Thin Solid Films 583 (2015) 5054

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Thin Solid Films

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

Microstructure characterization of the soda-lime-glass/copperindium

galliumselenium interface in Cu-poor Cu(In,Ga)Se2 thin lms
Jian Wang, Yi Qiao, Jie Zhu
State Key Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing, Beijing 100083, China

a r t i c l e

i n f o

Article history:
Received 20 August 2014
Received in revised form 23 March 2015
Accepted 23 March 2015
Available online 30 March 2015
Keywords:
Microstructure
Thin lms
Copper indium gallium selenide
Transmission electron microscopy
Ordered vacancy compound

a b s t r a c t
The microstructure characteristics of the soda-lime-glass/Cu(In,Ga)Se2 (SLG/CIGS) interface in Cu-poor CIGS
lms are investigated by transmission electron microscopy and selected area electronic diffraction (SAED). The
SAED patterns show very sharp and strong spots, indicating the main structure of CIGS chalcopyrite. Small dispersed crystals with size distribution from 2 to 5 nm seem to be embedded in amorphous matrix, and additional
spots indicate the presence of an ordered vacancy compound (OVC). This observation is consistent with the
Raman results, and the OVC phase with the nanoclusters exists in the CIGS matrix, instead of layer structure. Lattice distortion results in local changes in contrast. Some pseudo-disordered structure is observed, however, the
structure is actually the chalcopyrite CIGS structure. 180 rotation twins are also observed at the SLG/CIGS interface. Lattice distortion is widely observed at the interface of the Cu-poor CIGS lms, and the extra spots could be
caused by different lattice orientations.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Chalcopyrite Cu(In,Ga)Se2 (CIGS) is an attractive material candidate
for high-efciency thin-lm solar cells. Among all thin-lm type solar
cells, the record conversion efciency of CIGS has reached at highest
value of 20.8% by co-evaporation [1,2]. Up to now, most of the CIGS
thin lms used for high-performance solar cells are grown by either
the co-evaporation or the post-selenization processes. Despite the
great progress made on optimizing the preparation processes and photovoltaic performance of CIGS devices, the full potential of the CIGS absorber material has yet to be realized [2,3]. It is well known that the
microstructure, optical and electronic properties of CIGS thin lms
strongly depend on the Ga/(In + Ga) and Cu/(In + Ga) compositional
ratios, which plays a crucial role in achieving high conversion efciency
[4]. Generally, the CIGS absorbers of the high-efciency solar cells are
deliberately Cu decient. For Cu-poor CIGS material, the formation of
an ordered vacancy compound (OVC) on the surface is feasibility. This
Cu-poor OVC phase, like Cu(In,Ga)3Se5 or Cu(In,Ga)2Se3.5, which is indicated to be n type, creates a buried heterojunction to replace the p-n
junction between p-type CIGS chalcopyrite and n-type CdS [5].
Raman scattering measurements have shown that the presence of
the OVC phase not only at the surface, but also next to the back contact
in Cu-poor CuInSe2 lms [6]. Yan et al. reported on convergent-beam
Corresponding author. Tel.: +86 010 62334333; fax: +86 010 62333447.
E-mail addresses: wangjustb@gmail.com (J. Wang), jiezhu@ustb.edu.cn (J. Zhu).

http://dx.doi.org/10.1016/j.tsf.2015.03.053
0040-6090/ 2015 Elsevier B.V. All rights reserved.

electron diffraction and energy-dispersive X-ray spectroscopy (EDS)

study of the microstructure and composition of the surface region in
Cu-poor CIGS thin lms, and no OVC structure was detected in their
samples [3]. Additionally, Zhang et al. found the surface and the bulk
of the Cu-poor CIGS material exhibit a similar crystal structure, and
OVC phases have been not observed by transmission electron microscopy (TEM) [7]. Understanding the proper physics and growth mechanism for the OVC phase formation in CIGS material is critical for
further improvements of the devices performance. A Cu-deciency parameter, Z, dened as (1-Cu/Ga) was used to study the phase transition
in CuGaSe2 material, and a series of OVC phase formations were observed with an increasing Z-value [8]. Raman spectra intensity of the
chalcopyrite Cu(In,Ga)Se2 band progressively increases with higher Cu
content (Cu/(In + Ga) 0.60), and the contribution from the OVC
bands becomes negligible with higher Cu/(In + Ga) N 0.80 [9]. Therefore, the reason for the absence of OVC phases in TEM investigations
may be the higher Cu/(In + Ga)-value.
In our previous studies, we have found that the OVC phases are located not only at the surface region, but also inside and next to the
back interface in the Cu-poor CIGS layers [10,11]. Some groups have reported the microstructure and chemical composition of the surface
layer and the bulk region in CIGS thin lms by TEM [3,7,12,13]. However, so far, direct structural proof of the back interface is still missing. This
work reports the results of our investigations on the microstructure and
chemical compositions of the back interface regions in the Cu-poor CIGS
thin lms.

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51

2. Experimental details
The CIGS lms used in this study were grown by the postselenization process, as described in Ref. [11]. For CIGS-based solar
cells, the absorber lms should be deposited on Mo back contact layer.
To measure the optical properties of Cu(In,Ga)Se2 lms, however, we
prepared the CIGS layers on bare soda-lime-glass (SLG) without Mo
contact. The crystal phases and structures of the CIGS lms were characterized with grazing incidence X-ray diffraction by X-ray diffractometer
(XRD, Rigaku D/max2550HB +/PC, Cu K and = 1.5418 ). The stepscan covered the angular range 1090 in steps of 0.02, and the incidence angle was 1.0. The results revealed that the lms grown by the
post-selenization process are of the chalcopyrite phase (not shown
here). XRD result indicates no OVC phase detected in the CIGS lms,
and it is possible that the OVC phase may exist in a much thinner
layer in the thin lms than XRD can actually detect [3,7] and/or the
peaks overlapping of the OVC and CIGS phases [11]. To further investigate the structural properties of CIGS thin lms, depth-resolved
Raman spectra measurements were performed at room-temperature,
using a multichannel modular triple Raman system (JY-HR800) with a
solid-state diode laser excitation source ( = 532 nm) in backscattering
conguration. The depth-resolved measurements were achieved by acquiring sequentially a series of Raman spectra after sputtering the samples with the laser beam. The typical spectrum acquisition time was
200 s, leading to a total measurement time per line of 5000 s [11]. In
order to determine the microstructure of the SLG/CIGS interface region,
TEM investigations were performed on a Tecnai G2 F30 S-TWIN microscopy operating at 300 kV. The sample for TEM measurements was prepared by a dual-beam focused ion beam (FIB, Zeiss Auriga) operating
over a range of 530 keV with a milling current of 50 pA (Ga+ ions),
having a unique 2.5 nm resolution. By using Gatan DigitalMicrograph
(DM, Gatan Inc.) 3.7.0 software, a fast Fourier transform (FFT) and/or
an inverse fast Fourier transform (IFFT) of high resolution TEM
(HRTEM) images can be conducted in a small assigned area.
3. Results and discussion
Fig. 1 shows the depth-resolved Raman spectra measured after
sputtering the surface of the CIGS material at different depths. Details
of the depth-resolved Raman analysis were described in Ref. [11]. The
result indicated that the detected Cu-poor OVC phase was located not
only at the surface region but inside and next to the SLG/CIGS interface
in the Cu-decient CIGS layer, which is similar to the nding in Cu-poor
CuInSe2 lms [6,11].
The atomic percentage of Cu, In, Ga, and Se of the CIGS material by
EDS measurement was 19.89%, 21.86%, 4.31%, and 53.94%, respectively.
The Cu/(In + Ga) and Ga/(In + Ga) ratios calculated from EDS results
were 0.76 and 0.16, respectively, indicating a Cu-decient CIGS material
with a low Ga content [11]. To get a better understanding of inner structure, the microstructure of the SLG/CIGS interface region was analyzed
in the Cu-poor CIGS layer. Fig. 2(a) shows a cross-sectional bright eld
TEM image with four contrasts, denoted as P1, P2, P3, and P4, respectively. The substrate is on the left-hand side (not shown here). Similar
to the ndings at the Mo/CIGS [2,9,14,15] and/or GaAs/CIGS [16] interfaces by other research groups, voids are observed at the SLG/CIGS interface, which may be harmful to the device performance [10]. To examine
the local chemical composition, TEM-EDS data, as shown in Fig. 2(b),
were taken from the four regions P1, P2, P3, and P4, respectively. It
can be seen that the P1 (Cu:Pt = 96.68 at.%:3.32 at.%) region contains
only two elements Cu and Pt, originating from the copper TEM holder
and the ion assisted Pt protection during the FIB process, respectively.
In the P2 (Cu:Si:O = 77.05 at.%:3.87 at.%:19.08 at.%) region, Si and O
are detected, which may be from the thermal-excitation loss of the
SLG substrate during the selenization process. TEM-EDS data taken
from the P3 (Cu:In:Ga:Se = 87.59 at.%:2.48 at.%:4.05 at.%:5.88 at.%)
and P4 (Cu:In:Ga:Se = 68.52 at.%:5.69 at.%:3.23 at.%:22.56 at.%) regions

Fig. 1. Depth-resolved Raman spectra measured after sputtering the CIGS thin lm down
to various depths. The wavelength of the solid-state diode laser excitation source is
532 nm, and the step size is 200 s. The spectra are normalized to the intensity of the
Cu(In,Ga)Se2 A1 mode.

show the coexistence of four elements Cu, In, Ga, and Se, however, the
chemical composition in the two regions varies, indicating the presence
of different quaternary compound phases. Fig. 2(c) shows a selected
area electron diffraction (SAED) pattern along the [110] zone axis,
which is taken from the designated area within the square box in
Fig. 2(a). The SAED pattern indicates the coexistence of phases, including a chalcopyrite CIGS phase and an fcc Cu phase. Fig. 2(d) exhibits
an HRTEM image of the P3 region, where small dispersed crystals with
size distribution from 2 to 5 nm seem to be embedded in amorphous
matrix (marked by red ovals). Fig. 2(e) depicts an HRTEM image of
the selected area marked by the white circle in the P4 region (shown
in Fig. 2(a)). The SAED pattern shows very sharp and strong spots
(see inset of Fig. 2(e)), which can be indexed by chalcopyrite structure.
The spacing of the lattice fringes was measured to be 0.3378 nm,
which corresponds to the (112) lattice plane of the chalcopyrite CIGS
structure. Fig. 2(f) is the IFFT image of Fig. 2(e) (marked by red square),
and it reveals local changes in contrast (marked by red ovals), which
may be caused by the lattice distortion in CIGS lms.
To get a better understanding of the crystal structure, the microstructure of the regions P3 and P4 interface in the as-prepared CIGS
lm was analyzed. Fig. 3(a) exhibits an HRTEM image taken from the interface between the P3 and P4 regions, and the corresponding FFT
image given in the inset veries the chalcopyrite CIGS structure. The lattice structure of the CIGS is clearly visible in the P4 region, whereas
there are occasional crystals showing lattice fringe contrast in the P3 region. Interestingly, some pseudo-disordered structure is observed in P4
(marked by red square in Fig. 3(a)). However, the IFFT and FFT images
reveal that the structure is actually the chalcopyrite CIGS structure, as
shown in Fig. 3(b). Fig. 3(c) shows the IFFT and FFT images of the selected oval area in Fig. 3(a). The bright main diffraction spots indicated
by the white arrows are indexed to be ( 220 ), ( 112 ), and (004),
demonstrating almost the same as the structure of chalcopyrite
seen in Figs. 2(e) and 3(a). However, additional spots at (002), (110),
and ( 222) are seen as indicated by the blue arrows in the inset of

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J. Wang et al. / Thin Solid Films 583 (2015) 5054

Fig. 2. (a) Cross-sectional TEM image of the SLG/CIGS interface. (b) TEM-EDS data taken from the four regions P1, P2, P3, and P4, respectively. (c) SAED pattern taken from the designated
area in (a). (d) HRTEM image of the P3 region. (e) HRTEM image of the area marked by the white circle of the P4 region in Fig. 2(a), and inset of (e) is the SAED pattern taken from the
selected area. (f) IFFT image of selected square area in (e). (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

Fig. 3(c), indicating the presence of the OVC phase. This observation is
consistent with the Raman results above mentioned in Fig. 1. It can be
seen that the OVC phase with the nanoclusters exists in the CIGS matrix,
instead of layer structure [7]. Fig. 3(d) depicts the IFFT image taken from
the selected triangle area in Fig. 3(a), showing different lattice fringe
orientations between the regions P3 and P4. Severe lattice distortion is
widely observed at the interface between regions P3 and P4 (indicated
by the blue arrows in Fig. 3(d)), and there are extra spots indicated by
the red arrows in the FFT image, which may be caused by different lattice orientations.

Fig. 4(a) shows an HRTEM image taken from the selected dark oval
area in the P4 region of Fig. 2(a). It is evidenced that grain boundaries
are clearly visible, and twin boundaries are also clearly seen (indicated
by the white arrows). The corresponding SAED pattern of the crystals
is shown in Fig. 4(b). Consistent with the aforementioned results,
the bright diffraction spots (220), (112), (004), and (112) are marked
out, indicating the main structure of chalcopyrite. Additionally, there
are extra reections (indicated by the blue arrows) resulted from
twins in the CIGS lms, which correspond to 1/3 the distance of (220)
and (112) fundamental reections [13]. After a careful analysis of the

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53

Fig. 3. (a) HRTEM image taken from the interface of P3 and P4 regions, and inset in the gure shows a FFT image of (a). (b) IFFT image of selected square area in (a), and inset in the gure is
a FFT image of (b). (c) IFFT image of selected oval area in (a), and inset is the corresponding FFT image of (c). (d) IFFT image taken from the selected triangle area in (a), and inset is the
corresponding FFT image of (d). (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

SAED pattern, it suggests that the twins are actually 180 rotation twins.


The twins spots are marked as (112)T, 220 , and (004)T in Fig. 4(b),



T




where 112T 13 73 23 , 220 220 , and 004T 83 83 43 .
T

4. Conclusions
In this work, the microstructure of the SLG/CIGS interface regions in
Cu-poor CIGS lms is investigated by TEM. A cross-sectional bright eld

Fig. 4. (a) HRTEM image taken from the selected area marked by the dark oval of the P4 region in Fig. 2(a). (b) SAED pattern of the crystals in (a) showing twin diffraction spots indicated by
blue arrows. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

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J. Wang et al. / Thin Solid Films 583 (2015) 5054

TEM image shows four contrasts, denoted as P1, P2, P3, and P4,
respectively. The chemical composition in the four regions varies,
indicating the presence of different phases. The bright diffraction spots
(220), (112), (004), and (112) are marked out, indicating the main structure of CIGS chalcopyrite. In the region P3, small dispersed crystals with
size distribution from 2 to 5 nm seem to be embedded in amorphous
matrix. Additional spots at (002), (110), and (222) are marked out, indicating the presence of the OVC phase. This observation is consistent
with the Raman results, and the OVC phase with the nanoclusters exists
in the CIGS matrix, instead of layer structure. In the region P4, the SAED
pattern shows very sharp and strong spots, which can be indexed by
chalcopyrite structure. The spacing of the lattice fringes was measured
to be 0.3378 nm, which corresponds to the (112) lattice plane of the
chalcopyrite CIGS structure. The IFFT image reveals local changes in contrast, which may be caused by the lattice distortion. Some pseudodisordered structure observed in the region P4 is actually the chalcopyrite CIGS structure, determined by the IFFT and FFT images. Taken from
the selected area in the region P4, it is evidenced that grain boundaries
are clearly visible, and twin boundaries are also clearly seen. By careful
analysis of the SAED pattern, the twins are suggested in 180 rotation.
Severe lattice distortion is widely observed at the interface between regions P3 and P4, and the extra spots could be caused by different lattice
orientations.
Acknowledgment
The authors would like to thank Beijing Municipal Commission of
Education for its sponsorship of the research under the Research Fund
of co-construction Program (Grant No. XK100012026).
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