Thin Solid Films 431 432 (2003) 242248

Band offset of high efficiency CBD-ZnSyCIGS thin film solar cells

Tokio Nakadaa,*, Masashi Hongoa, Eiji Hayashib
a

Department of Electrical Engineering and Electronics, Aoyama Gakuin University, Setagaya-ku, Tokyo 157-8572, Japan
b
Toray Research Center, Inc., Otsu, Shiga Prefecture 520-8567, Japan

Abstract
The band offset at the CBD-ZnSyCu(In,Ga)Se2 (CIGS) interface and solar cells performance were investigated by means of
X-ray photoelectron spectroscopy (XPS). The valence band maximum and valence band offset at the chemical bath deposition
(CBD)-ZnSyCIGS interface region was directly measured using a XPS spectral multiplot. We found that the conduction band
offset (CBO) at the CBD-ZnSyCIGS (ordered vacancy compound, OVC) interface was smaller than that of the evaporated ZnSy
CIGS (OVC) interface. However, the CBO for the CBD-ZnSyCIGS (OVC) interface was still quite large for fabrication of high
efficiency devices, although, in fact, high efficiency CBD-ZnSyCIGS devices were fabricated with good run-to-run reproducibility.
The bandgap dependence of cell performance for CBD-ZnSyCIGS devices (large CBO) showed a tendency similar to that of
CBD-CdSyCIGS devices (small CBO). Therefore, the observed decrease in cell performance for high bandgap devices is not
interpreted in terms of the CBO. These results suggest that the band offset is not the predominant factor in achieving high
efficiency CBD-ZnSyCIGS thin film solar cells. This finding suggests that the recombination mechanism of those wide-gap alloys
is a bulk recombination.
2003 Elsevier Science B.V. All rights reserved.
Keywords: Cu(In,Ga)Se2 ; Band offset; CBD-ZnS; Thin film solar cells; X-ray photoelectron spectroscopy

1. Introduction
Over the past few years Cu(In,Ga)Se2 (CIGS)-based
thin film solar cells with efficiencies exceeding 18%
have been achieved by several groups w13x. These
CIGS solar cells were typically fabricated using a
cadmium sulfide (CdS) buffer layer deposited by chemical bath deposition (CBD) in order to protect junction
region from sputtering damage during subsequent zinc
oxide (ZnO) deposition andyor to modify the surface
of CIGS absorber w46x. However, further improvement
in the short-circuit-current (Jsc) can be achieved by
replacing CdS with other appropriate wider bandgap
buffer materials. Moreover, the use of cadmium is
undesirable from the viewpoint of environmental safety.
Therefore, non-Cd buffer materials including In(OH)3
w7,8x, In2S3 w7x, SnO2 w7x, Sn(S,O)2 w7x, ZnSe w7x,
Zn(Se,OH) w9,10x, In(OH,S) w11x, ZrO2 w7x, ZnS
w12,13x, ZnO w14x, Zn(O,S,OH) w15x, Zn(OH)2 w16x,
ZnInSe w17x have been investigated as alternative buffer
layers. Unfortunately, the conversion efficiencies of Cd*Corresponding author. Tel.: q81-3-5384-1198; fax: q81-3-53846410.
E-mail address: nakada@ee.aoyama.ac.jp (T. Nakada).

free devices fabricated using these materials were not

as high as those of devices fabricated using CBD-CdS
buffer layers.
One of the possible reasons for this is a conduction
band offset (CBO) of a heterojunction solar cell, since
a CdSyCuInSe2 solar cell shows a high conversion
efficiency for the CBO ranging from y0.5 to 0.4 eV
w18x. From this viewpoint, a CdS buffer layer seems
one of the best counter partners for CIGS-based thin
film solar cells, since the CBO of the CdSyCuInSe2
heterostructure is very small w1922x. In fact, a CIGS
thin film solar cell with an 18.8% total area efficiency
has been fabricated using this material combination w1x.
On the other hand, a large CBO of 1.58 eV has been
reported for a ZnSyordered vacancy compound (OVC)y
CuInSe2 thin film solar cell which showed poor cell
performance w23x. However, we have recently achieved
a Cd-free CIGS thin film solar cell with a conversion
efficiency of 18.1% using a CBD-ZnS buffer layer w24x.
In order to reveal the origins of this discrepancy, it is
necessary first to measure the band offset of the CBDZnSyCIGS interface, since the CBD-ZnS has different
properties from pure ZnS. We, therefore, have investigated the band offsets of a CBD-ZnSyCIGS stacked

0040-6090/03/$ - see front matter 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0040-6090(03)00265-7

T. Nakada et al. / Thin Solid Films 431 432 (2003) 242248

243

layer and an actual CIGS thin film solar cell by X-ray

photoelectron spectroscopy (XPS) analysis. We also
discuss the relationship between device performance and
the XPS results.
2. Experimental
CIGS films, 2.5-mm thick, were deposited onto Mocoated soda-lime glass (SLG) substrates by the three
stage process using a molecular beam epitaxy system.
CBD-ZnS layers were then chemically grown on the
CIGS thin films using a ZnSO4 (0.16 M)ammonia
(7.5 M)thiourea (0.6 M) aqueous solution at 80 8C
for 15 min. Approximately 100-nm thick CBD-ZnS
layers were deposited on the CIGS layers by repeating
the CBD process. The layer thickness was determined
by means of cross-sectional TEM. XPS analysis revealed
that a large amount of oxygen was included in the CBDZnS layers in the form of Zn(OH)2 and ZnO. Evidence
of NCS (N_ C_ S) bonds was also found by FTIR
measurements. Furthermore, thermal desorption spectroscopy analysis revealed that this material included
small amounts of C and S which probably originated
from the CS(NH2)2 (thiourea) during the CBD process.
X-ray diffraction analysis suggested that the film was
very complex and included ZnS, ZnO, Zn(OH)2 and
Zn(S,O) compounds. The film composition was estimated to be Zn:S:Os47.9: 27.8:24.2 from the XPS
analysis. A TEM analysis confirmed the coexistence of
wurtzite and sphalerite structures in the CBD-ZnS w25x.
The optical absorption coefficient a was derived from
the transmission and reflection curves of the 100-nm
thick CBD-ZnS thin films. The bandgap energy of CBDZnS was determined from the extrapolation of (ahn)2
vs. hn to 0, where hn is photon energy, and it was
estimated to be 3.7 eV. This value agrees well with that
of a CBD-ZnS thin layer published previously w26x.
The CBD-ZnSyCIGS stacked layers prepared by the
above method were divided into two pieces. One piece
was used for XPS analysis and the other was used for
fabrication of a CIGS solar cell in order to compare cell
performance and XPS results. The stacked layers were
air-annealed at 200 8C for 10 min in order to generate
similar interfacial properties as those of high efficiency
CBD-ZnSyCIGS thin film solar cells. XPS measurements were carried out using a ESCALAB220i-XL (VG
Scientific) with monochromatic Al Ka1,2 (1486.6 eV)
X-ray radiation under a base pressure of 1.0=10y7 Pa.
The XPS system was equipped with a magnetic focus
lens to increase the collection yield of photoelectrons,
which enables measurement of valence-band spectra.
The calibration of the Fermi energy was performed
using the Ag 3d5y2 (368.3"0.1 eV) peak of a sputtercleaned Ag surface. Ar ion-beam sputter-etching was
carried out with a differentially pumped ion gun operating at 3 keV at a pressure of 1.5=10y5 Pa. The

Fig. 1. XPS depth profile of a CBD-ZnS(100 nm)yCIGS(2 mm)

stacked layer after air-annealing, showing atomic concentration as a
function of the repeat number of sputter-etching (Level: L) and sputtering time.

accuracy of the XPS measurement is estimated to be

within "0.1%. XPS spectral multiplots were taken by
repeating the cycle of sputter-etching and measurement.
In order to avoid peak shifting due to specimen chargeup, the surface of specimen was grounded. The chemical
shifts of core-levels emissions such as the In 3d and Zn
2p are indistinguishable, hence, can be neglected. These
peaks are, therefore, suitable to serve as a monitor for
peak-shifts due to charge-up. No significant peak-shifts
due to charge-up were observed during all
measurements.
3. Results and discussion
Fig. 1 shows an XPS depth profile of a CBD-ZnS(100
nm)yCIGS(2 mm) stacked layer after air-annealing,
representing the atomic concentration as a function of
the repeat number of the sputter-etching (Level: L) and
sputtering time. The CBD process was carried out
immediately after the CIGS deposition in order to avoid
undesirable surface oxidization. A ZnO:AlyCBD-ZnSy
CIGSyMoySLG solar cell using the same CBD-ZnSy
CIGS stacked layer simultaneously deposited showed an
efficiency of 16.5% (open-circuit voltage Vocs0.610 V,
short-circuit-current Jscs36.9 mAycm2 , fill factor FFs
0.730) without an anti-reflection coating. The average
film composition measured by ICP was Cuy(InqGa)s
0.96 and Gay(InqGa)s0.33. An OVC such as
Cu(InGa)3Se5 is presumably present at the surface
region of CIGS thin film, since a Cu poor film composition was found at the surface of the CIGS layer as
shown in Fig. 1. It should be noted that the oxygen
content in the CBD-ZnS layer increases toward the
CBD-ZnSyCIGS interface boundary and a small amount

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T. Nakada et al. / Thin Solid Films 431 432 (2003) 242248

Fig. 2. XPS spectral multiplot of the same sample as shown in Fig.

1, indicating the In 4d peaks of CIGS, the Zn 3d peaks of CBD-ZnS,
and the valence structure of both layers.

Fig. 3. XPS multiplot for an actual MgF2yZn:Al(600 nm)yCBDZnS(110 nm)yCIGSyMoySLG thin film solar cell with an efficiency
exceeding 17%.

of oxygen is observed inside of the CIGS layer. In

contrast the sulfur concentration decreases rapidly at the
interface boundary and cannot be observed inside of the
CIGS layer. These results imply that oxygen is probably
more active than sulfur in the initial stages of the CBD
process. It is also evident that Zn is detectable within
the CIGS layer, whereas Cu decreases toward interface
boundary. This result may suggest the substitution of Zn
for Cu, resulting in an inverted surface layer due to the
formation of donor levels. However, further investigation
is required to confirm Zn diffusion, since our CIGS thin
films possessed grain boundaries.
Fig. 2 shows an XPS spectral multiplot of the same
sample as shown in Fig. 1, indicating the In 4d peaks
of CIGS, the Zn 3d peaks of CBD-ZnS, and the valence
structure of both layers. Two things are immediately
notable from the figure. First, the valence band maximum (VBM, the energy measured from Fermi energy
Ef) of both the CBD-ZnS and CIGS layers can be
clearly seen, and hence, the valence band offset (VBOs
DEVsVBMCIGSyVBMZnS) can be visually observed in
the low energy region. The VBO could be directly
determined from this figure to be approximately 1.3 eV.
Another finding is an energy-shift of the Zn 3d peak as
is discussed later.
A similar multiplot was obtained for a MgF2 y
ZnO:Al(600 nm)yCBD-ZnS(110 nm)yCIGSyMoySLG
thin film solar cell with an efficiency exceeding 17%.
The CBD-ZnS layer for this device was found to be
different from that shown in Figs. 1 and 2, although it
was prepared under the same conditions as described
above. For this structure, most of Zn 3d peak intensity
originated from the ZnO:Al (600 nm) layer, making it
more difficult to separate the Zn 3d signals of the CBDZnS layer from that of ZnO:Al at the CBD-ZnSyCIGS
interface. However, the abrupt-shaped VBO for the
ZnOyZnSyCIGS can be again seen in Fig. 3, and the

VBO between the ZnO and CIGS layers is estimated to

be approximately 3 eV. On the other hand, an energyshift of the Zn 3d peak was not observed due to the
large thickness of the ZnO:Al (600 nm) layer as compared to CBD-ZnS layer (100 nm).
In Fig. 4a, an enlarged version of the Zn 3d peak
from Fig. 2, a peak shift in the Zn 3d can be more
clearly seen. Similar data taken from Fig. 3 is also
shown for comparison. The Zn 3d peak of the CBDZnS layer shifts toward higher binding energies at the
interface and surface regions. On the other hand, the Zn
3d peak of the ZnO:Al appearing in Fig. 4b is approximately 0.3 eV higher in energy than that of the CBDZnS layer. Therefore, it is concluded that the Zn 3d
peak shifts towards higher binding energy due to oxidization. Based on this result, the peak-shift at the interface
in Fig. 4a may be attributed to grading of the OyS
atomic ratio in the CBD-ZnS layer. On the other hand,
the peak-shift in the surface region may be due to
surface oxidization of CBD-ZnS.
Fig. 5 shows the energy difference between the VBM
and the Zn 3d peak (EVZn3d) as well as the VBO and

Fig. 4. Zn 3d peak shifts for a (a) CBD-ZnS layer and (b) a sputtered
ZnO:Al layer.

T. Nakada et al. / Thin Solid Films 431 432 (2003) 242248

245

Fig. 7. Zn 3d core-level spectra taken from the middle part (L20) of

the CBD-ZnS layer.
Fig. 5. The energy difference between the VBM and the Zn 3d peak,
the VBO, and the CBO as a function of the number of sputter-etching
cycle (L), which corresponds to the distance from the surface of CBDZnS layer.

CBO as a function of the repeat number of the sputteretching cycle (L) which corresponds to the distance
from the surface of CBD-ZnS layer. The VBO (DEV)
can be derived from the equation DEVsEVIn4dy
EVZn3dyDECL, where DECL, EVIn4d and EVZn3d, are
the energy difference between the In 4d and Zn 3d
levels, the energy difference between the VBMCIGS and
the In 4d level, and the energy difference between the
VBMZnS and the Zn 3d level, respectively. The CBO
(DEc) can be derived from the equation DEcsEgZnSy
EgCIGSyDEV, where EgZnSs3.7 eV. The EgCIGS was
given by the equation, EgCu(In,Ga)3Se5s1.19q0.415xq
0.240x 2 w27x assuming the presence of the
Cu(In1yx,Gax)3Se5 (OVC) phase. As can be seen in the
figure, EVZn3d increases toward the interface, hence the
VBO decreases and the CBO increases at the CBDZnSyCIGS interface. This result originates from the

Fig. 8. XPS spectra from the CBD-ZnSyCIGS interface region (L44).

increase in oxygen content in the CBD-ZnS layer as

discussed above.
In order to obtain more precise values of the band
offsets, the peak separation of the In 4d and Zn 3d corelevels was measured. Fig. 6 shows In 4d core-level
spectra taken from the CIGS region (L80) of Fig. 2.
The positions of the In 4d5y2,3y2 spinorbit components
for the CIGS surface are 17.78 and 18.64 eV (17.38
and 18.27 eV relative to VBM), respectively. The spin
Table 1
The peak energies of the In 4d and Zn 3d core-levels relative to VBM
and the reference core-levels of OVC and evaporated ZnS measured
by UPS w23x

Fig. 6. In 4d core-level spectra taken from the CIGS region (L80) of

Fig. 2.

EVBMyEcore

This work (XPS)

UPS

EVBM In 4d5y2 (CIGS: eV)

EVBM In 4d3y2 (CIGS: eV)
EVBM Zn 3d (CBD-ZnS: eV)

17.38
18.27
8.83

17.19

8.94

T. Nakada et al. / Thin Solid Films 431 432 (2003) 242248

246

Table 2
The band offsets and core-levels of CBD-ZnSyCIGS (OVC)
CIGS (L80)

ZnS (L20)

ZnSyCIGS (L44)

Gay(InqGa)

VBMZn 3d5y2 (eV)

In 4dZn 3d (eV)

DEV (eV)

DEc (eV)

Middle part of CBD-ZnS (L20)

17.62
0.23a
17.38
0.33a
17.39
0.33b
17.37
0.60a

8.73
8.71
8.72
8.53

7.51
7.37
7.43
7.58

1.38
1.30
1.24
1.26

1.06
1.08
1.14
1.02

ZnSyCIGS Interface (L44)

17.62
0.23a
17.38
0.33a
17.39
0.33b

9.17
9.06
8.95

7.51
7.37
7.43

0.94
0.95
1.01

1.50
1.43
1.37

VBMIn 4d5y2 (eV)

L, number of sputter-etchings. DEcsEgZnSyEgCIGS yDEV , EV sEVIn4d yEVZn3d yDECL , EgZnS s3.7 (eV), EgCu(InGa)3Se5s1.19q0.415xq
0.240x 2 w27x.
a
After annealing.
b
Before annealing.

orbit components shift by approximately 0.4 eV to lower

binding energy. Fig. 7 shows Zn 3d core-level spectra
taken from the middle part (L20) of the CBD-ZnS layer.
The positions of the Zn 3d5y2,3y2 spinorbit components
for the CBD-ZnS are 10.13 and 10.36 eV (8.71 and
8.94 eV relative to the VBM), respectively. The spin
orbit components shift by approximately 1.4 eV to lower
binding energy. Fig. 8 shows XPS spectra from the
CBD-ZnSyCIGS interface. DECL is derived from this
figure. The peak energies of the In 4d5y2 and Zn 3d
core-levels relative to VBM are comparable to the
reference core-levels of OVC and ZnS measured by
UPS w23x, as shown in Table 1. The peak energy of the
In 4d5y2 emission maintained a constant value of 17.38
eV in the region from the interface boundary (L44) to
the bulk region of CIGS (L80). Therefore, it can be
considered that the influence of long-term sputter-etching on the peak shift can be neglected in this experiment.
Table 2 summarizes the band offsets of CBD-ZnSy
CIGS (OVC). As mentioned above, the Zn 3d5y2 peak
varies from the surface to the CBD-ZnSyCIGS (OVC)
interface. The upper and lower parts of Table 2 represent
data taken at the middle (L20) and interface regions
(L44), respectively. The VBO of the upper part is
approximately 0.3 eV higher than that of the lower part.
If the bandgap energy of CIGS becomes large, the CBO
could become small, since the VBO shows almost no
change with respect to Ga content in CIGS. However,
the VBO and CBO in both regions showed little change
with the average Ga content in CIGS within the accuracy

of the XPS measurement ("0.1 eV), although a slight

decrease in the CBO was observed for a Ga content of
0.6. At the interface region (L44), the VBO and CBO
were determined to be approximately 1.0 eV and 1.4
eV, respectively. On the other hand, the VBO and CBO
in the middle region of the CBD-ZnS (L20) were
determined to be approximately 1.3 and 1.1, respectively.

Table 3
The band offsets for the CBD-ZnSyCIGS and evaporated ZnSyCIGS
interfaces
Buffer

DEV (eV)

DEc (eV)

CBS-ZnS
Evaporated ZnS

1.4
0.8

1.0
1.6

Fig. 9. SEM photographs of CIGS thin films with various Ga content.

T. Nakada et al. / Thin Solid Films 431 432 (2003) 242248

247

Fig. 10. A comparison of basic cell parameters for CIGS solar cells fabricated with CBD-ZnS and CBD-CdS buffer layers.

Therefore, it is evident that control of the OyS atomic

ratio in CBD-ZnS is important in order to minimize the
CBO.
An additional experiment was performed to investigate the difference in the band offsets between evaporated pure ZnS and CBD-ZnS which includes impurities,
such as ZnO and Zn(OH)2. The XPS spectra were taken
from three individual samples, thin CBD (or evaporated)-ZnS(3 nm)yCIGS, thick CBD (or evaporated)ZnS(100 nm)yCIGS, and a CIGS thin film (2 mm),
The samples were annealed at 200 8C in air for 10 min,
and then sputter-etched for 20 s in order to eliminate
surface contamination. Table 3 shows the band offsets
determined by the same method mentioned above for
the CBD-ZnSyCIGS and evaporated ZnSyCIGS interfaces. The value of the CBO for evaporated ZnS agrees
well with that reported previously w23x. The CBO of
CBD-ZnSyCIGS (OVC) is 0.6 eV smaller than that for
evaporated ZnS, and is almost the same as that shown
in the upper part of Table 2. The reason for the decreased
CBO of CBD-ZnS may be interpreted as being due to
the compositional difference between pure ZnS and
CBD-ZnS. On the other hand, the intermixing or diffusion at the CBD-ZnSyCIGS interface during CBD process has been reported by several groups w46,28x.
Therefore, another possible reason is the intermixing or
diffusion, which may modify the energy band diagram

at the heterointerface. However, further investigation is

required to clear the cause for this result.
As mentioned above, the CBO of CBD-ZnSyCIGS
(OVC) is quite large for fabrication of high efficiency
devices. Furthermore, CIGS absorbers with different Ga
content have almost the same CBO values as shown in
Table 2. Therefore, if the band offset is the predominant
factor limiting cell performance, high efficiencies could
be obtained even for high-Ga CIGS devices (for instance
Gay(InqGa)s0.6). We have, thus, fabricated CBDZnSyCIGS thin film solar cells with various Ga contents,
and compared these to the CBD-CdSyCIGS devices.
The same CIGS absorber layers as shown in Fig. 9 were
used in this experiment. From this experiment it is
evident that high efficiency devices were not obtained
using CIGS absorbers with high-Ga content. Fig. 10
shows a comparison of basic cell parameters for CIGS
solar cells fabricated with CBD-ZnS and CBD-CdS
buffer layers. For the case of CBD-CdSyCIGS devices
(small CBO value), the efficiency decreased rapidly
with increasing bandgap energy above approximately
1.3 eV corresponding to a Ga content of 0.5. This
phenomenon is well known for CIGS devices w29x,
although the reason is not clear at present. On the other
hand, a similar bandgap dependence on the cell parameters was observed for CBD-ZnSyCIGS devices,
which had large CBO values. Therefore, the decrease in

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T. Nakada et al. / Thin Solid Films 431 432 (2003) 242248

efficiency found for Eg values above 1.3 eV are not

interpreted in terms of band offset. It is also found that
the band offset is not the predominant factor in achieving
high efficiency CIGS solar cells, since comparable
efficiencies were obtained for devices with both CBDCdS and CBD-ZnS buffer layers. Recent papers found
that the recombination mechanism of those wide-gap
alloys is a bulk recombination w30x. This is consistent
with the present finding that the CBO does not influence
the general trend.
4. Conclusions
The VBM and VBO at the CBD-ZnSyCIGS interface
region could be directly observed in a XPS spectral
multiplot. The CBO increased slightly near the CBDZnSyCIGS interface with a shift in the Zn 3d peak due
to increased oxygen content in the CBD-ZnS layer.
Therefore, control of the OyS atomic ratio in the CBDZnS layer is important to minimize the CBO. The
bandgap dependence of cell performance for the CBDZnSyCIGS devices (large CBO) showed a tendency
similar to that of CBD-CdSyCIGS devices (small CBO).
Therefore, the observed decrease in cell efficiency above
a bandgap energy of 1.3 eV should not be interpreted
in terms of the CBO. This finding suggests that the
recombination mechanism of those wide-gap alloys is a
bulk recombination. The CBO of a CBD-ZnSyCIGS
was smaller than that of evaporated ZnSyCIGS, which
may be interpreted as being due to compositional difference between pure ZnS and CBD-ZnS which includes
other Zn compounds such as ZnO and Zn(OH)2. However, the CBO for the CBD-ZnSyCIGS (OVC) interface
is still quite large for the fabrication of high efficiency
devices, although high efficiency CBD-ZnSyCIGS
devices were fabricated with good run-to-run reproducibility. These results suggest that the band offset is not
the predominant factor for achieving high efficiency
CBD-ZnSyCIGS thin film solar cells.
Acknowledgments
This work was supported in part by NEDO as a part
of the New Sunshine Program. The authors would like
to thank M. Mizutani and P. Ohashi for their experimental support.
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