degeneracy
factor for the acceptor, m* is the density of states effective mass for the holes, and E A is the
acceptor ionization energy.
At high temperatures p approaches the saturation value N A ⫺ N D; at low temperatures
p ⬍⬍ N A or N D and, provided the acceptor concentration is sufficiently low to avoid impurity
band conduction, Eq. (1) approximates to
p ⬀ (N A /N D ⫺ 1)T 3/2 exp (⫺E A /kT ) (2)
The concentration of free holes can be determined from the Hall coefficient R using
p ⫽ r/Re (3)
where r is the ratio of the Hall mobility µ H to the conductivity mobility µ c and e is the electronic
charge. The value of r depends on the scattering processes; in the case of a nondegenerate
semiconductor a number of simplifying assumptions lead to r ⫽ 3π/8 for acoustic phonon
scattering and r ⫽ 315π/512 for ionized impurity scattering (28). Phonon scattering is the domi-
nant mechanism at high temperatures, and standard analysis (28) suggests the mobility will
vary as T 3/2. In practice, the high-temperature mobility µ(T ) of natural type IIb diamond varies
approximately as (22)
µ(T) ⫽ µ(290) ⫻ (T/290)⫺S (4)
with S around 2.8.

Most workers have analyzed their Hall effect data using Eq. (1) with g a ⫽ 2 and Eq. (3)
with r ⫽ 3π/8. Elsewhere (29) I have argued that g a ⫽ 4 may be more appropriate, and perhaps
even g a ⫽ 6 at high temperatures. This makes relatively little difference to the analysis, since
effectively (m*) 3/2 /g a in Eq. (1) is an adjustable parameter used to obtain the best fit to the
experimental data.
Figure 1 shows a plot of hole concentration versus reciprocal temperature obtained by
Williams (30) for a natural type IIb diamond. We note that this approaches saturation at high
temperatures, as expected from Eq. (1), and varies almost linearly at lower temperatures as
expected from Eq. (2). Williams found that when the values for N A, N D, and E A that gave the
best fits were substituted into Eq. (1), m* was approximately constant at around 0.75m e below
room temperature and decreased in a nonmonotonic way at higher temperatures. (m e is the rest
mass of the electron.)
From measurements on five diamonds Collins and Williams (31) cite an average value
of E A ⫽ 368.5 ⫾ 1.5 meV, determined using Eq. (2) in the temperature interval 160 to 330 K.
Impurity concentrations for these diamonds were determined (23) as N A between 48 and 83 ⫻
1015 cm⫺3 and N D between 0.9 and 15 ⫻ 10 15 cm⫺3. The highest value of N A /N D was 56. Substitu-
tion of these data in Eq. (2) shows that this approximation becomes inaccurate at temperatures
above 330 K. At and below this temperature the approximation also requires N D ⬎⬎ 4 ⫻ 10 13
cm⫺3, and this condition is well satisfied.
The hole mobilities at 290 K for the diamonds used by Collins and Williams (31) lay in
the range 700 to 2010 cm 2 V⫺1 s⫺1, and similar data had been obtained by many previous workers.
More recently, measurements on natural type IIb diamonds have yielded (32,33) rather lower
values between 130 and 518 cm 2 V⫺1 s⫺1. At temperatures above room temperature the mobilities
of all specimens decrease rapidly, in accordance with Eq. (4).
372 Collins
Figure 1 Hole concentration as a function of reciprocal temperature for a natural semiconducting dia-
mond containing 8.3 ⫻ 10 16 cm⫺3 acceptors and 4.2 ⫻ 10 15 cm⫺3 donors. (From Ref. 29.)
C. Impurity Conduction and Hopping Conduction

Figure 2 shows the resistivity as a function of reciprocal temperature for a natural semiconduct-
ing diamond and two boron-doped synthetic diamonds. For the natural diamond we see that
there is a shallow minimum in the resistivity curve; this is because the carrier concentration
has almost reached saturation, Eq. (1), but the mobility is still decreasing at higher temperature,
Eq. (4). Between about 400 and 120 K the log(resistivity) increases linearly with an activation
energy of 0.37 eV, and at 120 K there is a sharp knee beyond which the resistivity increases
very gradually at lower temperature. Curve (b) for the first synthetic diamond has a substantial
linear section with a change of slope to a lower value at about 160 K, and curve (c) for the
second synthetic diamond has a short section, parallel to that for the other two diamonds, and
a change of slope to a lower value at about 280 K. The neutral acceptor concentrations for (b)
and (c) were estimated optically to be 3 ⫻ 10 17 and 1 ⫻ 10 18 cm⫺3, respectively (34).
The behavior shown in Fig. 2 can be understood if the conductivity σ is expressed as a
sum of three terms (35):
σ ⫽ σ 1 exp(⫺E 1 /kT ) ⫹ σ 2 exp(⫺E 2 /kT) ⫹ σ 3 exp(⫺E 3 /kT ) (5)
The activation energy E 1 is the normal acceptor ionization energy, associated with transitions
from the acceptor ground state to the valence band, and is observed in all samples provided the
acceptor concentration is not too high. The activation energy E 2 can be observed only in the
intermediate concentration range and is associated with conduction in an impurity band. When
the acceptor concentration is small E 2 is close to E 1, but when the acceptor concentration is
increased, so that there is an appreciable overlap between the wave functions of neighboring
Figure 2 Resistivity as a function of reciprocal temperature for (a) a natural semiconducting diamond
containing ⬃8 ⫻ 10 16 cm⫺3 neutral acceptors, (b) a synthetic diamond containing ⬃3 ⫻ 10 17 cm⫺3 neutral
acceptors, and (c) a synthetic diamond containing ⬃1 ⫻ 10 18 cm⫺3 neutral acceptors. (From Ref. 29.)
centers, E 2 is reduced. Finally, at the acceptor concentration for which the metal-insulator transi-
tion occurs, E 2 → 0. For boron in diamond this transition occurs (34) at a concentration around
2 ⫻ 10 20 cm⫺3. The activation energy E 3 is most prominent for specimens with a relatively low
impurity concentration and is interpreted in terms of the energy associated with the tunneling
transition (‘‘hopping’’) of a hole from an unoccupied to an occupied acceptor site.
In Fig. 2a the change of slope in the resistivity curve for the natural diamond is interpreted
(31) as hopping conductivity associated with activation energy E 3, whereas all three conductivity
mechanisms are believed (34) to be operative for the synthetic diamonds in Fig. 2b and c. For
the diamond used to obtain Fig. 2c the data may also be fitted, in the temperature range 80 to
250 K, to Mott’s formula (36) for variable range hopping. In this case
log σ ⫽ A ⫺ BT ⫺1/4 (6)
where A and B are constants. In this process carriers prefer to hop to a distant site that has similar
energy, rather than to nearest neighbors that have significantly different energy. Massarani et
al. (37) have also extensively investigated conductivity mechanisms in boron-doped synthetic
diamond and found that for heavily doped samples the behavior at low temperatures is dominated
by variable range hopping. They confirmed that the activation energy exhibited a T 3/4 depen-
dence, as expected for variable range hopping.
374 Collins
D. Polycrystalline CVD Films

Diamond films grown on nondiamond substrates are invariably polycrystalline, and doping with
boron produces semiconducting material. Von Windheim et al. (33) report that the carrier con-
centration shows a very sharp drop with decreasing dopant density. They note that similar data
are observed in B-doped polycrystalline silicon and attributed to surface states at grain bound-
aries acting as trapping centers. The grain boundaries also cause severe scattering of the carriers,
so that mobilities in polycrystalline CVD diamond are typically (38) in the range 1 to 30 cm 2
V⫺1 s⫺1.
At high doping levels impurity conduction is observed, as in synthetic type IIb specimens,
and for doping levels around 10 21 cm⫺3 metallic conduction is obtained. In that case the conduc-
tivity of the material decreases as the temperature is increased (39).
When a lightly boron-doped layer is grown on top of an oriented textured film with {100}
faces, mobility values up to 165 cm 2 V⫺1 s⫺1 may be obtained (38) and the acceptor ionization
energies for such films are around 0.35 eV, close to the value for natural type IIb diamond.
E. Homoepitaxial CVD Diamond Layers

In this section we will consider two representative studies—that by Fujimori et al. (40) using
a microwave plasma with doping by B 2H 6 and that by Visser et al. (41) using the hot filament
technique and boron doping by out-diffusion of the BN substrate holder. Both groups find that
growth onto a {100}-oriented diamond substrate produces a higher quality layer than on a {110}-
oriented substrate, that boron incorporation is lower in the {100} layer, and that the hole mobility
is very much lower in the {110} layers. The quality of homoepitaxial layers on {111} substrates
is also poor. It is found that {110} and {111} layers contain a high density of stacking faults
where the tetrahedral diamond packing sequence is disrupted by the hexagonal (Lonsdalite)
sequence (42).
Figure 3 shows the mobilities of the CVD layers grown by Fujimori et al. plotted as a
function of the carrier concentration measured at room temperature. We see that as the carrier
concentration increases from 7 ⫻ 10 13 to 7 ⫻ 10 16 cm⫺3 the mobility of the {100} layers falls
from 600 to less than 8 cm 2 V⫺1 s⫺1. The mobilities of all the {110} layers are less than 6 cm 2
V⫺1 s⫺1. Gildenblat et al. (42) have gathered together the {100} data in Fig. 3 with data inferred
from measurements on natural and synthetic type IIb diamonds and shown that there is a general
Figure 3 Mobility as a function of the carrier concentration at room temperature for boron-doped homo-
epitaxial films grown on substrates with {100} and {110} orientations. (From Ref. 68.)
decreasing downward trend in mobility values with increasing carrier concentration. Fujimori
et al. have also shown that the temperature dependence of the mobility for boron-doped CVD
diamond is similar to that observed for natural type IIb diamond [Eq. (4)] with S around 3.0
for the lightly doped material, decreasing to 2.2 for more heavily doped layers.
Visser et al. (41) show conductivity data from 110 to 500 K for four pairs of diamonds
with different impurity concentrations. Each pair had a {100} and a {110} layer produced in
the same growth run. The conductivity curves are very similar to those obtained for boron-
doped synthetic diamonds (Sec. II.C), showing a change in activation energy at 225 K for the
lowest doping and around 310 K for the highest doping. They show that their data can be fitted
using just two activation energies—E 1 and E 3 of Eq. (5). Their low-temperature data also fitted
the Mott T 1 /4 law [Eq. (6)] very closely, and they conclude that the dominant process at low
temperatures may be variable range hopping.
Visser et al. (41) also carried out Hall effect measurements as a function of temperature.
They found that they could not fit the data using Eq. (1) with the effective mass value m* ⫽
0.75m e used for natural type IIb diamond (Sec. II.B). For their most lightly doped {100} sample
they found m* ⫽ 0.35m e and N D /N A ⫽ 0.008. The room-temperature carrier concentration and
Hall mobility for this specimen were 1.3 ⫻ 10 14 cm⫺3 and 590 cm 2 V⫺1 s⫺1, respectively. These
values are similar to those for the most lightly doped sample studied by Fujimori et al. (40).
F. Hydrogen in CVD Diamond

Virtually all CVD diamond is grown in the presence of large quantities of hydrogen; if the
shutdown sequence of the growth system leaves the CVD film exposed to a hydrogen plasma,
then undoped films have a conductivity similar to that of doped films (42). Gildenblat et al.
(42) showed that the conductivity of the undoped films can be removed by chemical cleaning
and is due simply to a surface conducting layer. They showed that such a conducting layer
could also be produced on a natural type IIa diamond exposed to the hydrogen plasma. More
recently, it has been shown that hydrogenation of the surface leads to a p-type conducting layer
and that it is possible to fabricate a field effect transistor using this layer (25).
G. n-Type Conductivity
No technique has been found to produce a useful level of n-type conductivity in either synthetic
or CVD diamond. At high temperatures natural type IIa diamond and many samples of CVD
diamond exhibit a small amount of n-type conduction with an activation energy of about 1.6
to 2.0 eV (26). This is probably associated with the small concentrations of isolated substitutional
nitrogen (43).
III. OPTICAL PROPERTIES OF SEMICONDUCTING DIAMOND
In this section we will consider the absorption and luminescence transitions that occur at the
band gap of diamond and also the absorption associated with the boron acceptor.
A. Edge Absorption and Edge Emission

Diamond is an indirect-gap semiconductor with an energy gap of 5.49 eV at 77 K (44). Excitation
from the valence band to the lowest conduction band can therefore occur only with the participa-
376 Collins
Figure 4 Absorption edge of a high-purity synthetic diamond at room temperature and at 77 K. (From
Ref. 61.)
tion of phonons (45). Figure 4 illustrates the edge absorption of diamond in detail at room
temperature and at 77 K. In the room-temperature absorption three thresholds are visible. Thresh-
olds (i) and (ii) correspond to the creation of an exciton with the absorption of a transverse optic
(TO) or a transverse acoustic (TA) phonon, respectively, and (iii) corresponds to the creation of
an exciton with the emission of a TA phonon (44). At the lower temperature the phonon absorp-
tion component is ‘‘frozen out’’ and only threshold (iii) is visible. The figure also shows that
the energy gap is about 10 meV higher at 77 K than at room temperature. Although the edge
absorption is an intrinsic property of diamond, it is most easily studied in type IIa or type IIb
specimens in which there is no nitrogen-related absorption in this ultraviolet spectral region.
B. Free- and Bound-Exciton Luminescence

The only intrinsic luminescence observed in diamond is that associated with the recombination
of free excitons, following the generation of electron-hole pairs by, for example, the absorption
of ultraviolet radiation at wavelengths less than 225 nm or by using energetic electrons (of
typical energy 10 to 50 keV) to produce cathodoluminescence. Typical edge emission spectra
obtained from a high-purity synthetic diamond at 77 K and at ⬃4.2 K are shown in Fig. 5a and
b, respectively. The interpretation of the features in these spectra was first discussed by Dean
et al. (46). The valence band maxima in diamond are at k ⫽ 0 and the conduction band minima
are at k ⫽ k min ⫽ 0.76 of the 〈001〉 zone boundary (44,47). The peaks labeled A, B, and C are
due to the recombination of a free exciton with the emission of momentum-conserving phonons
of wave vector ⫾ k min, having energies of 87 ⫾ 2 meV (transverse acoustic), 141 ⫾ 1 meV
(transverse optic), and 163 ⫾ 1 meV (longitudinal optic), respectively. The low-energy threshold
of each peak occurs at an energy given by
hν ⫽ E g ⫺ E x ⫺ –hω (7)
Figure 5 Edge emission spectra from high-purity synthetic diamond at (a) 77 K and (b) 4.2 K. (From Ref. 61.)
where E g is the energy gap, E x is the exciton binding energy, and –hω is the energy of the
corresponding phonon. Features B 2 and B 3 are phonon replicas of the major peak B, involving
one or two k ⫽ 0 optic phonons, respectively. The shapes of the free-exciton peaks are accurately
described by a Maxwell-Boltzmann distribution (46,48) and the peaks are therefore very much
sharper at 4.2 K (Fig. 5b) than at 77 K. Measurements at higher resolution (48) have shown
that at 4.2 K there is additional fine structure to the low-energy sides of peaks A and B, the
origin of which is not currently understood.
The spectrum of Fig. 5a is compared in Fig. 6 with the edge emission from a natural type
IIb diamond. Here, in addition to the free exciton peaks, we see features D 1 and D′1, which are
associated with the recombination of excitons bound to the boron acceptor. The very weak zero-
phonon lines D 0 and D′0 (not visible in Fig. 6b) occur at energies E(D 0 ) ⫽ E gx ⫺ E 4x and
E(D′0 ) ⫽ E′gx ⫺ E′4x where E gx and E′gx are the energies of the excitons associated with the upper
and lower valence bands, and E 4x and E′4x are the binding energies of the upper and lower valence
band excitons to the neutral acceptors. The peaks D 1 and D′1 are TO phonon replicas of D 0 and
D′0, and a further replica D 2 is clearly visible.
The intensity of the bound-exciton peaks, relative to that of the free-exciton features, gives
an indication of the uncompensated boron concentration in the region of the diamond examined.
For the diamond shown in Fig. 6b this is about 5 ⫻ 10 16 cm⫺3, as determined from Hall effect
measurements (31). A very weak peak D, due to the accidental presence of a small concentration
of boron (estimated as 3 ⫻ 10 14 cm⫺3 ), is also evident in the low-temperature spectrum in Fig. 5.
Edge emission can be detected only from diamonds that are relatively free from defects.
The first observation of free-exciton luminescence from CVD diamond was made by Collins
et al. (49), who examined individual particles grown by the microwave process. Kawarada et
al. (50,51) subsequently observed intrinsic edge emission from single particles of their CVD
material and also bound-exciton recombination from boron-doped polycrystalline diamond
films. Weak intrinsic free-exciton luminescence has also been observed from polycrystalline
378 Collins
Figure 6 Edge emission spectra at 77 K for (a) a high-purity synthetic diamond and (b) a natural semi-
conducting diamond. (From Ref. 60.)
films by Partlow et al. (52) and from single particles by Robins et al. (53). The emission is
observed only from the {100} growth sectors of the CVD particles (50,51,53), indicating that
these regions have the lowest defect density. The growth sector distribution of impurities is
considered further in the next section.
The free-exciton emission is strongest in diamonds with low concentrations of defects (46),
but even in the best natural diamonds this luminescence is weak compared with the luminescence
observed in the visible spectral region (discussed briefly in Sec. III.D). By contrast, measure-
ments in the author’s laboratory in 1995 have shown that in very high purity synthetic diamonds
the free-exciton emission is strong, compared with the visible luminescence. Some polycrystal-
line CVD specimens examined also exhibit relatively strong edge emission, and in a few homo-
epitaxial layers of CVD diamond the free-exciton luminescence is dominant. This indicates that
diamond can now be manufactured with a considerably lower defect density than that found in
the best natural diamonds.
C. The Absorption Associated with the Boron Acceptor

Transitions from the boron acceptor to the valence band give rise to a series of excited state
transitions that start at 0.304 eV and merge with the photoionization continuum at about
0.37 eV. Figure 7 shows this additional absorption produced in a natural type IIb diamond (54)
superimposed on the two- and three-phonon combination bands that are present in all diamonds.
The photoionization continuum extends into the red part of the visible spectrum and gives type
IIb diamonds their characteristic blue color. Absorption due to the higher energy excited states
is shown in more detail in Fig. 8. Six of the peaks in this spectrum disappear when the sample
is cooled to 4.2 K, and Crowther et al. (55) have associated this effect with a 2.1-meV splitting
of the acceptor ground state. The latter authors carried out uniaxial stress measurements on the
Figure 7 Absorption spectrum at 77 K in the near-infrared spectral region associated with transitions
from the boron acceptor to the valence band (full curve). The dotted curve shows the two- and three-
phonon absorption that is present in all diamonds. (From Ref. 29.)
acceptor absorption spectrum and were able to propose a plausible classification scheme for the
peaks at energies below 0.348 eV, but the full complexity of the spectrum is still not understood.
Absorption spectra of boron-doped synthetic diamond obtained by Collins et al. (56) re-
sembled the spectrum shown in Fig. 7, but even at low neutral acceptor concentrations the peaks
were much broader and the fine structure shown in Fig. 8 could not be detected. As the acceptor
concentration increased (assessed semiquantitatively from the depth of blue coloration associ-
ated with the photoionization continuum), the peaks became progressively smeared out and
Figure 8 Absorption spectrum at 77 K produced by the higher energy excited states of the boron ac-
ceptor. (From Ref. 29.)
380 Collins
merged with the photoionization continuum. Type IIb diamonds with much better quality than
those used by Collins et al. may now be grown by the temperature gradient method (16), but
in most cases the absorption peaks are still very much broader than those observed in natural
type IIb diamond; furthermore, the broadening of the spectrum is far more severe in some growth
sectors than others (57). To understand this latter phenomenon we need to consider the way
different impurities are incorporated into different growth sectors of synthetic diamond. This
can be summarized on a diagram of the type originally proposed by Kanda et al. (58) and
extended by Burns et al. (57), shown in Fig. 9. This diagram also has considerable implications
for the boron doping of CVD diamond and goes some way to explaining the results reported
in Sec. II.E.
The four horizontal lines in Fig. 9 indicate the relative concentrations of isolated substitu-
tional nitrogen in the major growth sectors of a standard nitrogen-containing synthetic diamond.
Figure 9 Behavior of the relative uncompensated boron acceptor concentrations (N A –N D ) in the various
growth sectors on moving from low (B L ) to high (B H ) levels of boron doping. Horizontal lines represent
the relative concentrations of nitrogen donors, N D, and sloping lines the total concentrations of boron atoms,
N A, in the various sectors, as a function of the doping level of boron. Semiconducting behavior begins in
each sector as N A exceeds N D for that sector. (From Ref. 29.)
The {111} sectors contain the most nitrogen and the {011} sectors least. Optical transitions
from the nitrogen donor to the conduction band give the synthetic diamonds a characteristic
yellow color, and in a polished section of diamond the different nitrogen concentrations in the
different growth sectors are evident from the depth of yellow coloration. The gradients of the
diagonal lines in Fig. 9 show the rates at which boron is incorporated in the different growth
sectors. A given growth sector becomes semiconducting when the boron concentration exceeds
the nitrogen concentration. The horizontal lines are effectively the origins of the uncompensated
acceptor concentrations (N A ⫺ N D ) in the corresponding growth sectors, as indicated on the
right of the diagram. We see that the {011} sector is the first to acquire semiconducting properties
and that at relatively low boron concentrations, B L, (N A ⫺ N D ) is highest in this growth sector.
Again this effect is visible by eye, because at boron concentrations between 0 and B L some
growth sectors are blue while others are still yellow. At higher boron concentrations, B H, the
neutral acceptor concentration is highest in the {111} sectors.
If there is a significant source of nitrogen in the growth capsule and a sufficient quantity
of boron is added to produce semiconducting diamond, then, although the electrically active
boron concentration may be small, the total impurity concentration can be quite large. The
relatively high concentration of defects, compared with less than 1 ppm in natural type IIb
diamond, almost certainly accounts for the much greater line widths observed in the acceptor
spectrum (59). This effect is expected to be most pronounced in the {111} growth sectors (see
Fig. 9), as observed experimentally (57,59). If the nitrogen in the growth capsule is very effi-
ciently ‘‘gettered’’ by adding materials such as Ti and Zr, the resulting crystals are sometimes
semiconducting by virtue of the accidental boron present. In these diamonds the line widths are
very much sharper than in the specimens examined by Burns et al. (57).
For CVD diamond grown in a low-pressure plasma the nitrogen content is normally very
low but can, nevertheless, be detected using luminescence spectroscopy (60). Semiconducting
CVD diamond may readily be produced in one of the ways described in Sec. II.E. The optical
absorption data for synthetic diamond suggest that the boron concentration in polycrystalline
CVD diamond (which certainly contains both {111} and {001} growth sectors) will be inhomo-
geneous and that the rate of incorporation of boron in homoepitaxial material will be greatly
influenced by the orientation of the substrate. This is exactly what is observed.
D. Visible Luminescence from Semiconducting Diamond

It is well known that, following electron-hole pair generation by electron beam excitation or
absorption of above-gap radiation, blue luminescence is observed in natural type IIb diamond.
In synthetic boron-doped diamond and boron-doped CVD diamond the luminescence may be
either blue or green (61). Interpretations of the mechanisms producing these emission bands
are controversial. The green luminescence shows some of the properties of donor-acceptor pair
recombination (62) but the picture is not fully consistent. Emission is expected at photon energies
given by
hν ≅ Eg ⫺ (E A ⫹ E D ) ⫹ e/(4π⑀r) (in eV) (8)
Here E D is the ionization energy of the donor associated with the boron acceptor, ⑀ is the absolute
permittivity, and r is the separation of the donor and acceptor. It is argued that the discrete
lines produced at different values of r overlap to form a broad band (62). The green emission,
characteristic of boron doping in synthetic and CVD diamond, requires a donor ionization energy
of around 4 eV, but it is puzzling, if this model is correct, that no recombination is observed
in the ultraviolet region from boron-acceptor, single-nitrogen-donor pairs (23).
In natural semiconducting diamond it has been demonstrated that the blue cathodolumines-
382 Collins
cence originates from dislocations (63), although it is not known whether these are ‘‘decorated’’
with some other defect responsible for the luminescence. Experiments with pure CVD diamond
have shown that the intensity of the blue cathodoluminescence is greatly increased in regions of
the material that have been subjected to plastic deformation—again confirming that the emission
originates from dislocations (64). Similar experiments have been carried out with nitrogen-
containing synthetic diamonds (65), and here too the intensity of the blue luminescence was
increased, although the predominant effect was the production of nitrogen–vacancy centers that
produce intense orange emission at 2.156 eV (575 nm).
Schottky diodes can be manufactured using boron-doped material, and some of these emit
a feeble blue luminescence when forward or reverse biased (66). However, the intensity of the
luminescence is much lower than that obtainable with SiC blue light–emitting diodes and many
orders of magnitude weaker than the recently developed LEDs based on GaN (67). Unlike
diamond or SiC, GaN is a direct-gap semiconductor, and the conversion of electrical power to
light is very much more efficient. It may be possible to obtain green injection luminescence
from a boron-doped diode structure, but this will not compete, in performance or price, with
the commercial LEDs based on GaP.
IV. SUMMARY
The electrical and optical properties of semiconducting diamond have been described in detail
and it has been shown that the electrical behavior of boron-doped CVD diamond can be under-
stood in terms of models used to interpret results obtained from bulk (natural and synthetic)
semiconducting diamond, once allowances have been made for the effects associated with grain
boundaries. High-quality synthetic and CVD diamond exhibit the free- and bound-exciton emis-
sion first studied in natural semiconducting diamond. The origins of the green and blue cathodo-
luminescence from boron-doped synthetic and CVD diamond appear to be similar, although the
mechanisms are still not fully understood.
Although this material has been extensively studied, there are many reasons why it is not
suitable for the device applications proposed (1–5) in the late 1980s. We have seen that there
is no known method of producing n-type material with a useful electrical conductivity. The
ionization energy of the boron acceptor is large (⬃0.37 eV) so that only around 0.2% of the
acceptors are ionized at room temperature; consequently, most device structures exhibit a large
series resistance. At higher temperatures the device conductivity improves, but there is a rapid
decrease in the hole mobility, which limits applications at high frequency. Both synthetic and
CVD diamond particles exhibit more than one growth sector (certainly {100} and {111} sectors
are present) and it is therefore impossible to obtain uniform doping with boron. In polycrystalline
CVD diamond there are additional problems arising from carrier scattering and carrier depletion
effects at the grain boundaries. Visible luminescence can be generated from suitable diamond
device structures, but the intensity of the luminescence compares unfavorably with that of the
existing and (particularly) newly emerging LED technologies.
The present author has pointed out on a number of occasions (19–22) that the early enthu-
siasm for the production of active electronic devices and optoelectronic devices based on dia-
mond was misplaced. At the time of writing the present chapter many laboratories set up to
exploit this ‘‘multibillion dollar market’’ are closing down or turning their attention to other
materials. The past decade of intense activity on diamond has revealed many interesting charac-
teristics of this unique material, some of which are recorded in this chapter, but sadly all the
research has confirmed the author’s long-held opinion that diamond is not a suitable material
for electronic device applications.
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17
Semiconducting Diamond and Diamond
Devices
Shinichi Shikata and Naoji Fujimori
Itami Research Laboratories, Sumitomo Electric Industries, Ltd., Itami, Hyogo, Japan
I. INTRODUCTION
The significant characteristics of diamond as a semiconductor have been expected to allow its use
in high-temperature and high-power operation devices and have generated numerous research
activities on diamond devices. Based on the electrical characteristics of diamond, which were
discussed in the preceding chapter, an overview of diamond device–related technologies as well
as recently developed devices will be given in this chapter.
First, the feature and possibilities of diamond as a semiconductor are briefly discussed.
The band structure of diamond, including exchange and correlation effects, is shown in Fig. 1
(1). Diamond is a material of indirect transition with a large energy gap of 5.47 eV from the
top of Γ25′ to the bottom of ∆ 1. As shown in Fig. 2, the lattice constant is too small compared
with other semiconductors; thus, unfortunately, it is unlikely to be possible to carry out ‘‘band
gap engineering’’ to generate structures such as high electron mobility transistor (HEMT),
heterojunction bipolar transistor (HBT), and quantum well (QW) devices. The only exception
is cubic BN (cBN), which has 1.3% lattice mismatch with diamond, which will be discussed
later. However, this largest energy gap among conventional semiconductors is expected to be
a prime characteristic of high-temperature and high-power operation devices associated with
high thermal conductivity up to 20 W/cmK. One of the largest problems of semiconductor
devices is thermal management, and various types of technologies have been developed to over-
come this problem. But for diamond devices, it is likely that the problem can be avoided owing
to its ultimate thermal conductivity. The semiconductor properties of diamond are summarized
in Table 1 and Fig. 3 (2) compared with typical semiconductors such as Si, GaAs, and SiC.
Utilizing these characteristics, several theoretical analyses have been performed. These are well
known as figure of merit (FOM) with the author’s name, such as Johnson’s figure of merit
(JFOM) (3), Keyes’ FOM (KFOM) (4), Baliga’s FOM (BFOM) (5), and Baliga’s high-frequency
FOM (BHFFOM) (6). This is also given in Table 1.
1. JFOM defines the power-frequency product for a low-voltage transistor.
JFOM ⫽ E c v s /2π.
2. KFOM defines a thermal limitation of the switching behavior of transistor.
KFOM ⫽ λ (CV s /2πε) 1/2
385
386 Shikata and Fujimori
Figure 1 Band structure of diamond including exchange and correlation effects. (From Ref. 1.)
Figure 2 Lattice constant versus band gap of semiconductors.

Semiconducting Diamond and Diamond Devices 387
Table 1 Typical Semiconductor Properties

Property Si GaAs 3C-SiC Diamond
Band gap (eV) 1.12 1.42 3.0 5.47
Dielectric constant 11.8 12.5 9.7 5.7
Thermal conductivity (W/cm K) 1.5 0.46 5 15–20
Melting point (°C) 1415 1238 2540 4000
Resistivity (Ωcm) E3 E8 E2 E13
Mobility (electron) (cm 2 /V s) 1500 8500 400 1800
(hole) (cm 2 /V s) 450 400 50 1200
Breakdown (10 5 V/cm) 3 60 40 100
Typical donor and level (meV) P 45 Si 5.8 Al 167 a
Typical acceptor and level (meV) B 45 Be28 B 254 a B 370
Effective mass (electron) 0.98 0.067 0.60 0.2
(hole) 0.16 0.082 1.00 0.25
Band Indirect Direct Indirect Indirect
JFOM 1 6.9 1138 8206
KFOM 1 0.46 6.54 32.2
BFOM 1 13.3 106.3 8574.1 n
6751.3 p
BHFFOM 1 9.5 13.1 453.7 n
357.2 p
a
Data for 4H-SiC.
3. BFOM defines the material parameters for minimizing the conduction losses in a
power transistor and applies to devices operating at low frequency.
BFOM ⫽ εµE 3g.
4. BHFFOM defines the BFOM in a power transistor operating at high frequency.
BHFFOM ⫽ 1/(R on , sp C in, sp )
Here,
R on,sp ⫽ 4V 2B /(εµE 30 ) and C in,sp ⫽ (εqN 3B /2V G ) 1/2
and E c is the breakdown field, V s the saturation velocity, µ the mobility, V B the break-
down voltage, and
N B ⫽ εE 3c /(2q V B )
As can be seen from the figure of merit in Table 1, diamond fulfills the expectations for
power devices from various points of view, unless the technologies are not mature at present.
One of the problems with diamond at this stage is that only p-type doping is possible with
boron. For varieties of devices and integrated circuits, n-type diamond is preferable, but this is
not inevitable because in most cases unipolar devices are possible.
For a heterojunction bipolar transistor (HBT), a theoretical study was also reported for
SiC/Si/diamond (emitter/base/collector, respectively) (7), and the HBT FOM is 22.21 times
larger than for an AlGaAs/GaAs/GaAs HBT. Here, the HBT FOM is defined as the product
of operating frequency and output power of the HBT with 3 dB gain. This is also possible
388
Figure 3 Carrier velocity versus electric field for typical semiconductors. (a) Electron; (b) hole.
Shikata and Fujimori
without n-type doping; that is, a pnp HBT is possible with a p diamond collector by using a
collector up-configuration device structure.
Hereafter, we focus on some of the technologies related to device structures, processing,
and characteristics.
II. DOPING
As described in the preceding chapter, p-type doping with B is the only successful technique
for the formation of channels in diamond at this stage. B atoms in substitutional sites of carbon
in diamond have a deep acceptor level of 370 meV.
As is well known for various kinds of semiconductors, there are three ways to dope impuri-
ties: vapor-phase doping, ion implantation, and diffusion. Following are short reviews of doping
technologies for B in diamond.
A. Vapor-Phase Doping
Vapor-phase doping of B in diamond has been realized by several methods. The first doping
was by ‘‘unidentified gaseous B compounds’’ by Spitsyn et al. (8). Currently, the major tech-
nique involves introducing B 2H 6 (diborane) diluted in H 2 into the chemical vapor deposition
(CVD) chamber during deposition. The results are described in detail in the previous chapter.
Most of the diamond devices utilize p-channels formed by this method, and the results will be
given in Sec. V.
As diborane is a toxic gas, the doping should be carried out in a leaktight deposition
chamber with a safety gas feed system. For this reason, some people use only B powder in the
CVD chamber for doping (9). Using B 2O 3 (boron trioxide) powder mixed in a liquid is another
way to perform B doping in safety conditions (10).
B. Ion Implantation
Ion implantation represents advances in reproducibility and throughput in device fabrication
and is used in most semiconductor device manufacturing processes. But for diamond, a region
damaged by ion implantation is graphitized during the subsequent annealing process. With doses
of B low enough to prevent graphitization, it is hard to obtain an appropriate carrier concentration
for device performance. To overcome this difficulty, Prinz (11) clarified the important role of
implantation temperature and spatial distribution of defects. According to this study, successful
results were obtained with ion implantation at a low temperature of 77 K by Zeisse et al. (12).
The advantage of this technique is low diffusivity of defects created during the implantation
process, which enhances the probability of B ions occupying vacant lattice sites. As is well
known in ion implantation, coimplantation techniques are also effective for diamond (13). Car-
bon coimplantation with B injects vacancies that overlap the B profile. The details of ion implan-
tation technologies for diamond and related materials can be found in the book by Dresselhaus
and Kalish (14). Despite these investigations, most of the high-performance transistors have
been accomplished with channels obtained by vapor-phase doping and ion implantation is not
recognized as an indispensable technology for p-channel formation in diamond.
C. Diffusion
The B doping by thermal diffusion associated with subsequent rapid thermal annealing (RTA)
was employed for the fabrication of a MESFET by Tsai et al. (15). They made a very shallow
channel of 50 nm by this method. This is the only successful result obtained with diffusion
doping.
III. SURFACE PROPERTIES AND CONTACTS

A. Schottky Contact and MOS Interface
Surface-related characteristics such as the insulator-semiconductor interface and metal-semicon-
ductor interface are among the most important factors in device structure and characteristics.
The influence of surface-related phenomena on device characteristics is briefly reviewed.
For the metal-insulator (oxide)-semiconductor (MIS or MOS) structure field effect transis-
tor (FET), the state density of the semiconductor-insulator interface is extremely important for
the inversion behavior of MOSFETs. For instance, the surface state density of the SiO 2 /GaAs
system (16) was expected to be over 10 13 cm ⫺2 eV ⫺1, two to three orders larger than that of the
SiO 2 /Si interface, and thus an inversion layer could not be observed. The influence of surface
state density is also found in metal-semiconductor (MES) FETs, that is, leakage of the Schottky
barrier, a low barrier height of the Schottky gate contact, and an increase in series resistance
from source to drain. It is well known that the the current density of the Schottky barrier is
related to the barrier height (Φ B ) of the Schottky contact, which is given by
J ⫽ J 0 exp(qV/nkT){1 ⫺ exp(⫺qV/kT )} (1)
Here, J 0 is given by
J 0 ⫽ A*T 2 exp{⫺ Φ B /kT } (2)
where A* is the effective Richardson constant. The interface constant S defined by the following
equation is conventionally used to express these phenomena.
S ⫽ d Φ B /dX m (3)
Here, X m is the electronegativity of the metal. As can be seen from Eq. (1), it is necessary to
have a higher barrier height to reduce the reverse direction leakage current J 0. It is thought that
the Schottky barrier height in metal-semiconductor systems depends on the metal work function
(Φ m ). However, when the Fermi level is pinned and the Schottky barrier height does not depend
on the metal work function, it is quite constant and sometimes only a low barrier height is
available despite using various kinds of metals. This not only affects the leakage current but
also leads to a small logic swing in some digital circuits, resulting in malfunction of the logic
circuit due to undistinguishability between high and low voltage levels. Also, in MESFETs the
surface depletion layer originating from the semiconductor-insulator interface affects MESFET
pinch-off characteristics and the series resistance from source to drain, which results in low
transconductance and nonuniformity of the transistor characteristics. As described before, the
surface state is one of the most important characteristics of a semiconductor when device applica-
tions are considered.
For diamond, research activities on surfaces by means of Schottky diodes have been car-
ried out at several institutes. From the late 1980s to early 1990s, Schottky diodes with p-channels
were investigated for diamond (17–22). Fine rectification rafios of forward and reverse were
obtained and were from 5 to 6. For the metal dependence of the Schottky characteristics, Fermi
level ‘‘pinned’’ results have been reported by several researchers for Schottky contacts fabri-
cated on KNO 3- or CrO 3-treated diamond surfaces. These treatments were required to eliminate
the graphitized surface of diamond. On the other hand, ‘‘unpinned’’ results have also been
reported for the surface of semiconductor diamond by several researchers and there have been
several discussions. These inconsistent results have been discussed for a long time and are now
considered to be due to a dependence on the surface treatment. In particular, surface treatment
with oxygen and hydrogen affects the surface characteristics. Oxygen treatment by both wet
and dry processes has been carried out, such as boiling in a saturated solution of CrO in H 2SO 4
and O 2 plasma, respectively. It was observed that when oxygen was adsorbed on diamond sur-
faces, the metal dependence of the Schottky barrier height vanished (23,24). The Schottky barrier
height of various kinds of metals on homoepitaxial CVD diamond on a hydrogen-terminated
surface has been measured and plotted as a function of metal electronegativity. This is shown
in Fig. 4 (25,26). As the metal electronegativity increases, the barrier height decreases. The S
factor, which is given in Eq. (3), is 0.7, which indicate that the surface is almost unpinned. As
shown in Fig. 5 (27), the surface Fermi level position has been estimated by electrical and X-
ray photoelectron spectrocopy (XPS) measurements. The oxygenated surface was estimated to
be depleted due to Fermi level pinning. It was also stated that remote hydrogen plasma treatment
of an oxygenated surface can only partially replace the adsorbed oxygen with hydrogen, whereas
the as-grown surface is considered to have an accumulation layer. This has been proposed to
explain the ‘‘surface conduction layer’’ of hydrogen-terminated diamond. The surface-depleted
layer has been confirmed to be p-type (28). The actual Schottky characteristics of diamond have
been intensively studied by Waseda’s group and the results are shown in Table 2. Most Schottky
metals show fine ideality factors with their own barrier height, which can be estimated from
their electronegativities. Recent results indicate that the Schottky contact for diamond can be
controlled by appropriate surface treatment to achieve the fine characteristics that are required
for MESFET applications.
The interface of SiO 2 and diamond has been studied by several research groups associated
with FET fabrication, looking for MOSFET applications. The first paper on MOS on diamond
Figure 4 Schottky barrier height dependence of metals on diamond as a function of metal electronegativ-
ity. (From Ref. 26.)
Figure 5 Position of Fermi level estimated from Kelvin probe and XPS measurements. (From Ref. 27.)
was by Grot et al. in 1990 (29). A sputtered film was used for SiO 2. They have obtained device
operation but without saturation. The first study of MOS interfaces was by Geis et al. in 1991
(30). The C-V characteristics were measured and the experimental results almost coincided with
the theoretical curve at 10 kHz. Results for a MOSFET with a hydrogen-terminated surface
associated with evaporated SiO 2 (31) seem to indicate a high-quality interface. Among insulators
other than SiO 2, a CaF 2 film was studied by Maid et al. (32). They observed MISFET operation
without an imperfect surface state measured by C-V characteristics.
At present, the surface state has not been intensively studied for diamond and the surface
state density is still unknown. Intensive investigations associated with surface physics are ex-
pected from the device viewpoint.
B. Ohmic Contact
A low-resistivity p-type ohmic contact to diamond is essential technology for reduction of series
resistance in order to realize a high-performance transistor. And a temperature-stable ohmic
contact is extremely important for diamond for high-temperature applications. It is well known
that for ohmic contacts of semiconductors, two solutions are provided. The first one is heavy
doping of the contact region, which enables an increase in the tunneling probability of electrons
or holes. The other is to prepare low-resistivity contacts to reduce the barrier height at the
interface, including an intermediate low-barrier-height semiconductor layer.
For the first solution, an ohmic contact with heavy doping of the semiconductor is realized
Table 2 Summary of FET Development

Studies Comment Year Center
Early studies
Bipolar transistor 1992 University of Witwatersrand
Point-contact transistor 1987 MIT
Permeable base transistor 1988 MIT
MESFET
p-MESFET First paper 1989 Sumitomo
p-MESFET First paper 1989 Penn State University
p-MESFET with i-diamond First paper for i-diamond 1990 Sumitomo
p-MESFET with i-diamond 310°C operation 1991 Sumitomo
p-MESFET Diffusion and RTA 1991 Varian Research Center
p-MESFET with i-diamond Polycrystal 1991 Kobe Steel
p-MESFET Gate-recessed 1994 Sumitomo
p-MESFET with i-diamond Polycrystal 1994 Kobe Steel
p-MESFET with SCL First paper for SCL 1994 Waseda University
p-MESFET with SCL Highest gm 1994 Waseda University
p-MESFET with i-diamond Pulse-doped 1995 Sumitomo
MOSFET
p-MOSFET with SiO 2 First paper 1990 Penn State University
p-MOSFET with SiO 2 Selective growth 1991 MIT
p-MOSFET with SiO 2 Ion-implanted channel 1991 Naval Ocean System Center
p-MOSFET with SiO 2 Gate-recessed 350°C 1992 Penn State University
operation
p-MOSFET with SiO 2 Polycrystal 1992 Kobe Steel
p-MOSFET with SiO 2 400°C operation 1994 Kobe Steel
p-MOSFET with SCL Highest gm (trans con- 1996 Waseda University
ductance)
by doping diamond with B. For the latter, there are two methods for obtaining low-barrier-
height materials. One is to insert a low-energy-gap intermediate semiconductor layer such as
InAs in the case of GaAs. The second is to have low-barrier-height metals. The first method
cannot be achieved for diamond, because of its lattice constant. However, a graded band gap
contact from Si to diamond, which, exactly speaking, is not a real semiconductor band gap
grading, has been investigated (33). This is formed by ion mixing with Kr ion implantation and
annealing at 1200°C to form an SiC layer. The contact resistance obtained was 5 ⫻ 10 ⫺3 cm 2.
In most of the studies, low-barrier-height materials associated with heavy doping are con-
sidered as ohmic contacts for diamond. In the early stage of the research looking for devices,
low-barrier-height metals such as Au (34–36) and Pt (37) were used for the ohmic metal. This
type is called a ‘‘nonalloy-type ohmic metal.’’ The contact resistance of Pt was 3.3 ⫻ 10 ⫺3
cm 2. The refractory metal–transition metal systems to p-type diamond are well known as ohmic
metals, such as Au/Ti (38), Au/Mo (39), Au/Ta (38), Mo/Ni/Au (40), TiC/Au (41), and TaSi 2 /
Au (41). These are ‘‘alloy-type ohmic metals.’’ For these ohmic metal systems, low contact
resistances of 10 ⫺5 to 10 ⫺6 Ω cm 2 have been obtained with highly doped channels. The depen-
dence of contact resistance on diborane doping concentration for Ti/Mo/Au metal is shown in
Fig. 6 (42). A contact resistance of order 10 ⫺6 Ω cm 2 is obtained. This is the same as that of
other semiconductor contacts and is low enough for device operation for integrated circuits. For
Ti-based contacts, a TiC layer is observed to be formed by the contact alloy.
As is well known in semiconductor devices, temperature degradation is determined by
Figure 6 Dependence of the contact resistance of Ti/Mo/Au ohmic metal on diamond on doping concen-
tration. (From Ref. 42.)
the temperature durability of the ohmic contact. Thus, for high-temperature operation of diamond
devices, high thermal stability of ohmic metals is required as well as low resistivity (42,43).
The aging characteristics of Ti/Mo/Au were studied and it was found that this system is superdu-
rable for high-temperature aging; that is, there was no degradation for 400 h at 800°C as shown
in Fig. 7 (42). Compared with GaAs and SiC, which have durabilities of 10 h at 650°C and
100 h at 500°C, respectively, diamond has far better temperature durability. This indicates that
diamond will be able to find high-temperature applications with superhigh temperature stability.
Figure 7 Aging characteristics of Ti/Mo/Au ohmic metal on diamond. (From Ref. 42.)
IV. GROWTH AND PROCESSING
Despite the purpose of this chapter, short descriptions of selective growth and heteroepitaxial
growth for band gap engineering will be given here.
A. Selective Growth of Diamond

Selective growth is important for the fabrication of device structures, especially for quite compli-
cated structures of high-performance devices. For diamond, various kind of insulators and metals
can be used for the mask in selective growth, because diamond is inert to acid and alkali solvents
as well as etching gas plasma, and there are few problems related to the fabrication of mask
materials on diamond. It has been reported that the SiO 2 was sputtered and patterned into a
mask by lithography and subsequent etching by buffered HF. Diamond 0.15 µm thick was
selectively grown for a 60 ⫻ 200 µm window (44). The evaporated tungsten metals have also
been used for the mask to grow diamond selectively for a 30 µm window (45). These are
successfully utilized in the fabrication of FETs.
B. Heteroepitaxial Growth for Band Gap Engineering

Heteroepitaxial growth of diamond for band gap engineering is limited to cubic BN (cBN). The
lattice constant of diamond is 3.267 Å and the lattice mismatch to cBN (3.615 Å) is 1.3%. Thus,
it is possible to grow diamond epitaxially on cBN. Koizumi et al. (46) succeeded in growing
diamond on cBN in 1990. This was followed by Tomikawa and Shikata (47), who found that
the lattice spacing of the diamond (111) plane on cBN is the same as that of the bulk crystal.
They also observed dislocations once in 82 planes, which almost correspond to lattice mismatch.
These results indicate that when cBN vapor-phase growth is achieved in the future, band gap
engineering is available for diamond, and various kinds of devices such as HBT, HEMT, and
QW devices will be possible using heterojunctions.
C. Etching
In order to enhance the characteristics of FETs, the series resistance and contact resistance might
be reduced with less effect of the surface depletion layer. For these purposes, microfabrication
technologies are essential to meet the requirements for the fabrication of devices, such as a
small size gate with a self-aligned structure, recessed structure, and so on.
Several techniques that are already used in Si large-scale integration (LSI) processes such
as ion beam–assisted etching, reactive ion etching, and electron cyclotron resonance (ECR)–
assisted etching have been adopted for the dry etching of diamond (48–51).
Typically, NO 2, O 2, and inert gases are used for the etching gas with SiO 2 and Al as
etching masks. An etching selectivity of 38 for diamond to SiO 2 is obtained with a gas composite
of Ar with 1% O 2, which is high enough for high-aspect-ratio etching of diamond with a high
process margin. Also, by using pure Ar, an etching selectivity of about 1 is obtained. The wide
range of etching selectivities from 1 to 38 enables complex fabrication processes of devices
using diamond. Utilizing this dry etching technique for diamond, microfabrication of diamond
Figure 8 Overview of diamond etched by RIE. (From Ref. 51.)
was carried out. Figure 8 shows an overview of etched diamond surfaces for various sizes of
lines and spaces. With regard to their lithography resolution, up to 1-µm line and space patterns
of diamond are fabricated. The minimum size of lines and spaces will be improved to the half-
to quarter-micrometer level by utilizing further lithography techniques such as i-line or excimer
laser stepper and electron beam exposure.
As can be seen from the foregoing studies, diamond can be fabricated by dry etching,
despite its inertness to wet etching by acid and alkali.
V. TRANSISTORS AND INTEGRATED CIRCUITS

A. Early Studies
Transistors of diamond have been investigated mainly with the p-channel MES type and p-
channel MOS type, because the only reproducible channels are available for B-doped p-type
diamond. However, from a historical viewpoint, research activities on MESFETs and MOSFETs
were preceded by several pioneering studies with other device structures.
The first work that utilized a bipolar transistor was that of Prins (52). Using a natural p-
type diamond bulk crystal as a substrate, carbon ions are ion implanted to form n-type-like
regions with 3.2-µm-diameter wire as a implant mask. The energy level and mechanism of the
carbon implantation cannot be estimated; however, bipolar transistor behavior was achieved.
The I-V characteristics are shown in Fig. 9. Although the current gain of h F ⫽ I C /I B is only
0.11, the impact on researchers in this field was not insignificant. This was followed by several
research activities, such as work on npn bipolar transistors with As implanted n-type-like regions
and a point contact bipolar-like transistor (53).
In 1987, the first high-temperature operation up to 500°C was achieved by Geis et al. (54)
using a point contact transistor.
A permeable base transistor with an Al metal base was the next type of the device tried
Figure 9 I-V characteristics of the first FET of Prins. (From Ref. 52.)
for diamond. This device is fabricated with ion beam etching to form the structure. A transcon-
ductance of 30 µS/mm was exhibited (55).
B. MESFETs
MESFETs are promising devices for diamond because of the characteristics obtained with unipo-
lar semiconductors associated with their simplified fabrication process. The device characteris-
tics of MESFETs depend highly on the device size, especially the gate length, and surface-
related characteristics.
The first papers on MESFETs were published in 1989 by Shiomi et al. of Sumitomo
Electric Industries (56) and by Gildenblat et al. of Pennsylvania State University (57). In the
former work, a p-channel of 2.0 µm was obtained with a B-doped epitaxial diamond layer on
an insulating bulk crystal. Al and Ti were employed directly on the p-channel for gate and
ohmic electrodes, respectively. The structure and I-V characteristics are shown in Fig. 10. The
gate length was 140 µm. Although the drain current saturation and pinch-off characteristics
were not observed, the drain current changed slightly with gate bias. These studies were followed
by improvement of structures as well as sophisticated fabrication processes.
In order to improve Schottky characteristics, intrinsic diamond was inserted between the
p-channel and gate metal (58). Intrinsic diamond of 0.23 µm was applied and improved charac-
teristics of 2 µS/mm were obtained. These structures are known in compound semiconductor
devices and are sometimes classified as MISFETs the ‘‘I’’ standing for insulating semiconductor.
In this chapter, these structures are classified as MESFETs regarding the general knowledge of
Figure 10 I-V characteristics of one of the first MESFETs. (From Ref. 56.)
silicon technology. Such a structure was also applied to high-temperature operation by Nishibay-
ashi et al. (59,60) utilizing selective epitaxy of intrinsic diamond, and they obtained high-temper-
ature operation at 310°C. The rapid thermal annealing associated with B doping by thermal
diffusion was employed for a MESFET by Tsai et al. (15); this is the only FET operation result
obtained with diffusion doping.
To improve MESFET characteristics, several techniques have already been introduced in
III-V compound semiconductor devices. There are two major directions for improvement. The
first one is to reduce gate length with fine lithography technique. The second is to reduce series
resistance. Reducing the spatial distance between the gate and a low-resistance region such as
a p⫹ doped region is a promising technique for the reduction of series resistance. An extreme
structure can be found in a self-aligned structure. The reduction of ohmic contact resistance is
also an important technique for reducing series resistance. It is also important to avoid influence
of the surface state. Utilizing some of these techniques, such as low ohmic contact and a gate
recessed structure associated with reduced gate length, the first pinch-off characteristics of a
diamond MESFET were observed by Sumitomo’s group (61). The structure and I-V characteris-
tics are shown in Fig. 11. For the recess etching process in this work, reactive ion etching (RIE)
was employed (51).
A shallow channel is also a promising approach to enhancing MESFET characteristics.
A pulse-doped (delta-doped) structure was applied for diamond by Shiomi et al. in 1995 (62).
By secondary ion mass spectroscopy (SIMS) measurement of the pulse-doped structure, the
channel thickness can be estimated to be less than 400 Å, and they observed a drain current
saturation characteristic with a high transconductance of 116 µS/mm with a 4-µm gate length
MESFET. This structure is promising for a diamond FET utilizing degeneracy of doping that
can avoid the difficulties caused by a deep acceptor level of 370 meV.
A unique MESFET utilizing a ‘‘surface conducting layer’’ as a channel was developed
at Waseda University (63,64). As described earlier in Sec. III, the hydrogenated surface of
diamond is known to behave as p-type. Using this layer as a channel, a MESFET has successfully
Figure 11 I-V characteristics of MESFET for first pinch-off. (From Ref. 61.)
been fabricated. The pinch-off characteristics and high transconductance of 200 µS/mm were
observed for FETs of gate length 10 µm (65). These characteristics have been improved and
the highest transconductances of 2.5 mS/mm obtained by a 7-µm gate length FET with pinch-
off and 4.1 mS/mm for a non-pinch-off FET (66). These are also shown in Fig. 12. This is the
highest transconductance of diamond ever reported for a diamond MESFET.
The preceding results were obtained with single-crystal diamond. However, a single crys-
tal is far from real applications because of the crystal size and cost. Thus, the fabrication of
FETs has been performed using polycrystalline diamond film. In particular, the advanced tech-
nology of heteroepitaxial growth, which can provide a large-area crystal, is expected to be
promising (67,68). The first FET operation using polycrystalline diamond was reported by Nishi-
mura et al. in 1991 (69). Silicon nitride (Si 3N 4 ) was used as a substrate. A MiSFET structure
with intrinsic diamond as the Hayer was fabricated, and it was observed that the drain current
changed slightly with gate bias.
Figure 12 Cross section and I-V characteristics of a MESFET using a surface conductive layer. (From
Ref. 64.)
C. MOSFETs (MISFETs)
For MOSFETs, inversion-type and non-inversion-type FETs are known for various types of
semiconductors; however, an inversion-type MOSFET had not been realized for diamond, be-
cause of the poor characteristics of the MOS interface. Thus, all of the reports on diamond
MOSFETs given here are for non-inversion-type FETs.
The first paper on MOSFET was by Grot et al. in 1990 (70). Silicon dioxide 0.1 µm thick
was employed for the insulator, which was deposited by sputtering with Ar and oxygen plasma.
The channel thickness was 0.1 µm. The device structure and FET characteristics for operation
at 300°C are shown in Fig. 13. The gate leakage current was as small as 10 pA at 300°C
operation, which indicates an advantage of MOSFETs compared with MESFETs. To improve
this FET, a gate recess structure was introduced by electron cyclotron resonance (ECR) etching
and high-temperature operation up to 300°C was achieved. The maximum transconductance
was 87 µS/mm (71,72). The first pinch-off characteristics of MOSFETs were achieved by Zeisse
et al. in 1991 (73). They introduced a sophisticated process of ion implantation of boron. Implan-
tation was carried out at 80 K with a multiple scheme to provide a uniform layer 210 nm thickn.
After implantation, the substrate was annealed to 1263 K to activate ions. The I-V curve shows
fine pinch-off characteristics with 3.9 µS/mm transconductance, which is shown in Fig. 14. This
is first report on pinch-off characteristics of a diamond MOSFET. Pinch-off characteristics have
also been reported for a MOSFET by Glass et al. (74), with an epitaxially doped channel MOS-
FET. As can be seen in Fig. 15, they observed fine characteristics at 400°C with transconduct-
ance of 0.26 mS/mm. The Waseda University group have obtained high transconductance of
16.4 mS/mm for a 6 µm gate length MOSFET with evaporated SiO 2 associated with a hydrogen-
terminated surface (75). This is the highest transconductance ever reported for diamond, includ-
ing various types of FET structures. This FET has been confirmed to operate at 327°C.
For polycrystalline diamond, a MOSFET with SiO 2 was reported by Tessmer et al. (75)
in 1992 (76).
These results for FETs, including early studies, MESFETs, and MOSFETs, are summa-
rized in Table 2.
D. Heterojunction Devices
As shown in a previous subsection, it is possible to grow diamond epitaxially on cBN with a
lattice mismatch of 1.3% (47). Utilizing this growth, a heterojunction of p-type diamond–n-
Figure 13 The first MOSFET characteristics operating at 300°C. (From Ref. 70.)
Figure 14 I-V characteristics of MOSFET for first pinch-off. (From Ref. 73.)
type cBN has been grown successfully, and using this junction, a heterojunction diode was
fabricated and operated up to a temperature of 500°C (76,77).
E. Integrated Circuit
For integrated circuits using p-channel diamond, bipolar logics and the complementary MOS
(CMOS) logic are not available and the circuits are limited to the logics of unipolar FETs,
which are familiar with compound semiconductor devices. The typical unipolar FET logics are
summarized in Table 3.
Integrated circuits using diamond are under investigation because of the progress in FET
characteristics. The first trial was by Zeiss and colleagues (78) using ion-impanted channel
Figure 15 I-V characteristics of a MOSFET operated at 400°C. (From Ref. 74.)

Table 3 Typical Logics of Unipolar FET

Mode Logic
Enhancement mode DCFL (direct coupled FET logic)
LPFL (low pinch-off voltage FET logic)
Depletion mode SDFL (Schottky diode FET logic)
BFL (buffered FET logic)
CCL (capacitor-coupled FET logic)
SCFL (source-coupled FET logic)
SSFL (Schottky-coupled Schottky FET logic)
MESFETs with a transconductance of 3.9 µS/mm. Two MESFETs were connected, including
one FET as a current source, to observe a gain (V out /V in ) of approximately 2. Using a logic
analyzer, two FETs were connected with load resistance to observe NAND operation in 1994
by Glass et al. (74).
A series of logics was successfully demonstrated by the Waseda University group using
a MESFET with a surface conductive layer in 1995 (66,80). The logics consist of enhancement
mode MESFETs with a MESFET load. The gate length of the FET was 5 µm and transconduct-
ances of FETs were from 1.5 to 2.2 mS/mm. They had fabricated logics of NAND, NOR, NOT,
and RS flip-flop. The logic operations were obtained up to 20 kHz and the RS flip-flop was
operated up to 5 kHz. An overview and I/O characteristics of the RS flip-flop are shown in Fig.
16. This series comprises the first logic and memory operations (RS flip-flop) of diamond de-
vices. More recently, the Waseda group have succeeded in fabricating logic with the
enhancement/depletion (E/D) type of FETs (79) and observed fine logic operation. These results
indicate that diamond is available for logic operations when these are applied to a specified
field such as a high-temperature environment where conventional device operations are not
available.
F. Applications in Future
As described in this chapter progress in semiconductor diamond is likely to verify the possibili-
ties of diamond devices. The applications of diamond for active devices are to be realized; the
Figure 16 Overview and I/O characteristics of an RS flip-flop. (From Ref. 74.)

distinction between diamond and conventional semiconductor devices should be the critical
point. High-temperature operation and durability in harsh environments are considered to be
prospects for diamond. Specifications of environmental conditions and related reliability and
temperature ranges of industrial applications are shown in Table 4 and Fig. 17 (81). Oil well
equipment electronics, military electronics, and space electronics are thought to be the applica-
tions that will be realized shortly due to their harsh environmental requirements, which cannot
be met with Si-based devices. The possible products for those applications include sensors,
devices for high-temperature operation, and power devices. Radiation-durable devices are also
candidates, finding applications in space and electric generation by atomic power (82).
With regard to the cost problem, the progress in heteroepitaxial growth on Si substrates
is promising for diamond device applications (67,68). This technique offers diamond crystals
of several micrometers with almost the same crystal configurations, as they are coalesced. This
is not a single crystal but can be used as almost a single crystal; that is, devices can be fabricated
on each diamond crystal and interconnected, crossing over the crystal boundaries. Utilizing this
technique, large waters of diamond-silicon are available at low cost due to the established Si
substrate.
VI. SUMMARY
The semiconductor characteristics of diamond and its device applications including recent prog-
ress have been reviewed in this chapter.
Concerning channel formation, B is the only atom used successfully for the formation of
channels in diamond with a deep acceptor level of 370 meV. Successful doping is available
mainly by vapor-phase doping during deposition. For the surface properties related to device
application, the Schottky and MOS characteristics of diamond have been summarized. The hy-
drogenated surface of diamond has been investigated; diamond was found to have a fine surface
and the Fermi level is thought to be unpinned. Thus, fine Schottky characteristics are available
with a small ideality factor. The ohmic contact plays an important role in device characteristics.
For diamond, Ti-based metal with a highly doped layer can provide a low-resistivity ohmic
contact. The aging characteristics of Ti/Mo/Au were studied and it was found that this system
is superdurable for high-temperature aging, that is, no degradation for 400 h at 800°C. For the
fabrication process, the selective growth and dry etching technologies are now possible for
diamond. Diamond has small lattice constant and band gap engineering ulitizing heteroepitaxial
growth is not available. The only exception is diamond on cBN, and this system is now undergo-
ing basic research. For semiconductor devices, MESFETs and MOSFETs have been developed
using unipolar channels. Several techniques have been performed for MESFETs and fine charac-
teristics have been reported. Also, utilizing unipolar MESFET logic, several logic circuits such
as NAND, NOR, and RS flip-flop were developed. For MOSFETs, a high transconductance of
16.4 mS/mm (6 µm gate length) has been achieved using evaporated SiO 2 associated with a
hydrogen-terminated surface. For both FETs, high-temperature operations were achieved up to
300–400°C. The characteristics of diamond, include high durabilities for temperature and radia-
tion associated with high thermal conductivity, oil well equipment electronics, military electron-
ics, and space electronics, and it is thought that these applications will be realized shortly because
their harsh environmental requirements cannot be met with Si-based devices. The possible prod-
ucts for those applications include sensors, devices for high-temperature operation, and power
devices.
404
Table 4 Specifications of Future Trends in Harsh Environment Applications
Oil well
Property Civil Military Instrumentation Automotive equipment Space Remarks
Operation Temp. ⫺55 to ⫹85 ⫺65 to ⫹125 0 to ⫹40 (⫹60) ⫺45 to ⫹85 ⫺45 to ⫹300 ⫺65 to ⫹125 Upper limit will
(°C) (max) (⫹150) (⫹175) (⫹280) (⫹400) (⫹175) go up
Vibrations 20 g sinus at 10 40 g random at 5 g sinus at 10 15 g sinus at 10 10 g sinus at 10 20 g sinus at 10
to 2000 Hz 10 to 2000 to 200 Hz to 500 Hz to 300 Hz to 2000 Hz
Hz
Mech. shock 30 g/3 mS 300 g/3 mS 1g 30 g 500 g/5 mS 300 g
Power supply ⫹10% ⫹10% ⫹10% ⫹30% ⫹10% ⫹10% Future tendency
EMI tendency Good and up Good and up Medium and up Poor and up Medium and up Good and up Going up
sharply
Shikata and Fujimori
Figure 17 Temperature ranges for industrial applications. (From Ref. 81.)
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18
SiC Boule Growth
Yuri M. Tairov
St. Petersburg Electrotechnical University, St. Petersburg, Russia
I. INTRODUCTION
SiC is the only semiconductor compound of subgroup IV elements—silicon and carbon. SiC
is a diamond-like semiconductor and is an electronic analogue of an elementary IVB semicon-
ductor: diamond, silicon, germanium, and α-tin.
Silicon carbide exists in a large number of structural forms called polytypes (more than
140), which represent modifications of hexagonal (wurtzite) and cubic (sphalerite) close-packed
crystal structures.
Polytypism is a special one-dimensional case of polymorphism. All polytypes consist of
identical close-packed Si-C double layers, whose stacking sequences differ along a certain direc-
tion. The nearest neighbor arrangement of atoms is identical in all crystal structures.
Because of the structural identity of layers, different polytypes have the same lattice pa-
rameters in the perpendicular direction. The unit cell dimension along the normal to layers or
unit cell height can vary in the range from several parts to several hundred nm. And because
of the identity of the elementary layers the unit cell height is equal to the product of the height
of the elementary layers and their number in the cell. More precise investigations show that
elementary layers of different polytypes of the same substance are not completely identical.
Their composition and lattice parameters can vary from polytype to polytype.
There are several forms of polytype notation in scientific publications. For describing
three-dimensional closely packed crystalline structures, a classical ABC scheme is widely used
in which the alternation sequence of two-dimensional layers is shown. Three positions of layers
in the most closely packed arrangement of hard-sphere atoms are denoted by A, B, and C. They
differ from each other by a translation period ⫾(1/3; 2/3) or by an angle ⫾60° (Fig. 1). Each
subsequent identical layer of spheres, if closely packed on layer A, can occupy positions of
either B or C type. Similarly, a layer in either position C or A can be placed on layer B or else
a layer in position A or B on layer C. Hence, any sequence of letters A, B, and C in which no
letter is immediately followed by the same one characterizes the most closely packed arrange-
ment. The height of a unit cell depends on the number of layers after which the packing sequence
is repeated. This number of layers, n, defines the identity period and varies from 2 up to infinity
for different closely packed arrangements. The mutual arrangement of atoms in layers is clearly
seen from the structure of the crystallographic plane (1120). The arrangement of atoms in this
plane for some silicon carbide structures is shown in Fig. 2. A structure of the wurtzite type is
represented by the sequence (AB)AB . . . with a repetition of two layers, that of a sphalerite
409
410 Tairov
Figure 1 Three possible positions (A, B, C) of layers in close-packed atom arrangement.
type by the sequence (ABC)ABCABC . . . with a repetition of three layers. A six-layer structure
is represented by the sequence (ABCACB)ABCACB . . . etc. The disadvantage of this notation
is that it is too bulky for long-period structures.
More conveniently, polytypic structures are described with Zhdanov symbols. The symbol
consists of numbers of which the first one indicates the number of successive cyclic A → B
→ C → A . . . packing arrangements, and the second one indicates that of anticyclic A → C
→ B → A . . . packings. The same numbers characterize the sequence of zigzags formed by
atoms in the (1120) plane (Fig.2). Often, if a preceding and a succeeding layer have a similar
orientation, the intermediate one is designated with the letter h (e.g., the layer is in a hexagonal
position), whereas a layer on both sides of which the adjacent layers have a different orientation
is denoted with the letter k (e.g., the layer is in a cubic position). Consequently, the hexagonality
D ⫽ n h /(n h ⫹ n k ), where n h and n k are the numbers of layers in hexagonal and cubic positions,
respectively, is more convenient for characterization of polytype structures.
Ramsdell’s notation includes the number of layers in a unit cell, which is followed by a
Latin letter indicating the crystallographic system to which the given structure belongs. It is
recommended that the letters C, T1, O, H, R M, and Tc be used to denote the cubic, tetragonal,
Figure 2 Arrangements of silicon (small circles) and carbon (big circles) atoms in (1120) plane of some
silicon carbide polytypes.
SiC Boule Growth 411
orthorhombic, hexagonal, rhombohedral, monoclinic, and triclinic crystallographic systems, re-

spectively. For instance, a 6-layer hexagonal and 15-layer rhombohedral polytype with layer-
packing sequences ABCACB and ABCBACABACBCACB or hkkhkk and hkhkkhkhkkhkhkk,
respectively, are represented as (33) and (32)3 with Zhdanov symbols and as 6H and 15R with
Ramsdell symbols. Polytypes having similar dimensions of the unit cell but different sequences
of packing arrangements of ABC are distinguished by subscripts, e.g., nH 1 and nH 2 .
These designations of polytypic structures of elementary matter are also applicable to
chemical compounds. In this case the elemental layers of the structure A, B, and C characterize
the positions of atoms of one type in the elemental layer, whereas the positions of the other
atoms in these layers are determined relative to these. For example, in SiC the elemental layer
of the structure consists of closely packed Si atoms, and above each of them one C atom is
located at a distance of 0.189 nm (Fig.2).
The arrangements of atoms in the first and second coordination spheres are identical in all
polytypes of silicon carbide and other diamond-like semiconductors. Each atom is tetrahedrally
surrounded by four nearest atoms of another type. The second coordinational sphere consists
of 12 atoms of the initial type. For most polytypes, surroundings of atoms of the same type in
the lattice can differ; e.g., nonequivalent atom states are probable. It is possible to define them
in the (1120) plane by use of the difference of the distances between atoms in the C-axis direction
(vertical lines in Fig. 2). In cubic SiC and in the 2H polytype the distances between two atoms
of the same type along the C-axis are the same and equal to heights of three and two layers,
respectively. There are two such nonequivalent positions in the 4H polytype (h, k), three of
them (h 1 , k 1 , k 2) in 6H, five (h 1 , k 1 , k 2 , h 2 , k 3) in 15R, etc. (Fig. 2).
According to symmetry groups, all polytypes are distinguished as follows: 3C-SiC of
cubic syngony has the symmetry group T 2d (F43m), polytypes of hexagonal syngony C 46v (P6 3mc),
polytypes of trigonal syngony C 13v (P3ml), and polytypes of rhombohedral syngony C 53v (R3m).
II. PROPERTIES OF SiC POLYTYPES
Up to now, more than 140 SiC polytypes have been reported, but their number seems to be
unlimited. Improvements in structural analysis have revealed new polytypes that differ from
each other by the number of layers and order in the unit cell. For instance, polytype 1200R has
parameter c ⫽ 301.56 nm. It is found that the presence of different polytypes in SiC and other
materials is caused by solid-state transformations caused by internal and external sources of
strain. Phase transformations of this type are observed for many types of matter, and as shown
by investigations polytypism is comparatively widely distributed in nature. The most important
physical-chemical parameters of the main SiC polytype structures are shown in Table 1. It is
clearly seen from the table that there is a linear correlation with the hexagonality for most of
the parameters.
The SiC phase diagram has a peritectical character (Fig. 3). The temperature of peritectical
transformation T p ⫽ 3103 K. The SiC compound is the only solid phase for the Si-C binary
system. Figure 3b and c represent parts of the diagram that border with silicon and carbon. In
the part of the diagram that borders with Si (Fig. 3b) is a decrease in the liquidus temperature
∆T l versus increasing carbon concentration C 1c in the solution. The equilibrium distribution coef-
ficient of carbon in silicon is k 0 ⫽ 0.07. It is hard to define phase diagrams for different polytype
structures because the physical-chemical analysis is not sufficiently accurate.
The incongruent melting of SiC at temperature T p can be described by the following peri-
tectic reaction:
412
Table 1 Crystallochemical Parameters of Silicon Carbide Polytype Structures

Ratio of Carbon and silicon
silicon and X-ray and practical vacancy concentration Formation
Chemical Effective carbon Lattice parameters density Debye- enthalpy Entropy
Hexagonality shift charge concentrations C SiB C BC temperature ∆H° 298 S° 298
Polytype D W SiKB (eV) q C Si /C c a(nm) c(nm) c/n(nm) α xg/CM 3 α pg/CM 3 10 ⫺20CM ⫺3 10 ⫺20CM ⫺3 ΘD (kJ/mol) (J/mol K)
3C 0 0.2 0.74 1.046 0.308269 0.755124 0.251708 3.2154 3.1584 2.0 2.3 1093 ⫺62.7 14.88
8H 0.25 0.26 0.96 1.029 0.308130 2.01516 0.251895 3.2159 3.1657 3.3 1.7 866 ⫺64.4 23.28
21R 0.29 — — — 0.308111 5.29034 0.251921 3.2159 — — — — —
6H 0.33 0.33 1.22 1.022 0.308086 1.51174 0.251955 3.2160 3.1661 4.3 1.5 907 ⫺65.2 21.61
33R 0.36 — — — 0.308075 8.31534 0.251980 3.2159 — — — — —
15R 0.40 0.32 1.19 1.012 0.308043 3.78014 0.252009 3.2162 3.1665 5.7 1.1 841 ⫺65.6 24.70
10H 0.40 — — — 0.308049 2.52011 0.252011 3.2161 — — — 926 — 20.69
27H 0.44 0.35 1.30 1.008 0.308028 6.80495 0.252035 3.2162 3.1665 6.2 1.0 891 — 22.28
4H 0.5 0.37 1.37 1.001 0.307997 1.00830 0.252076 3.2163 3.1673 7.1 0.7 1297 ⫺66.5 10.62
2H 1 — — — 0.30763 0.50480 0.2524 3.2151 — — — — —

Tairov
Figure 3 Phase diagram of silicon carbide: (a) big scale; (b) silicon side of the phase diagram; (c) carbon
side of the phase diagram; (d) liquid line of the SiC-Si system; (e) silicon and carbon interaction parame-
ter α L in the solution-melt; (f ) temperature dependences of vapor pressures of main components over 6H-
SiC (SiC-Si, ⋅  ⋅  -SiC-C).
414 Tairov
SiC s ⇔ [1/(1 ⫺ C p )] (Si 1⫺Cp C Cp )L ⫹ [(1 ⫺ 2C p )/(1 ⫺ C p )]C s

where C p ⫽ 0.19 is the molar part of the carbon in the melt at temperature T p . The liquidus
equation in the regular solutions approximation is
T l ⫽ (⫺∆H p ⫹ 0.76 ∆H m (c) ⫹ α L [0.19 ⫺ (C Lc )2 ⫺ (1 ⫺ C Lc )2]}/
{⫺∆S p ⫹ 0.76 ∆S m (c) ⫺ R ln 0.55 ⫹ R ln[(1 ⫺ C Lc )C Lc]}
where ∆H m (c) ⫽ 100 kJ/mol and ∆S m (c) ⫽ 24 J/(K mol) are the enthalpy and entropy of carbon
melting, respectively; ∆H p ⫽ 65 kJ/mol and ∆S p ⫽ 20.95 J/mol are the enthalpy and entropy
of the peritectic reaction; C Lc is the atom part of carbon in the melt at temperature T L; α L is the
interaction parameter of the components in the liquid phase; and R is the universal gas constant;
values of C Lc and α L are given in Fig. 3d and e. The activity coefficient of silicon in the solution-
melt at temperatures under 2400 K is equal to unity and at temperatures from 2600 to 3100 K
varies in the range 1.003 to 1.085. The native stoichiometric composition of silicon carbide
melt can exist at temperature 3460 K and pressure 1010 Pa. Reactions of SiC dissociative evapora-
tion (taking into account the main components of the gas phase) are
1. SiC s ⇔ Si g,s ⫹ C s ; k 1 ⫽ p Si
2. SiC s ⫹ Si g,L ⇔ Si 2C g; k 2 ⫽ p Si2C /p Si
3. 2SiC s ⇔ SiC 2g ⫹ Si g,L ; k 3 ⫽ p SiC2 p Si , where k 1 , k 2 , k 3 are equilibrium constants
The temperature dependences of the vapor pressures of the main components in the gas
phase for the temperature range 1300–3103 K are described by the equation
lg p i ⫽ A i ⫺ B i /T
The values of A i and B i for different systems are presented in Table 2. This equation describes
vapor pressure with good accuracy for the system SiC-Si. When approaching the temperature
of peritectic transformation T p the curves deviate from linear ones in the coordinates lg p ⫽
f (1/T) (Fig. 3f ). The silicon vapor pressure data presented are approximately two times higher
than the most reliable experimental data. Vapor pressures over other polytypes can be calculated
using the expression
lg p i(D) ⫽ lg p i(3C) ⫺ a j D
The values of a i are shown in Table 3. Vapor pressures of Si 2 C and SiC 2 according to
the constants of dissociative evaporation reactions depend on silicon vapor pressure. In order
to control the vapor composition over silicon carbide, it is extremely important to know the
equations
P Si2C ⫽ 2.85 10 2 exp(⫺1.79 ⫻ 10 4 /T)P Si
P SiC 2 ⫽ 9.41 10 28 exp(⫺14.35 ⫻ 10 4 /T)/P Si
Similar equations for vapor pressures over other silicon carbide polytypes can be defined
with the help of Table 3. The ratio of silicon and carbon concentrations in the gas phase, N Si /
N C , for most temperature values is greater than unity and can be estimated using the equation
C Si /C C ⫽ (P Si ⫹ 2P Si2C ⫹ PSiC2 )/(P Si 2 C ⫹ 2P SiC2 )
There are two types of deviations from the stoichiometric composition in the crystals of
silicon carbide polytypes. The first one is characterized by big deviations (Table 1), and it is
supposed that it is caused by structural regulation of silicon and carbon vacancies in the crystal
lattice. The SiC layers in cubic and hexagonal positions keep their composition in different
SiC Boule Growth
Table 2 Values of Constants in the Temperature Dependences of Vapor Pressures of Main Components Over 6H- and 3C-SiC Polytypes
6H-SiC-C 6H-SiC-Si 3C-SiC-C 3C-SiC-Si

Constant Si Si 2 C SiC 2 Si Si 2 C SiC 2 Si Si 2 C SiC 2 Si Si 2 C SiC 2
A1 12.74 15.10 15.98 10.82 13.23 18.05 12.89 15.35 16.11 10.82 13.28 18.18
B1 2.66 3.42 3.53 2.04 2.81 4.18 2.68 3.45 3.54 2.04 2.81 4.18
415
416 Tairov
Table 3 Values of a i Parameter for

Calculation of Components of Vapor Pressures
Over Different SiC Polytypes
ai SiC-C SiC-Si
a Si 0.75–6 ⫻ 10 /T 2
0.00
a SiC 2 0.38–3 ⫻ 10 2 /T 0.38
a Si 2C 0.75–9 ⫻ 10 2 /T 0.14
polytypes. This causes linear variation of the general composition, practical density, and other
physical-chemical parameters of crystals versus hexagonality (see Table 1). The second type of
deviation from stoichiometry has a small value 10 ⫺4 –10 ⫺3% (atomic) and is characterized by
the accidental distribution of silicon and carbon vacancies in the lattice. According to experimen-
tal data on 6H-SiC crystal quenching, the concentration of paramagnetic vacancies in the carbon
sublattice in the temperature range 1900–2450°C is
C vC ⫽ 1.5 10 20 exp(⫺∆W/kT)
where ∆W is the activation energy, equal to 2.1 eV.
Theoretical values for vacancy formation in the silicon and carbon sublattices are ∆W BSi ⫽
4.93 eV and ∆W vC ⫽ 2.92 eV, respectively; energies of antisite defect formation are ∆W SiC ⫽
3.2 eV and ∆W CSi ⫽ 2.9 eV. The experimental value of the carbon vacancy migration energy
is 1.2 eV for temperatures 1080–1300 K.
X-ray and practical density, lattice parameters a and c, interlayer distances c/n (n ⫽ num-
ber of layers in the unit cell), and enthalpy and entropy of formation (∆H°298 and S2°98 ) are pre-
sented in Table 1. Values of the chemical shift of the analytical line Sikα1.2 (W Sikα) in SiC poly-
types referring to pure silicon measured by X-ray spectral analysis are shown in Table 1. The
chemical shift of the analytical line observed in silicon carbide polytypes gives evidence of the
presence of positive charge on silicon atoms, values of which are given in Table 1. This charge
is caused by the fact that the carbon atom has greater electronegativity (2.5) than silicon (1.8).
An increase of the effective charge leads to increased ionicity of chemical bonds of polytypes
with increased hexagonality. This is caused by the difference in the coordinational spheres’
configuration. Ionicity of chemical bonding for SiC is 12% according to Poling.
Anisotropy of the temperature expansion coefficient for SiC polytypes at temperatures
100–1500 K is insignificant (α11 /α 芯 ) ⫽ 1–1.07. For some polytypes temperature dependences
α11 are known only for lattice parameter c/n and are described at temperatures 18–1000°C as
follows:
α3C ⫽ (3.2 ⫹ 4.1 ⫻ 10 ⫺3 t ⫺ 2.6 ⫻ 10 ⫺6 t 2 ) 10 ⫺6
α11 8H ⫽ (2.8 ⫹ 6.6 ⫻ 10 ⫺3 t ⫺ 3.8 ⫻ 10 ⫺6 t 2 ) 10 ⫺6
α11 6H ⫽ (2.3 ⫹ 8.9 ⫻ 10 ⫺3 t ⫺ 7.0 ⫻ 10 ⫺6 t 2 ) 10 ⫺6
α11 15H ⫽ (2.3 ⫹ 9.0 ⫻ 10 ⫺3 t ⫺ 7.9 ⫻ 10 ⫺6 t 2 ) 10 ⫺6
α11 10H ⫽ (2.8 ⫹ 6.6 ⫻ 10 ⫺3 t ⫺ 5.1 ⫻ 10 ⫺6 t 2 ) 10 ⫺6
α11 27R ⫽ (2.3 ⫹ 8.3 ⫻ 10 ⫺3 t ⫺ 6.7 ⫻ 10 ⫺6 t 2 ) 10 ⫺6
α11 4H ⫽ (2.9 ⫹ 4.6 10 ⫺3 t ⫺ 2.3 10 ⫺6 t 2 ) 10 ⫺6
Because of the absence of experimental data on α, one can suppose that α11 ⫽α芯 ⫽ α.
Table 4 Activation Energy and Frequency Parameters of Parabolic and Linear

Components of Oxidation Equation for (0001)C Facet of 6H-SiC
Atmosphere P H 2O(Pa) ∆W 1 (kJ/mol) R1 0 (nm 2 /c) ∆W 2 (kJ/mol) R2 0 (nm/c)
Wet oxygen 5 ⫻ 10 3 58.5 ⫾ 0.8 (2.0 ⫾ 0.2)10 3 276 ⫾ 13 (3 ⫾ 1)10 9
Dry oxygen ⬍10 62.7 ⫾ 0.8 (8.5 ⫾ 0.3)10 2 146 ⫾ 8 (3 ⫾ 1)10 4
Debye characteristic temperatures of polytypes, Θ D , obtained from the α temperature de-

pendences, are shown in Table 1.
Silicon carbide is chemically extremely stable. It does not interact with concentrated and
dilute acids, their mixtures, and water solutions of alkalides. The only exceptions are heated
orthophosphorous acid and a mixture of HNO 3 and HF. SiC interacts with chlor, melts of alkali
salts, and peroxides of alkali metals at the temperatures 400–900°C. SiC reacts with the vapors
of water and hydrogen at temperatures higher than 1500°C (Fig. 4). This is useful for crystal
etching and mass transfer intensification during vapor-phase growth of epitaxial layers. The
SiC etching rate in liquid and gaseous etchants depends on the crystallographic orientation and
conductance type of crystals. This fact is useful for facet identification, mesa structure produc-
tion, revealing p-n junctions, etc.
Dependences of thermal oxidation rates are of great importance for silicon carbide device
technology. It is not necessary to elaborate special technology for the oxidation of SiC monocrys-
tals. It can be carried out using silicon technology but at higher temperatures. In general, the
oxidation process can be described by a linear-parabolic equation.
h 2 /k 1 ⫹ h/k 2 ⫽ t
where h is the thickness of oxide layers; t is the oxidation time; k 1 ⫽ k 10 exp(⫺∆W 1 /RT) is the
constant of the equations parabolic component; and k 2 ⫽ k 20 exp(⫺∆W 2 /RT) is the constant of
the equations linear component.
The oxidation rate of (0001)C is 5–10 times higher than of (0001)Si in the temperature
range 1000–1300°C in dry and wet hydrogen flow at 15 liters per minute (Fig. 5). The oxidation
rate of other facets, for instance, (1120), has an intermediate value compared with {0001} facets.
The oxidation process of the (0001)C facet is limited by diffusion of the reaction components
through the growing oxide film. Hence the oxidation rate of this facet does not depend on the
crystal surface treatment, type and level of doping, or polytype structure. The constants of the
linear-parabolic equation for (0001)C oxidation are shown in Table 4.
The oxidation rate of (0001)Si is limited by chemical reactions at the oxide-SiC interface
and, for oxidation for more than 30 minutes, kinetic dependences became linear.
Values of the linear equation for 6H-SiC (0001)Si oxidation are shown in Table 5. The
oxidation rate depends on preliminary facet surface treatment, type of conductivity (the oxidation
Table 5 Activation Energy and Frequency Parameters of Oxidation

Equation for (0001) Si Facet of 6H-SiC Monocrystals
Atmosphere P H2O(Pa) ∆W 2 (kJ/mol) k 20 (Nm/c)

Wet oxygen 5 ⫻ 10 3
145.5 ⫾ 0.4 (9.5 ⫾ 0.15)10 2
Dry oxygen ⬍10 91.5 ⫾ 0.4 9.3 ⫾ 0.5
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Figure 4 6H-SiC etching rate dependences on the melt temperature for (a) different compositions and
(b) different planes. ● KOH ⫹ Na 2 O 2 (9: 1); 䊊 KOH ⫹ K 2 O 4 (9 : 1); ∆ KOH; 䊐 NaOH ⫹ Na 2 O 2
(9 : 1).
constant is 5% different for p- and n-type), and polytype structure. The hexagonality dependence
of the oxidation rate linear component (in nm/s) in dry hydrogen for (0001)Si is
k 2 ⫽ (10 ⫾ 0.5) exp{⫺[∆W 2 0 ⫹ (dW/dD)D]/RT}
where ∆W 2 0 ⫽ 89.0 ⫹ 0.4 kJ/mol—activation energy of 3C-SiC oxidation; dW/dD ⫽ (75 ⫾
1)102 J/mol. Differences in SiC polytype formation enthalpies can be estimated using this depen-
dence (Table 1). The parameters of the layers obtained on silicon carbide crystals by oxidation
are similar to those on silicon. The thickness of these layers can be estimated using color tests
elaborated for silicon.
Temperature dependences of the thermal conductivity coefficient (perpendicular to the c
axis) of 6H-SiC monocrystals for different doping levels are shown in Fig. 6.
The 3C-SiC microhardness according to Moos is 9.2 to 9.3 and it is strongly dependent
on facet and indenter orientation. Values of the microhardness according to Knoop are shown
in Table 6.
As follows from the 6H- and 3C-SiC microhardness temperature dependences, there is a
local phase transition at temperatures lower than 40°C and pressure about 29 GPa with the
formation of closely packed and more plastic phases. The activation energy of dislocation move-
Figure 5 Kinetic dependences of 6H-SiC oxide layer growth at 1180°C in dry oxygen (PH 2 O ⬍ 10
Pa) on (0001)C plane (curve 1) and (0001)Si plane (curve 2).
Figure 6 Temperature dependences of 6H-SiC thermoconductivity coefficient perpendicular to c-axis

(n- and p-concentrations in samples are for T ⫽ 293 K): (a) low temperatures; (b) high temperatures.
ment in 6H-SiC, equal to 1.7 ⫾ 0.1 eV, was estimated using this dependence in the temperature
range 500–1400°C. 6H-SiC has an exteremely high hardness, close to that of diamond, at tem-
peratures higher than 1300°C.
Destruction strain of bulk α-SiC monocrystals is lower than 0.98 GPa at room temperature.
This is due to the presence of defects. The strain for high-quality α-SiC whiskers is up to 21
GPa.
The stacking fault formation energy in 3C-SiC is 6.1 mJ/m 2 (3.1 MeV).
Table 6 SiC Microhardness According to Knoop at

20°C and 0.98 N Load
Indentor
orientation Microhardness
Polytype Facet to c-axis (GPa)
6H (0001) 储 (1010) 28.62
储 (1020) 28.98
(1010) 储 [0001] 20.89
芯 [0001] 27.03
(1120) 储 [0001] 23.45
芯 [0001) 27.03
3C (111) 储 [110] 26.00
芯 [110] 27.27
(001) 储 [110] 25.65
储 [100] 26.44
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Table 7 Mechanical Properties of Silicon Carbide

Properties Polytypes Value Temperature (K)
Shift modulus, GPa α 168 300
All-side press modulus, GPa α 96.1 300
Ung modulus, GPa α 385 300
350 1500
Plastic constants, ⫻10 2 GPa
C 11 6H 5.00 70–300
C 12 6H 0.92 70–300
C 33 6H 5.64 70–300
C 44 6H 1.68 70–300
C 66 ⫽ (C 11 ⫺ C 11 ) ⫻ 2 6H 2.04 70–300
C 11 3C 2.89 300
C 12 3C 2.34 300
C 44 3C 0.55 300
Pressing ability (up to 5 ⫻ 10 7Pa) 20.6 300
Some other important mechanical properties of silicon carbide are shown in Table 7.
Electronic and optical properties of silicon carbide are described in Ref. 1.
III. DIFFUSION AND SOLUBILITY OF DOPANTS IN SILICON CARBIDE
It is necessary to know the main components of self-diffusion coefficients for understanding of

diffusion in silicon carbide and a scientific approach to crystal growth technology. Temperature
dependences of self-diffusion coefficients of silicon and carbon in pure and doped n-type 6H-
SiC crystals obtained using isotopes 14C and 30Si are shown in Fig. 7. These dependences can
be written in the following form:
D i ⫽ D 0i exp(⫺W i /kT )
The parameters D 0i and W i are given in Table 8.

It is clear from Fig. 7 that the silicon self-diffusion coefficient in undoped crystals is
lower than in doped crystals. An opposite dependence was observed for the carbon self-diffusion
coefficient. According to the law of acting masses, the silicon vacancy (acceptor) concentration
increases with increasing donor dopant concentration (nitrogen). All this leads to an increase
in the diffusion coefficient in the presence of a vacancy mechanism of self-diffusion. Carbon
vacancies are donors, and their concentration decreases when the donor concentration is in-
creased. This leads to a decrease in the carbon self-diffusion coefficient.
The diffusive distribution of acceptor dopants has the following peculiarities:
1. Presence of near-surface (high concentration, low effective diffusion coefficients) and

volume (lower concentrations, high diffusion coefficients) regions (Fig. 8).
2. Presence of an abnormal layer on the border of volume and near-surface regions. This
layer is compensated p- and more often n-type in the case of Al and Be diffusion.
This layer is is low-doped and low-compensated (compared with neighboring ones)
p-type in the case of boron diffusion (Fig. 8).
Figure 7 Temperature dependences of 14 C qnd 30 Si self-diffusion coefficients in pure (curves 1, 4) and

nitrogen-doped (curves 2, 3) silicon carbide
Table 8 Parameters of Diffusion Coefficients of Different Atoms in 6H-SiC a

Coefficient, Activation
Element Temperature (K) D oi (sm 2 /S) energy (eV) Dopant concentration N
30
Si 2273–2563 (5.01 ⫾ 1.71)10 2
⫺7.22 ⫾ 0.07 Nitrogen 10 16 –10 17 cm ⫺3
30
Si 2273–2563 (5.01 ⫾ 1.71)10 5 ⫺8.18 ⫾ 0.10 Nitrogen 3 ⫻ 10 19cm ⫺3
14
C 2321–2453 (5.01 ⫾ 1.71)10 5 ⫺7.41 ⫾ 0.05 Nitrogen 10 16 –10 17 cm ⫺3
14
C 2321–2453 (5.01 ⫾ 1.71)10 7 ⫺8.20 ⫾ 0.08 Nitrogen 3 ⫻ 10 19 cm ⫺3
B 2273–2673 50.00 ⫺5.6 N s B ⱕ 3 ⫻ 10 18cm ⫺3
B(1) 1873–2823 3.20 ⫺5.1 N s B ⫽ (2–5) ⫻ 10 18cm ⫺3
B(T) 1873–2823 0.70 ⫺5.1 N S B ⫽ (2–5) ⫻ 10 18cm ⫺3
B* 1873–2823 0.12 ⫺3.4
Al 2073–2723 8.00 ⫺6.1 N s Al ⫽ (1–1.5) ⫻ 10 18cm. ⫺3 volume
region
Ga 2173–2623 0.17 ⫺5.5 ⫾ 0.02 N s Ga ⱕ (3–5) ⫻ 10 17 cm ⫺3
Be 1873–2573 0.3 ⫺3.1 N s Be ⬎ 2 ⫻ 10 18 cm ⫺3 volume region
Be 1873–2573 32.00 ⫺5.2 N s Be ⬍ 2 ⫻ 10 18 cm ⫺3 surface region
Be* 1873–2573 10 ⫺4 ⫺1.5 —
Li 1773–2473 1.2 ⫻ 10 ⫺3 ⫺1.7 —
O 2073–2623 11.00 ⫺6.9 N s O ⫽ (1–2) ⫻ 10 18
a
p-type crystal, volume region.
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Figure 8 Dopant concentration profiles for acceptor (Al, B, Be) diffusion in silicon carbide crystals
(hatched parts, compensated regions of the crystals).
3. Effective diffusion coefficients strongly depend on the annealing conditions of crys-

tals: N Si /N C ratio in the gas phase and on the surface, dopant concentration, presence
of a third component.
These pecularities are caused mostly by carbon vacancy (donor) generation near the crystal
surface and also by the formation of complexes by dopants and vacancies. Acceptor dopant
temperature dependences are shown in Fig. 9. Their parameters are given in Table 8.
Diffusion profiles of acceptor dopants have a standard form and can be described by one
diffusion coefficient when boron surface concentrations are low (N Bs ⬍ 3 ⫻ 10 18 cm ⫺3 ). Diffu-
sion profiles became more complicated with increasing boron concentration. A steep region
Figure 9 Temperature dependences of dopant diffusion coefficients in 6H-SiC.

Table 9 Ratios of Boron Diffusion Coefficients in Doped (N and Al) and Pure SiC
D BN /D Bi D BAl / D Bi
Temperature
(K) N N ⫽ 5 ⫻ 10 18 cm ⫺3 N N ⫽ 3 ⫻ 10 19 cm ⫺3 N Al ⫽ 5 ⫻ 10 19 cm ⫺3 N N ⫽ 5 ⫻ 10 18 cm ⫺3
2300 0.9 0.3 1.0 4.0
2150 0.6 0.2 3.0 10.0
1850 0.3 0.08 10.0 18.0
appears near the surface, and the diffusion rate increases significantly in the ‘‘volume’’ region
of the crystal. The volume region became stepwise at diffusion temperatures over 2100°C. It
is not possible to describe the near-surface region by one diffusion coefficient. Boron diffusion
is practically equal in polar directions [0001]C and [0001]Si. However, it is 1.2–1.3 times higher
in directions perpendicular to the c-axis. The rate of diffusion is slightly lower in the case of
diffusion perpendicular to dislocation lines. Boron diffusion in Al-doped p-type crystals is
higher, and diffusion to n-doped n-type crystals is lower than to undoped single crystals (N D-
N A ⬍ 10 17 cm ⫺3 ) (Table 9). Boron diffusion profiles depend strongly on the vapor phase compo-
sition. A significant increase (two to four times) in the diffusion coefficient is observed (espe-
cially in the near-surface region) with an N Si /N C ratio increase. In the volume region this effect
is not so strong. The rate of boron diffusion from the boron-doped epitaxial layer is lower than
from the vapor phase, especially at low values of N Bs . However, at N Bs close to the boron
solubility limit, a decrease of the diffusion coefficient is observed only in the near-surface region.
The boron diffusion coefficient also depends on the polytype.
The diffusion rate increases with decreasing polytype hexagonality in the row 4H, 15R,
6H, 21R, 8H, 3C (Fig. 10). All the characteristics described are in good agreement with the
vacancy diffusion model referring to boron atom–carbon vacancy complexes.
Aluminum diffusion distributions also have complicated profiles consisting of an abrupt
near-surface region and a less sharp volume region. Parameters of diffusion depend on surface
concentration, and there is a slight increase of the diffusion coefficient with decreasing Al con-
centration from 5 ⫻ 10 20 to 10 19 cm ⫺3 .
The rate of aluminum diffusion from the Al-doped epitaxial layer is lower than from the
vapor phase. It is assumed that Al diffuses via silicon vacancies.
The beryllium distribution at low concentrations (N Bes ⬍ 2 ⫻ 10 18 cm ⫺3 ) has the form of
a standard profile. At higher concentrations the Be distribution has a sharp form near the surface
Figure 10 Dependence of relative boron diffusion coefficient on polytype hexagonality.

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Table 10 Ratios of Beryllium Diffusion Coefficients in Doped (Nitrogen, Aluminum, Boron) and
Pure SiC
D NBe / D iBe D Be Be
Al /D i D BBe /D iBe
Temperature (K) N N ⫽ 4 ⫻ 10 19 cm ⫺3 N Al ⫽ 2 ⫻ 10 20 cm ⫺3 N B ⫽ 1.5 ⫻ 10 20 cm ⫺3
2323 0.6 40 10
2123 0.4 50 15
and a less sharp one in the volume region. Both of these regions can be described by an erfc
function.
In the near-surface region Be diffuses via carbon vacancies; in the volume region a sig-
nificant part of the dopant diffuses via interstitials as Be 2⫹ ions. This leads to high diffusion
coefficients and low activation energies of the process. Beryllium in the silicon carbide intersti-
tials is a donor. Diffusion of Be in SiC heavily doped with nitrogen is slightly slowed down.
Beryllium mobility is significantly higher in crystals doped with aluminum and boron (Table 10).
The diffusion coefficient of scandium is very low and for temperatures lower than 2673
K does not exceed 10–12 cm 2 /s.
As to donor dopants, only the diffusion of N, O, and Li has been investigated (see Fig.
9 and Table 8). The uncertainty in N diffusion coefficients is caused by problems of measurement
due to their low values. For instance, the N diffusion coefficient at 2550°C is about 10–12
cm 2 ⁄s.
Lithium has the highest diffusion coefficient among the investigated dopants. Lithium
diffusion is observed even at room temperature.
Ion implantation of SiC is also actively developed. This method is especially important
for SiC because of the high temperatures and durations of diffusion annealing. Also diffusion
of the most important dopant—nitrogen—is an extremely complicated problem. Now ion im-
plantation is used for doping with nearly all important donor and acceptor dopants. Parameters
of ion implantation with different ions are shown in Fig. 11. Radiation defect annealing is carried
out by either thermal (1400–1800°C) or laser annealing.
SiC crystal doping in vapor-phase crystal growth can be carried out with or without equi-
Figure 11 Dependence of the average run projection R p (a) and the average normal deviation of the
run projection ∆R p (b) in SiC on energy for different ions: 1, Be; 2, B; 3, N; 4, Al; 5, P.
Table 11 Limits of Dopant Concentrations in SiC Crystals Doped During Growth

Element T (K) Concentration Element T (K) Concentration
Li 2400 1.2 ⫻ 10 18 Ho 2600 6.0 ⫻ 10 16
Cu 2600 1.2 ⫻ 10 17 Ge 2600 3.0 ⫻ 10 19
Au 2600 4.9 ⫻ 10 16 Ti 2600 3.0 ⫻ 10 18
Be 2600 8.0 ⫻ 10 20 N 2500 5.0 ⫻ 10 20
B 2600 2.5 ⫻ 10 20 P 2100 2.8 ⫻ 10 18
Al 2600 2.0 ⫻ 10 21 As 2100 5.0 ⫻ 10 16
Ga 2600 1.8 ⫻ 10 19 Sb 2100 8.0 ⫻ 10 15
In 2600 9.5 ⫻ 10 15 Ta 2100 2.4 ⫻ 10 17
Sc 2600 2 ⫻ 10 17 Cr 2600 3.0 ⫻ 10 17
Y 2600 2.0 ⫻ 10 16 W 2600 2.5 ⫻ 10 17
Mn 2600 3.0 ⫻ 10 17
librium of dopant states in the source phase and in the volume of the crystal. The first case is
realized when growth rates are much lower than the diffusion rate in the crystal. In this case,
the dopant concentration depends only on the growth temperature and does not depend on the
growth rate and crystallographic orientation of the growing surface. The second case takes place
with growth rates comparable to dopant diffusion rates. In this case, the concentration of dopant
depends on the growth rate, temperature, and crystallographic orientation of the growth surface.
These cases can be described using the dopant distribution coefficient:
k ⫽ k 0 ⫹ (k s ⫺ k 0 ) exp(⫺v D /v)
where k 0 is the equilibrium distribution coefficient, k s is the ratio of the concentration of adsorbed
dopant atoms to their concentration in the vapor phase, v D ⫽ D/h is the dopant diffusion rate
in the crystal, D is the dopant diffusion coefficient, h is the thickness of a unit growing layer,
and v is the normal growth rate.
The same correlation governs concentrations of the main components (silicon and carbon)
and the deviation from stoichiometry of the growing crystal as a function of growth rate. Maxi-
mal concentrations of dopants achieved in silicon carbide are shown in Table 11.
Figure 12 Dependences of lattice parameter at 300 K (a), temperature linear expansion coefficient at
573–1073 K (b), and thermoconductivity coefficient (T ⫽ 300 K) (c) on (SiC) x (AIN)1⫺x solid solution
composition.
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IV. METHODS OF SILICON CARBIDE CRYSTAL GROWTH
Classical methods of crystal growth from melt are not applicable to silicon carbide because a
silicon carbide melt can exist only at extremely high pressure and temperature. Therefore meth-
ods of crystal growth from the vapor phase and from solutions in the melt are used. In the
second method Si; Si ⫹ Co; Si ⫹ Cr; and Si ⫹ rare earth metals Ge, Sn, Ga, Cr, Sc, Dy, Nd,
Pr, and others are used. Rates of growth from solutions in a melt are defined by the angles of
liquidus bending (Fig. 13). Using rare earth metals in the melting zone method, it is possible
to grow single crystals of 10 ⫻ 10 ⫻ 3 mm 3 with a growth rate over 1 mm/hr. But at such
growth rates droplets of melt are captured by crystals and the number of defects is increased. For
this reason, the method of growth from solution in a melt is used in silicon carbide semiconductor
technology only for epitaxial layer growth with low growth rates in order to avoid formation
of inclusions of the second phase.
There are three methods of vapor-phase growth:
1. Method of thermal decomposition of carbon-silicon–containing compounds in hydro-
gen on graphite at a temperature of about 1700–1800°C. For this purpose one can use silicon-
organic compounds that contain silicon and carbon in moleculas in a certain ratio [CH 3 SiCl 3 ,
(CH 3 )2SiCl 2 , CH 3 SiHCl 2 , etc.] or a mixture of components containing either silicon or carbon,
for instance, SiCl 4 and CCl 4 . In the last case it is possible to control the silicon-carbon ratio in
the vapor phase. With this method it is possible to grow α-SiC whiskers including 2H (with
length up to 3 mm and diameter up to 0.5 mm) and plates of 3C-SiC with basal plane (111),
hexagonal habitus, and dimensions up to 5–7 mm. The crystals obtained by this method have
a high defect density due to spontaneous nucleation. Low growth temperature and polyfacet
growth cause a sectorial distribution of dopants and probably of deviation from stoichiometry.
Because of these disadvantages, this method is used mostly for epitaxial layer growth for both
α-SiC and 3C-SiC.
2. Sublimation method with spontaneous nucleation (mass crystallization). Crystal
growth is carried out in cylindrical graphite crucibles (Fig. 14). Powder silicon carbide is used
as a source material. Crucibles are heated in cylindrical furnaces with resistive or inductive
heating. Growth proceeds in an inert atmosphere (argon, helium) at a temperature of 2500–
Figure 13 Silicon carbide solubility in low-temperature (a) and high-temperature (b) solvents: 1, Yb;
2, Sn; 3, Ge; 4, Ga.
Figure 14 Growth cell for SiC spontaneous growth. 1, graphite cylinder; 2, source material; 3, inside
graphite cylinder.
2600°C. Nucleation takes place both on the inside surface of the crucible and, most probably,
on silicon carbide grains in holes on the inside part of the crucible (Fig. 14). Crystals are obtained
in the form of plates with basal plane (0001) and a hexagonal habitus. Most of the crystals have
across dimensions of about 3 mm; some of them reach 30 mm. Crystals have a large scatter
(comparing different crystals or different parts of the same crystal) of dopant concentrations
and dislocation densities due to polyfacet growth and spontaneous nucleation. Every crystal
contains one or more disordered layers of thickness 4–50 µm parallel to the basal plane (0001).
There is also a big scatter in polytypes among one set of crystals. Moreover, crystals often have
different polytype structures on different sides from the disordered layer.
One method of this type is direct synthesis. In this case silicon is loaded in the low-
temperature part (2000–2200°C) of the crucible. Silicon vapors react with the crucible walls
and form Si 2 C, SiC 2 , and SiC molecules. These molecules form nuclei of silicon carbide crystals
and then crystal growth takes place. This method also has disadvantages mentioned above.
3. Sublimation method with seeded growth. The main advantage of this method is the
control of crystal nucleation (Fig. 15). Mass transfer is formed by the flows of the gas-phase
components Si, Si 2 C, and SiC 2 . These components are formed in the first stage by decomposition
of polycrystalline source material. In the next stage silicon vapor, which has the highest pressure,
interacts with colder graphite walls of the crucible and forms additional components SiC 2 and
Si 2 C:
C s ⫹ 2Si g ⫽ Si 2 C g 2C g ⫹ Si g ⫽ SiC 2g
So silicon transfers carbon in Si 2 C and SiC 2 molecules, and the graphite crucible is a
source of carbon and takes part in the formation of flows to the growing crystal. Crystal growth
is carried out in vacuum or an inert atmosphere (argon, helium) sometimes with additional
hydrogen at a temperature of 1800–2600°C. Mass transfer and growth rate are controlled by
the inert gas pressure. This is a very efficient method (growth rate up to 10 mm/h). Crystal
lengths and diameters are 50 mm or more, and there are no significant limitations to further
enlargement of crystals. Doping levels are controlled by controlling the amounts of dopants in
the source material or gas phase. For instance, concentrations of important donor and acceptor
dopants can be varied in the range 10 16 –10 21 cm ⫺3. It is possible to grow single crystals of
silicon carbide–alluminum nitride solid solution using the mixture (SiC) x (AlN)1⫺x as the source
material.
Detailed investigations of the process of mass transfer of SiC vapor in vacuum and differ-
ent gaseous media (argon, helium, hydrogen, carbon oxide) showed that it is possible to produce
428 Tairov
Figure 15 Growth cells for SiC crystal growth: (a) in patterned graphite channels; (b) in thin-wall graph-
ite crucible; (c) under pulling out of crucible.
bulk SiC single crystals at as low a temperature as 1800°C provided the process is performed
in vacuum. Depending on the composition and pressure of the gaseous medium in the growth
region, production of SiC single crystals with rather high deposition rates (up to 1–10 mm/h)
is possible in the temperature range 1800–2600°C. We note the most important features of the
method developed.
The main stages of bulk SiC single-crystal growth are the following: dissociative sublima-
tion of an original charge, mass transfer in the gas phase, and crystallization onto a seed. Figure
16 shows a growth cell schematically.
Figure 16 Growth cell for growing bulk SiC single crystals. Reactions of charge dissociations:SiC(s)
→ 1/2Si 2 C(v) ⫹ 1/2C(s); SiC(s) → 1/2 SiC 2 (v) ⫹ 1/2Si(v). Reactions on the crucible surface: C(s) ⫹
2Si(v) → Si 2 (v); 2C(s) ⫹ Si(v) → SiC 2 (v).
Investigations of SiC source sublimation in growing crystals and epitaxial layers demon-
strated that the composition of the vapor phase, in particular the ratio of silicon to carbon atoms,
N Si /N C , depends significantly on the preparation conditions and polytype composition of the
original source. If the charge is obtained by milling previously synthesized SiC cakes, the total
pressure of vapor and the ratio N Si /N c in the vapor phase are a strong function of the size of
the charge grains (Fig. 17). This phenomenon can be accounted for in terms of the mechanical
activation of chemical processes.
The plastic strain of a material during milling results in accumulation of an energy H,
whose value can be estimated as ∆H ⫽ E(∆a/a)V where E ⫽ 3 ⫻ 10 11 Pa is Young’s modulus
of silicon carbide, ∆a/a is the relative variation of the lattice parameters caused by strain, and
V is the molar volume of SiC.
Since Young’s modulus of SiC is large and molecules containing both silicon and carbon
are present in the vapor phase, shift of the reaction equilibrium due to the appearance of marked
additional free energy leads to variation of the ratio of silicon to carbon atoms in the vapor.
The increase in defectiveness of SiC grains with increasing milling duration and, accordingly,
with decreasing grain fraction size (8,9) was established by electron spin resonance (ESR) and
X-ray measurements of the powder lattice parameters. The values of N Si /N C calculated on the
basis of the measurements made are in good agreement with the experimental results (see Fig.
17). This, in turn, affects the mass transfer rate and can result in the formation of a silicon melt
film on the crystal surface and thereby induce the vapor-liquid-solid (VLS) growth mechanism,
which can influence the polytypism of growing crystals as well as the concentration of point
and linear defects. All these phenomena are observed experimentally (10–13).
In addition to mechanochemical activation of the original charge, the polytype structure
of the charge powders exerts an influence on the partial pressure of vapor components and,
consequently, the ratio N Si /N C in the vapor phase. From the results for precision oxidation of
SiC crystals of various polytype structures, the thermodynamic characteristics of the polytypes
have been evaluated, from which the partial pressures of basic components of the vapor phase
were calculated as a function of the degree of hexagonality of the polytype D (14). Within error,
the experimental results agree reasonably well with the calculated data.
As a result of studies of vapor compositions above the SiC charge, a basic conclusion
Figure 17 Temperature dependence of the ratio of Si and C atoms in the vapor phase on the grain size
of the original charge (dissociative process occurs in vacuum). Grain dimensions: (䉭) 0.065–0.2 mm; (䊊)
0.2–1 mm; (䉲) 2–3 mm.
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can be drawn: reproducible production of the SiC single crystals of a specified shape, growth
rate, polytype and dislocation structure, stoichiometric composition, doping level, etc. requires
careful control of the preparation of the original source and its composition. During research
on the mass transfer of SiC vapor from the source to the seed in a growth cell with graphite
walls, it was established that graphite can act as a catalyst. The main point of the phenomenon
is as follows. In dissociative sublimation of the charge, the vapor phase is enriched with silicon
atoms, i.e., N Si /N C ⬎ 1. When the vapor interacts with the graphite walls of the growth cell,
the excess silicon atoms are bound to carbon atoms. This raises the value of N C in the vapor
phase and, accordingly, increases the mass transfer rate, since one of the limiting conditions of
mass transfer when N Si /N C ⬎ 1 is the transport of the carbon component.
At a low crystal growth temperature, 1800°C, when N Si /N C ⬎ 1 the graphite walls of the
growth cell exhibit maximum catalytic properties, but they do not show them at 2600°C (by
the Lely method), because at these temperatures N SiC /N C approaches unity. Thus, in the method
we have developed the shape of the growth cell and the mutual arrangement of the growing
crystal and graphite walls permit precise control of the effectiveness of bulk SiC crystal growth
processes. Using this phenomenon, it is possible to control the processes of enlargement and
profiling of single crystals by varying the graphite cell geometry and, accordingly, the mass
transports of vapor phase components toward the growing crystal. In addition, this effect enables
us to lower the growth temperature, to obtain epitaxial layers at temperatures up to 1300°C.
The processes of SiC crystal growth can be intensified, making use of the effect of the
difference in the pressures of vapors above the SiC polytypes. An alternative implementation
of this effect is the joint growth of a single crystal of α-SiC (on seed) and of a polycrystal of
3C-SiC (on graphite) by condensing supersaturated vapor (Fig. 18). Under particular conditions
nucleation occurs on graphite. The curves of the growth rate of the [0001]-oriented single crystal
and the polycrystal versus supersaturation are shifted relative to each other owing to heteroge-
neous nucleation on graphite and are represented in Fig. 19. The value of the critical supersatura-
tion σ cr is dependent on the temperature, the conditions of graphite preparation, and a number
of other factors. Figure 19 shows the dependences of this effect. The variation in supersaturation
between the vapor source and graphite substrate was produced by changing the distance between
the source and substrate at a temperature gradient of 20°C/cm. With an increase in process
temperature, the critical distance, and consequently the critical level of supersaturation below
which deposition of SiC onto graphite is not observed, is seen to be reduced. At values of
supersaturation up to α cr , the single crystal leads to growth of polycrystal and will enlarge over
the area owing to the tangential component of the growth rate. Hence, because of its defects
and metastable structure, the 3C-SiC polycrystal deposited on graphite exhibits a higher vapor
pressure than the σ-SiC single crystals growing nearby do at the same temperature. So, the 3C-
SiC polycrystal is a side source of vapor for growing single crystals. When the front of single-
crystal growth lays behind the front of polycrystal growth, the polycrystal is enlarged because
Figure 18 Joint growth of SiC single crystals and polycrystals.

Figure 19 Growth rate of SiC single crystals and polycrystals versus supersaturation.
of substitution of the single crystal. Also, the single-crystal parts that are closer to the polycrystal
are fed better then the center, resulting in the formation of a pit in the center of the growing
crystal. If the growth rate of the single crystal drastically exceeds that of the polycrystal and
the single crystal begins to project above the polycrystal by a considerable height, the feed to
the periphery of the growth front deteriorates because it is distant from the polycrystal, which
gives rise to loss of stability of the flat growth front of these parts and faceting of the single
crystal. In particular, in growing the [0001]-oriented crystal, faceting occurs with pyramid faces
of type (1011), (1012), etc. This in turn eliminates further enlargement of the single crystal.
The best results are observed at the ratio V p /V s ⫽ 0.95–0.98.
The investigation of vapor deposition and crystallization on seeds has revealed the follow-
ing features. Because with dissociative components in the vapor phase N Si /N C ⬎ 1, whereas with
crystallization on seed the crystal has a more nearly stoichiometric composition, accumulation of
silicon atoms can take place in the vapor phase in a quasi-closed system, which both retards
mass transfer and leads to the formation of a silicon melt on the growing surface of the film.
As silicon is an SiC solvent, the creation of a melt film results in the vapor-liquid-solid (VLS)
growth mechanism. Theoretical and experimental studies of these processes (10) indicated that
the formation of a silicon melt film depends on the closure (quasi-closure) of a system as well
as on its volume, temperature, gaseous medium, and type of vapor source (single crystals, pow-
der, the polytype, and mechanical activation of the powder). Figure 20 represents the experimen-
tal dependence of the deposition rate of silicon film growing epitaxial SiC layers in a sandwich
system in a vacuum of 10 ⫺2 Pa in the temperature range 1800–2100 K at a difference in tempera-
ture between the SiC crystal vapor source and the crystal substrate of 0.5–3 K. The gap between
the source and the substrate amounted to 3 µm, and the sandwich on the edges was sealed with
dense carbon residue, formed as a result of phenolformaldehyde resin film annealing. From the
dependence it is seen that under the given conditions the crystal growth follows the VLS mecha-
nism at temperatures below 2030 K and the vapor-solid (VS) mechanism above this. As already
mentioned, the temperature of this boundary between growth mechanisms is dependent on the
parameters of the growth process.
The base and impurity compositions of crystals are influenced by the crystal growth kinet-
ics. Growth by sublimation is performed at rather low temperatures, below 0.7 T m . In addition,
the normal growth rates are considerably higher than those of self-diffusion of the components,
i.e., of silicon and carbon, in the lattice. It follows that SiC crystal growth takes place in the
432 Tairov
Figure 20 Experimental dependence of the deposition rates of SiC and Si on temperature.
absence of equilibrium between the crystal bulk and vapor phase, which leads to the dependence
of the base composition of the crystal on its growth rate. The investigations undertaken have
confirmed these considerations (14). Figure 21 shows the dependence of the difference between
the equilibrium (C Si and C C ) and real (C Si and C C ) concentrations of silicon and carbon in 4H-
SiC crystals on their reverse growth rate. The coefficients of silicon and carbon self-diffusion
Figure 21 Deviation from stoichiometry in SiC crystals versus the growth rate.
in the lattice determined from the slope of the curves agree closely with the data reported in
Ref. 15. Again, regular variations in lattice parameters, crystal density, and luminescent proper-
ties sensitive to point defects (13) are observed. Similar regularities, but now for the impurity
composition, are also observed for slowly diffusing impurities of nitrogen and aluminum. The
N or Al doping yields a specific crystal color (green or blue, respectively), and when a visual
sectorial nonuniformity over the base composition of crystals can be observed, when growing
faceted crystals, or when growing epitaxial layers on different crystallographic planes of seeds,
this is observed indirectly in terms of electrophysical properties [manifested more distinctly in
luminescent properties (13)]. Thus, for producing uniform SiC crystals (over the base and impu-
rity compositions) it is necessary to achieve one-face crystal growth.
We now consider the problems connected with control of the polytype structure of the
crystals being grown. As a result of investigations of the nature of polytypism (14), the following
methods of controllable production of crystals and layers of specified polytype structure have
been developed: (a) growth under close-to-equilibrium conditions of the desired polytype struc-
ture on the faces of seeds able to transfer structural information and (b) the formation of the
specified polytype strucure by control of the growth kinetics in the initial stage of crystallization.
Let us briefly characterize these methods.
In growing SiC crystals on seed with different crystallographic orientations in both ‘‘va-
por-bulk crystal’’ equilibrium conditions (the normal growth rate is much less than that of the
component diffusion) and ‘‘vapor-growth surface’’ equilibrium conditions, it was shown that
all faces of the seed except (0001)C exhibit good stability for structural information transfer.
On the basis of the investigations undertaken, a bank of SiC seeds of various polytype structures
has been created. In this case the growth of a crystal or epitaxial layer of a desired polytype
structure is conducted on seeds of the same polytype structure on the (1100), (1120) faces or
on the planes deflected from (0001)C by a small angle (up to 10°). The angle is determined
mainly by requirements of the morphology of the growing space:
Control of the polytype structure of the crystals and layers grown using the crystallization
kinetics is applied when it is necessary to develop heteropolytype structures, i.e., on seeds of
one to obtain a layer of another polytype stucture or in the process of crystal growth changing
periodically the polytype structure of the growing crystal. To change the polytype structure of
a growing crystal it is necessary, according to conclusions on the nature of polytypism (16) to
provide conditions in the crystal for initiating solid-phase transition in the initial stage. The
solid-phase transition can be initiated by mechanical stresses, e.g., by virtue of the layer-by-
layer change in the base or impurity composition of building up layers and, accordingly, lattice
parameters. To control the base composition of a growing crystal, the growth should take place
at rates comparable to or greater than the diffusion rate of the base components, silicon and
carbon. Consider the example of experimental implementation of this method.
SiC single crystals were grown on the (0001)C face of chemically well etched seeds of
6H-SiC. In order to outgas the graphite armature of the furnace, it was heated in vacuum at
1500°C and then argon was introduced into the furnace up to a definite pressure P 0 . Further
heating of the furnace was carried out up to the growth temperature T 0 . The value of argon
pressure P 0 was chosen so that the rate of SiC vapor diffusion mass transfer in argon and the
rate of crystal growth were negligibly small. Then argon was pumped off down to a certain
pressure P 1 defined by the rate of crystal growth. In the simplest pumping out, the variation in
argon pressure with time follows an exponential law with time constant τ. Because in an argon
atmosphere the crystal growth is limited by the rate of vapor diffusion mass transfer, during
pumping out the rate of crystal growth will be inversely proportional to the argon pressure and
hence will also follow an exponential law with time.
The growth temperature T 0 and operating growth rate were chosen such that the self-
434 Tairov
diffusion rate of silicon in SiC was three to five times less than the growth rate. On pumping
out with an increase in growth rate up to the operating level, the crystal layers building up have
a different ratio N Si /N C and, accordingly, different lattice constants. As a result, a layered struc-
ture is produced with composition and lattice parameter gradients normal to the growth surface,
which, along with the seed, forms a stressed composition. When the value of the shear stress
is reached, the solid-phase transition occurs in this composition, resulting in the formation of
dislocation centers on the growth surface, step sources defining the further growth of a crystal
of a certain polytype structure. Figure 22 represents the dependences of the polytype structure
yields in the initial stage of growth on the pumping time constant τ for T 0 ⫽ 2220 K, P 0 ⫽ 4
⫻ 10 4 Pa, and P 0 ⫽ 10 ⫺1 Pa. The yield S/S 0 is the ratio of the area S of an initial crystal layer
of a particular polytype to the entire area of the growing crystal S 0 . The averaged value for four
crystals growing simultaneously corresponds to each point of Fig. 7. The spread in values of
S/S 0 did not exceed 20% from crystal to crystal. As the crystal is growing, enlargement of
the main polytype modification takes place at the expense of the accompanying modifications,
depending on the value of vapor supersaturation. As a consequence, a crystal of only one poly-
type structure is formed at appropriate values of τ and supersaturation. With fast pumping out,
i.e., at small values of τ, the 4H-SiC structure is primarily formed. With slow pumping out,
i.e., at large values of τ, crystals of polytype modification 3C-SiC are grown. At intermediate
values of τ the growth of 6H-SiC crystals occurs. If required to produce a crystal of a layer-by-
layer structure with alteration of different polytypes, in particular for obtaining periodic polytype
structures, the crystal growth process is interrupted periodically by introducing argon up to
pressure P 0 , and then the pumping process is repeated again with the desired value of τ. If it
is necessary to obtain local epitaxial heteropolytype structures, the surface of the seed crystal
is treated in advance according to a specified topological pattern (e.g., by polishing with diamond
paste, by particle irradiation, by impurity deposition). For this problem we choose the boundary
value of τ between the polytype structures needed for a heteropolytype composition. The impu-
rity (N, Sc, Al, group IV elements Ge, Sn, Pb, etc.) doping of growing layers results in a signifi-
cant change in the shape of the kinetic diagram shown in Fig. 22 and the appearance of more
complex polytype structures. This is due to a different influence of doping impurities on the
lattice and, accordingly, the energy of packing defect formation during solid-phase transition
in the initial stages of crystallization. Also, it was established that the more the covalent radius
Figure 22 Dependences of SiC crystal yield of 3C, 6H, and 4H polytypes on the deposition kinetics
in the initial stage of growth.
of the impurity differs from that of the substituted atom (of silicon or carbon), the lower its
solubility in Si; at smaller concentrations of impurity an influence on the polytype structure of
the layers being grown is observed. As a rule, the most dramatic effect of the impurity is mani-
fested when its concentration is close to the solubility limit in the SiC lattice. Analysis of the data
reported in the literature on the influence of the impurity on the polytypism in other materials, in
particular, in metals (14), has revealed a similar tendency.
The possibility of device fabrication based on SiC depends on defects such as micropipes
in crystals and layers. Hence the investigation and control of the problem of micropipes are of
extreme significance. The first step of our laboratory in this direction is to study the micropipe
behavior in 6H-SiC single crystalls under high-temperature annealing (19).
REFERENCES
1. YM Tairov, VF Tsvetkov. In: VP Korizkiei, VV Pasynkov, BV Tareev, eds. Reference book on

Electrotechnical Materials. Vol 3. Moscow: Energoatomizdat, 1986, pp 446–457.
2. A Lely. Ber Dtsch Keram Ges 32: 229, 1955.
3. YM Tairov. Rost Krist 6:199, 1965.
4. DR Hamilton J Electrochem Soc 105:735, 1958.
5. WF Knippenberg. Philos Res Rep 18:16, 1963.
6. YM Tairov, VF Tsvetkov. Silicon Carbide 1973:146, 1973.
7. YM Tairov, VF Tsvetkov. Rost Krist 13:14, 1980.
8. YM Tairov, AA Kalnin, NA Smirnova. Neorg Mater 9:125, 1973.
9. VA Ilyin, VI Kolynina, YM Tairov, VF Tsvetkov. Zh Prikl Khim (J Appl Chem Sov) 5: 1205, 1987.
10. YM Tairov, EG Ivanov, VF Tsvetkov. Neorg Mater 21:588, 1985.
11. F Raihel, YM Tairov, TVF Travadzhyan. Neorg Mater 16:1011, 1980.
12. YM Tairov, MA Chernov, VF Tsvetkov. Kristallogr (Crystallogr Sov) 24:772, 1979.
13. LI Levin, YM Tairov, VF Tsvetkov. Tech Poluprovodnikov (Phys Tech Semicond Sov) 14:1194,
1984.
14. YM Tairov, VF Tsvetkov. In: Progress in Crystal Growth and Characterization. Vol 7. London:
Pergamon, 1983, p 2485.
15. JD Hong, RF Davis. J Mater Sci 16:2485, 1981.
16. JE Gegusin. Physics of Sintering. Moscow: Nauka, 1984, pp 149–234.
17. JD Hong, RF Davis, DE Newberry. J Mater Sci 16:2485–2494, 1981.
18. DL Barret, JP McHugh, HM Hobgood, RH Hopkins, PG McMullin, RC Clarke, WJ Choyke. J Cryst
Growth 128:358–362, 1993.
19. AS Bakin, SI Dorozhkin. Transactions Second International High Temperature Electronics Confer-
ence (HiTEC) Charlotte, NC, June 5–10, 1994, p 169.
19
Epitaxial Growth, Characterization, and
Properties of SiC
Sadafumi Yoshida
Saitama University, Urawa, Saitama, Japan
I. INTRODUCTION
There is no SiC crystal in the natural world except in meteoric stones. However, historically,
SiC is rather an old semiconductor, which has been known since the beginning of the 19th
century. Since Acheson succeeded in synthesizing SiC powder industrially in 1892, SiC has
been used as a grinding powder and for high-temperature heaters and firebricks because of its
thermal and chemical stability and hard nature. However, research on SiC as a semiconducting
material started after the development in 1955 of the Lely method, by which high-purity single-
crystal platelets of SiC can be obtained. In the 1960s and 1970s, physical and chemical properties
of SiC were studied using Lely crystals and their excellent properties for electronic and optical
device applications were shown. Based on these properties, many attempts have been made to
fabricate devices (1,2). However, because it was difficult to make electronic devices using small
Lely crystals in industry, the research on SiC declined in the latter half of the 1970s. In the
early 1980s, two important advances were made to break through the problems of SiC research,
which again stimulated the research on SiC. As a result, SiC has attracted much interest again
since the middle of the 1980s. One is the development of a growth method for large-area 3C-
SiC epilayers on Si substrates by chemical vapor deposition. The other is the growth of bulk
SiC, which makes it possible to obtain SiC wafers. By using homoepitaxially grown layers of
6H and 4H-SiC and heteroepitaxially grown layers of 3C-SiC, more precise studies of the proper-
ties of SiC have been done (3), as well as the fabrication of electronic devices, such as diodes
and transistors, and optical devices, such as light-emitting diodes and optical detectors.
In this chapter, the epitaxial growth techniques are reviewed in Sec. II, the characterization
of single crystals and epilayers is discussed in Sec. III, and finally the physical properties of
SiC are summarized in Sec. IV.
II. EPITAXIAL GROWTH

SiC has been grown epitaxially by the methods of liquid-phase epitaxy (LPE), chemical vapor
deposition (CVD), and molecular beam epitaxy (MBE). Because the epitaxial growth tempera-
ture of SiC is very high compared with other semiconductors, the materials suitable for the
substrates are restricted to refractory crystals. SiC itself (homoepitaxial growth) and other materi-
als, such as Si and TiC (heteroepitaxial growth), have been used as substrates.
437
438 Yoshida
Figure 1 Schematic diagram of the dipping method for liquid-phase epitaxy (LPE) growth of SiC.
A. Methods of Epitaxial Growth

1. Liquid-Phase Epitaxy (LPE)
As a liquid phase of SiC cannot exist under atmospheric pressure, LPE of SiC has been carried
out using the dissolution of SiC into molten metals, such as Fe, Ni, or Cr (4,5). However, SiC
crystals grown from metal solution contain a high density of metal impurities. Comparatively
high purity 6H-SiC crystals have been grown using the Si–Sc–C system (6). To avoid uninten-
tionally doping with impurities, Si solution has been used (7), although the solubility limit of
carbon in Si is not so high, for example, compared with Si–Fe alloy solution (8).
When Si is melted in a graphite crucible, carbon atoms dissolved in the higher temperature
part of the crucible are transferred toward the lower temperature part by thermal convection
and supersaturated carbon reacts with Si to form SiC on the substrates immersed in the Si melt.
Usually, α-SiC (6H-, 4H-, and 15R) itself is used as a substrate material for the growth of α-
SiC. The dipping method (9), in which SiC substrates are dipped in Si melt to grow SiC and
then pulled up, has been used. Figure 1 shows a schematic diagram of the dipping method for
the LPE growth of SiC. Growth rates are typically in the range between 5 and 12 µm/h at a
Epitaxial Growth of SiC 439
substrate temperature of 1600°C. Unintentionally doped epilayers show n-type conduction. P-

type epilayers are obtained by adding Al into Si melt. Low conductivity n-type epilayers are
grown in an N 2 atmosphere. Using three crucibles, for the growth of p-type and n-type layers
and for rinsing, epilayers with pn junctions can be obtained. This method has been used to
produce SiC light-emitting diodes (10).
2. Chemical Vapor Deposition (CVD)

For the growth of SiC by CVD, many kinds of reaction gases have been used (11). As the
source gas for Si, SiH 4 , SiH 2 Cl 2 , SiHCl 3 , and SiCl 4 have been used. As the source gas for
carbon, hydrocarbon gases such as CH 4 , C 2 H 6 , C 3 H 8 , C 2 H 4 and C 2 H 2 have been used. As single
source gases for SiC growth, organosilane gases having Si–C bonds, such as methyltrichrolosi-
lane CH 3SiCl 3 (12) and silacyclobutane c–C 3 H 6SiH 2 (13), have been reported. Hydrogen is
usually used as a carrier gas. Figure 2 shows a schematic diagram of a CVD system for the
growth of SiC. A graphite plate coated with SiC is used as a susceptor and heated inductively
by a radio frequency (RF) generator. SiH 4 diluted with H 2 or 100% SiH 4 , C 3 H 8 diluted with
H 2 or 100% C 3 H 8 , and H 2 carrier gas purified by a palladium-silver alloy cell are introduced
into a water-cooled, quartz reaction tube previously evacuated to a vacuum below 10⫺6 torr.
The flow rate of each reaction gas is controlled by using a mass flow controller. For doping,
Al(CH 3 ) 3 (trimethylaluminum, TMA), Al(C 2 H 5 ) 3 (triethylalumium, TEA) (14), or B 2 H 6 for p-
type dopant and N 2 or NH 3 for n-type dopant are added in the reaction gases. The amount of
TMA(TEA) is controlled both by the H 2 flow rate for bubbling TMA(TEA) and by the tempera-
ture of a TMA(TEA) cylinder. Usually, CVD has been carried out at atmospheric pressure.
Reduced-pressure CVD has been reported to improve the thickness uniformity of the epilayers
(15). Growth by alternative supply of SiH 2 Cl 2 and C 2 H 2 has also been reported to reduce growth
temperatures (16).
A typical growth temperature for 3C-SiC is 1300–1400°C and for 4H and 6H-SiC, 1600–
1800°C. By using off-axis (0001) SiC substrates, the epitaxial growth temperature for α-SiC
has been reduced to around 1500°C, which will be described in Sec. II. B on homoepitaxy.
High-temperature CVD growth at around 1800–2300°C (HTCVD) has been reported (17). Very
high growth rates, as high as 0.5 mm/h, have been achieved by HTCVD, whose growth mecha-
nism may include usual chemical vapor transport and sublimation.
3. Molecular Beam Epitaxy (MBE)

The MBE technique attracts much interest because of its low growth temperatures compared
with LPE and CVD and its feasibility of in situ observation of crystal structures during growth.
As sources for Si and C, Si and C molecular beams obtained by thermal evaporation of solid
Si and C have been used (18). An electron beam gun is used for the evaporation of carbon.
Instead of solid sources for carbon, gas sources such as C 2 H 4 and C 2 H 2 have also been used,
which is called gas source MBE (19). In the case of using Si and C solid sources, as sticking
coefficients of Si and C at around 1000–1200°C are both almost unity, it is hard to control
the stoichiometric composition of the films deposited. On the other hand, in the case of using
hydrocarbon as a C source, films with stoichiometric composition can easily be obtained, be-
cause, at around 1000°C, these hydrocarbon molecules do not dissociate thermally, but react
only with Si to form SiC and the remains reevaporate. For an Si source, gas sources such as
Si 2 H 6 and SiHCl 3 have been used (20).
To realize atomic layer epitaxy, it is important to study the surface structures under an
Si source beam and a C source beam. 3C-SiC (001) surfaces were investigated by medium
energy ion scattering spectroscopy (MEISS), Auger electron spectroscopy (AES), low-electron
440
Yoshida
Figure 2 Schematic diagram of a chemical vapor deposition (CVD) system for the growth of SiC.
energy diffraction (LEED), and scanning tunneling microscopy (STM) (21). Several kinds of
surface structures, i.e., surface reconstruction patterns, have been reported (22). 3C-SiC surfaces
were cleaned with an Si beam at 900°C, at which oxides evaporate by the reaction with an Si
beam. Then a (3 ⫻ 2) surface reconstruction pattern was observed. After stopping the Si beam,
the surfaces were heated up to 1065°C and kept at this temperature in high vacuum below 10⫺10
torr. The surface structure changed from (3 ⫻ 2) to c(2 ⫻ 2) via (5 ⫻ 2), (2 ⫻ 1), and (1 ⫻
1). By Auger electron spectroscopy, the surface with (3 ⫻ 2) is assigned as Si terminated and
that with c(2 ⫻2) as C-terminated. Figure 3 is an STM image of a 3C-SiC (001)-(3 ⫻ 2) surface.
Each oval-shaped atom group consisting of the whole surface is the (3 ⫻ 2) unit cell, which
includes the Si dimers, that is, four Si atoms. When an Si 2 H 6 beam was applied to a c(2 ⫻ 2)
C-terminated surface, the Si/C AES peak ratio increased with exposure time and the surface
structure changed from c(2 ⫻ 2) to (3 ⫻ 2) via (1 ⫻ 1) and (2 ⫻ 1), which shows that the
surface became Si-terminated. When the surface shows (3 ⫻ 2) structure, the Si/C ratio saturates,
as shown in Fig. 4a, which indicates self-limiting of Si monolayer absorption. On the contrary,
when a C 2 H 2 beam was supplied to a (3 ⫻ 2) Si-terminated surface, the Si/C AES peak ratio
decreased with exposure time and the surface structure changed from (3 ⫻ 2) to c(2 ⫻ 2), which
indicates that the surface became C terminated. When the surface shows c(2 ⫻ 2) structure, the
Si/C ratio saturates as shown in Fig. 4b, which also indicates self-limiting of C monolayer
absorption. These results suggest the possibility of atomic layer epitaxy of SiC by alternative
supply of Si 2 H 6 and C 2 H 2 .
It has been reported that epitaxial growth temperature can be reduced to around 800°C
by using a mass-separated C⫹ ion beam (23) or a C-related beam from a C 3 H 8 thermal cracker
cell (1200°C) (24).
Figure 3 Scanning tunneling microscopy (STM) image of a 3C-SiC (001)-(3 ⫻ 2) reconstructed surface.
442 Yoshida
Figure 4 Transition of elemental composition (a) from carbon-terminated to silicon-covered surface by

exposing disilane and (b) from silicon-covered to carbon-terminated surface by exposing acetylene at
1050°C. (From Ref. 21.)
B. Homoepitaxy
Bulk SiC substrates made by the Acheson method or the Lely method have been used as the
substrates for growth of α-SiC. Recently, SiC wafers sliced from an SiC ingot grown by the
modified Lely method have been used. Usually, (0001) Si or (0001) C surfaces are used, Here,
homoepitaxial growth of SiC by CVD using an SiH 4 –C 3 H 8 –H 2 reaction gas system is illustrated
as an example.
SiC substrates are etched with HF solution to remove oxide layers and are then set in the
reaction tube. Prior to the growth, the surfaces are etched with HCl gas at around 1500°C. SiH 4
and C 3 H 8 reaction gases with typical flow rates of 0.1–5 sccm and H 2 carrier gas of 3–10 slm
are introduced in the reaction tube. Growth rates are in the range of 1–3 µm/h. At 1600–
1800°C, epilayers with the same polytype as the substrates grow; i.e., 6H-SiC grows on 6H-
SiC substrates, 4H- on 4H-SiC, and 15R- on 15R-SiC. However, when (0001) on-axis surfaces
of 6H-SiC are used as substrates, 3C-SiC grows on them at 1500°C. The 3C-SiC epilayers
contain many twins, resulting in a mosaic patterned surface morphology. On the contrary, when
off-axis surfaces toward the [1120] direction, about 3–6 degrees, are used as substrates, 6H-
SiC epilayers with smooth surfaces grow even at 1500°C (25,26). These results have been ex-
plained as follows. It is plausible that nucleation tends to occur at the atomic steps rather than
at the terrace. In the case of on-axis substrates, as there are few steps, three-dimensional nucle-
ation occurs at the terrace. As the stable polytype is 3C type at 1500°C, 3C-SiC clusters nucleate
and grow. When adjacent nuclei with the stacking sequences ABCABC and ACBACB grow,
touch each other, and coalesce, a twin boundary is introduced at the boundary, as shown in Fig.
5a and b. To obtain 6H-SiC epilayers, temperatures above 1700°C are needed in the case of
on-axis substrates, where 6H-SiC is a stable polytype. On the contrary, on off-axis substrates,
Figure 5 Schematic image of the relationship between growth modes and polytypes of grown layers.
(a) On an on-axis 6H-SiC (0001) surface, 3C-SiC grows through three-dimensional nucleation and (b) an
antiphase boundary is introduced when the islands coalesce. (c) On an off-axis 6H-SiC (0001) surface,
on the contrary, homoepitaxial growth of 6H-SiC is achieved by step-flow growth.
444 Yoshida
there exist many atomic steps, and thus the nucleation occurs at the steps, not at the terrace. In
this case, called step growth mode, as films grow laterally, the stacking sequence follows that
of substrates, and thus the same polytype as that of the substrate grows as shown in Fig. 5c.
Therefore, 6H-SiC grows on 6H-SiC substrates even at 1500°C.
C. Heteroepitaxy
For heteroepitaxial growth, the selection of substrates is important, not only from the point of
view of matching the lattice constant and thermal expansion coefficient but also in terms of the
thermal and chemical stability of the surfaces at the growth temperatures. As the epitaxial growth
temperatures of SiC are very high, the materials suitable for the substrates are restricted essen-
tially to refractory materials. In the case of CVD, hydrogen is used as a carrier gas, and oxide
materials cannot be used as substrates. Usually, Si has been used as the substrate for the growth
of SiC. As the growth temperature of α-SiC is higher than 1500°C, only 3C-SiC is grown on
Si substrates, whose melting point is about 1420°C.
For the growth of 3C-SiC on Si, there exist serious problems. Mismatching of lattice
constants and thermal expansion coefficients between SiC and Si has been believed to be the
reason why SiC with good crystalline quality cannot be grown on Si (27). In 1983, Nishino et
al. (28) succeeded in growing good quality 3C-SiC epilayers on Si by CVD by using a carboniza-
tion process for Si surfaces before SiC growth. The typical growth sequence in CVD is as
follows. The Si surfaces are etched with HCl at around 1200°C to remove surface oxide layers.
Then the substrates are heated up to 1300–1400°C within a couple of minutes under the flow
of a hydrocarbon gas, where the surfaces are carbonized and covered with thin SiC layers about
10 nm thick. After the carbonization process, SiC layers are grown on the carbonized Si sub-
strates with SiH 4 and C 3 H 8 reaction gases. A typical growth rate is about 2 µm/h. Using 3C-
SiC epilayers on Si, Schottky barrier diodes (29), Schottky gate field effect transistors (MES-
FETs) and metal-oxide-semiconductor field effect transistors (MOSFETs) (30,31) were fabri-
cated in the 1980s, and the operation of MOSFETs up to high temperatures was demonstrated
(32).
The carbonized layers on Si substrates were thought to act as buffer layers for lattice
mismatch between SiC and Si (33). However, by cross-sectional transmission electron micros-
copy (TEM) of the interface between SiC and Si, there exists no interface layer between SiC
and Si and four Si lattices are commensurate with five SiC lattices (34,35), as shown in Fig.
6. It is hard to distinguish between a carbonized layer and a grown layer, although there exist
many crystal defects such as stacking faults and dislocations near the interface. Reflection high-
energy electron diffraction measurements for carbonized Si surfaces also indicate that the car-
bonized layer is stoichiometric SiC, not a mixed phase of SiC and Si. These results indicate
that the carbonized layers cannot relax the lattice mismatch between SiC and Si. However,
without the carbonization process, 3C-SiC epilayers with good crystalline quality cannot be
obtained. The role of the carbonized layers is thought to be to prevent the diffusion of Si atoms
to the surface of SiC (36). At the growth temperature of SiC, 1300–1400°C, which is just below
the melting point of Si, the Si atoms are very mobile. As SiC grows after the manner of a three-
dimensional nucleation and growth mode on Si, the grown SiC layers do not cover whole the
Si surfaces in the early stage of the growth, and thus Si atoms in the substrates move through
the uncovered part (SiC holes) to the surface. At the surface, SiC grows with Si and C from
reaction gases, which changes the Si/C ratio, and SiC with good crystalline quality cannot be
obtained. However, when Si surfaces are covered with SiC layers, Si atoms are not supplied
from Si substrates by diffusion, because the diffusion constant of Si in SiC is very low (37).
Figure 6 Lattice image of a 3C-SiC/Si interface obtained by cross-sectional transmission electron mi-
croscopy (TEM).
Therefore, carbonized SiC layers are thought to act as diffusion barriers for Si atoms from Si
substrates. The important point is how to cover Si surfaces with thin dense SiC layers before
the substrate temperature reaches the growth temperature, 1300–1400°C. If the substrate temper-
ature rises in a hydrocarbon atmosphere, Si surfaces react with hydrocarbon gas molecules to
form uniform and dense SiC layers around 800°C. These layers are thought to prevent the
diffusion of Si from the substrates. Therefore, two-step growth has been proposed (38), where
polycrystalline SiC layers are grown first at around 800°C and then heated up to 1300–1400°C
to grow SiC single crystals. It is noted that although the SiC layers grown at around 800°C are
polycrystalline or amorphous, they change to single crystals after heating at the growth tempera-
ture of 1300–1400°C.
Compared with the growth of SiC epilayers on Si (001), it is hard to grow SiC with good
crystalline quality on Si (111) surfaces, where substrates sometimes bend due to the difference
in thermal expansion coefficient between SiC and Si and many cracks are introduced in the
epilayers. For the use of an SiC/Si heterointerface as the emitter of heterobipolar transistors
(HBTs), low-temperature growth of SiC on Si has been tried using an SiH 2 Cl 2-C 2 H 2 reaction
gas system (39). However, it is hard to reduce the growth temperature well below 1000°C for
the accommodation to an Si large-scale integration (LSI) process.
Antiphase boundaries (APBs) are seen in the epilayers on Si (001) substrates, as in the
case of GaAs on Si. APBs can be observed by the etching pattern of the epilayers or by the
boron decoration method (40). The formation of APBs can be avoided by using off-axis (001)
surfaces of Si substrates instead of on-axis surfaces (41).
446 Yoshida
Another substrate for the heteroepitaxial growth of SiC is TiC (42), whose lattice constant
is only 0.8% different from that of SiC. However, large single crystals of TiC are difficult to
produce.
The technique for growing 3C-SiC epilayers heteroepitaxially on Si substrates is attractive
from the viewpoint of obtaining large-area single-crystal substrates. And 3C-SiC is the most
attractive polytype, because of its isotropic properties and large electron mobility compared
with other SiC polytypes. However, at present, the quality of the epilayers is inferior to that of
homoepilayers on modified Lely crystals due to the heteroepitaxial growth with large mismatch
in lattice constants and thermal expansion coefficients between SiC and Si. More research to
find methods for improving the crystal quality is needed.
Kitabatake et al. (43) studied the mechanism of SiC heteroepitaxial growth by the carbon-
ization of Si (001) surfaces at the atomic scale using molecular dynamics (MD) simulations.
Possible heteroepitaxial growth mechanisms of 3C-SiC on Si (001) surface are elucidated by
the MD simulations as shrinkage of the [110] rows of the Si lattice atoms with the C adatoms
and breaking of the deeper Si–Si bonds in the Si lattice. The carbonization process in this model
results in clear and abrupt interface formation (not a buffer layer) between the carbonized 3C-
SiC crystalline and the Si substrate lattice. This agrees with cross-sectional TEM images of 3C-
SiC/Si interfaces.
III. CHARACTERIZATION
A. Crystal Structures (Polytype Identification)
One of the most prominent characteristics of SiC is the existence of more than 100 kinds of
polytypes. Therefore, the control of polytypes is very important for the growth of SiC. There
are several methods for identifying SiC polytypes: X-ray diffraction (XRD); Raman scattering,
high-resolution transmission electron microscopy (HRTEM); reflection high-energy electron dif-
fraction (RHEED); and measurements of optical absorption and luminescence spectra. It is easy
to identify the polytypes by the lattice images observed using the HRTEM method. However,
for TEM observation, very thin samples on the order of 10 nm thick are required, and thus this
method is not convenient for the identification of SiC polytypes. By RHEED observation, it is
possible to identify polytypes of thin films in the growth chamber. However, if the surface is
flat, distinction of the polytypes is rather hard because of their streaky diffraction patterns.
Compared with these methods, Raman scattering measurements are useful for identifying SiC
polytypes without pretreatment of the samples.
Many Raman lines peculiar to the polytypes are observed in the Raman spectra of SiC
crystals. The spectra can be explained by using the concept ‘‘large zone and zone folding.’’
When the period of the polytype is n times that of 3C-SiC, the size of its Brillouin zone is 1/n
that of 3C-SiC, resulting in n times folded modes of the phonon dispersion curve as shown in
the insets in Fig. 7. Each phonon branch in the large zone is folded into the real Brillouin zone.
In the case of 3C-SiC, the large zone is the real Brillouin zone itself; in the case of 6H-SiC,
the large zone is six times larger than the real Brillouin zone and the Γ point in the real Brillouin
zone corresponds to the position of k ⫽ 0.00 (the original mode), 0.33, 0.67, and 1.00 in the
large zone. Therefore, the folded modes can be observed for SiC polytypes with longer periods
in Raman scattering spectra. Nakashima et al. (44,45) have calculated relative intensities of
Raman lines for several polytypes, 6H, 8H, 15R, 21R, 27R, and 33R, using a linear chain model,
and shown the calculated results are in good agreement with the experimental results. These
results suggest that the polytypes can be identified by measurements of Raman scattering. Both
Figure 7 Raman spectra from (a) a 3C-SiC epilayer and (b) a 6H-SiC bulk crystal. The position and
the symmetry of each peak are shown. The insets show schematic diagrams of the large zone and the zone
folding. (From Ref. 46.)
transverse optical and acoustic modes are folded. To identify the polytypes, observation of the
folded transverse acoustic (TA) modes in the lower frequency region is useful because the
Raman lines are sharper than those of the folded transverse optical (TO) modes in the high-
frequency region. Figure 7 shows the observed Raman spectra for typical SiC polytypes, 3C-
and 6H-SiC. In case of 6H-SiC, we can see Raman peaks corresponding to the folded modes
in the regions 140–150 cm⫺1 (TA region) and 760–800 cm⫺1 (TO region), which are not seen
in the case of 3C-SiC. Okumura et al. (46) and Yoshida et al. (47) have identified the polytypes
of the SiC epilayers grown on 6H-SiC (0001) and 3C-SiC (111) and (001) surfaces by CVD
using Raman scattering. The distribution of the polytypes can be obtained by using Raman
scattering measurements with micrometer-size focused laser beams.
Measurements of optical absorption and luminescent spectra can be used to identify the
polytypes based on the difference in the band gaps between polytypes. Because of the band gap
energy difference, it is easy to distinguish between 3C- and 6H-SiC from the absorption edge
and/or luminescence peaks. By using a focused light beam for absorption measurements or a
narrow laser beam for excitation in photoluminescence (PL) measurements, the distribution of
the polytypes can be obtained. Mapping of an SiC wafer to separate 4H and 6H modifications
has been carried out using the deference of band gaps between 4H (3.2eV) and 6H (2.9eV)
polytypes (48). It is easy to separate with a bandpass filter around 400 nm (3eV). A more high-
resolution distribution of polytypes can be obtained using a focused electron beam in cathodo-
luminescence measurements.
448 Yoshida
B. Crystal Defects
The methods for characterizing crystal defects can be divided into two categories: direct observa-
tion of crystal structures, i.e., TEM, Rutherford backscattering (RBS), and XRD, and indirect
characterization through measurements of physical properties, i.e., Raman scattering, PL, and
electrical measurements. Crystal imperfections can be divided into three categories: points de-
fects (vacancies, interstitial atoms, antisite atoms, and impurities), structural defects (disloca-
tions, stacking faults, and grain boundaries), and combined defects. The defects can also be
classified by their origins—those due to crystal growth, those induced by the device process
such as like etching and polishing, and those induced by irradiation with energetic particles.
Characterizations of the crystal defects in SiC have been done in all these categories. The
defects in bulk crystals are described in another chapter in this book. Radiation damages are
discussed in Sec. IV.D of this chapter. Here, the crystal defects in 3C-SiC epilayers grown on
Si by CVD are described.
Lattice imperfection, i.e., displacement of atoms from the lattice sites and the existence
of interstitial atoms, has been studied by using RBS measurements. The ratio between the yield
for the channeling direction and that for random directions, χ min ⫽ 1.8%, has been reported for
3C-SiC epilayers grown on Si by CVD (49) and is almost the same as the theoretical value.
This indicates that the 3C-SiC epilayers have excellent crystallographic structures. However,
as the atomic mass of carbon is much different from that of Si, the scattering peaks from the
carbon sublattice overlap those from the Si sublattice in usual RBS measurements using an He⫹
beam. Therefore, information about the carbon sublattice cannot be obtained. Nashiyama et al.
(49) have proposed a new method in which D⫹ ions are used and information about the Si
sublattice and carbon sublattice can be obtained independently from the RBS signal of D⫹ and
from the nuclear reaction 12 C(d, p)13C, respectively. Using this method, they found that about
5% of C atoms shift from the lattice sites to the tetrahedral-like interstitial sites, although the
Si sublattice is almost perfect.
As shown by the cross-sectional TEM image in Fig. 6, there exist many stacking faults
and misfit dislocations near the SiC/Si interfaces. The densities of these defects decrease with
distance from the interface. Yoshida et al. (36) have shown that the electron mobility increases
from 750 to 850 cm 2 /Vs at room temperature when the substrate side of the epilayers is etched
away. This indicates that the substrate side of the epilayers has poor crystalline quality.
C. Internal Stress
Because of the difference in thermal expansion coefficients between SiC and Si substrate, the
3C-SiC epilayers grown on Si may come under stress in the process of cooling from the growth
temperature to room temperature. Large lattice mismatch between SiC and Si may also bring
about internal stress in the epilayers. The existence of tensile stress is obvious from the fact
that the substrates bend toward the epilayer side after deposition and sometimes the epilayers
crack. Mukaida et al. (50) have estimated the internal stress by using Raman scattering measure-
ments. When a Si substrate was etched away, the peak corresponding to the LO phonon shifted
by 1.4 cm ⫺1 toward the higher energy side. Annealing in an H 2 atmosphere at 1750°C brought
about a further 0.3 cm ⫺1 shift. The internal stress in SiC epilayers on Si was estimated assuming
that the annealed sample has no internal stress. The stress in the epilayers was estimated to be
5.4 ⫻ 10 9 dyn/cm 2 tensile using the results of a study of the pressure dependence of Raman
phonons (51). This value cannot be explained only by the thermal stress due to the difference
in shrinking between SiC and Si during cooling from the growth temperature (1350°C) to room
temperature after deposition, ⬃1 ⫻ 10 9 dyn/cm 2, which suggests the existence of other intrinsic
internal stress. Feng et al. (52) studied the thickness dependence of internal stress in 3C-SiC
on Si (100) and obtained a tensile stress of 3–11 ⫻ 10 9 dyn/cm 2 and strain of 0.1–0.2% for
3C-SiC epilayers 4–17 µm thick. These values are less than 1/1000 of that estimated from the
difference in lattice constants between SiC and Si. This is considered to be due to almost perfect
lattice relaxation at the interface on introducing misfit dislocations at every four Si lattices and
five SiC lattices, as shown in the TEM images of SiC/Si interfaces (Fig. 6). The difference
between four Si lattices and five SiC lattices is only 0.3%, which is the same order as in the
case of GaAs/AlAs interfaces. Mukaida et al. (50) observed the Raman peak corresponding to
the TO phonon for 3C-SiC self-standing epilayers, which should not be observed in the backscat-
tering configuration for (001)-oriented epilayers according to the selection rule. Feng et al. (52)
also reported the observation of forbidden TO lines, which they explained as follows. When an
Si substrate is etched away, the reflectance at the back surface increases from 4.7% (SiC/Si
interface) to 21% (SiC/air interface). This brings about scattering of light for the forward scatter-
ing configuration, which has different selection rules from backscattering and thus could lead
to the appearance of the forbidden TO line from 3C-SiC self-standing films.
D. Impurities
Impurities in SiC crystals have been estimated from PL, electron spin resonance (ESR), electron
nuclear double resonance (ENDOR), and Hall measurements and more directly by secondary
ion mass spectroscopy (SIMS) measurements. It is well known that the unintentionally doped
SiC epilayers show n-type conduction with a residual carrier density of the order of 10 15 –10 16
cm ⫺3. The residual carriers in SiC epilayers have been attributed to nitrogen impurities, which
is strongly supported by the observation of three-line electron spin resonance (ESR) signals
related to nitrogen impurities in 6H- (53) and 3C-SiC (54). However, it is hard to explain the
temperature dependence of carrier density and ESR signals only by the nitrogen impurities.
Here, the methods for studying nitrogen impurities in SiC crystals will be described. The origin
of the residual carriers will be discussed in Sec. IV.B.
Figure 8 shows ESR spectra observed in nondoped 3C-SiC epilayers at various tempera-
tures (55). Below 30 K, a three-line ESR signal can be seen in the spectra, which decreases
with temperature and disappears at 40 K. This three-line structure can be decomposed into
a nitrogen-related hyperfine structure with equally spaced three-line structure (g ⫽ 2.0049,
hfs ⫽ 1.08G, line width ⫽ 0.56G) and a narrow one-line structure with the same g value (line
width ⫽ 2.2G), as shown in Fig. 9 (56). The figures suggest that the nitrogen impurities exist
in the epilayers. Spin densities estimated from the three-line nitrogen-related structure at 4.2 K
are on the order of 10 15 cm ⫺3, which is one order smaller than that of residual carriers. ESR
signals can be observed for unpaired electrons quenched at donor levels. Above 40 K, unpaired
electrons at the nitrogen impurity level may ionize, and thus the three-line signal is not observed,
which is also different from the temperature dependence of the carrier concentrations.
Density of nitrogen impurities can be estimated directly by SIMS measurements. However,
it is hard to estimate nitrogen density below 10 16 cm ⫺3, because of the very low sensitivity of
nitrogen in SIMS measurements and difficulty of distinguishing adsorbed nitrogen from residual
gas in the SIMS chamber. Moreover, in the case of nitrogen in SiC, the overlapping of the
signals from 14N ⫺ and 28Si 2 ⫺ makes SIMS measurements difficult. In the case of nitrogen in Si,
the detection of N is estimated from the signals for compounds such as SiN. However, in the
case of SiC, a mass resolution M/∆M of more than 300,000 is required to separate 29Si 13C ⫺ and
28 14 ⫺
Si N . Nashiyama et al. (57) used a high-resolution and high-vacuum (⬍10 ⫺10 torr) SIMS
system, in which CN signals were used to detect nitrogen impurities. In this case, M/∆M more
than 7,000 is required to separate 12 C 14N ⫺ and 13C 2 ⫺. For the calibration of nitrogen content, 3C-
450 Yoshida
Figure 8 Electron spin resonance (ESR) signals observed in undoped 3C-SiC epilayers at low temperature.
Figure 9 Decomposition of the three-line structure into a nitrogen-related hyperfine structure with an
equally spaced three-line structure and a narrow one-line structure with the same g value. (a) Nitrogen-
related hyperfine structure, (b) one-line structure, (c) added spectrum of (a) and (b), and (d) observed ESR
spectrum.
Figure 10 Depth profile of nitrogen impurity concentration in a 3C-SiC epilayer implanted with 60-
and 160-keV nitrogen ions. (From Ref. 57.)
SiC epilayers were implanted with nitrogen ions at 2.5 ⫻ 10 15 cm ⫺2. Figure 10 shows the depth
profile of the nitrogen content in 3C-SiC implanted with nitrogen ions. For depth above about
0.6 µm, values about 4 ⫻ 10 15 cm ⫺3 are attributed to the residual nitrogen impurities in undoped
3C-SiC epilayers. The background level of the nitrogen in the measurements is 1 ⫻ 10 15 cm ⫺3.
3C-SiC epilayers grown with very pure reaction gases have a nitrogen content below the back-
ground level of ⬃1 ⫻ 10 15 cm ⫺3, although their residual carrier concentrations are in the range
10 15 –10 16 cm ⫺3.
IV. PHYSICAL AND CHEMICAL PROPERTIES

A. Optical and Luminescent Properties
1. Optical Absorption
SiC polytypes show different optical absorption spectra due to differences in the band gap energ-
ies (58,59). SiC crystals other than 3C type have anisotropic crystal symmetry and show dichro-
ism for light with the electric field E储 c-axis and E 芯 c. The shapes of the absorption curves
are characteristics of indirect transition, with shoulders due to phonon emission. The reported
values of the exciton energy gap and the exciton binding energy are listed in Table 1. The values
of phonon energies related to the optical absorption are shown in Ref. 3. It is well known that
nitrogen-doped SiC crystals show characteristic colors, green in 6H, yellow in 15R, and green-
yellow in 4H polytypes. These colors are attributed to direct optical transitions from the lowest
conduction band to higher empty bands (60). 3C-SiC shows a pale canary yellow color due to
the band edge absorption at 2.2 eV.
452 Yoshida
Table 1 Low-Temperature Band Gap Energies (E g ),

Exciton Energy Gap (E gx ), and Exciton Binding
Energies (E x ) of Various SiC Polytypes
Polytype E g (eV) E gx (eV) E x (meV)
3C 2.403 2.390 13.5
4H 3.285 3.265 20.0
6H 3.101 3.023 78.0
15R 2.946 2.906 40.0
2H 3.330
21R 2.853
33R 3.003
2. Refractive Index
The refractive indices of SiC are also different for light with E储 c-axis and E 芯 c. As the wave
at normal incidence to the c-plane, E 芯 c, is called the ordinary ray and that for E储 c the extraordi-
nary ray, the refractive index for E 芯 c is denoted as n o and that for E储c as n e. The refractive
indices of several polytypes have been measured. Powell (61) measured the refractive indices
of 2H-SiC in the wavelength range 435.8–650.9 nm by the method of minimum deviation. He
obtained a Cauchy dispersion equation by curve fitting of the experimental data. The empirical
fitting equations, as well as the values at wavelength λ ⫽ 515 nm, are listed in Table 2 (60).
An attempt has been made to relate the birefringence of SiC to the crystal structure. Figure 11
shows the birefringence δ at wavelength λ ⫽ 584 nm of several SiC polytypes as a function
of the hexagonality h (61). The figure shows the linear relation between δ and h as in the case
of ZnS polytypes, except for 3C and 2H.
Table 2 Refractive Indices of SiC Polytypes a

Parameters for empirical fitting
equation
Polytype at 515 nm C0 C ⫻ 10 4 C 2 ⫻ 10 8
3C 2.6823 2.55378 3.417
2H
n0 2.6615 2.5513 2.585 8.928
ne 2.7389 2.6161 2.823 11.49
4H
n0 2.6881 2.5610 3.40
ne 2.7450 2.6041 3.75
6H
n0 2.6789 2.5531 3.34
ne 2.7236 2.5852 3.68
15R
n0 2.6800 2.558 3.31
ne 2.7297 2.5889 3.74
a
Empirical fitting equation: n(λ) ⫽ C 0 ⫹ C 1 /λ 2 ⫹ c 2 /λ 4; n 0 , refractive
index for ordinary ray; n e , refractive index for extraordinary ray.
Figure 11 Birefringence versus hexagonal fraction h of SiC polytypes at 584 nm. (From Ref. 61.)
3. Luminescence
Luminescence spectra have peaks related to the excitons near the band edge, peaks related to
donor and acceptor impurity levels, and peaks related to deep levels due to impurities and de-
fects. From measurements of luminescence, therefore, much information about the exciton band
gap, impurity levels, and deep levels can be obtained. For SiC, many luminescence measure-
ments have been made by photoluminescence, cathodoluminescence, and electroluminescence
at low temperatures, as well as at room temperature, and analyzed to determine the band struc-
tures and identify the impurities and defects contained (62). However, in the case of SiC, the
existence of many polytypes and site-dependent impurity levels resulting from the lattice site
inequivalence, cubic sites, and hexagonal sites make the luminescence very complicated. More-
over, it has been difficult to analyze the luminescence spectra because of the lack of perfect
crystals with very low defect densities and background impurity concentrations. Recently, both
highly pure and intentionally doped epilayers have been obtained by CVD. The measurements
on these have made it possible to discuss the origins of the luminescence peaks more precisely,
which is of interest from the viewpoint of the origin of residual carriers in unintentionally doped
SiC. Studies of radiation damage using luminescence measurements have been done because
of the interest in damage due to ion implantation and in device tolerance for nuclear irradiation.
Luminescence related to irradiation-induced defects will be described in Sec. IV.D.
a. Exciton-Related Emission
Relatively sharp luminescence lines observed near the band edge arise from the recombination
of electron-hole pairs that form bound excitons (BEs) at impurity sites or free-to-bound (FB)
transitions that involve the recombination of free electrons (holes) with holes (electrons) bound
at neutral acceptors (donors). Figure 12 shows the PL spectrum at 1.96 K for an undoped 3C-
SiC epilayer grown on Si by CVD (63). In the energy range 2.4–2.2 eV, five sharp lines are
seen. Choyke et al. (64) have observed five similar sharp luminescence peaks for a 3C-SiC
crystal grown by the Lely method. These peaks have been assigned as the zero phonon line
(ZPL, 2.379 eV) and its phonon replicas TA, LA, TO, and LO. They attributed these lines to
454 Yoshida
Figure 12 Photoluminescence spectrum of an undoped CVD-grown epilayer of 3C-SiC at 1.96 K. (From

Ref. 63.)
recombination of excitons bound at neutral nitrogen donors (nitrogen at carbon site N c ) from
the analogy with PL spectra of nitrogen-doped 6H-SiC and 15R-SiC. From the value of the
exciton energy gap of 3C-SiC, E gx ⫽ 2.390 eV, determined from the optical absorption measure-
ments, the bound exciton binding energy to N c , E bx ⫽ 11 meV, and the phonon energies for
TA, LA, TO, and LO of 46, 79, 94, and 103 meV were obtained (65). Nedzvetskii et al. (66)
studied the temperature dependence of optical absorption and luminescence of 3C-SiC and ob-
tained the fundamental energy gap E g ⫽ 2.4018 eV, exciton binding energy E x ⫽ 13.5 meV,
and E bx ⫽ 9.1 meV at 4.2 K. Dean et al. (67) obtained the donor ionization energy as 53.6 ⫾
0.5 meV. However, there is no evidence for the attribution of these five-line PL peaks to nitrogen
donors. High-purity 3C-SiC epilayers on Si have been grown by CVD, and their PL spectra
have been reported, which are essentially the same as that for bulk 3C-SiC reported by Choyke
et al. (64). PL spectra of nitrogen-doped 3C-SiC epilayers have been measured (68). As seen
in Fig. 13, weak shoulders are observed on the low-energy side of each phonon replica, which
increase with nitrogen doping concentration. Similar peaks have been observed for undoped
3C-SiC epilayers grown with a lower C/Si ratio in the reaction gases in CVD growth (69).
These results suggest that the five-line peaks observed for nondoped 3C-SiC cannot be attributed
simply to nitrogen-bound excitons (70). The origin of the five lines is still unclear.
In the spectra of nitrogen-doped 6H-SiC, several tens of peaks are observed near the band
edge around 3 eV (71). These peaks have been attributed to excitons bound at neutral and ionized
nitrogen donors and their complexes. Because of the existence of three inequivalent carbon sites,
one hexagonal site and two cubic sites, three ZPLs are observed at 3.008, 2.993, and 2.991 eV,
respectively. The value for the free exciton band gap is obtained as 3.024 eV at 4.2 K.
The values of the exciton binding energy E x; the bound exciton binding energy to N c , E bx;
the exciton energy gap E gx; the fundamental energy gap E g; and the exciton binding energy at
4.2 K have been measured for several polytypes and are listed in Table 1 (63).
b. Luminescence Related to Donor-Acceptor Pairs
It is well known that nitrogen impurities at carbon sites in SiC bring about donor levels and
aluminum, gallium, and boron impurities at Si sites bring about acceptor levels. In samples with
both donor and acceptor impurities, electrons bound at neutral donors recombine with holes
Figure 13 Photoluminescence spectra of nitrogen-doped 3C-SiC epilayers at 4.2 K. (From Ref. 68.)
bound at neutral acceptors, which is called donor-acceptor pair (DA pair) recombination. The
photon energy of the luminescence for a DA pair is given by (72)
E(r) ⫽ E g ⫺ (E D ⫹ E A ) ⫹ (e 2 /εr) ⫺ (e 2 /ε) (a 5 /r 6 ) (1)
where E g is the fundamental energy gap, E D and E A are the isolated donor and acceptor binding
energies, respectively, ε is the static dielectric constant, a is the effective van der Waals coeffi-
cient for the interaction between a neutral donor and a neutral acceptor, and r is the distance
between an isolated neutral donor and acceptor. According to Eq. (1), a series of luminescence
peaks are observed and their low-energy limit, r → ∞ in Eq. (1), gives
E min ⫽ E g ⫺ (E D ⫹ E A ) (2)
Figure 14 shows the PL spectrum for Al-doped 3C-SiC around 2.2 eV at 6 K (63). Choyke (59)
attributed the sharp peaks observed in the figure to nitrogen donor–Al acceptor pair recombina-
tions and obtained E D ⫹ E A ⫽ 310 meV from E g ⫽ 2.4034 meV and E min ⫽ 2.0934 eV. From
the measurements at higher temperatures, an emission peak due to the recombination of a free
456 Yoshida
Figure 14 Photoluminescence spectrum of an Al-doped 3C-SiC epilayer at 6 K, showing a series of

peaks due to DA pair recombination. (From Ref. 63.)
electron with holes bound to Al acceptors (free-to-bound transition), the value E A ⫽ 257 meV
has been obtained. From Eq. (2), E D ⫽ 53 meV is obtained, which Choyke and Patrick (73)
denoted as the binding energy for nitrogen donors.
In cases of polytypes other than 3C, the spectra due to DA pair recombination consist of
several series of DA pair luminescences resulting from the inequivalence of the impurity sites.
Ikeda et al. (74) have analyzed DA pair luminescence for 3C, 15R, 6H, and 4H-SiC and obtained
the donor and the acceptor binding energies.
c. Luminescence Related to Deep Levels Due to Transition Metal Impurities
Luminescence spectra for 6H-, 4H-, and 15R-SiC doped with Ti and V have been reported (48).
The PL spectra of Ti in SiC have been explained by a model in which the silicon-substitutional,
isoelectronic neutral Ti (3d 0 ) impurities bind excitons (75). It is expected that Ti impurities act
as isoelectronic traps as in the case of nitrogen impurities in GaP, which bring about bright
luminescence of GaP emitting diodes. In the 1.3–1.5 µm near-infrared spectral range, emission
related to vanadium impurities substituting the various Si sites in the lattice was observed
(76,77). The spectra arise from the intra-3d-shell transitions 2E(3d 1 )→ 2T 2 (3d 1 ) of V Si 4⫹. Vana-
dium impurities have attracted much interest in the role of minority-carrier lifetime killer.
d. Raman Scattering and Infrared Absorption
Many Raman scattering lines are observed for SiC, reflecting zone folding effects in phonon
dispersion curves. These lines can be used to identify the polytype of SiC crystals, as mentioned
in Sec. III.A. From the shift of the Raman peaks and the discrepancy of the selection rules in
optical transitions, information about the internal stress and crystallinity of SiC crystals, respec-
tively, can be obtained, as mentioned in Sec. III.B.
Free carriers from plasmons in semiconductors, which interact with LO phonon modes
and form LO phonon–plasmon coupled modes. Figure 15 shows the Raman peak positions for
the TO and LO modes as a function of carrier concentration in 3C-SiC epilayers. The frequency
of the LO band increases with increasing free carrier density, which shows that the LO-phonon
band is coupled with the overdamped plasmon. Yugami et al. (78) have obtained the carrier
concentrations by line shape fitting of the coupled modes and compared them with the values
derived from Hall measurements. They found good agreement between the values derived by
Figure 15 Variation of the Raman peak positions for the TO- and LO-plasmon modes with the carrier
concentration in 3C-SiC epilayers. The solid lines show the values calculated using the equation driven
mainly by the deformation potential and electro-optic mechanisms. (From Ref. 78.)
the two methods. This result suggests that the free carrier concentrations can be estimated by
observing LO phonon–plasmon coupled modes in Raman scattering in the carrier concentration
range between 10 16 and 10 19 cm ⫺3.
B. Electrical Properties
1. Parameters for the Electrical Properties of SiC
SiC has a moderate value of carrier mobility (⬃1,000 cm 2 /V s for electrons at room tempera-
ture), which is of the same order as that of Si; a large saturation drift velocity (2.7 ⫻ 10 7
cm/s), which is twice as that of Si and the same as that of GaAs; and a large breakdown field
(5 ⫻ 10 6 V/cm), which is one order of magnitude larger than that of Si. The values of some
electrical parameters are listed in Table 3, compared with those for Si, GaAs, GaN, and diamond.
Values of the saturation electron drift velocity V s for 6H-SiC have been measured by Berman
et al. (79) and Muench and Pettenpaul (80). Ferry (81) has calculated theoretically the values
of V s for various semiconductors in terms of phonon frequency, as shown in Fig. 16. Figure 17
shows the electric field dependence of electron drift velocity for SiC and various semiconductors.
The open circles denote the breakdown field for the respective semiconductor. The figure shows
that the breakdown field of SiC is one order of magnitude larger than those for Si and GaAs,
and the saturation drift velocity is same as that of GaAs and twice of that of Si.
2. Polytype Dependence of Electrical Properties

The values of carrier mobility for n- and p- types and effective mass for electrons and holes in
various SiC polytypes are tabulated in the literature (82). The electron mobility differs between
458 Yoshida
Table 3 Properties of SiC Compared with Those of Si, GaAs, GaN, and Diamond (Room
Temperature)
SiC
Material 3C 6H Si GaAs GaN Diamond
Band gap energy 2.20 2.86 1.113 1.428 3.39 5.470
E g (eV)
Thermal conductivity κ 4.9 4.9 1.51 0.54 1.3 20.9
(W/cm ⋅ K)
Mobility (cm 2 /V ⋅ s)
µe 800 460 1500 8500 600 1800
µh 70 60 450 420 100 1600
Dielectric constant
ε0 9.72 9.66a,10.03c 11.4 12.91 10.4c,9.5a 5.93
ε∞ 6.52 6.52a,6.70c 11.6 11.10 5.8c,5.35a 5.76
Electron saturation 2.7 2.0 1.0 2.0 2.7 2.5
Drift velocity V s
(⫻10 9cm/s)
Breakdown field E B 40 25 3 4 40 35
(⫻10 5V/cm)
Figure 16 Saturation electron drift velocities of various semiconductors versus the parameter related
to energy relaxation. The solid line represents the calculated values. (From Ref. 81.)
Figure 17 Electric field dependence of electron drift velocity for various semiconductors. The open
circles denote the breakdown fields.
the polytypes as a result of the different number of conduction band minima lying at the Brilloiun
zone boundary and the difference in effective masses. At around room temperature, the electron
mobility is dominated by acoustic phonon and intervalley scattering. 3C-SiC has the highest
mobility in SiC polytypes (83), which was expected from its small intervalley scattering and
high energy of longitudinal acoustic phonons (84). Except for the neutral impurity scattering,
generally, the larger the effective masses, the larger the scattering is. The larger mobility of
15R-SiC compared with 6H is explained by the smaller effective mass of 15R than of 6H-
SiC (85). High-quality 4H-SiC epilayers have been grown homoepitaxially by chemical vapor
deposition (86), and a mobility of 800 cm 2 /V s was obtained (87), which is twice that for 6H-
SiC. Reflecting the different values of effective masses in different crystal directions, anisotropic
electric properties of SiC except for the 3C type have been observed. For 4H-SiC, however, a
nearly isotropic electron mobility, µ 芯 /µ 储 , was reported (88). Because of its wide band gap, high,
nearly isotropic electron mobility, and the highest breakdown field, the 4H polytype is believed
to be superior in applications for electronic devices, compared with 6H polytypes (89,90). The
hole mobility, in contrast, does not vary strongly with the polytypes, because the valence band
maximum is located at the Γ point for all polytypes.
Temperature dependences of intrinsic carrier mobilities for 3C- and 6H-SiC have been
calculated theoretically (91,92). Figure 18 shows the calculated and observed values of the
electron mobility for 6H-SiC (91). At low temperatures, ionized impurity scattering and neutral
impurity scattering dominate the mobility. At around room temperature, piezophonon scattering,
acoustic phonon scattering, and intervalley scattering dominate it, and optical phonon scattering
dominates it at high temperatures. In the case of SiC, the effect of piezophonon scattering is
460 Yoshida
Figure 18 Temperature dependence of the electron mobility for 6H-SiC. The broken lines show the
calculated values of the mobility determined by the impurity scattering µ imp , by the piezophonon scattering
µ piez , by polar optical phonon scattering µ pol , and by acoustic phonon scattering µ ac . The solid line shows
the values for the mobility determined by acoustic phonon and optical phonon scatterings, which is in
good agreement with the observed values above room temperature (m* ⫽ 0.2m 0 , N A ⫽ 10 14cm ⫺3, N A /N D
⫽ 0.5). (From Ref. 91.)
small and acoustic phonon scattering and intervalley scattering mainly dominate the mobility
at around room temperature.
Quantitative fits of the theoretical scattering mechanisms to the experimentally obtained
values of the carrier concentrations and mobility as a function of temperature have been carried
out for undoped 3C-SiC (93,94). By using a compensation model and assuming Matthiessen’s
rule for scattering mechanisms, curve fitting for the temperature dependence of carrier concentra-
tion gave an ionization energy of donors of about 20 meV (94–96), which is about a half of
that for nitrogen impurities determined by luminescence measurements. This discrepancy will
be discussed in subsection. 3. Yamanaka et al. (97) reported that the temperature dependence
of the Hall mobility µ H (T) cannot be fit by using values of the donor activation energy E d ,
donor concentration N D , and compensated acceptor concentration N A obtained by fitting the
temperature dependence of carrier densities, especially at low temperatures. Tsukioka (98) re-
ported that the introduction of dipole scattering may be able to resolve the contradiction between
experimental data for µ H (T) and n(T ).
Quantitative fits of theoretical curves to the experimentally obtained n(T ) values have
also been carried out for nitrogen-doped 6H- and 4H-SiC (87,99). The presence of two donor
levels (∆E N , 1 , N N , 1 ) and (∆E N , 2 ,N N , 2 ) is required to fit the experimental electron concentrations
over the entire temperature range. The ionization energies of the donor levels are ∆E N , 1 ⫽
85.5 meV and ∆E N , 2 ⫽ 125 meV. The ratio of the concentrations of these donors, N N ,1 /N N , 2 is
approximately 1 : 2. Hexagonal (h) and cubic (k 1 , k 2 ) lattice sites have a relative abundance of
1 : 2 in the 6H polytype, which is in good agreement with N N , 1 /N N , 2 . Therefore, we can speculate
that nitrogen atoms on h sites give donor level 1 and nitrogen on k 1 and k 2 sites give donor
level 2. For 4H- SiC, ∆E N , 1 ⫽ 45 meV and ∆E N , 2 ⫽ 100 meV are obtained, and N N , 1 /N N , 2 is
approximately 1 : 1, which is in good agreement with a relative abundance of h sites and k sites
of 1 :1 in the 4H polytype.
The mobilities of 6H and 15R-SiC change with temperature as T ⫺2.0 –T ⫺2.6 (87,100) above
room temperature. These changes are steeper than that due to acoustic phonon scattering, T ⫺1.5.
This is considered to be due to the contribution of intervalley scattering (100). While 3C-SiC has
cubic symmetry, higher crystal symmetry than 6H and 15R, intervalley scattering is restricted by
a selection rule (84), and the mobility of 3C-SiC changes with temperature as T ⫺1.5 (101), which
is slower in the reduction of mobility at high temperatures. As a result, at high temperatures,
3C-SiC has greater mobility than other polytypes, which is attractive from the viewpoint of the
use of SiC devices at high temperatures.
3. Doping Properties
One of the attractive characteristics of SiC for device application is easy control of the conduc-
tion type by doping, which is different from the situation with other wide band gap semiconduc-
tors, such as III-V nitrides, II-VI compounds, and diamond. n-type crystals can be obtained by
doping with nitrogen in the range between 2 ⫻ 10 16 and 1 ⫻ 10 19cm ⫺3 and p-type crystals by
doping with column III elements, B, Al, and Ga, in the range between 2 ⫻ 10 16 and 1 ⫻ 10 18
cm ⫺3 for 4H and 6H-SiC (102). As the diffusion coefficient of impurities in SiC crystals is very
low, doping is done by introducing impurities in the reaction chambers or crucibles during
growth.
Ion implantation is an attractive doping method for device processes. However, annealing
at high temperatures, more than 1500°C, is required to recover the crystallinity (103), which
prevents the use of ion implantation as a doping process. Implantation at temperatures around
500°C, called ‘‘hot implantation,’’ has been reported to be useful in reducing radiation damage
by ion implantation, as shown in Fig. 19 (104). However, to activate the impurities, annealing
at temperatures higher than 1400°C is required (105).
Acceptor levels with Al, B, and Ga in SiC are so deep that the activation rates at room
temperature are very low. For example, in the case of Al, the activation energy of acceptor
levels is around 160 meV, which is much larger than kT at room temperature, 25 meV, resulting
in a low activation rate, as low as 0.01. Therefore, high levels of doping more than two to three
orders of magnitude higher than the carrier density, is required.
It has been found that the doping efficiency depends on the C/Si ratio in the reaction gas
(106). For nitrogen doping, a smaller ratio brings about a higher doping efficiency, and for Al
462 Yoshida
Figure 19 Dependence of the density of residual defects in N 2 ⫹-implanted 3C-SiC on implantation

temperature. (From Ref. 104).
doping, a higher ratio brings about a higher doping efficiency. This phenomenon is explained
as follows. Nitrogen atoms occupy C sites to form donor levels. When the C concentration at
the growth surface is small, nitrogen atoms can easily occupy C sites instead of C atoms. In
the case of Al doping, Al atoms occupy Si sites to become acceptor impurities, which is easy
when the Si concentration at the surface is low. Therefore, this phenomenon is called ‘‘site
competition epitaxy.’’ This technique affords intermediate doping control as well as the produc-
tion of degenerately doped (⬃10 19 cm ⫺3 ) and very low doped n-type and p-type epilayers (⬃10 14
cm ⫺3 ).
Semi-insulating 6H-SiC crystals have been achieved by using controlled doping with deep-
level vanadium impurities (107). The resistively is 10 15 Ω cm at room temperature and 10 7 Ω
cm even at 300°C. The semi-insulating behavior is attributed to compensation of residual ac-
ceptors by the deep-level vanadium V 4⫹ (3d 1 ) donor located near the middle of the band gap.
4. Origin of the Residual Carriers in SiC

It is well known that unintentionally doped SiC crystals grown by LPE, CVD, and the sublima-
tion method show n-type conduction. For example, undoped 3C-SiC epilayers grown by CVD
usually have a residual carrier (electron) concentration of the order of 10 16 cm ⫺3. The origin of
the residual carriers has been considered to be nitrogen impurities because the existence of
nitrogen impurities in SiC crystals has been shown by ESR measurements, which suggest no
impurity inclusion other than nitrogen in SiC epilayers. However, some results inconsistent with
the attribution to nitrogen impurities have been reported (55,63). Curve fitting for the tempera-
ture dependence of the carrier concentration of 3C-SiC epilayers gives a donor ionization energy
of about 20 meV (94–96), which is far different from that for nitrogen impurities determined
by luminescence measurements, 53 meV (64,67). Segall et al. (95) tried to explain this discrep-
ancy by introducing the idea that the ionization energy for the nitrogen impurity level E N depends
on the donor concentration N D , as E D (N D ) ⫽ E D ⫺ αN D 1/3, following an empirical rule given
by Pearson and Bardeen (108). A curve fit gives α ⫽ 2.6 ⫻ 10 ⫺5 meV cm and E N (0) ⫽ 48 meV,
which is nearly the same as the generally accepted value of E D for nitrogen donors. Yamanaka et
al.(97), however, measured the temperature dependence of carrier concentrations and mobilities
of undoped and nitrogen-doped 3C-SiC and showed that the dependence of ionization energy
on carrier concentration is different in undoped and nitrogen-doped SiC. Okumura et al. (68)
and Freitas et al. (69) have shown that the nitrogen-doped 3C-SiC epilayers show other PL
peaks, about 8 meV lower than that observed in undoped 3C-SiC epilayers as discussed in Sec.
IV.A.3.
Nashiyama et al. (56,57) and Okumura et al. (55,109) studied the origin of residual carriers
in 3C-SiC epitaxially grown by CVD on Si by the Hall effect, ESR, and SIMS methods. Three
types of ESR signals were observed in the epilayers, including a three-line and a narrow single-
line ESR signal associated with nitrogen impurities and a broad single-line ESR signal, as shown
in Fig. 8. An apparent correlation was found between residual carrier density and total spin
density. These results suggest that nitrogen impurities exist in the epilayer. However, the total
spin density associated nitrogen impurity is usually smaller than the residual carrier density,
and a three-line signal disappears at around 40 K, which does not coincide with the temperature
dependence of carrier density. Undoped 3C-SiC epilayers with a residual carrier density of about
1 ⫻ 10 15 cm ⫺3 have been obtained by using highly pure SiH 4 (5N) and C 3 H 8 (6N) source gases
and a very clean growth system preevacuated below 10 ⫺8 torr (57). Epilayers having carrier
densities as low as 10 15 cm ⫺3 showed no significant ESR signals associated with nitrogen. These
results indicate that residual carriers in 3C-SiC with carrier concentration higher than 10 16 cm ⫺3
originate partly from nitrogen impurities. ESR centers corresponding to the broad single-line
signal, which is presumably associated with some defects, may be the main origin for the residual
carriers in 3C-SiC with carrier concentration less than 10 16 cm ⫺3. Nashiyama et al. (56) have
explained both the temperature dependence of carrier concentration and the ESR signal in 3C-
SiC epilayers simultaneously, assuming two donor levels and compensated acceptor levels.
C. Thermal Properties
SiC is thermally stable up to temperatures higher than 1500°C, and thus SiC has been used for
heaters and firebricks. At higher temperatures, SiC does not melt but sublimates under atmo-
spheric pressure. The predominant species of evaporated gas molecules from SiC are Si, SiC 2 ,
and Si 2 C (110). Scace and Slack (111) have reported that SiC possesses a peritectic point at
2830 ⫾ 40°C at 35 atm.
The thermal conductivity of SiC is around 5 W/cm K at room temperature, which exceeds
that of not only other semiconductors, such as Si and GaAs, but also the good thermal conducting
materials Cu, BeO, Al 2 O 3 , and AlN (112). Figure 20 shows the thermal conductivities of various
semiconductors as a function of Mδθ 3 , where M is the mean atomic mass, δ 3 the mean volume
of atoms in the crystal, and θ the Debye temperature (113). The figure suggests a linear relation-
ship between thermal conductivity κ and Mδθ 3. The thermal conductivity depends on polytype,
doping, and temperature. In the low-temperature regime, all of the heat flow is due to phonons,
and one expected κ ⬃ T 3. However, the observed κ for SiC is characterized by a T 2 dependence,
except for very pure samples. The T 2 dependence is explained by the additional thermal resis-
tance due to scattering of phonons by electrons in an impurity (nitrogen) band (114).
The thermal expansion coefficient of SiC also depends on polytype and temperature. Val-
464 Yoshida
Figure 20 Variation of thermal conductivities of various semiconductors as a function of Mδθ 3, where

M is the mean atomic mass, δ 3 the mean volume of atoms in the crystal, and θ the Debye temperature.
(From Ref. 113.)
ues of 3.3–3.7 ⫻ 10 6 deg ⫺1 at room temperature have been reported for 3C and 6H-SiC (115),
smaller than the value for Si but larger than that for GaAs. This discrepancy in thermal expansion
coefficients of Si and SiC brings about large internal stress in 3C-SiC epilayers grown on Si
substrates.
D. Radiation Damage
Studies of radiation damage in semiconductor lattices give information useful not only for in-
vestigating device tolerance of nuclear irradiation but also for knowing the radiation damage
in device processes, such as ion implantation, e-beam lithography, and reactive ion etching. The
studies of radiation damage are also important from the viewpoint of investigating the nature
of native crystal defects.
SiC has been said to be tolerant of nuclear irradiation compared with Si. However, it has
not been clarified why SiC is tolerant and how tolerant it is. In 1954, the first report on radiation
damage of SiC was published, and in the latter half of the 1960s many papers appeared on
radiation damage, which have been reviewed by Babcock (116), Campbell and Chang (117),
and Choyke (118). These papers treated the lattice swelling, changes of carrier concentration,
and I-V characteristics of pn junctions on neutron irradiation mainly in bulk α-SiC, from the
interest in the use of neutron and charged particle detectors. The data on the carrier removal
rate and defect introduction rate for neutron and proton irradiation were rather scattered, and it
is hard to insist on the tolerance of SiC for neutron and proton irradiation compared with other
Figure 21 Electron irradiation effects on the carrier density n and the Hall mobility µ at room tempera-
ture for 3C-SiC and Si. n 0 and µ 0 indicate the carrier density and the mobility before irradiation, respec-
tively. (From Ref. 121.)
semiconductors. However, it can be said that SiC is tolerant by one to two orders of magnitude
for irradiation with these particles when we use SiC detectors at high temperatures, because
SiC is stable up to high temperatures and radiation damage is recovered at high temperatures.
High crystalline quality SiC epilayers have been obtained by CVD, and more reliable data
have been reported on the radiation damage in SiC using these epilayers (119,120). Figure 21
Figure 22 ESR spectra of 3C-SiC irradiated with 1-MeV electrons at 3 ⫻ 10 18 cm 2. The spectra were
observed at room temperature (a) and at 60 K (b), when a magnetic field was applied parallel to the 〈011〉
axis. The arrows indicate five lines of the T1 center.
466 Yoshida
Figure 23 Temperature dependence of the Hall mobilities for as-grown, electron-irradiated, and an-
nealed 3C-SiC epilayers. (From Ref. 121.)
shows the changes of carrier density and carrier mobility of 3C-SiC epilayers on irradiation
with 1-MeV electrons compared with those for Si (121). The figure suggests that the carrier
removal rate and mobility reduction rate of SiC are both smaller than those of Si, which indicates
that SiC is more tolerant than Si. The annealing behaviors of the radiation-induced damage have
been studied by use of ESR, Hall, and PL measurements (121,122). Five-line isotropic ESR
centers as well as four anisotropic centers have been observed for 3C-SiC irradiated with 1-
MeV electrons, as shown in Fig. 22. Five-line centers, called T1 centers, have three annealing
stages, 150, 350, and 750°C, and disappear at around 800°C. As this annealing behavior is
similar to that of the carrier removal rate and mobility reduction rate, it is considered that T1
centers introduced by irradiation act as electron traps and the annealing out of T1 centers brings
about recovery of the carrier density and mobility. Figure 23 shows the temperature dependence
of the mobilities. The mobilities decrease in the low-temperature region, which can be explained
in terms of charged electron traps acting as electron scattering centers like ionized impurity
centers.
T1 centers have been also observed for 3C-SiC irradiated with 2-MeV protons (123). The
generation rates of T1 centers per fluence were obtained as 0.02 and 200 cm ⫺3 for 1-MeV
electrons and 2-MeV protons, respectively, which are almost the same as the ratio of defects
induced by the knock-on of atoms from the lattice sites.
The origin of the T1 center has been studied by measurements of the angular dependence
Figure 24 ESR spectrum at 10 K of 3C-SiC irradiated with 2-MeV protons at 1 ⫻ 10 16cm ⫺2 when the
magnetic field was applied parallel to the 〈100〉 axis. The T1 spectrum consists of the five lines (a,b,c)
indicated by the solid-line arrows and the satellite five lines (d,e,f) indicated by the broken-line arrows.
(From Ref. 124.)
of ESR spectra (124) and positron annihilation measurements (125). Figure 24 shows the wide-
range ESR spectrum for 3C-SiC irradiated by 2-MeV protons. Three sets of five lines can be
seen. From the intensity ratio and the angular dependence of these lines, five lines can be ex-
plained quantitatively by the hyperfine interaction of paramagnetic electrons at the Si lattice
sites with one or two 29Si (I ⫽ 1/2, existing 4.7%) nuclear spins at 12 Si sites around the Si
site and three sets can be explained by the modulation of one 13C (4%) nuclear spin at four C
sites around the Si site. In Fig. 25, the calculated values of intensity ratio are given, which are
in good agreement with those observed. Therefore, the T1 center is presumably due to electrons
trapped at Si vacancies.
Figure 25 Schematic representation of the ESR lines calculated from simultaneous hyperfine interac-
tions of a paramagnetic electron with 13C and 29Si nuclei. Terms in parentheses indicate the interaction
types exhibiting each ESR line. (From Ref. 124.)
468 Yoshida
Positron annihilation experiments have also supported this conclusion (125). In the fluence
range above 5 ⫻ 10 16 e/cm 2, the S parameter, defined as the integral of the γ-ray intensity in
the central energy region (511 ⫾ 0.5 keV) divided by the total intensity of annihilation γ-rays,
increases with increasing electron fluence; i.e., narrowing of the Doppler-broadened energy spec-
trum of annihilation γ-rays was observed. This electron fluence dependence of the narrowing
is explained by the introduction of monovacancies in 3C-SiC by the irradiation.
Radiation damage caused by ion implantation as well as fast particle irradiation has been
studied by use of PL measurements. Choyke (118) reviewed the PL spectra observed for SiC
samples implanted with a variety of ions and annealed. Two dominant peaks have been observed.
These peaks are referred to as D 1 and D 2 ; their wavelengths do not depend on the implanted
ion species, and they become large with annealing temperature and dominate the luminescence
spectra even above 1600°C. From the stability of these centers at high temperatures, D 1 and D 2
are thought to originate from defect complexes, divacancies, and carbon diinterstitials. Freitas
Figure 26 Photoluminescence spectra at 4.2 K for (a) an as-grown 3C-SiC epilayer and (b) an epilayer
irradiated with 1-MeV electrons at 2 ⫻ 10 17 cm ⫺2. The impurity-bound exciton (BE)–related zero-phonon
line (ZPL) and its phonon replicas are represented by arrows with the phonon combinations labeled in
(a). The defect-related D 1 line and G band in as-grown 3C-SiC are also shown. Irradiation-induced lines
labeled E, D 1 , α 1 , α 2 , β 1 , β 2 , and γ are indicated by arrows with the emission energies in (b).
et al. (126) have reported their relative intensity to the edge emission increase with increasing
annealing temperature. Itoh et al. (122) have measured PL spectra of 3C-SiC epilayers irradiated
with 1-MeV electrons. They found a pronounced peak at E ⫽ 1.913 eV, as well as a D 1 center,
in the PL spectrum for electron-irradiated 3C-SiC (Fig. 26), which disappears on annealing at
700°C. As this annealing behavior is quite similar to that of T1 ESR centers, they attributed
the PL peak at 1.913 eV to T1 centers or Si vacancies.
With γ-ray irradiation up to 10 7 Gy, no appreciable ESR center has been observed, which
Figure 27 Absorbed dose dependence of the radiation-induced (a) interface traps ∆N it and (b) oxide
traps ∆N ot in 3C-SiC MOS capacitors, as well as those of an Si MOS capacitor, irradiated under open-
circuit conditions. (From Ref. 128.)
470 Yoshida
suggests that no lattice defect is introduced in SiC crystals by γ-ray irradiation up to 10 7 Gy.
However, this does not imply radiation hardness of devices using SiC for γ-ray irradiation.
Nashiyama et al. (127) have studied the effect of γ-ray irradiation of up to 10 5 Gy for 3C-SiC
MOSFETs and MESFETs. In case of MESFETs, little change of drain current was observed
with γ-ray irradiation, which suggests that SiC MESFETs are quite tolerant of γ-ray irradiation up
to 10 5 Gy. However, in the case of MOSFETs, the drain current and, therefore, transconductance
decreased markedly on γ-ray irradiation. These changes are considered to be due to an increase
in the interface trap density N it and oxide trapped charges N ot . Yoshikawa et al. (128) have
obtained the changes of N it and N ot with absorbed dose, separately, by use of C-V measurement
at high frequency and pulsed C-V measurements for 3C-SiC MOS structures. Figure 27 shows
the absorbed dose dependence of the radiation-induced interface traps ∆N it and oxide trapped
changes ∆N ot in 3C-SiC MOS capacitors irradiated with 60Co γ-rays, as well as those in an Si
MOS capacitor. Both ∆N it and ∆N ot start to change at around 10 4 Gy. In the case of Si MOS,
they start to increase at around 100 Gy. Radiation effects on 3C-SiC MOS structures depend
on the oxidation process. The filled circles in Fig. 27 show those for 3C-SiC MOS capacitors
fabricated by pyrogenic oxidation at 1100°C. The generation of interface traps and oxide trapped
charges is much suppressed in the case of pyrogenic oxidation. These results suggest that with
3C-SiC MOS structures, especially those with pyrogenic oxide, it is hard to generate interface
traps and oxide-trapped charges compared with Si MOS structures. This supports reasonably
the fact that 3C-SiC MOSFETs have significant tolerance against γ-ray irradiation compared
with Si MOS devices.
V. CONCLUSION
Epitaxial growth, characterization, and physical properties of SiC have been reviewed. The most
pronounced characteristic of SiC is the existence of polytypes, and the proper growth methods
and properties depend strongly on the polytypes. High-quality epilayers of 3C, 6H, and 4H-SiC
have been grown, mainly by CVD, and by using these epilayers, physical properties have been
elucidated. However, the quality of the SiC crystals is still not enough to determine the material
parameters. Therefore, the growth of higher quality crystals of SiC is needed, not only for device
application but also for the clarification of physical properties. In the case of SiC polytypes
other than 3C, 6H, and 4H-SiC, it is necessary to grow single-phase single crystals to elucidate
their physical properties.
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20
Silicon Carbide Power Electronic Devices
B. Jayant Baliga
North Carolina State University, Raleigh, North Carolina
I. INTRODUCTION
Semiconductor devices are required for a large variety of power electronics applications. In fact,
it is recognized by the power electronics community that the growth in ratings and improvements
in performance of these systems are strongly dependent on the availability of semiconductor
devices with better electrical characteristics. This has motivated enhancement of the performance
of devices by the industry.
The blocking voltage and current-handling capability demanded from a power semicon-
ductor switch for some prominent applications are shown in Fig. 1. At relatively low blocking
voltages (under 100 V) there are important applications in power supplies [e.g., for integrated
circuits (ICs) used in computers and their peripherals] and multiplex-bus automotive electronics
systems. These applications require significant current levels because a large number of ICs are
usually connected to the power supply in computers and because typical lamps and motors in
cars demand up to 10 A during operation. The other applications fall on a trajectory of increasing
voltage and current. At the low-power end of this spectrum, displays and telecommunication
needs can be satisfied by using power ICs that monolithically integrate power devices with their
control circuits, as well as CMOS encode-decode and bipolar analog protection circuitry. At
medium power levels, the application needs for factory automation (robotics) systems and motor
control (heating, ventilating, air-conditioning) systems are satisfied at present by using discrete
power devices driven by high-voltage ICs. For the high power levels typical of traction (street-
cars and electric locomotives) and HVDC (power transmission and distribution) systems, dis-
crete thyristors have been developed with single devices capable of handling over 1000 A and
blocking over 6000 V. From Fig. 1 it is obvious that the demands of power electronic systems
require a very broad range of operating voltages and currents for the power switching devices.
At present, only silicon devices are available for this purpose. This chapter discusses the benefits
of development of power switches from silicon carbide and explores the merits of various device
options.
II. FIGURE OF MERIT
The forward voltage drop of a device determines its on-state power loss and hence the efficiency
of power electronic systems in which it is utilized. It is therefore desirable to reduce the internal
477
478 Baliga
Figure 1 Ratings for power devices required for various power electronic applications.
device resistances to reduce the forward voltage drop. In order to analyze the forward voltage
drop of power devices, a fundamental relationship between the specific on-resistance of the drift
region of a power semiconductor device and the material properties was first derived more than
15 years ago (1):
4BV 2
R on,sp ⫽ (1)
εsµE 3c
Based on this equation, Baliga’s figure of merit (BFOM) has been defined as (2)
BFOM ⫽ εsµE 3c (2)
which can be used to compare the relative merits of various semiconductor materials for power
device development. Using the BFOM, it can be concluded that semiconductors with high break-
down electric field strength are favored.
Silicon Carbide Power Electronic Devices 479
Figure 2 Comparison of the critical electric field for silicon carbide and silicon.
III. RELEVANT PROPERTIES OF SILICON CARBIDE
One attractive property of silicon carbide is the relatively high breakdown electric field strength
for the various polytypes. The critical electric field for breakdown is a function of the doping
concentration in the drift region (3). A comparison of the reported (4,5) variation of the critical
electric field (E c ) for the primary polytypes (6H, 4H, and 3C) and silicon is provided in Fig.
2. In general, the breakdown electric field for SiC is a factor of 7 to 8 times larger than for
silicon at the same doping concentration. However, it is misleading to use this ratio in Eq. (2)
because the doping concentration for the SiC device is much higher than for the silicon device
for the same breakdown voltage. When this is taken into account, a much larger figure of merit
is predicted (5).
The other important semiconductor material parameter required for analysis of the R on,sp
and BFOM is the mobility. Because the electron mobility is larger than that of holes, it is relevant
to consider only n-type drift regions. A comparison of the mobility of electrons in the three
SiC polytypes (6) with that in silicon is provided in Fig. 3. In general, the mobilities in SiC
are lower than those in silicon, offsetting some of the benefits of the higher breakdown electric
field strength.
IV. SPECIFIC ON-RESISTANCE OF DRIFT REGION
Using the critical electric field and mobility values shown in the figures, the specific on-resis-
tance can be calculated for each breakdown voltage. A comparison of the specific on-resistance
480 Baliga
Figure 3 Comparison of the electron mobility for silicon carbide and silicon.
calculated for the three polytypes with that for silicon is provided in Fig. 4. From this plot, it
can be concluded that the specific on-resistance of the drift region for all three polytypes lies
within a factor of 2, which is within the range of uncertainty created by the relatively sparse
data reported for E c and mobility for the SiC polytypes. More important, a conclusion that can
be derived from this plot is that the specific on-resistance of the drift region for SiC is about
200-fold smaller than that for silicon devices with the same breakdown voltage.
In order to gain a good perspective on the implications of the lower specific on-resistance
for SiC drift regions, it is beneficial to compare the on-state voltage drop for a 5000-V SiC
field effect transistor (FET) with that for the silicon Gate Turn-Off Thyristor (GTO) (the best
commercially available silicon bipolar power switch). The on-state operating point for any power
switch is decided by the maximum power loss that can be tolerated. For silicon devices in
typical packages, this power dissipation is about 100 W/cm 2. Although a higher value may be
anticipated for SiC because of the lower leakage currents arising from its wider band gap struc-
ture, it will be assumed here that the power dissipation is the same as for a silicon device. The
operating points for the SiC FET and the silicon GTO can then be compared with the aid of
Fig. 5. The silicon GTO operates at a current density of 35 A/cm 2 with an on-state voltage drop
of 3.5 V. In comparison, the SiC FET operates at a current density of 100 A/cm 2 with an on-
state voltage drop of only 1 V. Thus, the analysis predicts a greatly reduced on-state power loss
(factor of 3.5) in systems together with the benefits of a smaller (factor of 3.5) device area. In
addition, the SiC FET will be much easier to control because it does not require the large
Figure 4 Comparison of the specific on-resistance of the drift region for silicon carbide and silicon.
(typically one-third of the on-state current) gate drive current of the GTO, it will have a very
fast switching time (0.1 µs versus 10 µs for the GTO) because of majority carrier transport,
and it will have a very large forward-biased safe operating area allowing snubberless operation
in hard switching Pulse Width Modulation (PWM) circuit topologies. For high-voltage applica-
tions, the silicon Insulated Gate Bipolar Transistor (IGBT) structure has been widely accepted
for applications, and many MOS-gated thyristors are under development (3). Although develop-
ment of similar MOS-bipolar structures from SiC has been proposed (7), this approach is flawed
because of the very large built-in potential of the P-N junction in SiC, which makes the on-
state voltage drop for these structures much larger than for the SiC field effect transistors.
V. IDEAL EDGE TERMINATION
In the preceding section, the SiC FET was compared with a silicon GTO using the ideal specific
on-resistance of the drift region. In order to be able to exploit the benefits of the low drift region
resistance for SiC, it is essential that the breakdown voltage of devices not become limited by
the edge termination. Many edge terminations have been proposed and examined for silicon
devices that allow nearly ideal breakdown voltages to be achieved (3). In principle, the same
techniques should also work with SiC. However, the low diffusion coefficients for dopants in
482 Baliga
Figure 5 Comparison of the forward conduction characteristics of a 5000-V SiC FET with that of a
silicon 5000-V GTO.
SiC and the small depletion region widths preclude the development of the commonly used
multiple floating diffused field rings for silicon devices. Experiments performed using multiple
floating metal field rings and the resistive field plate structure have succeeded is producing only
50% of the ideal breakdown voltage (8).
A nearly ideal breakdown voltage was achieved in SiC Schottky barrier rectifiers by ion
implantation of argon at the periphery to create a high-resistivity amorphous layer (9) as shown
in Figs. 6 and 7. The presence of the high-resistivity layer reduces electric field crowding at
the edges of the metal because of lateral spreading of the potential as indicated by the depletion
layer boundary. This potential spreading has been confirmed by Electron Beam Induced Current
(EBIC) measurements (10). Numerical simulations of this edge termination structure indicate
that deep-level acceptor centers formed by the ion implant damage are responsible for the forma-
tion of the high-resistivity layer. The deep acceptor level must be located at least 0.6 eV below
the conduction band with a concentration several orders of magnitude greater than the doping
concentration for the potential spreading to occur. Such deep acceptor levels have indeed been
detected in the argon-implanted layer by Deep Level Transient Spectroscopy (DLTS) measure-
ments (11). This edge termination should be effective in all wide band gap semiconductors and
be generally applicable to rectifiers, FETs, and other high-voltage devices.
Figure 6 Argon-implanted edge termination for SiC devices for obtaining nearly ideal breakdown volt-
ages.
Figure 7 Measured breakdown voltage as a function of the argon ion implantation dose.
484 Baliga
VI. UMOSFET STRUCTURE AND DESIGN
The DMOS structure (3) is at present the most widely commercially available silicon power
MOSFET. The silicon UMOSFET structure (3) has been commercially introduced because of
its significantly superior specific on-resistance. This improvement arises from a combination of
the higher channel density and the elimination of the JFET component of the on-resistance
within the DMOS structure. In the case of SiC, the fabrication of the DMOS structure is not
practical because of the very low diffusion coefficients for dopants at temperatures at which
the refractory gate (polysilicon) is stable. The most viable power MOSFET structure from SiC
is therefore the UMOS structure shown in Fig. 8. In the case of SiC devices, the P-base and
N⫹ source regions can be fabricated using multiple epitaxial growth steps.
The electric field distribution in the UMOSFET during the blocking mode of operation
is depicted on the left-hand side in Fig. 8. Note that peak electric field occurs at the junction
with the depletion layer extending into the P-base and N-drift regions. In the case of silicon
devices, the doping concentration of the N-drift region must be low to obtain even relatively
small breakdown voltages. For example, a breakdown voltage of 100 V requires a doping con-
centration of the N-drift region below 5 ⫻ 10 15 cm ⫺3. Because the peak P-base doping concentra-
tion must be 1 ⫻ 10 17 cm ⫺3 to obtain an acceptable threshold voltage of 2 V, most of the
depletion extends in the N-drift region. In contrast, the doping concentration in the N-drift region
for SiC devices is much larger, leading to large depletion extension into the P-base region. In
order to prevent reach-through breakdown, the thickness of the P-base region must be made
larger than for a silicon device. This can add a significant channel resistance contribution to the
SiC UMOSFET, as discussed later.
Another important consideration during the design of the SiC UMOSFET is the high
electric field created at the sharp corners located at the bottom of the U-shaped gate regions.
In addition to producing premature breakdown in the semiconductor, this produces a high electric
field in the gate insulator (typically silicon dioxide). In accordance with Gauss’s law, the electric
field in the oxide will be higher than that in the semiconductor by a factor of 3. When the
maximum electric field (E m ) approaches the critical electric field (about 2 ⫻ 10 5 V/cm) for
silicon devices, the electric field in the gate oxide remains below its breakdown field strength
Figure 8 The power UMOSFET structure and the electric field profile in the blocking state.
(about 1 ⫻ 10 7 V/cm). However, in the case of SiC, when the maximum electric field approaches
the critical electric field (about 3 to 4 ⫻ 10 6 V/cm), the electric field in the oxide can exceed
its breakdown strength, leading to catastrophic failure. It is therefore imperative that the gate
insulator have a large dielectric constant to reduce the electric field.
The specific on-resistance of the UMOSFET can be analyzed by taking into account the
various components of the resistance in the current flow path between the source and the drain
electrodes. These components are (a) the resistance at the source and drain metal contacts; (b)
the resistance within the N⫹ source region and, more important, the thicker N⫹ substrate that
serves as the drain region; (c) the resistance of the inversion layer that serves as the channel in
the P-base region; and (d) the resistance of the drift region including the effect of current spread-
ing as shown in Fig. 9. The current spreading effect increases the specific resistance of the drift
region to a value greater than in the ideal case in which the current is assumed to flow uniformly.
It can be shown that the predominant components of the on-resistance are the channel and drift
region if the substrate component is reduced by thinning it.
As an example, the specific on-resistance calculated for the case of a 1000-V UMOSFET
is provided in Fig. 10 as a function of the inversion layer mobility (12). It can be seen that the
specific resistance approaches the ideal value for the drift region only when the inversion layer
mobility exceeds 200 cm 2 /V s. Unfortunately, the best reported value for the inversion layer
mobility in SiC is only 15 cm 2 /V s. Consequently, the channel resistance becomes dominant
with a contribution of 90% of the total resistance and the specific on-resistance is nine times
greater than the ideal value. The impact of poor inversion layer mobility for devices with other
breakdown voltages can be assessed by using Fig. 11. For the case of the measured inversion
layer mobility of 15 cm 2 /V s, much of the improved performance projected for SiC FETs is
lost unless the breakdown voltage exceeds 1000 V. Attempts at fabrication of SiC UMOSFETs
from 6H and 4H polytypes have produced very disappointing results with specific on-resistances
larger than those for silicon and breakdown voltages limited to less than 200 V (13).
Figure 9 Current flow path in the UMOSFET in the on state with the primary resistances in the current
flow path between source and drain.
486 Baliga
Figure 10 Impact of inversion layer mobility on the specific on-resistance of a 1000-V SiC UMOSFET.
The percentage contributed by the channel resistance can be read from the right-hand side.
Figure 11 Impact of inversion layer mobility on the specific on-resistance of SiC UMOSFETs with
various breakdown voltages.
Figure 12 Impact of cell pitch on the specific on-resistance of a 1000-V SiC UMOSFET for the case
of an inversion layer mobility of 15 cm 2 /V s.
One approach to solving this problem is to increase the channel density by using a smaller
cell pitch. The calculated specific on-resistance with an inversion layer mobility of 15 cm 2 /
V s for cell pitches reduced from 6 to 1 µ is plotted in Fig. 12, where the components of the
resistance are included for comparison. It is worth pointing out that the calculated drift region
resistance is smaller than the ideal value. This unusual result is due to the fact that a substantial
fraction of the blocking voltage is supported within the P-base region in the SiC UMOSFET,
allowing higher doping and a smaller thickness to be used for the drift region than in the ‘‘ideal
case.’’ It should be noted that the specific on-resistance becomes close to the ideal value only
when the cell pitch becomes close to 1 µm. This imposes severe technological challenges for
the development of high-performance SiC UMOSFETs because of the high-resolution lithogra-
phy and the very small trench width that must be etched and refilled with polysilicon.
VII. ALTERNATIVE SILICON CARBIDE POWER SWITCH STRUCTURES
Because of the problems with SiC UMOSFETs pointed out in the previous section, it becomes
important to consider alternative device embodiments. Two device structures described in this
section make it possible to circumvent these issues.
A. High-Voltage ACCUFET Structure

The problems with the poor inversion layer mobility in SiC can be addressed by using the
ACCUFET structure shown in Fig. 13 (14). Here, the P-base region has been replaced with a
very lightly doped N-region. If the spacing between the trench sidewalls is chosen so that the
488 Baliga
Figure 13 The power ACCUFET structure.
N-region is depleted at zero gate bias, a potential barrier is formed below the N⫹ source region
that prevents the transport of electrons between the source and drain. This allows the structure
to block current flow even at large drain voltages, providing its forward blocking capability.
When a positive bias is applied to the gate electrode, an accumulation layer is formed at the
sidewalls of the trenches, allowing the transport of electrons from the source to the drain. In
the case of silicon, it has been demonstrated that the accumulation layer mobility is close to
the bulk values (3). If this is applicable to SiC, the ACCUFET can be shown to have a smaller
specific on-resistance. As an example, the specific on-resistance is shown in Fig. 14 for the case
of a channel mobility of 100 cm 2 /V s for cell pitch ranging from 6 to 1 µm. It can be seen that
the specific on-resistance is now close to the ideal value even for a cell pitch of 6 µm. This
indicates that the ACCUFET is more technologically feasible.
B. The Baliga Pair Configuration

In the case of silicon bipolar transistors, the Darlington pair is a well-know configuration for
obtaining a higher current gain. In the same vein, it is possible to create an attractive power
switch configuration with a silicon carbide MESFET or JFET and a silicon MOSFET. This
circuit configuration, which will be referred to as the Baliga pair configuration for convenience,
is shown in Fig. 15. It consists of an Si power MOSFET connected in series with the source
region of an SiC high-voltage power MESFET or JFET. Either vertical channel or a lateral SiC
FET structures can be utilized. It is important to note that the gate region of the SiC MESFET
is connected to the reference terminal (or source region of the silicon power MOSFET) and the
composite switch is controlled by a signal applied only to the gate of the silicon power MOSFET.
The basic operating principles of this switch are discussed in the following.
If the half-width a of the MESFET channel is designed to be larger than the zero bias
depletion width of the MESFET gate structure, the MESFET behaves as a depletion-mode (or
normally on) device structure. When an increasing positive bias is applied to the drain (D B ) of
the Baliga pair with gate (G B ) shorted to the source (S B ), the voltage is initially supported by
Figure 14 Impact of cell pitch on the specific on-resistance of a 1000-V SiC UMOSFET for the case
of a channel mobility of 100 cm 2 /V s.
Figure 15 The Baliga pair power switch configuration utilizing a high-voltage SiC MESFET and a low-
voltage silicon MOSFET.
490 Baliga
the silicon MOSFET because the MESFET channel is not depleted. This results in an increase
in the potential of the source region S SiC of the SiC MESFET. Because the gate G SiC of the
silicon carbide MESFET is at zero potential, this produces a reverse bias across the gate-source
junction of the MESFET. As the voltage applied to the drain D B is increased, this reverse bias
produces pinch-off of the MESFET channel by the extension of a depletion region from the
gate contact. Once the MESFET channel pinches off, any further increase in the voltage applied
to the drain D B is supported by the extension of a depletion region in the drift region of the SiC
MESFET. It has been shown by two-dimensional numerical simulations that, once the channel is
pinched off, the potential at the drain D M of the MOSFET remains relatively constant and inde-
pendent of the voltage applied to the drain D B of the composite switch. Since a channel pinch-
off voltage of less than 25 V can easily be designed, this implies that a silicon power MOSFET
with relatively low breakdown voltage can be used in conjunction with a high-voltage silicon
carbide MESFET to form the Baliga pair. This is important from the point of view of obtaining
a low total on-state voltage drop for the composite switch.
In order to turn on the Baliga pair, a positive gate bias is applied to the gate G M of the
silicon power MOSFET, which also serves as the gate G B of the composite switch. This switches
the silicon MOSFET to its highly conductive state. When a positive voltage is applied to the
drain D B, current can now flow through the undepleted MESFET channel and the silicon MOS-
FET. The simulations have demonstrated that the specific on-resistance of the SiC MESFET is
very close to the ideal specific on-resistance for the drift region because of a uniform current
distribution in the drift region. The resistance contribution from the MESFET channel increases
the specific on-resistance by less than 25% because the current is transported in the bulk and
not along a surface. Thus, the Baliga pair is projected to have on-state voltage drops of only
0.1 V when the SiC MESFET is designed to block up to 1000 V.
The Baliga pair has several other important attributes. The first is an excellent forward-
biased safe operating area. This is achieved by simply reducing the gate bias applied to
the switch until it approaches the threshold voltage for the silicon power MOSFET. In this
case, when a voltage is applied to the drain D B, the MOSFET operates in its current saturation
regime. This limits the current flowing through the composite switch. When the voltage applied
to the drain D B is increased, the voltage across the MOSFET increases until the channel of the
MESFET is pinched off, allowing high voltages to be sustained with a current flow dictated by
the MOSFET channel. Numerical simulations indicate a square Forward Biased Safe Operating
Area (FBSOA) for the Baliga pair because no minority carrier transport is involved. The absence
of minority carrier transport in the Baliga pair is also important in obtaining a high switching
speed. As both the silicon MOSFET and the silicon carbide MESFET are unipolar devices, the
turn-off time for the composite switch is determined by the charging and discharging time con-
stants for the silicon MOSFET. Well-optimized silicon power MOSFETs can be designed at
the required low breakdown voltages, resulting in a very high switching speed for the Baliga
pair. This is attractive for the reduction of power losses in medium- to high-voltage power
electronic systems operating at high frequencies.
Another attribute of the Baliga pair is that it incorporates an excellent integral flyback
diode. In the case of the silicon power MOSFET, the junction between the P-base region and
the N-drift region can be utilized as a reverse conducting (flyback) diode. However, this diode
operates with the injection of minority carriers into the drift region, which compromises the
switching speed and power losses in the devices. In the case of the SiC MOSFET structure,
there is an additional disadvantage that the potential required for the injection of minority carriers
is much larger (typically 3 V) when compared with silicon (typically 1 V) because of its larger
energy band gap. This results in a severe increase in the power losses for the flyback rectifier.
In contrast to this, in the case of the Baliga pair, the application of a negative bias to the drain
D B forward biases the Schottky barrier gate structure. The SiC Schottky barrier rectifier has
been demonstrated to have excellent on-state and switching characteristics because it is a unipo-
lar device. Thus, the Baliga pair also contains an excellent flyback diode if implemented by
using a high-voltage SiC MESFET structure.
VIII. POWER RECTIFIERS
In conjunction with power switches, high-performance power rectifiers are required in all power
electronics systems. The most commonly used high-voltage power rectifier today is the silicon
P-i-N structure (3). A major problem with utilizing this device in circuits is the large reverse
recovery transient that occurs due to the stored charge within the i-region. This reverse recovery
produces significant power losses in the rectifier and the switches at each switching cycle. Im-
provements in silicon high-voltage power rectifiers have been achieved by combining a Schottky
contact region with the P-i-N region, but the reverse recovery current is not eliminated. Although
high-voltage P-N junctions have been reported in SiC (15), the large band gap for SiC results
in a very large on-state voltage drop (⬎3 V), making these devices unattractive compared with
silicon devices.
The development of SiC Schottky barrier rectifiers can provide a much superior high-
voltage power rectifier for applications. The basic structure of the high-voltage Schottky rectifier
is shown in Fig. 16 together with the band diagram and equivalent circuit. A unique feature of the
high-voltage Schottky rectifier is the lightly doped drift region needed to support high blocking
voltages. The on-state voltage drop in the high-voltage Schottky rectifier then consists of the
voltage drop across the metal-semiconductor barrier and that across the N-drift region (assuming
that the voltage drop across the N⫹ substrate can be neglected) (3):
VF ⫽
KT
q 冢冣
J
ln F ⫹ R on,sp J F
Js
(3)
Figure 16 Basic structure of a high-voltage Schottky barrier rectifier with its band diagram and equiva-
lent circuit.
492 Baliga
Figure 17 Calculated forward conduction characteristics of SiC Schottky barrier rectifiers with various
breakdown voltages.
As discussed earlier in conjunction with the SiC FETs, the specific on-resistance of the drift
region for SiC is 200-fold smaller than for the silicon device with the same breakdown voltage.
This makes it possible to design SiC Schottky rectifiers with high blocking voltages and low
on-state voltage drop.
The forward conduction characteristics of SiC Schottky barrier rectifiers can be calculated
for various breakdown voltages by taking into account the resistance of the drift region. In Fig.
17, the calculated forward characteristics are provided for breakdown voltages ranging from
200 to 5000 V for the case of a Schottky barrier height of 1.2 eV (3). This relatively large
barrier height was chosen to make the reverse leakage current small. From these plots, it can
be concluded that SiC Schottky barrier rectifiers with blocking voltages as high as 5000 V may
be feasible because their on-state voltage drop will be less than 2 V. This is superior to that of
silicon P-i-N rectifiers. The main benefit of such devices would be the elimination of the reverse
recovery transient in power circuits. Experimental verification of the feasibility of fabricating
high-voltage SiC-based Schottky rectifiers was first reported in 1992 with the fabrication of a
450-V device with an on-state voltage drop of only 1 V (16). These devices exhibited fast
switching with no reverse recovery transient as expected. Subsequently, the breakdown voltage
of SiC Schottky barrier rectifiers has been extended to above 1000 V (17). These rectifiers
already exhibit excellent performance for power electronic applications.
IX. CONCLUSIONS
Theoretical analysis indicates very positive prospects for the development of SiC power devices
that can outperform silicon power devices. High-voltage Schottky rectifiers have already been
fabricated with excellent performance. Although problems have been encountered with the de-
velopment of high-performance SiC power MOSFETs, it has been demonstrated in this chapter
that a high-voltage SiC MESFET can be used together with an Si power MOSFET to create
an excellent power switch with an integral flyback diode. Although the demonstration of high-
performance SiC MESFETs can be expected shortly, the commercialization of SiC technology
will require an increase in wafer size with a significant reduction in cost.
ACKNOWLEDGMENTS
The author wishes to acknowledge the encouragement and support of the sponsors of the Power
Semiconductor Research Center, which has enabled significant advances to be made in SiC
device and process technologies over the past 4 years.
REFERENCES
1. BJ Baliga. Semiconductors for high voltage vertical channel field effect transistors. J Appl Phys 53:
1759, 1982.
2. BJ Baliga. Power semiconductor device figure of merit for high frequency applications. IEEE Elec-
tron Device Lett 10:455, 1989.
3. BJ Baliga. Power Semiconductor Devices. Boston: PWS Publishers, 1995.
4. JW Palmour, CH Carter, CE Weitzel, KJ Nordquist. High power and high frequency silicon carbide
devices. Materials Research Society Meeting, 1994, p 133.
5. M Bhatnagar, BJ Baliga. Comparison of 6H-SiC, 3C-SiC, and Si for power devices. IEEE Trans
Electron Devices ED-40:645, 1993.
6. WJ Schaffer, HS Kong, GH Negley, JW Palmour. Hall effect and C-V measurements on epitaxial
6H- and 4H-SiC. Proceedings 5th Conference on Silicon Carbide and Related Materials, 1993, p
155.
7. A Bhalla, TP Chow. Bipolar power device performance: dependence on materials, lifetime, and
device ratings. International Symposium on Power Semiconductor Devices and ICs, 1994, p 287.
8. M Bhatnagar, H Nakanishi, S Bothra, PM McLarty, BJ Baliga. Edge terminations for SiC high volt-
age Schottky rectifiers. International Symposium on Power Semiconductor Devices and ICs, 1993,
p 89.
9. D Alok, BJ Baliga, PM McLarty. A simple edge termination for silicon carbide devices with nearly
ideal breakdown voltage. IEEE Electron Device Lett 15:394, 1994.
10. D Alok, BJ Baliga. A planar, nearly ideal, SiC device edge termination. International Symposium
on Power Semiconductor Devices and ICs, 1995, p 96.
11. D Alok, BJ Bliga, M Kothandaraman, PK McLarty. Argon implanted SiC device edge termination:
Modelling, analysis and experimental results. Sixth International Conference on Silicon Carbide and
Related Materials, Paper ThA-I-5, 1995.
12. M Bhatnagar, D Alok, BJ Baliga. SiC Power UMOSFET: Design, Analysis, and Technological Feasi-
bility. Proceedings 5th Conference on Silicon Carbide and Related Materials, 1993, p 703.
13. JW Palmour. Vertical power devices in silicon carbide. Inst Phys Conf Ser 137:499, 1994.
14. BJ Baliga. Silicon carbide field effect device. U.S. Patent 5,323,040, June 21, 1994.
15. LG Matus, JA Powell, CS Salupo. High voltage 6H-SiC p-n junction diodes. Appl Phys Lett 59:
1770, 1991.
16. M Bhatnagar, PK McLarty, BJ Baliga. Silicon carbide high voltage (400V) Schottky barrier diodes.
IEEE Electron Device Lett 13:501, 1992.
17. T Kimoto, T Urushidani, H Matsunami. High voltage (⬎ 1 kV) SiC Schottky barrier diodes with
low on-resistance. IEEE Electron Device Lett 14:548, 1993.
21
Science and Technology of Boron Nitride
Osamu Mishima
National Institute for Research in Inorganic Materials, Tsukuba, Ibaraki, Japan
Koh Era
Helios Optical Science Laboratory, Inc., Tsukuba, Ibaraki, Japan
I. INTRODUCTION
The compound boron nitride (BN) has no counterpart in nature on the earth. Up to the present
various types of BN have been synthesized, starting with the synthesis of a hexagonal layered
compound in 1842 (1).
In 1957, boron nitride with the zinc blende (sphalerite) structure was synthesized, by
Robert H. Wentorf, Jr. (2) of General Electric Company, under high-pressure and high-tempera-
ture conditions using an apparatus similar to that developed by his group for the synthesis of
diamond. This opened a field of important applications similar to those of diamond (3). Since
then, powders, grains, and sintered compacts of the compound have been mass produced in
high-pressure factories and have become very important materials for grinding and cutting appli-
cations, supporting modern industries.
This compound has been mainly called cubic boron nitride (cubic BN) after Wentorf (3)
(see also Table 1 for various names) and usually abbreviated cBN. (CBN or C-BN with capital
letter C may be confused with the material carbon-boron-nitrogen, usually written as BCN, or
a C/BN heterojunction and should be used with care.)
The potential of cBN as a semiconductor was also shown by Wentorf (4). cBN can be
regarded as the extreme of III-V compounds from the viewpoint of periodic table systematics.
Indeed, its band gap energy (estimated to be 6.3 eV; see Sec. III.A) is the widest among known
semiconductors including diamond. This fact gives us a hint that cBN has new potential in
electronic applications.
The present chapter deals mainly with cBN on the basis of references published up to
1995. Other phases of BN are described only in conjunction with cBN. The main body was
written by Mishima and revised and edited by Era.
Studies of cBN have also been reviewed in handbooks, conference proceedings, and jour-
nals (5–14).
II. STRUCTURE OF BN PHASES

Boron nitride has many names: hBN, rBN, cBN, wBN, zBN, αBN, βBN, γBN, tBN, pBN, iBN,
aBN, EBN, ABN, SBN, BORAZON, elbor, cubonite, and more. Although many names are
495
496 Mishima and Era
Table 1 Names of BN Phases

Crystal Amorphous
Hexagonal BN (hBN) Pyrolytic BN (pBN) Turbostratic BN (tBN)
BN αBN
Graphite-like BN (BNg)
Rhombohedral BN
(rBN)
Ion-bombarded BN (iBN)
Cubic BN (cBN)
Zinc blende BN (zBN), βBN sp 3-amorphous BN (aBN)
Borazon, sphalerite BN (BNsp)
Elbor, cubonite, okmal
[Trademark: powder]
BORAZON (GE)
SBN (Showa Denko)
ABN (DeBeers)
Wurtzite BN (wBN)
γBN, BNw, hexanite
BN? Explosion BN (EBN)
confusing, we can simply group these boron nitrides into four crystalline phases, amorphous
BN and their mixed states as shown in Table 1. These BN phases can exist at room temperature
at 1 atm.
The atomic and molecular weights of these boron nitrides are listed in Table 2. Note that
10
B has a large cross section for thermal neutron capture and changes to 7Li with the emission
of an alpha-particle [ 10B(n, α) 7Li].
A. Crystalline BN Phases
The structures of the four crystalline BN phases are shown in Figs. 1 and 2. Lattice data are
given in Table 3. The cBN (2,15) and wBN (16) have tetrahedral sp 3 BEN bonding and their
structures correspond to those of cubic and hexagonal diamond, respectively.
Table 2 Atomic and Molecular Weights of BN

Property Boron (B) Nitrogen (N)
Atomic number 5 7
Atomic weight ( 12 C ⫽ 12.000) 10.81 14.0067
10
B ⫽ 10.013 (19.7%)
11
B ⫽ 11.009 (80.3%)
Boron nitride (BN)
Molar weight 24.82 g (B, 43.6%; N, 56.4%)
(Avogadro’s number: 6.0225 ⫻ 1023 mol⫺1 )
Science and Technology of Boron Nitride 497
Figure 1 The four BN crystals.
The hBN (17) and rBN (18–20) have trigonal sp 2 bonding and their structures are similar
to, but not the same as, the graphite structure. The densities of sp 3 crystals (cBN and wBN) are
1.5 times larger than those of sp 2 crystals (hBN and rBN) under normal pressure-temperature
conditions.
These four crystalline structures of BN have hexagonal rings made of three boron atoms
and three nitrogen atoms, as shown in Fig. 2. Both hBN and rBN have flat sp 2 6-rings, and cBN
and wBN have puckered sp 3 6-rings. The BEN distance in the sp 2 6-rings (144 pm) is shorter
by ⬃8% than that in the sp 3 6-rings (157 pm), which indicates that the BEN bonding in the
6-ring plane of hBN and rBN is stronger than that in cBN and wBN. In contrast, the distance
(333 pm) between the layers of sp 2 6-rings in hBN and rBN is relatively long, indicating that
the binding force between the layers is weak. Hence, hBN and rBN may be regarded as molecular
crystals made of layers of a flat sp 2-network ‘‘molecule.’’ Roughly speaking, when molecular
crystals are subjected to high pressures, their structures generally change to more atomic forms.
Figure 2 Structural relations among the four BN crystals.

498 Mishima and Era
Table 3 Lattice Data for BN Crystals

hBN rBN cBN wBN
a ⫽ 250.441(7) pm a ⫽ 250.4 pm a ⫽ 361.58 pm a ⫽ 255.3 pm
c ⫽ 665.62 (4) pm c ⫽ 1001 pm (BEN: 156.56 pm) c ⫽ 422 pm
ρ ⫽ 2.34 g/cm 3 ρ ⫽ 2.2 g/cm 3 (cal.) ρ ⫽ 3.49 g/cm 3 ρ ⫽ 3.45 g/cm 3
P63 /mmc R3m F43m P63 mc
That is, the distance between the molecules contracts and the distance between the atoms in the
molecule expands relatively. When the sp 2 ‘‘molecular’’ BN crystals are subjected to high pres-
sures, they change to the atomic sp 3 crystals and we can see the common pressure-induced
structural conversion from molecular to atomic crystals.
The reported X-ray diffraction spectra of BN phases are reproduced in Fig. 3. The X-ray
diffraction data are given in Refs. 17 and 19 and Joint Committee on Powder Diffraction Stan-
dards (JCPDS): 34-421 for hBN; in Refs. 18–20 for rBN; in Refs. 16, 25, 27, and 59, JCPDS:
35-1365 and 25-1033, for cBN; and in Refs. 16, 25, 27, and 59, JCPDS:26-772 for wBN. The
spectral peaks around 2θ ⫽ 25° correspond to the distance (⬃333 pm) between the layers of
the sp 2 networks. Some peaks around 2θ ⫽ 40°–50° are due to the atoms in the sp 2 or sp 3
6-rings. The lattice data are summarized in Table 3.
Figure 3 Schematic X-ray diffraction patterns of BN phases. (Data from Refs. 20, 32, 42, 45, 61, 62.)
Regarding wBN, which can be made by compression of hBN at low temperatures

(16,21,23–25) or by shock wave compression (22,27–33), the cell constant along the c-axis of
wBN (421–422 pm, depending on defects in wBN) is reported to be ⬃1% longer (c/a ⫽ 1.653)
than that of the ideal tetrahedral structure (418 pm, c/a ⫽ 1.633) (21,33,35). Hence, the density
of wBN (3.45 g/cm 3) is thought to be ⬃1% lower than that of cBN (3.49 g/cm 3) (35).
Besides the four crystalline BN phases already mentioned, there is a crystalline material
called EBN. EBN was found in shock-compressed BN samples and was reported to have a face-
centered cubic structure with lattice constant a0 ⫽ 840.5 pm and a density ρ ⫽ 2.55 g/cm 3
(5,29–31,36) (JCPDS:18-251). A material having an X-ray diffraction pattern similar to that of
EBN has also been synthesized by the vapor deposition method (37,38). However, an unambigu-
ous structural analysis, using samples of an EBN single phase, has not been carried out and the
chemical composition of EBN is also unknown and may be different from that of stoichiometric
BN. There is a report indicating that EBN is BN1⫺xOx (39).
B. Noncrystalline BN
In this chapter, we define amorphous BN as the material having halo diffraction patterns. This
implies that amorphous BN has no translational long-range order and is either truly amorphous
(without lattice periodicity) or microcrystalline (from the presence of halo patterns ⬍⬃2 nm
in size).
Generally, it is difficult to distinguish experimentally between the truly amorphous states
and the microcrystalline states. Although high-resolution electron microscopy can provide
atomic-level information, knowledge of the detailed amorphous structure of BN is vague. Never-
theless, we usually think of two kinds of amorphous BN, tBN (sp 2-amorphous BN) and aBN
(sp 3-amorphous BN), by analogy with amorphous graphite and diamond-like amorphous (DLA)
carbon (Table 1 and Fig. 4).
According to Biscoe and Warren (40,41), the turbostratic structure (unordered layers),
first found in carbon black (amorphous graphite), consists of roughly parallel ⬃6-ring layers
that are piled up at translational and rotational random about the layer normal. The material
called tBN shows the halo X-ray diffraction pattern characteristic of this turbostratic structure
(Fig. 4). It has a broad diffraction peak around 2 θ ⫽ 25° to the distance between the layers
(⬃333 pm) (Fig. 3) (42).
Analysis of the diffraction patterns of tBN indicated that the average group of parallel
layers had several sp 2 sheets and had a thin ‘‘wafer’’ shape, although other tBN structures may
Figure 4 Plausible amorphous BN structures.

500 Mishima and Era
be possible depending on the conditions of synthesis. For example, we can expect a fine granular
group of parallel turbostratic layers and even a fully disordered sp 2 structure (isotropic tBN?—
see Fig. 4). However, these amorphous BN phases have not been observed to date.
The tBN can have a variety of macroscopic structures (43) (A, B, and C in Fig. 4). For
example, a hollow tubular shape with turbostratic BN walls (micron-tubes: C in Fig. 4) has
been made upon heating some amorphous BN material.
When these turbostratic layers become ordered, the tBN becomes so-called pBN. The
pBN is highly oriented tBN or tBN⫹hBN and is produced, for example, at high temperatures
and low pressures by the chemical vapor deposition (CVD) method (probably the D region of
Fig. 3 of Ref. 43) (A in Fig. 4). When the pBN structure is further ordered, it finally becomes
crystalline hBN. The details of how this structural ordering occurs are unknown (42).
We can also think of fully disordered ⬃BN structures as similar to diamond-like amor-
phous carbon (amorphous diamond). Here, we call this sp 3-amorphous BN, aBN. The aBN
would have a broad diffraction peak around 2 θ ⫽ 40°–50° and no peak around 2 θ ⫽ 25°
because of the absence of the sp 2-layer structure. Actually, there exists amorphous BN whose
2 θ ⫽ 40°–50° peak is relatively strong and its 2 θ ⫽ 25° peak is weak (45). This may be the
aBN with a small fraction of tBN. However, preferentially oriented tBN may show a similar
diffraction pattern and, therefore, conclusive evidence of the existence of the sp 3 aBN is lacking
at present.
There is a hard amorphous (or quasi-amorphous) BN that is made by the low-pressure
ion-beam deposition method. This amorphous BN is called iBN; the prefix ‘‘i’’ alludes to the
essential role of ions in this preparation method. The structure is supposed to have sp 3 and sp 2
bondings (46,47).
One may think that the general structure of amorphous BN is a homogeneous mixture of
the sp 2-amorphous tBN and the sp 3-amorphous aBN and that the structure changes continuously
between these two amorphous states. A first-order phase transition between two amorphous
structures of H2O has been reported, showing polymorphism in the amorphous structure of this
material (48,49). This idea (polymorphism in an amorphous structure) may be applied to amor-
phous BN; that is, like crystalline phases, the tBN and the aBN may be distinctly different
amorphous phases with well-defined different amorphous structures. Raman, infrared, and elec-
tron energy loss spectra (EELS) of BN have shown that vibrational frequencies of sp 2 and sp 3
bonding in all of the BN materials examined (including amorphous BN) were distinctly separated
and did not show any clear evidence of sp 2-sp 3 frequency merging. The absence of frequency
merging indicates absence of intermediate sp 2-sp 3 states and may suggest the possibility of
polymorphism in amorphous BN. It is difficult at present to resolve sp 2 and sp 3 BEN distances
in the radial distribution function of the X-ray diffraction pattern of amorphous BN (Fig. 5).
Although one diffraction analysis suggested that the amorphous BN has a structure of mixed
sp 2(hBN)-sp 3 (cBN) clusters (50), another analysis indicated that the structure is disordered even
at short range (52). Further studies are desirable. In this connection, there has been a study of
a pressure-induced phase change between a low-density liquid and a high-density liquid of high-
temperature carbon (51).
If a glass transition were observed in amorphous BN, we could associate the material with
supercooled BN liquid and melt-quenched BN glass. However, no glass transition in amorphous
BN has been reported so far.
C. Phase Diagram
Experimental results for the observed transitions between the four crystalline BN phases and
the amorphous BN are shown in Fig. 6.
Figure 5 Radial distribution function, G(r), of amorphous BN. (Data from Ref. 52.)
When hBN is compressed at room temperature, it transforms sluggishly to wBN around

10–15 GPa (F in Fig. 6, see also Fig. 7). (7,16,24). When rBN is compressed at room tempera-
ture, its structure changes to an unknown form [tBN?, hBN?, wBN? (53), cBN? (54)] at 4–8
GPa (G in Fig. 6). When it is further compressed beyond ⬃20 GPa and recovered at 1 atm, the
recovered phase is cBN according to Ref. 54 (E in Fig. 6).
Sluggish structural transformations and irreversible phase transitions are common at low
temperatures, where thermal agitation is inactive and atomic rearrangement is difficult. These
sluggish transformations are affected by kinetic factors and depend on individual experimental
conditions such as stress, time scales, and defects in crystals. Therefore, the observed transition
pressures and transition temperatures at low temperatures (B, C, D, E, F, and G in Fig. 6) do
Figure 6 The BN phase diagram. (Data from Refs. 16, 22, 23, 42, 45, 54, 61, 62, 65, 66.)
502 Mishima and Era
Figure 7 Transitions in BN during compression and heating. (Data from Refs. 16, 22, 23.)
not mean thermodynamic equilibrium phase boundaries and these transition regions vary with
experimental conditions.
When hBN with preferential ordering along c-axes (e.g., A in Fig. 4) was compressed at
relatively low temperatures and transformed directly to wBN, the preferential crystal orientation
in the starting hBN was found to be maintained in transformed wBN. This indicated that the
(002) planes of the wBN were parallel to the sp 2 planes of the hBN (24) (see also Ref. 21).
This structural relation suggested that the transition was a martensitic diffusionless transition.
Besides, some transitions observed in shock experiments (27,28,33,56) suggested that the mar-
tensitic transformation occurs from hBN to wBN and from rBN to cBN (Fig. 2). This martensitic
transition was also considered (57) and studied theoretically (58). Thus atomic diffusion during
the transitions was considered to be suppressed at low temperatures and in the short duration of
shock experiments (usually less than 1 µs). On the other hand, some experimental observations
contradict this simple martensitic mechanism. Shock experiments showed that transitions occur
from hBN to cBN and from rBN to wBN probably via an intermediate phase (59–61). With
static compressions of rBN at low temperature, the rBN transformed to wBN (53). Apparently
there are multiple transformation paths among these BN phases even if the transitions are mar-
tensitic.
The structural transformations occur more easily at higher temperatures. Roughly speak-
ing, over the usual time scale and in the 0–10 GPa region, crystallization of tBN usually starts
at 1000–1300 K (D in Fig. 6) (42,45,62), crystal-crystal transitions at 1500–2000 K (B and C
in Fig. 6 and Fig. 7) (23,63), and sintering and recrystallization at 1700–2200 K (64,65). When
cBN is heated at 1 bar, it transforms kinetically to hBN at ⬃1300°C in air and at ⬃1600°C in
vacuum (10).
Very little is known about the equilibrium pressure-temperature phase diagram of BN
(23,66) because of the retardation of the transformation at low temperatures and difficulty in
carrying out high-temperature experiments at high pressures. Tentative equilibrium phase bound-
aries are shown by the dashed lines in Fig. 6.
Hexagonal BN and cBN are thermodynamically stable at high temperatures at low and
high pressures, respectively. The boundary between hBN and cBN is approximately known
experimentally between 1500 and 3000 K (A in Fig. 6 is from Ref. 23). Compared with the
graphite-diamond boundary, the hBN-cBN boundary is located ⬃2 GPa to the low-pressure
side, suggesting that cBN is relatively stable at low pressures compared with diamond.
The low-temperature hBN-cBN boundary shown in the figure was obtained by thermody-
namic considerations, as mentioned in Sec. III. C. 1. The hBN-cBN boundary extrapolates to
nearly zero pressure at 0 K, which gives rise to the possibility of cBN being stabler than hBN
at low temperatures and at 1 atm, as has also been suggested by some theoretical studies (58,67)
and experimental analyses (68,69). There are discussions of the hBN-cBN equilibrium boundary
(70,71), and further study of the boundary is necessary.
Other phase boundaries of BN, shown by dashed lines in Fig. 6, are speculated upon by
analogy with the carbon phase diagram (72). There is a maximum in the melting curve of
graphite, so hBN is supposed to have a melting curve maximum, suggesting the presence of a
significant density change in liquid BN. The melting temperature of diamond is considered to
increase as pressure increases (73), so the melting temperature of cBN is speculated to increase
with pressure. From the Clausius-Clapeyron equation, this suggests that BN liquid is less dense
than the cBN crystal and that the melt-quenched BN glass, if obtainable, would also be less
dense than cBN. If the structure of sp 3-amorphous BN (aBN) resembles this melt-quenched
glass, its density would be lower than cBN’s and the aBN would be softer than cBN.
The cBN can exist up to at least ⬃100 GPa as shown by static (74) and shock compression
(75) experiments. No new BN phase, except for EBN as discussed in Sec. II.A, has been found
in these compression experiments. [Note that EBN, if it is a BN phase, has a low density (2.55
g/cm 3) and should be a low-pressure phase.] Theoretical work suggests that cBN is stable up
to about 1 TPa (⫽1000 GPa), where it would change to the rock salt structure (76,77). Theoreti-
cal and experimental work (27,78) also suggests that wBN is always thermodynamically meta-
stable. Theoretical work suggests that wBN is stabler than cBN beyond 133 Gpa (78).
Regarding the possibility of new BN phases, BN materials with an entirely sp 2-bonded
structure (bct-4 and similar crystals) and with unusual mechanical and thermal properties have
been theoretically proposed (Fig. 8) (79,80). A BCN material with an sp 2-layered structure is
claimed to exist (81,82). The possibility of a solid solution or compound of BC2N (or BCN)
with an sp 3-bonded structure was experimentally and theoretically studied; some experimental
studies claimed the formation of a BCN compound (see references in Ref. 83), whereas others
suggested that mixing of diamond and cBN (or formation of a solid solution) is difficult (83,84).
Figure 8 Hypothetical bct-4 and BN- and BCN-ball structures. (From Refs. 79, 80, 85, 86.)
504 Mishima and Era
There have also been some theoretical studies of BCN (85) and BN (86) balls with structures
similar to that of C60 (Fig. 8).
D. Structure and Polarity of Cubic BN

Is the electric polarity of cBN B ⫺N ⫹ or B 3⫹N 3⫺? As shown in Fig. 9, the B ⫺ and N ⫹ atoms,
made by an N-B transfer of an electron to give four electrons each, may have covalent bonding
as is the case for diamond. Alternatively, the B 3⫹ and N 3⫺ atoms, resulting from a B-N transfer
of three electrons, may have ionic bonding.
From an analysis of the (200) X-ray diffraction intensity (85), which reflects any differ-
ences in the number of electrons on the B and N atoms, and experimentally obtained electron
density distributions (88) as well as theoretical analyses (90–96), cBN was found to have an
electric polarity of B ⫹δ N ⫺δ (δ ⬃0.4). Therefore, there is an electron charge transfer of about
0.4e from the B to the N atoms. As shown in Fig. 9, electrons forming covalent bonding shift
toward the more electronegative N atoms. This shift of the bonding electrons is characteristic
of III-V compound materials and provides properties different from those of diamond, which
has a symmetric electron distribution with two electron density peaks. Cubic BN is usually
considered to have both covalent (75%) and ionic (25%) aspects. The covalent radius of boron
is said to be ⬃20% larger than that of nitrogen in this connection.
Figure 9 Electric polarity of cBN. (Charge density from Ref. 95.)

1. Crystallographic Polarity
As shown in Fig. 10, the zinc blende structure has crystallographic polarity along 〈111〉 axes
by nature. That is, there are (111)B and (1¯1¯1¯)N surfaces in cBN crystals, which results in the
characteristic crystal habit and surface morphology. The crystallographic polarity of cBN should
also affect etching behavior, crystal growth, dislocations, strain and abrading properties, chemi-
cal reactivity, impurity concentrations, etc. as observed in other sphalerite compounds (97).
Absolute crystallographic polarity of cBN crystals was determined by Rutherford back-
scattering spectroscopy (RBS) using helium ion beam (98).
2. Habit, Morphology, and Etching

Crystal habit, surface morphology, and the etching behavior of cBN crystals made by the solvent
method at high pressures are discussed here because crystals made by other methods are too
small to be studied at present.
a. Habit and Morphology
In principle, growth habit and surface morphology depend on individual growth conditions.
Besides effects caused by the individual growth conditions, the usual cBN crystals, made by
using a solvent (such as Li3BN2 , LiCaBN2, or other boron nitrides) at high pressures, have
their own characteristic habit and surface morphology, which are caused by the crystallographic
polarity of cBN (10,15,100–103).
The growth shape of cBN crystals is essentially tetrahedral, although almost cubic shapes
with (100) faces sometimes appear and twins and cleaved faces complicate the crystal shape.
The tetrahedral crystals appear because the surface energy is different between (111)B and
(1¯1¯1¯)N: low-energy and inactive surfaces dominate during the crystal growth.
The (1¯1¯1¯)N faces are usually large, smooth, shiny, and flat (Fig. 11). Growth hillocks and
growth layers are observed on (1¯1¯1¯) faces, which make the faces incline from the exact (1¯1¯1¯)
and result in a relatively rough appearance. Boundaries between (1¯1¯1¯) and adjoining (100) faces
are sometimes vague due to this inclination from the exact (1¯1¯1¯).
The (111)B faces usually have a small and rough (or matted) appearance. The (111) faces
are flat throughout the face, and boundaries between (111) and adjoining (100) faces are usually
distinct. It seems difficult to observe growth layers on (111) faces.
The (100) faces are macroscopically nonpolar. There should be no gross differences be-
tween opposite (100) faces. (Reconstruction on the surface may change the arrangement.) Calcu-
Figure 10 Crystallographic polarity of cBN.

506 Mishima and Era
Figure 11 Habit, morphology, etching patterns, and polarity of cBN. (Data from Refs. 102, 111.)
lations indicated that 2 ⫻ 2 dimer reconstruction on the B-terminating surface might favor the
(100) surfaces (104). However, as seen in many sphalerite compounds (105), real (100) faces
of the cBN crystals are usually nonflat and have steps, presumably made of (1¯1¯1¯) faces, forming
striations with a 〈110〉 direction (101,106). Distinct striations are wavy looking macroscopically.
The striations are always parallel to the boundaries between (100) and adjoining (1¯1¯1¯) faces.
These habits and morphologies may be simply realized as overlapped tetragons with
(1¯1¯1¯)N faces, as shown in Fig. 12.
The cleavage plane of cBN crystals is (110) as in the other III-V sphalerite compounds
and different from the (111) cleavage plane of diamond (Fig. 13). When twins exist, they are
detectable by observing the (100) faces, because the twins make lines vertical to the growth
striations of the (100) faces (Fig. 14) (101).
b. Etching
Chemical etching studies of cBN crystals have revealed different etching behavior on different
kinds of surfaces (10,99,102,107–109). The reported etchants are LiOH, NaOH, KOH, and
Figure 12 The overlapped tetragons used to illustrate cBN morphology.
Figure 13 Cleavage planes of cBN.
Figure 14 The spinel-type twin.

508 Mishima and Era
Figure 15 Schematic etch pit configuration of (100) faces of cBN.
NaNO3. Note that the solvents (catalysts) of cBN synthesis can dissolve cBN crystals and are,
therefore, etchants (110) (see Sec. IV.A.2).
When cBN crystals were etched in molten NaOH for a few minutes, hexagonal (or triangu-
lar), large, shallow, smooth, flat, and randomly distributed pits were usually observed on (1¯1¯1¯)N
(Fig. 11). On the faces, which are inclined from the exact (1¯1¯1¯), rough etch patterns appear.
On (111)B, relatively small, triangular pyramids or triangular terraces usually appear. On (100),
long and slender pits, parallel to the 〈110〉 striations, are observed (102).
Although cBN is insoluble in usual acids at room temperature, it can be etched at high
temperatures under high pressures. When cBN crystals were etched in 2HCl ⫹ 2HNO3 ⫹ 5H2O
at about 450°C and 2 GPa for ⬃60 minutes (in a Teflon capsule), the etching behaviors were
different from that with NaOH etching and similar to the acid-etching character of other III-V
compounds (O. Mishima et al; unpublished work; see Ref. 200). That is, the long and slender
pits on (100) faces were perpendicular to the 〈110〉 growth striations (Fig. 11).
In general, etching patterns depend on the relative etching rates of etch-pit faces (111).
Regarding the long and slender pits on (100) faces of the III-V compounds, the pits are usually
considered to have two (111)III and two (1¯1¯1¯)V faces (105) (Fig. 15). A difference in the etching
rate of III and V faces makes the long pits. When the etchant was NaOH, the B faces reacted
rapidly, leaving relatively inert N faces as the dominant etch-pit faces. When HCl ⫹ HNO3 ⫹
H2O was used as the etchant, the N faces reacted rapidly, leaving relatively inert B faces as the
dominant etch-pit faces.
The relations among surface morphology (of the usual cBN crystals made at high pres-
sures), etching patterns, and polarity are summarized in Fig. 11. From these relations, we can
easily identify the polarity by observing the surface morphology of cBN crystals.
III. PROPERTIES OF CUBIC BN
From the periodic table systematics, cBN is the lightest III-V compound and has a chemical
bond isoelectronic with diamond. Thus, we may expect to have properties of both the III-V
compounds and diamond.
Difficulties in obtaining large, high-quality cBN crystals prevent precise measurements
of the properties of this material. Therefore, many properties of cBN are known with poor
precision or even not known with any precision. Recent progress in computational physics has
partly supplemented this information. Generally, various properties of crystals may be calculated
by using band theories, at least in the framework of one-electron theory (112). Experimental
judgments are inevitable, however.
A. Electronic Band Structure

Many band calculations have been carried out on cBN. Their results mostly agree qualitatively,
indicating that the minimal band gap occurs between the X1,c conduction band and the Γ15,v
valence band (76,78,89,91,93–96,113–126). The main values related to the cBN energy band ob-
tained from recent calculations lie in rather small ranges; the band gap energies lie in the range 4.2–
5.2 eV, the upper valence band width 10–11 eV, the lower valence band width 5.3–7 eV, the gap
between the upper and lower valence bands 3.3–4.0 eV, and the total valence band width 20–23
eV. However, differences between the calculated and experimental values are not small: the calculated
band gap (4.2–5.2 eV) and the upper valence band width (10–11 eV) are smaller than the available
experimental results (⬃6.3 eV and ⬃14 eV, respectively; see Fig. 17).
By using the local-density and GW approximations with the experimental dielectric con-
stant ε ⫽ 4.5, Surh et al. (125) obtained a band gap energy of 6.3 eV. Here, the GW approxima-
tion is the one which uses a product of functions usually written as G and W. G is a Green
function. W is a symbol of a function which expresses a dynamically screened electron interac-
tion. The above method used by Surh et al. has furnished very good results about band gap
energies of several compounds. Indeed, the value, 6.3 eV is very close to the onset of the
imaginary part of the complex dielectric function obtained from reflectance spectra explained
below (133–135). Using their calculated values at the symmetric points and interpolating them
graphically by referring to other researchers’ results, the energy band structure is drawn in Fig.
16. In the same figure, an electronic density of states (DOS) curve is drawn by summing up
reported cBN DOS curves (112,121–124,127,128).
Effective masses of electrons and holes have not been obtained experimentally and were
deduced by a calculation (123).
There have been several optical measurements of cBN in the short-wavelength spectral
region (127,129–132). Results of the measurements agree with one another, although the exact
value of the band gap energy has not been determined with enough accuracy.
In Fig. 17, two reflectance spectra are shown (133–135). These spectral profiles are
roughly similar to each other. Energy values of spectral peaks and shoulders are close to those
Figure 16 Band structure of cBN. (Data from Refs. 125, 130.)

510 Mishima and Era
Figure 17 The ε2 spectra and reflectance spectra of cBN. Solid line, single crystal; dotted line, polycrys-
tal. (Data from Refs. 125, 133–135.)
of theoretically expected singularities (indicated by arrows in the figure). However, even though
the experimental and theoretical results appear to agree (78,112,121,125,134,135), it should be
noted that unambiguous assignments of the experimental spectra have not yet been made.
The experimental value of the band gap of cBN is 6.2–6.4 eV (130,131,135), which is
larger than that of diamond (5.5 eV) and comparable to that of AlN (6.3 eV). Cubic BN, as
well as AlN, has the widest band gap among the existing semiconductors as shown in Fig. 18.
Note that aBN and wBN are considered to have larger band gaps than cBN [aBN, 7.4 eV (136);
wBN, ⬃1.1 ⫻ Eg of cBN (78)].
Both experimental (137) and theoretical (93,95,122) studies show that the indirect band
gap energy of cBN increases with pressure. The band gap is theoretically considered to change
from indirect to direct at 1.16 TPa (1160 GPa) (138), although cBN may be transformed to the
rock salt structure around this pressure (76,77).
B. Mechanical Properties
In general, mechanical or electric displacement in materials induced by an applied mechanical
or electric field can be described with a tensor equation that determines the mechanical properties
of the material. For weak applied fields, the displacement is approximately proportional to the
applied field (Fig. 19).
Because of the crystalline symmetry of cBN (F43m), only three elastic constants, one
piezoelectric constant, and one dielectric constant in the equation are of importance or have
Figure 18 Comparison of the band gaps of typical semiconductors.
Figure 19 An example of the tensor equation and its coefficients.

512 Mishima and Era
nonzero values (Fig. 19). Although these coefficients have not yet been determined precisely,
the mechanical properties of cBN have been estimated from experiment and theory. It is found
that cBN is the second hardest material after diamond.
1. Elastic Properties
There are various kinds of elastic constants, some of which are illustrated in Fig. 20. They are
correlated with one another by their definitions, as shown in Table 4. When two independent
kinds of constants are given, we can derive other elastic constants.
Plausible elastic constants of cBN are listed in Table 5 by summing up the theoretically
expected (10,94–96,124,140,141) and experimentally observed data (74,143–145). Grüneisen
parameters (143,144) and linear thermal expansion coefficients near room temperature (146,147)
are also listed. The elastic constants of cBN are about 20–40% lower than those of diamond
and several times larger than those of other covalent crystals such as Si and GaAs. Although
cBN is stiff, it is elastic and can be distorted: the volume of cBN decreases elastically by about
20% at 100 Gpa (Fig. 21) (74).
When the microscopic force constant along a BEN bond, C0, and the force constant in
a BEN bending direction, C1, of cBN are estimated according to Ref. 112 and compared with
those of other sphalerite compounds, the ratio C0 /C1 of cBN appears to be relatively small (as
is the case for diamond). This indicates that the bonds in cBN and diamond are rather difficult
to bend in a circular direction.
2. Hardness
When materials are strained beyond their elastic limits, they deform permanently and then frac-
ture. The measurement of hardness is a convenient method with which to evaluate these proper-
Figure 20 Illustration of some elastic constants.

Table 4 Correlation of Elastic Constants

Lamé
constants C11, C12, C44
λ, µ K, γ ε, σ [C11 ⫽ C12 ⫹ 2C44 ]
2 εσ
λ ⫽ C12 λ K⫺ γ C12
3 (1 ⫹ σ)(1 ⫺ 2 σ)
ε
Shear modulus, µ γ C44
µ ⫽ γ ⫽ C44 2(1 ⫹ σ)
2 ε C11 ⫹ 2C12
Bulk modulus, K λ⫹ µ K
3 3(1 ⫺ 2 σ) 3
µ (3λ ⫹ 2µ) 9K γ C44 (C11 ⫹ 2C12)
Young’s modulus, ε ε
λ⫹µ 3K ⫹ γ C11 ⫺ C44
λ 3K ⫺ 2γ C12
Poisson’s modulus, σ σ
2(λ ⫹ µ) 2(3K ⫹ γ) 2(C12 ⫹ C44 )
ties. The definitions of the Vickers hardness and the Knoop hardness are illustrated in Fig. 22.
The Knoop hardness is empirically 10–20% lower than the Vickers hardness.
The hardness of a crystal depends on its temperature, crystalline orientation, the time scale
of measurement, and possibly the defect content. The hardness of cBN is shown in Figs. 23
and 24 (10,100,148–151). Although cBN is the second hardest material after diamond, its hard-
ness (Hk ⬃4000) appears to be only half of that of diamond (Hk ⬃8000) and is close to the
hardness of SiC and B4C (Hk ⬃3000). Thus, cBN crystals can be polished rather easily with
diamond powders.
Table 5 Estimated and Observed Elastic Constants of cBN
C11 7–8 ⫻ 10 11Pa 7.12 ⫻ 10 11 Pa (139) a

8.3 ⫻ 10 11Pa (140)
7.83 ⫻ 10 11Pa (144)
C12 1–2 ⫻ 10 11Pa 4.2 ⫻ 10 11Pa (140)
0.8 ⫻ 10 11Pa (10)
1.46 ⫻ 10 11Pa (144)
C44 ⬃4 ⫻ 10 11Pa 4.5 ⫻ 10 11Pa (140)
3.34 ⫻ 10 11Pa (10)
4.18 ⫻ 10 11Pa (144)
C0 3.83 ⫻ 10 11Pa (139)
K ⬃3.8 ⫻ 10 11Pa 3.82 ⫻ 10 11Pa (142)
3.69 ⫻ 10 11Pa (74)
3.67 ⫻ 10 11Pa (95, 96, 141)
ε ⬃8.8 ⫻ 10 11Pa (polycrystal) (145)
γ: LO(Γ) 0.9 (142) 1.2 (143)
γ: TO(Γ) 1.2 (142) 1.5 (143)
a ⬃3.5 ⫻ 10 ⫺6 /K(0–400°C) (146) ⬃4.8 ⫻ 10 ⫺6 /K (430°C) (10)
3.7 ⫻ 10 ⫺6 /K (0–400°C) (polycrystal) (147)
a
Reference numbers in parentheses.
514 Mishima and Era
Figure 21 Compression curves of cBN and hBN. (Data from Refs. 74, 139.)
There are some approximate empirical relations between the hardness and elastic proper-
ties of materials (152), and we can speculate upon the elastic constants of cBN from its hardness.
3. Piezoelectricity
In principle, cBN should exhibit piezoelectricity because of its crystal structure. That is, when
a cBN crystal is located in an electric field, the boron atoms of the crystal with positive charges
and the nitrogen atoms with negative charges move in opposite directions. This induces macro-
scopic strains (and stresses) in the crystal. The induced strains (stresses) are approximately
proportional to the electric field. For cBN, there is only one direction in which strains (stresses)
are induced by the electric field. This is expressed by TXY ⫽ e14 EZ (SXY ⫽ d14EZ ), where TXY
(SXY ) is a stress (strain) along the y axis on the x plane, E Z an electric field along the z axis, and
e14 (d14) a piezoelectric constant. Here, e14 ⫽ C44 d14, as deduced from Hooke’s law: TXY (force)
⫽ C44 (a spring constant) ⫻ SXY (displacement). When the electric field is increased along a
〈001〉 direction, the cBN crystal deforms elastically as shown in Fig. 25.
The value of e 14 has been estimated theoretically to be ⫺1.36 (C/m2 ), ⫺3.3 (C/m2 ), and
⫺0.2 (C/m2 ) by different researchers (126). As yet, no experimental observation of piezoelectric-
ity from cBN has been reported.
4. Lattice Dynamics
Because of the strong covalent bonding of cBN, as suggested by its large elastic constants, and
the light masses of B and N atoms, cBN has high-frequency lattice vibrations, large sound
velocities, high Debye temperatures, and large thermal conductivities. These lattice properties
Figure 22 Definitions of the Vickers and Knoop hardnesses.
Figure 23 Surface orientation dependence of hardness of cBN. (Data from Refs. 149, 151.)
516 Mishima and Era
Figure 24 Temperature and time dependence of hardness of cBN. (Data from Ref. 149.)
of cBN are superior to those of all other materials except diamond. It should be noted, however,
that the bonding in the flat sp 2 6-rings of hBN is stronger than that in the puckered sp 3 6-rings
of cBN, as indicated by the higher frequency BEN vibrations exhibited by hBN [hBN, νLO ⫽
1610 cm ⫺1, νTO ⫽ 1370 cm ⫺1 (161); cBN, ν LO ⫽ 1304 cm ⫺1, νTO ⫽ 1054 cm ⫺1].
The energy values of lattice vibrations (phonons) of cBN have been determined from
measurements of the infrared (IR) absorption (131,146,154) and the Raman effect (143,144,154–
160) (K. Aoki and O. Mishima, unpublished work; see Ref. 106) and are shown in Fig. 26 and
Tables 6 and 7. Pressure (89,93) and temperature (158,159) effects on the vibrations have been
investigated.
Figure 25 Illustration of a piezoelectric effect of cBN.

Figure 26 Infrared and Raman spectra and phonon dispersion curves of cBN. (Data from Refs. 106,
131, 141, 146, 164.)
There was an attempt to calculate the phonon dispersion curve of cBN, which is shown
in Fig. 26 (141). The derived phonon density of states is also shown. However, the calculated
TO and LO modes (1200 and 1260 cm ⫺1, respectively) are quantitatively different from the
experimental results (1056 and 1304 cm ⫺1, respectively). Further studies are necessary.
Dielectric constants of cBN were derived by fitting experimental results for the infrared
reflectivity of cBN to the so-called damped-oscillator model (146). The high-frequency and the
low-frequency dielectric constants thus obtained, ε∞ and ε0, are 4.5 and 7.1, respectively.
The experimental value for the refractive index n of cBN in the visible region is 2.11
(Fig. 27) (135). The high-frequency dielectric constant estimated from this value by using the
relation ε ⫽ n 2 is 4.45, which agrees with the value of 4.5 obtained by the model fitting men-
tioned previously.
Using the Lyddane-Sachs-Teller relation, ε0 /ε∞ ⫽ νLO 2 /νTO 2, with the values ε∞ ⫽ 4.5, νTO
⫽ 1064 cm ⫺1, and νLO ⫽ 1304 cm ⫺1, ε0 is calculated to be 6.9, which is close to the value 7.1
obtained by the model fitting.
Thus, we have fairly reliable values (4.5 and ⬃7) for ε∞ and ε0. An experimental value
of ε0 for a polycrystalline cBN compact was reported to be 6.5 (147).
The bulk crystal is opaque for the light between νTO and νLO because of reflection originat-
518 Mishima and Era
Table 6 IR and Raman Frequencies of cBN

IR (from Ref. 146) IR (from Ref. 131) Raman (from Ref. 106)
438
650 694
700
884
928
1000–1260 1000–1300 1055 (TO)
1244
1305 (LO)
1370
1580 (1550)
(1700)
1785
1830 1818
(1840)
1885 1886
1920 1927 1990
2000 1985
2230 2140 2204
(2330)
2465
2560 2540
2700
2910
ing from the extraordinary dispersion effect of the lattice vibration (Figs. 26 and 28). However,
the damping effect makes the reflectance finite. This results in light transmission through thin
films. The transmission spectra are often used to identify a cBN phase in low-pressure syntheses.
For convenience, typical IR transmission spectra of thin-film cBN and other BN phases are
shown in Fig. 29 by summing up reported spectra (161,162,163).
The wide-range optical spectrum of cBN is drawn in Fig. 27. The spectrum becomes
complex around 10 3 and 10 5 cm ⫺1 because of absorption by phonons and by electrons, respec-
tively.
Generally, the difference between LO and TO vibrations of a compound material can
reveal its ionicity. The difference between νTO and νLO of cBN decreases slowly with pressure
while both νTO and νLO increase with pressure, indicating that the cBN lattice becomes hard and
tight under high pressure (143,144). The decrease in the νTO ⫺ νLO difference with pressure
indicates that the ionicity of cBN decreases with pressure as observed for other III-V compounds
(144).
Table 7 IR and Raman Frequencies of νTO and νLO Bands of

cBN
ν IR Raman
ν (TO) ⫺1
1065 cm (active) 1056 cm ⫺1 (active)
ν (LO) (inactive) 1304 cm ⫺1 (active)
Figure 27 Wide-range optical spectra of cBN. (Data from Refs. 135, 146.)
C. Thermal Properties
1. Thermodynamics
The thermal properties of a lattice are generally affected by the anharmonicity of the potential
between atoms and are described using lattice dynamic theories.
The specific heat capacities (Cp) of cBN (164–167), wBN (164,168,169), and hBN
(164,170), as well as their Debye temperatures deduced from the capacities, are shown in Fig.
Figure 28 Reflectivity and optical constants of cBN. (From Ref. 146.)

520 Mishima and Era
Figure 29 Reported IR spectra of thin-film BN phases. (Data from Refs. 161–163.)
30. The compression curves and the linear thermal expansion coefficients (10,146,147,171,172)
of these BN phases are also shown in Figs. 21 and 31. Using these experimental data as well
as thermodynamic relations, we can estimate differences in the Gibbs free energy among these
phases (164,169). The difference, ∆G, between cBN and hBN is shown in Fig. 32. The cBN-
hBN equilibrium phase boundary corresponds to the line where the difference becomes zero
(Figs. 6 and 32).
As shown in Fig. 32, Gibbs energy of hBN is lower than that of cBN at 1 atm and,
Figure 30 The heat capacities of cBN, hBN, and wBN. (Data from Refs. 165–171.)
Figure 31 Linear thermal expansion coefficient of cBN. (Data from Refs. 10, 146, 147, 172.)
therefore, hBN is more stable than cBN at 1 atm, which agrees with theoretical results (78).
The difference in the Gibbs energy between hBN and cBN at 1 atm and 0 K was estimated
from experimental data to be about 510 cal/mol (169). Because this difference is small (that is,
the experimental hBN-cBN boundary at high temperatures extrapolates to nearly zero pressure at
0 K), there is a possibility that cBN is more stable than hBN at low temperatures near 1 bar as
described in Sec. II.C.
The linear thermal expansion coefficients of materials with a diamond or zinc blende
structure (Si, Ge, GaAs, etc.) near 0 K are commonly negative. This is due to the bending action
Figure 32 Calculated Gibbs free energy surfaces of cBN and hBN.

522 Mishima and Era
Figure 33 Thermal conductivities of cBN, diamond, and Si. [cBN: sintered compacts (147,177–179);
(⫻) Single crystals (181); (⫹) calculation (181)].
of atomic bonds caused by thermal agitation; that is, as temperature increases from 0 K, bond
bending causes slight shrinkage of a lattice as in the case of bellows. For cBN, a negative
thermal expansion coefficient was suggested (173); further experimental confirmation is needed.
The reported Grüneisen parameters (γ) of cBN are listed in Table 5 (143,144,174).
2. Thermal Conductivity
If there is a difference in temperature in a material, a flow of thermal energy occurs. The flow
of thermal energy, Q, is proportional to the temperature gradient, dT/dx, and the coefficient is
called the thermal conductivity, K. Thus, Q ⫽ KdT/dx. The thermal conductivity, K, is approxi-
mately proportional to the heat capacity (Cv ), the phonon speed (v), and the mean free path of
phonons (l ) of the material; K ⬀ Cvvl (175). At low temperatures, the mean free path (l ) is
almost constant and the heat capacity (Cv ) is proportional to T 3. Thus, K is proportional to T 3.
At high temperatures, Cv is almost constant and l is proportional to T ⫺1. Thus, K is proportional
to T ⫺1. The thermal conductivity of cBN appears to have this general tendency as shown in Fig.
33 (147,176–178).
The thermal conductivity of cBN crystals is theoretically estimated to be 13 W cm ⫺1 K ⫺1
at room temperature, the second largest value after diamond (18–20 W cm ⫺1 deg ⫺1) (179).
Values of some single crystals (180) and polycrystalline cBN compacts (147,176) (see Fig. 33)
are 6–9 W cm ⫺1 deg ⫺1 around room temperature, which are larger than those of SiC (⬃5 W
cm ⫺1 deg ⫺1), silver (4.2 W cm ⫺1 deg ⫺1), and copper (3.9 W cm ⫺1 deg ⫺1). Defects in single
crystals and different phases in sintered polycrystalline compacts reduce the thermal conductiv-
ity (181,182).
D. Optical and Electrical Properties

1. Defect and Optical Properties
Crystals of cBN made by the high-pressure synthesis method usually contain twins, cracks, and
inclusions. Taking into account the band gap energy, defect-free cBN crystals should be color-
less. However, crystals usually exhibit colors: pale yellow, yellow, honey, amber, cinnamon,
brown, orange, light blue, blue, blue-black, or almost black. This shows the presence of various
lattice defects. Actually, impurities of O, Li, Ca, C, Mg, Si, Be, Al, Fe, P, As, Sb, Bi, etc. are
reported. Beryllium doping to form p-type crystals results in blue color (4,184) (see Sec. III.D.2).
It is worthwhile to point out here that p-type diamond also exhibits a blue color, suggesting
resemblance of the electronic states participating in these optical absorption transitions.
As shown by the transmission spectra in the upper graph of Fig. 34, colorless cBN crystals
are transparent in the range ⬃1 to ⬃6.3 eV (6.3 eV corresponds to the onset of the fundamental
absorption). Thin films of cBN made by a low-pressure method show similar transparency (207).
The gradual decrease of transmittance occurring around 3 eV results in a yellow color (131).
As the origin of the yellow color, nitrogen vacancies have been speculated (5), because the color
appears on crystals that are supposed, from their synthesis conditions, to be nonstoichiometric B-
rich crystals.
The main luminescence bands found in cBN crystals are summarized in Table 8 and Fig.
34. In most cases, the luminescence is excited by electron beams (cathodoluminescence, CL)
(185–198). Luminescence caused by recombination of electrons and holes in pn junctions (injec-
tion luminescence, IL) has been observed (189,199). The origin of any of the luminescence
bands is unknown at present, although there are discussions in the literature.
The CL band US-1 (200) [also known as UCL (188)] is commonly observed in cBN
crystals of various origins. This band shows a vibrational structure with remarkable anharmon-
icity. Participating vibrations are at 127–145 meV and correspond to the energies of characteris-
tic cBN optical phonons: TO, 131 meV, and LO, 162 meV (Fig. 26).
The band GC-1 (186,187,190,192) appears around 1.76 eV and shows Mössbauer-type
phonon structure. It resembles the CL band, GR-1, of diamond, which is associated with the
neutral vacancy. By analogy, GC-1 was then speculated to be related to N vacancies (190).
Be-doped and Si-doped crystals showed CL spectra called PCL and NCL, respectively.
When a pn junction was made under conditions similar to those for these crystals, two types
of IL specta were observed (188,199). Those IL spectra are quite different from the PCL and
NCL spectra.
In other Si-doped crystals, a CL band called the T band having an oscillating structure
has been reported in the region 4–5 eV.
Measurements of the nuclear magnetic resonance (NMR) (201,202) and the electron spin
resonance (ESR) (156,183,203–205) of cBN treated under various conditions have been re-
ported. The temperature dependence of the magnetic susceptibility of cBN was studied to evalu-
ate the contribution of the lattice impurities and defects (206).
In principle, impurities or nonstoichiometry of a crystal should be related to a composition
phase diagram as shown in Fig. 35 and should be homogeneously distributed in the crystal if
the crystal was annealed at sufficiently high temperatures. However, for example, in a blue Be-
doped crystal, the blue color is often inhomogeneously distributed, indicating an inhomogeneous
524 Mishima and Era
Figure 34 Luminescence bands and absorption coefficient of cBN. (Data from Refs. 135, 187–190,
192, 193, 195, 196, 199, 208.)
distribution of Be impurities. The inhomogeneous spatial distribution of cathodoluminescence

that has been commonly observed (e.g., Ref. 200) also indicates an inhomogeneous distribution
of some defects. Therefore, impurities and defects are not in their thermodynamically equilib-
rium states. This suggests that these defects are taken into crystals during growth and that they
have difficulty diffusing in the crystals at the growth temperature (usually 1500–1700°C). It
suggests further that doping of impurities by the diffusion method from crystal surfaces is rather
difficult at the growth temperatures commonly used.
Table 8 Luminescence of cBN

Peak
Peak wavelength
energy (nm)
E (eV) ⫽ 1240/E (eV) Mark a Notes Ref.
⬃4.8 ⬃260 AIL IL-A 189, 201
⬃4.2 ⬃300 T CL, Si-doped,4.8eV(max) 199
⬃3.8 ⬃330 BIL IL-B 189, 201
⬃3.5 ⬃350 PCL CL, Be-doped, p-type 189, 201
3.18 389 O CL, Si-doped 199
⬃3.0 ⬃410 US-1 CL, PL, undoped,(UCL) 189, 191
2.99 414 Γ CL, Si-doped 199
2.84 437 PC-1 CL 196
⬃2.7 ⬃460 NCL CL, Si-doped, n-type 189
⬃2.45 ⬃510 B CL 196
⬃2.4 ⬃520 C[EM] IL,CL 189, 201
2.33 533 PC-2 CL 196
2.27 546 RC-1 CL,(RK-1?) 193, 195
⬃2.2 ⬃560 A CL 196
2.15 577 RC-2 CL,(RK-2?) 193, 195
1.99 623 RC-3 CL,(RK-3?) 193, 195
1.86 669 RC-4 CL 200
1.79 693 PC-3 CL 196
1.76 705 GC-1 CL 187, 188, 192, 194
⬃1.7 ⬃730 C CL 196
1.63 761 GC-2 CL 187, 188, 192, 194
1.55 800 GC-3 CL 192
a
CL, Cathodoluminescence; PL, photoluminescence; IL, injection luminescence of pn diodes; PC, CL of pressure-
treated crystals (pressure cubic, from Ref. 196); RC (RK), CL of electron (ion)-irradiated crystals (radiation cubic,
from Ref. 193); GC, CL of common crystals (general cubic, from Ref. 187).
2. Semiconducting Properties
As pointed out in Sec. III.A, cBN has the widest band gap (⬃6.3 eV) among known semiconduc-
tors. Of course, undoped pure cBN crystals should be good electrical insulators at room tempera-
ture. However, the crystals usually made by the high-pressure method are slightly conductive,
having resistivities of 10 9 –10 10 Ω cm, due to unknown defects in the crystals (4,10,208).
The semiconducting properties of cBN were demonstrated in early cBN studies from mea-
surements of the thermoelectric power, resistivity, and temperature dependence of the resistivity
(4). Since then, upon doping with impurities such as Be, Si, S, C, As, P, Se, and Te, cBN has
been reported to have semiconducting properties (4,65,177,183,184,209). Be doping results in
p-type conduction and Si doping in n-type conduction. Although, to date, there has been no
convincing paper on the Hall effect and conduction types, the fact that light emission around
5.8 eV occurs in a forward-biased pn junction that consists of Be-doped p-type and Si-doped
n-type (199), as described later in Sec. VI.B, supports the existence of both Be-doped p-type
and Si-doped n-type crystals.
The spatial inhomogeneity of resistance in semiconducting cBN single crystals has thus
far prevented detailed measurement of their electrical properties. The large and unstable contact
resistances at the electrodes of cBN are also troublesome. Reported resistances of semiconduct-
526 Mishima and Era
Figure 35 Plausible phase diagrams of stoichiometry, (a) Ref. 5 and (b) Be doping of cBN.
ing cBN are summed up in Fig. 36. The resistance of n-type crystals is usually higher than that
of Be-doped p-type crystals. The activation energy of resistance of Be- (and Si-doped crystals
has been measured as ⬃0.23 and ⬃0.24 eV in the range 20–600°C, respectively (184).
Semiconducting cBN polycrystalline compacts, made by sintering Be-doped cBN pow-
ders, generally showed higher resistivity than Be-doped single crystals (65,210). The activation
energy of resistance (20–600°C) of these p-type compacts was similar to that of p-type single
crystals. The voltage-current (V-I ) relation of these compacts was found to be nonlinear, having
the characteristics of that of varistors. That is, the resistance of the compacts decreased with
applied voltage. With the Si-doped n-type compacts, the resistance was too large to obtain
reliable results.
The contact resistance between cBN and electrodes of conventional materials is usually
10 4 –10 6 Ω at room temperature (184). Although the contact resistance decreases at high tempera-
tures, it is still quite large. In order to form an ohmic contact and reduce the contact resistance,
a few materials have been examined. Trials of materials such as Cu (208), Ag (4,184), Au (210),
Al (210), Cr-Ni (177), and Mo and Pt (200) have been reported in the literature and patents.
Ohmic electrodes with relatively low contact resistance have been made using Ti-Au and Al-
Au on Be-doped p-type crystals (210). The contact resistance of Ti-Au was 10 2 –10 3 Ω at room
temperature. Annealing procedures are considered to be effective. Formation of Ti or Al nitride
probably occurred.
E. Chemical Properties and Thermal Stability

The chemical reactions of cBN are an important consideration when synthesizing cBN with
solvents, cutting materials with cBN tools, forming electrodes on cBN surfaces and so on.
Generally, wetting between a material and a molten metal depends on various conditions
such as the surface conditions of the metal and the material (e.g., the presence of oxidized films).
According to a study of the wetting between hBN and molten Al (211), interfacial reactions
such as the formation of nitride or boride films of metal components in contact control the
Figure 36 Electric resistance of cBN. (Data from Refs. 64, 178, 185, 210.)
wetting behavior. A similar mechanism presumably works in cases involving cBN. For example,
in cases of Ti and Al with cBN, TiN and AlN, respectively, or metal borides such as AlB12 are
considered to be formed at high temperatures. Metals Fe, Ni, Co, and Mo have been reported
to react with cBN above 1300–1400°C and Si above ⬃1500°C (10). Metals Sn, In, Ga, Ge,
Cu, Ag, Au, and Pb do not wet cBN below ⬃1200°C (10,212,213).
Etchants and catalysts (or solvents) of cBN also react with cBN (see Secs. II.D.2.b. and
IV.A.2). They are alkaline or alkaline earth metals, their nitrides and boron nitrides, H2O, alka-
line salt etchants (NaOH, LiOH, KOH, Na2CO3, NaNO3), and acid etchants (HNO3 ⫹ H2O).
The reaction occurs promptly at high temperatures (usually above 1300–1400°C at high pres-
sures). As described in Sec. II.D.2.b, some base etchants appear to react more rapidly with (111)
nitrogen surfaces of cBN crystals and acid etchants with (111) boron surfaces.
When cBN crystals are heated in air, oxidation occurs above ⬃900°C accompanied by
removal of nitrogen gas. Thus, B2O3 (melting point ⬃580°C and boiling point ⬎1500°C; glassy
at low temperatures) forms on the surfaces of cBN (10,214). If the heating is done quickly (or
in vacuum or in nitrogen gas), cBN is converted above 1400–1600°C to a black graphitic BN
phase (which may not be hBN) (10,215) or white hBN. Cubic BN may also react with its
container (or decompose) with formation of a boron-rich material and removal of nitrogen gas,
528 Mishima and Era
Figure 37 Change of cBN at high temperatures at 1 bar.
as observed in a vacuum-heating experiment with hBN in a carbon container (215). The conver-
sion of cBN occurs kinetically depending on the crystal quality and contaminants (Fig. 37)
(214).
IV. SYNTHESIS OF CUBIC BN
Because the structure and the properties of cBN resemble those of diamond, the synthesis of
cBN may also resemble that of diamond. Indeed, we can make cBN crystals with methods
similar to those used for synthesis of diamond, that is, the high-pressure method and the low-
pressure vapor deposition method (see Ref. 13 for a review). Cubic BN, a two-element com-
pound, is apparently more difficult to synthesize than diamond because of problems of stoichi-
ometry, antiphases, and so on.
A. High-Pressure Synthesis
We can make cBN crystals by subjecting a source BN material (hBN, tBN, etc.) to high-pressure
and high-temperature conditions in which cBN is thermodynamically stable. For example, hBN,
tBN, or wBN transforms directly to cBN (see Sec. II.C). Generally, we have difficulty in control-
ling nucleation and crystal growth in direct solid-solid transformations.
Cubic BN crystallizes when liquid BN freezes at high pressures (216). It is, however,
experimentally difficult to keep the high-temperature liquid state (⬎⬃3000 K) under high pres-
sures for a long time.
Cubic BN may be obtained by decomposition of materials containing B and N atoms. It
was reported that cBN crystals appeared when Mg3BN3 reacted with H2O at high pressures
(218).
Cubic BN crystals can be grown under relatively low-pressure and low-temperature condi-
tions (P⬃5 GPa, T⬃1500°C) when suitable catalysts are used, as described in the following
sections (for a review, see Refs. 11 and 218). Because the pressures and temperatures used for
the catalyst method are similar to those used for diamond synthesis, we can appropriate the
relatively well established high-pressure technology of diamond synthesis.
Two types of high-pressure apparatus are schematically illustrated in Fig. 38. They are
the so-called belt-type apparatus and the multianvil apparatus, both used in diamond and cBN
factories. The belt type is a modified piston-cylinder apparatus. There is also an apparatus called
the toroid type, which is a modified Bridgman-type anvil apparatus.
Materials held in the central chamber of these apparatuses are squeezed with anvils made
of tungsten carbide. To prevent outflow of the materials between the anvils, pressure-sealing
Figure 38 The belt type and the multianvil type of high-pressure apparatus.
gaskets are placed between them. High pressure is generated in the central chamber, whereas
the ends of the gaskets are at 1 bar. Therefore, a large pressure gradient exists in the gaskets.
The temperature is increased by having an electric current flow through a graphite (or
metal) heater located inside the chamber while the surrounding anvils are cooled with water.
1. The Catalyst (Solvent) Method: Principle

Spiral growth layers (219) and etching patterns (110) were observed on surfaces of cBN crystals
made by the catalyst method. This suggests that crystals grew in a liquid state and that the
catalyst acted as a solvent or a flux. As in the case of diamond synthesis with a catalyst, cBN
crystals are usually considered to precipitate in a molten catalyst (or solvent) when B and N
atoms in the liquid are supersaturated (220) [the liquid ⫹ cBN (‘‘liquid’’ abbreviated L hereafter)
region of Fig. 39]. Actually, phase diagrams of some BN-solvent systems have been reported
(220–223). Other reported catalysts are generally assumed to act as solvents even though their
solvent action has not been confirmed.
In accordance with the experience gained with diamond synthesis, we can think of two
solvent methods: the so-called high-pressure film method (224) and the temperature difference
(or temperature gradient) method (225,226). Both methods provide supersaturation of B and N
atoms in a solvent from which BN crystals are precipitated.
The high-pressure film method may be regarded as a solvent-mediated phase transition
in which hBN dissolves in a solvent and cBN crystals precipitate from it. Because hBN is
metastable and cBN is stable at high pressures, hBN should dissolve more in a high-pressure
solvent than cBN (Fig. 39). Therefore, B and N atoms supersaturate for cBN; as a result, deposi-
tion of cBN crystals occurs.
The temperature difference method utilizes the difference in solubility at different temper-
atures. Consider a solvent with high- and low-temperature regions. Generally, a material dis-
solves more easily in a higher temperature region than in a lower temperature region. Then, in
the low-temperature region, the material becomes supersaturated in the solvent and precipitates.
When this general method is applied for cBN growth at high pressures, the BN source material
dissolves in the high-temperature region and cBN crystals precipitate in the low-temperature
region.
530 Mishima and Era
Figure 39 Pressure-temperature-solvent composition phase diagram of cBN.
2. Catalysts (or Solvents)

Many catalysts are known for the synthesis of cBN at high pressures (7,13) (Table 9). They
are alkali metals (15), alkaline earth metals (15,219), their hydrides (236), their nitrides (15,219–
221,228,230,235), their borides (234) and boron nitrides (101,110,219–221,223,235), other met-
als (15,83), water (237–240,245), fluoride and fluoronitride compositions (241), ammonia com-
pounds (240,241,244,245), hydrochloric acid (246), aluminum nitride (247–250,251), and sili-
con and its compounds (251,252). Other materials such as Al-Ni, Al-Co, Al-Mn, inconel, Si3N4,
ZnO, and LiSrBN2 have been reported in patents. The pressure-temperature cBN synthesis condi-
tions for some catalysts (or solvents) are shown in Fig. 40. The best catalyst (or solvent) for
providing good cBN crystals under relatively low-pressure, low-temperature conditions is un-
known at present.
Alkali boron nitrides or alkaline earth boron nitrides (Li3BN2, Mg3BN3, LiCaBN2, etc.)
appear to be better solvents than alkali or alkaline earth metals and their nitrides (Mg, Mg3N2,
etc.) because the former boron nitrides already contain adequate B and N atoms in their composi-
tions and are ready to provide supersaturation of B and N atoms (Fig. 41a: X ⫽ Mg3N2, Y ⫽
Mg2BN3, etc.). The reported Mg3B2N4 (or Ca3B2N4) solvent (47,219,223) is probably Mg3BN3
(or Ca3BN3) as shown by chemical and X-ray analyses of Mg3BN3 (253).
When cBN crystals were grown at high pressure using an LiCaBN2 solvent and then cooled
slowly at high pressure and recovered to 1 bar, erosive patterns were observed on the surfaces
of the recovered cBN crystals (110). This suggests complexity in the BN-solvent phase diagram
and indicates the existence of a peritectic relation in the LiCaBN2-BN system (Fig. 41b). Thus,
when cBN crystals made in the L⫹cBN region of Fig. 41b were cooled, the crystals were
thought to dissolve in the L⫹Y region of the figure.
Boron nitride solvents also dissolve carbon, AlN, and BP. If a sufficient amount of AlN
(or BP) is dissolved with BN in a solvent such as Li3BN2 at high pressure, crystals of AlN (or
Table 9 Solvents for cBN Synthesis at High Pressures and Their References
(LiEBEN) (HELiEBEN) (HEBENEF) (LiEBENEF)
Li (15) LiH (236) NH4F (241) LiBF4 (241)
Li3N (15, 220) LiNH2 (236)
Li3BN2 (101, 220) (HENaEBEN) (HEBENECl) (NaEBENEF)
HCl (246) NaF (241)
(MgEBEN) NaH (236) NH4Cl (241)
Mg (15) (MgEBENEF)
Mg3N2(220, 228, 230) (HECaEBEN) (FEBENEBr) MgF2 (241)
CaH2 (236) NH4Br (241)
Mg3B2N4 (219, 221) (CaEBENEF)
MgB2 (⫹Bi) (234) (HEBaEBEN) CaF2 (241)
BaH2 (236)
(GaEBENEF)
GaF3 (241)
(CaEBEN) (HEBENEO) (BiEBENEF)
Ca (15) H2O (237–240, 245) BiF3 (241)
Ca3N2 (15, 220, 235) H3BO3 (240, 244)
Ca3B2N4 (223, 235) NH4NO3 (244) (HELiEBENEF)
(NH4)2B4O7 ⋅ 4H2O (244, 245) LiHF2 (241)
(LiECaEBEN)
LiCaBN2 (110) (HEBECENEO) (HEBESiENEF)
(NH2)2CO (240, 244) (NH4)2SiF6 (241)
(AlEBEN)
AlN (247, 249, 251) (NaEBESiENEF)
Na2SiF6 (241)
(other metals)
Sb, Sn, Pb (15) (BaEBESiENEF)
Co (83) BaSiF6 (241)
AgECd, SnECu,
Fe3Al
Figure 40 Phase diagram for cBN synthesis using solvents. (Data from Table 10.)
532 Mishima and Era
Figure 41 Proposed BN-solvent phase diagrams.
BP) grow with the cBN crystals (O. Mishima, unpublished work). The existence of compounds
such as Li3BN2, Li3AlN2, and Li3GaN2 suggests chemical similarity among BN, AlN, and GaN.
3. Preparation and Analysis

a. Powders
Cubic BN powders (usually ⬍⬃0.5 mm in size) are produced when hBN powders mixed with
solvent powders are subjected to pressure ⬎⬃5 GPa and temperatures ⬎⬃1500°C for several
minutes. Commercial cBN powders are mass produced in this way. For diamond synthesis by
the high-pressure film method, described in Sec. IV.A.1, a thin solvent film always exists be-
tween the graphite source material and the diamond crystal produced. The formation mechanism
of cBN powders is believed to be the same as that for the synthesis of diamond by the high-
pressure film method, although a solvent film between the hBN source material and the cBN
crystal produced has not been observed as clearly as it has been for diamond (223).
If the mechanism of the high-pressure film method is assumed, the degree of supersatura-
tion of B and N atoms in the solvent is determined from the solvent-BN phase diagram if
pressure, temperature, and solvent material are fixed (Fig. 42). Generally, the degree of supersat-
uration affects the nucleation and growth of crystals. If a pressure-temperature condition for
cBN synthesis is chosen near the hBN-cBN equilibrium boundary, the degree of supersaturation
of B and N atoms for the cBN phase is small (Figs. 39 and 42). Spontaneous nucleation is then
suppressed and the crystals grow slowly, producing relatively large, high-quality crystals. To
date, cBN crystals up to about 1 mm in size have been obtained by keeping the growth condition
near the hBN-cBN equilibrium boundary.
When a small amount of a semiconductor impurity is added to the solvent, semiconducting
cBN powders (p- and n-type powders) are obtained (4). By growing an n-type cBN crystal on
a p-type cBN seed, a functional pn-junction crystal (⬍⬃1 mm in size) was made using this
high-pressure film method [T. Okubo, private Communication; the diodes were described in his
patent (254)].
b. Larger Crystals
We can grow crystals larger than 1 mm using the temperature difference method (101,110) (Fig.
43). Growth of crystals by this method is controlled by the temperature and the temperature
Figure 42 Cubic BN formation by the high-pressure film method.
difference. When the temperature difference is small and thus the degree of supersaturation of
B and N atoms is small, spontaneous nucleation is suppressed and cBN crystals grow slowly
on seed crystals. High temperatures induce rapid growth of the crystals, providing relatively
large but low-quality crystals with cracks and solvent inclusions. At low temperatures, the crys-
tals grow very slowly. Under appropriate growth conditions, cBN crystals up to ⬃3 mm in size
grow in several tens of hours (5,101,110). Naturally, the size of the crystals produced is ulti-
mately limited by the size of high-pressure apparatuses, which is restricted to be smaller than
the size of synthesis apparatuses at normal pressure.
Using this temperature difference method, we can obtain semiconducting crystals by add-
ing a small amount of a suitable impurity to the solvent (184,201). To make a pn-junction
crystal, two compressions were carried out. In the first compression, a p-type crystal was made
by adding a small amount of beryllium (p-type dopant) to the solvent. In the second compression,
the p-type crystal was located at the low-temperature end of the growth cell as a seed crystal.
By adding silicon (n-type dopant) to the solvent, an n-type crystal was grown on top of the p-
type seed. A functional pn crystal was thus fabricated (184,199).
Regarding homoepitaxial growth of cBN on a cBN seed, a clear boundary between the
grown crystal and the seed crystal was obtained when LiCaBN2 was used as a solvent (184,199).
When Li3BN2 was used, it appeared difficult to make a clear interface.
Figure 43 Cubic BN formation by the temperature difference method.

534 Mishima and Era
c. Sintered Polycrystals
At high temperatures close to the melting point of materials (or at temperatures above about two
thirds of their melting temperature), atomic diffusion in a crystal becomes active and sintering,
recrystallization and plastic deformation occur. Cubic BN powders are thus sintered without
any sintering aid when they are subjected to high enough temperatures at high pressures (usually,
E in Fig. 40) (23,63–65,176,255,257). Sintering aids (or solvents) assist in sintering cBN pow-
ders at lower temperatures. Cubic BN compacts are also produced from an hBN starting material
by a simultaneous hBN-cBN conversion and sintering process using a small amount of solvent
(256). When cBN powders are well sintered, with or without a sintering aid, transparent (or
translucent) cBN compacts are obtainable (246,257).
Cubic BN composite materials with TiC, TiN, Al2O3, AlN, Si3N4, WC, etc. are also produced.
The mechanical properties of these materials depend on their microstructure such as grain size
distribution and voids in the composites (258). Because these composite compacts are useful as
cutting tools, they are usually described in the patent literature. Some reported elements for these
composites are listed in Table 10 (7). A BN material is sintered with these elements and/or their
nitrides, carbides, borides, and carbonitrides. Sintering of carbon precoated cBN grains and forma-
tion of BX CY NZ grain boundaries were claimed in a patent, as quoted in Ref. 7.
Polycrystalline compacts with a S, Se, or Te dopant have been reported (259). When Be-
doped cBN semiconducting powders were sintered without any sintering aid, semiconducting
compacts were obtained (65).
Cubic BN compacts were also reported to be made by shock wave compaction (260,261).
The properties of the compacts depended on the grain size of the starting cBN powders, and
coarse cBN powders were shown to be desirable for producing a consolidated compact.
4. Problems in Crystal Growth at High Pressures

Synthesis of cBN at lower pressures and lower temperatures may improve the productivity of
cBN and its cost performance. A method for growing large crystals quickly is also desirable.
A search for new solvents, as well as new synthesis methods, has therefore been carried out.
For diamond growth at high pressures, it seems to be possible to obtain a perfect diamond
crystal, as revealed by X-ray topography. Large single-crystal diamonds up to 17 mm in size
have been grown and 10-mm diamond crystals are now commercially available. Because the
high-pressure synthesis methods for cBN are similar to those used for diamond, perfect and
large cBN crystals may also be expected. However, growth of large cBN crystals is proving
more difficult than growth of large diamonds. Large and good cBN crystals are reproducibly
obtained but productivity is low at present. This is because of immature growth techniques in
areas such as controlling nucleation, pressure, temperature, solvent, and purity. Cubic BN, a
two-element compound, also has intrinsic problems, notably with easy cleavage, difficult control
of stoichiometry, and so on. Fine cracks, solvent-trapped pools, and twins, which are probably
caused by rapid crystal growth, are often observed in cBN crystals made at high pressures.
An inhomogeneous distribution of body color is usually observed in cBN single crystals,
Table 10 Some Reported Elements for cBN Composite Compacts
Transition elements 3a 4a
Al Si
Ti V Cr Mn Fe Co Ni Cu Zn
Y Zr Nb
Hf Ta W Zr
Figure 44 Schematic potential surface and formation of a metastable phase.
indicating an inhomogeneous distribution of defects in the crystal. To date, precise control of

doping levels and the distribution of impurities in cBN crystals, which determine semiconducting
properties, has not been achieved with high-pressure methods. Also, complicated devices are
obviously difficult to make under high pressures.
B. Low-Pressure Synthesis
Although cBN is metastable at low pressures, it can be synthesized below 1 bar in a manner
similar to the formation of diamond at low pressures. In the early 1980s, a small amount of
cBN was claimed to exist with a large amount of hBN (or tBN) in a BN deposited film. At
present, a small amount of hBN (or tBN) remains in a cBN polycrystalline film although the cBN
crystals forming the film are extremely small (⬍⬃0.1 µm). Studies of low-pressure methods for
producing cBN films are continuing with a view to future applications.
1. Principle
Under conditions in which hBN is thermodynamically stable, we can synthesize metastable
cBN.
As mentioned in Sec. IV.A.1 on the high-pressure film method, a metastable material
should dissolve more in its solvent than its stable phase. A stable material usually grows on the
stable-phase substrate. However, in hydrogen-mediated diamond synthesis at pressures below
1 bar, stable graphite crystals were etched by hydrogen (or hydrocarbon) gas while metastable
diamond crystals grew at the site where the graphite crystals were located. This phenomenon
(namely, etching of graphite and growth of diamond at low pressures) is apparently different
from the usual solution phenomenon, where metastable materials should dissolve easily. The
surface energy difference between a small nucleus of graphite and a small nucleus of diamond
in the presence of hydrogen (or the difference in their nucleation processes) is not influential
in the growth process because graphite crystals of stable phase already exist as the substrate.
From common thermodynamic phase diagram such as Fig. 39, we cannot explain this
graphite → diamond change and the corresponding hBN → cBN change (263) at low pressures.
Low-pressure synthesis of diamond and cBN involves growth under thermodynamically non-
equilibrium conditions. The formation of the nonequilibrium phase cBN may be understood in
terms of a schematic potential diagram of low-pressure conditions (Fig. 44). The Gibbs free
536 Mishima and Era
Figure 45 A schematic graph of the Gibbs free energy of stable, metastable, and liquid phases versus
temperature.
energy of the high-pressure phase is higher than that of the low-pressure phase. In other words,
cBN is in the metastable state. When a certain amount of energy is absorbed by the low energy
and equilibrium substance, hBN, a certain concentration of the metastable substance cBN is
formed through the excitation of route A in Fig. 44 beyond the concentration determined ac-
cording to the thermal equilibrium between the both states. Part of the metastable state substance
reverts back to the stable hBN through route B. The metastable state is prevented from staying
there by the peak (so-called transition state) in the middle of both states. If a certain concentration
of the metastable state substance thus formed is kept until it is taken out of the synthesis system,
one can obtain it as the product. Thus, excitation beyond the thermal equilibrium of the stable
state substance is a necessary condition for obtaining cBN by low-pressure methods. Actually,
various experiments on low-pressure cBN synthesis suggest that excitation of the surface of a
growing film, for example, by a ion beam, is important.
Experimental data are usually restricted to measurements of properties such as the deposi-
tion rate and film composition. It is difficult to clarify the underlying low-pressure synthesis
mechanisms from these measurements because the elementary reactions involved in the methods
are quite complex. We can think of various mechanisms for the reaction in the low-pressure
methods: for example, generation of high pressure and high temperature or generation of com-
pressive stresses in a ion-bombarded film (265,266), induced by thermal spikes due to impinging
ions (47,265). However, conclusive and detailed mechanisms have not yet been elucidated.
Generally, the low-pressure methods have the potential to produce new metastable materi-
als with novel structures and properties. The melting temperature of any metastable phase (Tm2
in Fig. 45) must be lower than that of a stable phase (Tm1 in Fig. 45). A new BN phase obtainable
by novel processes using the low-pressure method should have a lower melting temperature
than that of hBN near 1 atm.
2. Preparation and Analysis

There are some review articles on low-pressure syntheses of cBN (8,9,12). The reported low-
pressure methods have usually been named according to the techniques involved, and the variety
of the names has caused some confusion. Reported experiments can be categorized as employing
CVD and PVD methods. The CVD method is chemical vapor deposition in a reactive hydrogen
gas atmosphere. The PVD method is physical vapor deposition in vacuum or in a rather nonreac-
tive gas atmosphere. The PVD method can be further categorized into four types: (a) B deposi-
tion and simultaneous N (and Ar) ion bombardment, (b) B evaporation in reactive N (and Ar)
gas, (c) radio-frequency (RF) sputtered BN deposition in N and Ar sputtering gas, and (d) laser-
ablated BN deposition with or without N ion bombardment.
Synthesis of cBN by a low-pressure method was claimed by Vickery in 1959 without any
detailed description of his experiment or analysis (267). Around 1980, Sokolowski et al.
(268,269) and Weissmantel et al. (47,264,270) reported the synthesis of cBN (or iBN) and
showed electron diffraction patterns of the material so produced. Since then, confirmation of
cBN synthesis have been attempted by many researchers. Efforts to increase the cBN yield have
also been made. Nevertheless, clear identification of cBN formation has not been made because
of the smallness of BN grains and difficulty in distinguishing cBN from hBN, tBN, pBN, or
even from surrounding materials by IR (271,272) and diffraction methods (273–275) (Y. Matsui,
private communication). Combined analyses of the structure, the composition, and the atomic
bonding of the films produced by IR, diffraction, and electron spectroscopy etc. could improve
the situation.
In 1987, Inagawa et al. (276) and Chayahara et al. (277,278) succeeded in increasing the
cBN yield by applying a negative bias potential to the substrate. The importance of biasing to
the substrate has been confirmed by other researchers. At present, PVD and CVD methods can
provide films made of an apparently almost single (80–100%) cBN phase. Some important
factors to increase the cBN yield are a negative bias of the substrate, ion beam bombardment
of the growing surface, dilution with Ar gas, and so on.
The necessity for proper bias to the substrate has been well confirmed in CVD and PVD
(RF sputtering) methods (162,279–283). Ion bombardment by a bias potential during film
growth was often speculated to be important for cBN formation. Ions were accelerated by an
externally applied voltage or a negative self-bias of the substrate (which is caused by the higher
mobility of electrons than ions). However, films would be etched by sputtering if the bias poten-
tial was too large (162). The true mechanism of cBN formation with a negative bias of the
substrate is unknown.
By using B (or BN) deposition with simultaneous N (⫹ Ar) beam bombardment, cBN
was formed reproducibly without bias control (284–289).
a. Chemical Vapor Deposition
It seems to have been established that the bias to the substrate is important in increasing the
cBN yield in the case of RF plasma CVD (277), electron cyclotron resonance (ECR) plasma
CVD (277,280,290,291), and inductively coupled RF plasma (ICP) CVD (279,292). A suitable
amount of dilution gas such as Ar and a high ion flux to the substrate promote cBN formation
(263,280). The hydrogen content in the gas needs to be small because BN deposition with a
bias was difficult due to etching of the film by the gas (Fig. 46) (292).
Without the bias, formation of cBN (or hard BN) was reported with ECR plasma CVD
(293), microwave plasma CVD (275,294), RF plasma CVD with a thermal activation filament
(295), and reactive evaporation of B or H3BO3 in an NH3 discharge (296–298). The amount of
cBN in an hBN or tBN matrix of these films appears to be smaller than that of the films made
with bias control. Ion beam deposition from a borazine (B3N3H) plasma (299) or from ionized
borazine (264,270,300) was also reported to produce a hard BN material.
Formation of a cBN film by the DC plasma CVD method has also been claimed (301).
Laser-assisted plasma CVD, in which an excimer laser beam irradiated a growing film, was
reported to be effective for growing cBN crystals (302,303).
538 Mishima and Era
Figure 46 Chemical vapor deposition; parameters for growth of cBN. (Data from Refs. 278, 280, 281,
291, 293.)
b. Physical Vapor Deposition

B deposition and simultaneous N beam bombardment on a growing film. Films of an almost
single phase of cBN were reproducibly formed when evaporated or sputtered B atoms were
deposited with simultaneous bombardment by N and Ar ions. The Ar content and the ion beam
energy were shown to be important parameters for the formation of cBN (Fig. 47)
(284,285,288,289,304,305). [However, there is a report which suggests that the addition of Ar

plays an insignificant role when neutralized N atoms are bombarded (306).]
Without Ar ion bombardment or when the beam energy was not appropriate, deposited
films were mainly hBN, tBN, or iBN (47,264,270–272,308–310). Implantation of N ions in a
boron substrate did not result in any clear evidence of cBN formation (311–313).
B evaporation in reactive N and Ar gas. Nearly single-phase films of cBN were reproduci-
bly formed when B atoms were evaporated in a N and Ar plasma and B and N atoms were
deposited on a bias-controlled substrate (162,266,276,281,314). Formation of cBN was pro-
Figure 47 B deposition and simultaneous N beam bombardment. (Data from Refs. 285, 286, 289, 305.)
540 Mishima and Era
moted by mixing Ar gas and by controlling a negative RF self-bias potential of the substrate
(Fig. 48).
Radio-frequency sputtered BN deposition in an N and Ar sputtering gas. Radio-frequency
sputtered BN deposition in an N (and Ar) plasma without any proper control of the substrate
bias potential or the gas composition resulted in the formation of mainly hBN (or tBN) (315–
317). In 1987, a role of the negative bias potential of the substrate in cBN formation was sug-
gested (318). In 1990, films of an almost single phase of cBN were successfully obtained by
sputtering hBN in an Ar-rich gas and depositing B and N atoms on a sufficiently negatively
biased substrate. An additional magnetic field assisted cBN formation (282,283,319). Sputtered
matter from a BN target was suggested to be in an atomic state, not in a BN molecular state
(Fig. 49) (282).
Laser-ablated BN (or B) deposition with or without simultaneous N beam bombardment
Figure 48 B evaporation in reactive N ⫹ Ar gases. (Data from Refs. 163, 208, 277, 314.)
Figure 49 The RF sputtered BN deposition in N ⫹ Ar gases. (Data from Refs. 283, 284.)
on the growing films. When a BN material was evaporated by irradiation with a CO2 laser (λ
⫽ 10.6 µm) (286), a KrF laser (λ ⫽ 248 nm) (285,287,320–322), or a Q-switched ruby (λ ⫽
694 nm) or neodymium (λ ⫽ 1.06 µm) (163) laser in vacuum, the deposited films were tBN
or hBN and were nitrogen deficient. In the initial stage of deposition, epitaxial growth of a cBN
thin film on a Si crystal substrate up to ⬃10 nm and successive growth of a polycrystalline
hBN or tBN film on this cBN layer were indicated (321,323).
Laser-ablated BN deposition with a simultaneous supply of N ions on the growing film
was found to be successful in making cBN-rich films (Fig. 50) (286,287,320).
Laser-ablated BN (or B) deposition in N2 or NH3 (plasma) gas has shown, so far, no
evidence of cBN formation (163,322,324).
542 Mishima and Era
Figure 50 The laser ablation method. (Data from Refs. 287, 288.)
3. Problems in the Low-Pressure Synthesis

The size of the cBN crystals made at low pressures has been too small (⬍100 nm) for us to
observe the growth surfaces. The small size of the cBN crystals causes a slight suspicion that
the deposited microscopic (or nanoscopic) cBN might be different from the macroscopic cBN
bulk crystal. Growth of larger cBN crystals is a current problem. There is a paper that details
the growth of large cBN single crystals (⬎1 µm). The crystals were grown by a CVD method
with simultaneous laser irradiation of the growing film (302,303).
Epitaxial growth of a cBN film on a single-crystal substrate is another problem. Although
there have been reports of deposition of preferentially oriented cBN crystals on a Si substrate
(287,302,321), good growth of a cBN film on a single-crystal substrate has not yet been attained.
Another problem is the poor adhesion strength of cBN films on the usual substrates (e.g.,
Si crystals), which causes flaking and peeling off of the film with time when the film is exposed
to air. High residual compressive stresses in the deposited film were thought to be the reason
for the degradation (300). Unwanted trapping of gases might cause the degradation.
Selection of suitable substrate materials (or buffer layers) reduces the degradation of films.
Use of a diamond substrate hindered the peeling off of a cBN film (291). Buffer layers between
a cBN film and a Si substrate, such as B-rich layers (290,325,326) and SiNx layers, were reported
to be effective in preventing the peeling off. The usefulness of a thin hBN interlayer is a subject
of controversy at present (282,283).
V. HETEROJUNCTIONS
A heterojunction between cBN and diamond is possible (327,328), and theoretical calculations
(329,330) suggest that the junction has a type II alignment of the band-offset diagram (Fig. 51).
Geometric considerations are discussed in Ref. 330.
Regarding the formation of a diamond-cBN junction at high pressures, cBN can grow
epitaxially on a diamond seed when a suitable solvent, such as Li3BN2, is used (328). Generally,
growth of cBN, which is a two-element material, on a diamond lattice causes an antiphase
problem (Figs. 52 and 53). The surface morphology of a cBN crystal that was grown on a
diamond seed exhibited characteristic features of the antiphase (328) (see Sec. II.D.2.a). To
date, growth of diamond on a cBN seed by the high-pressure method has not been reported.
Synthesis experiments for the formation of a diamond-cBN junction are listed in Table
11. Regarding formation of the junction at low pressures, diamond was used as a substrate for
cBN deposition in order to improve adhesion of the cBN film to the substrate (291,294,313).
A low-pressure diamond film was also deposited on a substrate of a cBN single crystal (or
polycrystal) that was made at high pressures (275,329,332–335) or on a polycrystalline cBN
film made at low pressures (336–338). The diamond film could grow epitaxially on some kinds
of cBN surfaces (35,332,339). The (111)B surface of a cBN crystal was believed to be more
useful as a substrate for diamond growth than the (111)N surface (332). High-resolution electron
microscopy confirmed the diamond-cBN parallel epitaxy (335,339), showing almost no misfit
Figure 51 The type II alignment of the band-offset diagram for a C/BN (110) heterojunction. (From
Ref. 330.)
544 Mishima and Era
Figure 52 Formation of an antiphase at the C-BN interface.
Figure 53 The (100) surface morphology of cBN grown on a diamond single crystal.
Table 11 Methods of Synthesis for the Formation of a Diamond-cBN Heterojunction and Their
References
Diamond on cBN cBN on diamond

LP method HP method LP method HP method
cBN substrate cBN substrate Diamond substrate Diamond substrate
Film Bulk Film Bulk Film Bulk Film Bulk
302 298 280 263 293
303 292 297 260
304 299
300
245
dislocation at the diamond-cBN interface (one dislocation per 82–84 diamond lattice planes)
due to the small lattice mismatch of ⬃1.3% (339).
Epitaxial low-pressure deposition of cBN on a Si substrate (lattice mismatch ⬃33%) was
reported (321). Because further deposition layers consisted of an amorphous tBN phase, it was
suggested that, when the deposited BN layer became thicker than ⬃10 nm, the BN layer changed
from a cBN phase to an amorphous tBN phase (323).
VI. APPLICATIONS OF CUBIC BN
Because of the similarity of the properties and syntheses of cBN and diamond, the applications
of cBN resemble those of diamond. Possible applications of cBN, which are also applications
expected for diamond, are listed in Table 12.
There exist some differences in properties between the two materials, such as their chemi-
cal constituents, electronic band structure, chemical reactions, ionicity, neutron absorption, and
impurities. Because of these differences, cBN is superior to diamond for some applications.
Diamond, having perfect covalent bonding, is the hardest material and may be interesting
in mechanical and thermal applications. On the other hand, cBN, having about half as much
ionic character in its chemical bonding, has the largest band gap among existing semiconductors
with tetrahedral chemical bonding. These features of cBN may lead to novel optical and elec-
tronic applications.
A. Mechanical and Thermal Applications

Because diamond is harder than cBN, it should exhibit higher performance in grinding and
cutting than cBN. However, diamond reacts with some metals at high temperatures and forms
metal carbides. The reaction appears to occur more easily than the reaction of cBN, which forms
metal nitrides. Thus, tools made of cBN are preferable for cutting or grinding metals with which
diamond reacts seriously.
Today, an estimated ⬃20,000 kg/year (or ⬃100 million carat/year; 1 carat ⫽ 0.2 g) of
cBN powders is mass produced in high-pressure factories and used mostly for mechanical appli-
cations around the world (Fig. 54) (340,341). Cubic BN tools are used to grind and to cut
hardened steel or chilled cast irons, for which diamond tools are not usually applied. Use of
cBN tools has been growing in parallel with the growth of hard Fe-rich materials, in order to
fulfill the requirements for precise finishing and high productivity of these materials in automated
Table 12 (Potential) Applications of cBN

Abrasive Diode, transistor Optical window
Cutting High-T device Optical protector
Drill Harsh conditions device X-ray lithograph
Blade Light emitter Atomic reactor window
Hard lubrication Light detector Spacecraft window
Wear resistance High-E particle detector Piezoelectric device
Neutron detector Speaker
Electric insulator Dosimeter Oscillator
Substrate Photovoltaic device High-pressure anvils, etc.
Heat sink Photochemical device
546 Mishima and Era
Figure 54 Estimated consumption of cBN in the world. (Data from Refs. 341, 342.)
large-scale factories (such as automobile factories). Tools made of cBN have taken the place
of other nondiamond ceramic tools in these factories.
Abrasive cBN powders are used mainly for grinding, whereas cBN compacts, made by
sintering cBN powders with or without TiC, TiN, Al2O3, etc., are used for cutting (342). To
find the optimal operation conditions for an individual grinding or cutting application, the perfor-
mances of various tools are tested and compared by changing the tool materials, materials to
be machined, speed of grinding or cutting, operation time, and so on.
The application of a cBN single crystal for precise cutting of hard steel has been reported,
indicating that the cBN crystal can make mirror-finished surfaces of a steel material, eliminating
further grinding processes (343). However, the cBN crystal was severely worn and practical
applications for machining of hard steel appear to be difficult because of the lack of endurance
of the tool.
Films of cBN made at low pressures may be useful for mechanical application when good
cBN films are manufactured. Trial applications of cBN films for cutting materials may have been
carried out, but results are unclear at present (313). The possibility of a tribologic application for
cBN films has been suggested (344).
Because cBN is a good thermal conductor and has a thermal expansion coefficient close
to that of Si near room temperature, cBN is suitable as a substrate material for Si-based electronic
devices. Thus, sintered polycrystalline cBN has been made as a heat sink substrate (147). Poly-
crystalline cBN is also used in the tape-automated bonding (TAB) tool (147).
B. Electronic and Optical Applications

The band gap energy of cBN is the largest among those of existing IV, III-V, and II-VI semicon-
ductors and cBN can be doped, forming both p and n types. Because of these characteristics,
as well as other properties such as hardness and chemical stability, cBN is expected to have
potential as a wide-gap semiconductor that can be used under severe, extreme, or refractory
Figure 55 Rectification characteristics of a cBN pn-junction diode. [T. Tomikawa, private communica-
tion; the diodes were described in his patent (347).]
conditions. For example, cBN may be used as a high-temperature device, a short-wavelength

light emitter or detector, and so on (for a review, see Refs. 345 and 346).
Fabrication of a cBN pn-junction diode was first attempted by Wentorf (4) using a high-
pressure method, but the pn composites he made were too small for the junction characteristics
to be examined. A cBN pn junction large enough for some fundamental characteristics to be
measured was fabricated by a high-pressure method in 1987 by one of the authors (O.M.) and
others (184). Formation of the pn junction was clearly demonstrated by showing the existence
of the space charge layer in the junction region through electron beam–induced current (EBIC)
Figure 56 Injection luminescence spectra of a cBN pn-junction diode. (Data from Ref. 189.)
548 Mishima and Era
images and by observing the rectification characteristics (20–650°C) (Fig. 55) (347). The cBN
pn diode was also functional as an ultraviolet light–emitting diode (Fig. 56) (189,199,200).
These cBN diodes were, however, primitive prototypes, and improvements in many areas such
as synthesis methods, ohmic contacts, and doping control need to be achieved before various
applications are realized.
Semiconducting cBN polycrystalline compacts containing Be impurities may be used as
varistors, as memtioned in Sec. III.D.2.
VII. PROBLEMS AND PROSPECTS
One of the most important problems confronting cBN research is the synthesis of single crystals
of good and controlled quality and a certain size. This is particularly true for electronic applica-
tions and for elucidating detailed fundamental properties. For this purpose, improvement of the
high-pressure methods is important and very desirable. This might be accomplished by the low-
pressure methods in the future.
For electronic applications, lowering the resistivity of cBN (especially that of the n-type
crystal) is desirable. In conjunction with this, sulfur doping (4) is attractive and should be tested.
Forming ohmic electrodes is the important problem to be solved.
When light-emitting diode (LED) action of cBN was reported, there appeared expectations
for blue LEDs. However, the success of GaN systems has lowered the expectations for cBN.
Applications of cBN as electronic devices have not been developed. We must expect them
in the future. Utilizing unique properties of cBN, such as the large band gap energy, mechanical
hardness, good chemical stability, high thermal conductivity, large cross section for slow neu-
trons, and their combinations, may bring about new and novel applications in the field of elec-
tronics.
Although cBN has been used widely as an abrasive and cutting material for ferrous metals,
a cBN single crystal appears to be worn out easily for reasons that are as yet unclear.
Metastability of cBN at 1 bar limits any use of cBN at very high temperatures.
ACKNOWLEDGMENTS
The authors would like to acknowledge Drs. M. Kamo, H. Kanda, S. Komatsu, M. Mieno, S.
Nakano, T. Sekine, T. Taniguchi, S. Yamaoka, and many other NIRIM researchers for various
discussions. The authors also thank Dr. R. C. DeVries for information concerning some literature
and Dr. S. Lawson for advice on the English of the original manuscript by one of the authors
(O.M.).
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22
Boron Phosphide
Yukinobu Kumashiro
I. INTRODUCTION
Boron phosphide (BP) is a III-V compound semiconductor with zinc blende structure and dis-
plays rather peculiar behavior compared with other compounds of the III-V family. The constit-
uent atoms of BP are the light elements, and especially boron belongs to the first law of group
III of the periodic table, those with small inner shells, and exhibits strong covalent bonding
with small ionicity, as may be seen from its electronegativity difference of 0.1 eV.
The ionization energy of boron I(B) strongly deviates from that of Ga and In (P and As
having quite comparable ionization energies), which is believed to be the origin of the differ-
ences between BP and the other III-V materials. BP has the most compact crystal structure
because of the small atomic radius of boron. Consequently, the overlap of atomic orbitals in
BP exceeds the overlap in the other III-V semiconductors and stabilizes BP to a larger extent (1).
The other stabilizing factor is the small energy difference between the atomic orbitals that
constitute the valence band of BP. The difference between energies of molecule ∆I(BP) is much
smaller than ∆I for the other III-V materials. Both stabilizing effects can be thought of as origi-
nating from the small atomic radius of boron, which leads to both a larger orbital overlap and
a higher ionization energy.
When log ν t is plotted against log a where a is the lattice constant and ν t is the vibrational
frequency, approximately straight lines are obtained for the heavier III-V compounds but the
plot is no longer linear for boron phosphide, indicating that the nearest-neighbor force constants
are considerably larger in boron phosphide than in the heavier III-V compounds (2).
Boron phosphide is also known as a refractory semiconductor with a wide band gap and
has the potential for application in electronic devices in extreme conditions such as high-temper-
ature, radiation, and high-energy environments (3,4).
However, BP has been considered to have few outstanding features in comparison with
other III-V compound semiconductors for three basic reasons. First, it is difficult to prepare well-
characterized single crystals because of high melting points (⬎3000°C) and high decomposition
pressures (⬃10 5 atm at 2500°C) (5). Second, the material handling process is complicated be-
cause of its refractory hardness and brittleness. Third, it has lower electron mobility (6) than
other III-V compound semiconductors. The mobility of BP at a lower carrier concentration
might be slightly greater than that of Si; hence, BP can become a useful semiconductor material
if controlled doping can be achieved. A few studies were reported concerning device fabrication,
i.e., BP-Si heterostructures for wide gap window solar cells and wide gap emitter transistors
557
558 Kumashiro
(7). An Si-BP-Si double heterojunction prepared by alternate growth of BP and Si on an Si

substrate (8) and a p-n junction in BP prepared by use of B⫹ ion implantation (9) were re-
ported.
In this chapter, first various band calculations in relation to intrinsic properties and crystal
growth by various methods to clarify electrical, optical, and mechanical properties at room
temperature are reviewed. Second, high-temperature properties, which are indispensable with
the development of high-temperature devices, clarify impurity levels and lattice scattering pro-
cesses. Finally, the applications of new refractory semiconductors to electronic devices such as
junction devices and energy-related applications of photocathode and thermoelectric devices are
reviewed.
II. BAND STRUCTURE
There are limited experimental data on the electronic structure of boron phosphide. Although
several theoretical calculations are available, their results differ considerably. The existing theo-
retical data cannot be relied upon to provide accurate estimates of excitation energies, because
most band structure calculations performed to date rely on the Xα method (10) and the local
density approximation (LDA) to the density-functional theory (11–13). These theoretical meth-
ods can yield errors of up to several eV in band gaps or other excitation energies when compared
with reliable experimental results. It has become possible to compute with great accuracy a
number of electronic and structural properties from first-principles calculations. Among the
quantities obtainable with this kind of calculation are crystal structures, phonon spectra, lattice
constants, bulk and shear moduli, and other static and dynamical properties.
The unusual behavior appears to originate from the small core size and the absence of p
electrons in the cores of the atoms in the first row of the periodic table. These atoms are expected
to have deep and localized pseudopotentials compared with the atoms in other rows. Wentzcov-
itch et al. (12) used the total-energy pseudopotential technique employing the LDA for electron-
electron interactions to calculate the following ground-state properties of BP: bulk moduli, lattice
constants, cohesive energies, frequencies of the TO(Γ) phonon mode, and total electronic charge
densities. The computed equilibrium lattice constant a, elastic constant C ij , bulk modulus B,
frequency of the transverse optical vibrational mode at q ⫽ 0, TO (Γ), and shear modulus Cs
are given in Table 1. The calculated lattice constants are in good agreement with the measured
Table 1 Experimentaland CalculatedLattice Constant a, theElastic ConstantsC ij ofBP, the Elastic Constant
C 044, the Optical Γ-Phonon Frequency ω Γ , the Bulk Modulus B, and the Shear Modulus C s
C 11 C 12 C 44 C 44 0 ωΓ B Cs
Reference a(Å) (Mbar) (Mbar) (Mbar) (Mbar) (THz) (Mbar) (Mbar)
Exp. (14) 4.538
Exp. (15) 3.15 1.0 1.6 1.73
Exp. (16) 23.9
Exp. (17) 24.6
Calc. (12) 4.558 23.0 1.65
Calc. (18) 4.474 3.59 0.81 2.02 2.10 24.6 1.73a 1.39
1.72b
a
B ⫽ (C 11 ⫹ 2C 12 )/3.
b
From Murnaghan’s equation.
Boron Phosphide 559
values to within 0.4%. Comparisons with available reported data for the bulk moduli suggest
that the theoretical results are underestimated. Using the empirical relation B0 ⫽ 1761d⫺3.5 (19),
where d is the nearest-neighbor distance, gives B0 ⫽ 166 GPa, in excellent agreement with their
results.
Pseudopotential calculations (12,20) of the electronic structure confirm the lack of p char-
acter of B in the bottom of the conduction bands and suggest that a large amount of character
is associated with the B atom in the top of the valence bands, as generally happens with a typical
anion. These studies (12,20) also indicated that in the formation of the bonds in BP the charge
moves from the antibonding region associated with the group V element to the bonding region.
Usually this rearrangement of charge in zinc blende semiconductors is observed to proceed in
the opposite way, with the charge leaving the antibonding region associated with the group III
element and going to the bonding region.
Hernández et al. (18) obtained highly converged total energies, forces, and stresses in BP
to arrive at the elastic modulus, frequencies of the TO(Γ) phonon mode, and electronic band
structures. For all the calculations they used ab initio self-consistent pseudopotential calculations
in the framework of the LDA with a plane-wave basis. The equilibrium lattice constants, a 0 ⫽
4.474 Å, were determined by fitting the total energy to the empirical Murnaghan equation of
state. The calculated bulk modulus B and the frequency ωΓ agree remarkably well with the
experimental data (15–17). The calculated elastic constants (C 11 ⫽ 3.59 Mbar and C 12 ⫽ 0.81
Mbar) compare well with the Brillouin scattering results (15) (Table 1). Their results for BP
compare remarkably well with experiment.
The calculated band structure is shown in Fig. 1a. Although this approach fails to describe
accurately the energy of the excited states, it usually provides a qualitative description of these
Figure 1 Band structures of BP by (a) total-energy pseudopotential technique within the local density
approximation (18), and (b) GW approximation (21).
560 Kumashiro
states. Advances have made it feasible to perform ab initio calculations with enough quantitative
accuracy to provide information on the excitation energies. These calculations employ the GW
approximation to include properly the effects of exchange and correlation on the quasi-particle
energies (21). The GW approach has resulted in calculated band gaps with 0.1 eV accuracy when
a random phase approximation (RPA) dielectric matrix is used or with 0.1–0.3 eV accuracy with
use of an appropriate model dielectric matrix. Surh et al. (21) examined the electronic excitation
energies for high-symmetry points Γ, X, and L for BP in the GW approximation using a model
dielectric function (Fig. 1b). A model for the static screening matrix makes use of the ab initio
ground-state charge density and either experimental values or empirical estimates for ε∞ the
electronic contribution to the macroscopic dielectric constant. Wave functions from an ab initio
local density approximation calculation with norm-conserving pseudopotentials are employed
along with the self-consistent quasi-particle spectrum to obtain the energy-dependent one-parti-
cle Green function G.
The results of the LDA and GW calculations for BP are listed in Table 2 along with
experimental data. The reported reflectivity spectrum of BP (26) has three main peaks at ⬃5.0,
6.9, and 8.0 eV, which were tentatively assigned to direct transitions Γ v15 → Γ c15 , X v5 → X 1c , and
L v3 → L c3 , respectively. An indirect gap of 2 eV was obtained by optical absorption experiments
(24).
The direct band gaps for BP are 4.4, 6.5, and 6.5 eV at Γ, X, and L, respectively; they
are all approximately 1.0 eV larger than the LDA values.
An empirical pseudopotential method (EPM) calculation (23) was done to reproduce the
gap and the reflectivity spectrum adjusting the pseudopotential form factors. This study led to
a minimum direct gap at L and the lowest conduction state was obtained at Γ 1c . A band structure
calculation using a semi–ab initio approach (10) obtained an indirect gap (Γ v15 → Γ 1c ) of 2.0 eV
and a comparable direct gap (Γ v15 → Γ c1 ) of approximately 2.0 eV. The minimum band gaps of
BP have been reliably estimated from the experimental optical absorption. However, the direct
band gaps and other excitation energies must be estimated from structure in the optical response
versus frequency. The accuracy of the resulting experimental values depends on the correct
identification of features in, e.g., the reflectivity with particular transitions between band states.
Then the GW results may be more reliable estimates than the experimental direct band gaps.
Table 2 Summary of Important Features of the Band Structure of BP

Valence
Minimum gap (eV)
bandwidth
Method and reference Indirect Direct (eV)
Theoretical
Quantum dielectric theory (22) 4.9 (Γ v15 → Γ c15 )
EPM (23) 2.19 (Γ v15 → X c 1 ) 5.0 (L v3 → L c1 ) 17.9
LDA (12) 1.2 (Γ v15 → ∆ min ) 3.3 (Γ v15 → Γ c15 ) 15.3
LDA (18) 1.14 (Γ v15 → ∆ min ) 3.45 (Γ v15 → Γ c15 ) 15.75
LDA (21) 1.2 (Γ v15 → ∆c min ) 3.4 (Γ v15 → Γ c15 ) 15.5
Semi–ab initio approach (10) ⬇2.0 (Γ v15 → L c1 ) ⬇2.0 (Γ v15 → Γ c1 ) 11.8
GW (21) 1.9 (Γ v15 → ∆ min ) 4.4 (Γ v15 → Γ c15 ) 16.8
Experimental
Optical absorption (24) 2.02 ⫾ 0.05
Ultrasoft X-ray spectroscopy (25) 2.1 ⫾ 0.2 16.5 ⫾ 0.5
Reflectivity spectrum (26) 2.0 (Γ v15 → χc 1 ) 5.0 (Γ v15 → Γ c15 )
Boron Phosphide 561
III. CRYSTAL GROWTH AND CHARACTERIZATION

A. Crystal Growth
First, the preparations of powder and sintered specimens are mentioned. Polycrystalline boron
phosphide powder (27) material was prepared by the reduction of a boron tribromide–phospho-
rus trichloride mixture with hydrogen in a gas flow system in a fused silica tube furnace at
about 1100°C. An excess of phosphorus trichloride was used to maintain the stoichiometry of
the deposit. The deposition rate was approximately 2 g/h.
High-purity BP powders are prepared by hydroisostatic pressing. Boron and red phosphor
were mixed in a fused silica tube evacuated to less than 10 ⫺3 torr and sealed. The ampule was
hydrostatically pressed to 1300°C under pressure of 1.8 ton/cm 2 for 2 h. The BP powders thus
prepared are far purer than commercial ones. The specimens were sintered at 1300°C at a hydro-
static pressure of 2 ton/cm 2 for 1 h (28).
BP is a difficult material to sinter because of the high dissociation pressure of phosphorus.
Radio frequency (RF) hot pressing would be applicable (29). The powders were pressed up to
19.6 MPa at room temperature and the temperature was raised to 1000°C by RF heating with
a maximum applied pressure of 78.4 MPa. Subsequently, the temperature was kept at sintering
temperatures (1500–1800°C) for 1 h and then reduced to room temperature for 1 h. The density
of the specimen increases from 60 to 65% of the theoretical value with increasing sintering
temperature.
Kobayashi et al. (30) synthesized BP at high temperatures and high pressures with a girdle-
type high-pressure cell having a bore diameter of 15 mm and determined the temperature and
pressure conditions for the synthesis of BP (Fig. 2). Solid circles correspond to the case in which
BP was successfully synthesized. At relatively low pressure and low temperature no crystalline
materials could be observed, but at low pressure and high temperature the B 6P phase was de-
tected. A upper temperature limit for the synthesis and stability of BP is drawn as a solid line. The
lower temperature boundary line for the synthesis has a negative slope in a pressure-temperature
diagram, indicating that the reaction B ⫹ P → BP is promoted by the application of pressure.
Crystalline BP powder less than 100 µm in diameter was produced. The B 6P phase in the high-
temperature region shows a dissociation reaction. The dissociation pressure at 2000°C is as high
as 8 kbar.
Figure 2 P-T conditions for synthesis of BP. (From Ref. 30.)

562 Kumashiro
Niemyski et al. (31) also synthesized BP using an autoclave furnace under a high pressure
of 1.5 Mbar at a temperature of 1200–1300°C. Crystallization occurred with a temperature
gradient inside the chamber, and prolongation of the reaction time resulted in the formation of
larger crystals.
The growth of BP single crystals by conventional techniques such as zone melting and
growth from the melt is impossible, so preparation methods are limited to chemical vapor deposi-
tion (CVD), chemical vapor transport (CVT), and flux methods. Among these, the flux method
would produce comparatively large single crystals. A requirement for the flux material was to
have a eutectic temperature with B and P lower than the softening temperature of fused silica
(⬃1300°C).
Iwami et al. (32) grew large single crystals of dimensions 5 ⫻ 2 ⫻ 2 mm 3 from B-Ni-P
solution. Chu et al: (33) tried to grow large crystals 2–4 mm in size by means of recrystallization
in metal phosphide solution of nickel phosphide and copper subphosphide solutions.
Kato et al. (34) obtained larger and better crystals than those grown from Ni-fluxed melt
and also succeeded in growing crystals on a seed crystal by the supersaturation with a tempera-
ture gradient in the Cu-fluxed melt. The minimum temperature of the low-temperature zone was
kept at about 400°C to maintain the phosphorus pressure in the ampule at about 1 atm by
maintaining the top of the solution at the highest temperature (1200°C) and the bottom at a
temperature a few tens of degrees lower than the top temperature. The crystals had a maximum
size of 4 ⫻ 3 ⫻ 0.2 mm 3 and were in the form of planets with a small number of funnel-shaped
and needle-shaped ones. Crystals grown from the Cu-fluxed melt were always n-type, and those
grown from the Ni-fluxed melt were always p-type with a room temperature resistivity of about
0.5 Ω cm and a dopant concentration of about 10 18 /cm 3.
Using a unique high-pressure flux method (35), which is a modification of Chu’s method
(33), large BP single crystals would be obtained. Instead of a fused quartz tube, the crystal
growth was carried out in an RF induction furnace with a graphite crucible containing the
crushed BP-Cu 3P melt under a high pressure of 18 atm. The top of the solution was maintained
at about 1400°C for 20 h and the bottom was approximately 10–20 degrees cooler. Then the
crucible was slowly cooled down to room temperature. Dark reddish BP single crystals were
extracted from HF-HNO 3 solution to confirm that BP was recrystallized and coalesced in the
bottom of the crucible. The single crystals obtained (5 ⫻ 5 ⫻ 3 mm 3 ) are the largest with a
smooth main face of (111). The X-ray powder diffraction pattern shows small amounts of B 6P
and Cu 3P precipitate in the crystals, but the crystals have a lattice constant of a ⫽ 4.539 Å,
which is in good agreement with the value reported. The crystals exhibit p-type conduction due
to copper. Their electrical resistivity, carrier concentration, and mobility are 1.5 Ω cm, 1.67 ⫻
10 18 /cm 3, and 1.77 cm 2 /V s, respectively. The photoluminescence spectrum at 4.2 K excited by
a Cd-He laser (Fig. 3) has five peaks (denoted as A, B, C, D, and E). Peak C corresponds to
an LO-phonon replica of peak A, peak E to a second LO-phonon replica of peak A, and peak
D to an LO-phonon replica of peak B. Furthermore, the spectra caused by donor-acceptor pairs
are observed (not shown here) on the higher energy side than peak A and are in good agreement
with the theoretical value of type II in the zinc blende structure (34,36).
The crystal growth of boron phosphide by CVT (27) is based on the reversible reaction
between boron phosphide and the transport agent. Boron phosphide is transported from a high-
temperature source (1270–1290°C) to lower temperature regions in fused silica tubes of 10 mm
inner diameter, 16 mm outer diameter, and 12 cm long. The important parameters affecting the
quality of the transported crystals include the source temperature, the temperature gradient along
the reaction tube, the nature and pressure of the transport agent, and the surface condition in
the deposition region of the reaction tube. A phosphorus pressure of 3 atm and a transport agent
pressure of 1 atm were optimal for the transport process. The temperature gradient between hot
Boron Phosphide 563
Figure 3 Photoluminescence spectrum of BP single crystal at 4.2 K. (From Ref. 35.)
and cold regions should be as small as possible to approach equilibrium. Phosphorus trichloride
was found to be the fastest transport agent, but the transported material consisted of loosely
bound aggregates of small crystals. Iodine or bromine as a transport agent has produced better
results in the form of disks of about 5 mm diameter and 1–2 mm thickness and in the form of
polyhedrons. The deposition region flame-worked to remove any surface irregularities produced
only one tightly bound single crystal up to 2 mm at the tip of the reaction tube. Flame working
of the fused silica tube is a critical factor in achieving control of nucleation in the closed-tube
transport process. The transported boron phosphide crystals were p-type with a room temperature
resistivity of approximately 0.5 Ω cm.
The deposition of boron phosphide by CVD was carried out in a gas flow system by the
thermal decomposition of diborane-phosphine mixtures in a hydrogen atmosphere and the ther-
mal reduction of boron tribromide–phosphorus trichloride mixtures with hydrogen (37). The
hydrides are thermodynamically unstable at room temperature and decompose rapidly at above
500°C, which tends to promote homogeneous nucleation by pyrolysis in the gas phase. The
halides are thermally more stable than the hydrides, and higher substrate temperatures may be
used in the thermal reduction process with essentially no gas-phase reactions. At high substrate
temperatures, a phosphorus pressure equal to or greater than the vapor pressure of boron phos-
phide must be present over the substrate surface to maintain the stoichiometry of the deposit.
The reaction tube was water cooled to minimize the gas-phase reactions. For crystalline
cubic BP from BBr 3 and PBr 3 in a hydrogen atmosphere a narrow regime of temperature and
molar ratios of reactions is available (38). Furthermore, BP whiskers (39) were synthesized on
seed metals in the temperature range 850–1000°C. Nickel and silver acted as liquid forming
agents in a vapor-liquid-solid (VLS) growth mechanism (40). When saturation is reached, crys-
tallization of the product starts at the liquid-solid interface and after a while the formed crystallite
pushes the seed metal droplet away from the substrate, which results in whisker formation. The
564 Kumashiro
whiskers are of highly twinned single crystallinity, with preferred growth along the (111) direc-
tion. High-resolution transmission electron microscopy (TEM) pictures reveal a high density of
twin planes, spaced approximately 10–20 nm apart. Energy dispersive X-ray (EDX) element
analysis of the whisker tips did not reveal any traces of nickel, and X-rays attributed to nickel
were found when the electron beam grazed the graphite surface.
Although SiC substrates are most suitable from the viewpoint of lattice matching (37) in
the CVD process, the difficult etching of SiC prevents the removal of substrates from BP layers;
Si substrates are desirable for this purpose. Nishinaga et al. (41) reported the first experiments
on the growth of epitaxial BP layers on Si substrates, with a thermal reduction of the halide
system despite larger lattice mismatch of 16.5%. The crystals grown on Si{111} surfaces were
found to be monocrystalline with a zinc blende structure for a certain narrow temperature range.
Just outside this range, the grains of which the film is composed begin to rotate to take optimal
positions with respect to each other. Single-crystal BP layers have not been grown on Si{100}
surfaces. Takigawa et al. (42) performed thermal decomposition of diborane and phosphine and
concluded that Si{100} was the most favorable surface orientation for the hydride system in
contrast to the halogen system (41). One of the important differences between these two experi-
ments is the growth rate of BP. Takigawa et al. (42) employed a very low growth rate, as low
as 700 Å/min. Nishinaga and Mizutani (43) used a rate of approximately 1 µm/min, more than
10 times as high. When Nishinaga and Mizutani (43) performed experiments with growth rates
as low as 1000 Å/min, they confirmed that the arrangement of the three {100}, {110}, and
{111} substrates was the same and the best BP crystal was grown on the {100} substrate, in
agreement with Takigawa et al. (42). The conclusion of Nishinaga and Mizutani (43) should
be restricted to the case of high growth rates.
The TEM image of a BP layer grown on the Si(100) substrate indicates that the BP layer
is epitaxial with respect with a [100] surface normal, as evident from the superimposed fourfold
configuration visible in the selected area electron diffraction (SAED) pattern. However, fine
lines are observed along the (110) plane, showing a high density of planar defects primarily
originating at the substrate-epitaxial interface. These defects are mostly stacking faults and mi-
crotwins lying along the four equivalent {100} planes. High-resolution electron microscopy
(HREM) of the BP/Si interface (Fig. 4) shows a microtwin and misfit line. A huge lattice misfit
between BP and Si (⬃16%) produces no continuity of lattice planes across the interface. The
BP layer and Si substrate would match with misfit and microtwin.
During the epitaxial growth of n- or p-type boron phosphide (BP) on Si substrates using
a B 2 H 6-PH 3-H 2 system, either n-type (phosphorus) or p-type (boron) diffused layers are formed
on the Si substrate. At an early growth stage of BP on Si substrates a very small amount of
boron and phosphorus covers the substrate surface, which serves as a diffusion source (7). The
properties of the diffused layers are dependent on substrate temperatures and reactant gas flow
rates. The deviation from stoichiometry of boron monophosphide (BP) was controlled by heat
treatment of the BP surface cover with Si 3 N 4 (44). Qualitative characteristics of BP according
to the heat treatment are summarized in Fig. 5. The as-grown n-BP shows a high resistivity for
8 min of heat treatment at 1200°C and for 30 min at 1100°C. Longer heat treatment times result
in a change to p-BP. The resistivity of the p-BP becomes as low as 10 ⫺2 Ω cm as the heat
treatment time increases. With treatment times greater than 8 min at 1200°C and 30 min at
1100°C, in as-grown p-BP, the resistivity decreased as the heat treatment time increased. The
final value of the resistivity was less than 10 ⫺2 Ω cm. At 1050°C, a resistivity of more than
10 10 Ω cm was obtained for a heat treatment time of more than 2–3 h in both conduction types.
The stoichiometric BP after a preliminary heat treatment for 30 min at 1100°C of as-grown n-
or p-BP finally changed to n-BP after several hours of heat treatment at 1000°C.
The CVD growth of BP on a near (1120) oriented sapphire substrate (45) was conducted
Boron Phosphide 565
Figure 4 HREM feature of the BP-Si interface in our specimen. (Courtesy of Dr. Y. Fujita, Itami Labora-
tory, Sumitomo Electric Industries.)
Figure 5 Qualitative characteristics of BP due to heat treatment. (From Ref. 44.)

566 Kumashiro
by a two-step method: (a) predeposition of amorphous BP with 40 nm on the substrate at a

lower temperature of 550°C and (b) epitaxial growth on the substrate with buffer layers at a
higher temperature of 1000°C. The RHEED pattern for the [112] incident direction (Fig. 6) is
not the same for every 120° rotation in the same plane but has a periodicity of 60° rotation,
indicating the existence of a twin structure with sixfold symmetry. The RHEED patterns for
the [110] direction (Fig. 6) are composed of [110] and [110] patterns, showing the existence
of the twin. The twin would be at 180° rotation with respect to the perpendicular to the (111)
plane and in mirror relation with respect to the twinning plane. The film thus grown has n-type
conduction with a resistivity of 3.1 ⫻ 10 ⫺2 Ω cm, a carrier concentration of 4.8 ⫻ 10 18 /cm 3,
and a mobility of 37.7 cm 2 /V s, which is consistent with the plot of electron concentration in
the range of 5 ⫻ 10 19 to 1 ⫻ 10 22 /cm 3 versus Hall mobility (42).
A serious problem with the CVD process is the high carrier concentration and low electri-
cal resistivity arising from contamination with a substrate material. Gas-source molecular beam
deposition (GS-MBD) allows control of the flow rates of reactant gases at a lower growth tem-
perature, so that a high-purity boron phosphide film (46) can be obtained. A high-purity film
could be prepared on a sapphire crystal using cracked B 2 H 6 (2% in H 2 ) at 300°C and cracked
PH 3 (20% in H 2 ) at 900°C under a vacuum of 5 ⫻ 10 ⫺4 torr with an incident ratio of ν PH3 /
ν BZ2H6 of 12.7. The boron phosphide film grown at 600°C has the highest resistivity of 4.0 ⫻
10 4 Ω cm and lowest electron concentration of 6.0 ⫻ 10 10 /cm 3 ever obtained.
B. Fundamental Properties
The CVD BP wafers with an area of 10 ⫻ 20 mm and a thickness of 200–300 µm (47) for
long deposition times (24–28 h) were obtained by dissolving away the silicon substrate in an
HF-HNO 3 solution. From the back face of the BP, a characteristic diffraction pattern with extra
Figure 6 RHEED and indexed patterns for BP (111) plane with incident beam along the [112] and [110]
azimuth of BP. (From Ref. 45.)
Boron Phosphide 567
Table 3 Semiconducting Properties of BP Wafers

Si content by
Orientation Type (Ωcm) ρ(cm ⫺3 ) µ (cm 2 /V s) SIMS (atoms/cm 3 )
No. 1 (100) n 0.15 3.7 ⫻ 10 17 120 ⬃10 18
No. 2 (111) p 12.5 1.6 ⫻ 10 16 36.5 5 ⫻ 10 18
No. 3 (100) n 0.25 2.5 ⫻ 10 16 107 5 ⫻ 10 19
No. 4 (100) p 10.0 3.1 ⫻ 10 16 20.0 ⬃10 20
Source: From Refs. 3, 5, 8.
spots represents twinned lattices {111} (48). BP grows epitaxially on the (100) Si substrate,
but the (111) wafer inclines to the (100) plane with respect to the [110] direction, confirmed
by a back-reflection Laue photograph and the RHEED pattern. The majority of the impurities
consist of silicon, as determined by secondary ion mass spectroscopy (SIMS) analysis.
The electrical resistivity ρ, carrier concentration n, and mobility µ of CVD wafers mea-
sured by the van der Pauw method are shown in Table 3. The carrier concentration decreases
with increasing silicon content for the n-type specimens (samples 1 and 3) and increases for
the p-type materials (samples 2 and 4). The silicon atoms act as acceptors and are incorporated
at the phosphorus sites in BP. Results of measurements of the lattice constants by the Bond
method are shown in Table 4; they were obtained after calibration, using the thermal expansion
coefficient (49). The conduction types of the BP wafers were determined using excess boron
or phosphorus and were found to be either p- or n-type (50). The excess phosphorus atoms
occupy the boron sites in the BP lattice in the n-type material and vice versa for the p-type
material (44). The ionic radii of boron and phosphorus in BP are expected to be 0.88 and 1.10
Å, respectively. The lattice shrinks in the p-type materials (sample 4), whereas it expands in
the n-type materials (sample 3). The difference in the ionic radii of phosphor and silicon is not
so large and no appreciable effect of Si on the lattice constant could be detected.
The Vickers microhardness of the BP wafers varies from 3000 to 4000 kg/mm 2, depending
on orientation (47,51). The periodicity of the hardness curve of the (100) plane shows fourfold
symmetry (Fig. 7). Minimum and maximum hardnesses in the (100) plane correspond to the
〈110〉 and 〈001〉 directions, respectively. By analogy to the anisotropy of hardness in the (001)
plane of cubic boron nitride (52) compared with resolved shear stress curves, the primary slip
systems of BP are {111} 〈110〉. The elastic constants C 11, C 12 , and C 44 were determined by
Brillouin scattering (18) as given in Table 1.
The transmission spectra of polycrystalline and epitaxial BP layers are plotted as (αhν)1/2
versus hν to give a linear relationship (Fig. 8) (53), where α is the absorption coefficient. The
optical transition in crystalline BP is indirect and allowed. The optical band gap E g is derived
Table 4 The Precise Lattice Constant of BP Wafers

Half
Orientation Type Reflection bandwidth Lattice constant (Å)
No. 1 (100) n (400) 0.13° 4.538675 ⫾ 3 ⫻ 10 ⫺6
No. 2 (111) p (333) 0.14° 4.537983 ⫾ 3 ⫻ 10 ⫺6
No. 3 (100) n (400) 0.15° 4.538467 ⫾ 7 ⫻ 10 ⫺6
No. 4 (100) p (400) 0.14° 4.538205 ⫾ 6 ⫻ 10 ⫺5
Source: From Refs. 3, 5, 8.
568 Kumashiro
Figure 7 Vickers microhardness anisotropy of BP (100) wafers. (From Ref. 47.)
from the energy axis intercept of the extrapolated line. Absorption in polycrystalline and epitax-
ial BP extrapolates to an optical band gap E g of 1.8 and 2.0 eV, respectively.
The refractive index of BP was measured in the visible spectral range by the Brewster
angle method (Fig. 9) (15) and was in good agreement with the value of Takenaka et al. (54)
taken at 589.3 nm. The values of n are seen to be fairly large and increasing toward the band
edge. GaAs (E g ⫽ 1.47 eV) has n ⫽ 3.3–3.36 and ε ⫽ 12.5–12.9, and GaP (E g ⫽ 2.25 eV)
Figure 8 Determination of the band gap of polycrystalline and epitaxial layers of BP. (From Ref. 53.)
Boron Phosphide 569
Figure 9 Refractive index of BP (15). The data point at 589.3 nm is from Ref. 54.
has n ⫽ 2.9 and ε ⫽ 10–10.2. In the case of BP (E g ⫽ 2.0 eV), values of n ⫽ 3.1 and ε ⫽ 11
would well satisfy the relation of III–V compounds that the dielectric constant is slightly larger
than the square of the refractive index.
Raman spectra of natural and isotope-enriched boron phosphide single-crystal wafers indi-
cate one strong band at 828.6 cm ⫺1 and 846.2 cm ⫺1, respectively (Fig. 10) (55). The former is
in good agreement with 829 cm ⫺1 for BP powder (56) and a strong infrared absorption band at
12.1 µ 17. The frequency shift can be described by the change in mass of the isotopes:
ν(10 BP) ⫽ ν(11 BP) [m(11 BP)/m(10 BP)] 1/2 (1)
The Raman frequency in 10 BP is expected to be 833.9 cm ⫺1. The difference between this
value and the calibrated value of 847.4 cm ⫺1 is due to the volume decrease between 10 BP and
11
BP:
Figure 10 Raman spectra of isotopically enriched 10 BP and natural BP single crystal (From Ref. 55.)
570 Kumashiro
∆ν ⫽ ⫺13.5 cm ⫺1 (2)
The volume change ∆V/V required to produce this shift is obtainable from the measured
effect of pressure on the Raman line. The pressure dependences of the Raman shift indicate
that (57)
∆ν ⫽ ⫺2794(∆a/a) (3)
Equations (2) and (3) result in ∆a/a ⫽ ⫺1.7 ⫻ 10 ⫺3. The lattice constants of pure 11 BP and
10
BP result in ∆a/a ⫽ ⫺1.2 ⫻ 10 ⫺4, one order smaller than that from the Raman shift, which
would be due to such crystal imperfections (57) as lattice distortions and low-angle grains.
IV. HIGH-TEMPERATURE TRANSPORT PROPERTIES

A. Electrical Properties
The temperature dependence of the conductivity for n-type samples (Fig. 11) can be understood
as a competition between the decrease in mobility and the increase in carrier concentration (58).
The donor energies of 0.1 eV for sample 1 and 0.25 eV for sample 3 seem to correspond to
Figure 11 Temperature dependences of the conductivity σ, the carrier concentration n, and the Hall
mobility µ n of n-BP (100) (58). The result of conductivity for polycrystal is also shown (59).
Boron Phosphide 571
the doubly charged donors of phosphorus (P 2⫹ ) and to impurity donors such as magnesium,
manganese, and cobalt, respectively. Sample 3 contains more impurities than sample 1, corre-
sponding to the data showing that the mobility in sample 3 is lower than that in sample 1. The
result for a polycrystalline BP wafer (59) is shown for comparison as indicated by a smooth
line. The conductivity of the polycrystalline wafer shows steep rise at 900 K. The activation
energy at lower temperatures is 0.08 eV, corresponding to doubly charged phosphorus (P 2⫹ ).
A low carrier concentration of 9 ⫻ 10 15 cm ⫺3 at room temperature (59) would produce a steep
rise in the electrical conductivity at high temperature with an activation energy of 0.3 eV, which
would be due to the formation of impurity states and crystal defects and the contribution to
conduction by the excitation of carriers trapped by impurities and defect levels (60).
The mobility in the p-type wafers (Fig. 12) is lower than that in the n-type wafers. The
activation energy in sample 2 is calculated to be 1.8 eV for temperatures above 650°C, which
is nearly equivalent to a band gap of 2.0 eV and corresponds to the intrinsic conduction region
(37). This is a result of the fact that the carrier concentration in sample 2 is lower than that in
the n-type samples (Fig. 11). The activation energies associated with the acceptor levels are
0.20 and 0.32 eV for samples 2 and 4, respectively.
Above 600 K the value α in the relation µ ⬃ T α, determined from the slope of plots of
log µ versus log T, is ⫺1.5, so that lattice-phonon scattering prevails in the scattering process
in these temperature ranges.
High-temperature electrical properties for the (111) planes before and after irradiation
with a thermal neutron dose of 1.449 ⫻ 10 4 n/cm 2 s are shown in Fig. 13 (61). No appreciable
Figure 12 Temperature dependences of the conductivity σ, the carrier concentration ρ, and the Hall
mobility µ p of p-BP. (From Ref. 58.)
572 Kumashiro
Figure 13 Electrical properties of n- and p-10 BP (111) wafers before and after irradiation by thermal
neutrons. The temperature dependence of carrier densities with calculated values is denoted by dashed
curves. (From Ref. 61.)
change in electrical properties in the (100) plane is observed during irradiation because of no
blocking effect and high crystal perfection. A noticeable change in carrier concentration is a
typical characteristic of radiation damage in semiconductors. Alpha particles produced by nu-
clear reaction occur to a depth of about 15 µm in the boron phosphide wafer. The carrier concen-
tration for the n type increases and that for the p type decreases on thermal neutron irradiation
because of the formation of donors. The temperature dependence of the carrier concentration
of wafers with calculated values is denoted by the dashed curves in Fig. 13. The ionization
energies and density of donors or acceptors are estimated by fitting the calculated carrier densi-
ties to the experimental results. To estimate the ionization energies (E d and E a ) and density of
donors (N D ) or acceptors (N A ), the general formulas were used (3). The calculation indicates
that the ionization energies of donors and acceptors are independent of the irradiation, but the
increase in donor concentration is clarified quantitatively after irradiation by thermal neu-
trons (3).
The temperature dependence of the thermoelectric power is shown in Fig. 14. In general,
the thermoelectric power is described by the following expression:
S(T) ⫽ ⫺
冢
k (r ⫹ 2)F r⫹1 (η)
e (r ⫹ 1)F r (η)
⫺η
冣 (4)
where F r (η) is the Fermi integral, r is the scattering parameter, and η is the reduced Fermi
level. The S(T ) for an n-BP single crystal (solid and dotted lines in Fig. 14) was calculated
Boron Phosphide 573
Figure 14 Temperature dependences of the thermoelectric power S of BP single-crystal wafers (58).

Temperature dependences of experimental (smooth line) and calculated (dashed line) curves (62) and poly-
crystal (59) are also shown.
with a scattering factor r ⫽ 3/2 (phonon scattering), a donor concentration N d ⫽ 5 ⫻ 10 18 cm ⫺3,

and the energy level E d ⫽ 0.02 eV (62). The thermoelectric powers of the BP wafers are similarly
high with the exception of sample 3 (58). Sample 3 is compensated by silicon acceptors, which
raise the thermoelectric power. The thermoelectric power of the other n-type sample (sample
1) tends to saturate up to 650°C and then increase with increasing temperature owing to the
formation of acceptors. The higher the donor concentration, the higher the transition temperature.
The behavior of polycrystalline wafers (59) is similar to that of single crystalline wafers.
B. Thermal Properties
The specific heat capacity of BP single crystals (63,64) increases with increasing temperature
(Fig. 15). The Debye temperature and its temperature dependence reflect features of boron phos-
phide (65). A high Debye temperature indicates low atomic mass and strong interatomic bonding
in boron phosphide. The Grüneisen parameter γ is calculated as a function of the reduced temper-
ature T/θ (65). High γ means high anharmonicity, and a small variation would be attributed to
low ionicity (64,65).
The thermal diffusivity of a wafer is measured using a ring flash light, which originates
from multivariable analysis in a two-dimensional model (66). The temperature dependences
of thermal diffusivity together with the results of the photo-AC method show fairly good agree-
ment between the two methods (63), which justifies the ring flash light method. The thermal
diffusivity of a single crystal has a large value of 1.8 cm 2 s⫺1 at room temperature and shows
a pronounced decrease with increasing temperature, due to phonon scattering, and the thermal
diffusivity at room temperature of 0.06 cm 2 /s decreases to 0.04 cm 2 /s at 800 K for a polycrystal-
line wafer (59).
574 Kumashiro
Figure 15 Temperature dependences of specific heat capacity and Debye temperature of BP (63,64).
The temperature dependence of thermal conductivity, as calculated from the product of

the thermal diffusivity, specific heat capacity, and density, is shown in Fig. 16. The thermal
conductivity of boron phosphide single-crystalline wafers is ⬃ 4.0 W/cm K at room temperature,
which is in good agreement with Slack’s data (67) and is comparable to the value for boron
nitride. Boron phosphide single crystal is thus a promising material for heat sink substrates for
semiconductor devices. The electric contribution to thermal conductivity in a single crystal is
small and the thermal conductivity in Fig. 16 should correspond to the lattice thermal conductiv-
ity, being in very good agreement with the calculation by the three-phonon process (68), where
M is the mean atomic mass and δ is the cubic root of the atomic volume. In contrast, the
thermal conductivity of polycrystalline BP shows a weak temperature dependence over the entire
temperature range, so that thermal conduction is performed by phonon scattering at grain bound-
aries with a weak temperature dependence of the mean free path of phonons (59).
In the case of heteroepitaxial growth of BP on Si substrates, a difference in thermal expan-
sions between two materials is very important in addition to a lattice mismatch. The thermal
expansion coefficient α is given by
1 ∂a ∂(lna)
α⫽ ⫽ (5)
a ∂T ∂T
where a is the lattice constant. The values of α at each temperature are calculated from the
gradients of the curves between ln a and T. Thermal expansion of BP epitaxially grown on Si
{100} substrates has been investigated by using a high-temperature X-ray diffractometer (49)
(Fig. 17). The coefficient α varies from (4.0 ⫾ 0.3) ⫻ 10 ⫺6 to (6.2 ⫾ 0.3) ⫻ 10 ⫺6 K⫺1 in the
temperature range 400–800 K. The α value of BP is about 1.3 times as large as that of Si
through the whole range investigated, which explains well the phenomena of bending or cracking
of grown BP films with Si substrates on cooling after the reaction.
Boron Phosphide 575
Figure 16 Temperature dependences of thermal conductivity of BP wafers (64). The solid line represents
values calculated from the equation; the dashed line shows a T⫺1 dependence. The result for the polycrystal
is also shown (59).
Figure 17 Temperature dependences of the thermal expansion coefficient α of BP; α for Si is also
shown for comparison. (From Ref. 49.)
576 Kumashiro
V. APPLICATION AS ELECTRONIC MATERIALS

A. Electronics Devices
Diffusion layers formed in Si substrates during the epitaxial growth of BP realize various junc-
tions related to devices (Table 5) (7). Of these combinations, a wide gap window solar cell and
a wide gap emitter transistor have been fabricated. The current-voltage characteristic of the
nBP-pSi heterostructures obtained in growth region A suggests the existence of interface states
in the BP-Si heterojunction. The forward current has a region proportional to exp(eV/nkT) with
n ⫽ 6 ⫾ 2. The backward current is large and does not saturate. Spectral photocurrents excited
with monochromatic light at temperature (Fig. 18) indicate that the spectrum broadens toward
the short wavelength region compared with the spectrum of an Si cell, which is attributed to
BP having a wider forbidden energy gap than Si. Many recombination states in the BP-Si inter-
face due to the differences in lattice constants and thermal expansion coefficients would reduce
the conversion efficiency of the cell. The short-circuit current with an nBP layer is apparently
larger than that without an nBP layer, because of a difference in reflectivity of BP and Si. The
conversion efficiencies of solar cell with an nBP layer and without an nBP layer are η ⫽ 8.3%
and η ⫽ 6.5%, respectively.
Two types of wide gap emitter transistors—an nBP-pSi-nSi structure and an nBP ⋅ nSi-
pSi-nSi structure having a cascade junction nBP ⋅ nSi-pSi emitter—were fabricated. The com-
mon emitter current gain β in the latter transistor is about 16 and the injection efficiency of the
Table 5 Eight Junctions Realized by Combining Conducting Type of BP, Diffusion Layer, and Si
Substrate
Region BP crystal Diffusion layer Si substrate Energy band structure Device
A n p n Transistor
p Diode
B n n n Ohmic
p Diode
C p p n Diode
p Ohmic
D p n n Diode
p Transistor

Boron Phosphide 577
Figure 18 Spectral photocurrent of wide gap window solar cells with nBP-pSi and nBP ⋅ nSi-pSi struc-
ture. That of an nSi-pSi cell after removing the nBP layer from an nBP ⋅ nSi-pSi cell is shown for compari-
son. (From Ref. 7.)
emitter heterojunction is about 0.94 if the other gain factors are assumed to be unity. The forward
current of the emitter junction has two regions proportional to exp(eV/nkT) with n ⫽ 2.6 and
1.6. The backward current of the junction does not saturate and similarly to that of an Si p-n
junction was about 250 V.
By using the method in Fig. 5, an Si-BP-Si double heterojunction was obtained through
the alternate growth of BP and Si on an Si substrate. After BP was grown epitaxially and then
covered with Si 3 N 4 , it was heat treated at the stoichiometric temperature of 1050°C. Some
typical current-voltage characteristics of the n ⫹Si(epi)-BP-n ⫹Si (sub) structure are shown in Fig.
19. The heat treatment time to obtain highly resistive BP at the stoichiometric temperature of
1050°C was 1 h for sample A, 3 h for B, and 5 h for C. The same barrier height is formed at
both the n ⫹Si(epi)-BP and the BP-n ⫹Si(sub) heterojunctions. When a voltage of less than 0.1
V is applied, an ohmic current is observed. If the donor concentration in the BP is less than
10 18 cm ⫺3, BP as thin as 50 nm is depleted.
The characteristic values of the Si-BP-Si heterojunctions are summarized in Table 6. The
observed resistivity was determined in the ohmic region of current-voltage characteristics. The
barrier height V 0 obtained by extrapolating to V 1/2 ⫽ 0 was given by reducing by half the forbid-
den energy gap of BP to keep the electronic neutrality condition between ionized impurities in
the depleted BP and the accumulated carriers at the Si surface. The donor or acceptor concentra-
tion N BP was controlled by the length of the heat treatment time at the stoichiometric temperature
of 1050°C. The value of thermal emission over the barrier height was calculated from n or p
exp(⫺ qV 0 /kT ), where n ⫽ p ⫽ 5 ⫻ 10 19 cm ⫺3.
578 Kumashiro
Figure 19 Current as a function of the square root of applied voltage V 1/2 in the n ⫹ Si(epi)-BP-n ⫹ Si(sub)
structure. The heat treatment time is 1 h for A, 3 h for B, and 5 h for C. The transition voltage V T of 1.4
V is marked. (From Ref. 8.)
BP p-n junctions are especially desired for their potential application in electronic devices
to be used in an ambient high temperature. A step (one side) BP p-n junction was formed by
B⫹ implantation and subsequent annealing (Fig. 20). In the forward current of a semilog plot
of the forward direction, the factor n, the exponential ideality factor of the junction, decreases
gradually from n ⫽ 1.8 at V ⫽ 0.2 V to n ⫽ 1.4 at V ⫽ 0.5 V as the applied bias increases.
The backward current increases in proportion to the square root of the applied bias. The step
(one-side) p ⫹-n junction is formed by B⫹ ion implantation. A breakdown voltage of 160 to 170
Table 6 Characteristics of Si-BP-Si Heterojunctions

Value of Electron Donor or
Heat Observed Barrier thermal or hole acceptor
treatment resistivity height emission mobility µ density N BP
Sample time (h) ⫻ 10 6 (Ω cm) V 0 (V) ⫻ 10 10 (cm ⫺3 ) (cm 2 /V s) ⫻ 10 17 (cm ⫺3 )
A 1 0.12 0.45 60 — 2.4
B 3 3.5 0.52 3 70 2.1
C 5 48 0.59 0.2 70 1.8
D 6 13 0.55 0.7 70 20
Boron Phosphide 579
Figure 20 Typical current-voltage characteristics of a BP p-n junction. (From Ref. 9.)
V was observed. The depletion width spreading in n-BP (N D ⫽ 5 ⫻ 10 17 cm ⫺3 ) at the breakdown

is 0.6 µm and the electric field strength is 3 ⫻ 10 6 V/cm. A large current density extrapolated
to the zero bias of J 0 ⫽ 2.0 ⫻ 10 ⫺7 A/cm 2 is due to a short minority-carrier lifetime for the
electrons injected into the p-BP layer formed by B⫹ implantation. The p-BP works just as a
metal electrode. By taking into account the recombination in the depletion layer spreading in
the n-BP, the thermionic emission current of a metal-semiconductor contact is calculated. The
barrier height V 0 of 0.80 ⫾ 0.02 V is in good agreement with a built-in voltage from the junction
capacitance measurement as a function of an applied bias (54).
As for BP Schottky diodes, there has been only one study of the n-BP-Sb type (54) to
determine a dielectric constant of BP. Heat treatment of the wafer is an important process in
evaporating the Schottky metal (69). The n-BP-Sb diode with heat treatment exhibits excellent
I-V characteristics, which might be a result of the Sb-BP interface cleaning caused by Sb diffu-
sion into the BP wafer during heat treatment. Extrapolating the curve of 1/C 2 versus V from
the near-zero voltage region deduces the diffusion potential V 1 of 1.3 V (69). GaAs and InP,
580 Kumashiro
being isomorphic with BP, form Schottky barriers with gold (Au) for both n- and p-type materi-
als (70,71), so that Au works on n-type BP. In the forward direction, the turn-on voltage is
about 0.6 V, and in the reverse direction soft breakdown occurs at about ⫺5 V (Fig. 21) (72).
The capacitance plot is almost linear with V i of 1.2 V, and the depth profile of the carrier
concentration calculated from the plot is uniform within the depleted depth.
The barrier height (φ B ) is estimated from the following equation (71):
φ B ⫽ V i ⫹ V R ⫹ kT/q ⫺ ∆φ (6)
where V R is the depth of the Fermi level below the conduction band, kT the thermal energy,
and ∆φ the image force lowering of the barrier height at the interface. Measurements of the
temperature dependence of the carrier concentration (Fig. 11) indicate that the V R values of n-
BP-Sb and n-BP-Au are 0.09 and 0.23 eV, respectively. The value of kT is 25 meV at room
temperature and that of ∆φ ⬍ 10 meV (71). Therefore, the barrier height evaluated from the
capacitance measurement is 1.40 eV for n-BP-Sb diodes and 1.45 eV for n-BP-Au diodes, coin-
ciding with the (2/3)E g (E g ⫽ 2.1 eV) rule. The electron transport though the interface is gov-
erned not by the metal work function but by the intrinsic nature of BP, so that the Fermi level
is pinned by intrinsic defects introduced in the vicinity of the surface of a semiconductor during
metal deposition. It is convenient for device processes to use Au for both n- and p-type BP.
The BP-on-silicon devices (73) were tested as radiation detectors by irradiating them with
5.5-MeV alpha particles from an Am isotopic source and interrogating the current pulses arising
in the detector with conventional nuclear pulse height analysis. Figure 22 shows pulse height
spectra obtained by irradiating a BP-Si device both with and without the alpha particle source
present. Detection of the alpha particles is clearly indicated, but subsequent testing with a thermal
neutron reactor did not occur because of the high carrier concentration in the BP films.
For thermoelectric devices, thermal conductivity should be low to reduce loss of thermal
energy by thermal conduction between the hot and cold sides. The efficiency of energy conver-
sion of a thermoelectric device becomes high at a larger figure of merit and at high temperature.
A single crystalline wafer has comparatively high thermoelectric power, as shown in Fig. 14,
but the thermal conductivity is also high (Fig. 16), which reduces the thermoelectric figure of
Figure 21 I-V characteristics and 1/C 2 versus applied bias voltage for nBP-Au Schottky barrier diode.
(From Ref. 72.)
Boron Phosphide 581
241
Figure 22 Pulse height spectra obtained with a BP-on-Si device with and without an Am 5.5-MeV
alpha particle source present. (From Ref. 73.)
merit Z (⫽ S 2σ/κ); then the BP single crystalline wafer is not applicable for thermoelectric
devices. In contrast, the thermal conductivity of a BP sintered polycrystal is smaller than that
of a single crystalline wafer by two orders of magnitude (29), which would result in increasing
the figure of merit. The thermoelectric power of the BP sintered specimen, however, depends
on the purity of the starting powder. Commercially available BP powder contains many impuri-
ties that compensate each other, reducing the thermoelectric power to ⬃ 20 µV/K over the
entire temperature range (29). The Z value for a CVD boron phosphide polycrystalline wafer
calculated from Figs. 11, 14, and 16 increases with increasing temperature, reaching 10 ⫺7 /K at
800 K (59). However it would be ⬃10 ⫺6 /K if the thermal conductivity could be reduced as low
as that of a sintered specimen by introducing porosity and a disordered state.
B. Photoelectrochemical (PEC) Cells

BP is an intrinsically stable material, so it is a promising material for photocathodes. One of
the major requirements in practical application to photoassisted electrolysis of water using semi-
conductor electrodes (74) is that the semiconductor should be stable in any electrolyte environ-
ment. The attainment of quite stable photocurrents resulting in hydrogen production from a p-
BP electrode in acidic solution has been reported (75). The effect of ruthenium concentration
on the photocurrent-potential curves for BP treated with ruthenium (III) chloride in 0.5 M H 2 SO 4
indicates that the surface treatment should be carried out with a suitable ruthenium concentration
and treatment time. The wavelength dependence of the photocurrent for p-BP shows a threshold
of the photocurrent response of 600 nm (2.0 eV), in agreement with the direct band gap calcula-
tion, responding to sunlight of wavelength shorter than 600 nm. The photocurrent-irradiation
time profile for a p-BP photocathode shows no evidence of deterioration. Figure 23 shows the
power characteristic in a photoelectrochemical cell (PEC), Pt(H 2 )/0.5 M H 2 SO 4 (1 M ⫽ 1 mol
dm ⫺3 )/ /0.5 M H 2 SO 4 /p-BP. Curve 2 indicates that the open-circuit photovoltage is 0.45 V, the
582 Kumashiro
Figure 23 Photocurrent-photovoltage characteristic of the cell Pt (H 2 )/0.5 M H 2 SO 4 / /0.5 M H 2 SO 4 /

p-BP irradiation with 500 xenon lamp. (From Ref. 75.)
short-circuit photocurrent density is 2.4 mA/cm 2, and the fill factor is 0.25. The overall conver-
sion efficiency of optical to electrical energy for the PEC photovoltaic cell is still low with
respect to the case of InP. Therefore, improvement of the conversion efficiency is necessary
for a more practical device.
An attempt to use a large band gap semiconductor of BP on a smaller band gap semicon-
ductor of Si was proposed on the basis of significant stability and conversion efficiency as a
photoelectrochemical device (76), serving as a protective optical window by Takenaka et al.
(7). The utilization of degenerate single crystalline n-type BP as window material on n-type Si
and n-type GaAs electrodes has been proposed (76). The n-Si/n-BP system was stable in a ferri-
ferrocyanide redox couple and more than 10 4 Q charge could be passed through PEC cells with-
out a significant loss of efficiency of the cell. Their device basically resembled a metal-coated
semiconductor electrode. Hence, the band bending in the substrate material is in principle deter-
mined entirely by the work function of the coating material, and the electrolyte serves only as
an electrical contact between the counterelectrode and the ‘‘metal’’-coated photoelectrode. In
the band diagram that was derived from their semiempirical electronegativity model, the conduc-
tion bands of Si and BP are at about the same energy level, and a small band bending in the
Si substrate must be expected for n-Si/n-BP structures. Then the flat-band potential could not be
determined experimentally. Also, the Schottky barrier heterojunction could not be characterized
electrochemically.
Structural, optical, and electronic properties of n-Si/n-BP and p-Si/n-BP heterojunctions
have been investigated by Goossens et al. (77,78). Impedance spectroscopy has been used to
obtain Mott-Schottky (MS) plots of (C SC )⫺2 versus DC bias, V (Fig. 24). The slope of the MS
plot was positive and concordant with an effective donor density N D ⫺ N A of about 5 ⫻ 10 19
cm ⫺3 for all studied samples. For crystalline CVD layers of BP (100), the flat-band potential was
⫺0.55 V versus SCE at pH 4.6 and was observed to show a Nernstian ⫺60 mV/pH dependence.
The energy of the conduction band and that of the valence band of crystalline BP were
determined on the absolute energy scale with an experimental accuracy of 0.05 eV; that is,
versus vacuum:
E c (BP) ⫽ (⫹0.32 ⫹ 0.06 ⋅ pH) eV versus SCE
E v (BP) ⫽ (⫺1.68 ⫹ 0.06 ⋅ pH) eV versus SCE
Boron Phosphide 583
Figure 24 Mott-Schottky plot of C ⫺2 versus electrode potential for a shunted substrate electrode recorded
in the dark with KOH (1 M) as an electrolyte (78); when measured through the complete heterojunction,
identical MS-plots were obtained. The surface area of the electrodes was 7 mm 2.
The point of zero charge (PZC) (BP) lies at pH 6.4 and SCE ⬃ 4.75 eV below vacuum level.
The conduction band of Si matches excellently the conduction band of BP, allowing con-
duction band electrons to pass easily through the Si-BP junction. However, the valence bands
of Si and BP differ considerably. Valence band holes in Si face a 0.9-eV potential barrier at
the Si-BP junction and recombine with electrons instead of crossing. The band structures of the
n-Si/n-BP and p-Si/n-BP heterojunction configurations are presented in Fig. 25. When the elec-
trode potential is changed by means of an externally applied potential or by addition of a redox
couple to the electrolyte, an additional electric field is created in the space charge region of BP
at the BP/electrolyte interface. The electric field at the Si-BP junction, however, is not influenced
by external applied potential differences.
The band structure of the heterojunction agrees with optical features. The n-Si/n-BP elec-
trodes reveal an anodic photocurrent that was generated by photons with hν ⬎ 2.0 eV and was
generated only in the window material n-BP. Holes created in the Si are unable to reach the
BP-electrolyte interface, so that annihilation of the photoholes by conduction band electrons of
Si must occur at the n-Si/n-BP interface. Configurations comprising p-Si/n-BP electrodes pro-
duce large cathodic photocurrents when irradiated with low-energy photons, i.e., hν ⬎ 1.1 eV.
The photogenerated electrons in Si do cross the Si/BP interface and reach the electrolyte to
drive a reduction reaction there. The band structure of the Si/BP heterojunction prevents Si
holes crossing the Si/BP junction but does make it possible for conduction band electrons of
584 Kumashiro
Figure 25 Band structure of n-Si/n-BP and p-Si/n-BP heterojunction photoelectrodes (78). The redox
potentials of H⫹ /H 2 and OH-/O 2 are 4.5 and 5.73 eV respectively, below vacuum level.
Si to cross the window and reach the electrolyte. The p-Si/n-BP heterojunction photoelectrodes
produce large and stable photocurrents up to 15 mA/cm 2 when applied in liquid junction solar
cells. A maximum short-circuit photocurrent, i sc , of 15 mA/cm 2 could be reached with 80 mW/
cm 2 irradiation power. The open-circuit potential, V oc , was about 0.5 V and the fill factor, η,
about 0.5. The maximal gained power at 80 mW/cm 2 irradiation power equals (V ⫻ i)max ⫽ η
(V oc ⫹ i sc ) ⫽ 3.75 mW/cm 2, which yields a conversion efficiency of tungsten-halogen light of
4 to 5%. The characteristics of photoelectrochemical cells have been greatly improved in com-
parison with those of fluxed BP crystals (75).
In neutral and alkaline electrolytes the surface of BP is free of native oxide and the surface
state density is low, but native oxide is present on the surface of BP in acid electrolytes. The
presence of an oxide film in acid electrolytes explains the large potential shift in the observed
Mott-Schottky plots. Graphs of capacitance as a function of the cell potential (V versus SCE)
showed a peaked structure in acid electrolytes that are denoted as ‘‘modified,’’ since a native
oxide is present on the surface of BP and surface trapping or recombination is present on these
electrodes to a large extent (1). Reliable values for the flat-band potential could not be obtained
from these plots. Two additive contributions of the space charge capacitance and a superimposed
second capacitive component due to charge trapping in surface states would be suggested.
Photoholes at the BP/electrolyte interface give rise to surface recombination in optically created
surface states, which are assumed to be a consequence of photoanodic dissolution of n-type BP.
Oxygen formation is observed at irradiated n-type BP electrodes, and a competition between
the oxidation of the solid and of OH⫺ species occurs, reflecting the lower valence band position
of BP and the concomitant larger stability of BP against photoanodic oxidation.
VI. CONCLUSION
Semiconducting properties of BP have been clarified to some extent. Theoretical band calcula-
tions yield very useful information so that optical properties of BP should be clarified by compar-
ing calculation with experimental data. Theoretical band calculations also indicate that the funda-
mental gap in BP decreases with increasing pressure (12,79) as in most III-V compound
semiconductors, which should be confirmed by high-pressure experiment.
Boron Phosphide 585
Thermal conductivity is of technological importance. High thermal conductivity values

in single crystals are useful for power-dissipating devices such as diodes, transistors, or lasers
to assist in device and circuit design. A low thermal conductivity value is necessary to prompt
thermoelectric figure of merit at high temperatures so that the establishment of preparation of
sintered polycrystal controlling grain size should be performed by high-temperature and high-
pressure technologies.
The mobility µ and mean trapping lifetime τ of the charge carrier are critical to the opera-
tion of a BP neutron detector. The product µτ should exceed ⬃10 ⫺6 cm 2 /V in order to obtain
pulses of detectable magnitude for BP detectors (73). For this purpose the growth of high-quality
semi-insulating BP with stoichiometric film would be necessary in addition to the GS-MBE
process. New film growth techniques such as ion, plasma, and photo CVD methods would be
promising for low-temperature growth. Ion beam–induced epitaxial crystallization (IBIEC) has
been observed to occur at temperatures much below the thermally induced crystallization tem-
perature and to have a much smaller activation energy than in the pure thermal solid-phase
epitaxy (SPE) process. Epitaxial regrowth in BP was induced in the temperatures range 300–
400°C (80). A plasma CVD process would suppress the escape of phosphorus in BP by radicals
formed in the plasma atmosphere.
The photoexcited CVD process, being free of ion bombardment damage, allows selective
excitation of reactant gas in a surface process only. Then the film growth process would treat
as heterogeneous gas-phase reactions on the solid surface, which consist of series processes,
i.e., surface chemical reaction of adsorption species and transportation of gas phase. We would
control each process independently to grow stoichiometric BP films.
Investigation of the mechanism of reaction of metal with BP by Rutherford backscattering
(RBS) measurements (81) would be useful for the technological aspects of device applications
of BP.
Nanostructured BP film would be interesting as a new material, and high-surface-area
electrodes of the chemically stable BP would be applicable as gas sensors, in photocatalysis,
and for energy conversion (39).
ACKNOWLEDGMENTS
A number of figures and tables have been taken from the literature. The author would like to
thank the authors and publishers of these materials for permission to reproduce them here, expe-
cially the American Physical Society (Fig. 1 (Ref. 18)), the American Institute of Physics (Fig.
19 and Table 6 (Ref. 8)), the Electrochemical Society, Inc. (Fig. 5 (Ref. 44), Fig. 21 (Ref. 72)
and Table 5 and Fig. 18 (Ref. 7)), Elsevier Science Ltd. (Fig. 2 (Ref. 30), Fig. 3 (Ref. 35), Fig.
7 (Ref. 47), Fig. 9 (Ref. 15), Fig. 10 (Ref. 55), Fig. 11 and Fig. 12 (Ref. 58) and Fig. 13 (Ref.
61)), and Wiley-VCH (Fig. 24 (Ref. 78) and Fig. 25 (Ref. 78)).
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23
Boron and Boron-Rich Compounds
Helmut Werheit
Solid State Physics Laboratory, Gerhard Mercator University, Duisburg, Germany
ABSTRACT
Outstanding properties of the boron-rich solids in general include their high melting tempera-
tures, their extraordinary hardnesses, their small extension coefficients, and their high chemical
resistivity, which predestine them for technical application under conditions that are hardly
accessible for most other materials. The aim of this chapter is to describe the relationship of
structures, the interrelation of structural and electronic properties, and the possibilities for their
modification to tailor boron-rich solids for specific, in particular electronic, applications.
The complex structures of the different modifications of elementary boron and of the
boron-rich borides are essentially composed of nearly regular B 12 icosahedra and related struc-
tural elements, which consist of fragments or condensed systems of icosahedra. These structural
elements are bonded directly to one another or via single boron or foreign atoms, thus forming
a large variety of open frameworks. The icosahedra as common structural features are the reason
for more or less close relationships of the properties and distinguish the boron-rich solids qualita-
tively from crystals with periodic arrangements of single atoms. Nevertheless, translational sym-
metry is maintained in these complex crystal structures, and therefore the boron-rich solids
must be distinguished from amorphous solids, although early measurements suggested certain
similarities of properties.
The boron-rich solids are semiconductors with unique electronic properties that are essen-
tially determined by the icosahedra. This implies an interrelation of these properties as well,
which can be modified within sometimes large homogeneity ranges of chemical compositions,
by forming ternary compounds, by changing the chemical composition within the specific struc-
ture groups, and by going to the different structure groups.
Accordingly, the icosahedral boron-rich solids offer an excellent chance to study the elec-
tronic properties of complex structures and their modification by slight and considerable changes
of composition and structure. Some properties of particular interest for fundamental research
are the Jahn-Teller effect in the icosahedra; the formation of intrinsic traps by electron-phonon
interaction; the soliton-type transport of electrons and holes; the very long lifetime of electrons
under specific, externally controllable conditions; the electronic interaction between foreign
atoms and the boron framework; and the high, monotonously (up to very high temperatures)
increasing Seebeck coefficient of boron carbide.
The specific electronic structures make the boron-rich solids rather insensitive to influ-
ences of foreign atoms at concentrations that change the semiconductor properties of classical
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semiconductors decisively. Nevertheless, doping is possible in principle, indeed at higher con-

centration levels. This makes the material preparation much easier and less expensive than in
the case of the classical semiconductors, demanding extremely high purity.
The only electronic property that is at the threshold of technical application at present is
the high Seebeck coefficient for high-efficiency direct thermoelectric energy conversion and
measurement of very high temperatures under extreme conditions. Moreover, general application
for high-temperature electronic devices and at least in some structure groups for wide-gap semi-
conductors seems promising.
I. INTRODUCTION
The different modifications of elementary boron and the boron-rich borides exhibit complex
structures that are essentially composed of nearly regular B 12 icosahedra and related structural
elements consisting of fragments or condensed systems of icosahedra. These structural elements
are bonded directly to one another or via single boron or foreign atoms, thus forming comparably
open frameworks with a large variety of structures. The common structural features are the
reason for more or less close relationships of the properties (1–6) and distinguish the boron-
rich solids qualitatively from solids with simple periodic arrangements of atoms. Nevertheless,
translational symmetry is maintained in these complex crystal structures and therefore the boron-
rich solids must be distinguished from amorphous solids as well, although early measurements
suggested certain similarities of properties.
The simplest structure of this series of complex crystals is the α-rhombohedral modifica-
tion of elementary boron with 12 boron atoms arranged in one B 12 icosahedron per rhombohedral
unit cell. The most complex structure known up to now has been found in YB 66-type borides
with 1584 boron and 24 metal atoms; the boron atoms are arranged in eight (B 12 ) 13 supericosahe-
dra and eight noncosahedral B 42 units per cubic unit cell. In between there are several further
structural groups with different degrees of complexity. All of these structure groups allow the
insertion of foreign atoms by substitution or by interstitial accommodation, in many cases in
more or less extended homogeneity ranges.
Scientifically, these extraordinarily extended possibilities for modifying related structures
of solids offer excellent prerequisites for a systematic research on complex crystal structures
and on the interrelation between the degree of complexity and the physical properties. With
respect to technical applications, this variety promises the possibility of developing compounds
with optimized properties for specific applications, while the generally favorable basic properties
of the boron-rich solids (e.g., very high melting points, great hardness, low density, small thermal
extension coefficient, high resistance to chemical attack), allowing their use under conditions
inaccessible for most other solids, remain largely unchanged.
Besides of the common mechanical, thermal, and chemical properties of the boron-rich
solids, the following largely common structural and electronic properties of icosahedral boron
structures attract attention:
1. Common structural properties:

(a) In spite of the I h symmetry of the icosahedra forming the structural framework,
the space group R 3 m is obviously preferred in the crystal structures. This holds
not only for all representatives of the α-rhombohedral boron and the
β-rhombohedral boron structure group but also for most of the ion crystals based
on [B 12H 12]2⫺ ions as well, where the icosahedral arrangement of the 12 B atoms
Boron and Boron-Rich Compounds 591
is assumed to be only insignificantly affected by the covalently bonded H

atoms (7).
(b) In all reliable structure investigations of the covalent and ionic crystals mentioned
in 1. (a) and many other structures based on B 12 icosahedra, it was found that the
icosahedra are slightly distorted. This distortion was ascribed to steric interactions
with cations (7) and influences of the crystal field, respectively; however, initially
little attention was paid to the fact that this distortion is very similar in all these
cases (8).
(c) Except for the ionic crystals, the phonon bands in the infrared (IR) spectrum are
weak, indicating a low degree of ionicity of the bonds, and the Raman effect is
weak, indicating small polarizability of the structures.
2. Common electronic properties:
(a) The semiconducting icosahedral boron-rich solids are not in accordance with the
rule, which holds for simple periodic crystal structures in general, that atoms with
odd electron numbers form metals in the condensed state.
(b) The band gaps of the boron-rich solids do not depend essentially on the crystal
structure.
(c) In many cases of icosahedral boron-rich solids, a split-off valence band 0.19 eV
above the valence band edge has been found.
(d) Icosahedral boron-rich solids are p-type semiconductors. Overcompensation to n-
type demands donor densities of the order of 10 20 cm⫺3 (9–11).
(e) The mechanism of electronic transport is essentially determined by hopping with
an activation energy of about 0.2 eV.
Even if these general statements on common properties of the boron-rich solids are largely
reliable, at present the research on these very promising materials is far from complete. In
particular, systematic investigations of interrelations between structural and physical properties
have remained in their infancy and are largely restricted to a few materials. Therefore the aim
of this chapter is to review the results on electronic structure and electronic transport properties,
to demonstrate as far as possible with examples such interrelations between structural and elec-
tronic modifications, and to point out the possible extensions of such results to other boron-rich
materials. For a complete review of data the reader is referred to Refs. 2 and 3 with updates
completed in 1998.
The approach of the present chapter—considering the boron-rich solids as a unique group
of semiconductors with specific properties that are essentially determined by the icosahedra and
are different from those of crystalline and amorphous semiconductors—is in contradiction of
the ‘‘amorphous’’ concept of Golikova (1,12). She attributes to the different structures of boron-
rich solids a degree of amorphization that depends on the number of atoms per unit cell. Accord-
ingly, α-rhombohedral boron with 12 atoms per unit cell is assumed to behave nearly like a
crystalline semiconductor, whereas YB 66 with more than 1600 atoms per unit cell is assumed
to be nearly amorphous. Of the numerous contradictions of experimental results by this model,
only one is mentioned: The properties of the rather well-investigated boron carbide, with 15
atoms per unit cell, close to α-rhombohedral boron, are far from those of classical crystalline
semiconductors.
Another concept for describing the electronic properties of the boron-rich solids was devel-
oped by Emin et al. (13–16) on boron carbide. It is based on the assumption of hole bipolarons
in B 11C icosahedra, and the essential basis of this theory is the experimental fact of a very low
electron spin resonance (ESR) spin density. These authors were able to describe some uncom-
mon electronic properties of boron carbide with their model.
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However, on the one hand, low ESR signals alone are a weak argument for the assumption
of hole bipolarons. On the other hand, several experimental results are in contradiction of this
model. For example, (a) the electrical conductivity of boron carbide is maximum at the minimum
concentration of B 11C icosahedra in the homogeneity range; (b) polaron-type effects are re-
stricted to one electron per icosahedron and no corresponding electron-phonon interaction with
holes, in particular not with hole pairs in icosahedra, has been proved experimentally (c) the
distortion of the icosahedra in boron carbide depends to only a small degree on electron-phonon
interaction; and (d) the electronic transport in boron-rich solids is due to classical band-type
conduction and hopping processes side by side. Hence, the hole bipolaron theory for boron-rich
solids can hardly be maintained.
II. STRUCTURE GROUPS OF BORON-RICH SOLIDS

A. Icosahedral Structures
1. α-Rhombohedral Boron Structure Group
The vertices of the rhombohedral unit cell are occupied by one B 12 icosahedron each. One of
its trigonal axes is orientated parallel to the crystallographic c axis, coinciding with the main
diagonal of the unit cell. The six boron atoms forming the top and bottom triangles of this
oriented icosahedron are called polar; the six remaining ones arranged slightly above and below
the equatorial plane of the icosahedron are called equatorial. The unit cell of the α-rhombohedral
boron modification of elementary boron, which can be prepared only at temperatures below
about 1200°C, does not contain further atoms. The intericosahedral bonds of the polar atoms
along the edge of the unit cell are covalent, and the equatorial atoms of three neighboring
icosahedra form weak electron-deficient three-center bonds oriented approximately perpendicu-
lar to the c axis.
The structural variety of this structure group is particularly determined by additional atoms
accommodated on the main diagonal of the unit cell (Fig. 1). They form three-atomic chains
(e.g., in binary boron carbide), bonded atoms in pairs (e.g., in B 12 P 2, B 12 As 2 ), and noninteracting
atoms in pairs (e.g., in B 6 O, B 6 Be, B 6 S) (17,18). The only exception are Al atoms, which are
accommodated in sites outside the main cell diagonal (19). In B 2.89Si the Si atoms form bonded
pairs and substitute for boron on icosahedral sites as well. Ternary compounds such as
BCSi are known, in which unit cells with three-atom chains (CBC and CBB)
and bonded Si 2 pairs exist side by side (20,21), or Si-doped B 12P 2 with P 2 and Si 2 pairs (22,23).
The arrangement of these additional atoms leads to a qualitative change of bonding within the
structure compared with α-rhombohedral boron in cases in which they saturate the outer bonds
of the equatorial atoms, thus replacing their weak intericosahedral three-center bond by strong,
largely covalent bonds to the end atoms of the chain.
With the compounds known up to now, the possible compositional and structural variety
within this structure group seems far from being exhausted.
2. β-Rhombohedral Boron Structure Group

β-Rhombohedral boron is the high-temperature, thermodynamically stable crystalline modifica-
tion of elementary boron. Its unit cell consists of essentially 105 atoms (24,25) [106.5 atoms,
if some additional sites with very low occupation densities are taken into account (26)]. The
structural formula (B 12 ) 4 (B 28 ) 2B exhibits four icosahedra, one positioned at the vertex and three
on the edge centers of the unit cell (both sites are crystallographically inequivalent), and two
B 28 units, which consist of three condensed icosahedra each, arranged symmetrically around a
centered single atom on the main diagonal of the unit cell. For certain descriptions the alternative
Figure 1 Unit cell of boron carbide as a representative of the α-rhombohedral boron structure group.
The unit cell of α-rhombohedral boron contains the B 12 icosahedron only; in the other representatives two-
atom or three-atom chains or two single atoms are on the main diagonal. (䊊) Polar atoms; ( ) equatorial
atoms; (䊉) chain atoms.
structural formula B 84 (B 10 ) 2B is preferred, with the B 84 unit consisting of the B 12 icosahedron

at the vertex of the unit cell radially surrounded by 12 half-icosahedra, which complete each
other forming the B 12 icosahedra on the edge centers. Two B 10 units and the single atom on the
diagonal complete this structure description. The outer bonds of the icosahedra are largely radi-
ally directed and covalently saturated.
The essential bases for the structural diversity within this structure group are different
holes in the boron framework (Fig. 2), which are large enough to accommodate foreign atoms
up to certain solubility limits, which seem to be specifically determined by the number of suitable
sites, the size of the foreign atoms, or the degree of electron transfer to the boron framework
(see later). Numerous binary and ternary compounds of this type with Mg, Al, Ga, Si, Ge, Cu,
Sc, Ti, Zr, Hf, V, Nb, Ta, Cr, Mn, Fe, Co, and Ni atoms have been prepared (e.g., see Ref. 27
and references therein); for LiB 13 with the β-rhombohedral boron structure see (28).
Substitutional B 32Al 3 and B 14 Si compounds [structural formulas B 84 (B 6 Al 4 ) 2Al and
B 84 (B 7 Si 3 ) 2 Si] were reported by Matkovich et al. (29,30).
3. α-Tetragonal Boron Structure Group

The idealized unit cell of α-tetragonal boron (Fig. 3) (31) consists of 50 atoms, which are
arranged in four B 12 icosahedra with one of their fivefold axes parallel to the c axis, and of two
additional single B atoms on 2(b) sites. In the borides belonging to this structure group these
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Figure 2 Schematic arrangement of the structure elements in the β-rhombohedral boron unit cell. Icosa-
hedra: (䊐) B 28 unit; (䊉) central B atom. Interstitial sites: (䉱) A(1) (Me1); (䊊) D (Me2); (䉲) E (Me3);
(䉳) Si.
2(b) sites and also two voids at 2(a) are assumed to be partly or completely occupied by other,
preferably metal atoms. Compounds with Be, Al, C, N, Ni, and Cu have been synthesized (for
details and references see Refs. 4 and 26). However, in some cases the obvious difference in
phonon spectra (4) makes the attribution of the compounds to the same structure group question-
able. There are suspicions that α-tetragonal boron cannot be prepared in pure form but that the
structure concerned must be stabilized by foreign atoms.
Few investigations of physical properties of representatives of this group have been re-
ported (2–4).
Figure 3 Unit cell of α-tetragonal boron containing B 12 icosahedra and single B atoms in 2(b) posi-
tion (31).
4. β-Tetragonal Boron Structure Group

The three-dimensional framework of this structure with 190 atoms consists of chains of B 12
icosahedra alternately alligned parallel to the a and b axes and of twinned double icosahedra
linked to 10 adjacent B 12 icosahedra and to four neighboring double icosahedra (Fig. 4) (32).
The remaining B atoms are single. In the related borides, certain sites in the double icosahedra
remain unoccupied. The metal atoms are statistically distributed in interstices or replace the
single B atoms (for more details see Refs. 3, 4, and 33 and references therein). The best-investi-
gated compound of this structure group is α-AlB 12 (see later).
5. Amorphous Boron
Amorphous boron consists of B 12 icosahedra, which are statistically distributed. It has been
proved that the narrow-range and the medium-range orders of amorphous boron are closely
related to those of crystalline β-rhombohedral boron (34–38). Accordingly, it has been proved
that the external bonds of the icosahedra in amorphous boron are largely covalently saturated.
Therefore it seems a likely supposition that the electronic properties are closely related to those
of β-rhombohedral boron as well, and moreover there may be holes in the structure to accommo-
date foreign atoms for doping to modify the properties. This would give a favorable chance of
future application because well-established techniques could be used to prepare amorphous in-
stead of crystalline material, for example, in thin layers.
There are hints that the structure of amorphous boron deposited by evaporation on surfaces
at lower temperatures are essentially different from those in thermal equilibrium (see Ref. 38
and compare with Ref. 34).
6. Orthorhombic Borides (MgAlB 14 Type)

The boron framework with 64 atoms per unit cell (Fig. 5) (39) consists of B 12 icosahedra arranged
in a distorted hexagonal packing. Contrary to those in the rhombohedral modifications of pure
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Figure 4 Unit cell of β-tetragonal boron. (a) Chains of B 12 icosahedra; (b) twinned B 21 double icosahe-
dron and (䊉) single B atoms (32).
Figure 5 Structure of AlMgB 14 as a representative of the orthorhombic borides. Projection on the (a)
ab plane and (b) bc plane (39,40).
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boron, the direct intericosahedral bonds deviate from radial directions. This holds for the indirect
bonds via single boron atoms on sites between the icosahedra as well. The metal atoms are
accommodated in large holes outside the icosahedra and are rather weakly bonded to the boron
framework (40). The structural formula is (B 12 ) 4Me(1) 4Me(2) 4B 8; however, in most cases the
metal sites are not completely occupied. As for the α-rhombohedral boron structure group, there
are only B 12 icosahedra and single boron atoms in the structure; there are no complex structural
units of fused icosahedra as found in the β-rhombohedral boron (B 28 ) and β-tetragonal boron
(B 22 ) structural families or giant B 156 icosahedral arrangements as in the YB 66 structural family.
As indicated in the structural formula, ternary compounds have usually been prepared.
Because in most cases the crystals have been grown in Al 2O 3 crucibles from high-temperature
AlB solutions containing small amounts of other metal atoms, Al is usually one of these
metals. However, compounds without Al are known as well (NaB 0.8B 14 (41), Mg 2B 14 (42,43)).
For reviews of compounds of this structure group see Refs. 44 and 45.
7. YB 66-Type Structures
The cubic unit cell of YB 66-type compounds with 1632 boron atoms consists of 13 giant (B 12 ) 13
icosahedra and 8 nonicosahedral B 42 units [structural formula B 12 (B 12 ) 12 (B 42 ) 8] with the metal
atoms statistically distributed on defined interstitial sites (Fig. 6) (46,47). The B 42 units are
clusters consisting of 80 boron sites with occupancies ranging between 28 and 71% (48). The
homogeneity range is assumed to be considerable (YB n, 20 ⬍ n ⬍ 100). Besides Y, most of
the lanthanide and some actinide atoms are known to form this structure (see Refs. 3, 49, and 50).
Figure 6 Schematic structure of YB 66 (46,47) consisting of B 156 [(B 12 ) 13] giant icosahedra, B 48 nonicosa-
hedral units, and metal atoms.
As far as investigations of physical properties are concerned, they are largely restricted
to YB 66 (see later).
B. Nonicosahedral Structures
Besides of the icosahedral structures of boron-rich solids, two structure groups based on other
polyhedral arrangements of boron atoms are known:
1. Metal Hexaborides
The unit cell contains one formula weight of MB 6. The boron atoms form octahedra positioned
at the corners of the cubic unit cell, and the metal atoms are in its center. All rare earth metals
and Ca, Sr, Ba, Tl, and Pu form these isostructural hexaborides see (3,51–54).
2. Metal Dodecaborides
The structure can be described in terms of a modified face-centered cubic (fcc) unit cell with
the metal atoms in the center of regular cubo-octahedra consisting of boron atoms at each of
their 24 vertices or, alternatively, by a modified NaCl-type structure with metal atoms and cubo-
octahedral arrangements of 12 boron atoms, each occupying the structure positions. Lanthanides,
actinides, and many other metal atoms are able to form this structure (3,53–55).
In contrast to the icosahedral structures, which are semiconductors in general, the com-
pounds in these structure groups are preferably metals and will therefore not be discussed in
this chapter in detail. In the case of some metal hexaborides, the existence of semiconducting
phases seems to depend on the composition. Dodecaborides with divalent metals are expected
to be semiconducting or insulating, those with trivalent metals to be metallic (54).
C. Carbon in Boron Structures

Carbon is a very important foreign element for all boron structures. Its chemical affinity for
boron is very high. Because both light elements are immediate neighbors in the periodic system,
at present the resolving power of even modern imaging, scattering, and analyzing methods is
usually not sufficient to discern them directly in the solid structures.
Because the solubility coefficients of carbon in the solid and the liquid phase are almost
the same, zone melting, which is used to prepare high-purity crystals of many other elements,
is not suitable in the case of boron. Technical boron, which is often taken as the ingredient for
the preparation of boron compounds, contains up to about 0.5% carbon. However, in several
preparative methods for boron compounds the carbon content may be reduced by secondary
chemical or physical reactions. The purest β-rhombohedral boron crystals that have become
available up to now were produced by Wacker-Chemie, Munich, FRG. Despite the claimed
purity of 99.9999% with respect to other elements, even this high-purity boron contains carbon
in concentrations of typically 30 to 80 ppm. Therefore, apart from boron carbide containing
carbon as a determining bonding partner, in the assessment of the properties of boron and boron
compounds attention must be paid to the fact that a certain, usually unknown carbon content
could have influenced the properties determined.
Quantitative investigations of the effect of the carbon content on the structure and physical
properties of boron-rich solids have been restricted to β-rhombohedral boron and boron carbide
(56–61). Up to carbon contents of about 1 at.% in β-rhombohedral boron, the carbon atoms
substitute statistically for boron atoms at the polar sites of the B 12 icosahedra in the structure
with a maximum of one carbon atom per icosahedron. Compared with the boron atom, the
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carbon atom is radially shifted toward the center of the icosahedron by 6.7(3)% (56,57). This
distortion of the icosahedra is quantitatively related to the anisotropy of the change of the unit
cell parameters depending on the carbon content. For boron carbide it has been assumed that
carbon atoms substitute for boron at the polar sites of the icosahedra as well. However, a quanti-
tative correlation with the modification of the unit cell parameters of boron carbide was not
possible, because they are considerably influenced by the changes of the interior of the unit
cells depending on the carbon content as well.
For the influence of the carbon content on the physical properties of β-rhombohedral boron
and boron carbide, see later.
D. Accommodation of Foreign Atoms Within the B 12 Icosahedra

For the incorporation of foreign atoms in all the boron-rich structures discussed previously, only
interstitial sites between the icosahedra were taken into account. Although the size of the B 12
cage with its diameter of about 3.4 Å should be sufficient to accommodate small atoms within
the icosahedra, up to now no compounds of this kind have become known. The question arises
whether such compounds are possible or impossible in principle.
To answer this question, Beckel and Howard (62) calculated the possible configurations
of the complex [Mg⫹B 12H 12] and found one stable position of the magnesium ion in the center
of the B 12 cage. They concluded that incorporation inside the icosahedra should be possible for
atoms with low single and double ionization energies and sufficiently small steric radii.
III. THE B 12 ICOSAHEDRON AND ITS ELECTRONIC STRUCTURE
The B 12 icosahedra are periodically arranged in all crystalline boron-rich structures. Neverthe-
less, these solids differ decisively from molecular crystals. The overlap of intericosahedral and
intraicosahedral vibrations in the phonon spectra (see Refs. 27 and 63) proves, in agreement
with theoretical calculations (13), that contrary to molecular crystals, the intericosahedral bonds
are stronger than the intraicosahedral ones. This leads to a considerable interaction of the elec-
tronic states of the icosahedra in the solid structures, whose energy band structures are essentially
determined by the overlap of the electronic orbitals of the icosahedra.
A. The Isolated Icosahedron and Its Orbitals

The distortion of the icosahedra, which is largely independent of the specific structures, has
been attributed to the Jahn-Teller effect (64). This is a fundamental principle acting in all cases,
where in highly symmetrical atomic arrangements the orbit-degenerated electronic states couple
with asymmetrical vibrations. The only exceptions, twofold Kramer-degenerated states in arbi-
trary groupings and twofold orbit-degenerated states in linear arrangements of atoms, do not
apply to the B 12 icosahedron. The physical reason for this coupling, which leads to a distortion
and in consequence to a reduction of symmetry, is the reduction of total energy of the system
in the distorted state compared with the high symmetrical one.
By group theoretical methods it was shown (65,66) that by this distortion the icosahedral
point group I h is reduced to the subgroup D 3d, which is compatible with the space group R 3
m. This explains why this space group is preferred in icosahedral crystal structures.
Of course, this distortion of the icosahedra affects its molecular orbitals as well. From
theoretical calculations for the regular icosahedron by Longuet-Higgins and Roberts (67) and
Bambakidis and Wagner (68), it is known that the electronic ground state of the boron atom
2s 2 2p 2 is hybridized to 2s 2p x 2p y 2p z with 3 electrons available. For the regular B 12 icosahedron
the result is
25 bonding orbitals 36 electrons

23 antibonding orbitals 0 electrons
If the external bonds are assumed to be covalent, the electrons are distributed as
12 orbitals of outer bonds 12 electrons
13 orbitals of inner bonds 24 electrons
This electron-deficient structure leads to the intraicosahedral multiple-center bonds of the
icosahedron, which, according to Howard et al. (69), is stable in spite of lacking two electrons.
The low ionicity of the crystal structures indicated by the small phonon oscillator strengths (see,
e.g., Ref. 4) indicates that this electron-deficiency site remains largely uncompensated in the
crystal structures.
The influence of the Jahn-Teller effect on the intraicosahedral bonding orbitals was qualita-
tively derived by group theoretical methods for the clearest situation of exclusively covalent
external bonds of the icosahedron (64–66). Comparison of the character tables of I h and D 3d
yields immediately that all the three-, four- and five-fold degenerated irreducible representations
of the icosahedral group I h split, because they are not comprised in the D 3d group (Fig. 7). The
fourfold degenerated uppermost G u orbital of the regular icosahedron partly occupied by only
six electrons is thus split so that occupied and unoccupied orbitals become separated. The total
splitting range of the G u orbital was quantitatively calculated by Hori et al. (70) as 0.5 eV, in
rough agreement with the results experimentally obtained for β-rhombohedral boron (71).
B. Icosahedral Crystal Structures

For the case that in condensed matter the bonding conditions of the free icosahedron (covalent
intericosahedral bonds, which are weaker than intericosahedral bonds) remain largely unchanged
Figure 7 Jahn-Teller induced splitting of the icosahedral orbitals, when the symmetry is reduced from
I h (free icosahedron) to D 3d (icosahedron in rhombohedral crystal structure) (64,65,71).
602 Werheit
compared with the [B 12H 12]2⫺ cluster, the energy scheme of the intraicosahedral bonding orbitals
of the free icosahedron can be essentially transferred, although these orbitals will, of course,
spread to energy bands. Because the intericosahedral bonds are stronger, the concerned orbitals
are comparably lower in energy and do not contribute to the uppermost part of the valence band.
Then occupied and unoccupied electronic states of the solid are energetically separated, and
accordingly semiconductor behavior results in spite of the odd number of electrons in the single
boron atom. For example, this is the case in many representatives of the α-rhombohedral boron
structure group, in particular boron carbide (α-rhombohedral boron itself excluded), and all
representatives of the β-rhombohedral boron structure group.
α-Rhombohedral boron is an example of icosahedral structures with different conditions
of outer bonds. Perpendicular to the c axis, the equatorial atoms of the icosahedra form three-
center bonds, which are weaker than the intraicosahedral bonds, and accordingly positioned at
higher energies. Hence these orbitals could contribute to the uppermost valence band range and
accordingly change the situation described before. Theoretical band structure calculations for
such cases taking the Jahn-Teller effect into account are still lacking. However, the experimental
fact that all the icosahedral boron-rich solids are semiconductors seems to indicate that the
influence of the intraicosahedral bonds also prevails in these cases.
The density of states of the B 12 icosahedron in solids determined by cluster calculations
of Shirai and Nakamatsu (72) are shown in Fig. 8.
Figure 8 Density of states of the B 12 icosahedron as obtained from cluster calculations by Shirai and
Nakamatsu (72).
IV. PHYSICAL PROPERTIES OF ICOSAHEDRAL BORON-RICH SOLIDS
Up to now, the knowledge and understanding of the physical properties of icosahedral boron-
rich solids have been most extensively elaborated for β-rhombohedral boron and, with some
restrictions, boron carbide as well. Therefore these materials will be in the foreground of the
following description. Although both semiconductors belong to different structure groups, a
comparison of their properties is interesting because in both cases the external bonds of the
icosahedra are largely covalently saturated. Subsequently, the limited results available for other
structures will be discussed.
To understand and describe the electrical and optical properties of a semiconductor, it is
essential to have knowledge of its electronic band structure, which exhibits the relation between
energy and momentum E(k) of electrons and holes in the different possible states of the conduc-
tion and valence bands at the various symmetry points of the first Brillouin zone of the reciprocal
lattice. In particular, the band gap between the valence and conduction bands is important,
because it determines, e.g., the optical transition energy and the temperature dependence of the
intrinsic conductivity. In the case of the complex boron-rich solids with large numbers of atoms
per unit cell, the agreement between theoretical calculations of the band gaps and the experimen-
tal results has not yet been satisfactory.
As a second parameter of the electronic band structure, the curvature of the energy bands
is important for the electronic properties because the effective mass is determined by 1/m* ⫽
–h 2 ∂ 2E/∂k 2 In this respect, all theoretical calculations for icosahedral boron-rich solids yield the
corresponding result that the energy bands are rather small compared with classical semiconduc-
tors and hence the effective masses are expected to be comparably large.
A. ␤-Rhombohedral Boron
1. Optical Parameters
β-Rhombohedral boron is the only boron-rich icosahedral solid for which the spectra for interac-
tion with electromagnetic radiation are available in a very extended range. In Fig. 9 the reflectiv-
ity spectrum and partly the absorption spectrum are shown (73–77). The small change in the
reflectivity within the phonon range of the spectrum underlines the weak ionicity of the structure.
2. Energy Band Structure

a. Density-of-States Distribution
Theoretical studies of the electronic structure of β-rhombohedral boron have been performed
by Bullett (78,79). The density-of-states distribution reproduced from Ref. 76 is shown in Fig.
10 and reveals a gap close to 3 eV. Qualitative distributions of the density of states obtained
by different experimental methods (80–87) are plotted in Fig. 11.
b. Interband and Gap-State Related Transitions
Precise transition energies between valence and conduction bands of semiconductors have been
experimentally obtained by optical measurements in the low-energy limit of the fundamental
absorption range, which is called the absorption edge. As usual, this absorption edge is a superpo-
sition of several transitions; however, they can be checked and decomposed according to the
theories of interband transitions in crystalline semiconductors (direct and indirect, allowed and
forbidden) (see Ref. 88) or an Urbach tail as in amorphous semiconductors. In β-rhombohedral
boron the slope of the absorption edge is also complicated by optically excited electronic transi-
tions in connection with intrinsic states of high densities in the band gap. The energy dependence
604 Werheit
Figure 9 Reflectivity and absorption index of β-rhombohedral boron (collection of results obtained by
different methods and authors) (73–77).
Figure 10 Theoretical density of states of α-rhombohedral boron and β-rhombohedral boron (78,79).
Figure 11 Qualitative distribution of the density of states as determined by different experimental meth-
ods (see Ref. 2 and references therein, and Refs. 80–87).
of the optical absorption processes concerned correspond to Lucovsky’s theory of transitions

from deep levels to parabolic bands in semiconductors (89).
Figure 12 shows the absorption edge of different high-purity β-rhombohedral boron sam-
ples with low carbon contents measured at room temperature (71). The influence of low but
different carbon contents can easily be seen. A larger section of the absorption edge is shown
in Fig. 9 (90). The band gap is determined by indirect allowed interband transitions. The energies
obtained from the decomposition of the absorption edge are listed in Table 1 (71).
The essential band gap is 1.50 for E储c and 1.46 eV for E芯c, and the upper valence band
with a distance of 1.32 and 1.29 eV, respectively, from the conduction band is identified as the
split-off valence band caused by a static Jahn-Teller effect in the icosahedron as described in
Sec. II.A. It was shown that this effect acts on the icosahedra at the vertex of the unit cell only,
and accordingly the density of states of the band corresponds to the number of rhombohedral
unit cells (N ⫽ 1.35 ⫻ 10 20 cm⫺3 ) and is comparably low (56,57). This is important for the
electronic transport mechanism described in the following.
The temperature dependence of the transition energies can be quantitatively described by
the disorder caused by thermal fluctuations of the atomic positions related to phonons according
to
E g (T) ⫽ E g (T ⫽ 0) ⫺ βh–Ω phononn(h–Ω phonon )
with the temperature coefficient β in units of k B and the Bose-Einstein–type phonon excitation
density n(h–Ω phonon ) (91–93); the parameters used for β-rhombohedral boron are listed in Table
2 (68). All phonons implicated in the interband transitions of β-rhombohedral boron and their
temperature dependence are present in the IR phonon spectrum (94,95).
From the decomposition of the absorption edge tails of pure (71) and carbon-doped β-
rhombohedral boron (58,59) the energetic positions of six intrinsic trapping levels in the band
gap result. They are generated by electron-phonon interaction with intraicosahedral phonons
606 Werheit
Figure 12 Anisotropy of absorption edge and edge tail of high-purity β-rhombohedral boron (carbon
content 66 and 92 ppm, respectively) (71).
and are slightly different in energy for B 12 and B 11 C icosahedra (58,96). They are positioned
with energies of multiples of 0.188(2) eV for B 12 icosahedra and multiples of 0.208(2) eV for
B 11 C icosahedra off the conduction band edge (Fig. 13).
The generation of these intrinsic trapping levels by electron-phonon interaction requires
free electrons in the conduction band and the excitation of the phonons involved as well. The
involved phonons are antisymmetric breathing modes of the icosahedron described by a con-
Table 1 Anisotropic Optical Transition Energies and Band Gap Parameters of the Indirect Allowed
Interband Transitions in β-Rhombohedral Boron, Extrapolated to T ⫽ 0
E储c E ⊥c
IR phonon IR phonon
Transition assigned Transition assigned
No. energy (eV) Gap width (cm⫺1) energy (eV) Gap width (cm⫺1)
1 1.27(1) 1.23(1)
1.32(1) 476(1) 1.29(1) 478(1)
2 1.37(1) 1.34(1)
3 1.46(1) 1.42(1)
1.50(1) 355(1) 1.46(1) (358(1)
4 1.54(1) 1.50(1)
Table 2 Parameters Used to Describe the Temperature-

Dependent Shift of the Gap Energies in β-Rhombohedral Boron
E储c E ⊥c
βk B 1.03 meV K⫺1 1.25 meV K⫺1
⫺
hΩ phonon 121.9 meV/982 cm⫺1 94.1 meV/758 cm⫺1
tracting upper and expanding lower pentagon of the icosahedron (F 1u mode) and an oblate and
a prolate hemispheroid (F 2u mode), respectively. The symmetry axes of the atomic movements
concerned are the fivefold symmetry axes of the icosahedron. Because the icosahedron exhibits
six of these symmetry axes, the interaction of the electron can take place with up to six pairs
of phonons and accordingly the number of trapping levels is limited to six. The maximum
distortion of the icosahedron caused by such electron-phonon interactions takes place in the
equatorial plane perpendicular to the corresponding fivefold symmetry axis. This is the plane
of the Landau orbit of the trapped electrons, when the magnetic field is oriented parallel to the
fivefold axes of the icosahedron. Accordingly, it was possible to attribute the ESR resonances
of β-rhombohedral boron (97,98) to the trapped electrons and to take the ESR line widths (see
Fig. 13) as a measure of the distortion in agreement with the model described (58,59). These
results led to the energy band scheme of β-rhombohedral boron in Fig. 14.
From optical absorption spectra, photoabsorption, photoconductivity, and relaxation after
preceding optical excitation, important information on the transition probabilities between the
different levels in the band scheme has been derived (65,66,99–103). Optical transitions from
the lower into the upper valence band are forbidden. Electrons cannot be directly excited from
Figure 13 Energetic distance of the intrinsic electron traps from the conduction band edge for B 12 and
B 11 C icosahedra. ESR line widths demonstrating the degree of distortion of the icosahedra in case the
different traps are generated (58,96).
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Figure 14 Energy band scheme of β-rhombohedral boron (65,66,99–103).
the valence band into the electron trapping levels, because these levels do not exist without
trapped electrons. The recombination of trapped electrons into the valence band needs preexita-
tion into the conduction band.
All four B 12 icosahedra in the unit cell are able to form such traps with one electron
captured in one of the six possible levels. From the volume of the unit cell, V ⫽ 2.4616(4) nm3,
a maximum density of traps of about 5 ⫻ 10 20 cm⫺3 is possible.
According to very far ultraviolet (VUV) measurements of the optical properties, the range
of optical fundamental absorption essentially extends to about 9 eV (Fig. 15) (104). From the
second derivatives of ⑀ 1 and ⑀ 2, critical points in the energy band structure were determined at
2.6, 3.15, 3.8, 4.5, 5.4, 6.1, 6.6, 7.5, 8.1, 8.53, and 8.95 eV (104).
Steps in the photoconductivity spectra after optical excitation confirm the existence of the
trapping levels known from absorption and photoabsorption measurements [Fig. 15a (105)].
3. Electronic Transport Properties of β-Rhombohedral Boron

Figure 16 shows the temperature dependence of the DC electrical conductivity of pure and of
some selected examples of doped β-rhombohedral boron (see Ref. 2 and references therein). In
a large range of temperature the slope meets Mott’s law for variable-range hopping (Fig. 17)
(106,107). The striking step between 400 and 500 K is caused by the Fermi level pinned in the
trap states (65). The Seebeck coefficient (Fig. 18) (see Ref. 2 and references therein) is positive
and indicates p-type conductivity up to the highest temperatures reached. By comparing the
temperature dependences of electrical conductivity and Seebeck coefficient according to Bosman
and Crevecoeur (108) it was found that the mobility of the holes has an activation energy of
0.18(1) eV (101,106), which corresponds to the distance between the split-off and the lower
valence band.
Figure 15 (a) Second derivatives of the real and the imaginary parts of the dielectric function of β-
rhombohedral boron in the spectral range of fundamental absorption (104). (b) Photoconductivity of β-
rhombohedral boron in the low-energy tail of the fundamental absorption. Conditions of measurement:
155 K, sample annealed at 450 K, cooled down to 155 K, 1-h excitation by a xenon arc lamp, quickly
cooled down to 90 K, then measured; 320 K, sample annealed at 450 K, cooled down to 320 K, then
measured without (unexcited) or after 1-h excitation with a xenon arc lamp. The ionization energies of
the electron traps known from absorption and photoabsorption measurements are indicated (105).
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Figure 16 Temperature dependence of the electrical conductivity of pure boron and examples of differ-
ently doped β-rhombohedral boron. 1 and 2, High-purity boron; 3, lapped surface; 4, B 6 O surface layer;
5, Mn-doped; 6, Fe-doped, 7, 3% C-doped; 8, FeB 29.5; 9, C-doped (p ⫽ 3 ⫻ 10 20 cm⫺3 ). (See Ref. 2 and
references therein.)
The Hall effect indicates p-type behavior as well, and based on classical theory an in-
terband thermal activation of the carriers of 1.52 eV was derived from the slope. This agrees
quite well with the gap energy (101).
If the energy band structure of β-rhombohedral boron were based on the B 12 icosahedra
only, one would expect that the upper valence band is completely free from electrons. In reality
this is not the case, which can be seen, e.g., from the interband transitions of electrons into the
conduction band by optical absorption. These electrons may come from nonicosahedral structure
elements. Hence, in thermal equilibrium the Fermi level is positioned within this upper valence
band.
Accordingly, different electronic transport mechanisms seem possible in principle:
a. Thermal Equilibrium at Low Temperatures
Hopping at the Fermi level within the upper valence band
Band-type conductivity in the lower valence band
Figure 17 Electrical conductivity of β-rhombohedral boron plotted against T ⫺1/4 to show the temperature
dependence according to Mott’s law for variable-range hopping (106,107).
When the thermal energy is sufficient, free holes are generated by exciting electrons into
the upper valence band, which acts in this case like an intrinsic acceptor level. For these free
holes the partly occupied upper valence band has a further meaning for the holes in the lower
valence band. It acts as a trapping level of high density, hence reducing the relaxation time of
the free holes considerably. This explains the p-type behavior at low temperatures.
The simultaneously occurring band-type and hopping conduction has been proved in the
dynamical conductivity in the far infrared (FIR) spectral range (see Fig. 24) (75,109,110).
b. Thermal Equilibrium at High Temperatures
At sufficiently high temperatures electrons are thermally excited from the valence into the con-
duction band. However, because of the high density of electron traps, their contribution to the
charge transport is extremely low and p-type behavior prevails irrespective of a probably smaller
electron effective mass.
c. Thermal Nonequilibrium
In particular at lower temperatures, thermal nonequilibrium can be established, for example, by
optical interband excitation and subsequent trapping of electrons or by quenching from high
temperatures. Compared with equilibrium, the electrical conductivity increases, and this is due
to the shift of the quasi-Fermi level toward the lower valence band, which has two effects: The
excitation of free holes increases because the activation energy into the upper valence band is
reduced, and the trapping probability of the free holes decreases because the number of occupied
states in the upper valence band acting as traps for the free holes in the lower valence band
becomes smaller.
As shown before, the temperature dependence of the electrical conductivity follows Mott’s
law in a large temperature range. It seems that two mechanisms can possibly be attributed to
612 Werheit
Figure 18 Seebeck coefficient of β-rhombohedral boron according to the results obtained by different
authors (see Ref. 2 and references therein). For interstitially doped boron with negative Seebeck coefficient,
see Fig. 21.
this behavior. The first is variable-range hopping excited by phonons in the upper valence band,
which doubtless corresponds to the behavior that is the objective of Mott’s theory. For example,
the impurity band conduction in p-type silicon exhibits a metal-semiconductor transition for
concentrations of about 5 ⫻ 10 18 cm⫺3 statistically distributed acceptors (111) and the density
of states of the upper valence band in β-rhombohedral boron generated by 5 ⫻1020 cm⫺3 periodi-
cally arranged icosahedra is distinctly higher. However, a second process seems possible as
well, and this is multiple trapping of free holes in occupied states of the upper valence band.
This process is a type of thermal excitation of carriers as well, and one can imagine that this
could also follow a slope similar to Mott’s law. Theoretical calculations for such processes have
not yet become available, and therefore the question remains open whether one of these pro-
cesses or both side by side are responsible for the hopping processes.
4. Carrier Mobilities
In such complex conductivity processes characterized by a superposition of high-mobility micro-
scopic band-type conduction, low-mobility hopping, and low-mobility drift because of multitrap-
ping, it is very difficult to determine the mobility of the carriers reliably. Obviously, the results
depend on the method of measurement. For example, at high frequencies the carriers with band-
type mobility essentially determine the result, whereas at low frequencies hopping prevails.
Figure 19 Mobility of carriers in β-rhombohedral boron obtained by different methods and different
authors. 1, From space-charge limited currents; 2 and 3, µ H; 4, field effect; 6, thermally activated hopping;
䊊, from electrical conductivity and spin density; 䊉, µ H; 䉲, from electrical conductivity and ESR; 䊐;
magnetoresistance; ■, from ESR line width; ⫹, band mobility; 䉱, hopping mobility; 䉭, from photoconduc-
tivity; 䉮, from high-field conductivity, I, Hall mobility and photoconductivity. (See Ref. 2 and references
therein.)
Accordingly, all the results on carrier mobilities in β-rhombohedral boron (Fig. 19) based on
the assumption of a single transport mechanism are more or less questionable.
A reliable way to determine drift mobilities is based on the transit times of optically
excited electrons and holes depending on the drift field (112) Figure 20a–c show the electron,
hole, and electron-hole pair densities at different distances from the illuminated surface de-
pending on the space of time after steady-state excitation has been started. Shoulders in the
dispersion spectra separate an initial range determined by carriers slowed down by traps, which
are in steady exchange with the adjacent band, from the range that is essentially determined by
multitrapping in deep trapping levels. Qualitative differences between these transit time spectra
are the quenching of hole concentration in the initial range and the considerable delay of the
electron saturation compared with the hole saturation at long drift times.
The quenched hole conductivity in the initial range is caused by reduction of the electron
density in the upper valence band. This range is followed by an enhanced conductivity caused
by the decreasing activation energy for free holes in the lower valence band when the Fermi
level is lowered.
At the beginning, the first electron trap for free electrons and the upper valence band for
free holes in the lower valence band have similar effects on the carrier transport, because their
reexcitation energies are the same. Accordingly, the shoulders in the dispersion spectra are
similar. The delay of the electrons at long times is due to multitrapping in deep traps and to
614 Werheit
Figure 20 (a–c) Drift and diffusion of optically excited carriers in β-rhombohedral boron. Densities of
electrons, electron-hole pairs, and holes at different distances from the illuminated surface versus transit
time related to the onset of steady-state optical excitation (112). (d) Temperature dependence of the hole
drift mobility in β-rhombohedral boron derived from transient photoconduction (113).
the retardation of the recombination because the valence band is largely filled. The transport of
electrons and holes is of soliton type. The nonlinearity of the velocity required is evoked by
the time-dependent presaturation of the traps by preceding carriers. For details see Ref. 112.
Characteristic carrier mobilities determined are
for electrons µ e ⫽ 0.11 cm2 V⫺1 s⫺1
for holes µ h ⫽ 0.076 cm2 V⫺1 s⫺1
The relations of retrapping to recombination rates are
for electrons R retrapping /R recomb ⫽ 15

for holes R retrapping /R recomb ⫽ 1.2
which means that electrons cover average distances of more than 30 mm before they recombine.
This value exceeds those known from classical semiconductors by far.
616 Werheit
The temperature dependence of the hole drift mobility (Fig. 20d) yields a thermal activa-
tion energy of 240 meV (113).
5. Interstitial Doping
A fundamental prerequisite for the technical application of semiconductors is the possibility of
changing their conductivity characteristics by doping. In the case of boron-rich solids, this was
realized for the first time by the interstitial accommodation of Fe atoms in the β-rhombohedral
boron structure (9). Lateron Ni, Cr, and V (10) have been found to lead to n-type conductivity
of β-rhombohedral boron as well (Fig. 21); the highest negative Seebeck coefficient has been
obtained with vanadium.
According to the band scheme of β-rhombohedral boron (Fig. 14), it is obvious that n-
type conductivity requires the unoccupied states in the valence band range and the intrinsic
electron trapping levels to be filled by electrons originating from donor levels, which must be
positioned above the uppermost trapping level. Two states in the upper valence band originating
from the Jahn-Teller effect in the icosahedron at the vertex of the unit cell and four states of
intrinsic traps, which are generated by the electron-phonon interaction in the four B 12 icosahedra
in the unit cell, i.e., in total six sites, must be saturated by additional electrons to realize n-type
behavior.
This has been confirmed by Mössbauer investigations yielding the degree of ionization
of Fe atoms accommodated in the interstitial A and D sites of the structure (see Fig. 2) (11).
Figure 22 shows the concentrations of Fe 2⫹ and Fe 3⫹ ions. The accordingly calculated electron
transfer at the transition from p to n type (Fig. 23) confirms the number of six electrons within
the accuracy of measurement.
Figure 21 Seebeck coefficient of β-rhombohedral boron interstitially doped with Ni, Cr, Cu, and V
versus metal content (9,10).
Figure 22 Distribution of Fe 2⫹ and Fe 3⫹⫹ ions in the (a) A sites and (b) D sites of the β-rhombohedral
boron structure versus total Fe content. For the D sites the solid lines represent the distribution probabilities
for single Fe atoms and pairs, respectively; for A sites they represent the probabilities, whether all neigh-
boring D sites are completely occupied by Fe atoms or not (11).
618 Werheit
Figure 23 Seebeck coefficient of β-rhombohedral boron versus charge transfer from the Fe atoms to
the icosahedral boron structure (nominal charge and estimated effective charge) (11).
In n-type B :Fe the DC conductivity was found to meet Mott’s law of variable-range
hopping (9). More insight is obtained from the far-infrared reflectivity, which increases toward
lower frequencies, thus resembling the plasma edge in semiconductors. A convincing fit to the
experimental spectra is possible only when a superposition of hopping and band-type conductiv-
ity is assumed. This is demonstrated for the dielectric function of n-type largely vanadium-
saturated VB 32 with the β-rhombohedral boron structure in Fig. 24 (75). The variation depending
on the V content is as expected. For Fe doping this holds as well (75).
Accordingly, in the case of n-type conduction of β-rhombohedral boron a superposition of
band-type conductivity and hopping exists as well. Answering the question of how the hopping
processes take place in detail needs further investigation. Several models seem possible in princi-
ple: hopping within an impurity band due to the interstitial doping atoms, hopping within a
level evoked by the superposition of the uppermost trapping level and the donor level, and
multitrapping of electrons thermally excited into the conduction band.
6. Doping by Substitution
The substitution of foreign for boron atoms in the structure of β-rhombohedral boron should
be possible in principle, if the size of the foreign atoms fits the structure. Up to now, results
are available only for carbon atoms. Structural aspects of carbon doping have been discussed
in Sec. II.C.
With respect to the electronic structure, several influences of the C atoms are indicated
in the quotient reflectivity spectrum in Fig. 25 (114). Most important for the transport properties
are the effects at and within the band gap. The interband photoconductivity (105) increases, the
spin density of trapped electrons increases (see Ref. 58), and the hopping activation energy (see
Figure 24 Real (a) and imaginary (b) parts of the dielectric function of VB 32 in the far-IR spectral range
(75,110). For a satisfactory description of the experimental spectra hopping mobility and band-type mobil-
ity both must be taken into account.
Ref. 58) decreases with increasing carbon content. From these results, it has been concluded
that carbon forms a donor level as expected because of its excess electron. However, the ener-
getic position of this donor level is deep in the band gap and coincides with the split-off valence
band, which accordingly the occupied donor states join to. Hence within this band the density
and the occupation density both increase with increasing carbon content.
7. Mechanical and Thermal Properties

When before free electrons, which polarize their dielectric surrounding, generate traps by
electron-phonon interaction, well-defined distortions of the icosahedra result, which depend on
the number of pairs of phonons involved. Because of the thermal excitation of phonons required
for this interaction, the formation of specific traps is maximum at defined temperatures, when
electrons are available, e.g., by optical excitation (65,66,96). In thermal equilibrium the tempera-
ture range between about 500 and 600 K is of particular interest because the thermal energy
concerned is sufficient to exchange electrons between all the levels in Fig. 14 within rather short
relaxation times. With this consideration, Werheit et al. (71) were able to interpret the previously
unexplained hysteresis of the thermal expansion coefficient (115) and the maximum of internal
friction (116,117) in this temperature range consistently.
B. Boron Carbide
1. Details of the Structure
Boron carbide can be synthesized within a large homogeneity range extending from B 4.3C at
the carbon-rich limit (118) to about B 12C at the boron-rich limit (119–121). X-ray diffraction
620 Werheit
Figure 25 Quotient spectrum of the reflectivities of two differently carbon-doped β-rhombohedral boron
samples (114).
(122–125) and 13C nuclear magnetic resonance (NMR) spectroscopy (126–130) failed to deter-
mine the compositions of the structure elements and their variation within the homogeneity
range. The same applies to theoretical considerations (131).
The problem was solved quantitatively by the decomposition of the IR optical stretching
mode of the three-atom chain by model calculations taking the possible compositions and the
frequency shift depending on the mass distribution in natural and isotope-enriched boron carbide
into account (57). The determined concentrations of B 12 and B 11C icosahedra and CBC
and CBB chains are shown in Fig. 26. Other chain compositions can be excluded. Toward
the boron-rich limit of the homogeneity range, an increasing number of unit cells without chains
arise. Two alternative models are compatible with the optical spectra: completely chain-free
unit cells and unit cells in which single B atoms saturate the outer bonds of the equatorial atoms
of the adjacent icosahedra. Theoretical calculations of reaction kinetics based on the second
version (132) satisfactorily confirm the results in Fig. 26.
Obviously, the large interstices in these chainless unit cells are suitable to accommodate
foreign atoms. For example, in the ternary BCSi compounds the concentration of Si pairs
is exactly equal to the number of chainless unit cells of boron-rich boron carbide of the corre-
sponding composition (133,134).
Figure 26 demonstrates that at none of the compositions in the homogeneity range does
a completely homogeneous structure exist. This disproves, e.g., the idealized structure model
of boron carbide B 6.5 C [structural formula (B 12 )CBC], which is preferably used in theoreti-
cal band structure calculations (79,135,136). Obviously, the most homogeneous structure of
Figure 26 Structure elements in the unit cell of boron carbide. B 12 icosahedra, B 11 C icosahedra, CBC
and CBB chains, and chainless unit cells versus carbon content (57).
boron carbide is found at the carbon-rich limit B 4.3 C, and the somewhat deviating composition
B 6.5 C exhibits the least homogeneous structure.
2. Interband and Gap-State Related Transitions

The high unselected reflection of polished boron carbide surfaces in the visible range of the
spectrum makes it immediately clear that the absorption edge is in the IR range, in contrast to
all theoretical band structure calculations on boron carbide that have become available
(78,79,110,136–138). The densities of states of (B 12 )CBC calculated by Bullett (78,79)
and Switendick (135) are shown in Fig. 27.
Some optical transmission measurements indicate a minimum band gap of 0.48 eV
(139,140), and from the imaginary part of the dielectric function a gap of 1.6 eV was estimated
(141) in a somewhat questionable way.
Transmission measurements in a more extended spectral range of electronic interband
transitions were made by Werheit et al. (142). Figure 28 shows the isotherms of the absorption
coefficient of one sample between 80 and 590 K. The very high absorption level down to low
photon energies, two strong steps in the absorption at about 1.3 and 3.4 eV, and a strong thermal
reallocation of carriers depending on temperature are obvious. Quantitatively, besides a deep-
level to band transition at 0.18 eV, a series of indirect interband transitions starting at 0.48 eV
was derived (for details, see Ref. 134).
The real and imaginary parts of the dielectric function obtained by ellipsometric measure-
ment with synchrotron radiation indicate several interband transitions at higher energies (Fig.
29) (104). It is noteworthy that these transitions are obviously at energies that do not deviate
622 Werheit
Figure 27 Densities of states of (B 12 )CBC as calculated by Bullett (78,79) and Switendick (135).
Figure 28 Isotherms of the absorption edge of carbon-rich boron carbide (B 4.3 C) (142).
Figure 29 Real and imaginary parts of the dielectric function of boron carbides of different compositions
in the range of interband transitions determined by ellipsometric measurements (104).
essentially from those of β-rhombohedral boron; this is doubtless an indication of similarities

of the energy band structures probably due to the icosahedra. This is supported by satisfactory
agreement with the density of states distribution of the icosahedron calculated by Shirai and
Nakamatsu (72) in Fig. 8, but the energetic differences of the density of states maxima of boron
carbide calculated by Bullett (78,79) and Switendick (135) are not confirmed by these experi-
mental results.
3. Electronic Transport Properties

Figure 30 shows the electrical conductivity depending on temperature and chemical composition
(143,144). At all temperatures the maximum conductivity is related to the maximum concentra-
tion of B 12 icosahedra and the minimum concentration of B 11 C icosahedra, refuting the theory
of Emin et al. (14–16,145,146), who attribute the conductivity mechanism in boron carbide to
bipolaron hopping between B 11 C icosahedra.
The temperature dependence of the electrical conductivity (Fig. 31) (16,145–150) shows
that even at the highest temperatures reached intrinsic conductivity is not yet realized. The steps
are reminiscent of β-rhombohedral boron (see Ref. 68 and above), where the Fermi level is
pinnied because of high-density gap states. However, irregularities of the thermal expansion in
boron carbide (151) are less well correlated than in boron.
At lower temperatures the electrical conductivity is consistent with Mott’s law of variable-
range hopping (Fig. 32) (143,144,152,153). The conductivity level seems to depend somewhat
on the preparation method, which may influence, e.g., the grain size of the sample. This could
624 Werheit
Figure 30 Electrical conductivity of boron carbide versus composition and temperature (143,144).
Figure 31 Electrical conductivity of boron carbide at high temperatures (16,145–150).

Figure 32 Electrical conductivity of boron carbide at lower temperatures plotted against T ⫺1/4 according
to Mott’s theory of variable-range hopping (143,144,152,153).
also be the reason for the conductivity of some samples reincreasing toward very low tempera-
tures. According to Möbius (154) and Abrahams et al. (155), it can be checked whether a unique
conductivity mechanism exists in a system, even if determining parameters of the system such
as chemical composition are modified. Figure 33 (140,143) confirms that for boron carbide this
is largely the case independent of chemical composition, temperature, and preparation technic.
Typical results for the Seebeck coefficient are plotted against temperature in Fig. 34
(147,148,149,153). Boron carbide is the only semiconductor known whose Seebeck coefficient
increases monotonously up to such high temperatures. This confirms that up to 2000 K the
transport is not intrinsic. Emin (14) attributes this behavior to a phonon-drag effect. However,
if the Fermi level is pinned within a kind of impurity band in the band gap of boron carbide,
the temperature-dependent broadening of the Fermi edge would explain this behavior at least
qualitatively in a more classical way as well (156).
The Hall effect of boron carbide is small (Fig. 35a and b). It depends on composition and
temperature (14,147–149). Because the calculation of the Hall mobility from the measured Hall
constant depends strongly on the electronic transport mechanism, which for boron carbide has
not yet been finally solved, the mobilities calculated after classical theories and shown in Fig.
35 are somewhat questionable. Hall effect and magnetoresistance were measured up to 15 T
(Figs. 36 and 37) (157). The behavior expected from classical theory was confirmed in a large
range, and for B ⬎ 13 T the magnetoresistance seems to indicate beginning Shubnikov–de Haas
oscillations. The transport parameters obtained are listed in Table 3.
The frequency dependence of the electrical conductivity and the dielectric function of
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Figure 33 Scaling of the electrical conductivity of boron carbide (143).
boron carbide has been measured by several authors (143,150,158). Figure 38 shows the typical
behavior, confirming hopping processes as an essential transport mechanism. In cases of suffi-
ciently high conductivities the influence extends up to the optical range. This is the case in
boron carbide as well, whose FIR reflectivity spectra increase considerably toward lower fre-
quencies like those of many other icosahedral boron-rich crystals (Fig. 39) (95). For the interpre-
tation of the transport mechanism in boron carbide it is essential that the dielectric function of
boron carbide in this frequency range can be fitted neither by hopping processes nor by a classical
Drude behaviour of free carriers alone. However, an excellent fit is obtained when a superposi-
tion of both mechanisms is assumed (Fig. 40) (75,110). From the plasma frequency obtained
from this fit and the carrier density derived in Table 3, the effective mass of holes in boron
carbide is estimated to be approximately equal to the free electron mass in vacuum. This is an
upper limit, because not the high-mobility part but the total DC conductivity is used to determine
the density of high-mobility carriers.
These results prove that in boron carbide, as in β-rhombohedral boron, a superposition
of both transport mechanisms is present. Depending on frequency, on temperature, or on other
experimental conditions, one of both mechanisms may prevail; however, a superposition of both
mechanisms must not be excluded.
It is well known that excess carbon in boron carbide precipitates as graphite (see, e.g.
Refs. 159–162) if the carbon content sufficiently exceeds the carbon-rich limit of the homogene-
ity range. However, there seems to be a narrow transition region close to the carbon-rich limit
of the homogeneity range where carbon is atomically dispersed when the samples are carefully
prepared, e.g., by melting. For example, in a sample with the atomic ratio C/(C ⫹ B) ⫽ 0.199
(see Refs. 147 and 148) there is an excess carbon concentration of 0.155 C atoms per unit cell
Figure 34 Typical results for the Seebeck coefficient of boron carbide depending on temperature (147–
149,153).
compared with the carbon-rich limit of the homogeneity range. It can be largely excluded that
this low excess carbon concentration is sufficient to form joined graphitic layers forming con-
ducting channels across the macroscopic sample. Nevertheless, this excess carbon content leads
to a conductivity behavior that is qualitatively different from that at the carbon-rich limit of
the homogeneity range. The activation energy of the conductivity tends to zero toward low
temperatures, suggesting the existence of a concentration-dependent metal-semiconductor transi-
tion (147,148). Obviously, this effect exists in carefully prepared largely homogeneous samples.
4. Other Properties Important for Electronic Applications

The thermal conductivity is important for many applications in semiconductor technology, e.g.,
for thermoelectric devices. In Fig. 41 the thermal conductivity of boron carbide is plotted versus
chemical composition (163–165). The strong decrease from B 4.3 C at the carbon-rich limit of
the homogeneity range toward more boron-rich compositions can easily be explained by the
change of the most homogeneous structure at B 4.3 C to the most distorted one at about B 6.5 C
shown in Fig. 26. For temperature dependence, see Ref. 166.
C. Other Representatives of the ␣-Rhombohedral Boron Structure Group

1. α-Rhombohedral Boron
The electronic transitions of α-rhombohedral boron derived from the decomposition of the ab-
sorption edge and its low-energy tail are listed in Table 4 (167). The third transition agrees with
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Figure 35 Hall mobility of carriers in boron carbide (a) versus reciprocal temperature and (b) versus
B/C relation (147–149). Temperature dependence of the mobility as derived from conductivity and
Seebeck coefficient for B 6.3 C (14) in (a) for comparison.
Figure 36 Hall constant of single crystal B 4.3 C in high magnetic fields (157).
Figure 37 Magnetoresistance of single-crystal B 4.3 C in high magnetic fields (157).

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Table 3 Transport Parameters of Boron Carbide (Composition Approximately

B 4.3 C) Obtained from Measurements in Magnetic Fields up to 15 T
Mobility (cm 2 V⫺1 cm⫺1)
Hall Carrier density
T(K) σ (Ω⫺1 cm⫺1) effect Magnetoresistance (cm⫺3)
77 2.5 ⫻ 10 ⫺4 37 20 2.1 ⫻ 10 13
293 5 ⫻ 10 ⫺1 0.8 1 3.9 ⫻ 10 17
results in Refs. 2, 168, and 169. With respect to the second transition, two alternatives could
not be distinguished without investigating the temperature dependence.
The experimentally obtained results are in satisfactory quantitative and partly qualitative
agreement with calculations by Bullett (79) yielding a minimum direct transition at 2.3 eV and
a minimum indirect transition at 1.7 eV. Density of states calculations of Switendick (170) yield
a gap of about 1.5 eV; calculations by Shirai and Nakamatsu (Fig. 8) (72) exhibit a nonzero
density of states at the Fermi level in a rather small gap. The rather low effective mass (Table
4) is in qualitative accordance with the carrier mobility of about 100 cm 2 V⫺1s⫺1 derived from
transport measurements (171).
Information on the electronic properties of α-rhombohedral boron is scarce; nevertheless,
it proves that its transport properties differ qualitatively, for example, from those of β-rhombo-
hedral boron and boron carbide. As discussed in Sec. III.B, the reason is the difference in the
Figure 38 Frequency dependence of the electrical conductivity of boron carbide. The solid lines are
fits based on Dyre’s model (143,150,158).
Figure 39 Far-IR reflectivity spectra of boron carbide for different chemical compositions versus wave-
number (95).
external bonds of the equatorial atoms of the icosahedra. The high mobility and the direct gap
are favorable for some technical applications.
2. Compounds with Pairs of Bonded Atoms on the Main Diagonal of the Unit Cell
Si, P, and As atoms form two-atom chains in the α-rhombohedral boron unit cell. Both atoms
in these chains are bonded to one another and saturate the external bonds of the equatorial atoms
of the icosahedra (17). As can be qualitatively concluded from their transparency in the visible
range, these compounds are semiconductors with rather large band gaps when they are pure
(172). Quantitative spectroscopic investigations of the interband transitions are scarce.
In the case of B 6 P it was shown that, when deposited of Si surfaces, a considerable amount
of Si atoms is incorporated in the structure, and probably a ternary compound is formed in
which the Si 2 chains in the unit cells are partly substituted for P 2 chains (173). Compared with
that of pure B 6 P (174), the absorption edge is considerable shifted toward lower energies
(Fig. 42).
3. Compounds with Pairs of Separate Atoms on the Main Diagonal of the Unit Cell
Be, O, and S atoms can be accommodated in pairs on the main diagonal of the rhombohedral
unit cell without essential bonding forces between them. Investigations of electronic properties
are largely missing. Only for B 6 O can some indirect conclusions based on IR-optical investiga-
tions be made (57,175). B 6 O is a semiconductor similar to boron carbide—the electrical conduc-
tivity is somewhat higher as indicated by the reflectivity—whose increase toward low frequen-
cies is distinctly stronger than that of boron carbide.
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Figure 40 Real and imaginary parts of the dielectric function of boron carbide in the far-IR range (B 6.2 C
as example). The theoretical fit demonstrates that both hopping and band-type conductivity must be consid-
ered for a satisfactory description (75,110).
D. Other Representatives of the ␤-Rhombohedral Boron Structure Group

1. SiB 14 [Structural Formula B 84 (B 7 Si 3) 2 Si]
Some investigations of the electronic transport properties have been performed by Pistoulet et
al. (176–180). The fundamental properties seem to be rather similar to those of β-rhombohedral
boron. The material is p type (181), the Hall mobility is small (⬍1 cm 2 V⫺1 s⫺1 ), the Seebeck
coefficient is maximum at about 400 K with 470 µ V K⫺1, and there is a dominating trapping
level with an activation energy of 0.39 eV (see Ref. 3 and references therein).
Ternary compounds with Fe, Co, and Ni, which probably have an SiB 14 structure, exhibit
n-type behavior at low temperatures changing to p-type with increasing temperature (182). The
transition temperature depends on the kind of metal atom.
2. B 32Al 3 [Structural Formula B 84 (B 6 Al 4) 2Al]

No results for the electronic properties of this compound are known.
E. ␣-Tetragonal Boron Structure Group

Only a few results for the electronic properties of members of the α-tetragonal boron structure
group are available, which are not sufficient for a complete description of one or a comparison
of several members of this structure group. The band gaps (Table 5) seem to be comparably
large.
The dielectric function of C 2Al 3 B 48 between about 0.5 and 40 eV was determined by
Figure 41 Thermal conductivity of the boron-carbon system versus carbon content (163–165).
Peshev et al. (183). Temperature dependences of electric conductivity and Seebeck coefficient
are reported by Karlamov anf Loichenko (184).
F. ␤-Tetragonal Boron Structure Group

Very limited investigations of the electronic properties of representatives of this structure group
have been performed. Some experimentally determined band gaps are listed in Table 6. Theoreti-
cal band structure investigations (79) for α-AlB 12 yield a band gap of about 2.6 eV. The gap
Table 4 Electronic Transitions of α-Rhombohedral Boron Determined by the

Decomposition of the Absorption Edge
Transition Density Reduced mass
No. energy (eV) Transition type of states 2m r /m e
1 0.73(2) Deep level to band 1.2 ⫻ 10 19
2a 1.49(2) Deep level to band 1.25 ⫻ 10 19
or
2b 1.63(2) Direct allowed interband 0.029
3 2.055(2) Direct allowed interband 0.034
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Figure 42 Absorption edge of B 12 P 2 deposited on silicon (173), with spectrum of pure B 12 P 2 after Slack
et al. (174) for comparison.
Table 5 Transition Energies of Some Representatives of the α-Tetragonal Boron

Structure Group
Compound Gap (eV) Method References
β-AlB 12 2.5 Optical and electrical (1,12,198)
C 2 Al 3B 48 ⬎3 Estimated from yellowish transparency (4)
Table 6 Transition Energies of Some Representatives of the

β-Tetragonal Boron Structure Group
α-AlB 12 ⬃0.4 Urbach tail (optical) (12)
1.9 Optical (185)
1.96 Optical (186)
2.2 Electrical (187)
Al 1.44Mg 0.65B 22 1.85 Optical (188)
1.92
2.01
Be mAl nB 12 2.12 Optical (169,198)
2.1 Electrical
of β-tetragonal B 192 is almost the same; however, there are two narrow bands of considerable
density within the gap.
G. Amorphous Boron
Investigations of the electronic properties of amorphous boron based on icosahedra are scarce.
Some results for the absorption edge are available and yield an absorption edge of about 0.7
eV (38,189,190). Investigations of transport properties are missing.
The IR and Raman-active phonon spectra exhibit pronounced maxima in the ranges of
the intraicosahedral phonons of crystalline icosahedral boron-rich structures and in particular
of the covalent intericosahedral BB bonds known from boron-rich solids. This confirms that
the external bonds of the icosahedra are largely covalent, similar to those of β-rhombohedral
boron. Therefore a certain relationship between the electronic properties seems possible.
There are indications that the electronic properties are considerably influenced by the
method of preparing the samples (38).
H. Orthorhombic Borides (MgAlB 14 Type)

The gap energy of the orthorhombic borides seems to depend strongly on the composition. Some
results are shown in Table 7.
Some results for an orthorhombic AlB 10 compound were obtained by Golikova et al. (191).
Detailed optical absorption spectra of some of the orthorhombic borides (Fig. 43) show
that the interband transition energies of these compounds are not far from those of β-rhombo-
hedral boron (for details, see Ref. 45). This seems to suggest that the energy band structures
of both groups of boron-rich solids do not differ essentially, at least as far as they are relevant
for the electronic transport.
It has been shown that the prevailing carrier type of β-rhombohedral boron can be changed
from p to n by interstitial doping. However, the degree of doping is limited by the number of
interstices available for the accommodation of suitable atoms or by the number of electrons
transferred from the metal atoms to the boron framework, probably because the structure be-
comes destabilized by higher electron transfer. The maximum concentration does not exceed a
few atomic percent, and even for vanadium, with the strongest doping effect, only weak n-type
conductivity can be achieved (10,109).
The orthorhombic borides may yield a way to extend the metal content of boron-rich
structures considerably. If complete occupation of the metal sites is assumed to be achievable,
which has been approximately realized in LiAlB 14, the metal content amounts to about 14 at.%,
Table 7 Minimum Interband Transition Energies of

Some Orthorhombic Borides
LiAlB 14 1.55 Optical (45)
NaB 15 0.32 Electrical (192)
MgAlB 14 0.99 Optical (45)
1.55
ErAlB 14 0.97 Optical (45)
1.30
For detailed results see also Refs. 2 and 4.
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Figure 43 Absorption spectra of some orthorhombic borides (45).
Figure 44 Seebeck coefficient of some orthorhombic borides at room temperature (45).

Figure 45 Electrical conductivity of YB 66 and DyB 66 versus T ⫺1/4 (195). YB 66 (a), twice zone melted;
YB 66 (b), once zone melted; YB 66 (c), polycrystalline technical material; DyB 66, polycrystalline, porous.
Figure 46 Seebeck effect of YB 66 (see Fig. 45a) versus temperature (196).

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Figure 47 Hall mobility of YB 66 versus reciprocal temperature (195). For sample characterization see
Fig. 45.
and the lower limit, which is obviously necessary to stabilize the structure, seems to be about
7.8 at.%, at least according to the compositions hitherto reported (45). In the case of MgAlB 14
with occupation densities of 78 and 75%, respectively, of the metal sites, a very high negative
Seebeck coefficient has been found (Fig. 44) (45).
I. YB 66-Type Structures
There is no doubt that the crystal quality of the YB 66 crystals presently available (47) is very
high, as they are suitable for use as monochromator crystals for synchrotron radiation (193).
Nevertheless, some essential physical properties of YB 66-type crystals seem to suggest a rather
close relationship to amorphous structures. This holds, e.g., for the thermal conductivity, whose
temperature dependence reminds one of glassy structures (194); for the electrical conductivity,
whose temperature dependence corresponds to Mott’s law of variable-range hopping (Fig. 45)
(195); and for the low-energy tail of the absorption edge, exhibiting an exponential dependence
of the absorption coefficient seemingly similar to the Urbach tail in amorphous semiconductors
(Fig. 46) (196). However, there is some evidence that the electronic band structure of YB 66 is
characterized by trapping levels of high density in the band gap similar, e.g., to the case of β-
rhombohedral boron (196). Although the sign of the Seebeck coefficient of YB 66 proves p-type
conduction up to 700 K (Fig. 47), the Hall coefficient changes sign in a certain range, which
obviously depends on the structural quality of the sample (Fig. 48) (195).
The properties of other compounds belonging to this structure group seem to be qualita-
tively similar and deviate only quantitatively to some extent (195–198) (for electrical conductiv-
Figure 48 Absorption edge of YB 66 (196).
ity see, e.g., Fig. 45). In this respect the question has remained open of how far these deviations
are due to the quality of the structure or to the composition only. The dependence of the elec-
tronic properties on the metal content within the homogeneity range seems to be proved: Investi-
gations of GdB 66 show that the conductivity and the Seebeck coefficient both increase with
increasing metal content (197,198).
J. Correlation Between Structural Defects and Electronic Properties

Recently the immediate correlation between the structural and electronic properties of some
icosahedral boron-rich solids has been proved and opened completely new aspects of understand-
ing the basic reasons for their specific properties.
The configuration interaction (CI) calculation by Fujimori et al. (201) on the icosahedral
B12H12 cluster representing the bonding of B12-icosahedra in β-rhombohedral boron and boron
carbide proved that the Jahn-Teller effect, distorting the regular icosahedron to the D3d-Symme-
trie, causes a separation between ground and first excited state of about 1.5 eV. As shown, this
value is close to the typical band gaps of many icosahedral boron-rich solids, which seem to
be accordingly explained; however, it considerably exceeds the energetical distance between
the actual valence band and the split-off band in β-rhombohedral boron (see Fig. 14). Hence
its attribution to the Jahn-Teller effect could not be maintained and its identification required
new considerations.
In the former discussions of electronic properties summarized in this chapter the influence
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of structural defects has not been considered; they were assumed to be unsystematic or caused
by insufficient preparation methods. However, in reality, careful fine-structure investigations
indicate that, apart from α-rhombohedral boron, the structures of the other icosahedral boron-
rich solids contain appreciable concentrations of well-defined defects in the form of incomplete
occupations of specific atomic sites or of antisite defects. At least in many cases, insufficient
preparation methods can be excluded as the reason for these defects. This suggests that the
defects are fundamental peculiarities of the icosahedral boron-rich structures (202).
Examples of such defects are:
1. α-rhombohedral boron structure group (idealized structure formulas B12X 2 or B12X 3
(X ⫽ B or specific non-B atoms in two-atom or three-atom arrangements on the
trigonal axis of the rhombohedral unit cell)): incomplete occupied sites in the chains
(16,17,22,60,134,203–205).
In α-rhombohedral boron the two different atomic sites B(1) and B(2) are com-
pletely occupied, and hence the defect concentration is zero.
In boron carbide the concentrations of B12 and B11C icosahedra and of CBB and
CBC chains vary, and chainless unit cells occur when the composition deviates from
the carbon-rich limit B 4.3 C of the homogeneity range (204). According to Kleinman
et al. (206,207) B13 C2 with the structure formula B12 (CBC) is the most energetically
favorable structure. When it is therefore taken for reference, based on the 42% B12
icosahedra 58% B11C icosahedra, 62% CBC chains, 20% CBB chains and ⬃19%
missing chains experimentally determined by Kuhlmann et al. from phonon spectros-
copy (53,204), the defect concentration in B13 C2 is about 9.3 at.%.
2. β-rhombohedral boron structure group (idealized structure formula (B12) 4(B 28) 2 B or
B 84 (B10) 2 B): The regular B(13) position is occupied by 74.5(6)% (208) and the sites
B(16)-B(20) by 27.2%, 8.5%, 6.6%, 6.8% and 3.7% (in total 1.7 B atoms per unit
cell), respectively (209). This leads to an intrinsic point defect density of about 4.9
defects per unit cell (⬃4.7 at.%) (10,25,209).
3. α-tetragonal structure group (idealized structure formula (B12) 4 X 2Y2): missing or in-
complete occupation of the X, Y sites (210).
4. β-tetragonal structure group (idealized structure formula (B 21⋅2B12) 4 (X mYn)): missing
or incomplete occupation of X,Y sites, two missing B sites in B 21 double-icosahedra
(B19 in α-AlB12) (210).
5. orthorhombic MgAlB14 type compounds (idealized structure formula (B12) 4 Me(1) 4
Me(2) 4 B 8): incomplete occupation of the Me(1) and Me(2) sites, possibly incomplete
occupation of the non-icosahedral B sites (see Ref. 45 and references therein).
6. YB 66 type structures (idealized structure formula Y48⋅((B12)13) 8⋅(B 80) 8): The occupan-
cies of the sites B(10)–B(13) in the nonicosahedral B 80 unit of YB66 are 72, 65, 31
and 22% respectively leading to an actual number of ⬃42 B atoms in this B 80 unit
(211). Accordingly, the average defect concentration in the whole structure is 17 at.%.
Table 8 shows that, for α-rhombohedral boron, β-rhombohedral boron and boron carbide, the
electron deficiencies determined by electronic band structure calculations are correlated with
the densities of defects in the structures. Since calculations of the electronic properties of defects
in icosahedral boron-rich solids are missing, the following assumptions (202) were made in
accordance with general results obtained on defects in semiconductors.
1. Electronic Structure of β-Rhombohedral Boron

In the rhombohedral unit cell, there are 1.52 vacancies (partially occupied B(13) sites) and 3.38
interstitial atoms (weakly occupied sites B(16)–B(20)). Bullet (208) calculated for the idealized
Table 8 Calculated Electron Deficiencies for the Valence Bands of Idealized Crystal Structures and
Experimentally Determined Point Defect Concentrations in the Real Crystals
Idealized crystal structure Real crystal structure
Valence Electron Electronic Electronic Intrinsic
Valence states electrons deficiency character character point defects
[(unit cell)⫺1] [(unit cell)⫺1] [(unit cell)⫺1] (theoretical) (experimental) [per unit cell]
α-rhombohedral boron
36 [212] 36 0 Semicond. Semicond. 0 [3]
β-rhombohedral boron
320 [208] 315 5 Metal Semicond. 4,92(20) [209]
Boron carbide
B13 C 2 (idealized structure formula B12 (CBC))
48 [137] 47 1 Metal Semicond. 0,97(5) [53,204]
B 4,3 C (idealized structure formula: B11C (CBC))
48 [137] 47 0,17 Metal Semicond. 0,19(1) [53,204]
Hypothetical B 4 C (idealized structure formula: B11C (CBC))
48 [137] 48 0 Semicond. — — —
structure (sites B(1)–B(15) fully occupied, B(16)–B(20) unoccupied) 320 valence band states
occupied by 3 ⫻ 105 ⫽ 315 valence electrons. Hence the deficiency is 5 electrons.
Based on the properties of point defects, for each B(13) vacancy 3 electronic states and
three electrons are separated from the valence band. Moreover, 6 ⫻ 1/2 ⫽ 3 occupied localized
electronic states from the surrounding B atoms additionally reduce the number of regular valence
states by 3. In total, for each vacancy, 6 electronic states and 6 electrons are removed from the
valence band. However, the 3 electrons in the localized states may fall down into the more
energetically favorable unoccupied valence band states. Hence, from the 1.52 B(13) vacancies
per unit cell, 3 ⫻ 1.52 ⫽ 4.56 unoccupied localized states are generated. Compared with the
calculated deficiency of 5 valance electrons this would satisfactorily explain the semiconducting
character of β-rhombohedral boron.
Taking B(16)–B(20) as interstitial sites, in total there are 3 ⫻ 1.52 ⫹ 3 ⫻ 3.38 ⫽ 14.70
electrons per unit cell available compared with the valence electron deficiency of 5. Assigning
an error of only 2% to the site occupation densities determined by X-ray fine structure investiga-
tions, the completely occupied valence band leaves 10 electrons per unit cell to be distributed
on localized gap states originating from the B(13) vacancies or from interstitial B(16)–B(20)
states. If one assumes that the B(13) vacancy generates a gap state, which can be occupied by
two paired electrons, similar to the vacancy V⫹⫹ state in silicon (213,214), the number of intersti-
tial B(16)–B(20) atoms exactly corresponds to the number of unoccupied sites in this orbital.
If single ionization of the interstitial B atoms is assumed, the valence band and the B(13) vacancy
orbitals are exactly filled up.
That assumption easily explains the density of paramagnetic centers (about 1015 cm⫺3
(215), which is very low compared with the defect concentration (about 10 20 cm⫺3) and can
only be appreciably enhanced by heating or optical excitation (216,217). Moreover, it is consis-
tent with the charge transport in β-rhombohedral boron (see section A.3).
2. Electronic Structure of Boron Carbide
The idealized, most energetically favorable structure of boron carbide B13 C 2 (structure formula
B12 (CBC)) (206,207) was taken for reference to determine the composition dependent electron
deficiency and the concentration of structural defects (202).
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Band structure calculations of B13 C 2 yield 48 electronic states per unit cell in the valence
band, while the number of valence electrons depends on the carbon content. For B13 C 2 47 and
for B12 C 3 (structure formula B11C(CBC)) 48 valence electrons per unit cell are available (137).
The structural defects are antisite defects in the form of B11C icosahedra (donors) and
CBB chains (acceptors) and vacancies in the unit cells with missing chains. For chainless unit
cells, the following configurations have been taken into consideration: (i) α-rhombohedral bo-
ron-like, (i.e. no atom on the trigonal axis); (ii) B䊐B arrangements (䊐, vacancy) on the trigonal
axis with two separated B atoms and vacant B(3) site (B(3), central chain site), based on phonon
spectroscopy (53,204); (iii) B䊐B arrangements, based on reaction kinetics (132); (iv) vacancy
of B(3), no specification of the chain end atoms, derived from neutron diffraction (205). The
B䊐B configuration, that was shown to be the most probable one, yields two localized states
and two acceptors separated from the valence band.
Taking as the only experimental parameter the CBC to CBB relation from phonon spec-
troscopy (53,204), the CBC, CBB and B䊐B concentration were calculated (Fig. 49). Subse-
quently the concentrations of B12 and B11C icosahedra (Fig. 50) immediately follow from the
stoichiometry of the compound. The calculated B䊐B concentrations agree with the concentra-
tions of B(3) vacancies determined by neutron diffraction. Compared with Fig. 26 (based on
absolute oscillator strengths experimentally determined) the results in Fig. 49 and 50 (based on
the quotient of oscillator strengths) show remarkable differences in the more boron-rich range
only. The results in Figs. 49 and 50 are more reliable because in the quotient, systematic experi-
mental error is largely eliminated (for details see (202)).
At B 4.3 C the electron deficiency is exactly compensated by the obviously intrinsic concen-
tration of CBB chains and proves that electronic reasons are responsible for this composition
being the carbon rich limit of the homogeneity range that was previously experimentally deter-
mined by microprobe investigations (107,218).
Figure 49 Calculated densities of atom arrangements on the trigonal axis of the rhombohedral unit cell
of boron carbide (CBC and CBB chains, B䊐B arrangements); solid symbols (202); diamonds, B(3) vacan-
cies (B(3), center of the three-atom chain) determined by neutron scattering (205). Calculated valence
electron deficiency for comparison.
Figure 50 Density of B12 and B11C icosahedra calculated from the densities of the atoms on the trigonal
axis (Fig. 1) and the stoichiometry of the samples (202).
3. Electronic Structure of YB66

Unfortunately, there are no calculations of the electronic band structure available. However, the
high defect concentration of 17 at.% is at least qualitatively correlated with the very strong tail
of the absorption edge (Fig. 48) exceeding that of boron carbide by far.
The shown possibility to exactly explain the structural defects of some icosahedral boron-
rich solids by the electron deficiency considerably raises the estimation of the theoretical band
structure calculations, hitherto essentially based on the more or less significant shortage of agree-
ment with experimental results. Calculations of the electronic orbitals of defects are desirable
to improve the quantitative understanding of the different defects. It seems that, on one hand,
the electron deficiency is the driving force for the generation of structural defects in the icosahe-
dral boron-rich solids in general, and on the other hand, the influence of these defects on the
electronic properties is a main reason for their peculiar properties.
V. CONCLUSION
The boron-rich solids with icosahedral structures are semiconductors with unique electronic
properties, which are essentially determined by the icosahedra as general structural elements.
This implies an interrelation of their properties, which can be modified within sometimes large
homogeneity ranges of chemical compositions by forming ternary compounds, by changing the
chemical composition within the specific structure groups, and by going to the different structure
groups.
Accordingly, the icosahedral boron-rich solids offer an excellent chance to study the elec-
tronic properties of complex structures and their modification by slight and considerable changes
of composition and structure. Some highlights of these properties with particular interest for
fundamental research are the Jahn-Teller effect in the icosahedra; the formation of intrinsic
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traps by electron-phonon interaction; the correlation between electron deficiency and structural
defects; the soliton-type transport of electrons and holes; the very long lifetime of electrons under
specific, externally controllable conditions; the electronic interaction between foreign atoms and
the boron framework; and the high, monotonously (up to very high temperatures) increasing
Seebeck coefficient of boron carbide.
For technical application, the high melting point, the great hardness, and the strong resisti-
vity to chemical attack are of fundamental importance. The specific electronic structures make
the boron-rich solids rather insensitive to influences of foreign atoms at concentrations that
already change the semiconductor properties of classical semiconductors decisively. Neverthe-
less, doping is possible in principle, indeed at higher concentration levels. This makes the mate-
rial preparation much easier and less expensive than in the case of the classical semiconductors.
The only electronic property that is already at the threshold of technical application at
present is the high Seebeck coefficient just mentioned for high-efficiency direct thermoelectric
energy conversion and measurement of very high temperatures under extreme conditions. More-
over, general application for high-temperature electronic devices and at least in some structure
groups for wide-gap semiconductors seems promising.
Boron, aluminum, and gallium belong to the same group of the periodic table. Accord-
ingly, they have the same number of valence electrons, and therefore similarities of the crystal
structures and of the electronic structures as well should be expected. However, in the case of
aluminum and gallium, no elementary crystals with icosahedral structures have become known.
Nevertheless, these elements, too, generate icosahedra, namely in quasi-crystalline structures,
and Kimura et al. (199) have pointed to the structural similarities to the boron-rich solids. The
relation between their electronic properties has been proved by Werheit et al. (200), and hence
the aluminum- and gallium-based quasi-crystals may provide a further opportunity to utilize the
variation of electronic properties in icosahedral structures.
ACKNOWLEDGMENTS
At first I should like to thank the numerous students who have worked during the years in my
laboratory at the Gerhard-Mercator University of Duisburg and in particular the graduate scien-
tific coworkers Dr. Richard Franz, Dr. Udo Kuhlmann, Roland Schmechel, and Frank Kummer
for their effective cooperation, which was an essential basis for our scientific progress. I am
obliged to Prof. T. Lundström, Uppsala, Dr. I. Higashi, Wako, Dr. K.A. Schwetz, Kempten,
Asst.-Prof. Dr. Kimura, Tokyo, Dr. T. Tanaka and Dr. Y. Ishizawa, Tsukuba, Prof. V.N. Gurin
and Dr. M.M. Korsukova, Sankt Petersburg, Dr. Y. Paderno, Kiev, Dr. K. Shirai, Osaka, and
Prof. Y. Kumashiro, Yokohama, for providing samples, for interdisciplinary cooperation, and
for stimulating scientific discussions, which have made a large part of the work summarized in
this chapter possible. I acknowledge the provision of samples and material by the Consortium
für Elektrochemische Industrie (Wacker-Chemie) Munich, Elektroschmelzwerk Kempten, and
H.C. Starck, Goslar and Laufenburg, and I am grateful to the Deutsche Forschungsgemeinschaft,
the Ministry of Research and Technology of the FRG, and the Ministry of Science and Research
of the Nordrhein-Westfalen Region for financial support.
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24
Boron Films
Katsumitsu Nakamura
Nihon University, Setagaya-ku, Tokyo, Japan
I. INTRODUCTION
A large number of detailed studies of the properties of boron have been done by Werheit as
shown in Chapter 23. These studies have been carried out with bulk boron samples (mainly
single crystals). However, high-purity bulk samples are hard to obtain and that is an obstruction
for studies. In order to solve the problem, studies using film samples, which are easier to obtain
than single crystals, are considered. In the application of boron, the film form is more advanta-
geous than the bulk form.
Elemental boron is an interesting material because, at the same time, it has low density
(d ⫽ 2.35 g cm⫺3 ), is refractory (T m ⫽ 2075°C), has high hardness (H v ⫽ 3000 kg) and is
resistant to corrosion. It also has a high mechanical strength and a high capture section for
neutrons. Moreover, it is one of the elemental semiconductors. However, the resistivity of boron
is several hundred times larger than that of Si and Ge at room temperature. Although many
studies (1–3) of the properties of boron have been done, the physical properties reported are
not in agreement with each other because it is very difficult to obtain high-purity bulk boron.
However, we can obtain pure and uniform boron in film form. In the form of films, boron has
many potential applications, such as infusion reactor wall components or semiconductor films.
In particular, the first wall and limiter coatings in fusion reactors are very promising candi-
dates (4,5).
Many methods have been developed for preparing boron films. Hydrogen reduction of
volatile boron halides (such as BBr 3 or BCl 3 ) is a convenient method for producing boron films.
This technique has been extensively studied for some time.
Preparative methods for boron films have been developed and must be used properly.
However, contamination with halogens generated by reduction of the halogenide compound in
the case of CVD and with residual gas in the vacuum chamber in the case of evaporation and
sputtering prevents the formation of high-purity boron films. A preparative method using dibor-
ane and decaborane is superior to the preceding method. In particular, it is easier to prepare
high-purity boron films with decaborane than with diborane, which is hard to handle at present.
Boron films have been prepared by means of chemical vapor deposition (6–8), vacuum
evaporation using electron bombardment of boron (9–11), and sputtering of a boron target. The
several methods mentioned are summarized in Table 1.
Croft (26) has obtained high-purity boron films by pyrolysis of diborane.
However, diborane is a very dangerous gas that requires much care in handling. Pentabo-
655
656
Table 1 Preparations of Boron Films Developed Until Now

No. Method Source Activate Sub. temp. (°C) Substrate Purpose Film Year Ref.
1 Evapo Boron Electro-bombered Electrical properties Amorphous 1970 12
2 Evapo Boron Electro-bombered 450 Fused silica Characterization Amorphous 1975 13
3 CVD BCl 3 Resistive heat 930–950 Mo, silica Characterization Amorphous 1976 8
4 CVD BCl 3 RF heat 950–1200 Graphite, iron Preparation Amorphous 1976 6
6 CVD B2H6 RF heat 400–900 Graphite Fusion reactor α,β-rhombo., tetra. 1979 14
7 CVD B2H6 DC glow 150–350 Fused silica Electrical Amorphous 1980 15
10 CVD B2H6 RF heat, RF glow 150–500 Graphite Reduce the prep. temp. Amorphous 1981 16
11 Evapo. Boron Carbon crucible 260–420 Glass, mica Mechanical properties Amorphous 1982 17
12 Sputter CVD Boron DC glow RF glow Photoconductivity a-B:H 1984 18
B2H6
14 Evapo. Boron Electro-bombered Soft X-ray filter 1000 Å 1985 19
15 CVD BCl 3 RF heat 777–1227 Graphite Preparation β-rhombohedral 1985 20
16 CVD BBr 3 MW plasma 300–650 Graphite Reduce the prep. temp. Amorphous 1990 21
17 Sputter Boron Magnetron room Quartz, glass Multilayer Amorphous foil 1990 22
18 CVD B2H6 ECR 230–400 Quartz, Si Characterization Amorphous 1900 23
19 CVD BCl 3 RF heat 827–1227 Mo, Ti foil Crystallization Amorph., α-rhombo 1991 24
21 CVD B 10 H 1 DC glow 70–400 Stainless steel Fusion reactor 700–900 Å 1993 4
23 CVD B2H6 RF glow 300–800 Quartz, Si, sapphire Preparation Polycrystal. 1994 25
Nakamura
Boron Films 657
Figure 1 The purification apparatus used for decaborane.
rane (B 5 H 9 ; ⫺46.5°C melting point, 60°C boiling point) and decaborane (B 10 H 14 ; 99.6°C mp,
213°C bp) can be used as alternative boron hydride sources. Decaborane is safer and more stable
than pentaborane and diborane. Furthermore, decaborane has advantages as a source material
for boron films because high-purity decaborane is easy to obtain by a sublimation purification
process (Fig. 1).
Many studies of the electrical (8,14,27,28) and optical (10,11,14,29) properties of boron
films prepared by vacuum evaporation (28,29) and chemical vapor deposition (CVD) (7,14)
have been reported. However, the properties reported scatter widely (e.g., the values of electrical
conductivity and optical gap energy at room temperature).
In this chapter, method for preparing high-quality boron films by pyrolysis of decaborane
in the molecular flow region at temperatures between 350 and 1200°C is described. The deposi-
tion mechanism is discussed in terms of the dependence of the deposition rate on the substrate
temperature and the impingement frequency of decaborane molecules onto the substrate surface.
The temperature dependences of the electrical conductivity and of the thermoelectric
power of boron films deposited on sapphire substrates have been measured. The energy band
gap and optical constant (n, k) of boron have been estimated from the results for optical transmit-
tance and reflectance in the visible and infrared spectral regions.
In this chapter, preparation of boron films by pyrolysis of decaborane is discussed and
properties of the boron films deposited are described,
II. PREPARATION
A. Deposition
A schematic diagram of the apparatus used in this preparation is shown in Fig. 2. The vacuum
chamber was evacuated with an oil diffusion pump system, and the ultimate pressure was 2 ⫻
10⫺6 torr. Sapphire and silicon were used as the substrates. The substrate was fixed on the
tungsten sheet heater (0.05 mm thick) and was heated from 600 to 1200°C (Fig. 3). A tantalum
sheet was also used as a substrate and was heated between 350 and 700°C by direct resistance
heating. The sapphire substrate temperature was estimated from the heater temperature, which
was measured with an optical pyrometer. The relation between the substrate and heater tempera-
658 Nakamura
Figure 2 Schematic diagram of the apparatus used for deposition of boron films by pyrolysis of deca-
borane.
Figure 3 Assembly of the substrate and the heater.

Boron Films 659
tures was previously obtained. The tantalum substrate temperature was measured directly with
a welded thermocouple.
Decaborane (Arfa Product) was sublimated by heating at about 70°C and was introduced
into the vacuum chamber through a variable leak valve. Boron films were deposited on the
heated substrate by thermal decomposition of the decaborane.
The pressure of decaborane was measured as a corresponding nitrogen pressure by a B-
A-type ionization gauge and was kept between 1 ⫻ 10⫺5 and 2 ⫻ 10⫺4 torr. Deposition time
varied from 0.5 to 60 min, depending on the gas pressure and the substrate temperature.
B. Analysis
The thicknesses of the films on the sapphire substrates were measured with a multiple-beam
interferometer and ranged from 442 to 4740 Å. In the case of the films deposited on tantalum,
the film thickness could not be measured optically because of the rough surface of the tantalum
substrate. The thickness of boron films on tantalum substrates was estimated from the measured
X-ray fluorescence of boron deposited using electron probe microanalysis (EPMA) with a 7-
kV acceleration voltage, a 0.1-µA sample current, and a 100-µm beam diameter. The relation
between the X-ray intensity and the film thickness was previously obtained using boron films
on a sapphire substrate.
The crystal structure of boron films was studied by reflection electron and X-ray diffraction
techniques. The electrical conductivity and its temperature dependence were measured by a two-
probe technique at temperatures ranging from 300 to 1000 K in vacuum. A gold film, deposited
on the boron films by vacuum evaporation, was used as an electrode. Thermoelectric power of
the films was measured by using a Pt-PtRh (10%) thermocouple that was 0.2 mm in diameter.
The distance between two thermocouples was 10 mm (Fig. 4). The boron films measured were
5 ⫻ 13 mm2, and the film thicknesses were 1.2 and 1.5 µm. The thermoelectric power could
not be measured below 250°C because it was too small in comparison with the electrical noise
in this temperature range.
Transmission and reflection spectra of the boron films on sapphire were measured over
a wavelength range 200–2500 µm using an MPS-50 (Shimazu) spectrophotometer. In the trans-
mission and reflection measurements, an uncoated sapphire and an evaporated aluminum film
were used as the references, respectively. Absorption coefficient, refractive index, and extinction
coefficient of the boron films were calculated from the measured transmittance and reflectance
at normal incidence.
Infrared transmittance at normal incidence on boron films deposited on high-resistivity
silicon wafers was measured in the wavelength range 2.5–50 µm using a DS-701G (Jasco)
infrared spectrophotometer.
III. RESULTS AND DISCUSSION

A. Deposition Rate
The influence of the deposition parameters on the deposition rate is as follows. The deposition
rate of boron, D (Å/s), is linearly dependent on the decaborane pressure P (torr), as shown in
Fig. 5, and is given by D ⫽ 3.57 ⫻ 10⫺3 P for substrate temperatures of 750 and 1000°C.
It is thought that the deposition rate of boron films obtained by pyrolysis of decaborane
depends on the impingement frequency of decaborane on the substrate. From gaseous molecular
dynamics, the impingement frequency S of decaborane on the substrate surface is given by
660 Nakamura
Figure 4 Electric motive force measurement apparatus.

Boron Films 661
Figure 5 Deposition rate of pyrolytic boron films as a function of B 10 H 14 pressure. The films were
deposited at substrate temperatures of T s ⫽ 750°C (䊉) and T s ⫽ 1000°C (䊊).
S ⫽ P (M2π/RT g ) 1/2 ⫽ 5.8 ⫻ 10⫺2P(M/T g ) 1/2 (g/cm2 ⋅ s) (1)

where R ⫽ 62.36 torr ⋅ l/mol ⋅ deg is the gas constant, P is the decaborane pressure in torr, M
is the molecular weight of decaborane, and T g is the gas temperature considered to be at room
temperature (i.e., T g ⫽ 300 K).
The rate of chemisorption depends on the impingement frequency S of the decaborane
molecules on the surface, the condensation coefficient γ, and the fraction of collisions that take
place at available sites f (θ), where θ is the fractional surface coverage. The rate of chemisorption,
U is given by
U ⫽ Sγf (θ) exp (⫺E a /RT s ) (2)
where T s is the substrate temperature and E a is the activation energy for chemisorption.
As shown in Fig. 5, the deposition rate is independent of temperature, and the chemisorp-
tion is nonactivated; hence, the activation energy E a ⫽ 0. Under the experimental conditions,
we suppose that f (θ) ⱌ 1 and γ ⱌ 1; hence, the rate of chemisorption is equal to the impingement
frequency S. The theoretical deposition rate D t , in this high temperature range is
D t ⫽ 1.66 ⫻ 10⫺2P(cm/s) (3)
taking into account the ratio of boron weight to decaborane molecular weight (0.9) and the
density of boron (2.0 g/cm 3 ). Comparison with the experimental values of Fig. 5 shows that
662 Nakamura
D t must be multiplied by a factor of 0.22. This factor is due to either f(θ), γ, or the sensitivity
difference of decaborane and nitrogen in the ionization gauge.
Figure 6 shows the temperature dependence of the deposition rate of boron films in the
temperature range 350–700°C at two decaborane partial pressures, 2 ⫻ 10⫺5 and 8 ⫻ 10⫺5 torr.
In each case, the deposition rate increases steeply with an increase in temperature up to 416°C
and then saturates.
In the low-temperature range at T s ⫽ 416°C, the activation energy is found to be 39 kcal/
mol from the slope, and the deposition rate is given by
D ⫽ 7.16 ⫻ 10 9 P exp(⫺39,000/RT s ) (cm/s) (4)
The saturated deposition rate above 416°C can be explained by Eq. (2). The activation
energy of 39 kcal/mol is in agreement with 41.4 kcal/mol (30) and 41.6 ⫾ 0.5 kcal/mol (31),
both reported for the activation energy of the decomposition of decaborane at temperatures
below 250°C.
Figure 6 Logarithm of the deposition rate divided by the decaborane pressure as a function of reciprocal
absolute temperature of the substrate. The films were deposited at decaborane pressures of P ⫽ 2 ⫻ 10 ⫺5
torr (䊉) and P ⫽ 8 ⫻ 10 ⫺5 torr (䊊).
Boron Films 663
Figure 7 X-ray diffraction pattern of a pyrolytic boron film.
B. Characterization of the Films (Structure, Impurities)

The X-ray diffraction pattern of a boron film deposited on sapphire at a substrate temperature
of 700°C and a decaborane pressure of 2 ⫻ 10 ⫺5 torr for 15 min is shown in Fig. 7. The X-
ray and electron diffraction analysis indicates that the films are amorphous.
The electron spectroscopy for chemical analysis (ESCA) spectrum of the boron film depos-
ited at a decaborane pressure of 4.4 ⫻ 10 ⫺5 torr and a substrate temperature of 700°C is shown
in Fig. 8. The figure shows the spectrum of the film before and after ion etching. The peaks at
Figure 8 ESCA spectra of a pyrolytic boron film.

664 Nakamura
Table 2 ESCA Data for a Boron Film Deposited at a B 10 H 14 Pressure of 4.4

⫻ 10 ⫺5 torr and a Substrate Temperature of 700°C
Intensity (arbitrary units)
Sample Boron Carbon Oxygen C/B O/B
As deposited 95 28 6.1 0.298 0.065
After argon etching 131 12 5.7 0.092 0.044
Table 3 Data for Boron Films Analyzed by EPMA
Characteristic
B 10 H 14 Deposition
x-ray intensity (CPS)
pressure rate
(torr) (Å/s) Boron Carbon C/B
2 ⫻ 10 ⫺5
7 1740 18 0.0103
4 ⫻ 10 ⫺5 14 1020 6 0.0059
1 ⫻ 10 ⫺4 33 1320 4 0.003
binding energies of 191, 288, and 512 eV correspond to boron 1s, carbon 1s, and oxygen 1s,
respectively. The amounts of carbon and oxygen at the surface were estimated from the observed
peak intensities multiplied by the photoionization cross-section factor (B, 0.486; C, 1.00; O,
0.293) and are shown in Table 2. The table shows that oxygen decreased little on ion etching,
even though the apparent carbon content decreased to almost one third its original value. These
results indicate that it is difficult to remove oxygen from the film surface by ion etching alone.
The boron films were analyzed by EPMA because this method was not influenced by surface
impurities. The amounts of impurities in three films deposited on sapphire substrates at decabor-
ane pressures of 1.4 ⫻ 10 ⫺5, 3.3 ⫻ 10 ⫺5, and 4 ⫻ 10 ⫺5 torr are shown in Table 3. This table
shows that carbon decreases with increasing deposition rate. Oxygen impurities in boron films
on sapphire substrates cannot be analyzed by EPMA because the primary electrons penetrate
the film and extend into the oxygen-bearing substrate. On the contrary, no oxygen was found
in the films on tantalum substrates by EPMA.
The EPMA and the ESCA analyses suggest that oxygen impurities localized near the
surface are due to the exposing air, while carbon impurities are incorporated in the films from
a residual gas.
C. Electrical Properties
The conductivities of boron films as a function of reciprocal absolute temperature are shown
in Fig. 9. Conductivity varied from 3 ⫻ 10 ⫺3 S ⋅ cm ⫺1 at room temperature to 30 S ⋅ cm ⫺1 at
1000 K. The conductivity at room temperature is in agreement with that for amorphous boron
films deposited by CVD and vacuum evaporation (1 ⫻ 10 ⫺3 S ⋅ cm ⫺1 ) (28) but much larger
than that of single crystals (⯐ 10 ⫺6 S ⋅ cm ⫺1 ) (32,33).
The conductivity decreases slightly with increasing deposition temperature and is not af-
fected by the carbon impurities.
Generally, the conductivity of semiconductors in the intrinsic conduction region is
written as
Boron Films 665
Figure 9 Temperature dependence of the conductivity of pyrolytic boron films. The films were deposited
at substrate temperatures and B 10 H 14 pressures of T s ⫽ 700°C and P ⫽ 1.4 ⫻ 10 ⫺5 torr (䉱), T s ⫽ 700°C
and P ⫽ 2 ⫻ 10 ⫺5 torr (䊉), T s ⫽ 800°C and P ⫽ 3.3 ⫻ 10 ⫺5 torr (■), and T s ⫽ 750°C and P ⫽ 1.5 ⫻
10 ⫺5 torr (䊊).
666 Nakamura
σ ⫽ σ 0 exp(⫺E g /kT ) (5)
where σ 0 is a constant, E g is the band gap energy, k is the Boltzmann constant, and T is the
absolute temperature. The E g can be determined from the slope of the straight line in the plot
of log σ 0 against 1/T. By applying this method to Fig. 9, we obtained E g ⫽ 1.07 eV. This value
is in agreement with values reported for amorphous boron films (1.0–1.16 eV) (14,34,35) but
is smaller than those for polycrystalline and single-crystal boron (1.3–1.4 eV) (35–37). On the
other hand, because the boron films obtained are amorphous, the electric conduction is consid-
ered to be hopping conduction. Mott (38) has derived the equation for hopping conduction,
σ ⫽ σ 0 exp(⫺(T 0 /T) 1/4 ) (6)
where σ 0 and T 0 are constants.

Plots of log σ of the boron films as a function of T1/4 are shown in Fig. 10. The observed
values show a good linear relation between log σ and T1/4, and values of σ 0 ⫽ 3.2 ⫻ 10 11 S ⋅
cm and T 0 ⫽ 3.5 ⫻ 10 ⫺8 K are obtained. According to Mott, T 0 is given as a function of the
density of localized states at the Fermi level, N (E F ),
T 0 ⫽ 16 ε 3 /kN (E F ) (7)
where ε is the exponential decay factor of localized states (ε⫺1 ⱌ 5 Å) (8), and k is the Boltzmann
constant. From the value of T 0 and Eq. (7), N(E F ) ⫽ 3.8 ⫻ 10 18 cm ⫺3 ⋅ eV⫺1 is obtained. This
value is in agreement with the value for amorphous boron films, 5 ⫻ 10 17 –10 19 cm 3 ⋅ eV⫺1 (8),
and the value for amorphous bulk, ⱌ10 18 cm ⫺3 ⋅ eV⫺1 (39). As already mentioned, the conduction
of the boron films can be explained successfully by two conduction mechanisms. We cannot
decide which mechanism is valid within our experimental accuracy.
Figure 11 shows the temperature dependence of the thermoelectric power of the films
with the results obtained up to now. The films obtained in this experiment show p-type conduc-
tion. The thermoelectric power increases rapidly from 107 µV deg⫺1 at 230°C to a maximum
value of 400 µV deg⫺1 at 427°C; it then decreases gradually to 310 µV deg⫺1 at 730°C. As the
positive carrier concentration increases with increasing temperature, the thermoelectric power
also increases with increasing temperature. However, at higher temperature, the thermoelectric
power decreases with increasing temperature because the hole mobility decreases. Values of
the thermoelectric power reported for bulk boron (32,33,43) show a large peak at a lower temper-
ature, compared with those for the boron films we obtained (420 µV at 700 K). These results
can be explained by the assumption that the concentration of the impurities or defects in the
boron films should be much higher than that in bulk boron. Johnson and Lark-Horonitz (44)
have explained the same results for germanium by the higher concentration of aluminum.
The figure of merit for thermoelectric materials, Z, is given as
Z ⫽ r 2σ/κ(deg⫺1 ) (8)
where r is the thermoelectric power, σ is the electrical conductivity, and κ is the thermal conduc-
tivity. The thermal conductivity of boron is assumed to be 0.05 W ⋅ cm ⫺1 ⋅ deg⫺1 (45,46).
Figures of merit of the boron films as a function of temperature are shown in Fig. 12.
The value Z increases steeply with an increase of temperature. However, the Z values of the
boron films are smaller than those reported for the amorphous bulk material (47). A figure of
merit higher than 10 ⫺3 deg⫺1 is required for the material of a practical thermoelectric converter.
Figure 12 suggests that boron films deposited by pyrolysis of decaborane are useful for thermo-
electric devices at over 2000 K.
Boron Films 667
Figure 10 Dependence of conductivity S on T1/4; symbols correspond to those in Fig. 9.

668 Nakamura
Figure 11 Temperature dependence of the thermoelectric power. Numbers are listed in Table 4.
D. Optical Properties
The absorption coefficient of the boron films, α, is shown in Fig. 13 as a function of incident
photon energy hν. The absorption coefficient increases rapidly at about 1.3 eV.
It is well known that boron is an indirect energy gap type of material. The absorption
coefficient α near the absorption edge E g for the indirect allowed transition can be described
as a function of the photon energy hν,
αhν ⬀ (hν ⫺ E g ) 2 (9)
Table 4 List of Thermoelectric Power Studies for Boron

No.a Author Structure Form Year Ref.
1 W. C. Shaw Single Bulk 1957 3
2 R. Uno Poly. Bulk 1958 40
3 Sh. Z. Dzhamagidze Poly. Bulk 1968 35
4 A. Zareba Single Bulk 1970 37
5 O. A. Golikova Single Bulk 1970 41
6 H. Werheit Single Bulk 1970 33
7 G. Majini Single Bulk 1971 43
8 A. A. Berezin Amorphous single Bulk 1974 39
9 Bulk
10 J. Cueilleron Poly., 0.1% impu. Bulk 1978 32
11 Poly., 1% impu. Bulk
12 K. Nakamura Amorphous Film 1983 42
a
Number corresponding to Fig. 11.
Boron Films 669
Figure 12 EMF figure of merit Z of pyrolytic boron films as a function of absolute temperature.
Figure 13 Absorption coefficient of pyrolytic boron films as a function of incident photon energy.
670 Nakamura
Figure 14 The absorption edge fitted to the indirect allowed transition.
The variation of the square root of the adsorption coefficient multiplied by photon energy
(αhν) 1/2 for boron films with incident photon energy is shown in Fig. 14. The figure shows that
the boron film is an indirect energy gap type of material. The energy gap E g is estimated to be
1.28 ⫾ 0.08 eV by extrapolation of the linear part to the horizontal axis in Fig. 14. This value
is larger than the value obtained by electrical measurement (1.07 eV) and the values reported
for amorphous films by Adirovich and Goldshtein (34) and Morita and Yamamoto (13).
The refractive index n and the extinction coefficient k of the boron films are shown as a
function of wavelength in Figs. 15 and 16, respectively. These results agree well with the values
obtained by Murphy (11) and Morita and Yamamoto (13), for amorphous films deposited by
vacuum evaporation. The hillock of the refractive index at wavelengths around 1 µm corresponds
to the absorption edge. An increase in the extinction coefficient is also shown at wavelengths
below 1 µm. Figure 17 shows the infrared transmission spectrum of the boron film deposited
on a silicon substrate. As shown in Fig. 17, the absorption of the boron film in the IR spectral
region increases at about 8 µm and reaches a maximum at 12.5 µm. Blum et al. (48) studied
the effect of impurities such as carbon and hydrogen on the infrared absorption of amorphous
boron films and showed that the narrow band at 2560 cm ⫺1 observed in hydrogen-doped samples
is due to BH bond vibration. Also, the broad strong band from 1000 to 1200 cm ⫺1, which is
Boron Films 671
Figure 15 Refractive index of pyrolytic boron films as a function of wavelength.
correlated strongly with the amount of carbon in the films, is due to an overlapping and broaden-
ing of various BC bond vibrations. Therefore, the absorption band from 8 to 12.5 µm observed
in our films is not considered to be due to hydrogen and carbon impurities. Although many
absorption bands caused by the complex crystal structure of boron have been reported, they are
all in the wavelength region shorter than 8 µm (49). Werheit et al. (50,51) have studied the optical
properties of β-rhombohedral boron single crystals in detail and have shown that absorption has
a peak at 8 µm. According to Decker and Kasper (52), the absorption spectra of α-rhombohedral
boron have absorption peaks at 18.2, 10.9, 9.3, and 8.2 µm. These absorption bands are not in
agreement with those observed for boron films deposited by pyrolysis of decaborane. On the
basis of studies by Golikova et al. (36), it can be considered that the absorption at 12.5 µm is
associated with the short-range lattice structure in the boron films.
Figure 16 Extinction coefficient of pyrolytic boron films as a function of wavelength.

672 Nakamura
Figure 17 Infrared transmission spectrum of a pyrolytic boron film deposited on a silicon substrate.
The solid line and broken line correspond to the results of the author and Blum (48), respectively.
IV. CONCLUSION
Amorphous boron films have been deposited by pyrolysis of decaborane in the molecular flow
region. On the assumption that the deposition rate of boron films is determined by the impinge-
ment frequency of the decaborane molecules onto the substrate surface, we have derived an
equation for the deposition rate D at temperatures lower than 416°C. The equation, D ⫽ 7.16
⫻ 10 9 P exp(⫺39,000 Rt s )(cm/s), explains the experimental results successfully.
Electrical conductivity of these boron films is ⱌ 10 3 larger than that of single-crystal
boron and is in agreement with that of amorphous films deposited by CVD and vacuum evapora-
tion. The influence of impurities on the conductivity is not clear. The activation energy for
conduction of the boron films is estimated to be 1.07 eV in the intrinsic temperature range.
The temperature dependence of the electrical conductivity can also be explained by a hopping
conduction mechanism of amorphous materials. Plots of log σ against T 1/4 show a good linear
relation, and the density of localized states at the Fermi level, N(E F ), is estimated to be 3.8 ⫻
10 18 cm ⫺3 eV⫺1. However, we cannot decide which mechanism is valid within our experimental
accuracy.
The thermoelectric power of the boron films obtained shows a small peak at a higher
temperature, compared with those for bulk boron. This may be attributed to the fact that the
concentration of the acceptors in amorphous boron films is higher than that in boron crystals.
From the measurements of optical absorption, it is found that boron films are an indirect
band gap type of material and have an energy gap of 1.28–0.08 eV. Refractive indexes and
extinction coefficients of the boron films in the wavelength range 0.27–2.5 µm were obtained.
In the infrared spectral region, an absorption peak was observed at 12.5 µm, which is considered
to be associated with short-range order in the boron lattice.
It is well known that boron is a low-Z material and shows its characteristics in a semicon-
ductor. To our regret, these properties of boron have not been applied sufficiently until now. It
Boron Films 673
is to clear that boron films can be made easily. As an example of application the studies described
in Refs. 4 and 5 have been carried out.
REFERENCES
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2. OA Golikova. Phys Status Solidi A 51:11, 1979.
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4. M Saidoh, N Oriwara, M Shimada, T Arai, H Hiratsuka, T Koike, M Shimizu, H Ninomiya, H
Nakamura, R Jimbou, J Yagyu, T Sugie, A Sakasai, N Asakura, M Yamage, H Sugai, GL Jackson,
5. M Yamage, H Sugai. Jpn J Appl Phys Ser 10:184, 1994.
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9. VS Postnikov. J Less Common Met 47:255, 1976.
10. JS Lannin. Solid State Commun 25:363, 1978.
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13. N Morita, A Yamamoto. Jpn J Appl Phys 14:825, 1975.
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18. JP Schaffer, H Park, JH Lind, PL Jones. Phys Stat Solid (a) 81:K51, 1984.
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20. CS Park, JS Yoo and JS Chun. Thin Solid Films 131:205, 1985.
21. V Cholet, R Herbin and L Vandenbulke. Thin Solid Films 192:235, 1990.
22. DM Makowiecki, AF Jankowski, MA McKernan and RJ Foreman. J Vac Sci Technol A8:3910,
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23. K Shirai and S Gonda. J Appl Phys 67:6286, 1990.
24. U Jansson, M Boman, LC Markert, J-O Carlssson and JE Greene. J Vac Sci Technol A9:266, 1991.
25. K Kamimura, I Ohtake and Y Onuma. Japan J Appl Phys Series 10: 170, 1994.
26. OWJ Croft. Mater Res Bull 5:489, 1970.
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28. C Feldman, HK Charler Jr, FG Statkiewicz, J Bohandy. J Less Common Met 47:141, 1976.
29. K Moorjani, C Feldman. Electron Technol 3:265, 1970.
30. HC Beachell, JF Haugh. J Am Chem Soc 80:2939, 1958.
31. AJ Owen. J Chem Soc 5438, 1961.
32. J Cueilleron, JC Viala, F Thevenot, C Brodhag, JM Dusseal, A Elbiach. J Less Common Met 59:
27, 1978.
33. H Werheit, HG Leis. Phys Status Solidi 41:247, 1970.
34. EI Adirovich, LM Goldshtein. Sov Phys Semicond 3:196, 1969.
35. Sh Z Dzhamagidze, Yu A Maltsev, RR Shvangiradze. Sov Phys Semicond 2:320, 1968.
36. OA Golikova, DN Mirlin, AS Umarov, T Khomidov. Sov Phys Semicond 7:1091, 1974.
37. A Zareba and M Maszkiewicz. Phys Status Solidi A 3, K207 1970.
38. NF Mott, J Non-Cryst. Solids 1: 1 (1968) Philos Mag 19:835, 1969.
39. AA Berezin, OA Golikova, MM Kazanin, T Khomidov, DN Mirlin, AV Petrov, AS Umarov, VK
Zaitsev. J Non-Cryst Solids 16:237, 1974.
40. R Uno. J Phys Soc Jpn 13:667, 1958.
41. OA Golikova, A yu Kiskachi, T Khomidov. Sov Phys Semicond 4:683, 1970.
674 Nakamura
42. K Nakamura. Nihon Kagaku Kaishi 646, 1983.

43. G Majini and M Prudenziati. Phys Status Solidi A 5:K129, 1971.
44. VA Johnson, K Lark-Horonitz. Phys Rev 92:226, 1953.
45. OA Golikova, VK Zaitsev, VM Orlov, LS Stilbans, FS Tkalenko. Phys Status Solidi A 21:405, 1974.
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52. BF Decker, JH Kasper. Acta Crvstallogr 13:1030, 1960.
25
Single Crystal of AlN
Takeshi Meguro and Katsutoshi Komeya
I. INTRODUCTION
Aluminum nitride has a hexagonal crystal structure based on the wurtzite-type lattice. It has
not been found in nature. Although AlN has been synthesized for a long time, studies of the
growth of single crystals or whiskers are relatively new. Studies reported by Taylor and Lenie
(1) and Matsumura and Tanabe (2) in the 1960s are considered to be foremost with respect to
single crystals. Systematic studies have been performed by Drum (3–5), Pastrnak and Roskov-
cova (6), and Witzke (7). In particular, the detailed structural analyses by Drum contributed
much to the development of single crystals in later years.
AlN does not melt at a pressure of 1 atm but does decompose at 2200 to 2450°C. Typical
effective methods for synthesizing AlN single crystals depended exclusively on sublimation of
AlN. A variety of morphologies of single crystals, such as platelike, needle (prism), and whisker
morphologies, were confirmed by the preceding researchers. However, in all cases the details
of experiments were obscure, and therefore the formation conditions intrinsic to each crystal
morphology were not clarified. In addition, it was well known that impurities play an important
role in crystal growth, but the effect of the kinds and the amounts of impurity on AlN crystal
growth was not clarified either. These were comprehensively described by Ishii et al. (8–10).
In spite of the detailed studies of the crystallography of AlN by Drum and Witzke, the
mechanism for determing how various kinds of single crystals grow was insufficient. Drum (3)
stated that the assumption requiring the presence of an axial dislocation is doubtful and con-
cluded that inferring the relationship between defects and crystal growth mechanism is not valid.
Ishii et al. (10) proved experimentally that whiskers and prisms of AlN grow through the vapor-
liquid-solid (VLS) mechanism during the sublimation process.
II. MORPHOLOGIES AND CLASSIFICATION OF AlN CRYSTALS
Drum (3,4) studied synthesized crystals using a transmission electron microscope and classified
the crystals into the following five types: (a) platelets with an (0001) plane, (b) thin blade-
shaped whiskers with large surfaces (0001), (c) plates with a (1010) plane, (d) thin blade-shaped
filaments with large surfaces (1010), and (e) needles with a hexagonal cross section and 〈0001〉
growth direction. He focused on the shape of a blade with large surfaces (1010) and with growth
direction along [c ⫹ 2a] or [2423]. Witzke (7) related the morphologies of the single crystals
675
676 Meguro and Komeya
Table 1 Comparison of Classifications of the Morphology of AlN Crystals by Several Authors

Type of AlN crystals
Whisker and
Tabular Blade-shaped Blade-shaped needle Whisker
crystal crystal with Platy crystal filament with normal to normal to
Author with (0001) (0001) with (10-10) (1010) (0001) (10-11)
Drum (1) (2) (3) (4) (5)
Witzke (IV) (V) (III)? (I)(II)
Pastrnak and Type C Type C Type B Type A
Roskovcova
Ishi et al. T-type a-type P-type and c-type b-type
whisker platelike
and crystal crystal
to the temperatures of crystal growth and also classified them into five types. A comparison of
the classifications by Ishii et al. (10), shown in Table 1, is very helpful for understanding the
concrete content including the other researchers’ results.
Ishii et al. (10) investigated the conditions of formation single crystals of AlN by the
sublimation method and discussed the mechanism of crystal growth in relation to their morphol-
ogy. The crystals were classified into five types: whiskers of a type, b type, and c type and
crystals of p type and T type. These results are also included in Table 1. They conducted experi-
ments using a graphite resistance tube furnace and found that many single crystals, each crowned
with a black globe on the top, grew at temperatures between 1700 and 2000°C on the closed
graphite crucible wall and sometimes on the inside wall of the furnace. The morphologies of
the single crystals thus obtained were classified into the following three types. The first type
includes crystals with large (0001) faces elongated perpendicular to (1010) and was called an
‘‘a-type crystal.’’ An example of a blade-shaped crystal is shown in Fig. 1. According to their
explanation, this type of crystal corresponds to Drum’s type (2), Witzke’s (V), and Pastrnak
and Roskovcova’s type C. The central axis lies in the (0001) plane. A small black globe is
Figure 1 A typical blade-shaped crystal is an a-type crystal with large (0001) and elongated perpendicu-
lar to (1010).
Single Crystal of AlN 677
observed on the top of the central axis. They confirmed with electron probe microanalysis
(EPMA) that iron is distributed along the central axis and in the globe on the top. Moreover,
the globes are composed mainly of iron and small amounts of chromium and manganese. An
electron micrograph and an X-ray image of iron are shown in Fig. 2a and b. The temperature
at which a crystal of this type begins to grow was found to be above 1700°C in an open crucible.
The second type consists of whiskers with the growth direction making an angle of 5°
with the normal to (1011). Ishii et al. called this product a ‘‘b-type whisker.’’ A typical crystal
is shown in Fig. 3. This type of whisker was unlike any in Table 1, so they thought that this
was a new type. The whiskers are characterized by being needle-like and having a black globe
on the top. Such b-type whiskers were confirmed to have the same components as the a-type
crystals. However, there was a major difference between the a-type crystal and b-type whisker
in that no iron could be detected along the axes of the b-type whisker. Crystals of this type are
said to grow above 1850°C in an open crucible but are not found as frequently as the a-type
crystals.
The third type consists of whiskers and needle crystals with a growth direction along the
Figure 2 Electron microscopy of an a-type crystal (a) and X-ray image of Fe (b).
Figure 3 Whisker of a b-type one crystal with the growth direction making an angle of 5° with the
normal to (1011).
c-axis. This product was called a ‘‘c-type whisker.’’ This type of whisker was identified as
Drum’s type (5), Witzke’s types (I) and (II), and Pastrnak and Roskovcova’s type A. It is re-
ported that this type of whisker begins to grow at 1550°C in an open crucible.
They investigated the effect of iron on the crystal growth using the ‘‘L-type furnace’’
described later. The products obtained from commercial AlN and pure AlN powders were com-
pared after heating at 2100°C for 5 h in a nitrogen atmosphere. From pure AlN powder, tabular
crystals and prismatic crystals were found to form above 1700°C, whereas the three types of
crystals were formed. It was confirmed that adding iron to the pure AlN powder yielded three
types of crystals. The tabular crystals, shown in Fig. 4, have large (0001) basal faces. In contrast,
the prismatic crystals, shown in Fig. 5, have large (1010) prismatic faces and (0001) faces. Ishii
et al. called the former crystals T-type crystals and the latter P-type crystals. Both crystals
correspond to the types proposed by Drum, Witzke, and Pastrnak and Roskovcova as shown
in Table 1.
Figure 4 Tabular crystal (T-type crystal) with a large (0001) face.

Figure 5 Prismatic crystal (P-type crystal) with a large (1010) face and (0001) face.
III. METHODS FOR PREPARING AlN SINGLE CRYSTALS AND AlN FILMS
A. Sublimation Method
Because AlN does not melt at atmospheric pressure, the sublimation method has been applied
in many cases. Relatively large AlN crystals can be obtained because AlN sublimes rapidly at
high temperatures and recrystallizes easily.
Several systematic studies (3–7) using single crystals prepared by the sublimation method
are noteworthy. Drum has studied the axial imperfections (3), magnitude of the lattice twist,
and the Burgers vector of the axial dislocations (4). He synthesized AlN crystals by nitriding
aluminum powder in graphite crucibles placed in a vertical induction furnace in a nitrogen
atmosphere at temperatures between 1800 and 2200°C with a temperature gradient of 75°C/cm
(3). He also reported that basal platelets and whiskers grew at temperatures between 1950 and
2150°C, whereas only whiskers grew at temperatures lower than 1900°C. However, more details
of the experimental conditions are not found in his reports, so the crystal growth conditions are
unknown. Davies and Evans (11) prepared 18–20-mm-long AlN whiskers by heating AlN pow-
der at 1820°C in order to determine the bend strength. More details of the preparation method
are not provided.
In this section, an experimental method adopted by Ishii et al. (10), who reported their
experimental procedure in detail, will be introduced. They used a graphite resistance tube furnace
and a high-frequency induction furnace to investigate the growth of AlN crystals. The graphite
Figure 6 Schematic diagram of the closed crucible designed by Ishii et al. A, graphite crucible; B,
charged powder of AlN; C, space for crystal growth; D, graphite pipe to transport nitrogen gas; E, joint
made of graphite; F, outlet for nitrogen gas; G, inlet for nitrogen gas; H, holder (water cooled).
crucible they designed is shown in Fig. 6 and is called a closed crucible. The crucible enabled
most of the vapor sublimed from AlN as starting material to remain within the crucible. In
addition, a temperature gradient in the graphite crucible was derived by changing the length of
the junction between the crucible and water-cooling holder. A graphite crucible without a water-
cooling holder or lid was also used.
In order to change the temperature gradient, two kinds of induction coil for the high-
frequency induction furnace were employed. One furnace had a 60-mm-long coil and 160-mm-
long susceptor. The molded AlN specimen was placed in the middle of the susceptor, whose
ends were closed to enclose the sublimed vapor and to make the temperature gradient gentle.
Ishii et al. called this type of furnace an L-type furnace. The other type of furnace was heated
by a 6-mm-wide whirlpool-type induction coil. The graphite susceptor was 70 mm long. They
called this a W-type furnace. These furnaces were used horizontally as shown in Figs. 7 and 8.
At first, Ishii et al. prepared single crystals in the graphite resistance tube furnace using
commercial AlN powder. The commercial powder put in the closed crucible was set in the
region of the highest temperature in the furnace. The temperature was kept at 2150°C for 5 h
in a nitrogen atmosphere. Consequently, they found that blade-shaped crystals and whiskers
with a black globe on the top were formed at temperatures between 1700 and 2000°C on the
wall of the closed crucible. These crystals were confirmed to be single crystals by optical and
X-ray techniques. They confirmed that these crystals could also be formed in the high-frequency
induction furnace. The resultant crystals were classified into three types corresponding to the
morphologies mentioned earlier. Subsequently, they investigated the effect of iron on the crystal
Figure 7 Schematic diagram of L-type furnace. A, molded sample of AlN; B, graphite susceptor; C,
alumina tube; D, carbon felt; E, induction coil; F, graphite disk for thermal shield.
Figure 8 Schematic diagram of W-type furnace. A, molded sample of AlN; B, graphite susceptor; C,
alumina tube; D, carbon felt; E, induction coil.
growth using the L-type furnace. The experiment was performed at a temperature of 2100°C.
The results were also explained earlier.
Second, the pellet-drop technique devised by Slack and McNelly (12) will be introduced.
They assembled a furnace for crystal growth as illustrated in Fig. 9. The main parts of the
furnace are composed of the tungsten crucible, flat foil tungsten radiation shields, radio fre-
quency heating coil, fused quartz housing, rolled foil radiation shield, tungsten support tube,
and tungsten susceptor tube. They placed about 5 g of AlN in the left-hand end of tungsten
crucible C. The sharp tip of the crucible was placed in the center (2250°C) of the furnace at
the start of the run. The inside was constructed so that the crucible rotated at about 2 rev/h and
passed through the hot zone at about 0.3 mm/h. They reported that the largest single crystal of
AlN grown was a conical boule 12 mm long and 4 mm in diameter with a mass of 0.23 g and
that the c-axes of the AlN crystals are generally parallel to the long dimension of the tungsten
Figure 9 Tungsten tube furnace for growing AlN crystals devised by Slack and McNelly. A, alumina;
C, tungsten crucible; F, flat foil tungsten radiation shields; H, radio frequency heating coil; J, water cooling
jacket; Q, fused quartz housing; R, rolled foil radiation shields; S, tungsten support tube; T, tungsten
susceptor tube; W, clear fused quartz window; Z, rubber O-ring seal.
crucible. They mentioned that leaks through the pinhole developed on the tungsten crucible
grain boundaries during long runs limited the maximum size of the crystals.
Tanaka et al. (13) have investigated AlN single crystal growth by the sublimation method
devised by Slack and McNelly (12) in order to produce substrates for GaN-based diodes. They
reported that the morphology of AlN crystals depended on the sublimation temperatures.
B. Chemical Engineering Method

Manufacture of single crystals far larger than the whisker level has not yet been reported. How-
ever, expectations for whiskers are growing in industry because whiskers could be important
as reinforcing materials. Nevertheless, techniques for mass production have not been established.
In this section, a chemical engineering method designed by Hotta et al. (14–16) is introduced,
although their process still remains in the experimental stage. They investigated synthesis meth-
ods for AlN powder by floating-type fluidized-bed nitridation of aluminum powder. Later, they
also reported a process with alumina powder as a raw material. In addition, they tried to produce
tranparent AlN whiskers using the same apparatus. The apparatus they designed is shown in
Fig. 10.
Ultrapure Al powder was used as a raw material. The Al powder was continuously fed
in an N 2 stream from the lower end of a reactor made of alumina. A gas mixture of NH 3 and
N 2 was introduced in the reactor through another feeding tube. The nitridation temperature was
controlled from 1450 to 1550°C. After nitridation, the whiskers deposited on the walls of the
reactor and on the feeding tube of the gas mixture were collected.
The whiskers were transparent and hexagonal columnar. A typical scanning electron mi-
croscopy (SEM) photograph of whiskers is shown in Fig. 11. They reported that the rates of
growth of whiskers were 2 µm/s in the length direction and 0.0014 µm/s in the radial direction.
Figure 10 Schematic diagram of experimental fluidized-bed apparatus. A, Source of supply; B, nitriding

reactor; C, separator; 1, container; 2, nitrogen gas inlet; 3, Al powder inlet; 4, agitator; 5, alumina tube;
6, heater; 7, separator; 8, nitrogen outlet; 9, silicone tube.
Figure 11 Typical SEM photograph of whiskers obtained with a floating-type fluidized bed.
The maximum length and diameter were 15 mm and 120 µm. They thought that the mechanism
by which the whiskers grow is not VLS, which will be mentioned in Sec. IV, but VS, because
the tops of the whiskers did not have special elements such as Fe. It is noteworthy that the
oxidation resistance is high. The transparency of the whiskers was confirmed even after oxidation
at 900 to 1000°C in air for 4 h.
C. Physical Vapor Deposition Method

There were only few detailed studies of physical vapor deposition (PVD) of AlN. However,
publications on various deposition methods for AlN have increased because of the potential
applications in surface acoustic devices (SAWs) and in optical devices in the ultraviolet spectral
region. AlN films have important characteristics such as piezoelectricity, high ultrasonic veloc-
ity, and high-temperature stability. Although these studies were not always targeted at forming
AlN single crystals, some studies will be introduced in this section because the properties and
crystalline structure are considered to be very important in relation to crystal formation with
orientation. Also, AlN materials may receive much attention in the future as thermal barriers
or protective coatings in aggressive environments because AlN is an excellent oxidation-resistant
material.
Bienk at al. (17) have studied a method for preparing AlN films by reactive sputtering,
with a transition region in which the deposited films change their optical characteristics from
nontransparent to highly transparent films. The effects of accurate mass flow control of the
reactive gas under a constant argon flow on deposition of AlN films with well-defined stoichiom-
etry, crystalline texture, and morphology were examined using an Alcatel RF/DC sputtering
unit (SCM 650) with two cathodes of Al. Film depositions were performed in the RF model at
13.56 MHz with 1200 W. They found that the film composition and sputtering rate depend
strongly on the deposition conditions and, in particular, on the mass flow and the sputtering
pressure. Thus, for films prepared under three sputtering conditions, A, B, and P (P was called
the working point), the relation between experimental total pressure and mass flow of the reactive
gas was compared. The deposition conditions and Al/N ratio of the resulting films are listed in
Table 2.
Table 2 Deposition Conditions and Al/N Ratio of Films

Deposition Ar flow N 2 flow Pressure Al/N
point (sccm) (sccm) ⫻ 10 ⫺3 (mbar) ratio
A 40.0 3.53 19.4 1.2
B 3.53 19.9 1.1
P 3.30 19.8 1.1
A 8.0 3.76 4.6 1.5
B 3.76 5.7 1.1
P 2.98 5.4 1.1
A 4.0 3.47 2.4 1.6
B 3.52 3.6 1.1
P 2.57 3.3 1.1
They reported that the films prepared at points B and P are almost stoichiometric and
transparent independent of argon flow, whereas the nonstoichiometric films prepared at point
A are nontransparent.
The reflected X-ray diffraction patterns of P films showed that the crystalline texture is
very dependent on the sputtering pressure. At the lowest sputtering pressure, the characteristic
(002) orientation in AlN and (200) in Al were the only peaks observable. However, peaks
assigned to AlN(101) and AlN(102) appeared when the pressure increased.
For SAW applications, c-axis-oriented (a-axis-oriented) AlN films are required for longi-
tudidal (transverse) waves. Okano et al. (18) have investigated the orientation of AlN films
deposited by electron cycloton resonance (ECR) dual ion beam sputtering, using an ECR ion
source for irradiation and a Kaufman-type ion source for sputtering. The ECR ion beam sput-
tering system employs high-density ion beam irradiation, is a low-pressure process, and produces
plasma-free deposition. The apparatus they used is shown in Fig. 12. They found that c-axis-
oriented AlN films could be obtained by controlling the nitrogen ion beam energy and microwave
power of ECR and that the upper area of the films with c-axis orientation parallel to the substrate
was nearly single crystal.
Akiyama et al. (19) confirmed that highly c-axis-oriented AlN thin films can also be
formed on polycrystalline substrates such as MoSi 2 , Al 2O 3 , and SiC. They prepared AlN thin
Figure 12 Apparatus of the ECR ion beam sputtering system. A, ECR ion gun; B, target holder; C,
rotary pump; D, substrate holder; E, Kaufman ion gun; F, main valve; G, cryo pump.
Figure 13 Schematic diagram of electron shower apparatus. A, DC bias; B, substrate; C, anode; D,

tungsten filament; E, nitrogen inlet; F, Al; G, pump.
films using RF magnetron sputtering equipment and reported that the crystal orientation of the
thin films was not influenced by the difference in such substrate materials. However, the orienta-
tion on the polycrystalline substrates was worse than that of thin films deposited on single-
crystal substrates.
Ishihara et al. (20,21) devised a new type of PVD method called the electron shower. In
general, it has been difficult to obtain a-axis-oriented AlN films by sputtering and ion plating.
However, they succeeded in preparing a-axis-oriented AlN films by their method. A schematic
diagram of the electron shower apparatus is shown in Fig. 13. Thermal electrons emitted from
a heated tungsten filament are accelerated by a potential of 500 V between the filament and the
ring-shaped anode. Al was evaporated in an Al 2O 3-coated tungsten basket. The Al vapor and
N 2 gas were activated by passing through an electron shower, and AlN film was formed on the
substrate. They reported that both a-axis-oriented films and c-axis-oriented films could be pre-
pared, and the orientation changed to c-axis orientation when a negative bias of ⫺200 V was
applied.
D. Ammonothermal Reaction Method

Peters (22) proposed a new method for preparing AlN single crystals. This method is based on
the ammonothermal reaction of Al with ammonia using potassium amide as a transporting agent.
He used potassium amide, KNH 2 , as a mineralizer. KNH 2 reacts with Al and NH 3 to form
KAl(NH 2 ) 4 . Both compounds, KNH 2 and KAl(NH 2 ) 4 , are very soluble in ammonia. KAl(NH 2 ) 4
decomposes to KNH 2 , NH 3 , and AlN as expressed by the following equation:
KAl(NH 2 ) 4 ⇔ KNH 2 ⫹ 2NH 3 ⫹ AlN (1)
There exists an equilibrium in this relation. Only KAl(NH 2 ) 4 and AlN were detected at the end
of the experiments, although the actual Al transporting compound was not assigned. For this
reason, he thought that Eq. (1) was acceptable. He reported that AlN single crystals grown
predominantly in the direction of the c-axis were obtained in the temperature range 500 to 600°C
at pressures of 1 to 2 kbar.
IV. MECHANISM OF AlN CRYSTALLIZATION BY SUBLIMATION METHOD
Judging from the fact that many whiskers are known to be free from dislocations, Drum (3)
denied the necessity for the presence of an axial dislocation, which is required for the proposed
mechanisms for whisker growth from vapor. He pointed out that AlN whiskers of the 〈c ⫹ 2a〉
type might be unique in that every crystal with this orientation contained an axial imperfection.
He discussed the growth mechanism based on the presence of axial dislocation. However, he
could not present a consistent explanation and finally concluded that inferring the relationship
between defects and the crystal growth mechanism solely on the basis of data on growth direc-
tions is not valid. He also did not explain the growth mechanism of the other types of crystals.
The report by Witzke (7), who related the morphologies of single crystals to the growth tempera-
ture, did not mention the detailed mechanism. Pastrnak and Roskovcova (6) investigated the
effect of the degree of supersaturation on the types of crystals and suggested that small amounts
of oxygen, carbon monoxide, and carbon might affect the morphology. According to them, a
high degree of supersaturation yielded type A crystals, and a lower degree of supersaturation
yielded types C and B.
Ishii et al. (8,10) investigated the growth mechanism and the growth conditions of single
crystals of AlN prepared by the sublimation method. They found that P-type and T-type crystals
grow in a system containing no iron impurities. They thought that since {1011} is the least
important face among the three F-faces ({0001}, {1010}, and {1011}, crystals grown under
near-equilibrium conditions are expected to be bounded by {0001} and {1010} and {1011} is
absent. It was shown that T-type crystals were related to CO in an atmosphere without Fe.
For a system containing impurities such as iron, they described the VLS mechanism as
follows. A crystallite with a large (0001) face forms in a drop of liquid iron determing the size
of the crystallite. The Fe on the (0001) face causes the crystal to grow in the form of a whisker
perpendicular to (0001). This crystal is called a c-type whisker. The second and the third impor-
tant faces appear on the crystallite in Fe at high temperatures, resulting in the growth of whiskers
perpendicular to (1010) and (1011). The a-type and b-type whiskers grow by such a mechanism.
Kato (23) reported that the diameter of whiskers is proportional to the size of the globes con-
sisting mainly of iron.
V. THERMAL CONDUCTIVITY OF AlN SINGLE CRYSTAL
Slack (24) reported the thermal conductivity, κ, of AlN to be 200 W/m ⋅ K at 300 K using a
synthetic single crystal supplied by the company Peciney Compagnie de Produits Chimiques et
Electrometallurgiques of Grenoble, France. The crystal was grown by sublimation at about
2100°C. However, the details were not made clear. The only information given was that oxygen,
the dominant impurity, was (3 ⫾ 2) ⫻ 10 26 atoms/m 3 in total. He found that the κ of AlN is
sensitive to the oxygen content and at 300K varies from about 320 W/m ⋅ K for pure AlN to
about 50 W/m ⋅ K for AlN with 2 ⫻ 10 21 atoms/cm 3 of oxygen. He summarized the other
values for κ of AlN in the literature. Subsequently, Slack and McNelly (12) reported that a
single crystal had a value of 250 W/m ⋅ K (run W-154) at 300 K and that a polycrystalline
sample had a value of 220 W/m ⋅ K at 300 K.
In 1987, Slack et al. (25) studied the intrinsic thermal conductivity of single crystals. They
obtained high-purity single crystals by the sublimation method devised by Slack and McNelly
(12,26). A single crystal weighing 1.00 g and 1.41 cm long and with an average diameter of
0.54 cm was used for the measurements at temperatures of 0.4 to 300 K. The oligocrystalline
samples of sublimed AlN in the form of 1.2-cm-diameter, 0.3-cm-thick flat disks were used for
measurements between 370 and 1800 K. The impurity of oxygen was estimated to be 343 ⫾
17 ppm in weight (from starting powder). The tungsten content was about 50 ppm (from the
crucible). The other impurities were analyzed and found to be 10 ppm or less. The results are
shown in Fig. 14 and the numerical data are given in Table 3. The value for pure AlN in Table
3 are corrected for the residual oxygen content. In the figure, the solid curve plotted as circles
and squares shows the measured thermal conductivity. The circles are for the oligocrystallne
sample.
They discussed the effect of substitutional impurity oxygen in AlN on phonon scattering.
Oxygen replaces nitrogen, and the aluminum deficit produces vacancies in the aluminum sublat-
tice. When the density of AlN is 3.05, the number density, n 0 , of nitrogen atoms in AlN is 4.478
⫻ 10 22 . Since the AlN they used included 340 ppm, oxygen the number density of the oxygen
impurity, ∆n, is 3.902 ⫻ 10 19 . The ratio ε (⫽∆n/n 0 ) is then 8.713 ⫻ 10 ⫺4. Since the thermal
resistivity, ∆W 1 , is estimated to be 0.0375, the value of λ pure calculated from the following
equation is 319 W/m ⋅ K.
λ ⫺ 1 ⫽ λ pure ⫺1 ⫹ ∆W 1
They proved that this is very close to the value predicted by Slack (24) for pure AlN.
Figure 14 Measured thermal conductivity of high-purity AlN (solid curve) (W201 single crystal was
used). (䊉) Cornell; (䊐) Slack; (䊊) Tanzilli.
Table 3 Thermal Conductivity as a Function

of Temperature
Temperature W-201 Pure AlN
T (K) (W/m ⋅ K) (W/m ⋅ K)
0.4 0.38 0.38
0.6 0.97 1.3
1.0 3.2 5.8
2.0 21 48
4.0 108 380
6.0 240 2,000
10.0 570 5,800
15 1,020 19,500
20 1,500 45,000
30 2,000 70,000
45 2,300 46,000
60 2,200 20,500
100 17,500 4,700
150 1,100 1,570
200 650 780
300 285 319
400 180 195
600 96 100
1000 48 49
1800 24 24
VI. ELEMENTS THAT ACT AS IMPURITIES IN AlN
Knowledge and problems of the elements that act as impurities in AlN are important. Slack and
McNelly (26) carefully considered the related substances. In this section, an editorial by Slack
will be introduced. He thought that atoms with tetrahedral radii close to those of Al and N
would be able to substitute for Al or N. A difference in radii of 0 to 10% indicates high solubility,
a 10 to 20% difference indicates moderate to low solubility, and a difference greater than 20%
indicates very low solubility. He claimed from these criteria that C and O should have high
solubility in the Al sublattice and that Be, Cd, In, Hg, Tl, and Pb should have moderate to low
solubility in the Al sublattice. Both C and O are expected to act as highly soluble impurities
in AlN by substituting for N because Al 4 C 3 and Al 2 O 3 are stable to a temperature of at least
1500°C. Because only Mg 3 O 4 , Si 3 N 4 , and Be 3 N 2 , of the possible nitrides, exist above 1000°C
at 1 atm of N 2 , Si and Be are the possible substituents for Al. Judging from the tetrahedral radii
and the stability, he mentioned that Ti and Mn in the first transitional metal series might also
substitute for Al. He summarized by stating that Be, C, O, Mg, and Si have high solubilities and
that the other impurities such as S, Mn, or the rare earths may have lower maximum solubilities.
Contamination from crucibles is always a problem because high temperatures such as
1500°C or above are required to form AlN single crystals. The crucible materials whose melting
points are above 2500°C are Mo, Os, Ta, Re, W, and C. Mo is known to produce a low-melting
eutectic with Al. Os is toxic, and Ta reacts readily with N to form Ta 2 N and TaN. Therefore,
Re, W, C, and TaN are candidates for crucible materials. He confirmed that AlN powder can
be heated in sealed W crucibles up to 2275°C without visible attack. The W content of the AlN
was reported to be about 50 ppm. With the Re crucible, the Re content of the AlN was found
to be 60 ppm at 2370°C. Re is therefore not significantly better than W. The main disadvantage
of carbon crucible material is the carbon impurity in the crystals.
VII. CONCLUSION
In this chapter, single crystals of AlN were described primarily with respect to the preparation
method and the morphology. AlN whiskers are an additional important material, especially in
the field of composite ceramic materials. AlN is not only a semiconductor material but also a
refractory material, which may be considered suitable as a fiber-reinforcing material. In this
sense, the development of a mass production process is very desirable. Simultaneously, advances
in novel techniques for growing large single crystals are sought.
The current studies tend to concentrate on the preparation and the properties of highly
oriented thin films. Studies on the preparation and application of AlN films with exellent proper-
ties, in fields such as surface acoustic wave devices, should be accelerated in the future.
REFERENCES
1. KM Taylor, C Lenie. J Electrochem Soc 107:308, 1960.

2. T Matsumura, Y Tanabe. J Phys Soc Jpn 15:203, 1960.
3. CM Drum. J Appl Phys 36:816, 1965.
4. CM Drum. J Appl Phys 36:824, 1965.
5. CM Drum. Phil Mag 25:313, 1965.
6. J Pastrnak, L Roskovcova. Phys Status Solidi 7:331, 1964.
7. HD Witzke. Freiberg Forschungsh C195, 1965.
8. T Ishii, T Sato, M Iwata. Mineral J 6:323, 1971.
9. T Ishii, T Sato, M Iwata. J Miner Soc Jpn 11:127, 1973.
10. T Ishii, T Sato, M Iwata. Mineral J 8:1, 1975.
11. TJ Davies, PE Evans. Nature 207:254, 1965.
12. GA Slack, TF McNelly, J Cryst Growth 42:560, 1977.
13. M Tanaka, S Nakahata, K Sogabe, H Nakata, M Tobioka. Jpn J Appl Phys 36:L1062, 1997.
14. N Hotta, I Isao, M Tanaka. Kagakusochi 2:72–78, 1991.
15. N Hotta. Annu Rep Murata Sci Found 7:184–187, 1993.
16. T Watanabe, N Hotta, K Kotera, K Komeya, T Meguro, T Sasamoto. Proceedings of International
Ceram. Conference Austceram 94, Vol 1, 1994, p 184.
17. EJ Bienk, H Jensen, GN Pedersen, G Sorensen. Thin Solid Films 230:121, 1993.
18. H Okano, T Tanaka, K Shibata, S Nakano. Jpn J Appl Phys 31:3017, 1992.
19. M Akiyama, K Nonaka, K Shobu, T Watanabe. J Ceram Soc Jpn 103:1093, 1995.
20. M Ishihara, H Yumoto, T Tsuchiya, K Akashi. J Surf Finish Soc Jpn 47:152, 1996.
21. M Ishihara, H Yumoto, T Tsuchiya, K Akashi. Thin Solid Films 281–282:321, 1996.
22. D Peters. J Cryst Growth 104:411, 1990.
23. A Kato. Denki Kagaku 40:743, 1972.
24. GA Slack. J Phys Chem Solids 34:321, 1973.
25. GA Slack, RA Tanzilli, RO Pohl, JW Vandersande. J Phys Chem Solids 48:641, 1987.
26. GA Slack, TF McNelly. J Cryst Growth 34:263, 1976.
26
AlN Sintered Polycrystal
Fumio Ueno
Toshiba Corporation, Kawasaki, Japan
I. INTRODUCTION
Aluminum nitride (AlN) falls under a family of wurtzite structures (2H) and is the only stable
compound in the binary system between aluminum and nitrogen. The cell dimensions are a ⫽
311 pm, c ⫽ 499 pm, and become shorter when oxygen is dissolved in AlN lattice.
AlN has received much interest in the electronic industry in recent years because of the
need for devices with high power applications (Fig. 1) and the need for smaller and more reliable
high speed integrated circuits (Fig. 2). These electronic devices place a number of significant
demands upon materials, chief among which is the need to dissipate heat efficiently.
The thermal conductivity of pure AlN is predicted to be 319 W/mK (80% of that of pure
copper) (1). Aluminum nitride ceramics has a thermal conductivity ranging from 70 W/mK to
270 W/mK, about 5–6 times higher than aluminum oxide (Fig. 3). However, it is not only the
high thermal conductivity that makes AlN an excellent candidate for electronic packaging but
also properties like its low dielectric constant, low thermal expansion coefficient (close to that of
silicon) (Fig. 4), low dielectric loss at high frequencies, high electrical resistivity, high dielectric
strength, and nontoxic nature (2–4). Table 1 shows various properties of AlN ceramics and
related materials.
Research of AlN ceramics started in the late 1950s (5), and was based on numerous proper-
ties including corrosion resistance, piezo-electricity nature, thermal conductivity, fluorescence
characteristics, chemical inertness toward molten metals, high-temperature stability, optical
translucence, high hardness, shock absorption properties, et al. (6). Although pressure sintering
and reaction sintering were tried at the beginning, full dense ceramics were only obtained after
the 1970s when the sintering additives for AlN were discovered (7). Properties of AlN ceramics
improved after the 1980s and since then AlN ceramics has become a practical material.
All these properties and their unique combinations make AlN a very worthwhile substance.
As a result, AlN ceramic has many different applications. For example, couplers for acoustic
surface waves, microwave windows, windows for UV-light and infrared sources, neutron ab-
sorbers (in fusion reactors), heat sinks and heat exchangers, molten metal containers and cruci-
bles, heat jigs and refractories, sintering additives for SiC and Si 3 N 4 , fillers for polymers and
glass compounds, armor plates, etc. (2).
691
692 Ueno
Figure 1 AlN direct bond copper substrate for IGBT power device.
Figure 2 AlN package for a high-speed gate ally chip.

AlN Sintered Polycrystal 693
Figure 3 Thermal conductivity of AlN ceramics compared with other materials.
Figure 4 Thermal expansion of substrate materials.

694 Ueno
Table 1 Typical Property Values of AlN and Related Ceramic Materials

Property Unit AlN Al 2 O 3 SiC BN BeO
Thermal conductivity W/mK 70–270 25 70–270 25 260
Electrical resistivity Ohm cm ⭌10 14 ⭌10 14 ⭌10 11 ⭌10 11 ⭌10 14
Dielectric constant 1 MHz 8.6 9.9 40 4.1 6.7
Dielectric loss 10 ⫺4 (1 MHz) 5 4 500 45 4
Thermal expansion 10-6/K (RT-623K) 4.7 7.1 3.8 0.0 7.2
coefficient
Density G/cm 3 3.3 3.89 3.21 1.9 2.85
Bending strength MPa 280–480 440 440 50 220
Hardness GPa 11.8 19.6 27.5 2.7 9.8
Young’s modulus GPa 330 345 410 40 260
II. MANUFACTURING PROCESS AND PROPERTIES OF AlN POWDER
There are several industrial methods of producing AlN powder, but three of them are currently
utilized (8–10). Among these, carbothermal reduction of aluminum oxide powder and direct
nitridation of aluminum metal are the dominant methods.
In the case of carbothermal reduction (Fig. 5), aluminum oxide powder is reduced by
carbon and reacts with nitrogen gas to form AlN powder Eq. (1). Reaction temperature is ca.
1550°C.
Al 2 O 3 ⫹ 3C ⫹ N 2 → 2AlN ⫹ 3CO (1)
Excess carbon must be removed after the carbothermal reduction. This process is normally
carried out at around 700°C in dried air and residual carbon becomes less than 0.1 mass %.
Carbothermal powder typically contains about 1 mass % of oxygen which stays as a surface
oxide layer of AlN powder derived from the carbon removal process. Other impurities are mainly
driven by the alumina powder source. The morphology of the AlN powder tends to conform
to that of starting aluminum oxide powder. In most cases, carbothermal powders are fine, have
Figure 5 Carbothermal reduction furnace (11).

Figure 6 SEM photographs of AlN powders manufactured by a carbothermal process (left) and a direct
nitridation process (right).
equiaxial or spherical shape, and can be easily sintered. Electron microscope photographs of
carbothermal and direct nitridation AlN powder are shown in Fig. 6.
The direct nitridation method (Fig. 7) uses the nitridation of aluminum metal powder
under nitrogen gas Eq. (2).
2Al ⫹ N 2 → 2AlN (2)
In this case, exothermic self combustion reaction starts at above 800°C and careful treatment
is necessary to reach 100% nitridation. After the nitridation process, the crude product requires
milling that yields a powder with rough angular particles that exhibit relatively wide size distri-
Figure 7 Direct nitridation process of AlN powder (12).

696 Ueno
Figure 8 Particle size distribution of direct nitridation AlN powder and carbothermal AlN powder.
bution and gives high levels of impurities. Particle size distribution of direct nitridation powder
and carbothermal powder is shown in Fig. 8.
A surface stabilization process is adopted after milling because a major problem with AlN
powders is hydrolysis of the particle surface, resulting in oxidation of the powder that reduces
the thermal conductivity of the final product, and may produce ammonia during the storage or
prefiring process. Oxygen impurity of direct nitridation powder (more than 1 mass %) comes
from starting the aluminum metal and milling process in most cases. Direct nitridation powder
has high press density, but is difficult to sinter and the resulting ceramics have relatively lower
thermal conductivity.
Pyrolysis of organometallic compound is also adopted by a commercial powder process.
Chemical vapor deposition of triethylaluminum with ammonia yields a pure and very fine pow-
der (10). The main impurity in the AlN raw powder is oxygen, which is dissolved in AlN
lattice during sintering and substituted at the nitrogen site in AlN lattice Eq. (3). Consequently,
aluminum vacancy (VAl ) is produced to maintain the charge balance, and the formation of such
vacancies promotes sintering of AlN ceramics. On the other hand, thermal conductivity goes
down due to the defect generation accompanied by oxygen dissolution.
Al 2 O 3 → VAl ⫹ 2Al Al ⫹ 3O N (3)
When carbon is added to AlN powder, the oxide layer of AlN is removed by a carbothermal
reaction (⬃1600°C) during heating before the sintering starts (ca. 1800°C). In this case, grain
growth can be observed but shrinkage does not occur even with sintering additives. Existence
of oxygen is indispensable for the densification of AlN during sintering. Before the discovery
of sintering additives for AlN, more than 3% of oxygen was necessary for the densification
even in the case of hot pressing. Recently, grain size, particle size distribution, and the agglomer-
ation nature of AlN powder have greatly improved. As a result, AlN powder with 1 mass %
of oxygen can be sintered at 1900°C without sintering additives. Furthermore, pressureless sin-
tering of AlN below 1400°C is also possible with very fine powder prepared by a pyrolysis of
organometallic compound or plasma nitridation of aluminum metal. However, such a fine pow-
der usually has higher oxygen content and poor durability against moisture.
III. SINTERING OF AlN CERAMICS
Like silicon nitride, aluminum nitride is not easy to sinter. The high covalent bonding character
(60% covalent–40% ionic (13)) of AlN limits the atomic mobility and prevents complete densi-
fication. The condition of the starting materials—purity, particle size, particle-size distribution,
oxygen content and specific surface area—influences the sinterability and properties of AlN
ceramics (14).
There are three solutions proposed to accelerate the densification kinetics of AlN ceramics:
1. Use of hot isostatic pressing or hot pressing that gives an external driving force for
densification,
2. Use of pure powders with a high specific surface area (15,16) that promote diffusion
at the surface of grains and along grain boundaries, and
3. Use of sintering aids that densify the material by liquid-phase sintering as a liquid is
formed between aluminum oxide in the AlN powder and the additives.
Figure 9 shows the density and thermal conductivity of AlN ceramics sintered with various
compounds. There are three type of additives:
Figure 9 Thermal conductivity and density of AlN ceramics sintered at 1800°C for 2 hours with 3 mass
% of additives.
698 Ueno
Figure 10 The phase diagram of Al 2 O 3-Y2 O 3 system (21).
1. Additives that promote the sintering of AlN and increase the thermal conductivity of
AlN,
2. Additives that promote the sintering but has no activity to increase the thermal conduc-
tivity, and
3. Additives that have no effect on shrinkage nor on thermal conductivity increase.
Well known sintering aids in category (1) are alkali-earth oxides or rare-earth oxides such as
Y2 O 3 (17,18) and CaO (19,20). These can be added not only as oxide but also as nonoxide
compounds such as halide, nitride, carbide, nitrite, or carbonate. Some of the transition elements
such as NiO and TiO 2 can be classified as category (2) additives. Rare earth or alkali-earth
oxide additive reacts with aluminum oxide of AlN powder (i.e. oxide layer of AlN powder) to
form aluminate liquid at a high temperature Eq. (4) and promotes liquid-phase sintering of AlN
powder.
AlN ⫹ x/2Al 2 O 3 ⫹ y/2Y2 O → AlN ⫹ Al x Yy O 3(x⫹y)/2 (4)
The ratio of aluminum oxide in the powder and added Y2 O 3 gives the grain boundary phase
composition in the fired AlN ceramics, according to the phase diagram of the Al 2 O 3-Y2 O3 system
(Figs. 10 and 11).
The phase diagram (Fig. 10) consists of four different two-phase fields. One of these is
the field of Al 2 O 3-Al 5 Y3 O 12 , but AlN ceramics with grain boundary phase consisting of both
Al 2 O 3 and Al 5 Y3 O 12 were found in the ceramics sintered with Y2 O 3 . This is because of the
dissolution of Al 2 O 3 into AlN lattice, which gives lower thermal conductivity of AlN ceramics.
Figure 11 Grain boundary phase composition in AlN ceramics sintered with different amounts of Y2 O 3
at 1800°C for 2 hours. Oxygen content of starting AlN powder was 1 mass %.
On the other hand, Y2 O 3 traps Al 2 O 3 and prevents the dissolution into AlN lattice and thermal
conductivity increases as Y2 O 3 is added to AlN (Fig. 12).
There are some elements such as silica or boron, which improve sinterability when a small
amount is added with alkali-earth oxides or rare-earth oxides. Many of the transition elements
have almost no influence on sintering and thermal conductivity of AlN (22). Kasori sintered
AlN with 0.3 mass % of transition metal oxide (Fe, Ti, Zr, Ta, Nb, W, Cr, Co, Hf, and Mn)
and 3 mass % of Y2 O 3 . These oxides became nitride, carbide, metal, or alloy as dispersed
particles located inter- and intragranularly in AlN, as shown in Fig. 13. Body color of AlN
became black or gray (Fig. 14) but sintering ability, thermal conductivity, and electrostatic
properties were almost unchanged. The shading was attributed to optical absorption and multiple
reflections by the surface of the electrically conductive fine particles.
Effective sintering aids are insoluble in AlN and exhibit a high affinity for Al 2 O 3 . At a
suitably high temperature, the oxide coating the AlN grains reacts with the additive to form a
eutectic liquid. The liquid wets the grains and allows the material transfer that is essential for
densification. During this densification process, oxygen and metal impurities of the AlN grain
are incorporated into the grain boundary phase. With prolonged firing the liquid phase migrates
through the grain boundaries and either concentrates at grain boundary triple points or migrates
to the surface of the sintered AlN body. The role of the sintering aid can be summarized as
follows (23,24):
1. Promotion of particle rearrangement and grain growth through liquid phase sintering,
2. Prevention of oxygen diffusion into AlN grains due to high affinity for Al 2 O 3 ,
3. Removal of metal impurities within the grains, and
4. Elimination of the formed secondary phase from the sintered body, after full densifi-
cation.
This impurity gathering and the removal of the secondary phase by carbothermal reactions,
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Figure 12 The density and the thermal conductivity of AlN ceramics sintered with different amount of
Y2 O 3 at 1800°C for 2 hours.
during prolonged firing, drastically increases the thermal conductivity. So even though it is
possible to sinter AlN today without a sintering aid, an aid is still required to obtain high thermal
conductivity.
IV. THERMAL CONDUCTIVITY OF AlN CERAMICS
In AlN there are no free electrons so that the dominant mechanism of heat transportation is
phonon (25), i.e. energy quanta are transferred through the crystal body by lattice vibrations.
Therefore, it is expected that impurities or other lattice and microstructural defects, such as
vacancies, interstitials, dislocations, and grain boundaries, can cause phonon scattering and thus
lower the thermal conductivity. Incorporation of oxygen in the AlN, where oxygen substitutes
for nitrogen in the wurtzite structure, creates aluminum vacancies to maintain the charge balance
(25). With an increasing amount of oxygen (above 0.75 atom %) the topology of the primary
defect-type changes from isolated clusters to extended two-dimensional inversion domain
boundaries (26–29), with aluminum atoms octahedrally coordinated to oxygen (Fig. 15). This
critical oxygen content has also been noted by Slack (25) who observed a contraction of the
unit cell followed by a re-expansion at higher oxygen contents.
All nonmetals with a known high-thermal conductivity have either diamond-like, boron
carbide, or graphite crystal structure. The fundamental characteristics for a crystal to exhibit
Figure 13 TEM photograph of AlN ceramics prepared by pressureless sintering with WO 3 and Y2 O 3 .
W particles are located intragranularly in the AlN ceramics. White bar (at bottom right) indicates 200 nm.
these high values are high purity, strong interatomic bonding, simple crystal structure, low
atomic mass, and low anharmonicity (25,30). The thermal conductivity is given by Eq. (5) (31).
κ ⫽ 1/3 ⫻ C p ⫻ v ⫻ l (5)
where C p is the heat capacity, v the phonon velocity, and l the phonon mean free path.
At constant temperatures, l is controlled by the phonon–phonon interaction and is much
smaller (around 10–30 nm (1)) than the grain size (typically 3 µm). Therefore, phonon scattering
at the AlN–AlN grain boundaries has a negligible influence on thermal conductivity compared
to lattice defects such as oxygen. Figure 16 shows the oxygen concentration dependency on
the thermal conductivity of AlN ceramics and single crystals without second phase. Oxygen
concentration dependency can be seen very clearly, and single crystal and polycrystal show the
same oxygen concentration dependency.
Of course, the mean free path of phonon becomes longer at a low temperature and the
thermal conductivity of ceramics becomes lower than that of single crystal shown in Fig. 17.
Figure 18 shows the grain size effect for thermal conductivity of pure AlN ceramics without
grain boundary phases and with nearly the same oxygen content in AlN lattice. Thermal conduc-
tivity is independent from the grain size in this region at room temperature. The existence and
removal of the secondary phases is important to reach higher and final values of the thermal
conductivity (24,32) because:
1. Up to about 170 W/Km of the main mechanism is considered to be oxygen trap by
sintering aids (18), and
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Figure 14 AlN ceramics sintered with 3 mass % of Y2 O 3 (left) and AlN sintered with 0.3 mass % of
TiO 2 and 3 mass % of Y2 O 3 (right) at 1800°C. Thermal conductivity is 270 W/mK for translucent AlN
(left) and 250 W/mK for black AlN (right).
2. Over 170 W/Km of the mechanism changes from oxygen trapping to elimination of
oxygen in AlN grain, along with grain boundary phase elimination from AlN ce-
ramics.
Grain boundary phase (second phase) morphology is also important for the thermal con-
ductivity of AlN. Grain boundary phase morphology changes very much. If the cooling rate after
sintering is changed, then the interconnection of AlN grain is also changed, thereby changing the
thermal conductivity (33).
For low additive content, secondary phases are precipitated at triple junctions only, and
they do not scatter phonons severely, i.e. there is still contact between the AlN grains. For high
additive contents, wetting of the grains occur (even though wettability of Y2 O 3 on AlN is worse
than CaO (19)), and aluminates form a continuous layer around the AlN grains. This leads to
scattering of phonons at the interfaces and therefore a conductivity decrease. Another reason
for the lower values of the thermal conductivity at high additive contents is the fact that they
have very low conductivity themselves (Y3 Al 5 O 12 : 11 W/Km (34)). However, it should be
pointed out that if the addition is too low there will be a problem removing the oxygen from
Figure 15 Schematic representation of the oxygen-related defect evolution as a function of oxygen

content: (a) region I–isolated aluminum vacancy with associated oxygen, (b) region II–aluminum octahe-
drally coordinated to oxygen, and (c) extended defect–an inversion domain boundary consisting of alumi-
num atoms octahedrally coordinated to oxygen at the boundary (26).
Figure 16 Thermal conductivity vs. oxygen concentration of AlN single crystals and ceramics without
second phase at room temperature (1).
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Figure 17 Temperature dependency of thermal conductivity for AlN ceramics and single crystal.
Figure 18 The grain size effect for thermal conductivity of pure AlN ceramics without grain boundary
phases and with nearly the same oxygen content.
Figure 19 Reaction of rare-earth additive with AlN powder.
the surface of and inside the grains. Therefore it is important to achieve an optimum addition
(35,36).
Since most grain boundary phases are concentrated at triple points the AlN will exist as
a continuous phase and therefore the thermal conductivity can be expressed as follows (30).
κ ⫽ κ AlN ⫻ (1 ⫺ V) ⫹ κ gb (6)
As the volume fraction of the secondary phase (V ) usually is small and the thermal conductivity
of AlN(κ AlN ) is much larger than that of the grain boundary phase, the relation can be further
simplified to:
κ ⫽ κ AlN ⫻ (1 ⫺ V) (7)
Also, when one considers the activity of Al 2 O 3 in different parts of the phase diagram (37) of
the Al 2 O 3-Y2 O 3 system, one finds some explanation for the variation of the thermal conductivity.
Figure 20 SEM photographs of AlN ceramics sintered at 1700°C (left) and 1800°C (right) with Y2 O 3 .
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The phase diagram (Fig. 10) consists of four different two-phase fields—Al 2 O 3-Al 5 Y3 O 12 ,
Al 5 Y3 O 12-AlYO 3 , AlYO 3-Al 2 Y4 O 9 and Al 2 Y4 O 9-Y2 O 3 —where the activity of Al 2 O 3 dissolved
in AlN is highest in the last phase field above (38,39). Therefore, as long as the volume fraction
of secondary phase is low, the thermal conductivity of AlN increases with the amount of Y2 O 3 .
As mentioned before, when AlN is sintered with rare earth or alkali-earth oxide, thermal conduc-
tivity of ceramics is improved (Fig. 12). This is because such oxides react with aluminum oxide
in AlN powder preventing oxygen dissolution into the AlN lattice. The oxides segregate to form
rare-earth-aluminum oxide grain boundary phase but defect levels in AlN are minimized. Figure
19 illustrates the reaction scheme of this process.
To utilize such oxygen trapping during sintering, we must choose adequate compounds
that do not release oxygen at high temperature by decomposition or reduction, but form stable
aluminate compounds to trap aluminum oxide. TiO 2 or NiO are also good sintering additives,
but become second phase containing TiN or Ni-Al alloy, respectively, during sintering. As a
result of a no oxygen trapping effect, thermal conductivity of AlN ceramics with TiO 2 or NiO
additives become very low level. There is an optimum amount of addition depending on the
oxygen content of AlN powder. Carbonate, nitrites, halide, nitride, or carbide can be also used
as sintering additives. The effect is essentially the same but handling of powder improves. In
addition, some other benefits, such as improvement of thermal conductivity and lowering of
sintering temperature have been reported. After firing at 1200°C with Y2 O 3 for only 10 minutes,
Y3 Al 5 O 12 is observed at grain boundary already, but the shrinkage starts at around 1700°C which
is below the lowest eutectic temperature in the Al 2 O 3-Y2 O 3 system. On the contrary, shrinkage
starts higher than the eutectic point (1360°C) of grain boundary phase, ca. 1500°C in the case
of AlN with CaO additive. In both cases, in spite of a large difference in the eutectic temperature,
the temperature, which gives the full dense ceramics, is nearly the same. This might not indicate
liquid phase sintering. Figure 20 shows the microstructure of AlN sintered with Y2 O 3 at 1700°C
and 1800°C. The morphology of ceramics is very different.
Recently, partial phase diagram of yttrium aluminate and AlN was reported (40). The
eutectic point of the AlN-Y4 Al 2 O 9 system was 1790°C, and the AlN-Y3 Al 5 O 12 system was as
low as 1690°C, which indicated the liquid phase sintering of AlN (Fig. 21).
V. DIFFUSION OF ELEMENTS IN AlN CERAMICS
Diffusion constants of AlN are obtained by high temperature creep phenomena and shrinkage
behaviors during hot pressing (41,42). Lattice diffusion constant (D L ) from creep observation
is 10⫺12 cm 2 /s at 1700°C and the activation energy is from 530 to 630 kJ/mol, depending on
the grain size of the ceramics. The diffusion constants obtained by these experiments are thought
to be the diffusion of aluminum due to its large dependence on oxygen concentration because
point defect generation at the aluminum site, when the oxygen dissolves in the AlN polycrystal,
is well known. Sumino obtained the diffusion coefficient of nitrogen using nitrogen isotope
( 15 N) tracer technique in a very pure AlN polycrystal with only 400 ppm oxygen (43). The
lattice diffusion coefficient was 2.6 ⫻ 10⫺13 cm 2 /s at 1930°C and 3.1 ⫻ 10⫺14 cm 2 /s at 1700°C
and the activation energy was 370 kJ/mol, as shown in Fig. 22.
The grain boundary diffusion parameter δ D b is 1.0 ⫻ 10⫺16 cm 3 /s at 1930°C, where δ
means grain boundary width and D b is the grain boundary diffusion coefficient (Fig. 23). The
diffusion constants of nitrogen also show oxygen concentration dependency. The diffusion con-
stant calculated from creep or shrinkage during hot pressing for the sample containing % order
oxygen, may not be composed of aluminum but, rather, of nitrogen. Muller et al. measured
diffusion of oxygen in an Al 2 O 3-AlN diffusion couple to be 6.7 ⫻ 10⫺15 cm 2 /s at 1700°C and
Figure 21 Three-dimensional view of liquid phase formation temperatures determined by DTA measure-
ments in the system AlN-Y2 O 3-Al 2 O 3 (40).
Figure 22 Logarithmic plot of the intensity of mass number 69 against the depth squared for the sample
heat treated at 1930°C for 6 hours.
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Figure 23 The plot of the intensity of mass number 69 following Fisher’s equation for the sample heat
treated at 1930°C for 6 hours.
1.9 ⫻ 10⫺14 cm 2 /s at 1900°C (44). Compared to the D L from high temperature creep and hot
pressing, Muller concluded that the oxygen atom in AlN ceramics cannot go in and out of the
AlN lattice by a solid diffusion process during sintering of AlN. Oxygen dissolution, which
causes a decrease of thermal conductivity, is observed by the lattice constant change for the
sintered AlN. If the oxygen dissolution during sintering is not due to solid diffusion, this may
indicate the diffusion during liquid phase sintering. The diffusion constant of oxygen and alumi-
num is 10⫺11 cm 2 /s and 10⫺10 cm 2 /s at 1800°C for aluminum oxide (45), which means the diffu-
sion in AlN is about 100 times smaller that in aluminum oxide.
VI. LOW-TEMPERATURE SINTERING OF AlN CERAMICS
The sintering temperature of Al 2 O 3 is around 1500°C, while that of AlN is ca. 1800°C. This
difference can be understood by the difference of diffusion coefficient mentioned earlier. Several
attempts have been carried out to lower the sintering temperature of AlN ceramics for the pur-
pose of keeping processing costs down. If AlN fine powder is used, sintering temperature can
be decreased down to 1600°C with Y2 O 3 additive, but in this case, thermal conductivity also
decreases as low as 100 W/mK.
Fluoride is a promising low temperature sintering additive (46). AlN commercial powder
can be sintered with YF 3 at 1550°C, and the combination of AlN fine powder and YF 3 changes
the sintering of AlN at 1400°C. The thermal conductivity of YF 3 added to AlN and sintered at
1600°C becomes as high as 245 W/mK. However, the mechanical strength of AlN with YF 3
additive is relatively low. There is no lower eutectic composition in Y2 O 3-CaO-Al 2 O 3 system
compared to a simple Al 2 O 3-CaO system, but sintering temperature lowers with the combination
of CaO-Y2 O 3 . Sintering additives based on a 1 :1 molar ratio of Y2 O 3 and CaO can be a promis-
Figure 24 Shrinkage curve for AlN sintered with Y2 O 3 and low temperature firing compositions.
ing sintering additive system with good thermal, mechanical, and electrical properties. Small
amounts of boron, or other elements such as boron or lithium, added to the Y2 O 3-CaO system
improve the sintering ability of AlN (Fig. 24) (47,48). Fully densified AlN ceramic substrates
were obtained with Y2 O 3-CaO-LaB 6-WO 3 by a 1600°C continuous furnace firing. The resulting
thermal conductivity was 150 W/mK.
VII. PREPARATION OF PURE AlN POLYCRYSTAL
The grain boundary phase can be completely removed by prolonged firing in a carbon reductive
atmosphere (23,24). Sintering AlN with 5 mass % Y2 O 3 at 1900°C in a carbon sagger under
nitrogen atmosphere for 96 hours produces ceramics with 3.26 g/cm 3 theoretical density of AlN
(Fig. 25). This is free of grain boundary phase and with a thermal conductivity of 270 W/mK,
so the eliminated yttrium aluminates are found as YN and AlN deposited on the ceramic surface.
The elimination reaction of Al 2 O 3 under carbon reductive atmosphere with nitrogen gas occurs
above ca. 1500°C (Eqs. (8) and (9)).
Al 2 O 3 ⫹ C ⫹ N 2 → 2AlN ⫹ 3CO (8)
Y2 O 3 ⫹ C ⫹ N 2 → 2YN ⫹ 3CO (9)
This reaction is the same one used for AlN powder preparation, as mentioned earlier. Although
vapor pressure of carbon gas (C n ; n ⫽ 1,2,3, . . .) is very low at 1500°C, it becomes 3 ⫻ 10⫺3
Pa at 1900°C. Free energy change is ⫺40 kJ/mol and ⫹80 kJ/mol for Eq. (8) and Eq. (9),
respectively. This heat treatment is carried out under excess carbon gas and nitrogen gas flow
to eliminate CO gas. Such a condition expedites the carbothermal reduction of Y2 O 3 to YN at
the surface of AlN ceramics (Fig. 26).
Of course reaction of Eq. (8) is faster than that of Eq. (9) as grain boundary phase changes
from Al rich oxide (i.e. Y3 Al 5 O 12 YAlO 3 ) to Y rich (i.e. Y4 Al 2 O 9 , Y2 O 3 ) (Fig. 25). The overall
reaction mechanism of grain boundary phase elimination can be expressed as follows:
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Figure 25 Morphology change of AlN ceramics under high temperature heat treatment in a carbon
reductive atmosphere.
Figure 26 AlN grain boundary phase elimination mechanism at high temperature in a carbon reductive
atmosphere.
Figure 27 Grain boundary phase elimination kinetics. Weight loss by grain boundary elimination was
observed at 1930°C in different settings under nitrogen gas flow.
xAl 2 O 3 yY2 O 3 ⫹ 3(x ⫹ y)C ⫹ (x ⫹ y)N 2 → 2xAlN ⫹ 2yYN ⫹ 3(x ⫹ y)CO (10)
CO gas has no chance to produce YN Eq. (11) because the formation of YN is hindered when
CO gas is introduced to the furnace (49). This grain boundary phase elimination reaction is not
a diffusion controlled process because the rate of it is remarkably sensitive to sample atmosphere
(e.g. with different using setter or gas purity) and time dependency of grain boundary phase
elimination rate (Fig. 27).
xAl 2 O 3 yY2 O 3 ⫹ 3(x ⫹ y)CO ⫹ (x ⫹ y)N 2 → 2xAlN ⫹ 2yYN ⫹ 3(x ⫹ y)CO 2 (11)
This process is not limited to the initial stages of sintering, where the porosity is still open
(shown by oxygen gradients increasing from the ceramic surface (24) and the well-documented
phase associations). YN crystals can be easily removed from the ceramic surface by hydrolysis
in boiling water and pure AlN polycrystal can be obtained:
YN ⫹ 3H 2 O → Y(OH) 3 ⫹ NH 3 (12)
In summary, the Al 2 O 3 concentration in AlN results from two reactions: (i) a fast internal
reaction equilibrating dissolved oxygen content and the yttrium aluminates, and (ii) a slow exter-
nal reaction tending to equilibrate the ceramic with graphite and furnace atmosphere. Since
Y2 O 3 is thermodynamically more stable than Al 2 O 3 the continuous loss of oxygen with sintering
time leads to formation of aluminate that is richer in Y2 O 3 . Consequently, it will pump out
aluminum oxide inside the AlN lattice to form Y–Al–O grain boundary phase and the AlN
lattice is purified during heat treatment. Oxygen content is reduced as low as 400 pmm
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Figure 28 Reduction of yttrium and oxygen content in AlN ceramics under high temperature heat treat-
ment.
(Fig. 28). Hot pressed AlN without yttrium oxide (thermal conductivity is ca. 90 W/mK) cannot
be purified by this treatment but AlN sintered with Y3 Al 5 O 12 (thermal conductivity is also as
low as ca. 100 W/mK) becomes pure AlN polycrystal with its thermal conductivity of 250
W/mK (23, 24).
3YAlO 3 ⫹ Al 2 O 3 → Y3 Al 5 O 12
Y4 Al 2 O 9 ⫹ Al 2 O 3 → 4YAlO 3 (13)
2Y2 O 3 ⫹ Al 2 O 3 → Y4 Al 2 O 9
The developed oxygen gradient is relaxed by grain boundary migration of the liquid phase as
evidenced by an increase in the Y concentration near the surface. Grain boundary phase elimina-
tion reaction is also observed in the case of CaO added to AlN (50), but oxygen remains in the
AlN lattice and thermal conductivity does not change remarkably because CaO has high vapor
pressure and disappears before the elimination of oxygen in the AlN lattice.
CONCLUSION
Improvement of processing and properties of AlN powder and ceramics over the last two decades
has been remarkable. Although the performance of the AlN ceramics has advanced very much,
it is not yet widely used in the industry. Cost reduction processes, designs to make the best use
of high performance AlN, establishment of evaluation method, and standardization of properties

are necessary for a newly developed material such as AlN.
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27
GaN-AlN-InN Blue Light–Emitting Devices
Shuji Nakamura
University of California, Santa Barbara, California
I. INTRODUCTION
GaN and related materials such as AlGaInN are III-V nitride compound semiconductors with
the wurtzite crystal structure and energy band structures of direct interband transition, which is
suitable for light-emitting devices. The band gap energy of AlGaInN varies between 6.2 and
1.95 eV depending on its composition at room temperature (Fig. 1). Therefore, these III-V
semiconductors are useful for light-emitting devices especially in the short wavelength regions.
In the AlGaInN system, GaN has been most intensively studied. GaN has an band gap energy
of 3.4 eV at room temperature.
On the other hand, much research has been done on high-brightness blue light–emitting
diodes (LEDs) and laser diodes (LDs) for use in full-color displays, full-color indicators, and
light sources for lamps with the characteristics of high efficiency, high reliability, and high
speed. For these purposes, II-VI materials such as ZnSe (1–3), SiC (4,5), and III-V nitride
semiconductors (6) have been investigated intensively for a long time. However, it was impossi-
ble to obtain high-brightness blue LEDs with brightness over 1 cd and reliable LDs.
Research on III-V nitrides has paved the way for the realization of high-quality crystals
of GaN, AlGaN, and GalnN and of p-type conduction in GaN and AlGaN (7,8). The mechanism
of the acceptor compensation that prevents obtaining low-resistivity p-type GaN and AlGaN
has been elucidated (9–13). In Mg-doped p-type GaN, Mg acceptors are deactivated by atomic
hydrogen, which is produced from NH 3 gas used for the N source during GaN growth. After
the growth, thermal annealing in an N 2 ambient can reactivate the Mg acceptors by removing
the atomic hydrogen from the Mg-hydrogen complexes. High-brightness blue LEDs have been
fabricated on the basis of these results, and luminous intensities over 1 cd have been achieved.
These LEDs are now commercially available (14–17). Studies of (Al, Ga, In)N compound semi-
conductors are described.
II. UNDOPED GaN
GaN films are grown on a sapphire substrate with (0001) orientation (c face) at temperatures
around 1000°C by metalorganic chemical vapor deposition (MOCVD) as one of the growth
methods. The lattice constants along the a-axis of the sapphire and GaN are 4.758 and 3.189
Aº, respectively. Therefore, the lattice mismatch between the sapphire and the GaN is very
715
716 Nakamura
Figure 1 Lattice constant of III-V nitrides as a function of their band gap energy.
large. The lattice constant along the a-axis of 6H-SiC is 3.08 Å, which is relatively close to
that of GaN (Fig. 1). However, an SiC substrate is extraordinarily expensive to use for the
practical growth of GaN. Therefore, at present, there are no alternative substrates except for
sapphire, considering the price of substrates and the high growth temperature, although the
lattice mismatch is large. The grown GaN layers usually show n-type conduction without any
intentional doping. The donors are probably native defects or residual impurities such as nitrogen
vacancies or residual oxygen.
The surface morphology of the GaN films was markedly improved when an AlN buffer
layer was initially deposited on the sapphire, as shown first by Yoshida et al. (18). Amano et
al. (19,20) and Akasaki et al. (21) have obtained high-quality GaN films using this AlN buffer
layer by means of the MOCVD method. They showed that the uniformity, crystalline quality,
luminescence, and electrical properties of the GaN films were markedly improved. The carrier
concentration and Hall mobility, whose values were (2–5) ⫻ 10 17 /cm 3 and 350–430 cm 2 /V ⋅ s
at room temperature, were obtained by the prior deposition of a thin AlN layer as a buffer layer
before the growth of the GaN film (22). Those values became about 5 ⫻ 10 16 /cm 3 and 500 cm 2 /
V ⋅ s at 77 K.
Also, high-quality GaN films were obtained using GaN buffer layers instead of AlN buffer
layers on a sapphire substrate by Nakamura (23). He developed a novel two-flow MOCVD
reactor for the GaN growth (Fig. 2). It has two different gas flows. One is the main flow, which
carries the reactant gas parallel to the substrate with a high velocity through the quartz nozzle.
Another flow is the subflow, which transports the inactive gas perpendicular to the substrate
for the purpose of changing the direction of the main flow to bring the reactant gas into contact
with the substrate (Fig. 3). Sapphire with (0001) orientation (C face) was used as a substrate.
Trimethylgallium (TMG) and ammonia (NH 3 ) were used as Ga and N sources, respectively.
First, the substrate was heated to 1050°C in a stream of hydrogen. Then the substrate temperature
was lowered to about 550°C to grow the GaN buffer layer. Next, the substrate temperature was
elevated to about 1000°C to grow the GaN film. The total thickness of the GaN film was about
4µm. Hall measurements were performed on GaN films grown with a GaN buffer layer as a
function of the thickness of the GaN buffer layer. For the GaN film grown with a 200-Å GaN
buffer layer, the carrier concentration and Hall mobility were 4 ⫻ 10 16 /cm 3 and 600 cm 2 /V ⋅ s,
respectively, at room temperature. The values became 8 ⫻ 10 15 /cm 3 and 1500 cm 2 /V ⋅ s at
77 K, respectively (see Fig. 4).
The carrier concentration and Hall mobility of GaN films grown with GaN buffer layers
GaN-AlN-InN Blue Light–Emitting Devices 717
Figure 2 Schematic diagram of novel two-flow MOCVD reactor for GaN growth.
Figure 3 Schematic principles of two-flow MOCVD.

718 Nakamura
Figure 4 The Hall mobility measured at 77 and 300 K as a function of the thickness of the GaN buffer
layer.
are shown as a function of the temperature in Fig. 5 (24). The GaN films were grown with an
approximately 200-Å-thick GaN buffer layer. The total thickness is about 4 µm. The Hall mobil-
ity is 700 cm 2 /V ⋅ s at room temperature. The crystal quality of this GaN film was characterized
by the double-crystal X-ray rocking curve (XRC) method. The full width at half-maximum
(FWHM) for (0002) diffraction from this GaN film was 4 min. Therefore, the value of the
FWHM is not directly related to the Hall mobility because the Hall mobility becomes smaller
than 600 cm 2 /V and the value of FWHM becomes smaller than 4 min as the buffer layer thick-
ness is decreased below 200 Å (23). The Hall mobility gradually increases as the temperature
decreases from room temperature (see Fig. 5). The Hall mobility is about 3000 cm 2 /V ⋅ s at
70 K. According to Amano et al. (19,20,22) and Akasaki et al. (21), maximum Hall mobility
(about 900 cm 2 /V ⋅ s) was obtained at around 150 K using AlN buffer layers. On the other
hand, GaN film grown with GaN buffer layers has a maximum value at around 70 K. Therefore,
the contribution of ionized impurity scattering in a GaN film grown with GaN buffer layers is
much smaller than that in a GaN film grown with AlN buffer layers. The Hall mobility varies
roughly following µ ⫽ µ0 T ⫺1 between 70 and 300 K, where µ is the Hall mobility, µ0 a constant
practically independent of temperature, and T absolute temperature. Thus, in this temperature
range, the Hall mobility is mainly determined by the contribution of polar phonon scattering.
Figure 5 Carrier concentration and Hall mobility of GaN films grown with GaN buffer layers as a
function of the temperature.
Below 70 K, ionized impurity scattering dominates and Hall mobility decreases. The carrier
concentration decreases drastically below 100 K and varies slightly between 100 and 300 K.
Therefore, it seems that a different donor level contributes to the generation of the carrier corre-
sponding to the two different temperature ranges. To consider these two different donor levels,
the carrier concentration as a function of the reciprocal of the temperature was plotted, as shown
in Fig. 6. The thermal activation energy of the electron from the donor level to the conduction
band can be obtained from the gradient of linear regions in Fig. 6, assuming that the carrier
concentration varies following the formula N ⫽ N 0 exp(⫺E/2kT ), where N is the carrier concen-
tration, N 0 a constant practically independent of temperature, E a thermal activation energy, k
the Boltzmann constant, and T the absolute temperature. A thermal activation energy of 34 meV
was obtained between 100 and 42 K and of 5 meV between 300 and 100 K.
III. n-TYPE GaN
Figure 7 shows the carrier concentration of Si-doped GaN films as a function of the flow rate
of SiH 4 . The carrier concentration varies between 1 ⫻ 10 17 and 2 ⫻ 10 19 /cm 3 (25). Good linearity
720 Nakamura
Figure 6 Carrier concentration as a function of the reciprocal of the temperature.
Figure 7 Carrier concentrations of Si-doped GaN films as a function of the flow rate of SiH 4 .
Figure 8 Photoluminescence spectra of Si-doped GaN films grown with GaN buffer layers under the
same growth conditions except for the flow rate of SiH 4 . The flow rates of SiH 4 were (a) 2 nmol/min and
(b) 10 nmol/min. The carrier concentrations were (a) 4 ⫻ 10 18 /cm 3 and (b) 2 ⫻ 10 19 /cm 3 .
is observed between the carrier concentration and the flow rate of SiH 4 . Therefore, Si is consid-
ered to be a good donor impurity for GaN in order to control the carrier concentration.
Photoluminescence (PL) measurements were performed at room temperature. The excita-
tion source was a 10-mW He-Cd laser. Figure 8 shows the PL spectra of Si-doped GaN films
whose carrier concentrations are 4 ⫻ 10 18 and 2 ⫻ 10 19 /cm 3, respectively. In spectra, relatively
strong deep-level (DL) emission is observed around 560 nm. The ultraviolet (UV) emission,
which is a band edge (BE) emission of GaN, is observed around 380 nm. The intensity of DL
emissions is always stronger than that of BE emissions in this range of the flow rate of SiH 4 .
Undoped GaN also shows strong DL emissions and weak BE emissions at room temperature.
The origin of these strong DL emissions has not been elucidated.
IV. p-TYPE GaN
It was impossible to obtain p-type GaN films for a long time. Unavailability of p-type GaN
films has prevented III-V nitrides from being used for light-emitting devices, such as blue LEDs
and LDs. In 1989, Amano et al. (26) succeeded in obtaining p-type GaN films using Mg doping
and post low-energy electron beam irradiation (LEEBI) treatment by means of MOCVD. After
the growth, LEEBI treatment was performed for Mg-doped GaN films to obtain a low-resistivity
p-type GaN film. The hole concentration and lowest resistivity were 10 17 /cm 3 and 12 Ω ⋅ cm,
respectively. These values were still insufficient for fabricating blue LDs and high-power blue
LEDs. The effect of the LEEBI treatment was considered to be Mg displacement by the energy
of electron beam irradiation. At the first stage of as-grown Mg-doped GaN, the Mg atoms lie
in sites different from Ga sites, where they act as acceptors. With LEEBI treatment, the Mg
atoms move to the exact Ga sites.
In 1992, low-resistivity Mg-doped p-type GaN films were obtained by N 2-ambient thermal
722 Nakamura
Figure 9 Resistivity of Mg-doped GaN films as a function of annealing temperature.
annealing at temperatures above 700°C by Nakamura et al. (27). Before thermal annealing, the
resistivity of Mg-doped GaN films was approximately 1 ⫻ 10 6 Ω ⋅ cm. After thermal annealing at
temperatures above 700°C, the resistivity, hole carrier concentration, and hole mobility became 2
Ω ⋅ cm, 3 ⫻ 10 17 /cm 3, and 10 cm 2 /V ⋅ s, respectively, as shown in Fig. 9. In PL measurements,
the intensity of 750-nm deep-level emissions (DL emissions) sharply decreased upon thermal
annealing at temperatures above 700°C, as did the change in resistivity, and 450-nm blue emis-
sions showed maximum intensity with thermal annealing at approximately 700°C, as shown in
Fig. 10.
Figure 10 Photoluminescence of Mg-doped GaN films that were annealed at different temperatures: (a)
room temperature, (b) 700°C, and (c) 800°C.
Soon, Nakamura et al. (9) proposed a hydrogenation process whereby acceptor-H neutral
complexes are formed in p-type GaN films as a compensation mechanism. Low-resistivity p-
type GaN films, which were obtained by N 2-ambient thermal annealing or LEEBI treatment,
showed a resistivity as high as 1 ⫻ 10 6 Ω ⋅ cm after NH 3-ambient thermal annealing at tempera-
tures above 600°C. In the case of N 2-ambient thermal annealing at temperatures between room
temperature and 1000°C, the low-resistivity p-type GaN films showed no change in resistivity,
which was almost constant between 2 and 8 Ω ⋅ cm, as shown in Fig. 11.
Figure 12a shows the PL spectrum of 800°C N 2 ambient thermal-annealed GaN film, Fig.
12b shows the film after NH 3-ambient thermal annealing at 800°C for the sample in Fig. 12a,
and Fig. 12c shows the film after N 2-ambient thermal annealing at 800°C for the sample in Fig.
12b. Before NH 3-ambient thermal annealing, the intensity of blue emissions is strong, and broad
DL emissions are not observed around 750 nm (see Fig. 12a). After NH 3-ambient thermal anneal-
ing at 800°C for the sample in Fig. 12a, the intensity of blue emissions becomes weaker, and
DL emissions around 750 nm appear (see Fig. 12b). The PL spectrum recovers after N 2-ambient
thermal annealing at 800°C. These changes in PL spectra were found to be reversible with
change in the annealing ambient gas from NH 3 to N 2, as is the case with the resistivity change.
These results indicate that atomic hydrogen produced by NH 3 dissociation at temperatures
above 400°C is related to the acceptor compensation mechanism. A hydrogenation process
whereby acceptor-H neutral complexes are formed in p-type GaN films was proposed. The
formation of acceptor-H neutral complexes causes acceptor compensation and deep-level and
weak blue emissions in photoluminescence. At temperatures above 400°C, dissociation of NH 3
into hydrogen atoms occurs at the surface of GaN films because dangling bonds exist mainly
at the surface, and the atomic hydrogen easily diffuses into the GaN films because the number
of hydrogen atoms is too great at the surface and the hydrogen atoms are very small. First, the
atomic hydrogen, produced by dissociation of NH 3 at temperatures above 400°C, diffuses into
p-type GaN films. Second, the formation of acceptor-H neutral complexes, i.e., Mg-H complexes
in GaN films, occurs. As a result, the formation of Mg-H complexes causes hole compensation,
and the resistivity of Mg-doped GaN films reaches a maximum of 1 ⫻ 10 6 Ω ⋅ cm (see Fig.
11). For PL measurements, it is assumed that DL emissions are caused by related levels of
Mg-H complexes, and blue emissions are caused by Mg-related levels. When these proposals
Figure 11 Resistivity change in N 2-ambient thermal-annealed low-resistivity Mg-doped GaN films as

a function of annealing temperature. The ambient gases NH 3 and N 2 were used for thermal annealing.
724 Nakamura
Figure 12 PL spectra of Mg-doped GaN films that were continuously annealed under different condi-
tions: (a) GaN film after 800°C N 2-ambient thermal annealing of the Mg-doped GaN film; (b) GaN film
after 800°C NH 3-ambient thermal annealing of the GaN film in (a); (c) GaN film after 800°C N 2-ambient
thermal annealing of the GaN film in (b).
are applied to the results of the PL measurements in Figs. 10 and 12, the results are quite
well explained.
The change in the PL spectra of Fig. 10 is easily explained using these models. When
the N 2-ambient thermal annealing temperature exceeds 400°C, removal of atomic hydrogen from
Mg-H complexes begins, the number of blue emission centers that are Mg-related radiative
recombination centers begins to increase, and the intensity of blue emissions of the PL spectrum
gradually increases. However, when the temperature reaches approximately 700°C, the effects
of N vacancies produced by the dissociation of GaN films (mainly near the surface) begin to
exceed those of the increased number of Mg-related radiative recombination centers. As a result,
the intensity of blue emissions shows a maximum around 700°C in N 2-ambient thermal anneal-
ing of as-grown GaN films (see Fig. 10).
In the NH 3-ambient thermal annealing of Figs. 11 and 12, Mg-H complexes are not formed
below 400°C, but Mg-H complexes are formed above 400°C in Mg-doped GaN films because
the amount of atomic hydrogen diffused into the bulk of the GaN films is not great until the
temperature exceeds 400°C. As a result, the resistivity of NH 3-ambient thermal-annealed GaN
films above 400°C becomes higher (almost insulating) in Fig. 11, and the intensity of blue
emissions of NH 3-ambient thermal-annealed GaN films at 800°C becomes weaker than that of
N 2-ambient thermal-annealed GaN films at 800°C because the number of Mg-related levels is
reduced by formation of Mg-H complexes under NH 3-ambient thermal annealing (see Fig. 12).
With NH 3-ambient thermal annealing at 800°C, DL emissions can be observed because Mg-H
complexes are formed. With N 2-ambient thermal annealing at 800°C, DL emissions cannot be
observed because atomic hydrogens are removed from Mg-H complexes and the number of
Mg-H complexes is reduced dramatically (see Fig. 12).
Usually, NH 3 is used as the N source for GaN growth in MOCVD. Therefore, an in situ
hydrogenation process in which Mg-H complexes are formed during MOCVD growth naturally
occurs, and the resistivity of as-grown Mg-doped GaN films becomes high (almost insulating).
After the growth, N 2-ambient thermal annealing can reactivate the acceptors by removing atomic
hydrogen from the acceptor-H neutral complexes in p-type GaN films. As a result, the resistivity
of p-type GaN films becomes lower and the intensity of blue emissions becomes stronger. This
hydrogenation process is now accepted as the acceptor compensation mechanism of p-type III-
V nitride by many researchers (9–13).
V. GaN p-n JUNCTION BLUE LEDS
High-quality GaN films were grown using GaN or AlN buffer layers as Hall mobility value of
undoped GaN films grown with GaN buffer layers was 600 cm 2 /V ⋅ s at room temperature (23).
The carrier concentration of n-type GaN films was controlled between 1 ⫻ 10 17 and 2 ⫻ 10 19 /
cm 3 by Si doping of GaN (25). The hole concentrations of p-type Mg-doped GaN films grown
with GaN buffer layers were of the order of 1 ⫻ 10 18 /cm 3 (28). Because of these results, there
is great interest in fabricating emitting devices using GaN films grown with buffer layers. Using
these techniques, Nakamura et al. (29) fabricated GaN p-n junction blue LEDs in 1991. Here,
GaN p-n junction blue LEDs are described.
The structure of a GaN p-n junction LED is shown in Fig. 13 (29). The carrier concentra-
tion of the n-type GaN layer was 5 ⫻ 10 18 /cm 3 and that of the p-type GaN layer was about 8
⫻ 10 18 /cm 3. Si was doped into the n-type GaN layer as a donor impurity. Mg was doped into
the p-type GaN layer as an acceptor impurity. After the growth, thermal annealing or LEEBI
treatment was performed in order to obtain a low-resistivity p-type GaN layer.
Electroluminescence (EL) of the LED is shown in Fig. 14. The peak wavelength and the
FWHM of the EL are 430 nm and 55 nm, respectively, at 10 mA. According to Amano et al.
(26) and Amano and Akasaki (22), the EL of GaN LEDs showed two peaks, one at 370 nm
(UV EL) and the other at 430 nm (blue EL), when the forward current was lower than 30 mA.
In the present LEDs, however, there was a strong blue EL and no UV EL when the forward
current was lower than 30 mA. Also, there were weak deep-level emissions whose peak wave-
Figure 13 Structure of the GaN p-n junction LED.

726 Nakamura
Figure 14 Emission spectra of the GaN p-n junction LED at different forward currents. Hole concentra-
tion of the p-type GaN of the LED was 8 ⫻ 10 18 /cm 3.
length was 550 nm. At 50 mA, a weak UV EL whose peak wavelength was 390 nm was observed
(see Fig. 14). This peak wavelength (390 nm) of UV EL is longer than that of previously reported
LEDs (370 nm) (22,26).
The forward current density of LEDs is almost the same as that of previously reported
LEDs because the chip size of the present LEDs (0.6 ⫻ 0.5 mm) is almost the same as that of
LEDs with AlN buffer layers (22,26). Therefore, it is difficult to conclude that the difference
in the current density caused these EL differences. Amano et al. (26) and Amano and Akasaki
(22) attributed the origin of the blue EL to the emission in the p-type GaN layer: electrons were
injected from the n-type GaN layer to the p-type GaN layer, and blue emission occurred through
recombination. Therefore, it is considered that the number of radiative recombination centers
of blue emission in the p-type GaN layer is much larger than that in the previous LEDs because
the intensity of the blue EL is much stronger than that of UV EL in GaN LEDs with GaN buffer
layers (see Fig. 14), assuming that the intensity of UV EL is almost the same in the present
LEDs and previously reported LEDs. Considering that the hole concentration of the p-type GaN
layer with GaN buffer layers (about 8 ⫻ 10 18 /cm 3 ) is much higher than that with AlN buffer
layers (typical value is of the order of 10 16 /cm 3 ), such a proposal is probably correct, because
blue emission centers are related to the energy level introduced by Mg doping in the energy
gap of GaN, and the intensity of the blue emission in PL measurement of the p-GaN layer
becomes strong when the hole concentration becomes high (26–28). Therefore, in the present
LEDs, UV EL was not observed below than 30 mA, and the UV EL intensity was very weak
above 30 mA in comparison with those of previously reported LEDs. The peak wavelength of
UV EL of the present LEDs (390 nm) is longer than that of the LEDs of Amano et al. (370
nm) (26). Amano et al. (26) and Amano and Akasaki (22) used an undoped GaN layer as the
n-type GaN layer for their LEDs, and the peak wavelength of UV EL was 370 nm. Considering
this result, the longer peak wavelength of UV EL (390 nm) may be caused by Si doping of the
n-type GaN layer, because the UV EL was caused by hole injection from the p-type GaN layer
to the n-type GaN layer, and UV emission occurred in the n-type GaN layer through radiative
recombination. A relatively strong UV EL against the blue EL was observed in the present GaN
LEDs when the crystal quality of the GaN film was poor and the hole concentration of the p-
type GaN layer was as low as 1 ⫻ 10 17 /cm 3. This is shown in Fig. 15. The shape of the EL
and the hole concentration of this LED were almost the same as those of the LEDs previously
reported by Amano et al. (26). Considering that the hole concentration is as low as 1 ⫻ 10 17 /
cm 3, this weak blue EL is related to the small number of radiative recombination centers in the
p-type GaN layer that contributes to the blue EL, and UV EL becomes dominant. The output
power of this LED, which had a low hole concentration (1 ⫻ 10 17 /cm 3 ), was very low (about
one fourth) in comparison with that of LEDs that had a high hole concentration (8 ⫻ 10 18 /
cm 3 ). This LED was easily broken over 50 mA. On the other hand, LEDs that had a high hole
concentration (8 ⫻ 10 18 /cm 3 ) were not broken even at 100 mA. The 550-nm deep-level emis-
sions may be caused by hole injection from the p-type GaN layer to the n-type GaN layer,
similarly to the UV EL, because the intensity of deep-level emissions becomes strong when the
UV EL becomes strong (see Figs. 14 and 15) and the PL measurement of the n-type GaN layer
shows deep-level emissions.
Figure 15 Emission spectra of the GaN p-n junction LED at different forward currents. Hole concentra-
tion of the p-type GaN of the LED was 1 ⫻ 10 17 /cm 3.
728 Nakamura
Figure 16 Output power (P) of the GaN p-n junction LED and the conventional 8-mcd SiC LED as a
function of the forward current (I F ). m is an exponent of I F when it is assumed that P is proportional to
I mF .
The output power is shown as a function of the forward current in Fig. 16. Commercially
available SiC LEDs whose brightness is 8 mcd and peak wavelength is 480 nm are also shown
for comparison with GaN LEDs. The output power of GaN LEDs is almost 10 times stronger
than that of SiC LEDs in the range of forward current between 1 and 4 mA. At 4 mA, the
output power of GaN LEDs is 20 µW and that of SiC LEDs 2 µW. At 20 mA, the output power
of GaN LEDs is 42 µW and that of SiC LEDs 7 µW. Generally in LEDs, the output power (P)
is proportional to I mF (I F is forward current). If the recombination current is dominant, m becomes
2; if the diffusion current is dominant, m becomes 1. In the range of DC current between 0.2
and 0.8 mA (low current range) in GaN LEDs, m is almost equal to 2.23. Between 1 and 4 mA
(intermediate current range), it is 1.15. Over 6 mA (high current range), it is 0.41. Therefore,
the recombination current is dominant in the low current range and the diffusion current becomes
dominant in an intermediate current range. Generation of heat may have caused the low output
power in the high current range. In SiC LEDs, m was almost equal to 0.73 between 0.2 and 30
mA. The highest external quantum efficiency, 0.18%, was obtained in an intermediate current
range for GaN LEDs and 0.02% was obtained for SiC LEDs. Blue EL was dominant below 50
mA (see Fig. 14). Therefore, these changes in output power are caused by the change in the
intensity of the blue EL.
High-power GaN p-n junction blue LEDs were fabricated using GaN films grown with
GaN buffer layers. The external quantum efficiency was as high as 0.18%. The output power
was almost 10 times higher than that of conventional 8-mcd SiC blue LEDs. The forward voltage
was 4 V at 20 mA. The recombination current was dominant below 1 mA. Therefore, further
improvement of the crystal quality is required to obtain high-power GaN p-n junction blue
LEDs.
VI. InGaN
Utilizing an (In,Ga,Al)N system, a band gap energy from 1.95 to 6.2 eV can be chosen. For
high-performance optical devices, a double-heterostructure is indispensable. This material en-
ables double-heterostructure construction. In this system, the ternary III-V semiconductor com-
pound InGaN is one candidate as the active layer for the blue and green emissions because its
band gap varies from 1.95 to 3.4 eV depending on the indium mole fraction. If the InGaN
semiconductor compound is used as an active layer in the double heterostructure, a InGaN/
AlGaN double heterostructure can be considered for blue-emitting devices because p-type con-
duction has been obtained for AlGaN in the (In,Ga,Al)N system.
Up to now, only a little research has been performed on InGaN growth (30–32). InGaN
crystal growth was originally performed at low temperatures (about 500°C), to prevent InN
dissociation during growth, by means of MOCVD (30,31). Later, relatively high-quality InGaN
films were obtained on a (0001) sapphire substrate by Yoshimoto et al. (32) using a high growth
temperature (800°C) and a high indium mole fraction flow rate. They reported that deep-level
emissions were dominant in PL measurements of the InGaN film at room temperature and that
the FWHM of the double-crystal XRC for (0002) diffraction from the InGaN films was about
30 min. Nakamura and Mukai (33) also grew InGaN films on GaN films with a high indium
source flow rate and high growth temperatures between 780 and 830°C. They observed strong
and sharp band edge (BE) emissions of InGaN between 400 and 445 nm in PL at room tempera-
ture.
Figure 17 shows the double-crystal XRC for the (0002) diffraction of InGaN films grown
on the GaN films. Curve (a) represents InGaN films grown at a temperature of 830°C (sample
A) and curve (b) those grown at a temperature of 780°C (sample B). Both curves clearly show
two peaks. One is the (0002) peak of the X-ray diffraction of GaN, and the other is that of
InGaN. The indium mole fraction of the InGaN films was estimated by calculating the difference
between the positions of the InGaN and GaN peaks assuming that the (0002) peak of the X-
ray diffraction of GaN is constant at 2θ ⫽ 34.53° and Vegard’s law is valid. These calculated
values of the indium mole fraction of the InGaN films of 0.14 for sample A and 0.24 for sam-
ple B, shown in Fig. 17. Therefore, the incorporation rate of indium in the InGaN film during
growth is increased when the growth temperature is decreased.
The FWHM of the double-crystal XRC for the (0002) diffraction from the InGaN film
was about 8 min and that from the GaN film was 6 min for sample A. The FWHM of the XRC
for the (0002) diffraction from the InGaN film was about 9 min and that from the GaN film
was 7 min for sample B. The values of FWHM of InGaN films are almost the same as those
of the GaN films that are used as substrates.
Figure 18 shows the results of PL measurements at room temperature. The excitation
source was a 10-mW He-Cd laser. Curve (a) represents sample A and curve (b) sample B.
Sample A shows a strong sharp peak at 400 nm and sample B at 438 nm. These emissions are
considered to be the BE emissions of InGaN films because they have a very narrow FWHM
(about 70 meV for sample A and 110 meV for sample B). The broad deep-level emissions,
which were considered to originate from defects such as nitrogen vacancies in InGaN films and
were dominant in the PL measurements of Yoshimoto et al. (32), were barely observed in this
study. These results of PL measurements also indicate that the crystal quality of InGaN films
grown on the GaN films is very good, as is also shown by the XRC measurements.
730 Nakamura
Figure 17 The XRC for (0002) diffraction from InGaN films grown on GaN films under the same
conditions except for the InGaN growth temperature. The growth temperatures of InGaN were (a) 830°C
and (b) 780°C.
Nakamura (34) also grew InGaN films with an indium mole fraction X up to X ⫽ 0.33
at temperatures between 720 and 850°C. The growth rate of InGaN films had to be decreased
sharply to obtain high-quality InGaN films when the growth temperature was decreased. Band
gap energies between 2.67 and 3.40 eV obtained by room-temperature PL measurements fit
quite well to parabolic forms on the indium mole fraction X assuming that the band gap energies
for GaN and InN are 3.40 and 1.95 eV, respectively, as shown in Fig. 19.
Figure 19 shows the band gap energy of grown InGaN films as a function of the indium
mole fraction X (34). The bandgap energy was obtained by room-temperature PL measurements
assuming that the narrow sharp emissions in the violet and blue regions are BE emissions. The
indium mole fraction of the InGaN films was determined by measurements of X-ray diffraction
peaks. Osamura et al. (35) had already shown that E g in ternary alloys In X Ga (1⫺X)N obeys para-
bolic forms on the molar fraction X:
E g (X) ⫽ X)E g,InN ⫹ (1 ⫺ X)E g,GaN ⫺ bX(1 ⫺ X) (1)
where E g (X ) represents the band gap energy of In XGa (1⫺X)N; E g,InN and E g,GaN represent the band
gap energy of compounds InN and GaN, respectively; and b is the bowing parameter. In that
calculation, E g,InN was 1.95 eV, E g,GaN was 3.40 eV, and b was 1.00 eV. These values calculated
from Eq. (1) are shown by the solid curve in Fig. 19. The solid curve fits the experimental data
quite well between indium mole fractions X ⫽ 0.07 and X ⫽ 0.33.
Figure 18 Room-temperature PL spectra of InGaN films grown on GaN films under the same growth
conditions except for the InGaN growth temperature. The growth temperatures of InGaN were (a) 830°C
and (b) 780°C.
VII. IMPURITY DOPING OF InGaN
Si-doped InGaN films were grown on GaN films by Nakamura et al. (36). Figure 20 shows
typical results of PL measurements of an Si-doped InGaN film that was grown at a temperature
of 830°C and a SiH 4 flow rate of 1.5 nmol/min. The PL measurements were performed at room
temperature. Very strong and sharp violet emission at 400 nm was observed, but deep-level
emissions were not observed in this spectrum, shown in Fig. 20. This violet emission is consid-
ered to be a BE emission of Si-doped InGaN because the FWHM of violet emission is very
small (about 140 meV). Nakamura and Mukai (33) also reported on undoped InGaN films that
were grown under the same growth conditions as in this study without SiH 4 gas flow. Comparing
the Si-doped InGaN with undoped InGaN, the peak position of 400 nm of the BE emissions at
an indium mole fraction (X) of 0.14 is not changed by Si doping, but the intensity of BE emis-
sions of Si-doped InGaN films becomes much stronger than that of undoped InGaN films. This
is shown in Fig. 21.
Figure 21 shows the relative intensity of BE emissions of PL measurements of Si-doped
and undoped InGaN films as a function of the SiH 4 flow rate. These InGaN films were grown
at a temperature of 830°C under the same conditions except for the SiH 4 flow rates. The peak
wavelength of BE emissions of these InGaN films was 400 nm and the indium mole fraction
determined by measurements of the X-ray diffraction peaks was 0.14. At an SiH 4 flow rate of
0.22 nmol/min, the intensity of BE emissions became 20 times stronger than that of undoped
InGaN films. At an SiH 4 flow rate of 1.50 nmol/min, the intensity of BE emissions became 36
times stronger than that of undoped InGaN films. However, at an SiH 4 flow rate of 4.46 nmol/
min, the intensity of BE emissions became weak. Therefore, it is considered that the optimal
SiH 4 flow rate is around 1.50 nmol/min, judging from the intensity of the BE emissions under
these growth conditions.
732 Nakamura
Figure 19 Band gap energy of In X Ga (1⫺X) N films as a function of the indium mole fraction X. The
indium mole fraction X was determined by measurements of the X-ray diffraction peaks. The solid curve
represents values that were obtained from Eq. (1) as discussed in the text, assuming that the band gap
energies for GaN and InN are 3.40 and 1.95 eV, respectively.
Figure 20 Room-temperature PL spectrum of Si-doped InGaN film grown at an SiH 4 flow rate of 1.5
nmol/min and a growth temperature of 830°C.
Figure 21 Relative PL intensity of the band edge emissions of Si-doped InGaN films as a function of
the SiH 4 flow rate. The growth temperature of the Si-doped InGaN films was 830°C.
This Si doping of InGaN films may form shallow donor levels in InGaN, as does Si doping
of GaN films (25). The carrier concentrations of InGaN increased from 10 17 to 10 19 /cm 3 with
Si doping at an SiH 4 flow rate of 1.50 nmol/min. This may explain why the intensity of the
BE emissions of Si-doped InGaN films becomes stronger.
Nakamura (37) performed Zn doping of InGaN for the purpose of obtaining blue emission
centers. Figure 22 shows typical results of room-temperature PL measurements of the Zn-doped
InGaN films. Spectrum (a) represents a Zn-doped InGaN film that was grown at a temperature
of 800°C and a diethylzinc (DEZ) flow rate of 8.0 nmol/min (sample A). Spectrum (b) represents
a Zn-doped InGaN film that was grown under the same conditions as sample A except for the
growth temperature and DEZ flow rate, which were changed to 810°C and 2.7 nmol/min (sample
B). Both spectra clearly show two peaks. Spectrum (a) shows peak emissions at 410 nm (3.02
eV) and 494 nm (2.52 eV). Spectrum (b) shows peak emissions at 398 nm (3.12 eV) and 462
nm (2.68 eV). The shorter wavelength peak is the BE emission of InGaN, and the longer wave-
length peak is Zn-related emission with a large value of FWHM (about 66 nm). The difference
in peak emission energy between the BE and Zn-related emissions is 0.50 eV for spectrum (a)
and 0.44 eV for spectrum (b).
Figure 23 shows the Zn-related emission energy as a function of the indium mole fraction
X of In X Ga (1⫺X )N. Curve (a) shows the band gap energy of In X Ga (1⫺X )N, which was calculated
using Eq. (1). Curves (b) and (c) show the energy levels that are 0.4 and 0.5 eV below the band
gap energy of In X Ga (1⫺X )N, respectively. From this figure, it is noted that 2.51 eV (494 nm) to
2.83 eV (438 nm) between X ⫽ 0.16 and X ⫽ 0.07 can be obtained as Zn-related emission
energy in Zn-doped InGaN. Also, the Zn-related emission energy is always between 0.4 and
0.5 eV lower than the BE emission energy of InGaN in this Zn doping range. Zn doping of
GaN has been performed by many researchers in order to obtain blue emissions for application
to blue LEDs (38,39). Peak energy shifts from blue emission at a low Zn concentration to red
734 Nakamura
Figure 22 Room-temperature PL spectra of Zn-doped InGaN films grown under the same conditions
except for the InGaN growth temperatures and DEZ flow rates. The growth temperatures of InGaN were
(a) 800°C and (b) 810°C. The flow rates of DEZ were (a) 8.0 nmol/min and (b) 2.7 nmol/min.
Figure 23 Zn-related emission energy as a function of the indium mole fraction X of In X Ga 1⫺X N. Curve
(a) shows the band gap energy of In X Ga 1⫺X N calculated using Eq. (1). Curves (b) and (c) show energy
levels 0.4 and 0.5 eV below the band gap energy of In X Ga 1⫺X N, respectively.
Figure 24 Room-temperature PL spectra of Si-and Zn-doped InGaN films. Spectrum (a) represents
typical Si-doped InGaN films grown at an SiH 4 flow rate of 1.5 nmol/min and a temperature of 800°C.
Spectrum (b) represents a Zn-doped InGaN film that was grown under the same conditions as in Fig. 22a.
The indium mole fraction X was 0.16 for both films.
at a high Zn concentration have been observed. Therefore, Zn doping of GaN forms many deeper
Zn-related levels above the valence band, depending on the Zn concentration in GaN. On the
other hand, Zn doping of InGaN results in values between 0.4 and 0.5 eV lower than the BE
emission energy of In X Ga (1⫺X )N as a Zn-related emission energy under these growth conditions.
Figure 24 shows PL spectra of Si- and Zn-doped InGaN films. Spectrum (b) represents
a Zn-doped InGaN film that was grown under the same conditions as in Fig. 22a at a DEZ flow
rate of 8.0 nmol/min. Spectrum (a) represents typical Si-doped InGaN films grown at an SiH 4
flow rate of 1.50 nmol/min and a temperature of 800°C. The indium mole fraction X was 0.16
for both spectra (a) and (b). Spectrum (b) shows strong blue emission at 492 nm with a broad
FWHM (66 nm) and weak BE emission at 410 nm, and spectrum (a) shows strong violet emis-
sion at 410 nm with a narrow FWHM (20 nm). The intensity of the blue emission of spectrum
(b) is almost the same as that of the violet emission of spectrum (a). Therefore, Zn-doped InGaN
films have potential for use as the active layer of InGaN/AlGaN DH-structure blue LEDs with
bright blue emissions.
VIII. InGaN/AlGaN DH LED
Figure 25 shows the structure of InGaN/AlGaN DH LEDs (14–17). As a buffer layer, GaN
was used instead of AlN. For cladding layers of DH structure, Al 0.15Ga 0.75N was used. As an
active layer, an InGaN layer codoped with Si and Zn was used to enhance blue emissions. When
736 Nakamura
Figure 25 Structure of the InGaN/AlGaN DH LEDs.
Si and Zn were codoped into an InGaN active layer, the intensity of blue emission became
maximum around the electron carrier concentration of 1 ⫻ 10 19 cm ⫺3. This codoping suggests
that the high-efficiency of this InGaN/AlGaN DH LED is the result of impurity-assisted recom-
bination, such as free carrier–acceptor (FA) recombination. A p-type GaN layer was used as a
contact layer for a p-type electrode in order to improve the ohmic contact. After the growth, N 2-
ambient thermal annealing was performed to obtain a highly p-type GaN layer at a temperature of
700°C. Fabrication of LED chips was accomplished as follows: the surface of the p-type GaN
layer was partially etched until the n-type GaN layer was exposed. Next, an Ni/Au contact was
evaporated onto the p-type GaN layer and a Ti/Al contact onto the n-type GaN layer. The wafer
was cut into a rectangular shape (350 ⫻ 350 µm). These chips were set on a lead frame and
were then molded. The characteristics of LEDs were measured under DC-biased conditions at
room temperature.
Figure 26 shows electroluminescence (EL) spectra of InGaN/AlGaN DH blue LEDs at
forward currents of 0.1, 1, and 20 mA. The carrier concentration of the InGaN active layer in
this LED was 1 ⫻ 10 19 cm ⫺3. A typical peak wavelength and FWHM of the EL were 450 nm
and 70 nm, respectively, at 20 mA. The peak wavelength shifts to shorter wavelengths with
increasing forward current. The peak wavelength is 460 nm at 0.1 mA, 449 nm at 1 mA, and
447 nm at 20 mA. At 20 mA, a narrower, higher energy peak emerges around 385 nm, as shown
in Fig. 26. This peak is due to band-to-band recombination in the InGaN active layer. This peak
becomes resolved at injection levels at which the impurity-related recombination is saturated.
The output power of the InGaN/AlGaN DH blue LEDs is 1.5 mW at 10 mA, 3 mW at 20 mA,
and 4.8 mW at 40 mA. The external quantum efficiency is 5.4% at 20 mA. The typical on-axis
luminous intensity of InGaN/AlGaN LEDs with 15° conical viewing angle is 2.5 cd at 20 mA.
The forward voltage was 3.6 V at 20 mA.
Blue-green LEDs were fabricated for application to traffic lights by increasing the indium
mole fraction of the InGaN active layer from 0.06 to 0.19 in the blue LEDs (16,17). Figure 27
shows the EL spectra of the blue-green InGaN/AlGaN DH LEDs at forward currents of 0.5, 1,
and 20 mA. A typical peak wavelength and FWHM of the EL were 500 nm and 80 nm, respec-
tively, at 20 mA. The peak wavelength shifts to shorter wavelengths with increasing forward
Figure 26 EL spectra of InGaN/AlGaN DH blue LEDs with different forward currents.
current. The peak wavelength is 537 nm at 0.5 mA, 525 nm at 1 mA, and 500 nm at 20mA.
The output power of the InGaN/AlGaN DH blue-green LEDs is 1.0 mW at 20 mA. The external
quantum efficiency is 2.1% at 20 mA. A typical on-axis luminous intensity of InGaN/AlGaN
blue-green LEDs with 15° conical viewing angle is 2 cd at 20 mA. This luminous intensity is
sufficiently bright for outdoor applications, such as traffic lights and displays. The forward volt-
age was 3.5 V at 20 mA.
Figure 28 shows the EL spectrum of the InGaN/AlGaN DH violet LEDs at forward cur-
rents of 1 and 20 mA (34). These violet LEDs were grown under the same conditions as blue
and blue-green LEDs, except for the InGaN active layer. During InGaN growth, only Si was
doped without Zn. The typical output power was 1.5 mW and the external quantum efficiency
was as high as 2.3% at a forward current of 20 mA at room temperature. The peak wavelength
and the FWHM of the EL were 385 nm and 10 nm, respectively. These InGaN/AlGaN DH
violet LEDs will be very useful for the realization of violet LDs in the near future because the
emission is very sharp and strong.
Figure 29 shows the external quantum efficiencies as a function of the peak wavelength
of various commercially available LEDs. Judging from this figure, there are no LED materials
except for InGaN that have high efficiencies over 1% below the peak wavelength of 550 nm.
Therefore, InGaN is one of the most promising materials for LEDs and LDs with peak wave-
lengths between 550 and 360 nm. Among II-VI materials, a ZnSe/ZnTeSe DH green LED has
been reported (1–3). The output power, external quantum efficiency, and peak wavelength of
those II-VI LEDs are 1.3 mW, 5.3%, and 512 nm at a forward current of 10 mA. A ZnSe/ZnCdSe
738 Nakamura
Figure 27 EL spectra of InGaN/AlGaN DH blue-green LEDs with different forward currents.
Figure 28 EL spectra of InGaN/AlGaN DH violet LEDs with different forward currents.

Figure 29 External quantum efficiencies as a function of the peak wavelength of various commercially
available LEDs.
DH blue LED also had an output power, external quantum efficiency, and peak wavelength of
0.3 mW, 1.3%, and 489 nm at a forward current of 10 mA. However, a lifetime of these II-VI
LEDs is only a few hundred hours at room-temperature operation. Because of this poor reliabil-
ity, II-VI LEDs and LDs have never been commercialized. Therefore, II-VI LEDs are not shown
in Fig. 29.
Table 1 shows a comparison of commercially available red, green, and blue LEDs in terms
of luminous intensity, output power, and external quantum efficiencies. From this table, the
peak wavelength of green and blue III-V nitride LEDs is much shorter than that of conventional
green GaP and blue SiC LEDs. Also, the output power and the external quantum efficiencies
of III-V nitride LEDs are much higher than those of conventional green and blue LEDs.
Table 1 Comparison of Commercially Available Red, Green, and Blue LEDS

External
Peak Luminous Output quantum
wavelength intensity power efficiency
LED Material (nm) (mcd) (µW) (%)
Red GaAlAs 660 1790 4855 12.83
Green GaP 555 63 30 0.07
InGaN 500 2000 1000 2.01
Blue SiC 470 9 11 0.02
InGaN 450 2500 3000 5.45
740 Nakamura
IX. QUANTUM WELL STRUCTURES
Nakamura et al. (40) grew two kinds of In 0.22Ga 0.78 N/In 0.06Ga 0.94 N multi-quantum-well (MQW)
structures on GaN films. One was MQW-100, in which the thicknesses of both barrier (L B ) and
well layers (L W ) were 100 Å (L B ⫽ L W ⫽ 100 Å) and the number of periods was 10. The other
was MQW-30, in which the thicknesses of barrier and well layers were 30 Å (L B ⫽ L W ⫽ 30
Å) and the number of periods was 20. Figure 30 shows the XRC for (0002) diffraction from
In xGa (1⫺X) N/In yGa (1⫺y) N MQW structures grown on GaN films. Curve (a) represents MQW-100
and curve (b) MQW-30. Both curves clearly show three peaks, which are the (0002) peak of
the X-ray diffraction of GaN, a zeroth-order peak marked ‘‘0,’’ and satellite peak marked ‘‘⫺1’’
associated with the MQW structures. The FWHMs of the zeroth-order peak and GaN underlayer
peak were 7.1 and 5.4 min for MQW-100, and 6.3 and 4.3 min for MQW-30.
The In x Ga (1⫺x) N/In yGa(1⫺y) N MQW period (L B ⫹ L W ) can be accurately determined using
the equation (2 sin Θ n ⫺ 2 sin Θ SL ) ⫽ ⫾ nλ/(L B ⫹ L B ), where λ is the X-ray wavelength, n
is the order of satellite peaks, Θ n is their diffraction angle, and Θ SL is the Bragg angle of the
zeroth-order peak. Using this equation, Nakamura et al. (40) estimated 194 Å as the period (L B
⫹ L W ) for MQW-100 and 64 Å for MQW-30. These values were almost equal to 200 Å for
MQW-100 and 60 Å for MQW-30, which were determined by the GaN growth rate and the
gallium source flow rate.
Figure 31 shows the results of room-temperature PL measurements of an In 0.22Ga 0.78 N/
In 0.06Ga 0.94 N MQW structure. Curve (a) represents MQW-100 and curve (b) MQW-30. MQW-
100 shows a strong sharp peak at 420 nm (2.952 eV) and MQW-30 exhibits one at 412 nm
(3.010 eV). Both curves show no deep-level emissions. The intensities of these peak emissions
Figure 30 The XRC for (0002) diffraction from In X Ga (1⫺X)N/In yGa (1⫺y)N MQW structures grown on
GaN films under the same growth conditions except for the period (L B ⫹ L W ). The periods were (a) 200
Å and (b) 60 Å.
Figure 31 Room-temperature PL spectra of In xGa (1⫺X) N/In yGa (1⫺y) N MQW structures grown on GaN
films under the same growth conditions except for the period (L B ⫹ L W ). The periods were (a) 200 Å and
(b) 60 Å.
were about twice as strong as that of BE emission of bulk InGaN, and the FWHMs were 26
and 22 nm for samples A and B. These emissions are considered to be due to radiative transitions
between quantum energy levels in the MQW structures.
High-quality In 0.22Ga 0.78 N/In 0.06Ga 0.94 N MQW structures were grown on GaN films with
periods of 60 and 200 Å. Double-crystal XRC measurements showed satellite peaks that indi-
cated the existence of the In 0.22Ga 0.78 N/In 0.06Ga 0.94 N MQW structure. The quantum effects were
observed through room-temperature PL measurements. These high-quality MQW structures can
be used for an active layer of blue LEDs and LDs.
X. InGaN LEDs WITH QUANTUM WELL STRUCTURES
High-brightness blue and blue-green InGaN/AlGaN DH LEDs with a luminous intensity of 2

cd have been fabricated and are now commercially available, (14–17). In order to obtain blue
and blue-green emission centers in these InGaN/AlGaN DH LEDs, Zn doping of the InGaN
active layer was performed. Although these InGaN/AlGaN DH LEDs produced a high-power
light output in the blue and blue-green region with a broad emission spectrum (FWHM ⫽ 70
nm), green or yellow LEDs that have a peak wavelength longer than 500 nm have not been
fabricated. The longest peak wavelength of the electroluminescence of InGaN/AlGaN DH LEDs
achieved thus far is 500 nm (blue-green) because the crystal quality of the InGaN active layer
of DH LEDs becomes poor when the indium mole fraction is increased in order to obtain a
green band-edge emission.
On the other hand, in conventional green GaP LEDs the external quantum efficiency is
only 0.1% because of the indirect transition band gap material and the peak wavelength is 555
nm (yellowish green) (41). As another material for green emission devices, AlInGaP has been
used. The present performance of green AlInGaP LEDs is an emission wavelength of 570 nm
(yellowish green) and maximum external quantum efficiency of 1% (41,42). When the emission
742 Nakamura
wavelength is reduced to the green region, the external quantum efficiency drops sharply because
the band structure of AlInGaP becomes close to an indirect transition band structure. Therefore,
high-brightness pure green LEDs, which have a high efficiency of above 1% at a peak wave-
length between 510 and 530 nm with a narrow FWHM, have not yet been commercialized.
Among II-VI materials, ZnSSe- and ZnCdSe-based materials have been intensively stud-
ied for use in green light–emitting devices, and much progress has been made. The performance
of II-VI green LEDs is an output power of 1.3 mW, external quantum efficiency of 5.3% at 10
mA, and peak wavelength of 512 nm (1–3). However, the lifetime of II-VI–based devices is
still short, which prevents their commercialization at present.
Nakamura (34) reported violet InGaN/AlGaN DH LEDs with a narrow spectrum (FWHM
⫽ 10 nm) at a peak wavelength of 400 nm originating from the band-to-band emission of InGaN.
However, the output power and the external quantum efficiency of the violet InGaN/AlGaN
DH LEDs were only 1 mW and 1.6%, respectively, probably because of the formation of misfit
dislocations in the thick InGaN active layer (about 1000 Å) caused by the stress introduced in
the InGaN active layer by lattice mismatch and the difference in thermal expansion coefficients
between the InGaN active layer and AlGaN cladding layers. When the InGaN active layer be-
comes thin, the elastic strain is not relieved by the formation of misfit dislocations and the
crystal quality of the InGaN active layer improves. A high-quality InGaN MQW structure with
30-Å well and 30-Å barrier layers has been described (40). Here, quantum-well (QW) structure
LEDs that have a thin InGaN active layer (about 20 Å) in order to obtain high-power emission
in the region from blue to yellow with a narrow emission spectrum are described.
The green LED device structures (Fig. 32) consist of a 300-Å GaN buffer layer grown
at a low temperature (550°C), a 4-µm-thick layer of n-type GaN: Si, a 1000-Å-thick layer of
n-type Al 0.1Ga 0.9 N: Si, a 500-Å-thick layer of n-type In 0.05Ga 0.95 N :Si, a 20-Å-thick active layer
of undoped In 0.43Ga 0.57 N, a 1000-Å-thick layer of p-type Al 0.1Ga 0.9 N: Mg, and a 0.5-µm-thick
layer of p-type GaN: Mg. The active region forms a single-quantum-well (SQW) structure con-
sisting of a 20-Å In 0.43Ga 0.57 N well layer sandwiched between 500-Å n-type In 0.05Ga 0.95 N and
1000-Å p-type Al 0.1Ga 0.9 N barrier layers. The indium mole fraction of the InGaN active layer
was varied between 0.2 and 0.7 in order to change the peak wavelength of the InGaN SQW
LEDs from blue to yellow.
Figure 32 The structure of a green SQW LED.

Figure 33 Electroluminescence of (a) blue, (b) green, and (c) yellow SQW LEDs at a forward current
of 20 mA.
Figure 33 shows typical EL of the blue, green, and yellow SQW LEDs with different
indium mole fractions in the InGaN well layer at a forward current of 20 mA. The longest
emission wavelength is 590 nm (yellow). The peak wavelength and the FWHM of typical blue
SQW LEDs are 450 nm and 20 nm, respectively; of green SQW LEDs 525 nm and 45 nm,
respectively; and of yellow SQW LEDs 590 nm and 90 nm, respectively. When the peak wave-
length becomes longer, the FWHM of the EL spectra increases, probably due to the strain
between well and barrier layers of the SQW, which is caused by mismatch of the lattice and
thermal expansion coefficients between well and barrier layers.
In the green SQW, the indium mole fraction of the InGaN active layer is 0.43, correspond-
ing to the band edge emission wavelength of In 0.43Ga 0.57 N of 490 nm under stress-free conditions
(34). On the other hand, the emission wavelength of green SQW LEDs is 525 nm. The energy
difference between the peak wavelength of the EL and the stress-free band gap energy is approxi-
mately 170 meV. In order to explain this band gap narrowing of InGaN in the SQW, quantum
size effects, exciton effects (electron-hole pairs correlated by Coulomb effects) of the active
layer, and mismatch of the lattice and thermal expansion coefficients between well and barrier
layers must be considered. Among these effects, the exciton effects and the tensile stress caused
by the difference in thermal expansion coefficients between well and barrier layers may be
primarily responsible for the band gap narrowing of the InGaN in the SQW structure.
The output power of the SQW LEDs is shown as a function of the forward current in
Fig. 34. The output power of the blue SQW LEDs slightly increases sublinearly up to 40 mA
as a function of the forward current. Above 60 mA, the output power almost saturates, probably
because of the generation of heat. At 20 mA, the output power and the external quantum effi-
ciency of blue SQW LEDs are 4 mW and 7.3%, respectively, which are much higher than those
of InGaN/AlGaN DH LEDs (1.5 mW and 2.7%). Those of the green SQW LEDs are 1 mW
and 2.1%, respectively, and those of yellow SQW LEDs are 0.5 mW and 1.2%, respectively.
The output power of green and yellow SQW LEDs is relatively small in comparison with that
of blue SQW LEDs, probably because of poor crystal quality of the InGaN well layer, which
has large lattice mismatch and difference in thermal expansion coefficients between well and
744 Nakamura
Figure 34 Output power of (a) blue, (b) green, and (c) yellow SQW LEDs as a function of the forward
current.
barrier layers. A typical on-axis luminous intensity of Green SQW LEDs with 10° cone viewing
angle is 4 cd at 20 mA.
The output power decreases when the peak wavelength becomes longer, probably because
of the large strain between well and barrier layers. The output power of green and yellow LEDs
is 1 mW (at 525 nm) and 0.5 mW (at 590 nm), respectively. The conventional green GaP LED
with a peak wavelength of 555 nm has an output power of 0.04 mW (41). Also, the output
power of green AlInGaP LEDs with a peak wavelength of 570 nm is 0.4 mW (41,42). Therefore,
the output power of green InGaN SQW LEDs is much higher than that of conventional yellowish
green LEDs. Also, the luminous intensity of InGaN green SQW LEDs (4 cd) is about 40 times
higher than that of conventional green GaP LEDs (0.1 cd), and the color of InGaN SQW LEDs
is greener than those of conventional GaP and AlInGaP LEDs. A typical example of the I-V
characteristics of the green SQW LEDs shows that the forward voltage is 3.6 V at 20 mA.
XI. SUMMARY
Highly efficient InGaN/AlGaN DH blue LEDs with an external quantum efficiency of 5.4%
were fabricated by codoping Zn and Si into the InGaN active layer. The output power was as
high as 3 mW at a forward current of 20 mA. The peak wavelength and the FWHM of the EL
of blue LEDs were 450 nm and 70 nm, respectively. Blue-green LEDs with a brightness of 2
cd were fabricated by increasing the indium mole fraction of the InGaN active layer.
High-brightness blue LEDs with a luminous intensity over 1 cd will pave the way toward
realization of full-color LED displays, especially for outdoor use. Total power consumption by
traffic lights reaches the gigawatt range in Japan. InGaN/AlGaN blue-green LED traffic lights,
with an electrical power consumption 12% that of present incandescent bulb traffic lights, prom-
ise to save vast amounts of energy. They have an extremely long lifetime of several tens of
thousands of hours, so the replacement of burned-out traffic light bulbs will be dramatically
reduced. Using these high-brightness blue-green LEDs, safe and energy-efficient roadway and
railway signals will be achieved in the near future.
High-brightness InGaN green SQW LEDs were fabricated. The luminous intensity was
4 cd and the external quantum efficiency was as high as 2.1% at a forward current of 20 mA
at room temperature. The peak wavelength and the FWHM of the green LEDs were 525 nm
and 45 nm, respectively, and those of yellow LEDs were 590 nm and 90 nm, respectively. The
color of green InGaN SQW LEDs was greener than those of conventional GaP and AlInGaP
LEDs. Fabrication of practical visible LEDs in the range from blue to yellow is possible at
present using III-V nitride materials.
In the near future, III-V nitride blue, violet, or UV LDs with high reliability will be realized
because high-quality III-V nitride films are already available and high-power blue LEDs with
quantum well structures are also available.
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INDEX
Ab initio self-consistent pseudopotential calcula- [amorphous (a)]

tion, BP, 559 a-BP, 264, 566
Absorption a-Si, 265, 289, 292
diamond, 375–376, 378–381 a-SiC, 482
SiC, 451 angle-resolved photoemission spectroscopy
Absorber (ARPES), 84–85, 234, 239
TiC, TiC x Ny , ZrC, ZrC x N y, ZrC 6, 314 NbC, 228–230
Absorption edge, 603 TMC, 226, 228, 231–232, 236, 241
a-B, 635, 666–667, 670 antiphase boundary (APB)
B 4C, 621 SiC, 443, 445
B 12P2, 631 VC, 36–37
β-B, 605 antiphase domain
diamond, 375–376 c-BN, 543
ACCU field effect transistor (FET), SiC, 487– SiC, 357–358
488 antisite defect
Acoustic surface wave (see also Surface acous- boron-rich solid, 640
tic wave), AlN, 691 SiC, 416
Activated reactive evaporation (ARE), 322
c-BN, 73 Baliga’s figure of merit (BFOM), 358, 387,
Active diamond electronics, 365 478–479
electronic device, 369, 382–383 Baliga’s high frequency (BHFOM), 385, 387
heterojunction device, 400 Baliga’s pair, 488
high-temperature operation, 394, 396, 398, SiC, 490–491
403 Band gap, 228, 246, 312, 666
industrial application, 405 B, 656, 666, 670
power device, 385, 387, 403 B4C, 621
Activity (coefficient) BP, 567–568, 571, 584
C and Nb in NbC, 192 β-B, 605
C and V in VC, 193 boron-rich solid, 603
C and Zr in ZrC, 194 c-BN, 495, 509–510, 523, 545, 548
Si in SiC, 414 diamond, 393
Zr in ZrN, 195 GaN, 715
AlGaInN, 715–718 In xGa 1-x N, 730
Aluminum nitride (AlN), 292, 294 SiC, 447, 459
Aluminum oxide (AlO x ), 289, 292, 299 Band gap engineering, diamond, 395, 403
Al In GaP light emitted diode (LED), 742 Band structure, 83, 120
Alkali metal adsorption on TMC, 241 α-B, 602
amorphous (a) B 4C, 620–621
a-B, 595, 635 BP, 558
a-BN, 499–500, 510 β-B, 603
747
748 Index
[Band structure] Boron-rich compound, 589, 591, 593, 632, 634–

c-BN, 509, 545 636, 643
diamond, 385 Bowing parameter b, In xGa 1-x N, 730
δ-TaN, 113 Brillouin (light) scattering
HfC, 112 BP, 559, 567
HfN, 112 MN superlattice, 14
MC x (x⬍1), 123–124 TiN, 12
MN, 85 Brillouin zone (BZ), 85
MN x (x⬍1), 123–124 δ-TaN, 113
NbN, 88 SiC, 446
TaC, 112 TiC, 123
TaN, 112 WC, 117
TiC, 82 Buffer layer
TiN, 82 AlN, 716, 725
TMC, 85 GaN, 718, 742
Si/BP, 583 Bulk modulus (moduli)
of surface state on TMC, 236 B, 153, 155–157, 171
WC, 118 BP, 558–559
ZrC, 90 TiC, TiN, VC, VN, 121
ZrN, 90, 258
B 11C icosahedra, 591–592, 599–600, 606–607, Carrier removal rate, SiC, 464
620, 623, 640, 642 Carbothermal (carbothermic) reduction (powder)
Bias voltage (potential), 322 AlN, 693–696, 700
c-BN, 537 NbB 2, 23
TiC, 59, 333–334, 343 TiB 2, 19
TiB 2, 328 TiC, 23
B 12 icosahedra, 590–592, 595–596, 598–600, Channeling (ion channeling), 119, 248
602, 606, 610, 620, 623, 639–640, 642 Characterization, 1, 3, 4
Bipolaron (hopping), B 4C, 591–592, 623 a-Si, 265
Blister, TiC, 333–334, 344 B, 662
Bloch-Grüneisen (BG) formula, 174–177, 186 diamond, 354
BN phase, 496–499 Charge distribution, 95
c-BN, 495–556 Charge transfer, 96–97, 99, 113
h-BN, 497–498 Chemical vapor deposition (CVD), 19–20, 30,
r-BN, 497–498 46, 55–57, 68, 75, 78, 219, 312, 322
t-BN, 499–500 AlN, 696
w-BN, 496–499 BN, 500, 537, 542
Bonding mechanism, 113 BP, 263, 562–564, 566, 581–582
MC-MN, 95 diamond, 347–351, 354, 357–360, 365–366,
MX x (x⬍1), 132 370, 374–375, 377–378, 380–382, 389,
TiC, 105 391
TiN, 105 NbN, 290
VN, 105 SiO 2, 295
Bond type TiB 2, TiC phase diagram, 32
TiC, TiN, 102 TiC, 32, 63, 70
Boron (B), 589 TiN, 32, 77
α-rhomb.B, 590–592, 602, 627, 630, 640– Chemical vapor transport (CVT), 46
641 BP, 562
α-tetra.B, 593–594, 632, 634, 640 TiB 2, 32
β-rhomb.B, 590, 592, 594–595, 599, 602– Cluster method, 83, 120
607, 608–612, 616–618, 623, 635, 639– Cohesive energy, 121, 165–168
641 Composite material, 1, 14, 29
β-tetra.B, 595–596, 633–635, 640 c-BN/TiC, TiN, Al 2O 3, Si 3N 4, WC, 534
Index 749
[Composite material] Diamond, 347–366, 369–383, 385, 388–399,

C/C, 336, 341–342 403
Ti/TiB 2, 184 Diamond single crystal, 354–355, 360–361,
TiB 2 /Al, 217 364, 374, 399
TiB 2 /TiC 0.5N 0.5, 30 Dielectric function
Computational method, 83 B 4C, 621, 625–626
Conversion efficiency (CE), 310, 317 BP, 560
Critical supersaturation σ cr, SiC, 430 c-BN, 509
Czochralski technique (growth), 43 C 2Al 3B 48, 632
TaC, 34 VB 32, 618
Diffusion coefficient (constant)
Debye (characteristic) temperature, 10, 153– AlN, 706–707
154, 158–159, 162, 169, 174, 176, SiC, 422–425, 444
185 TMC, 197
BP, 573–574 Diffusion profile, SiC, 422, 425
c-BN, 514, 519 Diffusion rate, SiC, 423, 425, 433
h-BN, 519 Direct current (DC) magnetron sputtering, 63
SiC, 417, 463 Ti-B-C, 74
TiB 2, 201 DC-superconducting quantum interference de-
TiC, 164–165 vice (SQUID), 300
TMC, 157 DC plasma CVD, c-BN, 537
VN, 203 Direct nitridation, AlN, 679, 693–695
w-BN, 519 Direct sputtering, 55, 62–63
Debye model, 153, 161, 165, 175 Donor-acceptor (D-A) pair
Debye-Waller (D-W) factor, 119, 161, 247 BP, 562
ZrC, 203 SiC, 454–455
Defect, 178, 188, 264 Donor in SiC, 424–425
AlN, 686, 696, 701–702 Doping (dopant)
BP, 248, 266, 564 by substitution, β-B, 618
c-BN, 522–525 Al in 3C-SiC, 455, 462
diamond, 354, 358–359, 378, 381 B in diamond, 370, 372–373, 375, 377, 379–
MB 2, 34 382, 389, 396–397
NbC, 248 of c-BN, 546
SiC, 419, 429, 448, 468 Be in c-BN, 523–525, 534
w-BN, 499 codoped InGaN, 735–736
Density of state (DOS), 107, 123 columm III element for 6H- and 4H-SiC, 461
B 12 icosahedron, 602 diamond, 359
β-B, 603 Ti in SiC, 456
c-BN, 509 V in 6H-SiC, 456, 462
HfC, HfN, 112 impurity
MB 2, 142–144 a-B, 595
M 2X, 138–139 AlN, 359, 688
MN, 88, 130, 132–133, 135, 242 B in diamond, 370, 374–375, 377–398
NbC, 227 c-BN, 525, 532, 546
TaC, 112 nitrogen in 3C-SiC, 454, 463
TiC, 121, 125–126 nitrogen in diamond, 351, 370, 375–377,
TiN, 121 381–382
TMC, 88, 130, 132–133, 135, 242 nitrogen in 6H-SiC, 454, 461
ZrC, ZrN, 90 nitrogen or Al in SiC, 433, 461
Deposition rate, 63 S in c-BN, 548
B, 659, 662 SiC, 434
Ti 1-xB x, 326 Si in c-BN, 523, 526
TiC, 332–333 Si in GaN, 719–721
750 Index
[nitrogen in 6H-SiC] Emission (emissivity), 191

Si in InGaN, 731–732 diamond, 376
Zn in InGaN, 733–735 TaC, 233
Drude behavior, B 4C, 626 TMC, 192
Ductile-brittle (D-B) transition ZrC, 195, 201
TiC, 214, 218 Emission current stabilization, 283
(Ti,Mo)C, 215 Emission spectra
TMC, 210 TaC, 232, 234
TiC, 237
Edge termination, 482 Emittance, 192, 308, 310
in SiC, 481 Empirical pseudopotential method (EPM), BP,
Effective mass 566
B 4C, 626 Entropy, 159, 162
c-BN, 509 NbC, 192–193
diamond, 371, 375 SiC, 414, 416
SiC, 459 Etching
Elastic constant (modulus), 12, 153, 155, 169, B, 663
171, 339 c-BN, 505–506, 508, 537
BP, 558–559, 567 diamond, 349, 363, 395
c-BN, 510, 512, 514 Exchange-correlation potential, 84
TiB 2, 158 Excitation, diamond, 376–378, 382
Electrical conductivity (see also Resistivity), 5, Excitation coefficient, B, 659, 670
173–174, 180 Exciton energy gap, SiC, 451
α-B, 633 Exciton
B, 658, 663, 665, 671 diamond, 376–388, 382
B 4C, 623, 625 SiC, 453–454
BP, 570–571
β-B, 608, 613 Far infrared (FIR) reflectivity
YB 66, 638 B 4C, 626
Electron cycloton resonance (ECR) ion beam β-B, 618
sputtering, AlN, 684 Fiber-reinforced material (FRM), 1
ECR assisted etching, diamond, 395 AlN, 689
ECR plasma CVD, c-BN, 537 TiB 2, 217
Electron deficiency TiC, 45
B, B 4C, 640–641, 644 Field effect transistor (FET)
boron-rich solid, 601, 644 diamond, 390–392
YB 66, 643 SiC, 480
Electronic structure, 81, 83 Field emission (FE), 269
MB 2, 142 Field emission current, TMC, 272, 280
MC, 82, 85, 112, 119–120 Field emission pattern, TMC, 270, 277, 280
MC-MN, 135 Field ion microscopy (FIM)
MN, 82, 85, 112, 119–120 HfC, 30
M 2X, 138 TiC, 271
WC, 117–119 Figure of merit of morphology (FOMM), 57
Electron-phonon interaction (scattering), 10, First-order (phase) transition (transformation)
154, 174, 179, 185, 619 BN, 500
β-B, 605–606, 616 VC, 202, 209
boron-rich solid, 644 V 2C, 194
Electron spin resonance (ESR) First wall, 321, 337
boron-rich solid, 591–592 Floating-type fluidized-bed nitridation, AlN, 682
β-B, 607 Flux method
c-BN, 523 BP, 562, 584
SiC, 429, 449, 462–463, 466–467 MB 2, TMC, 33
Index 751
Force constant, 10, 166 [Heat capacity]

c-BN, 512 TaC, 177
TMC, MN, 169 TiC, TiN, 207
Four-junction logic (4JL), NbN, 295–296 Heat sink
Fowler-Nordheim (F-N) plot, TMC, 281–282 AlN, 691
Fracture strength (toughness), 14, 341 BP, 574
TiB 2, 216–217 c-BN, 546
Free carrier-acceptor (FA) recombination, diamond, 347
InGaN/AlGaN DHLED, 736 Heteroepitaxy
Full width at half-maximum (FWHM) diamond, 360, 365, 395, 399, 400, 495
diamond, 354, 364 SiC, 444
GaN, 718 Heterojunction (heterostructure)
InGaN, 729, 731, 735 BP/Si, 557, 576–577, 582–584
InGaN/AlGaN, 736, 742 diamond/c-BN, 395, 400–401, 495, 543
SQW, 743 Si/BP/Si, 577
TiC, 61 Heteropolytype, SiC, 433
Fusion reactor, 321, 336–337 Hexagonality, SiC, 418, 452
High pressure/high temperature (HP/HT) syn-
GaN, 715–718 thesis
GaN diode, 682 BN, 495
GaP LED, 382, 456, 741 c-BN, 528
Grain boundary, 36 diamond, 347, 349, 355, 361
AlN, 701–703, 705–707, 709, 711 High pressure synthesis
diamond, 364 catalyst method, a-BN, 529–532
NbB 2, TiN, ZrB 2, 28 c-BN, 528–535
TiB 2, 29, 200–211, 214 High-resolution (transmission) electron micros-
TiC, 29, 198 copy [HR(T)EM]
Growth sectors, diamond, 352–353, 358, 363, BP, 546
380–381 c-BN, 543
Grüneisen parameter, TiB 2, 201 diamond, 365
GW approximation NbC, 36
BP, 559–560 SiC, 446
c-BN, 509 VC, 38
High strain rate superplasticity (HSRS), 217
Hall coefficient High-temperature device, c-BN, 547
HfC, TaC, VC, ZrC, 186 Hollow cathode-discharge (HCD) ion plating, 59
TiC, 186, 199 TiN, 61
YB 66, 638 Homoepitaxy
Hall measurement (effect) diamond, 355, 391
B 4C, 625 SiC, 442
BP, 567 Homogeneity range
β-B, 610 B 4C, 619–620
c-BN, 525 boron-rich boride, 590
diamond, 359, 371, 375, 377 MB 2, 39
SiC, 449, 456 Hopping conduction
Hardness (see Micro-Vickers hardness and a-B, 665, 671
Knoop hardness), 169 B 4C, 226
Hashin-Shtrikman bounds, 156, 183–184 B(:Fe), 618
Heat capacity (see also Specific heat capacity), boron-rich solid, 591
165, 181 β-B, 610–612
AlN, 702 diamond, 372–373
c-BN, 522 Hot electron bolometer (HEB), NbN, 300
NbC, 193 Hot implantation, SiC, 461
752 Index
Hot isostatic pressing (HIP) technique, 20, 28 Ion beam deposition, a-BN, 500
AlN, 697 Ion beam-induced crystallization (IBIEC), BP,
BP, 561 246, 262, 265, 585
TiB 2, TiC, 29 Ion beam-induced reaction, BP, 261
Hydrogenation Ion beam irradiation
GaN, 723, 725 BP, 259
diamond, 375 MN, 253–255
GaN, 723 VN, ZrN, 312
MN, TMC, 15 Ion implantation
Hydrogen atom diamond, 389
GaN, 723 SiC, 424, 461, 464, 482
diamond, 375 MN, 253–257
Hot electron bolometers (HEB), 300 Ion plating, 55
TiC, 330
Ideal solar absorber, 309 Irradiation, 245
Indentation hardness (see also Micro-Vickers BP, 259
hardness and Knoop hardness) NbC, 247
MB 2, 211 Isoelectronic trap, SiC, 456
TiN, ZrC, 11
TMC, 209–210 Jahn-Teller (J-T) effect
Impact-collision ion scattering spectroscopy B 4C, 639
(ICISS) β-B, 605, 616
TiC, 240 boron-rich solid, 600–602, 644
TMC, 224–225 Johnson’s figure of merit (JFOM), 385
Impurity, 178
AlN, 675, 687–688, 694, 696 Key’s FOM (KFOM), 385, 387
B, 672 Knoop hardness (see also Micro-Vickers hard-
c-BN, 523–524 ness)
SiC, 449 B 4C, c-BN, diamond, SiC, 513
InGaN, 729–731 NbB 2, 211
Infrared (IR) spectrum TiN/AlN, 74
B, 657, 670 Kondo effect, TiB 2, 186
BN, 500, 516, 518, 537
BP, 569 Laser diagnostic, ZrC, 198, 218
boron-rich solid, 591 Laser-ablated deposition, c-BN, 541
InGaN, 729–731 Laser-assisted CVD, diamond, 351
Integrated circuit (IC), 77 Laser-assisted plasma CVD, c-BN, 537
diamond, 396, 401 Laser diode (LD), 715
NbN, 291, 293, 300 GaN, 721
SiC, 477 InGaN/AlGaN, 737
Interband transition Lattice parameter (constant), 121, 203, 255
B 4C, 621 AlN, 691, 707
β-B, 605 BN, 496
Internal stress, 61 BP, 562, 567, 574
SiC, 448–449 diamond, 385, 393
TiC, 324 HfN, 253–255
Interstitial GaN, 716
accommodation (site), 590, 600 MB 2, 205–206
compound, 7, 82 MC, MC-MN, MN, 204
doping, β-B, 616 MN, 204
Intervalley scattering, SiC, 459–461 NbC, 246–247, 250–253, 255, 278
Inversion layer mobility, SiC, 485, 487 SiC, 409, 416, 429, 433–434
Ion beam bombardment, c-BN, 537 (SiC) x (AlN) 1-x, 625
Index 753
[Lattice parameter] Magnetic penetration depth, NbN, 291

TiB 2, 328 Magnetron sputtering, 63
TiC, 207, 332 TiB 2, 324, 334
TiN, 204, 207 TiC, 323–324, 331
ZrN, 253–257 Mass transfer, SiC, 427–431, 433
Lattice vibration, 10, 153, 159 Matthiessen’s rule, 178–179
AlN, 701 SiC, 460
c-BN, 514, 516, 518 VC, 202
LCAO-coherent potential approximation (CPA), Mean free path, 179
NbC, 245 of phonon, 181
LCAO partial l-like density of statue (DOS), 95 Mechanical alloying, 45
MXx (x⬍1), 125 MB 2, TMC, 22–23
TiC, TiN, VC, VN, 91 Melting point (temperature), 165, 291, 322, 336,
Light-emitting diode (LED), 715, 737, 739 343
AlInGaP, 741, 744 boron-rich solid, 589–590, 644
blue, red, 739 c-BN, 503, 536
c-BN, 547–548 diamond, SiC, 385
GaN, 721, 725–727 graphite, 322
GaP, InGaN, 741, 744 C/C, 336
green, 739–742 TiB 2, 322
InGaN/AlGaN, 736, 741, 744 TiC, 164, 322
SiC, 728 TiC-TiB 2, 337
Liquid-phase epitaxy (LPE), SiC, 437–438, 462 TiN, 21
Liquid-phase sintering, 20 TMC, MN, 168
AlN, 697–698, 700 Metal diffusion (diffusivity), 197
Local density approximation (LDA), 83 NbC, 198
BP, 558, 560 Metal organo CVD, 56
c-BN, 509 GaN, 715–716, 721, 724
Ti 2N, 141 Metal-oxide semiconductor (MOS)FET, 77
Local partial l-like DOS, 90, 104 diamond, 390, 392, 400, 403
MX x, 125 SiC, 444, 470, 484, 488, 490, 493
TaC, 112 Metal semiconductor (MES) FET, 390
TiC, 121 diamond, 392, 397–399, 402–403, 444
Ti 2N, 138 SiC, 444, 470, 488, 490, 493
Lorentz number, 180 Microhardness anisotropy, 10
Low-energy electron diffraction (LEED) BP, 567
diamond, 356 NbC, 36
graphite, 277 Micro-Vickers hardness (see also Knoop hard-
NbC, 277–279 ness), 171
SiC, 441 BN, 73–74
TMC, 223, 225, 277 BP, 567
Low-pressure synthesis, c-BN, 536–543 c-BN, 513
Low-Z material, 321–322 MN, 11–12
B, 672 NbB 2, TaB 2, 9
C, 336 NbC, 36
Luminescence SiC, 418
c-BN, 523 TiB 2, 28
diamond, 375–378, 381–382 Ti 1-x B x, 328
SiC, 447, 453–454, 463 TiC, 57, 59
Ti-C-B, 29
Magnesium oxide (MgO), 290, 292–296, 298– TiN/AlN, 74
300 TiN/VN, TiN/(V 0.6Nb 0.4)N, ZrC-ZrB 2, 14
Magnetic effect, TiB 2, 186 TMC, 70, 169, 209–210
754 Index
Microwave plasma CVD, c-BN, 537 n-type

Mobility diamond, 375
B 4C, 625 B 14Si, 632
BP, 567, 570–571, 578, 585 β-B, 616
β-B, 608, 612 Nucleation
diamond, 354, 364, 369–371, 374–375, 382 c-BN, 532, 534
GaN, 715, 718–719, 725 diamond, 361–364, 366
SiB 14, 632
SiC, 457, 459, 466, 479–480 Ohmic contact (electrode), 403
TiC, 199 c-BN, 526–527, 548
Modified variable threshold logic (MVTL), diamond, 392–394
NbN, 295 GaN, 736
Molecular orbital (MO), 102, 106 Ohmic metal, 393
B 12 icosahedra, 600 diamond/Ti/Mo/Au, 394, 403
MB 2, 142 Optical absorption
Monolayer graphite (MLG), 276–277 AlN, 700
Morphology β-B, 607, 610
AlN, 675, 686 SiC, 454
c-BN, 505, 543 Ordered compound (phase), 130
diamond, 352, 363–364 NbC, 36
NbN, 292 TiC, 125
TiC, 333 TiN, 125, 128
TiC/MO, 338 VC, 129
Mott-Schottky (M-S) plot, BP, 582–584 Order-disorder transformation
Mott’s law (formula) TMC, MN, 119
B 4C, 623 VC, 202, 209
β-B, 608, 618 V2C, 194
diamond, 373, 375 Oriented growth, diamond, 362, 364
YB 66, 638 Oxygen adsorption, TiC, 237
Muffin tin potential, 84
Multi-quantum well (QMW), InGaN, 740–741 Partial l-like density of state (DOS), 90, 102, 105
Phase diagram, 191
Nanocrystalline (nanosized) powder, 19–20, 45 AlN, 698
MC, MB 2, 23 BN, 500–504, 535
TiN, 28 BP, 561
Nanorod, 45 carbon, 350, 503
NbC, 32 carbon-boron, 337
TiC, 31 SiC, 411
Nb, 289–290, 294–296, 299–300 TiC, 32
Niobium carbide (NbC) tip, 276, 280–284 Phonon (abnormality) anomaly, 10
Nb(CN), 300 NbC, 253
NbN, 289–300 Phonon density of state (DOS), 159, 165
Niobium oxide (NbO x), 292, 297–298, 300 c-BN, 517
Nonstoichiometric compound (nonstoichiome- TiC, 163
try), 186 Phonon (dispersion) curve
AlN, 684 c-BN, 517
c-BN, 523 NbC, 278–279
HfC, HfN, 132 SiC, 446
MN, 119, 123, 135 Phonon drag, B 4C, 625
TiC, 125–126, 132 Phonon replica
TiN, 128–129, 132–134 diamond, 376–377
TMC, 7, 119, 123, 135, 178, 209 SiC, 453
VC, 129–130 BP, 562
Index 755
Phonon (scattering), 178 [p-n junction]

AlN, 687, 701, 703 GaN, 725, 728
β-B, 619 SiC, 417, 464, 481
BP, 558–559, 573 Poisson’s number, 156–157, 171
diamond, 354, 371, 376–379 Polar surface (polarity)
SiC, 456–457, 459, 461 c-BN, 504–505
Phonon (spectrum), 161, 165, 169, 177, 181 TMC, 225, 230
AlN, 701, 703 Polycrystalline material, 55–78, 155, 184
c-BN, 516, 518 insulator (excluding diamond), 339, 534, 543,
SiC, 448, 454 682, 687, 691–712
TiC, 163 metallic ceramics, 28–30, 35, 182–195, 200,
VN, 176 204–207, 214–218
Phonon velocity (speed), 522, 702 semiconductor (excluding diamond), 259–
Photoconductivity, β-B, 607–608, 618 263, 526, 561, 567, 571, 573–574, 581,
Photoelectrochemical (PEC) cell, BP, 580–581 589–644
Photoluminescence (PL) spectra Polytypes in SiC, 409–410, 416–418, 423, 427,
BP, 562 429–430, 433–434, 446–447, 451, 453,
GaN, 721–723, 726–727 456–457, 463, 470, 479
InGaN, 729, 731 Porosity, 158, 171
SiC, 447, 453–455, 468–469 AlN, 709
Physical vapor deposition (PVD), 3, 19, 55–57, NbB 2, 28
68 Porous material, 183
AlN, 483, 685 DyB 66, 638
BN, 537 Positron annihilation, SiC, 467
carbide, nitride, 70 Power device, diamond, 387
c-BN, 538 Preferential growth
Piezoelectricity BN, 502
AlN, 683, 691 TiN, 21
c-BN, 514 Pseudopotential calculation, 84
Plasma-arc heating BP, 559
MN, 20 p-type GaN, 721–723, 725–727
TiB 2, 28 Pyrogenic oxidation, SiC, 470
TMC, 20, 42
Plasma disruption, 338 Radial charge density, 97, 113
Plasma (enhanced) CVD, 67 Radiation damage, SiC, 464
BP, 585 Radiation detector, BP, 580
diamond, 348, 365 Radio frequency (RF)
TiC, TiC-TiN, TiN, 73 RF floating zone
Plasma-facing material (component), 321 MB 2, 20
C/C, 344 TiN, ZrN, 38
TiB 2, TiC, 336, 343 TMC, 20, 35
TiC-TiB 2-C, 337 RF ion plating, 61
Plasma frequency, B 4C, 626 RF magnetron sputtering
Plasma impurity, 321 AlN, 77, 685
Plasma oxidation, NbN, 292 TiB 2, 324, 334
Plasma zone melting, 192 TiC, 323–324, 331, 343
Plastic deformation, 191 RF plasma CVD, c-BN, 537
c-BN, 534 RF reactive ion plating, 322
TiC, 215 TiC, 336
ZrB 2, 211 RF sputtering, 61, 313
p-n junction AlN, 683
BP, 558, 578 c-BN, 537
c-BN, 523, 525, 532–533, 547–548 h-BN, 540
756 Index
[Radio frequency (RF)] Resistivity (see also Electrical conductivity)

HfN, 254 AlN, 691
NbC, 246 BP, 562, 564, 566–567
NbN, 291, 294 c-BN, 525–526, 533, 548
ZrN, 254, 256 diamond, 372–373
Raman spectra NbC x, 178
a-B, 635 MN, ZrB 2, 186
BN, 500 TiB 2, 186, 200
BP, 569–570 TiC, 178, 199
c-BN, 516–518 TMC, 9, 174, 178, 186
diamond, 352, 354 VC x, 178, 202
SiC, 446 ZrC, 201
Random phase approximation (RPA), BP, ZrN, 258
560 Resistivity saturation, TMC, 178
Ratherford back scattering spectrometry (RBS) Resonant photoemission spectroscopy
BP, 259–261, 263, 585 TaC, 232
c-BN, 505 TiC, NbC, 233
NbC, 248–249 Rippled reconstruction
SiC, 448 HfC, TaC, 223
Reactive evaporation, 55, 58
Reactive ion etching (RIE) Scanning tunneling microscopy (STM)
NbN, 294–295 diamond, 356–357
SiC, 464 SiC, 441
Reactive ion plating, 55, 58 VC, 225
TiC, TiC-TiN, 70 Seebeck coefficient (see also Thermoelectric
TiN, 70, 78 power)
Reactive sputtering, 55, 62–63 B 4C, 625, 644
AlN, 683 boron-rich solid, 590
Reflectance (spectra), 316 β-B, 608, 616
B, 657, 659 C 2 Al 3 B 48, 633
c-BN, 509–510 SiB 14, 632
TiC-TiN, 8 YB 66, 638
TiN, 75 Selective growth, diamond, 395
Reflection high energy electron diffraction Self-consistency, 83
(RHEED), Self-diffusion coefficient, 219
BP, 564, 566–567 NbC, 197
diamond, 356, 364 SiC, 420–424
SiC, 444, 466 TiC, VC, 197
Reflection (reflectivity) spectrum, Self-diffusion (diffusivity), 191
BP, 560 NbC, 252
TiN, 75 SiC, 420, 431
Refractive index, TMC, 197–198, 211
B, 659, 670–672 Self-propagation high temperature synthesis
BP, 568–569 (SHS), 19, 219
c-BN, 517–518 NbC, 23, 42
SiC, 452 TiB 2, 27
Relativistic effect, 84, 87, 112, 118 TiB 2 /Ti(CN), 30
Residual resistivity TiC, 41
VC, 9, 201 TiC-Ni-Al, TiC-TiB 2, 29
ZrN, 255 ZrB 2, 28
Residual resistivity ratio (RRR) Semiconducting
HfN, ZrN, 255 c-BN, 525–526
NbC, 250, 252 diamond, 369–372, 375, 377, 378, 381–382,
VC, 41 399, 402
Index 757
Shear modulus (G), 153, 155–156, 171, 215 Specific heat capacity (see also Heat capacity),
BP, 558 153–154, 159, 162, 181, 522
SiC, 512 BN, 519
TiN, 12 BP, 573–574
TMC, 157 TaC, 177
Shock-induced reaction, 19, 29 TiC, TiN, 207
Shock wave compression Specific on-resistance, SiC, 479–480, 484, 487–
c-BN, 503 488, 490
w-BN, 499 Spectral absorptance, 309
Shottky barrier height Spectral emittance, 191
BP, 578, 580 TMC, 192
diamond, 390–391 Spectral reflectance, 311, 316
SiC, 492 TiN x, ZrN x, 314
Shottky barrier rectifier, SiC, 482, 490–492 Spectral selectivity, 307, 316
Shottky diodes, Spin fluctuation, VN, 10, 186
BP, 579 Sputtering, 55, 62
diamond, 359, 365, 382, 403 B, 655
SiC, 290, 715 dielectric film, 312
SiC LED, 382, 728 NbN, 295
SiC polytype SiO 2, 295
3C-, 409, 411, 416, 418, 426, 430, 434, TiN, 77
437, 439, 442, 444, 446–448, 451, 454– Stagnation temperature, 309–310
456, 459, 461–464, 466, 468–470, ZrN x, 317
479 Step flow growth, diamond, 355, 357
4H-, 411, 416, 432, 434, 438–439, 442, 447, Step growth mode, SiC, 444
451, 456, 461, 479 Stoichiometric compound (composition), 122,
6H-, 411, 413, 416, 418–419, 434–435, 438– 219
439, 442, 446–447, 454, 456–457, 459, AlN, 683
461, 464, 479 HfN, 254
8H-, 416, 446 MN, 27, 85, 112
10H-, 416 TiB 2, 41–42, 328, 343
15R-, 411, 416, 438, 442, 446, 451, 456, 459, TiC, 126, 343
461 TiN, 23
27R-, 416 TMC, 7, 85, 112
Single crystal ZrN, 254
insulator, 256, 290, 361, 395, 400, 525, 532– Stoichiometry
534, 675–689, 702 AlN, 683
metal, 361 BN, 528
metallic ceramics, 10–12, 20, 30–45, 178, BP, 564
182, 186, 192, 197–199, 201–202, 209– MN, 8
211, 214–215, 223–242, 248–249, 269– NbC, 36
285, 291 SiC, 416
Semiconductor (excluding diamond), 290, VC, 193
363–364, 409–435, 426–470, 525–526, Structural defect, 644
562–564, 567, 570–574, 716 boron-rich solid, 639–640
Si 3N 4, 77, 399 Structural disorder, 245
Sintering additive, 20 NbC, TaC, 249
AlN, 691, 705–706, 708–709 Subcarbide, 138–141
NbB 2, TiB 2, TiC, TiN, 28 Sublimation method
SiO, 294–295, 391–392 AlN, 675, 679, 682, 686
Solar absorptance, 317 SiC, 426–427, 429, 431, 462, 476, 486
Solid state epitaxial (SPE), BP, 263 Substitutional impurity, AlN, 687
Sound velocity, 154, 174, 181 Superconducting transition temperature (T c), 9,
c-BN, 514 81, 185, 245
758 Index
[Superconducting transition temperature] Thermal CVD, 56, 63, 67

HfN, 255 diamond, 351
NbC, 22, 250–253 TiC, 71, 73
NbC xN 1-x, 135 TiC-TiN, TiN, 73
NbN, 35, 291, 299 Thermal emittance, 308–309
ZrN, 255–256, 258 TiN, ZrC 6, ZrC xN y, ZrN, 317
Superconductivity (superconducting), 10, 78, 81, Thermal expansion coefficient, 191, 203, 341,
185 521
NbC, 183, 203 AlN, 691
NbC xN 1-x, 9 boron-rich solid, 590
VN, 195 BP, 574, 567, 576
ZrN, 27 β-B, 619
Superlattice film c-BN, 512, 520, 522, 546
TiN/AlN, 74 h-BN, 520
TiN/VN, TiN/(V 0.6Nb 0.4)N, 14 MC-MN, 204–206
Supersaturation SiC, 416, 445, 448, 463–464
AlN, 686 (SiC) x (AlN) 1-x, 425
c-BN, 529, 532 TiB 2, 201
SiC, 430 w-BN, 520
Surface acoustic (wave) (SAW) device, 77 Thermal neutron irradiation, BP, 571–572
AlN, 683–684, 689 Thermal oxidation rate, SiC, 417
Surface atomic structure, TMC, 223 Thermal shock resistance, 337
Surface Brillouin zone (SBZ), 234 TiB 2, 339, 343
TaC, 235 TiC, 342, 344
Surface conducting layer, diamond, 398 Thermal stability, 317
Surface reactivity, TMC, 236 c-BN,73, 526
Surface reconstruction, SiC, 441 TiC, 330–331, 336, 343
Surface relaxation, 225 Thermodynamics, 191, 219
Surface state, 228–231 MB 2, 218
TMC, 225 TiC, 32
Surface state density, diamond, 392 TiN, 21
ZrC, 195
Tamm surface state, TMC, 228, 230 Thermoelectric device, BP, 558, 580
Thermal annealing, GaN, 721–725, 736 Thermoelectric FOM
Thermal conductivity, 81, 173, 180–181, 184, 341 B, 666
AlN, 686–687, 691, 695–698, 700–703, BP, 580–581
706–709, 711 Thermoelectric power (see also Seebeck effect)
B, 666 B, 657, 666, 672
B 4C, 627 BP, 572–573
BP, 574, 580, 585 c-BN, 525
c-BN, 73, 514, 522 TiC, 199
C/C, 336 Thin film (including single crystalline and ex-
diamond, 347, 354, 369, 385, 387 cluding diamond specimens), 55–78,
HfB 2, 207 251
NbC, 183 insulator, 292–294, 312, 536–543, 683–685
SiC, 418, 463, 522 metal, 295
Ti/TiB 2, 184 metallic ceramics, 12, 14, 246–248, 250–259,
TiB 2, 183, 186, 207, 336 290–300, 313–318, 322–344
TiC, 182, 186, 336 semiconductor, 259–265, 312, 317, 437–470,
VC, 186 477–492, 566, 569–570, 576–584, 655–
YB 66, 638 671, 715–745
ZrC, 186 Titanium carbide (TiC) tip, 207–274, 276, 283–
ZrB 2, 207 284
Index 759
Transconductance [Vacancy]
diamond, 400, 403 VN, 203
SiC, 470 ZrN, 259
Transition metal carbide (TMC), 2, 4, 10, 12, Vacancy state (band), 122
20, 24, 29–30, 33, 35–36, 39, 85–88, TiC, 123, 132
90–91, 95–105, 119–123, 125–126, TiN, 132–133
157, 162, 166, 168–169, 178, 185–186, VC, 129–130
192, 195, 197, 207, 209–210, 223–232, Vacuum evaporation, 55
234–242, 269–270, 276, 280–281, 285 B, 655, 659
Transition metal diboride (MB 2), 2, 6, 12, 20, Valence electron density (VED), 107
23–24, 30, 33, 41–42, 142–144, 166, MX, 102
186, 205–207, 211 TiC, 99–104, 108, 110, 121
Transition metal nitride (MN), 2, 4, 11–12, 14, TiN, 99, 103–104, 109–110, 121, 133–135,
20, 22–24, 30, 36, 38, 43, 46, 85–88, 138
90–91, 95–105, 119–123, 125–126, Ti 2N, 139–141
166, 168, 185–186, 198, 204, 207 TMC, TMN, 111
Transmission electron microscopy (TEM) VN, 99–102, 110
BP, 564 Vapor-bulk crystal, SiC, 433
diamond, 352, 361 Vapor-growth surface, SiC, 433
SiC, 444–445, 448 Vaporization, 191–192, 194
TiC, 31 C/C, 341
Transmittance, B, 659 MC, 194
Transparent ZrC, 195
AlN film, 683 Vapor-liquid-solid (VLS) mechanism, 30
AlN whisker, 682 AlN, 675, 682, 686
c-BN, 534 BP, 563
Trapping (trap), β-B, 605, 611–613, 616, 619 SiC, 429, 431
Travelling solvent float zone (TSFZ) technique, TiC, 46
TMC, 39–40 Vapor-phase (crystal) growth, SiC, 424, 426
Two-flow MOCVD, GaN, 716–727 Vapor-solid (VS) mechanism
Two-step growth (method) AlN, 482
BP, 566 HfC, NbB 2, ZrC, 30
SiC, 445 SiC, 431
Tungsten monocarbide (WC), 117–119 Variable-range hopping
B 4C, 623
UMOSFET, SiC, 484–485, 487 β-B, 608, 612, 618
Unipolar FET, diamond, 402 diamond, 373
Urbach tail, 603 YB 66, 638
YB 66, 638 Vibrational displacement, 160
UV electroluminescence (EL), GaN, 726–727 Vickers hardness (see Micro-Vickers hardness)
Vacancy, 178, 265 Whisker, 19, 45, 217

AlN, 687–688, 701 AlN, 675–679, 682, 686, 689
c-BN, 523 BP, 563
diamond, 359 HfC, HfN, NbB 2, TiC, TiN, ZrC, 30
HfC, HfN, 138 SiC, 419, 426
MN, 119–122, 130, 135 Wide gap
NbC, 252–253 emitter transistor, BP, 576–577
SiC, 420, 422–424 solar cell, BP, 557, 576–577
TiC, 36, 125–126 Wide-gap semiconductor, 4, 482
TiN, 125, 133 boron-rich solid, 644
TMC, 35, 119–122, 130 diamond, 369
VC, 201–202 GaN, SiC, 6
760 Index
Widmanstättaen-type precipitation [X-ray]

MB 2, 38 NbC, 245–246
ZrB 2, 211 SiC, 446, 448
Wiedemann–Franz law, 9, 180, 182 TiC, TiN, 207
NbC, 183 TiB 2, 328
TiC, 182 rocking curve (XRC)
Work function InGaN, 729
metal, 390, 580 InGaN/GaN, 740
TMC, 282 InGaN/InGaN, 741
Work hardening GaN, 718
(TiMo)C, 216 topography
ZrB 2, 211 c-BN, 534
ZrC, 214 HfC, TaC, ZrC, 46
Work softening, (TiMo)C, 215 TiC, 30
VB 2, 39
X α method
BP, 558 Yellow single-quantum-well (SQW), 742–745
NbC x, TiN, 120 Yield drop (point)
TiC, 135 TiC, 214
TMC, MN, 123 (TiMo)C, 215
X-ray ZrB 2, 211
detector, 299 Yield stress, TiB 2, 211
diffraction (diffractometry), 110, 119, 265 Young’s modulus (E), 153, 156–157, 171, 341
AlN, 684 BP, 558
B, 659, 663 SiC, 429, 512
BN, 498–500, 504 TiC, 209
BP, 562
diamond, 354, 359, 364 ZnSe, 715
GaN, 729 Zone folding, SiC, 446, 456

Electric Refractory Materials

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Electric Refractory

Marcel Dekker, Inc. New York • Basel

Copyright © 2000 by Marcel Dekker, Inc. All Rights Reserved.

This book is printed on acid-free paper.

Eastern Hemisphere Distribution

World Wide Web

Copyright  2000 by Marcel Dekker, Inc. All Rights Reserved.

Current printing (last digit):

PRINTED IN THE UNITED STATES OF AMERICA

1. Importance and Research Program of Electric Refractory Materials 1

2. Survey of Refractory Metalloids: Transition Metal Carbides, Nitrides,

3. Bulk Crystal Growth 19

6. Lattice Vibrations, Heat Capacity, and Related Properties 153

7. Electrical and Thermal Conductivity and Related Transport Properties

8. High-Temperature Characteristics 191

9. Surface Electronic Structures and Surface Reactivities 223

10. Irradiation Properties of Electric Refractory Materials 245

11. Transition Metal Carbide Field Emitters 269

12. NbN Superconducting Devices 289

13. Solar Absorbers—Selective Surfaces 307

14. Metalloids for Plasma-Facing Materials 321

15. Synthesis of Diamond from the Gas Phase 347

16. The Electrical and Optical Properties of Diamond 369

17. Semiconducting Diamond and Diamond Devices 385

18. SiC Boule Growth 409

19. Epitaxial Growth, Characterization, and Properties of SiC 437

20. Silicon Carbide Power Electronic Devices 477

21. Science and Technology of Boron Nitride 495

22. Boron Phosphide 557

23. Boron and Boron-Rich Compounds 589

24. Boron Films 655

25. Single Crystal of AlN 675

26. AlN Sintered Polycrystal 691

27. GaN-AlN-InN Blue Light–Emitting Devices 715

Masahiro Aoyagi, Ph.D. Electron Devices Division, Electrotechnical Laboratory, Tsukuba,

Robert Blickensderfer, Ph.D. Research Metallurgist, Consultant, Albany, Oregon

Masakazu Fujitsuka Department of Mechanical Properties, National Research Institute for

Göran Grimvall, Ph.D. Department of Physics, Royal Institute of Technology, Stockholm,

Naoto Kobayashi, Ph.D. Quantum Radiation Division, Electrotechnical Laboratory, Tsukuba,

Katsutoshi Komeya, Dr.Eng. Department of Engineering, Yokohama National University,

Yukinobu Kumashiro, Ph.D. Department of Engineering, Yokohama National University,

Takeshi Meguro, Ph.D. Department of Materials Chemistry, Yokohama National University,

Katsumitsu Nakamura, Dr.Eng. Department of Chemistry, College of Humanities and Sci-

Yuri M. Tairov, Ph.D. Department of Microelectronics, St. Petersburg Electrotechnical Uni-

Tatsuhiko Tanabe, Dr.Eng. Department of Mechanical Properties, National Research Insti-

Table 1 Functions and Applications of Refractory Materials

Figure 1 The relationship between various functions in refractory materials.

Table 2 Synthesis, Evaluation, and Measurement Technologies for Refractory Materials

Figure 6 Three-dimensional surface representing Young’s modulus of TiB2 in different crystallographic

transfer, such as hydrogenation, hydrogenolysis, isomerization, hydrodesulfurization (HDS), and

17. FA Modine, MD Foegelle, CB Finch, CY Allison. Electrical properties of transition-metal carbides

III. POLYCRYSTALLINE SPECIMENS

IV. SINGLE CRYSTALS

within carbides (153–158), such as conservative and/or nonconservative antiphase boundaries

Figure 14 A modiﬁed zone leveling method (164–175).

Figure 17 Schematic drawing of a tri-arc Czochralski furnace. (From Ref. 181.)

1. Y Ando, R Ueda. Preparation of ultraﬁne particles of refractory metal carbides by a gas-evaporation

91. A Niiler, LJ Kecskes, T Kottke. Shock consolidation of combustion-synthesized ceramics. In Ref.

In general classiﬁcation, a surface treatment consists of a thin-ﬁlm preparation (i.e., deposition

II. CONDITIONAL PARAMETERS FOR DEPOSITING THIN FILMS

B. Effect of Pressure on PVD and CVD Films

Figure 1 Characterization of thin-ﬁlm material. (From Itoh, 1986.)

III. PREPARATION OF CERAMIC FILMS

C. Reactive Ion Plating