JOURNAL OF MATERIALS SCIENCE LETTERS 16 (1997) 33—36
Chemical vapour deposition of silicon carbide by pyrolysis of
methylchlorosilanes
BYUNG JIN CHOI
Department of Welding Engineering, Taegu Junior Health College, Taejeun-dong san 7, Pook-gu, Taegu 702-260,
Korea
DONG WON PARK, DAI RYONG KIM
Department of Metallurgical Engineering, Kyungpook National University, Sankyuk-dong 1370, Pook-gu, Taegu
702-701, Korea
Silicon carbide (SiC) prepared by chemical vapour
deposition (CVD) remains of importance for both
structural [1, 2] and electronic [3,4] applications. A
variety of gaseous precursors has been used for SiC
deposition under widely varying conditions of input
gas composition, temperature and pressure [5]. For
CVD of SiC, in general, a carrier gas is bubbled
through a silicon containing liquid mixed with
another stream of carrier gas. The necessary carbon
is either contained in the chlorosilane or supplied by
introducing a hydrocarbon.
Methylchlorosilane (MTS: CH3SiCI3), as a pre-
cursor, is one of the most useful of the available
chlorosilanes because it contains silicon and carbon
in stoichiometric proportions [6]. Accordingly, it has
been expected to give stoichiometric SiC deposition.
Recently, from thermodynamic studies on the CVD
of SiC in the MTS + H2 gas system [7, 8], it has
been shown that SiC is the only stable solid phase
present in a wide range of temperature, pressure and
concentration of the reactant. In experimental works,
however, there have been many reports in the
literature [9, 10] showing that excess Si is codepos-
ited with SiC at lower temperature. Furthermore, in
our previous work [11] conducted with the
MIS + H2 gas system in the temperature range
l000—1500 °C, we always found excess Si deposition
at temperatures below 1400 °C. In order to obtain
stoichiometric SiC deposition, we recently reported
[12] the addition of propane (C3H8) as an excess
carbon source to the MTS + H2 gas system, which
resulted in the deposition of stoichiometric SiC.
Therefore, it is conceivable that silanes are more
reactive with the substrate than hydrocarbon and
supplying excess carbon is needed for stoichiometric
SiC deposition. There are some precursors that
supply excess carbon, such as dimethyldichlorosilane
(DDS: (CH3 )2 SiC12), trimethylchlorosilane (TCS:
(CH3)3SiCl) and tetramethylsilane (TS: (CH3)4Si).
These chlrorosilanes contain both silicon and carbon,
and the ratios of C/Si in the molecules are 2, 3 and
4, respectively. In addition DDS, TCS and TS
molecules decompose more easily than MIS and
supply sufficient hydrocarbon above the .substrate.
The purpose of the work reported here was thus to
prepare stoichiometric SiC deposit by supplying
0261-8028 1997 Chapman & Hall
DDS, TCS or TS as a reactant and to investigate
the change of the microstructure.
The SiC coatings were deposited in a horizontal
quartz reactor at 1000— 1500 °C and under atmo-
spheric pressure. The temperatures were measured
with an optical pyrometer and corrected to approx-
imate the temperature of substrate in accordance
with a previous calibration with a thermocouple.
Graphite plates and SiC-coated graphite were used as
substrate and susceptor, respectively. The three types
of methylchlorosilane (DDS, TCS and TS) were used
and they were carried by hydrogen from the
evaporator maintained at 0 °C. The concentration of
methylchlorosilane was controlled with hydrogen.
The total flow rate of X (X = DDS, TCS or TS) +
H2 gas mixture was kept constant at 1600 standard
cubic centimetres per minute (sccm). The growth
rate was estimated by measuring the weight increase
during deposition periods. The crystal structure was
analysed by X-ray diffractometry (XRD) and the
silicon content of the coating layer was determined
by energy dispersive spectrometry (EDS) and Auger
electron spectroscopy (AES). The surface morphol-
ogy of the coating layer was investigated by
scanning electron microscopy (SEM). Details of the
experimental procedure were similar to those
reported previously [11, 12].
The molar fraction dependence of the deposition
rate is shown in Fig. 1. The results of previous work
[11], carried out in the MTS + H2 system, are also
shown for comparison. The total flow rate of
methylsilane was 1600 sccm and the temperature of
the graphite substrate was 1300 °C. As shown in
Fig. 1, the deposition rate increased linearly with
increasing reactant concentration. Hunt and Stirl [13]
have shown that the growth rate r is determined by
the relationship expressed as r = 7E Po TF, where
11E, Po and TF are deposition yields in experimental
work, partial pressure of reactants and total system
pressure, respectively. Thus, increase of the molar
fraction (X/(X + H2), X = MTS, DDS, TCS or TS)
leads to linear increase in the growth rate. By using
DDS (C/Si = 2), a higher growth rate was achieved,
while it decreased with TCS or TS.
The temperature dependence of the deposition rate
is shown in Fig. 2. In the MTS + H2 system, as is
33
 250 always found the formation of SiC powder in front
of the susceptor while using TCS and TS as
reactants. This can be rationalized on the basis of
200 the fact that the thermal decomposition temperatures
E of the methylchlorosilanes decrease in the order
(2
MTS > DDS > TCS > TS.
150
C) Typical XRD patterns of the layer prepared with
E
a)
DDS are shown in Fig. 3. The samples were
deposited for 20 mm and the molar ratio of DDS
100
C
0 was 0.01. As shown in Fig. 3, (111), (220) and
0 (3 11) peaks of fl-SiC, belonging to the cubic
0
a) system, were observed. The diffraction pattern of
a 50 the layer deposited at 1100°C is relatively broad,
indicating micro-crystalline /3-SiC. With increasing
substrate temperature, the diffraction pattern became
0— sharp and the intensity of the diffraction lines
0.000 0.005 0.010 0.015 0.020 0025
increased. There was no evidence of excess silicon
Molar fraction (X/(X + H2))

(a
deposit. Graphite peaks of (0 02) were detected in
Figure / Deposition rate as a function of molar fraction of reactants: the deposits obtained at 1500 °C, showing the
substrate temperature 1300°C. (---), MTS [111; (•), DDS; (A), TS; existence of free carbon in the deposits.
(.), TCS. Figs 4 and 5 show the diffraction patterns of the
deposits obtained with TCS and TS. These patterns
100 are somewhat different to the results of DDS
9 (Fig. 3). As shown in Fig. 4, the diffraction pattern
8 of the deposit prepared at 1100 °C using TCS shows
7 sharp and narrow peaks compared to Fig. 3. This
means that the deposits were well crystallized at
6 lower temperature. Relatively weak carbon and
0) 5
E
II)
8
C
0
(I)
0
a.
oa) 3

(b
5.5 6.0 6.5 7.0 7.5 8.0 I I I I I

(c
Reciprocal temperature (1 04/T, K1) 80 70 60 50 40 30 20
20 (degrees)
Figure 2 Temperature dependence of deposition rate; molar fraction of
reactants 0.01. (- --), MTS [11]; (I), DDS; (A), TS; (.), TCS. Figure 3 XRD pattems of the deposits obtained in the DDS + H2
system at (a) 1100, (b) 1300 and (c) 1500 °C. DDS molar fraction:
the case with CVD, the temperature dependence was 0.01; deposition time: 20 mm. SiC: (V), (Ill); (s), (220); (0),
divided into two linear regions, following the (311). C: (V), (002); (•), (102); (•), (110); (•), (004).

Arrhenius-type relationship. With DDS, TCS and

TS, however, the deposition rate reached a maximum
and further increase of the temperature decreased the
deposition rate. The maximum temperatures were
1400°C (DDS), 1100 °C (TCS) and 1000 °C (TS). (a)——-—--————_—-————---——--'-—-—-—"
Decrease of the deposition rate in the high tempera-
ture region is often reported. Cheng et al. [14], with
the MTS + H2 system, showed that the maximum
deposition rate occurred at 1300—1400 °C, and they
explained that the decrease in the deposition rate at
high temperature was due to etching effects on the I I I I

substrate surface. In our present investigation, the 80 70 60 50 40 30 20

decrease of the deposition rate at higher temperature
can be explained by etching effects in the case of
DDS, while the decrease of the growth rate above
1100 °C in TCS or 1000 °C in TS is thought to be
caused by gas phase reaction above the substrate. We
34
20 (degrees)
Figure 4 XRD patterns of the deposits obtained in the TCS + H2
systcm at (a) 1100, (b) 1300 and (c) 1500 °C. TCS molar fraction: 0.01;
deposition time: 20 mm. SiC: (7), (111); (LI), (220); (0), (311). C:
(V) (002); (•), (I 02); (•), (004).
 (a
80
Co

70
a-
(\J

60 50
20 (degrees)
40 30

of the deposits obtained in the

Figui'e 5 X—ray ditilaction patterns
TS + H system at (a) 1200. )b) 1300 and (C) i500 C. IS molar
fraction: 0.01: deposition time: 20 miii.
20
here. TCS and TS also gave near stoichiometric SiC
deposition at ll00—1300°C. A large amount of
excess carbon was produced above 1400 °C by using
TCS and TS as a precursors.
As can be seen in the XRD patterns (Figs 3—5)
and EDS analysis, it is evident that chemical
composition is dependent on temperature and the
C/Si ratio of the reactant i.e. the tendency of carbon
codeposition is stronger when the substrate tempera-
ture and the C/Si ratio of reactants are higher. By
controlling these two factors properly, stoichiometric
SiC deposition can be obtained.
The surface appearance was investigated by SEM.
Fig. 7 compares the SEM micrographs of the as-
deposited SiC surfaces obtained by the pyrolysis of
DDS, TCS and TS. The substrate temperature was
strong /3-SiC peaks were detected in the deposits 1300 °C, the molar fraction of the reactants was 0.01
obtained at 1300 °C. The 13-SiC peaks were not seen and the deposition time was 20 mm. The SiC surface
at 1500 Of it is thought that the carbon peaks in Fig. deposited by the pyrolysis of DDS showed cellular
4c correspond to graphite substrate. We could find structure (Fig. 7a). It is supposed that a large
neither SiC nor carbon deposition at 1500 °C in the
TCS + H2 system. As can be seen in Fig. 5, carbon
peaks were always detected with /3-SiC peaks in
deposits obtained with TS regardless of the substrate
temperature, and the carbon peaks become stronger
with increasing substrate temperature. Therefire,
these results indicate that the deposition of carbon
is dependent on the substrate temperature and the C/
Si ratio of the reactants.
The chemical compositions of the deposits are
shown in Fig. 6. The chemical composition was
investigated by AES and EDS. In EDS analysis, only
the silicon contents of the samples were determined.
From the previous work, MTS yielded a considerable
amount of excess silicon at temperatures below
1400 °C; with increasing temperature, the amount of
excess silicon decreased gradually, and stoichio-
metric /3-SiC could be obtained only at 1500 0C.
DDS, however, produced almost stoichiometric SiC
at temperatures below 1400 °C in the work reported

100

80

in
60
C
5)
C
0
C)
C
0 40
0
Cl)

20

0—
900 1000 1100 1200 1300 1400 1500 1600
Deposition temperature (°C)

Fl gui-c 6 Si icon content as a function of substrate tenipelatuic: molar Figws 7 SEM micrographs of surface deposited at 300 C by using
fraction of reactant: 0.01. )———). MIS [Ii]: )•), DDS: (A). TS: (.). (a) DDS. )b( T(S and (c) TS. Molar fraction of reactants: 0.1)1:
'CS. deposition time: 20 miii.

35
 percentage of the cell boundary is composed of 2. K. MIYOSHI, D. H. BUCKLEY and M. SRINIVASAN,
carbon, which hindered the further growth of SiC Ceram. Bull. 62 (1983) 495.
crystal. The surface obtained with TCS (Fig. 7b), on 3. W. VON MUENCH and E. PETTENPAUL, .1. App!. Phys.
48 (1977) 4823.
the other hand, showed small worm-like structure. 4. J. KENDALL, .1 Che,n. Phys. 21(1953) 821.
The surface obtained by TS showed needle-like 5. J. 5CHLICHTING, Powder Metal!. tnt. 12 (1980) 141.
structure and the crystals were smaller than those of 6. R. J. PRICE, Nod. Technol. 35 (1977) 320.
TCS, as shown in Fig. 7c. These changes in 7. A. I. KINGON, L. J. LUTZ and R. F. DAVIS, I. Amer
microstructure are thought to be related to the Cera,n. Soc. 66 (1983) 558.
carbon content in the deposits, i.e. the crystal size 8. G. S. FISCHMAN and W. 1. PETUSKEY, ibid. 68 (1985)
185.
decreases with increasing C/Si ratio of the reactants 9. K. MINATO and K. FUKUDA, I. Mater Sci. 23 (1988)
because the excess carbon blocks the growth of the 699.
SiC crystal. 10. J. CHIN and T. OHKAWA, Nuci. Technol. 32 (1977) 115.
11. B. J. CHOI and D. R. KIM, .1 Mate,: Sci. Lett. 10(1991)
860.
12. B. J. CHOI, S. H. JEUN and D. R. KIM, I. Em: Ceram.
Acknowledgement Soc. 9 (1992) 357.
This paper was supported by the Non-Directed 13. L. P. HUNT and E. STIRL, .1 Electrochem. Soc. 135
Research Fund, Korea Research Foundation. (1988) 206.
14. D. J. CHENG, W. J. SHYY, D. H. KUO and M. H. HON,
ibid. 134 (1987) 3145.
References
1. M. K. BRUN and M. P. BOROM, I Ame,: Ceram. Soc. 72 Received 23 April
(1989) 1993. and accepted 1 August 1996

36