Solar Energy Materials & Solar Cells 67 (2001) 31}40

High-e$ciency Cd-free CIGSS thin-"lm solar cells

with solution grown zinc compound bu!er layers
A. Ennaoui *, S. Siebentritt , M.Ch. Lux-Steiner , W. Riedl
,
F. Karg

Hahn-Meitner-Institut Bereich Solarenergieforschung SE Glienicker Stra}e 100, D-14109 Berlin, Germany

Siemens Corporate Technology, Siemens Solar GmbH, Postfach 460705, Germany

Abstract
Zn-compounds Zn(X,OH) (X"S,Se) bu!er layers have been deposited by chemical bath
(CBD) process on Cu(In,Ga)(S,Se) (CIGSS) with the aim of developing Cd-free CIGSS-based

devices. The "lms are produced in alkaline aqueous solution containing ZnSO , ammonia NH


and XC(NH ) . Optimum deposition conditions were established. The temperature ( ) of



the chemical bath is found to be critical for the device quality. The thickness and good surface
coverage were controlled by XPS-UPS photoemission spectroscopy. SEM study showed that
the growth of ZnSe nuclei on CIGSS proceeds in lateral direction. Once the surface is covered
the growth takes place in vertical direction . The ZnSe clusters grow in size and their elongated
shapes cover the CIGSS surface. High e$ciency of over 13% was obtained for both CIGSS/
Zn(S,OH) and CIGSS/Zn(Se,OH)-based solar cells. Solar cells with CIGSS/Zn(Se,OH) /ZnO/
V
MgF structure show an active area e$ciency up to 15.7%. Using Zn(Se,OH) bu!er layer,

e$ciency of 11.7% was achieved with a 20 cm aperture-area monolithic minimodule.  2001
Elsevier Science B.V. All rights reserved.
Keywords: Cu(In,Ga)(SSe) ; Zn(Se,OH); Zn(S,OH); Thin-"lm mini-modules


1. Introduction
Thin-"lm ternary chalcopyrite semiconductors, CuInSe (E "1.04 eV), and its
 
solid solutions with CuGaSe and CuInS (CIGSS) are among the leading candidates


for low-cost terrestrial photovoltaic devices. Photovoltaic conversion e$ciencies up
to 18.8% on a laboratory scale [1}6] and 11.8% for monolithically integrated
* Corresponding author. Tel.:#00-49-30-8062-3038; fax:#00-49-30-8062-2434.
E-mail address: ennaoui@hmi.de (A. Ennaoui).
0927-0248/01/$ - see front matter  2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 7 - 0 2 4 8 ( 0 0 ) 0 0 2 6 0 - 9

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A. Ennaoui et al. / Solar Energy Materials & Solar Cells 67 (2001) 31}40

submodules (1.2 kW) [7] have been achieved. These high-e$ciency values have been
closely tied to the use of an interfacial bu!er layer deposited by CBD, which is CdS
layer in the best cells. However, for industrial production and for environment
protection, it would be desirable to replace CdS by a less toxic alternative bu!er
material which is, in addition, more transparent in the blue spectral range. Materials
such as Zn(X,OH) or In(X,OH) with X"S,Se deposited by chemical bath process are
promising candidates and have achieved an e$ciency up to 15% [6}18]. Previously,
we have investigated the growth conditions of the Zn(Se,OH) deposited on glass
substrate. The "lms have been characterized by XRD, TEM, RBS techniques. The
"lms were found to be Zn-rich with an optical band gap E of 2.9 eV. The "lms consist

of small nanocrystals with dimensions of 20}25 As . A typical lattice plane spacing of
d "3.2 As was observed which corresponds to the cubic structure of ZnSe [15]. We

reported a 13.7% total area e$ciency with CIGSS/Zn(Se,OH)/ZnO/MgF structure

[16]. The CIGSS absorber layers were provided by Siemens Solar Industry (California). The present paper reports on the preparation condition of chemical bath
deposited Zn(Se,OH) and Zn(S,OH) on CIGSS provided by Siemens Solar GmbH
(Germany). Conditions for the formation of good-quality "lms on CIGSS substrate
are presented. The growth mechanism of Zn(Se,OH) bu!er layers on CIGSS are
studied by scanning electron microscopy (SEM). Photovoltaic performance of
CIGSS/Zn(Se,OH)-based solar cell and mini-modules are reported.
2. Experimental details
2.1. Chemical bath for deposition of Zn(X,OH)
The preparative conditions for Zn(X,OH) are as follows. The metal precursor
ZnSO solution (0.4 M/l) and two di!erent ligands hydrazine hydrate NH NH



(25%) and ammonia NH (25%) were mixed under constant stirring. The resulting

solution (A) was turbid milky due to the formation of Zn(OH) . Excess of NH (25%)


was added to bind most of Zn(OH) as a complex ion. In order to decrease the free

metal ion concentration, the ratio of ammonia to hydrazine hydrate in this solution
was carefully adjusted.
The chalcogenide sources (solution B) consists of SeC(NH ) (8;10\ M/l) in an

alkaline bath or SC(NH ) (4;10\ M/l). The following conditions were used to

produce high-quality devices:
E Solution (A) is heated to .


E The CIGSS substrates are immersed, for few minutes.
E The solution B containing SeC(NH ) or SC(NH ) is added.


The #ow chart of the growth mechanism for Zn(OH) , ZnX and Zn(X,OH) is shown in

Fig. 1. The concentration of hydroxide [OH\] must be low enough for the hydrolysis
of XC(NH ) to take place mostly at the surface as follows:

XC(NH ) #OH\NHX\#CH N #H O,
(1)

 

HX\#OH\NX\#H O.
(2)


A. Ennaoui et al. / Solar Energy Materials & Solar Cells 67 (2001) 31}40

33

Fig. 1. Flow chart of growth mechanism for Zn(X,OH) (X"S, Se, O) by chemical bath.

This ensures that the ionic concentration product of Zn>and X\ in the bulk of the
bath is less than the solubility product of ZnX.
2.2. Device preparation
The CIGSS substrates were provided by Siemens Solar (MuK nchen). The CIGSS
thin-"lm solar cells were fabricated with two interface structures: CIGSS/Zn(Se,OH)
and CIGSS/Zn(S,OH). The window ZnO was deposited by sputtering in argon in two
layers: a high-resistivity layer of undoped ZnO to a thickness of 100 nm and a conductive layer of Ga-doped ZnO from a Ga O (5.7%)-doped ZnO to a thickness of
 
400 nm, evaporated Ni/Al grid formed as a front contact.

3. Results and discussion

3.1. Growth mechanism
To investigate the growth mechanism of Zn(Se,OH) bu!er layer, the Zn(Se,OH) was
sequentially grown on CIGSS absorber. X-ray photoemission spectra including In

and Zn core levels as well as the valence-band region were recorded after each

deposition step. Fig. 2 shows a plot of the normalized intensity of the In core-level

emission as function of the nominal thickness of the Zn(Se,OH) overlayer "lm.
Assuming a homogeneous coverage of the Zn(Se,OH) bu!er layer on the absorber "lm
and a vanishing elemental intermixing in the boundary layer, the substrate core-level

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A. Ennaoui et al. / Solar Energy Materials & Solar Cells 67 (2001) 31}40

Fig. 2. Normalized substrate In4d core-level emission intensity as function of deposition time. The inset
shows the XPS spectra of In4d and Zn 3d core levels and valence bands of CIGSS in the course of
Zn(Se,OH) deposition.

intensity is expected to decrease exponentially. A semi-Log plot of the experimental

data points vs. deposition time shows a linear "t indicating two-dimensional growth
mode. The deposition rate was determined from the slope to 0.6 As /s. We believe that
the stages of nucleation and cluster growth of chemically deposited ZnSe "lms occur
in the following steps [19]:
(1) Nucleation of ZnSe nuclei on CIGSS.
(2) ZnSe particle growth on CIGSS surface.
(3) Redissolution of small thermodynamically unstable ZnSe nuclei.
(4) Aggregation or coalescence of ZnSe particles. It should be noted that without
hydrazine hydrate (N H ) there is no indication of "lm growth. The use of N H as
 
 
second ligand in the chemical bath is a popular choice for the preparation of ZnS and
ZnSe and many authors have observed an improvement of the "lm quality and
nucleation rate in presence of hydrazine. The Zn> complex with hydrazine has
a lower coordination number compared to the complex of Zn> with ammonia
[20, 21]. Therefore, we believe that in the initial stage of nucleation (stage 1) the former
is sterically less of an impediment for the approach of the Se\ ion. A planar view of
the scanning electron micrographs of CIGSS and CBD-ZnSe on CIGSS for di!erent
deposition times are presented in Fig. 3. The micrograph for the virgin CIGSS surface
(Fig. 3a) is used as reference. The growth of ZnSe particles in lateral direction (stage 1)
can be observed in Fig. 3b after 20 s deposition time. A small change in the shape of
CIGSS crystallites is obvious. Small Zn(Se,OH) nuclei are grown on a CIGSS facets
which are not completely covered yet. We believe that the driving force for such
two-dimensional growth can be understood by the similarity of the ZnSe and CIGSS
lattice constants. Once the surface is covered laterally with ZnSe nuclei, the three-

A. Ennaoui et al. / Solar Energy Materials & Solar Cells 67 (2001) 31}40

35

Fig. 3. Scanning electron micrographs indicating di!erent steps of Zn(Se,OH) growth on CIGSS.

dimensional growth of ZnSe (stage 2) takes place. Fig. 3c shows such growth, The
ZnSe particles are grown in size. Their elongated shapes cover the whole surface.
Although the In signal decreases with increasing deposition time and disappears

completely after 120 s (see inset of Fig. 2), we believe that the deposition rate is
decreasing since even after 4 min deposition time the ZnSe over layer is very thin as
revealed by a close look to the high-resolution SEM-cross-section (Fig. 3d). Thus, the
growth rate of 0.6 As /s is valid only in the "rst 2 min of growth. Such self-limiting
growth allows the deposition of bu!er layer at a minimum thickness and with
a homogeneous surface coverage.
3.2. Device performance
For device optimization we investigate the in#uence of bath temperature ( ) on


the deposition of Zn(Se,OH) and Zn(S,OH) bu!er layers in the range of 40}703C. The
performance of CIGSS thin-"lm solar cells prepared under optimized conditions is
studied by measuring the J}V characteristics (Fig. 4). All measurements are performed
under AM 1.5 conditions (100 mW cm\). Fig. 5 shows the photovoltaic parameters
as function of the T . An e$ciency over 13% was achieved for CIGSS/Zn(Se,OH)

based device with the bu!er layer being deposited at a temperature "703C (see


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A. Ennaoui et al. / Solar Energy Materials & Solar Cells 67 (2001) 31}40

Fig. 4. J}V characteristics of CIGSS/Zn(Se,OH) and CIGSS/Zn(S,OH) without AR-coating measured

under AM1.5 conditions. The bu!er layers are prepared at di!erent temperatures.

Figs. 4a and 5a). As a result of the higher temperature this device exhibits an improved
FF. However, for CIGSS/Zn(S,OH) comparable e$ciency was achieved at lower
temperature. For this device high open circuit voltage was obtained at "503C


(see Figs. 4b and 5b). Two solar cells were tested at Fraunhofer Institute for solar
energy systems (FhG-ISE-Freiburg-Germany), the results are shown in Fig. 6. The PV
parameters are summarized in Table 1.

A. Ennaoui et al. / Solar Energy Materials & Solar Cells 67 (2001) 31}40

37

Fig. 5. In#uence of the bath temperature ( ) on the J}< parameters for CIGSS/Zn(Se,OH)- and


CIGSS/Zn(S,OH)-based devices.

Table 1
PV-parameters of CIGSS devices under AM1.5 condition. S1 and M1 are con"rmed by FhG/ISE
Cell

Area (cm\) < (mV) I (mA cm\)FF (%)




E$ciency (%)Bu!er thickness

(3C)



S1
M1

0.537
1.08

535.08
565.74

36.1
35.95

70.76
70.96

Zn(Se,OH) 7}8 nm
Zn(Se,OH) 7}8 nm

70
70

M2
M3

0.6
0.475

570
569.4

36.6
34.9

69
71.3

13.67
13.26
15.7

14.2
14.2

Zn(Se,OH) 7}8 nm
Zn(S,OH)

70
50

Total area with ARC (see [16]).

Active area.
Total area without ARC.

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A. Ennaoui et al. / Solar Energy Materials & Solar Cells 67 (2001) 31}40

Fig. 6. Power output characteristics of ZnO/Zn(Se,OH)/CIGSS/Mo/Glass for two cells with MgF

AR-coating measured at 253C under AM1.5G. The cell parameters are given in the insets.

Table 2
PV-parameters of CIGSS mini-modules (20 cm aperture-area) measured under AM1.5 condition. The
results of CBD-Zn(Se,OH) and CBD-CdS bu!ered mini-modules with di!erent ZnO windows are compared
Mini-module no Bu!er layer

ZnO window

I (mA cm\)


FF (%)

< (mV)


E$ciency
(%)

8048-M(0/1)
8049-M(0/1)
8050-M(0/1)
8050-M(2/3)

MOCVD-ZnO
DC-ZnO
MOCVD-ZnO
DC-ZnO

34.58
32.20
36.47
31.40

68.12
67.95
63.19
64.61

5926.03
6385.73
6091.25
6352.59

12.69
11.64
11.70
10.74

CdS
CdS
Zn(Se,OH)
Zn(Se,OH)

CIGSS/CdS minimodules with 11 interconnected cells.

CIGSS/Zn(Se,OH) with 12 interconnected cells.

Furthermore, CIGSS thin-"lm mini-modules with ca. 20 cm aperture-area were

fabricated by Siemens Solar (MuK nchen) [22]. Fig. 7 shows the PV characteristics of
CIGSS/CBD-CdS and CIGSS/CBD-Zn(Se,OH)-based mini-modules. E$ciencies up
to 11.7% were found with Zn(Se,OH) bu!er layer while the e$ciency of the
CdS-bu!ered reference mini-module is around 13%. Table 2 summarizes the PV
parameters for both CdS and Zn(Se,OH)-bu!ered mini-modules and di!erent ZnO
windows.

A. Ennaoui et al. / Solar Energy Materials & Solar Cells 67 (2001) 31}40

39

Fig. 7. J}< characteristics of ca. 20 cm aperture-area CIGSS thin-"lm minimodules measured under
AM1.5 (100 mW cm\) condition. The inset shows the appearance of the mini-modules with 11 series
interconnected cells.

4. Conclusion
Zn(Se,OH) and Zn(S,OH) bu!er layers have been successfully deposited on CIGSS
absorber using solution growth method. Best temperatures for the deposition are
found to be "703C for Zn(Se,OH) and "503C for Zn(S,OH). The growth rate
for Zn(Se,OH) decreases with the deposition time yielding a complete coverage of the
CIGSS absorber "lm at a minimized thickness. An active area e$ciencies of 15.7%
was achieved for cells with ca. 1 cm area and for the "rst time Cd-free monolithic
mini-modules with an e$ciency of 11.7 was fabricated with Zn(Se,OH) bu!er layer
and MOCVD-ZnO window layer, prepared by Siemens Solar GmbH (Germany).
Signi"cant gain in performance would be achieved by increasing the "ll factor which
depend on the bu!er layers as well as the ZnO windows. The above results revealed
that Zn(Se,OH) and Zn(S,OH) deposited by a CBD process might be an excellent
alternative bu!er layers for large-area Cd-free CIGSS thin-"lm solar cells.
Acknowledgements
The authors wish to acknowledge the support of the extended HMI teams especially M. Kirsch for technical assistance, I. Sieber for SEM. This work was in part

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A. Ennaoui et al. / Solar Energy Materials & Solar Cells 67 (2001) 31}40

supported by the European Commission within the framework of the Joule III project
`Wide bandgap CPVa under contract no. JOR3-CT97-0135 and by the BMBF.
References
[1] J.R. Tuttle, M.A. Contreras, T.J. Gillespie, K.R. Ramanathan, A.L. Tennant, J. Keane, A.M. Gabor,
R. Nou", Prog. Photovolt. 33 (1999) 235.
[2] J.R. Tuttle, J.S. Ward, A. Duda, T.A. Berens, M.A. Contreras, K.R. Ramanathan, A.L. Tennant,
J. Keane, E. D. Cole, K. Emery, R. Nou", Mater. Res. Soc. Symp. 426 (1996) pp. 143}151.
[3] J. HedstroK m, H. Ohlsen, M. BodegaK rd, A. Kylen, L. Stolt, D. Hariskos, M. Ruckh, H.W. Schock,
Proceedings of the 23rd IEEE Photovoltaic Specialists Conference, 1993, pp. 364}371.
[4] W.H. Bloss, Proceedings of the 12th European Photovoltaic Solar Energy Conference, Amsterdam,
The Netherland, 11}15 April 1994, H.S. Stephens & Associates, UK, 1994, pp. 37}43.
[5] R. Gray, M. Dietrich, C. Fredric, C. Jensen, K.Knapp, D. Tarrant, D. Willett, Proceedings of the 12th
European Photovoltaic Solar Energy Conference, Amsterdam, The Netherland, H.S. Stephens &
Associates, UK, 1994, pp. 935}938.
[6] M.A. Contreras, B. Egaas, K. Ramanathan, J. Hiltner, A. Swartzlander, F. Hasoon, R. Nou", Prog.
Photovolt. Res. Appl. 7 (1999) 311.
[7] Siemens Solar Press Relese, Camarillo, CA (September 29, 1998); electrinic mail: http://www.solarpv.com/0328.htm.
[8] D. Hariskos, R. Herberholz, M. Ruckh, U. RuK hle, R. SchaK %er, H.W. Schock, Proceedings of the 13th
European Photovoltaic Solar Energy Conference, H.S. Stephens & Associates, UK, 1995,
pp. 1995}1998.
[9] Y. Ohtake, T. Okamoto, A. Yamada, M. Konagai, K. Saito, Sol. Energy Mater. Sol. Cells (Special
volume PVSEC-9) 49 (1997) 269.
[10] K. Kushiya, M. Tachiyuki, T. Kase, I. Sugiyama, Y. Nagoya, D. Okumura, M. Sato, O. Yamase, H.
Takeshita, Sol. Energy Mater. Sol. Cells (Special volume PVSEC-9) 49 (1997) 277.
[11] F. Cooray, K. Kushiya, A. Fujimaki, I. Sugiyama, T. Miura, D. Okumura, M. Sto, M. Ooshita, O.
Yamase, Sol. Energy Mater. Sol. Cells (Special volume PVSEC-9) 49 (1997) 291.
[12] A. Ennaoui, C.D. Lokhande, M. Weber, R. Scheer, H. J. Lewerence, Proceedings of the 14th European
Photovoltaic Solar Energy Conference, Barcelona, Spain, H.S. Stephens & Associates, UK, 1997,
pp. 1220}1223.
[13] C.D. Lokhande, P.S. Patil, A. Ennaoui, H. Tributsch, Appl. Surf. Sci. 123/124 (1998) 294.
[14] A. Ennaoui, M. Weber, R. Scheer, H.J. Lewerenz, Sol. Energy Mater. Sol. Cells. 54 (1998) 277.
[15] C.D. Lokhande, P.S. Patil, H. Tributsch, A. Ennaoui, Sol. Energy Mater. Sol. cells 55 (1998) 379.
[16] A. Ennaoui, U. Blieske, M.Ch. Lux-Steiner, Prog. Photovolt. 6 (1989) 447.
[17] A. Ennaoui, M. Weber, C.D. Lokhande, R. Scheer, H. J. Lewerence, Proceeding of the Second World
Photovoltaic Solar Energy Conversion, Vienna, Austria, 1998, pp. 628}631.
[18] A. Bauknecht, U. Blieske, T. Kampschulte, A. Ennaoui, V. Nadenau, H.W. Schock, A.N. Tiwari, M.
Krejci, S. Duchemin, M-C. Artaud, L.M. Smith, S. Rushworth, J. SoK llner, M. Ch. Lux-Steiner,
Proceedings of the Second World Photovoltaic Solar Energy Conversion, Vienna, Austria, 1998,
pp. 2436}2439.
[19] A. Ennaoui, C.D. Lokhande, in preparation.
[20] J.M. Dona, J. Herrero, J. Electrochem. Soc. 142 (1995) 764.
[21] I.O. Oladeji, L. Chow, Thin Solid Films 339 (1999) 148.
[22] Siemens AG (MuK nchen), Private communication.