Materials Letters 174 (2016) 217–220

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Crystallized Si layer properties of novel aluminum-induced

crystallization
Doo Won Lee, Muhammad Fahad Bhopal, Soo Hong Lee n
Green Strategic Energy Research Institute, Department of Electronics Engineering, Sejong University, 98 Gunja-dong, Gwangjin-gu, Seoul, Korea

art ic l e i nf o a b s t r a c t

Article history: Aluminum-induced crystallization (AIC) is usually used for making silicon seed layer. In this paper, we
Received 4 January 2016 investigated the AIC process varied with different diffusion barrier materials. The barrier materials were
Received in revised form native Al oxide, directly deposited Al2O3, and SiO2 in AIC process. The effects of these diffusion barrier
17 March 2016
materials were analyzed by using electron backscatter diffraction (EBSD), Raman spectroscopy, field
Accepted 23 March 2016
Available online 24 March 2016
emission scanning electron microscope (FE-SEM). The results showed that the case of native Al oxide
showed diffusion-limited aggregation which usually resulted in polycrystalline structure. On the other
Keywords: hand, the case of SiO2 layer showed kinetic-limited aggregation, which generally resulted in the mono-
Aluminum-induced crystallization crystalline structure. Therefore, we introduced the novel AIC process with SiO2 layers.
Thin-film
& 2016 Elsevier B.V. All rights reserved.
Crystalline Si solar cell

1. Introduction enhanced chemical vapor deposition and flowable oxide methods

The aluminum-induced crystallization (AIC) process is one of the
methods for enlarging Si grain sizes of thin-film polycrystalline
(TFPC) Si solar cells. The conventional AIC process is as followed.
First, Al is deposited on foreign substrates such as graphite [1],
alumina [2], glass [3], etc. Then, native Al oxide layer is grown by
exposure to air. After that, the Si layer is deposited on native Al
oxide. Al/native Al oxide/Si structure is annealed below the eutectic
temperature (577 °C) of Al and Si for crystallization of Si. The Al and
Si layer is exchanged after the annealing process, which is called the
Al induced layer exchange (ALILE) process [3]. In the conventional
AIC process, the native Al oxide layer is important since the layer is
used as one of the Si diffusion paths. Therefore, research trends are
usually related with native Al oxide layer, such as increasing
thickness of native Al oxide for enlarging Si grain size [4, 5].
Especially, novel AIC using SiO2 layer instead of native Al oxide
layer was newly tried as a seed layer formation method in this
paper. Properties of crystallized Si were compared with the con-
ventional and novel AIC process. Moreover, 2 nm of Al2O3 was
deposited as a reference.
2. Experiment
Graphite substrate (Mersen, Korea) was used as a foreign sub-
strate. The SiOx/SiNx/SiOx layers were deposited using plasma
n
Corresponding author.
E-mail address: shl@sejong.ac.kr (S.H. Lee).
in order to prevent diffusion of impurities from graphite substrate
and planation. The Al and Si layer were deposited using a thermal
and electron-beam evaporator in 2.0 10 6 Torr, and the deposition
rate was controlled between 1.0 and 1.5 Å/s using thickness
monitor (STM-100/MF). Then each layer has 400 nm thickness.
Before Si deposition, the SiO2 was deposited without exposure to
air between Al and Si layers. The deposition rate was 0.1 Å/s. 2 nm
of Al2O3 was also separately deposited with the same deposition
rate as a reference. Moreover, another sample was exposed to air
for 24 h as another reference sample, referred to as conventional
AIC reference. After oxide layer and Si deposition, these samples
were annealed for 40 h to perfect Si crystallization.
3. Results and discussion
Firstly, Raman spectroscopy was used to analyze quality of crys-
tallized Si which was made by novel AIC, conventional AIC, and 2 nm
Al2O3 deposited AIC. The result of Raman spectroscopy showed the
intensity as a function of Raman shift (Fig. 1). Normally, the a-Si had
an intensity of 480 cm 1 Raman shift, and the c-Si had an intensity
of 520 cm 1 Raman shift. High crystallinity Si layer showed smaller
full width at height maximum (FWHM) of the Raman spectroscopy
at 520 cm 1 Raman shift [6]. As a result of Raman spectroscopy, the
conventional AIC and novel AIC had high quality crystalline Si
properties since both samples had a Raman shift peak at 520 cm 1.
On the other hand, the novel AIC had higher quality Si due to the
novel AIC had narrow the FWHM than the conventional AIC.
The surface morphology was analyzed by a field emission-
scanning electron microscope (FE-SEM) (Fig. 2). In the case of

http://dx.doi.org/10.1016/j.matlet.2016.03.126
0167-577X/& 2016 Elsevier B.V. All rights reserved.
218 D.W. Lee et al. / Materials Letters 174 (2016) 217–220
Fig. 1. Raman spectroscopy analysis results of the crystallized Si dependence on
the oxide materials.
conventional AIC, the surface morphology showed dendritic
structure known as the Brownian tree. The Brownian tree was
usually formed by the diffusion-limited aggregation model [7, 8].
The diffusion-limited aggregation model showed that diffusion
was a dominant factor for nucleation. Therefore, the diffusion-
limited aggregation system determined the surface morphology of
the crystalline structure by slow atomic diffusion. This diffusion-
limited aggregation was also shown in the Al2O3 deposited sam-
ples. The Brownian tree was evidently shown when diffusion-
limited aggregation phenomenon was strong, such as native Al
oxide. The Al2O3 samples, which were formed by exposure on air
and directly deposited Al2O3, thus had slow Si diffusion velocity.
On the other hand, in the case of SiO2 layer, the surface was almost
covered with crystallized Si. The reason for this difference be-
tween SiO2 and Al2O3 was that the Si nucleation with SiO2 layer
was shown in kinetic-limited aggregation. The kinetic-limited
aggregation phenomenon was shown in the system which had
Fig. 2. FE-SEM surface morphology images of crystallized Si which is made by AIC process with (a) SiO2
enough atom diffusion velocity. Hence, the SiO2 layer had faster Si
diffusion velocity than native Al oxide and 2 nm Al2O3 layer. In
theory, the crystallized Si layer with diffusion-limited aggregation
usually showed polycrystalline structure. However, the case of
kinetic-limited aggregation showed single crystalline structure [9].
Therefore, in this paper, the SiO2 layer was the recommended
method for enlarging Si grain size due to the kinetic-limited ag-
gregation had larger crystalline structure than diffusion-limited
aggregation in theory.
The crystallized Si was analyzed by electron backscatter dif-
fraction (EBSD) which was a useful technology for measuring Si
grain size and plain direction (Fig. 3.). While the novel AIC had
expected to enlarge grain size by kinetic-limited aggregation, a
trend of Si grain size differed from the results of surface mor-
phology. The average Si grain size of the conventional AIC was
larger than the novel AIC. These results were related with the Si
nucleation theory in the AIC process. First, the Si nucleation was
mainly started in the Al grain boundaries and the Al/a-Si interface
(oxide layer) when the Si concentration increased in saturation Si
concentration [10]. Second, the Al layer which was deposited by
the electron beam evaporator had naturally nano-crystalline
structure. The deposited Al grain size grew during the ALILE an-
nealing process. Once nucleated, Si grains in Al grain boundaries
had no influence each other [8]. Therefore, these mechanisms ef-
fected to the Si nucleation in the AIC process. The AIC processes
which used native Al oxide and deposited Al2O3 needed more time
to reach saturation Si concentration since the Al oxide layers had
slower Si diffusion velocity than the SiO2 layer. Moreover, the
deposited Al grain size also grew during the AIC annealing process.
In the case of the conventional AIC and 2 nm Al2O3 deposited AIC
processes, the primary Si nucleation sites in the Al grain bound-
aries had longer distance than the novel AIC since the Al grain
sizes increased during the annealing time to reaching saturation Si
concentration. Besides, in the case of the novel AIC, the primary Si
nucleation sites in the Al grain boundaries had shorter distance
than the conventional and Al2O3 deposited AIC. So as the time to
reach saturation Si concentration took less, the Al grain sizes had
smaller than the conventional and Al2O3 deposited AIC. The Al
2 nm, (b) Al2O3 2 nm, and (c) native Al oxide.
 D.W. Lee et al. / Materials Letters 174 (2016) 217–220 219

Fig. 3. EBSD images of the crystallized Si which is made by AIC process with (a) SiO2 2 nm, (b) Al2O3 2 nm, (c) native Al oxide.

grain boundaries which were used as the sites of primary Si nu-
cleation had a short distance. Therefore, the Si grain sizes of the
novel AIC showed smaller than the conventional AIC.
Consequently, the Si grain size which had SiO2 as an inter-
mediate layer was smaller when the Al/a-Si layer had fast Si
velocity. Therefore, in the AIC system, the final grain size was af-
fected by the Si diffusion velocity of Al/a-Si intermediate layer as
well as the Al grain size. For enlarging the grain size, these two
variations should be controlled.
The distribution of Si grain sizes was also analyzed by EBSD. As

Fig. 4. Si grain size area fraction as a function of Si grain size diameter; (a) SiO2 2 nm and (b) native Al oxide.
220 D.W. Lee et al. / Materials Letters 174 (2016) 217–220
Fig. 5. Inverted pole figure and pole figure of crystallized Si using (a) SiO2
a result of EBSD, the Si grain size area fraction was shown as a
function of the Si grain size diameter (Fig. 4.). The novel AIC had
narrow distribution of Si grain size area fraction at large grain
diameters than the conventional AIC (Fig. 4).
Moreover, this slow Si diffusion velocity also had an effect on
the Si plain direction as a result of the pole figure analysis of EBSD
(Fig. 5). The crystallized Si which was made by conventional AIC
showed the (111) Si phase which had been reported in the other
institutes as a defect site [11]. Therefore, a strong diffusion lim-
itation aggregation process was not recommended for high quality
crystalline Si due to possibility of a defect generation.
4. Summary
The maximum grain size of SiO2 had smaller grain than the
conventional AIC. In the case of SiO2, the average Si grain size was
17.56 mm. The average Si grain size which was made by conven-
tional AIC process was 20.59 mm. However, the SiO2 had still
possibilities for getting high quality and enlarging Si due to the
SiO2 showing kinetic-limited aggregation. Moreover, the novel AIC
showed narrow the Si grain size distribution than the conventional
AIC process at large Si grain diameter. In this paper, the reason of
Si grain size difference between SiO2 and Al2O3 was that the ef-
fectiveness factor for AIC was Si diffusion velocity as well as Al
grain size during AIC annealing process. Therefore, we would like
to attempt to increase the primary Al grain boundaries to enlarge
the distance of the primary Si nucleation site. Hence, we expect
that the crystallized layer will have narrow Si grain size distribu-
tion at large diameter. Moreover, the annealing time will be de-
creased due to fast Si diffusion velocity. The hillock formed on
crystallized Si layer will be decreased since fast Si diffusion velo-
city of SiO2.
2 nm, (b) Al2O3 2 nm, and (c) native Al oxide.
Acknowledgment
Thanks to almighty God for the completion of this paper. This
work was supported by the Korea Evaluation Institute of Industrial
Technology (KEIT) granted financial resource from the Ministry of
Trade, Industry & Energy, Republic of Korea (No. 10043793) and
thank all colleagues at the Green Strategic Energy Research In-
stitute, Department of Electronics Engineering, Sejong University.
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