Diamond & Related Materials 15 (2006) 117 – 120

www.elsevier.com/locate/diamond

Effects of graphitization degree of crucible on SiC

single crystal growth process
Junlin Liu *, Jiqiang Gao, Jikuan Cheng, Jianfeng Yang, Guanjun Qiao
State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University, Xi’an, Shaanxi 710049, P.R.C

Received 22 March 2005; received in revised form 19 July 2005; accepted 6 August 2005
Available online 8 September 2005

Abstract

Effects of graphite crucible on mass transport and crystal growth process has been investigated in the fabrication of SiC single crystal by the
seeded sublimation growth method. Different graphitization degrees of the crucibles were obtained by heat treatment at various temperatures between
2100 and 2300 -C. The crucibles were subjected to SEM and XRD in which the graphitization degree was determined quantitatively. The
experimental results indicate that the graphite crucible plays an important role in the SiC crystal growth by providing carbon. High crystal growth is
obtained by using the untreated crucibles (corresponding to low graphitization degree), which contributes to the reaction activity between Si and
graphite of the crucible. Increasing the graphitization degree results in degradation in crystal growth, even in the graphitization of the SiC seed crystal.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Mass transfer; Graphitization degree; Single crystal growth; Growth from vapor

1. Introduction Computer simulation is a good method to gain information

on growth process of SiC single crystal [6,9,11– 14], although
The seeded sublimation growth method (modified Lely it has some shortcomings. Mathematic models together with
method) is a widely applied technique for growth of single SiC their boundary and interface conditions have more or less
crystals [1– 6], in which graphite crucible is generally used. In discrepancy with the actual processes. Moreover, numerical
the process of crystal growth, graphite crucible acts not only as simulations usually need some simplifications for mathematic
a heater (for furnace using induction heating) but also as a models. So computer simulation cannot fully solve the actual
container. Moreover, it is very important in mass transport problems.
during crystal growth. X-ray imaging technique is another popular method for
In the quasi-closed crucible, the mass transport is difficult the research of SiC growth process. Digital X-ray imaging
for direct observation in the crystal growth process. So system can visualize the growth process. Wellmann used this
researchers have to investigate mass transport by some indirect method to research the growth process [15,16]. Herro [17]
experimental methods and gain information on growth by studied the mass transport by adding 13C into the source
computer simulation. powder. In his report, mass transport process was illuminated
In a crucible where argon acts as inert gas, the gas is by X-ray imaging technique. However, the effect of crucible
composed of several species, such as Si, SiC, Si2C and SiC2 in mass transport and crystal growth has never been fully
besides argon, [7– 10]. Reactions in the crucible are complicat- investigated.
ed, including reactions between vapor and crucible wall, vapor In this paper, the effects of graphitization degree of crucible
and crystal surface, vapor and SiC power source and between on crystal growth and mass transport are conducted.
vapor species inside crucible. Those reactions are objects
concerned by researchers. 2. Experimental procedure

6H-SiC bulk single crystals were prepared using the

* Corresponding author. Tel.: +86 2982665443. physical vapor transport (PVT) technique. The growth was
E-mail address: [email protected] (J. Liu). carried out in an inductively heated graphite crucible at high
0925-9635/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.diamond.2005.08.028
118 J. Liu et al. / Diamond & Related Materials 15 (2006) 117 – 120

temperatures (seeds temperatures were from 2050 to 2200 -C). (0 0 2)

The system pressure of the argon gas was 40 mbar and
temperature grads were about 30 -C/cm. The SiC seed crystals (0 0 4)
were 6H-SiC produced by the Acheson method and the (0 0 0
(1 0 1)
1) Si-face acted as the growth surface. The source material was
(1 0 0)
SiC powder with an average grain size of 120 Am. The distance
C
between the seed crystal and the source was about 20 mm.
Three kinds of the crucibles were used: original crucibles
(crucible A), crucibles treated at 2100 -C for 2 h (crucible B), B

and crucibles treated at 2300 -C for 2 h (crucible C).

Graphitization degree of crucible was measured by Rigaku A
X-ray diffractometer, using high-pure silicon powder as 20 30 40 50 60
calibrated standard material. Crucible walls were observed by 2θ / ( ° )
SEM after fabrication of the SiC single crystal.
Fig. 2. XRD results of different crucibles.
3. Results and discussion
A, the tendency of mass loss for the crucible B decreases
Fig. 1 shows the relationship between crystal growth rates obviously with some traces of original wall surface still
and temperatures. It can be seen that the growth rates in the remained. On the wall of crucible C are only some small pits
crucible A increase with the increase of temperature; however, and the original crucible surface is almost integrated.
the rates in the crucible B is very steady. In crucible C the seed According to Herro’s report [17], graphite crucible wall
crystals are graphitizated. Without crystal formation, the results exchanges carbon with gaseous species inside the growth
for the crucible C cannot be given. cell. The mechanism of exchange is described in formula (2)
Fig. 2 shows the XRD results of different crucibles. A, B, SiC2ðg Þ ¼ 2CðsÞ þ SiðgÞ ð2Þ
and C denote crucibles A, B and C, respectively. From A to
C, diffraction peaks become sharp and the intensities increase, In our experiments, graphite crucible wall not only
which indicates that crystallinity become much better. In other exchanges carbon with gaseous species inside the growth cell,
words, the graphitization is increased from crucible A to C. but also acts as expendable source during the growth process.
Graphitization degree of crucibles can be calculated by The main vapor species for the SiC + C system at high
formula (1) temperatures are Si, SiC2 and Si2C [18]. The mainly reactions
in growth process occurs as follows:
g ¼ ½ð0:344  d002 Þ=0:0086  100%: ð1Þ
SiCðsÞ ¼ SiðgÞ þ SiCðgÞ ð3Þ
Where g is graphitization degree, d 002 is crystal plane
distance of graphite (002) planes obtained from XRD results.
The d 002 and g values of the three kinds of crucibles are 2SiCðsÞ ¼ CðsÞ þ Si2CðgÞ ð4Þ
shown in Table 1.
SEM images of the crucible wall are shown in Fig. 3. An 2CðsÞ þ SiðgÞ ¼ SiC2ðgÞ ð5Þ
obvious mass loss can be seen for the wall of crucible A with
no original wall surface remained. Compared with the crucible Si2 CðgÞ ¼ CðsÞ þ 2SiðgÞ ð6Þ

SiðgÞ þ SiC2ðgÞ ¼ 2SiCðsÞ ð7Þ

2200 °C 2100 °C
10
Formulas (3) and (4) are the sublimation reactions of source
crucible A
SiC powder. Formula (5) is the reaction between graphite
crucible B
crucible and Si vapor. Formula (6) is the decomposing reaction
of Si2C vapor and (7) is the reaction for SiC crystal growth.
Growth rate (mm/h)

From above formulas, it can be seen that the SiC2 vapor ( p

1 (SiC2)) is from Reaction (3) ( p 1 (SiC2)) and Reaction (5) ( p 2
(SiC2), and the Si vapor ( p (Si)) is from Reaction (3) ( p 1 (Si))
and Reaction (6) ( p 2 (Si)).

Table 1
d 002 and g values of crucibles A, B and C
0.1 Crucible number d 002 (nm) g (%)
4.0 4.1 4.2 4.3
A 0.3371 80.2
10000/T (1/k) B 0.3366 86.4
Fig. 1. Growth rate versus seed temperatures. C 0.3362 90.7
 J. Liu et al. / Diamond & Related Materials 15 (2006) 117 – 120 119

Fig. 3. SEM images of different graphite crucible walls (a) crucible before growth, (b) crucible A after growth at 2150 -C for 5 h, (c) crucible B after growth at 2150
-C for 5 h, (d) crucible C after growth at 2150 -C for 5 h.

The equilibrium partial pressures of Si, SiC2 and Si2C as (SiC2)/p 1 (SiC2) is about 1.5. In Herro’s report [17], the content
functions of temperature for the SiC + C system are as follows of 13C and 12C of source powder are 88% and 12%,
[19]: respectively. However, the content of 13C crystal is only about
40% after growth. This means that graphite crucible is an
2:9341  104
log10 PSSi ¼ 8:9718  ð8Þ important carbon provider for crystal growth.
T Reaction (7) is the main route of crystal growth. The values
of Si and SiC2 vapor pressures are important to the growth rate:
3:5563  104
log10 PSSiC2 ¼ 10:8389  ð9Þ the decrease in the vapor pressures results in the decrease of
T growth rate. When either of them cannot reach their equilib-
rium partial pressures at the growth temperature, the growth
3:5397  104
log10 PSSi2 C ¼ 10:6352  ð10Þ
T
2200 °C 2100 °C 2000 °C
Where P s is the saturation vapor pressure (atm) at absolute
Si
temperature T. According to Formulas (8) – (10), the equilib- SiC2
rium partial pressures of Si, SiC2 and Si2C from 2000 to 2300 Si2C
100
-C are shown in Fig. 4.
Partial pressure (Pa)

From Fig. 4, it can be seen that the equilibrium partial

pressure of Si is higher than that of Si2C and SiC2. Yet Si and
SiC2 from Reaction (3) have the same partial pressure (i.e. p 1
(SiC2) = p 1 (Si)), so Reaction (6) is the main provider for partial 10
pressure of Si. In order to get enough Si vapor for the SiC
crystal growth, sufficient Si 2C vapor is needed. Thus,
sublimation of SiC powder is mainly according to Reaction
(4). In this case, p 1 (SiC2) cannot reach the equilibrium partial 1
pressure for crystal growth; p 2 (SiC2) offers the other part. For 3.9 4.0 4.1 4.2 4.3 4.4
4
the crucible A, about 88% SiC powder participates in Reaction 10 /T (1/K)

(4) at 2200 -C according to the weight of remnant carbon in the Fig. 4. Variations of the equilibrium partial pressure of Si, SiC2 and Si2C versus
source powder and the loss of crucible wall. The ratio of p 2 the inverse temperatures for the SiC + C system.
120 J. Liu et al. / Diamond & Related Materials 15 (2006) 117 – 120

will not process. Reaction (5) between Si vapor and the 2. Graphitization degree of crucible is important for the
graphite crucible wall plays an important role in providing the successful fabrication of SiC single crystal. In the case of
SiC2 vapor, and its reaction degree is closely related to the low graphitization degree, crystal growth rate is high and
graphitization degree of crucible. controlled by the temperature. The increase of graphitization
In the graphite with lower graphitization, low crystallinity degree of crucible slows the reactions between crucible and
together with more disordered structures and active carbon Si, resulting in the retarded growth or graphitization of the
atoms result in a greater activity for graphite [20]. In this case, seed crystal.
the crucibles have enough activity to react with Si, and have
obvious loss after growth, as shown in the Fig. 3 (b). The References
crystal growth rate is mainly determined by temperature. The
logarithm of crystal growth rate has a linear relationship with [1] Yu.M. Tairov, V.F. Tsvetkov, J. Cryst. Growth 43 (1978) 209.
the inverse temperature as shown in A of Fig. 1. [2] V.D. Heydemann, N. Schulze, D.L. Barrett, G. Pensl, Diamond Relat.
Mater. 6 (1997) 1262.
With the increase of graphitization degree, crystallinity of [3] G. Augustine, V. Balakrishna, C.D. Brandt, J. Cryst. Growth 211 (2000)
graphite is improved, and the disordered structures and active 339.
carbon atoms decrease gradually, which results in decreasing of [4] R.C. Glass, D. Henshall, V.F. Tsvetkov, C.H. Carter Jr., Phys. Status
activity of graphite. Reaction (5) becomes difficult, so the loss of Solidi, B Basic Res. 202 (1997) 149.
graphite decreased, as shown in Fig. 3(c). p 2 (SiC2) and p (SiC2) [5] A.R. Powell, S. Wang, G. Fechko, G.R. Brandes, Mater. Sci. Forum 264 –
268 (1998) 13.
reduce down. Accordingly, the crystal growth rate slow down, [6] D. Hofmann, M. Bickermann, R. Eckstein, M. Ko lbl, St.G. Muller, E.
and graphitization degree of crucible controls the reaction degree Schmitt, A. Weber, A. Winnacker, J. Cryst. Growth 198/199 (1999) 1005.
of Reaction (5), so under different temperatures, crystal growth [7] J. Drowart, G. De Maria, M.G. Inghram, J. Chem. Phys. 29 (1955) 1015.
rates are almost the same as shown in B of Fig. 1. [8] Nikolaus Bubner, Olaf Klein, Peter Philip, Jurgen Sprekels, Krzysztof
As the graphitization degree of crucible increased sequen- Wilmanski, J. Cryst. Growth 205 (1999) 294.
[9] Q.-S. Chen, H. Zhang, R.-H. Ma, V. Prasad, C.M. Balkas, N.K. Yushin, J.
tially, the Reaction (5) becomes far more difficult. In Fig. 3 (d), Cryst. Growth 225 (2001) 299.
there is almost no mass loss on crucible. In this case, p (SiC2) [10] Yu.M. Tairov, Mater. Sci. Eng., B, Solid-State Mater. Adv. Technol. 29
cannot reach the equilibrium partial pressure due to the reduced (1995) 84.
p 2 (SiC2), so that the crystal growth cannot progress, resulting [11] Q.-S. Chen, H. Zhang, V. Prasad, C.M. Balkas, N.K. Yushin, S. Wang, J.
in the graphitization of the seed crystal. This indicates that the Cryst. Growth 224 (2001) 101.
[12] M. Selder, L. Kadinski, F. Durst, D. Hofmann, J. Cryst. Growth 226
graphitization degree of crucible determines the crystal growth (2001) 501.
rate when graphitization degree is relatively high. [13] M. Pons, E. Blanquet, J.M. Dedulle, R. Madar, C. Bernard, Mater. Sci.
Eng., B, Solid-State Mater. Adv. Technol. 46 (1997) 308.
4. Conclusion [14] Olaf Klein, Peter Philip, Jurgen Sprekels, Krzysztof Wilmanski, J. Cryst.
Growth 222 (2001) 832.
[15] P.J. Wellmann, M. Bickermann, D. Hofmann, L. Kadinski, M. Selder, T.L.
Effects of graphitization degree of the crucible used for the Straubinger, A. Winnacker, J. Cryst. Growth 216 (2000) 263.
fabrication of SiC single crystal on the formation and growth of [16] P.J. Wellmann, D. Hofmann, L. Kadinski, M. Selder, T.L. Straubinger, A.
the crystal were investigated. The following conclusions were Winnacker, J. Cryst. Growth 225 (2001) 312.
obtained from the present study. [17] Z.G. Herro, P.J. Wellmann, R. P.usche, M. Hundhausen, L. Ley, M. Maier,
P. Masri, A. Winnacker, J. Cryst. Growth 258 (2003) 261.
[18] J. Drowart, G. De Maria, M.G. Inghram, J. Chem. Phys. 29 (1955)
1. Graphite crucible is consumed during the growth process, 1015.
and can be taken as an important carbon source for the SiC [19] Heqing Li, X.L. Chen, D.Q. Ni, X. Wu, J. Cryst. Growth 258 (2003) 101.
crystal growth through the formation of SiC2 by the [20] Charles L. Mantell, Carbon and Graphite Handbook, John Wiley and
reactions between crucible wall and Si. Sons, New York, 1968.