ARTICLE IN PRESS

Journal of Crystal Growth 311 (2009) 684–687

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Journal of Crystal Growth

journal homepage: www.elsevier.com/locate/jcrysgro

Segregation control of vertical Bridgman growth of Ga-doped germanium

crystals by accelerated crucible rotation: ACRT versus angular vibration
L.C. Wang a, Y.C. Liu a, W.C. Yu b, B. Roux c, T.P. Lyubimova d, C.W. Lan a,e,
a
Department of Chemical Engineering, National Taiwan University, Taipei, Taiwan 10617, ROC
b
Department of Molecular Science and Engineering, National Taipei University of Technology, Taipei, Taiwan, ROC
c
Laboratoire Modélisation et simulation numérique en mécanique, L3M/FRE 2405 MSNM: CNRS—Universités d’Aix-Marseille, France
d
Institute of Continuous Media Mechanics UB RAS, Perm, Russia
e
Photovoltaics Technology Center, Industrial Technology Research Institute, Hsinchu, Taiwan

a r t i c l e in f o a b s t r a c t

Available online 27 September 2008 The control of dopant segregation by accelerated crucible rotation was investigated for the vertical
Keywords: Bridgman growth of Ga-doped germanium crystals. The accelerated crucible rotation technique (ACRT)
A1. Accelerated crucible rotation and the angular rotation technique (AVT) were considered. Both techniques were found effective in
A1. Angular vibration radial segregation control; however, ACRT generated more global mixing and thus slightly larger axial
A1. Convection segregation. Computer simulation was also carried out for the experiments. The results were also
A1. Segregation consistent with previous simulation predictions and low-temperature transparent experiments.
B2. Bridgman method & 2008 Elsevier B.V. All rights reserved.

1. Introduction demonstrated for a low-temperature model material, and com-

The control of convection and segregation is important in
vertical Bridgman (VB) crystal growth. Because of a lack of control
over stirring conditions, the use of external forces is often
adopted. The accelerated crucible rotation technique (ACRT)
proposed by Scheel and Schulz-DuBois [1] is a promising way to
introduce a forced convection, i.e., the Ekman flow, and thus the
melt mixing. The control of rotation scheme, especially the cycle
period, is crucial to the flow structures and thus the segregation
during crystal growth [2]. As a general rule, in order to develop the
Ekman boundary layer, the time for affi spin-up or spin-down cycle
pffiffiffiffiffiffiffiffiffiffiffiffi
is usually in the order of 2RC = OR nm [3,4], where RC is the crystal
radius, OR the rotation amplitude, and nm the kinematic viscosity
of the melt. This time constant, as a quarter of the cycle period, is
usually several seconds for most of the materials having a
diameter of several centimeters. Although ACRT is an effective
way in flow control, the control of radial segregation often
requires an intensive flow, which leads to significant growth
striations. An alternative approach to ACRT is to use a cycle time
that is much shorter than the Ekman time. This method is known
as the angular vibration technique (AVT) [5,6]. In this technique,
the ampoule is vibrated in the angular direction at high frequency
(typically greater than 5 Hz). The control of solute segregation and
the morphological stability using this technique has been
 Corresponding author at: Department of Chemical Engineering, National
Taiwan University, Taipei, Taiwan 10617, ROC. Tel./fax: +886 2 2363 3917.
E-mail address: cwlan@ntu.edu.tw (C.W. Lan).
puter simulation has also been carried out for illustration [7].
Although numerical simulations and low-temperature trans-
parent have been carried out for both ACRT and AVT [7–9], they
have not yet implemented and compared directly on semicon-
ductor growth. In this paper, we present experimental results for
using both techniques on the segregation control of a VB growth
of gallium (Ga)-doped germanium (Ge) crystals. In the next
section, the experimental setup and procedures are briefly
described. Section 3 is devoted to results and discussion followed
by short conclusions in Section 4.
2. Experimental setup and procedures
The growth of Ga-doped Ge crystals in a quartz ampoule
coated with boron nitride was carried out in a directional
solidification furnace. The schematic sketch of the experimental
setup is shown in Fig. 1, where the measured temperature profile
is attached. The boron nitride coating was used to avoid the
reaction between the germanium and the quartz ampoule. Before
the growth, a (111) seed of 18 mm in diameter and 40 mm in
length was placed at the bottom of the ampoule. Then, Ga-doped
Ge pellets were placed in the ampoule, and vacuum sealed under
an argon pressure of 0.08 Torr.
The crystal growth experiments were carried out in a furnace
having a thermal gradient at the seed/feed interface of about
20 K/cm, which was controlled by a hot zone and a water-cooled
cold zone temperatures. Before crystal growth, the ampoule was
heated up at a constant rate of 10 1C/min and then was kept at

0022-0248/$ - see front matter & 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jcrysgro.2008.09.087
 ARTICLE IN PRESS

L.C. Wang et al. / Journal of Crystal Growth 311 (2009) 684–687 685

Fig. 1. A sketch of experimental setup, thermal profile, and the appearance of grown crystals: (a) no crucible rotation; (b) 10 Hz AVT; and (c) 60 rpm ACRT. The arrow in the
photographs indicates the interface after back melting.

1200 1C in the hot zone for 12 h to ensure a homogenous 1.0

dopant mixing in the melt. To start crystal growth, the ampoule No crucible rotation
was pulled down at 5.8 cm/h from for 30 mm at the beginning 0.9
10 Hz AVT
and then at 17.4 cm/h for the rest of the growth. Finally, the
furnace was cooled down slowly to room temperature in 14 h. 0.8 60 rpm ACRT
The same growth condition was applied to all the cases with and
without accelerated crucible rotation. The ACRT cycle scheme and 0.7
AVT amplitude are similar to the previous low-temperature
0.6
experiments [7–9]. Each ACRT cycle consisted of 5 s acceleration,
C/C0 (-)

5 s deceleration, and 2 s rest. For AVT, the amplitude of vibration

0.5
was set to be 0.15.
After crystal growth, the ingots were taken out and sliced into 0.4
a few wafers along the growing direction. These wafers were
polished and then etched for 10–30 s by an acid solution 0.3
(H2O2:CH3COOH:HF ¼ 1:1:1). With this etching procedure, the
seed/crystal interface could be revealed [10]. The axial and radial 0.2
dopant concentration profiles were determined by the resistivity
r measured by the four-point probe technique using the following 0.1
equation [11]:
0.0
r ¼ N a =B, (1) -1 -0.5 0 0.5 1
where N stands for the actual impurity concentration in r (cm)
atoms/cm3. The parameters a and B vary when the impurity Fig. 2. Comparison of radial dopant concentration profiles at the fraction 0.5 for
concentration switches into different orders. In our case, for the the three crystals.
impurity concentration of 1018oNo1019, the values of a and B are
0.653 and 1.61 1010, respectively.

case of no crucible rotation. However, in the case of 60 rpm ACRT,

3. Results and discussion
To examine the effect of accelerated crucible rotation on radial
and axial segregations during crystal growth, Ga-doped Ge single
crystals grown with and without crucible rotation were compared
in terms of their appearance, and the radial and axial dopant
profiles. Three photos of the grown crystals with different rotation
conditions are provided at the right corner of Fig. 1. The
demarcation of the back-melting interface and the growth area
can be clearly identified from the appearance of each grown
crystal. Because the thermal gradient was only 20 K/cm, the
amount of back melting, and so as the starting point of
the growth, was difficult to control. In the case of 10 Hz AVT, the
appearance of the grown crystal has no much difference from the
due to the longer acceleration and deceleration time in each cycle
(24 s), striation-like appearance was observed from the rougher
surface.
Because of the difference in the growth lengths from run-to-
run, the radial dopant concentration profiles were compared on
the basis of its solidification fraction of the entire growth.
Fractions of 0.5 and 0.8 were chosen to represent the radial
segregation of slow and fast growth stages for each case.
The radial dopant profiles at fraction 0.5 for the three cases are
compared in Fig. 2. The values of the concentration in Fig. 2 were
normalized by their doping concentration C0. It was supposed that
the growth without crucible rotation yielded the highest con-
centration at the center because the toroidal thermal convection
near the concave interface induces solutal accumulation there
 ARTICLE IN PRESS
686 L.C. Wang et al. / Journal of Crystal Growth 311 (2009) 684–687
[12]. However, as shown in Fig. 2, due to the asymmetric growth,
the highest dopant concentration moved to the right. In the case
of 10 Hz AVT, the uniformity of radial concentration was slightly
improved, and the values of C/C0 distributed from 0.3 to 0.75, but
not effective. In the case of 60 rpm ACRT, the overall concentration
was dramatically reduced to about 0.35, and the profile was the
most uniform among the three cases. It should be noted that the
radial dopant profiles in the case of no crucible rotation and 10 Hz
AVT were both asymmetric. Indeed, with a long melt height,
crucible tilting and asymmetric heating were difficult to avoid,
and they led to asymmetric flow and dopant fields [13]. Such an
asymmetry often enhanced dopant mixing, and thus reduced the
radial segregation. The effect of Schlitching flow generated by AVT
could be affected by the asymmetric flow as well, and this might
explain why AVT was not as effective as we anticipated in the
axisymmetric ones [6].
Fig. 3 shows the radial dopant profile at fraction 0.8 of each
grown crystal. Without crucible rotation, the dopant accumulated
more severely at the center in the grown crystal. Such a dramatic
distribution indicated that the radial segregation was severely
developed in the fast growth. Due to the shorter melt height, the
dopant profile became more symmetric as a result of the more
axisymmetric flow. Also, in the case of 10 Hz AVT, C/C0 distributed
from 0.9 to 2.2 indicating a much smaller radial segregation; the
10 Hz AVT yielded the most uniform profile among the three
cases. In the case of 60 rpm ACRT, C/C0 distributed from 1.0 to 3.0
and the improvement on radial segregation was also obvious.
In Fig. 4, the axial dopant profiles along the centerline of the
grown crystals are plotted for comparison. The values were also
normalized by their doping concentration and compared on the
basis of solidification fraction. In the case of no crucible rotation,
the concentration profile was very similar to that shown in
Ref. [10], which laid between the theoretical curves of no
convection and complete mixing. With 10 Hz AVT, the axial
segregation was not changed much, which was consistent with
the previous simulation predictions [6,7]. In the case of 60 rpm
ACRT, the curve tended to be closer to the complete mixing
and thus increased the axial segregation. It can also be seen from
Fig. 2 that the significant reduction of overall radial concentration
at the beginning for the case of ACRT was caused by the longer
7.0
No crucible rotation
10 Hz AVT
6.0
60 rpm ACRT
5.0
4.0
C/C0 (-)
3.0
2.0
1.0
0.0
-1 -0.5 0 0.5
r (cm)
Fig. 3. Comparison of radial dopant concentration profiles at the fraction 0.8 for
the three crystals.
3
No crucible rotation
10 Hz AVT
2.5
60 rpm ACRT
2
C/C0 (-)
1.5
1
0.5
0
0 0.2 0.4 0.6 0.8
fraction (-)
Fig. 4. Axial dopant concentration profiles along the centerline of the grown
crystals.
acceleration and deceleration times that developed larger Ekman
flow and generated stronger global mixing. Therefore, a larger
axial segregation was found in the case of ACRT. These axial
dopant profiles should be compared with care because the
measurement along the centerline might miss the highest values
when the radial profile was not axisymmetric.
Computer simulation using an axisymmetric model [7–9] was
also conducted for the previous growths, and the flow and dopant
fields are shown in Fig. 5 for comparison; the gallium diffusion in
the solid was neglected. Because of the asymmetric growth
conditions in reality, the one-to-one comparison is not possible.
Nevertheless, from the simulated flow structures, it is clear that
both AVT and ACRT generate a small flow cell near the growth
front. Because their flow direction is opposite to the thermal
convection, as a result, the dopant accumulation at the crystal
center caused by the thermal convection is significantly reduced.
As a result, the radial segregation with AVT and ACRT is improved,
which can be seen from the dopant fields in the crystal. Also, from
the maximum value of the normalized dopant concentration in
the crystal, the one with ACRT is also significantly lower (0.3081)
than the others. This indicates that ACRT generates a stronger bulk
dopant mixing than AVT, which is consistent with the measured
axial dopant profile in Fig. 4. The maximum dopant concentration
of AVT lies in the middle, which is consistent with the measured
one as well. Interestingly, from the dopant fields of ACRT shown in
Fig. 5c, significant dopant fluctuations are observed, which
indicates that growth striations may be generated by ACRT if
the solid state diffusion is not fast enough to smooth out the
inhomogeneity. Indeed, some striations were found in the crystal
grown with 60 rpm ACRT.
4. Conclusions
In this paper, we have compared the vertical Bridgman growth
of Ga-doped Ge crystals with different conditions of accelerated
1
crucible rotations: no crucible rotation, 10 Hz AVT, and 60 rpm
ACRT. Both AVT and ACRT were found effective in improving radial
segregation for both low and fast growths. In our observation, AVT
reduced radial dopant segregation and meanwhile generated less
 ARTICLE IN PRESS

L.C. Wang et al. / Journal of Crystal Growth 311 (2009) 684–687 687

No Rotation 10 Hz AVT 60 rpm ACRT

Ψmax = 0.000000 Ψmax = -0.02474 Ψmax = -0.01147

6.5 Ψmin = 0.230267 Ψmin = 0.22036 Ψmin = 0.05925

k(C/C0) (-) k(C/C0) (-) k(C/C0) (-)

6 0.58765 0.38804 0.30811
0.55428 0.36797 0.29336
0.52090 0.34790 0.27861
0.48752 0.32783 0.26386
0.45415 0.30776 0.24911
5.5
z (cm)

0.42077 0.28769 0.23435

0.38739 0.26762 0.21960
0.35401 0.24755 0.20485
0.32064 0.22748 0.19010
5 0.28726 0.20741 0.17535
0.25388 0.18734 0.16060
0.22051 0.16727 0.14585
0.18713 0.14720 0.13109
4.5 0.15375 0.12713 0.11634
0.12038 0.10706 0.10159

3.5
0 1
r (cm)

Fig. 5. Simulated melt flow fields (streamlines) and dopant fields in the crystal: (a) no rotation; (b) 10 Hz AVT; and (c) 60 rpm ACRT.

global mixing. Due to the longer acceleration and deceleration References

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