Solar Energy Materials & Solar Cells 55 (1998) 379—393

ZnSe thin films by chemical bath deposition

method
C.D. Lokhande!,1 P.S. Patil1!, H. Tributsch!, A. Ennaoui",*
! Hahn-Meitner-Institute, Bereich Physikalische Chemie, Abt. CS, Glienicker Stra}e-100,
D-14109, Berlin, Germany
" Hahn-Meitner-Institute, Bereich Physikalische Chemie, Abt. CG, Glienicker Stra}e-100,
D-14109, Berlin, Germany
Received 27 May 1997; received in revised form 6 March 1998

Abstract

The ZnSe thin films have been deposited onto glass substrates by the simple chemical bath
deposition method using selenourea as a selenide ion source from an aqueous alkaline medium.
The effect of Zn ion concentration, bath temperature and deposition time period on the quality
and thickness of ZnSe films has been studied. The ZnSe films have been characterized by XRD,
TEM, EDAX, TRMC (time-resolved microwave conductivity), optical absorbance and RBS
techniques for their structural, compositional, electronic and optical properties. The as-depos-
ited ZnSe films are found to be amorphous, Zn rich with optical band gap, Eg, equal to
2.9 eV. ( 1998 Elsevier Science B.V. All rights reserved.

Keywords: Thin films; ZnSe; Chemical bath deposition; Film characterization

1. Introduction

ZnSe is an important semiconductor material with a large band gap (2.7 eV) which
has a large potential use in thin film devices, such as photoluminescent and electro-
luminescent devices and as an n type window layer for thin film heterojunction solar
cells. Interest in ZnSe-GaAs heterojunctions has greatly increased in recent years

* Corresponding author. E-mail: Ennaoui@hmi.de

1 On leave from Shivaji University, Kolhapur, India.

0927-0248/98/$ — See front matter ( 1998 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 7 - 0 2 4 8 ( 9 8 ) 0 0 1 1 2 - 3
380 C.D. Lokhande et al. /Solar Energy Materials & Solar Cells 55 (1998) 379—393

because of the possible applications in a number of high speed and optoelectronic

devices. The wide band gap ZnSe and related ternary alloys such as Zn Cd Se,
1~x x
ZnSe S makes them promising materials for optoelectronic device technology in
1~y y
the blue region of the visible spectrum [1,2]. The lattice parameter of ZnSe is well
matched to that of GaAs (0.27% mismatch) so that high quality epitaxy of ZnSe on
GaAs is possible [3]. ZnSe is an attractive material as a buffer layer in CIS based solar
cells, as it has the following advantages over traditionally used CdS buffer layer; it is
Cd free and hence environmentally friendly. The band gap, E of ZnSe (2.7 eV) is wider
'
than that of CdS (2.4 eV) and allows transmission of higher energy photons than the
band gap of CdS and it has a better lattice match with CIGS thin films absorbers in
the band gap range of 1.3 to 1.5 eV than CdS [4,5,27].
A very attractive method for producing ZnSe thin films, due to the possibility of
large area deposition at low cost is the chemical bath deposition method. The method
requires the presence of reagents that act as a source of chalcogen ions and com-
plexion of the metal ions of interest whose stability equilibrium provides a concentra-
tion of metal cation small enough to produce the controlled homogeneous precipita-
tion of the film on the solid substrate. Chemical deposition of ZnSe has been reported
in the literature from aqueous alkaline medium using sodium selenosulfate [6—9],
selenourea [10,11] and dimethylselenourea [12] as selenide ion sources. Chaudhari et
al. [8,9] have reported on the deposition of ZnSSe films onto GaAs substrate by
addition of thiourea into the deposition bath of ZnSe films. However, the experi-
mental data are limited and because of the use of different selenide ion sources in the
bath, no definite conclusions about the deposition conditions and properties of ZnSe
films could be drawn.
In the present investigation we describe the deposition of ZnSe films onto the glass
substrate from aqueous alkaline medium using selenourea as a selenide ion source.
The preparation parameters have been studied in order to obtain good quality ZnSe
films. The ZnSe film characterization including optical, structural, compositional,
electronic properties will be presented.

2. Experimental procedure

The deposition of ZnSe is based on the slow release of Zn`2 and Se~2 ions in a solution
which then condense onto the substrate. For this, Zn salt with a suitable complexing
agent is used as a Zn`2 source and selenourea as a Se~2 source in alkaline medium.
The depositions were carried out using commercial glass slides (2.5]7.5 cm2).
These were cleaned with detergent, dried, degreased with ethanol in ultrasonic cleaner
and kept immersed in distilled water prior to the deposition.
Chemicals were used as received; ZnSO (E Merck), 80% hydrazine hydrate
4
(Riedel—de Haen), 25% ammonia (E Merck) and selenourea (E Merck). 0.7 M ZnSO
4
solution was prepared and 0.1 M selenourea solution was prepared, Hydrazine
hydrate and ammonia solutions were used as received. The above solutions were
further diluted during the optimisation of preparation parameters such as composi-
tion and concentration of the bath, temperature, pH, etc.
 C.D. Lokhande et al. /Solar Energy Materials & Solar Cells 55 (1998) 379—393 381

First, in a glass vessel, hydrazine hydrate solution was mixed with ZnSO solution
4
under a constant stirring. The resultant solution was turbid milky. To this, under
stirring, ammonia solution was added which is just sufficient to dissolve the turbidity
of the solution. Then the reactant vessel is kept in a constant temperature water bath.
When appropriate temperature ($0.5°C) is obtained, selenourea solution was added
to the bath and four glass substrates were kept vertically in the glass vessel using
a teflon substrate holder. After the deposition, the substrates were taken out of the
bath, rinsed with distilled water, dried with nitrogen gas and preserved in a plastic
container.
The film thickness was measured using a Dektak- 3030 profilometer. The structure
of these films was examined by X-ray diffraction (XRD), and transmission electron
microscopy (TEM). The XRD was performed in a h—2h coupled geometry with
a Siemens D-500 diffractometer using a copper anode. Transmission electron micro-
scope (TEM) analysis was performed with a Philips CM12 electron microscope (point
resolution 2.8 A_ equipped with a EDAX-DX-4 analyser to measure qualitatively the
sample stoichiometry. For the preparation of samples for TEM, the thin ZnSe film
deposited on glass was scratched and placed onto an amorphous carbon coated (ca.
50 A_ ). The grid was then transferred to an electron microscope. A number of grids
were prepared from each sample in order to check the reproducibility of the prepara-
tion procedure. The Rutherford back scattering (RBS) analysis was carried out using
2.0 MeV 4He` ions. The ZnSe film was deposited on glassy carbon substrates. The
incident beam was normal to the film surface and semiconductor detector (implanted
Si detector, solid angle 3.4]10~3 sr) was mounted at the scattering angle of 170°. The
energy resolution was better than 20 keV. About 1]105 to 3]105 counts per peak
were sampled to ensure a statistical error of 1%. The optical band gap was estimated
by measuring the optical absorption and transmission with UV-VIS-NIR spectro-
photometer. Transient photoconductivity measurement in the microwave frequency
range was performed using the time resolved microwave conductivity (TRMC)
method. The ZnSe film on glass substrate was illuminated by the third harmonic of
a Nd-YAG laser at 355 nm with excitation pulses, 10 ns FWHM. The excita-
tion intensity was adjusted by calibrated filters. Microwaves were generated by a
tunable Gunn oscillator operating in K band. The intensity of the laser pulse was
0
2.4 mJ cm~2.

3. Results and discussion

ZnSe films can be prepared by decomposition of selenourea in an alkaline solution

containing a Zn salt and a suitable complexing agent which allows for obtaining
a soluble species, Zn2` in this medium. The deposition of ZnSe occurs when the ionic
product of Zn2` and Se2~ exceeds the solubility product (K "10~31) of ZnSe. The
41
flow chart of the growth mechanism for the ZnSe film is presented in Fig. 1. The
reaction mechanism takes place in an alkaline medium, where Zn salt, liquid ammo-
nia and selenourea are present. Zinc may be present as soluble or insoluble species in
the reaction bath. Generally for the pH of the bath less than 7.5 or greater than 13.7,
382 C.D. Lokhande et al. /Solar Energy Materials & Solar Cells 55 (1998) 379—393

Fig. 1. Flow chart of the growth mechanism for a ZnSe film by the chemical bath deposition method.

soluble species such as Zn`2 and ZnO2~ are present respectively. However if the pH
2
of the bath is in between 7.5 to 13.7, then insoluble Zn(OH) species are present [12].
2
The presence of NH , gives place to the formation of the complex Zn(NH )`2 as;
3 34
Zn`2#4NH QZn(NH )`2 K"10~29.
3 34
The complex Zn(NH )`2 is soluble in the above pH range however, it could be forced
34
to form Zn(OH) at high temperature.
2
The selenourea releases selenide ions in the alkaline medium as [13,14]
SeC(NH ) #2OH~PSe~2#CH N #H O.
22 2 2 2
The formation of ZnSe films can take place from the bath containing Zn(NH )`2 and
34
Se~2 species as
Zn(NH )`2#Se~2#2OH~PZnSe#2NH #2H O.
34 3 2
The inclusion of oxygen into the chemically deposited chalcogenide thin films may
be understood with the flow chart shown in Fig. 1. The presence of Zn(OH) in the
2
deposition bath is unavoidable due to the aqueous alkaline nature of the bath. The
amount of Zn(OH) increases with increase in temperature of the deposition bath.
2
This results in the inclusion of Zn(OH) in the ZnSe film resulting in the formation of
2
a Zn (Se,OH) film rather than of a ZnSe film [15].
x y
With the aim of finding the best conditions for the deposition process, we have
studied the influence of the concentrations of reagents and temperature of deposition
on the growth and quality of the film. In our case, depositions were carried out with
ZnSO concentration between 5]10~3 to 7]10~1 M and selenourea in the range
4
1]10~3 to 1]10~2 M. The concentrations of hydrazine hydrate and liquid ammonia
 C.D. Lokhande et al. /Solar Energy Materials & Solar Cells 55 (1998) 379—393 383

Fig. 2. Variation of ZnSe film thickness with zinc ion concentration in the deposition bath. Bath composi-
tion: 5]10~3—7]10~1 M/l ZnSO , 6]10~2 M/l selenourea, 8]10~1 M/l hydrazine hydrate and 1.4 M/l
4
NH . Deposition temperature: 70°C, Substrates: Glass.
3

were kept constant. The influence of Zn ion concentration on the film formation and
thickness was studied for the following bath composition: 5]10~3 to 7]10~1 M/l
ZnSO , 6]10~2 M/l selenourea, 8]10~1 M/l hydrazine hydrate and 1.4 M/l NH .
4 3
The deposition temperature was 70°C and the deposition time was 30 min. It was
observed that the films are nonuniform at low zinc ion concentrations
(5]10~3!5]10~2 M/l). Fig. 2 shows the variation of film thickness with Zn ion
concentration in the bath. The film thickness increases linearly with Zn ions in the
bath, however saturation was observed when Zn ion concentration exceeds
5]10~1 M/l.
Deposition time and zinc selenide film thickness were studied for the bath consist-
ing of 5]10~1 M/l ZnSO , 6]10~2 M/l selenourea, 8]10~1 M/l hydrazine hydrate
4
and 1.4 M/L NH . The deposition temperature was 70°C. The relationship is shown
3
in Fig. 3. Initially, the film thickness increases at a rate of 50 A_ /min. with time and
after about 30 min of deposition time, a film of 0.16 lm is obtained. Further deposi-
tion time only yields a small increase in film thickness.
The temperature of the deposition bath is a critical parameter in the chemical bath
deposition method. It affects the rate of release of chalcogen ions and dissociation of
metal ions from the complexant. Films with the following bath parameters were
prepared: 5]10~1 M/l ZnSO , 6]10~2 M/l selenourea, 8]10~1 M/l hydrazine
4
384 C.D. Lokhande et al. /Solar Energy Materials & Solar Cells 55 (1998) 379—393

Fig. 3. Variation of ZnSe film thickness with deposition time. Bath Composition: 5]10~1 M/l ZnSO ,
4
6]10~2 M/l selenourea, 8]10~1 M/l hydrazine hydrate and 1.4 M/l NH . Deposition temperature: 70°C,
3
Substrates: Glass.

hydrate and 1.4 M/l NH . The deposition time was 30 min and the bath temperature
3
was varied between 25°C and 90°C using a temperature controller with an accuracy of
$0.5°C. It was observed that up to 40°C, bath solution became turbid, 3—4 min after
the addition of selenourea solution. However, this period was reduced to 1 min above
a bath temperature of 60°C. Above a bath temperature of 80°C, immediate turbidity
took place after the addition of selenourea solution to the bath and no film formation
was observed. Fig. 4 shows the relationship between the bath temperature and
thickness of the film. It is seen that the film thickness increases quasilinearly up to
70°C and decreases for further deposition temperature. This can be understood by
considering two processes which are taking place, the film formation and homogenous
precipitation [16]. A temperature increase favours the homogenous precipitation
against film formation. Similar results have been reported for ZnSe and ZnS films
[10,17]. Dona and Herrero [10] have reported that Zinc can form a complex with
hydrazine hydrate as Zn(NH !NH )`2 but its concentration is very low due to its
2 23
low equillibrium constant with respect to the Zn(NH )`2 equilibrium constant and
34
therefore we believe that the role of hydrazine hydrate is to obtain adherent ZnSe
films. However, Pramanik and Biswas [6] have reported that the absence of hydrazine
hydrate does not produce any film or precipitate of ZnSe. On the contrary, Chaudhari
et al. [8] obtained ZnSSe films without addition of hydrazine hydrate. Therefore, in
 C.D. Lokhande et al. /Solar Energy Materials & Solar Cells 55 (1998) 379—393 385

Fig. 4. Variation of ZnSe film thickness with bath temperatures. Bath Composition: 5]10~1 M/l ZnSO ,
4
6]10~2 M/l selenourea, 8]10~1 M/l hydrazine hydrate and 1.4 M/l NH . Deposition temperature: 70°C,
3
Substrates: Glass.

order to examine the role of hydrazine hydrate in the ZnSe film formation process,
some experiments were carried out. In the first experiment, the pH of the deposition
bath was raised with the addition of liquid ammonia and no hydrazine hydrate was
introduced in the bath and in the second experiment, pH was raised with the addition
of hydrazine hydrate without addition of liquid ammonia. In both cases, no ZnSe film
formation was observed. Therefore it is concluded that both hydrazine hydrate and
ammonia are necessary for the formation of ZnSe films and hydrazine hydrate might
be playing a complexing and/or a catalytic role in the film formation process.
ZnSe can form having either hexagonal, wurtzite-type structure or the cubic zinc
blende-type structure. Previous work on chemically deposited ZnSe films deposited at
90°C bath temperature on a glass substrate using sodium selenosulfate showed the
films to be polycrystalline in nature [6]. The room temperature deposited ZnSSe films
from sodium selenosulfate bath were found to be amorphous and became polycrystal-
line at the deposition temperature of 90°C. The same film on GaAs (1 1 0) substrates
were crystalline due to preferred orientations of the substrate [9]. However, the ZnSe
films from selenourea and dimethylurea bath at 50—90°C bath temperature on glass
substrate were found to be amorphous [10,12]. Fig. 5a shows that as-deposited ZnSe
films (0.4 l thick) in the present work are of very poor crystallinity. The XRD patterns
showed a broad hump indicating amorphous nature of ZnSe films and no well
386 C.D. Lokhande et al. /Solar Energy Materials & Solar Cells 55 (1998) 379—393

Fig. 5. X-ray diffraction patterns of ZnSe films onto glass substrates. Bath Composition: 5]10~1 M/l
ZnSO , 6]10~2 M/l selenourea, 8]10~1 M/l hydrogen hydrate and 1.4 M/l NH . Deposition temper-
4 3
ature: 70°C. (a) as deposited; (b) heat treated at 300°C for 30 min.

resolved peaks were observed. Generally the precipitates in the deposition bath are
found to be polycrystalline and hence structural information regarding the material
deposited or precipitated could be obtained irrespective of the amorphous or poly-
crystalline nature of the film deposited from the same bath. Therefore ZnSe precipitate
was collected from the deposition bath, made alkali free by repeated washing with
distilled water and XRD pattern was taken. However, in the present case ZnSe
precipitate was found to be amorphous leading to no definite conclusion about the
structure of the ZnSe films deposited from the bath. The ZnSe films were heated in
a furnace at 300°C for 30 min in air and the XRD pattern of such a film is shown in
Fig. 5b. Only a small improvement in crystallinity was observed after heating. In case
of the CdS films, CdCl treatment was found to improve the crystallinity of the films
2
[17—19]. CdS films were covered with saturated solutions of ethanol with CdCl and
2
heated in air at 400°C for 15—30 min to improve the crystallinity of the films. Similarly
in the present work ZnSe films were covered with saturated solutions of ethanol with
ZnCl and heated at different temperatures ranging from 200°C to 400°C for 15 to
2
30 min. The XRD studies showed that crystallinity of ZnSe film did not improve
significantly after heating. However, when the film was heated at 400°C, the peaks
such as (1 0 1), (0 0 2), (1 1 0), (1 0 2) corresponding to the formation of ZnO appeared
instead of showing improvement in the crystallinity of the ZnSe film. Recently similar
type of results about the conversion of amorphous MoS into polycrystalline MoO
2 3
by thermal oxidation at 550°C has been reported by Laperriere et al. [20].
In TEM studies, bright field images were taken under the condition of minimum
phase contrast [21]. Fig. 6 shows a transmission electron micrograph of the ZnSe
film. By high resolution the typical lattice plane spacing of 3.2 A_ (hkl"1 1 1) for cubic
ZnSe can be clearly seen. Small nanocrystal particles with diameters of 20 to 25 A_ are
recognised. The quantitative analysis by energy dispersive X-ray analysis (EDAX),
was performed only for Zn and Se on various samples at different points. The average
 C.D. Lokhande et al. /Solar Energy Materials & Solar Cells 55 (1998) 379—393 387

Fig. 6. High-resolution TEM showing the lattice plane with a spacing of 3.2 A_ , typical for a cubic ZnSe
samples.

atomic ratio Zn : Se was 3 : 2 showing that the samples are Zn rich as reported earlier
[10]. The typical EDAX spectrum is presented in Fig. 7.
Fig. 8 represents the transmission spectrum of a 0.175 l thick ZnSe film. The
spectrum is not been corrected for the glass substrate absorption. It can be seen that
the transmission of the film is greater than 60% for the wavelength values greater than
the wavelength corresponding to E . The square of the absorption coefficient, a2 ver-
'
sus hl for ZnSe film is shown in Fig. 9. The linear nature of the plot indicates that the
ZnSe is a direct band gap material. The intercept with the energy axis gives a value of
the direct band gap, E as 2.9 eV. This value is slightly higher than the standard
'
reported value (E "2.7 eV). This could be attributed to the size effect observed in
'
ZnSe films as evidenced by the presence of small grain size (nearly 20—25 A_ ) of ZnSe
film particles [22].
The RBS spectrum in Fig. 10 displays the number of detected He` ions as
a function of their energy which is plotted together with a stimulated spectrum. For
the calculation of the simulated spectrum, homogeneously distributed ZnSe in two
388 C.D. Lokhande et al. /Solar Energy Materials & Solar Cells 55 (1998) 379—393

Fig. 7. Typical EDAX spectrum of ZnSe thin film.

different layers has been assumed. Clearly the presence of oxygen and nitrogen could
be identified by the two small extra peaks with the edge energy of 724 and 622 keV.
The compositions in the presented ZnSe layers were Zn : Se : C : O : N"1 : 1 : 2 : 1 : 1
(surface layer of thickness 150 A_ ) and Zn : Se : C : N"1 : 0.7 : 4 : 0.4 : 0.4 (second
layer of thickness 650 A_ ). The presence of oxygen and nitrogen in chemically depos-
ited CdS films has been detected by Kylmer et al. [23] using the RBS technique.
Further, long-range tails are observable near the low energy part of the peaks. This
could be due to the following: (i) diffusion of substrate carbon into the ZnSe layer or
(ii) film is not closed, i.e. there are some regions on the glassy carbon substrate which
are not covered by ZnSe film. The diffusion of carbon into ZnSe is very unlikely
because this would be possible only at very high temperatures. Therefore, the long-
range tails near the low energy parts of the peaks are attributed to the non coverage of
the substrate of the ZnSe film. The presence of oxygen in chemically bath deposited
ZnSe films has already been discussed. The introduction of nitrogen in the ZnSe film
might take place during the reaction with hydrazine hydrate and /or selenourea
during the film formation.
The study of excess conductivity induced in a material by pulsed optical excitation
yields information on the optoelectronic properties of the material. These properties
 C.D. Lokhande et al. /Solar Energy Materials & Solar Cells 55 (1998) 379—393 389

Fig. 8. Plot of transmittance with wavelength for ZnSe film.

are of importance for the performance of the devices. The TRMC method is based on
the measurement of the relative change *P(t)/P, of the microwave power reflected
from a sample caused by a change of the conductivity of the sample which is induced
by a laser pulse. This method has been applied to several semiconductors to probe the
decay time as well as the photoresponse.
Time resolved (transient) microwave photoconductivity (TRMC) was performed to
probe the decay time of the excess carriers, without the use of electrical contacts.
A description of this technique is given in the literature [24]. Fig. 11a—d shows the
transients produced when ZnSe thin film is excited by a 355 nm (3.5 eV) laser pulse at
four different intensities. The intensity of the laser was varied from 1.8% to 100%. The
microwave frequency was 32 GHz. The overall shape of the decay is dependent on the
laser intensity in the covered range 0.033—2.4 mJ cm~2. Fast decay behaviour is
observable at all the intensities. Various processes responsible for such transients have
been given in [25]. The energy of the exciting light (3.5 eV) is higher than the band gap
energy of ZnSe (2.8 eV). Therefore absorption of laser light creates mobile electrons in
the conduction band and mobile holes in the valence band of the ZnSe. As the
mobility of electrons in ZnSe (450—600 cm2 V~1 s~1) is greater than that of holes
(11—16 cm2 V~1 s~1), the transient can be attributed to mobile excess electrons in the
conduction band of ZnSe [26].
390 C.D. Lokhande et al. /Solar Energy Materials & Solar Cells 55 (1998) 379—393

Fig. 9. Variation of (a)2 versus hl for ZnSe films.

Fig. 10. Rutherford back scattered (RBS) spectrum for ZnSe film deposited on glassy carbon substrates.
 C.D. Lokhande et al. /Solar Energy Materials & Solar Cells 55 (1998) 379—393 391

Fig. 11. TRMC signals for ZnSe film at four different laser intensities. (a) 100%, (b) 10%, (c) 4% and (d)
1.8%.
392 C.D. Lokhande et al. /Solar Energy Materials & Solar Cells 55 (1998) 379—393

Fig. 12. Plot of peak intensity, I versus the laser intensity.

.!9

The transient may be divided into two parts. The first part involves the signal
up to 40 ns after excitation while the latter part involves the signal after 40 ns.
To understand the mechanism in the first part; the peak amplitude, I , is plotted
.!9
versus the laser intensity as shown in Fig. 12. The nonlinearity of the plot may be
due to the possibility of recombination of excess electrons during the incidence
of the laser pulse. However, the detailed process is hard to understand from the
available data. The latter part of the transient is used to calculate the decay time
of excess electrons under the assumption that the process (which starts immedietly
after incidence of laser pulse) after 40 ns is not influenced by the laser pulse. This decay
time was calculated by fitting the exponential curve to the transient after 40 ns. The
decay time of electrons at 100% laser intensity was 46 ns and increased to 72 ns at
1.8% intensity.

4. Conclusions

We have found that ZnSe films can be deposited from a bath containing ZnSO ,
4
hydrazine hydrate, ammonia and selenourea in an alkaline medium. The ZnSe films
could not be deposited from a bath without hydrazine hydrate indicating that the role
of hydrazine hydrate is of complementary complexant and catalyst. The presence of
oxygen as shown by the RBS analysis showed that the films deposited are of the
composition Zn (Se,OH) . The films are nanocrystalline consisting of grains of sizes
x y
between 20 and 25 A_ . The TEM analysis indicated that ZnSe has a cubic structure.
The optical band gap, E "2.9 eV, obtained from optical absorption studies shows
'
that ZnSe is a direct band gap material. The TRMC study showed that the decay time
of excess generated electrons in ZnSe films is of the order of nanoseconds and is
increased as the illumination intensity is decreased.
 C.D. Lokhande et al. /Solar Energy Materials & Solar Cells 55 (1998) 379—393 393

Acknowledgements

The authors are grateful to Dr. K. Diesner and Dr. M. Muller for XRD and RBS
measurements, respectively, Dr. M. Giersig and U. Bloeck for TEM measurments, Dr.
M. Kunst for helpful discussions on TRMC studies. Dr. C.D. Lokhande wishes to
acknowledge Humboldt Foundation, Germany for the award of fellowship to carry
out the research work. Dr. P.S. Patil wishes to acknowledge DAAD, Germany for the
award of fellowship to carry out the research work.

References
[1] H. Luo, J.K. Furdyna, Semicond. Sci. technol. 10 (1995) 1041.
[2] C. Boney, Z. Yu, W.H. Rowland, W.C. Hughes, J.W. Cook, J.F. Schetzina, G. Cantwell, W.C. Harsch,
J. Vac. Sci. Technol. B 14 (1996) 2259.
[3] A. Franciosi, C.G. Van de Walle, Surf. Sci. Rep. 25 (1996) 1.
[4] Y. Ohtake, K. Kushiya, M. Ichikawa, A. Yamada, M. Konagai, Jpn. J. Appl. Phys. 34 (1995) 5949.
[5] J. Yoo, A.L. Fahrenbruch, R.H. Bube, Solar Cells 31 (1991) 171.
[6] P. Pramanik, S. Biswas, J. Electrochem. Soc. 133 (1986) 350.
[7] K.C. Sharma, R.P. Sharma, J.C. Garg, Ind. J. Pure Appl. Phys. 28 (1990) 539.
[8] G.N. Chaudhari, S.N. Sardesai, S.D. Sathe, V.J. Rao, J. Mat. Sci. 27 (1992) 4647.
[9] G.N. Chaudhari, S. Manorama, V.J. Rao, Thin Solid Films 208 (1992) 243.
[10] J.M. Dona, J. Herrero, J. Electrochem. Soc. 142 (1995) 764.
[11] G.A. Kitav, T.P. SoKolova, Russ. J. Inorganic Chem. 15 (1970) 167.
[12] C.A. Estrada, P.K. Nair, M.T.S. Nair, R.A. Zingaro, E.S. Meyers, J. Electrochem. Soc. 141 (1994) 802.
[13] Stability constants of metal ion complexes, Chemical soc., special publication No. 17, The Chemical
Soc., London, 1964.
[14] R.T. Morrison, R.N. Boyd, Organic Chemistry 4th ed., Allyn and Bacon Inc, Boston M.A., 1983.
[15] B. Mokili, Y. Charreire, R. Cortes, D. Lincot, Thin Solid Films 288 (1996) 21.
[16] C.D. Lokhande, Mater. Chem, Phys. 27 (1991) 1.
[17] J.M. Dona, J. Herrero, J. Electrochem. Soc. 141 (1994) 205.
[18] D.W. Niles, F.S. Hasson, Progress in photovoltaics; research and applications 1 (1993) 279.
[19] R.W. Birkmire, B.E. McCandless, S.S. Hegedus, Int. J. Solar Eng. 12 (1992) 145.
[20] G. Laperriere, M.A. Lavoie, D. Bélanger, J. Electrochem Soc. 143 (1996) 3106.
[21] W. Kunath, F. Zemlin, K. Weiss, Ultramicroscopy 16 (1995) 123.
[22] A. Henglein, Chem Rev. 89 (1989) 1861.
[23] A. Kylner, J. Lindgren, L. Stolt, J. Electrochem Soc. 143 (1996) 2662.
[24] M. Kunst, G. Beck, J. Appl. Phys. 60 (1986) 3558.
[25] K.M. Schindler, M. Kunst, Chem. Phys. Lett. 172 (1990) 137.
[26] M. Aven, B. Segall, Phys. Rev. 130 (1963) 81.
[27] A. Ennaoui, C.D. Lokhande, M. Weber, R. Scheer, H.J. Lewerenz, Proc. 14th European Photovoltaic
Solar Energy Conf. and Exhibition, Barcelona, Spain (1997) pp. 1220—1223.