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Solar Energy Materials & Solar Cells 58 (1999) 375}385

Electrodeposition of CuIn Ga Se thin "lms


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R. Friedfeld, R.P. Ra!aelle*, J.G. Mantovani
Department of Physics and Space Sciences, Florida Institute of Technology, 150 W. University Blvd.,
Melbourne, FL, 32901, USA
Received 19 October 1998

Abstract

CuIn Ga Se (CIGS) polycrystalline thin "lms with various Ga to In ratios were grown
V \V 
using a new two-step electrodeposition process. This process involves the electrodeposition of
a Cu}Ga precursor "lm onto a molybdenum substrate, followed by the electrodeposition of
a Cu}In}Se thin "lm. The resulting CuGa/CuInSe bilayer is then annealed at 6003C for 60 min
in #owing Argon to form a CIGS thin "lm. The individual precursor "lms and subsequent
CIGS "lms were characterized by X-ray di!raction, scanning electron microscopy, energy
dispersive spectroscopy and Auger electron spectroscopy. The as-deposited precursor "lms
were found to be crystalline with a crystal structure matching that of CuGa . The annealed

bi-layers were found to have the same basic chalcopyrite structure of CuInSe , but with peak

shifts due to the Ga incorporation. Energy dispersive spectroscopy results show that the
observed shifts correlate to the composition of the "lms.  1999 Elsevier Science B.V. All
rights reserved.

Keywords: CIGS; Electrodeposition; Photovoltaics

1. Introduction

CuIn Ga Se (CIGS) thin "lms have become the focus of many research groups
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in solar energy. This interest has been fostered by the development of thin "lm solar
cells with over 17% e$ciencies using CIGS as the absorber [1]. CIGS retains the
desirable photovoltaic properties of its predecessor CuInSe while allowing an in-

creased band gap due to its Ga incorporation. Various materials processing methods

* Corresponding author.
E-mail addresses: rfriedfeld@sfasu.edu (R. Friedfeld), rpr@pss."t.edu (R.P. Ra!aelle),
jmantova@pss."t.edu (J.G. Mantovani)
 present address: Stephen F. Austin State University

0927-0248/99/$ - see front matter  1999 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 7 - 0 2 4 8 ( 9 9 ) 0 0 0 1 0 - 0
376 R. Friedfeld et al. / Solar Energy Materials & Solar Cells 58 (1999) 375}385

exist which can yield good quality CIGS thin "lms including co-evaporation of
elemental sources [2], thermal crystallization in selenium vapor [3], physical vapor
deposition [4], chemical bath deposition and electrodeposition [5].
One of the main challenges in solar energy research is to "nd a fabrication method
that yields high-quality thin "lms at low cost and is easily scalable [6]. The scalability
and cost factors eliminate many vacuum deposition methods, although high-
quality thin "lms can usually be obtained this way. Chemical bath and electro-
deposition techniques have the natural advantage of being inexpensive and easily
scalable [7].
CuInSe (CIS), which has a band gap of approximately 1.0 eV, has been successfully

electrodeposited by several research groups [8}12]. Improvements to the as-deposited
CIS "lms by reaction with Se-vapor has resulted in solar cells with e$ciencies of
approximately 7% [13]. However, the band gap for CuInSe is less than the optimum

value of around 1.4 eV for the terrestrial solar spectrum. The addition of gallium to
CIS to form CIGS can increase the band gap to 1.7 eV, depending on the composition
[14]. This allows the band gap of CIGS to be `tailoreda to the terrestrial solar
spectrum. The ability to control the band gap also a!ords the possibility of producing
graded-band gap devices which can be used to improve the open circuit voltage and
short circuit current [15]. Recently, Bhattacharya et al. have reported the develop-
ment of a 12.3% e$cient CIGS cell using an electrodeposited precursor [16].

2. Experimental

In the present work, the copper}gallium precursor "lms were electrodeposited from
an aqueous solution onto mechanically polished Mo foil discs. The deposition
solution was based on the work by Mehlin et al. [17] and consisted of 1 mM Cu(SO ),

20 mM Ga (SO ) and 5 M NaOH. The "lms were potentiostatically deposited at
 
!1.95 V vs. SCE for 2 min using a 500 rpm rotating disk electrode. This precursor
"lm was then transferred to a CIS bath where a CIS overlayer "lm was elec-
trodeposited. The details of the CIS bath have been previously reported [18]. The CIS
layer was deposited at !1.20 V vs. SCE for 5 or 10 min.
The theoretical thickness of the electrodeposited Cu}Ga "lms was determined by

 
1 itM
¹" , (1)
nFA o
where n is the number of electrons transferred, F is Faraday's number, A is the
electrode area, i is the current delivered, t is the deposition time, M is the formula
weight, and o is the density [19]. For our calculation we used the formula weight
(202.98 g/mol) and density (7.21 g/cm) corresponding to intrinsic CuGa [20]. This is

an approximation, since the formula weight and density will vary with composition
and defect densities. The number of electrons transferred was taken as 8 according to
the electrode half-reaction of
Cu>2Ga>#8e\PCuGa . (2)

Table 1
Deposition conditions

Film Cu}Ga layer Cu}In}Se layer

Deposition Deposition Current Calculated Deposition Deposition Current Calculated Total "lm
voltage time density thickness voltage time density thickness thickness
(V vs. SCE) (min) (mA/cm) (lm) (V vs.SCE) (min) (mA/cm) (lm) (lm)

CIS1A NA NA NA NA !1.20 10.0 3.79 1.06 1.06


CIGS1A !1.95 2.0 44.56 1.951 !1.20 5.0 3.50 0.490 2.441
CIGS2A !1.95 2.0 31.83 1.393 !1.20 10.0 3.12 0.873 2.266
CIGS2B !1.95 2.0 31.19 1.365 !1.20 5.0 3.66 0.512 1.877
CIGS2C !1.95 2.0 31.83 1.393 !1.20 5.0 2.87 0.419 1.812
R. Friedfeld et al. / Solar Energy Materials & Solar Cells 58 (1999) 375}385
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378 R. Friedfeld et al. / Solar Energy Materials & Solar Cells 58 (1999) 375}385

For our CIS calculations, we used the formula weight (336.28 g/mol) and density
(5.77 g/cm) of intrinsic CuInSe [21]. The number of electrons transferred was taken

as 13 according to the total electrode reaction:
Cu>#In>#2SeO\#12H>#13e\PCuInSe #6H O. (3)
  
The as-deposited CIS on Cu}Ga "lms were annealed in a tube furnace in a #owing
argon atmosphere at 6003C for 60 min. Annealing temperatures were chosen so that
single phase CIGS may be formed [22]. The individual precursor "lms and the
resulting annealed CIGS "lms were characterized by X-ray di!raction (XRD), scann-
ing electron microscopy (SEM), energy dispersive spectroscopy (EDS), and Auger
electron spectroscopy (AES). A summary of the sample deposition conditions used in
this study is given in Table 1.

3. Results

3.1. Film morphology

Fig. 1 shows the typical surface morphology of the Cu}Ga precursor "lm. The
surface has isolated crystallites or grains of approximately 0.5 lm in size. XRD
analysis of the "lm revealed that it is crystalline with Bragg re#ections matching that
of CuGa (see Fig. 2). Compositional analysis using EDS was consistent with an

identi"cation of CuGa and yielded 34.47 at% Cu and 65.53 at% Ga.

Fig. 3 shows a comparison of the as-deposited "lm morphologies for a CIS "lm
electrodeposited for 5.0 min at !1.2 V vs. SCE on a Mo foil and to a Mo foil with

Fig. 1. SEM micrograph of electrodeposited Cu}Ga precursor "lm on mechanically polished Mo. The
white scale bar corresponds to 1.0 lm.
R. Friedfeld et al. / Solar Energy Materials & Solar Cells 58 (1999) 375}385 379

Fig. 2. XRD pattern of Cu}Ga precursor "lm with plane indices corresponding to the CuGa structure.


a CuGa prelayer. The SEM micrographs show that both "lms have a dense, smooth,
and polycrystalline morphology. However, the CIS "lm deposited on the CuGa

prelayer shows a dramatic increase in grain size as compared to the "lm grown on the
Mo substrate.
The surface roughness of the CIS on CuGa "lms after annealing at 6003C in

#owing argon for 1 hr (CIGS2C) is shown in Fig. 4. The grain sizes are larger than the
unannealed "lms and the individual grains appear to be merging. The average grain
size is shown to be on the order of 1.0 lm. This average size is similar to CIGS grain
sizes produced by RF sputtering, co-evaporation and thermal crystallization of
precursors in saturated selenium vapors [23]. Fig. 5 shows the surface morphology of
CIGS2A after annealing, which had a much thicker CIS over-layer than any of the
other CIGS "lms. This "lm is extremely smooth and appears to have lost most of the
indications of individual grains.

3.2. Composition

Table 2 shows the composition of the "lms used in this study as determined by
energy dispersive spectroscopy (EDS). The atomic percentage of Ga in the "lms
decreases with the thickness of the CIS overlayer. The CIGS "lms had varying Ga to
In ratios, with the atomic percentage of Cu and Se remaining relatively constant. All
of the "lms were only slightly Cu-poor with respect to the anticipated composition of
Cu(Ga,In)Se . The [Ga] to ([Ga]#[In]) ratios for the CIGS "lms range from 0.33 to

0.56. These ratios span the range necessary to achieve CIGS band gaps which are
optimized for the terrestrial solar spectrum [14].
380 R. Friedfeld et al. / Solar Energy Materials & Solar Cells 58 (1999) 375}385

Fig. 3. (A) SEM micrograph of CIS as-deposited on a mechanically polished Mo substrate. (B) SEM
micrograph of CIS as-deposited on a Cu}Ga-coated Mo substrate. The white scale bar in both micrographs
corresponds to 1.0 lm.

3.3. X-ray diwraction

Fig. 6 shows a comparison of the XRD patterns measured for an electrodeposited


CIS and CIGS "lm. It can be seen that both of the "lms have the basic chalcopyrite
crystal structure, which is conclusively identi"ed by the minor peaks labelled (101),
(103), (105), and (213). However, there is a noticeable shift of the main Bragg peaks to
larger angles for the CIGS as compared to the CIS. This shift is due to the fact that the
lattice parameters, and therefore d-spacings, decrease as Ga is substituted for In in the
structure. In particular, the (112) d-spacing for CIS is given as 33.51 nm as compared
R. Friedfeld et al. / Solar Energy Materials & Solar Cells 58 (1999) 375}385 381

Fig. 4. SEM micrograph of sample CIGS2C after annealing in #owing Ar at 6003C for 1.0 h. The white
scale bar corresponds to 1.0 lm.

Fig. 5. SEM micrograph of sample CIGS2A after annealing in #owing Ar at 6003C for 1.0 h. The white
scale bar corresponds to 1.0 lm.

Table 2
Compositional results

Film [Cu] (at%) [In] (at%) [Ga] (at%) [Se] (at%) [Cu] [Ga]
x"
[Ga]#[In] [Ga]#[In]

CIS1A 19.10 23.96 0 56.95 0.80 0


CIGS1A 21.80 14.99 13.87 49.34 0.76 0.48
CIGS2A 21.62 18.96 9.33 50.08 0.76 0.33
CIGS2B 23.98 15.35 12.28 48.39 0.87 0.44
CIGS2C 20.97 14.08 18.22 46.73 0.65 0.56
382 R. Friedfeld et al. / Solar Energy Materials & Solar Cells 58 (1999) 375}385

Fig. 6. XRD patterns for CIS1A and CIGS2A with plane indices corresponding to the chalcopyrite
structure.

Fig. 7. (112) Bragg peak positions for CIS1A and CIGS2A, 2B, and 2C. The x values shown represent the
Ga content in the various "lms and is de"ned by CuIn Ga Se , as in Table 2. Inset: The open squares
\V V 
represent the (112) d-spacings from the powder di!raction "les for CuInSe , CuIn Ga Se , and
     
CuGaSe . The line is a linear least-squares "t to these open squares. The solid circles represent the (112)

d-spacings of CIS1A and CIGS2A, 2B, and 2C as a function of their composition found by EDS.
R. Friedfeld et al. / Solar Energy Materials & Solar Cells 58 (1999) 375}385 383

Fig. 8. (A) Auger depth pro"le of anunannealed CIS on Cu}Ga "lm (CIGS1A). (B) Auger depth pro"le of
sample CIGS2C after annealing in #owing Ar at 6003C for 1.0 h.

to 32.79 nm for CIGS (Ga to In ratio equal to one). This would correspond to a shift
from 2h "26.63 to 27.23, assuming Cu X-rays. A comparison of the (112) peaks of
Ia
the di!erent CIGS samples shows the anticipated shift to smaller angles with increas-
ing Ga to In ratio (see Fig. 7). The inset of Fig. 7 shows the relationship between the
measured (112) d-spacing versus Ga content our CIGS "lms as compared to the
powder di!raction table values for CuInSe , CuIn Ga Se , and CuGaSe .
      
3.4. Auger electron spectroscopy

Fig. 8(a) shows the depth pro"le of the unannealed CIS on CuGa thin "lm. The

data shows little inter-di!usion between the two as-deposited layers. However, after
annealing at 6003C for 60 min, the Ga has di!used throughout the "lm (see Fig. 8(b)).
The [Ga] at% near the surface is close to 10% and increases through the bulk to the
384 R. Friedfeld et al. / Solar Energy Materials & Solar Cells 58 (1999) 375}385

Fig. 9. Auger depth pro"le of CIGS2A after annealing in #owing Ar at 6003C for 1.0 h.

back Mo substrate. An averaging of the atomic concentrations throughout the depth


of the sample show good agreement to the previous discussed EDS results.
The Auger depth pro"le on the sample with the thicker CIS overlayer shows that
the Ga has also di!used entirely through the top "lm (see Fig. 9). In fact, the results
suggest a Ga-oxide coating on the surface; which explains the smoothness seen in the
SEM micrograph of this sample (see Fig. 5). The atomic ratios of Cu, In, Ga, and Se
are relatively constant throughout the bulk of this sample. The sputtering time
necessary to reach the substrate for this sample was greater than the others which
agrees with the theoretical thickness (see Table 1).

4. Conclusions

We have demonstrated the ability to synthesize CuIn Ga Se thin "lms com-


V \V 
pletely by electrodeposition without a post-deposition selenization step. The resulting
"lms show good crystallinity as indicated by X-ray di!raction. The composition of the
"lm can be varied by a combination of deposition conditions and annealing condi-
tions. Auger depth pro"ling studies con"rm that Ga can be easily di!used throughout
the "lm when as-deposited "lms are annealed at temperatures of 6003C in an argon
atmosphere. These results suggest that it should be possible to make uniform CIGS
"lms and graded phase CuIn Ga Se with this method.
V \V 

Acknowledgements

We are grateful to Mike Shlepr of the Microanalytical Laboratory of Harris


Semiconductor (HSC) in Melbourne, Florida for his assistance with our SEM, EDS,
R. Friedfeld et al. / Solar Energy Materials & Solar Cells 58 (1999) 375}385 385

and Auger analysis. Also, we are grateful to Dr. Sheila Bailey and Dr. Al Hepp of the
NASA Lewis Research Center for their assistance with this work.

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