Applied Surface Science 238 (2004) 180–183

Structural and morphological properties of Cu(In, Ga)Se2

thin films on Mo substrate
R. Caballero*, C. Guillén
Departamento de Energı́as Renovables, CIEMAT, Avd. Complutense 22, 28040 Madrid, Spain

Available online 28 July 2004

Abstract

The objective of this work was to study the structural and morphological properties of Mo/Cu(In, Ga)Se2 thin films deposited
onto glass substrate by different techniques and thermal treatment in different atmospheres. Electron beam evaporated Mo thin
film was better back contact than the sputtered Mo film due to the structural improvements of CIGS film deposited on it. It was
also observed that an increase of the grain size and a better morphology for Ar selenized CIGS films than for the vacuum ones.
These results could lead to a decrease of the number of defects for Ar selenized CIGS films on evaporated Mo, which could
imply an enhancement of the solar cell efficiency.
# 2004 Elsevier B.V. All rights reserved.

PACS: 84.60.Jt; 68.55.Jk; 81.15.
z; 81.40.
z

Keywords: Cu(In, Ga)Se2; Mo; Selenization; Structural properties; Morphological properties

1. Introduction and Ar-atmosphere. To avoid the highly toxic H2Se,

Cu(In, Ga)Se2 (CIGS) film with direct band gap and
high absorption coefficient is one of the best candi-
dates as absorber material for thin film photovoltaic
devices [1]. The chalcopyrite semiconductor CIGS is a
promising material for the large-scale production of
economically viable solar cells and modules. Rama-
nathan et al. [2] reported a solar efficiency above 19%
in CIGS cells by co-evaporation from elemental
sources. Another promising approach is a two-stage
growth process [3,4]. In this study, we followed this
latter process to produce Cu(In, Ga)Se2 by (i) sequen-
tial evaporation of the metallic precursors on Mo and
(ii) selenization of this multilayer structure in vacuum
*
Corresponding author. Tel.: þ34 91 3466675;
fax: þ34 91 3466037.
E-mail address: raquel.caballero@ciemat.es (R. Caballero).
selenization was carried out by using elemental sele-
nium vapour [5].
Different thin film materials compose the CIGS
solar cells. The properties of each material can influ-
ence on the performance of the solar cell. It is known
that Mo prepared by different techniques presents
different electro-optical properties [6], which can
affect all the properties of CIGS thin films deposited
on it. The goal of this work was to study the effect of
the different deposition techniques and treatments
used on the structural and morphological properties
of CIGS in order to obtain high quality layers.
2. Experimental
Cu(In, Ga)Se2 thin films of 2 mm were prepared
using the two-stage process. The first stage consisted

0169-4332/$ – see front matter # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2004.05.207
 R. Caballero, C. Guillén / Applied Surface Science 238 (2004) 180–183
of the sequential evaporation of metallic precursors
In/Ga/Cu/In on 1 mm Mo-coated glass substrates. Cu
and In layers were grown using an electron beam
evaporation source (e-beam), whereas Ga-film was
deposited by thermal evaporation [7]. The substrate
was rotated during deposition to improve the film
uniformity. Mo thin films were obtained by means of
two different deposition techniques: e-beam eva-
poration and sputtering. The advantage of using
evaporated Mo is that all the metals were deposited
inside the same chamber without breaking the
vacuum, avoiding the back contact surface oxida-
tion. In the second stage, the multilayer structure
was selenized in order to form CIGS. For com-
parison purposes, the selenization process of iden-
tical precursor multilayers was carried out with
elemental selenium vapour in vacuum (10
5 mbar)
and Ar-atmosphere (Ar purity of 99.9999%).
This process was performed in a partially closed
graphite box, which was loaded into a quartz-tube
furnace. The temperature of the graphite box con-
taining the samples and the selenium was raised up
to 500 8C at 9 8C/min and thereafter held for 30 min
[7,8].
Chemical etching was performed by immersion of
the samples in an aqueous KCN solution at room
temperature. The structural properties of the thin films
were investigated by X-ray diffraction (XRD) using a
PHILIPS X’PERT instrument. The morphology of the
films was studied by scanning electron microscopy
(SEM) and the images were recorded using a HITA-
CHI S-2500 apparatus. The thickness and mean
roughness were measured by means of a DEKTAK
3030 profilometer.
3. Results and discussion
Different electro-optical properties of sputtered
and evaporated Mo thin films have been observed by
some authors [6]. These differences can affect all
properties of CIGS thin films deposited on it, like the
structural and morphological ones. Fig. 1 shows the
XRD spectra of vacuum selenized-CIGS thin films
on (a) sputtered and (b) evaporated Mo. The only
difference between these two samples is the Mo film.
The chalcopyrite Cu(In, Ga)Se2, with preferential
orientation in the (1 1 2) plane, was obtained for all
181
Fig. 1. XRD patterns of CIGS thin films deposited on (a) sputtered
Mo and (b) e-beam evaporated Mo.
the films after vacuum selenization as well as metal-
lic Mo with preferential orientation in the (1 1 0)
plane. These orientations are the most commonly
presented in the literature [6,9]. As can be observed,
the (1 1 2) plane intensity increases and its full width
at half maximum (FWHM) decreases for the CIGS
deposited on evaporated Mo. This indicates an
increase in the crystallinity and grain size for these
samples.
In Fig. 2, SEM micrographs of the previous samples
are shown. It can be noticed, a light increase of the
grain size and formation of conglomerates in the CIGS
film on evaporated Mo. However, this sample is little
rougher (76 nm) than the one deposited on sputtered
Mo (67 nm). This fact agrees with the conglomerates
observed.
From the structural and morphological studies,
evaporated Mo seems to be the more suitable back
contact, because of the increase of grain size and
improvement of crystallinity of the CIGS films depos-
ited onto it. This fact could lead to a decrease in the
number of defects. From now on, evaporated Mo was
chosen as back contact.
The structural and morphological properties of Ar
selenized-CIGS thin films on evaporated Mo was also
studied. XRD patterns of polycrystalline films sele-
nized in (a) vacuum and (b) Ar-atmosphere are shown
in Fig. 3. The only difference between these Cu-rich
samples is the atmosphere treatment during the sele-
nization process. Both samples showed Cu(In, Ga)Se2
182 R. Caballero, C. Guillén / Applied Surface Science 238 (2004) 180–183
Fig. 2. SEM micrographs of CIGS thin films deposited on (a) sputtered Mo and (b) e-beam evaporated Mo.
strongly orientated in the (1 1 2) plane as the main
phase as well as the CuSe binary phase and Mo. After
Ar-selenization, thin films also showed the MoSe2
phase, which has been observed by other authors
[10,11]. This new phase is associated with the Se
Fig. 3. XRD spectra of CIGS films on evaporated Mo selenized in
(a) vacuum, (b) Ar and (c) Ar with KCN etching.
excess observed after this thermal treatment and does
not imply necessarily a worse efficiency. An increase
of the grain size is obtained after Ar-selenization, as
can be seen by decreasing of FWHM. The presence of
the CuSe secondary phase was due to the fact that the
samples were Cu-rich. It is well known that KCN
solutions can dissolve Se and binary Cu–Se com-
pounds, leaving CIGS and binary In–Se compounds
intact [12]. The KCN etching was able to remove our
CuSe phase from the thin films as can be seen in
Fig. 3c.
The morphologies of CIGS thin films on evaporated
Mo are displayed in Fig. 4. Fig. 4a and b corresponds
to CIGS selenized in vacuum and Ar-atmosphere after
KCN etching, respectively. As it can be observed the
Ar selenized sample has a very smooth and dense
microstructure with bigger grain size than the vacuum
one which is much rougher. This coincides with the
results shown previously by XRD. It is well known
that the efficiency in polycrystalline solar cells
increases with increasing grain size in the absorber
materials [11]. Therefore, the bigger grain growth
obtained by Ar-selenization of the metallic precursors
 R. Caballero, C. Guillén / Applied Surface Science 238 (2004) 180–183
Fig. 4. Surface morphology of CIGS films selenized in (a) vacuum and (b) Ar after KCN etching.
on evaporated Mo is expected to fabricate CIGS thin
film solar cells with high efficiency.
4. Conclusions
Sequentially evaporated precursor layers onto sput-
tered or evaporated Mo films were selenized in
vacuum or Ar-atmosphere to form CIGS thin films.
(1 1 2) preferential orientation plane was obtained for
all CIGS thin films. However, CIGS films on evapo-
rated Mo showed an increase in the grain size and an
improvement of its crystallinity. Moreover, using the
evaporated Mo means not to break the vacuum avoid-
ing its possible oxidation. Therefore, evaporated Mo is
considered the best back contact. Ar selenized samples
were superior than the vacuum treated in terms of
structural and morphological features. Then, Ar sele-
nized CIGS films on evaporated Mo could result in a
decrease in the number of defects. The sequential
evaporation of the metallic precursors coupled with
the graphite box Ar-selenization process seems to be a
suitable method to get good quality CIGS films for
solar cell manufacturing.
183
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