77

D. Flandre et al. (eds.), Science and Technology of Semiconductor-On-Insulator Structures

and Devices Operating in a Harsh Environment, 77-84.
2005 Kluwer Academic Publishers. Printed in the Netherlands.
CVD DIAMOND FILMS FOR SOI
TECHNOLOGIES
V. Ralchenko
1
, T. Galkina
2
, A. Klokov
2
, A. Sharkov
2
, S. Chernook
2
and
V. Martovitsky
2
1
A.M. Prokhorov General Physics Institute RAS, Vavilov str. 38, Moscow 119991, Russia;
2
P.N. Lebedev Physical Institute RAS, Leninsky prospekt 53, 119991 Moscow, Russia
2
Abstract: Diamond films is an interesting material for silicon-on-insulator technologies
due to a unique combination of properties that can enhance to electronic
device performance. Current CVD techniques for diamond growth allow the
production of diamond layers with a thickness from less than 1 micron to a
few mm on Si substrates of large area. As the direct diamond-to-silicon
bonding requires high temperature (>1150C) and still is problematic, the use
of a Si substrate as the device layer after diamond deposition could be an
alternative. No dramatic degradation of silicon after diamond deposition at
750C by microwave plasma assisted CVD is found as revealed from
resistivity, X-ray diffraction and acoustic phonon scattering measurements.
Further studies of electronic properties of the diamond-coated Si are required
to evaluate the feasibility of Si-on-diamond (SOD) device fabrication.
Key words: SOI, diamond film, thermal conductivity, stress, silicon, interface, ballistic
phonons.
1. INTRODUCTION
Conventional silicon-on-insulator (SOI) technology uses a buried silicon
dioxide SiO
2
isolation layer to allow device fabrication operating at lower
voltage, at higher frequencies, in harsh environment. However, because of
low thermal conductivity of SiO
2
any increased integration density and
power dissipation may cause problems. Diamond can be investigated as a
novel dielectric material for SOI systems, as it possesses a unique
combination of properties useful to electronic device performance (Table 1).
In particular, its thermal conductivity, up to 22 W/cmK, is three orders of
magnitude higher that that of SiO
2
and five times better than for copper.
78 V. Ralchenko et al.
High breakdown field strength, low dielectric constant, high radiation
resistance, extreme hardness make diamond very attractive for high
temperature, high power, radiation-hard devices.
Currently, thin coatings (one micrometer) and thick (up to 2 mm),
polycrystalline diamond wafers can be grown at low pressure using a
chemical vapor deposition (CVD) technique
1-4
. The synthesis process is
based on the decomposition of a methane-hydrogen gas mixture by a variety
of methods (plasma, flame, hot filament and some others), which resulting in
the deposition of diamond on a hot (typically 600-1000C) substrate, in most
cases silicon. The most pure and high quality diamond films are produced by
microwave plasma enhanced CVD (MPCVD) technique. The MPCVD
reactor (5 kW, 2.45 GHz) developed at General Physics Institute RAS for
diamond synthesis, and a selection of produced diamond wafers and thin
films on Si substrates of up to 100 mm diameter, are shown in Fig. 1.
Table 1. Properties of Si and some dielectrics important for SOI devices @300.
Property Si SiO
2
sapphire diamond
Thermal conductivity, W/cmK 1.51 0.014 0.34 10-22
Resistivity, Ohm_cm 10
-3
-10
4
(*) 10
13
-10
19
10
16
10
12
-10
15
Dielectric constant, 11.7 3.8 9.4 5.7
Breakdown field, V/cm 3.710
5
10
7
(**) 6.410
5
10
7
Loss tangent, 10
-6
@145 GHz 3* 300 200 3-8
Thermal expansion coef., 10
-6
K
-1
2.5 0.5 8.2 0.8
Youngs modulus, GPa 160 73 380 1050
*doped with Au; **~10 nm thick film
Figure 1. MPCVD reactor for diamond deposition (left) and a selection of produced diamond
films and wafers (right).
The diamond can be separated from the substrate by chemically
removing the silicon in HF-HNO
3
acid to produce a free-standing film. The
CVD diamond films for SOI technologies 79
material is polycrystalline with randomly oriented grains, with a very rough
top surface. A surface roughness less than 10 nm can be achieved by
mechanical polishing, which, is a difficult and slow procedure because of the
extreme hardness of diamond. The bottom (nucleation) side is smooth, being
the replica of the mirror-polished Si substrate. Typically a surface roughness
R
a
< 15 nm is measured on the nucleation side provided high-density
diamond seeding of the substrate before deposition
5
. The machining of
diamond films, such as cutting, drilling, patterning, rough polishing can
conveniently be performed using lasers
6
.
The thermal conductivity of translucent thick (several hundreds microns)
films is k=16-18 W/cm K at room temperature. With the temperature is kk
increased to T=200C the thermal conductivity decreases down to 10-12
W/cmK (Fig. 2), mainly due to phonon-phonon scattering mechanisms
following the approximate relationship k ~ T k
-1 7
. Thin films consist of small
grains laced with defects and impurities, primarily Si and H, and the thermal
conductivity of the films with thickness up to 10 m typically is <10
W/cmK.
8
As the crystallite size and perfection increase with film thickness
there is a gradient in thermal conductivity across the film, the difference
between the conductivity at the top and bottom surfaces can amount to factor
of three
9
. The thermal conductivity displays an anisotropy because the grains
have columnar shape with their axes directed perpendicular to the film
surface. Perpendicular conductivity k

k is typically larger by 10-20% than the

in-plane values k
II
kk
7
.
300 350 400 450
2
4
6
8
10
12
14
16
18
T
h
e
r
m
a
l

d
i
f
f
u
s
i
v
i
t
y
,

c
m
2
/
c
T
h
e
r
m
a
l

c
o
n
d
u
c
t
i
v
i
t
y
,

W
/
c
m

K
Temperature, K
0
2
4
6
8
10
12
14
16
18
1
2
2
1
Figure 2. Temperature dependence of in-plane thermal diffusivity D (dotted lines) and
thermal conductivity k (solid lines) for two diamond films (Nos. 1&2) of approx. 0.3 mm
thickness
7
. The data are obtained using the laser-induced dynamic grating technique.
80 V. Ralchenko et al.
The device layer may be placed on the diamond substrate in two ways: (i)
by a bonding process, or (ii) via direct deposition of diamond film on silicon,
followed by Si thinning. Yushin et al.
10,11
found that the complete bonding of
diamond to Si is possible at temperatures above 1150C, however, cracks
always appear due to thermal stress caused by the high bonding temperature.
The thermal treatment of CVD diamond in vacuum should be limited to
1200-1300C, at which temperatures the internal graphitization takes place
at the grain boundaries (GB)
12,13
, and the diamond becomes electrically
conducting along the transformed GBs. The de-bonding of hydrogen which
passivates the grain boundaries and extended defects in as-grown material, is
believed to trigger the GB graphitization process.
In case of the diamond deposition a little is known about changes in Si
substrate structure induced by high temperature (700-900C), and its
interaction with hydrogen and carbon during the deposition process. When
the radial temperature gradient in the substrate takes place a plastic
deformation was observed in silicon near the film-substrate interface
14
. Here
we address the issue of possible defects formation in Si substrate as a result
of diamond growth on it.
2. EXPERIMENTAL DETAILS AND RESULTS
Diamond films were deposited on Si wafers at T=720-750C by
microwave plasma CVD using CH
4
(2.5%)/H
2
(97.5%) mixture as the source
gas
3
. Dislocation-free (dislocation density <10 cm
-2
) polished (100) Si
wafers 10 mm in diameter and 3 mm thick were used as the substrates.
Typically, 15 m thick films with grain size of 3-5 m were produced for
deposition runs of 9 hours at 5 kW MW power and 90 Torr pressure (Fig. 3).
Figure 3. SEM pictures of 15 m thick polycrystalline diamond film on Si: (left) cross-
section, (right) typical diamond surface morphology.
CVD diamond films for SOI technologies 81
MicroRaman spectroscopy (ISA, S3000 model) was used to identify the
diamond structure and stress in the film and substrate. The scattering was
excited at wavelength 488 nm of an Ar
+
laser. The laser spot diameter on the
analyzed surface was either 2 or 20 m. A sharp peak at 1333.5 cm
-1
with
width (FWHM) 6.7 cm
-1
in the spectrum (Fig. 4) confirms the cubic diamond
structure with a negligible inclusion of amorphous carbon (wide weak band
around 1550 cm
-1
). The peak is shifted to higher frequencies respective to
the peak position of 1332.5 cm
-1
characteristic of unstressed diamond. This
indicates a compressive stress = 0.6 GPa in the film, as estimated from the
correlation
15
between the stress and the shift in Raman peak position:
[GPa] = - 0.61 [cm
-1
]. This stress is very close to the thermal stress
value of 0.7 GPa for deposition temperature T=830C
14
, which is caused by
a mismatch between the thermal expansion coefficients of diamond and Si,
being generated upon sample cooling after the process finish.
1200 1250 1300 1350 1400 1450 1500 1550 1600 1650
peak position 1333.5 cm-1
H
u
f
e
u
c
u
e
u
o
c
f
u
,
o
f
u
.
e
p
.
Raman shift, cu
-1
Figure 4. Raman spectrum of diamond film.
A stress in silicon induced by diamond growth process has also been
evaluated by X-ray diffraction measured on the sample cross-section with
spatial resolution 200 m. The width (FWHM) of the (400) signal in the
rocking curve was 8 sec. for virgin Si. After the diamond deposition it
increased to 20 sec. only in a layer (<200m) adjacent to the film (Fig. 5),
but remained narrow (~8 sec.) across the rest thickness except the layer,
adjacent to the diamond film. This indicates the presence of some stress in
the silicon.
As an additional characterization of silicon substrate quality the
propagation of non-equilibrium acoustic phonons across the diamond/Si
structure was studied in transmission geometry at cryogenic temperature T=
1.8 K (Fig. 6). The phonons were generated either by direct photoexcitation
82 V. Ralchenko et al.
of silicon or diamond by the UV pulses of a nitrogen laser (=7.5 ns,
=337 nm)
16
. The temporal evolution of the bolometer signal from phonons
propagating through the virgin and exposed to diamond deposition silicon is
shown in Fig. 7. The insert in Fig. 7 shows the spatially resolved phonon
flux at the time t=700 ns after the laser pulse. The degree of darkness tt
corresponds to phonon flux intensity. The observed anisotropy is the proof
of low phonon scattering in silicon substrate after CVD deposition.
-40 -20 0 20
0
200
400
600
800
1000
I
n
t
e
n
s
i
t
y
,

p
u
l
s
e
s
/
s
Seconds of arc
Point 1
Point 2
CVD diamond
Si substrate
1 2
Figure 5. Rocking curves of (400) signal for the monocrystalline Si substrate measured at
Si/diamond interface (point 1) and from the back side (point 2).
The only scattering source in the virgin sample is the scattering by
isotopes. No increase of acoustic phonon scattering in Si was observed after
diamond deposition, so the generation of thermally activated defects by the
deposition process was insignificant. No change in the resistivity of Si
substrate compared to the virgin Si (3.3 kOhmcm) has been found after the
deposition process. Of course, a more detailed analysis is needed to better
characterize the Si modifications, yet there is a hope that the potential
degradation of Si in diamond growth environment can be minimized by the
careful choice of CVD process conditions. This would make possible to
obtain an adherent device layer on diamond substrate after for SOD
electronic devices fabrication.
CVD diamond films for SOI technologies 83
Superconducting bolometer
CVDdiamond film ll
Silicon substrate
Scanning laser beam
0 200 400 600 800 1000
0
50
100
150
200
50 52 54
16
18
X, mm
Y
,

m
m
Virgin Si
Si with CVD
B
o
l
o
m
e
t
e
r

r
e
s
p
o
n
s
e
s
,

a
r
b
.
u
n
.
Time, ns
Figure 6. Schematics of laser induced
phonon generation
Figure 7. Bolometric responses to laser-
generated phonons propagating in virgin Si
and diamond-on-silicon sample. The insert
shows the spatially resolved phonon flux at
t=700 ns.
3. CONCLUSIONS
Polycrystalline CVD diamond is a promising dielectric material for high
power, high-frequency, radiation-hard SOI systems, since it possesses
extremely high thermal conductivity, can be produced on large area Si
substrates in form of thin films as well as wafers. Potentially, silicon-on-
diamond should have advantage over silicon-on sapphire devices, if the
problem of Si/diamond bonding or direct diamond deposition on Si in mild
conditions could be solved. The present experiments reveal that the Si
substrates can withstand the MPCVD diamond growth environment without
significant degradation. Although currently some technological hurdles
(stress generation, polishing, high cost) retard the SOD development, the
impressive progress of CVD diamond technologies during the last decade in
growth of high quality, large size, uniform diamond films gives a hope that
the SOD systems will attract the adequate attention in near future.
ACKNOWLEDGEMENTS
The authors are thankful to K. Anisimov for preparation of diamond film
samples, I. Vlasov and S. Terekhov for Raman spectra measurements. This
work was supported in part by Russian Foundation for Basic Research, Nos.
02-02-17392 and 04-02-17060.
84 V. Ralchenko et al.
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