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Scripta Materialia 65 (2011) 556559

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Formation mechanism of twin boundaries during crystal growth

of silicon
Kentaro Kutsukake,a, Takuro Abe,a Noritaka Usami,a Kozo Fujiwara,a
Kohei Morishitab and Kazuo Nakajimab
a

Institute for Materials Research (IMR), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan
b
Graduate School of Energy Science, Kyoto University, Yoshidahonmachi, Sakyou-ku, Kyoto 606-8501, Japan
Received 5 October 2010; revised 10 June 2011; accepted 15 June 2011
Available online 21 June 2011

The formation mechanism of twin boundaries in multicrystalline Si was studied using an in situ observation technique. We
directly observed the growing interface and analyzed change in the growth rate. We found that the formation of twin boundaries
in crystal grains was always accompanied by a marked increase in the growth rate and they were rarely formed when the growth rate
was constant at a high value. The formation mechanism is discussed from the viewpoint of driving force.
2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: Twin boundary; Crystal growth; Silicon; Polycrystal; In situ

Twin boundaries are observed in almost all crystalline materials, including metals, semiconductors, oxides and organic materials. In particular, twin boun
daries in Si have attracted much attention from both
the scientic and technological viewpoints owing to their
unique features. The energy of twin boundaries is significantly low; it is less than one-fth of the energy of the
other grain boundaries in Si [14]. Twin boundaries
have very small electrical activity; their energy level is
outside the band gap of the Si energy band [1,5,6]. They
are the most frequently observed grain boundaries in
multicrystalline Si except for random grain boundaries;
typically the surface area of twin boundaries is more
than 60% of the total surface area of coincidence site lattice grain boundaries [7]. In terms of technological applications, twin boundaries are closely linked to the
generation of other crystal defects, such as dislocations
and precipitates, and are necessary for the growth of faceted dendrites [810]. These are used to control microstructures in multicrystalline Si for solar cells [1113].
To develop a novel crystal growth technique for controlling microstructures, a deep understanding of the formation mechanism of twin boundaries is essential.
However, the mechanism of twin boundary formation
during crystal growth is still obscure despite its importance. Although it is well known that plastic deforma-

Corresponding

author. Tel.: +81 22 215 2044; fax: +81 22 215

2041; e-mail: kutukake@imr.tohoku.ac.jp

tion under a shear stress introduces twin boundaries, it

is not clear that a similar mechanism can be applied during crystal growth. Fujiwara et al. [14] reported the
mechanism that a twin boundary forms parallel to another twin that forms rst along the {1 1 1} facet face
during crystal growth. However, they did not mention
the formation mechanism of the rst twin.
In this paper, we report on the formation mechanism
of twin boundaries on the basis of clear experimental
observation of a growing interface using our original
in situ observation system [9,10,14,15]. To investigate
the formation mechanism, we assumed that surpercooling of the Si melt, which is the driving force of crystal
growth, also works as the driving force of twin formation. On the basis of this idea, we focused on intentionally controlled crystal growth rate, because crystal
growth rate is proportional to the degree of supercooling when the degree of supercooling is low. We found
that the formation of twin boundaries is always accompanied by a marked increase in the growth rate, and
twin boundaries are rarely formed when the growth rate
is constant.
Small crystals (1 cm  1 cm  2 cm) were grown in a
small furnace equipped with an in situ observation system. Wafer chips of high-purity Si (nondoped, 11 N) were
set in a quartz crucible coated with Si3N4 powder. After
the Si wafer chips had completely melted, crystals were
grown under two dierent conditions. One is a constant
cooling rate, which corresponds to the conventional

1359-6462/$ - see front matter 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.scriptamat.2011.06.028

K. Kutsukake et al. / Scripta Materialia 65 (2011) 556559

casting method. Under the other condition, the crystal

growth initially proceeded with a constant cooling rate
and then the crystal growth rate was deliberately changed
by controlling the temperature of the heater based on the
in situ observation. Under both conditions, the constant
cooling rate was varied between 3 and 50 C min 1. During the crystal growth, the morphology of the growing
interface was monitored and recorded in situ using a
charge-coupled device camera and a video. The crystal
growth rate was calculated from the positions of the growing interface in the images captured from recorded movies
at constant time intervals. By performing the above calculation at each elapsed time, the growth rate was determined as a function of time, i.e. the interface position.
This is a benet of the direct observation of crystal
growth. Before the grain boundary characterization, the
surface where crystal growth morphology had been directly observed was etched using HF and HNO3 solutions. The etched thickness was about 30 lm, which is
suciently thin to allow the change in the position and
character of grain boundaries within the etched thickness
to be ignored. The grain boundary position and character
were analyzed by scanning electron microscopy and electron back-scattering pattern analysis (SEMEBSP). Note
that, even though the crystals grown in this study were
small, their grain shape and distribution and the percentage of the length of their twin boundaries relative to the
total length of all their grain boundaries were similar to
those of commercially available wafers sliced from large
ingots for solar cell applications. Therefore, the crystal
growth performed in this study could be a model for
large-ingot growth for use in investigating the twin formation mechanism.
Several twin boundaries were observed in Si crystals
grown under both the conditions described above.
Figure 1 shows sets of photographic images of a sample
surface, a crystallographic orientation image map analyzed by SEMEBSP and a captured image of the growing interface, for samples grown under (ac) a constant
cooling rate of 50 C s 1, (df) a constant cooling rate of
3 C s 1 and (gi) a changed cooling rate from 3 to
50 C s 1. In the crystallographic orientation images,
the coincidence site lattice grain boundaries are shown
as colored lines, with the twin boundaries, which are
R3 boundaries, shown as black lines. Note that the crystallographic orientation images are slightly distorted
from the photographic images due to the roughness of
the sample surface. The twin boundaries in the crystallographic orientation images are also distorted, though almost all of them are planar and on the {1 1 1} plane.
During the growth of multicrystalline Si, a twin
boundary across a growth interface continuously extends to the newly grown crystal until the twin boundary
meets another grain boundary. Therefore, in order to
investigate the formation mechanism of twin boundaries, the formation points, i.e. the starting points, of
twin boundaries were rst determined by comparing
the twin conguration in the crystallographic orientation image map and the crystal growth direction analyzed from the recorded movies of the growing interface.
In the case of a constant cooling rate of 50 C s 1,
dendrite growth proceeded from the periphery of the
Si melt. Almost all the twin boundaries extended from

557

a crucible wall as a backbone of the dendrite crystal

grain. These twin boundaries are expected to be formed
at a crucible wall.
In the case of a constant cooling rate of 3 C s 1, the
growing interface was almost at and no dendrite
growth was observed. As in the case of the fast cooling
rate, almost all the twin boundaries were formed at a
crucible wall and extended with crystal growth. These
results clearly demonstrate that a heterogeneous interface with a crucible wall strongly works as a formation
site of twin boundaries. Furthermore, by comparing
the density of twin boundaries in the crystal grown under the fast cooling rate with that grown under the slow
cooling rate, we found that the density of twin boundaries increases with increasing cooling rate.
In the sample grown under a changed cooling rate
from 3 to 50 C s 1, twin boundaries appeared in the
growing crystal grain around the time when the cooling
rate changed, in addition to the twin boundaries formed
at a crucible wall. To analyze the crystal growth rate
around the cooling rate change, isochrones of the growing interface were drawn, as shown in Figure 2(a). The
time interval between adjacent isochrones was 1 s. The
crystal growth rate was intentionally increased at
t = 10 s by markedly decreasing the heater power based
on the in situ observation of the growing interface. The
distance between adjacent isochrones shows the crystal
growth rate because the distance denotes the length of
crystal grown in 1 s, and it increases when the crystal
growth rate increases. A large change in the growth rate
can be seen clearly when the growing interface position
is at t = 10 s, which means that the growth rate changed
with hardly any time delay. Figure 2(b) shows superimposed isochrones on the photographic image of the sample surface. Both images were positioned by using the
striation line of the growing interface and the shape of
crystal grain with 100 lm accuracy. It is clear that a twin
boundary is formed when the distance between isochrones increases, i.e. when the growth rate increased.
In order to numerically check the timings (positions)
of twin formation and growth rate change, the growth
rate was plotted as a function of time. Figure 3 shows
the growth rate along the broken line in Figure 2(b) as
a function of time. The arrow indicates the timing of
twin formation, which matched the timing of growth
rate change well. In all of the samples grown at dierent
cooling rates before the intentional change, twin boundaries were newly formed at the moment of intentional
increase in the crystal growth rate. Importantly, new
twin boundaries were rarely formed in growing crystal
grains when the growth rate was constant though at a
high value. Therefore, a marked increase in the growth
rate is more eective than the absolute value of the
growth rate for forming twin boundaries.
We should discuss why twins form at the moment of
increase in the growth rate. As mentioned in the introduction, surpercooling of the Si melt is expected to be
the driving force of twin formation. The crystal growth
rate is proportional to undercooling under the condition
of a low degree of undercooling [16]. Therefore, twin
boundaries probably form more often when the crystal
growth rate is high. This tendency was actually observed
in the twin formation at the crucible wall. However, we

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K. Kutsukake et al. / Scripta Materialia 65 (2011) 556559

Figure 1. Sets of photographic images of a sample surface, a crystallographic orientation image map analyzed by SEMEBSP and a captured image
of the growing interface, for samples grown under (ac) a constant cooling rate of 50 C s 1, (df) a constant cooling rate of 3 C s 1 and (gi) a
changed cooling rate from 3 to 50 C s 1. The solid and broken white squares in the photographic images correspond to the areas of the
crystallographic orientation image maps and the captured images, respectively. The black contrast in the captured image of (c) is the shadow of the
observation window. The white contrasts in the captured images of (f) and (i) are artifacts due to light reected from the melt surface.

Figure 2. (a) Isochrones of the growing interface of the crystal shown in Figure 1(gi) at 1 s intervals. (b) Superimposed isochrones on the
photographic image of the sample surface. (c) The crystallographic orientation image map of the mentioned area.

found that a marked increase in the growth rate is more

eective than the absolute value of the growth rate for
forming twin boundaries in growing crystal grains. This
can be explained as follows. At the moment of the
marked increase in growth rate, the crystal growth transitions from steady growth to unsteady growth. This
transition should provide a marked undercooling owing

to a delay in the increase in growth rate, i.e. a delay in

the generation of latent heat, from the moment the heater temperature is decreased. This undercooling may be
more prominent than that in steady growth and probably generates twin boundaries.
We should also comment on another possible driving
force of twin formation: strain. During crystal growth, a

K. Kutsukake et al. / Scripta Materialia 65 (2011) 556559

559

This work was partially supported by a Grantin-Aid for Scientic Research from the Ministry of Education, Culture, Sports, Science and Technology of Japan, the New Energy and Industrial Technology
Development Organization (NEDO) and Nippon Sheet
Glass Foundation for Materials Science and Engineering (NSG Foundation).

Figure 3. Growth rate along the arrow in Figure 2(b) as a function of

time.

local strain might be produced by the local temperature

distribution. As discussed above, transition from steady
growth to unsteady growth at the moment of the marked
increase in growth rate provides a marked undercooling.
The transition must also provide local distributions of
temperature, hence a local strain might be applied at
the moment of the marked increase in the growth rate.
If the strain is the driving force of the twin formation,
the formation should occur in the bulk crystal region at
some distance from the growth interface. Our observation shows the position of the twin formation to be less
than 100 lm away from the growth interface because it
accords with the position of the marked increase in
growth rate with a position accuracy of 100 lm.
We investigated the formation mechanism of twin
boundaries during the growth of multicrystalline Si by
the direct observation of the growing interface and the
subsequent characterization of grain boundaries. We
demonstrated that a heterogeneous interface with a crucible wall is a formation site of twin boundaries. At the
crucible wall, twin boundaries are formed more often
when the crystal growth rate is high. It was also directly
proved that twin boundaries are formed in growing crystal grains at the moment of a marked increase in the
growth rate. The formation mechanism was discussed
on the basis of driving force. These results should contribute to a better understanding of the crystal growth
of Si, which can be utilized to realize high-quality Si
multicrystalline ingots.

[1] L.F. Mattheiss, J.R. Patel, Phys. Rev. B 23 (1981) 5384.

[2] M. Kohyama, R. Yamamoto, M. Doyama, Phys. Status
Solidi B 137 (1986) 11.
[3] M. Kohyama, R. Yamamoto, M. Doyama, Phys. Status
Solidi B 138 (1986) 387.
[4] R.E. Thomson, D.J. Chadi, Phys. Rev. B 29 (1984) 889.
[5] J. Chen, D. Yang, Z. Xi, T. Sekiguchi, J. Appl. Phys. 97
(2005) 033701.
[6] T. Nuonassisi, A.A. Istratov, M.D. Pickett, M.A. Marcus,
T.F. Ciszek, E.R. Weber, Appl. Phys. Lett. 89 (2006)
042102.
[7] A. Voigt, E. Wolf, H.P. Strunk, Mater. Sci. Eng., B 54
(1998) 202.
[8] M. Kitamura, N. Usami, T. Sugawara, K. Kutsukake, K.
Fujiwara, Y. Nose, T. Shishido, K. Nakajima, J. Cryst.
Growth 208 (2005) 419.
[9] K. Fujiwara, K. Maeda, N. Usami, G. Sazaki, Y. Nose,
A. Nomura, T. Shishido, K. Nakajima, Acta Mater. 56
(2008) 2663.
[10] K. Fujiwara, H. Fukuda, N. Usami, K. Nakajima, S.
Uda, Phys. Rev. B 81 (2010) 224106.
[11] K. Fujiwara, W. Pan, N. Usami, K. Sugawara, M.
Tokairin, Y. Nose, A. Nomura, T. Shishido, K. Nakajima, Acta Mater. 54 (2006) 3191.
[12] K. Fujiwara, W. Pan, K. Sawada, M. Tokairin, N.
Usami, Y. Nose, A. Nomura, T. Shishido, K. Nakajima,
J. Cryst. Growth 292 (2006) 282.
[13] K. Nakajima, N. Usami, K. Fujiwara, K. Kutsukake, S.
Okamoto, in: Proceedings of the 24th European Photovoltaic Solar Energy Conference, WIP-Renewable Energies, 2009, pp.12191221.
[14] K. Fujiwara, K. Maeda, N. Usami, K. Nakajima, Phys.
Rev. Lett. 101 (2008) 055503.
[15] M. Tokairin, K. Fujiwara, K. Kutsukake, N. Usami, K.
Nakajima, Phys. Rev. B 80 (2009) 174108.
[16] I.V. Markov, Crystal Growth for Beginners, second ed.,
World Scientic Press, Singapore, 2003.