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Formation of nickel nanoparticles on amorphous silicon thin film

and its effect on crystallization


Sung Bo Leea兲 and Duck-Kyun Choi
Department of Ceramic Engineering, Hanyang University, Seoul 133-791, South Korea
Fritz Phillipp
Max-Planck-Institut für Metallforschung, Heisenbergstrasse 3, D-70569 Stuttgart, Germany
Young-Min Kim and Youn-Joong Kim
Korea Basic Science Institute, Daejeon 305-333, South Korea
共Received 1 February 2006; accepted 10 April 2006; published 10 May 2006兲
Using in situ high-resolution transmission electron microscopy, we observe that, while annealed at
550 ° C in the TEM, a Ni-deposited amorphous silicon thin film is crystallized, which is preceded
by the formation of NiSi2 precipitates. In addition to the NiSi2 precipitates, nanometer-sized Ni
particles, single crystalline or multiply twinned, form. Their unusual formation is attributed to beam
heating effect by beam irradiation during the observations. Unlike the NiSi2 precipitates, no
crystallization occurs around the Ni nanoparticles. © 2006 American Vacuum Society.
关DOI: 10.1116/1.2201459兴

I. INTRODUCTION lization of a-Si in a Ni-deposited a-Si thin film by in situ


high-resolution transmission electron microscopy 共HRTEM兲.
Bulk amorphous silicon 共a-Si兲 crystallizes at about
During annealing at 550 ° C in the TEM, crystallization oc-
600– 700 ° C 共e.g., Ref. 1兲 and this intrinsic crystallization
curs with the NiSi2 formation. Nanometer-sized Ni particles
temperature is lowered by addition of metal impurities, such
are also observed, but crystallization does not occur around
as Au,2 Al,3 and Sb,4 which form eutectics with Si, and Ni,5–7
them. The dependence of crystallization behavior on the par-
which forms various silicides with Si. For the eutectic-
ticle types leads to the suggestion that crystallization is pro-
forming metals, Radnoczi et al. suggested that Au, Sb, and
moted by the presence of Ni, not by that of NiSi2.
Al dissolved in the a-Si film may loosen the covalent bond-
ing in the a-Si and make the a-Si even unstable, enhancing
II. EXPERIMENTAL PROCEDURE
crystallization.3
Unlike eutectic-forming metals, for the silicide-forming A Ni-deposited a-Si thin film was made in the following
metal, such as Ni, silicides are reported to mediate way: On Corning 1737 glass, thin 80 nm a-Si was deposited
crystallization.5–7 Hayzelden and co-workers5,6 observed that by plasma-enhanced chemical vapor deposition 共PECVD兲 at
after NiSi2 precipitates with CaF2 structure, which has a 280 ° C using Si2H6 and H2 as source gases. A thin 2 nm Ni
close lattice match to Si 共−0.4% 兲, form in a-Si in the shape layer was deposited on the a-Si layer on the glass by dc
of octahedra bounded by eight 兵111其 faces at about 400 ° C, sputtering. Disks of 3 mm in diameter were cut from the
then at a higher temperature of 500 ° C, the c-Si is epitaxially wafer using a disk cutter for TEM specimen preparation. The
nucleated on one or more of the NiSi2 兵111其 surfaces. The disks were mechanically back thinned to a thickness of about
NiSi2 precipitates are observed to migrate in the a-Si films, 20 ␮m and then ion milled on the glass substrate side at an
leaving c-Si needles behind 共NiSi2-mediated accelerating voltage of 4 kV using a precision ion polishing
crystallization兲.5,6 Erokhin et al.7 also observed similar phe- system 共PIPS, Gatan Inc.兲 . In situ observations were made in
nomena. They6,7 suggested that crystallization is enhanced plan view at a temperature of 550 ° C, using the Jeol JEM-
by solid-phase transport of Si through the silicides. However, ARM1250 at the Max-Planck-Institut für Metallforschung
in a Ni/ a-Si/ c-Si layered system, Mohadjeri et al.8 presented 共Stuttgart, Germany兲 and the Jeol JEM-ARM1300S at the
another possibility of crystallization mechanism than in the Korea Basic Science Institute 共Daejon, Korea兲, both of which
previous results:6,7 During annealing at various temperatures are operated at 1.25 MeV 共0.12 nm point-to-point resolution兲
between 350 and 425 ° C, nickel monosilicide 共NiSi兲 forms and equipped with a side-entry heating stage. The base pres-
at the Ni/ a-Si interface and Ni diffuses toward at the sure in the specimen chamber is in the range of 共2 – 3兲
a-Si/ c-Si interface through the a-Si layer. Crystallization ⫻ 10−6 Pa. The heating rate was 20 ° C / min. Electron current
starts at the a-Si/ c-Si interface, where the presence of Ni is densities at the specimens were in the range of
detected without any certain indication of NiSi2 formation, 15– 20 A / cm2 during the observations.
suggesting that the presence of Ni solutes promotes
crystallization. III. RESULTS
In this study, we reinvestigate the effect of Ni on crystal- Figure 1共a兲, taken after annealing for 124 min, shows a
high-resolution image of a 具111典-oriented NiSi2 共or Si兲. Lat-
a兲
Electronic mail: bolee@hanyang.ac.kr tice images of Si and NiSi2 are not distinguished from each

1405 J. Vac. Sci. Technol. B 24„3…, May/Jun 2006 1071-1023/2006/24„3…/1405/4/$23.00 ©2006 American Vacuum Society 1405
1406 Lee et al.: Formation of nickel nanoparticles on amorphous silicon thin film 1406

FIG. 2. Plan-view HRTEM image of misfit dislocation networks in the


NiSi2 / c-Si 兵110其 interface taken after annealing for 167 min.

Figure 2 shows another area, which was taken when an-


nealed for 167 min. The measured interplanar spacings cor-
respond to those of the NiSi2兵111其 共3.121 Å兲 or the Si兵111其
共3.136 Å兲 with the 具110典 zone axis parallel to the beam di-
rection. In the 具110典 surface orientations, zigzagged surface
defects are found. If only a disilicide layer forms, such de-
fects would not exist, and thus, these defects are likely to
arise from an overlap of the NiSi2 and c-Si layers Tung
et al.13 show that the interface between the NiSi2 and the
Si共110兲 关共110兲 interface兴 is faceted into 兵111其 interfaces 共in-
FIG. 1. 共a兲 High-resolution TEM image showing the 兵111其 surface of NiSi2 terfaces between NiSi2兵111其 and Si兵111其兲, and on the in-
taken after annealing at 550 ° C for 124 min. 共b兲 Plan-view HRTEM image clined 兵111其 interface facets, the 1 / 2 具11̄0典-type dislocations
of the NiSi2 / c-Si 兵111其 interface taken after annealing for 252 min.
are observed. When NiSi2 grows on Si兵111其 epitaxially, mis-
fit edge dislocations with a Burgers vector 共b兲 of 1 / 2 具11̄0典
are found, while edge dislocations with b = 1 / 6 具112典 form in
the twin boundary between the NiSi2 and the Si.11 Based on
other in the plan-view observation, because the silicide with the previous result,11 the HRTEM image of Fig. 2 is likely to
CaF2 structure has a close lattice match to Si 共−0.4% 兲. The be a two-dimensional projection to the 共110兲 surface of dis-
measured spacings of three sets of planes are nearly identical locations forming on the inclined 兵111其 facets. Figure 3 is a
to the 兵220其 spacings 共1.920 Å兲 of Si 共cubic, a = 5.430 Å兲 or schematic diagram showing the geometrical relationship be-
the 兵220其 spacings 共1.911 Å兲 of NiSi2 共cubic, a = 5.406 Å兲.9 tween the 共110兲 interface and the 兵111其 interface facets. 关The
It is understood in Fig. 1共a兲 that at this annealing stage 共i.e., 共110兲 interface plane and one of the 兵111其 facet planes form
after annealing for 124 min兲 the surface Ni layer reacts with an angle of 35.26°.兴 In the 关110兴 zone axis, the dislocation
the underlying a-Si to form NiSi2, as for Ni-deposited
line runs long along 关001兴 and short along 关1̄10兴 at an angle
c-Si.10–15 It cannot be excluded in Fig. 1共a兲 that a very thin
layer c-Si forms below the NiSi2 layer. After a prolonged
annealing 共e.g., for 252 min兲, in all 具111典 high-resolution im-
ages 关e.g., Fig. 1共b兲兴, the measured spacings of three sets of
planes are revealed to become larger than in Fig. 1共a兲. Such
spacings are not produced by the Si兵220其 reflections corre-
sponding to the spacings of 1.920 Å but seem to arise from
the forbidden 1 / 3 兵422其 reflections of Si corresponding to the
spacings of 3.327 Å. The forbidden reflections are attributed
to 兵111其 twins and stacking faults of c-Si.1 Thus, Fig. 1共b兲
clearly implies that a-Si crystallizes below the NiSi2 layer
and, with the increase of annealing time, will be thickened
and that we are observing the plan view of the overlap of the FIG. 3. Geometry of the 共110兲 interface plane and the 兵111其 interface facet
NiSi2兵111其 and c-Si兵111其 layers. planes viewed along 关1̄10兴.

J. Vac. Sci. Technol. B, Vol. 24, No. 3, May/Jun 2006


1407 Lee et al.: Formation of nickel nanoparticles on amorphous silicon thin film 1407

of 90° with the long components. The shear displacement


occurs along the short dislocation line in the 共110兲 surface,
which is represented by a vector of 1 / 2 关1̄10兴 共whose mag-
nitude is marked by a scale bar with a notation of 兩b兩, as
shown in Fig. 2兲, and this direction can appear also on the
共111兲 interface facet plane 关as exhibited in Fig. 3, the 关1̄10兴
direction is common to both the 共110兲 and 共111兲 surfaces.兴,
indicating that the displacement along the short dislocation
line is associated with a screw dislocation with b = 1 / 2 关1̄10兴.
It is thus accepted that the long dislocation line corresponds
to the edge dislocation with the same Burgers vector. The
dislocation line of the edge dislocation with the Burgers vec-
tor should have the 关1̄1̄2兴 direction on the 共111兲 interface,
and as shown in Fig. 3, its two-dimensional projection to the
共110兲 surface should be the 关001兴 direction, in agreement
with the present observation shown in Fig. 2. Because the
1 / 6 具112典-type screw dislocation in the 兵111其 surface will
produce a very small displacement, it cannot explain the ob-
served displacement projected to the 共110兲 interface in Fig. 2.
In addition to the edge and screw dislocations, a mixed dis-
location appears, whose dislocation line runs along 关1̄12兴 in
the projection of 共110兲, which corresponds to 关1̄01兴 in the
共111兲 interface facet. The observed dislocation line facets
imply the dislocation line energy anisotropy, of which a the-
oretical analysis is in progress. The presence of the 1 / 2
具11̄0典-type dislocations in the NiSi2 / c-Si interface indicates
the epitaxial relationship between the c-Si and the NiSi2.
In addition to the NiSi2, nanometer-sized Ni particles 关cu-
bic, Ni with 0 – 18 at. % Si, a = 3.525– 3.515 Å 共Ref. 16兲兴 are
observed, as shown in Fig. 4, during the in situ examination FIG. 4. High-resolution TEM images showing Ni nanoparticles: 共a兲 single
crystalline and 共b兲 multiply twinned. In 共b兲, the white arrows show the
at 550 ° C. Figures 4共a兲 and 4共b兲 were taken from different position of twin boundaries. 共a兲 and 共b兲 were taken from different particles
particles after annealing for 26 and 206 min, respectively. after annealing for 26 and 206 min, respectively.
The Ni particles seen in Figs. 4共a兲 and 4共b兲 are 具110典 oriented
and the measured interplanar spacings indicated in Fig. 4
correspond to the 兵111其 spacings 共2.035 Å兲 of Ni. Their sizes
Below the eutectic temperature of 993 ° C, NiSi2 is in
are in the range of 3 – 4 nm in equivalent-sphere diameter.
equilibrium with Si,20 and actually, it is reported to exist at
Some particles are single crystals revealing 兵111其 and 兵100其
the Ni/ c-Si interface.10–15 The Ni nanoparticles formed dur-
surface facets arising from truncated octahedral shape, as
ing the present observations by the high-voltage TEM
shown in Fig. 4共a兲, and the others are observed to contain
共HVTEM兲 such as ARM have not been reported in studies
more than one twin boundaries 共multiply twinned兲, as repre-
using different methods. Their formation in the present study
sented in Fig. 4共b兲. The particle in Fig. 4共b兲 also reveals flat
may be attributed to heat evolution effect by the high-energy
兵111其 surfaces, but faceting is not so distinct as compared
electron beam during the observations. Because of the poor
with Fig. 4共a兲. It is well known that small nanoparticles of
thermal conductivity of the a-Si layer and the glass substrate,
fcc metals take a structure of the decahedral or icosahedral
the heat generated by electron beam is not expected to be
multiply twinned particles 共MTPs兲.17–19 Figure 4共b兲 repre-
efficiently dissipated. In this situation, the formation of NiSi2
sents a decahedral MTP viewed along the fivefold axis in the
will be prevented, because it is an exothermic reaction.21
关110兴 direction. Unlike the NiSi2, crystallization does not oc-
Nickel is observed to be the dominant diffusing species in
cur around the Ni particles.
the formation of NiSi2,22 and in a Ni/ a-Si interface, Ni at-
oms will diffuse into the a-Si layer to form NiSi2. During the
formation of NiSi2, a small amount of Ni atoms may not be
IV. DISCUSSION
incorporated into the formed NiSi2. As in the case of the
The dislocation lines shown in Fig. 2 are interpreted as eutectic-forming metals suggested by Radnoczi et al.,3 such
forming at the interface between NiSi2 and c-Si, as observed free Ni atoms can diffuse into the a-Si layer, contributing to
by Tung et al.13 This finding indicates that the surface for- crystallization. Such a possibility can be found in the obser-
mation of the NiSi2 layer is followed by the crystallization of vation of Mohadjeri et al.,8 which shows that Ni diffuses
the a-Si below. through the a-Si layer toward a-Si/ c-Si interface and the

JVST B - Microelectronics and Nanometer Structures


1408 Lee et al.: Formation of nickel nanoparticles on amorphous silicon thin film 1408

presence of Ni enhances crystallization at the interface. Such thanks the Alexander von Humboldt Foundation for the fi-
a Ni solute effect also explains why crystallization is not nancial support for the visit.
observed around the Ni nanoparticles. Unlike the NiSi2, the
1
Ni diffusion into the a-Si is prevented around them, and the J. L. Batstone, Philos. Mag. A 67, 51 共1993兲.
2
a-Si matrix would not obtain enough Ni solutes to initiate L. Hultman, A. Robertsson, H. T. G. Hentzell, I. Engström, and P. A.
Psaras, J. Appl. Phys. 62, 3647 共1987兲.
crystallization, which leads to the inhibition of crystallization 3
G. Radnoczi, A. Robertsson, H. T. G. Hentzell, S. F. Gong, and M.-A.
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4
S. F. Gong, H. T. G. Hentzell, A. E. Robertsson, L. Hultman, S. E.
V. CONCLUDING REMARKS Hörnström, and G. Radnoczi, J. Appl. Phys. 62, 3726 共1987兲.
5
C. Hayzelden, J. L. Batstone, and R. C. Cammarata, Appl. Phys. Lett. 60,
We have shown through in situ HRTEM that the NiSi2 225 共1992兲.
6
and Ni particles form during annealing at 550 ° C in the C. Hayzelden and J. L. Batstone, J. Appl. Phys. 73, 8279 共1993兲.
7
TEM. The Ni particles are single crystalline or multiply Yu. N. Erokhin, R. Grötzschel, S. R. Oktyabrsky, S. Roorda, W. Sinke,
and A. F. Vyatkin, Mater. Sci. Eng., B 12, 103 共1992兲.
twinned. The formation of the Ni particles is due to beam 8
B. Mohadjeri, J. Linnros, B. G. Svensson, and M. Östling, Phys. Rev.
heating effect by the high-energy electron beam irradiation Lett. 68, 1872 共1992兲.
9
during the in situ observation by the HVTEM. Crystalliza- K. Schubert and H. Pfisterer, Z. Metallkd. 41, 433 共1950兲.
10
tion occurs with the formation of the NiSi2 precipitates but is K. C. R. Chiu, J. M. Poate, J. E. Rowe, T. T. Sheng, and A. G. Cullis,
Appl. Phys. Lett. 38, 988 共1981兲.
forbidden around the Ni particles. Around the NiSi2, Ni sol- 11
F. Föll, P. S. Ho, and K. N. Tu, J. Appl. Phys. 52, 250 共1981兲.
utes are expected to be dissolved in the amorphous silicon 12
R. T. Tung, J. M. Gibson, and J. M. Poate, Phys. Rev. Lett. 50, 429
共a-Si兲 matrix. However, the presence of the Ni nanoparticles 共1983兲.
13
suggests that Ni solutes cannot diffuse into the a-Si matrix. R. T. Tung, S. Nakahara, and T. Boone, Appl. Phys. Lett. 46, 895 共1985兲.
14
The formation of the Ni nanoparticles could not be observed J. L. Batstone, J. M. Gibson, R. T. Tung, and A. F. J. Levi, Appl. Phys.
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in the normal heat treatment without the electron beam irra- 15
J. M. Gibson and J. L. Batstone, Surf. Sci. 208, 317 共1989兲.
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W. Klement Jr., Can. J. Phys. 40, 1397 共1962兲.
17
particles suggests that Ni solutes enhance crystallization. S. Ino, J. Phys. Soc. Jpn. 27, 941 共1969兲.
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A. Howie and L. D. Marks, Philos. Mag. A 49, 81 共1984兲.
19
H. Hofmeister, in Encyclopedia of Nanoscience and Nanotechnology,
ACKNOWLEDGMENTS
edited by H. S. Nalwa 共American Scientific, Stevenson Ranch, CA,
This work was financially supported by Korea Research 2004兲, Vol. 3, pp. 431–452.
20
Foundation Grant 共KRF-2004-005-D00167兲. The in situ HR- Binary Alloy Phase Diagrams, 2nd ed., edited by T. B. Massalski 共ASM
International, Materials Park, OH, 1990兲, Vol. 3, p. 2859.
TEM observation was made during a research visit of one of 21
M. E. Schlesinger, Chem. Rev. 共Washington, D.C.兲 90, 607 共1990兲.
the authors 共S.B.L.兲 to Max-Planck-Institut für Metallfors- 22
F. d’Heurle, S. Petersson, L. Stolt, and B. Strizker, J. Appl. Phys. 53,
chung at Stuttgart, Germany. One of the authors 共S.B.L.兲 5678 共1982兲.

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