PROGRESS IN PHOTOVOLTAICS: RESEARCH AND APPLICATIONS

Prog. Photovolt: Res. Appl. (2013)

Published online in Wiley Online Library (wileyonlinelibrary.com). DOI: 10.1002/pip.2339

SHORT COMMUNICATION

Effects of combined heat and light soaking on device

performance of Cu(In,Ga)Se2 solar cells with ZnS(O,OH)
buffer layer
Taizo Kobayashi*, Hiroshi Yamaguchi and Tokio Nakada
Department of Electrical Engineering and Electronics, Aoyama Gakuin University, 5-10-1 Fuchinobe, Sagamihara, Kanagawa 229-8558,
Japan

ABSTRACT
The impacts of air annealing, light soaking (LS), and heat–light soaking (HLS) on cell performances were investigated for
ZnS(O,OH)/Cu(In,Ga)Se2 (CIGS) thin-film solar cells. It was found that the HLS post-treatment, a combination of LS and
air annealing at 130  C, is the most effective process for improving the cell performances of ZnS(O,OH)/CIGS devices. The
best solar cell yielded a total area efficiency of 18.4% after the HLS post-treatment. X-ray photoelectron spectroscopy
showed that the improved cell performance was attributable to the decreased S/(S + O) atomic ratio, not only in the surface
region but also the interface region between the ZnS(O,OH) and CIGS layers, implying the shift to an adequate conduction-
band offset at the ZnS(O,OH)/CIGS interface. Copyright © 2013 John Wiley & Sons, Ltd.

KEYWORDS
light soaking; air annealing; heat–light soaking; Cu(In,Ga)Se2; ZnS(O,OH); ZnO:B

*Correspondence
Taizo Kobayashi, Department of Electrical Engineering and Electronics, Aoyama Gakuin University, 5-10-1 Fuchinobe, Sagamihara,
Kanagawa 229-8558, Japan.
E-mail: kobayashi-t@ee.aoyama.ac.jp

Received 13 May 2012; Revised 14 September 2012; Accepted 29 October 2012

1. INTRODUCTION fill factor (FF) and open-circuit voltage (Voc) by exposure to

The development of Cd-free alternative buffer layers is
one of the major objectives in the field of Cu(In,Ga)Se2
(CIGS) technology from the view point of environmen-
tally friendly properties and low optical absorption at
short wavelengths [1–8].
Among the alternative buffer materials, Zn-compounds
such as ZnS(O,OH) deposited by chemical bath deposition
(CBD)[1–5,7] and Zn(O,S) deposited by atomic layer
deposition(ALD)[4,8] are most successfully used for high
efficiency CIGS solar cells and modules. In fact, a 19.1%
efficiency CIGS solar cell [7] and 17.8% efficiency
30  30 cm2 submodule [9] have been achieved using these
buffer materials.
In general, high-efficiency CIGS solar cells with Zn-
compound buffer layers are achieved after air annealing
at 200  C for 10 min after the CBD process [5] and light
soaking (LS) of completed solar cells under one-sun illumi-
nation at room temperature [10,11]. Regarding the LS effect,
the cell performances improve as a result of an increase of the
one-sun illumination. Several models for the LS effect have
been proposed, including reversible behavior of the p–n
heterojunction by temporal dehydration of Zn(OH)2 in
the Zn(S,O,OH) buffer layer [12] and a decrease in the
effective barrier height at the buffer/CIGS interface caused
by photogenerated electrons [13,14].
The Voc and FF were further improved and stabilized by
using a combination of LS and annealing at above 100  C,
namely heat–light soaking (HLS) [12,15,16]. The cell
performances after HLS post-treatment show an irreversible
behavior, and it is proposed that the H2O molecules in the Zn
(S,O,OH) buffer are released from the original sites as a
result of the photochemical reaction [12]. However, the film
composition in the Zn-compound buffer layers is of the
utmost significance, because it influences the conduc-
tion-band offset (CBO) at the CIGS/ZnS(O,OH) interface
[17,18]. The aim of this work is to investigate the effects
of post-treatments such as post-annealing, LS and
HLS before and after the completion of cell fabrication on
the cell performances and film properties. The compositional

Copyright © 2013 John Wiley & Sons, Ltd.

Combined heat and light-soaking effects in CIGS solar cells with ZnS(O,OH)buffer layer T. Kobayashi, H. Yamaguchi and T. Nakada
changes in S/(S + O) and (OH)2/[(O + (OH)2] in the ZnS(O,
OH) buffer layer, which affect the CBO at the CIGS/ZnS
(O,OH) interface, are discussed on the basis of X-ray photo-
electron spectroscopy(XPS) analysis.
2. EXPERIMENTAL
Cu(In,Ga)Se2 thin-film solar cells with a ZnO:B/ZnS(O,
OH)/CIGS/Mo/soda lime glass (SLG) structure were
fabricated as follows. A 1-mm-thick Mo back-contact film
was deposited by DC-magnetron sputtering on SLG
substrates at room temperature. A 2.4–2.6-mm-thick CIGS
absorber layer was deposited by a three-stage process
using a molecular beam epitaxy system at a maximum sub-
strate temperature of 540  C. The average film composition
was measured using inductively coupled plasma spectros-
copy (ICP). A ZnS(O,OH) buffer layer was deposited onto
the CIGS layer by CBD using a ZnSO4 (0.16 M)/ammonia
(7.5 M)/thiourea (0.6 M) aqueous solution. A 120-nm-thick
buffer layer was obtained by repeating the CBD process for
two runs. The temperature of the ZnSO4/ammonia/thiourea
aqueous solution was increased from room temperature to
72  C during one run. Total duration time for CBD was
120 min. Immediately after the CBD process, the films were
rinsed with 7–10% ammonia aqueous solution for 1 min
and then air-annealed at 200  C for 10 min to enhance Zn dif-
fusion into CIGS layer to form a shallow junction [19,20].
Subsequently, 1.4-mm-thick ZnO:B thin-films were depos-
ited by metal organic chemical vapor deposition (MOCVD)
at a substrate temperature of 185  C for 20 min under ultravi-
olet-light (l = 172 nm) illumination [21]. The solar cells were
completed by vacuum evaporation of the Al/Ni front
electrode. The J–V characteristics of the solar cells were
measured under AM1.5, 100 mW/cm2 illumination at 25  C.
The impact of heat soaking (HS), LS, and HLS were
investigated for a set of finished solar cells. These post-
treatments were as follows:
HS, heat soaking at 130  C for 120 min; LS, light soak-
ing under AM1.5; 100 mW/cm2 illumination for 120 min
without intentional heating; HLS, a combination of one-
sun LS and annealing at 130  C for 120 min,
The CBD-ZnS(O,OH) (120 nm)/CIGS (2.4 mm)/Mo/SLG
stacked layers used in these experiments were annealed in air
at 200  C for 10 min immediately after the CBD process.
Subsequently, HS, LS, and HLS post-treatments were
applied to each sample for 120 min at the previously
mentioned temperature and light intensity. The LS and
HLS post-treatments were carried out at open circuit
voltage condition. The film compositions of ZnS(O,OH)
buffer layers were investigated using XPS.
X-ray photoelectron spectroscopy measurements were
carried out using an AXIS-Ultra (Kratos) with monochro-
matic Al Ka1,2 (15 keV) X-ray radiation under a base
pressure of 2  10 9 Pa. Ar ion-beam sputter etching was
carried out using a differentially pumped ion gun operating
at 2 keV at a pressure of 5  10 8 Pa. The accuracy of the
XPS measurements was estimated to be within 0.1 eV.
In order to avoid peak shifting as a result of specimen
charge-up, the surface of the specimen was grounded.
The chemical shifts of the core-level emissions, such as
In 3d and Zn 2p are indistinguishable and are suitable to
serve as a monitor for peak-shifts as a result of charge-
up. No significant peak-shifts caused by charge-up were
observed in any of the measurements.
3. RESULTS AND DISCUSSION
Figure 1 shows the J–V characteristics for ZnO:B/ZnS(O,
OH)/CIGS solar cells treated with 10-min LS, 40-min
HLS, and 120-min HLS. The Ga/(Ga + In) and Cu/(In +
Ga) atomic ratios for the CIGS film were 0.38 and 0.83,
respectively. It is obvious from Table I that the total area
efficiency was improved from 8.5% to 11.3%, 16.7%,
and 17.5% after 10-min LS, 40-min HLS, and 120-min
HLS post-treatments, respectively. The Voc and FF
increased after 10-min LS post-treatment. In these experi-
ments, the same solar cell was used to investigate the
separate effects of LS and HLS from other factors. The FF
was slightly increased by LS under one-sun illumination
for 10 min. It should be noted that the HLS post-treatment
is the most effective in improving the cell performance
of ZnS(O,OH)/CIGS devices. The series resistance was
reduced to approximately one-third, and the shunt resistance
(Rsh) was increased approximately twofold by the LS post-
treatment. Not only Voc and FF but also Jsc increased as a
result of the HLS post-treatment. The series resistance (Rs)
was reduced to approximately one-half, and the Rsh was
increased approximately 10-fold by the HLS post-treatment.
The increased FF may be attributable to the decreased series
resistance Rs. The Rs and Rsh were calculated as the slopes at
Figure 1. J–V characteristics of metal organic chemical vapor
deposition-ZnO:B/ZnS(O,OH)/CIGS solar cells before and after
one-sun light soaking for 10 min and subsequent heat–light
soaking for 40 min and 120 min.
Prog. Photovolt: Res. Appl. (2013) © 2013 John Wiley & Sons, Ltd.
DOI: 10.1002/pip
T. Kobayashi, H. Yamaguchi and T. Nakada Combined heat and light-soaking effects in CIGS solar cells with ZnS(O,OH)buffer layer

Table I. Cell parameters of ZnS(O,OH)/CIGS solar cells before and after light soaking and heat–light soaking post-treatments.

Voc Jsc
Total Rs Rsh

2 2
(V) (mA/cm ) FF (%) (Ω cm ) (Ω cm2)

As-fabricated 0.665 31.4 0.408 8.5 6.85 63.2

LS 10 min 0.678 31.8 0.525 11.3 2.89 129.0
HLS 40 min 0.686 34.0 0.715 16.7 1.58 1025.6
HLS 120 min 0.686 33.8 0.756 17.5 1.48 1821.2

Jsc and Voc in the light J–V curve. The Rs and Rsh in dark for ZnO:B films prepared by MOCVD[22,23]. Thicker ZnO:
condition will be investigated in the future work. B films(0.9–1.4 mm) was thus used to decrease sheet resis-
To clarify the causes of the decreased series resistance tance in this experiment. The Rs depends not only on lateral
of the cell, the electrical properties of MOCVD-ZnO:B sheet resistance but also on the distance between the grid
were investigated. Table II shows the electrical properties fingers. Because the test solar cells have the same grid
of MOCVD-ZnO:B films (0.9 mm) prepared with same patterns and ZnO:B thickness, the decreased resistivity
deposition conditions on SLG substrates before and after probably contributed to reduction of the series resistance,
different post-treatments (HS, LS, and HLS) for 40 min. and thereby, to increase in the FF. It could be considered that
The resistivity decreased from 2.5  10 3 to 1.7  10 3 Ω the FF was improved not only by the lowering of the
cm after the HLS post-treatment because of the increased sheet resistance of the ZnO-B but also re-arrangement of
electron mobility, as shown in Table II. Although the the CBO at the ZnS(O,OH)/CIGS interface after post-
resistivity of ZnO:B films is relatively high as compared treatments[24]. The investigation on this is mentioned later.
with other TCO films, such as ZnO:Al by RF sputtering, The J–V characteristics and spectral response curve
the value of resistivity is similar to that reported previously of the best cell with an MgF2 anti-reflection coating are
shown in Figure 2(a) and (b), respectively. A total-area
efficiency of 18.4% with Voc = 683 V, Jsc = 35.4 mA/cm2,
Table II. Electrical properties of metal organic chemical vapor and FF = 0.761 was achieved after the 120-min HLS
deposition-ZnO:B films (0.9 mm) before and after different post- post-treatment, as seen in Figure 2(a). The excellent carrier
treatments for 40 min. collection observed in the short wavelength spectral region
is attributable to the wide band gap of the ZnS(O,OH)
m n r buffer layer, as shown in Figure 2(b). The carrier collection
Post-
treatment 2
[cm /(V s)] 20
(10 cm ) 3
(10 3
Ω cm) decreases slightly in the long wavelength region between
800 and 1000 nm. Because the optical transmission of
As-deposited 12.0 2.1 2.5 the ZnO:B film showed high transparency in this wave-
HS 11.2 2.1 2.7 length region, the possible reasons are related to the insuf-
LS 15.0 2.5 1.7 ficient crystalline quality of the CIGS absorber and to the
HLS 19.3 1.9 1.7
reduced absorption caused by the increased Ga content
HS, heat soaking; LS, light soaking; HLS, heat–light soaking. at the back contact.

(a) (b)
Figure 2. (a) J–V characteristics and (b) spectral response curve of the best metal organic chemical vapor deposition-ZnO:B /ZnS(O,
OH)/CIGS solar cells.

Prog. Photovolt: Res. Appl. (2013) © 2013 John Wiley & Sons, Ltd.
DOI: 10.1002/pip
Combined heat and light-soaking effects in CIGS solar cells with ZnS(O,OH)buffer layer T. Kobayashi, H. Yamaguchi and T. Nakada

Each post-treatment was carried out to understand the Figure 4 shows the XPS depth profiles of the S/(S + O)
impact of HLS post-treatment. All test cells were post- atomic ratios of air-annealing, HS, LS, and HLS-treated
treated for the same processing time of 120 min. The basic stacked layers. The amount of oxygen was estimated from
cell parameters of the as-fabricated and post-treated solar the O 1 s spectra, which can be separated between ZnO and
cells are shown in Figure 3. The open and filled symbols
represent the as-fabricated and post-treated (HS, LS, and
HLS) solar cells, respectively. Although the cell efficiency
deteriorated after the HS post-treatment, the cell efficiency
increased from
= 6.7% to 9.4% and from
= 3.6% to
14.7% after the LS and HLS post-treatments, respectively.
The Jsc and FF, in particular, increased as significantly
after the HLS post-treatment. After keeping the cells in
the dark for 2 months, the cell efficiencies of LS and
HLS-treated CIGS solar cells deteriorated from 9.4%
to 7.9% and 14.7% to 12.7%, respectively. All cell
parameters, especially FF showed a reversible behavior
for the LS-treated cell. Both of the Voc and Jsc gradually
increased during the LS. As a result, the efficiency of
LS-treated cell was recovered and increased from 7.9%
to 12.5% by LS for 30 min without intentional heating.
The HLS-treated cell showed almost no change in the
Voc and Jsc after keeping the device in the dark for
2 months. In contrast, the FF slightly deteriorated from
0.675 to 0.607, and it recovered to the initial value by LS
for 30 min without intentional heating. As a result, the cell
efficiency was recovered to the initial value of 14.7%. The
origin of the reversible behavior for the FF is currently Figure 4. X-ray photoelectron spectroscopy depth profile of S/
unclear, and further investigations are required to under- (S + O) relative atomic concentration ratios of ZnS(O,OH)/CIGS
stand this phenomenon. stacked layers. A indicates post-deposition annealing in air at
The same CIGS absorber films were used in the experi- 200  C for 10 min, HS indicates additional annealing in air at
ments. However, the efficiencies of the as-fabricated test 130  C for 120 min, LS indicates one-sun light-soaking with no
cells were slightly different as a result of post-processing such intentional heating for 120 min, and HLS indicates one-sun light
as CBD and MOCVD. The Ga/(Ga + In) and Cu/(In + Ga) soaking at 130  C for 120 min. Depth profiles of Cu, In, Ga, and
atomic ratios for the CIGS film were 0.29 and 0.89, Se of the HLS-treated sample are shown to indicate the ZnS
respectively. (O,OH)/CIGS interface.

Figure 3. Basic cell parameters of as-fabricated (open symbols: □, △, ○) and post-treated (HS ■, LS ▲, and HLS ● for a processing
time of 120 min) solar cells (without anti-reflection coating).

Prog. Photovolt: Res. Appl. (2013) © 2013 John Wiley & Sons, Ltd.
DOI: 10.1002/pip
T. Kobayashi, H. Yamaguchi and T. Nakada Combined heat and light-soaking effects in CIGS solar cells with ZnS(O,OH)buffer layer

Zn(OH)2 spectra. The amount of oxygen used for the calcu-

lation of “S/(S + O) ratio” means ZnO, which excluded Zn
(OH)2.from O 1 s spectra.
The atomic concentrations of all elements were calcu-
lated using relative sensitivity factors. The depth profiles
of the Cu, In, Ga, and Se relative atomic concentrations
in the HLS treated sample are shown in Figure 4 to indicate
the ZnS(O,OH)/CIGS interface. As can be seen in this
figure, the S/(S + O) ratio was hardly changed by the HS
post-treatment from that of the air-annealed layers. In
contrast, the S/(S + O) ratio was clearly decreased by LS
through the entire film thickness. It should be noted that
the sulfur concentration decreased more sharply toward
the surface of the CBD-ZnS(O,OH) layer in the case of
HLS treatment. The oxygen concentration increased
toward the surface of the CBD-ZnS(O,OH) layer. Further
experiments were performed to separate the effects of air
oxidation. It was found that no increase in oxygen was
observed in the CBD-ZnS(O,OH) layer when HLS was
carried out in a vacuum. This result suggests that the
Figure 5. X-ray photoelectron spectroscopy depth profile of
increase in oxygen in the ZnS(O,OH) layer was caused
(OH)2/[(O + (OH)2] relative atomic concentration ratios of ZnS
by oxidation during HLS post-treatment. A decrease in
(O,OH)/CIGS stacked layers shown in Figure 4.
the sulfur content was also observed. The low bond
dissociation energy of ZnS [25] suggests its decomposi-
tion under one sun illumination by a photochemical reac-
It has been demonstrated in a previous paper that the
tion [26]. The decomposed Zn atoms are then oxidized
conduction band offset (CBO) at the ZnS(O,OH)/CIGS
in air. As a result, the sulfur content decreased in ZnS
interface is a moderate “spike” of 0.2–0.3 eV for the S/
(O,OH) buffer layer. The photochemical reaction could
(S + O) ~0.6 eV, and it increases with increasing S/(S + O)
be enhanced at elevated temperatures under one-sun
atomic ratio[28]. The CBM value increases with increasing
illumination. An XPS peak of around 166 eV corresponding
S/(S + O) atomic ratio ranging from 0.58 to 0.75[28]. In
to sulfate [27] was not observed for the HS, LS and
contrast, the valence-band maximum (VBM) value is
HLS-treated ZnS(O,OH)/CIGS samples. Thus, it is
almost constant [28]. Although a more accurate analysis
suggested that the sulfate did not affect the cell perfor-
of the interface such as inverse photoemission spectros-
mances and film properties of the HS, LS and HLS treated
copy(IPES) [29] is required for further understanding of
samples.
the absolute CBO value, the S/(S + O) after LS and HLS
It is well-known that the conduction band minimum
decreased to around 0.6. This result suggests that the
(CBM) depends not only on the S/(S + O) ratio but also
CBO is a moderate “spike”. Therefore, we hypothesized
on the (OH)2/[O + (OH)2] ratio [28].
that the improvement in cell performances after LS
Although the hydroxide possibly decomposes in oxide
and HLS treatments was due to the obvious decrease of the
by annealing, there was almost no compositional change
S/(S + O) atomic ratio at the outer surface region and the
in (OH)2/[O + (OH)2] for the HS, LS and HLS-treated
slight decrease of the S/(S + O) atomic ratio at the interface
samples, as shown in Figure 5.
between the ZnS(O,OH) and CIGS layers, implying a rear-
In this experiment, HS, and HLS post-treatment were
rangement of the CBO at the ZnS(O,OH)/CIGS interface.
carried out to the completed CIGS solar cells at 130  C
for 120 min. However, air-annealing of ZnS(O,OH)/CIGS
stacked layer at 200  C for 10 min was carried out before
HS, LS and HLS post-treatment. Accordingly, it is sug- 4. CONCLUSIONS
gested that the hydroxide had already decomposed during
the air-annealing at 200  C after CBD process. Therefore, The effects of air annealing, LS, and HLS on cell perfor-
the (OH)2/[O + (OH)2] ratio was not changed. A further mances were investigated for ZnS(O,OH)/CIGS thin-film
experiment was carried out to check the detection limit of solar cells. It was found that the HLS, a combination of
the XPS system. In this experiment, an Ar ion-beam LS and air annealing is the most effective process for
sputter etching was operated at 0.5 keV as far as possible, improving the cell performance of ZnS(O,OH)/CIGS
to avoid the decomposition of Zn(OH)2 by the Ar ion- devices. The cell efficiencies of ZnO:B/ZnS(O,OH)/CIGS
beam sputter etching. The ZnS(O,OH) buffer layer clearly solar cells drastically improved from 8.5% to 17.5% after
showed a higher Zn(OH)2 concentration after the ammonia HLS treatment at 130  C, under AM1.5, 100 mW/cm2
rinsing treatment. In contrast, the (OH)2/[O + (OH)2] ratio illumination for 120 min. A total area efficiency of 18.4% with
showed almost no change after HLS post-treatment. Voc = 683 V, Jsc = 35.4 mA/cm2, and FF = 0.761 was achieved

Prog. Photovolt: Res. Appl. (2013) © 2013 John Wiley & Sons, Ltd.
DOI: 10.1002/pip
Combined heat and light-soaking effects in CIGS solar cells with ZnS(O,OH)buffer layer T. Kobayashi, H. Yamaguchi and T. Nakada
for the HLS-treated cell with an MgF2 anti-reflection coat-
ing. The FF and Voc slightly increased after LS treatment.
In contrast, not only the Voc and FF, but also Jsc were
increased by the HLS post-treatment. XPS analysis
revealed that the S/(S + O) atomic ratio decreased not only
in the surface region but also in the interface region
between the ZnS(O,OH) and CIGS layers, implying the shift
to an adequate CBO at the ZnS(O,OH)/CIGS interface.
REFERENCES
1. Nakada T, Furumi K, Mizutani M, Hagiwara Y, Ohashi
D, Kunioka A. High efficiency Cu(In,Ga)Se2 thin film
solar cells with CBD-ZnS buffer layers. Solar Energy
Materials and Solar Cells 2001; 67(1-4): 255–260.
2. Nakada T, Mizutani M. 18% efficiency Cd-free Cu(In,
Ga)Se2 thin-film solar cells fabricated using CBD-ZnS
buffer layers. Japanese Journal of Applied Physics
2002; 41(2B): L165–167.
3. Nakada T, Hongo M, Hayashi E. Band offset of high-
efficiency CBD-ZnS/CIGS thin film solar cells. Thin
Solid Films 2003; 431-432: 242–248.
4. Naghavi N, Abou-Ras D, Allsop N, Barreau N,
Bücheler S, Ennaoui A, Fischer C-H, Guillen C,
Hariskos D, Herrero J, Klenk R, Kushiya K, Lincot D,
Menner R, Nakada T, Platzer-Björkman C, Spiering S,
Tiwari AN, Törndahl T. Buffer layers and transparent
conducting oxides for chalcopyrite Cu(In,Ga)(S,Se)2
based thin film photovoltaics: present status and current
developments. Progress in Photovoltaics: Research and
Applications 2010; 18: 411–433.
5. Contreras MA, Nakada T, Hongo M, Pudov AO, Sites
JR. ZnO/ZnS(O,OH)/Cu(In,Ga)Se2/Mo solar cell with
18.6% efficiency. Proceedings of 3rd World Conference
on Photovoltaic Energy Conversion 2003; 1: 570–573.
6. Powalla M, Hariskos D, Jackson P, Kessler F, Paetel S,
Wischmann W, Witte W, Würz R. CIGS solar cells
with efficiencies > 20%: current status and new devel-
opments. Proceedings of the 26th European Photovol-
taic Solar Energy Conference, 2011; 2416–2420.
7. Hariskos D, Menner R, Jackson P, Paete S, Witte W,
Wischmann W, Powalla M, Bürkert L, Kolb T, Oertel
M, Fimmler B, Fuchs B. New reaction kinetics for a
high-rate chemical bath deposition of the Zn(S,O)
buffer layer for Cu(In,Ga)Se2-based solar cells. Progress
in Photovoltaics: Research and Applications 2012;
online published, DOI: 10.1002/pip.1244.
8. Zimmermann U, Ruth M, Edoff M. Cadmium-free
CIGS mini-modules with ALD-grown Zn(O,S)-based
buffer layers. Proceedings of the 21st European Pho-
tovoltaic Solar Energy Conference, 2006; 1831–1834.
9. Nakamura M, Chiba Y, Kijima S, Horiguchi K,
Yanagisawa Y, Sawai Y, Ishikawa K, Hakuma H.
Achievement of 17.5% efficiency with 30  30 cm2-
sized Cu(In,Ga)Se,S)2 submodules. Proceeding of
38th IEEE Photovoltaic specialists Conference,
2012, Austin.
10. Yagioka T, Nakada T. Cd-free flexible Cu(In,Ga)Se2
thin film solar cells with ZnS(O,OH) buffer layer on
Ti foils. Applied Physics Express 2009; 2: 072201.
11. Nakada T, Furumi K, Kunioka A. High efficiency Cd-
free Cu(In,Ga)Se2 thin film solar cells with chemically
deposited ZnS buffer layers. IEEE Electron Devices
1999; 46(10): 2093–2097.
12. Kushiya K, Yamase O. Stabilization of PN heterojunc-
tion between Cu(InGa)Se2 thin-film absorber and ZnO
window with Zn(O, S, OH)x buffer. Japanese Journal
of Applied Physics 2000; 39: 2577–2582.
13. Eisgruber IL, Granata JE, Sites JR, Hou J, Kessler J.
Blue-photon modification of nonstandard diode barrier
in CuInSe2 solar cells. Solar Energy Materials and
Solar Cells 1998; 53: 367–377.
14. Pudov AO, Sites JR, Contreras MA, Nakada T, Schock
H-W. CIGS J–V distortion in the absence of blue
photons. Thin Solid Films 2005; 480–481: 273–278.
15. Hariskos D, Fuchs B, Menner R, Naghavi N, Hubert
C, Lincot D, Powalla M. The Zn(S,O,OH)/ZnMgO
buffer in thin-film Cu(In,Ga)(Se,S)2-based solar cells
part II: magnetron sputtering of the ZnMgO buffer layer
for in-line co-evaporated Cu(In,Ga)Se2 solar cells. Prog-
ress in Photovoltaics: Research and Applications 2009;
17: 479–488.
16. Platzer-Björkman C, Kesseler J, Stolt L. Atomic layer
deposition of Zn(O,S) buffer layers for high efficiency
Cu(In,Ga)Se2 solar cells. Proceedings of the 3rd World
Conference on Photovoltaic Energy Conversion, 2003;
461–464.
17. Platzer-Björkman C, Törndahl T, Abou-Ras D,
Malmström J, Kessler J, Stolt L. Zn(O,S) buffer layers
by atomic layer deposition in Cu(In,Ga)Se2 based thin
film solar cells: band alignment and sulfur gradient.
Journal of Applied Physics 2006; 100: 044506-1–9.
18. Minemoto T, Okamoto A, Takakura H. Sputtered
ZnO-based buffer layer for band offset control in Cu
(In,Ga)Se2 solar cells. Thin Solid Films 2011; 519(21):
7568–7571.
19. Nakada T, Mizutani M, Hagiwara Y, Kunioka A. High
efficiency Cu(In,Ga)Se2 thin film solar cells with
CBD-ZnS buffer layers. Solar Energy Materials &
Solar Cells 2001; 67(1–4): 255–260.
20. Nakada T, Kobayashi T, Kumazawa T, Yamaguchi H.
Impacts of post-treatments on cell performance of
CIGS solar cells with Zn-compound buffer layers.
IEEE Journal of Photovoltaics 2012; online published.
DOI: 10.1109/JPHOTOV.2012.2223456
21. Kobayashi T, Yamauchi K, Mise T, Nakada T. Trans-
parent conducting ZnO:B thin films by UV-assisted
Prog. Photovolt: Res. Appl. (2013) © 2013 John Wiley & Sons, Ltd.
DOI: 10.1002/pip
T. Kobayashi, H. Yamaguchi and T. Nakada Combined heat and light-soaking effects in CIGS solar cells with ZnS(O,OH)buffer layer
MOCVD using TEB for Cu(In,Ga)Se2 solar cells.
Japanese Journal of Applied Physics 2012; 10NC09-01.
22. Sang B, Nagoya Y, Kushiya K, Yamase O. Solar
Energy Materials & Solar Cells 2003; 75: 179–184.
23. Liu X D, Jiang E Y, Li Z Q. Low temperature electri-
cal transport properties of B-doped ZnO films. Journal
of Applied Physics 2007; 102, 073708.
24. Minemoto T, Hashimoto Y, Satoh T, Negami T,
Takakura H, Hamakawa Y. Cu(In,Ga)Se2 solar cells
with controlled conduction band offset of window/Cu
(In,Ga)Se2 layers. Journal of Applied Physics 2001;
89(12): 8327–8330.
25. Amin EA, Truhlar DG. Zn coordination chemistry:
development of benchmark, suites for geometries,
dipole moments, and bond dissociation energies and
their use to test and validate density functionals and
molecular orbital theory. Journal of Chemical Theory
and Computation 2008; 4: 75–85.
Prog. Photovolt: Res. Appl. (2013) © 2013 John Wiley & Sons, Ltd.
DOI: 10.1002/pip
26. Hass G, Heaney J B, Hunter W R, Angel D W. Effect
of UV irradiation on evaporated ZnS films. Applied
Optics 1980; 19(15): 2480–2481.
27. Kundu S, Olsen CL. Chemical bath deposited zinc
sulfide buffer layers for copper indium gallium sulfur-
selenide solar cells and device analysis. Thin Solid Films
2005; 471(1-2): 298–303.
28. Terada N, Kirihara A, Takahae T, Shiota Y, Niki S,
Ishizuka S, Shibata H, Yamada A, Matsubara K.
Characterization of band alignment at buffer/absorber
interfaces and grain boundaries in CIGS-based solar
cells. Technical digest of the 21st International Photo-
voltaic and Science and Engineering Conference
(PVSEC-21), 2011, Fukuoka.
29. Fischer C–H, Bar M, Glatzel T, Lauermann I. Interface
engineering in chalcopyrite thin film solar devices.
Solar Energy Materials and Solar Cells 2006; 90(10):
1471‐1485.