Original

Paper

phys. stat. sol. (a) 203, No. 11, 2593– 2597 (2006) / DOI 10.1002/pssa.200669652

Fabrication of Cu(In,Ga)Se2 thin films by a combination

of mechanochemical and screen-printing/sintering processes
T. Wada*, 1, Y. Matsuo1, S. Nomura1, Y. Nakamura2, A. Miyamura2, Y. Chiba3,
A. Yamada4, and M. Konagai3
1
Department of Materials Chemistry, Ryukoku University, Seta, Otsu 520-2194, Japan
2
Department of Metallurgy and Ceramics Science, Tokyo Institute of Technology, Japan
3
Department of Physical Electronics, Tokyo Institute of Technology, Japan
4
Quantum Nanoelectronics Research Center, Tokyo Institute of Technology, Japan

Received 6 March 2006, revised 16 June 2006, accepted 26 June 2006

Published online 31 August 2006

PACS 68.37.Hk, 68.37.Lp, 81.15.– z, 84.60.Jt

We prepared fine Cu(In,Ga)Se2 (CIGS) powder suitable for screen printing using a mechanochemical
process. Particulate precursors were deposited in a thin layer by a screen-printing technique, the remain-
ing organic solvent was removed from the screen-printed CIGS film and finally the porous precursor layer
was sintered into a dense polycrystalline film by atmospheric-pressure firing. The crystal structure of the
film was analyzed by X-ray diffraction and the microstructure was observed in a SEM. The thickness of
the film was 5 – 10 µm with a grain size of about 2 µm. The films were also observed in a TEM. The grain
size of the as-prepared powder was less than 1 µm; however, it enlarged to 2 – 3 µm after firing at 575 °C
under a Se ambient. Preliminary CIGS solar cells with our standard Al grid/B-doped ZnO/i-ZnO/
CdS/CIGS/Mo/soda-lime glass structure were fabricated. An efficiency of 2.7%, a Voc of 0.325 V, a Jsc of
28.3 mA/cm2 and a FF of 0.295 was obtained.

© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1 Introduction
CuInSe2 (CIS) and its solid solutions with CuGaSe2 and CuInS2 are excellent thin-film photovoltaic (PV)
materials. However, vacuum-based deposition processes, such as physical vapour deposition and sputter-
ing, that are typically used to fabricate CIS thin-film photovoltaic devices are complex and expensive.
Recently, some research groups have proposed different non-vacuum deposition techniques for CIS solar
cell fabrication [1–4].
One class of non-vacuum deposition techniques is non-vacuum processing of particulate materials.
This form of deposition offers a simple, inexpensive alternative for fabrication of high-efficiency CIS
solar cells. Suitable particulate materials can be prepared by a variety of techniques, including precipita-
tion, pulverization, aerosol pyrolysis, vapour condensation, etc. Particulate precursors can be deposited
in thin layers using simple atmospheric-pressure techniques such as screen printing, spraying or dip coat-
ing. Porous precursor layers can then be sintered into dense polycrystalline films by atmospheric-
pressure heat treatments [2].
Recently, we successfully synthesized CIS and its solid solutions, Cu(In,Ga)Se2 (CIGS) and
CuIn(S,Se)2, from elemental powders by means of a mechanochemical process (MCP) without any addi-
tional heating [5, 6]. MCP is a process that induces physical and/or chemical changes by mechanical
energy, such as pulverization, friction or compression. This method has some advantages for mass pro-
*
Corresponding author: e-mail: [email protected]

© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

2594 T. Wada et al.: Fabrication of Cu(In,Ga)Se2 thin films

(1) Elemental Cu (3N), In (4N), Ga (3N) and Se (3N) powders are weighed with a fixed Cu:In:Ga:Se
ratio.
(2) Cu(In,Ga)Se2 fine powder is synthesized from the elemental powders by planetary ball milling.
(3) Particulate precursor ink is prepared by mixing the obtained CIGS powder with an organic solvent.
(4) A precursor layer is deposited onto a Mo-coated soda-lime glass substrate by a screen-printing tech-
nique.
(5) The organic solvent is removed from the screen-printed CIGS film by heating.
(6) The porous precursor layer is sintered into a dense polycrystalline film by heat treatment under an
atmospheric-pressure inert-gas ambient.

Fig. 1 Flow diagram for fabrication of Cu(In,Ga)Se2 films by combination of mechanochemical and screen-
printing/sintering processes.

duction of CIS solar cells, such as high energy efficiency, high productivity and short processing cycle
times.
For this study, we prepared CIGS powders suitable for screen printing by a MCP. The ink for screen
printing was prepared by mixing CIGS powder prepared by the MCP with an organic solvent. The ink
was deposited onto a Mo-coated soda-lime glass substrate by a screen-printing technique. Then, the
organic solvent was removed by heating from the screen-printed film. Finally, the porous precursor layer
was sintered into a dense polycrystalline film by atmospheric-pressure heat treatment. The microstruc-
tures of the obtained CIGS films were observed in scanning electron microscope (SEM) and transmis-
sion electron microscope (TEM). Preliminary CIGS solar cells were fabricated and the photovoltaic
performance was characterized.

2 Deposition of CIGS films

The optimal MCP preparation conditions for preparation of CIGS powder suitable for the screen-printing
process were explored. CIGS powder with an average diameter of less than 1 µm was prepared by opti-
mizing the size of the media (zirconia balls) and rotational conditions of the planetary ball milling
process. CIGS films were then fabricated by a screen-printing and sintering technique. The flow diagram
of the fabrication process of a Cu(In,Ga)Se2 thin film by this mechanochemical and screenprint-
ing/sintering technique is outlined in Fig. 1. The porous precursor layer was fired at a temperature of
550–575 °C under an N2 gas ambient.
In order to obtain high-quality CIGS films by the above screen-printing/sintering technique, a sinter-
ing additive such as CuSe should be added. Fig. 2 shows the surface microstructure of CIS films
observed by SEM with Cu-poor (a), stoichiometric (b) and Cu-rich (c) compositions. For CIS films with
Cu-poor and stoichiometric compositions, the CIS grains are very small and show little change upon
sintering. On the other hand, for Cu-rich CIS composition, the observed CIS grains are as large as 3 µm

a) b) c)

Fig. 2 SEM surface microstructure of CIS films with Cu-poor (a), stoichiometric (b) and Cu-rich (c) compositions.

© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.pss-a.com

 Original
Paper

phys. stat. sol. (a) 203, No. 11 (2006) 2595

b)
a)

Fig. 3 Surface (a) and cross-sectional (b) SEM micrographs of CIS films fabricated by a combination of mechano-
chemical and screen-printing/sintering processes.

and these grains are well sintered. The addition of CuSe is effective for the promotion of grain growth
and sintering of CIS particles. The atmosphere present during the sintering process is also important.
When the CIGS films were heat treated under a low Se partial pressure atmosphere, the CIGS crystals
tended to decompose and the grains in the obtained films were very small. Therefore, the atmosphere
present during the sintering process should be carefully controlled.

3 Characterization of CIS films

The surface and cross-sectional microstructures of the CIS film were observed in a scanning electron
microscope (SEM). SEM micrographs of a typical CIS film fabricated on a Mo-coated soda-lime glass
substrate are shown in Fig. 3(a) and (b). The film thickness was about 7 µm and the grain size about
2 µm.
The crystal structure and microstructure of the CIS film were investigated by transmission electron
microscopy (TEM). A TEM image and transmission electron diffraction (TED) patterns are shown in
Fig. 4(a), (b-1) and (b-2). Strong diffraction spots that originate from the sphalerite-type structure were
observed, as can be seen in Fig. 4 (b-1) and (b-2), and weak diffraction spots that originate from the
chalcopyrite-type structure were observed, as can be seen in Fig. 4 (b-2). It is understood from the uni-
form contrast in the TEM image and the sharp and clear electron-diffraction patterns that the CIS grains
in the CIS film prepared by the screen-printing/sintering technique assume a chalcopyrite-type structure
with good crystallinity.

(a) (b-1)

(b-2)

500 nm

Fig. 4 (online colour at: www.pss-a.com) TEM image (a) and TED patterns (b-1 and b-2) of CIS films
fabricated by a combination of mechanochemical and screen-printing/sintering processes.

www.pss-a.com © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

2596 T. Wada et al.: Fabrication of Cu(In,Ga)Se2 thin films

In the TEM image shown in Fig. 4(a), two triple junctions are observed in the region shown in the
circle. The grain boundary is very sharp and no secondary impurity phase can be observed between the
grains. The grain size of the as-prepared powder was less than 1 µm; however, the grain size enlarged to
2–3 µm after firing at 575 °C under a controlled Se atmosphere. These results showed that the screen-
printing/sintering technique was quite effective in the fabrication of a high-quality CIGS film.

4 Device fabrication
Preliminary CIGS solar cells were fabricated using the CIGS thin films deposited by the combined
mechanochemical and screen-printing/sintering technique. Cu(In0.95Ga0.05)Se2 fine powder was prepared
from elemental powders by a MCP. The precursor ink was prepared by the mixing of the obtained
Cu(In0.95Ga0.05)Se2 powder with a sintering additive such as CuSe and an organic solvent. The precursor
layer was then deposited onto a Mo-coated soda-lime glass substrate by a screen-printing technique. The
porous precursor layer was sintered at about 575 °C under a N2 gas atmosphere. The secondary Cu–Se
phase was subsequently removed by etching in a 10 wt% KCN aqueous solution.
Solar cells with our standard Al grid/B-doped ZnO/i-ZnO/CdS/CIGS/Mo/soda-lime glass structure
were fabricated [7]. A CdS buffer layer was deposited by chemical-bath deposition (CBD). Intrinsic ZnO
and B-doped ZnO layers were deposited by metal-organic chemical vapour deposition (MOCVD). The
Al electrodes were deposited by vacuum evaporation. The solar cells did not have an anti-reflection
coating layer. The performance of the solar cells was evaluated under standard AM1.5 illumination.
Figure 5 shows the I–V characteristics of some preliminary CIGS solar cells with an area of about
0.2 cm2. These solar cells had an equivalent open circuit voltage (Voc) of about 0.3 V and differing short
circuit current densities (Jsc). The best solar cell had an efficiency (Eff) of 2.7% with a Voc of 0.325 V, a
Jsc of 28.3 mA/cm2 and a fill factor (FF) of 0.295.
The quantum efficiency of the solar cell with an efficiency of 2.7% is shown in Fig. 6. The quantum
efficiency at about 540 nm was as large as 0.6 but decreased with increasing wavelength.
Furthermore, TEM observations revealed that the films developed in the early stages of the MCP
contained many voids and the sintering of the CIS grains preferentially occurred in the surface region of
the film. A cross-sectional TEM image of a CIGS solar cell fabricated in the early stages of the MCP is
shown in Fig. 7(a). These problems were overcome by modifying the screen-printing/sintering process.
Thus, the efficiencies of the CIGS thin-film solar cells were improved by controlling the mechanochemi-
cal and screen-printing/sintering processes, such as the quantity of CuSe additive, firing temperature,

0.6
30 2
Jsc :24.9 mA/cm
Quantum Efficiency

V oc :301 mV
F.F.: 0.311
eff. :2.33% 0.4
20
J(mA/cm )
2

2
Jsc :28.3 mA/cm
V oc :325 mV
F.F.: 0.295
eff. :2.71%
10 0.2
Jsc :16.6 mA/cm2
V oc :327 mV
F.F.: 0.26
eff. :1.42%
0 0
0 0.1 0.2 0.3 0.4 400 600 800 1000 1200
V(V) Wavelength [nm]

Fig. 5 (online colour at: www.pss-a.com) I –V Fig. 6 Quantum efficiency of a solar cell with an
characteristics of some preliminary CIGS solar efficiency of 2.7% shown in Fig. 5.
cells fabricated by a combination of mechano-
chemical and screen-printing/sintering techni-
ques.

© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.pss-a.com

 Original
Paper

phys. stat. sol. (a) 203, No. 11 (2006) 2597

(a) (b)

5µm 5µm

Fig. 7 Cross-sectional TEM images of CIGS solar cells with efficiencies of about 1% (a) and 2.7% (b).

firing atmosphere, etc. A cross-sectional TEM image of a CIGS solar cell with an efficiency of 2.7% is
shown in Fig. 7(b). It can be clearly seen that the high-efficiency CIGS solar cell has a denser micro-
structure than the lower-efficiency solar cell. We have already clarified the main issues, such as
thickness, uniformity and adhesion of the absorber layer and the substrate, to enhance solar-cell perform-
ance. Therefore, we believe that the efficiency of the solar cells can be further improved by optimizing
the process parameters in the fabrication of the CIGS absorber layer.

5 Summary
We successfully prepared CIGS powder suitable for use as screen-printing ink by a mechanochemical
process without any additional heating in a very short time. CIGS thin films were fabricated by a screen-
printing/sintering method. It was clarified that the addition of CuSe was very effective for grain growth
and sintering of CIGS grains in the film as well as for the case of preparation of CIGS films by physical
vapour deposition. Preliminary CIGS solar cells showed an efficiency of 2.7%, a Voc of 0.325 V, a Jsc of
28.3 mA/cm2 and a FF of 0.295. TEM observations revealed that high-efficiency CIGS solar cells had a
denser microstructure than the low-efficiency solar cells.

Acknowledgements This work was supported by the Incorporated Administrative Agency New Energy and Indus-
trial Technology Development Organization (NEDO) under the Ministry of Economy, Trade and Industry (METI).
This work was partially supported by a grant based on the Ryukoku University High-Tech Research Centre Program
for private universities from the Japan Ministry of Education, Culture, Sports, Science and Technology. The authors
would also like to thank Dr. P. Fons of the National Institute of Advanced Industrial Science and Technology (AIST)
for his critical reading of the manuscript.

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