Diamond Transistor Performance

and Fabrication
MICHAEL W. GEIS
Invited Paper

This article reviews some of the device properties of diamond as 1000

well as recently developed diamond device fabrication techniques.

Diamond as a semiconductor in high-fiequency, high-power tran-
sistors has unique advantages and disadvantages. Two advantages - 300

of diamond over other semiconductors used for high-frequency, Y

high-power devices are its high thermal conductivity and high 6 100
electric-field breakdown. The high thermal conductivity allows for
5
higher power dissipation over similar devices made in Si or GaAs >
-
and the higher electric-filed breakdown field makes possible the 2
I- 30
production of substantially higher power, higher fiequency devices 2
than can be made with other commonly used semiconductors. z
The lack of large area single crystal diamond substrates is the
one largest technical obstacles to the development of diamond
; '0

transistors. Boron is the only known p-type diamond dopant and r

because of its high activation energy (0.37 eV), only a fraction
of the boron atoms contribute carriers to the valance band at
room temperature. This makes even moderately doped, I 016 cm-3,
diamond considerably more resistive, 10 to 100 Qcm, than Si,
0.5 Rcm, doped to the same level. However, even with these
disadvantages, high voltage high power diamond transistors will
still have lower on resistance than similar devices in Si or GaAs
because of the diamond's high breakdown field.
Much of the development necessary for the production of di-
amond devices already exists. Doping by homoepitaxy, diamond
etching, device quality S i O ~ d i a m o n dinterface, and ohmic contact
technology will be reviewed. The remaining problems are the
development of large area single crystal diamond substrates, im-
provement of doping techniques, and refinement in ohmic contact
technology.
I. INTRODUCTION
This article reviews some of the device properties of
diamond as well as recently developed diamond device
fabrication techniques. Diamond as a semiconductor in
high-frequency, high-power transistors has unique advan-
tages and disadvantages. Two advantages of diamond over
other semiconductors used for high-frequency, high-power
devices are its high thermal conductivity and high electric-
field breakdown. The higher the thermal conductivity, the
Manuscript received September 15, 1990; revised January 4, 1991. This
work was supported by SDIO/IST through the Office of Naval Research.
The author is with the Lincoln Laboratory, Massachusetts Institute of
Technology Lexington, MA 02173-9108.
IEEE Log Number 9144418.
3
1 3 10 30 100 300
TEMPERATURE (K)
Fig. 1. Thermal conductivity of several solids as a function of tempera-
ture. The vertical lines around 300 K represent the temperature range from
-25 to 125OC. The thermal conductivity of IIa diamond is displayed 111.
more power a device can dissipate for the same temperature
rise. Figure 1 compares the thermal conductivity of dia-
mond with that of other materials. The thermal conductivity
of diamond at 40 to 500 K is excellent and at room
temperature it is the highest of any known solid [l]. The
electric-field breakdown of diamond has not been accurately
determined, but from our breakdown voltage measurements
of diamond diodes it is known to be above 4 ~ 1 V 0 ~
cm-' [2] and may be as high as 2x107 V cm-' [3], [4].
For comparison, the electric-field breakdowns of commonly
used semiconductors, Si and GaAs, are between 2 x lo5 and
'
4 x lo5 Vcm- [5]. Electric-field breakdown directly affects
the high-frequency performance and the on-resistance of a
transistor.
Figure 2(a) schematically illustrates a high voltage ver-
tical field-effect transistor. The projected properties of this
device made of diamond are compared with those made of
Si in Fig. 2(b). The drift region length X in Fig. 2(a) was

OOi8-9219/91/05004669$01.00 0 1991 IEEE

PROCEEDINGS OF THE IEEE, VOL 79, NO. 5, MAY 1991 669

~
 GATE 1
souRcE-l
i SUBSTRATE
DEVICE DRIFT DOPING LEVEL RESISTIVITY
LENGTH x ( p n ~ (cm-=i if1 cml
(b)
Fig. 2. (a) Schematic of a vertical-field-effect transistor. (b) Predicted
performance of Si and diamond vertical-field-effect transistors at room
temperature. The doping level, semiconductor resistance and on-resistance
are for the drift region. The dark columns on the left under each title are
for the Si device and the light columns on the right represent the diamond
device.
calculated from [6]
where VB is the maximum operating voltage and EB is the
electric-field breakdown. For a transistor with VB = 3 x lo3
V, made of diamond with EB = 4 x lo6 Vcm-' or of Si
with E B = 2.2 x lo5 Vcm-' [4], the drift region calculated
from (1) is only 15 pm for diamond compared with 280 pm
for Si. The maximum doping level P in the drift regions
was calculated from[6]
P = E B E ~~ ~ l 2 e V ~
where E is the dielectric constant of the semiconductor (5.7
for diamond and 11.9 for Si), E, is the permittivity of
vacuum and e is the charge of an electron. For diamond
and Si devices, P is 8 x 1015 and 5 x cmW3,respec-
tively. At these doping levels and on the assumption of no
compensating dopants, the resistivity is approximately -15
Rcm for diamond. This assumes a hole mobility of -2000
v-1 s-l and 3% of the boron dopant being ionized
cm-2
at room temperature, a carrier concentration of 2.5 x
cm-3 [7]. Si on the other hand has a resistivity of 70 Rcm
[81.
Despite diamond's disadvantage of having most of the
boron dopant atoms not being ionized at room temperature,
the electric-field breakdown of diamond allows for devices
with shorter drift region lengths and higher doping levels
than those of the same device made in Si or GaAs.
670
HOMOEPITAXIAL BORON
DOPED DIAMOND
ON-RESISTANCE
METALLIZATION AND OHMIC
DIAMOND ETCHING CONTACT FORMATION
Fig. 3. Device fabrication sequence of a vertical-field-effect transistor.
This results in diamond devices with an estimated on-
resistance in the drift region of 0.07 cm2, about 30 times
less than that of the same devices made in Si. For high-
power, high-voltage devices the on-resistance is usually
limited by the drift region resistance, even though the total
device resistance includes not only the resistance of the
semiconductor between the gates shown in Fig. 2(a), but
also the resistance of the wires bonded to the device, neither
of which is considered here. The transit time of the carriers
through the length of the drift region limits the frequency
cutoff f ~ which
, is given by [9]
.f~
= EBVS/~VB (3)
where Vs is the carrier saturated velocity, 2 x lo7 and
1 x lo7 cm s-1 for diamond and Si, respectively. The
cutoff frequency for diamond is 2 GHz, which is 35 times
that of Si.
Although diamond transistors have spectacular projected
device properties, to date no devices [lo]-[13] have been
made, with the exception of high-temperature diamond
diodes and transistors [14], [15], that even come close to the
performance of presently available transistors. The reason
for this is the substantial technical barriers to device fabri-
cation. A possible vertical-field-effect transistor fabrication
(2)
sequence is shown in Fig. 3. The important fabrication steps
include the manufacture of a highly conductive diamond
substrate, the growth of device-quality lightly doped and
heavily doped homoepitaxial diamond, diamond etching,
the deposition of device-quality Si02 insulation layers, and
the formation of ohmic contacts. At present, the technical
problems in manufacturing a highly conductive diamond
substrate have not been solved, so this article concentrates
on homoepitaxy, etching, the deposition of Si02 insulation
- layers, and the formation of ohmic contacts.
DIAMOND
11. HOMOEPITAXIAL
Homoepitaxial diamond has been grown by both plasma
and hot-filament techniques [16], [17]. In this discussion,
the device properties of homoepitaxial diamond produced
by the hot-filament technique are reviewed [18]. Figure 4
is a schematic drawing of the homoepitaxial system. The
PROCEEDINGS OF THE IEEE, VOL. 79, NO. 5 , MAY 1991

0.5 mm - TUNGSTEN WIRE
-,
2100 - 2300C
Fig. 4. Schematic drawing of a homoepitaxial diamond growth system.
diamond substrate is placed on a heated pyrolytic graphite
table, and a tungsten or tantalum filament, 0.5 to 2 mm in
diameter, is resistively heated to produce reactive chemical
species necessary for diamond growth from a gas mixture
of hydrogen and 2 to 3% acetone. The diamond films are
doped p-type using boron introduction via the addition of
B(OCH3)3.
The surface morphology and growth rates of lightly and
heavily boron doped homoepitaxial films on (100)- , (110)-
and (111)-oriented substrates are shown in Fig. 5. Lightly
doped films have boron concentrations of 5 x l0l8 to
10 x 10l8 cm-3 and resistivities of 8 x lo3 to 1 x lo3
Rcm. These high resistivity values are a consequence
of both compensation of some of the boron dopant by
donor impurities, possibly nitrogen or nickel, and the high
activation energy (0.37 eV) required to ionize the boron
dopant atoms. From experimental measurements of di-
amonds resistivity as a function of compensation and
doping, the compensation is estimated to be about 10%
Fig. 5. Scanning electron micrographs of homoepitaxial diamond films. The substrate crystal orientations are shown in the top left corner of the
micrographs. Micrographs on the left and right show lightly and heavily boron doped films, respectively.
GEIS: DIAMOND TRANSISTOR PERFORMANCE AND FABRICATION
TEMPEAATURE (K)
L
lo4 =
lo3
102
10 r 0 (100)
+ (110)
I I
1
1 2 3
Fig. 6. Resistivity as a function of temperature for (100)- and (110)-ori-
ented lightly boron doped diamond films. E is the thermal activation
energy of the resistivity.
of the total boron concentration, assuming that the hole
mobility is limited by ionized impurity scattering. If the
compensation could be reduced to less than 0.01%, the
room-temperature resistivity of these diamond films would
be expected to decrease by three order of magnitude. The
variation of resistivity for the lightly doped diamond films
as a function of temperature is shown in Fig. 6. The
author is uncertain, at present, why the thermal activation
energy, E , of the resistivity deviates from the ionization
energy (0.37 eV) of the boron dopants. The heavily doped
films have boron concentrations of 1 x 1021 to 10 x
1021 cm-3 and are very conductive. At such doping
671
 ...
[ ' I I
-0.(110)
(loo)

E c 2 ' lO+eV

E 2 A 10-~,v
IONS -1
c-

c-
ION GUN

0001 I I
DIAMOND
I
I I
O 5 10 15

IOOOiT ( K ' )

Fig. 7. Resistivity as a function of temperature for (100)- and (110)-ori-

ented heavily boron doped diamond films. E is the thermal activation
energy of the resistivity. HIGH P R E S S U R E LOW P R E S S U R E

levels the boron atoms are sufficiently close for mobile

carriers (holes) to hop between boron atoms. Thus the
Fig. 8. Schematic drawing of an ion-beam-assisted etching system. The
resistivity of the films is nearly constant with temperature, ion gun is isolated from the reactive gas, NO2, by the LN2 trap.
as shown in Fig. 7. The impurities in these films as
determined by secondary ion mass spectroscopy are boron,
tungsten, molybdenum, and nickel. The tungsten appears
to be electrically inactive, but nickel is known to have
electronic states in the bandgap [19] and may compensate
2000 -
some of the boron doping. --
C
E
4 1500 -
ETCHING
111. ION-BEAMASSISTED w

The device fabrication sequence shown in Fig. 3 requires s

controlled etching, capable of producing structures several 4I 1000 -

micrometers deep with vertical sidewalls. Previously, excel-

lent results were obtained with carbon-containing materials, 500 -

such as polymers and graphite, using the dry etching

technique of reactive ion etching with 0 2 [20]. However,
with diamond the same technique resulted in low etching -25 25
TEMPERATURE ("C)
50 75 100

rates (20 nm min-'), poor selectivity between the masking

material (Ni or Cr) and the diamond, and uncontrollable Fig. 9. Etching rate of diamond as a function of substrate temperature.
results [21], [22]. An ion beam with a flux of 1 mA cm-' and a NO2 flux equivalent
pressure of 5 x lop3 torr were used to obtain this data.
Efremow et al. [22] have reported on a different dry
etching technique, ion-beam-assisted etching, which uses
a beam of 2-keV Xe+ ions and a directed flux of NO2
molecules. This etching system is shown schematically in
Fig. 8. It is believed that the NO2 adsorbs on the surface
of the diamond and that the energetic Xe+ ions catalyze a
reaction between NO2 and diamond forming CO and C02.
As the diamond substrate temperature is reduced, more
NO2 adsorbs on the diamond surface and the etching rate
increases, as shown in Fig. 9. For temperatures below OC,
the adsorbed NO2 film is believed to be too thick for the
ions to deposit enough energy at the NO2-diamond interface
to catalyze a reaction. Below -25OC no etching occurs and
the adsorbed NO2 film is thick enough to be visible with
the naked eye. This etching technique has been used to
fabricate devices, and an example of an etched diamond
structure is shown in Fig. 10.

I v . Si02-DIAMOND INTERFACE
- -- - m a

Crucial to the operation of the device depicted in Fig. 3 is Fig. 10. Scanning electron micrograph of a grating etched into diamond.
a device-quality SiO2-diamond interface [23].Such device- Aluminum was used to mask the diamond during etching.

672 PROCEEDINGS OF THE IEEE. VOL. 79. NO. 5 , MAY 1991

 sr I I I I I I I I
1
/1/ DIAMOND 1 VACUUM LEVEL

l t
0 1 1 1 1 1 I l l
-50 30 -10 10 30 50 70 90 110
BIAS VOLTAGE (V)

(a)
7
I I I I I 1 I
BIAS VOLTAGE (V)

A
T Fig. 12. Energy diagram of a metal-SiOz-diamond structure for a
(100)-oriented substrate. E c is the minimum energy of electrons in
Ilb
the conduction band, Ev is the maximum energy of electrons in the
valence band, and EF is the Fermi energy level. A lower estimate of the
MOS STRUCTURE
positive-interface trap level density is plotted versus energy (the energy
axis coincides with the SiOz-diamond interface).

'!ii -54 -30 -10 10 30

BIAS VOLTAGE (V)

(b)
50 70 90

Fig. 11. Theoretical and experimental capacitance data for a (lOO)-ori-

110
09ev

t
32ev
I
A
VACUUM LEVEL

EC

=o 6 e~
07eV
............. ..............

f
48eV

BORON
ACCEPTORS
ented substrate plotted as (a) capacitance versus bias voltage and (b)
inverse capacitance squared versus bias voltage. The substrate was held
at 25OoC. Capacitance was determined with a 10-kHzsignal. The inset
EF
I /
~ __-_---- ----- EF
-.________---------_._.____
______.__ 0 0 030 0 0 0
4 d
EV
in (a) shows energy levels of a metal-SiOz-diamond structure biased into
depletion. The inset in (b) is a schematic drawing of a metal-SiOz-diamond 9 eV
structure. 514

AI DIAMOND

quality interfaces have been formed, and their properties + <ill>

were shown to depend upon the cleaning procedure, the EV

deposition temperature of the Si02, and the crystalline 7 '

orientation of the diamond surface. The p-type diamond
substrates, with boron doping densities on the order of
N 10l6 ~ m - ~were
, cleaned in a plasma asher using a
gas mixture of 2% 0 2 in He, followed by an immersion
in a 2OOOC solution of (NH4)2S208 and H2SO4 and a
rinse in water and acetone. The Si02 was chemically vapor
deposited on the diamond at 45OOC from a gas mixture of
SiH4, Ar, N2 and 0 2 .
The electrical properties of the interface were character-
ized by measuring the capacitance between the diamond
substrate and an aluminum electrode on top of the Si02
as a function of bias voltage between the electrode and
the diamond substrate. Figure ll(a) shows the results of
a typical measurement. When the electrode is negatively
charged, positive carriers (holes) in the diamond move
under the electrode, and the capacitance is proportional
to the area of the electrode divided by the thickness of
the Si02 film. When the electrode is biased positively,
the holes are forced away from the electrode forming a
region depleted of mobile carriers in the diamond, and
the capacitance decreases. As shown in Fig. ll(b), for a
/
uniformly doped semiconductor, the inverse capacitance
squared plotted as a function of bias voltage is a straight
line, indicating a well-behaved Si02-diamond interface.
Most semiconductors do not form device-quality interfaces
with Si02. For example, the SiO2-GaAs interface is not of
device quality and the bias voltage has little or no effect on
either holes or electrons in the semiconductor, as indicated
by a capacitance that is nearly independent of bias voltage.
From this and similar measurements of capacitance as a
function of Si02 thickness and bias voltage, the conduction
and valence band energy levels were calculated with respect
to the Fermi energy of the aluminum electrode. Figures 12
and 13 show the calculated energy levels of (100)- and
(1 11)-oriented diamond substrates in relation to those of
Si02 and aluminum. A lower estimate of the electronic
interface states at the Si02 and (100)-oriented diamond
surface as a function of energy is shown in Fig. 12. The

GEIS: DIAMOND TRANSISTOR PERFORMANCEAND FABRICATION 613

estimate of interface states, which was determined from
the variation of capacitance as a function of temperature,
is discussed in detail elsewhere [23].It is surprising that
the energy levels of (100)- and (111)-oriented diamond
surfaces as shown in Figs. 12 and 13 are different, since Si
and Ge, which have the same crystal structure as diamond,
have little or no variation of their energy levels with
different crystal surfaces. Himpsel et al. [24] and Pate [25]
determined that a clean (111)-oriented diamond surface
in an ultrahigh vacuum has a negative electron affinity,
that is, the energy of electrons in the conduction band
is above the vacuum energy. However, it is surprising
that the (111)-oriented surface still has a negative electron
affinity even when coated with SiOz. Both the (100)-
and (1 11)-oriented diamond surfaces have device-quality
interfaces with Si02, and the (111)-oriented surfaces neg- DEPTH Inm)
ative electron affinity may make diamond cold cathodes Fig. 14. Conductance of the modified diamond layer on (100)-oriented
possible. substrate as a function of etched depth into the diamond. Ion-beam-assisted
etching was used to etch the layer.

V. OHMICCONTACTS
Since it is often difficult to make ohmic contacts to large-
bandgap semiconductors, several groups have pursued the
development of these contacts on semiconducting diamond.
Fang et al. [26] have found that ohmic contacts can be
formed on diamond by depositing a metal on the diamond
surface and mixing the diamond-metal interface by ion
implantation through the metal into the diamond. Moazed
et al. [27], [28] demonstrated ohmic contact formation by
using a metal that reacts with diamond to form carbides.
He deposited the metal (tungsten or molybdenum) at room
temperature and annealed the structures near 900C to
cause the reaction between the diamond and the metal and
thus producing an ohmic contact.
We have found that indium forms ohmic contacts to
diamond without high-temperature processing or ion im-
plantation. However, its low melting temperature, 156C
makes it impractical for high-power, high-temperature de-
vices. Ohmic contacts can also be created by intense argon-
fluoride excimer laser radiation, which modifies the surface
of diamond forming a conductive layer [29]. This layer
forms an ohmic contact to p-type diamond. Its thickness
(approximately 50 nm) is determined by measuring the con-
ductivity as a function of etched-depth, as shown in Fig. 14.
Transmission electron diffraction patterns and micrographs,
shown in Figs. 15 and 16, respectively, indicate that this
conductive layer is a composite structure of diamond and a
graphite-like material. The layer is stable to 1800C and is
not etched by standard techniques known to etch graphite,
plasma ashing in He containing 2% 0 2 or in a solution of
Cr03 and H2S04 at 200C.

Fig. 15. Typical transmission electron diffraction pattern from the modified layer. The Miller indexes for diamond and the lattice spacing associated
with the modified region are shown.

674 PROCEEDINGS OF THE IEEE, VOL. 79, NO. 5 , MAY 1991


+---t(r~~~---+
Fig. 16. (a) Bright-field and (b) dark-field transmission electron micro-
graphs of laser-modified (100)-oriented diamond. The inset in (a) shows
the electron diffraction pattern and the portion of the pattern used to form
the dark-field image. Transmission electron micrographs of the unmodified
diamond used in these experiments showed no defects except for a very
occasional dislocation.
Heavily boron doped diamond ~ m - ~also
) forms
ohmic contacts with most evaporated metals without any
additional processing. These ohmic contacts have very low
contact resitance of [30], which is equivalent
to that of Si [31]. Ohmic contacts will not limit device
preforance.
VI. SUMMARY
Many of the fabrication sequences necessary for dia-
mond device production have been developed to the level
where interesting devices can be made. However, device
fabrication still presents two major difficulties, namely, the
production of a highly conductive single crystal diamond
substrate and the ability to grow lightly doped diamond
films with compensation levels less than 0.01% of the
boron doping concentration. There is no fundamental reason
why these difficulties cannot be overcome, and when the
problems are solved the production of useful diamond
transistors will become possible.
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675
 Michael W. Geis received the B. A. degree
in physics and the M. S. degree in electrical
engineering from Rice University, Houston, TX,
in 1970. He received the Ph.D. degree in
space physics and astronomy also from Rice
University in 1976.
During his graduate work, he studied atomic
and molecular physics with emphasis on charge
exchange reactions. From 1976 to 1978 he
worked as a postdoctoral student in the
Chemistry Department of Rice University,
studying laser-driven chemical reactions between molecular beams.
In 1978 he joined the submicrometer technology group of Lincoln
Laboratory, Massachusetts Institute of Technology, Lexington. He has
been involved with semiconductor-on-insulator technology using zone-
melting recrystallization, submicrometer structure fabrication, and dry
etching with reactive ion etching techniques, diamond growth, and device
fabrication.

676 PROCEEDINGS OF THE IEEE. VOL 7Y. NO 5 , MAY ICJCJI