Met. Mater. Int., Vol. 20, No. 4 (2014), pp.

687~693
doi: 10.1007/s12540-014-5013-y

Mapping Analysis of Single Crystal SiC Polytypes Grown From

Purified β-SiC Powder
1 1 1,2 2 1, *
Jun Gyu Kim , Si Jung Park , Eunjin Jung , Younghee Kim , and Doo Jin Choi

1
Yonsei University, Department of Materials Science and Engineering, 134 Shinchon-dong,
Sudaemun-ku, Seoul 120-749, Korea
2
Korea Institute of Ceramic Engineering and Technology, 233-5 Gasan-dong,
Guemcheon-gu, Seoul 153-801, Korea
(received date: 22 October 2013 / accepted date: 4 January 2014)

The most important consideration when growing single crystal silicon carbide by the physical vapor trans-
port method is to minimize defects. To minimize defects caused by temperature gradient, we used β phase
SiC powder, which has a low sublimation temperature, and purified the β phase SiC powder to improve the
purity of single crystal SiC. Furthermore, we performed thermodynamic computational simulations based
on compositions of purified and non-purified β-SiC powders to study the impact of metallic impurities
within SiC powder on the composition of single crystal SiC. We grew SiC at temperatures about 200 °C lower
than the previous growth temperature using purified β-SiC powder and mapped the phase change behavior of
SiC according to different growth temperatures. Moreover, we compared and analyzed the characteristics
of SiC polytype formation and crystallinity according to growth temperature. We compared the distribution of
defects and dislocations of single crystal 4H SiC grown from purified and non-purified β-SiC powder to study
the impact of source purification on defect generation. We also investigated the effect of metallic impurities on
the formation of defects and dislocations through content analysis of metallic impurities.
Keywords: β-SiC powder, purification, single crystal SiC, defect distributions, dislocation

1. INTRODUCTION and seed caused by temperature gradient, and (3) polytype,

Silicon carbide (SiC) has remarkable physical and electronic
properties and has therefore been investigated intensively.
There are more than 250 polytypes of SiC, among which β
phase 3C SiC and α phase 4H and 6H SiC are the most fre-
quently used. Different polytypes of SiC have different prop-
erties. 4H SiC has outstanding electrical properties such as a
high bandgap, breakdown voltage and carrier mobility, and
is mainly used in power device applications that require high
voltage, power, and frequency. 6H SiC, which has a small
lattice mismatch, is used in light emitting diodes (LEDs) and
as a replacement substrate for sapphire for epitaxial GaN
growth [1-6]. The physical vapor transport (PVT) method is
frequently used to grow single crystal 4H and 6H SiC. SiC
produced using this method is characterized by a large diam-
eter and high growth rate. When growing single crystal SiC
using the PVT method, defects including micropipes, pores,
polytypes, and dislocations including screws, edges, and basal
planes occur. There are three reasons for this: (1) damage to and
contamination on the seed surface, (2) stress to the source
*Corresponding author: drchoidj@yonsei.ac.kr
KIM and Springer
Si/C ratio, and impurity of the SiC powder source [7-10].
Our aim in this study was to reduce defects in SiC growth
using the PVT method by decreasing impurities such as excess
carbon, SiO2, and metallic impurities (Fe, Al) in the SiC
powder. To evaluate the impact of impurity content of the powder
on the final crystals, we utilized thermodynamic computa-
tional simulation. Based on the actual composition of the pow-
der before and after purification, we identified and analyzed
the effects of the decomposition behavior of SiC powder and
intermediate products according to temperature. We grew
single crystal SiC from purified β-SiC powder using the PVT
method and examined the reasons for the occurrence and
behavior changes of single crystal SiC polytypes at different
growth temperatures. Moreover, we analyzed the necessity
of powder purification by comparing defect distributions in
single crystal 4H SiC grown from unpurified and purified
powders and determining the content of metallic impurities.
2. EXPERIMENTAL PROCEDURES
We used a vaporization-condensation method to purify β-
SiC powder. β-SiC powder was placed into a graphite cruci-
688 Jun Gyu Kim et al.
ble and heated under Ar ambient to 1850 °C at a rate of 15 °C
/min, and held for 15 min. Temperature was then increased
up to 2000 °C at 2 °C/min and held again. Temperature was
decreased down to 1850 °C, then increased to 2000 °C again.
This was repeated three times. We used glow discharge mass
spectrometry (GDMS, VG9000, Nu Instruments) to precisely
analyze changes in the purity and metallic impurities of β-
SiC powder before and after purification. Furthermore, we used
thermodynamic computational simulation (HSC Chemistry,
Outotec, 2011) to compare changes in the decomposition
behavior of β-SiC powder and intermediate products caused
by purification according to the composition of the SiC wafer.
We grew SiC crystals using purified β-SiC powder as a source
under Ar ambient by the PVT method, using a growth tem-
perature of between 2150 °C and 1900 °C. Grown bulk 6H and
4H SiC crystals were sliced into wafers, which were then
lapped and polished. Wafers with a (0001) Si face were also
treated with chemical-mechanical polishing (CMP). To confirm
the polytype of grown single crystal SiC, we used a Raman
spectrometer (Jobin-Yvon, LabRam HR) with an excitation
laser wavelength of 514.5 nm (Ar laser). Furthermore, we calcu-
lated the full-width-at-half-maximum (FWHM) after measuring
ω rocking curves using high resolution X-ray diffraction (HRXRD)
to analyze the crystallinity of single crystal SiC. We analyzed
4H SiC wafers grown with purified and non-purified β-SiC
powder using synchrotron white beam X-ray topography
(SWBXT, 9D beamline PLS Pohang, Korea), which is a
non-destructive method that can be used to analyze the distri-
butions of defects and dislocations of an entire wafer. Finally,
we used time of flight secondary ion mass spectrometry
+
(TOF-SIMS) with a Cs primary ion source to analyze the
metallic ion content of the purified and unpurified powders.
3. RESULTS AND DISCUSSION
We analyzed the purity of β-SiC powder before and after
purification using GDMS, and the results are shown in Table
1. Purity of β-SiC powder before and after purification was
89.1% and 99.7%, respectively. Content of free carbon and
SiO2 in non-purified β-SiC powder was 10 times higher than
that of purified β-SiC powder. Furthermore, we confirmed
that the concentration of metallic impurities, such as Al and Fe,
was 0.051% in the unpurified powder, which was approxi-
mately 200 times larger than the concentration of metallic
impurities in purified β-SiC powder. Decomposition of SiC
powder and changes in the composition of the final products
in accordance with temperature changes were assessed by
Table 1. Chemical component percentages of non-purified SiC powder and purified SiC powder (at.%)
Chemical components of SiC
SiC Free C
β-SiC powder 89.1 1.14
Purified β-SiC powder 99.7 0.11
thermodynamic computational simulation using the actual
purity of the powders and SiC growth conditions as input; results
are shown in Fig. 1. During sublimation, pure SiC power
decomposes into the gas phases of SiC2, Si2C, Si, and C [11].
In contrast, a large amount of CO gas in addition to the other
four gas phases was produced from non-purified SiC pow-
der, as shown in Fig. 1(a). We speculate that oxygen atoms
produced when 9.74 % of SiO2 in the powder decomposed
into SiO as the temperature increased reacted with carbon
atoms generated when SiC decomposed, resulting in the pro-
duction of CO gas. The concentration of CO gas increased further
with increasing temperature due to continuous decomposi-
tion of SiO. Non-purified powder decomposed at a lower
temperature than the sublimation temperature of about 2000 °C
due to reaction between SiC and SiOx. Purified powder
decomposed into gas phase a certain time after reaching the
sublimation temperature. If the powder decomposes before
reaching the sublimation temperature, reaction gases are sup-
plied to the powder source due to the graphitization phenom-
ena, which results in unstable polytypes. Because of this, it is
difficult to generate the desired polytype. Moreover, a carbon
layer is easily created on the seed surface due to the presence
of CO, and can cause defects (seed contamination). Figure
1(c) shows the behavior of Al and Fe in the non-purified SiC
powder at different temperatures. As SiC decomposed, Fe
and Al in the SiC interacted with Si, and existed independently at
temperatures of 1500 °C and higher. Fe and Al atoms at high
temperatures can substitute for Si due to their similar atomic
sizes when SiC is crystallized. This creates an empty lattice
due to transformation of the Si core and generates defects
due to misorientation [12]. Furthermore, if Al atoms are adsorbed
onto the growth surface, the surface kinetics are altered and
growth rate decreases [13]. Purification reduced the content
of Fe and Al in the powder, but very small amounts of Fe and
Al were still present. Because these metal impurities have
negative effects on the resulting product, as shown in Fig. 1(c),
it is important to reduce the amount of metallic impurities
and SiO2 as much as possible through purification to improve
the quality of single crystal SiC growth.
Figure 2 shows photos of single crystal SiC grown at 2070 °C;
these SiC wafers were green. At growth temperatures between
2000 °C and 1960 °C, wafers were a mixture of green, light
green, and brown. At below 1920 ˚C, SiC wafers were yellow.
We utilized Raman spectra to distinguish the polytype of
grown SiC. SiC polytypes have direct energy in transversal
(TA, TO) and longitudinal (TA, LO) phonon mode, so pho-
non band positions differ according to crystal phases, which
SiO2 Fe Al Other
9.73 0.05 0.05 0.01
0.18 0.0002 0.0003 0.01
 Mapping Analysis of Single Crystal SiC Polytypes Grown from Purified β-SiC Powder 689

Fig. 1. Simulation results of decomposition behavior and intermediate product of non-purified and purified β-SiC powders according to tempera-
ture: (a) nonpurified SiC powder, (b) purified SiC powder. Comparison of changes in decomposition behavior and intermediate metallic ion
products for non-purified and purified β-SiC powders according to temperature: (c) metallic ions within non-purified SiC powder, (d) metallic
ions within purified SiC powder.

Fig. 2. Transmitted visible light photo images of single crystal SiC wafers grown from purified SiC powder at different temperatures.

makes it easy to distinguish phases by Raman spectra [14].
Analysis of the green A area revealed peaks at 144, 149, 265,
-1
504, 514, 767, 789, and 964 cm in the Raman spectra (Fig.
3(a)). This coincides with 6H SiC (Table 2), confirming that
the green part is 6H SiC [15]. In specimens 3 and 4, which
showed mixed colors, we analyzed the light green B area
and brown C area. In the B area, in addition to the 6H SiC
frequency band, a 15R SiC frequency band with peaks at
690 Jun Gyu Kim et al.

Fig. 3. Raman spectra result of areas A to D of the wafers with different colors.

Table 2. Comparison of Raman band positions of common SiC polytypes and the Raman frequencies of our experimental wafers
SiC Polytype TA LA TO LO
4H (α) 196 204 266 610 776 796 838 964
6H (α) 145 150 236 266 504 514 767 789 797 889 965
15R(α) 167 173 255 331 337 569 767 785 797 800 932 965
Measured frequency
A 144 149 265 504 514 767 789 964
B 150 172 255 266 505 569 767 785 964
C 195 203 265 609 776 796 976
(TA,TO :transversal acoustic, LA,LO: longitudinal acoustic)

-1
173, 255, 569, 767, and 785 cm also appeared (Fig. 3(b)).
This indicated that both 6H and 15R were present in the B
area [15]. Brown C area had peaks at 195, 203, 265, 609,
-1
776, and 976 cm , consistent with the Raman positions of
4H SiC (Fig. 3(c)) [15]. D area of specimens 5 and 6 also
had a 4H SiC Raman peak similar to that of the C area, but
this area was more yellowish, indicating that the 4H poly-
type was dominant. Many factors affect the SiC polytype
generated, including impurities, seed orientation, Si/C ratio,
growth rate, and growth temperature [16]. Our results indicate
that temperature had the largest impact. In general, polytype
transformation varies in accordance with temperature changes.
Among the 4H, 6H, and 15R SiC polytypes, 6H SiC has a
wide range of process parameters and is produced at the highest
temperature, whereas 4H SiC has a narrow range of growth
parameters and is formulated at the lowest temperature [17].
In the case of specimens 3 and 4, the energy difference for
each polytype was very small, at around ~0.2 meV/atom [18].
Thus, they were both present in the temperature range from
1960 °C to 2000 °C where their temperature equilibria over-
 Mapping Analysis of Single Crystal SiC Polytypes Grown from Purified β-SiC Powder
Fig. 4. Crystallinity results based on the FWHM obtained from rock-
ing curves of single crystal SiC wafer grown by purified SiC powder.
lapped. In the mixed area, the brown area was present only
in the center due to the radial nature of the temperature gra-
dient [19]. Temperature of the center area was lower than
that of the periphery, and 4H SiC was generated in the center
area where the temperature was lower. This phenomenon also
explains the location of green 6H in the peripheral area of the
dotted circle of the sample prepared at a temperature of
691
1920 °C. There was a large difference in the position of the
Lo band between Raman spectra of samples grown at tem-
peratures lower than 1920 °C, where 4H SiC is dominant, and
samples grown at higher temperatures, because of the gap in
carrier concentration. Other phonon modes had a similar
position to the reference frequency. Doping increases with
hexagonality. Compared with other polytypes, the hexago-
nality of 4H SiC was the highest at 50%, indicating nitrogen
doping during growth. Furthermore, the Lo band became
broader and shifted to a higher wave number [20]. Raman
spectra analysis revealed the presence of green 6H SiC at
high temperatures. As the temperature decreased, a mixed area
of 15R and 4H SiC appeared. As the temperature decreased
even further, yellow 4H SiC grew.
FWHM rocking curves obtained by omega-scanning to
evaluate the crystallinity of SiC wafers of specimens 1, 3 and
6 with different polytypes are shown in Fig. 4. Specimen 1,
in which the 6H polytype was dominant, had a FWHM value
of 41.65 arcsec while the 4H SiC polytype had a FWHM
value of 28.76 arcsec. FWHM value of specimen 1 was higher
than that of specimen 6 because the composition temperature
of the 6H SiC polytype was the highest, and it therefore
experienced the largest thermal stress during crystal growth.
In general, 4H SiC, which is used in power electronic devices,
requires better crystallinity than 6H SiC. Considering that
the commercialization condition for single crystal SiC wafers
is a FWHM value of less than 50 arcsec, both specimens
showed excellent crystallinity. We attributed this to a reduc-
tion in thermal stress as the growth temperature was lowered
by about 200 °C due to use of purified β-SiC powder. The
rocking curve of specimen 3, comprising three mixed poly-
types, was very wide and had a mosaic orientation with a shoulder
peak with a poor crystallinity of 302 arcsec FWHM. This is
because hexagonal close packing was not generated in the
(0001) direction due to the non-uniform arrangement of SiC
atoms and because of the presence of defects in the SiC crystal
structure due to the mixture of various polytypes [21-22].
We measured and compared 2-inch 4H SiC wafers grown
using purified and non-purified SiC powder by SWBXT; results
are shown in Fig. 5. 4H SiC wafers from non-purified SiC
powder had a basal plane dislocation distribution and some
micropipe and screw dislocations (Fig. 5(a)). However, 4H
SiC wafers produced using purified powder had no basal plane
dislocations, and micropipe and screw dislocations were present
only in the periphery (Fig. 5(b)). Micropipe and dislocation
densities of 4H SiC wafers grown from purified powder were
lower than those of 4H SiC wafers grown from non-purified
powder, and the overall quality of the former wafers was bet-
ter than that of the latter wafers. We measured the Al and Fe
metallic ion content within the wafers by TOF-SIMS (Figs.
4(c) and (d)). We confirmed that 4H SiC wafers grown from
purified powder contained far lower amounts of Al and Fe
than the corresponding wafers grown from non-purified pow-
692 Jun Gyu Kim et al.

Fig. 5. Comparison of defects distributions of 4H SiC wafers grown from non-purified β-SiC powder and those grown from purified β-SiC pow-
der using synchrotron white beam X-ray topography (MP: micropipe, SD: screw dislocation, BPD: basal plane dislocation). TOF- SIMS mea-
surements of Al and Fe atom content within 4H SiC wafers grown using non-purified or purified powder. (a) SiC wafer grown by Non-purified
β-SiC powder, (b) SiC wafer grown by Non-purified β-SiC powder, (c) metallic ion content of SiC wafer grown by non-purified β-SiC powder
and (d) metallic ion content of SiC wafer grown by purified β-SiC powder.

der. Our thermodynamic simulation results indicated that Al
and Fe impurities within powder exist in gas phase, not solid
phase, at high temperatures. Around the SiC growth tem-
perature of 2000 °C, these metallic ions may be present in the
wafer in gas phase. Use of purified powder effectively reduced
the Al and Fe atom content within the wafer based on TOF-
SIMS analysis. Process conditions affecting the growth of
crystals such as growth temperature, pressure, and the distance
between the source and the seed were the same; only the
purity of the SiC powder was varied. This indicates that the
differences in the growth aspects of micropipes and disloca-
tions were caused by differences in metallic impurities in the
powders. Such metallic impurities can substitute for Si during
growth of crystals or cause lattice transitions by interrupting
contacts between lattices, resulting in voids and vacancies in
the lattice bonds [23-24]. We argue that these defects have
the largest impact on the formation of micropipes and dislo-
cations. Our results indicate that the amount of micropipes
and dislocations can be decreased drastically by using puri-
fied SiC powder to reduce impurities.
4. CONCLUSIONS
We used a vaporization-condensation method to improve
the purity of β-SiC powder. SiC composition in the non-puri-
fied and purified β-SiC powders was 89.1% and 99.7%,
 Mapping Analysis of Single Crystal SiC Polytypes Grown from Purified β-SiC Powder
respectively. The non-purified β-SiC powder had a relatively
higher portion of free carbon, SiO2, and metallic impurities
than the purified β-SiC powder. We carried out thermody-
namic simulations based on the composition analysis results,
and found that non-purified β-SiC powder showed SiC
decomposition at temperatures lower than 2000 °C, resulting
in the formation of SiOx and CO. However, when purified β-
SiC powder was used as the source, SiC remained stable at
temperatures below 2000 °C and only decomposed at higher
temperatures. We verified changes in SiC polytypes accord-
ing to different growth temperatures using purified β-SiC
powder. At temperatures of 2070 °C and higher, green 6H
SiC was the dominant growth form. At temperatures between
2000 °C and 1920 °C, 4H, 6H, and 15R polytypes all formed,
while yellow 4H SiC grew at temperatures of 1900 °C and
lower. Single crystal 4H and 6H SiC had a crystallinity of
28.76 arcsec and 41.65 arcsec, respectively, indicating that
these polytypes are sufficiently crystalline for commercialization.
By analyzing defects and impurities in 4H SiC grown using
non-purified and purified β-SiC powder, we found that the
4H SiC grown using purified powder had fewer metallic
impurities than the 4H SiC grown using non-purified β-SiC
powder. Basal planes, screw dislocations, and micropipes were
also reduced in the samples grown from purified powder
versus those grown from non-purified powder.
We conclude that use of purified β-SiC powder as a source
is economical because it allows a reduction in growth tem-
perature of single crystal SiC. At the same time, the resulting
product is high quality due to a reduction in defects caused
by impurities and high temperature gradient.
ACKNOWLEDGEMENT
Experiments at PLS were supported in part by MSIP and
POSTECH.
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