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

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Journal of Non-Crystalline Solids


journal homepage: www.elsevier.com/ locate/ jnoncrysol

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,


there have been only a few reports on fabrication of one-step electro-
Thin film solar cells based on CuInS2 and that alloyed with gallium deposited CuInS2 films. For the electrodeposition of CuInS2, therefore,
(Cu(In,Ga)S2) have reached conversion efficiencies as high as 11.4% a sequential route consisting of electrodeposition of Cu and In staked
[1] and 13.0% [2], respectively. These CuInS2 and Cu(In,Ga)S2 thin layers followed by sulfurization under H2S gas or sulfur vapor has
films have been prepared by various methods, such as coevaporation been studied [8, 9]. In this route, physicochemical properties of both
of elements [3], sequential sputtering of thin layers of elements fol- Cu and In layers, e.g., compactness, thickness variations (uniformity),
lowed by sulfurization [4], electrodeposition [5] and spraying [6]. and surface roughness, have significant effects on the formation of a
Highest conversion efficiencies of CuInS2- and Cu(In,Ga)S2-based well-controlled absorber for an efficient solar cell. Although electro-
solar cells have been achieved by those prepared from sputter- deposition of Cu is a well-known reaction and has been studied in de-
deposited CuInS2 and Cu(In,Ga)S2 thin films [1, 2]. However, the use tail using several substrates [10, 11], there is no report on the effects
of such vacuum techniques has many disadvantages for a large-area of structural differences of electrodeposited Cu layers in Cu and In
application, such as high equipment costs and significant losses of staked layers on properties of CuInS2 films. Hence, we prepared two
raw materials. As an alternative non-vacuum approach to prepare types of Cu layers with different structures from acidic CuSO4 solu-
CuInS2 and Cu(In,Ga)S2 thin films, electrodeposition is an attractive tions containing organic additives as complexing agents, and exam-
method because of its cost effectiveness, scalability, and negligible ined structural aspects of CuInS2 films and solar cell properties of
waste of chemicals. In fact, the latest conversion efficiency of a solar cells with an Al:ZnO/CdS/CuInS2/Mo/glass structure prepared by
cell based on an electrochemically prepared CuInS2 film was 11.0% these Cu layers.
[5], which is close to the best efficiency of a CuInS2-based cell fabricat-
ed by vacuum processes [1]. 2. Experimental
There have been many reports on direct electrodeposition of a sel-
enide analogue (i.e., CuInSe2) [7]. However, due to the specific 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
⁎ 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:
a Hokuto Denko HSV-100 potentiostat-galvanostat. A molybdenum-
+ 81 6 6850 6699. coated soda-lime glass (Mo/glass, 20 Ω/sq) was used as a working
E-mail address: sikeda@chem.es.osaka-u.ac.jp (S. Ikeda). 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 2425

in acetone, followed by immersion in 25 vol.% ammonia solution for stable at potentials less than 0.03 V (vs. Ag/AgCl) in acidic regions
5 min to remove the molybdenum oxide layer on the surface [12]. with pH less than 4 [16]. Moreover, hydrogen evolution would
Cu deposition was performed at −0.4 V (vs. Ag/AgCl) in occur at −0.36 V and − 0.44 V (vs. Ag/AgCl) with pH 2.3 and 3.8, re-
10 mmol dm − 3 CuSO4 solutions containing 10 mmol dm − 3 citric spectively. Hence, cathodic current flow at relatively positive poten-
acid (pH 2.3) or 8 mmol dm − 3 sodium citrate (pH 3.8). As separate tials with peaks at ca. −0.25 V on all of the LSV curves is attributed
experiments, linear sweep voltammetry (LSV) curves in to reduction of Cu 2 + to form a metallic Cu deposit, i.e., efficient depo-
10 mmol dm − 3 CuSO4 solutions with and without these organic addi- sition of Cu without an appreciable current flow derived from hydro-
tives were also investigated at a sweep rate of 10 mV s − 1. After depo- gen evolution seems to occur at potentials ranging from − 0.25 V to
sition of Cu layers, an In layer was deposited on the Cu-covered Mo/ −0.4 V (vs. Ag/AgCl). In this study, therefore, we chose the potential
glass surfaces at −0.8 V (vs. Ag/AgCl) in 12 mol dm − 3 of aqueous of −0.4 V (vs. Ag/AgCl) for deposition of Cu layers using CuSO4 solu-
InCl3 solution with pH adjusted to pH 2.2 by adding HCl. All of the tions containing citric acid and sodium citrate.
electrochemical experiments were carried out at 24 ± 1 °C by using Fig. 2 shows top-view SEM images of the thus-obtained Cu layer
a thermostatted water bath. The amount of each metal layer was con- from the solution containing citric acid (Cu(A)) and that from the
trolled by maintaining electric charges using a Hokuto Denko solution containing sodium citrate (Cu(B)). The SEM image of Cu(A)
HF-201A coulomb/amperehour meter. In the present study, electric indicated that it consisted of less-compact roundish grains with a rug-
charges of Cu and In depositions were fixed at 0.83 C cm − 2 and ged surface morphology (Fig. 2a), whereas the SEM image of Cu(B)
0.95 C cm − 2, respectively, i.e., the composition ratio of Cu and In showed a compact morphology composed of large angular grains
(Cu/In) in Cu and In stacked layers was fixed at a Cu-rich composition (Fig. 2b). A difference is also apparent in their visual observations,
(Cu/In = ca. 1.3) compared to the stoichiometric ratio of the final i.e., Cu(A) exhibited a frosted surface, while the surface of Cu(B)
CuInS2 film. had a metallic luster.
Sulfurization of as-prepared Cu and In stacked layers was per- On both Cu(A) and Cu(B) layers, deposition of an In layer was per-
formed to form CuInS2 films by using a three-step temperature profile formed at − 0.8 V (vs. Ag/AgCl) using the same deposition solution.
as reported previously [13]. The CuInS2 films thus-formed were then Both In layers showed a similar island-shaped morphology (data
treated with a 10% KCN solution to remove a small amount of CuxS not shown). Island-shaped deposits of In were also observed previ-
impurity component [14]. ously on several Cu substrates such as a vacuum-deposited Cu layer
Morphologies of films were observed using a Hitachi S-5000 FEG on Mo/glass [17]. Thus, the growth pathway of the In layer might be
scanning electron microscope (SEM). The X-ray diffraction (XRD) insensitive to the kind of substrate used, as long as the same deposi-
patterns were measured using a Rigaku MiniFlex X-ray diffractometer tion condition is employed.
(Cu Kα, Ni filter). For evaluation of solar cell properties of CuInS2 Cu and In stacked layers were then sulfurized in 5% H2S in Ar at
films, they were processed to form an Al:ZnO/CdS/CuInS2/Mo/glass 520 °C. Fig. 3 shows XRD patterns of thus-obtained films derived
structure. On CuInS2 films after KCN etching, a CdS buffer layer was from the Cu(A) layer (labeled CIS(A)) and the Cu(B) layer (labeled
deposited successively by chemical bath deposition (CBD) [13]. An CIS(B)). Both of the films indicate typical diffraction peaks assignable
Al:ZnO window layer was then deposited on top of the CdS layer by to (112), (004)/(200), (204)/(220), and (116)/(312) reflections of the
radio frequency (RF) magnetron sputtering [13, 15]. Properties of CuInS2 chalcopyrite phase (JCPDS 27-0159) and no detection of any
completed solar cells were investigated by current density–voltage secondary phases except for the Mo substrate. The CIS(A) film exhib-
(J–V) characteristics under simulated AM1.5 irradiation ited relatively intense reflections with narrow widths in comparison
(100 mW cm − 2) by using a Bunkoh-Keiki CEP-015 photovoltaic mea- with those of the CIS(B) film, suggesting better growth of CuInS2
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. 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

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
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). 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
crystallites in the CIS(A) film than in the CIS(B) film. Another point (pKa2) and 5.69 (pKa3), respectively, one of the protons of citrate in
worth noting is that the CIS(A) film exhibited a salient (112) reflec- the sodium citrate solution (pH 3.8) should be dissociated, whereas
tion at 2θ = 27.8°, indicating significantly enhanced crystal growth none of the protons are fully dissociated in the citric acid solution
with preferable (112) directions. The (112) preferred orientation in (pH 2.3). Hence, the difference in proton dissociation is a probable ex-
the CuInS2 film is advantageous for fabrication of an efficient solar planation of the different abilities for complexation with Cu 2 + in
cell because it can minimize lattice mismatch with the CdS buffer these two solutions. It is also noted that the addition of Na2SO4 in a
layer to reduce interface recombination of photogenerated certain amount (4 mmol dm − 3) to the CuSO4 solution containing
carriers [18]. citric acid did not change the onset potential, indicating no effect of
Fig. 4 shows SEM images of CIS(A) and CIS(B) films. Top-view SEM the Na + ion in the solution on the Cu deposition behaviour in the
images of both films showed formation of large grains of more than citric acid solution.
1 μm in size. However, there is an appreciable difference in their The relatively positive onset potential of the CuSO4 solution for
roughness: CuInS2 grains were homogeneously distributed in the Cu(A) deposition in comparison with that for Cu(B) deposition indi-
CIS(A) film, whereas some large aggregated blisters were observed cates that a higher overpotential was applied for the Cu(A) deposition
on the CIS(B) film. In cross-sectional views, CIS(A) showed good ad- than that for the Cu(B) deposition when the deposition was per-
herence between the CIS(A) film and Mo/glass, whereas the CIS(B) formed at the fixed potential (i.e., −0.4 V (vs. Ag/AgCl)). Moreover,
film was partially exfoliated from Mo/glass, thus leading to inhomo- the rate of Cu(A) deposition was faster than that of Cu(B) deposition,
geneous and irregular surface morphologies. as was observed in the difference in current densities between the
Solar cells with a device structure of Al:ZnO/CdS/CuInS2/Mo/glass CuSO4 solutions used. Based on these facts, frequencies of nucleation
were prepared by depositing CdS and Al:ZnO layers on CIS(A) and of Cu crystallites during Cu(A) deposition are likely to be larger than

Fig. 4. Top-view (a, b) and cross-sectional (c, d) SEM images of (a, c) CIS(A) and (b, d) CIS(B).
S.M. Lee et al. / Journal of Non-Crystalline Solids 358 (2012) 2424–2427 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,
Fig. 5. J–V characteristics of Al:ZnO/CdS/CuInS2/Mo/glass cells made from (a) CIS(A) Ga)Se2 (CIGS) and Cu2ZnSnS4 (CZTS) absorbers using the electrode-
and (b) CIS(B). position technique.

those during Cu(B) deposition, leading to the decrease in compact-


Acknowledgments
ness of the resulting Cu layer (see Fig. 2).
Due to the incorporation of a sulfur component to transform Cu
This work was partially supported by The KAITEKI Institute, Inc.
and In stacked layers into a CuInS2 film, a significant volume expan-
The authors would also like to thank Dr. Ahmed Ennaoui (Helm-
sion should occur during sulfurization. Since the Cu(B) film formed
holtz-Zentrum-Berlin, Germany) for his stimulating suggestions and
a dense and compact structure (Fig. 2b), large volume expansion
discussion.
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) References
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