Japanese Journal of Applied

Physics

REVIEW Related content

- Study on capacitance–voltage
Diamond field-effect transistors for RF power characteristics of diamond field-effect
transistors with NO2 hole doping and
electronics: Novel NO2 hole doping and low- Al2O3 gate insulator layer
Makoto Kasu, Kazuyuki Hirama, Kazuya
Harada et al.
temperature deposited Al2O3 passivation
- Thermal Stabilization of Hole Channel on
H-Terminated Diamond Surface by Using
Atomic-Layer-Deposited Al2O3 Overlayer
To cite this article: Makoto Kasu 2017 Jpn. J. Appl. Phys. 56 01AA01 and its Electric Properties
Makoto Kasu, Hisashi Sato and Kazuyuki
Hirama

- High-Current Metal Oxide Semiconductor

Field-Effect Transistors on H-Terminated
View the article online for updates and enhancements. Diamond Surfaces and Their High-
Frequency Operation
Hiroshi Kawarada

Recent citations
- Chemical and semiconducting properties
of NO 2 -activated H-terminated diamond
M.W. Geis et al

- Characterization and mobility analysis of

MoO3-gated diamond MOSFET
Jin-feng Zhang et al

This content was downloaded from IP address 130.202.237.31 on 10/05/2018 at 18:29

Japanese Journal of Applied Physics 56, 01AA01 (2017) PROGRESS REVIEW
https://doi.org/10.7567/JJAP.56.01AA01

Diamond field-effect transistors for RF power electronics:

Novel NO2 hole doping and low-temperature deposited Al2O3 passivation
Makoto Kasu1,2*
1
Green Electronics Laboratories, Saga University, Saga 840-8502, Japan
2
Department of Electrical and Electronic Engineering, Saga University, Saga 840-8502, Japan
*E-mail: kasu@cc.saga-u.ac.jp
Received May 13, 2016; accepted October 14, 2016; published online December 28, 2016

Diamond possesses a combination of exceptional physical properties and is expected to be used as a semiconductor material in high-efficiency
and high-power electronic devices. In this study, hole doping was observed when using NO2 molecules on a H-diamond surface. The activation
energy of hole concentration in NO2/H-diamond was measured as 0.006 eV, and holes were fully activated at room temperature. A thermal
stabilization of the hole channel was realized by passivation with an atomic-layer-deposited Al2O3 layer. The passivation method enabled the
realization of a thermally stable high-performance diamond field-effect transistor (FET), which exhibited high-performance DC and RF
characteristics. NO2 hole-doping and Al2O3-passivation technologies enabled reproducible measurements of MOS structure electric properties.
Such technologies also facilitated observations of two-dimensional holes at the MOS interface and type-II band alignment of Al2O3/NO2/
H-diamond. Additionally, the band diagram under various gate bias conditions was proposed on the basis of capacitance–voltage measurements
and analysis using Poisson’s equations. © 2017 The Japan Society of Applied Physics

1. Introduction 䠄㼃㻕 Diamond will replace the TWT

vacuum tubes now used for
Diamond possesses the highest thermal conductivity [22 10 K RF high-power applications
W=(cm K)] and a high breakdown electric field (>10 Broadcasting
Output Power

1K stations
MV=cm).1) Table I shows a comparison of the physical Communications

properties and device figures of merit between diamond and 100 SiC GaN
satellites
Diamond
other semiconductors. Baliga’s figure of merit (BFOM) 10
Wireless
base
Communications
station to station Radar
indicates power capability,2) and it can be expressed as stations
systems
1 Mobile Wireless LANs
BFOM ¼
E3BR : ð1Þ terminals
Car radar
0.1 systems
Si GaAs
The BFOM of diamond is ∼100 times higher than that of 0.1 1 10 100 1000
SiC. Furthermore, diamond has a relatively high carrier Operation Frequency 㻔㻳㻴㼦㻕
mobility [3800 cm2=(V·s)]3) and saturation velocity (1.1 ×
107 cm=s)4) for holes, which enable fabrication of high- Fig. 1. (Color online) Prospects of semiconductors and the requirements
frequency RF devices. Johnson’s figure of merit (JFOM) of RF power systems. Reprinted with permission from Ref. 6. © 2014 John
Wiley and Sons, Ltd.
shows RF power capability5) as given below.
 
EBR vsat 2
JFOM ¼ ð2Þ targeted to power amplifiers for mobile phone base stations
2 at ∼0.9 GHz. However, traveling-wave tubes (TWTs) are
The JFOM of diamond is 2.8 times higher than that of SiC. still used since the requirements from broadcasting stations,
Hence, diamond exhibits the highest power and RF power communication satellites, and radars exceed the capability of
capability among semiconductors. conventional semiconductors. However, the availability of
Figure 1 shows the prospects of diamond as an RF power diamond could replace vacuum tubes and boost RF output
device compared with conventional semiconductors.6) The power.
figure shows the capability of the respective semiconductors Doping is the most difficult issue with respect to diamond.
and the requirements of the RF power applications. GaN is The ionization energy of the B acceptor is the lowest.

Table I. Comparison of the physical properties and device figures of merit between diamond and other semiconductors.
EG EBR vsat μ λ
Material εr
(eV) (MV=cm) (×107 cm=s) [cm2=(V·s)] [W=(cm·K)]
1.5 (e) ∼4500 (e)
Diamond 5.47 >10 5.7 22
1.05 (h) ∼3800 (h)
Ga2O3 4.8 8 — ∼300 (e) 10 0.14
∼900 (e)
SiC 3.27 3.0 2 (e) 9.7 4.9
∼120 (h)
GaN 3.4 2.5 1–2.5 (e) ∼2000 (e) 8.9 1.5
∼8500 (e)
GaAs 1.4 0.4 1–2 (e) 12.9 0.55
∼400 (h)
∼1400 (e)
Si 1.1 0.3 1 (e) 11.7 1.3
∼450 (h)

01AA01-1 © 2017 The Japan Society of Applied Physics

Jpn. J. Appl. Phys. 56, 01AA01 (2017) PROGRESS REVIEW

(a) gas
N2 NO2 5 ppm
3.5x10
13 N2 exposure
O2 100%

13
Ar 100%
3.0x10

ps (cm )
-2
13
2.5x10

13
2.0x10

13
1.5x10

13
1.0x10
0 60 120 180 240 300
t (min)

25 ppb
NO2 N2 flow
Fig. 2. (Color online) Hole concentration ps changes for H-diamond in
the gas exposure (O3, NO2, SO2, NO, O2, CO2, and so on) and in N2 (b) 9x10 13

atmosphere. The O3, NO2, SO2, and NO gases increase hole concentration, air 25 ppb NO2
but H2O (humid N2), CO2, and N2O did not affect the hole concentration. 8x10 13
air
Reprinted with permission Ref. 18. © 2010 The Japan Society of Applied
Physics.
7x1013
ps (cm )
-2

However, its ionization energy of 0.37 eV is sufficiently high

to prevent the ionization of all B impurities at room
temperature (RT). Recent studies have indicated that hole
carriers are generated by NO2 on H-diamond. The activation
energy of hole concentration in NO2-exposed H-diamond
was measured as 0.006 eV.7) The details of the generation
of hole carriers by NO2 on H-diamond are described in the
next section.
2. NO2 hole doping
Experimentally, hole conduction on a H-diamond surface
was observed only on the surface exposed to air.8) Therefore,
it is widely understood that the formation of hole channels
requires both the H termination of surface diamond dangling
bonds and adsorption of unknown molecules that exist in air
on the H-diamond surface.
There are several proposed models of hole generation on
a H-diamond surface.8–20) Ri et al. reported that NO2 gas
increased the hole carrier concentration on a H-diamond
surface,11–13) and explained this phenomenon in relation to
H3O+ oxonium ion. Ristein et al. reported adsorbates that
generate hole carriers on H-diamond to be H2O and=or
CO2.16) Hirama et al. reported the model in which polar-
ization of C–H bonds induces hole carriers.17)
Therefore, in this study, we first investigated the molecules
in the atmospheric air that generated hole carriers on H-
diamond. Figure 2 shows the change in hole concentration
with time when a specific gas was supplied and removed
(exchanged by pure N2 gas).18) Thus, we investigated which
gas molecules generate the hole carriers by supplying
appropriate gas molecules. All gases were diluted with pure
N2 gas. It was clearly observed that the hole concentration was
drastically increased by four molecules, namely, NO2, NO,
SO2, and O3. In contrast, N2 gas with a humidity of 100%
(H2O) and CO2 gas did not change the hole concentration.
Atmospheric air contains NO2 gas at a concentration of
∼20 ppb. Therefore, as shown in Fig. 3, we prepared ∼25 ppb
NO2 gas diluted with pure N2, and compared the time change
01AA01-2
6x1013
5x1013
4x1013
0 1 2 3 4 5 6 7 8 9 10
t (h)
Fig. 3. (Color online) Change of hole concentration ps with time during
the supply of (a) 5 ppm NO2, 100% O2, 100% Ar, and (b) 25 ppb NO2 gas
diluted with pure N2 and atmospheric air. In the atmospheric air, the NO2
concentration was ∼20 ppb.
of hole concentration during exposure to ∼25 ppb NO2 gas
and atmospheric air. The figure clearly shows that the
change in hole concentration with time for ∼25 ppb NO2 gas
reproduced that for atmospheric air exactly. Therefore, hole
generation on H-diamond in air is attributed to NO2 existing
in air.
Figure 4(a) shows the increase in the hole sheet concen-
tration at different NO2 gas concentrations. Given 2% NO2,
the hole concentration increased for ∼1 min and reached the
saturation value. The saturated concentrations for 300 ppm
and 2% (20000 ppm) were almost identical at approximately
9 × 1013 cm−2.19) Therefore, 2% NO2 gas was normally used
for hole doping in FET fabrication. The change in hole
concentration during evacuation was demonstrated only for
2% NO2. An extremely slow decrease in the hole concen-
tration over 50 h was an important observation of this study,
which suggests that the decrease did not merely involve
physical adsorption. Similarly, Fig. 4(b) shows a change in
hole mobility during NO2 exposure. As the NO2 gas con-
centration during exposure increased, the mobility of H-
diamond after the exposure decreased. This behavior could
be explained in terms of the domain size of the adsorbed NO2
molecules.19)
This raises the question why NO2, NO, SO2, and O3
generated hole carriers on H-diamond, but not CO2 and H2O.
© 2017 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 56, 01AA01 (2017) PROGRESS REVIEW

1.4 x 1014 NO2 exposure

Vacuum level
14
1.2 x 10

1 x 1014 start of evacuation

20000 ppm

300 ppm
ps (cm-2)

8 x 1013
in vacuum
13
6 x 10

4 x 1013
5 ppm
13
2 x 10
increase no change
hole density
0
0 10 20 30 40 50
Fig. 5. (Color online) Energy levels of H-diamond for various surface
(a) orientations and the various molecular orbitals. Here, VBT refers to the
Time (h)
valence band top, CBB to conduction band bottom, HOMO to the highest
occupied molecular orbital, LUMO to the lowest unoccupied molecular
80
orbital, and SOMO to the singly occupied molecular orbital. Reprinted with
NO2 exposure permission from Ref. 20. © 2013 Elsevier B.V.

70 doping were in descending order as follows: (110) > (111) >

(001).20) The details are described in the next section. The
5 ppm LUMO or SOMO level of O3, NO2, SO2, and NO is located
μ (cm V s )
-1 -1

below or near the VBT level of H-diamond. LUMO and

60
2

SOMO have unoccupied orbitals and the capabilities to

300 ppm
50
20000 ppm
start of evacuation
40
0 10 20 30
(b) Time (h)
Fig. 4. (Color online) Comparison of the (a) hole sheet concentration ps
and (b) mobility μ of H- (001) diamond surface at RT during exposure to
NO2 of different concentrations. The changes during evacuation (in vacuum)
after exposure are shown only for the 20,000-ppm case. Reprinted with
permission from Ref. 19. © 2012 Elsevier B.V.
Figure 5 shows the energy levels of the conduction band
bottom (CBB) and valence band top (VBT) of H-diamond
for various surface orientations, namely (100), (110), and
(111).20) It also shows the highest occupied molecular orbital
(HOMO), lowest unoccupied molecular orbital (LUMO), and
singly occupied molecular orbital (SOMO) levels of specific
molecules, namely, O3, NO2, SO2, NO, CO2, N2O, and H2O,
as calculated by the first-principle theory method. H-diamond
shows negative electron affinity, as generally known, and its
CBB levels are higher than the vacuum level (VL). The CBB
levels of the (110) H-diamond and (111) H-diamond exceed
that of the (100) H-diamond because the C–H densities of
(110) H-diamond and (111) H-diamond exceed that of the
(100) H-diamond. This trend was experimentally confirmed,
and the hole concentrations of H-diamond with NO2 hole
attract an electron.
Figure 6 details the mechanism of NO2, O3, SO2, NO hole
doping determined from the first-principle theory method
results as follows:20) (a) Prior to molecule absorption, the
in vacuum band alignment was the same as that shown in Fig. 5, and
the LUMO=SOMO level of the molecule was located below
the VBT level of H-diamond: (b) Following the molecule
40 50 absorption, the electrons were transferred from the valence
band of H-diamond to the LUMO=SOMO level of an
adsorbate molecule until equilibrium was reached. The
electron transfer induced hole carriers on the H-diamond
surface and the upward band bending toward the surface of
H-diamond. It could be summarized from the mechanism that
there were three factors determining the equilibrium states.
The first factor was the Coulomb repulsive interaction
between the transferred electrons and the native electrons in
the adsorbate molecule. The second factor was an electric
dipole induced by the electron transfer. The third factor was
the permanent electric dipole in adsorbate molecules.
Figure 7(a) shows the local density of states (LDOS) of the
NO2-adsorbing (100) H-diamond surface.20) In the calcula-
tion, it is assumed that one-monolayer NO2 molecules were
adsorbed. The peak structure originated from the SOMO
level of NO2 that exists around the valence band maximum
(VBM). The Fermi level lies on the peak structure. The
analysis based on the LDOS revealed that the peak structure
was composed of mainly SOMO level of NO2 and partially
valence band states of diamond. This indicated that hole
carriers were generated in H-diamond by the absorption of
NO2, which acted as an acceptor. The states around the C–H
bonds did not contribute to the peak structure. This suggested
that NO2, which was an acceptor, was spatially separated
01AA01-3 © 2017 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 56, 01AA01 (2017) PROGRESS REVIEW

VL

Fig. 6. Explanation of NO2 hole doping with a change in energy band diagrams of H-diamond and molecular orbitals. (a) Before molecule adsorption,
(b) after adsorption, during which the electron transfer to the molecule and hole accumulation in diamond occur, and (c) until the energy balance between the
Fermi level of diamond and the SOMO=LUMO level is reached, the electron transfer and hole accumulation continue. Here, LUMO denotes the lowest
unoccupied molecular orbital, and SOMO denotes the single occupied molecular orbital. Reprinted with permission from Ref. 20. © 2013 Elsevier B.V.

Molecular Molecular
orbital orbital
level level

SOMO LUMO LUMO

VB CB
VB CB

SOMO

(a) Atomic structure Atomic structure

(b)

Fig. 7. (Color online) LDOS of (a) NO2-adsorbed (100) H-diamond surface, and (b) H2O-adsorbed (100) H-diamond surface. Reprinted with permission
from Ref. 20. © 2013 Elsevier B.V.

from the hole-doped region. The calculated hole sheet con-

(111)> (110)~ (100)
centration ( ps) of this system was approximately 3.8 × 1013
cm−2. In addition, the conduction band was bent upwards 140 H-terminated diamond surfaces
With 20000 ppm NO2 adsorption
toward the surface. The shift of the conduction band was 120 Rs of 719.3 Ω/sq
approximately 0.4 eV. Rs = 0.5 kΩ/sq lowest value ever reported
100
In addition, Fig. 7(b) shows the LDOS of the H2O-
μ (cm2V-1s-1)

80 Rs = 1 kΩ/sq
adsorbed surface. The absorption of H2O did not result in any
(111)
peak structures around the VBM of H-diamond. The Fermi 60 (100)
level lies at the center level of the band gap. The peak
40
structures originating from the HOMO and LUMO levels (110)
Rs of 5~10k Ω/sq
for conventional diamond
of H2O were located at approximately −7.7 and 1.8 eV. The 20 Rs = 2 kΩ/sq

molecular orbitals had a very limited influence on ps. The 0

calculated hole sheet concentration ( ps) was approximately
0.35 × 1013 cm−2. The calculated hole sheet concentration
was one order of magnitude lower than that of H-diamond
owing to the absorption of NO2. This implies that H2O does
not produce hole carriers.
3. Surface orientation dependence of NO2 hole
doping
Figure 8 shows the experimental results of the comparison of
various orientations of the hole concentrations and mobilities
on the NO2-adsorbed H-diamond surface.21) The hole con-
centrations were higher for the (111) and (110) H-diamond
01AA01-4
5x1013 1x1014 1.5x1014 2x1014
ps (cm-2)
Fig. 8. (Color online) Comparison of various orientations of hole
concentrations ps and mobilities μ on NO2=H-diamond surface. The lowest
sheet resistance of 719.3 Ω=sq for the (111) diamond surface orientation was
obtained. Reprinted with permission from Ref. 21. © 2013 Elsevier B.V.
surface orientations. This result was in agreement with the
theoretical explanation shown in Fig. 6 that the VBM levels
of the H-diamond surface were in descending order as
follows: (110) > (111) > (100). The difference in the VBM
© 2017 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 56, 01AA01 (2017) PROGRESS REVIEW

LG: 0.4 μm VGS: -4 +2V, 1V step LG: 0.2 μm

-700 -700
-600 (111) -600 (111)
-500 -500

IDS (mA/mm)
IDS (mA/mm) -400 -400
-300 -300
-200 -200
-100 -100
0 0
100 100
0 -2 -4 -6 -8 -10 0 -2 -4 -6 -8 -10
VDS (V) VDS (V)
(a) (b)

Fig. 9. (Color online) DC drain voltage–current characteristics of the (111) NO2=H-diamond FETs for Lg values of (a) 0.4 µm and (b) 0.2 µm. The drain
current of (111) NO2=H-diamond FETs is higher than that of the (001) NO2=H-diamond FETs.

LG: 0.4 μm LG: 0.2 μm

30 30
H21 H21
MAG+MSG MAG+MSG

VGS = -0.5 V VGS = -0.5 V

20 20
Gain (dB)
Gain (dB)

VDS = -15 V VDS = -15 V

10 10
fT = 40 GHz fT = 50 GHz
fmax > 100 GHz fmax = 68 GHz
0 0
1 10 100 1 10 100
Frequency (GHz) Frequency (GHz)

Fig. 10. (Color online) RF small-signal characteristics of the (111) NO2=H-diamond FETs. The cut-off frequencies fT and fMAX of the (111) NO2=
H-diamond FETs are higher than those of the (001) NO2=H-diamond FETs.

among the surface orientations originated from the strength

of the surface electric dipole induced by the C–H bond. On
Al electrode
the (111) H-diamond surface, the lowest sheet resistance of
719.3 Ω=sq was obtained.
Previously, we reported the high-performance FET char- Al2O3 (~8 nm)
acteristics of (110) highly orientated H-polycrystalline
diamond due to high hole concentration.22) We23) and Hirama IIa-type diamond (001)
et al.24) reported that the hole concentration on (111) H-
diamond without NO2 hole doping is higher than that on
(100) H-diamond. 5 nm

Figure 9 shows the DC characteristics of the FET on the

(111) NO2=H-diamond FET. The DC current of the (111)
diamond FET was much higher than that of the (001)
diamond FET. Figure 10 shows the RF small-signal char-
acteristics of (111) NO2=H-diamond diamond FETs. The cut-
off frequencies fT and fMAX of the (111) diamond FET were
higher than those of the (001) diamond FETs. The fT of
50 GHz was the highest in diamond FETs.
4. Stabilization of the hole channel: Al2O3 overlayer
There was a slow decay of hole concentration when NO2
was changed to N2; therefore, the stabilization of the hole
channel was necessary. After comparison of various methods,
we reached the conclusion that the atomic layer deposition
01AA01-5
Fig. 11. (Color online) Cross-sectional transmission electron microscopy
image of the Al=Al2O3=NO2=H-diamond. Reprinted with permission from
Ref. 25. © 2014 IEEE.
(ALD) of Al2O3 was the best way to stabilize the hole
channel formed by NO2 hole doping.7) Figure 11 shows a
cross-sectional transmission electron microscopy image of
the Al=Al2O3=NO2-adsorbed H-diamond.25) The sources
were trimethylaluminum (TMA) and H2O in ALD. The
deposition temperature was less than 150 °C. The capaci-
tance–voltage (C–V ) and current–voltage (I–V ) measure-
ments confirmed the relative dielectric constant ε = 7.4 and
the break down voltage Vbr > 5 MV=cm.
© 2017 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 56, 01AA01 (2017) PROGRESS REVIEW

6 x 1013 concentration did not change at all at a high temperature of

H-terminated (100) diamond surface 150 °C in a vacuum. In the case of the NO2=H-diamond
without an Al2O3 passivation layer, the hole sheet concen-
With Al2O3 passivation layer tration suddenly decreased. Hence, the usage of the Al2O3
13 passivation layer successfully stabilized the hole channel
4 x 10
formed by the NO2 hole doping.
ps (cm-2)

Without Al2O3 passivation layer 5. Diamond FET characteristics

Figure 13(a) shows the IDS–VDS characteristics at RT during
2 x 1013
heating at 200 °C, and at RT after the heating at 200 °C in
150 rC vacuum.25) The IDS values of 200 mA=mm at RT both before
In vacuum and after heating at 200 °C were evidently in agreement.
Therefore, there was no degradation of the FET even after
0 heating at 200 °C. Figure 14(b) shows the IDS–VGS character-
0 500 1000 1500
Time (min) istics. The threshold voltage did not change even after
heating at 200 °C. Therefore, the thermal stabilization of
Fig. 12. (Color online) Hole sheet concentration ps changes of H- Al2O3 passivation on the NO2=H-diamond surface was
diamond with and without Al2O3 passivation. This shows the thermal effective for the FET.
stabilization of the hole channel by the Al2O3 overlayer. Reprinted with Figure 14 shows the hole sheet concentration and sheet
permission from Ref. 7. © 2014 The Japan Society of Applied Physics.
resistance of Al2O3=NO2=H-diamond measured during the
heating and cooling between RT and 400 °C. There was no
Figure 12 shows a comparison of hole concentrations degradation in the hole channel of this structure. Separately,
with and without the Al2O3 overlayer.7) In the case of NO2= Daicho et al. reported H-diamond with an Al2O3 layer
H-diamond with an Al2O3 passivation layer, the hole sheet deposited at 450 °C stabilized up to 500 °C.26) With this

3×10-3 Pa 3×10-3 Pa

-250 30 °C (Before 200 °C heating) -250 30 °C (Before 200 °C heating)

200 °C 200 °C
30 °C (After 200 °C heating) VGS 30 °C (After 200 °C heating)
IDS (mA/mm)

-200 -200
IDS (mA/mm)

-4 V
VDS = -5 V
-150 -3 V -150

-100 -2 V -100

-50 -1 V -50 Vth

0V
+1 V
0 +2 V 0
0 -2 -4 -6 -8 -10 -12 -14 3 2 1 0 -1 -2 -3 -4 -5
VDS (V) VGS (V)
(a) (b)

Fig. 13. (Color online) IDS–VDS characteristics of Al2O3=NO2=H-diamond FET at 200 °C and RT before and after the heating at 200 °C in vacuum.
Reprinted with permission from Ref. 25. © 2014 IEEE.
Sheet hole concentration (cm )

Sheet resistance (ohm/sq.)

-2

10
14 20000

15000

10
13 10000

5000

10
12 0
0 100 200 300 400 0 100 200 300 400
Temperature (oC) Temperature (oC)
(a) (b)

Fig. 14. (Color online) Hole sheet concentrations and sheet resistances of Al2O3=NO2=H-diamond during heating and cooling.

01AA01-6 © 2017 The Japan Society of Applied Physics

Jpn. J. Appl. Phys. 56, 01AA01 (2017) PROGRESS REVIEW

Hole concentration Mobility

14
1 x 10
in Vacuum Boron doped diamond
H-terminated (100) diamond surface
8 x 1013 with ALD Al2O3 overlayer 1000

6 x 1013
μ = AT -1.035

μ (cm2V-1s-1)
13 A = 2.897 x 104
4 x 10
ps (cm-2)

μ = AT -2.859
A = 1.867 x 1010
100 #3
Ea = 6.147 meV #2
13
2 x 10 #1

H-terminated (100) diamond

in Vacuum surface with ALD Al2O3 overlayer

1 x 1013 10
0 1 2 3 4 5 6 7 8 100 1000
-1
1000/T (K ) T (K)
Fig. 15. (Color online) Temperature dependence of hole concentration ps and mobility μ of Al2O3=NO2=H-diamond. The ionization energy of 6.1 meV was
extracted. The mobility is almost inversely proportional to the temperature. Reprinted with permission from Ref. 7. © 2012 The Japan Society of Applied
Physics.

㻝㻚㻟㻡㻭㻛㼙㼙 㻔㼜㼞㼑㼢㼕㼛㼡㼟㼘㼥 㻜㻚㻟㻡㻌㻭㻛㼙㼙㻕

-1400
-1200 㻳㼍㼠㼑㻌㼢㼛㼘㼠㼍㼓㼑㻦
㻰㼞㼍㼕㼚㻌㼏㼡㼞㼞㼑㼚㼠㻌㻔㼙㻭㻛㼙㼙㻕

㻗㻝㻝㻌∼ 㻙㻡㻌㼂㻌㻘㻌 Al2O3

-1000 㻞㻌㼂㻌㼟㼠㼑㼜

-800 Gate
Source Drain
-600
-400 Hole channel

-200 H-diamond (001) (IIa-type)

0
0 -2 -4 -6 -8 -10 -12
㻰㼞㼍㼕㼚㻌㼢㼛㼘㼠㼍㼓㼑㻌㻔㼂㻕

Fig. 16. (Color online) DC IDS–VDS characteristics of Al2O3=NO2=H-diamond FET. The schematic cross section is also shown. The drain current level of
1.35 A=mm was the highest. Reprinted with permission from Ref. 28. © 2012 The Japan Society of Applied Physics.

technique, Kawarada et al. realized operation at 400 °C and to 35 and 70 GHz for fT and fMAX, respectively. The RF large-
at >500 V off-state breakdown voltage.27) signal characteristics at 1 GHz [Fig. 17(b)] show that the
Figure 15 shows the Hall measurement results.7) In maximum output power density POUT was 2 W=mm.25) The
Fig. 15(a), the ionization energy of 6.1 meV was extracted RF large-signal measurements were performed using contact
from the slope of concentration. This value was considerably probes. If we use direct bonding instead of contact probes, we
lower than that of B doping (0.37 eV), which indicated the would obtain a higher RF output power in the measurements.
availability of NO2 hole doping for diamond. Figure 15(b) Previously, we reported an fT of 45 and an fMAX of 120 GHz
shows a comparison in mobility between NO2 hole doping for the FET without NO2 hole doping and Al2O3 passiva-
and B doping. The mobility was inversely proportional to the tion.22) Recently, Russell et al. have reported an fT of 53 GHz
temperature for NO2 hole doping. This suggests that the hole and an fMAX of 90 GHz for an LG of 50 nm.29)
carriers were degenerated, resulting in two-dimensional hole
accumulation, and that the mobility is limited by the phonon 6. Analysis of Al2O3/NO2/H-diamond MOS structure
scattering.7) Figure 18 shows the X-ray photoelectron spectroscopy
As shown in Fig. 16, the drain current increased to 1.35 (XPS)=X-ray absorption near-edge structure (XANES) spec-
A=mm in Al2O3=NO2=H-diamond FET.28) This was the tra of Al2O3=NO2=H-diamond before and after the sputtering
highest current level observed in diamond. Figure 17 shows of an 8-nm-thick Al2O3 layer.30) The sample before and after
the RF characteristics of the Al2O3=NO2=H-diamond FET.25) sputtering showed thick and thin Al2O3, respectively. For the
In Fig. 17(a), the RF small-signal characteristics of the thick Al2O3 layer, the spectra originated from the Al2O3 layer
Al2O3=NO2=H-diamond FET with LG = 0.1 µm corresponded itself, and an Al2O3 band gap of 6.7 eV was extracted. For
01AA01-7 © 2017 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 56, 01AA01 (2017) PROGRESS REVIEW

40 50
LG: 0.1 μm |H21|2 LG: 0.2 μm
30 P :
WG: 390 μm out
2 W/mm @ 1GHz

Gain (dB), PAE (%)

WG: 100 μm MSG
Pout 40
30
Gain PAE: 33 %
fT: 35 GHz

Pout (dBm)
PAE
Gain (dB) 20 30
fmax: 70 GHz
20
Gain: 18 dB 20

fmax 10
10
10
fT
0 0 0
1 10 100 -10 0 10 20
Frequency (GHz) Pin (dBm)
(a) (b)

Fig. 17. (Color online) RF characteristics of Al2O3=NO2=H-diamond FET. Reprinted with permission from Ref. 25. © 2012 IEEE.

㻭㻸㻰㻙㻭㼘㻞㻻㻟 㻺㻻㻞㻛㻴㻙㻯㻔㻜㻜㻝㻕
Hole accumulation
㻯㻮
Intensity (arb. unit)

Δ㻱㻯㻩㻌㻞㻚㻣㻌㼑㼂
㻱㼓㻩㻌㻢㻚㻣㻌㼑㼂 㻱㼓㻩㻌㻡㻚㻡㻌㼑㼂
Interface 㻜㻚㻟㻌㼑㼂 㻱㻲
oxygen 㼂㻮
Δ㻱㼂㻩㻌㻟㻚㻥㻌㼑㼂

㻭㼘㻌㻞㼜㻌㻦㻌㻣㻡㻚㻟㻌㼑㼂
Binding Energy (eV) 㻯㻌㻝㼟㻌㻦㻌㻞㻤㻠㻚㻟㻌㼑㼂
㻻㻌㻝㼟㻌㻦㻌㻡㻟㻞㻚㻞㻌㼑㼂
Fig. 18. (Color online) Synchrotron XPS=XANES spectra of Al2O3=
NO2-adsorbed H-diamond. Reprinted with permission from Ref. 30. © 2014
Fig. 19. (Color online) Energy band diagram of Al2O3=NO2=H-diamond
AIP Publishing LLC.
interface structure determined by synchrotron XPS=XANES. Reprinted with
permission from Ref. 30. © 2014 AIP Publishing LLC.

the thin Al2O3 layer (after sputtering), the spectra originated

from the interface and the partial diamond surface. Hole 㻣㻜㻜 㻳㼍㼠㼑
accumulation below the VBM was confirmed in a range from
0 to 4 eV by comparing the spectra corresponding to the thick 㻢㻜㻜 㻯㻳 㻳
㻯㻳㻘㻌㻳㻛ω㻌㻔㼚㻲㻛㼏㼙㻞㻕

and thin Al2O3 layers. A specific signal appeared in O K-edge 㻯㻳

㻡㻜㻜 㻿㼛㼡㼞㼏㼑 㻰㼞㼍㼕㼚
XANES spectra in the range of −1 to −3 eV. This originated
from interface oxygen, which in turn probably originated 㻠㻜㻜 䖃 㻦 㻸㻳 㻩 㻟 μ㼙
from the acceptors at the interface. 䕿 㻦 㻸㻳 㻩 㻞 μ㼙
Figure 19 shows the energy diagram of Al2O3=NO2= 㻟㻜㻜
㽢 㻦 㻸㻳 㻩 㻝 μ㼙
H-diamond. The energy difference of the peak position 㻞㻜㻜
between the thick and thin Al2O3 layers was used to extract
ΔEC = 2.7 eV and ΔEV = 3.9 eV.30) The band diagram of the 㻝㻜㻜
type-II band alignment of Al2O3=NO2-adsorbed H-diamond G/ω 㻸㻳 㻩 㻟 μ㼙
㻜
was constructed as shown in Fig. 19. Liu et al. reported 㻙㻠 㻙㻞 㻜 㻞 㻠 㻢 㻤
ΔEV = 2.9 eV for an Al2O3=H-diamond sample without NO2 㻳㼍㼠㼑㻌㼢㼛㼘㼠㼍㼓㼑㻌㻔㼂㻕
hole doping.31) The difference in ΔEV could be attributed to
Fig. 20. (Color online) Capacitance–voltage characteristics of Al2O3=
NO2 hole doping. NO2=H-diamond. Reprinted with permission from Ref. 32. © 2016 The
Figure 20 shows the C–V characteristics of Al2O3=NO2= Japan Society of Applied Physics.
H-diamond.32) The depth profile of hole concentration was
obtained from the C–V results, and it indicated a two-
dimensional hole channel. Hole accumulation was observed 3 V.32) A band diagram of the diamond MOS structure under
at zero gate bias and under forward bias. Hole depletion was the gate biases of −3, 0, and 3 V was obtained by fitting the
observed under reverse bias. In the diamond layer far from experimental C–V curve by Poisson’s equations.
the surface, EF was located at 0.3 eV above EV.
Figure 21 shows the band diagram of the Al2O3=NO2= 7. Conclusions
H-diamond structure for gate biases of (a) −3, (b) 0, and (c) This study demonstrated high-performance and thermally
01AA01-8 © 2017 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 56, 01AA01 (2017)
(a)
㼂㻳 㻩 㻙㻟 㼂
(b)
㼂㻳 㻩 㻜㼂
(c)
㼂㻳 㻩 㻟 㼂
Fig. 21. (Color online) Band diagram of Al2O3=NO2=H-diamond
structure for gate biases of (a) −3, (b) 0, and (c) 3 V. Reprinted with
permission from Ref. 32. © 2016 The Japan Society of Applied Physics.
stabilized Al2O3-passivated=NO2-adsorbed=H-terminated di-
amond FETs. With respect to the NO2 hole doping, the
hole concentration increased to ∼1 × 1014 cm−2. In the case
of the Al2O3 passivation, there was no degradation and it
was carried out at 400 °C. The thermally stable FET showed
IDS,max = 1.35 A=mm, fT = 35 GHz, fMAX = 70 GHz, and
Pout = 2.1 W=mm at 1 GHz. The Al2O3=NO2=H-diamond
MOS structure analyzed by synchrotron XPS=XANES
measurements and C–V measurements revealed a type-II
band alignment.
Acknowledgments
This work has been carried out together with Drs. Kazuyuki
Hirama, Michal Kubovic, Hisashi Sato, Kenji Ueda, Haitao
Ye, and Alexandre Tallaire at NTT Basic Research Labo-
ratories. Recent works were performed in collaboration with
Professors Toshiyuki Oishi and Kazutoshi Takahashi, Dr.
Kenji Hanada of Saga University, and Professor Kenji
Shiraishi of Nagoya University. Part of this work was
supported by the SCOPE project of the Ministry of General
Affairs and Communications, the Japan Society for the
01AA01-9
PROGRESS REVIEW
Promotion of Science (JSPS) Grants-in-Aid for Scientific
Research (Nos. 24360124 and 15H03977), the Mazda
Foundation, the Kyushu Bureau of Economy, Trade, and
Industry, and the Research Institute for Applied Mechanics,
Kyushu University.
1) L. S. Pan and D. R. Kania, Diamond Electronic Properties and Applications
(Kluwer Academic, Boston, MA, 1995) p. 472.
2) B. J. Baliga, J. Appl. Phys. 53, 1759 (1982).
3) J. Isberg, J. Hammersberg, E. Johansson, T. Wikstrom, D. J. Twitchen, A. J.
Whitehead, S. E. Coe, and A. Scarsbrook, Science 297, 1670 (2002).
4) L. Reggiani, S. Bosi, C. Canali, F. Nava, and S. F. Kozlov, Phys. Rev. B 23,
3050 (1981).
5) E. O. Johnson, RCA Rev. 26, 163 (1963).
6) M. Kasu, in CVD Diamond for Electronic Devices and Sensors, ed. R.
Sussmann (Wiley, Chichester, U.K., 2009) p. 288.
7) M. Kasu, H. Sato, and K. Hirama, Appl. Phys. Express 5, 025701 (2012).
8) M. Kubovic, M. Kasu, H. Kageshima, and F. Maeda, Diamond Relat.
Mater. 19, 889 (2010).
9) M. I. Landstrass and K. V. Ravi, Appl. Phys. Lett. 55, 975 (1989).
10) H. Kawarada, M. Aoki, and M. Ito, Appl. Phys. Lett. 65, 1563 (1994).
11) R. S. Gi, T. Mizumasa, Y. Akiba, Y. Hirose, T. Kurosu, and M. Iida, Jpn. J.
Appl. Phys. 34, 5550 (1995).
12) R. S. Gi, T. Ishikawa, S. Tanaka, T. Kimura, Y. Akiba, and M. Iida, Jpn. J.
Appl. Phys. 36, 2057 (1997).
13) R. S. Gi, K. Tashiro, S. Tanaka, T. Fujisawa, H. Kimura, T. Kurosu, and M.
Iida, Jpn. J. Appl. Phys. 38, 3492 (1999).
14) K. Hayashi, S. Yamanaka, H. Okushi, and K. Kajimura, Appl. Phys. Lett.
68, 376 (1996).
15) H. J. Looi, R. B. Jackman, and J. S. Foord, Appl. Phys. Lett. 72, 353 (1998).
16) J. Ristein, F. Maier, M. Riedel, M. Stammer, and L. Ley, Diamond Relat.
Mater. 10, 416 (2001).
17) K. Hirama, H. Takayanagi, S. Yamauchi, J. H. Yang, H. Kawarada, and H.
Umezawa, Appl. Phys. Lett. 92, 112107 (2008).
18) M. Kubovic and M. Kasu, Jpn. J. Appl. Phys. 49, 110208 (2010).
19) H. Sato and M. Kasu, Diamond Relat. Mater. 24, 99 (2012).
20) Y. Takagi, K. Shiraishi, and M. Kasu, Surf. Sci. 609, 203 (2013).
21) H. Sato and M. Kasu, Diamond Relat. Mater. 31, 47 (2013).
22) K. Ueda, M. Kasu, Y. Yamauchi, T. Makimoto, M. Schwitters, D. J.
Twitchen, G. A. Scarsbrook, and S. E. Coe, IEEE Electron Device Lett. 27,
570 (2006).
23) M. Kasu, M. Kubovic, A. Aleksov, N. Teofilov, R. Sauer, E. Kohn, and T.
Makimoto, Jpn. J. Appl. Phys. 43, L975 (2004).
24) K. Hirama, K. Tsuge, S. Sato, T. Tsuno, Y. Jingu, S. Yamauchi, and H.
Kawarada, Appl. Phys. Express 3, 044001 (2010).
25) K. Hirama, H. Sato, Y. Harada, H. Yamamoto, and M. Kasu, IEEE Electron
Device Lett. 33, 1111 (2012).
26) A. Daicho, T. Saito, S. Kurihara, A. Hiraiwa, and H. Kawarada, J. Appl.
Phys. 115, 223711 (2014).
27) H. Kawarada, H. Tsuboi, T. Naruo, T. Yamada, D. Xu, A. Daicho, T. Saito,
and A. Hiraiwa, Appl. Phys. Lett. 105, 013510 (2014).
28) K. Hirama, H. Sato, Y. Harada, H. Yamamoto, and M. Kasu, Jpn. J. Appl.
Phys. 51, 090112 (2012).
29) S. A. O. Russell, S. Sharabi, A. Tallaire, and D. A. J. Moran, IEEE Electron
Device Lett. 33, 1471 (2012).
30) K. Takahashi, M. Imamura, K. Hirama, and M. Kasu, Appl. Phys. Lett. 104,
072101 (2014).
31) J. W. Liu, M. Y. Liao, M. Imura, and Y. Koide, Appl. Phys. Lett. 101,
252108 (2012).
32) M. Kasu, K. Hirama, K. Harada, and T. Oishi, Jpn. J. Appl. Phys. 55,
041301 (2016).
Makoto Kasu received his B.E., M.E., and Ph.D.
degrees in electrical engineering from Kyoto Uni-
versity, Kyoto in 1985, 1987, and 1990, respectively.
From 1990 to 2011, he joined NTT Laboratories.
From 2003 to 2004, he was a visiting researcher at
the University of Ulm. In 2007 he was an invited
professor at the University of Paris XIII. In 2011, he
was appointed as a professor at Saga University. He
is also an invited professor at ISAS, JAXA, and a
cross-appointment fellow at AIST. He is engaged in
the research of ultra-wide-gap semiconductors such as diamond and gallium
oxide for power electronics.
© 2017 The Japan Society of Applied Physics