Documente Academic
Documente Profesional
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NommJ.M. Horing
stewwas Institute of Technology
Hoboken, NJ
World Scientific
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Dedication
This book is dedicated to the memory of Adele and Werner Enderlein (par
ents of R.E.), and to t h e memory of Joseph and Esther Morgenstern (hfor
ganstein)(grandparents of N.J. M. 11.).
Vii
Preface
People come to technical books with a vast array of daerent needs and
requirements, arising from their differing educational backgrounds, profes-
sional orientations and career objectives. This is particularly evident in the
field of semiconductors, which stands at the juncture of physics, chemistry,
electronic engineering, material science and mathematics. No longer just
an academic discipline. this field is at the heart of an ongoing revolution in
communications, computation and electronic device applications, that inno-
vate many fields and change modern life in myriad ways, large and small. Its
profound impact and further potential command interest and attention from
all corners of the earth. and from a wide variety of students and researchers.
The clear need to address a broadly diversified and variously motivated
readership has weighed heavily in the authors considerations. It poses a
pedagogical problem faced by many teachers of intermediate level courses
on semiconductor physics. Generally speaking, every student has previously
studied about half of the course materiaL The difficulty lies in the fact that
each students exposure is likely to have been to a &fleerent half, depend-
ing on which lower level courses and teachers they have had, and where the
emphasis lay. To accommodate readers with varied backgrounds we start
from first principles and provide fully detaiIed explanations and proofs, as-
suming only that the reader is familiar with the Schrodinger equation. This
intensively tutorial treatment of the electronic properties of semiconduc-
tors includes recent fundamental developments and is carried through to the
physical principles of device operation, to meet the needs of readers inter-
ested in engineering aspects of semiconductors, as well as those interested in
basic physics. Clarity of explanation and breadth of exposure relating to the
electronic properties of semiconductors, from first principles to modern de-
vices, are our principal objectives in this fraddy pedagogical book. We offer
full mathematical derivations to strengthen understanding and discuss the
physical significance of results. avoiding reliance on hand waving arguments
alone.
To support the readers introduction to the physics of semiconductors, we
provide a thorough grounding in the basic principles of solid state physics,
assuming no prior knowledge of the field on the part of the reader. An ele
mentary discussion of the crystal structure, chemical nature and macroscopic
properties characterizing semiconductors is given in Chapter 1. Moreover,
we also include an extensive appendix to guide the reader through group
theory and its applications in connection with the symmetry properties of
semiconductors, which are of major importance. Beside spatially homoge-
neous bulk semiconductors, we undertake a full exposition of inhomogeneous
semiconductor junctions and heterostructures because of their crucial role
Preface iu
The book has emerged from lectures which the authors presented for physics
students at the Humboldt-University of Berlin. Germany, and the State Uni-
versity of Sao Paulo, Brazil, and for physics and engineering physics students
at the Stevens Institute of TeFhnology in Hoboken, New Jersey, C.S.A. Part
of the book has similarities with the german book "Grundlagen der Halbleit-
erphysik" ("Fundamentals of Semiconductor Physics") which was written by
one of us (R. E.) together with A. Schenk. We are thankful to Dr. Schenk
(now at ETH Zurich) for allowing us to use part of his work in the present
volume. In writing this book we have had excellent suppoIt from many
of our colleagues at our own and other Universities. We are particularly
thankful to Prof. Dr. J. Auth (Humboldt-Lniversity Berlin), Prof. Dr. F.
Bechstedt (Friedrich-Schiller University Jena), Prof. Dr. W. A. Harrison
(Stanford University), Prof. Dr. M. Scheffler (Fritz-Haber Institut, Berlin),
Prof. Dr. J. R. b i t e , Prof. Dr. A. Fazzio, and Prof. Dr. J. L. Alves
(State University Sao Paulo), as well as to Prof. Dr. H. L. Cui, Prof. Dr.
G. Rothberg, Mr. G. Lichtner (Stevens Institute of Technology), and Prof.
Dr. G . Gumbs (Hunter College, CWNY, New York), who read parts of the
manuscript and contributed helpful suggestions and critical remarks. The
technical assistance of Mrs. Hannelore Enderlein is gratefully acknowledged.
Contents
1 Characterization of sernicond uct ors 1
1.1 Inlrnduclion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Atomic structure of ideal crystals . . . . . . . . . . . . . . . . 5
1.2.1 Cryst.al latlices . . . . . . . . . . . . . . . . . . . . . . 6
1.2.2 Point groups of equivalent directions arid crystal classes 12
1.2.3 Space groups and crystal structures . . . . . . . . . . 14
1.2.4 Cubic semiconductor structures . . . . . . . . . . . . . 16
1.2.5 Hexagoiial semiconductor st.ructures . . . . . . . . . . 22
1.3 Chemical nature of semiconductors. Material classes . . . . . 28
1.3.1 Group IV elemental semiconductors . . . . . . . . . . 29
1.3.2 111-V semiconductors . . . . . . . . . . . . . . . . . . . 30
1.3.3 11-VI semiconductors . . . . . . . . . . . . . . . . . . . 31
1.3.4 Group \'I elemental semiconductors . . . . . . . . . . 31
1.3.5 IV-VI semiconductors . . . . . . . . . . . . . . . . . . 32
1.3.6 Other compound semiconductors . . . . . . . . . . . . 32
1.4 hlacroscopic properties and their microscopic implications . . 33
1.4.1 Electrical conductivity . . . . . . . . . . . . . . . . . . 34
1.4.2 Depenclenre of conductivity on the semiconductor state 35
1.4.3 Optical absorption spectrum and the band modcl of
srmicoiiductors . . . . . . . . . . . . . . . . . . . . . . 38
1.4.4 Electrical conductivity in the band model . . . . . . . 43
1.4.5 The Hall effect and the existence of positively charged
freely mobile carriers . . . . . . . . . . . . . . . . . . . 45
1.4.6 Seinicondiictors far from thermodynamic equilibrium . 49
7.1.2
Mechamism of current transport through a pn-junction 577
Chemical potential profiles for electrons and holm . . 580
7.1.3
Dependence of current density on voltage . . . . . . . 583
7.1.4
Bipolar transistor'. . . . . . . . . . . . . . . . . . . . .
7.1.5 585
7.1.6 T u n e 1 diode . . . . . . . . . . . . . . . . . . . . . . . 593
7.2 yn-junction in interaction with light . . . . . . . . . . . . . . 595
7.2.1 Photocffect at a pn-junction . Photodiode and photo-
voltaic element . . . . . . . . . . . . . . . . . . . . . . 595
7.2.2 Laser diode . . . . . . . . . . . . . . . . . . . . . . . . 599
7.3 Metal-semiconductor junction in an external voltage.
Rectificrs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 606
7.4 hwulator-semiconductor junction in an external voltage . . . 612
7.4.1 Field effect . . . . . . . . . . . . . . . . . . . . . . . . 612
7.4.2 Inversion layers . . . . . . . . . . . . . . . . . . . . . . 614
7.4.3 MOSFET . . . . . . . . . . . . . . . . . . . . . . . . . 620
Appendices
A Group theory for applications in semiconductor physics 623
A.1 Definitions and concepts . . . . . . . . . . . . . . . . . . . . . 623
A . l .1 Group definition . . . . . . . . . . . . . . . . . . . . . 623
A.1.2 Concepts . . . . . . . . . . . . . . . . . . . . . . . . . 624
A.2 Rigid displacements . . . . . . . . . . . . . . . . . . . . . . . 627
A.2.1 Definition . . . . . . . . . . . . . . . . . . . . . . . . . 621
A.2.2 Translations . . . . . . . . . . . . . . . . . . . . . . . . 628
A.2.3 Orthogonal transformations . . . . . . . . . . . . . . . 629
A.2.4 Geometrical interpretation . . . . . . . . . . . . . . . . 631
-4.2.5 Screw rotations and glide re3ections . . . . . . . . . . 632
A.3 Translation. point and space groups . . . . . . . . . . . . . . 635
A.3.1 Lattice translation groups . . . . . . . . . . . . . . . . 635
-4.3.2 Point groups . . . . . . . . . . . . . . . . . . . . . . . 636
A.3.3 Space groups . . . . . . . . . . . . . . . . . . . . . . . 654
A.4 Representations of groups . . . . . . . . . . . . . . . . . . . . 655
A.4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . 655
A.4.2 Irreducible representations . . . . . . . . . . . . . . . . 661
4.4.3 Products of representations . . . . . . . . . . . . . . . 667
A . 5 Representations of the full rotation group . . . . . . . . . . . 673
4.5.1 Vector representation of the rotation group and gen-
erators of infinitesimal rotations . . . . . . . . . . . . 674
A.5.2 Representations for dimensions other than three . . . 676
A.6 Spinor representations . . . . . . . . . . . . . . . . . . . . . . 682
A.6.1 Space-dependent spinors . . . . . . . . . . . . . . . . . 682
mi Cootents
Bibliography 747
Index 757
FUNDAMENTALS OF
SEMICONDUCTOR PHYSICS AND DEVICES
1
Chapter 1
Characterization of
semiconductors
1.1 Introduction
Semiconductors are identified as a unique material group on the basis of
their common macroscopir properties, as is done for metals, dielectrics and
magnetic materials. The name semiconductor stems from the fact that
such materials have moderately good conductivity, higher than that of in-
sulators, and lower than that of metals. However, if this were the only
property which these materials had in common, the term semiconductor
would have only a very weak foundation. But such is not the case. In fact,
many materials having conductivity between that of metals and insulators.
display simultaneously a series of further common properties. In particular,
their conductivity depends very strongly on material staie, for example, on
temperature and chemical purity, much more so than in the case of met-
als. For sufficiently pure semiconductors, the conductivity decays by orders
of magnitude while cooling down from room temperature to liquid helium
temperature. ,4t absolute zero temperature, semiconductor conductivity al-
most vanishes, in contrast to the conductivity of metals, which rises modestly
with falling temperature. The conductivity of metals reaches its maximum
at low temperature, and for superconductors it effectively becomes infinitely
large. In regard to the dependence of semiconductor conductivity on the
degree of purity, it has been found that a given semiconductor in a very
pure state can resemble an insulator. while in a highly polluted state it acts
like a metal, among other peculiarities. Furthermore, irradiation with light
can cause a transition from insulator-like behavior to metal-like behavior of
one and the same semiconductor.
There are yet other optical properties shared by semiconductors: The op-
2 Chapter I. Characterization of semiconductors
heavily polluted and have too many structural defects. Natural diamondrr,
for example, are semiconductors only in rare cases. Accordingly, clean fab-
rication of the materials in the laboratory and the controlled incorporation
of chemical elements played a crucial role from the very beginning. The lack
of such control in preparation presented fundamental difficulties which had
to be overcame in the early days of semiconductor rasearch. The necessary
accuracy of composition control, which amounts to one atom in one hundred
thousand or less, excccdcd the accuracy that prevailed in chemistry at the
t h e by orders of magnitude. It was necessary to raise the accuracy of chem-
ical composition control to a level wherein one could measure one millionth
of a mole haction instead of one thousandth. only in this way could reliable
results be achieved with semiconductors. Since such accuracy was achieved
4 Chapter 1. Characterization of semiconductors
means that,, for a given atom, there are remote atoms possessing the same
short-range order complexes as the original atom, rand that the positions of
the remote atoms are related to the position of the origina1 atom by sirn-
ple transformations. 'l'hp crystal is considered t o be inhitely large in this
context. Atoms having identical short-range order complexes are termed
equivalent. Equivalent atoms are necessarily of the same chemical species,
but chemically identical atoms need not necessarily be equivalent.
Definition
The smallest possible unit cell is called a primitive unit cell In the extreme
case this cell can contain only 1atom, but as a rule, it has several atoms. If
there is only one atom per cell, then the short-range order merges into the
long-range order.
If the unit cell is taken to be a primitive one, the vectors Al, A2, &
are some minimal vectors a l , az,w. The parallelepiped spanned by these
vectors is a primitive unit cell, Each translation by a vector R of the form
with integer coefficients r l , r2, r 3 transforms the crystal into itself. One refers
to this property as the trunslation~lsymmetry of the crystal. The point set
defined by the vectors R forms a spatial lattice called the crystal lattice. The
vectors al,a2, are termed primitive lattice vectors, The volume 00of a
primitive unit cell may be written as the triple scalar product of al,ag,a,
Ro = al . [ag x a].
1.2. Atomic structure of ideal cestals 7
While the lattice of a crystal and the volume Qo of its primitive unit cell
are well defined, this is not the case for its primitive lattice vectors al,a2,a3
and also it is not true for the form of its primitive unit cell. Any set of
linear combinations of the primitive vectors al,a2,a3 which yields a triple
scalar product equal to the volume Qo is again a set of primitive lattice
vectors, and the parallelepiped spanned by them forms a primitive unit cell.
The corners of the parallelepipeds do not necessarily have to lie on lattice
points. Each parallelepiped, shifted arbitrarily in space, is again a primitive
unit cell. The 'parallelepiped form is also not imperative, as there are also
other forms possible. An especially compact primitive unit cell is the so-
called Wzgner3eit.z cell. The center of this cell lies on a lattice point and its
surface is formed by the perpendicular bisector planes which divide in half
the line segments joining the center to adjacent lattice points.
Translations which transform a crystal into itself, by definition, do the
same for the lattice of the crystal. Here, the translations are through lattice
vectors R, called lattice tramtations The set of all lattice translations forms
a group. This term describes a mathematical set of elements among which
a 'multiplication' is defined that results in products which are also elements
of the set. Further properties of a set forming a group are listed in A p
pendix A. In particular, there must be an identity element, and the inverse
of an element must also be an element of the set. In the case of translations
the 'multiplication' is the consecutive application of two of these transfor-
mations. Since two consecutive lattice translations constitute yet another
lattice translation, and also the requirements of Appendix A are satisfied,
the set of all lattice translations of a crystal forms, in fact, a group, called
the translation symmetrg, group or simply the tramlation group. Groups of
symmetry elements play a central role in the description of the atomic struc-
ture and other microscopic properties of crystals. Appendix A provides a
thorough discussion of groups as needed in this book.
We now ask whether there are other possible spatial transformations, besides
translations, which transform lattices into themselves. From the outset it is
clear that the only transformations which may be considered are those that
do not change the distances between lattice points, i.e. mgzd drsplacernents
of the lattice (see Appendix A). One can show that, besides translations,
there is a second class of transformations fitting this description, namely
rotatoom and reflectzons, as well as all products which are compounded from
them, such as rotation-reflections, rotatton-znverstonsand znverszon itself.
Taken together, they are termed orthogonal traasfomattom. These differ
from translations inasmuch as they leave one or several lattice points un-
changed, while the remaining points are shifted by vectors depending on
8 Chapter 1 . Characterkstion of semiconductors
their positions. In a t,ranslation, all points are shifted by the same vector,
with no points fixed. Rotations transform right-hand4 Cartesian coordi-
nate systems into right-handed systems, but the application of reflections
and inversion to right-handed system results in left-handed ones.
It turns out that there are orthogonal transformations which transform
lattices into themselves. They are called point symmetry operations of lat-
tices. The set of all point symmetry operations of a lattice forms a group,
as does the set of all lattice translations. The multiglicslion of two of these
operations is again understood to represent their consecutive application.
Groups of point symmetry operations are termed point gvoups. In Appendix
A we describe thwn in detail. Not all of the various point groups listed
in Appendix A are allowed as symmetry groups of crystal lailices, but only
parlicular ones which are called holohedral point groups. We will derive them
now by demonstrating that lhey must have three special properties.
First, all uf these point groups must contain the inversion transformation
with r e q e t t to the lattice point R = 0. This may be seen as fullows:
Inversion with respect to 0 transforms a lattice point R into -EL Considered
joiutly with R, the point -R is a lattice point having -q, -r2, -7-3 as integer
coefficients. Therefore, inversion with respect to 0 transforms an arbitrary
lattice into itself. It follows immediately that inversion with respect l o any
other lattice point will do h e same.
Second, it turns out that rotation symmetry axes Ohrough lattice points
can only be 2-, 3-, 4- and 6-fold while ri, 7- and more-fold axes are not
compatible with the translation symmetry of the lattice. One may prove
this as follows: Let C, be a rotation about such an axis t,hrough an angle
2?r/n. We consider a lattice plane perpendicular to this axis and denote a
primitive lattice vector of the corresponding planar lattice by f (see Figure
1.1). Rotating it through 2a/a, it becomes C,f, and a rotation by - 2 ? r / R
transforms it into Cqlf. If, as w e suppose, Cmbelongs to the point group of
the lattice, them s n d o a C;'. Thus both C,f and C i l f are vectors of the
plane lattice. The same holds for the sum Cnf i Cg'f ol t,he two vectors.
Moreover, C,,f + CGLf represents a vector parallel to f. This means that
C,f + CF'f must be an integer multiple of f. Since the largest possible
+
length of Cnf Cg'f can only he 2 / f J ,one has Cnf f C'L'f = p,F with
pn - -2. -LO, 1 or 2. This is indicative t.hat, the relation
p , = 2COS (?)
must hold for p,. For p n = -2, equation (1.4) yields n 2. For pn -= -1
1
Bravais lattices
Within a given crystal system, several different types of lattices may exist.
Their common property is that they all have the same point symmetry, but
they may differ otherwise. Figure 1.2 visualizes them by means of their unit
cells. These differences give rise to diflerenf lattice types. The simplest lat-
tices ef a given point symmetry are represented at the far left of each row
in Figure 1.2. They axe called primitive lattices. Even these simple lattices
are not unambiguously &ermined by their point symmetry. If one, for in-
stance, multiplies all lattice vectors by the same real number, i.e. stretches
or compresses the lattices evenly on all sides, the point symmetry remains
unchanged. In less symmetrical crystal system one may even change cer-
tain length relationships or angles between primitive lattice vectors without
disturbing the point symmetry. In the tetragonal system the height of the
10 Chapter 1. Characterization of semiconductors
Chic F
Cubic P Cuhic 1
Tetragonst I
pj$,
I
.# .\
@
Triclinic
Monocfinic P Monoclinic 1
In this w q ,one finds that, in totul, 14 diEerriit Bravais lattices are possible
in the 7 crystal systems. The assignment ol Iht.sr lattices to the crystal
systems is indicated in Table 1.1. The Bravais lattices themsehps are shown
in Figure 1.2.
Ri=Rti. (1.5)
Without loss of generality one may always set onr of the vectors il, e.g. i l .
equal to zero. If the primitive unit cell canlains only 1 atom, it may be
placed in o m o f the roriiers of the cell. A crystal without basis may thiis be
describd as a laltice whosp points are dl occupied by ahoms. For L 2 2,
the crystal may be generated in such a way that one multiples its crystal
lattice L-fold, then shifts the resulting sublattices relative to t,he first by,
respcctivcly, the vectors 6 , . . . ,?I,, and finally occupies the points of the
shift,ed lattices, respectively, with atoms of t,he species 2,. . . , L.
With only one atom per primitive unit cell! any point symmetry opera-
tion of the lattice will ncccssatily transform the whole crystal into itsdf. For
cryst,alswith basis, however, this is not true in general. For this reason it is
meaningful to consider, besides the point symmetry operations of the crys-
tal lattice, also orthogonal transformations which map physically equivalent
direchns of Ihe crystal into each other, without necessarily bringing the
crystal back onto itself. We explain the meaning of physical equivalence by
using the example of the relation between the vectors of the electric current
density j and the electric field strength E in a crystal. Generally, j is a
non-lincar fimrtioii of E and, because of crystal snisotropy, the direct.ions
of the two vectors may be different. If E and j are transformed from their
original directions reht.ive to the crystal into new ones, without changing
their relative orientation, the relation betwccn the new j and E, in general,
will differ from the relation before rotat,ion. Analogous statements hold for
reflections and rotation-reflections. If tbcre are orthogonal transformations
1.2. Atomic structure of ideal crystals 13
+
system group lattk class groups
r
tnclinic
monoclinic '2h
c
1
C, ! I
1
1
1
rhombic
trigonal
tetragonal
I
hexagonal
I
)
cubic p bc fc
14 Chapter 1. Characterization of semiconductors
which leave the relation between the two vectors unchanged - which ulti-
mately must be verified experimentally - the original and the transformed
directions are called physically equivalent. The group of orthogonal trans-
formations which map physically equivalent directions of a crystal into each
other, is called the point group of equivalent directions. It defines the crystal
class. Each crystal class corresponds to a particular point group of equivalent
directions. In crystals without basis the point group of equivalent directions
coincides with the holohedral point group. For crystals with a basis this is
no longer true in general, and the point groups of equivalent directions are
generally subgroups of the holohedral groups. There are as many different
point groups of equivalent directions, or crystal classes, as there are different
subgroups of the 7 holohedral groups. Using Appendix A one can easily
show that their number amounts to 32 (see Table 1.1).
Not all crystal classes can be realized in all crystal systems - the point
group which defines the crystal class has to be a subgroup of the holohedral
group of the crystal lattice. Each crystal class is, however, found in at
least one crystal system, several in more than one. In assigning the crystal
classes to the different crystal systems one proceeds as follows: A class which
exists in several systems is attributed to the one with the lowest common
symmetry. In this way one obtains the assignment between crystal systems
and crystal classes shown in Table 1.1.
(zincblende st ruct ure) , F m3m (rocksalt st ruct ure) , P63m c (wurt zite st ruc-
ture), and P3121 or P3221 (selenium structure). Each of these crystal struc-
tures is more or less closely tied to a particular material group. We consider
this connection in more detail in the next section, which deals with the
chemical nature of semiconductors.
The five crystal structures above belong to just two different crystal sys-
tems - t h e diamond, zincblende and rocksalt structures belong to the cubic
system and the wurtzite and selenium structures belong to the hexagonal
system. We start with the three cubic structures. Table 1.2 summarizes
their properties
The lattice constants for a series of semiconductors with fcc lattices are listed
in Table 1.3. We stress that the cubic lattice constant is neither the distance
between two lattice points (it is u / f i for the fcc lattice), nor the distance
between two atoms in a crystal with this structure (which is &/4). For
the volume Ro of the primitive unit cell one obtains the value u3/4 from
equation (1.3). In the case of silicon this yields Ro = 4.00 x cm3. A
silicon crystal of volume 1 cm3, therefore, contains 2.5 x primitive unit
cells.
The lattice does not determine the positions of the atoms. This is done
by the basis of the crystal, in which respect the three cubic semiconductor
structures differ.
1.2. Atomic structure of ideal crystals 17
Table 1.2: Characteristicz of the five most comnion structure types of seniiconduc
tors. 0 < C < h, 0 < n < $. More details are given in the text.
F#m P3121
P3221
fy
,3;
4 - 2
43m Gmm 32
Primitive
lattice
vectors
Basis
I
I I
18 Chapter 1. Characterization of semiconductors
1:
Diamond structure
, I
1:
C Si Ge a-Sn
5.43 5.65 6.46
Zincblende structure
Rocksalt structure I I
PbS PbSe PbTe SnTc CdO MgS MgSe
5.93 6.12 6.45 6.3 4.70 5.20 5.46
Wurtzite structure I I
ZnS CdS CdSe MgTe AlN GaN InN
3.82 4.14 4.31 4.53 3.11 3.19 3.54 a
1.64 1.62 1.63 1.62 1.60 1.62 1.61 cla
Selenium structure
Se Te
4.36 4.47 a
1.14 1.33 cl a
For diamond and zincblende structures, the basis consists of two atoms
which, respectively, have the same or different chemical natures. The two
atoms are shifted with respect to each other in the direction of the body
diagonal of the primitive reference cube by a quarter of its side. If the basis
atom 1 is put at a lattice point, then the position of atom 2 is given by
1.2. Atomic structure of ideal crystals 19
Figure 1.3; Spatial model of a crystal having diamond (a) and zincblende structure
(b). In the diamond structure all atoms arc of the same chemical clement, in the
zincblendc structure the atoms are of two different chemical elements.
0 1A (1111
02 8 a IA
3A r, 2 0
0 4B 3A
(J 40
P
6 3 * 5A
60
Cmll cfm
Figuw 1.5: Stereograms of the paint groups Oh (left) and 7'6 (right) of, respectively,
the diamond and zinchlmde structiires.
rotation, and the planrs through opposite cube dges are mirror planes. Both
structures are theiefore tramformd into themselves by the point group T d ,
the symmetry group of a tetrahcdron. It follows that their point groups of
equivalent directions are at least T d . For the zincblende structure there are
no further point symmetry operations which transform equivalent directions
into each other. The point group of equivalent directions is therefore T d , and
the space group turns out to be symmorphic. It is denoted by F13m.
In the raw of diamond structure, thew i s yet another symmptry oper-
ation, namely that which transforms the two chemically equivalent atoms
of the basis into cach other. It may be described as reflection in a plane
perpendicular to a cubic axis, say e,, which cuts the connecting line be-
l w r n two atoms at its center, followrd hy a translation in that plane by
+
(e/4)(ex ey). One, therefore, has a glidereflection as additional symmetry
dement. The space group of diamond structure becomw non-symmorphir
in this way The point group of directions of this structure may be obtained
from the point group T d of the zincblende structure by adding the reflections
in planes perpmdicular to the thrw cubic axes. This yields the full cubic
group Oh, as one can easily determine by means of the stereograms of the
Iwo groups rn Figure 1.5 (for a n introduction to the stereograms of point
groups, see Appendix A). The group o h can be generated from t h e tetra-
hedral group in yet anothcr way, namely by adding the inversion operation.
As an element of the space group, inversion must be relative to the site of an
atom and be followed by a tradation through the vector T2 or -?zr depaid-
ing on whether m c considers a 1- or 2-atom. For future reference we bear
in mind that for the diamond and zincblende structures, inversion always
involves an exchange of the two sublattims.
We now extend our discussion to thc neighborhood-relations in the two crys-
21
tal structures, the so-called coordmatatm Consider atom 1 of thc Lesis of the
unit cell at R = 0. The basis atom 2 of this cell is one of its nearebt neigh-
bors. If all rotation-reflections are executed with respect to the axis through
atom I, then the basis atom 2 of the primitive unit cell at R = 0 gives
rise t o three more basis atoms of type 2. They are all at the same distance
from atom 1 as thP 2-atom first considered, but naturally they lie in three
other primitive unit cells. This means that each 1-atom has, altogether,
four nearest neighboring 2 atoms. Since it would also have been possible
to start from a 2-atom in this consideration, the mme also holds with re-
spect to a %atom, and, of course, independently of whether t h 2-atom is
of the same chemical nature as the 1-atom (diamond structure) or is not
(zincblende structure). The four nearest neighbor atoms lie at the corners of
a tetrahedron, whose center is occupied by the atom itself (see Figure 1.3).
Their relative positions are given by the vectors (a/4)(1, 1, l),(e/4)(T, 1,l),
(a/4) (1,7,l), (a/4)(1,1,i). Thr distanrc betwrrn nearest neighbor atoms
is &a/4. For silicon this is 2+35 A . The second nearest npighbors belong
to the same sublattice. Therefore, for both structures, they arc atoms of
thP same chemical species. They are located at thc nearest-neighbor lattice
points of the fcc lattice. relative to the central atom, thus their positions are
( u / 2 } ( * e 9 f ef), ( a / 2 ) ( f e y f e z ) ,(a/2)(*e, f ey). This means that
thew are 12 second nearest neighbors in each slructurr.
Rocksalt structure
The basis of this crystal structure consists, like that of zincblende structure,
of two atoms of diffprent chemical nature which arc displaced relative to each
other in the direction of the space diagonal of the reference cube. In contrast
to zincblende structure, the displawmcnl i s not, however, a quarter but half
of the length o the space diagonal of the reference cube, whence
22 Chapter 1. Characterization of semiconductors
(1111
1A 1A
01B 028
4 2A 3A
0 28 48
-
0
5A
0 6B
Figure 1.7: Projection of a crystal having rocksalt structure in the (100) plane
(left) and the (111) plane (right). The vertical sequences of atomic layers is shown
on the right hand side of the projections. In the (LOO) case the stacking repeata
itself after 4 Iayem, and in the (111) case after 6 layers.
h
ai y- ae,,
a h
a2 - --ex
2
+ -&e,",
a
2
h
ce,.
Here ek, I$, e," are unit vectors of a cubic coordinate system whose z-axis
points in the direction of the c-axis of the hexagonal lattice and whose z-axis
is identifird arbitrarily with one of the three symmetric lattice directions in
the plane perpendicular to the c-axis. The two primitive lattice vectors a1
1.2. Atomic structure of ideal crystals 23
and a2 in this plane have equal lengths and form an angle of 2x13 with
each other. The volume 5-20 of a primitive unit cell is &a2c/2. The lattice
constants a and c of some semiconductors with a hexagonal lattice are listed
in Table 1.3.
Wurtzite structure
Here, ( is a parameter which may take any value between 0 and 1/2. A
wurtzite type crystal can be understood as a composite superposition of
four interpenetrating hexagonal lattices, with the lattice points of two of
them occupied by atoms of chemical species M, and two of them by atoms
of species X. The two M-lattices are displaced relative to each other by
F M ~ ,likewise as the two X-lattices. The displacement of the XI-lattice
with respect to the MI-lattice is Fx1. In Figures 1.8 and 1.9 these relations
are illustrated in, respectively, spatial and planar displays. The M-atoms
are shown in black and the X-atoms in white. From these figures one can
easily determine the symmetry of the wurtzite structure. The c-axis through
the center of one of the empty hexagons in Figure 1.9 forms a 6-fold screw
axis 63: a 2n/6-rotation about this axis must be connected with a parallel
displacement by c/2 in order to transform the crystal into itself. This also
mean8 that this axis represents a %fold proper axis of rotation. The axis
contains six inequivalent mirror planes, among them three proper reflection
planes and three glide-reflection planes joined with translations by c/2 in
the direction of the c-axis. The corresponding point group of directions is
c 6 v (see Figure 1.10). The space group of the wurtzite structure is non-
symmorphic and is denoted by P6amc.
Consider the atom M I in the unit cell at R - 0. Its neighbor in
the same unit cell is atom X 1 at the site ?XI. Another neighbor of M I is
the atom Xz at the site -ce,h I Fxz of the unit cell at R - -c$. Since
the c-axis through atom M i is a %fold symmetry axis (sep Figure t.9), one
obtains from Xz two additional X-atoms at the same distance but in other
unit cells. Altogether, there are four neighboring X-atoms. In order that
all four be at the same distance from M I , and, correspondingly, all four be
24 Chapter 1 . Characterization of semiconductors
0 1 A
028
3A
0 4B
c = , 1t 9 ( ;1) . (1.11)
(z) fi=
= 1.633. (1.12)
Table 1.2 shows that all wurtzite type semiconductors listed there also satisfy
this condition quite well. This indicates that the ordering of the nearest
neighbors in the wurtzite structure is almost the same as in the zincblende
structure. If a wurtzite crystal exactly obeys conditions (1.11) and (1.12),
one says that it has an ideal w u r t z i t e structure. The distance between two
nearest neighbor atoms in the zincblende structure is &all4 with a the
cubic lattice constant. The corresponding distance in the wurtzite structure
is Cc = (3/8)@ a. For the two distances to be equal, the equation
a= h a (1.13)
must hold. This result means that in a crystal having wurtzite structure
which fuEUs conditions (1.11) and (1.12), the nearest neighbor atoms are
positioned at exactly the same sites as in a crystal having zincblende struc-
ture with lattice constant 4 a. If one multiplies the lattice constants a,
of thc wurtzitc type crystals in Table 1.2 by 4,then one in fact obtains
values which fit well witahthe cubic lat,t,iccconstants of the zincblendc struc-
ture crystals of this table. The volume &a2c/2 of a primitive unit cell oi
the ideal wurtzitc structure is d 3 / 2 , which is twice that of thc zincblende
reference structure given by 8 1 4 .
Of course, this does not at all mean that the wurtzite structurc may
be traced back to lhe zincblende slruclure, Indeed, the actual positions of
the second nearest neighbors differ in the two crystal structures, although
they are all at the same distances a = a/& This may be seen most easily
from the projections of the two crystals on the plane perpendicular to the
c-axis (see Figure 1.4) or to the space diagonals e, -t e$ - t e, (see Figure
1.9). In the wurtzite structure the vertical stacking repeats itself after two
double layers of nearest neighbor atoms, but in the zincblende structure only
after three. The wurtzik structure can be set up, therefore, by stacking one
upon another two different double layers A and B, the zincblende structiire
by stacking three double layers A, B,C (see Figure 1.11). The uppermost
double layer A of the zincbbnde structure in Figure 1.llb coincides with the
26 Chapter 1. Characterizrrtion of semiconductors
A B
-
* A - A
-
-B - B
-A - C
-
. B -A - B
-C
:
Selenium structure
The basis of trigonal selenium and tellurium crystals consists of three atoms.
The vectors of the basis may be written in the form
2c
~3 = -2craez +-
3 e,h, (1.14)
where a is a parameter ranging between 0 and 112. The atoms are ordered
on parallel spirals, in which successive atomic positions are rotated with
respect to each other by an angle of 120' (see Figure 1.12). The space
group can be determined from the projection of the crystal on the plane
perpendicular to the c-axis (see Figure 1.13). It contains one %fold screw
axis parallel to the c-axis which goes through a center of one of the empty
triangles in Figure 1.13. A rotation by 120 or 240' must be followed by
a displacement by c/3 or 2c/3 in the direction of the c-axis, to transform
the crystal into itself. Beside these screw operations, rotations are allowed
with respect to the three inequivalent 2-fold axes perpendicular to the c-
axis. These rotation axes pass through the %fold screw axis and through
one of the three surrounding atoms. The symmetry operations mentioned
correspond to the space group P312. Beside this, the selenium structure
may also have symmetry corresponding to the space group P322, where the
spiral differing from P312 has not a right-handed thread, but a left-handed
one. The point group of directions is, in both cases, D3 (see Figure 1.14).
Concluding this discussion of the characterization of the most common
semiconductor crystal structures, it should be emphasized that these struc-
28 Chapter 1 . Characterization of semiconductors
(00011
o c c 3
tures apply to the ideal case of infinite, structurally perfect, and chemically
absolutely pure materials. Real crystals deviate from this ideal case in vary-
ing degrees. There are structural defects such as stacking faults, step- or
screw-dislocations, vacancies, or atoms on interstitial crystal sites. Such de-
fects will be considered in detail in Chapter 3, in the context of the electronic
structure of yprturbrrl semiconductors. In the next section we will discuss
the chemical composition of idea1 semiconductor crystals.
3 c N 0
Mg A1 Si P S
Zn Ga Ge As Se
Cd In Sn Sb 're
Hg T1 Pb Bi
Table 1.4: Part of the periodic table t o which Inany element.al and compound
semiconductors are associated.
Semiconductors of this group are, starting at the top of column IV? carbon
(C) in the form as diamond, silicon (Si), germanium (Ge), and tin (Sn) in
its gray modification known as a-Sn. All cited semiconductors of this group
crystallize into the structure of diamond. They differ from each other in
regard to their position Let,weezl metals and insulators. Diamond behaves
much like an insulator! and tin, on the contrary, much like a metal. Retween
them one has the two typical semicondnctors silicon and germanium. Both
mat.&& play an essential role in micro- and optoelectronics. It is weU-
known that silicon is the material of preference in microelectronics and,
with this, one of the most important materials in dl modern technology.
Beside the pure elemental semiconductors Si a i d Ge, alloys of bath ma-
terials also have semiconducting properties. The notation for such alloys is
(Si,Ge), or Sil-,Ge, to indicate the rpspcctive mole fractions 1 - z and z
of the two alloy components. According to their structure, the alloys may
be identified as mixed crystals. These are crystals with the same geomcb-
ric order of atom sites as in the case of the alloy components here that
~
of diamond in both CBSW. The regular crystal sites are occupied, however.
randamly by Si or Ge atoms. T'he probability of finding a particular el*
ment on a given site is determined hy the mole frclctiou of this element. in
t,he alloy. In the case of Sil-,Ce, the probability of finding Si is 1 - 2.
and of finding Ge is x. The lattice constants of inixcd cryst.als, in many
30 Chapter 1 . Characterization of semiconductors
cases, follow from the lattice constants of the constituents by means of En-
ear interpolation. This result is known as Vegards rule. The cubic lattice
constant a(si,ce)of a Sil-,Ge, alloy, for example, is given by the relation
~ ( s i= +
, ~(1)- z)asi Z U G ~ ,where asi and a& are the cubic lattice con-
stants of Si and Ge, respectively. A mixed crystal strongly deviates from
an ideal crystal, but the semiconducting property of the two pure crystals
is often retained in the mixed crystal. This is important, and by no means
obvious. It was recognized at the beginning of the sixties in (Si, Ge) alloys.
Later it was also shown to be true in many other material combinations.
The discovery of semiconducting alloys significantly expanded the family of
semiconductor materials. It became possible to tailor materials with desired
properties, just by varying the alloy elements and mole fractions.
The common feature of the elements of the main group IV of the peri-
odic table is that there are four electrons in the outer shell of their electron
clouds, the so-called valence shell. The primitive unit cell, which here has
two atoms, therefore contains 8 electrons. Later we will prove that semi-
conducting properties are related to the crystal structure and the number of
valence electrons per primitive unit cell. Using this result, one may conclude
that compounds of elements from main groups III and V, and from main
groups 11 and VI of the periodic table should also be semiconductors. pro-
vided they have zincblende structure, since the crystals of these compounds
also have 8 electrons per primitive unit cell. Actually the GI-V compounds
(with a few exceptions) do crystallize into the zincblende structure, In the
case of ILVI-compounds the wurtzite structure can also occur, besides the
zincblende structure. The two structures are, however, very similar, as has
been pointed out above, so that semiconducting behavior may be expected
also in their case.
is a promising material for blue LEDs and laser diodes. The quaternary alloy
system (Ga, In)(As, P ) is used in making laserx and pholodiodes for optical
fiber communications at 1.55 p m wavelengths, which provides maximum
transmission for SiOa-based fibers. GaAs and, lately, also (Gtr,Al)As are
employed for transistors with extremely short time delay. BN and GaN can
be used for electronic devices to be operated at high temperatures.
This group includes compounds like ZnS, ZnSe, ZnTe, CdTe, HgSe and HgTe,
which crystallize into the zincblende structure, and compounds like CdS,
CdSe and MgTe which have the wurtzite structure. For most of these mate-
rials the one of the two structures which has not been mentioned corresponds
to a metastable phase, and for ZnS both structures are, in fact, stable. The
cubic phase of ZnS is the mineral zincblende, and the hexagonal phase is
the mineral ururtzite. It i s from these mineral names that the designations
of the two crystal structures are derived. CdO, MgS and MgSe form crys-
tals with rocksalt structure, HgS (vermilion) has a rocksalt-like structure.
As in the case of the 111-V compounds a large number of semiconducting
alloys may also be realized from the IT-V1 compounds, e.g. (Hg,Cd)Te,
Zn(S,Se), Cd(S,Se) and others. Up to now, technical applications involve
mainly (Hg,Cd)Te. It is utilized for detectors of radiation in the medium
infrared spectral region, which is of particular interest since the emission
maximum of the thermal radiation of bodies lies in this region for a broad
range of temperatures. Some semiconductors of this material class, e.g. CdS,
have very good photoelectric properties and are used accordingly. Other such
compounds, like ZnS, are good luminescent materials. They make it pos-
sible to fabricate largearea electroluminescence displays, an alternative to
the traditional vacuum-tube. The operation of blue-green LEDs and injec-
tion lasers made of 11-VI compound semiconductors was demonstrated very
recently.
Table 1.5: Electrical conductivity 0 and charge carrier concentrations for metals,
serniconduct.ors,and insulators.
j=uE (1.15)
Here, it is assumed that anisotropies either do not exist or are negligible.
The following example gives an idea of the order of magnitude of the con-
ductivity: Consider a cube with edge length of 1 cm, and apply a voltage of
1 V between two of its opposite planes. Then a current of 1 A will flow if
the cube material has a conductivity of (T = 1 ern-'. The order of mag-
nitude ranges spanned by the U-values of the three material classes metals,
semiconductors, and insulators are assembled in Table 1.5. The striking
features of this table are the large changes both between the three classes of
substances as well as within the semiconductor material class. The question
arises how these sharp changes may be understood 011a physical basis.
To construct an explanation, we use the known representation of the
electrical conductivity IT as the product of the electron concentration n, the
mobility ,u, and the electric charge -e of an electron,
u = enp. (1.16)
The mobility p is defined as the ratio of the magnitude of the average ve-
locit,y of an electron to the strength of the electric field driving it (for a
derivation see Chapter 5). Formula (1.16) for the Conductivity o shows that
its variations may, in principle, be caused either by different values of the
mobility p and/or by different electron concentrations n.
The mobility is actually determined by the scattering processes which
electrons undergo due to the perturbations of the crystal lattice. One ex-
1.4. IlIacrascopic properties and their microscopic implications 35
P M E E? P S C = P I S . (1.17)
This conjecture is confirmed by experiment, and consequently it follows that
the large conductivity differences between the three material groups are es-
sentially due to their different electron concentrations. If one assumes for
metals one free electron per atom, which amounts to approximately 10
electrons per m 3 , then the conductivity values in Table 1.5 yield the elec-
tron concentrations of semiconductors and insulators listed in this table.
(1.18)
Here, rrg is a factor which depends only weakly on temperature, k is the
Boltzmann constant and Eg is an energy of about 0.7 eV in the case of ger-
manium and 1.1el in the case of silicon. Formula (1.18) also describes the
temperature dependence of the conductivity for other pure semiconductor
materials fairly well at sufficiently high temperatures, save that the values
for cro and E, must be changed. In Table 1.6 the &.-values are listed for
some import ant semiconductors.
There is a second way of varying the conductivity of a semiconductor
over a wide range, namely to intentionally pollute it with atoms of certain
chemical elements. One calls this process doping wzth impup.ity atoms. In
this context, the doped semiconductor materials are called extrinsic semi-
conductors. As an example we choose silicon, doped with arsenic a t o m
36 Chapter 1. Characterization of semiconductors
Table 1.6: E,-values for several semiconductor materials at 300 K (in eV).(Aftar
Lundoldt-Bumstein, 1982.)
Material GaN GaP GaAs (Mh InN IriP Iiub IrlSb ZnS
100 -'
Valence bond
O0 X--- HL
0 1
f [El--)
0 L 0 L
X- X 4
(1.19)
Here E F is the so-calld Fwmz mevyy. Like temperature, the Fermi en-
ergy is an intensive thermodynamic state variable, namely the free enthalpy
per particle or the chemical potential. A more detailed treatment of the
Fermi distribution function will he given in Chapter 4. The probability of
orcupation of a particular energy value E: depends decisively on the relative
position of E with respect to the Fermi energy. If E < E F holds, and in
addition J E- E F J>> kT,then f ( R ) essentially has the value 1. If, on the
contrary, E > E F and again IE - EFI >> k T , then f ( E ) is approximately
zero. The shape of f(E)is shown schematically in Figure 1.20. The width
of the e n e r a region where the transition horn 1 to 0 takes place is cf the
order of magnitude kT. The lower the temperature, the more abrupt this
transition becomes. At T = 0 K thc transition is steplike. Qccesionally, one
says that f(E)has the form of an iceblock at T 0 K , which melts at
higher temperatures. 111 Figure 1.20 we have also implied that Pi, lies below
E F and E, above E F , in order for the valence bend to be almost completely
occupied and the conduction band to be almost empty. This means that
1.4. hfacroscopic properties and their microscopic implications 41
0 L
X--L
the Fermi energy must be located within the energy gap between Ev and
E,, sufficiently far away from the two band edges (measured in units of kT).
In this. we have described an essential microscopic property of pure semi-
conductors. Their Fermi level lies in the energy gap between the valence
and conduction bands. The electrons are distributed over the two bands as
shown in Figure 1.21. This knowledge provides a complete explanation of
the absorption spectrum in Figure 1.18. The explanation is illustrated in
Figure 1.22 and needs no further comment.
The differences in the properties of semiconductors and metals may be
traced back, in essence, to the different positions of the Fermi levels in these
two different types of materials. In metals the Fermi level lies within the
conduction band. Insulators do not differ from semiconductors qualitatively
with respect to their Fermi level positions, i.e. the Fermi levels are found
in the energy gap in both cases, but the gap of insulators is typically larger
than that of semiconductors. If Eg > 3.5 e V , as a rule, one has an insulator.
We will now show that the temperature dependence of the electric con-
ductivity of pme semiconductors also follows from the energy band scheme
discussed above and the position of the Fermi level in it. Again, we employ
the relation u = enp. The mobility p can be assumed to be a relatively
weakly varying function of temperature, T . This means that the strong ex-
ponential T-dependence of CT must be due to the electron concentration IZ,
42 Chapter 1. Characterization of semiconductors
(1.20)
and the conduction band is completely empty. The electrons in the fully oc-
cupied valence band cannot contribute to carrier transport. The reason for
this is again the Pauli principlc, according t o which an electron state may be
occupied by only one electron. Since all valence states are occupied, no stste
change is possible in the valence band by redistribut,ing the electrons. This
means that the T = 0 K state will remain unchanged in 8x1 electric Eeld, and
consequently no current will flow. However, a current will arise from the rel-
atively few clectrons which, according to thc Fermi distribution function: are
populating the conduction band at ftnite temperature. Their concentration
can be easily calculated. For a pure semiconductor Ec - EF >> 6T holds.
Thus, in the Fermi distribution function j ( E ) of ecpation (l.l!J),out3 m a y
neglect the 1 of the denominator for emrgies E in the conduction band,
i.e. energies with E > EC Iu so doing, one obtains, approximately, the
Boltzmann distribution function
(1.21)
(1.22)
(1.23)
where
(1.24)
1.4. Macroscopic properties and their microscopic implications 43
1
E F = Ev + -E
2 g '
(1.25)
i.e. the Ferini level lies exactly in the middle between the valence and con-
diistion bands. Strictly speaking, this is only true for T = 0 K , as we will
see later. The corrections at higher temperatures are, however, quite smaI1,
and they can bc ignored here. Another inaccuracy of the above considera-
tion that. we have ignored is that, at, finite temperatures, the valence band
population also changes. so that no longer are all states of this band ocm-
pied. Under these circumstances t.he electrons of the valence band also make
a contribution to the current. The temperature dependence of this contri-
bution is roughly the same as that of the conduction band. The electric
charge transport due to the electrons of a not-completely-occupied valence
band will be considered more fully later. It is connetted with a remarkable
observation of the Hall effect, which we will discuss below.
However, we will first clarify how one may understand the strong change
of conductivity with impurity concentration in extrinsic semiconductors. For
this purpose we again m e the energy band model of Figure 1.19 for an ides1
semiconductor. If arsenic impurity atoms are present in a silicon crystal,
then this model has to be altered. Wc will later prove (see Chapter 3)
that each of the arsenic impurity atoms g i v ~ rise to an energy level in the
forbidden gap, just below the conduct.ian hand edge, and that the electrons
in these levels are localized at the site of the impurity atom. For this reason,
we have marked these levels in Figure 1.23 by short line segments.
At temperature T = 0 K each of these levels is occupied by one dec-
tron, namely the fifth valence elcctron of an arsenic atom replacing a silicon
atom having only four valence electrons (see Figure 1.23). If temperature
i s increased, these electrons are excited into the conduction band. In this
way, bound electrons which formerly could not participate in carrier trans-
port, become freely mobile electrons (see Figure 1.24) which can contribute
to transport. If the concentration N D of arsenic atoms is not too large: and
the temperature 7' not too law, then practically all arsenic atoms are ionized
and the concentration n of free electrons is equal to the that of the arsenic
atoms, i.e. one has R = N D . This corresponds to the approximate propor-
tionality between cr and N o observed in Figures 1.16 and 1.17. If the carrier
concentration has Ihe value NLI>which at sufficiently high temperatures T i s
actually the caw, then the conductivity becomes independent of T. The only
remaining source of a temperature dependence for u is the T-dependence of
the mobility p. It is this relatively weak temperature effect which shows up
44
2
-
I
0 L
X--c
T-0 T.0
0 L
X- X-
Figure 1.24; Distribution of the electrons of a silicon crystal doped with arsenic
over the allowed energy values. 011the left for T 0 K , OIL the right for T > 0 K .
7
45
*)U1-Phosphorus
doped Si
u
Boron
doped Si
Current 4 Current- a)
Current - Current- bl
Phosphorus
doped Si
~ a i current
i H ~ Icurrent
I + Cl
Figurc 1.25: nlrlstration of the Hall effect in two silicon smrples, one doped with
phosphorus, and the other with boron.
of Figure 1.25 no current can flow in this direction, and therefore there will
be a voltage UH such that the current caused by it will just compensate
the Hall current. Experimentally one finds that the Hall voltage UH has
different polarities in the two samples. This means that the corresponding
Hall currents flow in opposite directions. If we assume that the magnetic
field is directed normal to the plane of the figure and that it points into this
plane, then the Hall current flows upwards in the boron-doped sample, and
downward in the phosphorus-doped one.
The Hall effect can also be measured in metals. In this case the direction
of the Hall current is the same as in the silicon sample doped with phospho-
How can the dlfemnt behauiior of thesiicon sample dupd with born
be understood?
The explanation is quite clear if one assumes that, in contrast to metals
and the phosphorus-doped silicon sample, the current in the boron-doped
sample is not carried by negative charge carriers but by positive ones. This
is illustrated in Figure 1.25d. A charge q , which moves with velocity v in a
magnetic field B,experiences the Lorentz force
F = 4- [ v x S ] . (1.26)
C
Since negative charges move to the left, and positive ones to the right, the
Lorentz force F, which depends directly on the sign of the charge, has, for
both charge signs the same direction, namely upwards. For the boron-doped
sample this means a Hall current directed upwards, but in the phosphorus-
doped sample the Hall current is downwards, since in this case the charge
carriers are negative. This is just the observed behavior, which means that
the assumption of positive freely mobile charge carriers is successful in ex-
plaining the unusual sign of the Hall current in boron-doped silicon. In this
way the experimental observations of the Hall effect reveal a remarkable gen-
eral property of semicondiictors: For doping with certain atoms, the current
is not carried by negative charges as one would expect considering the nega-
tive charge of electrons, but by positive ones. In other words, in addition to
the electrons as negative freely mobile charge carriers, one also has positive
ones in semiconductors under certain conditions.
This surprising observation may be understood as ~OUQWS.One may
demonstrate - as we will do later explicitly - that boron atoms whi& sub-
stitute silicon atoms in tf silicon crystal, give rise to energy levels in the
forbidden zone just above the valence band edge. This is illustrated in Fig-
ure 1.26. Electrons in such energy levels are localized at the sites of the
boron atoms. At very low temperatures these states are not occupied, and
the boron atonis are electrically neutral. At finite temperatures electrons
from the valence band are excited into the boron levels (Figure 1.27), leav-
ing behind unoccupied states, or occupation hole3 in the valence band. We
1.4. Macroscopic properties and their microscopic implications 47
immediately recognize that these occupation holes of the valence band be-
have jubt like freely mobile positive charge carriers in an applied electric
field. This is illustrated in Figure 1.28. For simplicity only one hole is as-
sumed to be in an otherwisr rompletely occupied valence band, placed at the
upper band edge. The population of the bend edge is shown in Figure 1.28
at different points of time. At the beginning, the hole is at the outermost
left position. The adjacent electrons experience a force which tends to move
them to tho left. Rut only the electron neighboring the hole on its right
hand side can follow this force, since all other electrons are blocked because
the states to their left are already occupied. The electron immediately on
the right hand side of the hole, moves into the hole and leaves behind an-
other hole to the right of the first one. The hole has thus moved one site
further to the right in this way. 111 the next time interval this process is
repeated, and the hole again moves one site further to the right etc. Thus,
in an electric field, the hole moves like a freely mobile electron, but in the
opposite dirwtion, as if carrying a positive charge. In summary, holes in the
valence band behave like freely mobile positive charge carriers. This quali-
tative introduction of the concept of holes will later be elaborated by more
quantitative considerations.
As we have seen above, the sign of the Hall voltage tells one whether
the free carriers of an extrinsic semiconductor are negatively or positively
charged, Le. whether they are electrons or holes. In the first case one speaks
of a n-typr semzcondurtov (the n stands for negative), in the second of a
p-type semarondector ( p for positive). The antranszc semiconductors intro-
48 Chapter 1. Characterization d semiconductors
L 0 1
X- X-
Figure 1.27: Distribution of elect.rons of a silicon crystal doped with boron over
allowed energy values.
duced earlier haw neither electrons nor holes from impurity atoms. Their
mobile electrons arr generated by thermal excitation of bound electrons from
the valence band to the rondiiction band. Since each excited electron leaves
behind a hole in the valence bmd. one also has mobile holes in intrinsic semi-
conductors. Their number is equal to that of the mobile electrons. Holes
are also present in n-type semiconductors, but, in very small numbers com-
pared to elwtrons. Analogously, a few electrons occur in p t y p e materials
with mob1 of the carriers being holes. One calls the many mobile carriers
of extrinsic semiconductors m a j o n l y cariwrs and the few mobile carriers
mzrrortty earners.
The Hall effect can also be used for purposes other than the determi-
nation of whethrr an extrinsic semiconductor is n- or p-type. The absolute
valup of the Hall voltage determines the concentration of majority carriers.
We will veTify this assertion for an n - t y p ~semicondiictor. In this case the
rurrcnt density j can be expressed in the form j =- --env. which permits us
l o rewrite equation (1.26) as
1
F=-[j X B ] . (1.27)
RC
This is the same force caused by the electric field E ~ I= F/(-e). The
voltage corresponding t,o EH is by dehition the Hall voltage Ufi. With b
as the width of the sample normal to j and 3,the expression below for U x
follows:
(1.28)
where
1
Rff = - (1.29)
PrtC
I I
1~-7 - I
10-4 10-3 lo-7 10-1 ma r]'
I h o t t om* --+
shows that t.he carrier concentration was increased from about 10'' cm4
(equilibrium value) up to ~ light of intensity 10 Wcm-'. The
c ~ n . -by
electron-hole pairs created by the radiation decay, however, after a short
t,ime. 'lhis follows from the fact that continuous irradiation leads to tt sta-
lionary conductivity value, and lienre a constant carricr concentration, and,
on the other hand, from the observat.ionthat the conducbjvity decays down
to the dark value after switching off the light source. The 1at.ter observa-
t.ion means that, thermodynamic equilibrium i s reestablished by so-called
wxnnbinaiion, p7nuesses.
Rwidr irradiation with light, extreme nun-equilibrium states in semicon-
ductors can also be created in other ways, for example, by putting an n-type
semiconductor in contact with a p t y p e semiconductor or with a metal, or
by applying voltage to a. semiconductor which previously had been isolated
by a thin insulating layer from one of the electrodes. The ability to c r e
at,? extreme non-equilibrium states in semiconductors i s extensively used in
electsonic devices. Almost all applicat.ionsof semiconductors in such devices
rest on this uniquc pQssibility-.
Non-equilibrium processes in semiconductors and the most important
scmiconductor devices based o n them, such as electric rect.%ers, bipolar and
unipolar transistors, tunnel diodes, photodetectmu: solar cells, as well as
luminescence and laser diodes, will be dealt with in the second part of this
book, i.e. in Chapters 5 , 6 and 7. In the first part of the book, the basic
concept.s, discussed above in a heuristic way, will be developed from first
principles. This applies to the stationary electron states of an ideal semi-
conductor (Chapt,er 2), their niodifications by impurity atoms and other
deviations from the ideal crystal, as well as by external fields (Chapter 3)
and t h e statistical distribution of charge carriers over aiergy levels in ther-
modynamic equilibrium (Chapter 4).
51
Chapter 2
In sections 1.2 and 1.3 of the preceding chapter we discussed the spatial
order and chemical nature of the atoms in ideal semiconductor crystals. The
present chapter is focused on the quantum mechanical energy eigenvalues
and corresponding eigenstates of electrons in such crystals. The substance
of this subject is summed up under the designation electronic structure. We
will show how the simple model of electronic structure of a crystal, the
energy band model, which we heuristically introduced in section 1.4, can be
rigorously deduced from the Schrodinger equation. The periodic ordering
of the atoms of a crystal in space is crucial for this proof. It will also be
seen that the eigenstates of electrons in a crystal devolve upon the electron
states of the free unbound atoms. This is immediately understandable if
one imagines that the crystal is grown from the gas phase, i.e. by chemical
bonding of previously isolated individual atoms. In this process the electron
states of the atoms will change, of course, but the resulting states, i.e. the
electron states of the crystal will also depend on the initial electron states
of the isolated atoms prior to crystal formation.
Table 2.1: Characterization of atomic cores and valence electrons of main group
elements from which semiconducting mat,erialsmay be formed.
B 5+ 222p
C 6+ 18 2922p2
N 7f 2s22p3
A1 13+ 323p
St 14+ 132222p6 323p2
P 15- 3s23p3
Ga 3 1+ 424p
Ge 32- ls22s22p633s23p63d10 3s24p2
AS 3 3+ 4Ap3
ble 2.2). Because the electrons of these deep shells are localized so close to
tlirir rrspertive nuclei. they feel potential changes produced by siirrouud-
ing atoms as being almost uniform. Strictly speaking, this means that the
wavefunctions of these electrons are essentially unaltered. Their eneqy lev-
els shift, however, specifically by the change of the constant potential value
arross their localization region. The term d i d d a t P shtjts is iised for t h e s ~
shifts of the inner electron levels. By measuring these shifts m e can obtain
information about the chemical nature and geometric striicturc of the envi-
ronnient of an atom in B solid. In B way, the inner electrotla threby serve
as probes.
Table 2.2: Energy levels -E, and -4 of the valence electrons and - E , of the shal-
louwt core electrons for some chemical elements which may occur in semiconducting
materials. All energies are given in el/. (Afcer Herm.an. and SkiIlman, 1963.)
Atom 3 C N 0 A1 Si P S Zn Ga
-tp 6.6 9.00 11.5 14.1 4.9 6.5 8.3 10.3 3.1 4.9
-t, 12.5 17.5 23.0 29.1 10.1 13.6 17.1 20.8 8.4 11.4
-ec 195 291 405 537 87.5 116 147.4 182 20.7 31.7
-cP 6.4 7.9 9.5 3.4 4.7 5.9 7.2 8.6 3.5 5.8
the inner shcll drrctruns jointly as subsystems of the crystal, whose intrrnal
structure i s of no further interest sirire it does nut change. The structure is,
so to speak, frozen. In this sense t.hc subsystcms composed of atomic iuiclei
and inner electrons are elementary building blocks of the crystal. One rekm
t,o them as atom.ic ~ 0 : ~ s .
The frozen nature of the electron states of the cores of a crystal! and
their lack of rcsponse to external influences, generally prevails, but as always,
there arc exceptions. In heavy metals such like zinc, t.he inner &shells are,
energetically, rather close t,o the oubar valence shells (see Tables 2.1 and 2.2).
In this case the d-electrons significantly participate in chemical bonding and
can no longer be included in t.he core, which is iinchangeahle by definit,iou,
Moreowr, the inner shell eledrons of crystals can be excited by means of
electromagnetic radiation in thc far UV and X-ray region. This can also
occur by means of an electron beam In solid state nuclear reactions, ~ W R
the states of the nuclei of the crystal atoms change.
54 Chapter 2. Electronic structure of ideal crystals
/; +
0
\ 0
Figure 2.1: 13escription of the positiom of the atomic cores ( 0 ) and valence elm
trons {a) {left part) as well as the interactions between these particles (right part).
ciently large, they will encompass all types of motions of an infinite crystal
with desired accuracy. The concept of the periodicity region makes it possi-
ble to pass from the original infinite space problem of motion to a finite one
without thereby losing the translational symmetry of the infinite crystal.
We use Xj t o denote the center-of-mass coordinates of the j-th atomic
core, and xi for the position of the i-th electron, which is further assumed
to be point-like {see Figure 2.1)- The j-th core mass will be denoted by
Mj. Of course, there are only as many diferent values of M j as there are
chemically different types of atoms in the crystal, so most of the Mj-values
are identical. In the case of electrons we can omit the index i from their
masses since they have the common mass m. The momentum of the j-th
core is called P3,and that of the i-th electron pi, such that
We are interested in the motion of the interacting atomic cores and valence
electrons of the infinite crystal, which can only be adequately treated by
means of quantum mechanics. The state of the system is described by a
wavefunction @, which depends-on the coordinates xi of all electrons and
Xj of all atomic cores, as well as on the time t. Since we assume periodicity
of the motion with respect to a periodicity region, it suffices to consider @
as a function of the coordinates xi of the N-electrons and the coordinates
Xj of the J cores of only one periodicity region. The state of the particles
in the remaining periodicity regions can then be described by means of a
periodic continuation of this function, i.e. by means of the relation
56 Chapter 2. Electronic structure of ideal crystals
+ + V.
H =- Tc Te (2.3)
The kinetic energies Xc and T, ran be expressed in terms of the momenta
Pj and pa of the cores and electrons as fOllOW8:
(2.4)
(2) The interaction of the electrons with the atomic cores due to their mutu-
ally attractive Coulomb forces, and also due to (repulsive) forces of quantum
mechanical origin, which become effective if the valence electron wavefunc-
tions overlap the inner electron shells of the atomic cores. The electron-core
interaction potential energy V,, depends on the locations of both the elec-
trons and cores. With respect to the electrons, it is evidently additive, i.e.
i3
iFL-e = H6,
at
whose solution may be determined in terms of the eigeiivalue problem for
the Hamilt,onittn 7f, which is given by the time-independenl Schrodinger
equation
smaller than that of a valence electron. 'l'his can be seen in the following
way: If the cores and valence electrons were fwe particles, i.e. if they did not
interact, then the average kinetic e n p r o of a core would be approximately
(3/2) h7'. That of a valencp dzctron would be about (3/6) Eli where E F
is defined as the Fwmi energy of an electron gas of the same density. The
daerence between the average kinetic energies of the two types of particles
arises from the fact that the electrons obey Fermi statistics, whereas atomic
cores obey Boltzmann statistics. For typical concentrations of valence elec-
trons in a crystal of about 10" C W L - ~ the Frrmi e n e r a EF i~of the order
of m~gnit~ude of e V , while kT reaches only about 0.1 eV below the melt
mg point of the crystal. The average kinetic energy of a core is therefore
generally smdlcr than that of an electron. This remains true when the in-
teractions between the electrons and coresi which were omitted above, are
taken into account. Writing (M,/2) < X: > and (m/2) < x: > as the
avrragP kinetic enmgies of a core and an electron in a crystal, we thus have
Mj 1 7 1 . '
-2< X j > < -<xq>.
2
(2.12)
and it, follows that
(2.13)
Corrmpondingly, one may say that, on statistical average, the cores move
much slower than the electrons. This observation plays an important role in
the following considerations.
To simplify the notation, we replace the N-component sequence o the
vectors (XI,x2,.. . , X N )by x, and the J-component sequence of vectors
(X\,Xz,. . .,XJ)by X, ie. we write
(2.16)
2.2. The dynarnical problem 59
(2.17)
1% + v,,,c] X),
$(x,X)= U(X)@(X, (2.18)
where, for brevity, we have set
The set {$4) of the eigenfunctions of the Schriidinger equation (2.20) forms
an orthonormalized basis set in the Hilbert space of the crystal. Therefore,
relation (2.20) is satisfied if it holds for the Fourier type coefficients relative
to all basis functions Qd of this set, i.e., if the identity
The first two terms on the right-hand side of this q u a t i o n turn out to be
small compared to thr kinetic cuergy term of elwtrons in equation c2.20).
One has the order of magnitude relations
(2.23)
(2.24)
Here .n/E is a typird value of the core masses M,. The two equations (2.23)
and (2.24) are of fundamental importance in crystal dynamics, because they
are ultimately responsible for the drroupling of rloctron dynamics from the
dynamics of the cores. Therefore we present the proof of thwc equations
in Appendix B. Here we proceed a n the assumption that these relations are
proven.
The terms of rplativeorders of magnitude (rn/M)1/2 2 lov2 and ( m / h f )w
l W 4 , will be nPglatrd henceforth. With this the operator T, for the ram-
bined kinetic energies of all cores satisfies the approximate relation
the cores, for without such an interaction the eigenvalue U in the electron
Schrodinger equation (2.18) would be a constant independent of X, which
could be omitted. The potential contribution U(X) caused by the electron-
core interaction does not depend, however, on the electron coordinates. It
is an average value over all their positions X. The weight with which the
various positions x enter this average over the probability I + ( x ,X)1 d 3 N ~
of finding the electron system in a volume element d 3 N ~at the position x,
since equation (2.18) implies that
(2.28)
ing of this term. The term adiabatic thus refers to the essential character
of the approximation in neglecting (rn/M)/. This approximation is use-
ful, of course, only as long as transitions between different eigenstates $$
play no important dynamical role. This is actually the case in regard to
many crystal properties and phenomena. There are, however, also effects
for which this does not hold, notably electric current transport. The fact
that the electric conductivity of an absolutely pure crystal does not become
excessively large is due in large part to the scattering of carriers from the
oscillations of the atomic cores, i.e. to non-adiabatic quantum transitions
between different electron and core states. Also, in the recombination of
electron-hole pairs mentioned in Chapter 1, these transitions play a decisive
role, with the lattice of atomic cores absorbing the energy which is released
during recombination. Formally, one may understand non-adiabatic transi-
tions as the result of an interaction between the electrons and the motion of
the atomic cores. Since such core motion, as we will see below, represents a
superposition of lattice oscillations, also known as phonon excitations, this
interaction is called the electTon-phonon interactaon
We have yet to explore how the two Schrodinger equations (2.18) and
(2.26) for the electrons and cores can be actually solved. The problem is
that both equations, are, at the outset, not completely determined - the one
for the cores contains the adiabatic potential U(X),which can be known
only after the equation for the electrons has been solved; and the electron
equation can be fully d e h e d , however, only if the positions X of cores in the
potential Vee,..-,-(x, X) are known. The direct way to overcome this difficulty
would be the following: One assumes a particular spatial ordering Xof the
cores and uses it to determine for them the potential Ve,ec(x,X).The lat-
ter is then used to solve the electron Schrodinger equation (2.18) (we will
not discuss here how this is accomplished, as it will be the subject of the
next subsection, 2.2.3). From the solution of the Schrodinger equation (2.18)
one obtains the value of the adiabatic potential U at the position X of the
cores. The same procedure is then applied to all other possible positions X,
whereby the adiabatic potential U(X) and the Schrodinger equation (2.26)
for the cores are completely determined. This equation can then be used to
calculate the core wavefunction t#(X). It follows that the dynamical problem
for the crystal as a whole is solved, since one would know its eigenfunctions
@(x, X)= y(x, X)q(X). In reality, however, this procedure is unsuccessful.
One cannot solve the electron Schrodinger equation for all possible core po-
sitions. Therefore, a simplified procedure is necessary. It contains additional
approximations, but has the advantage of being feasible in practical terms.
In this approach, one ignores the motion of the atomic cores completely and
assumes that they are resting in certain equilibrium positions Xq. In re-
ality, they execute oscillations around these positions with amplitudes that
become smaller as the temperature of the crystal decreases. However, due to
2.2. The dynamical problem 63
xo - - X" I.ke,ec(X,Xn)
? v,v,(xy -0 ?
no
J
xn+1
I
Figure 2.2: Iterative calculation of the equilibrium positions of the atomic cores.
+
Vo(X) = U(X) VC(X) (2.29)
of the crystal in equilibrium have a minimum at Xq. Equivalent to this
is the requirement that the forces -VxVo(X) on the cores, the so-called
Hellman-Feynman forces, vanish at the equilibrium positions:
--vxvo(x)~x,xeq
= 0. (2.30)
Bearing this in mind, we may employ the iteration process below for the
solution of the two coupled adiabatic equations (see Figure 2.2): In this pro-
64 Chapter 2. Electronic structure of ideal crystah
cess, one assumes ccrtain trial equilibrium positions Xo, enters them in the
electron Schrodinger equation, and determines the eigerivalue U(Xo). This
solution is then used to determine the potential Vo(Xo) and the liellmaii-
F e y m m forces. Thanks to the Fe'egrman theorem, taken jointly with appro-
priate analytical transformations, one can determine these forces without
numerically calculating Lhe potentid in the environment of X'. After the
first iteration cycle, t.he Hcllman-Feynman forces will, in g~neral.not yet
vanish. signifying that thc cmes arc still not at equilibrium posibians. By
nieans of the non-vanishing f o r c e one det.ermines new trial positions XI.
'The new positions are then substituted again onto the electron Schrudinger
equation (z.18)! to calculate a new eigenvalue U(X1),and the latter deter-
mines the corresponding Heban-Feynrnan forces. This procedure is to be
repeated until the forces become zero. The corresponding core positions are
then the equilibrium positions XeQ.In this way one reaches a very impor-
tant result, the determination of the atomic structure of the crystal. Such
structure calculations are successfully carried out currently fw many solid
state systems, including a series of semiconductor cryst.als. With regard to
semiconductors, it can he shown, for instance, that under normal conditions,
Si haas the diamond structure, and that its Lattice constant a iR 5.49 A.
where. for simplicity, Vo(Xeq) = 0 has been assumed. Equation (2.32) de-
scribes a system of coupled harmonic oscillators. The restoring forces are
determined by the second derivatives of the potential Vo(X). Using the
eigenvectors and eigenvalues of the matrix of restoring forces (actually, of the
so-called dynamical matrix which also includes the kinetic energy term), one
can easily transform to a system of uncoupled harmonic oscillators. Their
motions are called normal mode osciliataom or lattace oscillations,and their
excitation quanta are phonom.
Phonons are a good example of the introduction of a concept which is
of fundamental importance for the dynamics of many body systems, includ-
ing the many-electron system of a crystal which will engage us in the next
subsection. The concept we have in mind here is identified by the terms
elementary excztatzons or quast-particles (both terms are commonly used).
This concept is based on the possibility of decomposing the motion of a
system of mutually interacting particles - in our case of the atomic cores
of a crystal - into non-interacting components of motion - phonons in ow
case. The phonons or, more generally, the elementary excitations are. so
to speak, the elements of n o t z o n of the system, while the atomic cores or,
more generally, the actual particles. form the ~ ~ T U C ~ U Telements
-Q~ of the sys-
tem. ,413elementary excitation involves coordinated motion of all structural
elements of the system. Conversely, the motion of an individual structural
element is a superposition of all elementary excitations - the motion of the
atomic cores, for example, is a superposition of all normal mode oscillations
or phonons.
Besides the oneelectron and one-hole excitations, the phonons are the
most important elementary excitations, or quasi-particles, of a crystal. In
this book we will deal mainly with electronzc elementary excitations, and
will include phonons only if it is otherwise impossible to properly describe
electron dynamics. Relevant phonon information will simply be cited with-
out detailed justification, since a thorough development of the theory of
phonons is beyond the scope of this book. O w choice of subject matter here
is conditioned by the fact that electrons and holes are much more important
for understanding the properties of semiconductors as they are used in elec-
tronic devices, than are phonons. Readers who are particularly interested in
phonons are referred to other books (see, e.g., Born and Huang, 1968; Bilz
and Kress, 1979; Bonch-Bruevich and Kalashnikov. 1982).
We return now to the Schrodinger equation (2.18) for electrons. In the
sense of Figure 2.2, we approximate the core positions X by their equilibrium
values Xeq. As far as the latter are concerned, we take the point of view
that they are known from experimental structure investigations, e.g., by
means of X-ray diffraction. For common semiconductor crystals this is in fact
true in all cases. Taking this approach, the potential b=,- in the electron
Schriidinger equation (2.18) is well-defined from the very beginning. To
66 Chapter 2. Electronic structure of ideal crystals
Hartree approximation
+
pv(x)= pu(x Cajj j = 1,Z, 3. (2.35)
Secondly, they are assumed to form a complete orthonormal set of functions
in Hillert space, sylribolically
oneparticle state pv[x), i.e. particle 1 with state pull particle 2 with state
puL,etc., up to partick N which is associated with the state. , ,oy Alterna-
tively, WP may say that we occupy state pw with particle 1, state p , with
particle 2, etc. Due to the Pauli exclusion principle, each state can host only
1 particle, ignoring spin (which we do at this stage). Thus a given state
p1, p2,. . . ,pm may occur among the papdated ones lpy, 'py, . , ,pVNnot
more than once. Most of the states will not even orcur o n r ~ i.a, , not at all
(bear in mind that there is an i n h i t e number of them). These states remain
unoccupied. The set of quantum numbers, (q, vz, . .. , VN),termed configzs-
ratzon, definea the state of the N-electron system uniquely if we understand
that the h s t number in this set refers to the state of particle 1, the second
to the state of particle 2 etc.. Henceforth, we abbreviate the configuration
( V l , V a l . . . ,w )by (.I.
Thirdly. we assign to each configuration (IJ)of the N-electron system a
wavefunction $(y)(xl,x2,. XN) which is given by the bllowing product of
I I
oneparticle wavefunctions:
Disregarding the miitual interaction of the electrons for the moment, the
product (2.37) forms an eigenstate of the N-electron system if the one-
particle wavefunctions pV,(xJ)are energy eigenstates of the individual o n e
electron subsystem Hamiltonians. This suggests t h e question whether a
similar result might be possible for interacting electrons, i.e. whether it will
be possible to choose the py,(xj) in such a way that the product statc +ivi
obeys the Schriidinger equation
(2.40)
(2.42)
On the right-hand side of this equation only the first three terms depend on
the electron coordinates x1 while the last two are constants in this regard. If
one substitutes the expression (2.42) into equation (2.41),then the last two
terms can be grouped together with U{'(.}to h m the new eigenvalur
(2.44)
(2.45)
we rewrit,e (2.41) as
The final relation (2.46) has the form of a Schrodinger equation for the 7-th
particle where V'{(")(xp)is the potential energy of this particle and EV,is
its energy eigenvalue. Beside the potential energy ITc(&) due t o the atomic
cores. V'Iv}(x,) also contains the contribution \#'}(x,). It is caused by the
mutual interaction of electrons, and is commonly called the Hartree p o t e n t d
In explicit form, ITH%{.I (x,)reads
(2.47)
70 Chapter 2. Electronic structure of ideal crystals
Here the integration runs over a periodicity region. The Hartree putential
V~(X~) describes the potential energy of the i-tb particle in the Coulomb
potential produced by the charge distribution --e Ck+% i(oV,(x)l2of the re-
4
maining particles. The factor of the electron-electron interaction potential
(2.5) does not occur in expressions (2.45) and (2.47) for the Hartree poten-
tial since each electron pair contribntes only once. Obviously. the Hartree
potential and the corresponding energy cigenvalues depend OB the configu-
ration { v } of the N-electron system, and also on the index i of the particle
which was removed.
The one-particle Schrdinger equation (2.46) derived above for the i-th
elpctron, holds for each other electron as well. only with a somewhat different
potential. This difference will now be removed, together with the dependence
of the H a r t r e potential on the configuration {v} of the N-electron system.
We argue as follows: If the number A; of electrons is macroscopically large,
as in the case of the electron system of a crystal, and if we consider only
oneparticle states which are spatially spread out more or less evenly aver
the entire crystal, there is no signifkant difference if we extend the sum over
k in equation (2.47) for the potential V;,[(x,)t o include k - i . Then the
2-dependence of the potential no longer exists. The emor thereby incurred is
of relative order of magnitude l/N. If one considers, on the othcr hand, only
states ( v } of the &--electron system which are similar to each other, one may
also neglect the {v)-dependence of the potential and replace V{}(x) by the
value for a representative configuration {vo). The question is, does such a
representative codguration exist in the case of a semiconductor, and if so.
what is it. The answer to the former question is under normal conditions,
yes. For a representative configuration in the abovementioned sense, we
have the state of the N-electron system with lowest total energy, the so-
called ground state. In this state all one-particle states p with energies
Ev below a special energy value (the Fermi energy) are occupied, and the
states with energies above are empty. Under normal conditions the states
of the N-electron system which occur in semiconductors, and also in other
solids, deviate very little from the ground state, Non-normal conditions
are associated with large deviations, e.g., such as semiconductors which are
displaced to a highly excited state by intense laser irradiation. Excluding
such extreme cases, the Hartree potential Vrj}(x) for the configuration {v)
is almost the same as that for the ground state configuration {v}, and
correspondingly we have
(2.48)
(2.51)
The Hamiltonian of this equation is the same for all particles and no longer
depends on the configuration of the N-particle system. Equation (2.51) is
therefore the oneparticle Schrodinger equation par excellence, devoid of any
reference to a particular particle or configuration of the N-electron system.
We may therefore omit the index i in equation (2.51). TJsing the oneparticle
Hamiltonian
P' (2.52)
ff = 2, I v(x),
this equation becomes
solution has a well defined and sufficiently simple connection with the solu-
tion of the N-electron problem.
The idea that the (py(x)are energy eigenstates and the E , are energies
of single electrons, underlying the above consideration, needs to be made
more precise. Because of the electron-electron interaction, the motion of a
particular electron is always tied to the motion of all others, and the energy
of an electron is also, in part, energy of interaction. The latter statement
manifests itself clearly in relation (2.43) between the one-particle energies E,
and the total energy U{.} of the N-electron system, which we will explore in
more detail. First of all, it can be further simplified. Using the one-particle
Schrodinger equation, one can re-express the terms on the right-hand side
of equation (2.43) by one-particle eigenvalues, leading to
The energy of the N-particle system is therefore not just the sum of all one-
particle energies. It is necessary to subtract the Coulomb interaction energy
of the particles. Therein is reflected the fact that the E, contain a certain
portion of interaction energy with other electrons. This is doubly counted in
the sum xi E , of one-particle energies, once in summing over the particles
themselves, and once in summing over their interaction partners, which is
done in E, automatically. To correct this, one must subtract the Coulomb
interaction energy.
This shows that the (p,(x) may be interpreted as states of single elec-
trons only in a generalized sense. In reality the (py(x)describe stationary
states of the motion of the N-electron system in which all electrons are in-
volved. These states of motion are not mutually coupled, as in the case of
normal oscillations of a system of interacting atomic cores. Using the ter-
minology introduced in that context one may consider the states q , ( x ) as
states of quasi-particles or elementary excitations of the N-electron system.
The E, are the corresponding quasi-particle or excitation energies. There
is, however, a qualitative difference between these elementary excitations
of the electron system and the normal oscillations of a crystal. This may
be made clear as follows. If one adds to the N-electron system (which we
will assume to be in the ground state) one more electron, i.e. if one passes
+
over to a ( N 1)-electron system, then the one-particle Hamiltonian (2.52)
does not change within the framework of the approximations made above.
The oneparticle wavefunctions pV of the N-electron system therefore also
approximately describe the elementary excitations of the system of ( N 1) +
+
electrons. This means that an eigenstate of the ( N 1)-electron system
may be realized by keeping the previously available N electrons in their one-
2.2. The dynamical problem 73
+
particle states and adding the ( N 1)-th electron in one of the oneparticle
states pu* of the N-electron system which were previously not occupied.
Thus, by adding an electron, the energy of the system rises approximately
by Ey*.This means that the eigenvalue Ev* of the one-particle Ilamiltonian
may be understood as the energy of an electron added to the system. This
statement is called Koopman h e o r e m . From it, one can learn more about the
kind of elementary excitations of the N-electron system that are described
by the p,. These are states in which, as always, all electrons of the system
are involved, but not all in the same way. Only one of the electrons is mov-
ing in such states, while the others play a passive role; they determine the
potential in which this movement occurs. One therefore refers to these states
as one-particle excitations of the N-electron system, and to their energies as
one-particle excitations energies or, in short, one-particle energies.
In addition to the one-particle excitations considered above there may yet
be others. This can be confirmed by taking a (N -1)-electron system instead
+
of the ( N 1)-electron system. The missing clectron corresponds to a hole
in a previously occupied oneparticle state ( p y ~ . The excitation energy of the
hole is -EvO, which did not occur among the oneparticle excitations consid-
ered above. It therefore represents an additional one-particle excitation. If
an electron is removed from state vy and simultaneously an electron is added
in statevT, then this corresponds to the excitation of the N-electron system
from state ($, Y:, . , . , v k ) into state (v;, v:, ..., I&). The energy difference
with respect to the ground state amounts to EV;- F 0 . It corresponds
5
to the excitation energy of a11 electron-hole-pair with the electron in state
pu; and the hole in state p 0 . If one excites a second electron from state
v1
'p o into state p,,;, the energy difference with respect to the ground state is
u!2
+
(Eq - Ey:) (By;- E e ) , etc. The excitation energies of the N-electron
system can thus be written as a linear superposition of oneparticle energics.
This is valid only within the one-particle approximation. In a strict seiisc
one also has many-particle excitations, which will be considered in more de-
tail below. As far as the one-particle excitations are concerned, there are no
others than the ones considered above, at least as long as one ignores spin
and the magnetic interaction between electrons.
It.is now appropriate to clarify how the oneparticle wavefunctions cpv(x)
111wbe calculated from the Schrodinger equation (2.53). The potential in
Uhis equation, more specifically the Hartree part VH(X), dcpends on the
wavcfunctions pV(x)which are involved in the construction of the ground
state of the N-electron system. One must know these functions in order to
write down the potential and thus define the oneparticle Schrodinger equa-
tion. On the other hand, these functions can only be obtained by solving this
equation. The situation is similar to that in the preceding section on the
coupled Schrodinger equations for the interacting system of electrons and
74 Chapter 2. Electronic structure of ideal crystals
d? - PU
n
+
V"(X) = t'c(x) VG(X)
atomic cores. As was done there. we may also solve the present problem it-
eratively (see Figure 2.3). We employ one-particle wavefunctions pf(x) close
to the true stationary oneelectron states. r s i n g cp:(x) we determine a PO-
tential t$(x) according to equation (2.491, form the total potential Vo(x) by
means of (2.50), and use this to solve the one-particle Schrodinger equation
(2.53). The solutions vt(x)are then substituted into formula (2.49), thereby
determining new potentials TG(x) and V l ( x ) . With the latter one recalcu-
lates the eigenfunctions p:(x) etc. One continues this iterative procedure
until the eigenfunctions, and with them also the potential in the follow-
ing iteration step. no longer change within a specified limit of accuracy. The
eigenfunctions and potential are then said to be determined self-consistently.
(2.55)
In general, however, the orbital and spin motions are coupled. This is mainly
due to the fact that, on the one hand, the spin motion is accompanied by a
magnetic moment of the electron, and that, on the other hand, the orbital
motion gives rise to a magnetic field which couples that magnetic moment.
In quantum theory it i s shown that this interaction, which is called spin-ovhit
intemction, can be represented by the following additional term H,, in the
oneelectron Hamiltouian:
Tz
H,, - -[VV(X) x p] . (7. (2.56)
4m c
Here V(x) denotes, as before, the periodic crystal potential of equation
(2.50)) and 3 is the vector whose three components are Pauli's spin matrices.
In spin space one usually refers all quantities to the basis X I = (1,0),X I =
( 0 , l ) . Then the components of are
Taking account of spin and the spin-orbit interaction, the one-particle Schro-
dingw equation (2.55) in Hartree approximation t,akes the form
76 Chapter 2. Electronic structure of ideal crystals
(2.58)
Hartree-Fock approximation
(2.59)
+
form (2.55) in such circumstances. The sum VH(X) Vx(x) of the Hartree
and cxchange potentials can then be written in a relatively simple form. It
can be shown thilt theii action on the coordinate dependent factor of the
oncparticle wavefunction cpl,(x)takes the form
(2.61)
The Erst term on the right-hand side of this cquation is t,heHartree potential.
The factor of 2 results from summing over the t,wo spin states associated with
each wavefunction cpvk(x).The second term corrcsponds to the exchange po-
tential. Formally, it differs from the first term by exchanging the states at
the two positions x and x. The factor of $ reflects the fact that, firstly,
the exchange potential acts only between electrons of the same spin, and,
secondly, that for the ground state with total spin 0, half of the electrons are
in spin-down states, and half are in spin-up states. In this way the magni-
tude of the exchange potential is influenced by the existence of electron spin,
although its value is the same for spin-up and spin-down states. Equation
(2.61) also shows that, unlike the Hartree potential, the exchange potential
is non-local. The effect of the exchange potential on the wavefunction p,(x)
is represented by an integral operator. In actual calculations one often uses
a local approximation for Vx(x). The exchange potential proofs to be at-
tractive, which is to be expected: the anti-symmetric form (2.59) of the total
wavefunction ${A} means that the probability of finding two electrons with
the same spin at the same position is zero so that one has an exchange hole
around each electron. This lowering of electron density in the vicinity of an
electron results in an attractive potential in addition to the repulsive Hartree
potential since the total Hartree wavefunction (2.37) does not account for
the exchange hole.
The improved oneparticle Schrodinger equation with the potential of
(2.60) and (2.61) is called the Hartree-Fock equation, and the oneparticle
approximation, which underlies it, is called Hartvee-Fock approximation
Thereby, the Hartree and exchange potentials are understood as those for the
78 Chapter 2. Electronic structrrre of idea? crystah
Correlation effects
Correlation effects are, first of all, manifested in the fact that the true one-
particle excitation energies of an N-electron system differ from those in the
Hartree-Fock approximation. In particular, these excitation energies depend
on the configuration of the system, one has tt, configuration dependence. Sec-
ondly, Slater determinants which in Hartree-Fock approximation are con-
sidered to be eigenstates of the total Hamiltonian, in fact do not diagonal-
ize tbis Harniltouian ezactlv; there are non-vanishing offdiagonal elements,
an effect which is termed configuration interaction. The exact eigenstates
of the total Hamiltonian are linear combinations of diflerent Slater deter-
minants, and the corresponding energy eigenvaluea are no longer s u m of
oneparticle excitation energies, as had been the case for individual Slater
determinants. In other terms, the exart,eigenalates of the N-elwtrronsystem
are not oneparticle excitations! but many-particle excitetians. Examples of
many-particle excitations include two-particle ezcitation.5 of an electron and
a hole which are bound together by their Coulomb Interaction. The exci-
tation energy of such a hound electron-hole pair, the so-called ezcitan, is
smaller than that of the excitation energy of a free electron and hole pair,
differing by the binding energy of the pair. The reason for the designnation
correlation effect for this phenomenon is obvious: binding may be under-
stood as a correlation between the positions of the electron and the hole,
since their separation by a distance of about a Bohr radius is more probable
than all others. This interpretation presents the correct concept of correla-
tion in other cases also the states of the electrons are no longer independent
~
of each other, but, are correlated contrary to the assumptions implicit in the
oneparticle approximation. Collective many-particle excitations are excita-
tions of states in which all electrons of the system participate in comparable
measure. Examples include the plasma o s c i l - t i a m of an electron system.
They form a direct electronic analogy to the lattice vibratious of the atomic
cores of a crystal. Their excitation quanta are called plasmons.
The consideration of correlation effects stands along the most difficult
problems of solid state thmry which, even today, is not completely solved.
A comprehensive analysis of this problem i s far beyond the scope of the
present book. Readers who are particularly interested in correlation effects
will find discussions in a number of textbooks (see, e . g , hbrikosov, Gorkw,
md Dzyaloshinski, 1963; Fetter and Walecka, 1971; Ziman, 1974; Callaway,
1976; Madelung, 1978; Harrison, 1981). Below we summarize some results
2.2. The dynamical problem 79
(2.62)
where cpvi(x) denote the one-particle states which, in the ground state of
the N-electron system, are populated by electrons z = 1,2, ..., N. According
to the variational principle of quantum mechanics, the wavefunctions cpv,(x)
adjust so that, while keeping their norms (cpudlqv,) constant, the total en-
vrgy Eo[n(x)]is minimized. This requires the vanishing of the variational
-xi
derivative of the functional E o [ n ( z ) ] E,(cp,Ip,) with respect to p:*(x),
where the factors E , are variational parameters, therefore
(2.63)
exchange and correlation energies which are usually summed in the exchange-
correlation energy E x c [ n ( x ) ] .Thus
+
Eo[n(x)]= Ekin[n(x)l Ec[n(x)l &dn(x)l + + Exc[n(x)l. (2.64)
(2.65)
E ~ [ n ( x=
)]
2
//
R R
d3x'd3x
n(x') . n ( x )
Ix' - XI '
(2.66)
(2.67)
(2.68)
(2.69)
(2.70)
2.2. The dynamicd problem 81
(2.71)
(2.72)
where
(2.73)
(2.75)
with
v(x) = VC(X) I Vrr(X) + i<Tc:(x) (2.76)
as an effective one-elcrtron potential. Th? electron ind~xa has heen omitted
here bwauw thP equation is the bame for all electrons.
Relation (2.75), with the potential V(x) given by (2.76), is known as
Kohn-Sham equatzon. ,4s rompnred t o the oneeleclron potential V(X) of
the Hartrw ur Hartret-Fock equations, that of the Kohn-Sham equation
additionally accounts or correlation effects. The physical significance of
tlir solutions of the Kohn-Sham equation is, however, less direct than that
of the solutions of thP llartree or Hartrw-Fock equations. Generally, the
eigcnvalucs of the Kohn-Sham equation cannot be understood in the sense
of oneparticle excitation energies of the N-electron system. as it is possible
for the eigenvalues of the IIartree or HartrePFock quations according to
Koapman's theoiern. A misinterpretation of this kind may lead to large
errors. This applies, in particular, to electron-hole excitation energies in
senlimnductor crystals, defining the energy gap. The resulting erroneous
gaps are about 50% smaller than the experimental values. However, the
82 Chapter 2. Electronic structure of ideal crystals
tRx =x + R. (2.77)
2.3. General properties o f stationary oneelectron states in B crystal 83
The set of all lattice translation operators forms the translation group, which
we already encountered in Chapter 1. Since the lattice translation operators
are symmetry dements of the crystal, the translation gioup is B subgroup of
the space group which, by definition: contains all symmetry elements of the
crystal. As in the case of translations, we also assign operators to rotations,
reflections and rotation-reflmtions of the point group of directions. These
operators also art on the spatial vectors x, and W P denote them by the
symbol a and call them point symmetry operataorw. For the symrnorphic
space groups considered here, each element y may be thought of as a product
0 . t or r a translcttion t~ and a point syrnrnetrg operation a. Since an
~ t ~ r of
arbitrary position vector x may be represented in a basis spanned by the
three primitive lattice vectors al.a 2 and a3, it suffices to s p e d y the &ect
of a on these. We define (see Appendix A}
(2.78)
x -czja3 (2.79)
t
with respect to the three primitive lattice vectors aj. The xj are the com-
ponents of x with respect to these vectors. Applying a ,
(2.80)
j
(2.81)
from which it follows that the transformation a , which was ariginaIly defined
as a transformation of the basis vectors ai with fixed coordinates zz,may also
be understood as a counter-tra~sformation of thc coordinates with fixed basis
vectors. Indeecl, lh coordinate counter-transformation takes place with the
84 Chapter 2. Electronic structure of ideal crystals
(2.82)
a S ( x )= S ( a - l x ) . (2.84)
It is striking that the operators t~ and a act on S(x) in such a way that
x ifireplaced by tR1x or m - l x . but not by k ~ orx c k x . as one might hme
expectd. The rhosen deftnition strms from the rrcognition that the trans-
formed property is that of the transfarmrcl crystal at the original position
x. This is the Sam?, howewr. as the proprrty o f t h e original crystal at
the inverse transformd position. Formally the definitions (2.83) and (2.84)
giiarantee the correct multiplication order of two no11 commuting operators
2 . Applying these
under the fiinction symbol, because ( q c q ) - ' - rtl-1 a -1
definitions to the potential V ( x ) and simultaneously requiring crystal sym-
metry, w r have
(2.89)
(2.W)
follow, with IA, B ] = A B - B A as abbreviation for the commutator of two
operators A and 3. One says that t~ and 1y commute with the potential
V ( x ) . Such cornmutivity also holds for the uthcr contribution of the Hamil-
tonian, the kinetic enerw operator ?' = p2/2m. For t~ this follows directly
2.3. General properties of s i a i h n a r y oneelectron s&atwin a crystal 85
2-1 = 0.
[tR,TI = [a, (2.91)
Taken together with ('2.89) and (2.90), these relations yield
[ t R ,HI = 0, (2.92)
H ] = 0.
]u, (2.93)
Since the elements g of a symmorphic space group may be written as prod-
ucts of t~ and C Y , one also has
(2.100)
Consider now the eigcnfunction g i p p If the symmetry operation g ranges
over the whole space g o u p , the totality of vectors g p spans ~ a subspace of
the Hilbert space w l i o s ~dimension d i s in general larger than 1. This is to
say that the eignvalue E, for symmetry reasons, is d-fold degenerate. It
can be shown that, apart from spmial cases, d equals the number of dif-
ferent elements m of the point group, and then the d basis functions of the
subspace may be chosen in the form with Q ranging over the entire
point group. This result will not. howevpr, be usrd in what follows and the
basis funrtions will be written in the general form p ~ lp, ~ 2 ,. .. , IpE& They
span that subspace of the Hilbert space which contains the eigenfunctions
of the Hamiltonian with the eigenvalue E . According to i t s construction
this space is invariant under the operation of an arbitrary element g of
the space group. In terms of the concept of rmducible represenfatema of
groups (an introduction is provided in Appendix A), we may alternatively
express this observation by saying that the eigenfunctions of H for a partic-
ular eigenvalue E give rise to a &dimensional irreducible representation of
the space group. The same statement also follows for each subgroup of this
group, particularly for the subgroup of all translations. The space spanned
by r p ~ lP, E T , . . . , ( p ~ d :thus also provides B representation of the translation
group. However, this representation is, in general, no longer irreducible.
That means that the original basis p ~ pl ,~ 2 .,. . ,( P E may ~ be transloorrued
(d-1) x I
into a new basis (p~,(pk,'plh;,.,pE in such a way that the represen-
tation matrices of all translation operators t~ written in the new basis are
constructed from lower dimensional matIices, odered along the diagonal. It
is of special importance that the translation group is a group of Abehan type:
The resiilt of two translations t~~ and t~~ does not depend on the sequence
in which they are executed. Formally this is expressed by the equation
(2,101)
As is demonstrated in Appendix A, all irreducible representations of Abelian
groups are 1 dimensional. This means that the lower dimensional matri-
ces along the diagonals of the tH-representation matrices are 1-dimensional.
(d-1) x I
Each of the basis functions &, ,p;c . . . , ' p E therefore forms a repre-
srtntation space of the translation group by itself. Thus, su functionstRpE,
with t~ an arbitrary element of the translation group, are linearly dependent
on p~ and dl functions t ~ &are linearly dependent on & etc. 'I'his means
that thp t p p itself
~ may be written in the form
tRcPE(x) = c(R)rFE(x) (2.102)
where r(R) is a complex coefficient. Analogous equations hold for all o t h a
functions t ~ l p btR&.,
, , . .. This is equivalent to the statement that the cho-
2.3. General properties of stationary oneelectron states in a crystal 87
(2.103)
(2.105)
(the subscript indices k l , k2, Ic3 on c(R) and P(R) will be suppressed tem-
porarily). The proof is based on the normalization of p~ according to equa-
tion (2.97), which leads to
I I
(tR(PE t R P E ) = ( P E (PE). (2.106)
I
(tRLPE tR(PE) -I c(R) l2 (PaE I P E ) . (2.107)
Considering (2.106) and (2.107) together, (2.103) is verified at once. Sec-
ondly, we show that
Comparison of the last two relations immediately shows that (2.108) is also
true. Employing (2.103) for c(R), equation (2.108) now yields
. ~xP[WWI,
exp[iP(Rl+ Rdl = exp[iP(R~)I (2.112)
whence
P(Ri t R2) = P(R.1) t P(R2). (2.113)
This means that P(R) is a homogeneous linear function of the components
TI, 7-2, r3 of R. As such P ( R ) must have the form (2.104).
We now proceed to the eigenfunctions of the translation operator. Em-
ploying ( ~ ~ k(x) ~ to
k denote
~ k ~ the eigenfunction having eigenvalue Ck1kzk3 ( R )
of equation (2.103), we claim that pEklkzks(x) can be written in the form
(2.114)
where u ~ k ~ k ~ k denotes
~ ( x ) a lattice-periodic function, such that, for any
lattice vector R,
2.3. General properties of stationary oneelectron states in a crystal 89
= e x ~ l i P k , k ~ k - , ( ~ ~ ~ ~ R ) l ~ ~ ' ~ ~ k ~ k(2.117)
~ k ~ ( ~ ) .
(2.118)
j i
(2.119)
(2.121)
3
EQ ' bj = 2 ~ 5 i j (2.122)
These equations state that the vectors of the T & P T Q C ~ basis me normal to,
respectively, one of the three planes spanned by pairs of direct basis vectors.
2.3. General properties of stationary oneelectron states in a crystal 91
2x 27r 2x
bl= -[a2 x q], bz - x a11 , b3 :-[a1 x az] . (2.123)
00 00 Qo
Here Ro = a1 . [a2x a31 is the volume of a primitive unit cell of the crystal
lattice.
If one s u bj et s the direct basis to a rotation or reflection, this induces
the same rotation or reflection of the rwiprocal basis, as follows immediately
from the defining equations (2.122) or (2.123). Because of these relations the
'reciprocal' basis (bl, bz, b3) is rigidy joined with the direct basis (al:a2,ag)
and will transform when the latter is tranaformd However, since the recip-
rocal basis is different from the direct one (only if (al,az,a3) are orthogonal
unit vectors are the two basis sets the same), the matrix LY which describes
the rotation or reflection of the a i is different from that which transforms the
bj. Using equation (2.123) one may easily show that the bj are transformed
with the transposed inverse of the transposed matrix u p which transforms
the q ,that is, with the inverse matrix a;'. In other words, the inverse
matrix describes the same rotation OF reflection of the reciprocal basis as the
transposed matrix docs fur the direct basis.
Consider now an arbitrary vector k of reciprocal vector space, which can
be written as
(2.124)
i
Bklkpl~3(R-
) -k. R. (2.126)
Using this expression the eigenvalue of t,hP treiistntion operator (2.103) be-
comes
(2.128)
-
~ g k ( X R) UEk(X) . (2.129)
A further consideration illuminates the physical meaning of the reciprocal
vector k. For this p u r p o s ~we first assume the potential V(X) to be a constant
independent of x. appropriate to a free electron. All the abovementioned r e
s u l t s hold. of roursc, in this caw. Rut thrrp is m o m In this caw translations
through arbitrary vectors r and rotations about any axis and through arbi-
trary angles are symiwtry opcrations, for they do not change the potential
and, consequently, also leave the Hamilt onian innriant. Therefore.
(2.131)
This is just the well-known result that the stationary states of a reeelectron
may be taken as plane waves of a given wavwwtor k. If the potentid is not
completely constant but. as happens in a crystal, it remains constant only
under translations through lattice vectors, the meaning of k as wavevector
is largely prwervd. It is thrrefore called a qaasa-wavevector: Of course, the
dimension of the quasi-wsvevector is also that of a reciprocal length. The
Bloch functions y ~ k ( x )of (2.128) may be understood as travelling waves.
modulated spdiallJ by thr latticeperiodic Bloch factor U E ~ ( X ) .That the
stationary oneelectron states may be chosen in this form, is the content of
B l o c h ~thwrpm. This theorem d o e riot say, howevrr, that these states are
necessarily modulated tmvellzng plane waves, just as t h e stationary states
2.3. General properti= of stationary one-electron states in a crystd 93
of a free electron need not be travelling plane waves. One ran also h a m
standing plane waves, sphrriral waves d c .
Discretization of k-space
'The periodicity condition (2.96) for the eigenstates of the Hamiltonian has
largely been ignored so far. Fortunately, it can be satisfied very simply. The
Ebch fuucfions V E ~ ( X )obey the relation
The k-vectors defined by (2.133) form a finely meshed net in k-space (see
Figure 2.4). The only permissible k-vectors must be points of this net since
the Bloch functions are periodic with respect to the Periodicity region. The
k-space thus has a discrete structure; its set of points is countable. The
distance betwren different k-vectors is, however, so small because of the
large size of C that k can pract,ically be treat4 as it continuously varying
quantity despite its discrete character. This approximationwill be used later
extensively.
Reciprocal lattice
Just t t h in direct spaw, one may also consider a point lattice in reciprocal
space. In this context, the so-called mciprocal lattice i s especially useful. It
is dehed by taking the reciprocal basis vectors bl,bz,b3 of (2.123) aa its
94 Chapter 2. Electronic structure of ideal crystals
K =CKjbj (2.135)
3
with arbitrary integers K j . As in coordinate space, one also has 14 different
lattice types in reciprocal space, namely the 14 Bravais lattices. The recip-
rocal lattices bear a close relation to the corresponding direct lattices. The
following properties can be verified easily:
(i) A reciprocal lattice has the same point symmetry as the direct lattice
with which it is associated.
(ii) The reciprocal lattice of a reciprocal lattice is the direct lattice.
(iii) If the direct lattice is primitive, then the same holds for the correspond-
ing reciprocal lattice. The reciprocal lattice of a centered direct lattice is
also centered.
The Bravais types of primitive direct lattices are the same as those of
their reciprocal lattices, while the Bravais types of centered direct lattices
and of their reciprocal lattices differ in certain cases, For example, a body
centered cubic reciprocal lattice corresponds to a face centered cubic direct
lattice, and, conversely, a face centered cubic reciprocal lattice corresponds
to a body centered cubic direct lattice.
1
-(P
Izm
t rzk)2 -1- v(x)
1 UE&) = EUEk(X). (2.136)
however, just from the space and time symmetry of V(x). We will discuss
this now, beginning with point symmetry, whose implications are relatively
easy to examine.
Point symmetry
We consider the Schrodinger equation (2.95), on the one hand, for the quasi-
wavevector crk, where TY i s taken to be an arbitrary element of the point
group of the crystal:
(2.137)
and, on the other hand, for the quasi-wavevector k, but with an application
of the transformation (Y as follows
E(k) = E ( a k ) . (2.140)
The assumption that there is only one eigenfunction of the Hamiltonian for
the quasi-wavevector k holds for almost all k. There is an exception for
those special k values for which ak does not differ from k or from a vector
+
k K equivalent to k for all a. One refers to such vectors as symmetrical k-
vectors. They will be considered in section 2.5, but we exclude symmetrical
k-vectors at this point. For non-symmetrical k-vectors, the fact that there
is only one eigenfunction of H , follows from the onedimensionality of the
irreducible representations of the translation group (see Appendix A).
time reversed Bloch function of wavevector k has wavevector -k. Since both
Bloch functions have the same eigenvalue, one obtains
E ( k ) - E(-k). (2.141)
K .R- (2.143)
1
Table 2.3: Representation of band structure in the cxtcnded and reduced zonc
schemes.
I
Wavevector Eigenvalue of tR Eigenvalue of H Represent at ion
I
[-ik. R]
~ X PE(k + K) General
~ exp [-ikl . R]
k from
1Extended
Infinite Zone Scheme
Space
k = kl from
Unit
' Reduced
Zone Scheme
Cell
discontinuities of the branches EK(k) do not occur in the interior, but only
on the surface of the primitive unit cell. If such a special primitive unit
cell exists at all, it must have at least the symmetry of the point group of
direclionb, as followb from the symmetry reletion (2.140). This nieans that
only the Wigner-Seitz cell of the reciprocal lattice is a possible candidate for
siich a primitive unit cell. Of course, its point group is that of the crystal
lattice and, theIefore, larger than the requisite point group of directions.
98 Chapter 2. Electronic structure of ideal crystals
We know, however, that lattices have fewer point groups than there are
point groups of equivalent crystal directions. The next-lower lattice point
group would not contain the needed point group of directions. The issue
in question thus revolves upon whether the function branches EK(k) are
continuous in the interior of the Wigner-Seitz cell of the reciprocal lattice at
K = 0. We will prove that this is indeed the case for the branch Eo(kl) in
the next section. Moreover, it will be shown that the other branches EK(k1)
of the infinitely multi-valued function E(k) may be redefined in terms of
new branches such that each single-valued branch is also continuous over
the Wigner-Seitz cell at K = 0. One calls these continuous branches energy
bands and the Wigner-Seitz cell of the reciprocal lattice at K = 0 is the f i r s t
Brillouin zone.
Having started from general considerations and obvious conjectures, we
thus arrive at the important conclusion that the spectrum of allowed energy
values of crystal electrons will have the form of energy bands, and that these
energy bands arise by varying the quasi-wavevector k over the first Brillouin
zone. We will discuss the concept of Brillouin zones along with the still
outstanding proof of the continuity of E(k) over these zones more fully in
the next section.
H o = -.P2 (2.145)
2m
The perturbing operator H I , which together with Ho forms the total Hamil-
tonian
H = Ho Hi, + (2.146)
is then the periodic potential
H I = V(x). (2.147)
2.4. Schriidinger equation solution in the nearly-freeelectron approximation 99
+
E(k) = Eo(k) 6E1(k) + 6E2(k)+ . . . (2.149)
with respect to the perturbation potential, here with respect to the periodic
potential V(x). In this discussion, we suppress the energy index E of the
eigenfunctions for the sake of brevity. This leads to no ambiguity since we
work in the extended zone scheme, where the energy is a unique function of
the quasi-wavevectors k. The zero-th order terms obey the equation
In order that the perturbation theory be applicable, the zero-th order solu-
tions must form a complete orthonormal set of functions, such that
and
-yCpp(x)Cp;(x) = 6(x - x) (2.152)
k
must hold. The k-summation of (2.152) is extended over all points of the
infinite finely meshed net of Figure 2.4. The two relations (2.152) and (2.153)
are in fact valid for the solutions
(2.153)
(2.155)
(2.156)
The energy correction 6E1(k) of the first order i s the average value (cpg I
V I pi) of the periodic potential. This value may be set equal to zcro. The
off-diagonal matrix element of the potential involved in (2.1551, (2.156) are
given by
(z.157)
Because of the lattice periodicity of V(x) we can transform the integral over
the periodicity region in (2.157) into a sum o f integrals over the primitive
unit cell Qo(0) at R = 0:
Noling that
(2.159)
(2.160)
Using this result, the correction 6 ~ :to the wavefunction takes the form
(2.162)
One recognizes that this has the expected Bloch form (2.128) b r energy
eigenfunctions of the crystal Hamiltonian. Moreover, (2.163) yields the Bloch
factor as
(2.16 4)
The second order energy correction E2(k) may be determined using (2.161)
as
(2.165)
-&
\ -K
f
For incoming waves with k-vectors close to the Bragg reflection plane of the
reciprocal vector -K, the scattered part dpk contains a p a r t i d a r l y large
plane wave component of wavevector k + K. This is due t o the fact that,
in this case, the incoming plane wave and the Ecaltered wave of wavevec-
tor k + K, have almost the same wavelengths. They are thus rapable of
constructive interference which strongly enhances the amplitude of this par-
ticular scattered wave. If k is located exactly on the Bragg reflection plane,
one may understand the scattered wave with wavevector k +
K as the plane
wave reflected at this plane in the sense of geometrical optics. This follows
immediately from the construction of the k h g g reflection plancs in Figure
2.5. The scattered wave of wavevector k +K is strengthened by inter-
ference, w h c h makes it the refkected wave (bear in mind that in the wave
picture reflection represents an interference phenomenon). This interpreta-
tion can be universally applied to the propagtltion of plane waves of any kind
in a system of scattering centers periodically ordered on a lattice, including
X-rays. Actually, the above results for elwtron waves were discoverd iisinE
X-ray radiation.
The amplitudes of plane waves reflected at Bragg planes, according to
formula (2.162), become idnitely large formally What is expectd. how-
ever. is that the amplitudes of the refiected and incoming waves should be
comparable. This contradiction arises from the misuse of non-degenerate
perturbation theov, w h h is no longer applicable under the conditions of
reflection. For k-vectors which obey the Bragg condition (2.167), one must
apply degenerate perturbation theory.
2.4. Schrdinger equation solution in tho nearly-free-electronapproximation 103
Eo(k) - E
( V(K)
V(K)*
Eo(k$ K ) - E
(2.171)
For the set to have a non-trivial solution, its determinant must vanish,
whence
Eo(k) - E V(K) = 0
(2.172)
V(K)* Eo(k+ K ) - E
must hold. The two solutions are E = Ek(k) with
1 1
Ek(k) -- ,[Eo(k)
2
+ Eo(k + K)] f -\/[Eo(k)
2
- Eo(k + K)]*+ 4 I V(K) I*.
(2.173)
For further evaluation of this expression, we assume that Ak is directed
parallel to K (see Figure 2 . 6 ) . Expanding the square root in powers of
I Ak I and terminating the series with the second order, we find
jpK2
E*(k) = Eo(ko)f I V(K) I 4 li2 [
1 f 2m
I V(K) I] Ak2.
(2.174)
104 Chapter 2. Electronic structure of ideal crystals
Figure 2.7: The degeneracy of the two energy parabolas E(k + Ak) and E(k +
K + Ak) at the Bragg reflection plane Ak = 0 (left part of figure) is removed by
the periodic crystal potential. In the formerly continuous energy spectrum a gap
arises at this plane (right part of the figure).
The remarkable feature of this result is that the 2-fold degenerate energy
+
eigenvalue Eo(ko) = Eo(ko K ) at the Bragg reflection plane, i.e. for
Ak = 0, splits into two different eigenvalues which are shifted by IV(K)I
to higher and lower energies, respectively. Between them there is a region
of width 2 I V ( k ) I where no allowed energy values may exist (see Figure
2.7). This means that, in the formerly continuous energy spectrum of the
free electron. an energy gap appears as a result of the periodic potential.
This occurs at all Bragg reflection planes, provided that the corresponding
Fourier components I'(K) of the periodic potential do not vanish. Except
for the Bragg planes, the function E ( k ) and the energy spectrum remain
continuous. The result derived here by means of perturbation theory is
also valid well beyond the framework of validity of this approximation. The
following statement remains true also in the general case.
The energy f u n c h o n E(k) LS continuous everywhere in k-space, with the
exceptzon of the Bragg reflectLon planes where, 271 generat, discontinuities
occur and the energy spectrum exhihts gaps.
In regard to the shape of the function E*(k) close to the Bragg planes,
the relation (2.174) provides the following picture (see Figure 2.7). The two
branches E+(k) and E-(k) approach Ak = 0 with horizontal tangents to
+
the limiting values Eo(k) IV(K)I and Eo(k)- ll'(K)I, the upper branch
with positive curvature, and the lower with a negative one. The latter ob-
servation follonrs from (2.174) since the applicability of perturbation theory
is restricted in validity by 1 V(k) I << h 2 K 2 / 2 m ,which means that the sign
2.5. Band structure 105
Definition
ZONE 1 2 3 4 5 6 7 8 9 1 0
Figme 2.8: The first, 10 Rrillouin zones or H sqimre plane 1al.tic:e. (After Brillouin,
1953).
first body jointly with the Bragg planes bonnding i t . If one removes the
first body from the second, then one obtains a hollow body of the volume of
one Wigner-Seitz cell, which is bounded by Bragg planes inside and outside,
but contains no siirh planes in i t s interior. This conhtruction may be carried
+
further. Removing the v-th body from the (v 1)-th one again obtains a
hollow body having the volume of the primitive unit cell in k-space. It i s
boiindd by Bragg planes, and has no such planes in its interior. These
difference bodies are called Brdloum zones (abbreviated 8 8 s ) . The v-th
body i s called the v-th R%, the Wigner-Seitz cell at K = 0 is, accordingly,
the first B Z . In Figure 2.8 the first 10 Brillouin zones are shown for a
2-dimensional square reciprocal lattice. The first B Z for two important 3-
dimensional lattices, i.e. the frr lattice and the hexagonal lattice, are shown
in Figure 2.9. We will derive the shape of the first of them below.
Focusing on a point k, of the v-th R Z , a v e t o r K(k,) of the reciprocal
lattice is attached k, such that k,- K(k,) represents a vector kl of the first
BZ,
kl = k, - K(k,). (2.175)
2.5. Band structure 107
Figure 2.9: The first Brillouin zones of the two Bravais lattices which apply to many
semiconductors: (left) the face centered cubic lattice of diamond, zincblende and
rocksalt structures; (right) the hexagonal lattice of wurtzite and selenium structures.
We omit the formal proof for this important result here. For the square
lattice it follows immediately from Figures 2.8 and 2.10. Its validity in the
general 3-dimensional case is clearly plausible. If, instead of k,, another
point kh of the v-th B Z is chosen, another reciprocal lattice vector K(kh)
may be necessary in order that kh - K ( k l ) shall be a vector of the first
B Z . The set of reciprocal lattice vectors K(k,), K(kL), . . . which arises if
k, varies over the whole v-th B Z , is just the set of K-vectors which defines
the internal boundary planes of the v-th B Z . The correspondence of the
points of the v-th B Z to points of the first B Z given by equation (2.175)
is unambiguous in both directions - each k, corresponds exactly to one kl,
and each kl exactly to one k,. One terms this correspondence folding of
the v-th B Z into the first. The term displacing would probably provide a
better description. During such folding or displacing, the external or internal
boundary planes of v-th B Z may be translated to the interior of the first
B Z . There, they border on other boundary planes of the v-th B Z . This
means that original kl-vectors which lie immediately to the right and to the
left of such planes will involve different reciprocal lattice vectors.
The folding operation (2.175) provides the mechanism for changing from
the extended description of the energy function E ( k ) over all infinite k-space
to the reduced description within the first B Z . The transfer of the function
values is, defined above by relation (2.144). It states that the value E(k) at
a point k = k, of the v-th B Z is assigned to that particular point of the
first B Z which arises from k, by folding the v-th B Z into the first. By this
assignment a multi-valued function E,(kl) is defined within the first BZ.
The unique function E(k) over the whole k-space is mapped into the multi-
valued function E,(kl) within the first B Z . Formally, this is expressed by
108 Chapter 2. Electronic structure of ideal crystals
Figure 2.10: Folding of the second through ninth Rrillouiri zones into the first R Z
for the plane square lattice of Figure 2.9. (After Brillouin, 1953)).
the equation
Figure 2.11: Rcduction of the energy parabola of a free electron into the first B Z
of a 1-dimensional lattice. The changes caused by a weak, periodic lattice potential
are indicated by dashed lines.
but also at its center at k = 0. This is due to the fact that, during folding,
surface points of the first B Z are displaced to the B Z center, and the energy
gaps from those points also appear at the center.
The folding procedure into the first B Z must also be carried out for the
eigenfunctions of the Harniltonian. Let p v k l denote the Bloch function of
energy E,(kl) and of reduced wavevector kl. In the extended scheme the
same wavefunction reads q q k , ) k v ( x ) . Thus,
f f ~ v / c ( x=
) &(k)pvk(x). (2.178)
The first RZ is the fully symmetric primitive unit cell of the reciprocal
lattice. The relation between the reciprocal and the direct lattices was dis-
cussed in section 2.3, where it was seen that each of the 14 direct Bravais
lattices corresponds to a particular reciprocal lattice of the same symmetry,
although not necessarily of the same Rravais type. Accordingly, there are
14 different reciprocal Bravais lattices, which ah0 means 14 different first
B Z s . Two of them, the two that are most important for semiconductors,
are shown in Figure 2.9.
Empty-lattice band s t r u c t u r e
The corresponding basis vectors of the reciprocal lattice follow from equation
(2.123), with the result
27r 27r - 2n - -
bl = -(I, T, I), b2 = -(l, 1,T), b3 = -(I,
a 1,l). (2.180)
2n 27r - 2x - - 2n
-(i,i, T), -(I, 1,T), -(I, 1,I), -(T,T,T),
a a a a
27r - 2s 2n 27r
-(1, 1,1), -(I, T, I), -(I, 1,T), -(I, 1,i). (2.181)
27r 27r 2n
-4%
a 0, O ) , -(0,2,0),
a -(O,
a 0,Z). (2.182)
2.5. Band structure 111
Figure 2.12: Symmetry points and irreducible parts of the first BZ of the fcc
lattice (left) and the hexagonal lattice (right).
The first B Z of the fcc lattice obtained by means of these reciprocal lattice
vectors is shown in Figure 2.9. Perpendicular to the three cubic axes it is
bounded by squares, and normal to the four space diagonals by hexagons. It
is common to denote the symmetry points of the first BZ by capital letters.
Greek letters are assigned to symmetry points in the interior of the first BZ,
and latin letters to symmetry points on its surface (see Figure 2.12). The
center of the B Z , for example, is I?, the point at which a cubic axis cuts the
B Z surface is X , and the connecting line between I? and X is A.
We will now reduce the energy parabola E(k) = (fi2/2m)k2 of a free
electron along the A-line, i.e. for points
r = 2R
-(o,
a
o,o) 2R
A = -(o,
a
2?r
o , ~ ) ; x = -(o,
a
0, 1) (2.183)
E,(k) = -h2
(k
2m +K ( ~ Y ) ) ~ . (2.184)
Using the above listed 14 reciprocal lattice vectors K(k,) in this relation,
the second and third BZ's are folded into the first. For convenience we
~ an energy unit, and set
introduce Eo = ( T ~ ' / 2 m ) ( 2 7 r / a )as
With lattice constant a of 5 A, a value of 5.9 eV follows for Eo. For ty(k)
we have
112 Chapter 2. Electronic structure of ideal crystals
(2.186)
where the K,, Kvy,K,, are the components of the vectors K, in units of
2nla. In Table 2.4 we show the reduced energy functions ty(<) for the 14
vectors K, together with those for 0. In some cases the same value of the
function E,(C) is obtained for 4 different K,s, meaning that the correspond-
ing energy bands are 4-fold degenerate. In Figure 2.13 the content of Table
2.4 is illustrated graphically, along with the band structure parallel to the
A-line between 0 and L not given in Table 2.4. Again, one recognizes that
there are k-points associated with the same energy value several times.
The band structure shown in Figure 2.13 is that of an empty fcc lattice,
i.e. a fcc lattice whose lattice points are not occupied by atoms, since the
latter would create a non-zero periodic potential V(x)if they were present.
For a vanishing potential V(x),no definite lattice exists because of its arbi-
trary translation symmetry. Nevertheless, a definite lattice, the fcc lattice,
and a definite lattice constant, were chosen in the above procedure. This
was an arbitrary choice, in the sense that we could have also chosen any
other of the 14 Bravais lattices, and any other lattice constants. However, if
we want the empty lattice band structure to resemble the band structure of
a really existing crystal, then we cannot take any empty lattice band struc-
ture but must chose the one for the lattice applying to the crystal under
consideration. Later we will verify that the band structures of real crys-
tals and the pertinent empty lattice band structures have in fact common
features. In Figure 2.11 such features are, for example, the appearance of
the lowest energy eigenvalue at the I?-point and the development of several
non-degenerate energy bands from this level along the A-line, one of them
crossing another band at the X-point. It is also consistent that the energet-
ically high-lying bands display a relatively high degeneracy at the I?-point,
although for real fcc crystals the degeneracy at maximum can be only 3-fold,
and not 8-fold as for the empty fcc lattice at the energy E = 3&, and not
&fold as for the fcc lattice at E = 4Eo. A degeneracy higher than %fold
turns out be accidental, i.e. not caused by symmetry, but by the particular
values of the potential, which is identically zero in this case. The width of
the lowest energy band in Figure 2.11 is about Eo, i.e. 6 eV. Also, this
result is not too far from the actual widths in fcc crystals, as we will verify
below.
As with the reduction along A- and A-lines, one can plot the band struc-
ture along other symmetry lines in the interior and on the boundary of
the first B Z . A complete representation of the functions E,(k) over the
points of 3-dimensional k-space would require a Cdimensional space. In the
3-dimensional space available to us it is only possible to represent bands
E,(k) over planes in k-space. Such representations are, however, uncom-
2.5. Band structure 113
mon. -4s a rulc, one plots the energy against lines in k-space,as in Figure
2.13.
The question of what valws the energy band functions E,(k) take out-
side the first B Z does not arise or is meaningless, since the E,(k) were
"L A r A
Wavevector - X
just defined by transferring the function values from other B Z s to the first
one. For this reason, the E,(k) already encompass the entire spectrum of
eigenvalues as k varies over the first B Z . If one wishes to also consider the
functions E,(k) outside of the first B Z , one has to define them there. The
most natural manner to do this is the periodic continuation.
Periodic continuation
(2.187)
where k is in the interior of the first B8. This condition is also siifFicient,
since the continuity of the periodically continued function E,(k) implies
that equation (2.188) holds. Therefore, the boundary condition (2.188) for
the function E,(k) defined over the first R E , and the continuity of the
periodically continued function E,(k) are just different descriptions of the
same property. Tising continuity of the function &(k) defined over all k-
space, this property may be expressed in a more convenient way. This is the
reason why one continues the e n e r a bend fiinctions R,(k), which actually
2.5. nand structure 115
have meaning only within the first BZ,periodically over the entire k-space.
One could also forego this, and use the condition (2.188) directly.
We will now prove that the energy bands E,(k) actually obey the bound-
ary condition (2.188), and thus, are continuous everywhere as periodically
continued functions. To this end, we use the Schrodinger equation (2.178)
for the eigenvalues E,(k). The corresponding Bloch functions p,k(x) may be
expanded in plane waves with wavevectors k + K , where K is an arbitrary
reciprocal lattice vector, as follows:
(2.189)
Using this result, the Schrodinger equation (2.178) takes the form
(2.190)
The E,(k) are the eigenvalues of the matrix of coefficients of this system of
equations and their k-dependence i s determined by that of the matrix. The
latter is manifpstly continiioiis. That it also exhibits the periodicity of the
reciprocal lattice, one may verify as follows. Consider the coefficient matrix
+
of (2.190) at the point k K with K an arbitrary reciprocal lattice vector.
If one replaces the column and row indices Kand K , respcctively, by K+K
+
and K K, using the relation (K KIVJK+ + K) - (KIVIK), one
obtains the matrix at the original k-vertor. This implies that the eigenvalues
Ev(k t K) and E,(k) are identical, as stated.
The above proof employs only the lattice translation symmetry of the
potential V(X). The continuity of the periodically rontinued function E,(k)
in the entire reciprocal space is therefore an immediate consequence of the
periodicity of V(x) in the direct lattice. The continuity of the periodically
repeated energy band functions E,(k) is often very useful. It ensures, on the
one hand, that the E,(k) may be npproximctted fairly closely by a Fourier
series with relatively few terms. On the other hand, mathematical theorems
dealing with the types and numbers of extrema of periodic analytic functions
may also be applied. This i s particularly important for the theory of the
optical proprrties of semiconductors.
We return now to a question which was previously explored in section
2.3, namely the implications of point symmetry for band structure. This was
discussed above in the extended zone scheme, and symmetric k-points were
excluded. NOW we USP the reduced zone scheme description and concentrate
on symmetric k-vectors.
116 Chapter 2. Electronic structure of ideal crystals
&(k) = E v ( a k ) , (2.19 1)
where a is an element of the point group of equivalent directions of the
crystal. This group is generally smaller than the point symmetry group of
the lattice, but in special circumstances it can also be the same. The latter
rase occurs for the diamond structure, where the point group of equivalent
crystal directions is likewise o h .
In section 2.3, symmetric k-vectors, i.e. vectors which are transformed
by at least one element o f the point group 1 of equivalent directions, into
themselves or into an equivalent vector, were excluded. Now we also admit
such k-vectors to consideration. In r q a r d to their effect on symmetric k-
vectors, the elements cr of P split into two subsets. The Erst contains those
elements which transform k into itself or, at points on the surface of the
first B Z , inlo a vector crk equivalent to k which differs from k only by a
reciprocal lattice vector K. This set forms a subgroup pk of P , and is called
the s n ~ a l lpoznt group of k. The second subset contains all those elements
of P which transform k neither into itself nor into a vector equivalent to k.
The set of all different and non-equivalent vectors a k is called the star ofk.
We denote the number of elements of the point group P by p , and the number
of different star points of k by S k . Since each star point has the same point
symmetry, the number pk of elements of the small point gToup Pk is given by
the relation p k p l s k . A general k-vector bas no point symmetry, whence
7
Onc therefore also calls this symmetry the Y~UT degunrrucy OJ e n e r g y bands.
Bmause of star degeneracy, the energy band functions E,(k) need to be
calculatcd only for a scction of the first B Z which covers the region between
adjacent star points (Figure 2.12). One calls such a section an zrrediiczble
part of the first R E . The energy eigmvulues for the remainder of the first
B Z are obtained by means of the symmetric continuation (2.191) of the
values of the irreducible part. The irreducible part is the p-th part of the
first BZ. If one considers that, in the case of diamond structure, the number
p of elements of the point group 01, is 48, one can appreciate how greatly the
description of band structure is simplified by exploiting the point symmetry
of crystals.
In section 2.3 it was shown that for any eigenfunction (p,k(x), acp,k(x) =
cpVk(cr-x) is also an eigenfunction of the Haniiltonian H with the same
eigcnvalue B,(k), provided (1 belongs to the symmetry group of 11. Those
elements a of this group which also do not change the wavevector k, or
change it only by a reciprocal lattice vector, will thus transform an eigen-
fiinction pvk(x) of a particular Land v and k-vector, into an eigenfunction
cp,k(~u-~x) of the same band and the same k-vector. Thus, lor the case in
which not all wp,k(x) are linearly dependent, t h e are several linearly in-
dependent eigenfunctions for a given band index 11 and wavevector k. Let
their number be d,k. This means that t h e energy band E,(k) i s d,k-fold de-
generate at the point k. One calls this kind of degeneracy band degeneracy.
We employ q l k ( x ) ,1 - 1 , 2 , . . ,duk, to denote a basis set in the subspace
of eigenfunctions or H having the eigenvalue E,(k). The functions crcplk(x)
are then likewise eigenfunctions with the eigenvalue E,(k). As such, they can
be expressed as linear combint\tions of the basis functions pVk(x),whence
(2.192)
-
A
-
X
-
c
K
is quite remarkable. It holds not only for the energy bands of crystals,
but for the eigenvalues of any Hsmiltonisn in quantum mechanics. It is a
good example how a relatively abstract mathematical theory - the theory of
groups has immediate physical consequences.
~
(2.193)
(2.194)
order
(2.196)
IJsing this tensor, the expansion (2.195) of E,(k) may be written in the form
(2.197)
(2.198)
(2.199)
This propat,y follows directly from the defining equation (2.196) for M&.
As is well-known from linear algebra, such a real symmetric tensor cau be
brought l o diagonal form by a coordinate transformation, in our case of the
components of the k-vector, to the principal axis system. With ms' being
the principal diagonal elements of M l l in this system, one has
The m;;' are real. Ifn general, they can take both positive and negative
values. The same applies to thc inverse quantities, the effective masses rnk
themselves. Taking k, as componenls of k in the principal axis system, we
have
(2.201)
If all three effective masses are positive, the energy function E w ( k ) has a
minimum at the critical point kc,and if all three are negative it is a maxi-
mum. If the three effective masses do not all have the same sign, then E , ( k )
has a saddle point.
Consider the particular case in which the critical point lies on a 4-
fold symmetry axis of the first 3 2 . and that this is simultaneously one of
the principal axes. Then, for symmetry reasons, the two principal tensor
elements normal to this axis must be equal. With LY = 3 for the symmetrical
principal axis we thus have
mC1 = m t 2 (2.202)
The corresponding element for the symmetrical principal axis m:3 E m:,,in
general differs from mZI. If k,, however, lies on a symmetry center of the
first B Z , then all three elements are in fact identical, i.e.
(2 203)
For the frequentIy observed case of a symmetry point at the center of the
first BZ!i.e. with k, = 0, one gets the simple dispersion law
E,(k) = E v( 0) + -k2.
F12
(2.204)
2m;
2.5. Band structure 123
This differs from that of a free electron only in that the effective mass rn;
appears instead of the free mass and that the energy at k = 0 assumes a
value E,(O) which depends on the band index and, therefore, cannot be set
equal to zero for all bands by changing the zero of energy.
In the following subsection we will again deal with band structure in its
general form E,(k). We will introduce the so called density of states that
encompasses essential information on band structure in just one function of
energy. Often, a knowledge of the density of states is enough to calculate
important macroscopic properties of semiconductor crystals.
2
p ( E ) = - C 6 ( E - Ei). (2.205)
O i
is called the density of states (DOS) of the system. We will show that this
designation is justified, i.e., that p ( E ) does represent the number of o n e
particle states of energy E per unit energy and volume. To this end we
integrate equation (2.205) over a small energy interval E < E' < E A E , +
obtaining
P(E)AE
=
2
FL E+AE
dE'6(E' - E i ) . (2.206)
+
Thus, each state i whose energy lies between E and E A E contributes '1'
to the sum on i, with no contributions from all other states. The sum in
(2.206) equals, therefore, the number A z ( E )of states having energy in this
interval. Considering spin, one has
2
~ ( E ) A=E- A z ( E ) , (2.208)
51
124 Chapter 2. Electronic structure of idcal crystals
p ( E ) = --Im Tr (2.209)
7T
where trace sytxho1 Tr denotes the sum over all diagonal elements with
respect to any basis set in Hihert space. If this set is identified with thr
eigmstatcs 12) of ff, expression (2.209) transforms immediately into (2.205).
We now consider the DOS p ( E ) defined by (2.205) for an ideal crystal.
The cigenstates li) are Rloch states Ivk), in this case, and the DOS p ( F )
therefore reads
2
-
p(E)-
C 6 ( E-
uk
(2.210)
The k-sum is over all points of the finely meshed net of Figure 2.4 which lie
within the first B Z . Because of the fineness of this network, the result of the
summation is almost identical to that of an integration. The substitution of
the s m by an integral is done in accordance with the prescription
k
-1
c...= 8T3
R d3k ...
(2.211)
(2.212)
(2.213)
and it differs from zero only for energy values for which the argument of the
6-function may brrome zero, i.r. for energies in the v-th band. Summing
over d l bands one again obtains the entire density of states
(2.214)
2.5. Rand structure 125
(2.215)
(2.2 16)
(2.2 17)
1 [S(z - ZO)
E - EA - x 2 - y2 - z 2 ) = - +6(z+ ZO)] (2.2
2zo
with
where
1 f o r E > Euo
B(E - Euo) = (2.221)
0 for E < Euo
is the Heaviside unit step function. If one considers, instead of an isotropic
parabolic band, an anisotropic one with three different effective masses
m:l, m:2, m:3 corresponding to the principal axes of the effective mass ten-
sor, then the density of states is again given by expression (2.220), but m:
must be replaced as follows
(2.222)
= 3-
<
I
vl
2-
0
0
1- -
0
-1 0 1 2 3 4
Energy lorb. unlts)
The square root enerw dependence of the density of states in the case of a
parabolic dispersion law may also be demonstrated in the following, more
vivid way (also see Figure 2.15). For simplicity we set E,o = 0. and omit
factors which do not depend on k or E. The n m b r r A Z of b m d states
with energy between E and E .f A E is the number of different k-points of
the finely meshed net which yield energy values in t,his interval. These k-
values lie in a thin spherical shell in k-space [see Figure 2.15) which, because
E o(. k2, has radius k~ 6: &.and thickness Ak which, since Ah' CK k&k,
is given by
1
Ak 0; -AE. (2.223)
fi
For the volume AV of this shell, it follows that
AV m k L A k cc A A E . (2.224)
Since the density of the finely meshed net of k-points of the first BZ i s the
same everywhere, the number of k-points in the spherical shell is propor-
tional to its volume AV. Hence AZ cy v%AE and
b C
Figure 2.15: Counting states in (a) 3D, (b) 2D, and (c) 1D k-space.
p ( E ) 3: const. (2.226)
The density of states of a 2D-electron system is therefore independent of E.
In the case of a ID k-space: AV is replaced by the length Ak of the k-interval
itself. Thus,
1
p ( E ) DC -AE. (2.227)
fi
2.5.5 Spin
Thus far, spin has been omitted from our discussion of the general properties
of stationary oneelectron states of crystals. It turns out. however, that spin
and spin-orbit interaction play an important role in most semiconductors.
Therefore, the question arises as to how the results derived above for scalar
wavefunctions change when electron states are no longer scalar but spinor
functions and the spin-orbit interaction H , is taken into account.
The starting point to address this question is the one-electron Schrodinger
equation (2.58) with spin, which may be written in the following short form
(2.228)
2.5. Band structure 129
The first point we will consider is that of spatial symmetry in the presence
of spin.
Spatial symmetry
zti)
where I ~ X ~ [ X . are the spin-dependent Bloch factors. If k is restricted to
the first B Z . then E x ( k ) rrprwents a continuous function of k. Thc band
index X here refers to both the state of the orbital motion and also to spin
state.
Second, we consider point symmetry operations u , whose action in tram-
forming t,hc components of a spinor is discussed in Appendix -4. The results
of Appendix A are applied here in the form
130 Chapter 2. Electronic structure of ideal crystals
with
(2.234)
To prove this assertion, one executes the time reversal operation on the
spin-orbit interaction operator H,, of equation (2.56) explicitly. The vector
a' then transforms into -a*, and p into -p, so that the net change in Hso is
the replacement of d by a'*. Employing the operator K , on the other hand,
the effect of timc reversal on H , , may be expressed in terms of the similarity
transformed operator KH,,K-'. For the two expressions to be identical,
K must have the form given above in equation (2.234), apart from a phase -
factor which remains undetermined. The wavefunction {cpx(x,
- i), cpx(x,$)}
must be replaced by K{cpx(x, i), cpx(x, $)} for the Schrodinger equation
(2.180) to remain valid.
The question, under what conditions time reversal symmetry includes
degeneracy of eigenfunctions not accounted for by spatial symmetry alone,
is treated in Appendix A in full generality. Here we deal only with a specjal
case. We consider a non-symmetric wavevector k. Let {cpxk(x, i),cp~(x, i)}
be an eigenfunction with energy Ex(k). If the point group of directions -
contains the inversion, then the eigenfunction {cpx-k(x, i), cpx-k(x, i)}
cor-
responds to the same eigenvalue Ex(k) -= Ex(-k). The time reverse of
the Bloch function {cpx-k(x, i), cpx-k(x, $)} likewise has energy Ex(k) and
-
i),
wavevector k. It is linearly independent of {(Px~(x, cpxk(x, $)}, since
as one may easily show by evaluating the scalar product (here, one also has to
sum over the spin coordinate s ) . Thus, two linearly independent eigenstates
of the same energy have the wavevector k. Since k was chosen arbitrarily, it
follows that, due to time reversal symmetry, all bands of inversion-symmetric
crystals are at least twofold degenerate.
2.5. Band structure 133
There are many methods, quasi-analytic and numerical, for calculating the
band structure of crystals. In the following we will give an overview.
In band structure calculations one is confronted with two problems,
firstly with the formulation of the one-elcctron Schrodingcr equation, i.c.
with the determination of the effective periodic oneelectron potential V ( x )
of the crystal, and secondly with finding the eigenvalues and eigenfunctions
of that equation. The various methods of band structure calculation differ
in the manner in which thcsc two problcms are resolved. Hcre we will deal
mainly with the second problem, i.e. with the solution of the Schrodinger
equation whose potential is known. The first problem, the determination
of thc cffectivc oncclcctron potential V ( x ) , has in principle brcn solved
in section 2.2, where we dealt with the one-electron approximation for the
many-electron system of a crystal. Here, we only address some further dctails
of this problem.
The solution procedures can be divided into three groups, firstly! the matrix
methods, secondly, the cell methods, and thirdly, the muffin-tin methods.
Matrix methods
has as many columns and rows as the basis set has functions per k-vector.
The calculation of band structure is thus traced back to the determination
of the eigenvalues and eigenvectors of a k-dependent Hamiltonian matrix.
The basis sets employed differ by the number and kinds of functions
they contain. One would like to manage with the fewest possible functions,
to minimize the numerical effort. The price for this is a loss of precision,
because with fewer basis vectors the eigenfunctions are necessarily approxi-
mated more crudely than with a larger number - in the extreme, one needs
an i n h i t e number of functions. For a fixed number of basis functions the
level of precision achieved is higher for basis functions which are better ad-
justed to represent the eigenstates. The following basis functions prove to
be of practical use:
-Plane waves Iki-K) with k being a vector of the first BZ and K a reciprocal
lattice vector. This constitutes a generalization of the nearly free electron
approximation.
~ Bloch sums of atomic orbitals, also called LCAO's (Lznear Combznatzons
of Atomzc Orbatuls), or of other localized functions. This includes the tight
binding met hod.
~ Bloch functions with Bloch factors for a special wavevector, referred to as
Luttznger-Kohn funetzons. The so-called k . p-method uses these functions.
In some circumstances, the tight binding and k pmethods may be used
to derive analytic expressions for the k-dispersion of energy bands. Such
expressions are extremely useful to achieve a physical understanding of band
structure. Therefore, we treat these two methods in greater detail below
(sections 2.6 and 2.7).
- Orthogonalized plane waves, called OY W's. An OPW-function IOPW~+K)
is obtained from n plane wave Ik+K) by subtracting a certain linear combi-
nation of core band eigenfunctions Irk) of the crystal Hamiltonian. Within
the frozen core approximation, the core band eigenfunctions (ck) may be
taken as Bloch sums of the core states of single atoms. The linear combi-
nations to be subtracted are chosen such that the OPW's are orthogonal to
all core eigenstates, so that
(2.236)
holds. The OPW's must have the form
+
l O l ' W k + ~ )= Ik. K ) - C(cklk + K ) Ick) (2.237)
C
Pseudopotential method
The idea underlying the pseudopotential method is to transfer the core state
orthogonality term in equation (2.237) from the OPW's to the one-electron
Hamiltonian H of the crystal. This transfer is done as follows. Consider
the core electrons. which we have hitherto taken jointly with the atomic
nuclei to form the cores, to be independent particles, just like the valence
electrons. This means that the potential created by the core electrons is no
longer included in the core potential Vc, but is added to the eEective o n e
+
electron potential 1 ' ~ 15-cof the electron-electron interaction. Because of
this reinterpretation of the oneelectron Hamiltonian H , its eigenstates now
also include core states, for which we have
H i c k ) = E,lck). (2.238)
The valence band eigenvalues E and eigenfunctions ~a
similarly satisfy the
eigenvalue equation
Removal of the core states from the expansion functions mandates changing
from the eigenfunctions $ato other functions v p i that have the same
expansion coefficients, but plane waves as expansion functions:
(2.241)
(2.242)
H P S= H + E ( E - E,)lck)(ckl . (2.243)
C
H P s = -p2+ v
2m
H + Vxc + Vc+ C ( E - E,)lck)(ckl . (2.244)
C
The last two terms in this expression jointly constitute the so-called pseu-
dopotential V,p"
(2.245)
The second term on the right is significant only in the core regions. There,
it is preferentially positive, indicating that it repels valence and conduction
band electrons away from the cores. One can show that it largely compen-
sates the variation of the core potential V, in these regions. Because of this,
the pseudopotential V,p" is relatively smooth throughout the cores. It can
he made even smoother if one exploits a property of V,p" which has not yet
heen discussed. We refer to the non-uniqueness of the repulsive part of V,p"
in equation (2.245). If there the bra-vectors (E - E,)(ckl in (2.245) are r e
placed by completely arbitrary functions (while keeping the ket-vectors Ick)
unchanged), the eigenvalues of the pseudo-Schrodinger equation (2.242) re-
main the same, only the pseudo-wavefunctions change. This freedom may be
used to make the pseudopotential still smoother, and also fulfill other require-
ments, such as, for example, norm-conservation of the pseudo-wavefunctions.
The smoothness of the pseudoptential makes it possible to restrict the plane-
wave expansion (2.241) of the pseudo-wavefunction to terms having small
reciprocal lattice vectors K. Consequently, the representation matrix of the
pseudo-Hamiltonian HPS is small and easy to diagonalize. This is the reason
138 Chapter 2. F k t m n i c structure of ideal crystals
Cell methods
Muf&n-tin methods
In the present method one delimits spheres around the atoms, and leaves
some empty space around them. The crystal then looks something like
2.5. Band structure 139
a muffin-tin, whence thc methods narnp. Within the spheres one uses the
spherimlly syuunelric potentials of the atoms, trnd in the surrounding regions
one takes the potential to be uniform.
2.6.1 Fundamentals
Atomic Orbitals
atomic oibatnls. The spinor character of the orbitals may be taken into ac-
count, but we will omit it here brevity. The mobt important property of
the orhit&, which turns out to be decisive for the TB approximation, is
their spatial symmetry. The latter i s determined by the symmetry of the
Hartree o i HartrecFock potentials of the atomic cores. These potentials are
isotropic if all core shells are fully populated by electrons. In the case of
atoms forming diamond and zincblende type semiconductors, this condition
is always satisfirul. Thus we may assume isotropic core potentials, and the
atomic orbitals of given energy eigcnvalues form basis sets of irrediicible rep-
resentations of the full orthogonal symmetry group. These representations
are characterizd by an angular momentum quantum number 1 which may
assume all non-negative integral values. The irreducible representation of a
+ +
given quantum number 1 is (21 1)-fold degenerate. The 21 1 basis func-
tions are distinguished by the magnetic quantum niimbcr 7n which takes all
integei values between - 1 and + l . The energy spectrum of the free atom
is degenerate with respect to m. Foi the hydrogen atom there is also a d c
generacy with respect to 1. This is not due to the spatial symmetry of the
potcntial but to its purr Coulomb form. Here this additional degeneracy
may not be assumed. For each value o l lhe quantum number 1 one has an
infinite set of different energy eigenvalues. These are distinguished by the
+
mdin quantum number n which may take all intcgcr values horn 1 1 to 00.
In this way the energy levels E,l of an atom depend on thc two yuanturn
numbers r~ and 1 , and the corresponding eigenfunctions dnlm(x)depend on
thrw quantum numbers r ~I ,, m. 'l'ht. eigcnfunctions &,jrn(x) can be written
as products of the radial wavefunctions &(I x I) and spherical harmonics
Km(xl I x I),
(2.246)
Here, it is assumed that the tttorriir core is located iit the coordinate origin
x = 0. A wavefunction with the quantum number I = 0 is called an s-orbital,
one with 1 = 1 a p-orbital, with 1 - 2 a d-orbital etc.
In order to represent the eigenstates of the valence electronb: of a crystal,
one needs, rigorously speaking, nll orbitals of the cores of its atoms since
only the totality of all orbitals forms a complete basis set in Hilbert space.
However, not all of these contribute in an essential manner. 'l'he largest
contributions are to be expccted from orbitals forming the valence shells of
the free atoms. Within the TB approximation one takes only these orbitals
into account, This corresponds to a perturbation-theoretic treatment of the
Hamiltonian matrix with respect to the atomic orbital basis; only matrix
clcmerits between valence orbitals are considered while those involving other
orbitals are neglected. For the elemental semiconductors of the fourth group
of the periodic table the valence shell orbitals are formed by the four ns-
142 Chapter 2. Electronic structure of ided crystals
The latter are also energy eigenfunctions because of the degeneracy of qbn1l
aiid 0 ~ 1 - 1 with respect to the magnetic quantum number m. For the sake
of uniformity, one sets
2.6. Tight binding approximation 143
Figure 2.16: Polar diagrams of the atomic s-and p- orbitals in Cartesian represen-
tation.
Two different orbitals & f j f R ( X ) and & ~ R ( x ) with identical values of R and
R as well 8s of j and j , but different values of a and a, are also orthogonal
to each other. For R f R or j # j , i.e. for orbitals at different cen-
ters, no such orthogonality exists. Although the two orbitals are localized
in different spatial regions, and the integral over the product of the two, the
so-callcd ovcrlap integral, turns out to be relatively small, it may not be n e
glected because its influence on the energy eigenvalues is of the same order
of magnitude as the matrix elements of the Hamiltonian between orbitals
at different centers. The latter elements are essential because they are r e
sponsible for the bonding between atoms in a crystal and for the splitting of
the atomic energy levels into bands. The non-orthogonality overlap integrals
must therefore also be taken into account. This may be done directly, by
writing down and solving the eigenvalue problem for the crystal Hamilto-
nian in the non-orthogonal basis set of the atomic orbitals. This procedure
144 Chapter 2. Ektranic structure of ideal crystds
is, Iiowcvcr, quite inconvenient becaiise the matrix of overlap integrals has
to be calculated explicitly and diagonalized together with the Hamiltonian
matrix. It is more useful to employ a set of orthoganalizd orbitals by form-
ing suitable h e a r combinations of the q a j ~ ( x )Here,
. 'suitable' means that
the new orbitals should have t,he same spatial symmetries a s thc original
atomic nrhitrals Q U j ~ ( xbecause
), these symmetries are the essential proper-
ties that allow the matrix elements of the Ilamiltonian to be reduced to a few
const.ants. Consequently, the new orbitals must, likewise form basis sets of
irreducible representations of the full orthogonal group, each set heing char-
a c t w i d by a particular angular morrieriturri quantum miniber 1. That there
are indeed linear combinations of atomic orbitals possessing these properties,
forms the content of Liimdin,'<sthcowm (we, e.g., Slater, Koster, 1954). We
will iise this theorem below. The orbitals m U j ~ ( xwhich
)! thus far have been
taken as ordinary atomic orbitals, will henceforth be understood as atomic
orbitals in the sense of Ldwdin's theorem. The orbitals q a j ~ ( xare ) now,
of course, no longer given by the expressions [2.246) to (2.250), but their
indices n E nlm will retain the meaning they previously had for the ordi-
nary atomic orbitals. hlthough explicit expressions for the G w d i n orbitals
& j ~ ( x )can in principle be providd, they will not be given here since thcy
are nut, n m d d if one proceeds in thc manner to be discussed below. The
Lowdin orbitals arc, by definition, aIso orthogonal for different centers, such
that
(2.254)
The sum over R extends over all lattice points of the periodicity region. By
means of (2.254) one may readily verify that
(2.2 56)
2.6. Tight binding approximation 145
cPvlc(x) = x ( J j k I c P v k ) c P a j k ( x ) (2.258)
jQ
where the matrix elements of the Hamiltonian are given by the expressions
with
(aj0 I H I ajR) =
s ( xR - 5,).
d 3 x ~ ! J : (-x? ~ ) H ~ , I -
been used. For a given wavevector k, the (ajk I H I ajk) form a square
matrix with a finite number of rows and columns, the same as the number
of different orbitals per primitive unit cell which were used for the represen-
tation of the eigenfunctions, i.e. number J of atoms per primitive unit cell
times number A of orbitals per atom. The integrals ( a j 0 I H I ajR) in
(2.261) describe the interaction of electrons in orbitals a and a, where one of
the orbitals belongs to the atom at ? and the other to the atom at R+ ?,I.
These integrals substantially decrease with increasing distance between the
atoms, so that it suffices in most cases to extend the sum on R in (2.260)
over the nearest, or if need be, the second nearest neighbor atoms only. Once
the integrah ( a j 0 I H I ajR)and, through them, also the matrix elements
(ajk 1 H 1 ajk) are known, the energy eigenvalues and eigenfunctions of
146 Chapter 2. Electronic structure of ideal crystals
It follows that the energy eigenvalues Ens(k) of the Schrodinger equation are
P 2s
PlS
-
-IT
D
0
Wavevector (O,O,k,) -
l-r
-
a
but several. This means that the valence electrons in the free atom do not
occupy only one 5 level, but several s-levels ens differing in the value of n. To
justify the application of the results obtained above in the present case, the
matrix elements of H between s-orbitals having different values of n must be
negligibly small. We assume this to be true. In addition, we suppose that ens
is negative for all n, and that the sign of pns alternates, such that for n = 1
it is taken to be negative, for n - 2 positive, for n - 3 negative etc. This
behavior reflects the differing numbers of nodes of thc atomic wavefiinctions
for different values of n. The absolute values of Pns are expected to increase
with growing n , corresponding to the larger values which the ns-orbitals
with larger n have at the nearest neighbor aloms. The separation between
adjacent energy levels cn8 should, however, always be larger than 4Pns.
If the above conditions are met, the energy band dispersion along the line
(0, 0, kz) of the first B Z of the simple cubic lattice under consideration, has
the form shown in Figurr 2.17. Each level ens of the free atom gives rise to
an energy band of the crystal. The width of these bands amounts to 4&.,
thus increasing with increasing n. The bands are separated by forbidden
energy regions. Their widths decrease with growing n. If the distance be-
tween nearest neighbor atoms increaees, then the parameters fins of equation
(2.263) decrease because of decreasing ovrrlap of the orbitals, as has been
148 Chapter 2. Electronic structure of ideal crystals
pointed out above. The same holds for the widths of the energy bands, they
become narrower if the distance between neighboring atoms grows. They
approach the discrete levels ern of free atoms as this distance becomes in-
finitely large, corresponding to ,&, = 0. In the latter case. electron states
with different values of the wavevector component k, have the same energy,
ens. These levels are, therefore, highly degenerate. If the infinitely remote
atoms again approach each other, then the ,&,-values become finite. because
of the onset of overlap of neighboring orbitals. Correspondingly, the degen-
eracy of electron states with different kz is removed. and the discrete levels
of the free atoms spread into bands. The TB approximation quite naturally
explains, in this way, how discrete energy levels of the free atoms transform
into energy bands of the crystal. The gaps between the bands occur nat-
urally in this approach, since the discrete atomic levels are separated by
energy gaps from the outset. This stands in contrast to the approximation
of nearly free electrons, where the occurrence of energy gaps calls for an
explanation. On the other hand, 'bandwidth', in the form of the infinitely
broad energy continuum of the free electron. is present at the outset in the
latter approach. The gaps induced into the energy continuum were seen to
arise because of the strong perturbation of plane wave states by the peri-
odic lattice array of atomic coTes fox wavevectors on the Bragg reflection
planes. Comparison of the two approximation procedures reveals the differ-
ence between the underlying concepts - the TB approximation emphasizes
the atoms and the short-range ordered complexes of the crystal. while the
approximation of nearly free electrons focuses on the crystal as a whole and
the long-range ordering of the atoms. Such comparison also shows that the
short-range and long-range order concepts are equivalent in the sense that
they result in the same characteristic features of the electronic structure of
crystals -both concepts predict the existence of energy bands separated by
gaps. Figure 2.18 depicts the manner in which the bands and gaps arise in
the two approximations.
Figure 2.18: Illustrat,ion of the origin of energy bands and gaps in the enerw
spectrum of a crystal.
to the cubic crystal axes. The main quantum number n will be suppressed
below because it may assume only one value here for each of the t,wo atoms,
although not necessarily the same. As a first step we determine the 8 x 8-
Hamiltonian matrix for diamond type crystals. Later: it will be generalized
to zincblende type structures.
Hamiltonian matrix
(2.266)
4
(ujk I H I a'j'k) = x e i k ' ( R t f 5 f - % ;(. )~ j IH
0 I U'j'Rt). (2.267)
t=1
The values of j and j' are complementary to each other because the nearest
neighbor atoms lie in the other respective sublattice. For j = 1 one has
j' = 2, and for j = 2 then j' = 1. We will restrict ourselves to the first case,
i.e. j = 1,j' = 2, because the second may determined from the first with
minor changes. The four nearest neighbors of a 1-atom are located in the
primitive unit cells at
(see Figure 2.19). The calculation of the matrix elements (a10 I H I a'2Rt)
between the different Cartesian orbitals and the four different values of Rt is
2.6. Tight binding appmxhation 15 1
24
Figure 2.19: Atom of sublattice 1 and its four nearat neighbors in sublattice 2.
somewhat laborious. It will be carried out in several (five) steps. In the first
step we determine the matrices (a10 I H I a2Rt) between spherical orbitals.
(0010 (2.271)
(0010
(1010
are independent of each other: and the two elements
(2.273)
Since the atomic orbitals under consideration are those of bound states, and
since the eigenvalues of the Hamiltonian for bound orbitals are generally
negative, one may expect negative values for k<3n, Vm, and positive ones
for Ifaw, IT&,. Taking account of the strength of the overlap of the orbitals
2.6. Tight binding approximation 153
12
v s su
21
= vuG
-= vssu
21 21,
=V p p u = VPPT
-
=Vppcr
in Figure 2.20, one can conclude that the absolute values of these elements
should obey the relations
To this end, the Cartesian orbitals 2,y, z related to the cubic-axes system
must be expressed in terms of the pair-related Cartesian orbitals ?,c,Z.
To determine this relation, we consider a rotation which transforms the
crystal-related axes system into the pair-related one. The transformation is
characterized by Euler angles $, 6 and 'p. Since the orientation of the pair-
related system is defined only up to an arbitrary rotation about the Z-axis,
the Euler angle 'p may, without any loss of generality, be set equal to zero. As
noted in Appendix A, the rotation matrix A of equation (A.31) transforms
the coordinates before rotation into the rotated one. The basis vectors are
transformed by the transposed matrix, which, in the present case of rotation,
is also the inverse matrix. Since the 2 ,y, z and ?,y, Z are understood here
in the sense of basis vectors, we have
(:) cos @
= (sin@
0
- cos 6 sin $
c o ~ e c o ~
sin 0
sin 0 sin $
-sinecos$)
~
cos e
(i). (2.276)
Below, we will see that the direction cosines (PI,q1, 71) of the pair-related
2 -axis with respect to the crystal-related cubic z-axis play an important
role. These are the elements of the third column of the rotation matrix in
equation (2.276), i.e.
These relations are valid for matrix elements involving the two nearest neigh-
bor atoms belonging to the same unit cell at R = 0. From these elements
we may determine the elements with the nearest neighbor atoms of different
unit cells. This will be done in the next step.
The vectors pointing from the central 1-atom to the four nearest neighbor
atoms will be denoted by dt, t = 1,2,3,4, such that dt = Rt +
- TI.
For the diamond structure, the two sublattices are displaced with respect to
each other by the vector (a/4)(1,1,1). Using equation (2.268) for Rt and
the explicit form of the primitive lattice vectors of the face-centered cubic
lattice, we obtain
a - a - -
dl = a(l,
4 4
U
1, l ) , d2 = -(1,1,1),d3 = -(l, 1,I), d4 = -(l, 1,l).
4 4
(2.279)
v) fifth step
The elements (a10 I H I a2Rt) determined above are used to calculate the
k-dependent matrix elements (alk I H I a2k) between Bloch sums. For
complex conjugate elements, again, only one relation will be given. With
the help of equation (2.267), we obtain
4 4
(slk I H 1 s2k) = ~ e i k - d f ( s 1I0H I s2Rt) = V,,,xeik.dt, (2.280)
t=l t=l
4 4
(slk 1 H I 22k) = x e i k . d t ( s 1 0 I H 1 22Rt) = Vswxeik-dtpt.
t=l t=1
2.6. Tight binding approximation 157
4 4
The seven different t-sums which enter t,he matrix elements (2.280) may be
reduced to just four because of the obvious relations ptpt = r t , p t r t = qt. and
qtrt = p t . The four independent sums are
158 Chapter 2. Electronic structure of ideal crystals
To obtain the band structure of diamond type crystals, one has to calcu-
late the eight eigenvalues El(k),Ez(k), . . . , Es(k) of the Hamiltonian matrix
(2.283) at the various points k of the first BZ. The k-dependence of the
eigenvalues stems from the factors 91, 92, g3,g4 in (2.282), which are univer-
sal functions of k. The constants r,, e p , E,,, E,, E,, and E,, are related to
material properties. In principle, these constants can be calculated from the
defining equations (2.280) and (2.281) and the Hamiltonian matrix elements
(2.261) between atomic orbitals. In quantum chemistry one often proceeds
in this way. However, one also may forego the calculation of these Hamil-
tonian matrix elements and considers them as empirical parameters. Their
values may obtained as follows. First of all, one calculates the eigenvalues
of the Hamiltonian matrix (ajk I H I ajk),at at least 6 special k-points as
functions of the unknown parameters cg, epr E,,,E,, E,, and E,. Then one
measures the band energies at these points 01calculates them by some other
2.6. Tight binding approximation 159
1 1 1 1 1 1 1;1
Table 2.7: Tight binding matrix elements for diamond type semiconductors (in
eV). (After Harrason, f9RO.)
~i 6s EP VsSa V v vma
-17.52 -8.97 -4.50 5.91 10.41 -2.60
Table 2.9: Intra-atomic TB parameters (in eV) to be used in conjunction with the
universal inter-atomic TB parameters of Table 2.8. (Source same as in Table 2.8.)
(2.284)
tors. They represent atomic s- and p-level energies which deviate somewhat
horn the energy levels given in Table 2.1.
A k-point of prtictilar interest is the 32 center k = 0. Here, the
eigenvalues and eigenfunctions of the Hamilton matrix (2.283) may br o b
tained ~ I closed
I analytic form. The results me the following 8 eigenvalues
&(a). i = 1,2,. . . , 8 .
These relations Inem that the E'c;(O)-levelmoves down with respect to the
other two levels as the size of the atoms increases.
162 Chapter 2. Electronic structure of ideal crystals
It turns out that the ordering of the eight energy bands at k = 0 remains
the same over the entire first BZ. This is important because the positions
of the energy bands relative to each other determine the likelihood of their
population by electrons. As already mentioned at the beginning of this
section, not all of the bands are expected to be populated, just as the s- and
p-levels of the free atom whose orbitals were used as basis functions were not
completely filled. Electron population of the ground state of the crystal, i.e.
at temperature T = 0 , may be obtained as follows:
For a simple band, each k-value corresponds to 2 eigenstates of opposite
spin. For a periodicity region of volume Q = G3Ro, the first B Z contains,
as does every primitive unit cell of reciprocal space, G3 allowed k -values
(see section 2.3). A simple energy band therefore has 2 x G3 states. Four
such bands are necessary to host the (2 x 4) G3 = 8G3 valence electrons
of a periodicity region. In the ground state of the crystal, therefore, the
four lowest bands are populated, and the four highest bands are empty.
This means that in the case of C , Si and Ge, E l ( k ) , E2(k), E3(k), E4(k) are
the populated valence bands, and Es(k),&(k), E7(k), Es(k) are the empty
conduction bands. For a - Sn, El(k) and &(k) form valence bands, together
with two of the three bands E2(k), E3(k), E4(k). The remaining band of the
three is a conduction band. Since it is degenerate at k = 0 with the highest
valence band, the energy gap of a-Sn vanishes.
The above band assignment allows us to determine the symmetry of the
valence and conduction band states at r.
the latter elements 'exchanging', and the former ones 'non-exchanging'. The
eigenfunction (l/&)[ls 1 0 ) + 1 sZO)] for E l ( 0 ) transforms into itself under
the action of both types of elements, thus it belongs to the unit representa-
tion rl. For the eigenfunction (l/fi){l sl0)- I s 2 0 ) ] of the Es(O)-level, the
transformation into itself occurs only under the action of non-exchanging el-
ements, while a factor -1 is generated in the case of exchanging elements. It
follows from the character table of the irreducible representations of Oh given
in Appendix A, that this transformation corresponds to the representation
r;.
The upper valence band level E z ( 0 ) = E3(O) = E4(0) possesses the
three eigenstates ( ~ / f i210)-) [ l 1 220)],( l / f i ) { Yloj-
l I Y ~ o )(1/]&)[1.
~ 1 0 ) - I d o ) ] . Under the action of the non-exchanging elements of oh.
these functions transform like vector components. Inversion, which is part
of the exchanging elements. reverses the sign of the vector components, and
the exchange of the two sublattices also reverses the sign of the whole eigen-
functions. The three eigenfunctions therefore transform as they w o d d under
the action of the corresponding non-exchanging elements. The character ta-
ble of the irreducible representations of Oh in Appendix A shows that this
transformation is characteristic of the representation J&. Similarly, one finds
that the eigenstates (1/&)[1x10)+ I d o ) ] ,(1/&)[1 y 1 0 ) + I Y ~ O ) ](, 1 / f i ) [ I
zl0j-t I ZZO)] belonging to the eigenvalues E s ( 0 ) = E e ( 0 ) - E7(O), trans-
form according to the irrcduciblc representation rl;.
We summarize the results of our TI3 band structure calculations as fol-
lows: For crystals which have the diamond structure, i.e. for C, Si, Ge,
as a rule, the highest valence band is 3-fold degenerate and belangs to the
irreducible representation r&, of the point group oh. The lowest conduction
band at r exhibits either a similar %fold degeneracy, in which case it be-
longs to the repraentation f 1 5 (C, Si), or i t is non-degenerate and belongs
t o the representation I 'i (Ge). For LY - Sn, the F2-band lies below the I'g
-band, which in this way, is partially a conduction band. These results are
illustrated graphically iu Figure 2.21.
r, - 6, - r;, - conduction
6, - r, - r, - bands
r;, - valence
6 - bands
Figure 2.21: Ordering of energy bands at the center 1 of the fint B Z for semicon-
ductors of diamond and zincblende type.
in that at the lower right. Secondly, the relation V$$ -V:$ G -V3w of
equation (2.273) cannot be used in the zincblende case because it rests on
the chemical identity of lhe two atoms of A unit cell. For the matrix element
z;l 2 , the s-state belongs to a 1 atom, and the p-state to a 2-atom, while for
the s-state belongs to a 2-atom, and the p-state to a 1-atom. Therefore,
thr matrix element, V& is given by an independent constant -espc
rather
than by -V:$, (the parameters iSwin Table 2.8 are associated with csF by
meany of equation (2.284). The other excliangr relations in (2.284) remain
valid because they refer to matrix elements whose orbitals at the two different
atoms belong to the same state. With these two changes, in equation (2.283)
the TB Hamiltonian matrix for zincblende type semiconductors becomes
2.6. Tight binding approximation 165
with ESP= (l/fi)c&,. TTsing this matrix, the band structure and the
eigenstates of zincblende type semiconductors may be calculated. YIPspa-
tial symmetry of the eigcnstatcs a t thr R Z rentpr is similar to thtlf, which
was found for diamond type crystals above, except that the point group Ott
has to he r ~ p l a r dby the tetrahedron group T d . The wprPsPntaliun ri, of
Oh thereby becomes the representation r15 of T d , I 'i is replaced by rl, and
r1.5 remains ri5. In contrast to diamond type crystals, one has practically
only one energetic ordering of the conduction bands here - the rl-band being
the deepest.
23 23
23 23
1
I h31R) = 5 [dslR(X) - # z l r t ( X ) -tb y d x ) - $zlR(X) 1 1
1
I h d R ) = 5 [ $ s ~ R ( x-) 4 z d X ) - &lR(X) + d'.zlR(X) 1
In Figure 2.22 the probability distributions of the four sp3-hybrid orbitals are
shown in the form of polar diagrams. The orbitals resemble clubs pointing
to one of the nearest neighbor atoms in the sublattice 2, e.g., I hllR) to
atom 21, 1 h z l R ) to atom 22 etc.
2.6. Tight binding approximation 167
These orbitals point to an atom of type 1. The following four orbitals are
directed to the 1-atom in the unit cell at R: orbital 1 h12Rl+ R) at atom 21,
I h 2 2 R 2 f R) at atom 22, I h32R3+ R)at atom 23,and I h42&+ R)at atom
24. Hybrid orbitals at the same center are orthonormalized with respect to
each other, as the s- and porbitals from which they are constructed. If the
latter are understood in the sense of Liiwdin, orthogonality also holds for
hybrid orbitals at different centers. For each unit cell there are 8 associated
hybrid orbitals 1 &jR)with t = 1,2,3,4and j = 1,2, as there are 8 atomic
orbitals for the two free atoms of a unit cell. From the hybrid orbitals of a
given sublattice one may form Bloch sums I htjk) by means of the relation
(2.291)
expressions for the eigenvalues and eigenvectors which may be used to ex-
plicitly determine the total energy of the valence electrons of a crystal in
closed analytical form.
. (2.296)
Table 2.10: Hybrid matrix elements calculated from the TB parameters in Table
2.7 (in eV).
r X
wovevector
Figure 2.23: Evolution OF the energy bards of semiconductors with the diamond
slructura within the TB approximation The right-hand part shows the band struc-
t,ure of Si calculated by meam of equations (2.297).
turns out that this task may even be carried out analytically if a suitable
additional approximation, the so-called bond orbital approsirnation. is made.
(htlk 1 b4k) = ( l / J z ) ( O , 0: O , l , O , O , O , e : ) ,
1
I kR)= - 11 h t l
1/2
R)+ I h2Rt + R)], t - 1 , 2 , 3 , 4 . (2.301)
Thc exponential factors eF of the eigenvectors (2.299) and (2.300) were com-
pensated by the et-factors of the Bloch sums. In the case of a-states the
hybrid orbitals are subtracted, and the corresponding linear combinations
I a , R ) are given by
The polar diagrams of these functions are shown in Figure 2.22. For reasons
which will be clarified later, one refers to the orbitals I h t R ) as bondiny and
to the orbitals 1 arR)as anhi-bonding orbitals. With the help of bonding and
anti-bonding orbitals the eigenfunctions of the Hamiltonian matrix (2.296)
with b1' -- 0 may be written in the form
1
I btk) - eik'R I b t R ) , 1 - 1 , 2 , 3 , 4 , (2.303)
aR
(2.304)
In the second step of the diagonalization procedure the Vl-terms are in-
cluded. The Hamilton matrix (2.296) is transformed iuto the basis set of
the previously calculated eigenvectors 1 btk) and 1 atk). This results in the
(8 x 8)-matrix
(2.305)
{2.307)
as block elements. The expression for If, follows from that or H & if in the
latter q, is replaced by E,. The structure factors g t p and &) in (2.306) and
(2.307) are defined as follows:
The (4 x 4)-matrix H M couples the various bonding states, and H,, couples
the various anti-bop.ding states. The non-diagonal matrix Hab describes the
interaction between the two types of states. It gives rise to corrections to
the eigenvalues of relative order of magnitude I 11 I /2 I V2 I. Considering
the actual values of V1 and V2. these corrections are rather small. This
suggests treating them as perturbations. The zero-th approximation, i.e. the
complete neglect of the interaction between bonding and anti-bonding states,
is referred to as the b o d ovbital approximation. Within this approximation
the valence and conduction bands follow from separate eigenvalue equations,
the former by diagonalizing the matrix Hbbq the latter by diagonalizing Hw.
To calculate the total energy of the crystal one needs the total energy
of all valence electrons. T h e latter may be calculated by means of formnla
(2.54) which expresses the total energy of an interacting electron system by
means of its one-particle energies. One has
(2.310)
combinations of the bonding states I bik) only. In this matter, the linear
combinations are generated by the unitary transformation which diagonal-
izes the Hermitian matrix H a of (2.306). If one sums the eigenvalues @(k)
over all i , and takes advantage of unitarity, then the diagonal elements of
Hw with respect to the eigenvectors become the diagonal elements of this
matrix with respect to the bonding states, i.e. q,, as is stated in relation
(2.310). One may also prove this relation in another way, using Vieta's the-
orem, which states that the sum of all zeros of a polynomial of degree n
equals the negative of the coefficient of the (n - 1)- th degree term. In
the case of the characteristic polynomial of a matrix, this coefficient repre
sents the negative of the sum of all diagonal elements, here, therefore, -4q,
confirming the validity of equation (2.310).
(2.311)
To get the total energy of the crystal, the energy of the atomic cores must be
2.6. Tight binding approximation 175
added to the energy value of equation (2.311). In doing so, one may again
use the fact that the core states of the crystal do not differ from those of the
free atoms. This means that only the mutual electrostatic interaction of the
cores results in a structuredependent energy contribution, while the internal
core energies sum to a constant Eo. The core-core interaction energy has,
approximately, the same value as the electron-electron interaction energy
E d between the valence electrons on different atoms. This is true because
the valence electron charge of an atom equals its core charge for the crystals
considered here. The corecore interaction energy approximately cancels,
therefore, against the negative Coulomb energy -E,1 of valence electrons
in expression (2.311). Finally, the total energy of the crystal is given by
(2.312)
The d-dependence of this energy is due to the fact that both Eh and Vz
depend on d - the hybrid energies Eh have d-dependence as they are defined
by the diagonal matrix elements of the Hamiltonian H between Lowdin
orbitals which contain overlap integrals between s- and p - orbitals of adjacent
atoms, and V2 because this quantity is the matrix element of H between
hybrid orbitals at nearest neighbor atoms. V2 decreases with decreasing
distance d, corresponding to an attractive force between the atoms. The
hybrid energy q, increases as d decreases, corresponding to a repulsive force.
For large d, the attraction dominates over the repulsion, and for small d, the
repulsion dominates over the attraction. Overall, the total energy E z l b l ( d )
of the crystal varies with d as shown in Figure 2.24 schematically. At the
equilibrium distance do, it takes its absolute minimum value. This means
that the initially free atoms will not remain free but form a diamond type
crystal with nearest neighbor distance do. They experience what is called
covalent chemical bonding.
In order to provide a better physical understanding of the nature of
covalent chemical bonding, we compare the total energy E g t p l ( d ) of the
crystal with the total energy E f $ T of 2G3 free atoms. For the elements
of the fourth group of the periodic table with their two electrons in atomic
,-levels and two in atomic cp-levels, one has
(2.313)
where Eo, again, accounts for the energy of the atomic cores. The negative
difference of the two energies (2.312) and (2.313) represents the cohesion
eriergy of the crystal. It is given by the expression
176 Chapter 2. Elecbronic structure of ideal crystals
distance d (schematically).
Ionic bonding
The ionic contributions to chemical bonding will now be calculated for mat,+
rials having the zincblende structure. A s is well-known, a scries of 111-V and
11-VI compound semiconductors form crystals of this type. For the Ilamil-
tonian matrix (2.305), the transit,ion from the diamond to the zincblendc
structure means that ch in the upper left (4 x 4)-block has to be replaced
by the hybrid energy EL of the 1-atom? and in the lower (4 x 4 )-block by
the hybrid energy e i of the 2-atom. With this replacement, the bonding and
anti-bonding energy levels become
where !+,
=c i - ~8.Thr energy separation betwren the two levels is larger
than that of diamond type crystals. This results in an enlargement of the
energy gap betwcm the valence and conduclion hands. The bonding and
anti-bonding oibilals arp given by the expressions
where the sum extends over a periodicity region. With EMad, the total
energy of the crystal is
(2.320)
with cy as the so-called Madelung constant. The latter depends on crys-
tal structure and can easily be calculated numerically. In Table 2.11, the
n-values are listed for crystal structures which are observed in materials
composed of group IV elements as well as 111-V, 11-VI and I-VII compounds.
The value for the wurtzite structiirp in Table 2.11 corresponds to the ideal
tetrahedral case with an equivalent cubic lattice constant &a (see Chap-
ter 1). The contribution of the Madelung energy to the total cnergy of a
given compound will be larger for larger effwtive charge number Z* of the
compound. This results in a tendency of compounds with larger 8* valiirs
to crystallize in structures with Madelung constants larger than that of the
zincblende structure. Therefore, in passing from the 111-V through the II-
VI to the I-VII compounds, one observes a transition from the zincblende
structure through the wurtzite to the rocksalt and cesium chloride struc-
tures. The cesium chloride structure follows from the rocksalt structure by
replacing the two facecentered cubic sublattices by two primitive cubic sub-
lattices, shifted in the same way with respect to each other as in the rocksalt
2.7. k . p -method 179
Zincblende 1.6381
Uurtzite 1.6410
Rocksalt 1.7476
2.7 k .p -method
2.7.1 Fundamentals
Luttinger-Kohn functions
[2.321)
(vkko(vkko)- 6 v l u 6 k ~ k , (2 322)
k .p - Hamiltonian
lhematrix elements (pkko I H I pkko) of the llarniltonian bptween T,uttingpr
Kohu functions can he t r a d back to matrix elements (pko I p j pko) ol the
momentum operator p between Bloch functions. if one uses the easily provcn
commutation relation
Ti2
E:(k) = E,(ko) + -(k
2m
- ko)2. (2.328)
The matriv on the right-hand side of (2.327) allows for an important rewrit-
ing. If one defines
In first, order perturbation theory the eigenvalue E$(k) arising from EE(k)
is given by the relation
(2.333)
and the Bloch function Ivk)' arising from 1.k)' E Ivkko) by the relation
This relation connects the effective masses with the matrix elements of the
momentum operator between different bands and with the energy separation
of bands at the critical point. The tendency indicated is that the absolute
values of the effective masses become larger for smaller momentum matrix
elements and larger band separations. One expects small effective masses
for large momentum matrix elements and small band separations. As far as
the band separations are concerned (only for them can one make an easy
estimate), we will later find conhmation of this tendency in all concrete
cases. For pairs of bands which are closer to each other than to all other
bands and, therefore, whose mutual interaction is stronger than that with all
other bands, relation (2.338) allows one to also draw a conclusion about the
signs of the effective masses. According to it, the energetically higher of the
two bands should have a large positive effective mass, and the energetically
lower a mass of the same large absolute value but of negative sign. This
184 Chapter 2. Electronic structure of ideal CFZ.S~~~S
Band degeneracy
Critical points are often symmetry centers or lie on symmetry lines, and
at these symmetry points, degeneracy of the energy bands often occurs. If
this happens, one must carry out second order k.pperturbation theory or
degenerate bands. In quantum mechanics, perturbation theory for degener-
ate energy levels is c o m o n l y of first order - the matrix of the perturbing
Hamiltonian operator between the degenerate states has to be diagonalized
(we remind the reader of the nearly free electron approximation in section
2.4). This procedure does not apply here because the perturbation matrix at
critical points vanishes in first order. One must therefore choose a variant of
perturbation theory for degenerate energies which works in second order. To
this end, one constructs the matrix of the perturbation operator not between
degenerate unperturbed eigenstates, as is commonly done. but between the
(also degenerate) eigenstates of first order of perturbation theory. By diago-
nalizing this matrix one obtains the eigenvalues in second order perturbation
theory. These are, in general, no longer degenerate.
An important case in which the k . p-perturbation matrix between the
degenerate unperturbed states vanishes, is the valence band maximum of
semiconductors with diamond structure. This case will now be investigated.
In doing so, w e initially neglect the spin-oIbit interaction. This approxima-
tion is valid for semiconductor materials composed of light elements only,
including, for example, Si. For other materials this procedure serves as a
zero-order approximation which can be used to proceed further (as we will
do below).
For the subgroup T d of oh the two representations F15 and r h 5 coincide. For
semiconductors having the zincblende structure, the three degenerate states
( v I O ) , IuyO), IuzO) of the valence band maximum may therefore be associ-
ated with I,y, z insofar as their transformation behavior is concerned. In
the case of the diamond structure, 2,y, z are merely a short hand notation.
The vanishing of the matrix (vmOlplum'0) of the momentum operator
between valence band states at I?, anticipated above, may easily be demon-
strated using the pertinent criterion for such vanishing given in Appendix A:
The operator p transforms according to the irreducible representation I'15
of oh. The matrix (umOlplvm'0) therefore belongs to the reducible repre-
sentation + + +
x r 1 5 x rl,, = I?;, x (rh ri2 I'15 r 2 5 ) , wherein the identity
representation does not occur. According to Appendix A this means that
the matrix (umOlplvm'0) must vanish. One can also obtain this result by
means of inversion symmetry alone. We have chosen the somewhat more
troublesome method of proof because it may also be applied in other, less
obvious cases, as we will see immediately below.
(2.339)
where we set E,(O) = for brevity, and the degenerate valence band energy
E J O ) is denoted by Ev. The third term in (2.339) guarantees the normal-
ization. (:onsidering the sum on p , tlir value 11 = 71m does not need to be
specifically excluded because the matrix elements ( p I p I vm') for p = 117n
vanish anyway. Expressions of tlic form (2.339) also hold for the approxi-
mate Bloch functions Ipk)' of the remaining bands p with p f urn, but we
omit an explicit presentation of them here. The states Ivmk)' and Ipk)'
with p # t m will now be used as a basis set to represent the IIamiltonian
H . The resulting matrix is 'almost' diagonal, because the basis functions
are 'almost' eigenfunctions. In particular, the submatrix of the three velence
bands is coupled to the remainder of the matrix only by elements of second
order in the k . p-perturbation. These elements give rise to corrections of the
valence band energies which are only of third order and can be neglected.
186 Chapter 2. Electronic structure of ideal crystals
In second order perturbation theory, the valence band energies Ev and For-
responding Rloch states I&,) therefore follow from an rigenvalue equation
which is decoupled from the remaining bands, namely
The initial occurrence of interaction betwren the valence band and the r e
maining bands is incorporated in the matrix (u>mk I H I wn'k) in first order
perturbation theory.
Harniltonian m a t r i x
where
Method of invariants
the most general invariant of the product space and thus the most general
Hamiltonian matrix compatible with Oh symmetry. This process is called
the method of invariants. It is applicable to arbitrary symmetry groups and
degrees of degeneracy, and it quickly leads to the goal if one considers spin
and spin-orbit interaction. It also allows one to determine the matrices for
perturbing Hamiltonians other than that of the k . p-interaction, such as
the interaction between the angular momentum of Bloch electrons and an
external magnetic field (see section 3.9) or the interaction with mechanical
strain. In this book, we will only use the method of invariants occasionally.
A comprehensive outline of the method with several applications i s given by
Bir and Pikus (1974).
Valence b a n d s t r u c t u r e
The eigenvalues of the matrix (2.344) form three valence bands E,l(k),
E,n(k), E,3(k). For the three symmetric k-directions [loo], [lll]and [110]
the dispersion curves are determined by simple analytical expressions as fol-
lows:
1 1
E,lp(k) = - [ L
3
+ 2M - N]k2, E,3(k) = - [ L
3
+ 2M + 2 N ] k 2 , (2.346)
E,l(k) = M k 2 , (2.347)
1
E,2(k) = - [ L
2
+ M + N]k2, E,3(k) = - [ L
2
1
+M - N]k2. (2.348)
Along the two directions [loo] and [lll], the valence band, being triply
degenerate at r, splits into two bands, one 2-fold degenerate and one non-
degenerate (see Figure 2.25). In the [llO]-direction and also for all more
asymmetric k-vectors, no degeneracy remains. This indicates a %fold split-
ting of the valence band for such k. All bands are parabolic, but evidently,
in general, not isotropic. One speaks of a warping of energy bands. In the
case of Si, one has L = -5.64, M = -3.60, N = -8.68 in units of ( h 2 / 2 m ) .
Using these values, the two degenerate bands E,l/a(k) of equations (2.345)
2.7. k . p method 189
Figure 2.25: Valence band dispersion for diamond type semiconductors in the
vicinity of the I'i5-maximum for different k-directions.
or (2.346) have smaller curvatures than the third band E,s(k) in these equa-
tions. Thus the first two bands correspond to the heavy holes and the third
band to the light holes of Si. Isotropy exists only if N = 0 and L = M .
Then, there also is no longer any distinction between light and heavy holes.
Conversely, anisotropy grows stronger as the difference between the masses
of the two types of holes becomes larger.
The results discussed above were obtained without consideration o l spin-
orbit interaction. However, for most of the diamond and zincblende type
semiconductors, the valence band structure is significantly influenced by this
interaction (in the case of Si it is small, hut often not negligible). We now
proceed to consider the effects of spin-orbit interaction.
we have
(2.3501
One has to be aware that the (sxlvuk) are eigenfunctions of H , but not
of H +H,. Correspondingly, the (xlvuko) signify the spin-dependent
Luttinger-Kohn functions of H , but not of fi + f l W .T h e matrix repre
senlation of the Schrtdinger equation with respect to the spin-dependent
Luttinger-Kahn basis reads
with
1
ii = p + ---[a
4m c=
x VV(X)]. (2.353)
With this the Luttinger-Kohn representation of H + H,, becomes
C ( ~ ( T O I H+ ~HsoIpuO)(pukOIEu)
.~ = E,(pnkOlE,). (2.355)
PU
Up to this point, we have kept the discussion general. Now we wish t o ex-
plore the particular consequences of spin-orbit interaction for the previously
2.7. k p method 191
considered valence band states. To this end, we need the matrix ele-
ments (vrnuO~Hso~wmuO) of H,, between the spin-dependent Bloch states
Ivm 0 . 0 )namely,
~
F,
( u ~ u O I H , , I ~ ~ U =O ~) ( v v ~ [VV(X)
O I x p] IumO) x (aldld). (2.356)
4m c
h A
,(uyO~[VV(x)x plrlvzO) = i - . (2.357)
4m c 3
Below, we will see that the constant A is the energy splitting of the valence
band at J? due to spin-orbit interaction. Applying equation (2.357) and the
explicit form of the spin matrices given in (2.57),the matrix (avmOlH,I
aw m 0j becomes
0 - i 0 0 0 1
i 0 0 0 0 - 4
A 0 0 0 - 1 i 0
(vmaOp,,Ivm.uO) =- (2.358)
3 0 0 - 1 o i 0
0 0 - i - i o 0
1 i 0 0 0 0
Here the rows end columns are associated with the basis functions in the
sequence Ivz T O j = Iz t), Ivy 7 0 ) = ly tj, . . ., It)z 1 0 ) 3 1s 1). Spin-
orbit interaction couples orbital states and spin states to each other. At
k = 0 the expressions E:(k) and k ii are both zero. The eigenenergies and
eigenfunctions of the total Hamiltonian Hk.a +
H , are therefore also those
192 Chapter 2. Electsonic structure of ideal crystals
c
u'm'
= E(wamO(E).
(vmaO~H,,lvm'a'O)(vm'a'O~E) (2.359)
1
IE ) T ( 1 ,i, o,o, O,O), IEv2) -
v1 -
~
Jz
1 i
IEv3) = z(l, - i , O , 0 , 0 , 2 ) , IEv4) = -(O, O,O, 1, - i , O ) , (2.361)
Jz
and a 2-fold degenerate eigerivslue
2
Ev5/6 - --A (2.3 62)
3
with the two corresponding eigenstates
1 i
IEv5) - -(o, 0, 1, 1, i, o), 1E ) - ----(--I, i, o,o, 0, 1). (2.363)
fi w6 - d3
emerge from the representation 213 of the full rotation group if, D Dis~taken
as a representation of the subgroup oh with +1 for inversion. It has also been
shown that the basis functions of this representation are the simultaneous
eigenfunctions of the angular-momentum-squared ' 5 or the eigenvalue j ( J +
1) (in units R 2 ), and of the z-component J z of J for the eigenvalues m j =
- -
L and -$
23 , 12 ., - 1 . =- 4.
One therefore denotes the first four eigenfunctions
of (2.364) by
33 1 31 i
I--)
22
= -1rz
4 + iy t), I--)
22
= -"-2Iz
fi t) + la: + iY 1 1 1 7 (2.365)
3T 1 33 i
I--)
22
= -[&
I. - iy T) +2/2 111%I--)
22
= 1.-
Jz -iY I),
The lEvs),IE,s) are basis functions of the irreducible representation I'y of
o h . These representations do not arise from any representation V3 of the
full orthogonal group. in particular not from a representation for J = 4
(this happens with rt
in the case of Oh or r:) in the case of T d . but the
expectation values of J2 and J z are the same as those in the Dl basis.
Therefore one also uses the angular momentum notation or the last two
eigenfunctiona of (2.3641, i.e. one sets
The above statements refer to valence band states at the center r of the first
B Z , where the k p-interaction vanishes. Off r,this interaction is no longer
zero and must be taken into account in addition to the spin-orbit interaction.
We have seen how this can be done approximately in the preceding section,
without consideration of spin. The method used there indicates the following
procedure in the presence of spin and spin-orbit interaction: One determines
the functions Ipok)' which diagonalhe the operator H k q of (2.352) in first
order perturbation theory. In analogy to equation (2.339), one finds for the
valence band states Ivmcrk)' the expression
(vmakIH,,lv7nak) (vmaOlH,qolvmaO).
Now we use the fact that H,, is diagonal in the angular momentum basis
Ijmj) of (2.365) and (2.366). It is clear that this basis follows from Ivma0) E
Imu) by a unitary transformation
~ j m j ) C U r r m j m j Ima). (2.370)
ma
The corresponding unitary transformation matrix UmjmJ can be readily
obtained from the rclations (2.365) and (2.366). One has
(2.371)
o $ o o 0 0
o o + o 0 0
(hjlff,oljm;) = (2.372)
o o o g 0 0
0 0 0 0 - 9 0
196 Chapter 2. Electronic structure of ideal crystds
The sum of the two matrices (2.372) and (2.373) is the new Hamiltonian
matrix. It has the same eigenvalues as the original matrix, even though its
form deviates from that of the original. The difference in form is, above all,
that the new matrix is already diagonal at k = 0. Kon-diagonal elements
occur for k # 0. Among them, the elements between basis vectors ] j m 3 )and
[ j ' r n $ ) with m3 # m i , , but = 3' play a different role than the ones with
.f j'. While the influence of the 2-diagonal elements on the eigenvalues is
independent of the size of the spin-orbit splitting A, it does depend on it for
the j off-diagonal elements. The magnitude of the latter can be estimated
as the larger of the two terms Nlki2 or IL - Mllkl'. If one assumes that
l L f a ~ ( ~ VIL, - AIl}lk12 << A holds, then a perturbation theoretical treatment
is possible. It yields an energy correction of order of magnitude [ M a r { N ,IL-
M1}]21k14/A. Under the assumptions made, this is small compared to A.
That means that the 3-off-diagonal elements of the transformed Hamiltonian
matrix can be neglected if the k-vectors are sufficiently close to r. We will
assume below that this is the case, although the Luttinger-Kohn model also
covers the general case of a (6 x 6 ) -Hamiltonian matrix. Neglecting ]-off-
diagonal elements the Hamltonian decomposes into two blocks, one (4 x 4)
-block conesponding to the basis vectors of the representation I'i,and one
(2 x 2)-block for the basis vectors of the representation I't.
The rsf-matrix
reads
The Hamiltonian matrix of thr rz-valence band can also be derivcd using
the method of iiivarinnts, which was discuss& at an earlier stagc. To do this,
one needs the angular momentum matricrs for spin J = as well aa their 4,
products with earh other. These matrices arp given in Appendix A. The
2.7. k . p +method 197
(2.376)
2
Using the explicit expressions for Q, T, R , S, this yields
1 1 1
A = -(L
3
+ 2M), B = -3( L - Ad), C 2 7 -[N2 - ( L - M)')].
3
(2.378)
I s; II [loo] 5; II [Ill]
I G+l
Figure 2.26: Valence band structure of diamond and zincblende type semicon-
ductors in the Luttinger-Kohn model. The dispersion for the two k-directions is
different (band warping).
h2 ha h2
A -----TI, B = -,2~, C2 = ---12(7,2 - 7:). (23 8 0 )
2m Lni 2m
Values of the Luttinger parameters are listed in Table 2.12. The constants
L , M , N , which were originally used, may be expressed in terms of the Lut-
tinger parameters by the relations:
Both energy band functions E&(k) and Er.,(k) depend on the square of
Ikl, i.e. they are parabolic. This would not have resulted if the interaction
between the rBf-states, and the spin-orbit-split r,f states, had not been
neglected as it in fact was. Concerning the dependencies on the direction
of k, the spin-orbit-split band Er7(k) is isotropic, while the heavy and light
f
hole bands Er8(k) are not. In their case one again has a warping of energy
bands as discussed above (see Figure 2.26). The constant C measures the
strength of warping. In the case C = 0, the warping vanishes. For C # 0,
the point k = 0 is a singularity of the energy band functions Erf,(k) in that
the second derivatives with respect to the components of k depend on the
direction from which one approaches the point k = 0. The effective mass
tensor, as given by equation (2.196), is not defined in such circumstances.
Instead, one can define an anisotropic effective mass, by differentiating in
equation (2.377) not with respect to the components of k,but with respect
to Ikl. If the warping of energy bands is ignored, for instance, by averaging
2.7. k.p -method 199
Table 2.12: k .p-band parameters for selected diamond and zincblende type serni-
conductors. E i , A, and E , in eV. E p = ( 2 m / h 2 ) P 2is a measure of constant P in
Kane's band model. The values for 71, yz, 7 3 are adjusted to the Luttinger-Kohn
model. Temperature below 70 K . (After Landoldt-Bomstein, 1982.)
Material 71 yz 73 Ei A Ep
C 0.94 0.23 0.23 5.48 0
Si 4.26 0.38 1.56 3.4 0.044
Ge 13.35 4.25 5.69 0.90 0.29 26.3
cz - S n 19.2 13.2 16.3 -0.4 0.8 39
GaAs 6.85 2.1 2.9 1.52 0.34 25.7
GaSb 11.8 4.03 5.26 0.70 0.8 22.4
InSb 35.08 15.64 16.91 0.18 0.98 21.2
ZnSe 4.8 0.67 1.53 2.67 0.42
HgTe 12.8 10.6 8.8 -0.30 1.08 17.5
over all directions, this yields the ordinary isotropic heavy and light hole
masses but in the sense of an average.
The Luttinger-Kohn model was described above for the case of diamond
type semiconductors. Formally, for materials having the zincblende struc-
ture, the model does not apply because the matrix elements of the momen-
tum operator p between the triply degenerate valence band states without
spin. IvrnO), are in general non-zero: These states transform according to
the vector representation r15 of the tetrahedral group T d r and the matrix
elements (vrnOlplvm'0) belong to the product representation I'15 x I'15 x r15.
The latter contains the unity representation, as distinguished from diamond
type semiconductors, where the unity representation does not occur in the
corresponding I'i, x r15 x product. The reason for this is the absence of
inversion symmetry in the zincblende structure. The non-vanishing matrix
elements (omOlplvrn'0) give rise to terms linear with respect t o k in the
I'15 valence band Hamiltonian, besides the quadratic terms which are are al-
ready present in the diamond case (see equation (2.344)).However, as a rule,
the k-linear terms are small, and the Luttinger-Kohn model also applies to
zincblende type materials, provided the other requirements which underlie
this model are satisfied. Table 2.12 therefore also contains Luttinger-Kohn
parameters for semiconductors of the zincblende type.
The most important requirement for the Luttinger-Kohn model to be valid is
200 Chapter 2. Electrunic structrrre of ideal crystals
the validity of the assumption that the k p-interaction of the valence band
with thc deepest conduction band is weak enough to be treated by means
of perturbation theory. This is justified as long as the encrgy separation
EF from the lowest condiiclion band and the I&-valenre band (not to be
confused with the fimdamental cnergy gap) is siifficiently large. One expects
deviations from the Luttinger-Kohn model to become noticeable if E i is
sinall Table 2.12 shows thal the EF-value for InSb, for example, clearly
lies below those for C, Si and Ge. In the case of a-Sn and HgTe, Ef; even
becomes negative. Simultaneously, the spin-orbit splitting energy A becomes
relatively large in some of the zincblende type materials, so that even A > /i$
holds. Describing of l h e valence band of such semiconductors by means
o l the Luttingrr-Kohn model would entail treating the effect of the remote
spin-orbit-split band exactly, while taking iuto account only the energetically
closer conduction band by means of perturbation theory. Such a procedure is
not meaningful and one must seek a different, more appropriate description.
A model which is tailored exactly to such circumstances is the Kana
model, which we will now discuss. In this matler, we asbume that the point
group of equivalent directions is the tetrahedral group rh, and no longer the
cubic group o h as above, thercby encompessing both typeb of semiconduc-
lois, those of zinrldende type EM well as those of diamond type. In the latter
case, inversion symmetry still has to be added. This involves a spwialization
of the results, which may be casily done, should thc need arise.
We analyzr the generally valid Ychrbdinger equation (2.351) using the as-
sumptions and approximations discussed, above. considering spin md spin-
orbit interaction horn the outset. We again denote the thrw valence band
indices by urn, ni - I.u, z. The conduction band index c will be augmented
by 3 . idirating the 3- or rl-synlm&-y of the conduction band state at r
(the coincidence of this notation s with that of the s p h variable 9 is unfortu-
nate, but unavoidable, and the reader should keep the dxerent meaning of
s dearly in mirid to avoid confusion). The pertinent spin-dependent Bloch
functions at k - 0 are IvmuO) and I c s v O ) , rmpectively. The matrix elements
of the term Ho(k] of f f k X are given by
ri2 2 ,
(vmaO)Ho(k)jvm'dO)= bmm~6umi-k (2.382)
2m
h2 2
(csdlHo(k)lcsdO) = 6,,)-k , (2.383)
2m
(wmOlHo(k)IcsO)= 0. (2.384)
Iii the otkw o p ~ a t o rterm of A V ~ .namely
~, {Fa/m)k-.?i,WP may neglect thc
spin-dqwndcnt part by virtue of the same arguments as in the Luttinger-
kohn model. The three needed matrix elements of this operatw may then
be determined as
(2.385)
m
~ c s o ~ p , ~=7~~r r8o~~~ p v =
~ I( cv syo~/ p
) , ~ ~=
~ ti .F,-o- )~ (2.386)
The factor 2 giiarantws that P i s real, if the Bloch factors are real as we
assume. The other factor (m/Ta)was introduced for convenience in the final
dispersion rclations. With the moinentiim matrix elements of (2.3861, thp
Hamiltonian matrix (pu01Hk ,(k)lpuO) takes the form
(2.387)
Ec ,iPk, iYk, 0 0 0 0
--iPk, 0 0 0 0 0 0
-iPkg 0 0 0 0 0 0
-iPk, 0 0 0 0 0 0
0 0 0 E C iPk, iPk, iPk,
0 0 0 -iPk, 0 0 0
0 0 0 -iPk, 0 0 0
0 0 0 -iPk, 0 0 I]
where thr lines and columns arp ordprcd in the sequence /s I), la I), Ig I),
I2 th I. 1). lz 1), IY 11, 12 1).
Finally ihe matrix demerits (puO1HsolpmO) nl t h e spiri-orbit interaction
operator ITrn haw to lie detrrminpd. For the Flj-vaknrc band rlernents
(wmcrOlH,,lwmaO), one can adopt the results which were formerly derived
for the valence band. because li5 coincides with I15 for the tetrahedral
group. There are new matrix elPrnents (vmuOlH,lrsaO) and (csuQIH,oj
cscr0) involving the conduction band states. The coordinatedependent fac-
tor of the first matrix element transforms according to the representation
r15 x l?25 x Il - Iz+ I15 +
r25. The unity representation does not oc
cur here, thus this factor vanishes and with it the whole matrix element
(umaOIH,,I csaO), whence
(um.aOlHsIcsrr0)= 0. (2.388)
The caordinatedeyendrnt factor of (csuOlH,olcsdO) belongs to the product
representation rlx r 2 5 x rl :rztj arid must therefore likewise wnish,
2.7. k . p -method 203
Thus, the total Hamiltonian Hk.T + H,, is gken by the following matrix
representation
,
Ec iPk, iPk, iPk, 0 0 0 0
-iPk, 0 -ig
A 0 0 -
0 O ?
-iPkg i$ o o 0 0 0 -27
.A
-iPk, 0 0 0 0 -- $ i+ o
0 0 0 0 Ec iPkz iPk, iPk,
0 0 0 -A
-
3 --iPk, 0 i+ o
0 0 0 -2z .A
-iPkY -+ 0 0
0 a
- .A -iPk, 0 0 0
\
3 2 5 O
Here, the order of rows and columns is the same as in (2.387). For k = 0
and vanishing Ec, this matrix reduces to the spin-orbit interaction opcrator
WSw If one rearranges the rows and columns of this matrix in such a way
that those relating to the conduction band states 1s 1) and 1s J) occur in the
left upper corner, side by side, then the matrix decomposes into a (2 x 2)-
block for the conduction bt~ncl,and B (6 x 6)-block for the valence band.
The eigenfunctioiis of the two blocks arc simultaneously also e i g e h c t i o n s
of the total matrix. T h {2 x 2)-co,nduction band block is already diagonal,
i.c. 1s t) and 1s J] are eigenhnctions of the Hamiltonian matrix (2.390) at
k - 0. The (6 x G)-vdencr band block is identical with the matrix of the
spin-orbit interaction operator H,, of (2.350) for the Luttinger-Kohn model.
The eigenfunctions at k - 0 here are therefore also the vectors 1$ms) and
i$rn 1) of ihe ctngpubr momentum basis (2.366).
T
The latter basis should be particularly suitable for solution of the eigen-
value problem for the Hamiltonian matrix (2.490) at k # 0. The matrix
(2.390) is, however, so simple, indeed, that one can also obtain the secular
equation directly. We will do t h s . before we h r t h w consider the angular
momentum basis. To diminate the free elmtron part ( h 2 / 2 m ) k 2from the
eigenvalues Elk), we write them in the form
h2
E(k) :E(k) -I--k2 (2.391)
2m
where E(k) satisfies the following
204 Chapter 2. Electronic structure of ideal crystals
Secular equation
(2.392)
The fact that the two factors in round brackets appear squared, signifies an at
least 2-fold degeneracy of all eigenvalues. The reason for this is. again, time
reversal symmetry jointly with spatial inversion symmetry (we remind the
reader that the term of the Hamiltonian which can break inversion symmetry
in the case of Td-symmetry has been neglected). Accordingly, one has in
general four 2-fold degenerate bands Ei(k).Ei(k),E$(k),Ei(k). It is also
noteworthy that in the secular equation (2.392). k enters only in the form of
k2. This means that all four bands are isotropic, in contrast to the Luttinger-
Kohn model where a warping of the valence bands occurs. In the case of
k = 0, the energy levels of (2.392) are given by
One may draw conclusions from these expressions in regard to the meaning
of the four energy bands E,(k): El(k) is the J?s-conduction band. E z ( k )
2nd Es(k) are the two upper degenerate rs-valence bands at r. and E4(k)
corresponds to the spin-orbit-split rT-valence band. The energy separation
EL of the r6-conduction band and the I'g-valence bend at. r is obtained as
(2.394)
sions. To avoid these below, the 4 x 4 block matrix of the remote band
interaction will be reduced to a special case before proceeding further. We
put L = M -- A,, and N = 0, which means physically that the remote
bands affect heavy and light holes in the same way, and do not disturb
the isotropy of the bands. -Ordering rows and columns in the sequence
1s t), 1s l),I);:, I;$), . . . , I$$), the transformed 8 x 8 Hamiltonian matrix
with simplified remote band interaction becomes
U 0 aP,
0 U D -&
-iP- 0 V 0 0 0 0
-fiP- 0 0 0 D 0
-i& -i$&P, 0 v 0 0 O
0 V 0 0
0 0 W 0
0 0 0 U'
(2.3
2
i
E'(k) + -A
3
- A,k2
I-i E'(k) +
3
This equation only differs from equation (2.392) in that the factors whose
vanishing define the conduction and valence bands contain, respectively, the
additional terms A,k2 and A,k2.
The zeros of the h s t factor in (2.396) yield, as seen previously, the I's-band
of heavy holes (i = 2). However, the dispersion relation for it now reads
A ii2
En(k) = -
3
+ A , k 2+ -k2
2m
(2.397)
2.7. k.p -metbod 207
We consider energy values Ei(k)in the various bands with energy separations
IEi(k) - &(O)( from the respective band exbrema which are small compared
with EF. For such energies, the conduction band El(k) approximately obeys
the equation
bi(k) - $1 bi(k)
21
+ TA E, + [&(k) + - I: P2k2 = 0, i = 3 , 4 . (2.400)
(2.401)
2
1 A P2 A P2 8
E3/4(k) = --
2[-
3
+ -k
E, 2]*ij[?f-Kk2]+m' (2.402)
-(2 13)(P2/E,) k2
E3/4(k) = (2.403)
- (2/3)A - (1/3)(P2/E, ) k2.
The energy values Ei(k) now have energy separations IEi(k) - Ei(O)I from
the respective band extrema which are small compared to A. This means
they can be comparable to E i . For the conduction band and the light hole
band one then gets from (2.398), approximately,
= 0, i = 1,3, (2.404)
from which
follows. In general, the dispersion laws for the electrons and light holes are
again non-parabolic. Only for energy separations from the band extrema
which are small compared to E,, more exactly for P2k2 << (8/3)E,, a k2-
dependence emerges, namely
\i
2.7. k . p -method 209
b)
7
A r,
2
I 4
I 4
Figure 2.27: Valence band structure of zincblende type semiconductorsin the Kane
model for limiting cases: (a) E, >> A, ( b ) E g<< A, E: > 0, ( c ) E , << A, E; < 0.
Since the energy region of width Eg above the band extrema is relatively
narrow for the narrow gap semiconductors considered here, one has in these
materials, even at relatively small separations from the band edges, non-
parabolicities in the dispersion laws of the electrons and light holes. As far
as these particles are concerned, small energy gaps and non-parabolicities
occur together.
For the spin-orbit-split band, one obtains, without further approxima-
t ions,
2 PZ2
E4(k)= --A - -k . (2.407)
3 3A
The dispersion curves of all four bands in the limiting case considered here
are depicted in Figure 2.27b.
conduction band level lies below the rglevel. The relation lEil << A
guarantees that the spin-orbit-split r;.-level is found further below it (see
Figure 2 . 2 7 ~ ) .If. again, only energy values are considered with separations
IE,(k)- E,(O)I from the respective band extrema which are small compared
to A, one obtains dispersion relations having the same form as in the previ-
ously considered case EF << A , E , > 0 (see equation (2.406). For electrons
and light holes they yield. under the condition (P2/A)k2 << IEil, the ap-
proximate parabolic dispersion laws
Because of the negative sign of E:, band 1 now lies energetically lower and
exhibits a negative effective mass, and band 3 lies higher and has a positive
effective mass. For the spin-orbit-split band E4(k), equation (2.407) holds
unchanged, and for the band E i ( k ) of the heavy holes, relation (2.397) also
remains the same. Thus, the band E 3 ( k ) is, among all four bands, the highest
energetically with the exception of I', where it degenerates with the band of
the heavy holes. Since the 8 valence electrons of a zincblende type semicon-
ductor are only enough to occupy 6 of the 8 bands of the I?;.--. FS-. ??&band
complex - 2 electrons per unit cell are necessary to fill the deepest I's -valence
band, omitted from consideration here - the E3[k) band remains empty. It
becomes the conduction band, which is also in accord with its positive effec-
tive mass. At r, its separation from the uppermost valence band, the Ez(k)
band of heavy holes, is zero. This means that the energy gap vanishes in this
case. Negative d u e s of the parameter E i . which signifies the energy gap
when it is positive, cause EF to lose this significance, and the real energy
gap becomes zero. Materials with vanishing energy gap are called zero-gap
semtconductors. Examples are HgTe as a zincblende type semiconductor,
and D - SR as a semiconductor of the diamond type.
In Table 2.13. the effective masses m t are listed for the three limiting
cases considered above. Generally, one has 1m.I I 5 I rn31 < IrnZl. The ef-
fective masses of the electrons and light holes are proportional t o / E g l / P 2
throughout. The rule discussed above for degenerate bands is thereby con-
firmed to be valid also for non-degenerate bands wherein mass decreases as
lEgl decreases and P increases. For IE,l << A the effective masses of the
electrons and light holes are almost identical, for E, >> A the electrons are
lighter than the light holes. For the spin-orbit-split band, the proportion-
ality of the effective masses to IE,l/P2 exists only in the case E, >> A; for
<< A the mass mS becomes independent of Es and proportional to A.
2.8. Rand structure of important seniiconductors 211
obtain this. one is nhliged to carry out band structure calculations. Expai-
meutal data enter thrse calculatiolis in various ways. Tlus is obvious if em-
pirical methods are cmployed their results have to be fitted to experimental
data, as, for example, to energy separations between bands at critical points
obtained from modulation spectroscopy. Less obvious. but nevertheless ex-
isting, is the need of experimental data for ab-initio calculations. Although
these methods are free of fitting parameters, various approximations are in-
volved which call for experimental confirmation or even corrections of the
results. as, for example, in the case of the erroneous fundamental energy gap
in the local density approximation.
Below we represent the results of of uumprical hand structure calcula-
tions using one or mother of the methods described in section 2.5. We will
not specify which particular method was applied since that is not of interest
here. Our main concern is with the qualitative features of the energy bands.
We will demonstratp that thew may be understood. at least partially, just
by means of the general results derived in the preceding sections and in Ap-
pendix A. This is particularly true for features irivolving the degree of band
degrnrracy at symmetry points of the first B Z , which follow from the i r r e
dudble representations of the space group of the crystal under consideration
(see Appendix A). The band structure models derived by the empty lattice
approach. the k . p method, and the tight binding method in sections 2.4,
2.6 and 2.7, respectively. will also be helpful. We begin our discussion with
silicon.
2.8J Silicon
In Figure 2.28 the band structure of Si is shown. Spin-orbit interaction plays
only a minor role for the ovcwJl behavior of energy bands in Si, 80 the energy
levels may be classified by means of the ordinary irreducible representations
of the small point groups of the wavevectors k. l'hesr are subgroups of the
full point group 01, of eqiiivalent dirrctions. According t o what we already
know about the dimensions of these representations at the various symmetry
points of the first B Z (see Table 2.5 and Appendix A), one expcrts at most
%fold degenerate levels at the symmetry center I', only 2-fold a t the the
symmetry point X. and at most 2-fold on thp symmetry lines A, A and at
L. This expectation is codinned by the band structure shown in Figure
2.28. The deepest energy level of the entire band structure occurs at r, i s
non-degenerate. and belongs to the irreducible representation r'1. The same
result was previously obtained in the band structure analysis of diamond
type crystals by means of t h e empty lattice altd tight binding approaches in
earlipr swtions (see, Figwrs 2.13 and 2.2L rcspectively). Also, off of l?, the
numerical calculation of the PI-band of Figure 2.28 exhibits the behavior
prdictfd by these simple approaches. DiEmmrw between the numerical
2.8. Band structure of important semiconductors 2 13
Figure 2.28: Rmid structure of Si. The energy unit i eV. (After Chelikowskp and
Cohen, 1974.j
and empty-lattice band structures occur at the second level at as may ber
seen from Figure 2.29. The second empty lattice has an 8-fold degeneracy
which exceeds what is compatible with the Oh-symmetry of r.
In a real
diamond type crystal this degeneracy is removed. As indicated in Figure
2.29, a splitting into levels of rl-,I'b-, I'b5-, and r l 5 - s y m e t r y will occur.
In this way the corresponding rk5-, rls-, and I'k-levels in Figure 2.28 could
have emerged from the 8-fold degenerate empty lattice level. The tight
binding analysis of the band structure of diamond type semiconductors in
section 2.5 has already shown that the second level (from below) at I? has
symmetry For the third level at r, the representations r15 or were
possible, according to this analysis. 4 s Figure 2.28 shows, r15 applies in the
case of Si, while the I'b-level is the fourth.
A410ngthe A- and A-lines, the two 3-fold degenerate let~lsI'L and r15
must split since only 1- and 2-dimensional irreducible representations are
possible there. Both a %fold splitting into 3 simple bands as well its a 2-fold
splitting in a 2-fold degenerate and a simple band are conceivable. From
Figure 2.28 one sees that the latter case holds, both along the A and A-
lines. and for the I?&- and the I'ls-levels. Since there are only 2-dimensional
representations at X (for an explanation see Appendix A), two simple bands
along the A-line must merge at this point, as actually happens in Figure 2.28.
214 Chapter 2. Electronic structure of ideal crystals
r, 62 5;
r; 5' 5 5 6;
r1
r A
Wavevector - X
A 2-fold degenerate band along A cannot merge with another band at X , but
miist terminate in a doubly degenerate level at X. From this it follows, for
example, that the upper of the two bands arising from the I'k5-level along the
A-line must be 2-fold degenerate, and the lower band must be simple. A look
at Table 2.4 shows that the only 2-dimensional representation of the small
point group of A is A5. At X this representation is compatible either with
X 1 or X 3 (the compatibility relations between irreducible representations
are derived I n Appendix A). Figure 2.28 shows that X 1 is correct in this
case. In a similar way one may conclude that the representation of the lower
level at X ,arising from the I'i,-level, must be X z . A similar analysis for the
splitting of the rls-level along the A-line shows that the lower level is non-
degenerate and belongs to the irreducible representation A l , and the upper
level is 2-fold degenerate and belongs to .As. The intersection between the
Ah-band emerging from the r!+vel, with the As-band emerging from the
l'ls-level, is not due to symmetry, but reflects an accidental degeneracy.
Consider next the two bands arising from the l'$s-level on the A-line.
The upper is the 2-fold degenerate As-baud, and the lower is the simple
A1-band. The simple band does not merge with another simple band at
L , but remains separated from it by a finite gap, in contrast to the band
behavior at X. This is possible because at L there arc also 1-dimensional
representations, L1 and L i , which give rise to the two lowest levels at L .
The splitting of the rls-level along the A-line is quite similar to that of the
l?~5-level;the lower band is non-degenerate and belongs to A l , and the upper
2.8. Band structure of important semiconductors 2 15
axe8 of the effective mass tensors of the various valleys. Each principal axis
represents a Cfold rotation symmetry axis. To p r o r d further. we select,
arbitrarily, the valley centered at (O,O, kJ. The band structure of this valley
is given by the expressions (2.201) and (2.2@2), which are applicable here,
as their conditions of validity are satisfied. Setting the band index v equal
to c, which refers to thp coiiductioii band, the dispersion rdation EJk) of
this band becomes
(2.409)
If t,hc zero point of the energy scale is put at. t h r valence band maximum, as
we do here. then E , is t,he fundamental energy gap.
In the vicinity of the valencc band maximum, the general results of the
k . p-method of section 2.7 are applicable. Without spin-orbit interaction
(see cqiiations (2.345) to (2.348)) one has two valence bands for each of
the two symmetry directions A and A, an upper E,l,z(k) which is 2-fold
degenerate, and a lower &(k) which i s non-degenerate. Along less sym-
mdricnl k-directions E,l/z(k) split 5 into two bands. However, spin-orbit
interaction cannot be neglected; although it has little effect on the overall
band structure of Si, it inftuences the valence band structure considerably
in an energy interval of several kI' below the rnaxiniurn at r, which is the
energy region where most of the holes B r e located. Spin-orbit interaction
makes the uppermost valence band level at r, which has a 6;-fold degener-
acy in Si if spin i s considered, split into an uppm &fold degenerat.e I?$-level
and a lower 2-fold degenerate I';-lcvel. The splitting rncrgy amounts to
44 m e V . Away from I?: the upper ra-level decomposes into the two bands
Efp(k) of heavy and light holes according t o equation (2.377). The lower
r$-levd givw rise to the spin-orbit-splitr;-band. The heavy and light hole
bands are strongly warped and each exhibits %oldspin-degeneracy, which
is due to timc reversal syrrirriet,ryin coinbination wihh spatial inversion (see
Appendix A). If warping i s neglected the two bands Era(k)can he described
by isotropic effective mass# m$. 'I'hey are negative because of the maximum
at .'I Extracting the negative sign, we define the positive effective masses
rnEh and m.G1of, respectively, heavy and light holeb;: setting m:,,= - m ; , and
ntl = - m l . For the heavy and light hole valence bands EF8(k) G E,h(k)
and E&(k) = E,,,(k): we h a w
(2.410)
Numerical values for the effective hole masses of Si are given in Table 2.14.
A vivid view of the conduction and valence band structure in the vicinity
of the band edges is provided by the corresponding iso-enerm surfaces. These
2.8. B i d structure dimportant semiconductors 217
are obtained by k i n g a specific energy and then drawing all k-vectors for
which the bands of equations (2.409) and (2.411) yield this energy value (see
Figure 2.30). For the conduction band, the iso-energy surfaces are ellipsoids
of revolution, pointing in the direction of the symmetry axis. Each of the six
star points is the center of such an ellipsoid. For the valence bands, within
the isotropic approximation, the iso-energy surfaces are concentric spheres
centered at I?. The inner sphere corresponds to the light hole band, and the
outer to the heavy hole band. In reality the valence bands are not isotropic
but have only cubic symmetry. Thus their iso-energy surfaces are warped, as
shown in Figure 2.30. If the conduction band is populated by electrons up to
a given energy, then the k-vectors of these electrons lie within the ellipsoid
of revolution corresponding to this energy. Accordingly, the k-values of the
holes lie within one of the two spheres or the two bodies bounded by the
warped surfaces.
218 Chapter 2. Electronic structure of ideal crystals
Figure 2.31: Band structure of Ge. The energy unit is eV. (After Chelikowsky
and Cohen, 1.974.)
2.8.2 Germanium
In Figure 2.31 the band structure of germanium is depicted. It is similar to
that of silicon, owing to the fact that both materials have diamond struc-
ture. The differences between the two band structures are, apart from other
reasom, due to the fact that the spin-orbit interaction is considerably larger
in the case of Ge as compared to Si (see Table 2.14). This results from the
larger orbital velocity of the valence electrons of Ge because of the larger
atomic nucleus of this element. With the regard of spin-orbit interaction
the valencp band maximum at r is formed by an upper 4-fold degenerate
rsf-level and a lowcr 2-fold degenerate I';-level, separated from the upper
level by 340 meV. Away from I',the upper I',f-level decompoaes into the two
2-fold degenerate bands of heavy and light holes of, respectively, A6 and A7
symmetry, As in the case of Si, the bands are warped but often considered
in an isotropic approximation.
The lowest conduction band level r, at 2! arises from the ri-level without
spin, which was the second conduction band level in the case of Si. In Ge this
level i s shifted down considerably so that it becomes lower than the r, and
,?I doublet which arises from the I'15-level without spin. The most important
2.8. Band structure of important semiconductors 219
i_
rial
.
Mimirnurn Gap hl
I_
II
Si A 1.1 1 0.044 0.54 0.15
GI2 L 0.66 0.29 0.3 0.044
GaAS r 1.43 0.34 0.45 0.087
GaP X 2.27 0.08 0.67 0.17
CdTe r 1.43 0.7 0.4 0.1
Figure 2.32:Band structure of 111-V semiconductors GaAs (top) and GaP (hot
tom). The energy unit is el. (AfLer Chelikousky rand Gohen, 1974.j
2.8. Band structure of important serniconductors 22 1
I 1 I
i r x U,K r -61
L A rI A XU,K E rI
Figure 2.33: Band structure of IT-VI sernimnductom Cdk (left) and IIgTe (right).
The energy unit is el.. (After Chadi, Walter, Cohen, Patroff and Balkanski, 2972.)
-2
I
L r X
lxc,
I
4
K.U r
Figure 2.35: Band structure of PbTe. The energy unit is eV. (After Martinez,
Schliiter and Cohen, 1975.)
the conduction band. Since it is degenerate with the uppermost valence band
at I', the fundamental energy gap is zero. According to the general definitions
of Chapter 1, this means that HgTe is no longer a semiconductor, because
in semiconductors the valence and conduction bands must be separated by
a finite energy gap. It is more fitting to term HgTe a semimetal.
12
-4
-8
r z H K r 1 - z H K r
Figure 2.36: Band structure of Te (left) and Se (right). The energy unit is eV.
(After Maurhke, 1 g71; Stuff, Maachke and Laude, i973.)
Chapter 3
Electronic structure of
semiconductor crystals with
perturbations
Real semiconductor crystals are imperfect. They differ from ideal crystals
in their atomic structure as they contain structural defects, and their chemi-
cal cornpodmn is not exactly lhal of the correspondiug ideal crystals. It is,
however, not the atomic structure which provides real semiconductor crystals
with special scientific and technological importance. but their peculiar elec-
tronic structure that is manifested in pronounced macroscopic effmts such
as. for example, the increase of electrical conductirity by orders of magni-
tude. With some justification one can even say that the particular scientific
and technological importance of semiconductors rests on the peculiarities of
the electronic structure of amperfeet semiconductor crystals. Nevertheless,
one must also deal with the atomic structure of imperfect semiconductor
crystals since that is, ultimately, the source of the particular nature of their
electronic structure. This will be done in section 3.1. The one-electron
Schrodinger equation of imperfect semiconductor crystals will be derived in
section 3.2. - 4 important
~ theoretical method or its solution, the so-called
effective mass theory, will be developed in section 3.3. This equation allows
one to determine the effects of perturbations whose interaction potentials
with electrons are slowly varying over the atomic length scale. Interaction
potentials of this kind apply to many perturbations of atomic structure, in
particular to the so-called shallow centers which will be treated in section
3.4. There are. however. also other perturbations. like the so-called deep
centers, to be dealt with in section 3.5, in which potentials exhibit consider-
able change over the atomic length scale. They cannot be treated by means
of effective mass theory, but require other methods. This is also true for
clean semiconductor surfaces considered in section 3.6.
226 Chapter 3. Electronic s-tnictirre of semiconductor crystals with perturbations
3.1.1 Classification of p e r t u r b a t i o n s
The perturbations to be treated can be classified in accordance with several
points of view. On the one hand, one can distinguish them on the basis
of whether they are of a purely chemical nature, or purely structural, or
mixed type. In the first case, only regular sites of the crystal are occupied,
but. not with chemically 'correct' atoms throughout. One refers t o this as
chemical or cornpositzonal dzsorder. In the case of elemental crystals, this
kind of disorder necessarily means the presence of impuaty atoms. In this
context the perturbed crystal, which hosts the impurity atom. is called the
host crystal. A crystal formed from a chemical compound may also exhibit
compositional disorder without impurity atoms, namely because of a per-
turbed stoichiornetrical composition. In the case of structural perturbations,
only chemically 'correct' atoms are present, but these are not always posi-
tioned on regular crystal sites but also on irregular ones. Furthermore, not
3.1. Atomic structure of red semicoriductor crystals 227
all regular siles are occupied by atoms, some sites remain empty. Structural
perturbations are also called strurtural & f w h or simply dpferts. The third
case is the most general one - regular or irregular sites of the crystal are
partially occupied by rhrrnirnlly wrong atoms, end also the correct atoms
partially occupy wrong sites.
Deviations from an ideal crystal may, on the other hand, be distinguished
according to the macroscopic extension of the perturbations. A perturbation
that is limited to one or a few neighboring regular or irregular crystal sites
is called 0-dimensional or a poznt perturbatzon. If the perturbation extends
over sites located on a line or a planc, it is referred to as a 1-dimensional
or lzne perturbatton and a 2-dimensional or planP perturbatton, rpspert ively,
Combining the two classification schemes, one may refer to structural point
or line perturbations, compositional point perturbations etc. The dimen-
sions in the second classification scheme apply to the microscopic core of
the perturbation. There may be smaller perturbations induced by that core
which extend in three dimensions. Examples are charged impurity atoms,
which, due to their long-range Coulomb forces, change the potential energy
of an electron even over distances large compared to the lattice constant.
Below we will characterize the various perturbations in more detail, start-
ing with point perturbations.
C a A s : S A (and
~ not GaAs : S G ~ )and
, the doping of GaAs with Si leads to
G a A s : Sica (and not GaAs : S ~ A ~ ) .
(2) An unoccupied regular crystal site is called a vncuncy, as depicted in
Figure 3. Ic. Tn semiconductors made of binary chemical compoiinds, one
has to distinguish between cation and anion vacancies, as shown Figure
3 . 1 ~ .Vacancies occur in all important semiconductor crystals; the general
symbol is V. The vacancy in Si is denoted by S i : c': the cation vacancy in
C h 4 s by G a A s : T;&, and the anion vacancy by GaAs : VA*.
(3)If the impurity atom does not occupy a repular crystal site but a site
between regdar ones, one has an interstitial ampurity atom (Figure 3.16).
In order for an impurity atom to stay at an interstfitrialsite, it must have
sufficiently low energy there. It is quite clear that this will be satisfied for
interstitial sites which either haw high local symmetry or which lie on a
bond between two at'orns. In thc latter case t,he crystal has bond centered
interstitiah. The high symmetry interstitial sites in t e t r a h d a l seniiconduc-
tors may be such with tetrahcdral local symmetry in the neighborhood of
the cation or of the anion (for group IV elemental semiconductors the latter
distinction is void, of course). Moreover, there are high symmetry sites with
hcxagonal symmetry. One refers to these7 respectively, as f e t v u h c h l and
hexagonal interatitiak The incorporation of impurity atoms on interstitial
crystal sites is especially likely when the impurity atom deviates relatively
strongly from the atoms of the host crystal as! for example, in t,he case of
transition metal atoms in semiconductors composrd of elements of the main
groups. The general symbol for an interstitial is I . An interstitid Fe atom
in Si on a tetrahedral site is denoted by Si : I;,.
(4) If a chemically 'correct' atom of the crystal occupics an interstitial site
rather than a regular one, one has a self-interstitial (as shown in Figure
3.le). In order for such a structural point defect to develop in a crystal,
there must h e enough space between the host ntmns, i.e., the crystal should
not be packed too densely. This happens, for example, in the case of tatra-
hedral semiconductors, particularly in Si and Ge which have purely covalent
b ondinE.
( 5 ) If,a crystal consists of two different chemical elements, then an atom of
the h s t may occupy a regular site of t h e sccond, and vice vcrsa Such point
perturbations are called antisite defects, as i l h s t r a t d in Figure 3 . 1 In
~ the
case of CiaAs, for example, a Ga atom may be located ttt an h - s i t e this is
~
called B I ~As-antisite defect,, and tla As atom may occupy a Cia-site - this is
called a Ga-antisite defect. The symbols are As& for the As-antisit>edefect,
and G U Afor ~ the Ga-antisite defect.
Interstitials, vacancies and antisite defects are structural point perlur-
bations, or point defects. The compositional point perturbations, i.e. the
3 . 1 . Atomic structure of real semiconductor crystals 229
Ideal crystal
A -Atom
4
0 B-Atom
Impurity atom
Vacancy (V)
Interstitial ( I 1
e)
Table 3.1: Electron corifiguratiori of main group elements. In the rightrnost column
the respective closed shells are indicated.
n Iron m o w
ziSc =Ti 23V z4Cr wMn mF'e z7cO Ni
3d4~3~ 3d248' 3d34s2 3d5& 3d"4s2 3d'4s2 3d74s2 3d64aa 3a23p6
era1 they are the not completely occupied oms. Because of the relation
R 2 I +
1 between the main quantum number ?a and the angular mornen-
turn quantum numbe1 E. the d-shells (I - 2) are possible only for n >_ 3.
the f-shells ( 1 - 3) only for n 2 4, etc. Accordingly, one has the shells
36,&, 4f, 5d, Sf, ;1g, 6 4 Sf, 69, fih ptc. Since among the first 98 elemmts of
Table 3.3: Electron configuration of rare earths and actinides. In the right column
the respective closed shells are indicated.
Actinides
232 Chaptcr 3. Electronic slructure of semiconductor cr,ystals with perturbations
the periodic tablc, however, the 5g-shell already remains unoccupied, only
d- and f-shells are to be considered, namely the d-shells 3 d , 44 5 d , 6 d , and
the f-shells 4f and 5 f . The filling of the 3d-, 4d- and 5d-shells takes place
in the series of transztzon metals (together with the Elling of the 4s-, 5s- and
6s-shells). Among the transition metals, one distinguishrs the iron groixp in
which the 3d- and 3s-shells are being filled, the palladium group in which
the samc happens with the 4d- and 4.s-shells, and the platinum group where
the 5d- and 5s-shells are being Elled. The 4f-shells are being filled in the
rare earth elements, and the 5f-shells in the actinides. In comparison with
the s- and p-orbitals, the d - and f-orbitals have a smaller extension in spacc,
they lie mostly within the s- and p-shells of the same main quantum number
'l'herefore, mainly s- and p-electrons are involved in chemical bonding.
7 ~ .
This explains the remarkable chemical similarity of thc rare earth elements
with each other, a n d a certain similarity of these elements with the elements
of the main groups.
Donor-acceptor pairs
When there are two vacancies, the mechanism for the formation of bound
pairs can also be easily undertitood the (internal) surfacc of thc crystal i s
reduced if two previously isolated vacancies move together to occupy neigh-
3.1. Atomic structure of red semiconductor crystah 233
boring cryYtal sites. One caIls this associate a ddvacancy. Analogous atate-
ments holds for the association of more than two vacancies, which are called
multrvarunczes.
Frenkel defects
If, in a crystal, an atom moves froin a regular site to an interstitial site, then
it h v e x behind a vacancy which attracts the interstitial. Thus a defect pair
is formed in this process which consists of a self-interstitial and a vacancy.
It is called a Freibel defprt.
There arr important puint perturbation complexes which occur only in
a specific material or matrrial group. We now consider some examples for
si snd G A S .
typical defect associate in GaAs and other Ill-V semiconductors is the com-
plex formed by an As-antisite defect (a Ga atom on an &-site) associated
with an As-interstitial. Now, this complex is believed to form t h e care of the
so-called b;L!Lcentei- in GaAs. This center manifests itself as deep level hav-
ing strong influence OR the electrical and optical properties of GaAs (more
detail on the EL2-rcnter may br found in section 3.5).
Latticc relaxation
this splitting proceeds such that the center of gravity of the levels remains
unchanged. Thus, along with levels shifted up, there are also levels which
are shifted down. If only the latter are predominantly occupied, then the
energy of the electrons localized at the point perturbation decreases. This
energy reduction can compensate the increase in total energy due to the
removal of atoms from their equilibrium sites. If this happens the relaxation
is energetically favorable and will take place spontaneously.
In the case of the Jahn-Teller effect, the displacements of atoms are of
the order of magnitude of one tenth of an Angstrom, i.e. they are relatively
small. Larger displacements, of the order of magnitude of one Angstrom,
are observed at point perturbations for which different atomic structures are
stable, depending on external conditions as, for example, the position of the
Fermi level. This phenomenon is observed at the D X centers in GaAs and
(Ga, A1)As mentioned above (see section 3.5 for more detail).
All of the above mentioned defects of ideal crystal structure may in fact
exist in real semiconductors. There are various reasons for their occurrence,
the most important and general being the second law of thermodynamics.
According to this law, the thcrrnodynamic cqiiilibrium state of a crystal at
temperature T and pressure p , is characterized by a minimum of the Gibbs
free energy G = H - TS. Here H is thc enthalpy and S the entropy of the
system. The entropy of a macroscopic state is proportional to the logarithm
of its microscopic realization probability (or thermodynamic probability)
and the proportionality factor is given by Boltzmanns constant k. The
system considered here is the totality of the atoms of the crystal. Lets
assume that there arc only chemically correct atoms, and that these are
randomly distributcd in space. Then the idedl crystal is formed wherein the
atoms move to the regular crystal sites. This corresponds to a very special
state of the system. It is extremely improbable compared to the large number
of states in which deviations from the ideal configuration of atoms appear
as described above. The entropy S of the ideel crystalline state i s smaller,
therefore, than that of the imperfect crystalline states.
The minimum of enthalpy II i s reached in the ideal crystalline state.
Since the entropy S takes larger values in other states, the minimum of H
is not necessarily coincident with a minimum of the Gibhs free energy G .
Depending on temperature, a minimum of G = H - T S can also be adjusted
for a state of the crystal which is less advantageous with respect to enthalpy,
but more advantageous with respect to entropy, i.e. for a b t a k with a non-
vanishing concentration of structural defects. As a concrete examplcs we
236 Chapter 3. Efectronic structure of semiconductor crystals with perturbations
As=kln[ J!
n!(J - It)!
1,
In a more rigorous treatment, the entropy of lattice oscillations has yet to
bP considered in AS, more accurately, the change of this entropy because of
the alteration of the spectrum of lattice oscillations in the presence oI the
vacancies. We will neglect this effect in what follows. What must, however,
he taken into account is the enthalpy Rf necessary for the formation of n
vacancy (at constant pressure). For R independent vacancies the enthalpy
requirement is n H f . Altogether, the gain of Gibbs free energy AG due to
the formation of n. vacancies becomes
Incorporation of impiirity a t o m s
stantially smaller. They lie in the region between lOI4 cm-3 in the case
of the elemental semiconductors, where the transition metal atoms can be
incorporated both substitutionally and interstitially, and 1017 ~ r n -in~ the
case of thc compound semiconductors where, as a rule, substitutional incor-
poration is preferred. Generally, solubilities for interstitial impurities depend
strongly on the sizes of the impurity atoms. Small atoms, like H, may be
interstitially incorporated in higher concentrations than larger atoms, such
as atoms of the transition metals. It is remarkable that rare earth atoms are
predominantly incorporated substitutionally in tetrahedral semiconductors
of the main group elements. This may be understood by means of the fact
that the not-yet-completed 4f-shells are smaller than the already filled 5p-
and 6s-shells, so that 3- and pshells are involved in chemical bonding, just
as in crystals of main group elements. The solubilities of the rare earths are
nevertheless relatively small, typical values being of the order of magnitude
I 014 cm-3.
There are various procedures to introduce impurity atoms into crystals.
The easiest one exploits the growth of the crystal from the melt: the impuri-
ties are added to the melt of the host material, &henthe melt is rooled down
to cause crystallization. Another method proceeds in the solid state: the irn-
purity atoms are diffused-in from an outer source. To speed up diffusion,
the crystal is heated. Besides the two processes mentioned, which introduce
impurity atoms under equilibrium conditions, there are also non-equilibrium
procedures to reach this goal, among them the so-called i o n i m p l a n t a t z o n
In the latter, the impurity atoms, after they have initially been ionized and
then accelerated by an electric field, penetrate into the crystal where they
are implanted. This implantation process must be followed by heating of
the crystal in order to heal out the defects which arise during implantation
(annealzng). The heating also makes it possible for the impurity atoms,
which were initially placed at sites relatively indiscriminately, to reach their
equilibrium sites. If the concentration of implanted impurity atoms should
be larger than the equilibrium solubility, the surplus atoms are later ex-
cluded from the crystal to a certain extent (precipitation). In many cases, a
relatively large number of surplus atoms remains in the crystal, which then
is in a frozen-in non-equilibrium state.
Point perturbations interact with the atoms of the crystal surrounding them.
Both the point perturbations themselves as well as the environment atoms
are in permanent motion because of the lattice oscillations. This results in
more or less chaotic forces on the point perturbations. Due to the effects
of these forces the perturbations move over to equivalent crystal sites in
adjacent primitive unit cells. This is referred to as a m i g r a t i o n of point
3.1. Atomic structure of real semiconductor crystals 239
impurity atom B Ga P H Au Cu
activation enthalpy (eV) 3.7 3.9 3.7 0.5 0.39 0.43
(3.11)
- _ _ _ Si_ Si_ _
Si Si Si Si Si
v; = v, pert -v,
v
Figure 3.3: Illustration of thc origin of long-range (left-hand side) and short-range
(right-haritl side) core perturbation potentials.
increasing distance fiorn the center than does tlic Coulomb potential of a
point charge, they are therefore described as short runqe. These arc also the
potential contributions, whicb in the context of the ibocoric impurity atoms
abovc, gave rise to central cell corrections.
The exact &termination of the pertrirhatiori potential is a problem which,
like the determination of the periodic core potential of an ideal crystal, can
ultimately be solved only by numerical calculations. These show, in fact,
that the pet turbation potentials of isovdlenl impurity atoms differ horn zero
substantially only over a distance of a few lattice constants. Consequently,
we have
Finally we foiego the requirement that the core charges of the two non-
isocoric atoms be the same. Examples of this most general case are Cd
atoms with their 2-fold core charge in a crystal of S i atoms with their 4-
fold core charge, or Sn atoms with their Cfold core charge on a G&site
in GaAs, thereby substituting a triply positively charged host atom core.
In these cases, the perturbation potential represents a superpobition of the
screened Coulomb potential (3.11), which accounts for the different core
charges, and a short-range potential which takes accoimt of all remaining
differences bctween the cores d5 well as aspwts of the spatial dispersion
of screening beyond those accounted for in equation (3.11). The effects
of the two potential contributions are not independent of each other. The
same bhort-range potential has a greater effect if the Coulomb potential, due
to a larger core charge difference between the impurity and host atoms, is
stronger. This comes about because the stronger Coulomb potential pulls the
electrons closer to the core, where the the short range potential is essential.
Just like the elwtron-core inteiaction potential, the Hartree potential
V,(x) and the exchangecorrelation potential V,,(x) also undergo chan-
ges in the prrsence of point perturbationb. Below, we describe these changes
for the Hartrre potential V I y t ( ( x )and the exchange potential V,((x) of
the liartree-Fock approximation. Similar results can be derived for the
exc~iaiig~rorrt~ation potential vzt(x)of the LDA mettiod.
Hartree potential
The Hartree potential V r t ( x z ) of the r-th electron is, as before (see relation
2.49), given by the expression
(3.13)
However, the oneparticle states $,(x2) here are not those of the ideal crystal,
but those of the pertiirbed crystal and the summation runs over the o n e
particle states u i occupied in the ground state of the pcrturbwl crystal.
From the physical point of view it is quite clear that the prrtiirbed rrys-
tal ~ H two
S kinds of stationary one-particle states; first, those with energy
eigenvalues which were already allowed for the ideal crystal, i.e. those within
the bands and, secondly, those with F I I C I eigenvalues
~~ within the energy gap
between the valence and conduction bands. The states of the first kind rep-
resent pure Bloch states only in zero-order approximation with respect to
the perturbation potential, while, in higher approximations, superpositions
246 Chapter 3. Electronic structure of semiconductor crystals with perturbations
(3.14)
with
extd
V g t d ( x i )= e2 / d3x'
k J
and
(3.16)
Here we assume that the electron i on which the potential acts is located at
the center. This assumption will also be maintained below.
The localized part VhOC(xi)of the Hartree potential depends on the num-
ber n of electrons at the center. There are two sources of this dependence.
First, the number of electrons which enter changes with n, Vfi"(xi)becomes
more repulsive if n is large, and less so if n is small. Second, the wave
'
functions of localized occupied states vLOC over which the sum in (3.16) is
extended, depend on n. They become more localized if electrons are removed
from the center, and less localized if electrons are added. One says that the
wavefunctions relax.
For reasons similar to those causing the localized part VhOC(xi)of the
Hartree potential of the perturbed crystal to depend on the number n of
electrons at the center, the extended part V;&(xi) also differs from that
of the ideal crystal, firstly, because the number N of extended electrons
is decreased by the localized ones and, secondly, because the states of the
extended electrons relax. The first change causes a relative potential cor-
rection of order of magnitude 1 / N and thus can be omitted (a comparable
3.2. One-electron Schriidinger eqmtim for point perturbations 247
(3.17)
Exchange potential
As we know from section 2.2, the exchange potential describes the Coulomb
interaction with the exchange hole which occurs because two electrons of the
same spin cannot reside at the same position. For the localized electrons of
the perturbed crystal, the positional uncertainty is smaller than that of the
extended ones. Accordingly, their exchange interaction will be stronger than
that of the extended electrons. It is therefore again expedient to decompose
the entire exchange potential V,Pt(x,),which an electron a localized at the
center feels, into the two parts V,..td(&) and l r ~ ( x of,
~ )respectively, the
(N - n ) extended and n localized electrons. We replace the extended part
by the exchange potential V x ( x i ) of the ideal crystal and simultaneously
substitute the localized part by an effective exchange potential Vi(xz).With
this replacement, we have
= VX(Xi)
v,pt(X,f + Vfi(X2). (3.19)
(3.20)
where the summation over k inrlirdes only particles whose spin W k equals the
spin LT? of particle i.
Substituting trhe three potential parts (3.91, (3.17) and (3.19) into the
oneelcctron Schrbdinger equation of the perturbed crystal, the various terms
may bc arranged such that the effective oneelectron potential E'(x} of the
ideal crystal (2.60)occurs. The equation reads
[ H f q x ) ] ls'v(x) - E U T h ( X ) , (3.22)
+
whcrt. I1 - p2/2na V(x), as bcfore. signifies the oneelectron Hamiltonian
operator of the ideal ciystal. The index i is omitted because all electrons
feel the same core perturbation potential. If only one particle is localized at
the center, equation (3.22) is exact.
Hartree energy
The energy correction due to the Hartrcc potential for an electron z in local-
ized stateqVt i s given in first order perturbation theory b - ~the rxpectation
valri~($V, 1 VAw I vv,).[!ring (3.181, this expression may be written as
3.2. One-electron Schrodinger equation for point perturbations 249
(3.23)
We extract the factor (E-'(x, x')/ I x-x' 1) from the x'-integral by evaluating
it at an average position X in place of x'. The remaining x'-integral yields 1
because of the normalization of the wavefunction @,,(x'). The integral over
X, multiplied by e 2 , will be denoted by Uy,, i.e. we set
(3.24)
With this, the expectation value of the perturbation of the Hartree potential
becomes
Exchange energy
Next we will calculate the corresponding energy correction due to the pertur-
bation of exchange potential V%{x)of (3.19). The latter depends on the spin
of the electron because. contrary to the ideal crystal case where the num-
bers of electrons with 'spin-up' and 'spin-down' are equal in ground state,
the corresponding numbers n~ and nl of electrons localized at the center can
differ. In terms of the total number n = n~+nl and the total spin projection
M S = (1/2)(nT - "1) of the localized electrons, the two partial numbers ny
and nl may be written in the form
1 1
"1 = - ( n
2
+
2 h l s ) , nl = -(n - 211iIS) .
2
(3.26)
For the expectation value (&,t 1 1 5 I iu,) of the perturbation of the exchange
potential, equation (3.20) yields the expression
I ~ I'+v,)
( ~ v , i -(no, - I ) J , f o r not 2 1. (3.27)
where g, is the spin quantum number of the state v,, and
(3.28)
longer true if the bonding is covalent or partially covalent. Then some of the
bonding electrons remain at the impurity atom, and the true number of its
elementary charges differs from V. The n valence electrons of the impurity
atom, which remain after the departure of the V electrons into the bonds
with the crystal, and are available for occupation of the localized levels in the
energy gap, are sometimes called active electrons. In the case of an impurity
atom with Vi valence electrons one has n = Vi - V active electrons.
So far, the charge state of the impurity atom prior to its incorporation
into the crystal was taken to be neutral. However, positively or negatively
charged ions can also be introduced into the crystal, and atoms introduced
in a neutral charge state can have electrons removed or added within the
crystal. Similar statements hold for structural defects. If a particular per-
turbation center X is not neutral for the lack of Q electrons, in the sense
just specified, one says that the charge state of X is Q and writes X ( Q )
(where negative Q mean surplus electrons). The charge state should not be
confused with the oxidation state. In the purely ionic case, the distinction
between the two can be expressed most easily: the charge state counts the
elementary charges of the atom outside the crystal, and the oxidation state
counts its elementary charges inside. Generally, the oxidation state of a cen-
ter in charge state Q will be X('+Q)+ if the oxidation state of the neutral
+
center is V . The reason is that, in this case, V Q valence electrons are not
available for occupation of localized states. The number n of electrons which
are available, i.e. the number of active electrons, amounts to Vi - (V Q )+
if V,, as before, denotes the number of valence electrons of the neutral im-
purity atom. The notations for the oxidation state and the charge state are
summed up in the common symbol X('+Q)+(Q+).
A simply ionized sulphur atom in a Si-crystal, for example, is denoted by
S5+(l+).Of the 6 valence electrons of the S atom, 6 - 5 = 1 are available
for occupation of localized energy levels in the gap, instead of 2 electrons in
the case of the neutral center S4+(O+). Transition metal (TM) atoms can
be installed in Si- and other tetrahedral semiconductor crystals both sub-
stitutionally as well as interstitially. The oxidation states V and, therefore
also the numbers n of electrons at the impurity atom, are different in the
two cases. For substitutional TM atoms, V equals the number of electrons
which are left at the atom after it is bound to the crystal. Interstitial im-
purity atoms are only weakly bound, i.e. the number V of electrons of the
T M atom which occupy bonding valence states, is almost zero. The oxida-
tion state is therefore T M o f . Oxidation and charge states coincide in this
case, and the number n of electrons at a TM atom equals the number of its
valence electrons. Interstitial Fe atoms in Si are found in the oxidation state
F e o f , substitutional in the oxidation state Fe4+. In the first case, n = 8
(six electrons in 3d-orbitals and two in 4s-orbitals), and in the second case
the value of n = 4.
With the background analysis set forth above, we are now sufFiciently p r e
pared to address t h e solution of the one-electron Schriidinger equation for the
crystal with a point pcrturbation. Which solution methods can be applied
with succcss depends decisively on whethe1 lhe core yrrt iulmlion potential
is long- or short-range. Of course, t h r lattice translation symmetry, which
drastically simplifirs the bolution of t h ~Schriidinger eqiiation hi the casr
of an ideal crystal is perturbed by both kinds of potentials. but only for
short-rangepotentials in an e s s e a t d mannet-. For long-range potentials the
dec iations from lattice trauslation symmetry are relatively weak. In this
case the Scfirodinger equation, in a certain sense, may be decomposed into
two quations, one for the periodic potential of the ideal crystal, which was
solved previously, and one for the perturbation potential. T he latter is called
the LPffectivemass equation, which we will derive in the following section.
tials, hilt also for macroscopic perturbations, such 8s that associatd with
an external electric Geld, which are smooth on the atomic length scale by
definition.
The goal of the following consideralions is l o simplify the oneelectron
Schriidingcr eyiiation
(3.29)
for t,he perturbed crystal in stages, so that., ultimately: a mare easily solvable
equation, namely the effective mass equation, results. In this mat,ter, we
will employ t,he fact that, in the vicinity of critical points of a certain band
v , the energy of an electron of an ideal crystal depends quadratically on
quasi-wavevector k, i.e. in the same way that the energy of a free electron
depends on its momentum. However, the free electron mass 7 n is replaced
by the effective mms rnc of the particular band and critical point chosen.
The e&ct.ivc mass includes the effects of interaction of the electron with the
periodic potential of crystal. Therefore, it is generally a tensor, and if il can
be reduced to a scalar maw, the value of the lat.ter generally differs horn the
mass of a free electron. Having in mind the effective mass description of the
band energy versus quasi-wavevector k relat,ion, one may suspect that the
influence of a perturbation potential V(X) on an &&on of the cryisla1 can
be calculated in an appr0ximat.e way as follows: One eliminates the periodic
potential of t h e oiic cltrtron Schrdinge~equation for the perturbed crystal!
while simultaneously replacing the free mass m in the kinetic energ); operator
by the effective mass m:. The resulting Schrodinger equation represents
the one-bend e#ective mass eyuatian in its simplest form It can be solved
much more easily than the original Schrodinger equation? which includes
the periodic crystal potential ill explicit form. For a siibstitutioiial P atom
in Si, for example. t.he effective mass equation is twsentinlly the same a8
the Schrodiuger equation for the hydrogen atom whose solutions are already
known.
The procedure described above needs, of COZITSC, further justificat.ion. To
provide this, quest,ions have to bc addressed which have been left, open so
far, for example, how the wavefunction of the e f l d i v e mass equation reiates
to the wavefunction of the original Schrodinger equation, and the matter of
what conditions must be placed on the perturbation potential V(x) and the
wavefunction 7;j(x)in order for bhe effectivp mass equation to be applicable.
expanding ~ ( xwith
) respect to the complete set of Bloch functions pvk(x),
whence
(3.30)
Since the (pYk(x) are eigenfunctions of H with eigenvalue E,(k), the Schrodinger
equation (3.29) takes the following form:
+
[ E y ( k ) 6 v f y f 6 k k ~ (vklUjvk)] (JklV) = E ( v k l $ ) . (3.32)
vk
To transform this equation into the effective mass equation, the assumption
made at the outset that U ( x ) should be a smooth potential, must be specified
further. This is done by assuming that the change of U ( x ) over a primitive
unit cell is small in comparison with the change of the periodic crystal po-
tential t ( ~over
) such a cell. To formulate the condition for smoothness in
this sense quantitatively, we decompose U(x) in a Fourier series, using the
same notation introduced previously in Chapter 2. We have
(3.33)
(3.34)
The sum in (3.33) is extended over the entire infinite k-space, meaning over
all Brillouin zones. Smooth functions U ( x ) in the above sense have Fourier
coefficients (klU) which, for large k-vectors, more strictly speaking, for k-
vectors outside of the first BZ,are small compared to the Fourier coefficients
(kll.) of the periodic crysta1 potential V ( x ) . The latter components were
calculated in section 2.4. According to formula (2.161), they are non-zero
only if k is a reciprocal lattice vector K differing from zero. This means that
the smoothness condition for U ( x ) may be expressed its
(3.37)
U v o k ( X ) ZS .mo(x). (3.38)
In the following subsection 3.3.2 we will see that the two last requirements
can be justified when eigenstates of the perturbed crystal exist having energy
eigenvalues just above and below the edge of band vo, and if only these
eigenstates are considered. If, additionally, the band edge lies at k : 0,
the small energy deviations also correspond to small k-values, and relation
(3.38) holds approximately. The restriction of the location of the band edge
to k = 0 can be omitted, and the derivation procedure can also be applied to
band extrema other than the center of the first B Z , the only modification
being the replacement, of the R X center k = 0 by the non-central critical
point k,as well BY of k by k - k, in the corresponding equations.
The above four conditions will now be used to simplify the Schrodinger
equation (3.32). Applying relation (3.38) the wavefunction (3.37) may be
written as
256 Chapter 3. Electronic structure of semiconductor crystals with perturbations
Tihe k-sum is the Fourier transform F,(x) of the function F,(k), whence
1
F,(x) = - CFvo(k)eik.x. (3.40)
& k
Therefore $ ( x ) may bc written as
$44 = ~ , O ( X ) ~ Y l ( X ) . (3.41)
The function F,(x) is termed the envelope functzon or, in short, the enve-
lope. The envelope function, by definition, i s a bmooth function. Equation
(3.41) means that the truc wavefunction + ( x ) is obtained by enveloping the
rapidly oscillating Bloch lactor uvgo(x) with the smooth cnvelope function
Fuo ( X ) .
The two ronditions conccrning the smoothness of U(x) and Fvo(x) make
it possible to represent the matrix element (uk(l/(vk)in the Schrodinger
equation (3.32) in a substantially simpler form. We rewrite this element
using thc Fourier representation (3.33) of U(x) and the product form of the
Bloch functions p v k ( x ) , obtaining
(vklUlvk)
1
= - C ( k - k + KIU)Ci$(K), (3.44)
f i K
wherein the notation for the so-called Bloch integral
(3.45)
3.3. Effective mass equation 257
1
(vklUlvk) N -(k - klU)C$t(O). (3.46)
a
Approximating the Bloch factors u,k(x) and U v l k t ( X ) by, respectively, ud(x)
and uU,o(x),and applying the orthogonality of the Bloch functions, the Bloch
integrals of equation (3.45) c : ~ : (follow
o ) as
c,,,
kk (0) = .6
t, (3.47)
Substituting this relation in expression (3.44) we obtain
One can easily prove that this transformation is correct by expanding E,(k)
in a power series and by using the identity
258 Chapter 3. Electronic structure of semiconductor crystals with perturbations
The second term on the left-hand side of equation (3.49) can be written in
the form
h2
E,(-iV,) = E,(O) + -(-iVx)2,
2mg
(3.54)
and
h2
[ L . d O ) - -a2
2m&
1
I U ( x ) F,(x) = E F , ( x ) . (3.55)
With the derivation of this equation, initially conjectured and now verified,
it, is quite clear that the influence of the perturbation potential can be ap-
proximakly determined from an equation in which the periodic potential
no longer appears and the effective mass replaces the free electron mass.
Equation (3.55) is therefore the desired effective muss equation The eigen-
function Fvo(x) of this equation plays the role of an envelope function for
the Uloch factor uvoo(x)in equation (3.41) for the true wavefunction $J(x).
Equations (3.53) or (3.55) are also called envelope function equatioas in t,his
context .
The essential requirements involved in the derivation of the effective mass
equation were the smoothness of the perturbation potential, the smoothness
of the wavefunction and its composition of Bloch functions from only one
band, as well as the k-independence of the Bloch factors. These assumptions
are decisive, and are often not fulfilled. Short-range perturbation potentials,
for example, are not smooth. Nevertheless, the effective mass equation (3.55)
is a suitable instrument for the solution of a series of important problems
of solid state physics. Point perturbations with smooth potentials are only
one example of this. Other problems which can be solved with the help
of the effective mass equation include artificial superstructures in a crystal
and external electric fields. These will be treated later in section 3.7 and
3.8, respectively, Also, the Coulomb attraction between electrons and holes
- which results in the formation of excitons as pointed out in Chapter 2 -
3.3. Effective m a w equation 259
?clW= cuk
(.kl$)(xtvk), (3.56)
and the Schrodinger equation (3.29) in this representation takes the form
where hi&8 are the elements of the reciprocal effective mass tensor accord-
ing to formula (2.337). Using the Ansatz (3.59) for '(vklp) and expression
(3.631 for l(vk)H]vk)', the Schrodinger equation (3.57) yields
262 Chapter 3. Electronic structure of semiconductor crystals with perturbations
This equation is in agreement with the effective mass equation (3.53) if the
latter has E,,,(--zV) replaced by a parabolic expression in the components of
-iV,refraining, however, from the assumption of isotropy of the band struc-
ture. If the effective mass tensor reduces to a scalar quantity ( l / m ~ & ) 6 ~ 0 ,
then (3.65)yields the effective mass equation in the form (3.55). The deriva-
tion of the effective mass equation based on k . p perturbation theory thus
produces this equation automatically in parabolic approximation. In the ear-
lier derivation of subsection 3.3.1, an effective mass equation was obtained
that did not yet contain this approximation, which was invoked only later.
The advantage of the derivation of the effective mass equation within the
framework of k * p-perturbation theory is clearly manifested when degener-
ate bands are considered, which we will address next.
Degenerate bands
We direct our attention to the valence band maximum of semiconductors
with diamond type structure (see section 2.7). Accordingly, we assume that
at k = 0 a degenerate band level E,(O) exists with either symmetry rhs
or r: depending on whether spin is omitted or not. First we consider the
case without spin. The three degenerate ,b'T Rloch states of energy E w ( 0 )
arc- distinguished, as before, by an integer index m. The Bloch functions
at k = 0 arc therefore written as ) o m O ) . If we are interested in eigcnstates
$(x) of the Schrodinger equation of the perturbed crystal whose energy
eigenvalues are expected to be near the valence band edge, we can represent
$(x) as a superposition of the Bloch functions Ivrnk)' in first order k . p
perturbation theory. Thus, we set
(3.66)
(3.67)
3.3. EEective mass equation 263
where the coefficients D;:, are defined in equation (2.342). The matrix ele-
ments '(vklUlvrn'k')' of the perturbation potential U follow from equation
(3.59). They vanish if v # wm'. For v = urn' they differ only from zero if
m = m'. With this, the Schrodinger equation (3.57) takes the form
+$
+ Ci(X)h,,!
1 Fm'(X) = E F m ( x ) .
@
(3.70)
($
follows. Using the notation D for the fourth-rank tensor D:fm, I
*
~ ~ l ~ =
for the unit matrix 6,i, and F (x)for the vector (F,(x),F,(x).F,(x)),t,his
equation may be written in matrix form as
(3.71)
In the case of the &I valence band the Hamiltonian matrix is given by rela-
t,ion (2.344). With t,his, the envelope function equation then reads, explicitly,
264 Chapter 3 . Electronic structure of semiconductor cry.staLs with perturbations
Here, derivatives of the type 62/6z2 are denoted by symbols like a;, and
those of type a 2 / d r d y by symbols like a&.
Consideration of spin leads to two changes. Firstly. one has to use spin-
dependent Bloch functions (sxlvmak0)' and, therefore, also spin-dependent
envelope functions Frrw(x, s ) , and secondly the spin-orbit interaction oper-
ator H,, is to be added to the Hamiltonian operator H . Thereby, Hk.p
U
becomes Hk.=, which has the consequence for D that the matrix elements of
p are replaced by those of ii from equation (2.353). If interference terms be-
tween the k ' p-interaction and the spin-orbit interaction H , are neglected,
the representation of the latter in the approximate Bloch basis leads to a
*
k-independent tensor Hs,.The envelope function equation then reads
+ =
1
--(L+ 5n/I)(d2+ a;)
6
- -(2L
1
3
+Mp:, (3.76)
The energy origin in (3.74) was moved to the valence band maximum, which
was previously located at A/3. The envelope equation (3.74) makes it pos-
sible to calculate acceptor states and hole bands in superlattices of the dia-
mond and zincblende type semiconductors. One can derive a similar equation
within the Kane model of the rs-valence-band-rs-conduction band complex
of zincblende type semiconductors.
3.4. Shallow levels. Donor and acceptor states 265
AZ = Z I - XI?, (3.79)
and assume that it is non-zero. The sign of AZ can be both positive as
well as negative. In this sense we can speak of positive and negative point
perturbations the point perturbation is positive if the core charge number
of the impurity atom is larger than that of the host atom, negative, if it
is smaller. For the pcrtiubation V,'(x) of the core potential, we m a y use
expression (3.11) which here we write as
(3.80)
In general, V,'(x) does not yet represent the entire perturbation potential in
the one-particle Schrodinger equation (3.21) for the perturbed crystal. One
still must add the Hartree potential Vh(x) and the exchange potential Vfr(x)
caused by other electrons localized at the center. For impurity atoms with
only one valence electron more or less than the host atom, these potentials,
as a rule, have the effect that only one electron or hole can be bound at the
center. For this one electron or hole, the Hartree and the exchange parts of
the perturbation potentials vanish, i.e. V,'(X) is itself the entire perturbation
potential, and the one-particle Schrodinger equation has the form (3.22). For
impurity atoms with lAZl > 1, Vb(x) and Vfr(x)do not vanish. The effect
of a non-vanishing VA(x) will be discussed later.
To solve the one-electron Schrodinger equation (3.22) with the potential
V,'(x) of (3.80), we may use the effective mass theory derived in section
3.3. Here, effective mass equations must be written down for those critical
points of energy bands where changes of the spectrum of energy eigenvalues
dae to the perturbation potential are to be expected. In Chapter 1, it was
pointed out that such changes occur at the bottom of the conduction band
and the top of the valence band - for impurity atoms with A 2 > 0 discrete
levels appear in the energy gap just underneath the conduction band edge,
266 Chapter 3. Electronic structure of semiconductor crystaIs with perturbations
and for impurity atoms with A 2 < 0 one has such levels in the energy
gap just above the valence band edge. Effective mass equations are needed,
therefore, both for the conduction band edge as well as for the valence band
edge. In writing down these equations we start with a simple twc-band
model. The minimum of the conduction band (vo = c ) , and the maximum
of the valence band (v, = w) are assumed to be non-degenerate and to lie
at k = 0. Furthermore, the k-dispersion of the two bands is assumed to be
isotropic and parabolic in the vicinity of k = 0, whence we have
(3.81)
Ti2
&(k) = -----k2, (3.82)
2m;
with rn; and ml, as effective masses of electrons and holes, respectively. In
reality, for many semiconductors such as Si and Ge. the conduction band
edge does not lie at k = 0. The valence band edge zs found at that point for
many semiconductors including the ones mentioned; but there is degeneracy
between heavy and light hole bands at k = 0. Nevertheless, we will initially
proceed with the above simplifying assumptions. The relevance and neces-
sary improvements of this idealized model are yet to be discussed separately.
For reasons which will become clear below, the model is often referred to as
the hydrogen model
(3.83)
(3.84)
(3.86)
3.4. Shallow leveb. Donor and acceptor states 267
Apart from notation, signs, and constant factors these are the Schrodinger
equations for charged particleu in the potential of a point charge, just like
in the case of the hydrogen atom. From experience in quantum mechanics,
we know that h r an dttrtlclite potential, there is a continuum of positive
eiierpy eigmvalues and, in addition, there ale discrete energy levels which
occur for negative energies. Fur repulbive potentials there are only pusitixe
energy eigenvalues, but no bound statrs at negative energies. From this it
follows that for a positive point perturbation (upper sign in equations (3.851,
(3.86)), discrete e n e r a levels are to b e expected just below the conduction
band edge, and for negative point pertiirhations such levels are exppctpd
just above the valence band edge. Thew dibcrele levels lie in the emrgy gap
between the conduction and valence bands where, as we know, no energy
eigenvalues can appear in an ideal crystal. We consider first the cwe of the
conduction band.
Conduction band
(3.87)
with
(3.88)
m - 0 reads
(3.89)
with
(3.90)
(3.91)
268 Chapter 3. Electronic structure of semiconductor crystals with perturbations
Compared with the width of the energy gap which is of order of magnitude
1 el/, the discrete energy level El lies closely below the conduction band
edge (see Figure 3.4). Even closer are the states with n = 2 , 3 , . . .. The des-
ignation shallow levels is used in this situation. The wavefunction for energy
level El decays exponentially with distance from the core of the impurity
atom with the characteristic decay length a g . In contrast to band states,
which are evenly spread out over the entire crystal, we have, therefore, lo-
calized electron states (see Figure 3.4). The localization radius a g is clearly
larger than the distance between two crystal atoms, which is approximately
2.5 A. This means that the localization of an electron at an attracting
impurity atom is weak if considered on the interatomic length scale of the
crystal. Exactly this is to be expected considering the smoothness require-
ment made at the outset, which states that only Fourier components of small
wavevectors k should contribute to the wavefunction. We can also examine
the validity of this requirement quantitatively. Omitting a k-independent
factor, the Fourier transform of Fcloo(x)is given by the expression
(4.93)
AZ a 0 dZ.0
L1 O k r\ O k
Valence band
For a negative point perturbation there appear discrete energy lpvels in the
energy gap closely above the valence band d g r . The energies ol thew levels
are given by the exprcssiorrs
EB
En - -
z, ' (3.94)
(3.95)
The pcrtinent wavefunctions are localized at the perturbation center. The
wavefunction of the ground state, n = 1 and 1 = m = 0, has the form (3.89)
270 Chapter 3. Electronic structure of semiconductor crystals with perturbations
with
(3.96)
as the effective Bohr radius. In Figure 3.4 (lower part) the energy levels and
localization regions are shown schematically.
Although the population of energy levels by electrons will not be treated
systematically until the next chapter, we wish to deal now with a special
case, namely with the occupation of the shallow impurity levels discussed
above at absolute zero temperaturc, 7 = 0 K . This consideration will lead
us to a better understanding of the nature of these impurity states. First of
all, wc assume the case of a positive point perturbation, i.e., the core charge
number 21 of the impurity atom is taken to be larger than the core charge
number Z H of the host atom. For simplicity, we assume 21= ZH 1. Then+
the impurity atom also has one valence electron more than the host atom.
To be specific, we can imagine it as a P atom in a Si-crystal. According to
Levinsons theorem, which mandates that the total number of states must
remain the same both with and without perturbation, one can proceed on the
assumption that nothing will change due to the impurity atom regarding the
number of states in the valence band. Therefore, all the valence electrons of
the host atoms and all those of the impurity atom, except for the additional
electron, can be placed in the valence band. The additional impurity electron
has to reside in the lowest unoccupied energy level. That is the shallow n =
1-level just below the conduction band edge which, according to the above
results, arises from the impurity atom. The resulting occupation is shown
in Figure 3.4. If the temperature is increased this electron can easily be
excited from the shallow level to the conduction band. There, it is no longer
localized but spread out uniformly over the whole crystal. representing a
freely mobile negative charge carrier. The shallow energy level therefore
functions as a donor of a free carrier. One calls it a donor level and the
impurity atom itself as a donor. One can also say that a donor atom (with
AZ = 1) has one surplus valence electron which is bound relatively weakly
and can be transferred easily by thermal excitation to the conduction band.
The impurity atom remains in the single positively charged state, i.e., it is
singly ionized. For A 2 2 2 one has doubly or multiply ionizable donors. We
will discuss this later more exactly.
Next, we consider an impurity atom with Z I = Z H - I, i.e. with one
positive elementary charge in the core and, with this, also one less valence
electron than in the host atom. Due to the substitution of a host atom by
such an impurity atom, the number of states in the valence band decreases
- according to Levinsons theorem by one if only the n = 1-level is counted.
With this, the number of valence band states is still large enough to host all
3.4. Shallow Jevels. Donor and acceptor states 271
valence electrons, but, also, there remain no unoccupied states in the valence
band. The n = 1-level in the energy gap remains empty at T = 0 X. If the
temperature is increased, an electron from the valence band can easily be
excited into the impurity level. The level accepts an electron, it functions
as an acceptor. In the valence band itself, a hole remains which, as we
know from Chapter 1, behaves like a positive freely mobile charge carrier.
Consequently, we can also say that, under thermal excitation, the acceptor
transfers a hole to the valence band, whereas at T = 0 K the hole was
bound to the acceptor. This picture corresponds to the model of a negatively
charged point perturbation which binds a positive hole and transfers it to
the valence band under excitation. The analogy to the positively charged
donor center which binds an electron and donates it to the conduction band
is obvious. Similar interpretations are available for doubly and multiply
ionizable acceptors.
Donors
rx
k j
h2
-
2
[
(k - kilMClk - ki) 6ij6kkl + (klVlk)] Fj(k - kj) =
= EFi(k - ki), (3.98)
where Mi is the effective mass tensor of valley i.
The wavevectors k - ki and k - k j vary in a small neighborhood about
the zero point, i.e. k and k are vectors near the respective minima ki and
kj. For i # j , the matrix elements (kJVJk)of the perturbation potential
V(x) can approximately be replaced by the k- and k-independent expres-
sions (kilVlkj). The latter can easily be transformed into coordinate space
where they result in an additional 6-function-like potential. With i = j , the
matrix elements (kJVJk)result in the perturbation potential V(x) which
is already present in the hydrogen model. The effective mass equation (3.98)
in coordinate space thus reads
= EFi(X). (3.99)
If V(x) is the screened Coulomb potential of equation (3.80), as was as-
sumed, the absolute values of the inter-valley Fourier components (kilV1kj)
are negligibly small in comparison with the intra-valley Fourier components,
because of the large wavevectors ki - k j occurring in the former combined
with the (l/lkl)-dependence of (klV) on k. However, as we know from sec-
tion 3.2, the true perturbation potential V(x) differs from the pure Coulomb
potential, because the screening of a point charge by the semiconductor is
wavevector dependent, and on the other hand, because V(x) contains a
short-range part, which cannot be traced back to the potential of a point
charge in any way. Both modifications can cause the inter-valley matrix
elements (hlVJkj) of V(x) to take larger values. Nevertheless, they still
remain so small that they can be considered by means of perturbation the-
ory. In zero-order approximation they may be omitted completely. Thereby,
one obtains a separate effective mass equation for each valley from (3.99).
In case of k, = ( O , O , k z ) , it reads, in coordinate space
3.4. Shallow levels. Donor and acceptor states 273
Analogous equations hold for the other valleys. This means that, neglecting
inter-valley coupling, all valleys give rise to the same donor level.
Inter-valley coupling
- 0.03
-0,04
-0.05
O b b c b b
b O b b c b
b b 0 b b c
c b b O b b 7 (3.101)
b c b b O b
b b c b b o
b = fi(k~lv'lky)l~z(0)12,
r = ~t(kzIv'lkz)l.)IFz(0)12 (3.102)
_ _ Lines and columns in (3.101) are written in the sequence
have been-used.
k,, k,, kzrk,, k,, k,. The matrix (3.101) has the three eigenvalues
A&I = 4b + C, 1 - fold
AEz = -2b + C, 2 fold
AEg - -c, 3 - fold (3.103)
3.4. Shallow lwels. Donor and acceptor states 275
(3.104)
With this, one obtains b as -2.36 mel and c as -1.2 met. This yields
AEl = -10.8 meV. A E z = 3.6 met and AE3 = 1.2 meV.
A 3-fold splitting of the P-donor ground state level in Si has, in fact,
been observed experimentally (Aggrawal and Ramdas, 1965). The simple
theoretical estimate presented above agrees remarkably well with the ex-
perimental splittings of 11.6 meV between the A l - and T2-levels, and of
1.3 meV between the E - and T2-levels (not resolved in Figure 3.5). The
results of a numerical treatment of inter-valley coupling shown in Figure 3.5
are even closer to the experimental values. However, the agreement is not
as good for the absolute position of the ground state level. The addition of
A E l , i.e. of 10.8 meV to the binding energy of 29 meV without inter-valley
interaction yields a corrected binding energy of 39.8 meL which is closer to
the experimental value of 45 meV, for Si:P but still clearly below.
Chemical shifts
Table 3.5: Experimental binding energies of several shallow donors and acceptors
in Si, Ge and GaAs. (After Landoldt-Bornstein, 1982.)
Material
Si
Sb Ga
In 153
P 13 B 11
Ge As 14 A1 11
Sb 10 Ga 11
Bi 13 In 12
GaAs
ionizable donor and acceptor atoms in Si, Ge and GaAs. Not only are the
absolute values of these energies striking, but also the fact that they are
not equal for donor or acceptor atoms of different chemicals stands out.
Contrary to the prediction of the above theory, there are dependencies of
binding energies on the chemical nature of the impurity atoms. One refers
to these as chemical shifts.
The absence of chemical shifts in the calculated binding energies is a
consequence of the approximation of the perturbation potential V(x) as a
purely Coulombic potential in the hydrogen model. As we know from section
3.2, the correct perturbation potential of an impurity atom also contains a
short-range part, to which all central cell corrections contribute. Among
these, there are also contributions which depend on the chemical nature of
the donor. The latter are the main reason for the experimentally measured
chemical shifts of the donor binding energies. The effects of central ceE
corrections are particularly large in the case of the 1s-ground state, as one
can recognize from Figure 3.5 for the special case of the P-donor in Si. A
weaker influence, and, accordingly, better agreement between experiment
and the predictions of a theory omitting central cell effects occurs for the
excited states with n = 2 , 3 , . . .. This is to be expected since the excited state
wavefunctions have maxima that do not lie at the perturbation center x = 0
3.4. ShalIow levels. Donor and acceptor states 277
(which does happen in the case of the ground state) but further outside.
Electrons in the excited states are therefore less affected by changes of the
potential in the central cell than are electrons in the ground state.
Generally, the occurrence of pronounced chemical shifts means that the
perturbation center is no longer shallow and the effective mass theory is no
longer applicable for its theoretical treatment (see section 3.5 for further
discussion).
Acceptors
Corrections to the simple hydrogen model are also necessary for acceptors.
Of course, the maximum of the valence band lies in the center r of the first
B Z for all diamond and zincblende type semiconductors, as is assumed in
the hydrogen model. However. this maximum is degenerate: depending on
whether spin-orbit interaction is important or not one has, respectively. the
%fold degeneracies of the representations l'b5 (diamond) or (zincblende)
in the space of scalar functions. or the 4-fold degeneracies of the representa-
tions I?$ (diamond) or Ts (zincblende) in the space of twc-component spinor
functions. In the vicinity of r, this degeneracy splits off and one has ihree
or two anisotropic valence bands. In section 2.7 these were approximated by
two isotropic parabolic bands. one for heavy holes and one for light holes.
If one also uses this approximation here, then there are two hydrogen-like
series of acceptor le\-els, one for each sort of holes. Calculating acceptor bind-
ing energies by means of expression (3.95) in the case of Si yields 50 met7
for heavy holes which are expected to form the ground state. In the case
of Ge. the result is 17 meV for heavy holes. One can hardy expect these
values to be in agreement with experiment. In fact, they differ apprecia-
bly from the measured ground state binding energies shown in Table 3.5.
Evidently. non-parabolicity and anisotropy of the band structure play an
essential role and must be taken into account in realistic calculations. This
may be done by means of the multfband effective mass theory developed in
the preceding section. Below. we will explain the application of this theory
to simply ionizable acceptors in Si. Owing t o the small spin-orbit splitting
energy A of 44 meV and the relatively large acceptor binding energies E B
(68 me\' for the isocoric impurity atom Al). spin-orbit interaction initially
will be neglected. Later this approximation needs to be corrected since E g
is not much larger than A. Without spin and spin-orbit interaction the
wavefunction ~ A ( x ) is a linear combination of the three Bloch functions
(xlumO),m = x. y, z of the representation Ti,, which are enveloped by the
*
components F,(x) of the envelope function vector F (x). Thus
(3.105)
278 Chapter 3. Electronic structure of semiconductor crystals with perturbations
(3.107)
3.4. Shallow levels. Donor and acceptor states 279
(3.108)
shown in Table A.27 of Appendix -4. Relation (3.108) determines the symme-
tries of the three-component auxiliary functions under rotations, therefore
the angular dependencies of these functions. In order to also get their ra-
diaI dependencies one expands the rl-, r12-, and ri5-functions with
respect to angular momentum eigenfunctions with the various quantum num-
bers 6, rn and multiplies the expansion coefficients of different values of I by
corresponding radial wavefunctions r1exp(-T/q). These are formed in anal-
ogy to the eigenfunctions for the Coulomb potential, but with &dependent
localization radii rl. The latter are treated as variational parameters, just
like the Coefficients of the auxiliary functions belonging to different irre-
ducible representations. Applying this procedure to the acceptor ground
state of Si, a binding energy of 31 me&' is obtained (Schechter, 1962). More
recent calculations, taking spin-orbit interaction into account, have resulted
in a value of 44 mel/ (Baldereschi and Lipari. 1977), which is very close to
the experimental value of 45 meV for 3 in Table 3.5 but, of course, does not
account for the pronounced chemical shifts seen in this table.
Calculations of acceptor binding energies have also been performed for
materials like Ge whose spin-orbit splitting energies are large compared to
the acceptor binding energies. Spin has to be taken into account under
such circumstances, i.e. the T'& valence band has to be replaced by the two
rg- and r$-bands. Owing to the large spin-orbit-splitting energy, however,
the spin-orbit-split I'F-band can be omitted. For the expansion of the 4-
component envelope function of the remaining rg-band one needs auxiliary
functions of + +
x I'i = ri fk + +
2r15 2r25 symmetry (see Table
280 Chapter 3. Electronic structure of semiconductor crystals with perturbations
is taken into account, then the 1s-level is shifted up by just this energy
Us.By exciting one electron into the conduction band, the neutral S-donor
3.8. Deep lewls 28 1
S(D+) bccarnes a single positively charged S(1+) donor. For the Is-lad
01 h e S ( l 1 ) ioii thr shift in energy by Us do= not occur. Thus this level
i s shifted down by I/, in comparison with the 1s-level of tbc S(0 +-) atom.
Exprrirneniully, one finds t,hat the ionk-ation energy of the neutral S(O+)
donor is 0.31 eV, and the ionization energy of the S(1t) donor j s 0.69 eV
(see Figure 3.6). From thefie values a Hubbard energy I i , of 0.28 eV may
be deduced. IIowever, both ionization energies are suhstantially larger than
the result. 4 x 0.03 el7 = 0.12 eb which follows from the hydrogen model.
Evident.ly, the central cell short-range poteniid cont,ribution is ewedial in
the case of the S-donor in Si. l l i s donor is a deep center rather than a
shallow me.
part of the potential increases, then a point will be reached at which the
short range potential is itself able to bind states. Provided the pertinent
binding energy i s Iargcr than that due l o the Coulomb potential, binding to
the center will be dominated by the short-range potential contribution, and
the chararter of the bound state will change. The spatial cxtension of the
eigenfunctjon of the ground state is then no longer dekrrninml by the Bohr
radius, but by thr lattice constant. The Coulomb potential only leads to
corrections to t h r binding energy and the cigmfunctions, which are mainly
determined by the short-range potential alone.
States which are primarily bound by the short range potential part, are
termed d w p . h e rorresponding la-& arc called deep levels, and the point
perturbations at which they occur, are called as deep centers. Literally, the
term deep level refers to an energy eigenvalue that lies deep in the energy
gap, far away from the two band edges, in contrast to shallow levels which
lie close to one of these edges. Actually. the location of deep levels deep
in thr energy gap is only a particularly important special case. as there
are also yet other case. - derp levels can also be close t o or even wzthm
one of the bands. The essential features of deep levels are their binding
by a short-range potential and, in combination with this, their localization
radius bring restricted to magnitude of the lattice constant. Because of their
strong localization, deep states resolve the spatially periodic fluctuations of
the rrystal potential while the eigenfunctions of shallow levels average them
out. The shallow levels can therefore be treated by means of an effective mass
equation. in the case of deep levels the requirements of effective mass theory,
namely smoothness of the perturbation potmtial and of the corrpsponding
wavefunction, are not fulfilled. Contrary to the assumptions of PEective mass
theory, these states cannot be s p t h e s i z d by Bbch functions of k-vectors
drawn from a small vicinity of a rritical point, and also not from Bbch
functions of only one-band. In a theory of deep states, therefore, neither the
effective mass is meaningful, nor can such a theory be based on a oneband
equation, not even a degenerate multi-band equation. Attempts t o retain
the effective mass concept and to consider solely ihe multi-band character
of deep level theory met with little success. In this context one can say that
skidow levels are eigenvalues of point perturbations which are capable of
description by means of effective mass theory (the concomitant short-range
potential contribution can be treated by rncans of perturbation thcorg in this
rase), while deep levels are eigcnvaliies whose treatment by effective mass
theory is impossible.
The discussion above is amply intuitive. it anticipates, in part, results
which are i n d d plausible, but which have yet to be proven rigorously.
This applies, in particular, to the fundamental feature which distinguishes
between shallow and deep levels, namely, that short-range potentials can
dominate binding only if they exceed a minimum threahold potential strength
283
2 1 0 -2 -4 -6
.3
Acceptors 2
.4 - - - _ aF:
.-
.5
.6 (eV)
2 1 -2 -4 -G -8 -1OleV)
Atomic Electronegativity
- in the discussion above, the periodic potential of the crystal was omitted
from consideration. An experimental proof of the threshdd behavior of
short-range potentials in crystals may be taken from Figure 3.6. There: the
ionization emrgies of a series of substitutional impurity a t o m are plotted
as a function of the difference! between the atomic valence shdl energy levels
of the host and impurity atoms. This difkrence can serve as a measure of
the strength of the short-range potential. The fact that for donor states
284 Chapf,er3. Electronic structure of semiconductor crystals with perturbations
the diffrrence of 8-levels is taken, and for acccptor states the differenre of
p-levels, is not important foi the present discussion (we will return to this
point later). With increasing horizontal scparation of the impurity atom
from the host atom in the periodic table, the potential strength increases
more or less continuously. The ionization energies initially retain their small
valucs characteristic of shallow lcvels, Starting at a threshold distanre, they
suddenly become substantially larger, a manifestation of the fact that the
short-range potential has takm over binding and the level has become deep,
.Just like shallow levels, decp levels can also act as donors or acceptors
(sometimes even as both of them). Due to their mostly larger separation
from the hand edges they are, however, generally less effective than shallow
levels in enhancing the concentrations of free charge carriers. They exhibit
their greatest efiectiveness in just thp opposite process, the lowering of free
carrier concentrations for which, in turn, shallow levels are not very effective.
If, in addition to the neutral center, the single negatively charged center also
forms a deep level in the gap with sufficient separation from the conduction
band edge, the neutral center will capture electrons from the conduction
land, which are available there eithrr as equilibrium charge carriers due to
n-doping, or ~ L non-eyujlibiium
Y cariiers due to optical or other excitation of
the semiconductor. In the first case, one has a c o m p e ~ w u t i o nof the donors
by the deep center (for more 5ee Chapter 4), and in the second case, a cup-
ture of non-equilibrium electrons by the center (see Chapter 5). A center
which forms deep levels in the gap both in the neutral and simply posi-
tively charged state, plays an analogous role in regard to the compensation
of acceptors and the capture of non-equilibrium holes. Centers which can
capture both electrons as well as holes act as catalysts for the radiation-
less recombination of electron-hole pairs (see Chapter 5). If one wants to
enhance radiative recombination as strongly as possible, such as in semi-
conductor light emitting diodes or laser diodes, non-radiative recombination
processes have to be avoided, which involves the elimination of the corre-
sponding deep centers. On the other hand, if one is interested in having a
short lifetime for non-equilibrium charge carriers, as in the case of fast tran-
sistors and photodetectors, one should intentionally introduce deep centers
in order to enhance non-radiative recombination. In general, deep centers
play a role of similar importance to that of shallow ones for semiconductor
devices, although in a completely different way.
Having discussed the general character and importance of deep centers,
we now will treat their electronic structure. In subsection 3.5.2 we will de-
velop a simple model of a deep center, the so-called defect-molecule model.
In subsection 3.5.3 we treat some methods of solution of the one-electron
Schrodinger equation for deep centers. The consequences of many-electron
effects in the electronic structure of deep centers will be discussed in subsec-
tion 3.5.4. In section 3.5.5 we display experimental and theoretical results
3.5. Deep levels 285
for selected deep centers, among them the vacancy in Si. the substitutional
impurity at,oms of the main groups of the periodic table. the group of 3d-
transition metals. and the group of rare earths. Also, we discuss the D X -
center and the EL2-center in GaAs.
Vacancy
erations make clear that the origin of the vacancy is not important, whether
it originated by removal of a Si atom from sublattice 1 or from sublattice
2. Here, we consider the removal of an atom from sublattice 1, and to be
still more specific, from the primitive unit cell at R = 0. The perturba-
tion potential V(x) is the negative of the potential produced by this atom
in the crystal. Because of the removal of the 1-atom, the hybrid orbitals
lht2Rt),t = 1 , 2 , 3 , 4 , of the four surrounding 2-atoms in the unit cells Rt,
pointing inwards, no longer have a hybrid orbital of a 1-atom to which they
can bind. They are called danglzng hybmds. The three other hybrid orbitals
at a surrounding 2-atom interact with inwardly directed hybrid orbitals at
atoms lying still further away (these atoms are not shown in Figure 3.7).
The hybrid orbitals at a pal ticular siirrounding 2-atom also interact among
themselves, including the one dangling hybrid at this atom. This means that
the dangling hybrids are coupled to the entire crystal through nearest neigh-
bor interactions. If interactions between hybrid orbitals at the same atom
are omitted, i.e. if the matrix element V1 introduced in section 2.6 is set to
zero, which means - cp, then the dangling hybrids are decouplcd from the
remainder of the crystal. They still interact only among themselves. Since
the atoms at which these hybrids are located are second-nearest neighbors,
this interaction is not within the framework of Erst-nearest neighbor inter-
action which we have been exclusively considering in the treatment of an
ideal crystal in section 2.6, but, rather, it ha6 the sense of second-nearest
neighbor interaction. The latter must be taken into account here in order to
arrive at non-trivial results.
we can refer to the first partial system as a vacancy molecule: and to the
second the rest-of-crystal. This designation also encompasses h e term
tts
defect molecule model for the tight binding approximation described above.
For each hybrid of the rest-of-crystal another hybrid exists in the rest-
of-crystal which points to it. The Hamiltonian matrix elements between the
various pairs have the same value, namely the value given above in equation
(2.292) defining matrix element T/2. The energy spertriim of the rest-of-
crystal is therefore identical with t , h d of the infinite idea1 cryslal in bhe
simplest TB approximation? consisting of the bonding level t b = th - IVzl,
+
and the anti-bonding level E, = E,+ I&I. The splitting of these highly
degenerate levels into bands remains incomplete because of the neglect of
Ihe interaction between hybrids at. the same &om? i.e. the neglect. of r/l.
In calculating the energy spectrum of the first partial system, i.c., the
vacancy-molecule, we need the matrix elements of the pertarbed Hamilta-
nian H + V of the crystal with vacancy. The diagonal elements (ht2RtlH +
Vlht2Rt) are simply the hybrid energies ~h since the elements (h,t2Rt(V
lht2Rt) of the vacancy potential V between hybrid orbitals localized off the
%mancysit.e are small. One therefore has
(3.113)
(3.114)
IEY)=
Jz [IIZL~RI)
- IhaZRz)], (3.116)
1
IE,
VaC
) - -[ I ~ I ~ R
- IJh2R3)]
) I (3.117)
v5
~
1
138"")= - [lh12R1)- lh42R9)]. (3.118)
45
One can easily demonstrate that IEI") belongs to the irreducible represen-
tation A1 of the symmetry group Td of the vacancy, and the three functions
IE$uc), IEY'), IEiWc)to the irreducible representation T2 of this group (see
Table A.6 of Bppendix 4 ) . The eigenfunction of the A1-level resembles an
atomic s-orbital of a Si atom. and the three Tz-eigenfunctions are similar to
the three p-orbitals of such an atom. Evidently, the sp3-hybridization of the
atomic orbitals in a Si crystal is removed at a vacancy. The states are more
atom-like. in consequence of the fact that the crystal potential is no longer
fully effective in the vicinity of a vacancy.
In Figure 3.8. the e n e r e spectrum of the defect molecule model of a
vacancy is shown along with that of the rest-of-crystal. The A1-level lies
below the Tz-level because of the negative value of Vt-. Whether it lies
below or above the bonding level of the crystal depends on whether we
have 31W1 < l\Jzl or 31WI > lF'21. The question of whether it is found
in the valence band or in the energy gap, cannot be answered within the
defect molecule model because. therein, the valence band has shrunk to the
bonding energy level. It is just as difficult to decide whether the Tz-level lia
in the conduction bend or in the energy gap. Experiment and more exact
calculations, which we will discuss later in more detail. show that the -41-
level lies in the valence band. and the 7'2-level in the energy gap. With this,
3.5. Deep levels 289
Figure 3.8: Energy spectrum of the defect molecule model of ~ 1 .Si-vacancy along
with that. of the rest-of-crystal. The distribution of thc 4 electtona of the defect
molecule over the energy levels is also shown.
the T2-level is the actual deep level of the vacancy. Of the four electrons
of lhe neutral vacancy - each of the four dangling bonds yields one two ~
must he hosted by this lcvcl while the other two occupy the A1-level in the
valence band. IJsing the terminology introduced above, we may say that the
oxidation state of the neutral vacancy is V2+.
The defect moleciile model of the vacancy reflects the actual relation-
ships remarkably well. In any case it, provides a qualitatively correct phys-
ical picture of the electronic structure of a vacancy in group-IV elemental
semicondiictors. Refinements of this picture will be discussed further b e
low. Here we treat a second example to illustrate the defect molecule model
which emerges from the v.mancy by occupying its empty lattice site with an
impurity atom.
pointing toward each other, and W describes, as in the vacancy case, the sec-
ond nearest neighbor interaction between differing host atom hybrid orbitals
+
pointing toward the impurity atom. All elements ( h t j R t l H VlhtJRt,)not
listed above are neglected, among them also the Vl-like elements (htzRt(H +
Vlht,i&,) between different hybrid orbitals at the impurity atom, i.e. with
t f t. With these approximations, the Hamiltonian matrix of the defect
molecule may now be written down in explicit form. In doing so the rows
and columns are ordered in the sequence IhliRl), lh2iR2), lh3iR3), lh4iR4),
lh12R1)) lh22R2), lh32R3), I@&), and the Hamiltonian matrix is
L i 0 0 0 1720 0 0
0 e,O 0 0 vzo 0
0 0 6 i 0 0 0 v20
o a o a o v2 (3.124)
v2a o o ; W W W
0 v2o 0 W E k W W
0 0 v20 W W E k W
(0 0 0 I$ w w w e;.
This matrix has four distinct eigenvalues, two simple and two triply degen-
erate. The eigenfunctions of the two simple levels (we distinguish them by
indices b and a ) belong to the 1-dimensional irreducible representation A1 of
the tetrahedral group T d , and the two triply degenerate (again distinguished
by indices b and a ) belong to the 3-dimensional irreducible representation T2
of T d . The corresponding energy levels are, respectively, denoted as EiT/b
and E&Y:,b, whence
In Figure 3.10 these levels are plotted as functions of the difference ( c i - E);
between the hybrid energies of impurity and host atoms. This difference rep-
resents a measure of the strength of the short-range perturbation potential
of the impurity atom. In order to better understand the physical meaning of
the energy levels derived above, it is helpful to consider two limiting cases.
First, we assume the impurity atom to coincide with the host atom, which
means t i = c.; If one also neglects the second nearest-neighbor interaction
energy W , then the energy spectrum of the perturbed crystal of equations
(3.125) and (3.126) must coincide with that of the ideal host crystal in the
292 Chapter 3. Electronic structure of semiconductor crystals with perturbations
(3.127)
(3.128)
we have
EiT = tk + 3W, (3.129)
3.5. Deep levels 293
zmp = Ezmp ~
(3.130)
EAlb Tzb - + --O0.
In the limiting case t i -+ +m, the two anti-bonding levels EiT and EkYZ
of (3.127) tend, along with t i , toward 00, i.e. leaving the energy spectrum
on its high energy side, while the two bonding levels EiY and EkYl limit
toward, respectively, the two Al- and Tz-levels of the vacancy of equations
(3.113) and (3.114). This is understandable because the limiting case EL ---f
+m means that no impurity hybrid energy level exists at finite energy and,
therefore, there is also effectively no impurity atom. In other words, there
is a vacancy.
With E ; -+ -m the two bonding energy levels EiY and E$T leave the
energy spectrum at its low energy side, while the anti-bonding levels limit
toward the two A l - and T2-levels of the vacancy of equations (3.113) and
(3.114). This occurs for the same reason as above in the limit t i -+ +m,
namely because t i + -00 means that there is a vacancy at the impurity
site.
For finite positive values of (EL - E;), the bonding Al- and Tz-levels can
occur in the energy gap, forming deep levels there, and for finite negative
values of (tL-~k) the same can happen with the two anti-bonding Al- and Tz-
levels. A look at Figure 3.10 shows that the most favorable candidate for an
impurity level to be in the energy gap is the bonding Tz-level if ( ~- 6;)i > 0
holds, and the anti-bonding A1-level if ( 6 ; - 6 ; ) < 0 holds. More rigorous
calculations confirm this conjecture in that they find exactly these levels to
be in the gap. Below, we will describe such calculations and discuss methods
for solving the one-electron Schrodinger equation (3.8) for the crystal with
a point perturbation.
Cluster method
Employing the cluster method, the infinite crystal with a point perturbation
is replaced by a finite part which contains the point perturbation at its cen-
ter and which. on the one hand, is large enough that the band structure of
the infinite crystal is almost completely devploprd and, on the other hand,
is small enough that the Schrodinger equation for it can be solved easily.
This finite part of the crystal is called a rlwter. The cluster with the point
pprturbatinn at its center is clearly just a large molecule. Its atomic and elec-
tronic struclureb can be calculated ubing the methods of quantum chemistry
for the determination of the structure o f molecules. In contrast to infinite
Lrystals, clusters have a surface. The latter also acts as a perturbation of
the periodic potential and can gi%erise to bound slates in the gap. Such
statrs must be remowd in a suitable way in order for the cluster method to
be applicable. To this end, different procedures h a w been proposed such as,
far example, the saturation of the dangling bonds at the surface by hydro-
gen atoms. Correspondingly, the surface levels are lowered deep below the
valence band edge and raised high above the conduction band edge, where
they cause no further difficulty.
Supercell method
1
GO@) = (3.132)
Eti6-H'
296 Chapter 3. Electronic structure of semiconductor crystals with perturbations
Non-trivial solutions me possible only for energies E for which the deter-
minant of the matrix of the operator [ C 0 ( E ) V '- 11, in an appropriate or-
thonormalized basis set, vanishps, i.r. if
-
Uet[G"(E)V' 11 = 0 (3.134)
holds. The energy eigenvalues E satisfying this equation are deep levels.
These levels ran thus be determined by calculating the Green's function
G o ( E )of the unperturbed crystal and solving equation (3.134). This p r o w
dure is rcfrrred to as Koster Slater method, and equation (3.131) as Koster-
Slater equation
The Green's operator @ ( E ) can be cdriilattul if the band structure
E,(k) and the Bloch functions of the ideal crystal are known. The matrix
represenlation of d ' ( E ) in the Bloch basis reads
(3.135)
With this we only need to know the matrix elements (uk(V'1u'k') of the
perturbation potential V' in Bloch representation in order to determine the
deep levels using equation (3.134). However, i t would be more expcdicnt
for the matrix representation of the perturbation potential to use localized
wavefunctions as) for example, atomic orbitals. If one does so, then the
matrix representation of the (heen's opertrtoi is not as simple as in the Bloch
basis. A particular compromise in choosing a basis set for the representation
ol the eigenvalue equation (3.134) is the use of so-called Wunnzer finctzons.
Wannirr functions are linear combinations of all Bloch functions for a given
band index v of the form
3.5. Deep levels 297
(3.136)
Here the summation is over the whole first BZ,G is the number of primitive
unit, rdls in a ppriodicity rcgioa. and t k are certain phase a~glru.If the latter
are chosen properly, the Wunnier h c t i o n s IvRJturn out to be well localized
in the unit cell at the lattice point FL If the eigenvalue equation (3.134) i s
written in terms of this basis, it reads
(3.140)
{ 3.141)
Equation 13.141) forms a closed set of equations for the central cell compo-
nents ( ~ O ~ I Jof) $ only. If the latter are known, all other components (vRI$)
follow at once from equation (3.140). For a non-trivial solution of the ho-
mogeneous system (3.141) to exist, its determinant has to vanish separately,
i.e.
298 Chapter 3. Electronic structure of semiconductor crystals with perturbations
1 1
G;(E) =3
(vOlG*(E)IvO) (3.143)
G Ic E+ir-EE,(k)'
The dominant bands in equation (3.142) are those which form the gap, i.e.
the uppermost valence band u and the lowest conduction band c. If we
consider only them and neglect all others equation (3.142) becomes
or more explicitly
To solve this equation, the host Green's functions G:(E) and G : ( E ) , as well
the perturbation potential matrix elements, have t o be known. Below we
calculate the host Green's functions for isotropic parabolic bands of finite
widths. In expression (3.143) for G : ( E ) we rqlace the k-sum by an integraL
This yields
G 0J E ) = -- '
G 3 8x3 , 1 s t
d%i
~ ~E
1
-I- i t - E,(k) '
v = c, v. (3.146)
(3.147)
whrre p v ( E ) is the density of states per unit energy and spin state
R
p,(E) : - d3kd(E - &(k]) , v = c,w, (3.148)
h3 1.232
3.5. Deep levels 299
which differs from the DOS in equation (2.213) by a factor (0/2). In eval-
uating p,(E), we approximate the true valence and conduction bands by
isotropic parabolic ones, however, taking their band widths A E , to be the
same as those of the original bands. This corresponds to the use of an effec-
tive mass for each band averaged over the whole first B Z . The bandwidths
are introduced by putting the total number of states of the approximate
isotropic parabolic bands equal to G3. Then it follows that
(3.149)
3 G3
pc(E) = ~ ~ ~ ~- Eg)- O E, - AE,)]
[ B(E - ( E . (3.150)
where B(E) is the unit step function. We substitute these expressions into
the Greens function G ; ( E ) of equation (3.147). The E-integral is readily
done. The imaginary part ofG;(E) equals (-TI times pv(E). The real parts
ReG:(E) and ReG:(E) are given by
-I.;TIF] (3.152)
Although complex numbers appear in these expressions, they Eare in fact real.
This would hP obvious if we rcplaced the In-function by an arctan-function.
We avoid this because it is more convenient to handle the many-valued char-
acter of the In-function rather than that of the arctarz-function. Altogether,
the host Greens functions of OUT model depend on three parameters. the
energy gap EB, and the two band widths A& and AE,. The latter are
measure3 of the awrage kinetic energies of electrons in the vakncce or con-
duction bands large bandwidths mean large average kinetic energies (or
~
Scattering states
The perturbation potential also gives rise to changes within the energy bands
of the i d e a l rrystal. Of course, the w e r g i a of t h e w bands are still allowed
quantum mechanically in the presence of the perturbation, so that in this
rwpeet there is 110 change. However, change within the energy hands of the
ideal rrysttll IS indured by the perturbation in the form of a modified density
nf allowed energy levels pcr unit mnergy, i.e. in the form of a modifid density
ol statvs. To calculat? this change it is expedient to introduce the Green's
fiirirtion of the perturbed crystal,
1
(3.153)
G ( E ) - I; 4- i6 - [H+ V ' ].
According to formula (2.209). the imaginary part Im T r [ G ( E ) of
] the trace
represents (apart from a factor -1/ir) the density of states p ( E ) of the
syst,em, here thai of the crystal with the point perturbation. The Green's
function of the p e r t u r b 4 crystal oLrys the equation
1 d
p(E) - I m -In D e t [ G ( E ) ] . (3.155)
A dE
of the unperturbed crystal may be
In an analogous way? the DOS P O ( ! ? )
expressed in terms of the unperturbed Green's function Co(E). We seek the
change
M E ) = P(E)- P O ( W (3.156)
ol t h r nos clue l o the point perturbation. This change may be obtained
from (3.155) and (3.156) as
1 d
Ap(E) = --Irrt-lnDDet[l- G'(E)V'I. (3 157)
xdE
This relation can be used to ralculatc the total change of the DOS in the
entire enerRy range between -oo and t o o . Integrating A p ( E ) over this
interval, and considering the fact that G ' ( f i ) vanishes for li: -+ f m , yields
lm M
~ E A ~ (=.E0.) (3.158)
3.5. Deep levels 30 1
This relation signiEes that under the action of the perturbation potential,
the total number of states remains unchanged. This result already was used
in section 3.4 in lhe context of shallow levels, and there it was referred to
as Levznsons theorem. Here, this theorem means that for each new state of
the crystal created by the point perturbation, a state which existed without
perturbation must cease to exist. The deep states in the energy gap occur
therefore at the expense of band states. For each state occurring in the gap,
R stale is lost fiom a band,
dEAp(h:)- -
Lap. dBAp(E).
Configuration dependence
(3.160)
of the total energy R t o ~ ( { v ) of) the N-electron system in the ionized stair
{v}, and the total energy E t o d ( { v } ]in theground state {v}. Theionized
state (v) differs from the ground state (v) in that a particle, which in the
ground state of the system occupies a oneparticle state of energy E,, is
transferred to a oneparticle state of energy 0 corresponding to the vacuum
level. Like in section 2.1 one says that a31 electron is removed from the
system. This expression has to he used with care, however, for if taken
literally i t misrepresents the charge neutrality of the system. The total
energy of the ground state follows, according to formula (2.541,by summing
all occupied oneparticle energies, followed by subtraction of the electrostatic
interaction energy of the electrons because the latter is doublecounted in
forming the sum of one-particle energies.
The equation E , = - I , is the content of Koopmans theorem, which
was explained in section 2.1. The essential requirement for the validity of
this theorem is the approximate population independence of the Hartree and
exchange potentials or, more generally, of the effective one-particle potential.
This requirement is not satisfied for a crystal with a point perturbation.
The potentials depend on the number n of electrons occupying oneparticle
states localized at the center, and so do the energy eigenvalues E , of the
one-particle Schrodinger equation of the crystal with a point perturbation.
We will denote these oneparticle energies by E:) henceforth to emphasize
this dependence explicitly. Of course, the definition (3.160) of the ionization
energy is also valid in this case, but it is no longer true that I,, represents the
negative oneparticle energy -E$.( That this cannot hold is immediately
clear if one recognizes that the eigenvalues IT?) and E P - l ) of the one-
particle Schrodinger equation with. respectively, n and n - 1 electrons at
the center differ from each other - the level EP- is deeper than the level
E p ) because the removal of an electron results in the positive core being
less strongly screened, so that the remaining electrons are more strongly
attracted. In this situation, we say that the electrons at the center relax on
the removal of an electron from the center. If one further considers that the
total energies of both systems enter in the definition (3.160) of I,, that of the
relaxed system with (n- 1)electrons at the center, and that of the unrelaxed
3.5. Deep levels 303
system with n electrons at the center, there is no way to explain why the
energy difference E b t d ( { v } v )- E ~ M ( { V } 'should) be equal to the negative
eigenvalue - E Z( ) of the unrelaxed system and not equal to the negative
eigenvalue -EP-') of the relaxed system. In reality, the ionization energy
E b t a l ( { v } v ) - E ~ M ( { v } ' )is not equal to either one, but lies somewhere in
between the two. It can be shown that it is approximately given by the
negative of the one-particle energy eigenvalue of the N-electron system with
the fictitious number ( n - 1/2) of electrons at the center. This is plausible
because the electron, during its removal, feels, so to speak, the potential with
n localized electrons half of the time, and feels the potential with ( n - 1)
localized electrons there also half of the time.
To carry out an exact calculation of the ionization energy of a center
which, in its ground state, has n localized electrons, the one-particle energy
eigenvalues E P ) are not sufficient. Applying equation (2.54),these one-
particle energies provide the total energy E b ~ ( { v } ' of ) the ground state,
but they cannot be used to calculate the total energy Etotal({v}v) of the
ionized state with n - 1 localized electrons at the center. To obtain the
latter, one also needs the one-particle energies EP-') of the N-electron
system with n - 1 localized electrons. In density functional theory, the two
total energies follow more directly: one determines the eigenfunctions of the
Kohn-Sham equation for the centers with n and n - 1 electrons, then forms
the corresponding ground state densities, and evaluates the total energy
functional (2.64) using these densities.
Ionization, i.e. exciting an electron to the vacuum level, is only one of the
various possible one-particle excitation processes of the N-electron system
of a crystal having a perturbation center. Generally, one may examine an
excited state { v } ~with ' ~ an electron in a formerly unoccupied one-particle
state Y' of energy below the vacuum level, and a hole in a formerly occupied
one-particle state v. The corresponding excitation energy Iuiv is given by
the total energy difference between the excited state { Y } ~ and ' ~ the ground
state {v}',
(3.16 1)
As in the case of ionization, the excitation energy Iulv is not equal to the
one-particle energy difference E,i - E,. Here, we are interested in excitation
processes involving changes of the populations of one-particle states local-
ized at the deep center. There are different types of such processes. Firstly,
in the final state, all electrons may still be localized at the center, but with
one electron having changed its localized one-particle state. Such excitations
are called internal transitions of the center. Secondly, an electron originally
localized at the center may undergo a transition to the bottom of the con-
duction band. This is referred to as a donor transition Thirdly, an electron
304 Chapler ,7. Electronic structure of semiconductor crystals with perturbations
from the t,op of thevalencr band may be transferred into a previously empt,y
one-particle state Iocalized at the center. This type of excitation is called
an acceptor transition. The excitation energy for an electron from the t,op
of the valence band to the bottom of the rnnduct,ion band defines the en-
ergy gap. As excitation energies of the N-electron syst.em of the perturbed
crystal, all transition energies discussed above may be plotted in the same
energy scheme, just as if they- were oneelectron levels. But. they are not:
they are one-particle ezcitation levels. More strictly speaking, one has donor
excitation levels E$V - E , - and acceptor excitation lcvels ~2~ =1 ~ 1 ~ .
The donor excitation level for a center D in the neutral charge state D(O) is
denoted by n(O/+),and the mceplor excit,ation level for a center A in its
neutral charge state A(0) is denoted by A ( O / - ) . If the donor excitation level
D ( + / 2 + ) at t.he single positively chargcd donor center D ( + ) also lies in the
gap, one has a dovhly i u n i m b k , OT d o u h k donor. If only the excitation level
D ( O / + ) lies in the gap, the donor D ( 0 ) is simply ionizable, or a single donor.
In the general case, t,here are m d t i p k donors. An analogous terminology i s
used for acceptors. Viewing the hand edges as int.erna1vacuum Icvcls one
0ft.m refers to donor and acceptor transitions as donor and acceptor ion-
izut,iuab, and to & curraponding excitation energies as ionization lez~elx..
Below, we will use this terminology
Acceptor ionization lcvcls may be traced back to donor ionization levels.
In fact, ionizing a neutral acceptor center A(0) leaves this center in singly
negative charge state A ( - ) , and a hole appear8 at the valcncc hand edge.
If one subjects the centex A(-) E D ( - ) t o a donor transition D ( - / O ) then
the center returns t.o its neutral charge slate D ( 0 ) A(O), and an electron
appears at the conduction band edge. As a resdt of this t,wo-step ioniza-
tion process of the center A(O), an electron-bolc pair is excited while the
state of the center has not changed. The sum of the two ionizalion energies
A ( O / - ) and D ( - / O ) equals, therefore, the (minimum) excitation energy of
an electron-hole pair, namely, the gap energy E , (see Figure 3.11). Gener-
ally, for an x:cept.nr A ( Q ) in charge state &, one has
(3.162)
edge instead of the valence band edge (as is done in equation (3.162)), thus
setting A(&/(& - 1))= Eg - A(Q/(& - l)),then it follows from (3.162)
that
Configuration interaction
Below we discuss the structure of several deep centers which are important
either from the scientific or technological point of view. Knowledge about
these centers is, in every, case the product of combined experimental and
theoretical investigations. Since we have thus far treated only theoretical
methods, we first present a short overview of the experimental methods.
Experimental methods
One can divide the experimental methods for investigation of deep centers
into two groups, on the one hand, methods which measure ground state
properties of the centers, and on the other hand, methods which give exper-
imental data on center properties in thermally or optically excited states.
Among the methods of the first kind are measurements of magnetic
properties, like Electron-Paramagnetic Resonance (EPR);Electron-Nuclear-
Double Resonance (ENDOR) and magnetic susceptibility. These methods
provide data concerning the total spin S of the centers and, if anisotropy
effects are measured, also spatial symmetries. The chemical identity of the
centers can be determined (in addition to other methods) by means of mass
spectroscopy or of Rutherford Backscattering (RBS). Measurements of the
Extended-State X-ray Absorption Fine Structure (EXSAFS) provide data
about the geometrical ordering of the atoms in the vicinity of a point per-
turbation.
To investigate the excitation properties of deep centers, optical and elec-
trical methods are available. Ionization energies can be determined by means
of optical absorption spectroscopy and photoconductivity measurements,
mainly in the infrared spectral region. The cross-sections of deep centers
for emission of free charge carriers can be determined by means of time
resolved current or capacitance measurements at pn-junctions or at other
depletion layers. By suddenly applying a reverse bias at such a junction, the
deep levels are lifted relative to the Fermi level The new equilibrium state
of the junction corresponds to fewer electrons in the deep levels than previ-
ously. This state does not occur suddenly, however. it adjusts exponentially
through emission of electrons from the deep levels into the conduction band
(we assume deep donor levels here, the case of deep acceptor levels may be
treated analogously). In the conduction band, the electrons are freely mobile
carriers and are immediately sucked up by the positive electrode at the n-
region. This results in an exponentially decaying current, which for its part
leads to an increasing positive charging and. thus. an increasing capacitance
of the junction. The decay time of the current and the rise time of the asso-
ciated capacitance change are determined by the emission probability from
3.5. I?wp let& 309
the dttep centers. Measuring the capacitance rise time yields experimental
values for the emission probability. Of particular importatice is the so-called
Deep Level Trawaerat Spectroscopy (DLTS), wherein a reverse biased pn-
junction is exposed to periodically repeted voltage pulses of forward {deep
level filling) polarity. The recovery time for the capacitance change after a
filling pulse has been switched off, is measured as a fimrtion of temperature.
This fiinction exhibits maxima which, under certain conditions, can be used
to determine the ionization energies of the deep centers. Ionization energy
values from LILTS measurements and other thermal quililrrium technique
are, as a rule, smaller than optically measured values: the lattice has time to
rrlax if ionization proceeds thermally, and this lowers thc enerm of the finel
stat?. Optical ionization occurs instantaneously, hence lattice relaxation is
is not possible.
Perhaps the best understood point perturbation is the vacancy in Si, so
we initiate our discussion of particular deep centers with it.
Vacaricy in Si
The defwt molerule model of the vscancy was treated in section 3.2. It
predicts the existence of two bound one-particle states, a non-degenerate
al-state, and a tripiy degenerate t2-state. More rigorous calculations within
one-particle approximation (3araff, Schliiter, 1980; Bernholc, Pantelides.
1980) show that the al-level can be excluded as a deep state in the gap
because it lies in the valence band (see Figure 3.12a). As such, it is fully
occupied having two electrons. The t 2 -level can lie in the gap depend-
ing on how many electrons it hosts. ,4t maximum, this can be 6, and
at minimum 0. Thus there exist 7 charge states of the vacancy, namely
t7(2+),I,(+), i(O), I,(-), V(2-), Ir(3-) and V(4-). The one-particle en-
ergies of these centers differ by the Hubbard energy U. A simple estimate
yields 0.3 el for C3. Thus, many-body effects, more strictly speaking. con-
figuration dependencies of one-particle energies: should be important in the
case of the Si-vacancy. Other many-body effects, including configuration
mixing, are small, and a description of the vacancy in terms of one-particle
states, albeit configuration dependent ones. is approximately justified.
Owing to the value of about 0.3 e V for U , it may be expected that three
or four ionization levels codd fit in the Si gap of about 1.1e V . A4ctualIy,the
donor levels 5(+/2+), t(O/+), and the acceptor levels V ( - / 0 ) and V ( 2 -
/-1 are found there (as above the acceptor levels are counted relative to the
conduction band edge). In Figure 3.12 (part b). calculated positions of these
levels are shown. These are not yet final positions because lattice relaxation
has not yet been considered. The latter leads to changes which are discussed
below (see Figure 3.13). In charge state V(Z+), no electrons are available
310 Chapter 3. Electronic structure of semiconductor crystals with perturbations
Figure 3.12: Deep levels of avacsncy in Si: a) Calculated ionization levels without
Hubbard corredions and lattice relaxation. b) Levels of a) with Hubbard correc-
tions. c ) Fsxperimetital ionization levels which, in addition, include Jahn-Teller
shifts. The numbers give the level distances from the valence band edge in eV.
(After Watkins, l S S 4 . )
The elements of the main groups of the periodic table are distinguished by
the fact that their valence shells arise born 3- and p-orbitals. The group-
IV elements, as well as thc IV-IV,111-VI.and 11-VI binary compounds,
form crystals with, respectively, diamond and zincblende structure in most
caws. Relow we refer to them as 'tetrahedral semiconductors'. If main
group elements appear as impurity atoms in such crystals, then they are
chemically bound in a manner similar to that of the hust crystal atoms which
they replace, i.e. through sp'-hybrids. That implies that the incorporation
of impurity atoms should be mainly substitntional in such crystals. In the
case of a compound semiconductor, the lattice site which is prpferred is the
one that belongs to the chemically most similar atom of the host crystal,
therefore the anion site, if the impurity atom is a nan-metal atom. and. the
cation site, if it is a metal atom. The solubility of the main group elements in
tetrahedral senlicntiductors is, accordingly, high. It lies between 10"
for chemically very similar systems such as GaAs.Al, and l O I 5 ~ r n -for ~
312 Chapter 3. Electronic structure of semiconductor crystals with perturbations
cl v
D2d - Dzd
d) v-
-o+d
-btc
Figurr 3.13: Defect molecule model of a vacancy in Si. Different charge states of the
vacancy are shown, taking into account the torresponding Jtthn-Teller distortions.
On the right-hand side, the basis functions of the irreducible representations of the
deep k v e l ~are indicated (a, b, c Bnd d bband for the dangling hybrids of the 4
surrounding atom). (After Watktns, l U U 4 . )
?r
Be B C N 0
- - Ec - 0.14
hk A1 Vac. P S
- EC - 0.43 - Ec - 0.31
Zn Ga Ge As Se
+
E1, 0.32 - - - E, - 0.3
Cd In Sn Sb Te
E, + 0.55 E, t 0.15 - - Ec - 0.20
Hg T1 Pb Bi Po
1
Ec - 0.31 E, + 0.25 ~ -
>"
QI
Y -1
W
-2 L I I I I I
11 I I!
I
0
Eandedge
t -
A -1
>
Q)
u
w
-2 -
Cation Site
-3 I I I 1 I I A
The fact that the perturbation potential is negative (attracting) for the anti-
bonding al-level and positive (repelling) for the bonding &level allows an
important conclusion on the nature of the deep impurity states: in both
cases, the corresponding wavefunct ions have larger amplitudes at the sur-
rounding host atoms than at the impurity atom. In this sense these deep
impurity states are more host-like than impurity-like.
Quantitatively, the al-level positions in Figure 3.14 differ from the experi-
mental ones. This is to be expected because of the great simplifications made
in the calculations. many-body effects, particularly, configuration dependen-
cies of the one-electron levels, have been neglected, and lattice relaxation has
not been taken into account (Scherz and Scheffler, 1993). To get an idea how
these effects would modify the results, we show in Figure 3.15 the expected
occupancy of the deep oneelectron levels in the particular case of Si as host
crystal, using the level ordering suggested by the above-quoted calculations
316 Chapter 3. Electronic structure of semiconductor crystals with perturbations
d) el fI
Figure 3.15: Energy levels and their populations for sp3-bonding main group im-
purity atoms in elemental semiconductors of group IV,within the defect molecule
model. The partial illustrations a) to h) correspond to impurity a t o m of groups I
to VII as follows: a - V, b - \I, c - VII, d - HI, e - 11; f - I.
differences from this model occui for elements of the first main group which
have no occupied p-states but relatively shallow closed d-shells (Cu, Ag) or
d- and f-shells (Au). Foi these atoms, d-electrons participate in chemical
bonding with the host crystal. We will discuss this problem in more detail
in the context of the transition metal impuiity atoms.
The question of whether deep levels exist or not for a particular substi
tutional impurity atom, ran he treated arralytzrally, employing the Wannier
representalion of the Greens function derived above. As lhis calculation
provides further physical insight into the formation of deep levels, we will
discuss it hclow, agdin taking Si as the host crystal. The Chens function
in Wannier representation has already been determined above (see equa-
tions (3.158) and (3.159)). For the evaluation of the Koster-Slatcr equation
(3.152) we need the matrix elemeuts V,,,,V,, V ,of the perturbation poten-
tial V in this representation. To calculate them we use the results of the
TR approximation of scction 2.5. In the simplest veision of this upproxi-
mation, the ILamiltonian of the ideal crystal is diagonalized by the bonding
and anti-bonding Bloch functions Ibtk) and In&), t = 1 , 2 , 3 , 4 , of equations
(2.303) and (2.304). Thus, in an approximate sense, the bonding and anti-
bonding orbitals IbtR) and latR) are the Wannier functions of the eigenvalue
equation (3.152). We will use thmn to grt explicit expressions for V,,,,,V,,,
and V,. Fiist, we write down the matrix representation of the unperturbed
Hamiltonian H between bonding orbitals. It is given by
(btRIHI4R) fhGRR,
h (3.165)
where E; is the hybrid energy of a host atom. For the perturbed Hamiltonian
EZ fV, one has t h e same matrix elements for all R and R with the exception
of R R= 0. The latter elements are
1
(btOlH i-
VlbtO) - S(E; + EL), (3.166)
where EL is the hybrid energy of the impurity atom. Siiicc none of the matrix
elements of (3.165) and (3.166) depend on t , one may identify IbtO) with the
Wannier function of the uppermost valence band. Then, taking the difference
of equations (3.166) and (3.165), an expression for (vO1V(wo) G V,, follows
SS
elements between bonding and anti-bonding orbitals yield the expression for
(wO1V'lcO) V,. It turns out that all elements are the same, i.e.
Solutions of equation (3.169) within the gap do not exist for all possible
values of the 4 parameters entering, i.e. the gap energy Eg, the two band
widths AE,, A&, and the perturbation potential constant Vo. This is evi-
dent if one considers the particular case AE,,v >> Eg,which can be realized.
The arguments of the logarithmic functions in G : ( E ) and G:(E) are close
to 1 in thia case, and the logarithms themselves become negligibly small. If
one assumes, in addition, that A & = AEw,then
+
Re[G:(E) G:fE)] - (F)--&[,,/=-
. fi] (3.170)
With this exprwsion! the deep level condition (3.169) takes the form
(3.171)
It has solutions Et only in the energy gap 0 < Et < E,, within which Et has
to be restricted anyway because the deep level condition (3.170) is valid only
there. For negative Vo, one necessarily has Ef > Eg/2,and for positive Vo,
Et < E,/2. For Vi -t +m, El approaches the value E,/2, i.e. the deep level
is pinned at the midgap position. This corresponds to the pinning of & to
the vacancy level discussed in subsection 3.5.2. In order for a solution Et of
equation (3.171) to exist at all, lV01 must exceed a minimum value J V O ) ~ ~ ~
given by
(3.172)
Table 3.7: Perturbation potential matrix elements Vo = (1/2)(~: - $) (in eV) for
substitutional impurity atoms of main groups in Si, calculated by means of Herman-
Skillman s- and p-orbital energies. The latter are partially reproduced in Table 2.2.
(After Herman and Skillman, 1963.)
B e B C N 0 F
1.57 0.08 -1.41 -3.04 -4.8 -6.71
Mg A1 Vac P s c l
2.18 1.05 8.28 -1.12 -2.31 -3.56
Zn Ga Ge As Se Br
1.82 0.88 -0.04 -0.99 -1.97 -2.98
Cd In Sn Sb Te I
1.91 1.14 0.35 -0.42 -1.22 -2.03
Hg TI Pb Bi Po At
1.87 1.17 0.47 -0.24 -0.96 -1.68
the rritprion is correct in all caws. pxrept for In and TI, which are close to
the border line of our model but still on thp side where no deep level6 exist.
while experimentally surh 1wrls art- found.
The transition metal ('YM)-impurity atoms of the iron group, i.e. those
with closed ad-shells (see Table 3.2), are incorporated in Si crystals prdom-
inantly on interstitial sites of tetrahedral symmetry, while the 5d-TM atoms
prefer substitutional cation sites. The position of t h e 4d-TM atoms in Si
lies between the two, i.e. both interstitial and substitutional incvrpuretions
are observed. In III-V and 11-Vl semiconductors, all three groups of TM
atoms prefer substitutional incorporation on cation sites. The solubility of
most transition metal elements in Si is relatively small, lying in the range of
rm-3. Higher values in the range of 101frm.3arc? reached in tetrahedral
compound semiconductors, and for M n in GaAs the solubility reaches as high
as 10" ~ r n - ~R;In
. also is a transition metal which gives rise to alloys with
cerhizl 11-VI compound semicondudors, such as, for example, (Zn, b1n)Te
or (Cd.hln)Te. Semiconduct,or alloys exist also with Fe and Co.
In tetrehdral semiconductors, most of the TM atmns form deep levels.
Among them, the levels of 'I'M-elements with closed 3d-shells (the so-called
3d-TM cleinents) are by far the bestst known. Concerning 4d- and 5d-TM
imyurily atoms, it is understood that. deep levels also exist in their rasp
(Beeler, Andersm. Sdieflcr, 1985 and 1990; Alves, Leihe, 1986). This is not
surprising since the Thl elements are all chemically very similar. Here, wc
restrict our considerations to the 3d-TM atoms. Them are the elements Sc!
Ti, V, Cr, Mn, Fe, Go and Xi. Sometimes, the neighbors of Ni to the right
in the periodic table, CU and Zn? are also included, although, owing t.o their
respective 3d1'4s- and 3d1'4s2-confi~~ations. these are not in fact transition
metals. In tetrahedral semiconductor crystals, however, they behave simi-
larly. Special interest in the investigation of 3d-Thl atoms results mainly
from t,he fact that their deep levels play an import.ant part in electronic de-
vices. They can serve as recorrilrizlation centers through which the lifetime of
non-equilibrium carriers is shortened, or as capture centers for h e carriers
which partially compensate the effect of dopant atoms. These effects are
imclesirable in most caws, thus one must. try to minimize the contamination
of the devicw by 3d-'I'M atoms. Occasionally, 3d-TM impurities can elso be
useful. 'I'his happens, for example, in the case of Cr in GaAs which, due to
its compensating effect! makes the crystals serui-insulitting.
There are numcrouq experimental investigations on 3d-'l'h.I impurit.y &oms
in tehahedral semiconductors (interested readers are referr4 to the book by
Fkurov and Kikoin, 1994). Beside donor and acceptor transitions alsn in-
ternal transitions of the 3d-TM imp1irit.y atoms are observed. Below we
3.5. Deep levels 32 1
(3.174)
where
322 Chapter 3. Electronic structure of semiconductor crystah with perturbations
Figure 3.16: Experimental d'/do d%' d?d2 dyd' d%l' d?d5 d?da d%' d%lnd'o/d9
ionizatjon energjes of free 3d- I I I I I I I ' 1 11
Tzvl ions (lower part), as well
as donor and acceptor ioniza-
tion energiea of 3d-TM impu-
rity atoms and ions in various
host semiconductors (upper five
parts). (After Zernger, 1986.j
GoAs to/-
2.4
where we set
1 s
a2 = - ( I - -
a)' a 2 = -1( l + - s) . (3.177)
2 A
3.5. Deep levels 323
c -band
t2a \ t2
4s
3d
v - band
Figure 3.17: Energy level diagram of the defect molecule model for a substitutional
3d-TM impurity atom in a tetrahedral semiconductor. Explanations are given in
the text.
Since the two bonding and anti-bonding eigenvectors Itzb) and Itza) of equa-
tion (3.175) are linear combinations of basis functions with tz-symmetry,
they also have t2-symmetry (as already indicated by the notation). It turns
out that the bonding tzb-level lies in the valence band, the non-bonding e-
level in the valence band or the gay, and the anti-bonding tk-level is in the
gap above the e-level or in the conduction band. In regard to deep levels of
the 3d-TM atom i s in the energy gap, therefore, the 2-fold degenerate e-level
and the abovelying triply degenerate anti-bonding tp,-level are candidates
(see Figure 3.17). The eigenfunctions of the e-level are linear combinations
of the &orbitals of the TM atom and are therefore strongly localized at the
latter. Considering localization of the t a b and tn,-leveh, the position of the
two orbital energies F d and t h relative to each other is decisive. If Ed lies
deeper than Ch, then a! > ,8 holds, meaning that the bonding tzb-level is
mainly formed from the d-ststes of the TM atom, while the anti-bonding
tza-level, which forms the deep level, arises to a considerable extent from the
tz-components of the four sp3-hybrid orbitalb of the surrounding host crys-
tal atoms. Exactly this picture emerges from the above-mentioned Greens
function ab initio calculations (Zunger, Lindfeldt, 1983). In Figure 3.18 the
calculated oneparticle energy levels are shown for some 3d-TM atoms in
Gap.
The most striking feature of the above description of the electronic struc-
ture of substitutional 3d-TM impurities is the existence of deep levels whose
wavefunctions are spread out over the surrounding host atoms. These levels
324 Chapter 3. Electronic structure of semiconductor crystals with perturbations
*\1-
-jFq
-2
-3
are host-like to a certain extent rather than purely TM atom-like. This pic-
ture stands in remarkable contrast to the so-called ionic model, which was
long believed to be correct for substitutional TM atoms also. In this model,
the deep level is strongly localized at the TM atom. Today there exists clear
experimental evidence that this is not the case. The ionic model is based
on the so-called ligand field theory. This entails an approach to the deep
level problem for impurity atoms which differs fundamentally from the one
used in this book. Within ligand field theory, it is assumed that an impurity
atom X in the crystal has essentially the same electronic structure as the
free X"+-ion, where V + means the oxidation state of the impurity atom in
the crystal introduced above. The energy levels and wavefunctions of this
ion are weakly disturbed by the crystal field at the impurity site, an effect
referred to as crystal field splitting. While this model applies relatively well
in the case of ionic crystals (where ch lies deeper than c d ) , it evidently fails
in the case of the covalent or partially covalent tetrahedral semiconductor
crystals. The oxidation states of ligand field theory are, however, also r e
produced in the approach taken here. To demonstrat,e this we consider the
example of a Co atom substituting the metal atom in a 111-V compound.
There are 9 electrons in the 3d74s2 valence shell of Co, and 5 in the valence
shell of the group V atom to which the Co atom binds. 8 of these 14 electrons
are hosted by bonding states of the deep center (2 by the bonding al-state,
and 6 by the bonding t 2 state). S i x electrons remain for the population of
the deep impurity states, i.e. the non-bonding e-states and the anti-bonding
t2-states. Since 9 electrons are expected at a neutral Co atom, the oxidation
state of Co in a 111-V compound is Co3+. Substitutional Co in a 11-VI com-
pound has the oxidation state Co2+ since one additional valence electron is
provided by the group VI atom of the host crystal.
3.5. Deep levels 325
3.0
-552 2.0
LT
W
z
w
1.o
0.0
Ligand field theory accounts for the fine structure of the deep impurity lev-
els, which is not explainrd by the approach taken above. Although this
approach provides qualitative understanding of deep 3d-TM centers in tetra-
hedral semiconductors, the excitation energies it yields are not correct quan-
titatively, particularly not for the internal transitions of the 3d-TM centers.
To be quantitatively correct, this approach must be refined by including
many-body effects, in particular, configuration interaction. While the latter
effect does not play an important role for main group impurity atoms, as we
have scen above, it becomes important for T M impurity atoms with their
strongly localized open d-shells (as was specultited in section 3.5.4 using the
analogy with frcc I'M atoms). Figure 3.19 demonstrates this in thc case of
TM atoms in ZnS.
The differences between the donor or acceptor ioniaation energies of a
particular TM atom in different host crystals exhibit interesting behavior.
Experimentally one finds that these diffeiences are almost independent of the
atom considered. Therefore the ' ionization-encrgy-versus-'I'M atom curves'
of different semiconductors are parallel t o each other and ran be translated to
overlay by rigid displacements along the energy axis (Caldas, Fazzio, Zunger,
1984; Langer, Heinrich, 1985). In Figure 3.20 this fact is shown for acceptor
326 Chapter 3. Electronic structure of semiconductor crystals with perturbations
and donor ionization levels of a 3d-TM impurity atom in a series of I11 V and
11-VT compound semiconductors. The rigid displacement along the energy
axis has an important physical meaning as we will discuss further below.
Here, we will provide a simple explanation for the similarity of the 'ioni-
zation-energy-versus-TM atom' curves in different semiconductors (Tersoff,
Harrison, 1986). In this discussion we will use the defect molecule model
of 3d-TM impurity atoms presented above, in addition, however, the depen-
dence of the energy levels f d and Eh on their population will be taken into
account in a self-consistent way. Let n d , n h and n:, n: be the electron num-
bers in, respectively, the atomic d- and sp3-hybrid orbitals, the former after
charge transfer between the impurity atom and the crystal has taken place,
and the latter before. The dependence of the levels Ed and ~h on population
may, in the linear approximation of equation (3.25), be written as
n d = nbu! 2 + nap2 i-
n, (3.179)
3.5. Deep levels 327
n h = n b P 2 +,,a2 (3.180)
are in h-states. The bonding T2-level Eb lies in the valence band, its three
states are therefore completely occupied and it holds n b = 6. The difference
6 = (Ed - h ) / 2 between the d- and h-states adjusts self-consistently: if Eh
increases, then 6 becomes small and, with this, also ,B and n h are small. As
a consequence of this, n d increases which, according to (3.178), results in an
increase of d and, hence, an increase of 6. Self-consistency is then achieved
if the two equations (3.178) for the level positions t d and Eh are satisfied with
values n d and n h from equations (3.179) and (3.180), respectively, and values
a 2 , P2 from (3.177). For the level difference 6 = ( d - ~ h ) / this
2 condition
yields
ci)
" ,(nu
1
+ 6 ) - -(nu
2
6
- 6)-A - n:)] (3.18 1)
1
+ 6 ) + s1( n u- 6 ) A-6
i ( ~ a
0
1 ne - n d w 0, (3.182)
the gap are pinned at the hybrid level F ? ~of the surrounding host anions.
If the coupling hetwccn the anion-hybrids and the rest-of-crystal is taken
into account, the anion-hybrid energy Eh has to be replaced by the average
cation-anion hybrid energy of the crystal.
The rebUlt8 above explain lhe experimental finding that the deeplevel-
versus-Thl atom-curves for two different semiconductors ran be tranbleted
to overlay each other by rigid displacements. Moreover. they associate the
magnitude of the displa~ementswith the difference between the average hy-
brid energies of the two semiconductors. Thls quantity has a close relation
to the valence band discontinuity at a semiconductor heterostnicture. as will
be discussed iu more delail in section 3.8
The large Hubbard energies of the atomic d-states of the IM impurity
atoms and thFir pinning at lhc dangling hybrid lev& of the surrounding
atoms are also contributo~yto the striking phenomenology noted above. in
that the deep levels of TM atom8 depend only relatively weakly on their
population, so that levels of several charge states can fit in the gap. In fact,
if an additional electron is put in the deep tzo-lwel, and, with this, also part
ofit IS added to the TM atom, the d-level of the latter will be shifted up and
the bondmg tB-level will be depolarized ( a becoming smaller and /3 larger
in equtliiori (3.177)). This means that electron charge density will flow from
the Thl atom to the surrounding host atoms. in almost the same measure as
was added t o the T M atom when the additional electron was placed in the
deep ant i-bonding &-level. Since the Hubbard energies of the s- and p-shells
of the host atoms are substantially smaller than those of the &orbitals of
the Thl atoms, the deep TM-levels are shifted up only by several tenths of
an e V rather than 10 el, for the case of the free TM-ion if one more electron
is p l a ~ e dat the center (Haldan, Anderson, 1976).
Cu, Ag, Au in Si
These three elements (abbreviated below as Nhl, for noble metal) play
an important part in silicon device technology. As impurity atoms, they
constitute effective capture centers for non-equilibrium charge carriers. Their
high solubility in Si is remarkable (in the region of cmd3 to ~ r n - ~
at melting temperature), as is their fast diffusion. Their incorporation in
the host crystal is predominantly substitutional. The elements tend to form
complexes with other elements. for example, Au with 0. Fe or 3d-TMs. This
makes it somewhat difficult to identity the pure substitutional NM centers.
Although the elements Cu, Ag and Au belong to the fast main group of
the periodic table, their behavior its impurity atoms in tetrahedral semicun-
ductors resembles that of transition metals. This is understandable if one
considers that for these elements only the outer s-shell, but not the outer
p-shell, is occupied, and that the closed d-sheIl (Cu, Ag) or d - and f-shells
3.5. Deep levels 32 9
(Auj lie energetically relatively shallow below the s- and p-shells. According
to calculations by Fazzio, Caldas and Zunger (1985). the anti-bonding t 2 -
state lies in the energy gap, just as in the case of transition metals, and as in
the latter case, this state arises from the interaction of the impurity-derived
d-states (more exactly their tg-component) with the tg-components of the
dangling bonds of the surrounding host atoms. Because of the relatively
weak localization of this deep impurity state, its Hubbard energy is small
so that. again. several ionization levels can fit within the gap. For all three
K M atoms, the calculations result in a Nh/l(O/+) donor level, and a NM(-/O)
acceptor level. In the case of Ag and Au, the amphoteric character has also
been conhmed experimentally.
The rare earth (RE) atoms are among the following elements: Ce, Pr, Nd,
Pm, Sm, Eu. Ac. Th. Pa, U. Np, P u , Am, and Cm. The valence shell config-
uration of the majority of these atoms may be described as 4fn6s2 with the
number n of f-electrons varying from 2 for Ce to 14 for Yb (see Table 3.3).
Exceptions are Gd and Tb which have one 5d valence electron in addition.
The investigation of RE impurities in Si as well as in the 111-V and 11-VI
semiconductors has received new stimulus very recently. The reason for this
is the luminescence of RE impurity atoms in these crystals in the technologi-
cally interesting visible and infrared spectral regions. In equilibrium the RE
atoms are installed both substitutionally as well as interstitially. The equi-
librium solubility of the RE atoms is, however; rather small. For practical
applications, non-equilibrium incorporation techniques like ion implant ation
must be used, although, generally, only parts of the implanted atoms are
optically or electrically active. For Erbium (Er), impurity concentrations of
- ~ been reported in Si, and of about 10l8 C W I - ~ in Ga4s.
about lo1 ~ r n have
The technologically interesting luminescence discussed above is caused
by internal transitions within the 4f shell of the RE atoms, more strictly
speaking, between the various levels arising from the many-particle levels of
the 4f-shell under the influence of the crystal field. The 4f-orbitals remain,
in fact. almost unchanged by installation of the RE atoms in the crystal. This
may be traced back to the fact that these orbitals are strongly localized and,
moreover, strongly shielded by the 6s-electrons shutting out influences of the
surrounding crystal. Furthermore, for RE elements heavier than Nd, there
is also strong shielding by the completely occupied 5s- and 5p-shells lying
outside the 4f-shells for these elements. While internal electron transitions
within the 4f-shell have been studied already for a long time, transitions to
energy levels outside of the 4f-shell, including donor and acceptor transitions
into conduction and valence band states of the crystal, have been subjected
to more detailed investigation only recently.
330 Chapter 3. Electronic structure of semiconductor crystals with perturbations
Ce Pr Nd Fm
' Sm Eu Gd Tb Dy Ho Er Tm Yb
8 ! ' I ' I j 1 1 1 I " ,
6
4
2
5 0
v
P -2
g-4 k E(3+/4+) I
-6
-8
-10
1I I
-12 , I ! I I / I I , ! I
I
Ce Pr Nd Rn Sm Eu Gd Tb Dy Ho Er Tm Yb
Figure 3.21: Donor ionization levels of substitutional rare earth impurity atoms in
different semiconductors. (After Delerue and Lannoo, 1994.)
The position of the If-shell with respect to the above levels still has to be
determined. In the model by Delerue and Lannoo this is done assuming that
the distance between the 4f-shell and the average 5d-level in the crystal is
the same as that between the 4f-shell and the 5d-shell in the free RE atom.
The ionization levels of the 4J-shell calculated by means of the above
defect molecule model are shown in Figure 3.21 for various RE atoms and
host crystals. Two diffcrcnt oxidation states of the RE atom, RE3+ and
RE2+, have been assumed. One recognizes that, for InP, the oxidation state
RE3+ is stabk in most rasrs, because the RE(3-t /4 t ) ionization levels are
still below the Fermi level, while the RE(2 t/3+) ionization levels are above
it. For CdTe, the oxidation state RE2+ is found to be stable in most rases.
With a few exceptions, these predictions are confirmed by experimental in-
vestigations. Oxidation states can also be derived in a more direct way from
the above defect molecule model. In a 111-V compound host crystal, the RE
+ + +
defect molecule has 2 n 5 electrons, 2 n of them from the HE atom, and
5 of them from the host crystal anion. These electrons orrupy either states
in the 4f-shell, or are in bonds between the RE atom and the crystal. The
bonding al- and t2-states host 2 f 6 = 8 electrons provided that they are
energetically lower than the f-shell, which in fact turns out to be the case.
+ +
Thus, 2 n 5 - 8 = JZ - 1 electrons remain for the f-shell. The oxidation
state of a neutral RE atom is RE3+ in such circumstances, because 3 elec-
trons are missing at the RE atom, the one f -electron and the two s-electrons
in bonds with the host crystal. In 11-VI compounds, the oxidation state of a
neutral RE atom should be RE2+ according to this consideration, since the
host crystal anion delivers 6 electrons instead of 5.
A striking feature of the ionization-energy-versus-RE-atom-curves for
different semiconductors in Figure 3.21 is that they can be brought to over-
lie each other by rigid relative displacements. This is reminiscent of the
ionization energies of the 3d-TM atoms where the same feature is observed.
The reason is similar to that of the 3d-TM case: one the one hand, the
4f -levels are pinned electrostatically to the average 5d-levels by means of
the self-consistent charge exchange between the d- and the f-shell with its
large Hubbard energy, and on the other hand, the 5d-levels are pinned at
the average hybrid energy levels.
The interest in this defect arises mainly from the fact that it is closely con-
nected with the so-called EL2-center which is one of the most common point
perturbations in GaAs. The EL2-center is a double donor and plays an im-
portant role in GaAs electronics. Through deliberate use of its properties,
p-type GaAs, which normally arises in crystal growth, can be transformed
into semi-insulating GaAs which is required for the manufacture of GaAs
332 Chapter 3. Electronic structure of semiconductor crystals with perturbations
Direction
Figure 3.22: Geometry of the stable and metastable state of the As-antisitc defect
in GaAs. (After Dabrowski and SchrJler, 1992.)
interstitial As atom and Ohe three adjacent, A s atoms, st,rong sy2-bonds can
be formed similar to the bonds in the graphite structure of carbon and that
of g a y As. The non-bonding p-orbital of the A s atom, which lics rcla-
tively high enmgetically, does not increase t,he total energy of thc interstif,ial
s h t e because it remains largely unoccupied, the two remaining electrons are
hosted by the dangling bond of t,hc fourth remotc lying As atom.
DX-centers
one has 5 x loz2 bulk atoms and only 4 x 1015 surface atoms. Beside the
above mentioned bulk properties, there are other properties or processes,
like crystal growth, oxidation, etching or catalysis, which are determined by
the surface atoms only. In these rases, the model of an infinite solid does not
apply, of course. Moreover, in semiconductors, bulk properties like transport
are often not controlled by all atoms but only by dopant atoms. Then the
number N s of surface atoms per cni i s to be compared with the number
of dopant atoms. For a semiconductor sample of thickness d , area 1 cm2,
and doping concentration N D , the number N o x d of dopant atoms per c7n2
can easily become as small as the number IV, of surface atoms. This means
that the transport properties of such a semiconductor sample will depend
on its surface. In the history of semiconductor physics, this was recognized
at a very early stage. Examples which demonstrate this are the electric
rectification at a semiconductor-metal contact (discovered by F. Braun in
1874), and the unsuccessful attempts to build a field effect transistor in
the late thirties of this century. The failure was caused by electron states
localized at the surface which captured all the electrons induced by the
extcrnal voltage.
lhe surfaces used in the early field effect experiments were far from
perfect. They were made by cutting or cleaving a semiconductor sample in
air. If at all, they were clean and smooth in a macroscopic sense, but not
so microscopically. They exhibited surface roughness on the 100 nm scale,
structural defwts on the 1 nm scale, and impurity atoms at and below the
surface. The surface states responsible for the difficulties of the early field
effect transistor were due to these imperfections. In the present section we
will deal with surfaces which are free of such imperfections. Perfect surfaces
of semiconductor crystals in this sense necessarily represent a particular
lattice plane occupied only by chemically correct atoms at regular sites.
No impurity atoms are allowed above or below the surface. The surface is
reduced to what it means ideally, the termination of the crystal.
Perfwt surfaces in this sense cannot, of course, be realized in practice.
One may only try to approximate them so closely that the existing imper-
fections do not essentially change the properties of the surface as compared
to the properties which a perfect surface would have, if it really could be
made. One calls such almost perfect surfaces clean. Although this term
refers only to chemical composition, it also implies structural perfection or
atonzc smoothness. There are essentially t h r w ways to manufactwe clean
surfaces. All thrw need ultrahigh vacuum (UHV), i.e. pressures below
Torr:
(i) Treatment of imperfect surfaces by ion bombardment and thermal an-
nealing (generally in several cycles).
(ii) Cleavage under UHV conditions (only surfaces which are cleavagc planes
336 Chapter 3. Electronic structure of semiconductor crystals wilh perturbations
n - h l b l + h2bz +h ~ b 3 . (3.182)
Hrre, reciprocal lattice vectors are understood without the factor 27~in def-
inition (2.122). If the normal direction n is given, the roefkients ( h l h ~ h 3 )
are only determined up to a common integer factor. We chose this factor
such that h l , h 2 , hs have no common divisor. Then the coeffirients hi,h2, h 3
are the Miller indices of the lattice plane under consideration, however, r e
ferring to the primitive lattice vectors al,a 2 , a 3 as coordinate axes rather
than to the crystallographic axes. The latter are parallel to the piimitive
lattice vectors only in the case of primitive Bravais lattices. For centered
laltires, like the face rentrred cubic one, they have different directions, and
the coefficienls ( h l h ~ h 3differ
) from the corrirnon Miller indices. Tf necessary,
one can rasily switrh from one representation to the other. The ( h l h 2 h 3 )
are, apart from a co~linionfactor, obtained by multiplying the ( h k l ) with the
matrix which transforms the three nun-primitive crystallographic axis vec-
tors into thc three primitive lattice vectors. Using the above characterization
of lattice planes by their normal direction n, the lattice points
Ri = w a l + v z a 2 +w a ~ (3.185)
of the infinite family of parallel plancs are obtained by replacing the right
hand side of quation (3.181) by arbitrary integers 1,
(3.186)
The points of the lattice plane defined by equation (3.184) form a 2D lattice.
The primitive vectors of this lattice will be denoted by fi and f2. This i s
done in such a way that the three vectors f1, f2, n form a right hand coor-
dinate system. The f1, f2 may be expressed in terms of the primitive lattice
338 Chapter 3. Electronic structure of semiconductor cryst& with perturbations
Table 3.8: Primitive surface lattice \rectors and stacking vectors of low index sur-
faces of semiconductor crystals.
n Crpst'alStructures
I
I1 Diamond, Zincblende, Rocksalt.
1 WurtBite, Selenium
Ro = S l f i + sgh. (3.187)
The lattice planes Rr defined by equations (3.185 and (3.186) can be written
in the form
way, i . ~ .by means of the Euclidean algorithm. BS the vectors Fi,fid were
obtained above. The choice of $3 is not uniquc. of course, and any vector fi
which differs from f 3 hy a vector aithiii the latticr plan? can also be used.
We call f 3 the stacking vector because it determines how the lattice planes
arc stacked in the crystal.
The considerations above show that the primitive unit cell of a crystal
may be chasm as a parallelrpiyed with one of its pair6 of parallel laws par-
allel to a gwen lattice plane. This implies that the structure of a crystal
3.6. Clem semiconductor surfaces 339
Figure 3.23; Construrtion of a crystal from its lattice planes. The lattice points of
a given plane are occupicd by identical atoms. Different planes may host different
atoms if the crystal has a basis. In the figure, a crystal with o~ilyone atom per
primitive unit cell is shown.
(3.189)
The complete set of locations of atoms in an infinite 3D crystal can be
obtained by assigning all possible integer values from --oo to +m for 1, s 1 , s 2 ,
and all integer values from 1 to J for j . The normal direction n, upon which
the whole construction of lattice planes is based, is arbitrary in the case of
an infinite 3D crystal. Any choice of n yields the same crystal.
We can immediately employ the above representation of an infinite crys-
tal in describing a crystal with a surface. The normal direction n is then,
however, fixed by the direction perpendicular to the surface. We start with
the description of a crystal having an ideal surface. The exact meaning of
ideal in this context is explained immediately below.
n . R(j, 1 , s 1 , 5 2 ) = I + n . Tj 5 0. (3.190)
The surface or first atomic layer is obtained if the left hand side of this
relation is taken to be zero. A solution of (3.190) is 1 = 0 and = 0.
3.6. Clean semiconductor surfaces 34 1
itself, this also holds for any other layer. It immediately follows that the
group of translations of a crystal with a surface is identical to the translation
group of the first atomic layer. The lattice vectors r of a crystal possessing
an ideal surface perpendicular t o the normal direction n are therefore those
of equation (3.187), so that
holds. The vectors f1, f 2 are the primitive lattice vectors of the 2D lattice
of the ideal surface. The primitive unit cell of the crystal with surface has
the form of a prism bounded above by the parallelogram spanned by f1, f 2
and extending to minus infinity in the direction of -f3. For the low-index
surfaces of the common semiconductor crystal structures, the three vectors
f1, f2, f 3 are listed in Table 3.8.
As in the 3D case, 2D lattices may be divided into crystal systems and
Bravais lattices according to their symmetry with respect to rotations and
reflections. We now consider the possible plane crystal systems and plane
Bravais lattices. Their point symmetry elements are necessarily rotations
about axes which are perpendicular to the 2D lattice plane, and reflections
at lines within the 2D lattice plane. Thus, the point groups are either C ,
( n ) or C,, (nm, nmm). Since the rotation through 180' is always a sym-
metry element of a plane lattice, only even n are allowed. The highest value
of n may be readily obtained from the derivation of the possible rotation
symmetry axes of 3D crystals in Chapter 1. There, n 5 6 was found. Thus,
the possible multiplicities of rotation symmetry axis of plane lattices are
n = 2,4, and 6.
A lattice which only contains a 2-fold symmetry axis is either a com-
pletely general oblique lattice or a rectangular lattice. The point groups of
these lattices are, respectively, C 2 (2) and C2, (2mm). Lattices with a 4-fold
symmetry axis also possess 4 reflection lines which are rotated through 45'
with respect to each other. The point group of such a lattice is therefore C4v
(4mm). Similarly, lattices with a 6-fold axis have 6 reflection lines which
meet at an angle of 30'. In this case the point group is c 6 v (6mm). There
are thus 4 different plane crystal systems - the oblique with holohedral point
group 2, the rectangular with holohedral point group 2mm, the quadratic
with holohedral point group 4mm and the hexagonal with holohedral point
group 6mm (see Figure 3.24).
The possible plane Bravais lattices are obtained as follows. First, one
takes the four primitive lattices with unit cells which are parallelograms
having either no particular symmetry, or that of a rectangle, a square or an
equilateral hexagon. Then one adds additional points to each of the unit cells
of these lattices in such a way that their point symmetries are not lowered.
Only one new lattice is obtained in this way, namely the 'body' centered
3.6. Clean semiconductor surfaces 343
Figure 3.24: The 5 plane Bravais lattices of the 4 plane crystal systems.
We wish to establish, on the one hand, point groups which transfer equivalent
directions of a crystal with surface into one another and, on the other hand,
space groups which transform the crystal with a surface into itself. In the
latter case this implies that not only does the 2D lattice transform into
itself, but so do equivalent atoms occupying the primitive unit cells. These
atoms are located at positions R(j,I, sir92) given by equation (3.189). To
express the 2D nature of the translation symmetry of a crystal with a surface
explicitly, we denote the atomic positions by Rjl(s1, s2) R(j,I , ~ 1 , s and
~)
write
344 Chapter 3. Electronic structure of semiconductor crystals with perturbations
Table 3.9: Structural properties of ideal low index surfaces of the five common
semiconductor crystal structures. Column 6 and 7 give, respectively, the number
of atomic layers of an irreducible crystal slab and the number of basis atoms per
layer.
hexagonal 3m p3ml 6 1
hexagonal 3m p3ml 6 1
square 4mm P h m 2 2
prectangular 2mm p2mm 2 2
hexagonal 3m p3ml 4 1
prectangular m P W 4 4
hexagonal 1 Pl 3 1
(ioio) p-rectangular 1 Pl 6 1
where
represents the basis of the crystal with surface. This basis contains an in-
finite number of vectors corresponding to the infinite number of atoms in a
primitive unit cell. The point and space group elements of a crystal with
surface must leave the surface invariant, i.e. only 2D symmetry groups need
to be taken into consideration. Here, as in the case of translation symmetry,
we therefore also have the situation that, although a crystal bounded by
a surface extends in three dimensions, its point and space groups are only
2-dimensional.
The point groups of directions of crystals with plane surfaces are nec-
essarily subgroups of the holohedral point groups of the plane lattices, i.e.
subgroups of the point groups 2,2mm, 4mm and 6mm. There are exactly
3.6. Clean semiconductor surfaces 345
a @
..
@ ..
0c3
2
1
2 mm
m
(Ii
.4 m m
4
a 6mm
@ 3m
(I>
3
Figure 3.25: The 10 point groups of equivalent directions of crystals with plane
surface.
10 such groups. Their stereograms are shown in Figure 3.25. This implies
the existence of 10 different crystal classes which are associated with corre-
sponding crystal systems as indicated in Figure 3.25.
The possible plane space groups can be found as follows (see Figure 3.26).
To start with, it is evident that each of the 10 point groups of equivalent
directions combined with the corresponding associated lattice gives rise to a
space group. The space groups p l , p 2 1 1 , p l m l , p 2 m m , p 4 , p 4 m m , p 3 , p 3 m l , p 6
and p 6 m m originate in this manner. Since the point groups of the rectan-
gular crystal system are each associated with two Bravais lattices, primitive
and centered, we find two further space groups, c l m l and c 2 m m . In the case
of the point group 3 m , there are two different possibilities of positioning the
reflection lines relative to the hexagonal lattice vectors, either through the
vertices of the equilateral hexagon of the Wigner-Seitz cell, as assumed in
the case of p 3 m 1 , or such that ,hey bisect its edges. In the latter case one
346 Chapter 3. Electronic structure of semiconductor crystals with perturbations
-
crystal
svstem
Bravais
lattice
ooint soace 1
oblique
2
LLZ
rec- p-rec-
t angular
2mn
t a n g ul o r
6
I I
p'g'
Ip- I
c-rec-
tangular
has the group p31m as a 13-th space group. One should further note that
the point group of directions of a crystal remains unchanged if, in its space
group, a glide reflection line is substituted for an ordinary reflection line. One
must therefore examine the 13 space groups already established to determine
whether the substitution of a reflection line m by a glide reflection line g (i.e.
a reflection in m in conjunction with a translation 7' by half of the shortest
lattice vector parallel to m ) leads to a new space group. One easily finds
that this is not the case for the hexagonal crystal system. In the quadratic
crystal system it is possible to substitute a system of glide reflection line for
one but not both of the non-equivalent reflection line system. This yields the
additional space group p4mg. The additional space groups in the case of the
3.6. Clean semiconductor surfaces 347
2mn
c2mn I
I
p-square 4
- p4
4mn
p4mn I
-
,-hexa- 3
gonal
p3m1 I
Figure 3.26: Continuation: The 17 space groups of crystals with plane surface.
situated parallel to the surface into themselves. More precisely, they con-
tain elements which transform directions in a lattice plane into equivalent
directions in that plane as far as point groups are concerned, and transform
atomic layers located parallel to the surface into themselves if space groups
are under consideration. The 2D point and space groups of the three low-
est index surfaces of the five common crystal structures are summarized in
Table 3.9, columns 4 and 5. The point and space group symmetry of an
ideal crystal surface may also be derived from the projection of the crystal
onto its surface. In Figure 3.27 such projections are shown for the three
low index surfaces of diamond and zincblende type crystals. Atoms from
different layers below the surface are illustrated differently with sizes as in-
dicated. After some number of atomic layers (6 for (lll),4 for (loo), and
2 doubly occupied layers for ( l l o) ) , the projections repeat themselves. A
crystal slab which contains the minimum number of atomic layers necessary
for completing the projection, is called an irreducible crystal slab. The point
and space group symmetries of a crystal with an ideal surface are those of
its irreducible crystal slab.
In the preceding section the atomic structure of crystal surfaces was con-
sidered under the assumption that the atoms of the crystal bounded by a
surface occupy the same positions Rjl(s1,s2) as they did in the infinite 3D
crystal, if the former is generated from the latter by removing one half of
it. As already noted, this assumption is actually not valid. The atoms of
the surface layer experience different forces than those acting in the bulk
of the crystal, and are thus subjected to displacements from their original
sites in the crystal bulk. Since the forces acting on the atoms of the second
layer are in part determined by the positions of the atoms in the first, these
forces are also subjected to changes accompanied by displacements in the
second layer and so on for each successive layer. All one can assume is that
the displacements decrease from one layer t o the next and vanish altogether
at a depth that is relatively far from the surface. Here, we present a more
detailed description of the surfaceinduced displacements of atoms and dis-
cuss the resulting altered symmetries as compared to those of ideal crystal
surfaces.
(1111
(1101 coiii
0 1 A 0 1 A 0 1 A
O2B 0 2 6 016
0 3A 0 3A 2A
Figure 3.27: Projections of a diamond or zincblende type crystal onto its low index
surfaces.
by Rj~(s1,
sz). Then
The displacements 6Rjl may be divided into two classes with regard to their
effect on translation symmetry. If the latter is not affected, the displacements
are termed r-e-eluzation. In this case equivalent atoms in different primitive
unit cells are displaced in the same way, i.e.
350 Chapter 3. Electronic structure of semiconductor crystals with perturbations
Figure 3.28: Surface relaxation (a) and surface reconstruction (b) extending up to
the second atomic layer. A 2 x 2 reconstruction is shown in part (b).
T = Ts fl Tb (3.197)
of Ts and Tb. Alternatively, one can say that T is the largest common
subgroup of both groups Ts and Tb. There are two possibilities, either T
only consists of the identity translation, which means that the lattices defined
by Ts and Tb are non-commensurate and the crystal with surface does not
possess any lattice translation symmetry, or T contains more elements than
just the identity, in which case one says that the two lattices derived from
Ts and Tb are commensurate. The lattice associated with the T is called the
coincidence lattice. If, in particular, Tsis a subgroup of Tb then T is equal
3.6. Clean semiconductor surfaces 35 1
to T,, i.e. the coincidence lattice is identical to the lattice T, of the surface
slab. If T, is not a subgroup of Tb then T cannot be equal to T, and is
necessarily a proper subgroup of T,, i.e. it is smaller than T,. One can thus
distinguish between the following three cases with regard to the translation
symmetry of crystals having a reconstructed surface:
(i) no translation symmetry,
(ii) translation symmetry exists but is smaller than that of the surface slab,
(iii) translation symmetry exists and is the same as that of the surface slab.
If one assumes that, among the various conceivable surface reconstructions
with a given degree of translation symmetry, that particular reconstruction
will take place which allows for maximum translation symmetry of the crystal
with surface (the system surface slab plus bulk slab), then only the third
of the above possibilities can be realized. A formal proof of this assumption
does not exist, and it is probably not valid without exceptions, however, as
a rule, it generally yields correct results.
Using the above conclusions we are able to determine the primitive lattice
vectors of the reconstructed surface in terms of the primitive lattice vectors
f1, f 2 of the ideal surface. The latter are, by definition, also the primitive
lattice vectors of the bulk slab of the crystal with surface. Let be fi and fi
the primitive lattice vectors of the reconstructed surface slab. They may be
linearly composed of f 1 , f 2 according to
C(hlc1) n x m. (3.201)
(2) The off-diagonal elements of Q are not equal zero, i.e. fi is not parallel
to fi and/or fi is not parallel to f2. The angles L(f!, fi) and L(f&fz), which
are in general not equal to each other, are assumed to be equal in the case
under consideration. This means that the two vectors f1, f2 (with tails joined
at the same point) can be transformed into the two corresponding vectors
f;, fi by a rotation through the same angle L(f;, fi) = L(f4, f2) = a about
an axis which is perpendicular to the surface, with a subsequent rescaling
/ ~ f ~ ~ A, (hlcl) surface
of f1, f2 by the factors lfiI/fll and ~ f ~ ~respectively.
of a particular material C reconstructed in this way is characterized by the
symbolic notation
lfil x
C(hkl) - 141 - a.
- (3.202)
lfil If21
The factors lf~l/lf~land lfil/lf21 are in general irrational in contrast to the
qik, which in the case considered here are integers. Examples of both of the
special reconstruction forms discussed, as well as for the general reconstruc-
tion form in case (iii), are shown in Figure 3.29.
Sometimes, in the notation (3.201), n x m is replaced by p - n x m
or c - n x m. The lattice vectors fi = nfi and fi = mfz are then not
necessarily primitive as originally assumed in the notation (3.201), and in
addition to primitive ( p ) reconstructed surface lattices, also centered ( c )
ones are possible. This can only take place, however, for rectangular surface
lattices. Thus, the modified notation applies only to this case, although
it is also sometimes used (formally incorrectly) for square lattices. In the
rectangular case the notation c - n x m describes a type of reconstruction
which is not covered by one of the two notations (3.201), (3.202), and which
can otherwise only be characterized by the 2 x 2 matrix Q itself. For square
reconstructed lattices the c - n x m notation is just a simpler description of
a reconstruction of type (3.202).
The point symmetry of a reconstructed surface lattice is generally lower
than that of the ideal surface lattice from which it is derived. This im-
plies that the crystal with reconstructed surface belongs to a different plane
3.6. Clean semiconductor surfaces 353
crystal system than the crystal with ideal surface. For example, the 2 x 1
reconstruction of a square lattice leads to a rectangular lattice. The same
holds for the 2 x 1 reconstruction of a hexagonal lattice which also results
in a rectangular lattice.
The point and space symmetries of relaxed or reconstructed surfaces are gen-
erally of lower degree than those of the corresponding ideal surfaces. They
do not only depend on the point and space symmetries of the irreducible
crystal slab as in the case of an ideal surface, but also on the point and
space symmetries of the relaxed or reconstructed surface slab. If the surface
slab consists of more layers than the irreducible crystal slab, then its point
and space groups can be taken to determine the point and space groups of
the whole crystal with relaxed or reconstructed surface. If the surface slab
contains fewer layers than the irreducible crystal slab it is expedient to add
further atomic layers (which then do not contain displaced atoms) to make
up the difference. The point and space group elements of the thus extended
surface slab which are simultaneously point and space group elements of
the irreducible crystal slab form, respectively, the point and space groups of
the whole crystal with relaxed or reconstructed surface. Similarly like this
was done for the translation symmetry group above, one may argue that the
point and space groups of the relaxed or reconstructed surface slab should be
subgroups of the point and space groups of the corresponding ideal surface.
If this is the case, the point and space groups of the relaxed or reconstructed
surface slab are, respectively, the point and space groups of whole crystal
with relaxed or reconstructed surface.
The electrons and cores of a crystal with a surface undergo the same interac-
tions as the electrons and cores of an infinite bulk crystal, the only difference
being that the cores and electrons of the removed semi-infinite crystal above
the surface are missing, and the positions of the cores just below the surface
3.6. Clean semiconductor surfaces 355
differ from those in the infinite bulk. The two basic approximations of the
theory of the interacting electron-core system of an infinite crystal, namely
the adiabatic approximation and the one-electron approximation, are not
influenced by these modifications, so they may also be used in the presence
of a surface.
In the electronic structure calculations of infinite bulk semiconductor
crystals, the core positions commonly are taken as input data. This is pos-
sible because these positions are crystal sites of high symmetry which are
well-known from X-ray diffraction experiments. For crystals with a surface,
this can no longer be assumed. The positions of atoms in the surface layers
of relaxed or reconstructed surfaces are crystal sites of lower symmetry. In
many cases, they are not known or only incompletely known from experimen-
tal investigations, for these investigations are more difficult and less precise
than X-ray diffraction in the case of bulk crystals (a short review of these
methods will be given further below). X-ray diffraction cannot be applied
to surfaces because it lacks surface sensitivity. In such circumstances, the
positions of atomic cores at surfaces are to be treated as output, rather than
input, data of the electronic structure calculations. The way that this can be
accomplished was discussed in section 2.2 in general terms, and in section
3.5 with respect to point defects. It involves, first, the calculation of the
total energy of the electron-core system for a variety of different sets of core
positions and, second, the minimization of the total energy with respect to
these sets. The minimum set gives the core positions which really apply. The
most critical part of the total energy is the energy of the electron system.
In order to obtain it, the one-electron energies of the crystal with surface
have to be calculated for assumed core positions. Formally, this involves the
same task as in the case of bulk crystals, namely, the calculation of station-
ary one-electron states for given core positions. Below, we will demonstrate
how this problem can be solved in the case of crystals with surfaces. The
remaining parts of the procedure for determining the atomic and electronic
structures of surfaces, the calculation of the entire total energy including the
core-core interaction energy, and the minimization of the total energy with
respect to the core positions, will not be treated here because it is mainly a
numerical task.
The assumption of a priori known core positions is valid if ideal surfaces
are considered. In this case they are the infinite bulk positions. The elec-
tronic structures of ideal surfaces are important as reference data for the
electronic structures of relaxed and reconstructed surfaces. Thus we will
also deal with them.
(3.203)
as in the case of an infinite bulk crystal (see equation 2.53). The oneelectron
potential V(x) may be written as the sum
-W J
(3.205)
Bloch theorem
This theorem states that the energy eigenfunctions $E(x) of the Schrodinger
equation (3.203) may be chosen simultaneously as eigenfunctions of the sur-
face lattice translation operators t,.. This allows one to write these functions
in the form of Bloch functions @Q(x) with a 2D quasi-wavevector
(3.211)
with p1,pz as integers. This means that the q-vectors must belong to a
finely-meshed lattice similar to that of Figure 2.4. For the macroscopically
large values of G which we assume, q is practically continuous, although the
number of different q-values within a given region of q-space is finite.
In the reduced scheme, the energy function E(q+ g) over the whole q-space
is replaced by the manifold of functions E,(q) +
E ( q g ) defined only over
a primitive unit cell. As in the bulk case, there is a distinguished choice of
the primitive unit cell, as we will see below.
Using first order perturbation theory with respect to the periodic poten-
tial V(x), one may demonstrate that, in the extended scheme, E(q) repre-
sents a continuous function of q everywhere, except for the q-vectors with
lql = lq + gl or
q . g + -1 g2 = 0, (3.212)
2
where g is an arbitrary surface reciprocal lattice vector. Equation (3.212)
defines lines in the 2D q-space which are analogous to Bragg reflection planes
in the 3D k-space of a bulk crystal. On Bragg reflection lines, the energy
function E(q) has discontinuities. These lines may be used to define 2D
Brillouin zones in just the same way as was done in the 3D case in section
2.4. One speaks of surface Brillouin zones (BZs). The surface B Z s of the
square lattice have, in fact, already been used in section 2.4 as an illustration
for the 3D case. Of particular importance is the f i r s t surface B Z . It may
also be defined as the Wigner-Seitz cell of the reciprocal surface lattice.
Since there are 5 different plane Bravais lattices and, hence, 5 different
reciprocal surface lattices, there are also 5 different first surface B Z s . They
are shown in Figure 3.31. Their shapes are the same as those of the Wigner-
Seitz cells of the corresponding direct lattices since the Bravais types of the
direct and reciprocal surface lattices always coincide.
The first surface B Z s are, by definition, free of Bragg reflection lines.
Thus the energy function E(q) is continuous within these zones. Further-
more, any higher surface B Z of order p may be reduced to the first surface
B Z , and the energy function E(q) in the p-th surface B Z can be folded
back to the first surface B Z . There, it forms a continuous function E,(q)
which is called a surface energy band. Thus we may state that the energy
eigenvalues of a crystal with surface form energy bands over the first surface
BZ.
There are surface bands of different types, regarding their relations to
the energy bands of 3D bulk crystals without surface. Below we characterize
these differences in a qualitative way.
Types of eigenstates
Bulk states
Consider an infinite bulk crystal, and cleave it into two semi-infinite crystals
with a surface parallel to a particular lattice plane. The spectra of energy
3.6. Clesn semiconductor surfaces 359
t' tY
Figure 3.31: Surface B Z s of the 5 plane lattices: (a) oblique, (b) p-rectangular,
(c) c-rectangular, (d) square, (e) hexagonal. Symmetry lines and points are also
shown, and their notations are introduced.
eigenvalues of the two semi-infinite crystals will contain all energy levels
which were already eigenvalues of the infinite bulk crystal before cleaving.
This implies that each crystal with surface possesses an energy eigenvalue
spectrum which partially is made up from energy eigenvalues of the infinite
bulk crystals from which it is derived. The eigenfunctions of the crystal with
surface corresponding to these eigenvalues, if examined at positions outside
of the crystal, will decay exponentially with increasing distance from the
surface, while inside they will practically be the same as those of the infinite
crystal, i.e. they will exhibit undamped oscillations throughout the whole
semi-infinite crystal, as do the eigenfunctions of the infinite bulk crystal (see
Figure 3.32). Eigenstates of a crystal with surface exhibiting such properties
are called bulk states. The corresponding energy eigenvalues form bulk state
surface energy bands Ep(q). These bands can be obtained by projecting the
bulk bands E?"(k) of the infinite crystal onto the first surface B Z . Here,
'projecting' means that one assigns to a particular point q of the first surface
B Z all bulk band energies EF"(k) corresponding to k-vectors of the first
360 Chapter 3. Electronic structure of semiconductor crystals with perturbations
I
x C
f
.-0
P
W
-w
0
C C
3
w +
W
surface state
9- 0 x-
Figure 3.32: The three different types of electron energy eigenstates of a crystal
with surface below the vacuum level (schematically).
bulk B Z having the same projection q on the surface B Z plane, but with
various components kl perpendicular to it. Formally, this can be expressed
by the relations
The bulk state surface band index p in (3.213) replaces the bulk quantum
numbers v k l . As kl varies continuously, @ also does. This means that a
particular band of the infinite bulk crystal gives rise to a continuum of surface
bands. In this way, the infinitely large number of atoms in a primitive unit
cell of the crystal with surface manifests itself.
We illustrate the projection of bulk bands onto the surface B Z using the
(100) surface of a diamond type crystal as an example. The band structure
is taken from the empty lattice model introduced in section 2.4. As a first
step, the bulk B Z is to be projected onto the plane of the first surface B Z
(see Figure 3.32). In doing so, one notes that part of the projected bulk B Z
lies in the second surface B Z . This has to be folded back to the first surface
B Z , together with its energy values. In this way we obtain the projections
of the lowest three empty lattice bands shown in Figure 3.33. In addition
to q-vectors for which all energy values are allowed, there are also q-vectors
occurring for which certain energy values are forbidden. This peculiarity is
found in other, more realistic cases as well, it represents a general feature
of the projected bulk band structure. In the forbidden energy regions states
may occur which are localized at the surface.
3.6. Clean semiconductor surfaces 361
Surface states
Such states are to be expected for the same reason that localized states are
observed in the case of point or 0-dimensional perturbations. In contrast to
the latter, surfaces constitute 2-dimensional perturbations. The localization
occurs, therefore, only in 3 - 2 = 1 dimension, namely that perpendicular to
the surface. If the energy lies in the forbidden region of the projected bulk
band structure, the decay of the eigenfunction towards the bulk proceeds
exponentially (see Figure 3.32). The states are then called bound surface
states and the corresponding energy bands E,(q) are bound surface bands.
Besides these, one has surface resonances and antiresonances. The latter
occur at energies in the allowed region of the projected bulk band structure
and give rise to resonant or antiresonant surface bands Ep(q). They mani-
fest themselves in an increase (resonance) or decrease (antiresonance) of the
density of states. The eigenfunctions at these energies are also localized at
the surface, but decay less rapidly towards the bulk (according to a power
law) than the exponentially decaying bound surface states. Antiresonances
are necessary in order to satisfy Levinsons theorem, which holds for surfaces
as well as for point perturbations. If bound surface states exist, the antires-
onances must compensate the increase of the total DOS in the previously
forbidden energy region.
The spatial symmetry of a crystal with surface has implications for the pos-
sible degrees of degeneracy of surface energy bands Ep(q), p = p, (T,p, at a
362 Chapter 3. Electronic structure of semiconductor crystals with perturbations
r K r
I I I
Figure 3.35: Symmetry and degeneracy of the surface energy bands for the 5 space
groups of the p-rectangular Bravais lattice. [After Terzibaschian and Enderlein,
1986.)
to the surface. This point of view gives rise to the so-called slab method for
calculating the electronic structure of crystals with surfaces.
Slab method
(3.214)
The number of different Bloch sums is infinitely large even if a finite number
of orbitals is used per atom, because the integer 1 counting the primitive
crystal slabs, runs from 0 to -co. Consequently the Hamiltonian is given
by an infinite matrix in the atomic orbital representation &jl,.(x). Some
specific approximation is necessary to transform this to a finite matrix. One
possibility is to consider a slab of the crystal, i.e. to cut off the semi-infinite
crystal at a particular lattice plane parallel to the surface and discard the
remainder. One may say that, in the direction perpendicular to the surface,
the true semi-infinite crystal is replaced by a cluster (see Figure 3.36). The
latter has two plane surfaces, one of them being real (that of the semi-infinite
crystal), and the other one (obtained by cutting the semi-infinite crystal) not.
This differs from the cluster method in the case of point defects discussed in
section 3.5 where the whole cluster surface is artificial.
The slab method may be combined with any band structure calculational
method for infinite bulk crystals. Its combination with the tight binding
method will be illustrated below by means of an example.
We consider the ideal (111) surface of a diamond type crystal which
according to subsection 3.6.2, has a hexagonal Bravais lattice. Instead of
the one s- and three p-orbitals per atom we use the four hybrid-orbitals, i.e.
we replace a in the Bloch sum (3.214) by ht, t = 1 , 2 , 3 , 4 . Only nearest
neighbor interactions are taken into account. An illustration of this model
is given in Figure 3.37. To get the matrix elements of the Hamiltonian
H between Bloch sums, we first need these elements between the localized
hybrid orbitals +htjlT Ihtjlr). The diagonal elements are
(3.215)
3.6. Clean semiconductor surfaces 365
Figure 3.36: Illustration of the slab method for surface band structure calculations.
Figure 3 . 3 7 Defect molecule model of the ideal (111) surface of a crystal with
diamond structure.
and the non-diagonal elements between different hybrids at the same atom
j = j are
(htllrlH(htJ1lr)= VI , t # t . (3.216)
The two types of matrix elements in (3.215) and (3.216) are equal for atoms
at the surface and in the bulk. This is not true for elements between hybrids
located at different atoms. Let j = 1,1= 0, designate the surface atom layer
and consider the elements (ht10rJH]ht20rt)between the hybrid ht located
at the surface atom 10r and the hybrid lht20x-t) at its nearest neighbor 20rt
below the surface, pointing toward (htlOr). Since no nearest neighbor hybrid
exists for the hybrid )hllOr) pointing out of the surface, all nearest neighbor
elements involving IhllOr) vanish. The other three elements with t = 2 , 3 , 4
are equal to the parameter V2 introduced in equation (2.292),
366 Chapter 3. Electronic structure of semiconductor crystals with perturbations
Using equations (3.215), (3.216) and (3.217), the matrix elements between
the corresponding Bloch sums (3.214) may be formed. They are
(htlOq(Hlht,lOq)= v1 , t # t . (3.219)
(3.222)
The eigenvalues of this matrix are plotted in Figure 3.38 for different sym-
metry lines of the first surface B Z of the hexagonal lattice of Figure 3.31.
3.6. Clean semiconductor surfaces 367
r M K r
W avevec tor
Figure 3.38: Band structure of the ideal (111) surface of a diamond crystal within
the defect molecule model. The TB parameters are V1 = 2.13 e V , V2 = 6.98 e V .
The hybrid energy Eh is used as the energy origin.
The three lowest and three highest bands are bulk state surface bands. They
arise from the three hybrids of the surface atom, which bind this atom back
to its nearest neighbors in the second layer. More strictly, they correspond
to the 3 back bonding and antibonding states. The band in the gap is due
to the dangling hybrid of the surface atom. It forms a bound surface band.
If we were to consider more than 2 atomic layers, the region where the bulk
bands in Figure 3.38 occur would be covered by more bulk state surface
bands, while the bound surface band in the gap would hardly change.
Supercell method
Figure 3.40: Illustration of the defect method for calculating surface energy band
structure.
create the same number of vacancy layers (see Figure 3.40). What remains
are two identical semi-infinite crystals which are only displaced with respect
to each other. They do not interact provided the number of vacancy layers
is large enough, which we will assume. The electronic structures of the two
semi-infinite crystals coincide, and are identical with that of the considered
crystal with surface. As in the case of a single vacancy, the states bound at
the defect may be obtained by means of the Greens function G o ( E )of the
unperturbed 3D crystal, more strictly, by the vanishing of the determinant
of [Go(E)V - 11 (see equation (3.134)). Here, the perturbation potential
V(x) represents the difference of the potential energy of an electron in the
perturbed and unperturbed crystals. It is the negative of the sum of the
potentials of the removed atoms or the sum of all vacancy potentials. It has
the 2D lattice symmetry of the surface so that
If only nearest neighbor interactions are taken into account, a single layer
of vacancies is enough to decouple the two semi-infinite crystals. For the
analysis of the bound state condition (3.74), one has to use a particular basis
set, just as in the case of a point perturbation. Wannier functions are again
a possible choice, but here they involve localization only in one direction,
namely that perpendicular to the surface. We denote these functions by
IvqRl) where RI is the component of a 3D lattice vector R perpendicular
to the surface, such that
370 Chapter 3. Electronic structure of semiconductor crystals with perturbations
(3.224)
For the perturbation potential V1(x) we take that of a single layer of vacan-
cies located at RI = 0. Then the matrix representation of V1(x) is
with
(3.228)
If one compares this equation with the corresponding relation (3.94) for deep
centers, it will be noted that the q-dependence which occurs here was absent
there. This dependence in the case of surfaces causes the eigenvalues in the
gap to form deep bands rather than deep levels (which was the case for
point perturbat ions).
Finally, still another method for surface band structure calculations should
be mentioned. It is based on the transfer matrix concept of quantum mechan-
ics. The transfer matrix M ( E ) is formed from solutions of the Schrodinger
equation upon one unit cell of the bulk crystal for particular boundary condi-
tions in the direction perpendicular to the surface. The energy E is arbitrary
first of all. Transferring the wave function from the surface unit cell to the
3.6. Clean semiconductor surfaces 371
n - th unit cell below the surface can be done by applying the n - t h power
W ( E ) of M ( E ) . Bound surface states are obtained for such energy values
E for which M n ( E ) decays exponentially with n. The practical use of this
method seems to be limited, however.
In this subsection we will deal with the atomic and electronic structures of
some important semiconductor surfaces, including the various reconstruction
states of the Si (111) surface, the Si (100) surface, the (110) surface of GaAs
and other 111-V compound semiconductors as well as the (111) and (100)
surfaces of GaAs. It is advisable to treat the atomic structure together with
the electronic structure because of the close relation between the two kinds
of structures, as was pointed out earlier. We begin with a short introduction
to the experimental methods of surface structure analysis, again referring to
both the atomic and electronic aspects.
(3.230)
A solution of the two equations (3.230), (3.231) always exists for given vec-
tors ki and g (this is in remarkable contrast to coherent scattering of elec-
trons from 3D bulk crystal, which can only occur if k, lies on a Bragg re-
flection plane). The solution of equations (3.230) and (3.231) can be readily
carried out using the construction shown in Figure 3.41. The points at which
the vertical lines passing through the reciprocal lattice points g intersect the
3.6. Clean semiconductor surfaces 373
sphere Jk,]= lkzl, determine the directions in which diffraction maxima oc-
cur. There is exactly one maximum for each reciprocal lattice point g. The
reciprocal surface lattice can thus be read immediately from the distribution
of the diffraction maxima on the registration screen. The direct surface lat-
tice is the reciprocal of the reciprocal surface lattice. Some typical LEED
images are shown in Figure 3.42. The bright points correspond to the re-
ciprocal lattice of the ideal surface, and the less bright points to the finer
reciprocal lattice of the reconstructed surface. In this way it is relatively
easy to determine the surface lattice by means of LEED. To obtain the ac-
tual positions of atoms is more diacult. One needs additional experimental
and theoretical information about the intensity of the diffraction maxima as
a function of the energy of the incident electrons (dynamical LEED).
Besides LEED, there are other methods for surface structure analysis
which, although they are not a substitute for LEED, can supplement it.
These methods include diffraction of energetic electrons in the region of some
10 k e V , known as Re5ection High Energy Electron Diffraction ( M E E D ) ,
diffraction of X-rays incident almost parallel to the surface, and diffrac-
tion of slow Helium atoms (of M I00 meV). Scattering of energetic ions
( M 1 M e V ) is used in techniques like Rutherford backscattering (RBS) and
ion channeling. Imaging procedures of significance are transmission elec-
tron microscopy (TEM), scanning tunneling microscopy (STM) and atomic
force microscopy (AFM). The latter two methods have become particularly
important.
Like for atomic structure determinations, a variety of methods exist to
study the electronic structure of surfaces, in particular the bound surface
states in the energy gap of the bulk crystal. The most powerful and uni-
versal method is photoemission spectroscopy (PES). This method relies on
the external photoeffect in which an electron is emitted from the crystal by
374 Chapter 3. Electronic structure of semiconductor crystals with perturbations
x6
Figure 3.42: LEED pictures of six differently prepared GaAs (100) surfaces.(After
Drathen, Ranke and Jacobi, 1978.)
11101 hi01
Figure 3.43: Geometry of the ideal Si (111) surface (left) and of the Si (111) 2 x 1
surface according to the buckling model (right).
pied surface states one may use inverse PES in which electrons captured
by such states emit photons. Beside photoemission, a variety of other tech-
niques exists which can provide data on surface states. In principle, any
experimental technique which probes the electronic structure of bulk crys-
tals can be employed for surface electronic structure investigations, provided
it can be made surface-sensitive. This applies to optical reflectivity, elec-
trical transport, photoconductivity, and capacity measurements, as well as
electron energy loss spectroscopy (EELS). Experimental techniques like field
effect measurements fulfill this requirement from the very beginning. Con-
trolling the energy of tunneling electrons in scanning tunneling microscopy,
surface states can be resolved spatially and energetically (scanning tunneling
spectroscopy).
Experimental techniques which primarily measure the electronic struc-
ture, can also provide data on the atomic structure. The solid state shifts
of core levels (see section 2.1) are an example. These shifts differ for atoms
in the bulk and at the surface because of the altered atomic structure at
the surface. The difference (typically some tenths of an e v ) can be mea-
sured by means of PES and UPS. On the other hand, they can be calculated
on the basis of a particular surface structure model. By comparing theory
and experiment one can evaluate the feasibility of various models of surface
structure.
The calculation of the total energy is a purely theoretical test of the
validity of a particular surface structure model, and it may be used to deter-
mine the parameters which can be varied in such a model. If the model has
optimized parameters and results in a lower total energy than other models
it may be given preference over them.
376 Chapter 3. Electronic structure of semiconductor crystals with perturbations
t i
*!:!
!ii
::I .....
-5 - *
.. .*....
..
..
,-I I I...
ll
iii
r I K r
2D wave vector
Si surfaces
(111) surface
The geometry of the ideal (111) surface of diamond type crystals is illus-
trated in Figure 3.43 (left). The surface lattice is hexagonal, and the two
primitive lattice vectors are fi, f2 of Table 3.8. There is one surface atom per
primitive unit cell, and one dangling bond per surface atom. The (111) sur-
face is the cleavage plane of diamond type crystals. By cleaving a Si crystal
in UHV at room temperature, one obtains a 2 x 1 reconstructed (111) sur-
face. After annealing it at 500 C , a 7 x 7 reconstruction state evolves, which
remains stable at room temperature. The occurrence of a 2 x 1 reconstruc-
tion immediately after cleavage is to be expected if one examines the band
structure of the ideal (111) surface (see Figure 3.44) and considers, in partic-
ular, the electron occupancy of the bound surface band in the fundamental
gap. This band arises from dangling sp3-hybrids of surface atoms, and can
host 2 electrons per surface unit cell. Since 3 of the 4 valence electrons of
a surface atom are in bonds with second-layer atoms, only 1 electron per
surface unit cell is left for the bound surface band. Thus this band remains
only half-filled. The ideal Si (111) surface is metallic.
3.6. Clean semiconductor surfaces 377
r?
'P
Ur-
[1?01 [I101
Side view
a) b)
Figure 3.45: a-bonded chain model of the Si (111) 2 x 1 surface (After Pandey,
1982). Part (a) shows the unreconstructed surface in top and side views. The top
view in the second row has been rotated with respect to the top view in the first
row in order t o allow for the side view below. Part (b) shows the same views of the
surface as in part (a), but after reconstruction has taken place.
3.6. Clean semiconductor surfaces 379
raised above. This implies the creation of an electric dipole which is too
costly in energy to actually take place. Using the terminology of section
2.2 we may say that correlation effects of electron electron interaction, more
strictly speaking, the configuration dependence of oneelectron states, pre-
vents the buckled Si (111) surface to be lower in energy than the ideal one.
The reconstruction model which actually applies to the Si (111) surface
is the so-called s-bonded chain model, illustrated in Figure 3.45. In this
+
model, second layer atoms in rows parallel to fi f2, i.e. along the [lo3
direction in Figure 3.45a (including atom number 2) are raised into the first
layer as shown in Figure 3.45b, breaking their bonds with atoms in the third
layer (for example, the 2-5 bond). The dangling bond of the new surface
atom (say atom 2) is used to establish bonds with atoms of the first layer
(the 2-1 bond in this case). These can only be s-bonds (indicated by double
lines in Figure 3.45b) because the dangling bonds are perpendicular to the
surface. In this way s-bonded chains occur along the [ l O q direction (Pandey,
1982). The dangling bonds left at the third layer atoms (for example, atom
5) are saturated by hybrids of the first layer atoms which have been lowered
down to the second layer (for example, atom 3). The surface is in fact 2 x 1
reconstructed. This may be seen by taking the primitive lattice vectors of
the ideal surface to be f 1 + f 2 and -f2. Doubling -f2 yields the rectangular
lattice indicated in Figure 3.45b by dashed lines. Its primitive lattice vectors
are f1 + f 2 and - 2 f 2 + (fi + f 2 ) = f 1 - f 2 so that the short side of the rectangle
is parallel to the chain direction [lOT], and the long side perpendicular to it
(parallel to [121]).A peculiarity of the n-bonded chain model is that it has
a different bonding topology in comparison with the ideal (111) surface and
also with respect to the buckling model. While the latter exhibit rings with
6 mutually bonded atoms (see Figure 3.45a), the former shows alternating
rings with 5 and 7 bonded atoms (Figure 3.45b). This is due to the fact that
bonds existing at the ideal and buckled surfaces are broken and new bonds
are established in the s-bonded chain model.
The total energy of this model is clearly below that of the ideal surface
(about 0.5 eV per surface atom). Thus it represents a good candidate for
the reconstruction of the (111) Si surface. Further evidence is provided by
ARUPS and optical measurements. Figure 3.46 shows the wavevector dis-
persion of the two bound surface bands as obtained from ARUPS measure-
ments together with the calculated dispersion of these bands. The agreement
is quite satisfying. The strong dispersion of the bound surface band on the
r-X-line and the weak dispersion on the X-M-line of the rectangular sur-
face B Z is easily understandable: the long r-X-side of the rectangular unit
cell in q-space corresponds to the short side of the rectangular unit cell in
coordinate space, which is also the direction of the s-bonded chains. One
expects strong dispersion along the chains and weak for the perpendicular
direction, exactly what is seen in Figure 3.46.
380 Chapter 3. Electronic structure of semiconductor crystals with perturbations
-1
r X nf
20 wave vector
Support for the r-bonded chain model comes also from optical measure-
ments. The differential reflectivity spectrum of the 2 x 1 reconstructed (111)
surface of Si is shown in Figure 3.47. There is no doubt that the observed
peak at 0.5 eV is due to optical transitions between occupied and unoccu-
pied bound surface bands. Such bands exist both in the buckling model
as well as in the 7r-bonding chain model (in the latter one has 7r-bonding
and x-antibonding bound surface bands). However, the two models differ in
regard to their predictions on polarization dependence of optical reflectiv-
ity. According to the 7r-bonded chain model, transitions with light polarized
parallel to the chains, i.e. parallel to [lOq, should be allowed and transi-
tions for light polarized parallel to the perpendicular direction [121]should
be forbidden, while this should be reversed for the buckling model. The ex-
perimentally observed polarization dependence shown in Figure 3.48 is that
predicted by .I-bonding chain model. It rules out the buckling model.
(100)surface
The (100) surface is the surface of choice for electronic device applications
of Si. The geometry of the ideal (100) surface is shown in Figure 3.51. The
surface lattice is a square one, with primitive lattice vectors f 1 , f2 given in
Table 3.8. The primitive unit cell has one surface atom, and each atom
has two dangling bonds which point out of the surface like rabbit ears (see
Figure 3.51a).
Each dangling bond is only half-filled as in the case of the (111)surface
considered above. Thus, the ideal surface is metallic, and this state is un-
likely to be stable. A state of lower total energy can be established by a
2 x 1 reconstruction as follows: The atoms of two neighboring rows parallel
to [ O l i ] (or [Oll]) move slightly towards each other in order to allow bonding
between two of their four dangling hybrids. This dimerization of the sur-
face gives rise to bonding and antibonding bound surface states, the lower
bonding state being completely filled and the upper antibonding state being
completely empty. The primitive lattice vector in the direction of f 1 doubles,
thus a 2 x 1 reconstruction takes place, and the surface lattice becomes rect-
angular. The remaining two dangling bonds of a dimer are still half-filled,
however, so that the surface is not yet stable. It is stabilized by buckling,
3.6. Clean semiconductor surfaces 383
a1
which turns out to be energetically favorable in this case. One of the two
atoms of a dimer moves above the surface and one below. The dangling
hybrid at the lowered atom, being p-like, takes a higher energy and is corre-
spondingly empty, while the dangling hybrid at the raised atom, being s-like,
takes a lower energy and is filled. Rigorous structure calculations essentially
confirm this simple tight binding picture. They only add displacements of
the dimer atoms parallel to the surface in addition to the perpendicular ones.
Due t o the two kinds of displacements, the dimers become asymmetric. The
described 2 x 1 reconstruction of the Si (100) surface is therefore called the
384 Chapter 3. Electronic structure of semiconductor crystals with perturbations
I-- 0
0'- -0
n
It-
-?
0
U
10113
Side view
a) b)
Figure 3.51: Geometry of the ideal Si (100) surface (a), and of the asymmetric
dimer model of this surface.
(110) surfaces
The (110) surface represents the cleavage plane of zincblende type crystals.
The best understood (110) surface of all zincblende type 111-V semiconduc-
tors is the (110) surface of GaAs. Its surface geometry is shown in Figure
3.6. Clean semiconductor surfaces 385
I?
I
I
I
I
I
I
5
0
I
1
I
I
I 1 Y
I I
I I I I
I I
[?I0 1
Side view
-
0
c-
7
U
[?I01
a) b)
Figure 3.52: Geometry of the ideal GaAs (110) surface (a), and of the same surface
after relaxation (b).
3.52. The surface lattice is p-rectangular. The primitive lattice vectors are
given in Table 3.8. There are two surface atoms in a primitive unit cell, one
Ga and one As atom. Two bonds of each surface atom lie within the surface,
one is directed back and one is dangling. The two dangling hybrids per unit
cell have different energies since they belong to either a Ga- or an As atom.
Thus one expects two bound surface bands, one Ga-like and one As-like.
These are in fact seen in the band structure of the ideal (110) GaAs surface
depicted in Figure 3.53. The lower As-like bound surface band is completely
occupied, and the higher Ga-like band is completely empty. Thus the ideal
surface is semiconducting. Nevertheless, it does not yet represent the stable
state, as the gap between the two bound surface states is too small. It can
be enlarged by moving the As atom above the surface, rendering its dangling
hybrid more s-like and lowering its energy, and moving the Ga atom below
386 Chapter 3. Electronic structure of semiconductor crystals with perturbations
Ga As
(111) (1101 (1001
-10
r M K r r x ' M X r r i ~ l r
2 D wave vector
Figure 3.53: Band structure of the ideal GaAs (110) surface. (After Talwar and
Ting, 1992.)
the surface, rendering its dangling hybrid plike and raising its energy (see
Figure 3.52). These displacements do not change the translation symmetry
of the surface because the two atoms belong to the same unit cell. One
therefore has a relaxation instead of a reconstruction of the (110) surface.
This is consistent with LEED measurements, which do not show spots other
than those due to the ideal prectangular lattice. The experimental value
for the rotation angle w of a Ga-As bond with respect to the [ l i O ] direction
is close to 30, in good agreement with structure calculations. Experiment
and theory also agree in regard to an essential feature of the band structure
of the relaxed (110) surface. As indicated in Figure 3.54, relaxation moves
the bound surface bands completely out of the fundamental gap, the As-like
band merges into the valence band, and the Ga-like band merges into the
conduction band. This implies that perturbations of the surface such as,
for example, coverage by an insulator, can easily create surface states in the
gap. Such states are in fact present at GaAs/insulator interfaces. They pin
the Fermi level and preclude the possibility of making GaAs-based field ef-
fect transistors in the same way as the Si-based MISFET (see Chapter 7 for
further discussion).
Relaxations similar to that of the (110) surface of GaAs are also observed
at the (110) surfaces of other 111-Vcompounds. For all materials except Gap,
relaxation moves the bound surface states out of the gap (see Figure 3.54).
3.6. Clean semiconductor surfaces 387
(110)cleavage face
GaP GaAs GaSb In P In As In Sb
- A
2
-
h
-3-
-0
5 -4-
3
u
9 -5- U n
g
3 -6-
x
e
E -7-
w
Figure 3.54: Energy level diagrams of bound surface states and bulk states of var-
ious 111-Vcompound semiconductors below the vacuum level. Solid lines represent
experimental results, and dashed regions represent dangling bond surface bands.
F'ramed undashed regions indicate bulk bands. (After Bertoni, Bisi, Calandra, and
Manghi, 1978.)
Other surfaces
Besides the (110) cleavage surface, investigations have mainly been focused
on the low index (111)and (100) surfaces of GaAs. (100) is the preferred sur-
face orientation of GaAs wafers used in device fabrication (partially because
the (011) plane perpendicular to this surface represents the cleavage plane
of GaAs). The geometrical structures of the ideal surfaces are the same as
those of the corresponding Si surfaces shown, respectively, in Figures 3.43
and 3.51. The (111)and (100) surfaces of GaAs differ from the (110) surface
of GaAs mainly in regard to the fact that two different surface terminations
are possible in their case, one by Ga atoms and another by As atoms. One
says that these surfaces are polar, in contrast to the (110) surface, which is
said to be non-polar. In forming a polar surface, an electric dipole is created
between a Ga-layer and an As-layer which is costly in energy. This explains
why for GaAs and other 111-V compound semiconductors, the cleavage plane
is neither ( l l l ) , like in the case of group-IV materials, nor (loo), but the
non-polar (110) plane. In the latter case the 1:l ratio of Ga- and As atoms
is strictly k e d by chemical stoichiometry. For the polar surfaces, there are,
however, no stoichiometrical reasons which cause a surface termination by
388 Chapter 3. Electronic structure of semiconductor crystals with perturbations
only Ga- or only As atoms. Both kinds of terminations can occur simulta-
neously at a given surface, and in order to define the surface uniquely one
has to specify the percentage of Ga and As it contains. A rough distinction
is that between Ga-rich and As-rich surfaces.
The structure of a particular polar GaAs surface depends decisively on its
termination. For the Ga-rich (111) surface one finds a 2 x 2 reconstruction,
and for the As-rich case there are f i x 8- 30 and a x - 23.4''
reconstructions in addition. For the Ga-terminated 2 x 2 (111) surface, a
model has been proposed with a quarter of the surface atoms missing. The
remaining first-layer Ga atoms and the second layer As atoms undergo a
buckling, which raises the As atoms close to the surface.
The structure of the GaAs (100) surface exhibits an even greater vari-
ety, depending on surface termination, surface treatment and temperature.
Some of the possible reconstruction states can be seen in the LEED pic-
tures of Figure 3.42. The c - 2 x 8 structure is found for an As-stabilized
surface, which is important for MBE-growth because this commonly begins
and ends with As-rich conditions. For the Ga-stabilized surface, the c - 8 x 2
reconstruction is found to be stable.
3.7.1 Heterojunctions
Below we describe the electronic structure of semiconductor heterojunctions.
The two semiconductor materials are taken to be undoped. Free carrier ef-
fects on the electronic structure can be neglected in these circumstances.
In the case of heterostructures formed from doped semiconductors, such ef-
fects might be important. They are treated in Chapter 6 in a systematic
way. Below, we discuss the various stationary one-electron states of undoped
heterostructures, omitting free carrier effects.
3.7. Semiconductor microstructures 389
Material 1 I Material 2
P
a,
L.
may also occur, their energy levels lie in one of the bands and their wave
functions are weakly localized at the interface. If the two materials forming
a heterojunction are composed of chemically similar atoms as in the case
of GaAs and AlAs and in many other cases of practical importance, then
no bound interface states will be possible, because the perturbation at the
interface is too weak.
(3.232)
The difference AE, zz [E,1 - E,2] between the two valence band edges
is called valence band discontinuity or valence band offset of the material
l/material 2 heterojunction. By means of equation (3.232) the valence
band discontinuity AE, is expressed as
(3.233)
Beside the pure bulk contribution [E$ - E&], the band discontinuity also
contains the dipole contribution -e[cpi-pg]. The latter generally depends on
the properties of the interface. If one were to ignore this dipole contribution,
then AE, would obey the so-called transitivity rule which states that the
AE,-values for a succession of two heterojunctions 1/2 and 213 should
add up to the AE,-value of the combination 1/3. In practice this rule is
rarely fulfilled, which points up the importance of the dipole contribution to
A E,.
The dipole contribution -e[cpl - cpz] may be estimated by means of the
tight binding method developed in section 2.6. The bonding energy level
b considered there forms a rough measure for the average valence band
energy. In formula (2.315) b is given for a zincblende type semiconductor.
The corresponding bonding orbitals IbtR) of equation (2.316) describes the
charge transfer from the cation c (there denoted by an upper index 1)to the
anion a (there denoted by an upper index 2) in terms of the hybrid energy
difference EL - 2. If the hybrid energies were equal, no charge transfer
would occur. A semiconductor material i composed of cations ci and anions
ai, forms a big molecule of the average hybrid energy 2 +
; = (2 &/2.
Thus the charge transfer between material 1 and material 2 is governed by
the average hybrid energy difference S i - 2;. If this difference is non-zero,
valence electron charge will be transferred into the material with the lower
value of 2;. As pointed out above, the charge transfer will result in an
electrostatic potential difference at the interface. The potentials on either
side of the interface will add to the average hybrid energies and diminish their
difference. Charge will flow until the average hybrid energy difference has
been equilibrated by the potential jump. This is described by the relation
-1
ch - ecpi = F; - ecp2, (3.234)
3.7. Semiconductor microstructures 393
i.e. the average hybrid energy levels on the two sides of the heterojunction
align, and the potential contribution -e[cpl- 1,721 to the valence band offset
matches IS; - T i ] .
At this point it is advisable to recall a result concerning deep levels of
transition metal (TM) atoms obtained in section 3.5. There, it was shown
that the difference between the position E+M of a deep level of a particular
TM atom in a semiconductor material 2, and the position E&M of the same
deep level in a semiconductor material 1, equals the average hybrid energy
difference between the two materials,
ETM
2 - E&M = 7; - Sk. (3.235)
Taking the deep level positions to be measured with respect to the valence
band edges E& of the two infinite bulk materials, we denote these positions
by E ) ~ , i = 1 , 2 , so that
E ) ~ E k M - EVi.
= 0 (3.236)
Considering relations (3.234) to (3.236), the difference [ c $ ~- t+M] between
the positions of the deep level in the two materials is just the valence band
discontinuity A E , of the two materials, hence
2
AEIJ= [ETM - 61 ~ ~ 1 . (3.237)
This relation reduces the experimental determination of valence band discon-
tinuities to measurements of deep level positions of TM atoms with respect to
the valence band edge. Other experimental methods rely on measurements
of photoemission, optical or transport properties of heterojunctions. Ex-
perimental values for valence band discontinuities of several heterojunctions
are shown in Table 3.10. Often, different values are obtained by different
methods or even by different authors using the same method. This points
up the experimental difficulties in determining valence band discontinuities,
and also to the dependence of the discontinuities on the preparation of the
heterojunctions. In order to obtain theoretical values for valence band dis-
continuities, electronic structure calculations are required with an accuracy
of less than 0.1 eV. Such an accuracy is difficult to achieve so that, in many
cases, calculated valence band discontinuities have also considerable uncer-
tainty. To this day, a great deal of effort is devoted to the task of obtaining
more reIiable experimental and theoretical data for AE,, even in the case of
the most thoroughly explored heterojunction, that being between GaAs and
(Ga,Al)As alloys.
O t h e r band discontinuities
Knowing the lineup of the valence band edge at I? for a particular hetero-
junction, the lineups of all other energy levels at I' and off I' can be deter-
mined from the known bulk band structures of the two materials. Below we
394 Chapter 3. Electronic structure of semiconductor crystals with perturbations
where E,l,2 are the gap energies of the two materials. For the conduction
band discontinuity AE, = E,2 - E,1 of the material l/material 2 hetero-
junction, it follows that
where AE, = E,2 - E,1 is the discontinuity of the energy gap. If AE,
and AE, are known, AE, can be calculated by means of relation (3.239).
The gap discontinuity AE, follows from the gap energies Egl,Eg2 of the two
infinite bulk materials. The lineup thus obtained for the conduction band
edge of a GaAs/Gal_,Al,As heterojunction with x < 0.42 is schematically
plotted in Figure 3.58a, together with the lineup of the valence band edge.
Often, the two band offsets AE, and AEc are expressed in percent of the
gap discontinuity AE, by means of the ratios Qv = AE,/AE, and Q c =
+
AE,/AE,. Because of AE, A E , = AE,, one has Q , Qc = 1. +
In the second case, i.e. for GaAs/AlAs or GaAs/Gal-,Al,As hetero-
junctions with alloys having an indirect gap (z > 0.42), the conduction band
3.7. Semiconductor microstructures 395
0.4
-.+ ---.- Fe(1+/2+)
Composition x -
Ec2 X
r I tc2
r
I Ev2
Ev2
Figure 3.58: Conduction and valence band lineups for a GaAs/Gal-,Al,As hetero-
junction. In part (a) ( x < 0.42) the alloy gap is direct, and in part (b) (x > 0.4!2),
the alloy gap is indirect. In the latter case, the r and X levels forming the con-
duction band edges in, respectively, GaAs and Gal-,AI,As are also plotted in the
respective other material where they do not form the conduction band edge.
396 Chapter 3. Electronic structure of semiconductor crystals with perturbations
Types of heterojunctions
Consider two direct gap semiconductors with the valence and conduction
band edge at I?. There are several qualitatively different possibilities for the
lineup of the two band edges E,i and Eci, i = 1 , 2 (see Figure 3.59). The
conduction band edge of one material, say of materiai 1, may lie below the
conduction band edge of material 2, while simultaneously the valence band
edge of material 1 may lie above that of material 2. This case is referred
to as heterojunction of type I. In this case the gap of material 1 is located
entirely within the gap of material 2. If both the conduction and valence
band edges of a particular material, say, again 1, are, respectively, below the
two edges of material 2, one has a heterojunction of type II. The staggered
type II heterojunction occurs when we have Ec2 < E,1, and also E,1 < Ec2,
E,1 < Eva holds, and the misaligned case applies if Ec2 > E,1. In the
staggered case the heterojunction still has a gap, while in the misaligned
case the conduction band of material 1 overlaps with the valence band of
material 2 so that the gap of the heterojunction disappears. Sometimes, type
ZZI heterojunctions are defined. These are heterojunctions of type I with zero
energy gap in material 1. A look at Table 3.10 shows that the heterojunction
Ge/GaAs is of type I, CdS/InP of type 11- staggered, InAs/GaSb of type
11-misaligned, and HgTe/CdTe is of type 111.
Type
staaaered
>r
+ EC2
P
W
C
W
Ev2 tvi
misaligned
F
x
A
d
15
0 2 0 2
material 1 material 2 material 1 material 2
this kind of growth the underlying crystal, the so-called substrate, imposes
its structure onto the growing layer, in contrast to ordinary deposition of an
evaporated material which commonly results in a non-regularly structured
layer. For epitaxial growth to be possible, the two materials must have sim-
ilar crystallographic structures, and their lattice constants must be close to
each other.
Epitaxial growth
The principle of MBE is shown in Figure 3.61. The whole growth process
takes place in a vacuum chamber under UHV conditions (typically about
2 x 10-l' T o w ) . In this chamber, the substrate is placed in front of a
number of effusion cells which contain the various chemical elements to be
deposited on the substrate. If one, for example, wants to grow a AlAs layer
on top of a GaAs substrate, two cells are required, one for A1 and one for As,
and their shutters must be open at the same time. Doping of the layer may
be achieved by opening a third effusion cell containing the dopant atoms. If
one wants to proceed with a GaAs layer on top of the AlAs layer, one needs a
fourth cell with Ga. In order to grow a GaAs/AlAs superlattice, the shutters
of the Ga and A1 cells have to be opened and closed alternatively while the
As shutter has to be kept open all the time. There are many parameters
which influence the growth process, in particular, the temperature of the
substrate, the flux from the effusion cells, and the partial pressures of the
various elements involved. The atoms or molecules from the effusion cells
may have different sticking coefficients on the substrate. Arsenic atoms, for
example, stick much less well on GaAs then Ga atoms. Thus the As partial
pressure must be much larger than the Ga partial pressure in the epitaxy of
GaAs on a GaAs substrate.
The fact that MBE proceeds entirely in UHV may be exploited in con-
trolling the growth process. One may employ characterization techniques
which require UHV, such as RHEED for studying surface perfection, or
mass spectroscopy for analyzing the composition of the residual gas in the
growth chamber (for more on MBE see, e.g., Herman and Sitter, 1989).
Unlike MBE, MOCVD takes place in a chemical reactor at atmospheric
3.7. Semiconductor microstructures 399
RHEED GUN
LIQUID NITROGEN
COOLED SHROUDS / MAIN SHUTTER
FLUORESCENT TO VARIABLE
SCREEN SPEED MOTOR
ANDSUBSTRATE
HEATER SUPPLY
a) d)
Type II-staggered
Type II - misaligned
P
Q,
c b
2 2
Figure 3.62: Double heterostructure of type I acting as a quantum well both for
electrons and holes (a), and of type I1 acting as a quantum well for electrons and
a barrier for holes (b, c). In the misaligned case of type I1 (c) an energy region
occurs where electrons and holes may coexist. Parts (d), (e) and (f) of the figure
show the correponding superlattices giving rise to minibands on top of the bulk
band structure. Further discussion is given in the main text.
perlattices of the staggered type I1 shown in Figure 3.62e; solely the gap
becomes indirect in coordinate space in this case. For misaligned type I1
superlattices shown in part f of Figure 3.62, Bloch states are formed from
the electron and hole states of the respective wells.
It is not surprising that the layer thicknesses must lie in the nanometer
range for the confinement and tunneling effects discussed above to occur:
1 nm = 10 A is close to the distance between nearest neighbor atoms in a
natural crystal (in GaAs the nearest neighbor distance is about 2.5 A). Het-
erostructures with such thin layers possess, so to speak, an artificial atomic
superstructure which is likely to result in a modified electronic structure.
402 Chapter 3. Electronic structure of semiconductor crystals with perturbations
Compositional microstructures
3.5
' ZnS ' I \ I I I I I I I
MnSe _ .-
3.0
h
2
v 2.5
g0
2.0
>r 1.5
P
2
w
1.0
0.5
0.0
5.4 5.6 5.8 6.0 6.2 6.4 6.6
Lattice constant ( LI
Figure 3.63: Energy gap versus lattice constant for diamond and zincblende type
semiconductors. Full lines represent alloys with direct gaps, and dashed lines rep-
resent alloys with indirect gaps.
their lattice constants. Such a diagram is shown in Figure 3.63 for elemental
and compound semiconductors of diamond and zincblende structure. Lines
connecting two different materials indicate the gap energies of alloys made of
these materials. The composition of an alloy is related to its lattice constant
by means of Vegard's rule which linearly interpolates between the lattice con-
stants of the two alloy components. For two direct gap materials 1 and 2, the
gap difference AE, provides some hints about their band edge discontinu-
ities. If the gap discontinuity AE, vanishes, then band edge discontinuities
may, but need not, occur. If a gap discontinuity does exist, then at least one
of the two band edges must also exhibit a discontinuity. In general, both the
valence and conduction band discontinuities AE, and AE, differ from zero
and their magnitudes reflect the gap discontinuity to a certain extent.
Lattice mismatch
As the materials shown in Figure 3.63 are all of zincblende type, their main
404 Chapter 3. Electronic structure of semiconductor crystals with perturbations
with cll(i) and clz(i) being the elastic stiffness constants of the cubic layer
of material i. Because m t z ( i ) = 0, it follows from (3.240) that
3.7. Semiconductor microstructures 405
(3.241)
4 2 ) - &(1) = tyy(2)- E v y ( l ) = t, t = . - ai
-a2 (3.242)
ai
The total strain E defined in equation (3.242) equals the lattice misfit f
divided by 100%. Using the stress and strain components, the total elastic
energy Eda of the two layers may be calculated, with the result
(3.243)
where
(3.245)
According to these relations, the thin layer is more heavily strained than
the thick one, provided the elastic constants of the two layer materials are
comparable. This means, in particular, that the substrate will be almost
unstrained and the epitaxial layer will accommodate almost the whole misfit
strain. This was anticipated in the discussion above.
Another general point to be mentioned in the context of lattice mismatched
heterostructures concerns the effect of strain on the band structure. From
theoretical considerations and experimental studies it is well known that such
effects can be quite large (Bir, Pikus, 1974). To give an example, we consider
a Si layer on top of a Ge substrate. The strain components in the Si layer
are e X x = cyy = 0.04, corresponding to a lattice misfit of 4% (see below), and
e Z z = -0.03, using the elastic stiffness constants c11 = 16.1 x 1011 dyn/crn2
and c12 = 6.4 x 1011 dynlcm of Si. The degenerate heavy-light hole valence
band maximum of Si splits by 0.31 el/ under this strain. To produce the
same splitting by means of uniaxial strain applied from outside, a pressure of
73 Kbar would be necessary. This example shows that considerable changes
of the band structure are to be expected because of the lattice mismatch
strain in heterostructures. In this context, energy levels in different materials
or at different points of the first B Z can shift in dserent ways. One may take
advantage of this to adjust the band discontinuities of a heterostructure to
specified conditions. The strain becomes, so to speak, an additional degree
of freedom for tailoring the properties of a heterostructure.
406 Chapter 3. Electronic structure of semiconductor crystals with perturbations
GaAs/(Ga,Al)As
(In,Ga)As/Ga( Sb,As)
Si and (Si,Ge)
The lattice constants of Si and Ge are, respectively, 5.43 A and 5.65 A. This
gives the lattice mismatch of 4 %, which has already been used above. The
critical thickness d, amounts to about 30 A which is rather small. Therefore,
one also considers heterostructures between Si as substrate and Sil-,Ge,
alloys with low Ge content (x < 0.5) as epitaxial layers. In this case d, can
be 100 A or larger depending on the actual value of x. (Si, Ge) alloys may
also be used as substrates. Consider, for example, a Sil-,Gey substrate on
which a Sil-,Ge, alloy layer is grown first, followed by a pure Si layer. Both
layers are strained in this case. For 0 < y < x, the strain in the alloy layer
3.7. Semiconductor microstructures 407
(Ga,In)(As,P)/InP
(Hg,Cd)Te/CdTe
HgTe and CdTe are lattice matched because the lattice misfit is smaller than
0.4 %. Being a zero gap material, HgTe forms a type I11 heterostructure with
CdTe. The valence band offset turns out to be rather small ( M 0.02 e v ) . In
Hgl-,Cd,Te alloys the gap opens at 2 = 0.15. For 0.15 < 2 < 1 the alloys
are direct gap materials with the valence and conduction band edges at.'I
In this range, Hgl-,Cd,Te/CdTe forms type I heterostructures which, for
sufficiently small 2 , can be applied in infrared detectors.
(Pb,Sn)Te/PbTe
The lattice misfit between PbTe and SnTe is about 2 %, so that strain effects
in Pbl-,Sn,Te/PbTe heterostructures are not negligible. Pbl-,Sn,Te alloys
are direct gap materials with the conduction and valence band edges on the
first B Z boundary at L. For PbTe, the L$ state forms the valence band
edge, and the Lg-state forms the conduction band edge (see Figure 2.35).
For SnTe, this level ordering is inverted. Thus, the gap of Pbl-,Sn,Te alloys
must go through zero for some composition TO. At 77 K , one has zo M 0.4.
Thus, Pbl-, Sn,Te/PbTe heterostructures are of type I for z < 20,of type
I11 for z = zo, and again of type I for 2 > 2 0 , however, with inverted band
edges of the well material in this case. Depending on strain, type I1 situations
also seem to be possible. Microstructures based on Pbl-, Sn,Te/PbTe have
a potential for applications in infrared laser diodes.
Doping microstructures
nipi-structures
Semiconductor samples with alternating n- and p-type doped layers may ex-
hibit properties similar to those of superlattices composed of two different
materials (Esaki, Tsu, 1970; Dohler, 1972). Such doping superlattices may
be thought of as periodic arrays of pn- and np-junctions with alternating neg-
atively and positively charged intrinsic (i) regions between the neutral n- and
p-layers. In this context they are sometimes referred to as nipi - structures.
The oscillating space charge distribution gives rise to an oscillating electro-
static potential which modulates the valence and conduction band edges as
shown in Figure 3.64a. If the modulation period approaches the nanometer
range, minibands arise just as in the compositional superlattices considered
above. Doping superlattices are principally of type I1 because the two band
edges, at a given position, are shifted by the same amount of energy, namely
the electrostatic energy of an electron. Their periods, generally, cannot be
made smaller than 10 nm because of the unavoidable diffusion of dopant
atoms. The most common nipi-structures are those based on GaAs.
3.7. Semiconductor microstructures 409
a) m
+ - + - + - +
b)
+
+
+
+
+
+
+
+
+
+
+
+
+
+
-1 I
z
- - I
I
v
Z
Figure 3.64: Valence and conduction band lineup for doping microstructures in a
direct gap material for a) a nipi-structure and b) a n-type &doping structure.
&doping structures
Bulk methods
We consider SLs composed of two zincblende type materials as, e.g., GaAs
and AlAs. The interface is taken to be parallel to a (001) lattice plane. A
GaAs layer of the SL contains a number 2n of (001) lattice planes alterna-
tively occupied by Ga and As atoms, and the AlAs layer contains a number
2m of (001) lattice planes alternatively occupied by Al- and As atoms. The
notation (GaAs),/(AlAs), is used for such a SL. The primitive unit cell of
410 Chapter 3. Electronic structure of semiconductor crystah with perturbations
[IIO]
0 Ga OAs 8At
+
The volume of the first B Z of the SL is a ( n m)-th fraction of that of the
first bulk B Z . In Figures 3.65 and 3.66we show, respectively, the primitive
unit cell and the first B Z of a (GaAs)g/(AlAs)~SL as an example.
The stationary states of the SL are Bloch states with quasi-wavevectors
k of the first SL B Z . The energy eigenvalues form bands in this B Z , re-
ferred to as minibands in regard to k-dispersion parallel t o the SL axis, and
as subbunds if k-dispersion parallel to the SL layers is considered. The mini-
bands arise from bulk bands folded back upon the first SL B Z . As the bulk
+
B Z encompasses ( n m ) first SL B Z s , one bulk band gives rise to ( n m) +
SL minibands. The minibands are separated by m i n i g a p s which occur at
the Bragg reflection planes of the reciprocal SL lattice perpendicular to the
z-axis. The minigaps become wider for stronger perturbations of the bulk
crystals due to the superlattice structure, i.e. the larger the difference of the
periodic potentials of the two bulk crystals, and the shorter the SL period
is (as long as it does not become too short), the wider the minigaps open.
All methods for determining band structure of bulk crystals can also be
used to calculate the band structure of SLs, the only difference being the
larger size of the primitive unit cell. Figure 3.67 shows the results of such a
calculation performed by means of the TB method. The valence band disper-
sion of a (GaAs)a/(Ga0,~A10,3As)3SL is plotted along the r - Z symmetry
3.7. Semiconductor microstructures 41 1
1".
-to
3 -1
-A
ol
!i
W
-2
-3
-4
-F;
changes of these few minibands are small. The bulk methods are often not
accurate enough to reproduce them sufficiently well. The situation is similar
to the case of the shallow levels of impurity atoms - if one would try to ob-
tain these levels by means of a full bulk band structure calculation method
the same difficulties would occur. Fortunately, another method, namely the
effective mass theory, exists in the shallow level case. It is particularly well
tailored to calculate the small changes of electronic structure occurring at
the conduction band minimum and the valence band maximum, where the
kinetic energy is small enough to allow the perturbation potential to produce
measurable effects. The situation in the case of artificial microstructures is
comparable: the perturbation potential is relatively weak, and changes of
the band structure are expected only for selected bands and in the vicinity
3.7. Semiconductor microstructures 413
GaAs A1As r X
Figure 3.68: Localization of the lowest valence and conduction band states of
the SL at the center r of the first SL B Z (left), and the symmetry character of
these states (right), for a (GaAs)7/(A1As)7SL. While the valence band states are
well localized in the GaAs layers and are dominantly composed of GaAs-r-states,
conduction band states extend over both layers, and are composed of both AlAs-
X-states and GaAs-I'-states. h l = -0.11 eV,h2 = -0.19 e V , el = 1.75 eV,e2 =
1.77 eV, e3 = 1.88 eV.(After Rucker, 1985.)
of critical points. There are, however, also differences between the shallow
level problem and the microstructure problem. The perturbation potential,
i.e. the difference of the periodic oneelectron potentials of the two m a t e
rials of a heterostructure, is far from being smooth on the atomic length
scale. Even if one averages out the microscopic potential fluctuations over
a unit cell, the average potential difference has still an abrupt change at an
interface. For this reason one has to determine at the outset whether or not
the effective mass theory developed in section 3.3 can in fact be applied to
artificial microstructures. We will address this question below (for a detailed
discussion see, e.g., Burt, 1992).
414 Chapter 3. Electronic structure of semiconductor crystab with perturbations
In the case under consideration, the eigenfunctions & l ( x ) and $ 4of~ the)
two material regions 1 and 2 having energies, respectively, close to the band
edges Evl and E,2 at f,may be written as
The two envelope functions F,l(x) and Fv2(x) obey the effective mass equa-
tions
F V ~ ( X=) E , F , ~ ( x ) , x in m a t e r i a l 2. (3.249)
Formally, these equations may be written as one equation for the envelope
function
3.7. Semiconductor microstructures 415
(3.250)
(3.252)
(3.253)
(3.254)
h2 h2
_- v2 -.+ --v.- v. (3.25 7)
2m*(z) 2 m*(z)
With this replacement the effective mass equation (3.252) becomes
(3.259)
where EL is given by
h2
EL = E , - -k i (3.261)
2m*,
with l/E; as the average inverse effective mass (m;:' + m;T1)/2.
418 Chapter 3. Electronic structure of semiconductor crystals with perturbations
(3.262)
derived in equation (3.73), and the components Fym(X) of the envelope func-
*
tions F~ ( x )obey the effective mass equations
[-~g$r(z)aaaat + ~ v ( z ) 6 m m iFumt(x)
] = ~ v ~ v r n ( x z) ,# 0,
m a d
(3.263)
with DE$(z) = DYZAl for z < 0, and Dg$l(z) = D;ELl for z > 0. The
solution of equation (3.263) may again be taken as a plane wave
(3.264)
=+
parallel to the layers. The boundary conditions for F v ( x ) at the interface
follow in the same way as in the non-degenerate case. The z-dependent
* *
factor F~ (2) of F,, ( x )in equation (3.264) must be continuous at z = 0, i.e.
* *
F U (z)lz=-6 = F u (z)I~=+6 (3.265)
must hold for 6 + 0. To determine the condition for the derivative with
respect to z , one defines the Hermitian Hamiltonian matrix
(3.266)
($
which exists for any value of z including z = 0 and equals H 1 for z < 0 and
e
H z for z > 0. Integrating the effective mass equation for this generalized
Hamiltonian with respect to z over a small interval across the interface leads
to the conclusion that the expressions
(3.268)
k(z)= --a
[y2(zj(k: - k i ) - 2i73(z)k,kg] . (3.272)
L
XJ
Figure 3.69: Geometry of the SL whose stationary electron and holes states
are calculated in the text.
Electron states
For the zincblende type materials we are considering, the conduction bands
are non-degenerate and isotropic in the vicinity of I. The two effective
electron masses m:l and mE2 generally differ, but we will initially assume
that they are equal, denoting their common value by m;. In the case of
SLs composed of GaAs and Gal_,Al,As this is a reasonable approximation.
Later, we discuss the modifications which occur if m;l and m:2 are different.
The effective mass equation for the electron envelope function Fc(x)of the
3.7. Semiconductor microstructures 421
where E; is given by
EA = E , - (3.276)
Fc(ld + d l - 0 ) = F,(ld + d l + 0 ) ,
d d
-Fc(ld
dz
- 0) = -F,(ld
dz
+ 0),
d
-F,(ld
dz
+d l - (3.277)
(3.279)
The effective mass equation (3.275), the matching conditions (3.277), and
the Bloch condition (3.278) define an energy eigenvalue problem which differs
from the well-known Kronig-Penney problem only by notation. The latter
problem constitutes an exercise of elementary quantum mechanics and is
commonly used to demonstrate the existence of energy bands. In the case
of SLs this exercise takes on real physical meaning. In the following we
sketch its solution. We restrict ourselves to energy values 0 < E' < A E ,
or E,1 < E < E,1 + +
AE, (7i2/2mr)ki, meaning energies below the lowest
allowed energy in material 2 for a given value of kll.
According to classical mechanics, an electron with such an energy cannot
penetrate within the superlattice layers made of material 2, it will be confined
to layers consisting of material 1. If it hits the interface to material 2, then
it will be reflected back to the interior of its material 1 layer. In quantum
mechanics, the reflection is not complete, there is a certain probability for the
electron to tunnel through a material 2 layer and reach the next neighboring
material 1layer. Although the probability for an electron to stay in material
1 is not unity, as in classical mechanics, but smaller, it is still much larger
than that for material 2. As has already been mentioned, one uses the
terms quantum wells for the layers of material 1, and bamiers for the layers
of material 2. In the wells and barriers the wavefunction F,]F(z)is given
by different expressions. For the wells 0 < z < d l , Schrodinger's equation
(3.276) yields
E ,I = - h2
K2 (3.281)
2 m ~ '
and a l , bl as coefficients which are still to be determined. For the barrier
d l < z < d one has
2 2mE
KE.= -(AE, - EL). (3.283)
Ti2
The four coefficients a l , b l , a2, b2 are governed by a set of linear equations
which follows from the 4 matching conditions (3.277). These equations read
For this set to have a non-trivial solution, the determinant of the matrix of
exponentials must vanish. This yields the secular equation
tc2 - K~
cos(Kd1) cosh(tid2) +- 2Kn:
sin(Kd)l sinh(~d2)= cos(kd). (3.285)
h2
Em(k) = E&(k) + Egi + -kll
2mr
(3.286)
Figure 3.70: Mini- and subbands of a superlattice. Also shown are the two
limiting cases of extremely wide and/or high barriers and of narrow and/or
flat barriers. In the lower part of the figure the wavefunctions are illustrated.
Figure 3.70 also shows two enlightening limiting cases. If the thickness d2
of the barriers between the wells becomes large, and/or the barriers AE,
are high, then the hyperbolic terms in equation (3.285) dominate over the
cos(kd)-term on the right hand side which is responsible for the k-dispersion.
Neglecting the latter, the minibands degenerate into discrete energy levels,
termed sublevels. These levels are just the discrete energy eigenvalues of a
single quantum well. Obviously, the superlattice decomposes into isolated
quantum wells in the limiting case under consideration. The electron states
are almost completely confined within a well, and practically zero within the
barriers. One uses the term multiple quantum well for a superlattice in this
limit.
For infinitely high potential walls the secular equation (3.285) becomes
sinKd1 = 0. The solutions of this equation are K-values of the general form
K = (7r/dl)nwhere n is an integer. They give rise to the energy eigenvalues
2
Elcn = , n = 1 , 2 , .. . , (3.287)
2mE
3.7. Semiconductor microstructures 425
(3.288)
(3.291)
Each subband n gives rise to a step-like partial DOS, being zero below the
+
band bottom E L E g l , and non-zero but constant above. Such behavior
of the DOS of an electron which is free to move only in two dimensions
was already found in section 2.5. The summation in expression (3.291) for
p ~ over ~ all w subbands results in a staircase-like DOS as schematically
shown in Figure 3.71. The heights of the steps have the constant value
( m * / n 2 h 2 ) ( n / d )while
, the step widths depend on n. If the barriers of
the QW are taken to be infinite, then the energy levels EAn are given by
( h . 2 / 2 m E ) ( n ~ / d 1 and
) 2 , the step widths of the staircase scale with ( n / d ~ ) ~ .
For very wide QWs, i.e. in the limit d l -+ 00, the staircase-like DOS trans-
forms into the smooth square-root-like DOS p 3 ~ ( Eof ) an electron free to
move in three dimensions. Equation (3.291) yields
(3.292)
3.7. Semiconductor microstructures 427
7 3
3
0
1
3
0 2
Q
Refinements
In the above treatment of the electron states of a SL, the effective masses
mzl and mE2 were assumed to be the same in the two materials. If this is not
the case, the following modifications will occur. First, in the boundary con-
ditions (3.277) for the derivative ( d F , / d z ) , different mass factors will appear
on the two sides of the interface and they will not cancel. For the secular
equation (3.285) this means that all K ' s except those which are factors in
arguments of trigonometric functions, have to be replaced by (m&'mal)K.
Second, in solving the secular equation, the relations (3.281) and (3.283)
between K and E i and, respectively, n and E' must be written with m;
and mE2 instead with mE. Finally, the kll-dispersion of the total energy
eigenvalue in relation (3.286) becomes different in the two material layers.
This results in an additional contribution (h2/2)[mZ-'(z) - E ~ - ' ] k to ~ the
SL potential, as may be seen from equation (3.260). The additional term
introduces a kll-dependence of the envelope function F& which otherwise
depends only on the z-component k .
Another simplification made in the above treatment of the electron states
of a SL, was the assumption that no electrons are available to occupy the SL
428 Chapter 3. Electronic structure of semiconductor crystals with perturbations
Figure 3.72: Self-consistently calculated potential profiles and energy levels for
a Alo.aGao..rAs QW of 100 A width containing different numbers of electrons per
cm-2.
bands. If there are such electrons present, the potential seen by an electron
will change due to its interaction with other electrons in the SL bands. As in
the case of bulk semiconductors, this potential change may be decomposed
into a Hartree and an exchange-correlation part. The expressions derived for
these potentials in Chapter 2 also apply here if the stationary states of the
bulk crystal are replaced by the stationary states of the SL. As the latter
states are only known after the effective mass equation has been solved,
the inclusion of the Hartree and exchange-correlation potentials must be
performed in a self-consistent way. The net effect of the two potential parts
is repulsive, thus the SL potential well will flatten. For a given number of
electrons in SL states, this flattening will be enhanced by greater localization
of the electrons in the well regions. It will be particularly pronounced for
isolated QWs. In Figure 3.72 we show self-consistently calculated potential
profiles and energy levels for a Alo.3Gao.7As QW of 100 A width, containing
different numbers ng of electrons per ~ r n - ~The. well bottom bends up with
rising n s , and the energy levels are shifted to higher energies.
Hole states
We consider a QW structure composed of zincblende type well and barrier
materials which are both described within the Luttinger-Kohn model. The
effective mass equation for the hole states of such a QW with energies close to
the well bottom follows from equation (3.268) by installing there the valence
band edge profle E,(z):
0 forO<z<d
E,(z) = (3.293)
AE, f o r z < 0 and z > d.
3.7. Semiconductor microstructures 429
In this way, a set of second order differential equations for the four hole
envelope function components arises. The solutions must be normalized
and must guarantee for the continuity of the expressions (3.273) at the two
interfaces. Solutions of this kind can be found in different ways. One can,
for example, numerically calculate normalized solutions for various values
of E and kll, valid in one of the three regions -m < 0, 0 < z < d and
z < +m. Matching these solutions in such a way that the continuity of
the expressions (3.273) is guaranteed for a given value of kll, will only be
possible for certain discrete energy values E,,(kll). These are the subband
energy eigenvalues which are sought. Subband structures calculated in this
way are shown in Figure 3.73 for a A10.3Ga0.7As QW of 100 A width. The
lowest subband ( h h l ) in the vicinity of kll = 0 arises mainly from hole states
of GaAs with the heavy hole mass parallel to z , and the second level ( I h l )
mainly from hole states with the light hole mass parallel to z. Perpendicular
to z , the curvature of the hhl subband at starts stronger than that of
the Ihl subband. Thus the two bands would cross, if this were allowed. In
reality, the bands repel each other leading to the anticrossing behavior seen
in Figure 3.73. The alternating heavy- and light-hole-like curvatures parallel
and perpendicular to z are consequences of the Luttinger-Kohn Hamiltonian
(2.374).
If the subbands of the QW are partially filled by holes, then hole-hole inter-
:::
430 Chapter 3. Electronic structure of semiconductor crystals with perturbations
8.0x 10 cm-*
-50 -250
-200 -100 0 100 200 -200 -100 0 100 200
z (4 z (A)
Figure 3.74: Potential pofiles and energy levels of an isolated p-type &doping layer
(left hand side) and an isolated n-type-&dopinglayer (right hand side) of the same
sheet dopant concentration 8 x 10l2 ~ r n - ~The
. Fermi energy is shown by dotted
lines. (After Sipahi, Enderlein, Scolfaro, and Leite, 1996.)
&doping structures
0
40
>
20
0
0 10 20 30 40 SO 60 70 I D
E [kV/cml
well depth in the p-type case as compared to the n-type case results mainly
from the fact that heavy holes are more strongly localized at the ionized
dopant sheet and thus are more effective in screening out the sheet potential
then the lighter electrons.
2 4 6 0 3
BIAS (VI
until it reaches the inflection point of Eil(k). Thereafter, its effective mass
becomes negative, causing deceleration instead of acceleration. Since the
electron is inevitably scattered by phonons and impurities, its velocity takes
a stationary value in a dc field. The latter increases with increasing field
strength E if the corresponding k-value is below the inflection point, and
it decreases with increasing E if the k-value of the electron is above this
point. However, a superlattice contains a gas of many electrons, populating
the miniband E:(k). For low field strengths, most of the electrons have low
k-momenta and positive effective masses. Thus, the total current density of
the gas increases if E is further increased. Simultaneously, the electron gas
is heated up by the electric field, which implies that more electrons populate
k-points with a negative effective mass and less with a positive one. This
reduces the current increase if E raises further because a larger subgroup of
electrons is decelerated instead of being accelerated by the field increase. If
the subgroup of electrons having negative effective mass is sufficiently large,
further increase of the field strength will actually decrease the current. This
explains the negative differential drift velocity seen in Figure 3.75.
An example of an optical experiment is shown in Figure 3.77. There,
the absorption spectra of GaAs/Al,Gal-,As QW structures of different wen
widths are shown. The staircase-like shape of these spectra reflects the DOSs
of the electron and hole subbands of a QW which above have been shown
to be staircase-like as well. Also other features of the QW band structure
observed above, as the widening of the fundamental energy gap and the
shift of the steps towards higher energies with decreasing well width, can be
clearly seen in the spectra of Figure 3.77. The enhancement of absorption
at the step edges, which correspond to optical transitions from the tops of
hole subbands to the bottoms of electron subbands, is due to the Coulomb
3.8. Macroscopic electric fields 433
V(x)= e E . x. (3.294)
{ E y ( - i V ) + e E . x } F V ~ , ( x )= EvFv~,(x). (3.296)
We consider this equation in the particular case of an isotropic and parabolic
band. Assuming the z-axis of our Cartesian coordinate system parallel to
the field direction, the electron motion in 2- and y-directions is that of a free
particle. Thus the envelope function F,(x) can be written as
F~E,(x)E F ~ E , ~ , ~ (=
X)e i k ~ ~x,,
. x (2).
~ (3.297)
where x l and k,l denote, respectively, the components of x and of the
wavevector perpendicular to the field. The z-dependent envelope function
factor X , , ( t ) obeys the equation
X,,(z) =E ~ X , ~ ~ ( Z ) , (3.298)
with
li2
E , = E + -2m
k:l. (3.299)
For the conduction and valence bands, in particular, equation (3.298) reads
(3.300)
(3.301)
The second equation can be interpreted as the effective mass equation for
a hole with (positive) mass Im:l and energy (-.,). As the equation shows,
the charge of the hole is positive, i.e. fe, in contrast to the electron with
charge -e.
The spectra of energy eigenvalues of equations (3.300) and (3.301) are
continuous, and vary between -co and fco as a direct consequence of the
unrestricted motion of the electron or hole in the field direction. This allows
one to use the energies E , as continuously varying quantum numbers of the
stationary states X V C v ( z )and
, to assume normalization in terms of Diracs
&function with respect to these energies, thus
(3.303)
(3.304)
with
(3.305)
0.4
C
0.3
.-
u
0
(D
g3 0.2 rn
Lc
g 0.1
-e
N
-0 P
g
W
0.0
c
2
rt
v)
Y
-0.1
-0.2
-Eg/eE 0 Z
Figure 3.78: Envelope functions of stationary electron and hole states in an electric
field, taken at energy cC = E, = 0. Oc = OU = 8.
$v(x, t ) = ~ V O ( X ) F V ( Xt ,) . (3.306)
a
+
{&,(--iV) eE . z} Fv(x,t ) = iTi-F,(x, t ) .
at
(3.307)
In solving this equation we assume that the electron was in a Bloch state
(p,k(x) at t = 0. Then the initial condition for F,(x,t ) may be stated as
(3.309)
with
kt = k - ZEt. (3.3 10)
fi
This is readily verified by a straightforward calculation. Owing to the en-
velope function (3.309) and the previously made approximation U& = Uuk,
the total non-stationary wavefunction & , k ( x , t ) evolving from a Bloch state
(pvk(x)at t = 0 remains a Bloch state for t > 0 also, however, with a
time-dependent quasi-wavevector kt,
(3.311)
This important result may also be established without approximating the
Bloch factor U v k by u,o as is done in effective mass theory. The only ap-
proximation needed is the neglect of interband transitions induced by the
electric field.
Equation (3.311) states that the quasi-wavevector k of a Bloch state in
the presence of an electric field changes with time in just the same way as
does the ordinary wavevector of a free electron. Differing from the latter,
the quasi-wavevector is restricted to the first B Z . However, relation (3.310)
results in kt-values which can also lie outside the first B Z . This means
that in the above derivation we inadvertently changed from the reduced
to the extended zone scheme. According to the general considerations of
Chapter 2, one may recover the description in terms of the first B Z by
subtracting a suitable reciprocal lattice vector K(t). For electric fields in
symmetry directions of the first B Z , there will be a particular point in time
t = T(E) at which, with increasing t , the reduced wavevector kT - K(T)
equals the wavevector kt at t = 0 for the first time. This means that the
time-dependent Bloch state (3.311) returns, at t = T , to the Bloch state
at t = 0 (not counting a phase factor). The same holds for time points
2T,3T etc. The time development of Bloch states in an electric field is
therefore periodic, hence the term Bloch oscillations. The period T of these
oscillations may be obtained from (3.310) as
(3.312)
The Bloch oscillations affect not only the wavefunctions but also the perti-
nent energies E,(kt), meaning that Bloch electrons execute periodic motion
within their energy bands.
Oscillations also occur in the velocity of Bloch electrons, defined by the
quantum mechanical expectation value < ( d x / d t ) >= (qJvhI(dX/dt)IVvk,)of
3.8. Macroscopic electric fields 439
(3.313)
instead of their simple effective masses m,*,,. One thus obtains the interband
transition probability W , as
W,, oc A i 2 (z) .
For realistic field strengths E, is measurably larger than TLB,,.
(3.315)
Therefore,
the asymptotic approximation
(3.316)
for the Airy-function applies. To understand what this result means phys-
ically we may argue as follows. Expression (3.315) for the transition prob-
ability W , was derived using the stationary electron states in an electric
field of subsection 3.8.2. The same expression follows if one uses the non-
stationary states of subsection 3.8.3. In this, the electro-optic energy Ti@,,
may be understood as the energy uncertainty of an electron-hole pair due
to its finite lifetime in the presence of an electric field. Without such an
uncertainty interband tunneling would not be allowed by reason of energy
conservation: the final state in the conduction band would differ in energy
from the initial state in the valence band by the gap energy E,. The energy
uncertainty relieves the need to satisfy energy conservation and permits the
interband transition probability W , to be nonzero. The non-stationary
approach also provides a rough estimate of the proportionality factor in re-
lation (3.315). The probability W,, for an electron to tunnel per second
from the valence into the conduction band at k,l = kl = 0, may be ob-
tained from Ai2(E,/7iB,,) by multiplying this expression with the frequency
1/T of Bloch oscillations. This is plausible since this frequency indicates
how often a valence band electron, per second, reaches the upper band edge,
from which it can tunnel into the conduction band. It is just the probabil-
ity for this tunneling step which the Airy-function expression A i 2 ( E g / W , )
represents. The complete expression for W , thus reads
1
W , = -Ai2
T
(2). (3.317)
holds. In typical cases this condition is fulfilled sufficiently well for field
strengths of the order of magnitude lo5 V / c m , while it is definitely not valid
for field strengths close to the inner-atomic fields of 10' V / c m . At least
for such fields interband transitions are important. By means of tunneling,
holes are generated in the valence band and electrons in the conduction band.
These diminish the resistivity of a semiconductor material and initialize other
processes such as carrier heating and impact ionization of the valence band
which may finally result in electric breakdown.
The inequality (3.318) transforms into the condition (3.295) for the ap-
plicability of effective mass theory if the gap energy Eg is formally identified
with (h2/2m5,)1/a2. The latter energy represents an average energy gap in
effective mass approximation. It has the same order of magnitude as E,, so
that the two conditions (3.318) and (3.295) are equivalent.
(3.319)
In an external electric field, the optical transition probability and, hence, the
optical absorption coefficient, is also non-zero for photon energies below the
gap. It decays exponentially as hw decreases. This phenomenon is called
the Franz-Keldysh effect (Franz, 1958; Keldysh, 1958; Boer, Hansch and
Kummel, 1959). Above the gap, the absorption coefficient with electric field
oscillates with photon energy about the absorption coefficient without field,
and we have Franz-Keldysh oscillations (Tharmalingan, 1963).
Field induced changes occw not only in the absorption coefficient, but
also in other optical constants including the real part of the complex refrac-
tive index. Besides the changes at the fundamental absorption edge consid-
ered above, one also has changes of optical constants at any higher van Hove
singularity of the joint density of states of the interband energy Ec(k)-E,(k)
3.9. Macrmcopic magnetic fields 443
- ( E,-ho)/eE 0 2
Figure 3.79: The same envelope functions as in Figure 3.78, but with the energy
of the electron exceeding that of the hole by the photon energy iiw.
(Aspnes, 1967; Enderlein and Keiper, 1967). This fact is exploited in elec-
trorefiectance spectroscopy, in which field induced changes of the reflectivity
of a semiconductor sample are measured by means of a modulation tech-
nique. Photon energies which give rise to strong electroreflectance signals
correspond to optical transitions at critical points of the interband energy
(see Figure 3.80). By measuring the electroreflectance spectra of semicon-
ductors one obtains experimental data relating to their valenceconduction
band separation at critical points. These can be used as input parameters
for empirical band structure calculations (Cardona, 1969) as well as for the
characterization of semiconductor heterostructures, including superlattices
and quantum wells (Pollak, 1994; Enderlein, 1996).
-
-121 I I I I I I I
1.0 1,5 20 25 30 35 400 4s
Energy ( e V )
(3.321)
As in the derivation of the effective mass equation for perturbing scalar po-
tentials in section 3.3, we use the k . p-perturbation theory, i.e. we represent
the Schrodinger equation in the approximate Bloch basis Iuk)', whence
u'k'
'(vk(H + LmcA ( x . p ) + l
(:) 2
A2(x)IvAk')l '(vhk'lg) =E '(vkI$).
(3.322)
with H = (p2/2m) + V ( x ) as Hamiltonian of the crystal without a magnetic
field. Initially, we consider a non-degenerate band extremum at k = 0, and
assume the form (3.60) for '(vkl$). In order to satisfy the Schrodinger
equation (3.322) with this Ansatz, the component with u = vo must obey
the relation
k'
l(vok(H + emAc ( x ) . p + 1
f) A2(x)(uok')'Fw(k') = EF,,(k).
(3.323)
Components '(vkl$) with v # vo must vanish according to equation (3.322).
To verify this we consider the matrix elements '(vklHlvok')' of the unper-
turbed Hamiltonian H , which were already evaluated above. The expression
(3.63) derived there is applicable here as well. Accordingly, t-hematrix ele-
ments of H with v # vo vanish.
Because of the assumed smoothness of the vector potential A(x), its
matrix representation '(vkJAlv'k')' is approximately diagonal with respect
to band indices, whence
446 Chapter 3. Electronic structure of semiconductor crystals with perturbations
The diagonality of the matrix for A extends to the matrix for A2, as well,
and therefore one also has
(vkl A2Ivk) M 6
1
,( klA21k) . (3.325)
What remains to be evaluated in the Schrodinger equation (3.323) now is
only the matrix of the operator ( e / m c ) A .p. This operator has the same
structure as the k . p-perturbation operator. Just as the matrix represen-
tation of the latter with respect to the approximate Bloch basis (vk) is
band-diagonal in second order perturbation theory, the same also holds for
the matrix representation of the operator ( e / m c ) A . p. We have
(3.326)
(3.329)
Here all terms depending on the magnetic field have been neglected since
they only give rise to quadratic terms with respect to B in the matrix ele-
ments (3.328). Substituting relation (3.329) in expression (3.328) for these
elements, and using the notation L , = zap^ - @pa for angular momentum
components (c.Pr signifies the ordered triplet z y z or a cyclical permutation
of it), we obtain
3.9. Macroscopic magnetic fields 447
(3.330)
In this, we used the fact that the interband matrix elements of the momen-
tum operator are diagonal with respect to k and k. The matrix elements
(vokO)L,lvokO) do not depend on k, so we may use the relation
(3.332)
In section 3.3 we found that the symmetric tensor M,Lp describes the k-
dependence of the band-index- and k-diagonal Bloch matrix elements of the
Hamiltonian (see equation (3.63)). Here we find, that the antisymmetric
tensor L, determines the B-dependence of these elements. The latter
evidently describe the interaction of the magnetic moment of the orbital
motion of a Bloch electron with the magnetic induction vector B. In order
that it differ from zero, the angular momentum of the Bloch state IvoO)
must differ from zero, too. In principle, this is possible because the motion
of a Bloch electron cannot in general be reduced to a translation, since it
contains a rotational part about the atoms which form the crystal. The
tensor L, measures the average angular momentum of this rotation in the
Bloch state 1~00). In cubic materials it vanishes for symmetry reasons, at
least as long as only non-degenerate Bloch states IvoO) at the center of the
first BZ are considered and spin and spin-orbit interaction are omitted from
consideration, as we do here. The situation is comparable with that for
s-states of free atoms.
Second step
Beside the k-diagonal term discussed above, which describes the coupling of
the magnetic field to the rotational part of the motion of a Bloch electron, the
448 Chapter 3. Electronic structure of semiconductor crystals with perturbations
6kk,h-1pBB. L, +-1
2m
[k,e(k(Aa(k) +
kp(kja,jk)] . (3.334)
4
Summing the three terms (3.63), (3.334) and (3.335) obtained in rewriting
the Schrodinger equation (3.323), and simultaneously transforming from k-
space to coordinate space, the following equation results for the envelope
function Fvo(x):
(3.336)
This equation changes if spin and spin-orbit interaction are taken into ac-
count. The assumption of a non-degenerate band vo will be adopted, initially.
Considering the role of spin and spin-orbit interaction, the Schrodinger equa-
tion (3.321) may be written as
= EF,(x,s). (3.338)
In obtaining (3.338), we used the fact that the diagonal elements '(voaklH,,
Ivoa'k)' of the spin-orbit interaction operator vanish at k = 0 for symmetry
reasons, while the non-zero k-linear terms in these elements are negligible.
The matrix elements L, of the angular momentum operator emerge from
the corresponding expressions (3.330), (3.331) without spin-orbit interaction
by replacing p in the latter with the spin-dependent operator ?i of equation
(2.353), obtaining
In accordance with their definition, the L,, are matrices in the two-compo-
nent spin space. In regard to their transformation properties in coordinate
space, they are components of a pseudovector. Apart from a constant factor,
there is only one such pseudovector in the case of systems with the symmetry
group oh, namely the vector of Pauli's spin matrices a. This means that
L, is a multiple g,Acr' of cr'. The constant gvo is determined by the matrix
elements of (3.339). With + 1
= guo 29, we may write
1
h-lLm + 2g cr' = i g & d . (3.340)
Using this expression, the effective mass equation (3.338) takes the form
The factor gEo is called an effective g-factor. Just like the effective mass,
it represents a characteristic of an energy band vo at a particular critical
point. In Table 3.11 experimental g:,-values for the conduction band min-
imum of several diamond and zincblende type semiconductors are listed.
As one may see, all values gE are less than 2, the g-factor of the free elec-
tron. The deviation from 2 is determined by the induced magnetic moment
of the orbital-motion component of a Bloch electron. As in a free atom,
this moment is always negative, in other words it results in a diamagnetic
450 Chapter 3. Electronic structure of semiconductor crystals with perturbations
Bornstein, 1982.)
contribution to the total magnetic moment of the Bloch electron. For Si,
the effective electron g-value is close to 2, indicating that the diamagnetic
contribution is small in this case. A negative effective g-value and hence a
larger diamagnetic contribution occurs in Ge. This is to be expected since
the diamagnetic moment is determined by the average angular momentum
L
, which according to expression (3.339), and similar to the effective elec-
tron mass of expression (2.338), increases if the gap decreases. The same
behavior of the effective g-factor for decreasing gap is observed among the
111-V compound semiconductors: InSb, the material with the smallest gap,
has the largest negative value of g:.
To describe the top of the valence band of diamond and zincblende type
materials, we need an effective mass equation for degenerate bands, and will
address this below.
Degenerate bands
It follows that the envelope function vector of the degenerate valence band
in a magnetic field satisfies the equation
(3.344)
has been used for the angular momentum term. Like the first tensor in equa-
9
tion (3.343), the second tensor H M can also be determined, apart from cer-
tain constants, by means of the point symmetry of the crystal. The method
of invariants, which was formulated in section 2.7 for the k-dependent term
9
of the Hamiltonian, is also well suited for the B-dependent operator H M .
The only change is the replacement of the wavevector k by the magnetic
induction B. To apply this method to the I?;, valence band of a diamond
type semiconductor, one needs a complete set of 9 linearly independent basis
9 9 9
vectors in the 3 x 3-matrix space formed from the three matrices I z rI y rI z
of angular momentum quantum number j = 1 and from the six products
of these matrices which transform according to the irreducible parts of the
product representation x I?;, = I?l +I?12+I':,+I';, (for the explicit form
of the angular momentum matrices see equations (A.143) of Appendix A).
Since the magnetic field B, as a pseudovector, belongs to the representation
I?:, of the point group oh, only subsets of matrices transforming according
to the irreducible representation ,:?I of Oh are allowed to form an hvari-
9
ant H M under the point group operations of oh. The subset of matrices
which transforms according to the representation I?:, is the pseudovector
9 9 9 9 9
-
I = (Iz,I y rIzLitself. Thus the scalar product (BI I ) emerges as the only
invariant, and H M follows as
(3.345)
with K being a constant which has to be determined from band structure
calculation or by means of experimental investigation. The same result for
9
H M follows for the I'l5-valence band of zincblende type semiconductors.
The above consideration shows that, in the case of degenerate bands,
there is coupling of the orbital motion to the magnetic field which does not
occur for non-degenerate bands. The source of it is the non-vanishing of
angular momentum matrix elements between the degenerate valence band
states. Of course, the average angular momentum of all valence band states
also vanishes in the degenerate case. However, the various angular mo-
mentum states, averaging to zero in the absence of a magnetic field, are
452 Chapter 3. Electronic structure of semiconductor crystals with perturbations
(3.346)
where K and q are again constants which must be determined either from
band structure calculations or experimentally. That the presence of spin
involves not only K , but also a second constant q, is understandable because
the orbital and spin motions have different gyromagnetic ratios. In most
(z
cases q is negligibly small (see Table 3.11). The result (3.346) for H M which
has been derived here for diamond type semiconductors, holds unchanged
for materials with zincblende structure also.
because for this gauge the vector potential A = (--By, 0,O) also commutes
with the momentum operator p. The same holds for the more complex
effective mass equation (3.343) for degenerate bands without as well as with
spin. Using the present gauge, the effective mass equation (3.336) for a
non-degenerate band without spin takes the form
2-
am:, [
(Pz + $Y)2 +Pp +pq F d X ) = ( E , - E,o)F,(x). (3.347)
(3.351)
Equation (3.349) describes a harmonic oscillator with center at yo, mass lm&1
and eigenfrequency wcw. It is well-known that in this case the eigenstates
can be described by integer quantum numbers n = 0 , 1 , 2 . . . ,00, with the
corresponding eigenenergies E L given by
EL, E &=
~ FAW,,,
( + a> . sgn(m&).
n - (3.352)
These energies are called Landau levels. For the eigenfunctions Xvo(y),we
have
454 Chapter 3. Electronic structure of semiconductor crystals with perturbations
(3.353)
(3.354)
For mC, = 0.2 m and B = 1 Tesla, this frequency amounts to 140 G H z , i.e.
it lies in the microwave region. According to equations (3.352) and (3.353),
the spectrum of allowed energy values forms a set of 1-dimensional energy
bands, the Landau subbands,
v)
.-
% 4
Q-
2
0 I I I I 1
0 2 4 6 0
E - Eg(hwCc)
Chapter 4
Electron system in
t herrnodynamic equilibrium
p* = e - ( H - p f i ) / k T
where H and denote, respectively, the Hamiltonian and the total particle
number operators of the many-electron system, in the so called occupation
number representation This representation is well suited to describe Slater
determinants in a more compact way than was done in Chapter 2. Before
proceeding further, we will introduce this representation (for more detail see
Appendix C). We number the possible one-particle states by an integer i
which can take the values 1,2,. . . ,m. If a particular one-particle state i
occurs in a Slater determinant one says that it is occupied or that its oc-
cupation number Ni is 1. If the state i does not occur, then Ni is 0. A
given one-particle state cannot occur more than once, otherwise the Slater
determinant vanishes in conformance with the Pauli exclusion principle for
electrons. The occupation numbers Ni can therefore only take the values 0
and 1. Using occupation numbers, the Slater determinants can be described
4.1. Fundamentals of the statistical description 459
fiiIN1, N27... N w )
j NilN1, N 2 , . . ' 7 Nw), (4.2)
and the total particle number operator k of the electron system follows by
summing the f i i over all i,
00
N = p i . (4.3)
i=l
Moreover, (4.2) and (4.3) imply that
The occupation number vectors IN1, N z , . . . , N,) form a complete basis set
in Hilbert space of the many-electron system. These vectors may be used to
represent an arbitrary many-electron operator. If only extended oneparticle
states are involved, like in the case of an ideal crystal, the occupation number
representation of k reads
W
H= EiNi. (4.5)
i=l
Using equations (4.2) to (4.6) one may easily show that the occupation
number space matrix representation of the equilibrium density matrix of
equation (4.1) is in fact diagonal with respect to the basis set of Slater
determinants "1, N z , . . . , N,), with the diagonal elements given by
460 Chapter 4. Electron system in thermodynamic equilibrium
The average value < fii > of the particle number operator fii, like the
average of any other operator of an observable quantity of the many-electron
system, is formed in accordance with the relation
Here, the symbol Tr[. .I stands for 'Trace' and means the summation over
all diagonal elements of the operator within the brackets with respect to
any basis in the Hilbert space of the many-particle system. One may easily
demonstrate that the value of the trace is independent of the particular basis
chosen. Of course, it is advantageous to use the set of Slater determinants
IN1, N z , . . . , N,) as basis, since the matrices of 6 and Ni are known in this
represent ation.
where we have set p = l / k T for brevity. The two expressions (4.9) and (4.10)
can be written as products of sums over particle numbers for a particular
state j , as indicated in equation (4.10). In the quotient, all factors cancel
except the two with j = i. These remain and give rise to the expression
4.2. Calculation of average particle numbers 46 1
Since the particle number Ni may take only the values 0 and 1, it follows
that
(4.12)
The average particle number in the one-particle state i thus depends only
on the energy of the state. If one identifies the chemical potential p with
the Fermi energy E F , and uses the notation
(4.13)
(4.14)
We conclude that the average particle number for configuration-independent
one-particle state i is given by the Fermi distribution, just like for an ideal
gas. The distribution function of classical statistics, the B o l t z m a n n distri-
bution
(4.15)
follows from the Fermi distribution for energies E with E - E F >> k T . This
also means f(E)<< 1. Under this condition the average particle number in
the one-particle state is small compared to 1, and thus the state is almost
unoccupied. Substantial deviations from the Boltzmann distribution occur
when E - EF is no longer large in comparison with k T and, therefore, f ( E )
no longer small compared to 1. In this case of substantial occupancy the
limited capacity of a one-particle state to host electrons (remember the Pauli
exclusion principle) becomes important, and the average particle number in
it deviates from that in classical statistics in which the hosting capacity of
states is not limited.
The deviation of the average particle number in a oneparticle state from
the value given by the Boltzmann distribution is called (statistical) degen-
eracy. A particle system is referred to as non-degenerate if it is described
by the Boltzmann distribution, otherwise it is called degenerate. The ap-
pearance of statistical degeneracy is a purely quantum mechanical effect - it
reflects the quantization of energy levels and the indistinguishability of elec-
trons. Statistical degeneracy applies to other elementary particles as well.
Indistinguishability refers to the fact that, in the exchange of two identi-
cal elementary particles, the total wavefunction of the many-particle system
transforms either into its negative (this holds in the case of electrons and
leads to the Pauli exclusion principle and with it to the Fermi statistics),
462 Chapter 4. Electron system in thermodynamic equilibrium
or the total wavefunction transforms into itself (then the population of the
oneparticle states is not limited, but the quantization of energy yields a
distribution function which also deviates from the Boltzmann distribution).
While the Fermi distribution emerges in the former case, in the latter case
it is the Bose distribution function, which may be formally obtained from
the Fermi distribution function (4.13) by setting the chemical potential zero
and replacing +lby -1in the denominator.
In the particular case of band states, the quantum number i is the pair
vk of band index v and quasi-wavevector k. In order that the wavefunction
luk) really represent only one quantum state, which is the case here, u must
also describe the spin state, or, alternatively, we must augment v to include a
spin quantum number CT. We use the latter description, i.e. we will write the
band states, henceforth, in the form lvko). With this, we assume that both
the band and spin quantum numbers I/ and u are compatible and meaningful
simultaneously. This is only justified if the spin-orbit interaction plays no
+
role and the two states (uk $) and lvk - g). have equal energy E,(k),
which we take to be the case here. In such circumstances, equation (4.14 )
yields
1
< fiuk6 > = f(E,(k)), ff = f-, (4.16)
2
and the average particle number < NUk+& + NUk-+ > for band u and
wavevector k follows as
(4.17)
The Fermi distribution (4.14) solves the problem of determining the average
equilibrium particle number < I?i > for one-particle states li) having energies
which are independent of the configuration of the many-electron system.
This distribution cannot be applied to configuration-dependent one-particle
states. In the latter case the above calculation of average particle numbers
has to repeated, taking account of the configuration dependencies of o n e
particle energies because of Coulomb repulsion effects.
I D a ) l % IDu)2 = p a ) , (4.18)
as was the case before, and consequently also only one type of particle num-
ber operators Nou, u = fi,Using the pertinent occupation numbers No,
of localized states, the N-particle states of system may be characterized as
IND+rNo-+, NJ, ...Nm), where N3, ..., N, denote the occupation numbers
of ex&nded band states. We use these N-particle states as a basis for the
calculation of the average particle number < N 1 > in localized state IDa)
D2
according to expression (4.8). We have
(4.19)
The factors referring to extended states are the same in the numerator and
denominator of expression (4.16), thus they cancel. In the remaining factors
referring to localized states, the following four configurations are possible:
No; = 0, N0-i = 0, N o + = 1, ND-l= 0, No+ = 0, ND-1= 1, No+ =
2
464 Chapter 4. Electron system in thermodynamic equilibrium
1
[,-P(%-P) + .-2P(E2d-d] , 2
= f-. (4.20)
The average number of particles occupying the center is the sum of < I$ 1 >
D;i
and < iD-+
>, given by
Using this expression, we will now discuss how the average number of par-
ticles localized at a center is influenced by configuration dependencies of
one-particle energies due to Coulomb repulsion. In Figure 4.la this num-
ber is shown as a function of chemical potential p for T = 0 K . As long
+
as p < EA, we have < I? 1 f i D - ~> = 0. If p exceeds EL, then
D;i
< N
D5
1 + kD-&> suddenly increases to the value 1, which is maintained
as long as E b < p < E g holds. When p becomes larger than E g , then
+
< fi 1 ND-+ > increases to the value 2, which is never exceeded even if
D-i
p increases further. In regard to dependence on chemical potential one has,
therefore, the values 0, 1 or 2 for the average particle number at the center.
If there were no Coulomb repulsion effects, then E g = E& would hold and
the 1-fold occupied state would cease to play a distinct role, as in the case
of band states (see Figure 4.lb). For temperatures above zero Kelvin, the
+
variation of < N 1 kD-i> with p is qualitatively the same, except that
D2
the sudden changes which occur at zero temperature are smoothed out. The
fact that the ionization level E$ rather than the oneparticle level E$ of the
2-fold occupied donor center determines the probability for two electrons to
be at the center, is physically understandable: on a microscopic scale, ther-
modynamic equilibrium is a dynamic state in which ionization (excitation)
and de-excitation processes balance each other.
The above results for a double donor may be readily transferred to a
double acceptor. If one replaces D by A , equation (4.21) gives the average
number < $ 1
AT
+ > of electrons (rather than holes) at such a center,
provided the energy levels EA and Eil in this expression are understood
as electron rather than hole energies. Thus the average number of holes is
(2- < NA+ 4 NA-+ >).
The method of calculating the average particle number at double donor
and acceptor centers may be easily generalized to centers with more than
4.2. Calculation of average particle numbers 465
. ElD E':
1
ED= ED
21
E:
21
ED+w
+
Figure 4.1: Average electron number < N D 3 f i D - + > according to formula
(4.21) of a double donor for T ---t 0 K as a function of chemical potential p. The
energy levels E A and E$ are both negative but different from each other in case
a), both negative and equal in case b), and only E A is negative in case c) while E S
tends to +m. In the latter case one actually has a simply ionizable donor. In case
b) there are effectively no configuration dependencies due to Coulomb repulsion
which is actually only true for band states.
two ionization levels in the energy gap. For n-fold ionizable centers one has
+
n 1 charge states. In calculating the average number of particles at such
centers one must include all of them, and take account of the fact that their
oneparticle energies and ionization levels differ. We omit this calculation
because it is rather cumbersome, and does not provide new physical insight.
Instead we turn to simply ionizabIe centers which, from a practical point of
view, are particularly important ones in semiconductors.
Formally, the transition from a double donor to a simply ionizable donor can
be represented by E E becoming infinitely large. In this case, E b plays the
role of the binding energy E D of the simply ionizable donor, and all terms
in equation (4.21) involving E g automatically vanish. Thus one obtains
(4.23)
466 Chapter 4. Electron system in thermodynamic equilibrium
with
(4.24)
becomes the average number of electrons at the acceptor. The average hole
number at the acceptor follows from this as
(4.26)
Here, the one-electron energy E A of the acceptor state represents the binding
energy E B of the hole at this level.
4.2. Calculation of average particle numbers 467
< C fiDnl-
nlmu
> = 1 + C g D n e -P(ED,-P)
[ n I-' n
gDne-fl(EDn-p),
(4.27)
This expression may be written in the form (4.24) if the ground state energy
ED' is denoted by E D , and if the factor f multiplying the exponential term
in the denominator in (4.24) is replaced by the temperature-dependent factor
(4.28)
468 Chapter 4 . Electron system in thermodynamic equilibrium
(4.29)
4,
Since y* < the average particle number at the center is enlarged as com-
pared to the case without excited states where y* = 4.
The excited states
therefore lead to an increase of the average particle number at the cen-
ter. This is physically understandable because more states are now avail-
able for occupancy than without excited states. If, on the other hand,
p - E D >> kT, i.e. the ground state is almost completely occupied, then
one has y*exp[P(ED - p ) ] << 1, and correspondingly
(4.31)
4.3. Density of states 469
so that one gets the same average particle number at the donor center as
without excited states. This is also physically clear immediately - because
the donor can host only 1 electron, and, with high probability it will occupy
the ground state, so excited states play practically no role.
As in the case without excited states, the results for donors can also be
transferred directly to acceptors but we will not write down the correspond-
ing expressions explicitly.
(4.33)
i= I
i)
The one-particle states l i ) comprise band states l v k f and localized states
lyf i)where y abbreviates the orbital state quantum numbers and the posi-
tion of the center. The band states are assumed to be 2-fold spin-degenerate,
as before. With this, we presuppose that spin-orbit splitting is negligibly
small which, as we know, is often not justified. The generalization of the
results to the case in which spin-orbit splitting has to be taken into account
i)
is straight forward. The localized states (7 f are taken to be the ground
states of simply ionizable donors (y = D ) or acceptors (y = A ) at various
positions in the crystal. We assume that there are no excited localized states.
The i-sum of equation (4.33) is decomposed in two partial sums, one over
the band states, and one over the localized states. Correlations between the
two sets of states which disturb this decomposition are neglected. With this,
we obtain the expression
470 Chapter 4 . Electron system in thermodynamic equilibrium
(4.35)
with f(E)as the Fermi distribution function. The localized part in equation
+
(4.34) can be written as a sum over the average values < k 1 k7-; > for
7F
the various centers 7,because they are independent of each other, whence,
Using the effective distribution function f*(E)for localized states from equa-
tions (4.24) and (4.25) we have
Altogether, we obtain
NtOta1= +
2 C f ( E u ( k ) ) Cf*(E,). (4.38)
uk 7
The total electron number Ntotd is an extensive quantity. Generally, the
corresponding intensive quantity, i.e. the total electron concentration related
to the volume of the periodicity region, is of interest. It is defined by the
expression
Ntotal
nbtal = -
0 '
(4.39)
(4.40)
(4.41)
(4.42)
where
2
pid"'(E) = - C 6 ( E - E , ( k ) ) . (4.43)
uk
1 ENERGY
GAP
The DOS of the conduction band thus exhibits square root-like behavior at
the band edge (see top part of Figure 4.2). Formally, it continues to follow
a square root law also for energies deep in the band. However, for such
energies, expression (4.44) does not apply. Qualitatively, the shape shown
by the dashed curve in the top part of Figure 4.2 is more realistic.
Expression (2.220) may not be used directly for the valence band, since its
derivation presupposes that the effective mass m t is positive, while for the
valence band it is in fact negative. The calculation above can, however, be
modified easily to the case m: < 0. With v = v, E,o = 0, and mz -mt >
0, we have
(4.45)
The density of states of the valence band is thus seen to have square root-like
dependence at the upper band edge and formally also continues to increase
according to a square-root law for energies deeper in the band (see bottom
part of Figure 4.2). The dashed curve again shows the more realistic shape.
The entire density of states pideaz(E)of an ideal semiconductor having one
valence and one conduction band is given by the expression
sequence of the fact that no stationary electron states exist there (see Fig-
ure 4.2). Finally, we write down the total electron concentration n&%: of
the ideal semiconductor having one conduction band and one valence band.
From equation (4.42) it follows that
In the case of the elemental semiconductors Si and Ge, the conduction band
edges consist of several valleys, and the iso-energy surfaces of the valleys
are anisotropic. This has consequences for p,(E). For Si, for example, the
conduction band density of states p p ( E ) takes the form
The valence band edges of diamond and zincblende type materials are de-
generate. The degree of degeneracy depends on whether spin-orbit splitting
is important or not. In the case of Si, the spin-orbit splitting energy A is
small in absolute units (44 m e V ) , but still large enough to compete with k T
(25 meV for T = 300 K ) . Thus, for temperatures that are not extremely
high, most of the holes are hosted by the I?$ valence band while the spin-
split I?$ band remains practically devoid of holes. This means that there are
two hole states per k-vector (apart from the 2-fold spin degeneracy), one for
heavy holes, and one for light holes. Thus , the corresponding hole density
of states p p of Si, calculated in the isotropic parabolic approximation of
equation (4.45), is given by the expression
(4.50)
p p ( E )= 4
27r
k 2 S ( E - E,(k)) (4.51)
Pc
Kane(E) 1
-
27r2
(-)3
2P2
3/2 (.- 5 - 3)
3 2
.-/
(4.52)
If E lies close to E,, then p p ( E ) given by (4.52) takes the form of ex-
pression (4.44) for a parabolic band. To see this, the effective mass rn; has
to be replaced by the expression from Table 2.13. That is to be expected,
because the band structure is also almost parabolic for energies close to the
edge within the Kane model.
Teal ( E ) = NDG(E - E D )
pgap + N A ~ ( E- E A ) . (4.56)
The densities of states of the valence and conduction bands of the real semi-
conductor will be denoted by pLd(E) and p:"'(E), respectively. The band
states of real semiconductor are, of course, no longer pure Bloch states, but
Bloch states perturbed by scattering from the impurity atoms. Similar to
pure Bloch states, they are, however, still spread out over the entire crys-
tal. Correlation effects therefore play no important role in their occupancy.
This means that the total electron concentration in the bands of the real
semiconductor may be expressed by p;T'(E) in the same way as the total
electron concentration of the ideal semiconductor was expressed by p Z d ( E )
in equation (4.47). Therefore,
,Teal
total = 1,
0
dE P:az(E) f(E) + /Or d E PF%)
Eg
f(-w
00
+I,dE PEW f*(E) . (4.57)
The band densities of states pLY'(E) of the real semiconductor differ from
p ; Y ' ( E ) in accordance with the considerations of sections 3.4 and 3.5, where
it was shown that localized states occur at the expense of the band states
476 Chapter 4. Electron system in thermodynamic equilibrium
0
dE pLal(E) = dE p i k d ( E ) - NA, (4.58)
--M
(4.59)
l,m
dEp'"l(E) = Jrn
-m
dEpiM(E). (4.61)
Concerning the band state densities p,':'(E), we initially know, apart from
the integral relations (4.58) and (4.59), nothing further than that it must
reproduce p Z z ( E ) if N D and N A are zero. Below, we will see that it is
possible, under certain conditions, to replace the real state densities p T f ( E )
approximately by the ideal state densities p : p z ( E ) even when N D # 0 and
N A f 0.
In the following, we calculate the average electron concentrations in the
energy bands and the donor and acceptor levels separately. Such separate
calculations of the concentrations are necessary because the electrons in these
different parts of the energy spectrum behave quite differently. The electrons
localized at an impurity atom, for example, do not contribute to electric
charge transport. The electrons of the conduction band do, just as do the
electrons of the valence band, the latter, however, provide such a contribution
in a different sense, not as electrons, but as holes. Therefore, facilitate to
calculation of the conductivity of a semiconductor, one needs the average
electron concentrations in the conduction band, in the donor and acceptor
levels, and in the valence band, separately. The same remarks apply to the
calculation of other measurable quantities.
4.4. fiee carrier concentrations 477
This equation says that the total concentration nitg: of electrons equals
the total concentration of valence band states of the ideal semiconductor.
This statement is, of course, independent of temperature. The total electron
concentration of the real semiconductor may therefore be written for any
temperature as
0
n Ttotal
fd -
1, d E pid"'(E) + N o - NA. (4.63)
(4.64)
(4.65)
(4.66)
478 Chapter 4. Electron system in thermodynamic equilibrium
(4.67)
n- p - ND+ + N; = 0. (4.71)
This expresses the conservation of total electron number for a real semicon-
ductor. The electrons may be redistributed between the four energy regions,
i.e. valence band, acceptor levels, donor levels and conduction band, but
their total number cannot change thereby. One may also understand rela-
tion (4.71) as the neutrality condition for a real semiconductor - the negative
charge of the electrons of the conduction band and of the ionized acceptors
must compensate for the positive charge of the holes of the valence band and
the ionized donors.
the Fermi energy. In particular, this means that the relative distribution
depends on the total particle concentration. By changing the total concen-
tration, the ratios of the average particle numbers in the various energy levels
can be altered. This is a clear manifestation of the statistical correlation be-
tween the electrons of an ideal Fermi gas. It also shows that the chemical
potential, or Fermi energy, is much more important in quantum statistics
than in classical statistics.
In evaluating the integrals of (4.67) and (4.68), we note that the occu-
pancy factors f (E) and [l- f ( E ) ]decrease monotonically with, respectively,
increasing or decreasing energy and effectively cut off the integration range.
The cutoff energies are separated by an interval of about kT from the respec-
tive band edges. We assume that the densities of states of a real semicon-
ductor, which are required in equations (4.67) and (4.68) for the effectively
contributing energy intervals, may be approximately replaced by the state
densities of the ideal semiconductor. This approximation is justified as long
as the concentrations of donors and acceptors is small compared to the con-
centration of significantly contributing band states. Furthermore, we assume
that in the contributing energy intervals, the densities of states (4.44) and
(4.45) of the ideal semiconductor, which are predicated on parabolic band
structure, are approximately valid. Thus we obtain
(4.72)
(4.73)
(4.74)
(4.75)
(4.76)
with
(4.77)
480 Chapter 4. Electron system in thermodynamic equilibrium.
In the frequently occurring case that the Fermi level lies not only in the
energy gap, but is separated by at least several k T from the two band edges,
the arguments of the Fermi integrals in (4.75), (4.76) are negative and have
absolute values large compared to 1. For such arguments the Fermi integral
is approximately given by
(4.78)
so that
(4.82)
As in the case of conduction band electrons, the holes of the valence band are
also described by a Boltzmann distribution if the Fermi energy is sufficiently
remote from the band edges. One may say in this situation that the electron
system of the conduction band and the hole system of the valence band are
non-degenerate carrier gases. We emphasize that in the case of the valence
band this statement refers to the holes and not to the electrons, which are
highly degenerate. In further considerations we will always assume that the
electrons of the conduction band and the holes of the valence band form
non-degenerate carrier systems. The expressions (4.75) and (4.76) for n and
p , respectively, provide a simple criterion for the validity of this assumption:
The electrons are non-degenerate if n << Nc and the holes are non-degenerate
if p << Nu. This may be seen as follows. If n << Nc holds, then the Fermi
integral F L [ ( E F- E , ) / k T ] in (4.75) must be much smaller than 1, which
is possible only if - ( E F - E , ) / k T >> 1, meaning that degeneracy does not
exist. The same argument holds for holes.
The quantities Nc and Nv in equation (4.77) have the dimensions of spa-
tialdensities and are termed the effective densities ofstates of the conduction
4.4. f i e e carrier concentrations 481
(4.84)
which is of the order of magnitude of the number of primitive unit cells per
cm3, i.e. M ~ m - ~ With
. this number, the order of magnitude of the
effective band densities of states is obtained by multiplying it by the ratio
of k T to the whole band width. With a value of k T M 10 meV and a band
width of 10 e V , N,,, FZ lo1 follows.
The values of n and p determined by equations (4.75), (4.76) still depend
on the Fermi energy E F , which is, as yet, unknown. The equation which
determines E F is the neutrality condition (4.71). In this equation all quan-
tities may be considered to be known except the Fermi energy, for which the
equation is to be solved. Even without any calculation it is clear that the
position of the Fermi level will depend on the donor and acceptor concentra-
tions N D and N A . This dependence is transferred directly to n and p. There
is, however, a simple function of the two concentrations, their product np,
which in the case of non-degenerate carrier systems does not depend on E F ,
and hence not on N D and N A . This may be seen using equations (4.79) and
(4.80), from which it follows that
np = ni,
2 (4.85)
with
ni = (NcNV)3e-iEg/ICT. (4.86)
482 Chapter 4. Electron system in thermodynamic equilibrium
n, 2.7 x 10' 1.8 x lo6 1.5 x 10" 2.4 x 1013 8.6 x lOI4 1.6 x 10l6
This equation may be understood as the law of mass action for a 'chemical
reaction' in which bound electrons in the valence band and at the donor
atoms on the one hand, and bound holes in the conduction and at the ac-
ceptor atoms on the other hand, generate free electrons in the conduction
band and free holes in the valence band. The concentration of the bound
electrons can approximately be set equal to the effective density of states
Nu of the valence band, since in the non-degenerate case, the concentra-
tions of holes and of occupied donors are small in comparison to N,,. A
similar statement holds for the bound holes which, here, also include the
non-occupied states of the conduction band. Their concentration roughly
equals the effective density of states Nc of the conduction band. According
to the mass action law, one then has, for an ideal gas, n p = K ( T ) N , N , , with
K ( T ) = exp[-(gc +
g,,)/,kT]as mass action constant. Here, gc and g,, are,
respectively, the free enthalpies of an electron in the conduction band and
+
of a hole in the valence band. With gc gv = E,, equation (4.86) is indeed
the mass action law, as stated above.
n - p = 0. (4.87)
This equation reflects the fact that the electrons of the conduction band
are created solely by thermal excitation of electrons from the valence band,
leaving behind an equal number of holes. If we substitute p = n in equation
(4.85), then we have
This relation was already stated in Chapter 1 on the basis of empirical facts
(see equation 1.20). One refers to ni as intrinsic concentration, because it
4.4. Free carrier concentrations 483
1 1
EF=
~ -E,+ -kTh (4.90)
2 2
1 3
EF=
~ -Eg
2
+ -kT
4
h (4.91)
For T = 0 K , the Fermi level thus lies exactly in the middle of the gap
between the valence and conduction bands. It remains there even for finite
temperature if rn; = rn:. If rn; # m:, a temperature dependence emerges
which is schematically shown in Figure 4.4. For rn: > rn; or N , > N,, EF(
moves away from the valence band edge, and for rn; > rn; or Nc > N,,
away from the conduction band edge. This may be understood as follows:
If the effective density of states in the valence band is larger than that in
the conduction band, one would have more holes in the valence band than
electrons in the conduction band if the Fermi level were to stay in the middle
of the gap. It must move away from the valence band edge to assure the
equality of n and p . An analogous interpretation can be given in the case of
Nc > N,. In short, one can say that the Fermi level is repelled by regions of
high density of states, and is attracted by regions of low density of states.
We next determine n and p for the case of real semiconductors with
donor and acceptor atoms present. In Chapter 1, the designation eztrznsic
semiconductors was already introduced to describe them.
484 Chapter 4 . Electron system in thermodynamic equilibrium
IO~/T/K- -.
Figure 4.4 Variation of
Fermi level with tempera-
ture for an intrinsic semi-
conductor.
n-type-semiconduct ors
Initially, we assume that there are only donors, and no acceptors are present,
N D # 0 and N A = 0. The neutrality condition (4.71) is then transformed
into an equation for the electron concentration n. In this regard, we need
the concentration Ngf = N D ( - ~ ED)] of ionized donors. The donor
population probability f * ( E D ) is given by equation (4.24) as
4.4. fiee carrier concentrations 485
(4.92)
where EB denotes the donor binding energy. In general, the donor levels,
unlike band energies, do not lie well above the Fermi level. They may be
close to, or even below it. This means that the degeneracy of the Fermi
distribution, which could be neglected for carriers in the bands, must in
general be taken into account in the effective donor distribution function
!*(ED). The expression (4.92) for f*(Eo)must therefore be used in its
original form. The Fermi energy can be eliminated from it by introducing
the electron concentration n given in equation (4.79), with the result
(4.93)
(4.94)
Apart from the factor 1/2, the quantity nl represents the electron concen-
tration in the conduction band of a non-degenerate ideal semiconductor with
a (fictitious) Fermi level at the position of the donor level. If we replace p
in terms of nT/n using equation (4.85), then the neutrality condition takes
the form
(4.95)
From this equation one may easily derive the magnitude relations
(4.96)
In a semiconductor containing donors but no acceptors, the electron concen-
tration is always larger than the intrinsic concentration ni, and the latter is
larger than the hole concentration p. It is therefore called an n-type semi-
conductor. The electrons are majority carriers in this case, and the holes
are minority carriers. To solve the neutrality condition (4.95) for n, we
transform it into the third-order polynomial equation
1) N D <( ni :
Considering the inequalities (4.96), the term proportional to N D in equation
(4.97) may be neglected in comparison with the second term. Thus we have,
approximately,
n3 + n1n2 - n f n - ninl
2 = 0. (4.98)
The only positive real solution of this equation is
n = ni. (4.99)
For p , one gets p = p i . This means that in case l),the carrier concentrations
n and p do not differ from those of an intrinsic semiconductor. If the values of
N D are not extremely large, then the inequality N D <( ni may always be ful-
filled, simply by making the temperature and therefore also ni large enough.
For sufficiently high temperatures and not overly large N D values, one thus
always has the intrinsic case. Only if the donor concentration becomes suffi-
ciently large, and the temperature so low that the inequality N D << ni does
not hold, then the donors can influence the carrier concentrations n and p
considerably.
We turn now to the other extreme case
2 ) N D >> ni :
Because n > nil one then also has N D n >> n:. Under this condition, the
last term in (4.97) may be neglected in comparison with the term n l N D n .
With this, one has the approximate equation
n2 + n1n - n l N D = 0. (4.100)
Its positive solution is given by
(4.101)
If N D << n l , i.e. for relatively light doping, but sufficiently high tempera-
tures, it follows, approximately, that
n =No. (4.102)
All donor atoms are ionized and have donated their additional electrons to
the conduction band. Understandably, for this to occur one needs sufficiently
high temperatures and, maintaining the validity of N D >> nil sufficiently
small donor concentrations. The latter restriction is necessary in order to
4.4. n e e carrier concentrations 487
b
I I I I
tion of temperature for N D =
loi5 ~ r n - (After
~ . Smith, 1979.)
"I
- -- I INTRINSIC RANGE
SLOPE = Eg
7 1
-5
E
Id6
!I
:I
*
t - I SATURATION RANGE
I
$ E
c
; lo"=
I
\
f \nl
1 1
10'3- 1 1 I I 1 I I 1 I I
insure that all donor electrons can be hosted by the conduction band. One
terms this case the exhaustion of doping centers or the saturation of carrier
concentration.
If, conversely, N o >> n1 holds, which means very high donor concentra-
tions and low temperatures, equation (4.101) approximately yields
n= JnTNo. (4.103)
Because of the assumption nl << N o , this concentration is substantially
smaller than N o , i.e., only a small fraction of the donor atoms have been
ionized and have transferred their electrons to the conduction band. One
terms this a reserve of doping atoms or a freez-out of carriers at the im-
purities. Even in this case n can be substantially larger than the intrinsic
concentration ni, provided n1 is larger than or at least of the same order
of magnitude as ni. This occurs for shallow levels with nl >> ni, and is
also still valid for levels E D = ( 1 / 2 ) E g at the middle of the gap for which
nl = ( 1 / 2 ) n i follows. The property of impurity atoms to be effective electron
donors for the conduction band is not restricted, therefore, to the case where
the impurity levels lie just beneath the conduction band edge. Even from
the middle of the forbidden zone they can increase n far above the intrinsic
concentration. This can change only for yet deeper levels with n1 << ni.
The largest increase, however, is caused by shallow levels. This explains
why impurity atoms forming shallow levels are particularly important for
semiconductor doping. Figure 4.5 shows the temperature dependence of the
free carrier concentration in such a case. The three qualitatively different
488 Chapter 4. Electron system in thermodynamic equilibrium
0 20 40 60 80
T/K -
regions - freez-out of carriers for low temperatures, saturation for medium,
and intrinsic behavior for high temperatures - may be clearly recognized in
this figure.
The minority carrier concentration p in case 2) is always substantially smaller
than p i of the intrinsic case.
We have yet to determine the position of the Fermi level in the case with
considerable n-type doping where N D >> ni holds. Employing the relation
(4.104)
we obtain, for N D << n1, i.e. for high temperatures and low doping, the
result
(4.105)
and, for N D >> nl, i.e. for low temperatures and high doping, we find that
(4.106)
The dependence of the Fermi level on temperature is shown in Figure 4.6 for
n-type germanium with typical values of N D and EB. At T = 0 K the Fermi
level lies exactly in the middle between the donor level and the conduction
band edge, the donors being only partially ionized. With increasing temper-
ature the degree of ionization increases. In order for this to be possible, the
Fermi level must shift to lower energies. This may again be understood as a
repulsion of the Fermi level by the group of states with higher density - the
effective conduction band density of states is larger than the donor density
of states, which equals the donor concentration.
p-type semiconductors
(4.107)
(4.108)
p l = 2 N , e - E /kT. (4.109)
With p instead of n as independent variable, the neutrality condition (4.71)
takes the form
(4.110)
P = ni, (4.112)
which results in n = ni. For N A >> ni we obtain
P=NA (4.113)
if NA << p l , and
P = & K (4.114)
if N A >> p l . In both cases the minority carrier concentration n is much
less than p . For the Fermi level position, we have results analogous to those
obtained for an n-type semiconductor.
n: n1
n---- N A = 0, (4.115)
n n+n1 N D + nf +pin
where n and p are to be taken from equations (4.79) and (4.80). The relation
(4.115) can be transformed into a fourth-order equation for n or p. Since
this is not solvable in compact form, we consider certain limiting cases which
allow for simple solutions and provide some physical insight. Under the
assumption n << n1, p << pl we find, approximately,
n2 - ni2 - n ( N o + N A ) = 0. (4.116)
This equation corresponds to the limiting case of completely ionized donors
and acceptors. Its solution is given by
492 Chapter 4. Electron system in thermodynamic equilibrium
tration N D - N A = 10l6 is
assumed. The various curves corre- 104
spond to different degrees of com-
pensation N A : 1- 0, 2 - 3-
loL5, 4 - loL6 (After Bonch-
Bruevich and Kalashnikov, 1982.)
0 2 4 6 8 1012
IOOT-/K-L
n?
p = (NA- No), n= if N A > ND. (4.119)
(NA- N D )
Thus a partially compensated n-type semiconductor occurs for N D > N A ,
and a partially compensated p t y p e semiconductor occurs for N A > ND.
In both cases the majority carrier concentration is J N D- NAJ. For not
completely ionized donors or acceptors, this simple relationship is no longer
valid. In Figure 4.8, partial compensation as a function of temperature is
illustrated using the example of n-doped germanium.
+
additional term N D j / ( n n j ) into the neutrality condition, and each addi-
tional type of such an acceptor (described by an index k ) gives rise to an
+
additional term NAkn/(n: n p k ) . The neutrality condition for this more
general case therefore takes the form
n2
n - 2 - z ~ D j - nj + ) : N A ~ zpkn = 0. (4.120)
n j n+nj ni + P k n
(4.121)
61 = y*2n1. (4.122)
Since y* < f, and therefore 6 1 < n l , the concentration n of free electrons
is decreased in general. This is readily understandable since the excited
elect,ron states of the donors result in more electrons being bound.
For acceptors with excited bound states one gets analogous results. The
concentration p l is replaced by
$1 = y*-12-lp1. (4.23)
in the neutrality condition (4.111). Now, j1 > p l holds, which means that
the number of free holes is increased. This is immediately clear because
494 Chapter 4. Electron system in thermodynamic equilibrium
the acceptors bind fewer holes if there are excited electron states at the
acceptors.
n-type semiconductors
n- p -N D ~= 0, (4.124)
one needs the hole concentration Ngf localized at the donors. It is given by
the relation
+
Substituting < fi I fiD-l > as given by equation (4.21), replacing the
DI
chemical potential p by E p l Z E bby Eg - E h , and E g by Eg - E i l where
E L and E i l are, respectively, the ionization energies of one electron at the
1- or 2-fold occupied center, it follows that
(4.128)
With this result (and using n!/n for p ) , the neutrality condition (4.124)
takes the form
4.4. Free carrier concentrations 495
(4.129)
which means that the doping should not be too heavy, nor the temperature
too low, then (4.129) approximately yields
n =~ N D . (4.130)
In this case, all donors are 2-fold ionized and one has the case of exhausted
doping atoms. To fulfill the condition n << n7, it is necessary that N D <<
7x7. The exhaustion of a doubly ionizable donor is thus characterized by
an inequality similar to that which formerly was found for simply ionizable
donors .
In the limiting case
n >> n;,n$
(4.131)
Here, we have set n* = na2/n7 for brevity. The positive solution of this
equation is given by
n = n* Jq- I] (4.132)
With the assumption N D << n*, it yields n = N o , i.e. each donor atom is
simply ionized. One has exhaustion of the doping centers with respect to
1-fold ionization, and reserve with respect to 2-fold ionization. This result
can be understood in the following term: In order to fulfill the conditions
ND << n* and ND >> n7 simultaneously, n* >> ni and with this also nz >> nT
must hold. This means that n* << n$ and ND << na, so that n? << N D << na
496 Chapter 4. Electron system in thermodynamic equilibrium
follows. The condition for donor exhaustion is therefore fulfilled for the
2-fold occupied center, but not for the 1-fold occupied center.
A different situation occurs in the case ND >> n*, in which one finds
from (4.132), approximately,
n= Jm. (4.133)
Because nT < n4, the condition ND >> n* also insures that ND >> na. This
means that the reserve case also occurs with respect to the 2-fold occupied
center. In comparison with a one-particle center having an ionization energy
E B equal to the ionization energy EB of the simply occupied two-particle
center, the carrier concentration due to the two-particle center is enlarged by
the factor 2(n$/n;). The 2 is a consequence of the doubling of the electron
number at the non-ionized donors. The factor ( n ; / n ; ) , which exceeds 1,
reflects the fact that the ionization of the 2-fold occupied center has a larger
probability than that of the simply occupied center.
p-type semiconductors
p - - n5
-2N~
(4.134)
P P2 + 2PIP + P2
with
(4.135)
Here EL and Eil refer to electrons (rather than holes) and denote, respec-
tively, the ionization energies of the acceptor with, respectively, 2 holes (no
electron) or 1 hole (1 electron) at the center. Because Eil > EL,one always
has pT > pz. The neutrality condition will again be solved in limiting cases.
In these cases the acceptor concentration NA will always be assumed to be
large compared to the intrinsic concentration p i = ni of holes, so that the
intrinsic term in (4.134) can be neglected. We first assume that
P 2NA, (4.136)
corresponding to all acceptors being 2-fold ionized, the case of exhaustion.
In the opposite case
4.4. Free carrier concentrations 497
(4.137)
P = $%lP;, (4.138)
p = NA. (4.139)
All acceptors are simply ionized, and there is exhaustion of the acceptors
with respect to 1-fold ionization, and reserve with respect to 2-fold ionization.
this, on the position of the Fermi level (see Figure 4.9). The latter is co-
determined by the concentration of Au atoms, and it also depends, however,
on the concentrations of other donors and acceptors if there are such. In
p-type doped germanium, Au acts as donor because, in this case, the Fermi
level lies just above the valence band edge so that the charge state Au(l+)
occurs. In n-doped germanium, Au forms a double acceptor due to the Fermi
level position lying slightly below the conduction band edge, which results
in the charge states Au(1-) and Au(2-).
499
Chapter 5
Non-equilibrium processes
in semiconductors
Boltzmann equation
We will write this equation down explicitly for the extended one-electron
excitations of the system, i.e. the Bloch states uk. The distribution function
f(uk, x,t ) in this case is the probability that, at a position x and at a time
t , the Bloch state having quasi-wavevector k and band-index u is occupied
5.1. Fundamentals of the statistical description of non-equilibrium processes 501
by an electron. Since, in reality, the Bloch states are infinitely extended, the
specification at a position x must be understood in the sense of a region
centered at x, whose spatial extension A is large compared to the electron
wavelength X = 2 n / J k J .For the concept of a spacedependent distribution
function f(vk, x, t ) of Bloch states to make sense, f(vk, x, t ) must change
very slowly over a length of the order of magnitude A. A similar condition
holds for the variation of the distribution function with time.
In the absence of external perturbations of the type which drive a current
or energy transfer, the system of Bloch electrons is in thermodynamic equi-
librium, such that it may be described by the Fermi distribution function
(4.13) with E = E,(k). To drive the system out of equilibrium, appropriate
external perturbations must be applied, such as particle density gradients or
an external electric field E(x, t ) , as we will assume here. In addition to ex-
ternal perturbations, internal perturbations also act on the Bloch electrons,
such as scattering by phonons and impurities. The term collisions is used
in this context which means that the scattering events take place in a very
short time, practically instantaneous. Both types of perturbations, external
ones and collisions, result in temporal changes of the distribution function,
denoted as (df(vk, x, t ) / d t ) e z t and (df(vk, x, t ) / d t ) , d l , respectively. Accord-
ing to a general theorem of statistical mechanics, the Liouville theorem, the
total change o f f , taken at a position x(t),iik(t) of phase space which moves
together with the particles, must vanish. Thus,
Performing the derivative, the first term of this equation may be written as
Boltzmann equation are mainly due to its collision term, a statement which
applies both to the derivation as well as to the solution of this equation.
Lets suppose that the Boltzmann equation has been solved. Then, as in the
case of equilibrium, one may use the known distribution function f(vk, x,t )
to determine statistical average values < A > of any one-particle quantity
A of the many-electron system. Such quantities represent sums over cor-
responding individual electron quantities a. Like the distribution function
itself, the average values are functions < A > (x,t ) of space and time coor-
dinates, such that
Insofar as information about the state of the system is concerned, the Boltz-
mann equation provides much more detail than the phenomenological equa-
5.1. Fundamentals of the statistical description of non-equilibrium processes 503
tions. The latter can be derived from the Boltzmann equation with addi-
tional assumptions, but the reverse, i.e. the derivation of the Boltzmann
equation from the phenomenological equations, is not possible. The transi-
tion from the Boltzmann equation to phenomenological equations represents,
essentially, a coarse graining of the length and time scales on which the non-
equilibrium processes proceed. If processes must be analyzed on the space
scale of the average mean free path length and the time scale of the mean
free flight time, then Boltzmanns equation is required. If a macroscopic
average description suffices, one can use the phenomenological equations. In
semiconductor physics, the latter case often applies. Accordingly, we will r e
strict our considerations to the phenomenological equations in our treatment
of non-equilibrium processes.
These equations are valid only within prescribed limits. One can con-
sider these limits, like the equations themselves, to be empirically given.
However, deeper insight can be gained by using Boltzmanns equation. The
question to be answered in this context is: Under what assumptions can
the phenomenological equations be derived from the Boltzmann equation?
The answer depends on the phenomenon under consideration. Equations as,
for example, that for the temporal change rate of a given physical quantity,
may be obtained by multiplying the Boltzmann equation by the value of this
quantity in a Bloch state vk and subsequently summing over all states. The
simplest equation of this type is that for the temporal change rate of the free
carrier concentration of a single band, which later will explicitly be written
down. To obtain this equation from Boltzmanns equation in the manner
indicated above, simplifying assumptions are necessary concerning the quan-
tum mechanical transition probabilities between bands and localized states
occurring in the collision term: These probabilities must be approximated
by their values in thermodynamic equilibrium.
In the derivation of phenomenological equations for particle currents,
to consider another example, one assumes that the non-equilibrium state
deviates only slightly from a spatially and temporally local equilibrium state.
In the latter state, the distribution function depends on the Bloch states only
through their energies, and the form of the dependence is that of the Fermi
distribution function f ( E ) , just like in global equilibrium. However, the
temperature T and chemical potential p occurring in f(E), are understood
as functions T(x,t ) and p(x, t) of space and time coordinates. Thus we have,
If << TIIVTI, P I P P I ?
and
tf << TllaTlatl, P l l a P l a t l (5.7)
must be satisfied. Typical values for the mean free path length of electrons
and holes in semiconductors are of the order of magnitude 100 A. This means
that local equilibrium is a reasonable zero order description if important
spatial inhomogeneities occur on or above a length scale of 1000 A = 0.1 p m .
The mean free flight time has typical values close to s. Temporal
changes with frequencies of 10l2 s- can therefore still be accepted within
the local equilibrium framework, although no light frequencies are allowed
which lie in the region of 1014 s-. The regime of validity of the local
equilibrium assumption is nevertheless still relatively broad.
If the local equilibrium distribution were to describe the non-equilibrium
state exactly, no currents would flow at all since the corresponding average
values would be zero. In the presence of currents, the local equilibrium
distribution function can, therefore, only be a zero-th approximation. It
must be corrected by a perturbation term fl(vk, x, t ) , such that one has
with respect to the electric field E(x, t ) . The vector g(vk, x, t ) is understood
to be field-independent. It may be calculated from Boltzmanns equation in
linear approximation with respect to E. For this approximation to be justi-
fied, the field must be sufficiently weak. This represents a second condition
for the validity of Ohms law.
5.2. Systematics of non-equilibrium processes in semiconductors 505
The above derivation of this law yields not only a phenomenological equation,
but also an expression for the electrical conductivity involved in it. It relates
this coefficient with characteristic microscopic quantities of the system such
as, for example, its band structure, as well as with external state parameters
like temperature and chemical potential. This is to say that derivation from
the Boltzmann equation yields the phenomenological equation, Ohmss law,
and, simultaneously, a microscopic theory for the conductivity, or, if other
phenomenological equations are considered, for the other respective kinetic
coefficients. If the phenomenological equations are taken as empiricaI laws,
these coefficients are material parameters whose magnitudes and tempera-
ture dependencies can only be determined from experimental investigations.
However, by means of Boltzmanns equation the kinetic coefficients can be
predicted. Without the use of such an equation, this opportunity is lost. Be-
side the somewhat lower precision of the phenomenological equations, due
to simplifications and approximations, the principal loss lies in the inability
to predict the kinetic coefficients, given only phenomenological equations in-
stead of Boltzmanns equation. For the purposes of this book, where we do
not intend to develop a detailed understanding of the magnitudes and state
dependencies of material parameters, we will accept this loss and use the
phenomenological equations to gain insight into non-equilibrium dynamics
quickly.
In the next section we present, first of all, a systematic survey of the non-
equilibrium processes which are essential in semiconductors. More detailed
treatment of each process is provided in following sections.
(5.10)
506 Chapter 5. Non-equilibrium processes in semiconductors
with
(5.11)
(%) = -
(5.12)
With the right hand sides known, these equations determine the relaxation
of non-equilibrium charge carrier concentrations.
1) n = no, p = p o , E = c o n s t . # 0.
The potential energy of an electron is eE . x in this case, i.e. the system
is in fact spatially inhomogeneous despite its homogeneous charge carrier
concentration. An electric current will flow in this case. This phenomenon
is commonly referred to as drift, and the current itself is called drift current.
The pertinent current density is spatially homogeneous and decomposes into
a current density for electrons, j,, and another one for holes, j,. With nn and
a, as conductivities for electrons and holes, respectively, Ohms law yields
total electron and hole current densities j, and j, obey the phenomenological
equations
s, d3xp(x) = 0. (5.17)
The electric field E(x) due to the charge distribution p(x) follows from the
pertinent potential p(x) by means of the relation
1
V2p(x) = --p(x) (5.19)
=0
n = n ( x ,t ) , p = p ( x ,t ) , E = E ( x , t ) # 0.
Here, the generation and annihilation of charge carriers is also possible be-
cause of the fact that there are sources and sinks of the current densities j n
and j,. This follows from the continuity equations for j n and j , , where the
rates of change of the charge carrier concentrations due to relaxation enter
as source terms. Thus. we have
j p ( x ,t ) = u p E ( x ,t ) - ~ D , ~ P (t )x , (5.23)
free electron, while the transition of a conduction band electron into a deep
level only removes a free electron. A free hole, which could vanish, does not
exist in the latter case. If free electrons and holes are simultaneously gen-
erated or annihilated in equal numbers, we speak of bipolar generation and
annihilation processes. If only one type of free charge carrier is generated or
annihilated, we have unipolar processes. We first treat generation processes,
including uni- and bipolar ones.
(g) unip.gen.
=gnI
unip.gen.
= gp. (5.25)
In the case of bipolar generation by means of light (see Figure 5.1) one has
gn = g p = g , so that
(5.26)
a)
I
.
...
.
Figure 5.1: Unipolar generation of electrons (a), holes (b), and bipolar generation
of electron-hole pairs (c).
Electron capture
After an electron of the conduction band is captured by a deep center, there is
a finite probability that it may be re-emitted back into this band. The anni-
hilation rate -(an/dt),,,ihii is therefore the net capture rate (dn/dt),pture,
defined as the negative of the difference between the gross capture rate C,
and the emission rate En, i.e.
5 12 Chapter 5. Non-equilibrium processes in semiconductors
(5.28)
The capture rate C , is, on the one hand, a function of the concentration of
free electrons available for capture, i.e. of n. On the other hand, it depends
on the concentration of deep centers available for a capture. If we denote
by N t the total concentration of deep centers, and by f the probability that
they are already occupied by an electron, then the concentration of available
centers is Nt(1 - f ) . Thus,
En = en f Nt. (5.30)
The proportionality factor en is called emission coefficient. It measures
the emission capability of an occupied center. For one occupied center the
emission probability per second is just en. The net capture rate follows as
($) capture
= - [cnn(l- f ) N t - e n f ~ t ~ . (5.31)
Consider first the special case of thermodynamic equilibrium. In this state all
macroscopic quantities are independent of time, so that (dn/bt)capture = 0
holds. The concentrations n , p take their equilibrium values no and PO, and
5.3. Generation and annihilation of free charge carriers 513
the same holds for the occupation probability f of the deep level, which is
given by
(5.32)
where -ytn denotes the ratio of the statistical weights of the unoccupied and
occupied center. Equation (5.31), with vanishing left hand side, yields a
relation between en and cn in thermodynamic equilibrium, namely
with
(5.34)
(5.35)
The relations (5.35) and (5.36) together form a system of non-linear differen-
tial equations, which can be solved exactly in closed form. However, we will
514 Chapter 5. Non-equilibrium processes in semiconductors
not exhibit this solution here, restricting our discussion to a linear approxi-
mation. In this, we assume that the functions n and f deviate only weakly
from their equilibrium values. Formally, this means that n = no An and +
+
f = f o A f with lAnl << no and lAf I << 1, whence
(g) capture
= - c n N [-(nt + no)Af + An(1- f o ) ] . (5.37)
Bilinear terms were neglected in this derivation, and equation (5.33) was
used. We consider that the generation of non-equilibrium electrons before
time t o arises from an initial equilibrium distribution with subsequent exci-
tation of electrons from deep levels into the conduction band. The resulting
total concentration of electrons in deep levels and in the conduction band
+
jointly have the equilibrium value no Ntfo at all points of time t before
and after to. Therefore
An + NtAf = 0. (5.38)
With this, the linear expression
(5.39)
follows from (5.37), where for the sake of brevity we have defined
1
7, = (5.40)
cn[nt + no + N t ( 1 - f o ) ]
where An0 = An(t = t o ) has been used. This result demonstrates that rn
represents the decay time of a non-equilibrium charge carrier distribution.
One also calls rn the lifetime of non-equilibrium electrons with respect to
capture at deep centers. In the case of completely unoccupied deep centers,
i.e. at fo = 0, and for very high concentrations Nt, more exactly for Nt >>
+
nt no, rn is given by
1
I
rno = -. (5.43)
CnNt
5.3. Generation and annihilation of free charge carriers 515
In accordance with its meaning, rn0 is the time interval in which the totality
of Nt unoccupied deep level per cm3 capture one non-equilibrium electron
from the conduction band. One therefore calls r,,o the capture time. The life-
time r,, and the capture time rno differ because of the occupation dependence
of the capture rate and the occurrence of reemission. If N t ( 1 - fo) >> nt+no,
then one has r,, > rno. This result is immediately understandable because
the lifetime r,, contains contributions only from unoccupied deep centers,
whereas all deep centers, including occupied ones, enter in rno.
Hole capture
As in the case of electrons, deep centers can also capture and reemit holes.
The capture of a hole means that a deep center, which in its ground state
binds a certain number of electrons, transfers one of these electrons to the
valence band and annihilates a hole there. The emission of a hole is to
be understood in the sense that a deep level captures an electron from the
valence band (see Figure 5.1). All considerations involving the capture and
emission of electrons, and all relations derived for these processes, can be
immediately transferred to holes. The capture and emission rates C p and
E p are given by the expressions
In this, cp and e p denote the capture and emission coefficients for holes.
They are related to each other by the equation
ep = PtCp 7 (5.45)
where pt is the hole concentration
(5.46)
(5.48)
516 Chapter 5. Non-equilibrium processes in semiconductors
Table 5.1: Experimental capture cross sections for particular deep centers in Si
and Ge at T = 300 K in units cm2.(Data compiled from various sources.)
n Si
Center on UP
Au(l+) 35-63
Au(0) 1.7-5
Au(1-) 10-110
140) 0.1 Cu(1-) 0.1-0.18 500
In(l-) 170 Cu(2-) 0.0036-0.3 1-3.6
(5.49)
Experimentally determined capture cross sections for some deep centers are
listed in Table 5.1.
5.3. Generation and annihilation of free charge carriers 517
Capture mechanisms
one hole in the valence band. Auger recombination is important mainly for
high charge carrier concentrations, since its probability is determined by the
product of the concentrations of the three carriers involved. Thirdly, the en-
ergy released during recombination can be transferred again to the lattice.
This direct band-band recombination with emission of as many phonons
as needed to match the energy gap, proves to be extremely unlikely. The
reasons for this are, on the one hand, that the number of phonons which
would have to be emitted simultaneously is very large, and secondly that
the electron-phonon interaction for electrons and holes in band states is rel-
atively weak. Recombination processes in which deep levels are involved
as intermediate states for an electron making the transition from the con-
duction band to a hole in the valence band are much more effective. This
mechanism is called Shockley-Read-Hall recombination Auger recombina-
tion and Shockley-Read-Hall recombination together are jointly referred to
as non-radiative recombination processes. Because of its dominating role in
electronic devices, we treat Shockley-Read-Hall recombination below in more
detail.
Figure 5.3: Capture and emission of an electron and a hole at the same deep center.
Figure 5.4: Effects of deep levels for differing relations between the capture and
emission rates for electrons and holes.
would be impossible. Since the capture of an electron from the valence band
is equivalent to the emission of a hole to this band, the first condition to be
satisfied may be expressed as Cn >> Ep. On the other hand, the electron
captured from the conduction band must make the transition to the valence
band more quickly, or, in other words, the deep center must capture a hole
from the valence band more quickly, than the time it takes the electron cap-
tured by the deep center can be re-emitted back to the conduction band.
Thus C p >> En must hold. If different order of magnitude relations exist
between the four rates, the deep center can no longer function as a recom-
bination center, but has other effects (see Figure 5.4). We summarize these
in the following survey: The deep center works as
a) recombination center for Cn >> E p , C p >> En
b) electron capture center for C, >> Ep, C p << En
c) hole capture center for Cp>> En, C,<< Ep
d) generation center for Cp << En, Cn << Ep.
Verification of the three last cases, which were not explicitly discussed above,
520 Cbapter 5. Non-equilibrium processes in semiconductors
is left to the reader. With the background of these considerations, the unipo-
lar annihilation of charge carriers at deep centers appears in a new light. It
is a special case of the more general situation considered here, in which the
deep center can capture and emit both electrons and holes.
Thus far, recombination through deep centers has been considered only
qualitatively. To exhibit a quantitative treatment, we present equations
for the temporal rates of change of the electron concentration n, the hole
concentration p, and the occupation probability f of the deep center. These
equations are generalizations of the relat,ions which were already employed
above in describing the capture of carriers by deep centers. Here, they read
(5.50)
By means of relations (5.33) and (5.45) between, respectively, en, cn and ep,
cp, and using notation rno and rPo,introduced above, we have
(5.53)
1
= - [(l- f ) P t - fPl . (5.54)
(%)recomb TPo
Consider the case of stationary recombination. Then the occupation of the
deep level does not change in time, so that
(g) = 0, (5.55)
(5.56)
i.e., the numbers of electrons and holes vanishing per volume and time unit,
are the same. Their common value is the number of electron-hole pairs
recombining per unit volume and time, so that the recombination rate R is
R=-($)
recomb
=-(a) recomb (5.57)
The relation
CI
with
An#O, A p = O .
It follows that
An
R=- (5.64)
Tn
with
7, = no+ntTpO I Po+Pt,nO
~
(5.65)
PO PO
as the recombination lifetime of non-equilibrium electrons. In the case of
a n-type semiconductor, i.e. if p o << p t << no holds, then T n >> ~ p o , ~ n o ,
which means that the recombination lifetime is substantially longer than
the capture times for electrons and holes. This result is due to the fact
that the holes necessary for recombination of the non-equilibrium electrons
522 Chapter 5. Non-equilibrium processes in semiconductors
Ap#O, An=O,
one obtains analogous relations, and
(5.66)
with
rp =
no
~
+ nt rpo + PO-
+ pt TnO (5.67)
n0 n0
as the recombination lifetime of non-equilibrium holes. For an n-semiconduc-
tor one has rp = rPo,and for a p-type semiconductor rp >> rno, rpo.
The above results for the case of unipolar excitation may be summarized
by stating that the recombination lifetimes of minority carriers are substan-
tially smaller than those of majority carriers - provided the deviation from
equilibrium is weak.
Finally, we consider the case of bipolar excitation of non-equilibrium
carriers. In this case,
An = Ap.
The recombination rate is now given by
(5.68)
with
(5.69)
and
r = rpo(no nt) + + T,O(PO + P t ) (5.70)
no +PO
For an n-type semiconductor one has r = rpo, and for ap-type semiconductor
r = r,~. The recombination lifetime therefore equals the capture rate for
+
minority carriers. For an intrinsic semiconductor, we have no p o = Pni, so
that the recombination lifetime in this case is given by the expression
(5.71)
5.4. Drift current 523
In Table 5.2 typical values of the lifetimes q for some semiconductors are
listed. It should be noted that there is a large variation of q , between
3.4 x 10l2 s for the indirect wide gap semiconductor GaP and 7.3 x s
for the direct small gap semiconductor InSb. For extrinsic semiconductors,
we have no + P O > 2 n i , so that T < q. This means that the recombination
lifetime through a particular deep center reaches its maximum value when
the semiconductor is in its intrinsic state. Doping reduces the recombination
lifetime of bipolarly excited non-equilibrium carriers.
component in the direction of the field. Its rate of change [$ < m i i n > field
1
per second, according to equation (3.110), equals the force impressed by the
field on a Bloch electron. whence
In addition to the electric field there are frictional forces acting on the Bloch
electron which arise from the semiconductor itself. The interactions of an
electron with lattice vibrations and impurity atoms or defects result in scat-
terings which act to brake its acceleration along E, producing a frictional
effect similar to that in a viscous medium. Often, this frictional resistive
force grows stronger in proportion to the average electron speed, so that one
may put the corresponding rate [$ < mkxn >Iez of momentum change per
second due to collisions with phonons and crystal imperfections, proportional
to the average momentum, whence
(5.73)
whence
d 1
- < mkxn > = -eE- - < mn
* kn >. (5.76)
dt r
;
For steady state dc current flow, the left hand side of this equation vanishes
and the concomitant constant value of the average velocity is
5.4. Drift current 525
(5.77)
(5.78)
j , = enp,E. (5.81)
For the electron conductivity D,, as it occurs in Ohms law, one t,hus obtains
on = enp,. (5.82)
This conductivity expression will be used frequently below. It can be trans-
ferred to holes without difficulty, reading
Tp = eppp, (5.83)
where the hole mobility p p is given by
er;
Pp= - - y I (5.84)
mP
j = .in +j p , (5.85)
and the total conductivity D is the sum of the two partial conductivities,
T = un
C + up. (5.86)
526 Chapter 5. Non-equilibrium processes in semiconductors
Table 5.3: Electron and hole mobilities for pure semiconductor materials at T =
300 K . (After Landoldt-Bornstein, 1982.)
1000
Si
200
40
N=10"
100
20
Temperature ("C) I O U
-50 0 50 100 150 200
Temperature ("C 1
Figure 5.5: Temperature dependence of the electron and hole mobilities of Si for
various doping concentrations.
In Table 5.3 the mobilities of electrons and holes are given for some important
semiconductors at room temperature. That the mobilities of electrons exceed
those of holes, is to be attributed to the smaller effective masses of the
electrons in these materials.
The mobility depends on the interaction of the carriers with phonons through
5.5. Diffusion and annihilation of free carriers 52 7
Doping concentration ( ~ r n - ~ )
the momentum relaxation time, and the same may be said for temperature
dependence. In Figure 5.5 this dependence is shown for Si. The decrease
of mobility with rising temperature is to be attributed to the growth of
the amplitudes of the lattice oscillations or, in other terms, of the num-
ber of phonons. In extrinsic semiconductors the mobility also depends on
the doping concentration, because doping atoms constitute collision centers.
Generally, the momentum relaxation times, and through them also the mo-
bilities pn and p p , decrease with rising doping concentrations. Examples of
such dependencies are shown in Figure 5.6.
in = -DnVn. (5.88)
Because of its inhomogeneity, this current leads to temporal changes of the
local electron concentration, whereby the latter may take values which de-
viate from local equilibrium. As a result, generation and annihilation pro-
cesses will take place which tend to restore local equilibrium values. The
overall balance of the electron concentration change is described by the con-
tinuity equation (5.20). The right-hand side of this equation is specified
such that generation processes are omitted while capture and emission pro-
cesses at deep centers are taken into account. Then the annihilation term
- ( d ~ ~ / d t ) ~ ~ equals
~ i h i l (dn/dt),,pture. For small deviations from equilib-
rium, (an/dt)capture may be identified with expression (5.39), whence
dn n - no
-+V.i n- (5.89)
at 7,
(5.91)
(5.93)
5.5. Diffusion and annihilation of free carriers 529
0
X-
where
L,= &. (5.95)
The solution (5.94) admits the following simple physical interpretation (see
also Figure 5.7). Diffusion tends to disassemble existing concentration gra-
dients, transferring part of the distribution near z = 0 further to the right.
However, since the lifetime of non-equilibrium charge carriers is limited, this
process cannot be fully accomplished, as electrons are captured during the
transfer process, leading to the exponentially decaying profile of the electron
concentration given in equation (5.94). The characteristic decay length L ,
can be interpreted as the distance to which an electron diffuses, on the aver-
age, before it is captured. One refers to L , as the dzfluszon length. L , is the
larger for larger lifetime 7,. One can illustrate the interpretation above by
means of a fluid current moving over porous ground. At a particular point
x = 0 the fluid current level is maintained at a fked height. In the direction
of the current flow, the fluid level drops because fluid is absorbed into the
porous ground. Sufficiently far downstream, practically no fluid will arrive
because most of the h i d was absorbed into the ground further upstream.
Nevertheless, one has a continuous fluid current at x = 0, which provides
exactly as much fluid as is absorbed along the entire pat,h between x = 0
and z = 00. The analogy to the diffusion of electrons with finite lifetime is
obvious. Furthermore, the current flow at z = 0, in this case i,(z = 0), may
be determined from (5.88) and (5.94) as
(5.96)
Table 5.4: Diffusion coefficients and diffusion lengths for several pure semiconduc-
tors at T = 300 K . Diffusion coefficients are calculated by means of mobility data
of Table 5.3 using Einstein's relation.
Si
Ge 100.8
GaAs 227.5 10.3 10-8 3.2
(5.97)
with
(5.99)
Complete equilibrium of the total system can only exist then if the inho-
mogeneities have equalized out in both partial systems. This means also
that the doping of the semiconductor material must have become spatially
homogeneous. The process which brings this about, the diffusion of dopant
atoms, is so very slow, however, as compared to the carrier processes, that
one can completely neglect it. This means that, the subsystem of atomic
cores effectively remains in the non-equilibrium state in which it started;
this state is frozen, so to say. The subsystem of the free charge carriers,
however, will relatively quickly pass into a new stationary state. On the one
hand, this state will differ from the equilibrium state of free charge carriers
in a homogeneous semiconductor - the concentrations n and p of the elec-
trons and holes will depend on position coordinate x,as a consequence of the
inhomogeneity of the dopant concentrations. On the other hand, all current
densities of the free charge carriers will also vanish in the inhomogeneous
case, just as in the homogeneous case. A stationary final state conforming
to this characterization may be understood as a thermodynamic equilibrium
state of the free charge carriers of the spatially inhomogeneous semiconduc-
tor. The nature of thermodynamic equilibrium in this sense will be discussed
below.
We consider only spatial inhomogeneities in the x-direction. The com-
ponents j , and j , of the electric current densities of electrons and holes in
this direction are given by the phenomenological equations
(5.100)
dP
, = a,E(x)
j - eDp-. (5.101)
dx
Here E(x) represents the electric field that occurs in consequence of the
spatially inhomogeneous charge carrier distributions, initially omitted in the
previous section. In equilibrium the current densities of electrons and holes
must vanish. That this must hold for the electron and hole currents sepa-
rately, and not just for the sum, follows from Boltzmanns equation which
states that in equilibrium the partial currents of the subsystems of electrons
having a fixed energy must vanish separately (not just after summing over
all energy values). The holes are, of course, also a subsystem of the total
electron system with particular energy values, namely the energies of the
unoccupied states of the valence band. Hence, in equilibrium we have
+ dn
0 = ~ , E ( x ) eDn--,
dx
(5.102)
The two electron current contributions in (5.102), the drift current v n E and
the diffusion current eD,(dn/dx), need not vanish separately. The same
holds for the hole current contributions a p E and - e D p ( d p / d x ) in equation
(5.103). Only the sum of these contributions must be zero. Thus we arrive
at the conclusion that in thermodynamic equilibrium the drift and diffusion
currents of each type of carrier must exactly compensate each other.
Our object now is to transform this observation into a general condition
for thermodynamic equilibrium in systems with spatially inhomogeneous
doping. To this end we express the field strength E of equations (5.102)
and (5.103) in terms of the electrostatic potential cp, and replace c n and up,
respectively, by the right hand sides of equations (5.78) and (5.83). Thus,
we obtain
dYJ
o=- ~ n -
dx
+ Dn-ddx [Inn ( x ) ], (5.104)
dcp d
O = -pp- - Dp- [ h p ( ~ ) ] (5.105)
dx dx
In the case of local equilibrium, the charge carrier concentrations n(x) and
p(x) depend on the chemical potential p(x) in just the same way that n and
p in expression (4.59) depend on E F ,
(5.106)
Substituting these expressions in (5.104) and (5.105) we have
(5.107)
(5.108)
(5.109)
Einstein relation
Because the chemical potential for holes is the same as that for electrons,
we can restrict ourselves to the latter. We assume that at a given position
z = xo there is an infinitely high potential wall for these particles (see Figure
5.8). Electrons can reside on the right side of the wall, but not on the left, as
5.6. Equilibrium of free carriers in inhomogeneously doped semiconductors 533
I
I
xo
X
they are reflected by the wall if they move toward the left. The situation is
comparable with that of molecules of air above the surface of the earth. As
in the latter case, in which the equilibrium vertical distribution of particles
is given by the law of atmospheres, we have here
(5.111)
This equation is the Einstein relation It holds for holes as well as electrons,
kT
D, = - p P . (5.112)
Combining equations (5.111) and (5.107), we obtain the desired general con-
dition for thermodynamic equilibrium of free charge carriers,
9-e d- v = 0 (5.113)
dx dx
or
p ( z ) - ecp(z) = const (5.114)
The quantity on the left hand side of this equation is referred to as the
electrochemical potential. In the case of vanishing electric potential, the
electrochemical potential is just the same as the simple chemical potential.
This also remains true if the electric potential has a non-zero but spatially
534 Chapter 5. Non-equilibrium processes in semiconductors
(5.115)
In thermodynamic equilibrium, the electrochemical potential of the free
charge carriers is spatially constant, and the constant value is equal to the
Fermi energy. The chemical potential and the electric potential themselves
can change, however. It is appropriate to bear in mind here that the ini-
tially assumed spatial inhomogeneity of the semiconductor is based on the
inhomogeneity of its doping. The formal expression of this inhomogeneity is
the spatial variation of the chemical potential. To properly adjust the ther-
modynamic equilibrium state, the spatial variation of the electric potential
must just compensate the spatial variation of the chemical potential.
The equilibrium state of equation (5.114) represents an equilibrium in
both the local and in the global senses. That in the local sense was pre-
supposed (approximately) at the outset with the use of phenomenological
equations for the current densities of the charge carriers. Moreover, the equi-
librium state described by (5.114) represents a relative equilibrium, because
it was derived under the assumption that the initial spatial inhomogeneity
of doping, and thus the inhomogeneity of the chemical potential, remains
unchanged. Over very long periods of time, this is assumption ceases to be
valid. However, this does not affect the equilibrium condition because it is
only essential that the inhomogeneity of doping does not change during the
relaxation of the charge carriers towards equilibrium, a condition which is
always fulfilled.
As one may expect, the equilibrium condition (5.114) or (5.115) will
play a central role in the treatment of semiconductor junctions in the next
chapter.
535
Chapter 6
Semiconductor junctions in
thermodynamic equilibrium
a)
n -type
b)
cnSemic. Metal
6.1 pn-junction
pn-junctions are fabricated such that either the surface region of a homoge-
neously doped n (or p)-type sample, is p (or n)-doped by means of diffusion
or ion implantation, or that a p (or n)-type layer is deposited on a n (or
p)-type substrate by means of epitaxy. In the particular case of Si, neutron
bombardment may also be used. Due to the nuclear reaction ;gSi n + ---f
+
:aSi y -+ + p, a previously p-doped sample becomes n-doped in the
surface region exposed to the neutrons.
In the following theoretical description of the pn-junction we assume
homogeneously doped p - and n-regions left and right of the plane normal
to the z-axis of a Cartesian coordinate system (see Figure 6.2a). The p -
region extends to -00 and the n-region to +co. The transition from the p -
to the n-region takes place abruptly at z = 0. We refer to this position as
the nominal transition. In the transverse plane normal to the z-axis, the
two semi-infinite semiconductor samples are taken to extend to infinity in
all directions. Thus, there are no dependencies on y and z , provided the
semiconductor materials are homogeneous in the transverse plane, which we
take to be the case. With this, the problem is effectively one dimensional.
The carrier concentration distribution along the x-axis before equilibrium is
established is shown schematically in Figure 6.2a. Conceptually, this corre-
sponds to the instant at which the junction is formed, so that the carrier
distribution has not yet had enough time to adjust to form a new equilibrium
state. Considering that the p-region also has electrons which are minority
carriers in it, and that the n-region also has holes as minority carriers there,
one must distinguish the region in which these concentrations are meant.
We indicate this by affixing a subscript to n and p . The concentrations in
the n-region will be denoted by n, and p,, and those in the p-region by np
and p p . Thus, n,, and p p are majority carrier concentrations, while np and
p, are minority carrier concentrations. The different values of the charge
carrier concentrations in the n- and p-regions are related to different values
E F , and E F of ~ the bulk Fermi energies in these regions, such that
538 Chapter 6. Semiconductor junctions in thermodynamic equilibrium
1---
I
D i f f h o n tc Drift
-ecp (x)
I I
C)
I
I
Recombi-
nation I
I
I
I
I
1 I
I
I
X
I I
Figure 6.2: Non-equilibrium state of a pn-junction (a), from which the establish-
ment of thermodynamic equilibrium develops (b,c).
6.1. pn-junction 539
and for the envelope function Xv(x) of the valence band holes it has the
form
According to equation (6.3), the electrons at the conduction band edge ex-
hibit a potential energy E, - ep(z), and the holes at the valence band edge
exhibit a potential energy ecp(z). These energy functions are depicted in
Figure 6.2b. In this, one has to recognize that the energy e p ( z ) of the holes
counts negatively, so that on the positive electron energy scale one must
therefore plot -ep (z).
The electric field in the space charge region drives a current in the direction
opposite to that of the diffusion current (Figure 6.2b). The concentrations
540 Chapter 6 . Semiconductor junctions in thermodynamic equilibrium
of carriers which diffuse from the region where they are majority carriers
into the regions where they are minority carriers, are much larger than the
equilibrium minority concentrations there. Thus they will recombine with
the abundantly available majority carriers in these regions (Figure 6 . 2 ~ ) In .
this process, the concentrations of both types of free charge carriers decrease
in the space charge region, as shown in Figure 5.2. The electric charge bal-
ance as well as the electric field and potential distributions are, however,
not influenced by such recombination since the annihilation of electrons and
holes takes place simultaneously, and in the same measure. Overall, a p n -
junction, in the time interval immediately following its formation, undergoes
a relatively complicated interplay between various non-equilibrium processes
- the diffusion and drift of majority carriers, the formation of a space charge
region and of related electric field and potential distributions, as well as re-
combination of non-equilibrium minority carriers with equilibrium majority
carriers.
The processes under discussion act in such a way that thepn-junction ap-
proaches thermodynamic equilibrium. The state to which the system relaxes
is, however, not a static but a dynamic equilibrium state. Of course, it has no
net current, but only because the drift and diffusion currents fully compen-
sate each other. In regard to the equilibrium state which finally emerges, the
details of the processes which establish equilibrium do not matter, what is
important is only that there are such processes. Independently of the nature
of these processes, specific local values of the chemical potential p ( z ) , electric
potential p(z), and charge carrier concentrations n ( z ) ,p(z) are established
in equilibrium. The latter are given by the relations (5.106) discussed in
Chapter 5, and we display them here once again:
Before doing this and solving the Poisson equation, we will first determine a
relatively easily accessible integral quantity, namely the potential difference
U D , which exists between the left and the right end of the pn-junction in
consequence of the charging of the two regions. This potential difference is
called &;fusion voltage, because diffusion is the agent actually responsible for
its existence. The diffusion voltage provides one of the boundary conditions
needed for the solution of the Poisson equation.
The Fermi levels may be expressed in terms of the majority carrier con-
centrations nn and p, employing equations (6.5) to (6.8). First of all, we
have
(6.13)
+- - + bl
+- P I:
-+
n ;:
I Metal I -- ++
I 1
+
+
+
(Figure 6.3a), or by bringing the two ends directly in contact with each other,
bending the p - and n-regions (Figure 6.3b). No current will flow through
closed circuits obtained in this way. The total voltage drop in such circuits
is zero, since, beside the original pn-junction already present a second one is
created by closing the circuit, acting in the opposite direction. The metallic
connections in Figure 6.3a only play a passive role and do not affect the
voltage balance of the circuit - the sum of the diffusion voltages of the two
metal-semiconductor junctions exactly equals the negative of the diffusion
voltage of the pn-junction. Nevertheless, the diffusion voltage can actually
be measured, namely, in an electrostatic experiment. This can be done, for
example, when the two ends of the p- and n-regions are bent to be close
to each other, leaving only a small gap between them (Figure 6 . 3 ~ ) .In the
gap there is an electric field associated with the diffusion voltage, whose
existence may be demonstrated by means of a small test charge.
whence
(6.16)
and with 6.13) we find
2
n ( x ) p ( z ) = ni (6.17)
The mass action law, which was written down for spatially homogeneous
semiconductors in equation (4.85), therefore also holds locally for inhomo-
geneous semiconductors. Such a result is not surprising since this law is
predicated on the existence of thermodynamic equilibrium, and local equi-
librium was assumed in the inhomogeneous case considered here.
The concentrations of ionized donors NDf and acceptors N Z depend on
the potential (p(z),at least in the general case. In a frequently occurring
special case, namely that of complete ionization, this dependence no longer
exists. We will assume that this case applies, so that
) N&),
~ o f ( x= N A ( X )= N A ( Z ) . (6.18)
Since donor atoms are present only in the n-region, and acceptor atoms
only in the p-region, and since they are homogeneously distributed there in
accordance with our initial assumption, it follows that
(6.19)
0, x > 0,
N ~ ( X=) (6.20)
N A , x < 0.
The Poisson equation for cp(x) thus reads
(6.21)
We seek a solution of this equation which accounts for the existence of the
diffusion voltage (6.9). In order to get a unique solution one more condition
is needed. This may be obtained from the observation that far from the
nominal transition at x = 0, everything should behave as it would in an in-
finite bulk sample. This means, in particular, that the electric field strength
has to vanish at x = f c o , whence
(6.22)
544 Chapter 6. Semiconductorjunctions in thermodynamic equilibrium
The first part of this relation holds because of total charge neutrality of
the pn-junction. It is not an independent condition, and does not provide
additional information.
The scalar potential p(z) is determined only up to an additive constant.
Without any loss of generality we may chose this constant such that
(6.23)
n= N,
I Depletion region
---- I+++,+
Bulk region Ispace charge region1
I
Bulk region
Figure 6.5: Space charge region, depletion region and bulk region of a pn-junction.
V ( x n - A X , ) = cp(xn) - k T / e . (6.24)
The electron concentration n ( x ) of (6.15) at 2 , - A x , has already decreased
down to the e-th part of its equilibrium value nn (see Figure 6.4). Since it
decreases further as x decreases, one can approximately set it to zero for
x , - A x , , whence
0, x <~ n A-x , ,
n(x)= (6.25)
n,, x > x,.
An analogous conclusion can be drawn for the hole concentration p(x). Us-
ing similar notations x p and A x p for holes as were used for electrons, we
approximately have
(6.26)
If it turns out, as is actually the case, that A x , << x , and A x p <<I x p I hold,
then we can make the further approximation of taking the two intervals A x ,
and Axp to be vanishingly small. We will do this, understanding this change
to be made in equations (6.25), (6.26) without rewriting these formulas.
The simplification described in the resulting equations (6.25) and (6.26) is
called the Schottky a p p r o x i m a t i o n In the pn-junction, we can now identify
four regions in which the total charge density has constant values, with
jumps from region to region (see Figure 6.5). For x < x p and x > x , the
546 Chapter 6 . Semiconductor junctions in thermodynamic equilibrium
charge density is zero, because the charge of the ionized impurity atoms is
compensated by the charge of the free electrons and holes. Between x p and
I , , free charge carriers are absent, so for x p < x < 0 we have the charge
density - e N A of the ionized acceptors, and for 0 < x < x , the charge density
e N D of the ionized donors. Because of the absence of free charge carriers
between x p and 0 and between 0 and x,, these two regions are called depletion
regions. Jointly, the two regions together form the space charge region, The
adjacent regions on the left and right hand sides are called bulk regions. The
Poisson equation associated with the charge distribution described above
reads
d2P
--
dx2 - {I -No,
NA,
0,
O < X <xn,
xp
x
< x < 0,
< xp.
(6.27)
(6.29)
x < xp.
At the position x = 0, cp(x) is automatically continuous and vanishes, as it
should according to equation (6.23). The continuity of the h t derivative
at x = 0 follows from the charge neutrality condition (6.28). The diffusion
voltage condition (6.9) yields
(6.30)
6.1. pn-junction 547
NA ND
(6.31)
2, =
ND + N Aw , xp=-
+N A ~ .
Applying equation (6.30) we get the result for w as
(6.32)
(6.34)
f i <J-J~TT;;,
< p-region. (6.35)
In order for these relations to be fulfilled, the potential energy of an electron
due to the diffusion voltage must be much larger than its average thermal
energy. Considering equation (6.13) for U D this is the case if
1< [ n;y]
ln- (6.36)
or
The uniform Fermi level of the junction is uniquely determined by the indi-
vidual Fermi levels and doping concentrations of the n- and p-regions. The
fact that p - and n-type materials exist at a semiconductor junction despite
the common, uniform Fermi energy, is due to the bending of the conduction
and valence band edges. This bending is such that, on the left-hand side
6.2. Heterojunctions 549
Figure 6.6: Lineup of the band edges and the chemical potentials for a pn-junction
with N D = 2N.4. The chemical potential p ( z ) and the Fermi level are also shown.
of Figure 6.6, the valence band edge is close to the Fermi level so that the
material is p-type there, and on the right-hand side it is the conduction band
edge that is close to the Fermi level so that material is n-type there.
e6.2 Heterojunctions
The pn-junction is a semiconductor structure based on a single semiconduc-
tor material, except the state of the semiconductor, specifically, the value of
the chemical potential, is different on the two sides of the junction. In the
case of semiconductor heterojunctions not only are the states different but
also the materials differ - left of the nominal transition at z = 0 one has
a particular material 1, and right of it there is a different material 2. The
material inhomogeneity means that the valence and conduction band edges
E,, E,, the energy gap E,, the effective band densities of states N,, N,, the
Fermi level E F and other quantities have different values on the two sides
550 Chapter 6 . Semiconductorjunctions in thermodynamic equilibrium
Material 1
I *
Then, within the framework of effective mass theory, the continuous func-
tions E c ( z )and E,(z) describe position-dependent potential energies of elec-
trons and holes, and one may expect that the gradients VE, and VE, play
the role of driving forces, which result in additional contributions to the
electron and hole currents. The same may be said for the gradients V N , ( z )
and V N v ( z ) of the effective densities of states in contributing to diffusion
current. The exact forms of these current parts are not known a priori.
They can be determined either by means of Boltzmanns equation, or one
can formulate them phenomenologically on the basis of experience as we did
in the case of the electric drift and diffusion currents in equations (5.100)
and (5.101). Using Einsteins relations (5.111) and (5.112) for, respectively,
D , and D,, as well as equations (5.82) and (5.83), the electron and hole
diffusion currents in these equations can be written as u , ( k T / e n ) V n and
- u , ( k T / e p ) V p , respectively. Since the negative gradients of N c and N ,
should play a role similar to that of the gradients of n and p , we write the
generalized phenomenological equations for the electron and hole currents
as
kT
- ecp) + -Vn - (6.39)
n
1
j, = up; [O(,T~ kT
- ecp) - - 0 p
n
+ -kT
VN,
Nw 1 . (6.40)
(6.44)
The right-hand side of this equation is, in fact, the diffusion voltage in-
troduced above in the discussion of the pn-junction. The second boundary
condition is again the vanishing of the electric field at x = +00 and x = -00,
as in the case of the pn-junction. Because one of the latter two conditions
follows from the other by means of charge neutrality, it suffices to require
dio
dx l2=--00 - 0. (6.45)
The calculation of the electrostatic potential along the general lines described
above will now be demonstrated in the particular case of a heterojunction
between GaAs (material 1) and Gal-,Al,As with x < 0.4 (material 2),
illustrated in Figure 6.8. Accordingly, we assume that the relations Ec2 >
Ecl, Ncl = Nc2, and 1 = 2 t are valid. Moreover, we suppose that both
6.2. Heterojunctions 553
0 X
(6.46)
We further assume that the donor concentrations in both materials are the
~ E F of~ the two bulk semiconductors
same, so that the Fermi energies E F and
have the same energy separations from the respective conduction band edges
E,1 and Ec2 of the two materials, whence
Considering that Ec2 > Eel, we also have E F Z > E F ~and , consequently
electrons originating in material 2 diffuse into material 1. There, they accu-
mulate close to the interface, and one thus identifies an accumulation layer.
Correspondingly, in material 2, a depletion layer is formed, and n < N o
holds so that the Schottky approximation can be applied. However, in the
accumulation layer, one has n >> N o , thus the Schottky approximation is
not valid in material 1. The character of the Poisson equation here is fun-
damentally different from that of the depletion layer - the source term on
the right-hand side depends on the potential p(z) itself through the carrier
concentration n ( z ) . In fact, from relations (6.41) and (6.44), it follows that
n(x) becomes n 0 1 , as one should expect. Using (6.48) the Poisson equation
takes the form
(6.49)
(6.51)
where the '-1' in the rectangular bracket of (6.50) has been neglected in
comparison with exp(AE,/kT). The square root factor in equation (6.51) is
the Debye length, which already played an important role in the case of the
pn-junction. There the Debye length was small compared to the width of
the space charge region, which was a depletion region for a pn-junction. For
the accumulation region of a heterojunction, the result is just the opposite
- the width of this region is reduced relative to the Debye length by a factor
E
l21 - eY4-w) Ec2 - ecp(+w), (6.52)
is undoped. In this case the electrons in the GaAs well are not exposed
to ionized donors because there are none. Therefore the mobility of these
electrons is particularly high, it can reach several millions crn2V-ls-'. An
electronic device which exploits this effect is the High Electron Mobility
Transistor (HEMT), which was already mentioned several times in somewhat
different contexts.
I L
0 X
0 X
Figure 6.10: Positional dependence of the Fermi levels of a metal and a semicon-
ductor, as well as of the band edges of the semiconductor in a metal-semiconductor
junction at the instant of its inception, before equilibrium is established. Four dif-
ferent cases are shown: n-type semiconductor (a, b), p-type semiconductor (c, d),
E F S > E F M (a, d), and EFS < E F M (b, c).
prior to emission. There are as many different values of Einitfal as there are
occupied energy levels of the metal. Thus the kinetic energies &in span the
whole occupied part of the energy spectrum of the metal, shifted by hw. The
work function represents the lower threshold energy of this distribution.
The energy separation between the conduction band of the semiconduc-
tor and the vacuum level is referred to as the electron affinity X . It, too,
is a quantity which can be determined experimentally. One measures the
photothreshold a P h of the semiconductor (see section 3.7), and subtracts the
energy gap Eg from it, obtaining the electron affinity X from the relation
X = QPh - Eg.
If a voltage U is applied to a metal-semiconductor junction, a current will
flow through it. In Chapter 7 we will show that the magnitude of this current
essentially depends on the energy EA,(M + SC) necessary, at minimum, for
6.3. Metal-semiconductor junctions 559
(6.53)
For a given semiconductor material, the sum of the two Schottky barriers,
one referring to n-type doping and another referring to p-type doping, should
be independent of the metal and equal the gap energy E , of the semicon-
ductor. The Schottky barrier determines the current density j through the
metal-n-type semiconductor junction by means of the relation
(6.54)
as will be shown in Chapter 7. Here B is a coefficient which depends only
weakly on temperature. Using equation (6.54), and measuring the current-
voltage characteristics of the metal-semiconductor junction, the Schottky
barrier @ B can be determined experimentally.
Moreover, if the level ordering at the metal-n-type semiconductor junc-
tion is that shown in Figure 6.10a, then the equation
(6.55)
relates the Schottky barrier Q B of the junction, the work function Q of the
metal and the electron affinity X of the semiconductor. In employing this
relation we have, however, jumped ahead of the thermodynamic analysis
of energy level ordering at the metal-semiconductor junction. In Figure
6.10, in fact, the energy levels are shown at the instant when the metal-
semiconductor junction has just been formed. Since the chemical potentials
of the metal and the semiconductor are different, the situation shown in
Figure 6.10 surely does not represent thermodynamic equilibrium. Electrons
or holes of the semiconductor will diffuse into the metal (Figure 6.10a,c) or
from the metal into the semiconductor (Figure 6.10b,d). Thereby a space
charge region will arise at the interface (see Figure 6.11) with its concomitant
electrostatic potential cp(z) varying in space. This potential will now be
considered in more detail.
M S
I \ *
X
very thin boundary layer at the interface. The thickness of this layer is about
one A. This value follows from relation (6.34) if one takes the electron con-
centration of a metal to be of the order of magnitude crnV3, and replaces
the average thermal energy k T by the Fermi energy of the metal, switch-
ing over in this way from the Debye length to the Thomas-Fermi screening
length. Over a distance of an A the potential ~ ( x is) practically constant.
Deeper in the metal, because of screening by electrons in the boundary layer,
the potential is essentially constant anyway. It is therefore reasonable to ap-
proximate the potential in the metal as spatially uniform. At the nominal
transition from the metal to the semiconductor, the potential could be un-
derstood as in the case of semiconductor heterojunctions considered in
~
E, -elp( x 1
I c
0 X
I b
0 X
If the Fermi energy of the semiconductor lies close to the conduction band
bottom, the diffusion voltage approximately equals the Schottky barrier QB.
The latter typically has values of several tenths e V , which are also typical
values that one should expect for the diffusion voltage U D .
The details of the spatial dependence of the potential p(z) depend on the
relative positions of the Fermi levels in the metal and semiconductor. For an
n-type semiconductor, if EFS > EFM holds, then electrons transfer from the
semiconductor into the metal and an electron depletion layer develops in the
semiconductor close to the interface. The diffusion voltage U D is positive,
562 Chapter 6. Semiconductor junctions in thermodynamic equilibrium
i.e. the two bands are bent up at the interface (Figure 6.12a). One speaks of
a non-ohmic or Schottky contact in this case. If, for a n-type semiconductor,
the reverse ordering E F S < E F M holds, then electrons from the metal trans-
fer into the semiconductor, and an electron accumulation layer develops in
the semiconductor at the interface (Figure 6.12b). The diffusion voltage U D
is negative, i.e., the bands are bent down at the interface, as in the case of
the heterojunction of Figure 6.8, expect that here there is no development
of a potential well in which electrons are confined to two dimensions. This
is called an ohmic contact.
Consider next p-type semiconductors. For EFS > EFM there is a hole
accumulation layer, because electrons transfer from the semiconductor into
the metal or, what is the same, holes transfer from the metal into the semi-
conductor. The diffusion voltage U D is positive and the bands are bent
up at the interface (ohmic contact, see Figure 6.12d). For EFS < E F M ,
there is a hole depletion layer, U D is negative, and the bands are bent down
(non-ohmic contact, see Figure 6.12~).Below we first consider metal-n-type
semiconductor contacts which are non-ohmic.
The potential cp(x) can be calculated in the same way as for a pn-junction. In
particular, the Schottky approximation can, again, be used, provided that
the conditions (6.35) are satisfied. We denote the width of the depletion
layer in the semiconductor by XB. The arbitrary constant of the potential
will be chosen such that cp(x) vanishes deep in the semiconductor.
cp(x) Iz=w= 0. (6.59)
The two boundary conditions for p(x) are taken to be the same as in the
case of the pn-junction. Firstly, the potential difference c p ( 0 0 ) - cp(0) must
match the diffusion voltage U D in accordance with (6.58). Secondly, the field
strength deep in the semiconductor approaches zero, i.e.
-
dcp 12=w= 0. (6.60)
dx
With these conditions the potential cp(x) and the width X B of the depletion
layer can be calculated from the Poisson equation, with the result
(6.62)
6.3. Metal-semiconductor junctions 563
Below, we will assume that interface states are also present at the metal-
semiconductor junction. We denote their energy levels with respect to the
vacuum level by EA. The concentration of the semiconductor interface state
levels will be taken to be sufficiently large to host all electrons which, in
their absence, would otherwise occupy states at higher energies. We will
show that under these circumstances, the energy EL of the interface states
is also the electrochemical potential, i.e. the energy to which the common
Fermi level of the metal-semiconductor junction adjusts in equilibrium The
proof rests on the general relation (4.57) between electron concentration,
Fermi distribution and density of states, which will be applied to the case
under consideration. For simplicity, we consider zero temperature T , but the
conclusions to be derived also hold for T > 0. The semiconductor will be
taken as n-type, and the energy levels EL of the interface states lie below the
Fermi energy of the bulk semiconductor. In reality, the interface levels do
not concentrate exactly at E i , but are spread over a narrow interval about
EL. The interface state density is therefore not an exact &-function, but a
bell curve of finite width.
resents the Fermi energy of the semiconductor. Since it lies within the bell
curve of the state density it practically equals Ei. An increase or reduction
of electron concentration in the semiconductor bulk by changing its doping
will increase or reduce the number of electrons filling the interface levels.
Because of the assumed large density of interface states, however, the posi-
tion of the Fermi level needs to change only very little to account for such
an increase or reduction. Thus, the Fermi level is fixed at the interface state
energy levels. This is called a pinning of the Fermi level.
In the second step, the establishment of equilibrium across the interface
between the metal and the semiconductor, electrons are transferred across
the interface, strictly speaking between the thin charged boundary layer in
the metal and the interface states of the semiconductor. Thereby, a dipole
layer is formed at the interface. This is accompanied by a potential jump
[cp(+O) - p(-O)] between semiconductor and metal, which in equilibrium is
sufficiently large that the Fermi level of the metal is raised or, respectively,
lowered, to match that of the semiconductor, whence
@B = E , - E,. (6.65)
The latter expression for the Schottky barrier was first derived by Bardeen.
In it, the Schottky barrier, in contrast to Motts expression, is seen to be
independent of the work function of the metal. Figure 6.13 shows that the
experimental data for Si are closer to Bardeens relation than to that of Mott.
This statement also holds for other group-IV semiconductors, such as Ge.
For the 111-V semiconductors, the dependence of the Schottky barrier @ B
on @ is noticeable, although smaller than that in Motts relation, and for II-
VI semiconductors it corresponds approximately to Motts linear dependence
with slope 1. These observations suggest a relation for @B which interpolates
between Motts and Bardeens formulas. Accordingly, we write
I
0.6 )CdS
1 -
0 0.4 0.8 1.2
Electronegativity difference -
1.6 2. I
In accordance with above remarks about Schottky barriers for the various
semiconductor material classes, the value of S should increase monotonically
starting from the covalent group-IV semiconductors Si and Ge through the
moderately polar 111-V semiconductors up to the strongly polar 11-VI semi-
conductors. To examine this conjecture, S is plotted in Figure 6.14 as a
function of the electronegativity difference between the two types of atoms
paired in a given semiconductor, which represents a measure of the polar-
ity of the semiconductor material. The results verify the expected behavior
of S. The different properties of the interfaces of various semiconductors
with metals are, therefore, reflected by S in an overall way. Interface effects
are evidently more pronounced in the case of completely or preferentially
covalently bound semiconductors than in the case of more ionically bound
materials.
Experimental investigations show that Schottky barriers also depend on
the chemical and structural imperfections of a particular interface. This
means that, depending on the preparation of the interfaces, different Schott-
ky barriers may be obtained for the same metal-semiconductor junction.
Thus, for a theoretical understanding of Schottky barriers, it is particu-
larly important to study absolutely pure and structurally perfect metal-
semiconductor junctions, fabricated under UHV-conditions. From experi-
mental investigations of such junctions as, for example, with GaAs, con-
clusions have been drawn about the nature of the interface states assumed
in Bardeen's model. In the unified defect-model by Spicer for 111-V semi-
conductors, it is assumed that these states are due to point defects of the
semiconductor like vacancies or anti-site defects being induced by positioning
the metal on top of the semiconductor. In all, the microscopic understanding
of semiconductor-metal junctions still needs further investigation.
6.4. Insulator-semiconductorjunctions 567
Figure 6.15: Lineup of the band edges and the Fermi levels at an insulator-
semiconductor junction (a) before and (b) after equilibrium is established.
EF = E F S . (6.67)
ns = NDSX,. (6.68)
According to electrostatic laws, the interface charge density results in a
jump discontinuity [F(+O) - F(-O)] of the electric field strength given by
-(e/tto)n. Since the field in the insulator vanishes, a non-zero field strength
F S arises on the semiconductor side of the interface, as given by
(6.69)
One can also understand this interface field as being due to the positive space
charge region in the semiconductor below the interface, which in Schottky
approximation gives rise to a field strength F ( x ) that grows linearly towards
the interface, and a potential p ( x ) which decays quadratically. The value of
the potential at the interface,
d o ) = us, (6.70)
must have just the right magnitude so that the electrochemical potential is
uniform, i.e. that the difference [Ek - E k ] between the chemical potentials
at the interface and in the bulk of the semiconductor is equilibrated. Hence,
- e U S = [ E k - E$] (6.71)
must hold. Solving the Poisson equation in Schottky approximation subject
to the boundary conditions that the potential and the field strength vanish
deep in the semiconductor at x = m, and that the potential at the interface
is given by (6.71), we obtain
(6.72)
6.4. Insulat or-semiconductor junctions 571
with
x,= /s.
eND (6.73)
Combining equations (6.68) and (6.73) yields a relation between the interface
charge density ns and the interface potential U s , which reads
(6.74)
(6.75)
1 F S I = 18.97 x U s I /V)]1/2.
10-4(V/cm)[(~-1Ng/cm-3)(1 (6.77)
An estimate of about lev for e I U s I follows from (6.71) if we assume the
bulk Fermi level to be close the conduction band bottom, and the surface
Fermi level to be deep in the energy gap. With N D = cm-3 and
6 = 10 we find ns = 3 x 10l1 cmA2 and F S = 6 x lo4 V/cm. The width
Chapter 7
Semiconductor junctions
under non-equilibrium
conditions
holds and the doping concentrations N A and N D are of comparable size. For
positive U equation (7.4) is not always satisfied. It becomes critical when
U approaches the diffusion voltage, and is definitely invalid when U > UD.
For negative external voltages, condition (7.4) may in fact be valid even if
it does not hold in the absence of an external voltage. If it is valid in the
unbiased case, then it is even better satisfied in the presence of a negative
voltage. In the following we will assume that condition (7.4) is fulfilled and
that the doping concentrations N A , N D are comparable. Then the Schottky
7.1. pn-junction in an external voltage 577
a1 u-0 Cl u>o
0 0 0 0 . .
0 0 0 0 0 0 0 0
0 0 0 0 0 . 0 0
0 0 0 0 0 0
+ l o o o 0 /. . . . ( ~
0 0 0 9 0 . 0 4 0 0 0-0 .to 0 .
c
+ ~ o o o o ( . . . .
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 -0 0 0-0 .to 0 o c
differ from that in an infinite semiconductor sample, i.e. the current in the
p-region will be carried mainly by holes, and that in the n-region mainly by
electrons. In this matter, one has the peculiar situation that a hole current
in the left part of the junction passes over into an electron current in the
right part of the junction. The mechanisms which can realize such a tran-
sition are the recombination and generation of electron-hole pairs, whence
we may conclude that the latter processes should play an important role in
current flow through the pn-junction.
states in the bands which become unoccupied in this way will be filled by
majority carriers from the bulk regions of the junction (Figure 7.3d), where
majority carrier currents therefore flow. The magnitudes of these currents
are determined by the speeds of the injection and recombination processes.
In the stationary state both speeds must be equal - all carriers which are
injected must recombine, and all carriers which recombine must have been
previously injected.
If one reverses the sign of the voltage, corresponding to U < 0, then one
has extraction of minority charge carriers instead of injection, and generation
instead of recombination. Since extraction and generation processes consume
energy, in contrast to injection and recombination wherein energy is released,
one must expect the current through the pn-junction to be much smaller for
U < 0 than for U > 0. This is in fact the case, as we will formally prove
below.
The above mechanism for current transport through a pn-junction will
now be formulated quantitatively. The total current density j ( x ) consists,
according to formula (5.85)) of the electron current density jn(x) and the
hole current density jp(x). For the two current constituents the continuity
equations (5.20) and (5.21) hold. In the present case, the generation term
is zero, and the annihilation term is determined by recombination. In the
stationary state one obtains
djp
- = -eR(x).
dx
where R ( z ) represents the recombination rate given by equation (5.61).
Adding (7.7) and (7.8), it follows that the total current density j ( x ) is free
of sources and must be spatially constant, so that
(7.10)
Integration of equation (7.7) provides the result
(7.11)
(7.12)
Setting
(a) 21 = -oo,z2 = +m, we find
(7.13)
j =j n ( 4 +jp(zn) +e /
XP
X,
d 4 z ) . (7.14)
We will later see that, under certain conditions, the two minority charge
carrier contributions jn(-oo) and jp(+oo) in (7.13) can be approximately
neglected. The same holds for the recombination contribution in (7.14).
Consequently, equation (7.13) means that the total current, in its essence,
represents a recombination current. Alternatively, in formula (7.14) the total
current is seen to be the sum of the minority carrier currents at the two space
charge boundaries. There, they are determined by the injection of minority
carriers. The total current represents, therefore, an injection current. The
two interpretations are equivalent, but they emphasize different aspects of
the total current.
With these considerations concerning the mechanism of the current trans-
port, we are sufficiently prepared to calculate the spatial profiles of the chem-
ical potentials of the two types of carriers.
-e(UD-u)/kT = eU/kT
n(q,) = n,e npe , (7.18)
(7.19)
For U = 0, the values n ( x p ) and p(;cn) are the minority carrier concen-
trations np and p , in equilibrium. If U > 0, the factor multiplying n p in
(7.18), and the factor multiplying p , in (7.19) is larger than 1, i.e., the
minority carrier concentrations exceed the values they would have in the
absence of an external voltage. This is the formal expression of the injec-
tion of minority charge carriers. How effective injection is can be recognized
through the following estimate. With U = 0.25 V and T = 300 K we obtain
exp(eU/kT) M elo M 2 x lo4. This is to say that the small voltage of 0.25 V
suffices to increase the minority carrier concentrations by more than 10000.
The steady state solutions of the diffusion-annihilation equations (5.90)
for n(x) and (5.97) for p ( z ) , under the respective boundary conditions (7.15),
(7.16) and (7.17), are given by
Figure 7.4: Lineup of the quasi Fermi levels of a pn-junction under an applied
voltage, (a) flow direction (U > 0 ) , (b) blocking direction (U < 0)). Dashed curves
correspond to the unbiased pn-junction. In the space charge region interpolated
values are used. The decay of the quasi Fermi levels in the two bulk regions is
drawn greatly exaggerated.
This means that in the two bulk regions, both minority carrier concentrations
are larger than their respective equilibrium values np and p,. The chemical
potential p n ( z ) of the electrons in the pregion, is therefore shifted to higher
energies with respect to its equilibrium value, and that of the holes in the
n-region is shifted to lower values. The same holds for the pertinent non-
equilibrium electrochemical potentials
region (see section 5.4), so that this lack of knowledge is not important. The
space charge regions function solely as potential barriers over which non-
equilibrium carriers are injected. The spatial expansion of the barriers can
be neglected in a first approximation.
(7.23)
(7.24)
(7.25)
j = js(e
eUlkT - 1) (7.28)
with
(7.29)
(7.31)
Adding these equations and applying relations (7.18) and (7.19), the expres-
sion (7.28) follows for j with
(7.32)
The two expressions (7.32) and (7.29) for j , are identical, since Ln =
(see equation 5.95) and L, = fi (see equation 5.99).
7.1. pn-junction in an external voltage 585
With this observation, the task of calculating the current through a pn-
junction under an applied voltage is completely solved, within the framework
of the conditions and approximations set forth above. We will now discuss
the results. The current-voltage characteristic (7.28) is extremely non-linear.
It exhibits the expected asymmetry with respect to a change of the sign of
voltage U . For a positive U of a few tenths of a Volt, j is several orders of
magnitude larger than j,, while for a negative U of same absolute value, j
approaches - j , (see Figure 7.5). The current density j,, which cannot be
surpassed at even larger negative voltages, is called the saturation current
density. To estimate the size of this current density in the case of Si, we
assume typical values for L,,p of 10 pm and for 7n,pof lo-' s. For the
minority carrier concentrations, we obtain, from np = n?/NA and p, =
n!/ND with ni = lo1' cm-3 and N A = N D = 1OI6 cmV3, the values np =
p, = lo4 c ~ L - Using
~. e = 1.6 x 10-lgA s, it follows that j, 10-l' A/cmz.
The saturation current density is therefore extremely small. Thus, for U < 0
practically no current flows, the pn-junction blocks the current flow. One
says that it is reverse biased or biased in blocking direction, The biasing
U > 0 refers to the forward bias or Bow direction because the current density
in this direction is orders of magnitude larger than j, as we have seen above.
The pn-junction operates as an electrical rectifier. It is called a rectifyingpn-
diode in this context. In Figure 7.5 a measured current-voltage characteristic
of a pn-diode made of Ge is shown.
PE PB (PCI (7.33)
and, accordingly,
(7.34)
holds. In this case the left pn-junction is biased in the flow direction, and the
right in blocking direction (see Figure 7.8). From the left n-region, electrons
are injected into the p-region in the middle, while the right n-region extracts
electrons from the p-region. One therefore calls the left n-region the emitter,
and the right the collector. The p-region in the middle is called the base.
Accordingly, the np-circuit will be referred to as the emitter-base circuit or,
in short, the base circuit and the npn-circuit as the emitter-collector circuit,
7.1. pn-junction in an external voltage 587
or in short, the collector circuit. Let the current in the base circuit be ig,
and that in the collector circuit ic. Then the current i E through the emitter
follows from Kirchhoffs current branching theorem as the sum of the two
currents,
i~ = iB + ic, (7.35)
One can also say that the emitter current splits in two partial currents, one
flowing through the base, and one flowing through the collector (see Figure
7.7 on the right).
Our goal is the calculation of the three currents i ~ iB, , ic. In this matter,
we can employ the results obtained above for the current flow through an
individual pn-junction, with the valence and conduction band edges of the
npn-transistor lined up as shown in Figure 7.8. The pn-junction on the
emitter side is subject to the flow voltage U g , and the pn-junction on the
collector side is subject to the blocking voltage U c - UB. The emitter current
i~ is the current flowing through the emitter-side pn-junction. As such it is
given by expression (7.12), multiplied by the emitter area A . Accordingly,
it consists of the injection current j n ( z p ) Aof the minority electrons into the
588 Chapter 7. Semiconductorjunctions under non-equilibrium conditions
base, the injection current jp(x,)A of the minority holes into the emitter,
and the recombination current in the depletion region. Neglecting the latter
contribution as before, and using relations (7.30) and (7.31), we have
Here the signs are opposite to those of relations (7.30) and (7.31) above, due
to the fact that the emitter-base junction has thep-region on the right-hand
side and the n-region on the left, whereas it was the opposite above. If
both regions were expanded infinitely, as we always assumed above in the
treatment of the pn-junction, then the minority charge carrier concentra-
tions n(x) and p(x) in (7.37) could be replaced by the previously derived
expressions (7.20) and (7.21). This procedure would result in expressions
for j,(xp) and j p ( z n )which are just the negatives of those in relations (7.30)
and (7.31). In the transistor, however, only the emitter can still be consid-
ered to be infinitely extended, while the width b of the base must be treated
as finite because it is not large in comparison with the diffusion length L, of
the minority charge carriers. Thus, only the injection current density jp(x,)
of holes may be taken from the previously derived expression (7.31). Ad-
justing this expression to the relationships at the emitter-base junction, we
find along with (7.27),
(7.38)
(7.39)
7.1. pn-junction in an external voltage 589
Dn
j n ( z p ) = enp- (eeuBjkT - 1) coth[(b - z p ) / L n ] . (7.40)
Ln
The current ig in the base circuit would be identical with the emitter current
iE, and both currents would equal the current through the emitter-base pn-
junction, if the base were to be infinitely expanded. For finite base width,
however, the emitter current differs from the base current because the latter
only takes contributions from the portion of the electrons injected into the
base which also recombine in the base. We denote the pertinent current
density as jnT. The first term of formula (7.23) expresses it as
(7.41)
The base current ig, like the emitter current in (7.36), also involves the
injection current j p ( z n ) Aof holes from the base into the emitter, besides
the electron current j,A. Altogether, we therefore have
The current amplification 1,3 is defined as the ratio of the current change in
the collector circuit to the current change in the base circuit. From (7.44)
and (7.45) it follows that
(7.46)
Here, the extent x p of the space charge region in the base has been neglected
in comparison with the entire base width b. If b << L,, a current amplifi-
cation occurs according to relation (7.46) in the sense that a small current
change in the base circuit leads to a large current change in the collector
circuit.
What is important, however, is not primarily amplification of current,
but amplification of electric power. Initially, one might think that power
amplification would be determined by the ratio of the power change in the
collector circuit to the power change in the base circuit. This ratio would
have, however, no value because in the switching scheme of Figure 7.7 all
the power of the collector circuit is transferred to heat. For electric power
to be useful, a working element must be included in the collector circuit,
say a resistor RL. The voltage drop across it is ~ c R L .Taken together with
the voltage between the emitter and the collector of the transistor, the total
+
voltage in the collector circuit is U c icRL. The transistor resistance is ap-
proximately given by the resistance of the blocked pn-junction between base
and collector. As such, it is practically independent of the base voltage. We
consider, in particular, the case in which R L equals the collector resistance of
the transistor. That means that the voltage drop across the working resistor
R L is the same as the voltage U c between the collector and emitter. What
we have to calculate are the power changes d P L in the working resistor R L
and d P B in the base circuit, if the base voltage U B changes by d U B while
keeping the collector-emitter voltage at a constant value U c . We have
(7.47)
592 Chapter 7. Semiconductorjunctions under non-equilibrium conditions
tor.
.......... ..........
.......... n-Silicon ..........
..........
.......... :::::::::A
I/.._.J ............ ...........
..........................................
n*-Silicon
p3iG-I
(7.48)
The ratio of the first term in the square bracket of (7.48) to the second is
kT to U g . Under normal conditions this is small, and neglecting it the ratio
of the power changes dPL and dPB takes the simple form
(Z) = P UUC
B. (7.49)
P I n n
Figure 7.11: Lineup of the valence and conduction band edges at a pn-junction
between moderately doped regions (a) and heavily doped regions (b).
reversed, as we will see below; there the input resistance is high and the
output resistance low.
Due to the planar fabrication technology of microelectronics, the bipolar
transistor, as it is actually used in integrated circuits, is structured differently
than the one used in our theoretical analysis. A more realistic structure is
shown in Figure 7.10.
strictly speaking, as long as the bulk Fermi levels Epn and EF, do not lie in
the respective bands (Figure 7.11a). When the latter occurs (Figure 7.11b),
then there are energy levels at the conduction band bottom which are at
the same position as some of the energy levels at the valence band top. The
two energy bands partially overlap. In the overlap region each energy level
belongs simultaneously to valence and conduction band states. However,
the corresponding wavefunctions are localized in different regions of the pn-
junction - those of conduction band states in the n-region, and those of
valence band states in the pregion. An electron from a conduction band
state with an energy level in the overlap region can transfer into a valence
band state at the same energy. One then says that the electron tunnels from
the conduction band into the valence band (also see section 3.8 on tunneling
due to an external electric field). Analogously, electrons from the valence
band can tunnel into the conduction band. The probability for a tunneling
transition is the same in both directions.
594 Chapter 7. Semiconductor junctions under non-equilibrium conditions
).
0 I
0 02 084
u/v-
An = Ap = I-g = I-
(E) (7.50)
where I- is the recombination lifetime of the electron-hole pairs and Tzw is the
photon energy of the radiation (the latter is taken to be monochromatic),
Using equations (7.11) and (7.12), the corresponding quasi Fermi levels p n
and pP of, respectively, electrons and holes may be calculated. Due to the
optical excitation they have different values - that of the electrons is raised
and that of the holes is lowered in comparison with the common equilibrium
value. If a voltage is applied to the sample, the current flow is stronger
when the sample is illuminated than without illumination. This phenomenon
is called the internal photoeffect. Alternatively, if one keeps the current
constant, then the photoeffect lowers the voltage drop across the sample.
The illumination leads, so to say, to a negative pre-voltage of the sample.
The latter is just the difference of the quasi Fermi levels of the electrons and
holes.
In these considerations, a spatially homogeneous distribution of light in-
tensity within the semiconductor sample has been assumed. However, since
the light is absorbed in the excitation of the electron-hole pairs, this assump-
tion is not justified. The intensity decays exponentially in the direction of
light propagation. This leads to a corresponding spatial inhomogeneity of
the electron and hole concentrations, which gives rise to diffusion. If the dif-
fusion coefficients of electrons and holes are the same, then diffusion makes
no contribution to electric charge transport since the electron and hole cur-
rents exactly compensate each other. If the diffusion coefficients are different,
however, as often actually happens, either a net current or voltage will arise
in the light propagation direction, depending on whether the two ends of
the sample are electrically connected or not. This phenomenon is called the
Dember effect.
The homogeneous semiconductor photoeffects discussed above are rela-
tively small in comparison with the photoeffects which occur at semicon-
596 Chapter 7. Semiconductor junctions under non-equilibrium conditions
(7.51)
This upper limit is reached if all optically excited holes diffuse as far as the
plane 3: = xn, which means that they do not recombine, neither at the surface
nor in the bulk of the sample. We assume this condition to be fulfilled.
The flow of positive charge through the np-junction from its n- to its p-
side, is just the opposite of what happened at the np-junction in establishing
equilibrium without illumination by light. In the latter case, the transfer of
charge results in the diffusion voltage. Therefore, exposure to light reduces
the diffusion voltage. The voltage change U$ooto is called the photovoltage. In
the case of the open pn-circuit considered here, in which the outer planes of
the p- and n-regions are not electrically connected, the total current density
jgbl in a stationary state must vanish. The latter is composed not only of
the photocurrent density, jphoto, but also of the current density j through the
pn-junction under the photovoltage U$ooto. This voltage takes a value which
7.2. pn-junction in interaction with light 597
(7.52)
If the outer planes of the p- and n-regions are electrically connected (see
Figure 7.14), and if the resistance R in this circuit is 0 (short-circuit), then
the voltage drop across the pn-junction is also zero, and the current
tota
.O at = iphoto. (7.53)
flows. If the resistance in the pn-circuit is neither 0 nor infinity, but has
a finite value R , then the photovoltage takes a smaller value UpRhoto than
Uphoto, and the total current density takes a smaller value jEtal than j:oM.
The two quantities jEbl and Ugot0 are determined by the equations
(7.54)
598 Chapter 7. Semiconductor junctions under non-equilibrium conditions
kT
(7.56)
This relation shows that Urhto is more sensitive to the light intensity I for
smaller saturation current density j, of the pn-junction. In subsection 7.1.4,
j, was estimated to be 10-"A/cm2 for a pn-junction made of Si. From this,
one can conclude that for hw = 1 e V , a light power of 10-l' W / c m 2 will
create a photovoltage of the order of magnitude 10 mV. The upper limit of
photovoltage is given by the diffusion voltage U D . This cannot be surpassed
because the space charge region would cease to exist if Upmbto were to exceed
Uo. In the latter case, no separation of optically excited electron-hole pairs
could take place, which is crucial for operation of the device.
Photodetectors involving semiconductor junctions are referred to as photodi-
odes. Beside the pn-photodiode discussed above one has also pin-photodiodes
with particularly wide depletion regions (symbolized by the 'i' in pin). Other
examples are met al-semiconductor or heteroj unction photodiodes.
Photovoltaic element
In the case of the photodetector, the usable electric power is very small and,
in fact, for R = 00 it vanishes. If the illuminated pn-junction is to produce
electric power, then R cannot be made infinitely large. On the other hand,
R also cannot be taken arbitrarily small, because then there would be no
voltage drop at the pn-junction at all and the power would vanish for this
reason. For finite values of R , a non-vanishing electric power is generated,
with light energy converted directly into electric energy. The useful electric
power R(Ajztd)2 can be calculated by solving equations (7.54) and (7.55)
with respect to jzhland Upbto. The calculation shows that the efficiency of
photovoltaic energy conversion can, theoretically, reach up to about 40 %.
In practice, it is not much more than 10 % in most cases currently. Photo-
voltaic elements have wide and important practical application as solar cells,
particularly those made of silicon.
7.2. pn-junction in interaction with light 599
(7.57)
(7.58)
where g is the so-called gain coefficient. The latter is defined as the negative
of the absorption coefficient, strictly speaking, that part of the absorption
coefficient which is due to the excitation of electrons from the valence into
the conduction band. The dimension of g is, therefore, that of a reciprocal
length.
In order for g to be greater than zero, the semiconductor must be put into
an excited state. The energy of this excited state (relative to that of the
ground state) is the energy emitted in stimulated emission when irradiating
the semiconductor with light. If the emitted radiation is to prevail over that
absorbed, the number of stimulated transitions from the excited state to the
ground state must be larger than the number of transitions in the opposite
direction. This case is realized when, in the excited state, the conduction
band edge is occupied by more electrons than the valence band edge. This
is called an occupation inversion In the case of equal occupation of the two
600 Chapter 7. Semiconductor junctions under non-equilibrium conditions
9= d ( n - ntr), (7.59)
Figure 7.15: Heavily doped pn-junction without voltage (a) and with voltage in
flow direction (b). In case (b) occupation inversion occurs in the vicinity of the
pn-boundary at x = 0.
as a function of applied voltage. Here, we need the relation between j and the
photon current density S, taking the electric current density j be given. As
we shall see, the functional dependence of S ( j ) can be calculated just from
the continuity equations for the carrier currents j,, j , and the photon current
density S. For simplicity, we assume a symmetric pn-junction, for which it
suffices to consider only the electron current density j,. Also, the active
region is symmetric with respect to x = 0 under this assumption, so that
it extends between -(1/2)x,4 and ( 1 / 2 ) z ~with ;CA being the total length
of the region. The continuity equation for the electron current density j ,
was written down in Chapter 5 in general form. The derived relation (5.20)
will be specialized here in the following way. First of all, we recall that the
total current density j = j n ( z ) +jp(z)is spatially constant in the stationary
state, while the two components j n ( x ) and &,(I) vary with I. On the right-
hand side of the active region, j n ( z ) is almost identical with j , while &(z)
practically vanishes. On the left-hand side of the active region, jp(x) has
almost the same value as j , while jn(x) is close to zero. Consequently, in
stationary state, we find for the active region the approximate relation
(7.60)
An
R-p= -. (7.61)
7-
Applying expressions (7.57), (7.58) and (5.60), (5.61) to the continuity equa-
tion (5.20) for the electron current, we have
an
---=
j An An
gs. (7.62)
at exA 78pDnT
(7.63)
where the left-hand side is the change of the photon density per second. We
are interested in the stationary state of the laser defined by
an dS
- -- - = 0. (7.64)
at at
We first consider g to be different from a. As we will see, in stationary state,
this necessarily means that g is less than a:
g<cw
The corresponding photon current density S< follows from equation (7.63)
as
(7.65)
Since S<, An and rSpT are positive quantities, only the case g < a is
meaningful, as indicated above. The photon current density S< given by
equation (7.65) is relatively small because the spontaneous radiative lifetime
T~~~~ has relatively large values and P is small compared to one. This is
true on the proviso that g does not approach the value of a very closely, or,
in other words, as long as the electron concentration n is distinctly smaller
than the threshold value nth defined by the relation
j
s<= (7.67)
ez~[g< + ( l / P ) ( l + rspa~/r)(a- g<)I
Here, g has been replaced by g< to indicate that the value of g has to be taken
as that which follows from g / ( n - ,ntT) for n < nth. If spontaneous emission
604 Chapter 7. Semiconductorjunctions under non-equilibrium conditions
(7.68)
This equation relates the electric current density j and the electron con-
centration n below the laser threshold. The threshold concentration nth
corresponds to a threshold carrier current density j t h as
(7.69)
Laser operation can occur only if the threshold current density j t h is ex-
ceeded. We will assume that this is the case. Then, by definition, we have g
equal to a:
The photon current density can now take non-vanishing values if rVar = 00.
This does not contradict the photon current continuity equation (7.63) under
the stationary conditions (7.64) because (g - a ) S now vanishes since (g - a)
does so. The actual value S> of S for a given current density j > j t h may be
obtained from the carrier continuity equation (7.62). In the approximation
rspar = 00, it yields
(7.70)
We will show that S> is in fact considerably larger than Sc. To this end,
we consider S> given by equation (7.70) for j = 2jth, and examine the ratio
of s>(2jth) to s<of (7.67) for j = j l h , obtaining
7.2. pn-junction in interaction with light 605
3
laser diode as a function of current den-
0
\
sity j (schematically). v)
I / *
Jth j 1a.u.
Generally, the spontaneous radiative lifetime 7spaT is much larger than the
non-radiative lifetime T. One has (7spaT//37) > 1 since ,B << 1. The ratio
( g < / m ) is a positive number measurably smaller than 1. Therefore, the
right-hand side of equation (7.71) is large compared to 1, meaning that
the value of the photon current density S, above the threshold current
density substantially exceeds the value S< below threshold. This is the
manifestation of the laser effect. One can also say that the pn-junction
functions as a laser diode when j > j t h holds. The functional dependence
of the radiation intensity over the entire current density range is shown
in Figure 7.17 schematically. The characteristic feature of the curve is its
steep rise at the threshold density jth. This point marks the transition from
spontaneous to stimulated emission, thus the onset of the laser regime.
To estimate the order of magnitude of the threshold current and of the
radiation intensity of a laser diode, we choose parameters close to those of
G ~ A SWe . take ntr = ~ ,= 2 . 1 0 ~ ' cmv3, X A = 1 p m , r =
c m ~ nth
lo-' s, and a = lo3 cm-'. With these values the threshold current density
of (7.69) is j t h = 103A ern-'. The corresponding current strength amounts
to 1 m A if a contact area of 10 x 10 ,urn2 is assumed. For current strength
2 m A the radiation intensity RwS within the resonator is about 10 mW. This
example shows that the radiation intensities of semiconductor laser diodes
are large enough to be employed for practical purposes, in particular in
information processing and communication. Currently, semiconductor laser
diodes are widely used in optical fiber communication, CD-players, scientific
instruments and in many other ways.
The spontaneously emitting diodes (LEDs) have also attained wide prac-
tical application, e.g., for signal generation and pattern display. Since the
radiation emitted by laser diodes and LEDs lies in the photon energy range
close to the band gap, one can theoretically cover the entire frequency spec-
trum from the infrared to the near UV by a proper choice of semiconductor
606 Chapter 7. Semiconductor junctions under non-equilibrium conditions
(7.72)
We will assume that the Schottky approximation can be used in the semi-
conductor, i.e., that the inequality (7.4) is fulfilled. Then the division of the
semiconductor into depletion and bulk regions also retains meaning here.
The width X B of the depletion region follows from (6.62) if U D there is re-
placed by U D - U . The current in the bulk region of the semiconductor
is carried by majority carriers, just as in the case of the pn-junction. For
the assumed metal-n-type semiconductor junction, the majority carriers are
electrons on both sides of the junction. At the interface between the two
materials, electrons are thermionically emitted from the metal into the semi-
conductor, and vice versa, electrons from the semiconductor are emitted into
the metal. We denote the particle current density from the metal by i M S ,
and that from the semiconductor by i S M . The two partial current densities
add up to the total current density i through the junction. All three current
7.3. Metal-semiconductor junction in an external voltage. Rectifiers 607
a) 0 - r 8 u-0
Metol n- Semiconductor
bl
c) +t+ UCO
___.
u70
c
---T'
---I---: L- \
i": I
x x x
I
iI ------
I
I
x x A_-
I
I
I
I
L
XB X
The total current density i in the presence of the voltage U may then be
written as
i ( U ) = i ~ s ( 0-) i s ~ ( U ) . (7.76)
We first calculate i ~ s ( 0 )In. this, we consider a metal electron which, after
passing into the semiconductor, has quasi-wavevector k and energy Ec(k).
Since no momentum and energy change takes place in crossing the interface,
the quasi-wavevector of this electron is k and its energy Ec(k) in the metal as
well. The probability to find an electron in the metal with energy E = Ec(k)
is given by the Fermi distribution f i ~ ( Eof) the metal,
(7.77)
The current density i ~ s ( 0is) the statistical average of the speed component
h-'(Ll/LlkX)Ec(k) in the positive 2-direction, per unit volume. According to
the general rule (5.3) for calculating statistical averages we have
The boundaries of the first B Z were put to infinity here, involving only a
slight error. In fM(Ec(k)) we replace -EFM by the work function @ of the
metal. This also indicates that, henceforth, the energy origin will no longer
be taken at the top of the semiconductor valence band, but at the common
vacuum level of the two materials. Since [Ec(k)+@] >> k T , the Fermi distri-
bution (7.77) can be approximated by the Boltzmann distribution, whence
(7.79)
For Ec(k) we use an isotropic parabolic dispersion law with effective mass
m:. Then relation (7.78) takes the form
7.3. Metal-semiconductor junction in an external voltage. Rectifiers 609
with
(7.82)
iSM(U) ,eU/kT Z S M ( 0 ) .
I (7.84)
Correspondingly, the total particle current density i ( U ) is
(7.85)
For the electric charge current density j = -ei it follows that
(7.86)
with
I -@p,/kT
j , = Tenvoe (7.87)
Lf
6 10 Chapter 7. Semiconductor junctions under non-equihbrium conditions
For positive voltages U , the current density j grows exponentially with in-
creasing U , while for negative U of increasing magnitudes, j approaches
the saturation current density -js. The latter occurs when 1UI >> kT holds.
The Schottky junction therefore operates as a rectifier, with positive voltages
corresponding to the flow direction, and negative to the blocking direction.
The following estimate shows that j , can assume quite large values. For
T = 300 K , N D = 10l6 cm-3 and @B = 0.25 e V , we have j , 0.2 A / c m 2 .
From this we may conclude that Schottky junctions are suitable for rec-
tification of relatively strong currents. This distinguishes them from pn-
junctions where the saturation current density is commonly much lower (see
section 7.1). The reason for this difference is that the saturation current of
a pn-junction is due to minority carriers, while the saturation current of a
Schottky junction is caused by majority carriers.
The conditions of validity for the current-voltage characteristic of a metal-
semiconductor junction derived above will now be examined. The applica-
tion of formula (7.83) to the calculation of the current density iSM(0) reflects
the assumption that thermionic emission of electrons from the semiconduc-
tor into the metal proceeds unhindered. To appreciate the significance of
this assumption one must first recognize that the emitted electrons originate
in the bulk region of the semiconductor, for in the depletion region none are
available. Unhindered emission can only occur, therefore, if the electrons,
during their flight through the depletion region suffer no collisions. That is
assured if the mean free path length Zf is larger than the space charge width
"B,
lf > X B . (7.88)
For practical Schottky junctions, operating in blocking direction, this con-
dition is often fulfilled, provided the blocking voltage is not too large. For
flow voltages of sufficient magnitude it is always correct. Condition (7.88)
excludes the possibility that the depletion region can even approximately
be in a local equilibrium state. In particular, chemical and electrochemi-
cal potentials cannot be meaningfully defined, not even in a local or 'quasi'
sense. This implies that an essential requirement for the applicability of
the phenomenological equations (5.14) and (5.15) for the current densities is
no longer valid. If the inequality (7.88) is satisfied, drift and diffusion lose
their meaning as transport mechanisms in the depletion region of a metal-
semiconductor junction. The transport proceeds by electrons flying through
the depletion zone unimpeded, which is termed ballistic transport. If, instead
of l f > ZB, the condition
lf << X g (7.89)
holds, then equation (7.83) is no longer valid for use in calculating i S M ( 0 )
and i s ~ ( U ) The
. magnitude relation (7.89) is just the upper part of the
general condition (5.9) for the validity of the phenomenological equations,
7.3. Metal-semiconductor junction in an external voltage. Rectifiers 611
row that the electrons can tunnel through the potential barrier, then even
the thermionic emission theory is no longer valid. This occurs in heavily
doped semiconductors. In this case the Schottky contact conducts well in
both directions, and it becomes an ohmic contact. This effect is exploited
in manufacturing contacts in silicon devices. The frequently used contact-
metal, aluminum, would in fact result in a non-ohmic Si-metal contact if the
doping were not sufficiently high. The heavy doping of Si makes this contact
ohmic, as is necessary for the proper operation of devices.
(7.91)
u<o
UO
from t, then the charge on the metal contact has to be multiplied by the
factor ( I / ) to get the induced charge. Since, in general, E I is smaller than
t (ferroelectrics are an exception), the induced charge is generally a fraction
of the charge placed on the metal contact. Inducing charge at an insulator-
semiconductor junction by applying a voltage is also referred to as field effect.
This effect has played an important role in the development of semiconductor
physics. The thought of exploiting it to induce a change of semiconductor
resistance by means of an external voltage, hence, to develop a kind of
a transistor, is obvious and was followed by several scientists in the late
twenties and thirties of this century. Initially, the efforts were not successful,
however. Instead of the field effect transistor, the bipolar transistor was
invented in 1949 - in a sense as a byproduct of the search for the former.
The main reason for the failure of the early work on the field effect transistor
614 Chapter 7. Semiconductor junctions under non-equilibrium conditions
is the existence of interface states at the junction of the insulator and semi-
conductor. If such states are present in sufficiently high density, which was
in fact the case in the early work, all of the induced carriers are captured
by them. Since carrier mobility in these states is zero, the resistance of the
semiconductor does not change. Generally, the number of electrons cap-
tured depends on how many unoccupied interface states are pushed below
the Fermi level by applying the external voltage (see Figure 7.19c), or how
many previously occupied states are lifted above the Fermi level (see Figure
7.19b). The amount of captured charge represents, in this way, a measure of
the number of interface states in an energy interval at the Fermi level of the
size of the applied voltage. By measuring this charge as a function of applied
voltage U , which can be done, e.g., by measuring the capacitance change of
the insulator-semiconductor junction with U , one may obtain experimental
data about the density of interface states at different energies.
(7.92)
holds. Increasing the voltage U further, the conduction band edge E,-ecp(O)
at x = 0 is pushed further down, and the region of the semiconductor in
which the conduction band edge lies below the Fermi level extends to the
right to a point xi > 0 given by the relation
E g - ecp(zi) = E F . (7.93)
(see Figure 7.21). In this region the free charge carriers are not predomi-
nantly holes, as otherwise in a p-type semiconductor, but rather, they are
electrons. The conduction carrier type is inverted in this region, which is
therefore called an inversion layer. The electrons in the inversion layer of a
7.4. Insulator-semiconductorjunction in an external voltage 615
(7.95)
If the Fermi energy E F lies below the conduction band edge, then the ma-
jority of electrons in this band have energy values at and a few kT above the
band edge E, - ecp(x). As long as [E, - ecp(z) - E F ]is substantially larger
616 Chapter 7. Semiconductor junctions under non-equilibrium conditions
than kT,f ( E ,x ) is approximately zero for the energy values mentioned. If,
on the other hand, the Fermi level lies above the conduction band edge,
i.e., if the expression [E, - ecp(x) - EF] is negative and its absolute value is
simultaneously much larger than k T , then f(E, x ) is approximately 1. The
energy interval in which f(E,x ) is neither 1 nor 0 decreases, as compared to
the whole potential interval eU, spanned by the potential e p ( x ) in the semi-
conductor, as eU, increases in comparison with k T . We therefore suppose
that
k T << eU, (7.96)
holds. In a sense, this relation represents a generalization of condition (6.35)
for the validity of the Schottky approximation. Then, considering (7.95) for
energy values of the conduction band, we can approximately write
(7.99)
Evaluating the energy integral for n ( x ) in (7.98) with the square-root ex-
pression (4.44) for the density of states p:&&(E) x p;"'(E), a concentration
+
n ( z )follows which is proportional to [ e p ( x ) EF - E g ] 3 / 2 .Substituting this
into the Poisson equation (5.24), the solution leads to inverse elliptic func-
tions which are difficult to handle analytically. We therefore replace the true
density of states by a model state density Fc which is constant in the energy
7.4. Insulator-semiconductor junction in an external voltage 617
+
interval between E, and EF ecp(x), with the constant 7, of the model de-
termined as follows: We form the average value of the true square-root-like
density of states p?(E) in the occupied energy interval at x = 0, i.e. be-
+
tween Eg and EF eUs. If we were to use this average value for the density
of states throughout the entire inversion layer without any correction, then
the resulting average electron concentration in the inversion layer would be
markedly larger than it really is. Therefore, a correction factor y having a
value between 0 and 1must be introduced in consideration of the decrease of
the upper limit of the averaging interval with increasing I . Thus, we make
the substitution
(7.100)
Using this constant density of states, the electron concentration n(x) in the
inversion layer may be rewritten in the form
where
(7.102)
is the effective density of states of our model. The substitution (7.100) has
the consequence that the true density of states, and with that also the true
electron concentration, is underestimated in the left part of the inversion
layer, and overestimated in the right part, provided that a reasonable choice
of y has been made. Because of this, the potential profile p(x) of the in-
version layer, whose calculation we will now discuss, has a curvature in our
model which differs somewhat from that in reality. Qualitatively, however,
no significant differences occur. For a quasi 2-dimensional electron system,
the results of our model even apply exactly, since in this case the density of
states is constant from the outset.
With the resulting concentrations of free charge carriers as derived above,
the Poisson equation (5.24) in the semiconductor takes the form
The solution of this equation must satisfy the boundary conditions (7.90) and
) 0
(7.91). The arbitrary constant of the potential is chosen such that ( ~ ( 0 0=
618 Chapter 7. Semiconductor junctions under non-equilibrium conditions
holds. From the Poisson equation it immediately follows that the potential
and the field strength also vanish at x = xp, i.e. that
V b P ) = 0, (7.104)
(7.105)
The field strength in the insulator is spatially constant and we denote it by
FJ. Then, in particular, we have
(7.106)
For the potential p(x) at x = -d, relation (7.90) and p(00) = 0 yield the
value
p(-d) = U . (7.107)
The four conditions (7.104) to (7.107), as well as the continuity condition
for p(x) and (dpldx) at x = 0 and x = xi, are sufficient to determine
the potential profile p(x) uniquely, along with the three as-yet unspecified
parameters xi,xp and FI. The solution of the Poisson equation under the
above conditions is determined as
(7.110)
as the electric field strength in the semiconductor at the interface with the
insulator, and
Ua = U - FId (7.111)
as the potential drop across the semiconductor. The inversion boundary xi
and the field strength F obey the equation
1
cosh(xi/L) [(Us - Uo)2 - (LF,) 2 = =-(xi
NA
N,
- xP)Fs(U, - Uo). (7.113)
xi >> L. (7.115)
The number ns of electrons stored in the inversion layer per cm2 may be
obtained from (7.101) and (7.108) as
-
ns = N,L. (7.116)
With and L taken from, respectively, (7.102) and (7.109), this expression
may be rewritten as
The sheet density ng of electrons in the inversion layer is zero if the voltage
drop Us across the semiconductor equals the threshold voltage Uo marking
the onset of inversion. Above this value, ng has a weak overlinear depen-
dence on Us. Thereby, U , depends on the applied voltage U through the
relation
(7.118)
(7.119)
7.4.3 MOSFET
Whether or not the charge density of a semiconductor inversion layer suffices
to cause a resistance change of sufficient magnitude to function as a transis-
tor, depends (among other things) mainly on the specific resistivity of the
semiconductor material in the absence of an applied voltage. This must be
as high as possible. The highest possible resistivity, or the smallest conduc-
tivity, of a semiconductor material is observed when it is in its intrinsic state.
This fact is used to advantage in the most important type of field effect tran-
sistor, the so-called MISFETs (Metal Insulator Semiconductor Field Effect
Transistor). Here, one exploits the fact that in a pn-junction a depletion
region is formed wherein the charge carrier concentrations have intrinsic val-
ues. The p-region is embedded between two n-regions, as shown in Figure
7.22. If one applies a positive voltage between the left n-region (source) and
the right n-region (drain) (Figure 7.22), then the left pn-junction is biased in
the flow direction, and the right in the blocking direction. Between the two
n-regions, one therefore has a p-region which is almost completely depleted
of holes. In the theory developed above, this may be taken into account
formally by adding a positive prevoltage Uv to the voltage U applied to the
insulator-semiconductor junction from outside, i.e. by the replacement
u-+utuv. (7.120)
For U = 0, the semiconductor region between source and drain, the so-called
channel, has high intrinsic resistivity. If a positive voltage U = UG is applied
between the bulk of the p-semiconductor (substrate) and the metal layer on
7.4. Insulator-semiconductorjunction in an external voltage 62 1
a1
I P
Substrat
Figure 7.22: Structure of a MISFET (a). In part (b) the switching scheme of the
MISFET is shown.
..
.
E
n
v)
Y
-0 4 8 12 16 20 24
top of the insulator (gate), large enough to create an inversion layer, then
the channel becomes a good conductor. The current in the source-drain
circuit can be tuned by the voltage UG of the gate-substrate circuit since the
electron density of the inversion layer depends on UG. The voltage UG is
called gate voltage, and the minimum gate voltage UG necessary to a achieve
inversion is the threshold voltage. If one also includes a working resistor
in the source-drain circuit and compares the power changes in this resistor
with those in the gate-substrate circuit, one finds that the former exceeds the
latter appreciably. In this sense, the MISFET operates as an amplifier, just
like the bipolar transistor. Because of the insulating layer below the gate
electrode, the MISFET has a much larger input resistance than the bipolar
622 Chapter 7. Semiconductor junctions under non-equilibrium conditions
transistor. The output resistance of the MISFET, i.e. that of the source
drain circuit, is small because of the accumulation layer between source and
drain.
If the MISFET is realized using Si as the semiconductor material and
SiO2 as the insulator, one has the Metal Oxide Semiconductor Field Effect
Transistor, abbreviated MOSFET, which is by far the most important MIS-
FET. The basic requirement that the electrons of the inversion layer shall
not be captured by interface states, are met by the MOSFET extremely
well. Just as the base of a bipolar transistor can be made either of p or
n-material, one also has two possibilities in the case of the unipolar MOS-
FET - the charge carriers in the conducting channel can either be electrons,
as has been assumed thus far, or holes. In the first case one speaks of a
n-channel MOSFET, and in the second of p-channel MOSFET. The prevolt-
age U V ,which was introduced above only formally to simulate the intrinsic
state, can really exist for various reasons, e.g., because of positively charged
centers within the oxide arising during its formation. The prevoltage can
take such large values that inversion exists even without an applied gate
voltage. Then the transistor is already in its conducting state at zero gate
voltage. To switch it into its blocking state, one must apply a negative gate
voltage in the case of the n-channel MOSFET, and a positive gate voltage
in the case of the p-channel MOSFET. One says that the transistor oper-
ates in the depletion mode. If the transistor is blocked without an applied
voltage and changes into the conducting state by applying a positive (for
n-channel) or negative (for p-channel) gate voltage, one has the enhance-
ment mode. The current-voltage characteristics of the source-drain circuit
of a n-channel-enhancement-mode MOSFET are shown in Figure 7.23 for
different gate voltages. One recognizes how the sourcedrain current at a
h e d value of U s 0 increases with increasing gate voltage UG. Somewhat
unexpectedly, for a k e d gate voltage UG, the current saturates at higher
source-drain voltages USD. This is a consequence of the fact that the effec-
tive gate voltage in the vicinity of the drain electrode becomes smaller and
smaller as the drain potential grows larger. This creates a pinch off of the
inversion layer, making the current stay constant.
The MOSFET represents the most important electronic component of
digital circuits in microelectronics. Here it is used as an electrically control-
lable switch, meaning that its control function is reduced to two states only,
one with maximum output power, corresponding to a binary l,and another
having minimum output power, corresponding to a binary 0. Today, MOS-
FETs can be made as small that millions can be integrated in one single
Si chip, more than of any other electronic component. It is this ultra-large
scale integration (ULSI) technique which has made modern computer and
communication technologies possible.
623
Appendix A
4) For each element 4, the set also contains its im-erse element 9-l: such
that
g.g-' =; g -1 - g - e . (A.3)
Onc may show that it suffices to dcmand the existence of only the left-sided
or only the right-sided inverse. This one-side inverse is thcn uniquely deter-
mined and its existcnce automatically leads t o the existence and uniqueness
of the other-siticd iiiverse. T h e other-sidd inverse thusly determined is iden-
tical with the original oneside in?-erse. Analogous dstements hold or the
identity dement discussed above.
The inverse (91 . g2)-' of tl product gl . g:! is given by gz1 . gl1: as one
may easily verify by explicit. mult.iplicat.ionof t h e two products.
The existence of the inverse ensures that t.he products g1 . g and g2 . g
of two elements g1 and g~ with an arbitrary group element g are different,
if the elements g1 and 92 differ from each other. The same is true for the
re-ordered products g .g1 and 9 92.
The number N of elements of a group is callrd its order. Depending on
whether N is finite or infinite, one has finiteor iu,~%ittgrotqs. ' h e dements
of infinite groups may be either discrehe or continuous. In the latter rase
one has a coatinuow group.
The group multiplication which i s associative by definition, need not also
be commutative. In general: g1 . $2 differs from g2 . gl. If the multiplication
is also commutative, the group is call& A h e l i a ~ ~
We now introduce some goup-thcoretical concepts which are n d e d in
this book.
A.1.2 Concepts
A suihject of a group which forms a group by itself with respect to the
multiplication tahle defined by that of the full group, is termed a subgroup.
Subgroups
For finite groups G, the theorem of Lagrange holds, wherein the order 1L"
of a subgroup G I is a divisor ol thp order N of the group. Thc proof of
this theorem will be briefly sketched because it also provides some insight
in other group properties. Let be ,g! = E,g$,. . , g h , the elements of a
subgroup G" of G We denote an arbitrary element of G not contained in
G' by gz. 'I'he products 92 gi, g 2 . gh,. . . , g2 . gh, of g:! with dl elements
of the subgroup G' form a 5et M,<, the elements of which are different from
each other as well as from the dementb of G'. For the sake of uniformity
of notation, w e set C' M,<. If the two sets M1< and M; together do
not cover trhed i r e group C , WP choose an element 93 of G not contained in
AT,< and M,<. We proceed in the same way with this element as we &d with
A.1. Definitions and concepts 625
92. The thus emerging set M3< contains N' mutually different elements, just
like M,< and M 2 , and none of these elements occurs in M1< and h42. If the
entirety of the sets M:, and M Z still do not yet cover the full group
G, we choose yet another element 94, and so on. After a finite number N f f
of steps a complete division of the group G into N" distinct subsets with N'
elements in each will be achieved. Therefore, one has N = N' ' N" which
proves the theorem.
Lagrange's theorem allows us to draw several conclusions. For groups
of prime order it means that only trivial subgroups can exist, namely the
identity element, and the group itself. This statement may also be reversed
- the order of a group which has no subgroups apart from the trivial ones,
must be a prime number.
Cyclic subgroups
Direct product
We consider two groups G and G' of, respectively, orders N and N', and
626 Appendix A . Group theory for applications in semiconductor physics
examine the products between all elements g k of G and all elements gh, of
G'. The whole set of these N . N' products g g i , = g k . gLi forms a group G"
of order N . N'. This statement may be easily verified by showing that the
product of two of the elements of GI' is again an element of G". The group
GI' is called the direct product of the two groups G and G I , for which one
writes G" = G x G'.
f = f( 9 ) . (A.4)
Such an association, or mapping, is termed homomorphic if it obeys the
condition
f ( g 1 ' 92) = f (91) . f (92) 7 (A.5)
where g1 and 92 are two elements of G. If the mapping is not only unique but
is also bi-unique, i.e. if not only each element of G corresponds to exactly one
A.2. Rigid displacements 627
and the space groups. The elements g of these groups are in all three cases
rigid displacements of certain point sets, which transform these sets into
themselves. As we will see, the point sets for the translation groups are
infinite lattices, those for the point groups are finite spatial bodies, and
those for the space groups are crystals, i.e. several infinite lattices of the
same Bravais type put into each other. The translation-, point- and space
groups are summed up under the term displacement groups.
A.2.1 Definition
Formally one may define rigid displacements as transformations g of 3-
dimensional space which shift its points x by vectors a(x) in such a way,
that the distance I x1 - x2 I between two arbitrary points ~ 1 ~ does
x 2 not
change. Thus, we have
or
2
2(x1 - x2) Ia(x1) - a(xz)l+ I 4x1) - a(x2) I = 0. (A4
The multiplication dot in (A7) and (A.8) signifies the internal or scalar
product. In order to satisfy equation (A.8), the displacement field a(x)
cannot be of higher order in x than of the first, i.e. a(x) must have the
general form
a(x) = px +a (A.9)
where /3 is a linear operator in x-space and a a constant vector. From (A.6)
it follows that
628 Appendix A. Group theory for applications in semiconductor physics
gx = a x + a, (A.lO)
+
with a = 1 0. The thusly defined operator cr is also linear. It is subject
to certain constraints due to the rigidity condition (A.7). If one enters this
equation with expression (A.lO) for gx,then one gets, first of all, (XI- xg).
( X I - xg) = a(x1 - xg) . a(x1 - x2). Using the adjoint operator a+ of a,
the last relation may be put into the form
(XI - xg) ' (XI - x2) = a+ ' a(x1 - x2) . (XI - x2). (A.ll)
The multiplication 'dot' between the two operators symbolizes the consecu-
tive application of the operations. Since (XI - xp) represents an arbitrary
vector, relation ( A . l l ) implies that
a + . a = 1. (A.12)
By this identity, a+ is seen to be the inverse operator a-l of a , whence
+
, = ,-I. (A.13)
Linear operators which act in a real vector space (as we assume here) and
satisfy the relations (A.12) or (A.13), are called orthogonal. The transfor-
mation they describe are orthogonal transformations.
A.2.2 Translations
For p = 0 or a = 1, g reduces to a rigid displacement of all points through
the same vector a, i.e. to a translation. We use the symbol t, for it, so that
tax = x + a. (A.14)
With ta, one can rewrite equation (A.lO) for gx in the form
(A.15)
whence
(A.16)
which is stated as theorem below.
Theorem
This theorem remains valid if one reverses the sequence of the orthogonal
transformation and the translation, but one must then use another transla-
tion in order to obtain the same displacement g as before, specifically
a =C C a i k ( a ) e z e k . (A. 19)
i k
av = c
i
Cai&)eiek
k
' v. (A.20)
It follows that
x =Cxiei, (A.22)
1
where
xi = e i . x (A.23)
are the Cartesian coordinates of x. We obtain
(A.24)
630 Appendix A. Group theory for applications in semiconductor physics
(A.25)
This is to say that the coordinates themselves transform with the matrix
A ( a ) , in contrast to the basis vectors whose transformation is governed by
the transposed matrix [ A ( a ) I T .
The product 0 1 . a2 of two orthogonal transformations a1 and ag, un-
derstood in the sense of sequential application, is represented by a matrix
A ( a 1 . ag) which one can easily determine with the help of relation (A.19),
obtaining
[ A ( a ) l T= [ A ( a ) ] - l . (A.27)
Real matrices with this property are called orthogonaL Thus orthogonal
transformations are represented by orthogonal matrices with respect to or-
thonormalized basis sets.
Relations which follow immediately from (A.27) are A . AT = 1 and
A T . A = 1, which may be written in terms of matrix elements as
This means that orthogonal matrices have the property that different rows
are orthogonal to each other, and so are different columns.
The product of two orthogonal matrices is again an orthogonal matrix.
Combining this result with equation (A.26), we arrive at the conclusion
that the product of two orthogonal transformations is also an orthogonal
transformation. The implicit assumption behind this result is that both
transformations have a common point which remains unchanged (the point
x = 0 here).
A.2. Rigid displacements 631
ae = e. (A.29)
Since only the direction, but not the length, of e is determined by this
relation, equation (A.29) means that all points given by xo = <e with <
as arbitrary real number which lie on a straight line in the direction of e
through the origin, are transformed into themselves. One says that they are
fixed points of the transformation a. The orthogonal transformation (Y with
Det[A]= +1 therefore corresponds to a rotation about the axis defined by
xo. A special rotation is the identity transformation a = E .
In the case D e t [ A ]= -1 one has
632 Appendix A. Group theory for applications in semiconductor physics
ae = -e. (A.30)
The transformation a therefore describes a rotation about the axis xo = e
followed by a reflection in the plane normal to the rotation axis through the
origin. It is called an improper rotation or a rotation-reflection . Among the
improper rotations are also pure reflections in the plane normal t o the axis,
and inversion with respect to the origin. In the first case the rotation angle
is 27r, and in the second case T. Since an improper rotation is constituted
of the consecutive application of a rotation and a reflection, all orthogonal
transformations may be traced back to pure rotations and pure reflections.
The orthonormality relations of (A.28) mean altogether six independent
equations. The nine elements of an orthogonal matrix may thus be thought
of as functions of three independent variables. The choice of these vari-
ables is not unique. The most common is the one by Euler, who uses three
angles $,8 and p. Two of these angles, $ and 8, determine the direction
(sin 8 sin $, - s i n 0 cos $, cos 0 ) in which the z-axis is turned, and cp is the rota-
tion angle about the transformed z-axis (see Figure A.l). The corresponding
transformation matrix reads
A= ( cos $ cosp
sin$ cosp
sin 6 sin p
- cos 6 sin$sinp
+ ws6 cos $ sin9
- cos$ sin p - cos 6 sin $ cos p sin6 sin$
-sin $ sin p + cos6 cos $cos
sin 6 cos p
p - sin 6 cos $
cos 6
Using this matrix, a reflection in a plane normal to the direction (sin8 sin$,
- sin 8 cos $, cos 0) may be traced back to a reflection in a plane normal to
the z-axis, which is easily described. The matrix A of the reflection in the
plane normal to the above cited direction thus reads
b) I
with
x o a = 0. (A.34)
The identity element Q = E must be excluded here because no rotation
axis is defined for it. What has to be proved is that, under the conditions of
equation (A.33), the transformation g itself has hed-points xb which form
a straight line, i.e. that the equation
cvxb+a=xb (A.35)
has a 1-dimensional solution manifold. To verify this, we express xb in the
form
+
xo = (2x0 ra + sa-la (A.36)
with q , r, s as coefficients which still have to be determined. Since the three
vectors xo, a and a-la, are linearly independent, such a representation is
always possible expect for the special case aa = -a in which the rotation
angle p of Q about the axis xo is equal to T. The latter case has to be
considered separately. Employing equation (A.36) for xo jointly with equa-
tion (A.35), we obtain a vectorial relation for q , r and s which is satisfied by
arbitrary values of q . Consequently, the result is an inhomogeneous vector
equation in the plane perpendicular to xo for r and s only. Considering the
components of this equation with respect to a and cra, we find a system
of two inhomogeneous equations, whose determinant equals laI2 2 sin2 cp. It
never vanishes since the two cases cp = 0 and cp = T have been excluded, and
thus there is a unique solution for r and s. In the excluded case cp = n one
may take s = 0, and then the above procedure yields a unique solution for r .
With this, our assertion is proved for a rotation with consecutive translation
normal to the rotation axis. In the case of a reflection accompanied by a
translation normal to the mirror plane, the proof is analogous.
There remain rotations and reflections followed by translations parallel
to, respectively, the rotation axis and the reflection plane. That these cannot
be replaced by pure rotations or reflections is obvious. The rotation axis
and the reflection plane are unaffected by the translation. Therefore a pure
rotation would have to be one about the same axis, and a pure reflection one
with respect to the same plane. But these have to be followed by translations
in order to get the complete transformations. Therefore pure rotations and
reflections do not exist in this case.
In summary, this means that rigid displacements can be traced back
to rotations and reflections only if translations which are directed parallel
to the rotation axis or mirror plane are not involved (see Figures A.2 and
A.3). Rotations followed by translations parallel to the axis are called screw
rotations, and reflections followed by translations parallel to the mirror plane
A.3. 'Ikanslation,point and space groups 635
are glide reflections. These results allow one to express the above stated
theorem in the following, more specific form:
Theorem 2
which yields
tR1 ' tRz = t R ~ + R ~ (A.38)
The latter relation means that the product of two lattice translations defined
in equation (A.37) is again a lattice translation. This set therefore forms a
group if points 2), 3) and 4) of the general group definition are also fulilled.
That this is so may be demonstrated easily. Using relation (A.4) one can
readily show that the product (A.38) obeys the associative law (point Z),
that an identity element exists, namely the translation through the lattice
vector 0 (point (3)), and that the inverse of each element t R belongs to the
group, namely the translation t-R through the lattice vector -R (point 4).
Each lattice translation can be expressed as a product of translations
through three primitive lattice vectors al,az, ag, so that
(A.39)
Since the sequence in which the primitive translations are executed plays
no role, all other lattice translations also commute with each other, i.e. the
translation group is Abelian.
636 Appendix A . Group theory for applications in semiconductor physics
Definition
main text we have shown that such sets include infinite point lattices. In
this case, however, only 7 special point groups are admissible as symmetry
groups. As far as ideal crystals are concerned, these are neither geometric
bodies nor infinite lattices. Therefore, the symmetry groups of crystals, the
so-called space groups, are not necessarily constituted of point groups. This
is not so for the symmetry groups of equivalent crystal directions, which
were also considered in the main text. These are point groups, but again
only special point groups are possible, altogether 32. One calls them point
groups of equivalent crystal directions or, in short point groups of directions.
ml
cn .t
-___---
"2
b)
I
I
el
?:'
Sni
I I
f)
The two factors commute for the same reason as in the case of rotation-
reflections considered above. Rotation-inversion axes, which are understood
as the set of all powers of S,i, are used in the international system. The
notation for an n-fold rotation-inversion axes is E.
Stereograms
sphere around the common fixed-point into another point on the surface
of the sphere. The elements of a point group are thus put into one-to-
one correspondence with points on the surface of a sphere. At best, one
imagines the sphere as a globe. To achieve a planar representation) one
utilizes, as in cartography, the stereographic projection. This is illustrated
in Figure A.5 with the south pole as the reference point. In this case the
northern hemisphere is projected onto the region within the equator, and
the southern hemisphere onto the region outside the equator. In order that
only interior points need to be considered) one takes the north pole as the
reference point for projection of the southern hemisphere. Points of the
northern hemisphere are shown as full circles in the projection, and points
of the southern are blank circles (see Figure A.5). It can be shown that the
stereographic projection preserves circles and angles, i.e. circles (including
straight lines as circles of infinite radius) are projected into circles, and the
angles between intersecting tangents of circular segments also remain the
same in the projection. As for the elements of the point group, one can
also represent rotation axes and mirror planes by means of stereographic
projection. Figure A.6 displays the corresponding graphic symbols. A n-
fold rotation axis, for example, is depicted as a small regular n-angle placed
at the projection of the intersection of the axis with the northern hemisphere.
A mirror plane is illustrated by the projection of the arc on which the plane
intersects the northern hemisphere. That the equatorial plane is a mirror
plane may be recognized by the fact that for each full circle one has a blank
circle at the same place. The procedure described here allows a 2-dimensional
illustration of the point groups. The result of the projection is called a
stereogram.
The stereograms may also be used to obtain the product of two group
elements. As an exercise, the reader should try to verify, in this way, the
following helpful relations between generating elements:
u2 . U v = U v .u2 = U h ,
u2. U h = U h . u2 = U V ,
where U2 is the horizontal axis given by the intersection of the two planes
uv and Uh. Analogous relations hold with U d replaced by uv. Furthermore,
one has
Uh.c 2 = c 2 Uh = I ,
' (A.43)
I .Uh Oh ' I =c 2 , c2 ' I = I . c2 = U h ,
I . uv = U V 'I = u2 , u2. I = I . u2 uv.
Here U2 is understood to be orthogonal to uv.
6 42 Appendix A . Group theory for applications in semiconductor physics
cn (4
The simplest point group of the first kind consists of the n powers CA, C$-
. . . , Cg of the rotation C, around a vertical axis. These are rotations
through, respectively, ( 2 ~ / n (2n/n)
), . 2,. . . , (21r/n) . n = 2 ~ The
. rotation
C c is the unit element E. Using the terminology introduced above one may
A.3. Translation, point and space groups 643
U U
briefly say that the group consists of an n-fold rotation axis. Thus the nota-
tion for the group is C, in the Schonflies system, and n in the international
system. The multiplication of two rotations Ck and C i leads to
c,. c i = c y . (A.44)
If k + j is larger than n, one may replace C;+j by C,k+j-.. The product thus
belongs to the set of elements CA, C:, . . .. Table A . l shows the complete
multiplication table of the group CJ. The product in its kth line and Zth
column is the result of the multiplication of the lcth element as left factor
and the lth as right. In the group C, the multiplication order plays no role,
because this group is cyclic and thus also Abelian. Each element forms a
class of conjugate elements by itself. The stereogram of the point group C3
is shown in Figure A.7.
Starting from the point group C , one may set up other point groups of
the first kind by complementing the n-fold rotation axis with new generating
elements, along with the products of these elements among themselves and
with the elements of the original group.
D, (n2, n22)
The group C, is first of all complemented by a horizontal rotation U2. This
may also be expressed by saying that a horizontal 2-fold rotation axis is
added, for the identity element is already contained in C,. However, in this
way no group is yet obtained. The multiplication of the powers C$-, k =
1 , 2 , .. . , n, with U2 produces n - 1 new elements, namely U2k = Ck- . U2
(here Uzl is merely another notation for U2). The set of these elements is
identical to the set of elements U2 . Ck- arising by multiplication with U2
from the left, but the numbering is different. The n elements U2k correspond
to n different 2-fold rotation axes. Each pair of adjacent axes forms an an
angle x/n. For odd n all n rotation axes U2k are symmetrically equivalent to
each other, while for even n they fall into two distinct classes of inequivalent
axes, namely U21, U23, .., U2,-1 for odd 1,and U2, U22, .., U2n-2 for even
644 Appendix A. Group theory for applications in semiconductor physics
a) b)
Figure A.8: Stereograms of the point groups D2(222) (a) and D3(32) (b).
Figure A.9: Rotation symmetry of a tetrahedron (left) and stereogram of the point
group T (23)(right).
We still have to specify the division into classes of conjugate elements for the
point group D,. Applying the first rule for class division derived above one
finds that the n 2-fold rotations form one class for odd n , and two for even
n. The second rule implies that a rotation Ck and its inverse CLk belong
to the same class. These form ( n - 1)/2 classes if n is odd, and n/2 if n
is even. In addition one has the identity element E which forms a class by
itself. Altogether, this yields ( n - 1)/2 + 2 classes for odd n, and n / 2+ 3
classes for even n. The group Dz has the 4 classes E , C2, U21 and U22, i.e.
each element forms a class by itself. The group D3 has 3 classes, namely E ,
the three 2-fold horizontal rotations (U21,U22 , U231, and the %fold vertical
rotations (C3, C:} (here and below elements of the same class are shown in
curly brackets).
T (23)
Another point group of the first kind is the group of all rotations which
transforms a tetrahedron into itself (the full symmetry group of a tetrahedron
also contains rotation-reflections , and is therefore of the second kind). The
rotation axes of a tetrahedron are the four %fold vertical axes C3 through
a corner and the center of the opposite face, and the three vertical axes C2
through the centers of opposite edges (see left-hand part of Figure A.9). We
will not name the axes differently. The international symbol of the group
reads '23', and the Schonflies symbol T . The four %fold axes yield a total
of 8 different rotations, 4 of the form C3, and 4 of the form C:. The three
2-fold axes yield a total of 3 elements of the form Cz. Along with the identity
646 Appendix A . Group theory for applications in semiconductorphysics
element, the group T therefore consists of 12 elements. That the set of these
elements does in fact form a group is most easily verified by means of the
stereogram in Figure A.9. Each of the following sets of elements forms a
class: the 4 rotations C3, the 4 rotations Ci, the 3 rotations C2, and E.
There are, altogether, 4 classes.
0 (432)
The group of all rotations which transform a cube into itself is also a point
group of the first kind (the full symmetry group of a cube is of the second
kind). The group consists of the three 4-fold rotation axes C4 through the
centers of two opposite cube faces, the four %fold vertical axes C3 formed
by the diagonals of the cube, and the six 2-fold axes C2 through the centers
of opposite cube edges. Altogether, this comprises 24 symmetry operations.
They are illustrated in the stereogram of the group in Figure A.lO. The
international symbol of the group is 432, and the Schonflies symbol is 0.
The classes of 0 are the following: all 6 rotations C4 and C: (for the axes
C4 are two-sided), all 3 rotations Cz, all 8 rotations C3 and C i (the C3-axes
are likewise two-sided), and all 6 rotations C2 and E . One therefore has 5
classes. We abbreviate them in the form E , 6C4, 3C2, 8C3, and 6C2, the
symbol for each class being a representative element with the number of
elements in the class positioned in front.
Beside those already mentioned, there is only one other point group of
the first kind, namely the rotation symmetry group Y of a pentagondodec-
ahedron. This refers to a body with twelve faces, each of which forms a
regular pentagon. The group Y , which is also known as the icosahedral
group, contains &fold rotation axes which cannot occur in the symmetry
groups of crystals. Therefore we will not discuss the group Y here further.
A.3. fianslation, point and space groups 647
The simplest point group of the second kind consists of one n-fold rotation-
reflection axis s, of even order n. In the Schonflies system this group is
denoted by S,. It contains rotation-reflections S," with k = 1,2, . . . , n.
Since for even n the relation S," = (Uh . C,)" = E holds, there are no other
elements. For odd n one has S," = Oh, which means that the set of the n
powers Sk, with k = 1,2,. . . ,n does not form a group. Thus, we exclude
odd n.
The group S, is evidently cyclic. Each of its elements forms it own class,
for a total of n classes. The even powers Sk describe rotations through
angles ( 2 ~ k / n )= (27rg/?). Thus the n-fold rotation-reflection axis also
automatically generates a (n/2)-fold ordinary rotation axis. This also means
that the group C,/2 is a subgroup of Sn. For even n not divisible by 4, the
group S , contains the inversion I , namely the element S,"12= (Uh.Cn)n'2 =
a h . C2 = I . The group S 2 consists only of I and the identity element E.
One also denotes S 2 as Ci. Each group S, with even n, not divisible by 4,
can be understood as the direct product C,l2 x Ci of the two groups C,/z
and Ci.
In the international notation system one employs, instead of rotation-
reflections s,, the rotation-inversion s S,i as generating elements. In the
case of even n, the powers Sii with k = 1, 2, . . . , n already form a
group, because then Szi = E holds. For odd n one needs the 2n powers
Ski, k = 1, 2, . . . , 2n, to get a group. In both cases the international
symbol reads 6. If n is odd, the group ii is equal to S2n For even n one
must distinguish between those n which are divisible by 4 and those which
are not. In the former case, we have ii = S,, i.e 4 = S4, 8 = SB etc. In the
latter case the group fi can be generated by a (n/2)-fold rotation axis and
a vertical mirror plane q. The group 2 consists of only this mirror plane,
which implies that it contains only the two elements E and f f h . It is denoted
by C,. Generally, the group + i be written as the direct product C , / 2 x C ,
can
of C,p and C , if n is even and not divisible by 4.
Applying the above results to our original groups S, with even n, we
recognize that they can all be traced back to 6' groups. One has S2 =
T, S 4 = 1,s6 = 3, s8 = 8, Slo = 5, S12 = Tz etc. Some of these point groups
are illustrated by their stereograms in Figure A.ll.
The group C, gives rise to a new group if one adds the reflection O h at the
plane normal to the rotation axis. It contains besides the n elements C,"
648 Appendix A . Group theory for applications in semiconductor physics
@
Figure A.11: Stereograms of the point groups Sz(T) = Ci, S4 (4), s6 (3), and
2 = c,.
a) b)
Figure A.13: Stereograms of the point groups C3,(3m) (a) and C4v(4mrn) (b)
direct product C, x Ci of the groups C, and Ci. For odd n, Cnh is equal
toz, as shown in the previous subsection. In any case, the group Cnh is
Abelian. Each element forms a class by itself, thus there are 2n classes. The
stereogram of the group C3h is shown in Figure A.12 as an example.
a)
i-_)@
0
b)
The division into classes of D , corresponds to that of C,. This means that
+ + +
C,,, like D,, has 1 (n 1)/2 classes if n is odd, and 3 n/2 classes if n
is even.
Dnh (---,
n 2 2 2nm2)
-
mmm
In this case the group Cnh is complemented by the n 2-fold horizontal axes U2
of D,. Multiplying the 2-fold rotations with Th, one automatically obtains
n normal mirror planes, each of which cuts the horizontal plane f f h of Cnh
along one of the n 2-fold rotation axes. This yields 4n elements altogether.
The group can be interpreted as the symmetry group of a straight prism
upon a regular wangle. The Schonflies symbol reads Dnh. For odd n the
identity = 5 holds. This gives rise to the international symbol z 2 m
in this case. For even n , no uniform relation exists between the subgroup
-n and an rotation-inversion axis. Instead, in this case each mirror plane
m
is normal to one of the 2-fold axes. This leads to the international symbol
$26. Among the subgroups of Dnh are, in each case, the two groups D ,
and C,. Their direct product D , x C, is the full group Dnh. For even n,
D,h contains the inversion. Then the group may also be written as the
direct product Dn x Ci of the two groups D , and Ci. Figure A.14 shows the
stereograms of D2h and D3h.
The division of D,h into classes may easily be obtained from that of D,.
Each class of D , is also a class of Dnh. In addition one has the classes which
emerge from those of D , by multiplying them with f f hor, in the case of even
+ +
n , also with I . This yields n 3 classes if n is odd, and n 6 if n is even.
A.3. Tkanslation, point and space groups 65 1
a) b)
Figure A.15: Stereograms of the point groups D&2m) (a), and D3d(3$) (b).
7
are therefore isomorphic. Knowing this, the classes of Dnd may be obtained
directly from those of D2n. According to what we found earlier, the number
+ +
of classes of D2,, amounts to 2n/2 3 = n 3, whether n is even or odd.
+
The corresponding n 3 classes of D d are E , the n classes {Szn,'"-S,: }, {
sin,s::-'}>,. . . , { SF;', ST$+' 1, { ~ 2 of~powers
) of rotation-reflections
around the two-sided rotation-reflection axis Szn, the class of the n 2-fold
rotations U2, and the class of the n reflections uv.
The group Th may be obtained from the group T of all symmetry rotations
of a tetrahedron by adding the inversion I . The group is therefore the direct
product T x Ci, and contains 24 elements. Besides the inversion these are
the following: In forming the product of the three 2-fold axes C2 with I
one obtains three mirror planes uh perpendicular to these axes. Each of
the four %fold rotation axes gives rise to a 6-fold rotation-reflection axis
sf3 = 3, which means eight new group elements. In Figure A.16 we show
the stereogram of the group. Its international symbol is $3. The classes of
Th follow from those of T : each of the 4 classes of T is also a class of Th, and
in addition there are 4 further classes obtained by multiplying the former by
I . The group T h then has 8 classes altogether.
The full symmetry group Oh of a cube may be obtained from the symmetry
group 0 of its rotations by adding the inversion I . Therefore Oh = 0 x Ci.
The 24 new elements include, beside the inversion, the reflections at the
six planes Ud normal to the six 2-fold rotation axes of 0, and the three
mirror planes Uh normal to the three 4-fold rotation axes of 0. The or&-
6 54 Appendix A. Group theory for applications in semiconductor physics
nary rotation axes become rotation-inversion axes, i.e. one has four %fold
rotation-inversion axes 3 in the direction of the %fold ordinary axes of 0,
and three 4-fold rotation-inversion axes in the direction of the 4-fold ordi-
nary rotation axes of 0. The four %fold rotation-inversion axes lead to 8
new elements, and the three 4-fold ones to 6 . The 48 elements of O h are
depicted in the stereograms of the group in Figure A.18. The international
symbol of o h is $3$ (abbreviated as m3m).
The six planes Uh of O h may be interpreted as 6 planes uv which contain
the three 4-fold axes C4. If one observes that each rotation-inversion axis 4
is nothing but a 4fold rotation-reflection axis S 4 , then it becomes evident
how those elements of T d arise in o h , which are not already contained in 0
(these are the four %fold rotation axes and the even-numbered powers S t
of 5'4). From this one may conclude that, with 0, T d is also a subgroup of
o h . Since T d does not contain the inversion, one may understand O h as the
direct product T d x I of T d with I .
The classes of o h may be derived either from those of 0 or those of T d .
The 5 classes E , 6C4,3C;, 8C3 and 6C2 of 0 are complemented by the classes
I , 6 1 . C 4 , 3 I . C:, 8 1 . C3 and 6 I . (32 = Oh. If one refers t o T d , one has first of
all the 5 classes E , 6 S 4 = 6 I . C4,3C,2,8C3 and 6u,, which, by multiplication
with I , then yield the 5 missing classes I , 6 1 . S4 = 6 C 4 , 3 I . C:, 8 1 , C3 and
6 1 . uv = 6C2.
A further point group is the full symmetry group Y h of a pentagondodec-
ahedron. It follows from the icosahedral group Y by adding the inversion.
For the description of the symmetries of crystals, Y h is of as little importance
as Y .
It may be proven that the set of the possible point groups is exhausted
by the above list.
holds which means that the product is again a rigid displacement. The
crystal will transform into itself under the action of the product g1 . 92,if
it does under the factors g1 and 92 separately. Thus g1 . 92 belongs to the
set G . The other group properties can also be similarly verified using the
product (A.45). The group G represents the spatial symmetry group of a
crystal. If one imagines the crystal as the composite of several superimposed
A.4. Representations of groups 655
lattices of the same Bravais type, then it becomes evident that the lattice
translation group must be a subgroup of the space group.
Theorem 2 of subsection 2.1, wherein each rigid displacement is either a
screw rotation, a glide reflection or a product thereof, is important for the
construction of the space groups. It means that the generating elements of
these groups are screw rotations and glide reflections. Lattice translations
and orthogonal transformations belong to them as special cases. How space
groups may be set up from these elements is explained in the main text.
A.4.1 Introduction
9C
pW = (P(g-lx) (A.46)
a h e a r operator j in R d is uniquely assigned to each element g of G . we
will show that the operator 91.92 which according to equation (A.46) cor-
responds to the product g1 . g2 of two group elements g1 and 92,is equal to
the product of the two operators gl and 92, i.e. that the relation
91 ' 92 = Sl . 9 2 (A.47)
is valid. To this end we form ='p(x). By definition we have
656 Appendix A . Group theory for applications in semiconductorphysics
(8.48)
Applying the operator g1 to 92 p(x) = Cp(gF1x), the relation
(A.49)
follows. Comparison of equations (A.48) and (A.49) immediately yields
equation (A.47). This equation means that the linear operators g defined by
equation (A.46) form a group G.
The unique assignment of the original group G to a group G of linear
operators in a certain space Rd, is called a representation of the group G in
Rd. Applying the concept of homomorphy introduced in section 1, one may
also say that a representation of a group G is a homomorphic assignment of
G to a group of h e a r operators in a space Ed. As a general symbol for a
representation we choose D. The space R d is called the representation space.
The dimension d of the space is referred to as the dimension of the represen-
t a t i o n Not every subspace of the Hilbert space R can be a representation
space, although the multiplication rule (A.47) holds everywhere in R. In
order that a subspace Rd have this property, it must contain no vectors p ( x )
such that ~p(9-l~) ( g being any group element) does not also belong to Rd.
The statement that a particular subspace Rd forms a representation space
of a group G is therefore not trivial.
A formal difficulty for the representations of the displacement groups
under consideration, more strictly speaking, for the translation and space
groups, lies in their being infinite groups, i.e. their having infinitely many
different elements. The representations of infinite groups are more difficult
to treat than those of finite groups. Because of this we will focus our consid-
erations on finite translation and space groups. This may be done by means
of the the periodicity region concept introduced in Chapter 2 (the physical
meaning of this concept was also explained there). Instead of the Hilbert
space of arbitrary one-electron quantum states p(x), one uses that of states
being periodic with respect to the periodicity region. Then
(A.50)
holds for arbitrary integers n1, n2, ng. With respect to these states the
translations t R and tnlGlal+nzG2a2+n3G3a3are represented by the same op-
erator ifi. Thus, as long as one deals with representations in the Hilbert
space of functions obeying the periodicity condition (A.50), one can render
the translation and space groups finite by considering only translations t R
through lattice vectors R belonging to the same periodicity region. The
thusly reduced translation group T contains only G3 different elements, as
many as there are different primitive unit cells in the periodicity region.
A.4. Representations of groups 657
Theorem 1
(A.51)
holds. That these relations are in fact valid for the operators ij defined by
equation (A.46), may be shown as follows. We form the scalar product
(A.52)
of two arbitrary vectors cpl(x) and cp2(x) of Hilbert space R obeying the
periodicity condition (A.50), where the integral is taken over a periodicity
region. The integration variable x in (A.52) is then replaced by g-lx. Since
a rigid displacement does not change the volume element, we find
(A.53)
Representation matrices
(A.55)
(A.57)
(A.58)
Each group allows for several more or less obvious representations. One of
them is the so-called identity representation.
Identity representation
Every group element is associated with the identity operator or the identity
matrix, in this representation space. The 1-dimensional identity representa-
tion can be constructed as follows: One considers an arbitrary vector p(x) of
Hilbert space, and forms the new vector cgl p(g'-'x), where the summation
runs over all elements of the group G . This vector is then a 1-dimensional
representation space of G, and the representation in it is the identity repre
sentation. To prove this statement we apply an arbitrary element g of the
group to Cgl p(g'-'x). In this, the sum reproduces itself because g'-lg-l
runs through all group elements if g varies over the entire group. Thus we
may write
(A.61)
= [D(g)l*.
D*(!?) (A.63)
A representations is called real if its matrices are real, i.e. if
(A.64)
-
Conjugate representation D
= [D(g-l)lT. (A.65)
One can easily demonstrate that the matrices b ( g ) form actually a repre-
sentation if the matrices D(g)do so. In the case of a unitary representation,
the conjugate representation equals the complex conjugate representation
because
(A.66)
Equivalent representations
jM - M . j . M-1. (A.67)
The group property of G M follows directly from that of the original operator
group G. The associated matrices DM(g)of the equivalent representation
read
In the above definition of a group representation we did not exclude the pos-
sibility that the representation space R d contain several genuine subspaces
which are also representation spaces. If this is the case, the representation
space is called reducible and the representation of the group in it is called a
reducible representation. If the representation space does not contain such
genuine subspaces, which are also representation spaces, one calls it irre-
ducible. The representation of a group in an irreducible space is called an
irreducible representation. The following important theorem can be proved:
Theorem 2
\ ..... 1
One says that the matrices D ( 9 ) are block-diagonalized. The block-diagonal
form is thereby the same for all g , i.e. the matrices D,(g), Dvt(g), D,,i(g), . . .,
for all group elements are, respectively, situated at the same positions on the
main diagonal, and have, respectively, the same dimensions.
An irreducible representation V, exists for a subspace R, of Hilbert
space such that, firstly, every g maps R , into R, (which means that R,
indeed forms a representation space) and secondly that there is no yet smaller
nontrivial subspace of R , with this property. We already know a special 1-
dimensional irreducible representation, namely the 1-dimensional identity
representation. From this we conclude that each group has at least one
irreducible representation. In general there may be several.
That the degenerate eigenfunctions of a particular one-electron Hamilto-
nian having the same energy eigenvalue form a representation space of the
full symmetry group of the Hamiltonian, was already stated in theorem 1.
If the energy eigenvalues are degenerate only because of spatial symmetry,
i.e. if no accidental degeneracy exists due to the particular values of the
potential or to time reversal symmetry, then it is possible to make an even
stronger statement:
Theorem 1'
The subspace of eigenfunctiom of a given Hamiltonian having the same en-
ergy eigenvalue is a representation space for an irreducible representation of
the f i l l spatial symmetry group of the Hamiltonian
A.4. Representations of groups 663
We will now discuss important relations which hold for matrices of irreducible
representations.
Orthogonality relations
(A.70)
The factor 1/N with N being the number of elements of G is added for
reasons of normalization. Orthogonality in the sense of this scalar product
has the usual meaning (6 1 y ) = 0. With this definition, we have the following
theorem:
Theorem 3
The matrix elements Drk(g) and Dt",(g) of two inequivalent unitary irre-
ducible representations are orthogonal functions over the group, i.e. they
obey the relation
(A.71)
If the two representations Dp and V" are equivalent, then the matrix ele-
ments D & ( g ) and D z k , ( g ) are orthonormal functions, such that
1
(DCk, I DU) - - 6ij~6kkf,
-d,
(A.72)
(A.73)
follows.
Important instruments for investigation of the properties of representa-
tions are their characters. These will be treated now.
664 Appendix A. Group theory for applications in semiconductor physics
Characters of representations
(A.74)
has the property that it does not change under a unitary transformation of
the basis with a given matrix U . This is clear if we recall that the matrix
D in the new basis is given by U-IDU and that under the trace symbol
'Tr' the factors of a product of two matrices can be interchanged. We have,
therefore, TrIUDU-l] = T r ( U - l U D ] = T r [ D ] . This property gives rise to
the definition of the character of a representation in the following way. By
means of the relation
(A.75)
each element g is assigned a particular complex number X,(g). This number
is called the character of the element in the representation D,. The totality
of the character values X,(g) for the various elements g of a group constitute
the character X , of the representation One can thus say that the character
is a complex scalar function defined on the group. The character of the d-
dimensional identity representation has the constant value d over the whole
group.
Two different elements g' and g", which are conjugate to each other in
the sense of section A. 1, i.e. such that there is an element g of the group for
which gN = gg'g-' holds, have the same character X,(g') = X,(g"). This
follows, again, because of the commutativity of the operators under the trace
symbol. One can also say that the character function X,(g) has a uniform
value for each class of conjugate elements. The values change only in passing
between different classes.
In subsection A.4.1, starting from a given representation, a series of other
representations was constructed, among them the complex conjugate repre-
sentation, the conjugate representation and the equivalent ones. The char-
acters of these representations bear well defined relationships to those of the
original representation. For the character X v * ( 9 ) of the complex conjugate
representation D: of a given representation D, one obtains
(A.76)
Real representations have real characters. From the reality of the character
one cannot, however, deduce the reality of the representation, since complex
representations can also have real characters.
A.4. Representations of groups 665
(A.77)
Theorem 4
It follows that finite groups can have only a finite number of inequivalent
irreducible representations. In all cases, one of them is the 1-dimensional
identity representation.
Theorem 5
Ed: = N . (A.80)
U
Theorem 6
Using theorems 4, 5 and 6, and considering the fact that among the irre-
ducible representations there is always a 1-dimensional representation (namely
the identity representation), one often can determine the dimensions of the
irreducible representations of a group without knowing the representation
matrices themselves. The group &d, for example, has 8 elements and 5
classes. There is only one way to obtain the group order 8 by adding 5
+ + +
squares, namely by taking four squares of 1 (12 l2 l2 l2= 4),and one
of 2 (22 = 4). This means that the group D w has four 1-dimensional and
one 2-dimensional irreducible representations. For an Abelian group Burn-
side's theorem immediately implies that only 1-dimensional representations
are allowed for in such a groups each element forms its own class, so that
the number of classes equals the number N of group elements. Because of
(A.80) then all d , must then be 1.
Theorem 7
(A.82)
(A.83)
This relation provides a simple procedure for determining if and how often
a particular irreducible representation V, occurs in a supposedly reducible
representation 2). The reduction of V into VU1smay be written in the
symbolic form
= Cm,D,. (A.85)
V
g p ( x ) . p,(x) = p ( g - 1 x ) p y g - l x ) (A.87)
The direct product representation is therefore independent of the ordering
of the factors, i.e. we have
D,xV,=V,x~,. (A.88)
The matrices D P X u ( g )of the direct product representation V, x D, can
be easily calculated from the matrices D p ( g ) and D ( g ) of the two fac-
tors. To this end we introduce a basis in the product space. Let the vectors
p y ( x ) ,p g ( x ) ,. . ., p$@(x)
be a basis in R,, and the vectors pi(x),p ? ( x ) ,. . .,
p z p ( x )are a basis in R,. As a basis of R , x R,,we therefore have the prod-
ucts pf(x) . p;E(x) with 1 = 1,2,. . . ,d , and k = 1 , 2 , . . . ,d,. By definition,
or
Theorem 8
Theorem 9
The product space R u x , can always be decomposed in this case into two
representation subspaces R t x u and R;,,, where RExu is spanned by the
symmetrical combinations (l/a)[Cp;(x) . $(XI) +
$(x) . (p;(x)] of the
products of basis functions, and RExu by the antisymmetric combinations
(l/&)($(x). cpi(x)- (pi(x) . &(x)]. The dimension of REx, is given by
d(d f 1)/2, and that of RExu by d(d - 1)/2. The representation [V,x V,I8
of the group G in RExu is called symmetric product and the representation
[V,x V,],in RExu is the antisymmetric product. For the matrices DL:Jc(g)
of [Vvx V,],we find from (A.89) and (A.90),
(A.95)
(A.96)
(A.97)
(A.98)
670 Appendix A. Group theory for applications in semiconductor physics
A. (A.100)
(A.lO1)
k'
(A.102)
This means that the matrix elements (&&l(Pr) transform according to the
direct product representation 23; x V Ax D,. Summing over all elements g ,
we obtain from (A.103) the relation
(A.104)
If the identity representation does not occur among the irreducible parts
of the direct product representation V; x DA x D,, then the sum over g
vanishes according to relation (A.73). In this case, one correspondingly has
i.e. all matrix elements ($7kl&(pfl) vanish for symmetry reasons. If the
identity representation is contained in the direct product representation 21: x
DA x D p , the sum over g in (A.104) does not vanish and the matrix elements
($&1&1$7r) can be non-zero. Nevertheless, they may vanish for reasons
unrelated to spatial symmetry.
If some of the elements ( & [ A k l p r ) do not vanish by reason of symmetry,
questions remain open as to which of the elements are non-zero and what
symmetry-induced relations exist between them, in other words, how many
independent non-zero matrix element exist. We now proceed to discuss this
question. To this end we start with equation (A.103) and rewrite it using
the representation matrices
(A.106)
pxAxu
($7hI A k I $7); = Dmklmkl(g)($7& I AkIpF). (A.107)
lmk
(A.109)
Because of the orthogonality relation (A.73), the g - s u m results in a non-zero
value only for i such that Vx(i)is the identity representation. We assume
that this occurs in the matrices DLlKtLiMKL ( 9 ) for i = 1 , 2 , .. . ml. For
these values of i, the DL,,,,,,,,(g) are diagonal matrices with only one
non-vanishing element. The one non-zero element has the value 1. We denote
the position M'K'L' = M K L of this element by MiKiLi. Then equation
(A.109) may be written as
Theorem 10
holds in the case of infinite groups at all. We shall see below that there
is in fact an infinite number of inequivalent irreducible representations of
the rotation group, so that the formal application of theorem 4 is justified.
Generally, one ought to use care in transferring results for finite groups to
infinite ones. Luckily, it turns out that the construction of the irreducible
representations of the rotation group (being the aim of this section) does not
require the theorems derived above.
O n e of the irreducible representations of the full rotation group we know
already, namely that in the 3-dimensional vector space, which is called the
vector representation The corresponding representation matrices follow
from the matrix A of equation (A.31), if the Eulerian angles are allowed
to take all real values. The matrix A represents rotations in a special ba-
sis, namely that of the Cartesian coordinate system before the rotation. As
we will see, there exists in each representation space, also including that of
dimension 3, exactly one (inequivalent) irreducible representation. Each 3-
dimensional irreducible representation may, therefore, be obtained from the
matrix A of equation (A.31) by a unitary transformation. The reason that
we will once again deal with the 3-dimensional vector representation is that
this representation is suitable for introducing a concept which is of impor-
tance for irreducible representations of any dimension, namely the concept
of generators of infinitesimal rotations.
(A.111)
(A. 112)
0 0 i 0 -i 0
I, = 0 0 -i , Ip= 0 0 0
O i 0 -i 0 0 0 0 0
113)
The exponential function in (A.112) is to be understood in the sense of a
power series expansion with respect to -i(I. n)p. In the following we sketch
the proof of assertions (A.lll) and (A.112).
Initially, we consider a rotation about the z-axis through the infinitesimal
angle dp. The coordinates after rotation, obtained using the matrix A of
+
(A.31), are given by 2 = 2,y = y - zdq,, z = z ydp,. In matrix form
these equations read
(A.114)
with
D(ex,dp,) = E - iIxdvz, (A. 115)
and with E the 3-dimensional identity matrix. Analogous relations hold for
infinitesimal rotations with respect to the y- and z-axes. If the three in-
finitesimal rotations are executed one after another, then this corresponds,
apart from higher order corrections, to a rotation about an axis in the direc-
tion of the vector d$ = e,dp,+eydpy+e,dp, . With n as unit vector in the
+
direction of d$, d p as the absolute value of d$, and I = Izex Igey Izez, +
the result of the rotation can be written as
(A. 116)
with
D(n, d p ) = E - i ( I . n)dp. (A. 117)
Now consider a rotation through the finite angle cp with respect to the same
rotation axis n. The pertinent rotation matrix is D(n,p). After this ro-
tation we apply the infinitesimal rotation (A.117). The total rotation is
+
described by the matrix D(n, p dp). Because of the group property of the
representation matrices, we have
676 Appendix A . Group theory for applications in semiconductor physics
On the other hand, expanding D(n, cp+dcp) with respect to the infinitesimal
angle dcp, we obtain
(A.119)
d
-D(n, cp) = - i ( I . n)D(n, p), (A. 120)
dcp
This differential equation is to be solved with the initial condition D(n, 0) =
E. The result is just expression (A.112) for D(n, cp).
d d d
I , = i--D(ez, cp)lrP=0, Iy= i-D(eY, cp)lrPP=o,I , = i-D(e,, cp)lrP=o.
dcp dP dcp
(A.121)
These relations may be understood as the defining equations of the gen-
erators matrices. As such, they may also be applied to representations of
dimensions other than 3. With this in view we shall consider D(n, cp), and
I%,Iy,Iz as matrices of any dimension henceforth. With a knowledge of the
generator matrices for dimension d, one can then determine the rotation
matrices of a d-dimensional irreducible representation by means of equa-
tion (A. 112). In this way, the construction of the irreducible representations
of the rotation group is traced back to the determination of the generator
matrices. To accomplish the latter task, the commutation relations among
the matrices are of great value. In the 3-dimensional case the explicit form
(A.113) of the matrices I,, Iy, I, may be employed to show that
which dimensions are allowed for the irreducible representations, and how
many inequivalent representations exist for a given dimension.
Consider an irreducible representation 2) of the rotation group GR in a
d-dimensional space Ed. Being a representation space of GR, Rd will also
simultaneously be a representation space of the subgroup G , of all rotations
about the z-axis. Due to the Abelian type of G,, its representations are
1-dimensional. Thus, D considered as a representation of G,, falls into a
series of 1-dimensional representations. Let the corresponding basis vectors
be b l , b2, . . . , bd. we will relate the rotation matrices D of the representation
D to them in the following. For a rotation through an angle cp with respect
to the z-axis. we have
(A.129)
678 Appendix A . Group theory for applications in semiconductor physics
with E as the identity matrix in Rd. To prove this relation, one first verifies
the equation
I+ej = 0 (A.130)
arguing indirectly: If the vector I+ej were to be non-zero, then it would
be an eigenvector of I , having eigenvalue j +1. We have already assumed,
however, that j is the largest eigenvalue of Iz in R d . On the basis of this
contradiction, the assumption that relation (A. 130) does not hold must be
rejected.
Using this result, one first proves equation (A.129) for m = j , by express-
ing Ix and I, in terms of I+ and I-. To do the proof for arbitrary values
+ +
of m , equation (A.126) and the commutativity of I," I; I,"with I- are
sufficient.
Equation (A.129) makes it possible to calculate the effect of I+ on the
basis vectors em with m # j . To this end, one replaces em in terms of
I-e,+l. +
For I+I-, the relation I+I- = I 2 I, - I,"may be employed, with
the result
im = N m I-6,+1 (A.134)
with
1
Nm = (A.135)
J(j + m + l)(j- m )
as normalization factor. The elements of the matrices I+,I - and I, in the
normalized basis become
3 - m ) ! ( j+ m')!
X
(im 1 D j l i m t ) * = 1D j l L m t ) .
(- 1)m-ml (kLm (A.140)
To calculate the character X j ( g ) of a representation Dj it suffices to consider
a rotation about the z-axis, i.e. to set 6 and to zero. Rotations g with all
$J
other values of 6 and space $, but the same value of cp, belong to the same
class and thus have the same character X j ( g ) . Therefore
(A.141)
vj x vjt = c n.
j+jt
I= ( j - j l I
(A.142)
It is also worth mentioning that the generator matrices give rise to an irre-
ducible representation of the rotation group in yet another sense than that
discussed before: they are themselves the basis vectors of a representation.
The dimension of this representation is 3, i.e. the generator matrices trans-
form according to the vector representation of the rotation group. If one adds
inversion to this group, the result is the pseudovector representation. The
reason for this is that the sign of the generator matrices cannot change under
an inversion because of the commutation relations (A. 121). The transforma-
tion of the generator matrices as pseudovectors is employed in the invariant
method for construction of the k.p-Hamiltonian (see section 2.7). For that
purpose, the explicit form of these matrices is needed. By means of formu-
lae (A.136) and (A.137), one obtains, in the 2-dimensional case, the Pauli
spin-matrices multiplied by 1/2. For d = 3, it follows that
A.5. Representations of the full rotation group 68 1
(A.143)
( 0 0 -1
and for d = 4 the result is
0 id3 0
Id3
2 0 1
( 8 , 11, I &d)=
0 1 0
0 0 $d3
0 -$& 0
id3 0 -i
0 i o
0 0 id3
% o 0
0 ; 0
(A.144)
0 0 -4
0 0 0 - 32
(A'. 145)
The basis vectors -2 1 , - 2 - ~ which transform according to this representation,
5 2
are referred to as two-component spinors. We abbreviate them by Ii), i).
I-
In quantum mechanics, the states cp of electrons are described by just such
spinors with the two components (slcp) cp(s), s = i,
-$, corresponding to
the two possible spin states. The two spinor components are themselves vec-
tors in ordinary Hilbert space R having components (xlcp(s))z p(x,s) with
respect to the position vector x. For the quantum mechanical description of
electrons, the representations of the group of rigid displacements G in the
Hilbert space R of the two-component position dependent spinor functions
cp(x) are of central importance (the notation R should not be mixed with
that for a lattice vector). By definition, these representations imply that the
elements g of the displacement group G are uniquely assigned to a group of
linear operators g in the spinor Hilbert space R.Therefore, we must have
g1 . g2 = g 1 . g2. (A.146)
We now proceed to construct this assignment explicitly. To this end, we set
restricted to point and space groups. Using the basis I s) in spin space,
relation (A.147) can be written in the form
(A.149)
S
A.6.2 Representation D+
The two Euler angles cp and $ both vary between 0 and 2n. The ro-
+ +
tations a[cp 2a,8,$] and a[cp,8, $.J 2n] are identical with the rotation
a[cp,O,$]. Strangely enough this does not also hold for the pertinent ma-
+ +
trices D g ( a [ p 2n,8, $]) and D;(a[cp, 8, $ 2n]) from relation (A.145).
Both equal -Dr(a[cp, 8, $1). As long as one considers only single rotations
2
a [ p ,8, $1 this does not cause any difficulty because one can always restrict cp
and $ to the interval between 0 and 2n, and assign + D i ( a ) to the rotation
3
a. Difficulties arise, however, if two rotations a1 and a 2 are multiplied. Then
it may happen that one of the two angles (o12 or $12 of the product a1 . a 2
takes a value larger than 2n. In this case, the representation (A.145) assigns
the matrix - D ~ ( a 1. a 2 ) to a 1 . a 2 . As it is itself an element as well, a1 . a 2
2
has, however, already been assigned the matrix + D l ( a l . 4 ,which cannot
be changed because the assignment in a representation must be unique. The
only resolution of this difficulty is to allow the multiplication rule for the
two representation matrices D l ( a l ) , D i ( a 2 ) to differ from that of the two
group elements a 1 and a 2 by a minus sign. More precisely, the sign in this
rule must be allowed to depend on the particular combination of the two
elements a1 and a2. It must be a function w(a1, a 2 ) of a 1 and a 2 , with two
possible function values +1 and - 1. The corresponding multiplication rule
reads
684 Appendix A . Group theory for applications in semiconductor physics
for all cu1, a 2 which is not the case here. In fact, assignments of matrices to
group elements obeying the multiplication rule (A. 151) are representations
in a generalized sense, that of so called spinor representations. They form
a special case of projective representations or representations with factor
systems which will be considered below in greater detail.
For the complete determination of the representations of point and space
groups in spinor space we still need the matrix D i ( I ) for the inversion I . In
determining it one can take advantage of the fact?that I commutes with all
elements g of the space group. Therefore D i ( I ) must also commute with all
D i ( g ) . It follows from a theorem of group theory (known as Schurs l e m m a )
2
that D i ( I ) must then be a multiple of the identity matrix 1. Because of
I
[ D I J I ) ]=~ 1, only the identity matrix itself or its negative are allowed. The
two assignments
D.(I) = +1 or D l ( 1 ) = -1 (A.152)
I
give rise to two inequivalent irreducible representations of point and space
groups containing the inversion.
(A.153)
686 Appendix A . Group theory for applications in semiconductor physics
Theorem 11
order n is twesided (see section A.2), the elements Ck and CE-k = Q . Cqk
belong to the same class, and so do the elements Q . Ck and CGk, however,
the two classes are different. If an n-fold rotation axis is not two-sided, then
C;, C i k ,Q . Ck and Q . CLk form four different classes. For n = 2 the two
elements C2 and C,' of the simple group G are identical, but in the double
group G t they differ for it holds C; = Q which results in C2 = Q . C,' and
C', = Q . C2. The two elements C2 and C,' 3 Q . C2 form one class if
and only if the 2-fold axis is two-sided. An analogous statement holds for
reflections uh. In this case uh and Q . uh belong to one class if the 2-fold
rotation axis C2, associated with ah by the relation uh = I ' C2, is two-sided.
Similarly, u,, and Q . cr, are in one class if the rotation axis U2, associated
with u, by the relation u,,= I . U2, is two-sided.
We illustrate the above results using the tetrahedral group Td as an exam-
ple. In section A.3 we found 5 classes of the simple group T d : E , 8C3,6S4,3C;
and 60,. From them the following classes of the double group T d are obtained
by means of the rules mentioned above: ( E } , {Q}, {4C3,4Q . Cj}, (4Q .
C3,4C$}, {3C4,3Q.C,3},{3Q.C4,3c,3}, {3c,2,3Q.C,2}, { 6 u v 7 6 Q . ~ v }The
.
48 elements of the double group Ti belong therefore to 8 different classes.
Since the number of classes equals the number of different irreducible rep-
resentations, and since the simple group T d has 5 classes, there must be 3
irreducible spinor representations of the group T d . The sum of squares of
the dimension of these representations must be 24. There is only one way to
obtain the number 24 by summing three squares, namely 2' + +2' 4' = 24.
Thus two of the three spinor representations of Td have the dimension 2, and
one has the dimension 4.
The spinor representations of point and space groups were characterized
above as projective representations with a particular factor system. Later,
we will see that projective representations will also occur in another context,
namely the ordinary vector representations of space groups. These represen-
tations may be traced back to the projective representations of point groups
of equivalent directions with a particular factor system determined by the
crystal structure. This demonstrates that projective representations play
an important role in the applications of group theory in solid state physics.
In the following subsection, we discuss properties of these representations
which will be of use later.
The set of factors w(g1, 92) is called the factor system of the representation.
The assignment of G to the operator group G defined by the multiplication
rules (A.154) is referred to as a projective representation or representation
with factor system.
The factors w(gI,g2) are restricted by the group properties of the oper-
ator group G. The associative property results in the condition
(A.15 7)
A. 7. Projective representations 689
(A.158)
(A.159)
Unitary equivalence
avoid confusion with the term p-equivalence, one speaks of unitary equiv-
alence rather than just of equivalence, as we did in the case of ordinary
representations.
Reducibility a n d irreducibility
Characters
X(g) = 4 7 ) x ( g ) . (A ,160)
may show that the representations for factor system classes different from
the identity class must be 2- or higher dimensional. That this rule works
may be seen from the irreducible representations of the group T d considered
in the section on spinor representations. This group has two classes of factor
systems and, therefore, one set of non-ordinary representations. These are
the spinor representations of T d , and none of them is 1-dimensional.
Orthogonality
The orthogonality relations (A.71), (A.72) and (A.81) for the matrix el-
ements and characters of ordinary irreducible representations also remain
valid for projective irreducible representations with the same factor system.
Matrix elements and characters of irreducible representations with differ-
ent factor systems are always orthogonal to each other. Owing to these
properties of the characters, the same procedure for the decomposition of a
projective representation into irreducible parts can be applied as that used
for ordinary representations, namely, in accordance with equation (A.83),
the projection of the character of the representation onto the characters of
the irreducible representations. Being a consequence of the orthogonality
relations, Burnsides theorem holds also for projective representations:
Burnside theorem
The sum of the squares of the dimensions of all unitarily inequivalent irre-
ducible projective representations of a group having the same factor system
equals the order of the group.
Direct product
which are multiplied. A particular consequence of this rule is that the factor
system of the product of two spinor representations for which the factors
are either 1 or -1, equals the identity system. This confirms our former
conclusion that the product of two spinor representations forms an ordinary
or vector representation.
The consequences of spatial symmetry for the matrix elements of opera-
tors as expressed in theorem 10 are also valid if the wavefunctions transform
according to projective and, in particular, to spinor representations.
Finally, we sketch how irreducible projective representations may be con-
st ruct ed.
time inversion i.e. the transition from t to -t. The latter transformation is
commonly referred to as t i m e reversal, and is denoted by the symbol K .
If there is a magnetic field, one also has to reverse its direction in order that
lp* satisfy the Schrodinger equation.
In order that the Pauli equation remain valid under time reversal, the
operation K must be represented by an operator K in spinor Hilbert space
defined by
being the y-component of Paulis spin matrices. One can easily show that
for spinors the relation (klp I lp) = 0 holds, i.e. Klp is orthogonal to lp. If
lp is an eigenstate of the Pauli Hamiltonian for a given energy, and if there
is no magnetic field, then Klp forms a second linearly independent eigen-
state for this energy. That means that, because of time reversal symmetry,
all eigenvalues of the Pauli equation are at least doubly degenerate in the
absence of a magnetic field.
Without spin it is evident that K 2 = E , and K 2 = -E with spin.
This implies that without spin the unit element E and the time reversal
operation K form a group, while with spin the elements E , K , K 2 and K 3
do so. We denote both groups by 2 . Since K commutes with all elements
of the group G, the direct product G x 2 of G and Z is itself also a group.
We call it the space-time g r o u p and denote it by 6 . We are interested in the
694 Appendix A. Group theory for applications in semiconductor physics
K~ in case a)
1
- c
gEG
X(g2)= 0 in case b) (A.163)
- K ~ in case c),
other, the values +1 or -1, so that the product K K will ~ be either +1 or -1.
The matrices (I?& I Ak(t) I pr) and (pg I A k ( t ) I Kpr) are thus either
symmetric (nX2 = +1) or antisymmetric ( & K 2= -1) with respect to the
exchange of the pairs of indices p m and vl. How the number of independent
matrix elements follows from this observation in the general case is shown
in the book by Bir and Pikus (1974).
In the special case p = v , one can apply the procedure developed in
section A.4.3 for the determination of independent matrix elements without
taking account of time reversal symmetry, provided one makes a distinction
between symmetric products [D,x D,],and antisymmetric products [D,x
D,Ia, as defined in section A.4.3. The matrix elements (Rp; 1 A k ( t ) I p?)
transform themselves according to the representation [a,x v,]~ x Dd, if
nK2 = +1, and according to the representation [D,x V,Ia x V A ,if K K =~
-1. Following section A.4.3 the matrix (zpk I A ( t ) I (or)then has as many
independent elements as the number of times the identity representation
occurs in the product representation [V,x D,],x V A for K K =~ +l, or
in the product representation [D,x V,la x D A for r;K2 = -1. Analogous
statements hold for the matrix (p; I A&) I kp?), where V, is to be
replaced by VE.
-ik.R
ck(R) = e (A. 168)
as was demonstrated in Chapter 2 of the main text. In this, k i s a vector in
a vector space reciprocal to the space of position vectors x . We have
(A.170)
The basis functions (pk(x) may be thought of as Bloch functions, i.e. as
plane waves modulated by a lattice periodic factor u ~ ( x ) ,
(A.171)
Bloch functions (pk(x)of the same wavevector k, but different Bloch factors
Uk(x), give rise to the same representation of the translation group. As long
as one considers only the translation group, no relations exist between the
Bloch factors of the basis functions p k for different values of k - any Bloch
function can be used for a given k. Below, starting from an arbitrarily chosen
(but later h e d ) Bloch function ( p k ( x ) of wavevector k,we will construct basis
functions for an irreducible representation of the space group G. It turns
out that basis functions cpk,(x) will emerge in this process which transform
themselves according to irreducible representations of the translation group
with wavevectors k' # k. The Bloch factors up(x) of the basis functions
700 Appendix A . Group theory for applications in semiconductor physics
each star point kj, there is an associated basis function (Pg. We define the
latter by the relation
(A.174)
For the Bloch factor Uki(x) of ' p k j ( x ) , one then has
One can easily show that the space R { k } spanned by the p functions ' p k j ( x )
of equation (A.174), forms a representation space for the space group G. To
prove this, we write the elements t R . t T ( a j t ). a y of the space group G in the
form
where j', at fixed j , takes all values between 1 and p . That (A.176) is indeed
a possible way of writing of the space group elements g can be seen as follows:
first one commutes the translation t R in t R . t T ( a . , ). ajt with [tT(a.,). ajt],
simultaneously replacing t R by tujt-1 R in accordance with equation (A.17).
Multiplying [tT(ajt). aj,]. t ai-1l R with the particular space group element
[t,(,,, . aj]-', one obtains again an element of the space group. If j' runs
through all values between 1 and p , and R through all lattice points, then all
elements will be different, in accordance with the general group properties
derived in section 1. The set of these elements coincides, therefore, with the
space group G. This proves that the space group elements can indeed be
written in the form (A.176).
The application of g in the form (A.176) to one of the basis functions
f , D k j ( x ) of R { k } of (A.174) yields, in view of (A.173), the expression
(A. 177)
The function f,Dk,,(x) and therefore also g'pk2 ( x ) lie in R { k } . This means
that R { k } forms a representation space. R { k } is also irreducible, we omit
formal proof here. For non-symmetric k, the irreducible representations of
the space group can therefore be characterized solely by the k-vector itself
or, more strictly, by the star {k} of this vector. Thus, in this context we
write Z ) { k ] for the irreducible representations. The character x { k ) ( g ) of an
element g in the representation Z ) { k } reads
P
x { k } (9) = e- ikj-R- (A. 178)
j=1
702 Appendix A . Group theory for applications in semiconductor physics
where Dmn(a) denote the expansion coefficients. This relation means that
the assumed representation of the small space group assigns to each element
Q of Pk a specific matrix Dmn(a). Below, we will demonstrate that the
matrices Dmn(a) form a group with multiplication rules of the general form
(A.154), and thus, a projective representation of the small point group 9.
To this end we consider two elements g 1 = [tR1 . t7(,l) . 311 and 9 2 = [tRz
t T ( a 2 ) az] of Gk. For brevity we set T ( Q ~ =
) 7-1, and 7 - ( ~ 2=
) 7-2. Equation
(A.180) associates the elements g1 and 9 2 , respectively, with the matrices
Dmn(Qi1)and Dmn(~12). For the effect of the product element [tR1. t , . a l l .
[ t R z . t, . a21 on pkn, one obtains from (A.179) the relation
(A.181)
mmf
(A.182)
- ,-wRl+fi+al(R2+ii)I CDm,n(al
. a2)cPkm,(y+ (A.183)
m'
Comparing equations (A.181) and (A.183), one finds that the matrices D(a1),
D ( a 2 ) and D(a1 . a 2 ) are related by the equation
where
(A. 186)
For symmorphic space groups, no fractional translations 7' occur, i.e. the
vectors ?(a) are zero for all elements a of the small point group of a sym-
metric k-vector. Thus, the crystallographic factor system equals the identity
system for all symmetric k-vectors, and the projective representations of the
small point groups become representations in the ordinary sense. For non-
symmorphic space groups, a factor system different from the identity system
may occur, but only for vectors k on the surface of the first B Z . In fact,
if k is an internal point of the first B Z , then ak also lies in the interior of
704 Appendix A. Group theory for applications in semiconductorphysics
the first B Z and cannot differ from k by a non-zero reciprocal lattice vector
K. For surface points, however, it is possible that ak deviates from k by a
vector K # 0. If that is the case, then factors differing from 1 may occur
in the crystallographic factor system (A.185). The basis ( p k l , ( p k 2 , . . . , (pkd of
the irreducible representation v k of the small space group G k then gives rise
to a projective irreducible representation of the small point group P k of k.
cover the whole point group of equivalent directions P if g and i take all
A.9. Irreducible representations of space groups 705
(A.188)
with a fixed value of j which can be arbitrarily chosen and values of j' and i
depending on g . The lattice translation ta;iR in the second angular bracket
of expression (A.188) guarantees that the lattice translation described by the
whole product (A.188) becomes t R , as it has to be. If g in the form (A.188)
is applied to one of the basis functions qkjn(x), then one obtains by means
of (A.180) and (A.187), the relation
This means that the resulting functions are again in the space R k d spanned
by the basis functions (pk,n(x),n = 1 , 2 , .. . , d , j = 1 , 2 , .. . , s(k). Moreover,
the general definition (A.46) of the operators 9 ensures that the group mul-
tiplication relations 91.92 = g1 . 92 for any two elements g 1 , g 2 of the space
group G hold also in RM. This means that the space R k d forms a repre-
sentation space. It is irreducible, if the partial basis set for the particular
star points k used at the outset, gives rise to an irreducible projective rep-
resentation of the small space groups Gk, as we have supposed. Thus, our
assertion above is proved.
The question of whether one obtains all irreducible representations of a
space group for a symmetrical wavevector if one proceeds in the way de-
scribed above, is answered in the affirmative: By taking all stars {k} of the
first B Z and all irreducible projective representations Dkv of the small point
groups of the respective k-points with the crystallographic factor system, all
irreducible representations D{k}vof the space group follow.
For the character X { k } y ( g ) of an element g = tR++) . a in the space group
representation D{klv, equation (A.189) yields
706 Appendix A . Group theory for applications in semiconductor physics
Here ali is that element of the small point group of k = kl associated with
the element a through the relation ali = a;' . a . a j . Furthermore, j is
defined by the equation ak = kj, and the operators aj are the special star-
generating elements introduced above for the point group P of equivalent
directions, and s(k) is the number of different points of the star {k}. With
(A.191)
the projective representations of the small point groups for crystals with
diamond and zincblende structure both with and without spin.
(A.193)
(A.195)
The R-sum extends over all lattice points of the periodicity region and the
a-sum over all elements of the point group P of equivalent directions. The
R-sum differs from zero only for those a and j for which
Since the ali run through the set Mkl if the a vary over a set Mki, the expres-
sion under the j- sum in (A.197) is independent of j . Moreover x k v ( a f i )
may be replaced by x k , ( ( r 2 ) as has already been mentioned above. One
therefore gets
cx(I,>v(s2)
= 0. (A.200)
9
Using the last two relations, the left hand side of the Frobenius-Schur theo-
rem (A.163) for representations of space groups becomes
1 Ip(k)]-' CaEMk
e-iK'7'(a)Xkp(Lu2) {k} {-k}
- cx{I,}u(g2)
=
N L l
{k} # {-k)
1 0 (A.201)
Here, we have used the relation N = G3 . s(k) .p(k) for the total number
N of space group elements. For {k} # {-k} one obviously has the Herring
case b ) , as anticipated at the outset. For {k} = {-k}, all three Herring
cases are possible, depending on which of the relations
Table A.4: Characterization of the three Herring cases for space groups.
Herring Characteristics
case
a)
{k} = {-k} Ip(k)]-l e-iK'P(at X k u ( a 2 ) = K 2
The characterization of the three Herring cases for space group representa-
tions is summarized in Table A.4. Unlike the Frobenius-Schur theorem in
its general form (A.136), the sums in Table A.4 are carried out only over the
subset Mk rather than over the whole space group. Let us first consider a
star with {k} = {-k}.
{k} = {-k}.
In cases b) and c) time reversal symmetry joins the irreducible represen-
tations R{k}, and K R { k } , = R{k}fi into one eigenspace of the Hamiltonian.
One therefore has E,(k) = E,(k), meaning that each energy band is at
least 2-fold degenerate because of time reversal symmetry. In case b), the
two bands E,(k) and E p ( k ) belong to different irreducible representations
A.9. Irreducible representations of space groups 711
of the space group, and in case c) to the same one. For case a), p formally
becomes v, and the relation E,(k) = E,(k) is a tautology, devoid of new
information. For stars with {k} # {-k},
Example
In case ii), i.e. without inversion, one has {-k} # {k}. The Herring case
b) applies, and the two Bloch functions or spinors ' p k and Kpk = ' p I k belong
to the same energy: we have E(k) = E'(-k) where again E(k) and E'(k)
are, respectively, the energies of the states p k and pk. This means that both
with and without spin, time reversal symmetry causes an additional band
overlap.
712 Appendix A . Group theory for applications in semiconductor physics
A.9.7 Compatibility
From the main text we know that the Bloch functions p k u and the pertinent
energy eigenvalues E,(k) are continuous functions of wavevector k within
the first B Z . Therefore the irreducible representations z ) ( k } , , of the space
group in the eigenspace of the Hamiltonian for a given energy eigenvalue
E,(k) must likewise be continuous functions of k. From this observation
one obtains compatibility relations between the small representations v k p
for a symmetry line k and the small representations v k o u for a symmetry
center ko, which lies on this line.
Here, we will study these relations in greater detail. To this end we as-
sume that there is an energy eigenvalue E,(ko) at the symmetry center ko.
The corresponding eigenfunctions should belong to the irreducible repre-
sentation Vh,,of the small point group P k o of ko. The small point group
P k of a symmetry line on which the symmetry center ko is located forms
a subgroup of P b . A particular irreducible representation Vb,,of P b is
therefore simultaneously also a representation of P k , in general, however,
not an irreducible but a reducible one. Let Z ) b / k p , D b / k p ! , . . . be the ir-
reducible parts into which v k o u decomposes as representation of P k . Be-
cause of continuity of the energy eigenvalues and the representations with
respect to k, E,,(ko) must split along the symmetry line k into bands
E,(k), E,!(k), . . ., and their corresponding eigenfunctions belong to the irre-
ducible representations Vb/k,, D b / k p , . . .. One says that the representation
D b v at the symmetry center ko must be compatible with the representa-
tions V b / k , , v b / k , ! , . . . along the symmetry line k through ko. In partic-
ular cases, the set v k , , / k p , v b / k p j , . . . may reduce to the one representation
v b / k p alone. Then no band splitting occurs, and V b / k , is compatible with
PkOU.
Similar results hold for compatibility between representations at a sym-
metry line and a symmetry plane which is bounded by the symmetry line.
In section A.10 the compatibility relations are given for symmetry centers
and lines of crystals with diamond and zincblende type structure.
t o be considered are listed in Table A.5. We start with the structure of lower
symmetry, that of zincblende type crystals.
Zincblende structure
has the highest symmetry, namely that of the full point group T d of equiva-
lent directions. The star of I' consists only of I' itself.
The 24 elements of T d belong to 5 classes according to section 2: E , 6S4,
6S2, 8C3, 60~. As before, each class is characterized by a representative
element, the number in front indicating the number of different elements in
the class. Since there are as many inequivalent irreducible representations as
there are classes, the number of these representations equals 6 in the present
case. To satisfy the Burnside theorem two of them must be 1-dimensional,
one 2-dimensional and two 3-dimensional. The two 1-dimensional represen-
tations are denoted by I'l(A1) and I'2(A2), the 2-dimensional one by I'lz(E),
and the two 3-dimensional ones by I'Is(T2) and r25(Tl). The notations in
parenthesis are the ones which commonly are used to describe the symmetry
of localized one-electron states of of molecules and point perturbations in
Table A.5: Small point groups P and number s of star points for symmetric points
k of the first B Z in zincblende and diamond type crystals. Properties of the time
reversed k-point are also indicated.
k r A X A L K C
714 Appendix A. Group theory for applications in semiconductor physics
Table A.6: Irreducible representations of the small point group T,j of ? ! for
zincblende type crystals. Here and below, the vector representations are given in the
upper part of the table, and the spinor representations in the lower part. The right
column gives basis functions transforming according to the irreducible representa-
tions of the same line. The symbols for the representations given in parenthesis are
the ones commonly used in the context of localized oneelectron states of molecules
and point perturbations in crystals.
3T 1 33 i
I--)
22
= -[Iz
dz - iy t ) + 212 .!)I, I--)
22
= -Ix
fi - iy l), (A.205)
11 1
I--)
22
= ---[J?;
I. + iy 1) + Iz t)], I--)2i 2i = -[-I.J3i - iy t) + Iz l)]. (A.206)
For each representation, Table A.6 also gives a basis of linear combinations
of products of the three Cartesian components x,y, z of the position vector
x, or of the components Jz,Jg,Jz of the angular momentum pseudovector
J. According to their interpretation as basis vectors, these components
transform under the action of an orthogonal operator a-' according to the
A.lO. Irreducible representations of small point groups 715
As far as time reversal is concerned, the star {-k} equals the star {k} in
the case of I", and all 8 representations of the space group belong to the
716 Appendix A. Group theory for applications in semiconductor physics
Table A.7: Transformation of the position vector components x,y, z with respect
to the cubic axes under the symmetry operations of point groups
T d and Oh.
Herring case a). This means that time reversal symmetry does not result in
an additional degeneracy of energy bands at I?.
Table A.8: Irreducible representations of the small point group Caw of A for
zincblende type crystals. In the lower right corner those group elements are given
which transform the basis functions (shown in the last column) according to the
respective irreducible representation. The components z, y, z refer to the cubic axes.
double group one has, in addition, the class Q. The double group therefore
has 5 different irreducible representations (see Table A.8). The one extra
representation As must be 2-dimensional according to Burnside's theorem.
It coincides with the spinor representation V1 of the full orthogonal group
1
taken as a representation of CzV.Moreover, we have
~ A4 x D L= As.
A1 x V l = A2 x Vr.= A3 x 2 ) = (A.208)
The time reversed star {-k} differs from the star {k} in the case of A (see
Table A.5). Thus, all representations of the space group at A correspond
to the Herring case b). Since all 5 representations of the small point group
are real, time reversal symmetry joins a certain representation at k with the
same representations at -k. At A one therefore has
X
The boundary point (0, 0,27r/a)of the first B Z and all symmetrically equiva-
lent points are denoted by X . The star of X has 3 points, because (0, 0,27r/a)
and (0, 0, -27r/a) are equivalent (in the sense of reciprocal lattice transla-
tions). The small point group of X is D M . It contains the 8 elements
E , C2, S4, ,943,
odl, ad2, U21, U22 which form the 5 classes { E } ,{Cz}, ( 5 4 , S,"},
(U21, U22}, {adl, a d z } . Consequently, there are 5 irreducible representations
among which 4 are 1-dimensional, namely XI, X2, X3, X4, and one, X5, is 2-
dimensional (see Table A.9). In the double group one has the class Q in addi-
tion, and, instead of (S4, Sj}, the two classes (S4,QS;} and (QS4, S;}. The
718 Appendix A. Group theory for applications in semiconductor physics
Table A.9: Irreducible representations of the small point group &d of X for the
zincblende structure
The time reversed star {-k} coincides with the star {k} of X . All represen-
tations at X belong to the Herring case a), so that no additional degeneracy
occurs due to time reversal symmetry.
The point (./a)(C, C,6) with 0 < C < 1 and all the points on equivalent di-
rections are denoted by A. The star of A has 4 points. The small point group
is C3v. The 6 elements E , C3, Ci, u v l ,av2, a v 3 are distributed among the 3
classes { E } , {C3,C:}, { u v l ,r V 2 , u v 3 } . There are therefore two 1-dimensional
representations, A1 and A2, and one 2-dimensional representation, A3. In
the double group, each of the three classes of the simple group again forms
a class, and each gives rise to an additional class by multiplying it with &.
Thus there are three spinor representations, two 1-dimensional ones, A4 and
As, and one 2-dimensional one, As. Table A.10 shows all six representations.
The spinor representations are p-equivalent to the vector representations. D 1
z
taken as a representation of C3v coincides with As. One has the relations
A. 10. Irreducible representations of small point groups 719
Table A.lO: Irreducible representations of the small point group C3v of A and L
for the zincblende structure
In the case of A, the time reversed star of -k differs from that of k. Thus,
all representations of the space group at A correspond to the Herring case
b). The real representations A1, A2, A3 and at the point k are joined
by time reversal symmetry with the same representations in the point -k,
and the two complex representations A4, A5 at k with the complex conjugate
representation at -k. From this it follows that at A
L
The point L is the point of A with = 1. Therefore it also has 4 star points,
and the small point group remains also the same, i.e. C3,. Everything said
about the representations at A applies, therefore, to L as well (see Table
A.lO). The only difference between L and A is that for L the star {-k}
does not differ from, but coincides, with the star {k}. The representations
151,L2, LJ and Lg correspond to the Herring case a), i.e. no additional de-
generacy occurs between the corresponding bands. In the case of L4 and L5
one has the Herring case b), so that at L the additional degeneracy
720 Appendix A . Group theory for applications in semiconductor physics
(A .2 13)
occurs because of time reversal symmetry.
<
The point ( 3 ~ / 2 a ) ( < , < , O0) ,< < 1 and points on equivalent directions
are denoted by C. The point with C = 1 is denoted by K. The number of
star points amounts to 12 in both cases, and the small point group is C,.
Each of the two elements E and ah of C, forms its own class. Thus, there
are two 1-dimensional irreducible representations, C1 and Cz or K1 and Kz
(see Table A.ll). In the double group of C, each class of C, gives rise to yet
another class through multiplication by &. This means that there are also
two 1-dimensional spinor representations, C3 and C4 or K3 and K4 . These
are p-equivalent to the two vector representations. If taken on the point
group C,, Vi becomes reducible and decomposes into the 1-dimensional
5
spinor representations C 3 , C4 or K3, K4, respectively.
The star {-k} differs from the star {k} in the case of C and K , so that
the Herring case b) applies. Thus the following relations hold at C:
The diamond structure follows from the zincblende structure if the two prim-
itive f.c.c sublattices are occupied with identical, as opposed to different,
A.lO. Irreducible representations of small point groups 721
atoms. The operation which transforms the two sublattices into each other
thus forms an additional symmetry element of the diamond structure. One
can take it in the form of a glide reflection or the inversion joined with a frac-
tional translation. We choose the second possibility. The inversion is carried
out at the center of the line connecting the two atoms of a primitive unit cell,
and is accompanied by a translation along the connecting line by the amount
a / 4 . The point group of equivalent directions for diamond structure follows,
therefore, from the corresponding point group for the zincblende structure,
i.e. T d , by forming the direct product T d x ci = oh,
As for the zincblende structure, we consider the irreducible representa-
tions of the space group at the symmetric points I?, A, X , A, L , C and K . The
corresponding small point groups are shown in Table A.5. Adding inversion,
the number of star points either doubles in comparison with the point group
of the zincblende structure, or remains the same while doubling the number
of elements of the small point group. For all symmetry points mentioned
above the stars {k} and {-k} are the same in the diamond structure (see
Table A.5).
Due to the occurrence of fractional translations in the space group of the
diamond structure, not only vector and spinor representations of the small
point groups are required, as in the zincblende case, but also projective
representations with other factor systems. Actually, this applies only to
k-points at the boundary of the first B Z , i.e. to X , L , and K , for only
these k-points can have a crystallographic factor system different from the
identity system. As we will see below, only that of X differs essentially from
the identity system, while that of L is p-equivalent to the latter, and that of
K is equal to it. Those of I',A, A and C are equal to the the identity system
anyway.
The small point groups C3wand CzWoccur in both the diamond and zinc-
blende structures. Since the crystallographic factor systems of the respective
symmetric points A, K , and C are the identity systems in the diamond
structure as well, the same irreducible representations of these groups apply
as in the zincblende case.
On the other hand, there are small point groups in the diamond struc-
ture which can be obtained from small point groups in the zincblende struc-
ture by multiplying with Ci. In fact only one of the remaining small point
groups of the diamond structure cannot be generated in this way, namely
the point group C4w. In all other cases this construction is possible, one
has oh = 0 x Ci,D4h = D u x Ci and D u = D3 x Ci. If, in these cases,
the crystallographic factor system is the identity system also in the diamond
structure, then the irreducible representations found for zincblende case can
also be used to obtain the representations for diamond case. Let us consider
r: The small point group oh of I? in the diamond structure follows from
the corresponding small point group 0 of I' in the zincblende structure by
722 Appendix A . Group theory for applications in semiconductor physics
r12x D~ = r$ , r:, x v 1 x r, ,
A.lO. Irreducible representations of small point groups
-1 -
a"
0 (3 0 3 1
3 I 3 3 1
3 I 3 3 0 0 0 0 0 01;;
+ b 3
3 3 I 3 I 3 1
3 -I$ $
0- 3 1 3 0 0 3 3 1 3 0 c
0 0 0 0 0 0
Q 3 I 3 0 I 3 3 3 H 0 k3 -
N N V N N C"(h
Table A.12: Irreducible representations of the small point group oh of I? for dia-
mond type crystals.
724 Appendix A. Group theory for applications in semiconductor physics
Td Oh Basis functions
r15 for I =i c , ~ , z
r, r$ for I =1
A
The star of A has 6 points, and its small point group is C4,,. The 8 elements
are assigned to classes as follows: { E } , {C4,C43}, {Ci}, {cl,c3}, {ff2,c4}.
Thus there are five ordinary irreducible representations, among them four
1-dimensional ones, A l , A2, A3, A4, and a 2-dimensional one, As (see Table
A.14).
In the double group we find the new class {Q}, and the class {C4, C,"}
of the simple group splits into the two classes {C4, Q . Cl} and {Q . C4, Cz}.
There are thus two spinor representations, A6 and A?, of dimension 2. The
representation Vi coincides with A6 on C4,,. We have the relations
Table A.14: Irreducible representations of the small point group CdV of A for
diamond type crystals.
The star of X has 3 points. Its small point group is D4h. According to
section A.3, we have D4h = D2d x ci. For elements of the subgroup D 2 d of
D4h the crystallographic factor system w ( q , a 2 ) has the constant value 1
because D2d forms a subgroup of T d and none of the elements of T d is joined
with fractional translations in the space group of the diamond structure.
For the remaining elements, the factors w ( c r l , c q ) generally differ from 1
and must be calculated separately. For a(1,I),for example, it follows that
exp[i(4~/a).(a/4)]= -1. It turns out that the crystallographic factor system
of D a is not pequivalent to the identity system in the case of X and the
diamond structure. It belongs to a class different from that of the identity
system.
In constructing the vector representations of D4hr one may take advan-
tage of the identity D4h = D4 x Ci proved in section A.3. Then the 16
elements of D4h can be associated with the 5 classes of D4 as well as 5 fur-
ther classes, which are generated by the previously mentioned ones through
multiplication by I . Altogether one has, therefore, 10 classes and thus also
10 vector representations of D4h. These are shown in the upper part of Table
A.15 and are denoted by Xp,XH, ..., Xg and Xp', X;', ...,Xg'. For the space
group representations at X without spin the vector representations of D4h
are not helpful, one needs the projective representations of this point group
with the crystallographic factor system discussed above. These are shown
in the middle part of Table A.15. The characters are given for each element
individually because the character is no longer a class function for the pro-
jective representation under consideration. Remarkably enough, none of the
726 Appendix A. Group theory for applications in semiconductorphysics
Table A.15: Projective irreducible representations of the small point group D4h of
X with three different factor systems correspondingto diamond type crystals. The
vector representations (those with unit factor system) are given in the upper part,
the vector representations with crystallographic factor system in the middle part,
and the spinor representations with crystallograhic factor system in the lower part.
-
X E 2c4
-I
xt" 1 1 1
xz" 1 1 1
x; 1 i 1
x; 1 i 1 I 1 1
xs" 2 0 2 0 0 2
x;' 1 1 1 1 1 i
xz"' 1 1 1 I i I
x;' 1 i 1
xi' 1 i i 1 i 1 i
2 0 0 1 0 2 0 0
XgVI -
x1 2 0 0 0 0 0 0 0 0 0 0
x2 2 0 0 0 0 2 0 1 0
x3 2 0 0 0 0 0 0 0 0 0
x4 2
-
0 0 0 0 2 0 2 0
x5 4 0 0 0 0 0 0 0 0
-
E
-I
- C4I c; cir U21I U23' U22I u24r
The time reversed star {-k} equals the original star {k} in the case of
X . Time reversal symmetry does not result in additional degeneracy at X,
A.lO. Irreducible representations of small point groups 727
Table A.16: Irreducible representations of the small point group D 3 d for diamond
type crystals.
L1 1 1 1 1 1 1 *I;zx f uu
L2 1 1 I 1 1 I JZ
L3 2 i 0 2 i 0 { J z - Jz, Ja, - J r )
L; 1 1 1 i i 1 x i l l i =
L; 1 1 i i i 1 .( - U)(# - 2 x 2 - x)
Lb 2 I 0 2 1 0 t=- 2 , u - 2 )
with (xu.) -
Lq-basis from Tab.A.6
(JzJYJz)
with ( z v z ) -
L g - h i s from Tab.A.6
(JzJYJz)
0 0 II t),Ill}
Lq-basis from Tab.A.6
1 0
since all representations of the space group belong to the Herring case a).
A
The star of A has 8 points. The small point group is C B ~and , the crys-
tallographic factor system (A.186) equals the unit system, just as in the
case of the zincblende structure. Thus the same irreducible representations
apply as those shown in Table A.9 for the zincblende structure. Unlike
the zincblende structure, however, the time reversed star {-k} of A equals
the original star {k} of k in the case of the diamond structure. The rep-
resentations A l , A2, h3, correspond to the Herring case a), and the two
representations A4, A5 to the Herring case b). The energy levels A4 and As
are therefore degenerate because of time reversal symmetry. One has
L
The star of L has 4 points and its small point group is D M = D3 x Ci.
728 Appendix A . Group theory for applications in semiconductor physics
Therein elements occur which, like the inversion, are joined with fractional
translations in the space group of diamond type crystals. Some of these
elements, among them again the inversion, transform L into an equivalent,
but not identical point, whereby the crystallographic factor system differs
from the identity system. It can, however, be shown that this system is p -
equivalent to the identity system. The projective irreducible representations
of D3d to be considered here are, therefore, pequivalent to the ordinary
irreducible representations of this point group. Due t o the relation D3d =
D3 x Ci the latter can be generated from the irreducible representations of
D3 by multiplication with the two representations of Ci. The results are
shown in Table A. 16.
The 6 elements of D3 belong to the 3 classes { E } ,{C3, C,},{ U z l , U22, U23}.
In the double group, each of these classes gives rise to a further class. There
fore, two 1-dimensional representations L1, L2, and a 2-dimensional one, L3,
exist without spin, and also two 1-dimensional representations, Lq, L 5 , and
a 2-dimensional one, L6, with spin. In the group D u = D3 x Ci,one has the
vector representations L1, L2, L3, and the spinor representations Lsf, L,f, Lg
corresponding to +1 for the inversion, as well as the vector representations
L i , Lh, L3, and the spinor representations L 4 , L g , L;, corresponding to -1
for the inversion (see Table A.16). The repTesentation D1/2 of the full orthog-
onal group coincides with L$ on D 3 d . In addition, the following relations
hold:
The time reversed star {-k} equals the original star {k} in the case of L.
The representations L1, La, L.3, L i , Lh, L i as well as L$ and L; belong to
the Herring case a), and the spinor representations L z , L,: and L 4 , L c to
the Herring case b). Thus, time reversal symmetry joins L4f, L z as well as
L.4, L , to representations in the same energy eigenspace. We conclude that
at L,
(A.220)
The small point groups of C and K are both CzV,and the stars both have
12 points. The crystallographic factor systems (A.186) are identical and in
both cases equal the identity system. Therefore, only ordinary and spinor
representations have to be considered. We formulate the results for C. The
point group CzV has already been treated as the small point group of A
A.lO. Irreducible representations of small point groups 729
Table A.17: Irreducible representations of the small point groups CzVof C and K
for diamond type crystals.
Table A.38: C and K without spin. Table A.39: C and K with spin.
1-
734 Appendix A . Group theory for applications in semiconductor physics
Zincblende structure
A. 10. Irreducible representations of small point groups 735
Diamond structure
736 Appendix A . Group theory for applications in semiconductor physics
r; -A; r; ~ h2 r; - c2 L 1 ~
L2 -
r; ~ A; r; - ra ~ c3 L3-
L;
<
~
Appendix B
In section 2.2 it is verified that the factors @(X)at @(x, X)d(X)in the total
wavefunctions $(x,X)$(X)obey a Schrodinger equation with a Hermitian
Hamiltonian as well. Thus they also may be assumed to be orthogonal,
(4'14) = 0, 4 # 4. (B.2)
A second property of the total eigenfunction $(x, X)$(X)follows from the
X)+ Vcc(X)
invariance of the crystal potential Vee,ec(~, under a common
translation of the spatial coordinates of all electrons,
The third property we will use involves strong localization of the wavefunc-
tions +(X)at atomic cores. This follows from the large masses of cores - in
order for the kinetic energy operator Tc = &(l/Mj)P! in the Schrodinger
equation (2.25) to compete with the potential energy term, large second
derivatives of the core wavefunction +(X), i.e., strong spatial changes, are
necessary. These can be achieved only through strong localization of these
functions, because the normalization condition requires that d(X) shall de-
cay as X approaches infinity. In the case of a crystal, the core wavefunc-
tions +(X)can have non-zero values only in direct proximity of the lattice
points. In classical terms this corresponds to cores executing small oscilla-
tions around their equilibrium positions.
Fourthly and finally, we use that the electron wavefunction $(x,X),
taken as a function of X,is smooth compared with +(X)which was found
to vary rapidly with X. This may be understood as follows: First, we note
that, because of the small mass of electrons, the argument for strong local-
ization of the core wavefunctions +(X) with respect to core positions X is
not applicable to the variation of the electron wavefunctions +(x, X) with
respect to electron coordinates x. The electron wavefunctions @(x, X), taken
as functions of x,are rather spread out more or less uniformly over the entire
crystal. Second, we form the internal product of relation (B.6) with +(X).
Using the relation
(4IPjld) = 0 (B.6)
which holds because of the oscillatory character of the core motion, we arrive
at
The total number of terms on the left hand side of (B.7) is of the same order
of magnitude as the total number of terms on the right hand side, because
the number of (valence) electrons equals, apart of a factor of the order of
magnitude 1, the number of cores. Moreover, the order of magnitude of the
terms with different i is the same throughout, as is the order of magnitude
of the terms with different j . Therefore, the order of magnitude relations
Appendix B. Corrections to the adiabatic approximation 739
follow for all i, j , indicating that $(x, X)is as smooth with respect to X as
it is with respect to x. From relation (B.8) it follows also that
XI.
P?$(X, X) M Pj2$(X, (B.9)
The four properties of the wavefunctions $(X)and $(x, X)discussed above
will be used to rewrite the two correction terms ($4I4Tc$) and E j ( l / M j ) x
($#lPj$Pj4).The first term has the explicit form
(B.lO)
In rewriting this expression we use the third property concerning the wave
function 4(x) and the fourth concerning the wavefunction $(x, X).Accord-
ingly, the matrix element with respect to the electron states in B.10 depends
only weakly on X, and the factor @*(X)#(X) differs substantially from zero
only in small environments around the equilibrium positions of cores. Thus,
the matrix element can be approximately evaluated at the equilibrium values
of the core coordinates X and be factored out of the integral over X. In this
way one gets
(B.15)
The two order of magnitude relations (B.14) and (B.15) are the equations
(2.23) and (2.24) used in section 2.2.
741
Appendix C
Occupation number
representation
For electrons, a particular one-particle state vi (of definite spin) can either
be occupied with one particle, or not be occupied at all. This observation is
most naturally described by means of an occupation number Nv - if the state
v is occupied, then one has Nu = 1, and if the state is empty, then Nu = 0
holds. For simplicity, we identify the quantum numbers v of one-particle
state with integers i, where i runs from 1 to 00, as there are idnitely many
one-particle states.
The selection {v} = v1,v2,. . . ,UN of one-particle states entering a partic-
ular Slater determinant @iV},determines the entirety of occupation numbers
for all one-particle states, i.e. the sequence N1, N2,. . . ,N,, as follows: the
Ni-value of a state whose quantum number i coincides with one of the quan-
tum numbers vl, v ~ . ,. . , V N ,is 1, and the Ni-value of a state whose quantum
number i differs from all quantum numbers v1, v2,. . . , v ~ is, 0. Conversely,
742 Appendix C. Occupation number representation
(N1,N 2 , . . . , 0, . . . , N,), Ni 1,
1
ai I N1, N 2 , . . . , N i , . . . ,N,) =
0, Ni = 0.
0, Ni = 1,
at I N1, N 2 , . . . ,N i , . . . ,N,) =
JN1,N 2 , . . . , 1 . . . ,N , ) , N.j = 0.
The states 1 N1, Nq, . . . ,N i , . . . , N,) are therefore eigenvectors of a:ai, and
the particle number Ni of state i is the pertinent eigenvalue. One calls a r a i
the particle number operator of the state i. We abbreviate it by I?i, i.e. we
set
Using the definition of the Hermitian adjoint operator (a+)h.a.of a:, we may
write
[ A ,B]+= A B + BA.
With this definition we have
744 Appendix C. Occupation number representation
is valid. As far as the left hand side of this equation is concerned, one
easily verifies that the only non-vanishing matrix elements are those between
Slater determinants which differ solely in one column. This means that in
Appendix C. Occupation number representation 745
(v;,vi,. . . , v h ) only one component, say vi, can have a value different from
v1 in ( v l ,v 2 , . . . , v ~ ) .The non-vanishing matrix element reads
( N i ,N L , . . . ,N L I a$uu I N i , N 2 , . . . , N m ) . (C.16)
The matrix element of u$uU in (C.16) differs from zero only when v = v1
and v = vi hold. Thus, it follows that
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Chapter IV
Chapter V
Appendix A
Index
Abelian group 86, 624, 626, 666 anti-bonding orbital 166, 172, 177
ab initio methods 133 anti-resonance state 301
absorption 41, 433 anticommutator 743
acceptor level 474 antisite defect 228
acceptor transition 304, 321 APW method 139
acceptor 271, 276, 277, 279, 490, arsenic 44
507 artificial semiconductor microstruc-
accumulation layer 553, 555, 613 ture 402
actinides 231 As-antisite defect 331
activation enthalpy 239, 240 As-rich surface 388
active region 600 associates 232
additional degeneracy 710 asymmetric dimer model 384
adiabatic approximation 57, 59, 61, atomic core 51, 53, 54, 55, 60, 63,
355, 737 70
adiabatic potential 60 atomic force microscopy (AFM) 373
adiabatic 61, 62, 64 atomic layer 339
Airy-function 436 atomic orbital 135, 140, 141, 285
all electron problem 134 atomic structure 54, 64, 82, 177,
alloy 27, 403 234, 336, 371
a-Sn 29, 210 Au-center 497
amorphous semiconductor 2, 27 Auger recombination 517, 518
amphoteric center 305, 497 augmented plane waves (APW) 139
amplification 592 average value 460
angular momentum basis 192
angular momentum matrix 187 ballistic transport 610
angular momentum operator 681 banddegeneracy 112,116, 117,184
Angular Resolved UPS (ARUPS) band discontinuity 555, 567
374, 379 band edge 539, 549, 550, 551
anisotropic effective mass 273 band index 108
annealing 238 band model 38, 41
annihilation operator 742 band structure 105, 108, 109, 112,
annihilation 506, 527, 529 113, 133, 211
anthracene 28 band-band recombination 517
anti-bonding energy level 291, 292, Bardeens relation 565
3 14 barrier 422
758 INDEX
electron-hole pair 78, 511 Euler angle 130, 631, 632, 679, 683
Electron-Nuclear-DoubleResonance exchange energy 249
(ENDOR) 308 exchange integral 249
Electron-Paramagnetic Resonance exchange potential 77, 133, 247,
(EPR) 308 26 5
electron-phononinteraction 62, 517 exchangecorrelation energy 80
electronegativity 566 exchangecorrelation potential 81,
electronic elementary excitation 65 241, 245, 428
electronic structure of surfaces 363 excitation energy 73
electronic structure 51, 354, 371, excitation level 304
409, 420 excited state 274, 467, 468, 469,
electroreflectance211, 443, 444, 572 493
electrostatic potential 552 excitonic effects 433
elemental semiconductor of group exciton 78
IV 289 extended state 246, 457
elemental semiconductor 4, 28, 29, extended zone scheme 96, 97
31 Extended-State X-ray Absorption
elementary excitation 65, 72 Fine Structure (EXSAFS)
emission coefficient 512 308
emission rate 512 extra representation 686
emission 511 extraction 579
emitter 586, 587, 588, 589 extrinsic semiconductor 35, 43,47,
empirical TB (ETB) method 159, 483, 484
163
empty lattice band structure 214 f-shell230, 232 , 307
empty lattice 110, 113 Fabry-Perot resonator 600
energy band 2,39, 81,98, 108, 116, factor group 625
125, 149 factor system 687, 690, 703
energy gap 39, 41, 104, 108, 134, Faraday 3
219, 255, 403 fcc lattice 11, 13, 113, 118, 131
enhancement mode 622 Fermi distribution 39, 42, 461, 462
enthalpy of formation 236 Fermi energy 40, 58, 461, 478
envelope function equation 258 Fermi gas 479
envelope function 256, 259, 271, Fermi integral 479
278, 414, 435, 443 Fermi level 41, 250, 305, 477, 483,
epitaxial growth 336, 396 484,488,489, 534, 548
EPR 310 Fermi statistics 461
equilibrium distribution function 500 Feynman theorem 64
equivalent representation 660 Ficks law 239, 502
equivalent directions 12, 14 field effect transistor 4, 386, 613,
equilibrium position 54, 63, 64 620
Esaki diode 536, 593 fieId effect 612, 613
Euclidean algorithm 338 fine structure splitting 307
762 INDEX
finite group 624 ground state 70, 73, 274, 279, 468,
first Brillouin zone 98, 106, 107, 469, 491
110, 114, 116, 700 group IV semiconductors 28, 31,
first SL BZ 410, 411 313, 566
flow direction 585 groups 7, 82, 87, 623
Fock space 742 group theory 623
folding 107, 108, 411 GW approximation 134
forbidden zone 39, 108 gyromagnetic ratio 448
forward bias 585
Franz-Keldysh effect 442 Hall constant 49
Franz-Keldysh oscillations 442 Hall effect 43, 44, 46
free carriers 527, 533 Hartree approximation 68, 66, 76
freez-out of carriers 487 Hartree energy 248
Frenkel defect 233 Hartree potential 69, 70, 77, 241,
245, 247, 265, 428
frozen-core approximation 53, 133
Hartree-Fock approximation 68, 76,
full orthogonal group 636
134
full rotation group 636, 673
Hartree-Fock equation 77, 81
heavy hole 189, 197, 204, 210
Ga-rich surface 388
Hellman-Feynman forces 63, 64
GaAs 4, 30, 31, 220, 395, 384, 387, HEMT 407, 557, 574
398, 411, 429, 431 hermiticity 417
gain coefficient 599 Herring cases 710
GaN 30, 31 Herring criterion 695, 707, 711
gap discontinuity 394, 403 heterojunction 388, 390, 394, 396,
GaP 5, 220 535, 536, 549, 550, 552,
gate voltage 621 574
gate 621 heterojunction bipolar transistor (HBPT)
generating elements 637, 638, 639 406
generation center 519 hexagonal lattice 22, 23
generation of free carriers 509 HgTe 209, 221
generation 506 High Electron Mobility Transistor
generators of infinitesimal rotations (HEMT) 402
6 74 Hittorf 3
Ge 2, 29, 36, 218, 444, 456, 488, hole capture 515
492, 497 hole subbands 429
Gibbs free energy 235 hole trap 490
glide-reflection 14,15,632,633,635 hole 46, 47, 48, 428, 429, 489
grain boundaries 240 holohedral point group 8, 14
grand canonical ensemble 458 homomorphism 626
Greens function method 295, 368 Hubbard energy 249,280,305,309,
Greens function 79, 295, 298, 299, 310, 328, 463
369, 370 hybrid orbital 168, 285, 286
INDEX
solubility 237, 238, 311, 328 239, 242, 250, 265, 269,
sp-bonding elements 230 283, 289, 313, 319
space charge region 539 substitutional RE impurity 330
space charge 507, 508 substrate 397, 620
space group symmetry 343 supercell method 294, 367
space group 14, 15, 17, 81, 82, 85, supercell 294, 367
86, 95, 119, 131, 354, 362, superlattice 397, 400, 421, 424, 536
627, 654, 698, 704, 706 surface antiresonance 361
spin degeneracy 473 surface band structure 365
spin-orbit interaction 74, 75, 129, surface Brillouin zone 35, 358, 359
189, 216, 218, 264, 277, surface energy band 357, 363, 358
448 surface field 572
spin-orbit splitting 193, 194, 219, surface photo-efFects 572
279, 473 surface potential 572
spin-orbit-split band 210 surface reconstruction 350, 352, 353,
spinor function 75 354
spinor representation 130, 131, 682, surface relaxation 349, 350, 386
684, 690, 691, 706, 709, surface resonance 361
714
surface state 361
spinor 77, 128, 129, 130, 131, 682
symmetrical k-vector 95, 116
spin 74, 128, 129, 131, 132
symmetry operation 14, 15, 83
spontaneous emission 602
symmetry point 111, 119, 120
stacking fault 28, 240
symmorphic 15
stacking vector 338
star degeneracy 117
star of wavevector 116, 700, 707, Te 2, 27, 31, 224
710, 713 ternary compound 3
statistical average value 502 tetrahedral semiconductor 238, 315,
statistical correlation 479 320
statistical degeneracy 461 thermal annealing 335
statistical operator 458 thermal donor 233
step dislocation 28, 240, 241 thermionic emission theory 611
stereogram 20, 640, 641, 642 thermodynamic equilibrium 49,457,
stereographic projection 640 458, 499, 501, 503, 530,
sticking coefficient 398 533
stimulated emission 599, 603 thermoelectric properties 32
strained layer 404 thermoreflectance 211
structural defect 227 threshold current density 605
structural perturbation 226 tight binding (TB) method 135, 139
subband 410, 423, 424 tight binding approximation 140,
subgroup 624, 625 148, 170
sublevel 424 tight binding matrix elements 153,
substitutional impurity 227, 238, 159
770 INDEX
2 x 1 reconstruction 376
7 x 7 reconstruction 376, 381, 382
IL x m reconstruction 352
sp2-bonding 333, 334
sp3-bonding impurity atom 314
sp3-hybrid orbital 166, 290, 330
sp3-hybrid 165, 334
&doping structures 409, 430
A-line 111, 112
r-point 112, 118
A-line 112
n-bonded chain model 381,378, 377,
379, 380, 381
r-bonded chain 377
k . p-interaction 182
k . p-perturbation 185
k . p-method 179
k . p-perturbation theory 259, 262
k-space 93
k-vector 93, 95, 105
(100) surface 379, 387, 388
(110) surface 384, 387, 388
(111) surface 376
2-dimensional electron gas 536, 552,
620
2D lattice 337
2D quasi-wavevector 356
3d-TM atom 320
4d-atom 320
4f-level 331
4f-orbital329
5d-level 331
5d-TM atom 320