Thin Solid Films 332 (1998) 340±344

Synthesis and processing of a Cu-In-Ga-Se sputtering target

C. Suryanarayana a,*, E. Ivanov b, R. Nou® c, M.A. Contreras c, J.J. Moore a
a
Advanced Coatings and Surface Engineering Laboratory (ACSEL), Colorado School of Mines, Golden, CO 80401-1887, USA
b
Tosoh SMD, Inc., Grove City, OH 43213-1895, USA
c
National Renewable Energy Laboratory, 1617 Cole Blvd., Golden, CO 80401-3393, USA

Abstract
Formation of a homogeneous nanocrystalline CuIn0.7Ga0.3Se2 alloy was achieved by mechanical alloying of blended elemental Cu, In, Ga,
and Se powders in a planetary ball mill. X-ray diffraction and transmission electron microscopy techniques were employed to follow the alloy
formation during the milling process. It was observed that, depending upon the milling conditions, either a metastable cubic or a stable
tetragonal phase was produced. The grain size of the mechanically alloyed powder was about 10 nm. The mechanically alloyed powder was
consolidated to full density by hot isostatic pressing the powder at 7508C and 100 MPa for 2 h. Irrespective of the nature of the phase in the
starting powder, the hot isostatically pressed compact contained the well-recrystallized tetragonal CuIn0.7Ga0.3Se2 phase with a grain size of
about 50 nm. q 1998 Elsevier Science S.A. All rights reserved.
Keywords: Sputtering target; Mechanical alloying; X-ray diffraction; Electron microscopy

1. Introduction alloy phases including supersaturated solid solutions, inter-

Copper indium diselenide (CuInSe2)-based photovoltaic
solar cells have received considerable attention in recent
years because of their high conversion ef®ciency, reaching
a value of 17.7% for a Cu-In-Ga-Se device [1]. Research is
also being conducted on other materials to further improve
the ef®ciency and the results of these investigations are
summarized in a recent comprehensive review [2]. It has
been shown that the band gap of CuInSe2 can be continu-
ously modi®ed by substituting Ga for In [3]. A Ga/(Ga1In)
ratio of 0.3 has been found to be optimum in these structures
for maximum ef®ciency [4]. A slight de®ciency in the
copper content has also been found to be bene®cial.
The CuInSe2-based alloy ®lms are usually obtained by
either multi-source thermal evaporation and co-deposition
or reactive annealing of precursor ®lms. These processes are
very involved, contain a number of deposition and anneal-
ing steps, and can be expensive. Thus, we have developed a
simple and inexpensive process to produce stoichiometric
CuIn0.7Ga0.3Se2 (CIGS) alloy by mechanical alloying and
subsequent hot isostatic pressing.
Mechanical alloying (MA) is a high-energy ball milling
process involving repeated welding, fracture, and rewelding
of powder particles. This technique has been shown to be
capable of synthesizing a variety of stable and metastable
* Corresponding author. Tel.: 11 303 2733178; fax: 11 303 2733795;
e-mail: schallap@mines.edu.
0040-6090/98/$ - see front matter q 1998 Elsevier Science S.A. All rights reserved.
PII S0040-609 0(98)01033-5
metallics, and amorphous alloys. A recent review [5]
describes the process and the metastable effects achieved
by the MA process and the variety of investigations and
potential applications of MA can be found in a recent biblio-
graphy [6].
2. Experimental procedure
Elemental powders of copper (.99.9% pure) and sele-
nium (.99.9% pure) and ®ne chips/granules of gallium and
indium were weighed out to correspond to the formula
Cu0.95In0.7Ga0.3Se2. This blended elemental mixture (referred
to as CIGS powder mixture) and 13-mm diameter pure
copper balls were loaded into a copper container inside an
argon-®lled glove box. The ball-to-powder weight ratio
(BPR) was maintained either at 10:1 or 20:1. Milling was
conducted in a Fritsch Pulverisette planetary ball mill P5 at
a rotation speed of either 150 or 300 rev./min. The powders
were milled for different times ranging from as short as 1
min to as long as 8 h. In one set of experiments the powders
were milled continuously for the speci®ed period of time;
referred to as continuous milling. In another set of experi-
ments, the powders were milled for a given period of time,
milling was stopped and a small amount of the powder was
taken out (inside the glove box) for X-ray diffraction and
chemical analysis, and the remaining powder was milled
further for some more time. This will be referred to as
 C. Suryanarayana et al. / Thin Solid Films 332 (1998) 340±344
Fig. 1. X-ray diffraction patterns of the CIGS powder mixture milled at a
BPR of 20:1 for 5 and 20 min. The powder milled for 5 min contained the
tetragonal CuIn0.7Ga0.3Se2 phase and small amounts of Cu and In, while the
powder milled for 20 min contained only the tetragonal CuIn0.7Ga0.3Se2
phase.
interrupted milling. The alloying behavior of the mechani-
cally alloyed powders was followed by conducting X-ray
diffraction (XRD) on the powders using Cu Ka radiation at
40 kV and 40 mA settings.
The mechanically alloyed powder was consolidated to
full density by hot isostatic pressing it at 7508C and a pres-
sure of 100 MPa for 2 h. The as-milled powders as well as
the hot isostatically pressed (HIPed) material were exam-
ined in a scanning electron microscope and a transmission
electron microscope for obtaining the microstructural
features of the specimens.
3. Results and discussion
Fig. 1 shows the XRD patterns of the CIGS powder
mixture milled for 5 and 20 min at a BPR of 20:1. Alloying
amongst the constituent elements occurred even after
milling for 5 min as evidenced by the formation of a
quaternary Cu-In-Ga-Se phase. This phase has a tetragonal
Table 1
Summary of X-ray diffraction results on the Cu-In-Ga-Se powders milled under interrupted milling conditions for different times at a ball-to-powder weight
ratio of 20:1 and a milling speed of 300 rev./min
Milling time (min) Phases present
5 t-CIGS a, Cu, In
10 t-CIGS, traces of Cu and In
20 t-CIGS
40 t-CIGS
60 t-CIGS
120 t-CIGS, Cu
a
t-CIGS, tetragonal CuIn0.7Ga0.3Se2 phase.
341
Fig. 2. X-ray diffraction pattern of the CIGS powder mixture milled in air
for 2 h at a BPR of 10:1 showing the presence of a cubic CuIn0.7Ga0.3Se2
phase. The indices marked with an asterisk represent pure Cu peaks.
crystal structure with the lattice parameters a ˆ 0:5736 nm,
c ˆ 1:1448 nm, and c=a ˆ 1:9958 having the space group
I4Å2d [7]. Even though this quaternary phase exists over a
wide composition range [8], the present XRD pattern is
most satisfactorily indexed on the basis of the tetragonal
phase with the stoichiometry CuIn0.7Ga0.3Se2. It should
also be noted that small amounts of elemental copper and
indium are present in the powder milled for 5 min. Their
amounts decreased with increasing milling times; only trace
amounts of copper and indium are present in the powder
milled for 10 min. On milling for 20 min, the powder
contained only the above-mentioned quaternary phase.
However, on milling for a long time, e.g. 2 h or longer,
some copper peaks are again seen in the XRD patterns,
probably picked up from either the container or the milling
medium, or both. Table 1 summarizes the XRD results on
the phase constitution and crystallite size of the CIGS
powder milled under interrupted conditions.
The crystallite size, t of the milled powder was calculated
from the broadening of the X-ray peaks using the Scherrer
formula t ˆ 0:9l/Bcosu , where l is the wavelength of the
X-radiation used, B is the full width at half the maximum
Crystallite size (nm) based on
(112) re¯ection (312) re¯ection
23.0 12.3
16.7 10.4
15.1 7.9
13.4 7.8
13.5 7.8
14.0 7.5
342 C. Suryanarayana et al. / Thin Solid Films 332 (1998) 340±344
Fig. 3. X-ray diffraction patterns of (a) the CIGS powder mixture milled
continuously for 4 h in argon at a BPR of 10:1 and (b) as above after hot
isostatically pressing at 7508C and 100 MPa for 2 h.
intensity, and 2u is the diffraction angle [9,10]. The t values,
calculated from the (112) or (312) re¯ection of the tetrago-
nal CuIn0.7Ga0.3Se2 phase, were in the nanometer range and
the crystallite size decreased with increasing milling time
and leveled off to about 8 nm after about 40 min of milling.
The results appear to be different when the CIGS powder
mixture was milled at a BPR of 10:1. Fig. 2 shows the XRD
pattern of the powder milled continuously for 2 h. Even
though the gross features of the XRD pattern are similar
to those of Fig. 1, both the peak intensities and peak posi-
tions are signi®cantly different in the two cases. The major
peaks could not be satisfactorily indexed on the basis of the
tetragonal quaternary phase referred to above. Instead, satis-
factory agreement was obtained with the cubic CuInSe2
phase with a ˆ 0:558 nm and space group Fm3m. The
presence of some pure Cu peaks is also noted in the XRD
pattern. A similar situation was obtained when the powder
was milled for a shorter period of 1 h or a longer period of 4
h under interrupted milling conditions. A difference
between Figs. 1 and 2 is that the powder milled at the
lower BPR of 10:1 (Fig. 2) contained much more free
copper, even though the proportion of the starting elements
was the same in both the cases.
Fig. 3a shows the XRD pattern of the CIGS powder
mixture milled continuously for 4 h at a BPR of 10:1 in a
container that was used for milling the CIGS powder
mixture earlier. Consequently the inner walls of the
container were coated with a thin layer of the quaternary
tetragonal phase. The major phase present now is the tetra-
gonal CuIn0.7Ga0.3Se2 phase along with a small amount of
free copper, probably picked up from the container and/or
milling medium. The formation of the tetragonal phase
instead of the cubic phase at a BPR of 10:1 may appear to
be contradictory to the earlier observation (Fig. 2). But, it
should be realized that it is dif®cult to nucleate a metastable
phase in the presence of an equilibrium phase. When the
powder was milled in a fresh container, it was then possible
to synthesize the metastable cubic phase. The XRD pattern
of this powder HIPed at 7508C and 100 MPa for 2 h is shown
in Fig. 3b. It shows a well-recrystallized CuIn0.7Ga0.3Se2
tetragonal phase. Another point to be noted is that, irrespec-
tive of whether the starting powder had a cubic or a tetra-
gonal structure, the HIPed compact always consisted of the
equilibrium tetragonal CuIn0.7Ga0.3Se2 phase.
A comparison of Figs. 1 and 2 clearly shows that a cubic
phase is obtained on milling the blended elemental powder
mixture at a BPR of 10:1, while a tetragonal phase is
obtained at a higher BPR of 20:1. The occurrence of both
the cubic and tetragonal phases is reported in the ternary Cu-
In-Se system at a stoichiometry of CuInSe2 [11]. The cubic
phase has a sphalerite (ZnS) structure and is stable at
temperatures higher than 5708C, while the tetragonal
phase has a chalcopyrite (CuFeS2) structure and is stable
from room temperature to about 8108C. It has also been
reported that the cubic CuInSe2 phase is a high-pressure
polymorph obtained approximately at 40 kbar and 4008C
[12]. The lattice parameters of the tetragonal (T) and
cubic (C) phases of the ternary CuInSe2 are related to
each other according to the relationship aT ù aC and
cT ù 2aC . Thus, by stacking two cubic unit cells one over
the other and slightly readjusting the atom positions, one can
convert the cubic structure into the tetragonal structure and
vice versa. Further, the lattice parameters of the tetragonal
quaternary CuIn0.7Ga0.3Se2 phase are slightly smaller than
those of the tetragonal ternary CuInSe2 phase, an effect of
the substitution of Ga for In. Even though the presence of a
cubic polymorph has not been reported in the quaternary
alloy, it is most likely to occur due to the similarity between
the ternary and quaternary systems. It is possible that the
cubic quaternary phase produced in the present investiga-
tion is metastable at room temperature and atmospheric
pressure and may be a stable phase either at high tempera-
tures and/or pressures. Experiments are currently in
progress to investigate whether the tetragonal phase in the
Cu-In-Ga-Se system transforms to a cubic phase at high
pressures. Formation of high-pressure and/or high-tempera-
ture phases in mechanically alloyed powders at atmospheric
pressure and room temperature has been reported earlier
[6,13±16].
Fig. 4a shows a bright-®eld transmission electron micro-
graph of the powder milled continuously for 40 min at a
BPR of 10:1. Examination of the micrographs suggests that
the alloy powder particles are in the range of 50±200 nm and
 C. Suryanarayana et al. / Thin Solid Films 332 (1998) 340±344
Fig. 4. Transmission electron micrographs of the CIGS powder mixture (a)
milled continuously for 40 min at a BPR of 10:1 and (b) after hot isosta-
tically pressing the above powder at 7508C and 100 MPa for 2 h. Note the
retention of nanometer-sized grains after HIPing.
that each powder particle contained several grains. The
average grain size under these conditions is about 10 nm.
This observation con®rms the results of crystallite size
derived from the XRD patterns and that MA is capable of
producing nanometer-sized grains in this material. The main
advantage of producing nanometer-sized grains is that full
consolidation of the powder can be achieved at a much
lower temperature than is required for coarse-grained mate-
rials and this has been shown to be true in many alloy
systems [17]. Examination of the HIPed compact in an
SEM con®rmed that full density was obtained, as evidenced
Table 2
Chemical analysis of the mechanically alloyed Cu-In-Ga-Se powders
Ball-to-powder ratio (BPR) Rotation speed (rev./min)
20:1 300
10:1 300
10:1 150
Targeted composition
343
by the absence of porosity in the compact. Fig. 4b shows a
transmission electron micrograph of the HIPed compact.
Even though one can see that well recrystallized grains
are obtained in this case and that grain growth has occurred,
the grain size is still very small and is in the nanometer
range. The average grain size now is about 50 nm.
Ohtani et al. [18] synthesized the tetragonal ternary
CuInSe2 phase by mechanical alloying of the blended
elemental powder mixture for 2 h in a planetary ball mill
at a high rotational speed of 2800 rev./min. They had also
indicated that they were not able to synthesize the high-
pressure cubic form; possibly due to the very high energy
input associated with their experiments. Although not
clearly mentioned, the BPR used by them could also have
been high.
Formation of metastable phases during mechanical alloy-
ing is of common occurrence [5,6]. It has been reported that
the chances of formation of metastable phases are higher
when milling is carried out under `soft' conditions, i.e. at
low BPR values, small ball diameters, and/or low speeds of
rotation. That this is so is clearly demonstrated in the Zr±Co
system when an amorphous phase was obtained under `soft'
milling conditions, while a mixture of equilibrium crystal-
line phases was obtained under `hard' milling conditions
[19]. Similar results have also been reported in several
other alloy systems [20,21]. Results of our TEM studies
have suggested that stacking faults are present in this mate-
rial and are probably responsible for the cubic!tetragonal
transformation in this alloy. This is possible because of the
close similarity between the crystal structures of the two
phases involved.
Chemical analysis of the powder obtained by MA under
different milling conditions was obtained by atomic absorp-
tion spectrometry and the results are listed in Table 2. It may
be noted that at high BPR and/or rotation speeds, the powder
picks up a reasonable amount of copper from the container
and/or grinding medium. But, the powder milled at a BPR of
10:1 and a speed of 150 rev./min for 40 min did not pick up
much copper. Consequently, the chemical composition of
the powder milled under these conditions is quite close to
the starting powder mixture. Thus, it should be possible to
produce homogeneous and stoichiometric CIGS targets
through a combination of mechanical alloying for a short
time and hot isostatic pressing the powders.
Experiments on sputtering of the targets are currently in
Milling time (min) Chemical composition (at.%)
Cu In Ga Se
120 32.61 15.23 6.53 45.62
240 31.73 15.63 6.71 45.93
40 25.98 16.98 7.26 49.78
24.43 17.63 7.56 50.38
344 C. Suryanarayana et al. / Thin Solid Films 332 (1998) 340±344
progress to evaluate the structure of the sputtered ®lms and
correlate it with that of the target.
4. Conclusions
A homogeneous quaternary nanocrystalline CuIn0.7-
Ga0.3Se2 alloy was synthesized by mechanical alloying of
the blended elemental powder mixture for about 20 min.
The tetragonal form of the quaternary phase was obtained
at high BPR values (20:1) and the cubic form was obtained
at the lower BPR value (10:1). It is suggested that, similar to
the situation in the ternary Cu-In-Se system, the cubic
quaternary phase is a high-pressure polymorph of the tetra-
gonal phase stable at room temperature and at atmospheric
pressure. The mechanically alloyed powder was consoli-
dated to full density by hot isostatic pressing at 7508C and
100MPa for 2 h. Transmission electron microscopy investi-
gations have con®rmed that the average grain size of the as-
milled powder was about 10 nm and after hot isostatic press-
ing it was about 50 nm. While the CuIn0.7Ga0.3Se2 alloy was
not produced earlier using the method suggested here,
mechanical alloying combined with hot isostatic pressing
provides a means of producing a homogeneous, ®ne-
grained, and full density alloy by a simple and inexpensive
process.
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