Journal of Non-Crystalline Solids 358 (2012) 2424–2427

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Journal of Non-Crystalline Solids

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Structural regulation of electrochemically deposited copper layers for fabrication of

thin film solar cells with a CuInS2 photoabsorber
Sun Min Lee, Shigeru Ikeda ⁎, Yasunari Otsuka,Takashi Harada, Michio Matsumura
Research Center for Solar Energy Chemistry, Osaka University, 1–3 Machikaneyama, Toyonaka 560-8531, Japan

a r t i c l e i n f o a b s t r a c t

Article history: Electrodeposition of Cu layers on a Mo-coated glass (Mo/glass) substrate from CuSO4 solutions containing
Received 29 July 2011 citric acid and sodium citrate was studied for fabrication of CuInS2-based solar cells. When the deposition
Received in revised form 8 December 2011 was performed using the CuSO4 solution containing citric acid, a Cu layer consisting of less-compact roundish
Available online 5 January 2012
grains with a rugged surface morphology was obtained. On the other hand, a compact Cu layer composed of
large angular grains was formed from the CuSO4 solution containing sodium citrate. Electrochemical studies
Keywords:
Electrochemical deposition;
revealed that both organic additives worked as complexing agents to reduce the concentration of free Cu 2 +
Organic additives; ions, but complexation abilities of these additives were different, leading to the structural difference in the
Copper indium sulfide; resulting Cu layers. The CuInS2 film derived from the former less-compact Cu layer had good adhesion be-
Solar cell properties tween the CuInS2 film and Mo/glass, whereas the CuInS2 film obtained from the latter compact Cu layer
was partially exfoliated because of large volume expansion stresses during the transformation of Cu and In
stacked layers into the CuInS2 film. As expected from these differences, the solar cell with an Al:ZnO/CdS/
CuInS2/Mo/glass structure derived from the former less-compact Cu layer showed better properties than
those of the solar cell derived from the latter compact Cu layer.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction electrochemical irreversibility of sulfur different from selenium,

Thin film solar cells based on CuInS2 and that alloyed with gallium
(Cu(In,Ga)S2) have reached conversion efficiencies as high as 11.4%
[1] and 13.0% [2], respectively. These CuInS2 and Cu(In,Ga)S2 thin
films have been prepared by various methods, such as coevaporation
of elements [3], sequential sputtering of thin layers of elements fol-
lowed by sulfurization [4], electrodeposition [5] and spraying [6].
Highest conversion efficiencies of CuInS2- and Cu(In,Ga)S2-based
solar cells have been achieved by those prepared from sputter-
deposited CuInS2 and Cu(In,Ga)S2 thin films [1, 2]. However, the use
of such vacuum techniques has many disadvantages for a large-area
application, such as high equipment costs and significant losses of
raw materials. As an alternative non-vacuum approach to prepare
CuInS2 and Cu(In,Ga)S2 thin films, electrodeposition is an attractive
method because of its cost effectiveness, scalability, and negligible
waste of chemicals. In fact, the latest conversion efficiency of a solar
cell based on an electrochemically prepared CuInS2 film was 11.0%
[5], which is close to the best efficiency of a CuInS2-based cell fabricat-
ed by vacuum processes [1].
There have been many reports on direct electrodeposition of a sel-
enide analogue (i.e., CuInSe2) [7]. However, due to the specific
⁎ Corresponding author at: Research Center for Solar Energy Chemistry, Osaka Uni-
versity, 1-3 Machikaneyama, Toyonaka 560-8531, Japan. Tel.: + 81 6 6850 6696; fax:
+ 81 6 6850 6699.
E-mail address: sikeda@chem.es.osaka-u.ac.jp (S. Ikeda).
there have been only a few reports on fabrication of one-step electro-
deposited CuInS2 films. For the electrodeposition of CuInS2, therefore,
a sequential route consisting of electrodeposition of Cu and In staked
layers followed by sulfurization under H2S gas or sulfur vapor has
been studied [8, 9]. In this route, physicochemical properties of both
Cu and In layers, e.g., compactness, thickness variations (uniformity),
and surface roughness, have significant effects on the formation of a
well-controlled absorber for an efficient solar cell. Although electro-
deposition of Cu is a well-known reaction and has been studied in de-
tail using several substrates [10, 11], there is no report on the effects
of structural differences of electrodeposited Cu layers in Cu and In
staked layers on properties of CuInS2 films. Hence, we prepared two
types of Cu layers with different structures from acidic CuSO4 solu-
tions containing organic additives as complexing agents, and exam-
ined structural aspects of CuInS2 films and solar cell properties of
cells with an Al:ZnO/CdS/CuInS2/Mo/glass structure prepared by
these Cu layers.
2. Experimental
Electrodeposition of Cu and In layers was performed using a con-
ventional three-electrode system with a Pt foil as a counter electrode
and an Ag/AgCl reference electrode under potentiostatic control using
a Hokuto Denko HSV-100 potentiostat-galvanostat. A molybdenum-
coated soda-lime glass (Mo/glass, 20 Ω/sq) was used as a working
electrode. Prior to deposition, Mo/glass was precleaned by sonication

0022-3093/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jnoncrysol.2011.12.043
 S.M. Lee et al. / Journal of Non-Crystalline Solids 358 (2012) 2424–2427
in acetone, followed by immersion in 25 vol.% ammonia solution for
5 min to remove the molybdenum oxide layer on the surface [12].
Cu deposition was performed at −0.4 V (vs. Ag/AgCl) in
10 mmol dm − 3 CuSO4 solutions containing 10 mmol dm − 3 citric
acid (pH 2.3) or 8 mmol dm − 3 sodium citrate (pH 3.8). As separate
experiments, linear sweep voltammetry (LSV) curves in
10 mmol dm − 3 CuSO4 solutions with and without these organic addi-
tives were also investigated at a sweep rate of 10 mV s − 1. After depo-
sition of Cu layers, an In layer was deposited on the Cu-covered Mo/
glass surfaces at −0.8 V (vs. Ag/AgCl) in 12 mol dm − 3 of aqueous
InCl3 solution with pH adjusted to pH 2.2 by adding HCl. All of the
electrochemical experiments were carried out at 24 ± 1 °C by using
a thermostatted water bath. The amount of each metal layer was con-
trolled by maintaining electric charges using a Hokuto Denko
HF-201A coulomb/amperehour meter. In the present study, electric
charges of Cu and In depositions were fixed at 0.83 C cm − 2 and
0.95 C cm − 2, respectively, i.e., the composition ratio of Cu and In
(Cu/In) in Cu and In stacked layers was fixed at a Cu-rich composition
(Cu/In = ca. 1.3) compared to the stoichiometric ratio of the final
CuInS2 film.
Sulfurization of as-prepared Cu and In stacked layers was per-
formed to form CuInS2 films by using a three-step temperature profile
as reported previously [13]. The CuInS2 films thus-formed were then
treated with a 10% KCN solution to remove a small amount of CuxS
impurity component [14].
Morphologies of films were observed using a Hitachi S-5000 FEG
scanning electron microscope (SEM). The X-ray diffraction (XRD)
patterns were measured using a Rigaku MiniFlex X-ray diffractometer
(Cu Kα, Ni filter). For evaluation of solar cell properties of CuInS2
films, they were processed to form an Al:ZnO/CdS/CuInS2/Mo/glass
structure. On CuInS2 films after KCN etching, a CdS buffer layer was
deposited successively by chemical bath deposition (CBD) [13]. An
Al:ZnO window layer was then deposited on top of the CdS layer by
radio frequency (RF) magnetron sputtering [13, 15]. Properties of
completed solar cells were investigated by current density–voltage
(J–V) characteristics under simulated AM1.5 irradiation
(100 mW cm − 2) by using a Bunkoh-Keiki CEP-015 photovoltaic mea-
surement system.
3. Results
Fig. 1 shows LSV curves of 10 mmol dm − 3 CuSO4 solutions with or
without addition of citric acid or sodium citrate at pH adjusted to 2.3
or 3.8 using a Mo/glass substrate. A Pourbaix diagram for the aqueous
copper system suggests that the metallic Cu is thermodynamically
Fig. 1. LSV curves of aqueous 10 mmol dm− 3 CuSO4 solutions (a, b) without an organic
additive and those containing (c) 10 mmol dm− 3 citric acid and (d) 8 mmol dm− 3
sodium citrate. pH of solutions were adjusted to (a, c) pH 2.3 and (b, d) pH 3.8.
2425
stable at potentials less than 0.03 V (vs. Ag/AgCl) in acidic regions
with pH less than 4 [16]. Moreover, hydrogen evolution would
occur at −0.36 V and − 0.44 V (vs. Ag/AgCl) with pH 2.3 and 3.8, re-
spectively. Hence, cathodic current flow at relatively positive poten-
tials with peaks at ca. −0.25 V on all of the LSV curves is attributed
to reduction of Cu 2 + to form a metallic Cu deposit, i.e., efficient depo-
sition of Cu without an appreciable current flow derived from hydro-
gen evolution seems to occur at potentials ranging from − 0.25 V to
−0.4 V (vs. Ag/AgCl). In this study, therefore, we chose the potential
of −0.4 V (vs. Ag/AgCl) for deposition of Cu layers using CuSO4 solu-
tions containing citric acid and sodium citrate.
Fig. 2 shows top-view SEM images of the thus-obtained Cu layer
from the solution containing citric acid (Cu(A)) and that from the
solution containing sodium citrate (Cu(B)). The SEM image of Cu(A)
indicated that it consisted of less-compact roundish grains with a rug-
ged surface morphology (Fig. 2a), whereas the SEM image of Cu(B)
showed a compact morphology composed of large angular grains
(Fig. 2b). A difference is also apparent in their visual observations,
i.e., Cu(A) exhibited a frosted surface, while the surface of Cu(B)
had a metallic luster.
On both Cu(A) and Cu(B) layers, deposition of an In layer was per-
formed at − 0.8 V (vs. Ag/AgCl) using the same deposition solution.
Both In layers showed a similar island-shaped morphology (data
not shown). Island-shaped deposits of In were also observed previ-
ously on several Cu substrates such as a vacuum-deposited Cu layer
on Mo/glass [17]. Thus, the growth pathway of the In layer might be
insensitive to the kind of substrate used, as long as the same deposi-
tion condition is employed.
Cu and In stacked layers were then sulfurized in 5% H2S in Ar at
520 °C. Fig. 3 shows XRD patterns of thus-obtained films derived
from the Cu(A) layer (labeled CIS(A)) and the Cu(B) layer (labeled
CIS(B)). Both of the films indicate typical diffraction peaks assignable
to (112), (004)/(200), (204)/(220), and (116)/(312) reflections of the
CuInS2 chalcopyrite phase (JCPDS 27-0159) and no detection of any
secondary phases except for the Mo substrate. The CIS(A) film exhib-
ited relatively intense reflections with narrow widths in comparison
with those of the CIS(B) film, suggesting better growth of CuInS2
Fig. 2. SEM images of (a) Cu(A) and (b) Cu(B) on Mo/glass.
2426 S.M. Lee et al. / Journal of Non-Crystalline Solids 358 (2012) 2424–2427
Fig. 3. XRD patterns of Cu and In stacked layers after sulfurization in 5% H2S in Ar at
520 °C. The Cu components of these layers were derived from (a) Cu(A) and (b) Cu(B).
crystallites in the CIS(A) film than in the CIS(B) film. Another point
worth noting is that the CIS(A) film exhibited a salient (112) reflec-
tion at 2θ = 27.8°, indicating significantly enhanced crystal growth
with preferable (112) directions. The (112) preferred orientation in
the CuInS2 film is advantageous for fabrication of an efficient solar
cell because it can minimize lattice mismatch with the CdS buffer
layer to reduce interface recombination of photogenerated
carriers [18].
Fig. 4 shows SEM images of CIS(A) and CIS(B) films. Top-view SEM
images of both films showed formation of large grains of more than
1 μm in size. However, there is an appreciable difference in their
roughness: CuInS2 grains were homogeneously distributed in the
CIS(A) film, whereas some large aggregated blisters were observed
on the CIS(B) film. In cross-sectional views, CIS(A) showed good ad-
herence between the CIS(A) film and Mo/glass, whereas the CIS(B)
film was partially exfoliated from Mo/glass, thus leading to inhomo-
geneous and irregular surface morphologies.
Solar cells with a device structure of Al:ZnO/CdS/CuInS2/Mo/glass
were prepared by depositing CdS and Al:ZnO layers on CIS(A) and
Fig. 4. Top-view (a, b) and cross-sectional (c, d) SEM images of (a, c) CIS(A) and (b, d) CIS(B).
CIS(B). Light J–V characteristics of these cells are shown in Fig. 5. It
is clear from the figure that both of the solar cells exhibited apprecia-
ble performance; the solar cell derived from CIS(A) exhibited better
performance, with conversion efficiency (η) of 6.3%, short circuit cur-
rent density (JSC) of 20.5 mA cm − 2, open circuit potential (VOC) of
0.64 V and fill factor (FF) of 0.48, than that of the solar cell based on
CIS(B) (η = 2.4%, JSC = 15.3 mA cm − 2, VOC = 0.51 V, and FF = 0.29).
4. Discussion
The LSV curves obtained in the solution without organic additives
showed onset potentials at 0.09 V, irrespective of pH of the solution,
as shown in Fig. 1a and b. The presences of organic additives induced
appreciable shifts of onset potentials in a more cathodic direction
(Figs. 1c and d), indicating that both organic addtives in the present
Cu 2 + solution worked as complexing agents to reduce concentrations
of free Cu 2 + ions. It should be noted that the onset potential of Cu de-
position in the solution containing sodium citrate showed a larger ca-
thodic shift than that in the solution containing citric acid. This
implies that the sodium citrate solution was more effective than the
citric acid solution for forming a Cu 2 + complex. Since dissociation
constants of carboxyl protons in citric acid are 2.90 (pKa1), 4.35
(pKa2) and 5.69 (pKa3), respectively, one of the protons of citrate in
the sodium citrate solution (pH 3.8) should be dissociated, whereas
none of the protons are fully dissociated in the citric acid solution
(pH 2.3). Hence, the difference in proton dissociation is a probable ex-
planation of the different abilities for complexation with Cu 2 + in
these two solutions. It is also noted that the addition of Na2SO4 in a
certain amount (4 mmol dm − 3) to the CuSO4 solution containing
citric acid did not change the onset potential, indicating no effect of
the Na + ion in the solution on the Cu deposition behaviour in the
citric acid solution.
The relatively positive onset potential of the CuSO4 solution for
Cu(A) deposition in comparison with that for Cu(B) deposition indi-
cates that a higher overpotential was applied for the Cu(A) deposition
than that for the Cu(B) deposition when the deposition was per-
formed at the fixed potential (i.e., −0.4 V (vs. Ag/AgCl)). Moreover,
the rate of Cu(A) deposition was faster than that of Cu(B) deposition,
as was observed in the difference in current densities between the
CuSO4 solutions used. Based on these facts, frequencies of nucleation
of Cu crystallites during Cu(A) deposition are likely to be larger than
 S.M. Lee et al. / Journal of Non-Crystalline Solids 358 (2012) 2424–2427
Fig. 5. J–V characteristics of Al:ZnO/CdS/CuInS2/Mo/glass cells made from (a) CIS(A)
and (b) CIS(B).
those during Cu(B) deposition, leading to the decrease in compact-
ness of the resulting Cu layer (see Fig. 2).
Due to the incorporation of a sulfur component to transform Cu
and In stacked layers into a CuInS2 film, a significant volume expan-
sion should occur during sulfurization. Since the Cu(B) film formed
a dense and compact structure (Fig. 2b), large volume expansion
stresses occurred at the interface between the Cu(B) film and Mo/
glass. On the other hand, use of the Cu(A) film could decrease in
such stresses because of the less-compact structure of the Cu(A)
layer (Fig. 2a), resulting in preventions of exfoliation and void forma-
tion of the CuInS2 film [19].
As can be seen in Fig. 5b, the J–V curve of the solar cell based on
CIS(B) shows poor electrical rectification: it had a low shunt
resistance (Rsh = 0.04 kΩ cm 2) and a high series resistance
(Rs = 13 Ω cm 2). The presence of appreciable amounts of voids at
the interface of CIS(B) and Mo/glass (see Fig. 4d) is likely to have
caused such inferior qualities of (photo)diode properties: the low
Rsh significantly reduced VOC, whereas the high Rs not only resulted
in a drop in the FF value but also induced a decrease in short-circuit
current density (JSC). On the other hand, the solar cell based on the
CIS(A) film shows good rectification (Fig. 5a). Significant improve-
ments in all of the parameters compared to those of the solar cell
based on the CIS(B) film are due to the good adherence between
the CIS film and the Mo substrate, leading to relatively low Rs (6.4 Ω
cm 2) and large Rsh (0.2 kΩ cm 2). In addition to these favorable prop-
erties of the interface between CIS(A) and Mo/glass, the CIS(A) film
formed a good heterojunction with the upper CdS layer, owing to
the relatively high crystalline nature of CuInS2 crystallites with pref-
erable (112) orientations in the CIS(A) film (see above). This is anoth-
er probable factor for achieving good cell properties.
5. Conclusions
In this study, the effects of additions of citric acid and sodium cit-
rate to an acidic CuSO4 solution on morphologies, grain sizes, and
2427
compactness of Cu layers formed by potentiostatic electrodeposition
were examined. We found that the citric acid solution used enhanced
frequencies of nucleation of Cu crystallites, leading to the formation
of a Cu layer consisting of less-compact roundish grains with a rugged
surface morphology; the sodium citrate solution provided a dense
and compact Cu layer with large grains due to less frequent nucle-
ation of Cu crystallites. Structural properties of CuInS2 films and prop-
erties of solar cells with a structure of Al:ZnO/CdS/CuInS2/Mo/glass
derived from these two types of Cu layers revealed that the former
less-compact Cu layer was a much more preferable structure than
the latter compact Cu layer. Hence, we have proved that dense and
compact morphologies are not necessary for the precursor metallic
layers for fabrication of solar cells. This idea would be applicable for
preparation of other thin-film compound solar cells based on Cu(In,
Ga)Se2 (CIGS) and Cu2ZnSnS4 (CZTS) absorbers using the electrode-
position technique.
Acknowledgments
This work was partially supported by The KAITEKI Institute, Inc.
The authors would also like to thank Dr. Ahmed Ennaoui (Helm-
holtz-Zentrum-Berlin, Germany) for his stimulating suggestions and
discussion.
References
[1] K. Siemer, J. Klaer, I. Luck, J. Bruns, R. Klenk, D. Bräunig, Sol. Energy Mater. Sol.
Cell. 67 (2001) 159–166.
[2] S. Merdes, R. Sáez-Araoz, A. Ennaoui, J. Klaer, M.Ch. Lux-Steiner, R. Klenk, Appl.
Phys. Lett. 95 (2009) 213–502.
[3] R. Kaigawa, T. Wada, S. Bakehe, R. Klenk, Thin Solid Films 511–512 (2006)
430–433.
[4] C. Von Klopmann, J. Djordjevic, E. Rudigier, R. Scheer, J. Cryst, Growth 289 (2006)
121–133.
[5] R. Friedfeld, R.P. Raffaelle, J.G. Mantovani, Sol. Energy Mater. Sol. Cell. 58 (1999)
375–385.
[6] I. Oja, M. Nanu, A. Katerski, M. Krunks, A. Mere, J. Raudoja, A. Goossens, Thin Solid
Films 480–481 (2005) 82–86.
[7] J.F. Guillemoles, P. Cowache, A. Lusson, K. Fezzaa, F. Boisivion, J. Vedel, D. Lincot, J.
Appl. Phys. 79 (1996) 7293.
[8] C.D. Lokhande, G. Hodes, Sol. Cell. 21 (1987) 215–224.
[9] R.P. Wijesundera, W. Siripala, Sol. Energy Mater. Sol. Cell. 81 (2004) 147–154.
[10] J. Vazquez-Arenas, G. Vázquez, A.M. Meléndez, I. González, J. Electrochem. Soc.
154 (2007) D473–D481.
[11] R.N. Bhattacharya, K. Rajeshwar, Sol. Cell. 16 (1986) 237–243.
[12] P.P. Prosoni, M.L. Addonizio, A. Antonaia, Thin Solid films 298 (1997) 191–196.
[13] S.M. Lee, S. Ikeda, T. Yagi, T. Harada, A. Ennaoui, M. Matsumura, Phys. Chem.
Chem. Phys. 13 (2011) 6662–6669.
[14] J. Klaer, J. Bruns, R. Henninger, K. Siemer, R. Klenk, K. Ellmer, D Bräunig, Semicond.
Sci. Technol. 13 (1998) 1456–1458.
[15] S. Canegallo, V. Demeneopoulos, L. Peraldo Bicelli, G. Serravalle, J. Alloy. Comp.
228 (1995) 23–30.
[16] S. Tamilmani, W. Huang, S. Raghavan, R. Small, J. Electrochem. Soc. 149 (2002)
G638–G642.
[17] Q. Huang, K. Reuter, S. Amhed, L. Deligianni, L.T. Romankiw, S. Jaime, P.-P. Grand,
V. Charrierb, J. Electrochem. Soc. 158 (2011) D57–D61.
[18] L.-X. Shao, K.-H. Changa, H.-L. Hwang, App. Suf. Sci. 212–213 (2003) 305–310.
[19] A. Gupta, S. Isomura, Sol. Energy Mater. Sol. Cell. 53 (1998) 385–401.