222 Electrochemical and Solid-State Letters, 2 (5) 222-223 (1999)

S1099-0062(98)12-082-5 CCC: $7.00 © The Electrochemical Society, Inc.

Electroless Deposition of Cu-In-Ga-Se Thin Films

R. N. Bhattacharya,*, z W. Batchelor, and R. N. Noufi*
National Renewable Energy Laboratory, Golden, Colorado 80401, USA

Copper-indium-gallium-selenium thin films have been prepared by electroless deposition technique on an Mo/glass substrate.
Electroless precursors are prepared by short-circuiting the Mo substrate to the Fe counter electrode. The films are characterized by
inductively coupled plasma and X-ray analysis. The device fabricated using electroless precursor films resulted in a solar cell effi-
ciency of 12.4%.
© 1999 The Electrochemical Society. S1099-0062(98)12-082-5. All rights reserved.

Manuscript submitted December 23, 1998; revised manuscript received January 27, 1999. Available electronically February 12, 1999.

Of the emerging materials for solar cell applications, CuInSe2

(CIS) and Cu(In, Ga)Se2 (CIGS) have received considerable atten- Table I. The electroless deposition of CIGS.
tion in recent years.1-8 Thin-film solar cell devices based on CIGS
E0 vs. SHEa Eq. no.
have already demonstrated a performance efficiency of 17.7%.1 The
direct energy gap of CIS and CIGS results in a large optical absorp-
tion coefficent, which in turn permits the use of thin layers (1-2 µm) Fe j Fe2+ + 2e -0.447 [1]
of active material. CIGS solar cells are also known for their long- Zn j Zn2+ + 2e -0.763 [2]
term stability. Al j Al3+ + 3e -1.662 [3]
In this paper, we describe a new electroless method for the fabri-
Cu+ + e j Cu 0.521 [4]
cation of CIGS films for photovoltaic applications. The device fab-
ricated using electroless precursor films has already resulted in a Cu2+ + 2e j Cu 0.342 [5]
solar cell efficiency of 12.4%. The electroless method is based on In3+ + 3e j In -0.338 [6]
short-circuiting the conducting substrate to an easily oxidizable Ga3+ + 3e j Ga -0.549 [7]
redox component in the electrolyte bath. This method, unlike its SeO32- + 3H2O + 4e j Se + 6 OH- -0.366 [8]
closely related electrochemical counterpart, has the advantage of
Cu, In, Ga, Se j CuxInyGazSen Chemical reaction [9]
simplicity in that it does not require instrumentation for potentiosta-
tic or galvanostatic control, and therefore is particularly promising a Standard hydrogen electrode.
for routine and large-scale fabrication of large-area thin films. The
electroless deposition process could provide (i) a low-cost, high-rate
process, (ii) a large-area, continuous, multicomponent, low-temper- about 500 Å CdS, followed by radio-frequency sputtering of 500 Å
ature deposition method, (iii) deposition of films on a variety of of intrinsic ZnO, and 3500 Å of Al2O3-doped conducting ZnO.
shapes and forms (wires, tapes, coils, and cylinders), (iv) freedom Bilayer Ni-Al top contacts were deposited in an electron-beam sys-
from the requirement or need to use expensive equipment, (v) con- tem. The final step in the fabrication sequence is the deposition of
trolled deposition rates and effective material use, and (vi) minimum an antireflection coating (100 nm MgF2).
waste generation (solution can be recycled). The films and devices were characterized by inductively coupled
Experimental plasma (ICP), X-ray diffraction (XRD), current-voltage (I-V), and
quantum efficiency (QE) characteristics.
Codeposition of Cu-In-Ga-Se by the electroless process was per-
formed from a bath containing CuCl2, InCl3, GaCl3, H2SeO3-, and Results and Discussion
LiCl dissolved in deionized water. The pH of the bath was adjusted The electroless process for preparing CIGS precursor films is
to 2.4 by adding incremental amounts of dilute HCl. The substrate accomplished by the combination of electrochemical and chemical
was Mo/glass. Iron foil was used as a counterelectrode to carry out reactions. The counter electrode (Fe) initiates and carries out the
electroless deposition. Electroless precursors are prepared by short- electrochemical reaction. The electroless deposition of CIGS is most
circuiting the Mo substrate to the Fe counter electrode. The films likely caused as shown in Table I. Zn and Al are also suitable counter
were deposited in a vertical cell in which the electrodes (both Mo- electrodes to carry out electroless deposition.
glass and Fe) were suspended vertically from the top of the cell. The The composition of the as-deposited CIGS precursor as analyzed
Mo film on glass was about 1 µm thick and was deposited by dc by ICP was CuIn0.35Ga0.02Se2.3. The thickness of the precursor film
sputtering. All chemicals were of Analar- or Puratronic-grade puri- was about 1.5 µm. The compositon of the precursor film was adjust-
ty and were used as received. The electroless deposition was per- ed by adding about 2500 Å Ga and 5800 Å In by PVD.
formed at room temperature (24°C) and without stirring. The Figure 1 shows XRD of an as-deposited precursor film, selenized
deposited films were rinsed with deionized water and dried in flow- film (annealed under vacuum conditions in the presence of Se at
ing N2. about 500°C), and of the absorber layer prepared after composition-
Additional In, Ga, and Se were added to electroless precursor al adjustment. The as-deposited film is amorphous or polycrytalline
film by physical vapor deposition (PVD) to adjust the final compo- in nature. The selenized film indicates the formation of the CIGS
sition to CuIn1-xGaxSe2. The substrate (precursor film) temperature phase. The absorber film after final film composition adjustment
during the PVD step was 550 ± 10°C. The films were also selenized shows only the CIGS phase. The International Center for
by exposure to selenium vapor during the cool-down time Diffraction Data card number used for the identification of CIGS X-
(~40°C/min). Addition of In and Ga and selenization at high tem- ray peaks is 40-1487.9
perature was crucial in obtaining a 12.4% device. Photovoltaic Figure 2 shows the I-V curve of the device prepared from an elec-
device fabrication was completed by chemical bath deposition of troless precursor film. The I-V characterization was carried out for
AM 1.5 spectrum (ASTM E 892-87 Global) in which the intensity
of illumination was 1000 W/m2. The solar cell made from the elec-
* Electrochemical Society Active Member. troless precursor material has a device efficiency of 12.4%. The
z E-mail: raghu_bhattacharya@nrel.gov
quantum efficiency of the cell under illumination (1000 W/cm2) is

Downloaded on 2016-04-25 to IP 144.122.201.150 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 Electrochemical and Solid-State Letters, 2 (5) 222-223 (1999) 223
S1099-0062(98)12-082-5 CCC: $7.00 © The Electrochemical Society, Inc.

Figure 1. X-ray difraction data of (a) electroless precursor film; (b) selenized
precursor film; and (c) absorber layer. Figure 3. Quantum efficiency of the 12.4%-efficient device prepared from
electroless precursor film (ASTM E 892 Global [1000 W/m2] Spectrum).

shown in Fig. 3. This figure indicates the bandgap of the absorber

layer is about 1.03 eV.
Conclusion
A simple electroless method has proved useful for the prepara-
tion of CIGS precursor films. The device fabricated using an elec-
troless CIGS precursor layer has already resulted in a solar cell effi-
ciency of 12.4%. Further optimization of the electroless method to
obtain stoichiometric CuIn1-xGaxSe2 is in progress.
The National Renewable Energy Laboratory assisted in meeting the publica-
tion costs of this article.
References
1. J. R. Tuttle, M. A. Contreras, K. R. Ramanathan, S. E. Asher, R. N. Bhattacharya,
T. A. Berens, J. Keane, and R. Noufi, AIP Conf. Proc., 394, 83 (1996).
2. R. N. Bhattacharya, W. Batchelor, H. Wiesner, F. Hasoon, J. E. Granata,
K. Ramanathan, J. Alleman, J. Keane, A. Mason, R. J. Matson, and R. N. Noufi,
J. Electrochem. Soc., 145, 3435 (1998).
3. K. Ramanathan, H. Wiesner, S. Asher, D. Niles, R. N. Bhattacharya, J. Keane,
M. A. Contreras, and R. Noufi, Paper presented at Photovoltaic Solar Energy
Conversion II, Wien, Austria, July 6-10, 1998.
4. K. Kushiya, M. Tachiyuki, T. Kase, Y. Nagoya, I. Sugiyama, O. Yamase, and
H. Takeshita, Paper presented at Photovoltaic Solar Energy Conversion II, Wien,
Austria, July 6-10, 1998.
5. B. Dimmler, E. Gross, D. Hariskos, F. Kessler, E. Lotter, M. Powalla, J. Springer,
U. Stein, G. Voorwinden, M. Gaeng, S. Schleicher, Paper presented at
Photovoltaic Solar Energy Conversion II, Wien, Austria, July 6-10, 1998.
6. T. Wada, S. Hayashi, Y. Hashimoto, S. Nishiwaki, T. Sato, T. Negami, and
Figure 2. Current-voltage characteristic of a device prepared from electroless M. Nishitani, Paper presented at Photovoltaic Solar Energy Conversion II, Wien,
precursor film. NREL official measurement (X-25 IV System; ASTM E892- Austria, July 6-10, 1998.
87 Global). Measurement temperature 25°C, Irradiance: 1000 W/m2. 7. D. Braunger, S. Zweigart, and H. W. Schock, Paper presented at Photovoltaic
Solar Energy Conversion II, Wien, Austria, July 6-10, 1998.
8. P. J. Sebastian, M. E. Calixto, R. N. Bhattacharya, and R. Noufi, J. Electrochem.

Downloaded on 2016-04-25 to IP 144.122.201.150 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).