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Silicon carbide (SiC) prepared by chemical vapour DDS, TCS or TS as a reactant and to investigate
deposition (CVD) remains of importance for both the change of the microstructure.
structural [1, 2] and electronic [3,4] applications. A The SiC coatings were deposited in a horizontal
variety of gaseous precursors has been used for SiC quartz reactor at 1000— 1500 °C and under atmo-
deposition under widely varying conditions of input spheric pressure. The temperatures were measured
gas composition, temperature and pressure [5]. For with an optical pyrometer and corrected to approx-
CVD of SiC, in general, a carrier gas is bubbled imate the temperature of substrate in accordance
through a silicon containing liquid mixed with with a previous calibration with a thermocouple.
another stream of carrier gas. The necessary carbon Graphite plates and SiC-coated graphite were used as
is either contained in the chlorosilane or supplied by substrate and susceptor, respectively. The three types
introducing a hydrocarbon. of methylchlorosilane (DDS, TCS and TS) were used
Methylchlorosilane (MTS: CH3SiCI3), as a pre- and they were carried by hydrogen from the
cursor, is one of the most useful of the available evaporator maintained at 0 °C. The concentration of
chlorosilanes because it contains silicon and carbon methylchlorosilane was controlled with hydrogen.
in stoichiometric proportions [6]. Accordingly, it has The total flow rate of X (X = DDS, TCS or TS) +
been expected to give stoichiometric SiC deposition. H2 gas mixture was kept constant at 1600 standard
Recently, from thermodynamic studies on the CVD cubic centimetres per minute (sccm). The growth
of SiC in the MTS + H2 gas system [7, 8], it has rate was estimated by measuring the weight increase
been shown that SiC is the only stable solid phase during deposition periods. The crystal structure was
present in a wide range of temperature, pressure and analysed by X-ray diffractometry (XRD) and the
concentration of the reactant. In experimental works, silicon content of the coating layer was determined
however, there have been many reports in the by energy dispersive spectrometry (EDS) and Auger
literature [9, 10] showing that excess Si is codepos- electron spectroscopy (AES). The surface morphol-
ited with SiC at lower temperature. Furthermore, in ogy of the coating layer was investigated by
our previous work [11] conducted with the scanning electron microscopy (SEM). Details of the
MIS + H2 gas system in the temperature range experimental procedure were similar to those
l000—1500 °C, we always found excess Si deposition reported previously [11, 12].
at temperatures below 1400 °C. In order to obtain The molar fraction dependence of the deposition
stoichiometric SiC deposition, we recently reported rate is shown in Fig. 1. The results of previous work
[12] the addition of propane (C3H8) as an excess [11], carried out in the MTS + H2 system, are also
carbon source to the MTS + H2 gas system, which shown for comparison. The total flow rate of
resulted in the deposition of stoichiometric SiC. methylsilane was 1600 sccm and the temperature of
Therefore, it is conceivable that silanes are more the graphite substrate was 1300 °C. As shown in
reactive with the substrate than hydrocarbon and Fig. 1, the deposition rate increased linearly with
supplying excess carbon is needed for stoichiometric increasing reactant concentration. Hunt and Stirl [13]
SiC deposition. There are some precursors that have shown that the growth rate r is determined by
supply excess carbon, such as dimethyldichlorosilane the relationship expressed as r = 7E Po TF, where
(DDS: (CH3 )2 SiC12), trimethylchlorosilane (TCS: 11E, Po and TF are deposition yields in experimental
(CH3)3SiCl) and tetramethylsilane (TS: (CH3)4Si). work, partial pressure of reactants and total system
These chlrorosilanes contain both silicon and carbon, pressure, respectively. Thus, increase of the molar
and the ratios of C/Si in the molecules are 2, 3 and fraction (X/(X + H2), X = MTS, DDS, TCS or TS)
4, respectively. In addition DDS, TCS and TS leads to linear increase in the growth rate. By using
molecules decompose more easily than MIS and DDS (C/Si = 2), a higher growth rate was achieved,
supply sufficient hydrocarbon above the .substrate. while it decreased with TCS or TS.
The purpose of the work reported here was thus to The temperature dependence of the deposition rate
prepare stoichiometric SiC deposit by supplying is shown in Fig. 2. In the MTS + H2 system, as is
0261-8028 1997 Chapman & Hall 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).
70
a-
(\J
60 50
20 (degrees)
40 30
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