JOURNAL OF APPLIED PHYSICS 98, 114911 共2005兲

Transmission electron microscopy observations of Cu-induced directional

crystallization of amorphous silicon
Sung Bo Leea兲 and Duck-Kyun Choi
Department of Ceramic Engineering, Hanyang University, Seoul 133-791, South Korea
Dong Nyung Lee
School of Materials Science and Engineering, Seoul National University, Seoul 151–744, South Korea
共Received 4 April 2005; accepted 31 October 2005; published online 14 December 2005兲
By annealing at 500 ° C for 1 h with an electric field of 180 V / cm, a Cu-deposited a-Si/glass
sample undergoes a partial crystallization of amorphous Si, whose microstructure is characterized
by conventional and high-resolution transmission electron microscopy. The Si crystallites grow in
the 具111典 and 具211典 directions with their 兵011其 planes parallel to the amorphous Si film surface,
assuming a needlelike shape. Copper silicides are not observed at the leading edges of the crystalline
Si needles. The growth directions of 具111典 and the 兵011其 surface plane orientations are accepted to
arise from elastic anisotropy of c-Si and can be explained by considering the strain energy under the
uniaxial stress state and the plane stress, equibiaxial strain state. Crystallization behavior of a-Si in
the Ni/ a-Si layer is also briefly discussed. © 2005 American Institute of Physics.
关DOI: 10.1063/1.2139835兴

I. INTRODUCTION bounded by eight 兵111其 faces. The lattice parameter of NiSi2

Polycrystalline silicon thin-film transistors 共poly-Si
TFTs兲 have recently attracted considerable attention for their
high-field-effect mobility and response velocity.1,2 For low
fabrication cost, poly-Si TFTs should be made on inexpen-
sive glass substrates. In order to lower the crystallization
temperature of amorphous silicon 共a-Si兲 below the intrinsic
crystallization temperature 共⬃600 ° C兲, the effects of metal
impurities on crystallization have been investigated 关metal-
induced crystallization 共MIC兲兴 using Au,3 Al,4 and Sb 共Ref.
5兲 forming eutectics with Si, and Pd 共Ref. 6兲 and Ni 共Ref. 7兲
forming silicides with Si. Following the MIC, its variants,
such as the metal-induced lateral crystallization 共MILC兲8 and
the field-aided lateral crystallization 共FALC兲,9–12 have been
introduced as attempts to lower crystallization temperature
and to reduce the contamination by a metal catalyst. For the
MILC process, the flux of the diffusing species is governed
only by the concentration gradient, but for the FALC pro-
cess, the flux can be affected by not only the concentration
gradient but also the applied electric potential gradient. In
the FALC process, the crystallization front typically migrates
from the negative electrode side to the positive electrode
side. In the FALC, the application of a dc electric field in-
creases the crystallization rate, as compared with the MILC
共without any electric field兲 and MIC. In the FALC process,
Ni and Cu, both of which are silicide forming metals, have
been reported to produce high crystallization rates.12
The mechanism of the crystallization induced by Ni was
examined in detail by Hayzelden and his co-workers13,14 us-
ing in situ transmission electron microscopy 共TEM兲 and
high-resolution TEM: First, the NiSi2 precipitates with CaF2
structure form in a-Si at about 400 ° C, which are octahedra
a兲
Author to whom correspondence should be addressed; electronic mail:
bolee@hanyang.ac.kr
共0.5406 nm兲 is nearly equal to that of crystalline Si 共c-Si兲
共0.5430 nm兲. At about 500 ° C, the epitaxial c-Si is nucleated
on one or more of the NiSi2 兵111其 surfaces and the c-Si
needles grow in the 具111典 directions in the amorphous matrix
with the 具011典 orientations parallel to the film surface
normal.13–15 The precipitates are observed to be always
present at the leading edges of c-Si needles. Hayzelden and
Batstone14 suggested that the chemical potential of the Ni
atoms is lower at the interface of NiSi2 / a-Si than that at the
interface of NiSi2 / c-Si, and the chemical potential of Si at-
oms shows the exact reverse. The chemical potential differ-
ences drive the diffusion of Ni atoms into the NiSi2 / a-Si and
that of Si atoms into the NiSi2 / c-Si interface, leading to the
migration of the NiSi2 precipitate toward the a-Si and the
formation of c-Si behind the precipitate.
Lee et al.12 examined effects of various metals on the
crystallization rate in the FALC process. Mask patterns with
various shapes and dimensions from 5 to 120 ␮m were used.
After annealing at 500 ° C with an electric field of 2.1 V / cm,
Ni produces the crystallization rate of 9.5 ␮m / h, but Cu in-
duces the crystallization of 35 ␮m / h, much higher than that
of Ni. For Cu, the crystallization rate with the electric field of
2.1 V / cm is much higher than that without an electric field
共1.5– 2 ␮m / h兲.12 However, the mechanism of crystallization
enhanced by Cu has not been clearly resolved.
Our purpose in this study is to explore how the Cu atoms
enhance the crystallization. In the present study, Si crystal-
lites grow in specific crystallographic orientations, having a
needlelike shape. Based on the strain energy consideration,
we predict growth directions of c-Si and find that the predic-
tion agrees with the observations. The analysis is also suc-
cessfully applied to the NiSi2-mediated crystallization.10,13–15
A specimen fabricated by the FALC process has been ob-
served by transmission electron microscopy 共TEM兲 for the
study. As indicated before, without any electric field, crystal-

0021-8979/2005/98共11兲/114911/7/$22.50 98, 114911-1 © 2005 American Institute of Physics

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114911-2 Lee, Choi, and Lee
FIG. 1. 共Color online兲 共a兲 A schematic diagram of the patterned structure
composed of the small patterns of 60⫻ 30 ␮m2 in size and 共b兲 an optical
image of the patterns between the electrodes.
lization does not occur very well, and therefore, it is ex-
pected that the observation of crystallization is facilitated in
a crystallized specimen fabricated with an electric field.
II. EXPERIMENTAL PROCEDURE
Thin 80 nm a-Si was deposited on Corning 1737 glass
by plasma-enhanced chemical vapor deposition 共PECVD兲 at
280 ° C using Si2H6 and H2 as source gases. The wafer was
cut into 3 ⫻ 3 cm2 square specimens for the subsequent pro-
cess. To deposit a metal 共Cu兲 on the a-Si film, the photoresist
共PR兲 was spin-coated and patterned by a photolithographic
process. In this study rectangular mask patterns of 60
⫻ 30 ␮m2 were used. A thin 2 nm Cu layer was deposited in
a dc sputtering system. Copper on the PR patterns was re-
moved by the lift-off method and only that deposited on the
a-Si was left.
The crystallization annealing was done at 500 ° C for 1 h
in N2 ambient. During the crystallization annealing an elec-
tric field of 180 V / cm was applied to the above metal-
deposited specimen by the dc power supply. Details concern-
ing the specimen preparation are presented elsewhere.12
From the crystallized specimen, 3 mm disks were cut
using an ultrasonic cutter for TEM specimen preparation. For
the plan-view studies of the a-Si film, the disks were me-
chanically back-thinned to a thickness of about 10 ␮m, and
then ion milled on the glass substrate side at an accelerating
voltage of 5 kV using a PIPS. The crystallization microstruc-
ture was characterized by transmission electron microscopy
共TEM; JEM2010, JEOL Co., Ltd., Japan兲. High-resolution
TEM 共HRTEM兲 was performed at 400 kV in a JEM4010
共point-to-point resolution: 0.15 nm, JEOL Co., Ltd., Japan兲.
Energy dispersive x-ray spectroscopy 共EDXS兲 was applied
for composition analysis of a-Si and c-Si regions.
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J. Appl. Phys. 98, 114911 共2005兲
FIG. 2. 共a兲 A low magnification TEM image of a partially crystallized
a-Si revealing a needlelike morphology of c-Si and the typical TEM image
共b兲 with the electron diffraction pattern 共c兲 showing the c-Si needles grow in
the directions of 具111典 and 具112典 directions with the 具110典 surface normal
orientations.
III. RESULTS
Figure 1共a兲 is a schematic diagram of the patterned
structure composed of the small patterns of 60⫻ 30 ␮m2 in
size. An enlarged view of the patterns between the electrodes
is shown in Fig. 1共b兲. The crystallization front migrates from
the negative electrode side to the positive electrode side. A
needlelike morphology of c-Si was clearly observed at the
interface between the fully crystallized and amorphous re-
gions 关indicated by an “O” in Fig. 1共b兲兴, as shown in Fig.
2共a兲. Interestingly, as revealed in Figs. 2共b兲 and 2共c兲, almost
all the c-Si needles exhibited 具011典 orientations with respect
to the a-Si film surface normal 共i.e., 兵011其 surface plane ori-
entations兲 and grew in the 具111典 and 具211典 directions, form-
ing an angle of 90° between the needles. The 关011兴 diffrac-
tion pattern taken from the needle “A” in Fig. 2共b兲 关Fig. 2共c兲兴
shows streaks along the 关111兴 direction, indicating that there
are many stacking faults or twins normal to that direction.
共The diffraction pattern taken from the needle “B” is not
shown here.兲 The a-Si region was measured to contain
共2.99± 0.97兲 at. % Cu on average by EDXS measurement of
five areas. In fully crystallized regions many needles were
interwoven, as shown in Fig. 3. The regions contained
共1.63± 0.15兲 at. % Cu on average by EDXS measurements of
four areas. The solubility of Cu in c-Si is negligible, and
therefore, the detected Cu is believed to arise from trapped
Cu solutes in the interfaces between the interwoven c-Si
needles. Figure 4共a兲 shows a high-resolution TEM image
114911-3 Lee, Choi, and Lee J. Appl. Phys. 98, 114911 共2005兲

FIG. 4. A high-resolution TEM image 共a兲 showing the growth directions of

具111典 and 具112典 with the 兵110其 surface orientation of a c-Si needle. The beam
direction 共zone axis兲 is parallel to 关011兴. At a higher magnification 共b兲 of the
area indicated by a white-lined box in 共a兲, three 兵111其 twin boundaries and a
stacking fault 共SF兲 are visible.

NiSi2-mediated crystallization,10,13–15 however, as shown in

Fig. 5, Cu silicides were not observed at the leading edges of
FIG. 3. A TEM image 共a兲 with the electron diffraction pattern 共b兲 of a fully
crystallized region.
the c-Si needles, indicating that the crystallization of the
Cu/ a-Si system in this study was not mediated by any Cu
silicides. Radnoczi et al.4 suggested that Au, Sb, In, and Al,
also revealing the growth directions of 具111典 and 具211典 with which form eutectic with Si, dissolved in the a-Si film may
the 兵011其 surface orientation. At a higher magnification 关Fig. loosen the covalent bonds in Si and make the a-Si even
4共b兲兴, three 兵111其 twins and a stacking fault were seen, in unstable, enhancing crystallization. Even though Cu is a
agreement with the indication of Fig. 2共c兲. In order to con- silicide-forming metal, Cu atoms appear to enhance crystal-
sider the role of any Cu silicides on the nucleation and lization in a similar way to the eutectic-forming metals.
growth of the c-Si needles, the edges of the c-Si needles Since Cu has a negligible solubility in crystalline Si,16 the Cu
were examined. Figure 5 displays the typical edge, where Cu
silicides were not observed, and instead, the Si lattice image
was shown. Furthermore, Cu silicides were not observed,
even in the a-Si matrix and the crystallized region within the
limited field of view. The c-Si region at the edge contained
many 兵111其 twins and stacking faults indicated by white tri-
angles and arrows, respectively. There also seemed to be
some lattice distortion in some areas, due to which defects
共twins or stacking faults兲 were not clearly visible.

IV. DISCUSSION

As for the NiSi2-mediated crystallization,10,13–15 in this

study, crystallization proceeded in the 具111典 directions with a
shape of needles as shown in Figs. 2共b兲 and 4共a兲. The c-Si
needles had the 兵011其 surface plane orientations. Addition-
FIG. 5. A high-resolution image of the typical edge without Cu silicides,
ally, as clearly shown in Figs. 2共b兲 and 4共a兲, the growth where the Si lattice image is shown. The 兵111其 twins and stacking faults are
occurred also in the 具211典 directions. At variance with the indicated by white triangles and arrows, respectively.

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114911-4 Lee, Choi, and Lee
solute atoms are repelled by the c-Si. The Cu atoms will
diffuse into the a-Si matrix, making the a-Si unstable, and
the Si atoms will migrate into the c-Si side from the a-Si,
resulting in crystallization. Diffusion of Cu atoms in a-Si
seems to be rate controlling. Without the application of any
electric field during annealing at 500 ° C 关i.e., in the MILC
process兴, the crystallization rate is reported to be
1.5– 2 ␮m / h.12 Copper is reported to diffuse in a-Si with
D ⬎ 10−12 cm2 / s in a temperature range between 400 °C and
600 ° C.17 From the diffusivity value of 10−12 cm2 / s, we cal-
culate the minimum diffusion length 共冑Dt兲 to be 0.6 ␮m for
1 h at 500 ° C. This diffusion length qualitatively agrees with
the crystallization rate obtained without any electric field in
the MILC process 共1.5– 2 ␮m / h兲. Lee et al.12 showed the
increase in the crystallization rate with an electric field of
2.1 V / cm to 35 ␮m / h. Although some crystallization pa-
rameters such as pattern size, shape, and the applied electric
field intensity are different in the present study, a high crys-
tallization rate of ⬃40 ␮m / h was obtained, as shown in Fig.
1共b兲. The crystallized pattern image in Fig. 1共b兲 reveals that
the macroscopic crystallization direction under an applied
bias corresponds to that of an electric field in the pattern.
It is suggested that the electric field in the FALC process
can cause a kind of electron wind effect 共electromigration兲
via current flow in the pattern at the elevated temperature.18
In Ref. 18, the electron wind effect is proposed to explain the
NiSi2-mediated crystallization13,14 and is limited to the diffu-
sion of Ni in NiSi2. When the current density is high enough,
the momentum exchange induces the 共Ni兲 atoms in NiSi2 to
migrate from the negative electrode side to the positive one
共along the electron flow direction兲.18 In the present study,
because no Cu silicides were observed at the leading edges
of the c-Si needles, the application of the above-mentioned
suggestion is not plausible. However, the electron wind ef-
fect is likely to hold for the diffusion of Cu in a-Si at the
high temperature of 500 ° C in the present study, because the
resistivity of a-Si decreases with the increase of temperature
because of the exponential increase in intrinsic carrier con-
centration, and at such a high temperature, the electron flow
in a-Si can cause the electron wind effect. 共A more theoret-
ical consideration of the electron wind effect in a-Si at high
temperatures is in progress.兲 The effect will accelerate the
diffusion of Ni along the electron flow direction, and con-
comitantly, the crystallization rate.
The crystallization behavior of a-Si in the Cu/ a-Si bi-
layer 共without any electric field in this case兲 was studied by
Russell et al.19 On heating to 175 ° C, the Cu3Si phase ap-
pears and subsequent heating to 485 ° C results in the crys-
tallization of the a-Si in the form of dendrites in the Cu3Si
matrix. Different from the results of Russell et al.,19 the ma-
trix was observed to be still a-Si in the present study and
discernible Cu silicides, including Cu3Si phase, were not ob-
served. In the study by Russell et al.,19 the thickness ratio of
Cu to a-Si was determined to obtain an average composition
of Cu3-␦Si, where ␦ is from 0.5 to 1. In this case the matrix
共continuous phase兲 could become Cu3Si phase. In the present
study, however, the deposited Cu film 共2 nm thick兲 is very
thin, with the thickness ratio to the a-Si underlying layer
共80 nm兲 of 1:40. Therefore, as mentioned in the Results sec-
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J. Appl. Phys. 98, 114911 共2005兲
tion, they could not be easily observed in the present study. It
may be that they act as heterogeneous nucleation sites for
crystallization. However, the difficulty in observing the
phases indicates that their nucleation density was too low
and their size was too small to explain the observed, overall
crystallization behavior, strongly implying that the presence
of Cu solutes, not Cu silicides, enhances crystallization.
The 具111典 growth directions and the 兵011其 surface plane
orientations observed in the present study may be caused by
anisotropic elastic properties of c-Si, although a-Si is isotro-
pic, because the strain energy can influence the crystalliza-
tion rate. The higher strain energy will give rise to the higher
crystallization rate. One of the major strain energy sources
may be the thermal strain energy due to differences in ther-
mal expansion coefficient between a-Si and the substrate
glass. The thermal strain energy can influence the crystalli-
zation rate, but is not related to the directional crystallization.
Since the thermal expansion coefficients of a-Si and c-Si are
expected to be almost the same, the thermal strain energy
between a-Si and c-Si can be negligible.
Another strain energy may arise from the accommoda-
tion strain between a-Si and c-Si due to different structures
and densities 关the densities of a-Si and c-Si are measured to
be 2.1–2.3 共Ref. 20兲 and 2.32–2.34,21 respectively兴. This
strain energy can be anisotropic because of anisotropic elas-
tic properties of c-Si, even though a-Si is isotropic. Since the
thickness of the Si film, including a-Si and c-Si, is much
smaller than the dimensions along the film surface, the stress
in the plane normal direction 共ND兲 is negligible, and the film
is under the plane stress. Initial Si crystallites will form in
the surface layer, where the Cu concentration is highest, and
they could be of a disk shape. The surface orientation of
c-Si disks is presumably random, because they formed from
amorphous Si. However, their growth rates will vary with
their orientations, because different orientations give rise to
different strain energies. The strain energy of the disk is ap-
proximated by that of a thin film under plane stress-
equibiaxial strain. When c-Si grows with the needlelike
shape, however, the stress is expected to be much higher in
the axial direction 共AD兲 than in the transverse direction 共TD兲
because of the longer axial dimension, and therefore, the
stress state of c-Si needles can be approximated by the
uniaxial stress state. That is, the stress state of the initial
stage of the crystallization of a-Si 共disk formation兲 is ap-
proximated by the biaxial stress and that of the growing
stage 共needlelike shape兲 by the uniaxial stress.
Elastic properties of thin films of the cubic system have
been studied by Lee.22 For a material under the uniaxial
stress, we define Young’s modulus, E, in the direction of
stressing, as the uniaxial stress divided by the longitudinal
strain in that direction. For a material with cubic symmetry,
Young’s modulus E is given by
1/E = S11 + 关S44 − 2共S11 − S12兲兴共a11
2 2 2 2
a12 + a12 2 2
a13 + a13 a11兲,
共1兲
where S11, S44, and S12 are the compliances referred to the
symmetric axes and a1i are the direction cosines of the
uniaxial stress direction referred to the symmetric axes. For
114911-5 Lee, Choi, and Lee J. Appl. Phys. 98, 114911 共2005兲

TABLE I. The M̄ values for planes parallel to the 关111兴 direction in Si.

兵hkl其 1̄12 2̄3̄5 1̄2̄3 2̄5̄7 1̄3̄4 1̄4̄5 1̄5̄6 1̄7̄8 1̄10

M̄ 共Si兲, GPa 209.4 209.7 210.3 210.8 211.2 211.8 212.1 212.5 213

the 关hkl兴 direction, a11 = h / 冑h2 + k2 + l2, a12 = k / 冑h2 + k2 + l2, strain energy per unit volume of a cubic-system crystal
and a13 = l / 冑h2 + k2 + l2. strained by ␧ along the 共hkl兲 plane is given by
For silicon, S11 = 0.007 86, S12 = −0.002 14, and S44 ⬘ + S22
␧2 S11 ⬘ − 2S12
⬘
= 0.012 56 GPa−1.23 From Eq. 共1兲, the maximum and mini- W= = ␧2M̄ , 共2兲
2 S11⬘ S22
⬘ − 共S12
⬘ 兲2
mum Young’s moduli of c-Si are calculated to be 185.9 GPa
in the 具111典 directions and 127.2 GPa in the 具001典 directions, where M̄ is designated as biaxial elastic modulus under
respectively. For reference, we calculate Young’s moduli equibiaxial strain state 共briefly, equibiaxial-strain elastic
along directions normal to the 关111兴 direction. The 具hkl典 di- modulus兲. The compliances S11⬘ , S12
⬘ , and S22
⬘ for a cubic crys-
rections normal to the 关111兴-oriented needle are obtained tal can be expressed in terms of the compliances referred to
from a relation of h + k + l = 0. For h + k + l = 0, 共a11 2 2
a12 the symmetric axes, Sij, and direction cosines of the 共hkl兲
+ a12a13 + a13a11兲 = 1 / 4 in Eq. 共1兲. Therefore, Young’s moduli
2 2 2 2
plane, aij, as follows:
along directions normal to the 具111典 directions are the same
⬘ = S11 + 关S44 − 2共S11 − S12兲兴共a11
S11 2 2 2 2
a12 + a12 2 2
a13 + a13 a11兲,
and calculated to be 166.7 GPa. The strain energy W per unit
volume of a specimen strained by ␧ under the uniaxial stress 共3a兲
is given by W = ␧2E / 2, and the Young’s modulus, E, can
1
function as measures of the stiffness and the strain energy for ⬘ = S12 − 关S44 − 2共S11 − S12兲兴共a11
S12 2 2 2 2
a21 + a12 a22
the uniaxial stress state. Thus, for Si, the 具111典 directions are 2
the stiffest and have the highest strain energy density, which 2 2
+ a13 a23兲, 共3b兲
indicates that the a-Si matrix contacting the 具111典-oriented
needles receive the highest strain energy density along the ⬘ = S11 + 关S44 − 2共S11 − S12兲兴共a22
S22 2 2 2 2
a21 + a21 2 2
a23 + a23 a22兲,
needle growth directions, accelerating the crystallization
共3c兲
along the 具111典 directions.
Likewise, for the plane stress-equibiaxial strain state, the with

冤 冥
−k h
0
冑h2 + k2 冑h2 + k2
− hl − kl h2 + k2
关aij兴 = 共4兲
冑h2 + k2冑h2 + k2 + l2 冑h2 + k2冑h2 + k2 + l2 冑h2 + k2冑h2 + k2 + l2 .

h k l
冑h2 + k2 + l2 冑h2 + k2 + l2 冑h2 + k2 + l2

Here M̄ can function as measures of the stiffness and the
strain energy for the plane stress, equibiaxial strain state.
The M̄ values for the 兵001其, 兵211其, 兵011其, and 兵111其
planes of silicon are calculated to be 175, 209.4, 213, and
223 GPa, respectively. Actually, out of the biaxial elastic
moduli of all orientations, M̄ 共111兲 is the highest and M̄ 共001兲 is
the lowest. Therefore, the 兵111其 layers in contact with a-Si
film are the stiffest and have the highest strain energy den-
sity, which also implies that the a-Si layers in contact with
the 兵111其 layers receive the highest strain energy density. The
a-Si layers with the highest strain energy density are likely to
undergo crystallization with the highest rate.
Because the 具111典 directions have the highest Young’s
moduli and the planes normal to those directions have the
highest M̄ value, it may happen that in the a-Si film surface,
the 兵111其 disks of c-Si are selectively nucleated parallel to
the film surface and the growth would occur in the 具111典
directions 共i.e., normal to the film surface兲. However, such
needles are unlikely to be observed due to their short dimen-
sion. When the 具111典 orientations are parallel to the film
surface, the c-Si needles can grow extensively and occupy
large areas within the a-Si films, resulting in more frequent
observations.
We want to find the orientation of initial crystal disks
formed in the surface layer that can develop into the 具111典-
oriented c-Si needles. We can expect that the disk crystals

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114911-6 Lee, Choi, and Lee
FIG. 6. A schematic diagram of the formation of the 兵110其具111典-oriented
needles.
whose planes have the highest M̄ value grow fastest among
those whose planes are parallel to both the film surface and
the 具111典-oriented needles. In this case, planes with maxi-
mum M̄ value among planes parallel to the 具111典 directions
are likely to be parallel to the surface. The 兵hkl其 planes par-
allel to the 关111兴-oriented needle are obtained from a relation
of h + k + l = 0. These planes and their M̄ values are given in
Table I. The maximum and minimum M̄ values are obtained
for the 兵011其 and 兵211其 planes, respectively. Therefore, the
initial disk c-Si crystals whose 兵011其 planes are parallel to
the surface grow fastest in the ND and have the best chance
to grow in the 具111典 directions, leading to the formation of
the 兵011其 具111典-oriented needles, as revealed in Figs. 2共b兲
and 4共a兲 and schematically shown in Fig. 6. As noted before,
the Young’s moduli along directions normal to the 具111典 di-
rections are equal, while M̄ values of planes parallel to the
具111典 directions have the highest value for the 兵011其 planes.
The growth of the 具111典-oriented needles may be inter-
rupted probably by inhomogeneity of Cu solute distribution
in the a-Si. At this time, the additional growth in the 具211典
directions may occur with the help of many 兵111其 twins and
stacking faults observed in the c-Si 关Figs. 4共b兲 and 5兴, which
are certainly due to the low stacking fault energy of Si
共⬃50 mJ/ m2兲, even though the 具211典 orientations are not
favorable in terms of the strain energy consideration. These
兵111其 twins and stacking fault planes can generate steps for
growth at the interface between the c-Si and a-Si, enhancing
the growth in directions parallel to the twin and stacking
fault planes. Because the 兵011其 planes have the highest M̄
value out of the planes normal to the 具111典 growth directions
共Table I兲, even though there is some change in the growth
direction into 具211典, the 兵011其 surface plane orientations will
remain unchanged, as revealed in Figs. 2共b兲 and 4共a兲.
For the NiSi2-mediated crystallization, the 兵011其 具111典-
oriented crystallization is obtained13,14 as for the Cu-
enhanced crystallization. However, for the NiSi2-mediated
crystallization,13,14 crystallization of a-Si occurs on the flat
兵111其 faces of the octahedral NiSi2 precipitates, and during
crystallization annealing, the initial octahedral shape of the
NiSi2 precipitates at the leading edges of the c-Si needles
changes into the thin plate shape,13,14 whereas for Cu-
enhanced crystallization, the Cu3Si phases are not observed
TABLE II. The M̄ values for planes parallel to the 关111兴 direction in NiSi2.
兵hkl其 1̄12 2̄3̄5 1̄2̄3
M̄ 共NiSi2兲, GPa 194.3 195.0 196.2
Downloaded 09 Jun 2009 to 147.46.233.104. Redistribution subject to AIP license or copyright; see http://jap.aip.org/jap/copyright.jsp
J. Appl. Phys. 98, 114911 共2005兲
and the leading edges are not flat. For the NiSi2-mediated
crystallization, the 具211典-oriented needles have not been re-
ported, which are easily observed for Cu-enhanced crystalli-
zation. The fan-shaped growth and thinning of the NiSi2
plate take place for the NiSi2-mediated crystallization. These
differences seem to be attributable to the stability of NiSi2.
We consider the effect of NiSi2 on the formation of the
兵011其 具111典-oriented c-Si needles. The NiSi2 crystal belongs
to the cubic system, and its measured elastic constants are
not available. Its calculated compliances are as follows:24
S11 = 0.012 19 GPa−1, S44 = 0.018 87 GPa−1 ,
S12 = − 0.005 05 GPa−1 .
From Eq. 共1兲, the maximum and minimum Young’s
moduli of NiSi2 are calculated to be 143 GPa in the 具111典
directions and 82 GPa in the 具100典 directions, respectively.
The 兵001其 and 兵111其 planes of NiSi2 are calculated to have
the lowest 共140 GPa兲 and the highest M̄ 共220.3 GPa兲, re-
spectively, as for c-Si. The M̄ values for planes parallel to the
关111兴 direction of NiSi2, M̄ 共NiSi2兲, are given in Table II. The
maximum and minimum M̄ 共NiSi2兲 values are obtained for
the 兵011其 and 兵211其 planes, respectively, as for c-Si. In addi-
tion to similar anisotropic elastic trends of c-Si and NiSi2,
any lattice plane of c-Si is likely to have a close match with
the same plane of c-Ni2Si, because the Ni2Si crystals have a
close lattice parameter match with c-Si 共−0.4% 兲.
Among the NiSi2 / c-Si interfaces, the 兵111其 NiSi2 / c-Si
interfaces are elastically the stiffest, because the 兵111其 layers
of the both crystals are elastically the stiffest. Therefore, the
region surrounding the interface edge is strained, which in
turn gives rise to crystallization along the interface plane as
well as along the needle axis. In this way, the c-Si needles
fan out during its growth, and simultaneously, the NiSi2 pre-
cipitates become thinner. As the interface area increases, the
accommodation strain increases to a point such that coher-
ency between the two crystals cannot be maintained, result-
ing in dissociation of the NiSi2 crystal into a few smaller
crystallites. These smaller precipitates continue to mediate
the growth.14 Because the growth is mediated by the NiSi2
whose equibiaxial-strain elastic moduli show a stronger an-
isotropy than that of c-Si 共Table II兲, the 兵011其 具111典-oriented
growth for the NiSi2-mediated crystallization remains with-
out growth in other directions 共e.g., 具211典 for the Cu-
enhanced crystallization兲.
V. CONCLUDING REMARKS
The crystallization behavior of a Cu-deposited a-Si/glass
sample annealed at 500 ° C for 1 h with an electric field of
180 V / cm has been examined by TEM. The Si crystallites
grow in the 具111典 and 具211典 directions with their 兵011其 planes
2̄5̄7 1̄3̄4 1̄4̄5 1̄5̄6 1̄7̄8 1̄10
197.4 198.3 199.6 200.4 201.3 202.4
114911-7 Lee, Choi, and Lee J. Appl. Phys. 98, 114911 共2005兲

parallel to the a-Si film surface, assuming a needlelike shape.
No Cu silicides are observed at the leading edges of the
c-Si needles, and therefore, it seems that the Cu atoms in the
a-Si film make the a-Si unstable, enhancing crystallization,
as in the case of the eutectic-forming metals. The growth
directions of 具111典 and the 兵011其 surface plane orientations
can be explained based on the strain energy consideration
using the concept of an equibiaxial-strain elastic modulus. In
c-Si, the 具111典 directions has the highest equibiaxial-strain
elastic modulus and can give the highest strain energy den-
sity to the a-Si film in that direction, resulting in the fastest
crystallization in the direction. The 兵011其 planes has the
highest strain energy density out of the planes parallel to the
具111典 directions and are likely to be parallel to the film sur-
face. The 具211典 directions will be possible with the help of
many 兵111其 twins and stacking faults in c-Si. The
NiSi2-mediated, directional crystallization of a-Si can be
also explained in terms of the strain energy consideration.
ACKNOWLEDGMENTS
One of the authors 共SBL兲 thanks Kyung-Sook Jeon for
the TEM specimen preparation and Young-Woong Kim and
Jeong-Ung Kim for the preparation of the crystallization
specimens. The help of Dr. Young-Ho Lee at the JEM 4010
is appreciated. This work was financially supported by a Ko-
rea Research Foundation Grant 共KRF-2004-005-D00167兲.
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