Chemical Deposition Method For Metal Chalcogenide Thin Films

Materials Chemistry and Physics 65 (2000) 131
Review
Chemical deposition method for metal chalcogenide thin lms

R.S. Mane, C.D. Lokhande*
Thin Film Physics Laboratory, Department of Physics, Shivaji University, Kolhapur 416004, India
Received 22 July 1999; received in revised form 28 December 1999; accepted 3 January 2000
Abstract
Metal chalcogenide thin lms preparation by chemical methods are currently attracting considerable attention as it is relatively
inexpensive, simple and convenient for large area deposition. A variety of substrates such as insulators, semiconductors or metals can be
used since these are low temperature processes which avoid oxidation and corrosion of substrate. These are slow processes which facilitates
better orientation of crystallites with improved grain structure. Depending upon deposition conditions, lm growth can take place by ionby-ion condensation of the materials on the substrates or by adsorption of colloidal particles from the solution on the substrate. Using these
methods, thin lms of group IIVI, VVI, IIIVI etc. have been deposited. Solar selective coatings, solar control, photoconductors, solid
state and photoelectrochemical solar cells, optical imaging, hologram recording, optical mass memories etc. are some of the applications of
metal chalcogenide lms.
In the present review article, we have described in detail, chemical bath deposition method of metal chalcogenide thin lms, it is capable
of yielding good quality thin lms. Their preparative parameters, structural, optical, electrical properties etc. are described. Theoretical
background necessary for the chemical deposition of thin lms is also discussed. # 2000 Elsevier Science S.A. All rights reserved.
Keywords: Metal chalcognide thin lms; Thin solid lms; Chemical bath deposition
1. Introduction
Thin lms have number of applications in various elds.
Few of them are A.R. coating, interference lters, polarisers,
narrow band lters, solar cells, photoconductors, IR detectors, waveguide coatings, temperature control of satellites,
photothermal solar coatings such as black chrome, nickel,
cobalt etc., magnetic lms, superconducting lms, anticorrosive lms, microelectronics devices, diamond lms,
reduction of fabrication through coating or surface modication i.e. epitaxy and heterostructure lms, high temperature wear resistance lms, hard coatings etc. Rapid progress
in lm devices has helped for ICs of monolithic and hybrid
microelectronics.
Thin chalcogenide lms are of particular interest for the
fabrication of large area photodiode arrays, solar selective
coatings, solar cells, photoconductors, sensors etc. Deposition of these lms by vacuum evaporation, sputtering and
chemical methods such as chemical vapour deposition,
spray pyrolysis, electrodeposition, anodization, electroconversion, electroless, dip growth, successive ionic adsorption
and reaction, chemical bath deposition and solutiongas
*
Corresponding author.
interface techniques are well known [17]. Chemical bath

deposition (CBD) which is also known as solution growth,
controlled precipitation, or simply chemical deposition,
recently has emerged as a method for the deposition of
metal chalcogenide thin lms. It is an analogue, in the liquid
phase, of the well known chemical vapour deposition in the
gaseous phase. The reaction takes place between the dissolved precursors generally in aqueous solution at low
temperature (30808C). Thiourea, thioacetamide, thiosulphate and sodium sulphide are generally used as sulphide
precursors. Metallic precursors are metal complexed ions
with ammonia ligands, for instance [8]. It is interesting to
note that the analogous between CBD and spray pyrolysis
used for the sulphide deposition is the use of same precursors (thiourea and thioacetamide and metal salts) dissolved in solvent [9,10]. In the case of CBD, solution
chemistry is chosen such that a spontaneous reaction from
the liquid phase is possible, contrary to spray pyrolysis
where due to different solution chemistry, the reaction needs
much higher temperature to process (3006008C) and thus
takes place from the vapour phase.
CBD method is presently attracting considerable attention
as it does not require sophisticated instrumentation like
vacuum system and other expensive equipments. Simple
0254-0584/00/$ see front matter # 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 2 5 4 - 0 5 8 4 ( 0 0 ) 0 0 2 1 7 - 0
R.S. Mane, C.D. Lokhande / Materials Chemistry and Physics 65 (2000) 131
equipments like hot plate with magnetic stirrer is needed.

The starting chemicals are commonly available and cheap.
With CBD method, a large number of substrates can be
coated in a single run with a proper jig design. Electrical
conductivity of the substrate is not the necessary requirement. Any insoluble surface to which the solution has a free
access will be a suitable substrate for deposition. The low
temperature deposition avoids oxidation and corrosion of
metallic substrates. Chemical deposition results in pin hole
free and uniform deposits are easily obtained since the basic
building blocks are ions instead of atoms. The preparative
parameters are easily controllable and better orientations
and improved grain structure can be obtained. A number of
review articles discussing the status of CBD have been
appeared in the literature [1115].
The formation of solid phase from a solution involves two
steps as nucleation and particle growth. The size of particles
of a solid phase is independent upon the relative rates at
which these two competing processes take place. For any
precipitate, there is some minimum number of the ions or
molecules required to produce a stable phase in contact with
a solution, called as nucleus. The formation of nucleation is
necessary for a precipitate formation. The concept of nucleation in solution is that the clusters of molecules formed
undergo rapid decomposition and particles combine to grow
up to a certain thickness of the lm. Depending upon
deposition conditions such as bath temperature, stirring rate,
pH, solution concentration etc. the lm growth can take
place by ion-by-ion condensation of materials or by adsorption of colloidal particles from the solution on the substrate.
Using chemical deposition methods, a large number of
binaries such as CdS, CdSe, Bi2S3, Bi2Se3, PbS, PbSe,
As2S3, Sb2S3, Ag2S, CuS, ZnS etc. and ternaries such as
CdZnS, CdSSe, CuInS2, CuInSe2, PbHgS, CdPbSe etc. have
been deposited as thin lms.
In the present review article, a survey of chalcogenides
thin lms deposited by chemical bath deposition method is
made. The theoretical background of chemical deposition is
discussed. Physico-chemical properties of binary and ternary chalcogenide semiconducting thin lms are summarized.
2. Theoretical background of chemical deposition
2.1. Concept of solubility and ionic product
Sparingly soluble salt AB, when placed in water, a
saturated solution containing A and B ions in contact with
undissolved solid AB is obtained and an equilibrium established between the solid phase and in the solution as
ABS A B
(1)
Applying law of mass action,

K
CA CB
CAB
(2)
where CA, CB and CAB are concentrations of A, B and

AB in the solution, respectively. The concentration of pure
solid is a constant number i.e.
CAB S a constant K
K
CA CB
K0
or
0
KK CA CB
(4)
0
Since K and K are constants, the products of KK is also

constant, say Ks, therefore Eq. (4) becomes
Ks CA CB
(5)
The constant Ks is called solubility product (SP) and (CA

CB) is called ionic product (IP). When the solution is
saturated the ionic product is equal to the solubility product.
When the ionic product exceeds the solubility product i.e.
IP/SPS>1, the solution is supersaturated (Sdegree of
supersaturation), precipitation occurs and ions combine
on the substrate and in the solution to form nuclei. There
are three main factors which affect the solubility product as
temperature, solvent and particle size [1618]. The direction
of solubility change as a function of temperature, since
increase in the temperature by a stress, the equilibrium
between a precipitate and its ions in solution will shift
according to whether the heat of solution is endothermic
or exothermic. Using a solvent of lower dielectric constant,
the solubility of moderately insoluble substance in water is
reduced by the addition of alcohol or some other water
miscible solvent. As particle size decreases, solubility
appears to increase.
Solubility constants have been reported by using different
methods which include calorimetric, cation exchange, conductivity, ion exchange, polarography, thermodynamic data,
rate of reaction etc. The solubility constants are found to be
dependent on temperature, medium and method of measurements and therefore a difference of several orders of magnitudes in solubility constants of a material has been
reported in the literature. Recently, S. Licht [19], using
thermodynamic data and incorporating a new free energy
of formation for aqueous S2 in alkaline medium has found
out that solubility products of the insoluble metal sulphide
salts are several orders of magnitudes smaller than previously considered [20,21]. Table 1 represents the solubility
constant data for the compounds deposited by chemical
methods. It consists of the data obtained by S. Licht [19]
and earlier reported data [22,23].
2.1.1. Formation of precipitate in the solution
The particle size of precipitate is determined to some
extent by the experimental conditions, prevailing at the time
of its formations. The temperature, rate of mixing of reagents,
concentration of reagents, and the solubility of precipitate at
the precipitation are variables affecting particle size. All of
Table 1
Solubility constant data for the compounds deposited by chemical methods
[1921]
stable phase (AB)n. The rate of growth is directly proportional to the supersaturation.
S. No.
Rate of growth Ko aQ S
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
Compound
Ag2S orthorhombic
Ag2S (b)
Bi2S3
CdS
CoS (a)
CoS (b)
CuS
CuxS
FeS
HgS (red)
HgS (black)
InS
In2S3
MnS (pink)
MoS2
Mo2S3
NiS (a)
NiS (b)
NiS (G)
PbS (a)
PbS (b)
SnS
SnS2
ZnS (S)
ZnS (W)
As2S3
Sb2S3
HgSe
MnSe
Fe2Se3
CoSe
NiSe
CuSe
ZnSe
PKsp [19]
36.3
36.1
63.1
15.9
7.2
13.0
22.1
35.1
3.7
39.1
38.7
16.4
44.3
2.6
40.9
55.8
6.9
12.2
13.9
44.8
15.2
60.1
16.3
11.5
8.7
PKsp [20,21]
where a is the surface area of the exposed solid and Ko is a

constant which is the characteristic of the particular precipitate. If the supersaturation is maintained at low level
throughout the precipitation process occurs. As a result there
are great number of centres upon which growth process can
take place, none of the particles grow very large and a
colloidal suspension consists of finely divided solid particles
in a liquid phase with diameter of 0.01 to 0.1 mm. Under the
same circumstances colloidal particles can come together
and adhere to one another and the resulting solid is called
colloidal precipitate and the process by which it is performed is called coagulation or agglomeration. Colloidal
particles when agglomerated have quite different properties
from a crystalline solid, since the particles are arranged
irregularly.
26.5
90.5
27.8
20.4
24.7
41.09
46.7
3.90
47.17
73.24
15.16
2.5
3.0
4.7
3.18
5.20
0.1
2.2
22.80
33.19
92.77
59
7.27
4.0
7.08
5.29
7.78
7.72
2.2. Experimental details

2.2.1. Chemical bath deposition method
Based on operation, experimental set up is employed for
the growth of the lms from bulk precipitation of the
solution, details of which can be seen from Fig. 1. In this
technique substrates and solution are stationary and solution
is stirred with the help of magnetic stirrer. Water or parafn
baths with constant stirring are used to heat the chemical
bath to the desired temperature. In some cases, stirring is
these can be related to the relative supersaturation of the

system. A state of supersaturation may be achieved by
lowering temperature of an unsaturated solution of the solute
in solutions. For any precipitate, there is some minimum
number of ions or molecules required to produce a stable
second phase in contact with a solution called a nucleus. The
rate at which nuclei form in a solution is dependent on the
degree of supersaturation. The rate of nucleation increases
exponentially in higher supersaturated solution.
Rate of nucleationKo(QS)X provided that X>1, where
Q is the concentration of solute in solution and Ko and X are
constants. The second step is the growth of particles already
present in the solution. This begins when nuclei or other seed
particles are present. In the case of ionic solids, the process
involves deposition of cation and anion on appropriate sites
[12].
ABn A B ) ABn1
ABn1 A B ) ABn2
(8)
0
(6)
(7)
where n is the number of A and B required for giving
Fig. 1. Experimental set up of chemical bath deposition.
continuous from room temperature, while in some cases, it is

started after attaining the desired temperature.
3. Metal chalcogenide films by CBD method
The following section deals with chemical bath deposition of various metal chalcogenide thin lms. The detailed
preparative conditions and properties are presented in
Table 2.
3.1. Metal sulphide thin films
3.1.1. Cadmium sulphide (CdS)
Polycrystalline CdS lms have received considerable
attention during recent years because of their proven and
potential applications in the photoconductors as well as in
the photovoltaic devices. CdS lms have been prepared by
various methods such as vacuum deposition, sintering, spray
pyrolysis, chemical deposition etc. CdS thin lms have been
prepared by chemical deposition from an aqueous acidic
and alkaline and non-aqueous baths by many researchers
[2273].
3.1.2. Zinc sulphide (ZnS)
ZnS is an important semiconductor material with a large
bandgap (>3.5 eV), which has vast potential use in thin lm
devices, such as photoluminescent and electroluminescent
devices. Besides, ZnS could be an important material in
short wavelength emitting diode too. Fabrication of graded
bandgap Cu (In, Ga)Se2 thin lm mini-modules with a (Zn,
O, S, OH) buffer layer has been reported [74]. The post
deposition light soaking led to over 14% efciency. Chemical deposition of ZnS thin lms has been carried out from
aqueous acidic and alkaline baths using thiourea and thioacetamide by many workers [7580].
3.1.3. Mercury sulphide (HgS)
Double layer thin lm systems of Se/HgSe, Sb2S3/HgS,
As2S3/HgS etc. show anomalous photoconductivity which is
characterized by a `spectral memory'. The dark conductivity
of these materials in thin lm form is not constant in a
certain temperature range but depends strongly on the
wavelength of light to which the lm was preliminarily
exposed. The alloy lms of HgS and PbS having variable
optical bandgaps (HgS-2 eV and PbS 0.37 eV) are promising semiconductivity materials for IR detection in the range
112 mm. Chemical deposition of HgS thin lms using
chemical method has been carried out by many workers
[8186].
3.1.4. Silver sulphide (Ag2S)
Thin lms of Ag2S have applications in photoconducting
cells, IR detectors, solar selective coating, photovoltaic cells
and photoelectrochemical storage cells. Kitaev et al. [87]
have rst studied in detail, the deposition of Ag2S from
aqueous solutions of thiourea and silver nitrate, over a wide

range of solution compositions. They found experimental
conditions where the formation of Ag2S lms was observed
and proposed on interpretation based on a thermodynamic
analysis. Later on many research groups have reported on
Ag2S lm deposition [8896].
3.1.5. Manganese sulphide (MnS)
During recent years, dilute magnetic semiconductors have
become a focus of intense research activity as they exhibit an
interesting combination of magnetism and semiconductivity. MnS is such a material with bandgap energy, Eg, 3.1 eV,
having potential use in solar cell applications as a window/
buffer material. The cubic a-phase of MnS appears to be
stable above room temperature. The b- and g-phases of MnS
can be prepared at low temperature, but they are turned to the
a-phase above 2008C. The a-phase is retained at all the
temperatures. Chemically deposited MnS lms have been
prepared by Pramanik et al. [97], Lokhande and Gadave [98]
and Lokhande et al. [99] using thioacetamide and thiosulphate as the S2 ion sources.
3.1.6. Bismuth trisulphide (Bi2S3)
Bismuth trisulphide occurring naturally in gray crystalline form is referred to as `Bismuth glance' or Bismuthinite.
Both natural and articial crystalline forms belong to orthorhombic crystal structure. Bi2S3 is the semiconductor material whose bandgap energy (Eg1.7 eV), lies in the visible
energy spectrum and can be used in optoelectronic devices,
particularly solar energy devices. Number of authors have
worked on chemical deposition of Bi2S3 thin lms from
aqueous and non-aqueous media [107120].
3.1.7. Antimony trisulphide (Sb2S3)
Antimony trisulphide is an important material in view of
its photosensitive and thermoelectric properties. It nds
special applications in target materials for television cameras, microwave devices, switching devices and various
optoelectronic devices. It has applications in paint and
polymer industries, microwave switching and various optoelectronic devices [121]. Antimony trisulphide thin lms
have been deposited from aqueous and non-aqueous and
acidic and alkaline media by using different S2 ion sources
[121130].
3.1.8. Arsenic trisulphide (As2S3)
Photoinduced effects in As2S3 are of importance having
applications in optical imaging, hologram recording and
optical mass memories. Photosensitive chalcogenide systems have potential as photoresists form microlithography in
fabrication of integrated circuits. Photoluminescence of
As2S3 has been investigated for amorphous and crystalline
forms with the conclusion that the same deep recombination
centers are present in both amorphous and crystalline forms.
Chemical reaction of As2S3 lms from acidic and alkaline
media have been reported [125,131136].
Table 2
Preparative conditions and properties of metal chalcogenide films by chemical bath deposition method
S.
No.
Bath
composition
Metal sulphide thin films

Cadmium sulphide (CdS)
1.
Equimolar cadmium
saltthioureaNH4OH
Thickness
Deposition Substrates
temperature used
(8C)
Deposition
time
Remarks
References
Alkaline 812
8090
Stainless steel,
tin oxide coated
glass, titanium
glass
3040 min
Yellow-reddish coloured films of CdS were obtained.

Films were adherent and sparingly reflecting. For higher
deposition time lower is the thickness, growth is either due to
ion-by-ion condensation or adsorption of colloidal particles.
Phases were mixed and polycrystalline in nature with n-type
conductivity and bandgap 2.4 eV
The substrates were covered with orange-yellow CdS
deposits. Thickness was decreased with addition of excess
TEA With increase in temperature, rate of growth of CdS
films increased but terminal thickness decreased
Films with equimolar ratios are found to be inferior. Sizes
of the crystallites vary considerably with a bath
temperature. Dark conductivity is 2109 O1 cm1,
photoconductivity decay time is 13 h/decade
The optical bandgap of CdS: Li films was 2.35 eV and low
electrical resistivity obtained with doping
[29]
2.
Cadmium
acetatetriethanolamine
(TEA)ammoniathiourea
Alkaline
7 mm
50
Glass
13 h
3.
Cadmium
acetateTEAthiourea in ratio
1:0.50.5
Alkaline
0.30.4 mm
75
Glass
4.
Li2O3 (105) doped 1 M

CdSO41 M
thioureaNH4OH
1 M CdSO41 M
thioureaNH4OH
Alkaline 1011
12 mm
85
Glass
12 h
Alkaline 1011
12 mm
85
Glass
12 h
6.
Na doped CdS films by adding

1 wt.% to a bath 1 M
CdSO41 M
thioureaammonia
Alkaline 1011
12 mm
85
Glass
12 h
7.
Cu doped CdS films by adding

copper salt (CuI, 0.1 wt.%) to
the bath 1 M CdSO41 M
thioureaNH4OH
Alkaline 1011
12 mm
85
Glass
12 h
8.
Bi doped CdS films by adding

bismuth nitrate 0.15 wt.% in
to bath. 1 M CdSO41 M
thioureaammonia
Alkaline 1011
12 mm
85
Glass
12 h
9.
Al doped CdS films by addition

of Al2(SO4) to bath (0.1 wt.%).
1 M CdSO41 M
thioureaammonia
Alkaline 1011
12 mm
85
Glass
12 h
5.
From XRD studies, CdS films were polycrystalline and

contain mixture of 90% b cubic and 10% hexagonal forms
of CdS
Crystallinity decreased with addition of sodium. CdS:Na
films showed n-type conductivity. Na acts a acceptor and
defect levels are shallow, photoconductivity properties of
CdS:Na indicated pinning of the fermi level at high
excitation level
Addition of cations like As, Cu, In, Zn etc. to the deposition
bath makes the film amorphous. Surface state density was
1091020 cm3 eV1 by field effect measurement. Carrier
density and mobility were 1014 cm3 and 5 cm3 V1 s1,
respectively
The thickness of CdS:Bi films increased with doping level
and attained maximum at 2 wt.% Bi doping. The bandgap
increased to 2.4 from 2.2 eV. The thermoelectric power,
mobility and conductivity were higher for Bi doped CdS
films and electrochemical characterization of CdS:Bi films
was also carried out
The crystallinity and electrical resistivity were improved
with Al doping. Surface state density was of the order
of 1017 cm3 eV1
[31,32]
[33]
[35]
[36]
[37]
[4]
pH
[38]
[3941]
Table 2 (Continued )
Bath
composition
pH
Thickness
temperature used
(8C)
Deposition
time
Remarks
10.
1 M CdSO4Na2S2O3
Acidic 24
0.10.15 mm
85
Glass
1520 min
11.
Cd
saltthioureanitrotetraacetic
acid
0.1 M CdCl2 (50 cc)0.1 M
thiourea (50 cc)
Alkaline 10.7
2002000 A
Glass
Cds films of yellowish colour were observed. Adherent was [30]

increases with increase in deposition temperature, i.e. 1008C.
Room temperature resistivity was 103104 O cm1 and
optical bandgap was 2.55 eV1
A blue shift in bandgap, Eg of 0.2 eV and grain size
[42,43]
were observed
between 3070 A
Alkaline 910
8002030 A
085
Glass
30 min and
65 h
Alkaline
150 nm
60
Glass
2h
Alkaline
60
Glass
12.
13.
14.
25 ml (0.1 M) cadmium
nitrate20 ml (1 M)
ammonia10 ml (1 M)
thiourea37.5 ml water
0.015 M CdSO40.15 M
thioureaammonia
15.
0.14 M CdI20.14 M
thioureaammonia
11.5
70
Glass
1039 h
16.
2 M ammonia5103 M
CdSO45102 M thiourea
Alkaline
Ni coated glass
17.
0.02 M CdCl20.5 M
KOH1.5 M NH4OH0.2 M
CS (NH2)2
10
Glass
40 min
with increase in
Grain size was changed from 30 to 70 A
deposition temperature. Blue shift of 0.3 eV was observed.
Electrical resistivity was decreased from 9108 to 2108
. Activation
with increase in thickness from 8002000 A
energy varied from 0.24 to 0.125 eV
At 3005008C, In is deposited by thermal evaporation on
CdS surface. Grain size was found to increase from
1317 nm after diffusion of In, whereas Eg decreased from
2.58 to 2.37 eV with increase in electrical conductivity
Films were n-type in conductivity. Growth was in two steps,
the formation of dense compact inner layer followed by
porous, less adherent layer
Microstructure was changed depending on pH of the
solution, at pH11.9, films have poor coverage on substrate.
At pH 11.8, oxygen content was minimum and observed
good stoichiometry by AES, Z17% has been obtained and
were used in CuInGaSe2 solar cells as a buffer layer
These films have been studied in situ using electrochemical
open circuit potential (EOCPC) change measurement. An
explanation of EOCPC dependence with film thickness in
terms of space charge region theory has been reported.
SEM showed high compactness. It showed nucleation
growth mechanism, hexagonal cubic structure. Eg was
2.48 eV and r was 107 O cm. Nd was calculated using
EOCPC
Parallel and perpendicular magnetic field (0.049 0.077
Torr) was applied to the substrate and bandgap was found
to increas by 0.1 eV with magnetic field, resistivity
changed from 105101 O cm and average grain size from
73 to 30 nm. Magnetic field induces the formation of
sulphur vacancies
References
[44]
[45]
[46]
[15]
[48]
[49]
S.
No.
18.
CdSO4thioureaNH4OH
11.7
Glass, Ti, FTO

coated glass and
filter paper
19.
0.55 M CdSO410150 mM
SC(NH2)2ammonia
12
70
Ni
20 min
20.
2 mM CdSO41 M Na2S2O3
38
<30
Glass
21.
37 ml (1 M) cadmium
acetate20 ml (13 M)
NH4OH10 ml triethanolamine
(TEA)100 ml waterthiourea
20 ml (0.2 M) CdCl220 ml
(7 M) NH4OH5 ml (2.5 M)
NH4Cl40 ml (1 M) CS(NH2)2.
Samples were immersed in ion
exchange solution containing
200 ml (0.025 M) thiosulphate
complex of AgNO3, pH7,
immersion 2030 s, heated
at 1508C for 24 h
5 ml (1 M) Cd salt2.5 ml
(7.4 M) TEA5 ml (14 M)
ammonia5 ml (1 M) thiourea
80
Glass
1025 min
10.8
80
Glass
2025 min
Considerable enhancement was observed in photovoltaic

cell parameters of SnO2/CdS: Ag/SnSxC cells
Alkaline 910
25
Glass
6.58 h
0.5 M cadmium acetate2 M

ammonium acetate14.8 M
NH4OH0.5 M SC (NH2)2
Alkaline 910
0.5 mm
85
Glass, SnO2 coated250 min

glass
[57]
Strong peak of CdS (2 0 0) was observed.
Photoluminescence shows band edge peak at 2.51 eV and
broad peak in red region associated with S vacancies. The
strain and defects in the lattice show large FWHM of the Lo
phonon in Raman scattering of an deposited film. Annealing
at 5008C leads to relaxation in strain impurity and improves
the crystalline quality of the film
The r103104 O cm and Eg2.3 eV were obtained. The
[58]
optimized parameters have enabled to maximize the
thickness of the deposited film in a single dip and to grow
thickness of films by periodically replacing the concentration
of reactants while the substrate remains continuously dipped
in reaction bath
23.
24.
[5052]
[53]
[54]
[55]
[56]
22.
For pH<9, yield larger crystalline size and pH>12 fine

particles. Crystallite size was controlled by reaction time,
pH, temperature of the solution and thickness of the deposit.
Bandgap was 2.4 eV for the bulk and 2.97 eV for
nanocrystalline sample of grain size 5.0 nm. Red shift was
observed from PL studies. Cells with Na2SO3 electrolyte
gave improvement over bulk CdS. Roughness was studied
by using AFM and RBS for different thicknesses. Roughness
was 8.95 nm from AFM and was 12 nm from RBS studies.
Thickness/crystallite size increases the surface roughness and
influences Raman scattering yield
The influence of cadmium salt and thiourea on the
morphological and structural properties have been studied.
Two different featured regimes have been distinguished,
inner continuous layer and outer porous layer. Root mean
square roughness was 1013 nm and average roughness was
711 nm. X-ray and EDS give cubic structure. Composition
showed that films are sulphur deficient and S/Cd atomic ratio
decreases when Cd salt concentration increases
The S2O32 ions absorb ultraviolet light of wavelength
shorter than about 300 nm and excited S2O32 ions supply
sulphur atoms and electrons to the metal ions such as Cd2,
reaction occur in illumination region. Films were polycrystal
line and hexagonal type, after annealing above 3008C,
stoichiometry was maintained
CdS films of nanocrystalline, wurtzite and highly oriented
in (0 0 2) direction, particle size was 2025 nm and blue
shift 0.050.13 eV was observed
S.
No.
Bath
composition
pH
Thickness
temperature used
(8C)
Deposition
time
Remarks
References
25.
100 mM CdCl2100 mM
SC(NH2)2
910
800203 A
085
Titanium
1h
[62]
26.
chlorideNH4OH50 ml
(0.1 M) thiourea
910
65
90 min
27.
(0.01 M) CdCl2(0.039 M)
NH4Cl(0.76 M)
NH4OH0.17 M SC (NH2)2
11
1.15 mm
73
Glass and
FTO coated
glass
28.
acetate812 ml (1 M) sodium
citrate15 ml (1.5 M)
NH4OH510 ml (1 M)
thioureawater
Cadmium acetate1 M
thioureaTEA14.4 M
NH4OH
5070
Glass
12 h
Films were nanocrystalline, n-type and photoactive in

polysulphide electrolyte. The rapid removal of one charge by
the electrolyte explains the low recombination loss. Charge
separation is due to different kinetics of electron and hole
transfer to the electrolyte
Films were doped with Al and Cu by 0.1 wt.%. The
photoconducting studies of such films showed that the
photoconductivity has been increased with 0.1 wt.%, Al
doping and decreased with 0.1 wt.% Cu doping
Resistivity of the film can be controlled within a certain
range by controlling annealing atmosphere, annealing in
forming gas has more effect than annealing in vacuum and
air. r of CdS film on ITO glass was smaller than a single
CdS layer and can be decreased. Further films can be used as
in solar cells after annealing
Very smooth and uniform coatings of CdS were formed
except at long durations of depositions
25 and 60
Glass
24 h at 258C
and 4 h at
608C
30.
1 M cadmium acetate1 M
thiourea1 M TEA30%
ammonia
0.350.5 mm
3085
Glass
2030 h
31.
1 M cadmium acetate0.5 M
thiourea30% NH4OH.
0.350.632 mm
24
Glass
1418 h
32.
nitrate10 ml 50% TEA15 M
NH4OH5 ml (1 M)
thiourea12 ml (1 M) sodium
citrate
chloride12 ml (1 M) sodium
citrate2 ml (50 M)
ammonia6 ml (1 M)
thiourea35 ml water
0.20.3 mm
75
Polyester
foil
116 h
300 nm
80
Glass
4h
33.
The growth mode was influenced by molar ratio. On film

surface, some organo-metallic impurities were observed
which can be removed by etching in acetic acid, optical
transmittance was improved after etching. Good quality CdS
films were observed at ratio 1:3:14:4.1 of
Cd:TEA:NH3:thiourea
Diffusion of CdS increases dark conductivity and
photoconductivity. Photoconductivity 102 (O cm)1 can
be used in solar cells and photodetectors. Long photocurrent
decay time 103 s was observed. The films were highly
photosensitive, giving Ilight/Idark106
Photocurrent in freshly prepared samples attributed to
photogenration of carriers. Increase of photocurrent after
storage may be explained by a photoenhanced mobility
arising from the chemisorption of oxygen at the grain
boundaries, n-type, r1 O cm
Films have cubic structure, with citrate, no organic
impurities in the CdS films were obtained. Optical bandgap
was 2.552.60 eV. Films were photosensitive with
photocurrent to dark current ratios of <10 under 600 W m2.
The CdS films have n-type and r1 O cm
Films are n-type. X-ray photoelectron spectroscopy studies
show that with the oxide film acting as a diffusion barrier. In
diffusion into CdS thin films lead to the conversion of the
chemically deposited intrinsic photosensitive CdS thin film
to n-type with conductivity up to 50 (O cm)1 with Eg>2.5 eV
[64]
[65]
[66]
[67]
[68]
[69]
[70]
29.
[63]
34.
1 M CdSO41 M
thiourea14 M NH4OH
Zinc sulphide (ZnS)

1.
0.1 M ZnCl27.4 M
TEA7.5 M NaOH1 M
thiourea
2.
2.5 M ZnSO43.5102 M
thiourea3 M NH2NH2
10
0.3 mm
90
Stainless steel
The Cds films were deposited by keeping stainless steel in

anodic and cathodic mode by applying 900 mV voltage. The
photoelectrochemical cells showed that anodic CdS films are
of better quality
[72]
89
0.1 mm
2760
Glass and quartz
8h
Growth rate of ZnS films depends upon the bath temperature
[75]
11.5
600 A
70
Glass
80120 min
[76]
[78]
3.
1 M ZnSO41 M
thioacetamide50% TEA
10 (buffer)
0.44 mm
75
Glass
36 h
4.
0.20 ZnCl24.0 M hydrazine

hydrate0.0350.1 M thiourea
0.0250.05 M Zn acetate1.1
1.2 M hydrazine hydrateTEA
(0.7 M)0.0350.1 M thiourea
0.0010.01 M Zn
acetate0.0010.1 M
thioacetamide0.53 M
hydrazine hydrate0.02 M
NH4Cl
0.1 M ZnCl20.1 M Na2S2O3
Alkaline
16.7
Glass
EDS showed films are microcrystalline with cubic structure.

SEM showed continuous and homogeneous films. Resistivity
was 109 O cm and Eg was 3.76 eV
Various films CuxS, Bi2S3, PbS were deposited on ZnS films
and improvement in solar control coating and solar
absorption was obtained
The optical band gap was 3.5 eV
Alkaline
25
Glass
The optical bandgap was 3.73.8. eV
[79]
Alkaline
Glass
The optical bandgap was 3.64.0 eV
[73]
24
0.10.5 mm
85
Glass, FTO coated10 min

glass, Ti
[21]
10
Glass
Non-uniform and powdery films were obtained. The

electrical resistivity was 106107 O cm and optical bandgap
was 3.40 eV
Optical band gap was 3.76 eV and XRD showed cubic
structure
Mercury sulphide (HgS)

1.
0.05 M HgCl20.1 M Na2S2O3
23
0.48 mm
2550
Glass
90 min
2.
0.05 M HgCl20.1 M Na2S2O3
23
5001800 A
075
Glass
72 h
3.
HgI4SC (NH2)2ammonia
Alkaline
0.7 mm
27
Glass
24 h
4.
50 mm HgCl2100 mm
Na2S2O3 (of equal volume)
23
04 mm
40
FTO coated glass
1h
6.
7.
8.
0.025 M ZnSO41 M
NH33 M hydrazine
hydrate0.035 M thiourea
Films were polycrystalline with hexagonal structure, reddish

in colour, Eg2.45 eV and a104 cm1. These films have
been used in storage cell with CdSe
With thickness shift of bandgap energy was found to be
0.45 eV, r103104 O cm and grain size was found to
increase from 3080A

At smaller thickness <0.7 mm, films were rough and smooth
at a reliable (1 mm) thickness. At the initial stage of growth
the thicknesstime dependence is best approximated by a
linear law
Films were annealed at 1508C for 2 h and
photoelectrochemical properties were reported by using
different electrolytes. Film was stable in potassium iodide
electrolyte (pH13), n-type, ideality factor for dark and
under light was 4.2 and 13.86, respectively, for as-deposited
film. Fill factor was 39% and conversion efficiency was
0.009. Films were photoconductive.
[80]
[83]
[86]
[81]
5.
[77]
[85]
S.
No.
Bath
composition
Manganese sulphide (MnS)

1.
1 M Mn acetate7.4 TEA1 M
NH4Cl, 0.2 ml hydrazine
hydrate1 M (15 ml)
thioacetamide
2.
0.5 M MnCl20.25 M Na2S2O3
3.
1 M Mn acetate1 M
thioacetatamide1.4 M
NH4Cl14.7 M TEA80%
hydrazine hydrate
Bismuth trisulphide (Bi2S3)

1.
20 ml (0.2 M) Bi (NO3)315 ml
(0.1 M) EDTA0.5 M
NaOH30 ml 0.1 M
thioacetamide
2.
20 ml (0.1 M) Bi
(NO3)3TEA1 M
thiourea17 M NH4OH
3.
Bi(NO3)3TEAthiourea
NH4OH
pH
Thickness
temperature used
(8C)
Deposition
time
Remarks
References
810
36 mm
27
Glass
15 min
Films were n-type and photoconductive
[91,92]
810
12 mm
855
Glass
20 min
[95]
2.22.6
0.14 mm
27
Glass
1h
At lower temperature, films were uniform polycrystalline

with r103105 O cm and bandgap energy0.80.9 eV. The
films were photoconductive
Films were black in colour, polycrystalline. Electrical
resistivity was 104 O cm and bandgap energy was 0.95 eV
810
0.30.6 mm
27
1h
0.5 mm
60
1h
Used as storage electrode with CdSe in photoelectrochemical

storage cell
Properties are improved by a thermal annealing treatment in
N2 at 2508C for 1 h. Effective mobility of carriers has been
measured by a Time Resolved Microwave photoconductivity
(TRMC). Band gap energy was 1 eV
[93,94]
Stainless
steel
Glass
910
0.26 mm
27
Glass
8h
[97]
9.79.8
0.60.7 mm
70
Glass
10 h
Alkaline
0.30.5 mm
2590
FTO coated
glass, glass,
glassy carbon
30 min
MnS films showed amorphous nature with pink-gray colour.

Indirect bandgap energy, Eg, was 3.25 eV. p-Type
conductivity was reported. Activation energy and electrical
resistivity were 1.5 eV and 105 O cm, respectively
Pinkish yellow MnS films were observed, films were
uniform and continuous, grain size was 0.10.2 mm, direct
bandgap energy, Eg3.1 eV was reported. Electrical
resistivity was 107108 O cm at 300 K
Pink coloured MnS films were observed. The grain size was
in between 34 nm in diameter. Direct bandgap energy was
found to be 3.02 eV and films were not good
photoconductors. The presence of oxygen was detected by
EDAX and RBS
89
12 mm
27
Glass
2.53 h
Films were amorphous with indirect bandgap equal to

1.68 eV, r107 O cm
[100]
0.050.1 mm
100
Glass
40 min
Films were amorphous with random distribution of small

crystallites. Eg was 1.47 eV and r was 1030106 O cm
[101]
9.29
0.05 mm
Glass
30 min
The effect of pH on solution precipitation was critical. Films

were n-type with carrier concentration 2.61014 cm3 and
mobility 0.07 cm2 V1 s1
Films were amorphous with optical bandgap energy equal to
1.7 eV and p-type
Films were po1ycrysta1line with direct bandgap energy
equal 1.67 eV
[102]
4.
Bi(NO3)3TEAthioacetamide
27
Glass
10 ml (0.1 M) Bi(NO3)38 ml
(0.1 M) EDTA6 ml (0.1 M)
Na2S2O3 5H2O
1.4 mm
27
Glass
9h
[96]
[90]
[98]
[99]
[103]
[104]
Silver sulphide (Ag2S)

1.
10 ml (0.5 M) silver
nitratethioureaEDTA
(2.5 ml, 1.5 M)NH4OH
2.
nitrate15 ml (0.1 M)
thioureaEDTANH4OH
3.
nitrate25 ml 0.1 M sodium
thiosulphate
4.
0.1 M silver nitrate0.3 M
thioureaNH4OH
5.
100 mm silver nitrate(0.75 M)
thioureaNH4OH
10
10 ml (0.1 M) Bi(NO3)310 ml
(0.1 M) EDTA12 ml (0.1 M)
thioacetamide
12 mm
27
Glass
8h
7.
10 ml (0.1 M) Bi(NO3)310 ml
(0.1 M) Na2S2O3
1.4
0.1 mm
27
Glass
4h
8.
30 ml (0.2 M) Bi(NO3)324 ml
(0.1 M) EDTA18 ml (0.2 M)
Na2S2O3
52218 nm
60
Glass
16 h
9.
5 ml (0.5 M) Bi(NO3)370 ml
(50%) TEA2 ml (1 M)
thioacetamide
0.16 mm
25
Glass
7h
10.
10 ml (0.5 M) Bi(NO3)370 ml
(50%) TEA4 ml (1 M)
thioacetamide
0.13 mm
25
Glass
6h
11.
0.5 M Bi(NO3)3TEA0.5 M
thioacetamide
0.05 mm
25
Glass
4575 min
12.
5 ml (100 mM) BiCl35 ml

(100 mM) Na2S2O3
(Acidic) 23 and
(alkaline) 1011
0.50.1 mm
2560
and 0.30.5 mm
Glass
4 h and
30 min
13.
5 ml (0.5 M) Bi(NO3)3
5H2O2 ml (1 M)
thioacetamide
8.5
0.16 mm
25 and 50
Glass
7 and 3 h
14.
10 ml (0.5 M) Bi(NO3)38 ml
(3.7 M) TEA8 ml (1 M)
thioacetamide
8.5
0.13 mm
24
Glass
6h
15.
5 ml (0.5 M) Bi(NO3)38 ml
(3.7 M) TEA8 ml (1 M)
thioacetamide
8.5
0.28 mm
25
ZnS on glass
1 and 22 h
Films were po1ycrystalline with optical band gap, equal to

1.84 eV and dark electrical resitivity was 105 O cm. Films
were photoactive and were used in photoelectrochemical
ce11s. Reported fill factor and conversion efficiency are
0.619 and 0.029%, respectively
Deposition was carried out from non-aqueous medium using
acetic acid and formaldehyde as solvents. Films are
amorphous and n-type. Non-aqueous medium results into
small grain size, Eg 1.9 eV and r106 O cm
Films were polycrystalline, with increase in thickness,
bandgap energy decreased from 2.22 to 1.67 eV and
electrical reistivity from 2.8104 to 5103 O cm, grain size
varied from 5.28.0 nm and was attributed to quantum size
effect
Films were amorphous with activation energy 0.88 eV, after
annealing at 2008C in air changed to polycrystalline form
with activation energy 3.0 eV. Mobility, conductivity and
grain size were found to increase after annealing
CdS films (0.3 mm) were deposited onto Bi2S3 films. After
air annealing at 2008C films were polycrystalline. CdS films
retained useful electrical and optical properties for annealing
temperature up to 3008C
CuxS films of 0.10.25 mm were deposited on Bi2S3 films at
258C for 36 h. After air annealing at 1508C for 30 min yield
well desired solar control characteristics. Sheet resistance
was 3060 O cm. Integrated transmittance was 1532% in
visible region and 1112% in the near infrared region and
films were used in solar control and solar absorber
Films were uniform, deposition at high temperature >608C
decreases film thickness due to formation of precipitate. At
room temperature deposition was not possible.
Eg1.21.3 eV and r105107 O cm. For acidic medium
films have n-type electrical conductivity
Films were photoconductive with light to dark ratios of 100
150 at 258C under 1200 W m2. After annealing at 2008C
for 1 h dark conductivity changed by factor 107 and an
amorphous to polycrystalline transition took place. Films
were used in solar control coating, solar photothermal
application etc
Films were amorphous and after annealing at 2508C become
polycrystalline. Oxygen chemisorption plays a dominant role
in the electrical conductivity of the films and reported
photoaccelerated chemical deposition process of Bi2S3 thin
films with a ZnS substrate layer and are used in metal
sulphide thin film photography
ZnS (0.09 mm) films are used as substrate for Bi2S3 thin
films and are applicable in electronic and photographic
techniques
[105,106]
[107]
[108]
[109]
[110]
[111,112]
[113]
[114]
6.
[115,116]
[77]
11
12
S.
No.
Bath
composition
pH
Thickness
temperature used
(8C)
Deposition
time
Remarks
References
16.
0.05 M Bi(NO3)30.05 M
Na2S2O30.1 M EDTA
10 ml (0.1 M) Bi(NO3)310 ml
(0.1 M) EDTA12 ml (0.1 M)
thioacetamide
23
200500 nm
27
10 min
[118]
100437 nm
Films were uniform and adhesive with bandgap

energy1.7 eV and electrical resistivity106107 O cm
Films were nanocrystalline. With thickness grain size was
found to increase from 7 to 34 nm, Eg from 2.04 to 1.60 eV
and r from 2.4106 to 0.72106 O cm. Films were n-type.
This is attributed to the quantum size. Effect of bath
temperature on structural properties is reported
9.29.5
10 ml (0.2 M) SbCl38 ml
(0.1 M) tartaric acid4 ml
(0.1 M) thioacetamide
10 ml (0.1 M) SbCl316 ml
(0.1 M) sodium thiosulphate
4.
525 h
12 mm
27
Glass
72 h
0.7 mm
27
Glass
8h
0.52 mm
27
Glass
9h
10 ml (0.1 M) SbCl38 ml
0.0420.47 mm
0 and 27
Glass
5h
5.
0.1 M Sb2O30.1 M
Na2S2O30.5 M NaOH
23
0.30.4 mm
27
Glass
12 h
6.
0.025 M potassium antimony

tartarate0.4 M TEA0.5 M
ammonia0.025 M
thioacetamide105 M
silicotungstic acid (STA)
1 mm
27
SnO2 coated
glass, stainless
steel, glass
60 h
7.
25 ml (0.1 M) potassium
antimony tartarate5 ml
(7.4 M) TEA3 ml (17 M)
ammonia25 ml (0.1 M)
thioacetamide
1 mm
27
SnO2 coated
glass and glass
96 h
8.
Methanolic solutions of Sb3

and S2 in 2:3 ratio
112
27
Stainless steel
2030 min
17.
Antimony trisulphide (Sb2S3)

1.
20 ml (0.2 M) SbCl315 ml
2.
3.
[119,120]
Films were amorphous and precipitate was polycrystalline.

Eg1.62 eV (direct) which is smaller than standard value
(1.88 eV) and is attributed to low average co-ordination in
amorphous phase, r107 O cm
At higher pH>5, deposition was not observed, films were
polycystalline, Eg was 1.87 eV and r was 107 O cm
[121]
Films were microcystalline n-type and Eg1.87 eV and

photoconductive. Polyiodide was used as an electrolyte; fill
factor (ff)0.326, conversion efficiency 0.006% flat band
potential Vfb1.2 V versus (SCE) were obtained
At 08C bath temperature films were amorphous and at 278C
were polycrystalline. With decrease in temperature (2708C),
grain size and electrical resistivity were found to decrease
and it is due to quantum size effect. Films were n-type
Films were uniform and compact. Bandgap decreased from
1.92 to 1.82 eV after addition of EDTA. 0.27 and 0.05 eV are
the activation energies for high and low temperature regions
Properties were improved with STA addition. Films were
annealed at 3008C for 1 h in N2. As deposited films were
amorphous whereas annealed were polycrystalline. Atomic
compositions were 34.3:65.7 and 36.2:63.8 for as deposited
and annealed films, respectively, r3.8108 and 5.3106,
carrier concentration nd1.21012 and 2.41012 and grain
size0.12 and 0.82 mm were obtained for as deposited and
annealed films, respectively
As deposited films were amorphous and were polycrystalline
after annealing. Grain sizes were 0.12 mm and 0.82 mm for as
deposited and annealed films on glass substrates. On SnO2
substrate thickness was 0.25 mm. Changes in electrical
parameters are due to removal of defect levels after
annealing
Films were polycrystalline. After annealing at 1208C for
1/2 h, films were changed from orange-red to dark gray
and n-type. PEC results show short circuit current,
Isc0.14 mA cm2, open circuit voltage, Voc0.155 V and
efficiency0.008%
[123]
[122]
[124]
[125]
[126]
[127]
[128]
Glass, tin oxide

coated glass, Ti
Glass
9.
0.050.15 mm
10
Glass
0.51 h
12
0.59 mm
25
Glass
30 h
23
0.20.3 mm
25
Glass
12 h
10 ml (0.1 M) As2O34 ml
(0.1 M) EDTA8 ml (0.1 M)
sodium thiosulphate
10 ml (0.1 M) As2O310 ml
(0.1 M) EDTA 8 ml (0.1 M)
thioacetamide
20 ml (0.1 M) As2O320 ml
(0.1 M) EDTA25 ml (0.1 M)
thioacetamide
Methanolic solutions of As3
and As2 (As2O3CH3CSNH2)
0.7 mm
25
Glass
5h
0.6 mm
25
Glass
9h
99.5
1.1 mm
25
Glass
7h
0.16 mm
27
Glass
12120 h
20 ml (0.1 M) As2O320 ml
(0.1 M) EDTA16 ml (0.1 M)
thioacetamide
50250 nm
Glass
525 h
Alkaline
0.1 mm
73
Glass
2h
Alkaline
1 mm
75
Glass
5h
Tin (IV) disulphide (SnS2)

1.
0.5 M Sn40.1 M
EDTA0.5 M Na2S2O3
1.6
27
60 min
n-type semiconducting, Eg2.35 eV, r103104 O cm. As

deposited films show photoconductivity. Films are
amorphous The SnS2 films were dipped in AgNO3 solution
to convert them into Ag2S films
[139141]
2.
1.6
55
Glass
(10 cm2),
FTO coated
glass, Ti, Plastic
(100 cm2)
FTO coated
glass, glass
20 min
Amorphous film, Eg2.6 eV, r103104 O cm. Annealing at

2008C in air was significant in decreasing the resistivity of
films by 23 orders
[142]
10.
0.65 g SbCl2 dissolved In 2.5 ml

(0.1 M) sodium thiosulphate
and rest of water to make up the
volume to 100 ml
0.1 M Sb2Cl3thioacetamide
Arsenic trisulphide (As2S3)

1.
10 ml (0.1 M) As2O310 ml
(0.1 M) EDTA10 ml (0.1 M)
Na2S2O3
3.
4.
5.
6.
Tin (II) sulphide (SnS)

1
0.1 M SnCl2.
2H2OTEAthioacetamide
16 ml (14 M) NH3
2.
1 gm SnCl22H2O (in
acetone)8 ml 1 M
thioacetamide4 M
NH312 ml 51% TEA
0.1 M SnCl20.1 M
EDTA0.5 M Na2S2O3
[129]
Complexing agent increased the rate of reaction Eg2.14 eV

and decreases to 2.0 with complexing agent, Ea, activation
energies are obtained as 0.29 and 0.13 eV for low and high
temperature regions, respectively
Films were polycrystalline without complex bath and were
amorphous with complex bath, Eg was 2.36 eV and r was
106 O cm
Films were polycrystalline and stoichiometric, Eg was
2.42 eV and r was 105 O cm
[125]
Films were amorphous. Eg was 1.54 eV (indirect) and

attributed to the tailing of density of states curve on to the
normally forbidden energy bandgap. r was 1.344105 O cm
Films were polycrystalline. Grain size was found to increase
with well defined grains, Eg was 2.35 eV (direct) and shifted
to higher energy side for heat treated samples, r was
109 O cm and n-type
Films were nanocrystalline, grain size was found to increase
from 2 to 20 nm with decrease in band gap energy and
electrical resistivity
Glacial acid was used to dissolve SnCl22H2O. Good,
uniform, brown coloured films were observed. Films were
amorphous with bandgap energy 1.5 eV. p-Type nature of
films was reported
Polycrystalline SnS films with bandgap energy 1.3 eV were
reported from transmission spectra. Films were
photoconductive with light to dark ratio 10 under 500 W m2
illumination. Conductivity increased with increase in
thickness, r was 104105 O cm
[130]
[132]
[133]
[134]
[135]
[136]
[137]
[138]
2.
Upon annealing at 3008C for 1 h the films become

photosensitive with light to dark current ratio 23 orders of
magnitude under 2 kW m2. Annealed films were
crystalline. Eg was 1.78 eV
Films were polycrystalline and crystallinity was increased
and optical bandgap was decreased from 1.75 to 1.63 eV
after annealing in H2 gas for 2 h
13
14
S.
No.
Bath
composition
Indium trisulphide (In2S3)

1.
1 M In2(SO4)31 M
thioacetamide1.4 M
NH4ClTEAhydrazen
hydrate
Thickness
temperature used
(8C)
Deposition
time
Remarks
References
Acidic
0.2 mm
2770
Glass, FTO
coated glass
45 h
Films on glass substrate were amorphous and on FTO coated

glass were polycrystalline ("-phase). Eg was estimated to be
2.75 eV. The as-deposited films were photoactive as evidenced
by TRMC studies. The presence of oxygen was detected by
RBS analysis. The grain size was between 20 and 40 A

In optical properties, a decrease in the average transmission
for both visible and infrared intervals was obtained for
increasing both thioacetamide and acetic acid
concentrations. Films contain In, S and O. Eg2 eV (In2S3)
to 3.7 eV (In2O3), depending upon film composition were
obtained, with r between 107108 O cm. AFM showed that
grain size is a function of thioacetamide and acetic acid
concentration. Larger grain size is associated with slower
growth rates
Solar cells based on Cu(In, Cu)Se2 were prepared with In2S3
as buffer layers. The Z was 16%
[146]
2.
(0.025 M) In (III) Cl3acetic

acidthioacetamide
(0.30.1 M)
0.2 mm
70
Glass
30 min
3.
5 mM InCl30.15 M
CH3CSNH2
Acidic
10 nm
70
Cu (In, Ga) Se2

films, glass
20 min
1 mm
30
Glass
0.086
0.16 mm
36
Glass
45145 min
Lead sulphide (PbS)

1
Lead
acetateammoniathiourea
2.
5 ml, 1 M lead acetate5 ml,
1 M thiourea20 ml
NaOH5 ml TEA
3.
1 M lead acetate1M
TEANaOH
1011
0.1 mm
2426
Glass
1 h 45 min
4.
Lead acetatethioureaNaOH
56
27
Glass
5.
0.1 M Pb (CH3COO)0.1 M
Na2S2O3
56
80
Glass
1h
6.
1 M lead acetate1 M
thiourea1 M TEA
1011
2224
Glass
1.304.30 h
7.
1 M lead acetate1 M
thiourea1 M TEA
1011
0.1 mm
60
Glass
4h
PbS films were polycrystalline, activation energy for high

temperature was 0.16 eV and low temperature was 0.04 eV
Photothermal, solar control and photodetector applications
of the PbS film do not necessarily require the higher
deposition rate achievable through photoaccelerated
deposition, use of PbS films in decorative coatings and
imaging techniques have been reported
PbS films have been utilized as solar control coatings. Further
PbS films were also used as substrates since they can provide
the necessary nucleation sites for the formation of CuxS films
By an addition of 0.05 mol% of Cu conductivity increased,
and decreased for further addition. This may be due to
increase in number of charge carriers. Crystalline size
increased from 10 to 100 mm upon Cu doping. Mobility
increases with Cu doping, due to decrease in carrier density.
Bandgap was 0.78 eV for doped PbS thin films
Greyish-black PbS films were observed. Films were very
adherent to the substrate and were polycrystalline with
electrical resistivity of the order of 105106 O cm
PbS thin films satisfy the basic requirements in basic solar
control coatings for window glazing, colours can be
improved by using ternary compounds
PbS thin films offer superior solar control characteristics as
against commercial solar control coatings deposited by
capital-intensive vacuum technique, but were unstable for
long term
[149]
[144]
[160]
[162]
[162]
[164]
[163]
[159]
[11]
pH
Copper sulphide (CuxS)

1.
0.5 M CuCl2, 2.5 H2O9.4 M
TEA30% thiourea
0.1 mm
Room tem-Glass
perature
3 h 15 min
2.
15 ml (0.1 M) CuSO415 ml
(1 M) thiourea
0.5
0.37 mm
60
Glass
40 min
3.
1 M CuSO41 M sodium
acetate7.4 M TEA1 M
thiourea
9.4
500 A
40
Glass
1h
4.
0.15 M CuSO47.4 M
TEM14 M ammonia10.5 M
digol
CuClNaClEDTA
hydraxylamine hydrochloride
0.260.42 mm
3080
Glass
10 h
10
35 mm
3090
Glass, iron, steel,

Al, Zn and C
6.
Copper nitrateNaOHTEA
thiourea
25
Glass
12 h
7.
0.5 M CuSO42.5H2O9.4 M
thiourea in volume ratio 1:2
0.160.14 mm
Glass
2h
8.
0.5 M CuCl22.5 H2O9.4 M

TEA30% 1 M thiourea
1012
0.15 mm
24
Glass
2.15 h
9.
5 ml CuCl25H2O9 ml (1 M)
Na2S2O310 ml 0.5 M
dimethyl thiourea
0.5 mm
2770
Glass
6h
10.
CuCl2TEAthiourea
0.10.25 mm
50
Glass
36 h
0.020.07 mm
25
Glass
67 h
Films were black in colour and polycrystalline. The Eg was

0.6 eV. Films were having p-type electrical conductivity and
r106 O cm
[179]
4.2
0.10.2 mm
80
Glass
30 min
[180]
1112
200400 nm
2560
Glass
615 h
Polycrystalline, uniform and adherent films with

Eg0.94 eV, r103104 O cm and p-type electrical
conductivity were obtained
At molar ratio 1:2:5, films were uniform. The properties
were improved after heat treatment with r0.64
1.91103 O cm
[156]
[157]
[168]
[169]
[170]
[171]
[172]
[173]
[112]
[181]
15
Cobalt sulphide (CoS)

1.
10 ml (0.25 M) CoCl216 ml
(7.4 M) TEA14 M
NH4OH10.4 ml (0.25 M)
thioacetamide
2.
25 ml (0.1 M) CoSO425 ml
(0.74 M) Na2S2O310 ml
(0.1 M) Na2EDTA
3.
0.4 M CoCl21 M
thiourea30% ammonia4 M
NaOH
Stoichiometry range was 1.83<x<1.85, the optical bandgap

was 1.45 eV with electrical resistivity 104103 O cm and
changed to 102101 O cm after air annealing, after
cadmium doping fluctuation was found to be minimum
At 508C deposition was faster, T (IR) was about 10%, T
(VIS) was about 30%, with annealing sheet resistance was
decreased from 106 to 102101 O cm. Films were used in
high efficiency solar control coatings
CuxS thin films on glass substrate with or without protective
polymer coatings possess ideal solar control characteristics.
Electrical conductivity was 1800 (O cm)1, gives adhesive
coating for sticking directly on to existence sheet glass
Bath temperature increases rate of reaction reduces induction
period and produces films with poor adhesion to the glass
substrates. Induction period is also reduced by concentration.
CuxS films were used in photothermal applications and were
also tried in photovoltaic cell
Above 6 h at 708C resulting peeling of the films from the
substrate was observed. After annealing in N2 at 100 mTorr,
there is conversion of CuSCu1.8S and Cu1.96S. It is also
reported that this films can be combined with others to form
ternary compound
Films were deposited onto 0.05 mm Bi2S3 films and reported
that after annealing at 1508C for 30 min, yield well desired
solar control characteristics. Sheet resistance was 30
60 O cm, integrated transmittance was 1532%
[11]
5.
Chemically deposited CuxS films had superior solar control

characteristics. Stability of films over 34 months was found
to be very satisfactory
Substrates were well covered with CuxS films with average
grain size 0.060.8 mm. The bandgap was 2.40 eV and
electrical resistivity of the order of 104 O cm was reported
About 1 h dark brown CuxS films were observed, the optimal
bandgap was 1.8 eV and electrical resistivity was
3 103 O cm. Films were non-uniform and poor in quality
at composition Cu1.8S
Deep brown co1oured films were observed with temperature,
initial growth rate increases but terminal thickness is smaller
16
S.
No.
Bath
composition
pH
Thickness
temperature used
(8C)
Deposition
time
Remarks
References
Nickel sulphide (NiS)

1.
2 ml (0.1 M) NiSO425 ml
(0.8 M) Na2S2O3
78
0.30.4 mm
27
Glass
35 h
[183]
2.
0.030.09 mm
27
Glass
4h
Films were black in colour having a mixture of amorphous

and polycrystalline, Eg0.8 eV and r104105 O cm were
obtained
Films were black in colour with polycrystalline nature.
Eg0.35 eV, p-type electrical conductivity and r10 O cm
were obtained
RT
Glass
1/2 h
Films are amorphous. Eg is 1.17 eV and thermoemf

measurement showed n-type conductivity
[184]
Iron disulphide (FeS2)

1.
1 M FeCl30.1 M Na2S2O3
(1:1)
80
Glass
1h
[185]
Chromium sulphide (CrS3)

1.
0.5 M chromium oxide0.5 M
sodium thiosulphate
The XRD showed that the films were amorphous. The

optical bandgap is estimated to be 3 eV. The electrical
resistivity is of the order of 105 O cm
34
11.5 mm
27
Glass
45 min
[186]
2.
11
1.15 mm
27
Glass
45 min
Brownish coloured films which are thin reflecting,

polycrytalline and adhesive to the glass substrates were
obtained
Structural, optical, PEC properties are reported
911.4
800 A
2860
Glass, Si, Ge
10
Stainless steel
Molybdenum sulphide
1.
5% ammonium
molybdate13.4 M
NH4OH20% sodium
dithionite1 M thioacetamide
0.5 M chromium oxide0.5 M

thioacetamideammonia
Metal selenide thin films
Cadmium selenide (CdSe)

1.
(0.5 M) cadmium
acetate(5 M) potassium
hydroxide(0.125 M)
Na2SeSO3
2.
0.1 M CdSO40.13 M
Na2SeSO3
3.
CdSO4NTANa2SeSO3
Alkaline
Glass
4.
(0.09 M) CdCl2(0.1 M)
sodium nitrilothiacetate
Na2SeSO3
Ti
Below 9 pH value, films were non-uniform and nonadherent, deposition and growth is explained on the basis of
nucleation. Rate of deposition depends upon pH,
composition and deposition temperature
Adhesive and uniform CdSe film was deposited on the
substrate. Absorption coefficient was 104 cm1 and bandgap
was 1.7 eV. n-Type conductivity was reported. Efficiency of
CdSe was 0.098% in polyiodide electrolyte
Films showed blue shift of 0.5 eV in optical bandgap energy.
Mixed structure (cubic and hexagonal) was observed.
Depending upon deposition technique, crystal size was
and CdSe thin films exhibit
increased from 4080 A
quantum size effect
Films were polycrystalline. Photoluminescence and Raman
scattering were studied. After annealing average grain size
and Eg was
was found to be increased from 42 to 180 A
decreased from 2.00 to 1.74 eV
[182]
[187]
[188]
[189]
[190]
[191]
10 ml (0.8) NiSO415 ml
(7.4 M) TEA14 M
ammonia10 ml (0.8 M)
thioacetamide
5 ml (0.1 M) CdSO45 ml
(0.13 M) Na2SeSO32 ml
ammonia
10
0.30.5 mm
7080
Stainless steel
6.
0.5 M CdSO40.1 M potassium

nitrilotriacetate0.2 M
Na2SeSO3
8.5
Ti, SnO2 and

Glass
10 hfew days
7.
0.3 ml (0.5 M) Cd
(CH3COO)21 ml (7 M)
NH4OH30 ml (0.13 M)
Na2SeSO3
3 ml CdCl21 ml NaOH3 ml
NH4NO33 ml selenourea
Alkaline
0.13 mm
90
Ti
3060 min
7.047.90
2.5 mm
80
Glass
8.
Films were polycrystalline, n-type and photoactive. PEC cell

was formed with 1 M polysulphide electrolyte. Polyaniline
layer was deposited on CdSe and configuration was stainless
steel/CdSe/polyaniline. Junction heated at about 751008C
for 60120 min, showed rectifying nature. Junction ideality
factors were 5.45 and 3.82 for the diodes heated in vacuum
for 2 and 3 h, respectively
Films were nanocrystalline, surface photovoltage
spectroscopy was used to study photovoltaic effects.
Photovoltaic properties were dominated by their surface state
distribution, preferential trapping is surface localized states
and may be considerably influenced by the ambient of the
quantum dot films. Surface states play a major role in the
photovoltaic phenomenon
Films were hexagonal, specularly reflecting. Films were used
in photoelectrochemical solar cells, temperature improves
the deposition rate. Conversion efficiency was >6% with
polysulphide electrolyte
Photoluminescence was studied. Stoichiometry and thermal
treatment have strong effect on the photoluminescence
spectra, lines with higher energetic portions were observed in
nearly stoichiometric films
Films were polycrystalline and crystallinity and
photosensitivity were found to be increased after air
annealing. Control over grain size was not possible through
air annealing. Further, quantum refinement effect is reported.
Fine grain size was found to be increased initially and then
decreased. Films can be used in photovoltaic solar cells
Films were photosensitive and it increased after thermal
treatment at 4008C for 1 h. The photocurrent response curves
are expected to show differences in detail under the short
pulse illumination. Photocurrent to dark current ratio was
<10 under white light of intensity 12 kW m2. The
photocurrent rise and decay time are short typically of the
order of milliseconds
CdSe films were used in three electrode storage cells. It was
found that the storage of chemical energy is possible by
using chemically deposited CdSe electrode
[192]
[193]
[194]
[195]
9.
30 ml (0.1 M)
Cd(NO3)34H2O15 ml (0.8 M)
Na2COH5O72H2O1.4 ml
(30%) NH4OH30 ml (0.4 M)
dimethylselenourea
Alkaline
0.49 mm
24
Glass
10 h
10.
salt12 ml (1 M) sodium citrate
or tartarate12 ml (0.1 M)
NH4OH30 ml (0.4 M) N,Ndimethylselenourea
Alkaline
0.170.28 mm
24800 A
Glass
56 h
11.
0.1 M CdSO4, 0.13 M

Na2SeSO314 M NH4OH
10
0.8 mm
30
Stainless steel
30 min
11.411.7
5080
Glass
360 min
Films were highly stoichiometric, microcrystalline with

mixed cubic and hexagonal structure. r was 109 O cm and Eg
was 2.73.1 eV
[28]
910
0.050.12 mm
100
Glass
1h
Films were polycrystalline with Eg2.63 eV r104

105 O cm, n-type electrical conductivity, photoconductive
[204]
910
0.3 mm
50
Glass
8h
Films were uniform and spectrally reflective with yellow

orange colour, polycrystalline, Eg2.63 eV, r1012 O cm
and were n-type in electrical conductivity
[205]
[198]
[199]
17
Zine selenide (ZnSe)

1.
3.51035102 M
ZnSO40.41.7 M
ammonia1025102 M
selenourea
2.
1 M ZnCl27.4 M TEA7.5 M
NaOH14 M ammonia0.4 M
Na2SeSO3
3.
35 ml (0.1 M) Zinc
acetate16 ml (0.8 M) sodium
citrate5 ml (7.4 M)
NH4OH20 ml (0.07 M) N,N0 dimethylselenourea
[196,197]
5.
18
S.
No.
Bath
composition
pH
Thickness
temperature used
(8C)
Deposition
time
Remarks
References
4.
10 ml (0.5 M) ZnSO40.06 M
selenourea10 ml hydrazine
hydrate0.7 M ammonia
ZnSO480% hydrazine
hydrate25%
ammoniaselenourea
35 ml (0.1 M) zinc
acetate16 ml (0.8 M) sodium
citrate5 ml (7.4 M)
ammonium hydroxide0.29
N,N0 -dimethyl
selenourea(0.01 M) Na2SO3
ZnSO4Na2SeSO3
7.5
0.2 mm
70
7.5
0.175 mm
30 min
Films were amorphous and photoconductive
[29]
70
Glass, FTO
coated glass, Ni,
GaP
Glass
30 min
[206]
0.3 mm
50
Glass
8h
From RBS composition of film was Znx(Se, OH)y. Films

were nanocrystalline with grain size (25 nm), cubic
structure and Eg was 2.9 eV
The ZnSe films possess optical bandgap 2.63 eV and suffer
degradation at temperatures >3508C. Films were very
resistive with sheet resistance 1013 O cm, structural,
compositional, optical and electrical characteristics of films
were discussed
9.25
11.30 mm
50
Glass
12 h
[208]
Alkaline
2790
GaAS (l l l)
min1, films were polycrystalline

Rate of deposition was 30 A
with r0.031.4109 O cm1, a1.32.8104 cm1,
Eg2.682.14 eV and n-type electrical conductivity
At room temperature, films were amorphous, whereas at
908C were polycrystalline. The film composition was
Zn0.056Se0.944
1011
27
Thermodynamical data is used to find deposition conditions
[203]
Bismuth triselenide (Bi2Se3)

1.
Bismuth nitrateTEANH4OH
Na2SeSO3
9.810
0.2 mm
30
Glass
2h
[214]
2.
0.5 mm
2240
Glass
1070 min
For pH>10, deposition rate was very slow. Crystallites were

randomly distributed and photoconductive. Films showed
low resistivity in hydrazine hydrate (4.5102 O cm)
containing bath
With increase in thickness sheet resistance was found to be
decreased. Dark conductivity was found to be increased after
annealing through the air and N2 which may be due to the
enhancement of crystallites
0.91.2 mm
30
Glass
10 h
Films were amorphous having Eg1.88 eV and electrical

resistivity 107 O cm
[216]
0.60.25 mm
30
Glass
30 min
Films were p-type with r102 O cm
[217]
Alkaline
27
Glass
15 min
Gold and silver gave ohmic contacts. Films were p-type

semiconductor and polycrystalline with r103101 after
indium doping. Spectral response peaks at 1.1 mm. Films are
5.
6.
8.
9.
5 ml stock solution of Zn2

(0.5 ml zinc nitrate)25 ml
NaOH65 ml water7 ml
(1 M) thiourea0.4 M sodium
selenosulphide
ZnCl2NH4OHN2H4CSe
Na2SO3 of 103 M
0.5 M bismuth nitrate3.7 M

TEA0.066 N,N0 dimethyleselenourea
Antimony triselenide (Sb2Se3)

1.
25 ml potassium antimony
tartarate (2.5 M)12.5 ml
Na2SeSO3TEA30 ml
(17 M) NH4OH
Nickel selenide (NiSe)
1.
0.4 M NiSO40.7 M
TEA14 M ammonia5 M
NaOHhydrazine
hydrateNa2SeSO3
Thallium selenide (TlSe)
1.
0.5 M thallus acetate0.03 M
Na2SeSO340% NaOH
hydrazine hydrate
[209,210]
[215]
7.
[207]
2.
Thallium sulphateTEA
NH4OHNa2SeSO3
Alkaline
0.30.5 mm
Glass
Films are polycrystalline and uniform with r105 O cm and

Eg1.12 eV. Mobility was 0.25 V cm2 eV1 and carrier
concentration was 8.51019 cm3
[174]
Lead selenide (PbSe)

1.
10 ml (0.3 M) lead
acetate10 ml (14 N)
ammonia10 ml (1 M)
NaOH10 ml (0.3 M)
Na2SeSO3
2.
Lead acetateselenourea
902
Glass
30 min
Films were crystalline in nature with FCC structure,

. After annealing peak intensity was found to be
a6.124 A
increased and grain size was changed from 50 to 73.5 A
[219]
30
Glass
1h
[220]
3.
0.1 M lead acetate7.5 N

NaOH0.1 M DMS having
0.01 M sodium
sulphateNa2SeSO3
Lead acetatesodium
citrateNa2SeSO3
98
27
Glass
30 min
Films were microcrystalline and used in photoconductive

cells
Films were smooth. Glass slide was dipped in gold sulphide
solution prior to deposition to get best results
23 and 910
1.1 mm
27
Glass
1824 h
[206]
5.
0.5 lead acetate0.82 M

trisodium citrate
hydroxide0.125 M Na2SeSO3
10.4
250450 nm
27
Glass, Ge, Si,

mica, copper
30 min
6.
0.1 M lead acetate17.4 M

TEA2 M NaOH0.5 M
11.2
0.26 mm
30
Glass
23 h
In acidic and alkaline media, citrate bath has good stability.

Films were amorphous and showed crystalline phase at
3508C
With increasing pH, terminal thickness was found to be
increased. There was increase in deposition rate with
deposition temperature. Rate of deposition was maximum
for Ge followed by Si, Cu and glass. Films were
polycrystalline with FCC structure
Polycrystalline films as evidenced by X-ray and
stoichiometry by EDAX were obtained. Hall mobility was
3 cm2 V s1. Films were p-type
752
Pt (1 1 1)
2h
Copper selenide (CuSe)

1.
30 ml (3 M) copper
acetate9 ml (98%) TEA7 ml
(25%) ammonia(0.1 M)
Na2SeSO3
2.
Tetraamine copperNa2SeSO3
in stoichiometric ratio
79
55
Glass
12 h
3.
0.5 M CuCl2; 2.5 H2O0.5 M

Na2SeSO37.4 TEA13 M
NH4OH
10
23 mm
9095
Glass
30 min
Alkaline
0.50.6 mm
27
Glass
1/2 h
Molybdenum selenide (MoSe)

1.
5% ammonium
molybdate20% ammonia
acetateglacial acetic
acid20%, sodium dithionite
0.45 M Na2SeSO3
[188]
[223]
Film has FCC structure. From SEM studies, it was found that
first layer is compact whereas surface layer is less compact.
At room temperature there was an electrochemical
transformation to the orthorhombic phase and is attributed as
this transformation is catalyzed by the Cu3Se2 impurity
phase present in the cubic copper (I) selenide
min1. Annealed films at 5508C
Rate of deposition was 35 A
for 30 min gave stable and reproducible results as Eg1.44
1.39 eV. From XRD, cubic structure was confirmed. p-Type
electrical conductivity with Hall mobility and carrier
concentration 103 cm2 V1 s1 and 1020 cm3,
respectively, were obtained
Films were homogeneous with average grain size 0.7 mm,
having cubic structure (Cu2xSe) with bandgap energy
1.2 eV. P-Type electrical resistivity, r0.12102 O cm
were obtained
[225]
XRD showed that the films are polycrystalline and

Eg1.1 eV. Films are n-type with r104 O cm
[184]
[226]
4.
[221]
[227]
19
20
S.
No.
Bath
composition
Thickness
temperature used
(8C)
Deposition
time
Remarks
References
Alkaline
0.4 mm
Glass
4h
Amorphous and n-type films were obtained. Role of PVP

was discussed
[228]
100
Glass
15 h
Amorphous films with Eg0.4 eV, p-type and uniform over

the substrate were obtained
[229]
Alkaline
275 nm
Glass
1h
Polycrystalline NiO films were obtained. Optical bandgap is

1.75 eV. Films are p-type semiconductor with r105 O cm
[230]
Zinc oxide (ZnO)

1.
Zinc acetate (ammonical)
Alkaline
0.11 mm
27
Silicon, silica
[231]
2.
6.2
0.6 mm
70
24 h
1011
50
Glass activated
using PdCl2
CuInSe2 films
10 min
Alkaline
0.20.4 mm
8090
Glass
The films were annealed to convert from zinc acetate to zinc

oxide films. Such films were converted into ZnS films by
heating in H2S:Ar gas
The bandgap was 3.3 eV. The crystal structure was wurtzite
(0 0 0 1). Grains size was 0.3 mm
Nanocrystalline films (2030 nm) were obtained with 3.3 eV
bandgap and 80% transmittance
The films were deposited from KCN containing bath. The
electrical resistivity was 108 O cm, XRD showed that the
ZnO films are polycrystalline
11.5
0.050.1 mm
27
Glass
10 h
As deposited films were AgO which turned to Ag2O after

annealing at 1258C. Films are insulating. Ag2O films have a
bandgap of 2.25 eV, while AgO transmit in UVVIS.
Breakdown voltage of about 625 V mm1 and 500 V mm1
have been obtained for AgO and Ag2O, respectively
[235]
10.511
0.2 m
3580
Glass
30 min
The films have electrical resistivity between 106 and

108 O cm. The optical bandgap, Eg was 2.6 eV. TEP
measurement showed p-type electrical conductivity. The
transmittance was >78%
[236]
Alkaline
10002000 A
80
Glass
The as-deposited films were heated at 2503008C for short

time. The XRD confirmed the formation of CdO films. The
electrical resistivity was 11035103 O cm
[234]
Tin selenide (SnSe)

1.
2 M, SnCl22H2O7.4 M
TEA2.5 M NaOH2.5
NaOH0.5% PVPNa2SeSO3
Cobalt selenide (CoSe)
1.
0.4 M CoCl2TEA80%
NaOH80% hydrazine
hydrate0.4 M Na2SeSO3
Metal oxide thin films
Nickel oxide (NiO)
1.
1 M NiSO40.25 M
K2S2O814 M NH4OH
3.
4.
0.05 M Zinc nitrate 0.01

0.15 M dimethylamine borane
0.1 M ZnCl2ammonia
0.05 M NaOH1 M ZnSO4,
precipitate was dissolved by
addition of granular KCN
Silver oxide (Ag2O)

1.
0.5 M silver nitrate0.1 M
NaOH. Silver hydroxide was
removed and to it, 5 ml TEA
(dropwise) was added
Manganese oxide (MnO)
1.
0.02 M MnCl24H2O0.28 M
NH4OH0.8 M NH4Cl
Cadmium oxide (CdO)
1.
0.5 M cadmium nitrate 0.5 M
KOH, solution was made with
H2O2 in H2O, KCN to dissolve
precipitate
[232]
[233]
[234]
pH
Mixed metal chalcogenide thin films

Cadmium sulphoselenide (CdSSe)
1.
50 ml (0.1 M CdCl2)(50x)
ml (0.1 M) Na2SeSO3(0.1 M)
x ml thiourea
2.
Cadmium acetatethiourea
Na2SeSO3InCl3 was doped
from 0.01 to 1 mol%
Thallaus sulphoselenide (TlSSe)

1.
10% Thallous acetate1.5 N
thiourea20% NaOH10%
Na2SeSO3
Copper indium disulphide (CuInS2)
1.
10 ml (0.1 M) CuCl25.5 ml
(0.5 M) thiourea6 ml (0.5 M)
TEA20 ml (13.4 M) ammonia
Lead-cadmium sulphide (PbCdS)
1.
Pb2, Cd2 complexed with
NaOH, NH4OH and TEA,
(CdS)x(PbS)1x composites
with 0.2x0.8
Mercury cadmium sulphide (HgCdS)

1.
0.5 M CdCl20.05 M
HgCl20.5 M thiourea0.4 M
KOHtriethanolamine
(HgxCd1xS), 0x0.5
Cadmium zinc sulphide (CdZnS)
1.
Zinc chloridecadmium
sulphidethioureaammonia
InCl3 used for doping
(0.15 mol%)
60
Glass
45 min
Films were cubic, hexagonal or mixed in structure and

amorphous in nature. Eg was varied from 2.51.8 eV while
going from CdS to CdSe and r was 3.31067.2104 O cm,
films were n-type
Crystallinity was found to be increased up to 0.05% of
indium and bandgap energy was decreased initially and then
increased. PEC cell performance was improved after doping
and is optimum at 0.05 mol%. In doping, enhancement in
performance is attributed to increased grain size and
conductivity. Increase in mobility is because of the reduced
grain boundary potential
10.4
55
Glass, FTO
coated glass
75 min
2790
GaAs (1 1 1)
Films were amorphous at room temperature and

polycrystalline (20 nm) at 908C. XRD and TEM showed
that the crystallize size increased with increase in bath
temperature. Fluorescence confirmed the enhancement in
sulphur content at the interface and also established
composite ratio
[209,210]
Alkaline
0.51 mm
5090
Glass
60 min
Bandgap variation has been observed from 1.1 to 0.8 eV for

Tl2STl2Se mixture. The electrical resistivity was of the
order of 109 O cm. Bandgap Eg was 1.01 eV. Films showed
photoconductivity
[240]
Alkaline
0.10.15 mm
80
Glass
45 min
The electrical and optical properties were reported
[241]
11
85
Glass
45 min
The electrical resistivity is found to be decreased with

increase in composition parameter x upto 0.5 and then
increases for further increase in x. The composites are
polycrystalline with hexagonal CdS, CdO and PbS and
tetragonal PbO and PbO2, a104 cm1 with direct gap
transition. Additional transitions at 1.05 and 1.8 eV are
observed due to oxide formation during growth process
[242]
Alkaline
85
Glass
75 min
The films grew in two different phases, depositions are

polycrystalline of hexagonal type for composition ratio 0
0.5, for higher composition separate formation of CdS and
HgS occurred, the Eg was decreased to 1.76 as x increased
from 0 to 0.5 in CdS. The transition is direct gap
[245,246]
Alkaline
85
Glass
75 min
Films of Cd0.7Zn0.3S were deposited and doped with indium

from 0.01 to 5 mol%. Electrical conductivity was increased
upto 0.1 mol% (109104 O cm)
[247]
[237]
[238,239]
Zinc sulphoselenide (ZnSSe)

1.
0.5 M zinc nitrate25 ml
NaOH65 ml water (stock
solution) 7 ml (1 M)
thiourea0.4 M Na2SeSO3
10
21
22
Bath
composition
pH
Thickness
temperature used
(8C)
Deposition
time
Remarks
References
2.
0.5 M Cd acetate0.5 M Zn
acetate7.4 M TEA13.4 M
ammonia
Alkaline
0.10.2 mm
9095
Glass
15 min
As grown films were composed of a hexagonal phase in the

range 0x0.8 and of cubic phase for x1.0. The bandgaps
are found to vary linearily from 2.5 eV for CdS to 3.6 eV for
ZnS. The resistivity was increased from 109 to 1012 O cm in
the whole range 0x1. By Indium doping resistivity was
reduced to 104 O cm. In hydrogen annealing (2008C, 30 min)
resistivity was reduced to 10 O cm
[248]
Alkaline
Glass
[253]
Alkaline
1090
Glass, Ge, Si
40 min
The films have both phases (a and b) of HgS into PbS lattice
up to 33 at.% of Hg
Electron microscopy and electron diffraction studies show
the predominance of [1 1 1] and [1 1 1] orientations in films
grown on [1 1 1] Ge and [1 1 1] Si substrates, respectively.
The films grew initially as b0 -PbHgS up to a thickness of
, beyond this thickness the films were a0 -PbHgS
about 800 A
810
0.3 mm
80
Glass
20 in
Films were n-types by TEP measurements. r is of the order

of 103 O cm and n is 1019 cm3
[255]
0.45 mm
60
Glass
1h
Films were crystalline, with Eg1.40 eV and electrical

resistivity 0.834105 O cm and were n-type in nature
[256]
0.7 mm
80
Glass
1h
Films were polycrystalline, continuous and adherent to the

substrate, Eg2.6 eV, r1.44105 O cm, n-type and can be
used in solar cells
[257]
80
Glass
1h
The films were heated at 3008C for 2 h. The optical bandgap

was 2.55 eV. The XRD studies showed that the material is
spinel (cubic)
[259]
0.5 mm
80
Glass
2h
Films were amorphous whereas collected powder was

polycrystalline. Films were uniform and smooth with
Eg2.7 eV and r2.39105 O cm. Large resistivity of the
film may be due to large grain boundaries, discontinuous and
small film thickness
[258]
0.40.5 mm
80
Glass
1h
The XRD showed that the films are amorphous. The optical
bandgap of the film was 2.5 eV. The electrical resistivity was
of the order of 103 O cm
[260]
Lead mercury sulphide (PbHgS)

1.
Lead acetatethiourea mercury
(II) chloride
2.
Lead acetate
(400 g l1)mercury (II)
chloride (50 g l1)thiourea
(100 g l1)NaOH (5 N)
Copper bismuth sulphide (CuBiS2)
1.
Copper sulphatebismuth
nitratethiourea in the
volumetric ratio 1:1:2
Cadmium chromium sulphide (CdCr2S4)

1.
2.5 ml (0.1 M) cadmium
35
chloride5 ml (0.1 M) chromic
acid7.5 ml (0.1 M)
thioacetamide
2.
0.1 M cadmium
10
chlordie0.1 M chromic
acid0.1 M thiourea25%
ammonia
3.
0.01 M CdSO40.01 M
10
CrO30.5 M
thioureaammonia
Mercury chromium sulphide (HgCr2S4)
1.
0.25 M HgCl20.25 M
3
CrO30.25 M Na2S2O3
Copper chromium sulphide (CuCr2S4)

1.
0.1 M CuSO40.1 M
CrO31.0 M Na2S2O3 in ratio
(1:1:2)
45
[161]
S.
No.
Cadmium lead selenide (CdPbSe)

1.
Lead acetatecadmium
acetatesodium selenosulphate
Copper indium diselenide (CuInSe2)
1.
10 ml (0.5 M) CuCl218 ml
(0.15 M) Na2SeSO36 ml
(74 M) triethanolamine20 ml
(13.4 M) ammonia
910
10004000 A
Glass, Cu, Ge, Si
Films were continuous and reported growth is epitaxial. a

and b phases are observed. Films on Ge substrate are thick in
comparison with glass and Cu
[261]
10
1.32 mm
5090
Glass
30 min
Films were polycrystalline and crystallinity was found to be

increased with increase in deposition temperature. p-Type
electrical conductivity with electrical resistivity 101 to
101 O cm was reported. 0.9 eV is the reported bandgap
energy
Photoconductivity of the CuInSe2 films was studied.
Photoresponse was maximum at wavelength 1.06 mm. Room
temperature life time of photogenerated carriers was 2 ms at
1.06 mm
Films were polycrystalline with grain size 0.08 mm and
reported bandgap energy is 1.08 eV
[263]
2.
Cu1, In3, Se2 ions in

aqueous medium
>9
300 nm
40
Glass
4h
3.
12.5 ml (0.05 M) InCl310 ml

(0.05 M) CuCl20 ml (0.3 M)
Na2SeSO30.04% ammonia
CuClInCl3Na2SeSO3
200300 A
27
SnO2:F coated
glass
10
27
Glass
Films were uniform for the composition Cu0.9In0.1Se2 and

and c11.88 A
.
were chalcopyrite with a5.75 A
Absorption coefficient was 104 cm1 with direct bandgap
1.13 eV with electrical resistivity 500 O cm. Films were
photosensitive
9.5
1.012.03 mm
50
Glass
12 h
Annealed films were polycrystalline with single phase

[271]
and hexagonal structure at x0.3 and cubic at x0.7. Eg
varies from 1.702.56 eV with x from 0 to 1. a (absorption
coefficient) is different for different values of x due to
existence of defects when the films are far from stoichiometry
Cadmium zinc selenide (CdZnSe)

1.
Cadmium chloridezinc
chlorideNa2SeSO3
[265]
[266268]
4.
[264]
23
24
3.1.9. Tin (II) sulphide (SnS)

Tin sulphide (SnS) has a bandgap of 1.3 eV and hence it is
a potential material in solar energy conversion. The high
conversion efciency 25% is obtainable in photovoltaic
devices, according to PrinceLoferski diagrams and its
acceptability from the points of view of cost, availability,
toxicity and stability ascribe to SnS a unique position among
the metal sulphides, probably to be shared only by FeS2.
Deposition of SnS lms by chemical method is appropriate
for the production of SnS lms in the SnS-CuxS thin lm
combination for solar control coatings and all-glass tubular
solar collectors and for any forthcoming photovoltaic applications of SnS. Very few reports are available on chemical
deposition of SnS lms [137,138].
3.1.10. Tin (IV) disulphide (SnS2)
Tin disulphide is a layer compound with CdI2 type
structure, it is composed of a sheet of tin atoms sandwiched
between two close packed sheets of sulphur atoms. It shows
different electrical and optical properties: visible light
absorption, Raman scattering, for IR refractive index etc.
which are useful in many devices such as current controlled
devices, switching devices and photoconducting cells. Chemical deposition of SnS2 has been carried out from acidic
and alkaline media [139142].
3.1.11. Indium sulphide (In2S3)
Indium sulphide belongs to group IIIVI compound
material and depending upon temperature and pressure,
it exists in different modications (a, b, g). Its bandgap
varies between 2.0 and 2.45 eV, depending upon composition. The Cu(In, Ga)Se2 based solar cell prepared with
chemically deposited In2S3 as a buffer layer have reached
the efciencies (15.7%) near to those obtained by devices
made with the standard CdS buffer layer. Deposition of
In2S3 thin lms from a bath containing indium salt and
thioacetamide as a sulphide ion source have been reported
[143149].
3.1.12. Lead sulphide (PbS)
PbS with its direct bandgap of 0.4 eV and its absorption
coefcient continuously increasing from the infrared
(150 cm1 at 3 mm) through the visible region, has been
used in infrared detectors since the mid 1940s. It was for this
applications that the chemical deposition technique for PbS
thin lms, known since 1910 [150] was initially developed
in the late 1940s [151]. The typical deposition process
involved the immersion of glass substrates in alkaline lead
thiourea solutions [152]. Later in solar energy research, PbS
thin lms were investigated for photothermal conversion
applications either independently on metallic substrates
[153,154] or in multilayer stacked of PbS-CdS-PbS [155]
and (PbS)1x(CdS)x composites [156]. For solar control
and other applications PbS thin lms were deposited
(0.050.15 mm thick) on glass substrates in single layer
[157164].
3.1.13. Copper sulphide (CuxS)

Chemically deposited CuxS thin lms have been found to
possess near ideal solar control characteristics: Transmittance in the infrared region, low reectance <10% in the
visible region so as to avoid glare and relatively high
reectance >15% in the near infrared region. The coatings
can be made on sheet glass, acrylic or polyester sheet and
foil with equal ease. This lm can also be used in laminated
glazing. Chemically deposited CuxS thin lms have been
used in air-glass tubular solar collectors as absorber coating,
in photodetectors and photovoltaic applications. Chemical
deposition of CuxS from uncomplexed and complexed alkaline and acidic media has been investigated [11,165178].
3.1.14. Cobalt sulphide (CoS)
Cobalt sulphide is a semiconductor with bandgap energy
equal to 0.9 eV and has potential applications in solar
selective coatings, IR detectors and as a storage electrode
in photoeletrochemical storage devices [179].
Basu and Pramanik [179] have deposited CoS thin lms
by using thioacetamide as S2 ion releasing source at pH9.
Reaction mechanism proposed is as
CoTEA2 CH3 CSNH2 2OH O2
t25 C
! CoS TEA CH3 CONH2 H2 O
(9)
Lokhande [180] has deposited CoS thin films from an acidic

medium onto glass substrate using sodium thiosulphate as a
S2 ion source. Reaction mechanism proposed in acidic
medium is
Co2 S2 ! CoS
(10)
E'ze and Okeke [181] have deposited cobalt sulphide films

using cobalt chloride and thiourea as Co2 and S2 ion
sources, respectively.
3.1.15. Nickel sulphide (NiS)
Nickel sulphide thin lms have number of applications in
various devices such as IR detectors, as an electrode in PEC
storage devices etc. It can be used as solar selective coating
[182]. Chemical deposition of nickel sulphide from an
alkaline medium using thioacetamide has been carried
out by Pramanik and Biswas [182] and Uplane et al. [183].
3.1.16. Molybdenum disulphide (MoS2)
The optical and electronic properties of layered group VItransition metal dichalcogenides make these semiconductors promising candidates for efcient solar energy conversion. With low energy indirect transition followed by highly
absorptive direct transitions (a105 cm1) at photon energy
around 1.5 eV shows promise to convert solar to electrical
energy in thin lm structures. Chemical deposition of MoS2
using hydrazine hydrate as a reducing agent was reported.
However, sodium dithioanite was used as a reducing agent
which helps in uniform, adherent and rapid deposition of
MoS2 lms at 363 K temperature [184].
3.1.17. Iron disulphide (FeS2)

Due to their high optical absorption coefcient
(105 cm1) and semiconducting nature, FeS2 is a promising
candidate for ultra-thin solar cells, as very little material is
needed and the contact materials do not have to be high
quality optoelectronic materials. FeS2 thin lms have been
deposited by chemical method using acidic bath [185].
3.1.18. Chromium trisulphide (CrS3)
Recently efforts have been made for the preparation of
magnetic semiconductor CrSx. The magnetic and electrical
properties of CrSx (1.32<x<1.50) have been studied earlier
for an interesting transition at the Neel temperature of about
120 K. The electrical properties of CrSx depend critically on
the value of x.
Chemical deposition of CrS3 lms has been reported
[186] onto glass substrate from acidic and alkaline baths.
The strong oxidizing agent bromine water was used to
convert the trivalent chromium to hexavalent chromium.
The lms showed photoactivity.
3.2. Metal selenide thin films
3.2.1. Cadmium selenide (CdSe)
Cadmium selenide has shown great promise as a photoconductor and solar energy material. These lms have
applications in the manufacturing of optoelectronic devices,
thin lm transistors and g-ray detectors. Chemical deposition of CdSe thin lms has been carried out by a number of
workers [39,187202].
It is well known that the sodium selenosulphide hydrolyses in alkaline medium to give Se2 ions as
Na2 SeSO3 OH , Na2 SO4 HSe
(11)
HSe OH , H2 O Se2
(12)
In the presence of Cd2 ions in the bath, CdSe will be formed

if the ionic product of Cd2 and Se2 exceeds the solubility
product of CdSe. The rate of release of Cd2 ions from the
ammonia complex affects the rate of film deposition further,
the rate of release of Cd2 ions is affected by pH, temperature
and concentration of metal and chalcogen ions [188].
3.2.2. Zinc selenide (ZnSe)
ZnSe is a semiconductor material with a band gap
(2.7 eV) which has a large potential use in thin lm devices,
such as photoluminescent and electroluminescent devices
and as an n-type window layer for thin lm heterojunction
solar cells. Interest in ZnSe-GaAs heterojunctions has
greatly increased in recent years because of the possible
applications in a number of high speed and optoelectronic
devices. The wide bandgap ZnSe and related ternary alloys
such as Zn1xCdxSe, ZnSe1xS make them promising materials for optoelectronic device technology in the blue region
of the visible spectrum [28,203,204]. The lattice parameter
of ZnSe is well matched to that of GaAs (0.27% mismatch)
25
so that high quality of ZnSe on GaAs is possible [205]. ZnSe

is an attractive material as a buffer layer in CuInSe2 or
Cu(In, Ga)Se2 based solar cells, as it is Cd free [206].
Chemical deposition of ZnSe has been reported in the
literature from aqueous alkaline medium using sodium
selenosulphate [204,205], selenourea [206] and dimethylselenourea [207]. Chaudhari et al. [209,210] have reported
on the deposition of ZnSSe lms onto GaAs substrate by
addition of thiourea into the deposition bath of ZnSe lms.
3.2.3. Bismuth triselenide (Bi2Se3)
Over last two decades, many experimental data have been
gathered on electrical, optical and thermoelectric properties
of Bi2Se3 material, owing to its applications such as precise
temperature control of laser diode, optical recording devices
etc. [211213]. This lm has great technical importance
owing to its potential applications in photoelectrochemical
devices, solar selective coatings, optoelectronic devices,
thermoelectric coolers and decorative coatings. Solid solutions of bismuth selenide with bismuth telluride are well
known thermoelectric cooling materials. Chemical deposition of Bi2Se3 lms has been reported by many workers
[214,215].
3.2.4. Anitimony triselenide (Sb2Se3)
The use of chemically deposited antimony triselenide
semiconductor thin lms was of basic interest i.e. to improve
efciency and stabilities in photoelectrochemical solar cell
conguration. Very little experimental data is available on
chemical deposition on Sb2Se3 thin lms. Pramanik and
Bhattacharya [216] deposited Sb2Se3 thin lms by using the
mixture of solutions of potassium antimony tartarate and
sodium selenosulphate.
3.2.5. Nickel selenide (NiSe)
Deposition of NiSe thin lms from an alkaline medium
has been reported by Pramanik and Biswas [217]. NiSO4
solution (0.4 M ) was mixed with 7.4 M TEA, 14 M ammonia and 5 M NaOH solutions. In it, 80% hydrazine hydrate
and 0.4 M Na2SeSO3 solutions were added successively.
After about 30 min, the glass slide was covered with dark
deposit. Thickness of the lms was in between 0.06
0.25 mm. Polycrystalline nature of the NiSe lms was conrmed from XRD studies. Films were p-type in electrical
conductivity.
3.2.6. Thallium selenide (TlSe)
Thallium selenide is reported to have a bandgap of 0.8 eV
and extending the photosensitivity from 0.75 to 1.5 mm with
a peak at 1.1 mm. These lms have been chemically deposited onto glass substrates by Mangalam et al. [218] and
Bhattacharya and Pramanik [174].
3.2.7. Lead selenide (PbSe)
Thin lms of PbSe are used in IR-detectors, photographic
plates, selective and photovoltaic absorbers etc. [219].
26
Chemical bath deposition of PbSe thin lms has been carried

out by a number of researchers [188,219225].
and Fort [235]. Peroxide of silver was converted into oxide

of silver at about 1258C.
3.2.8. Copper selenide (CuSe)

Cu2xS (Eg1.4 eV), a p-type semiconductor having
, is
cubic Fm3M structure with lattice constant a5.76 A
used as window materials in Cu2xSe/Si solar cells. The
cubic form (a-Cu2xSe), named as a high temperature phase
is a superionic conductor. The conversion of the orthorhombic phase to the cubic phase has been accomplished either by
heating the material or by electrochemical polarization.
Such transformation occurs when copper vacancies reach
a critical value of x<0.15. Chemical deposition of copper
selenide has been reported from aqueous alkaline baths
[225227].
3.3.4. Manganese oxide (MnO)

Manganese oxide electrodes have promising character of
practical use in water electrolysis, photoelectrochemical
cells and superconductivity. Thin lms of manganese oxide
have been prepared by Mandlik [236]. The lms of
Mn(OH)2 were used for conversion into Mn2O3 lms.
3.2.9. Molybdenum diselenide (MoSe2)

MoSe2 lms were chemically deposited by Pramanik and
Bhattacharya [184] from an alkaline medium using
Na2SeSO3 as Se2 ion source.
3.2.10. Tin selenide (SnSe)
Pramanik and Bhattacharya [228] have deposited SnSe
thin lms from an alkaline medium. For this, 2 M
SnCl2:2H2O solution was mixed with 7.4 M TEA, 2.5
NaOH and 0.5% polyvinyl pyrollidone (PVP).
3.2.11. Cobalt selenide (CoSe)
Cobalt selenide is an important semiconductor which has
applications in solar cells, solar selective coatings and
optoelectronic devices. Pramanik et al. [229] have deposited
cobalt selenide lms from an alkaline medium using cobalt
chloride and Na2SeSO3.
3.3. Metal oxide thin films
3.3.1. Nickel oxide (NiO)
Nickel oxide is an antiferromagnetic oxide semiconductor. It can be used as a catalyst and also as an electrochromic
material. Pramanik and Bhattacharya [230] have deposited
nickel oxide lms.
3.3.2. Zinc oxide (ZnO)
Zinc oxide has been of interest in the optical and electronic industries, because of its electrical, optical and acoustic
characteristics. Thin lms of ZnO have been prepared from
alkaline medium using zinc salt and ammonia solution and
subsequently heating the lms at elevated temperatures
[231234].
3.3.3. Silver oxide (Ag2O)
Thin lms of silver oxide are known to have spectrally
selective characteristics suitable for applications in photothermal and architectural applications. Thin lms of silver
peroxide (AgO) and silver oxides (Ag2O) have been prepared by the chemical bath deposition method by Varkey
3.3.5. Cadmium oxide (CdO)

Cadmium oxide has been of interest in the optical and
electronic industries. Its bandgap is about 2.4 eV and low
conductivities make it useful in optoelectronic devices. A
chemical method of deposition of CdO has been developed
by Call et al. [234] using granular KCN in the bath.
3.4. Mixed metal chalcogenide
3.4.1. Cadmium sulphoselenide (CdSSe)
Cadmium sulphoselenide is a ternary chalcogenide semiconductor whose bandgap varies from 1.7 to 2.5 eV. It is
widely used as a semiconducting material, mainly as photoconductors but with increasing interest focused on their use
in photovoltaic and photoelectrochemical devices. Mane
and Lokhande [237] deposited CdSSe thin lms onto glass
substrates. Shahane et al. [238] and Deshmukh et al. [239]
have prepared CdS0.9Se0.1 lms and doped with indium
(0.01 to 1 mol%). Properties were improved with
0.05 mol% indium doping.
3.4.2. Zinc sulphoselenide (ZnSSe)
Mixed crystals of ZnSxSe1x (0<x, 1) are semiconductors
with a direct band gap ranging from 3.7 to 2.7 eV. They are
found to be very promising materials for various optoelectronic devices such as light emitting diodes in the blue
region of spectrum. For device applications, high quality
epitaxial layers of the materials are required. ZnSe grown on
GaAs gives rise to lattice mismatch of 0.255%. Assuming
Vegard's law exact lattice matching of ZnSe and GaAs can
be achieved by incorporating small amount of sulphur into
the selenium sublattice to give the composition of
ZnS0.056Se0.944 on GaAs (1 1 1) substrate. Chaudhari et
al. [202,210] deposited ZnS0.056Se0.944 thin lms onto GaAs
(1 1 0) substrate by using zinc nitrate, thiourea and sodium
selenosulphate as a Zn2, S2, Se2 ion sources, respectively.
3.4.3. Thallous sulphoselenide (TlSSe)
Thin lms of thallous sulphoselenide have been deposited
by Chocklingan et al. [240]. The observed well dened
crystallites of the lms without any post heat treatment show
that the reported method is capable of producing good
quality photoconducting compound semiconductors. The
compound Tl2S0.8Se0.2 lms show promise for the optoelectronic devices.
27
3.4.4. Copper indium disulphide (CuInS2)

Padam and Rao [241] have deposited CuInS2 thin lms by
using chemical bath deposition onto glass substrates. For
deposition of CuInS2, they mixed 10 ml (0.1 M) CuCl2, 2 (1/
2) H2O, 5.5 ml (0.5) InCl3, 40 ml (0.5 M) thiourea, 6 ml
(0.5 M) triethanolamine and 20 ml (19.4 M) ammonia.
Films obtained by stirring the mixture were extremely
adherent to the substrates and were homogenous in appearance.
energygap and structural properties Hg(II) sulphide has been

used for alloying with PbS. Mercury (II) sulphide is known
to exist in two forms: trigonal a-HgS (Eg2 eV) and b-HgS
(Eg0.1 eV) which is stable above 2808C. The lattice
) and
parameters of PbS and b-HgS (aPbS5.939 A
abHgS5.854 A also favour alloy formation. Chemical

deposition of Pb1xHgxS (x0.33) has been carried out
using thiourea as a S2 ion source from alkaline medium
[253,157,161,155].
3.4.5. Lead cadmium sulphide (PbCdS)

Sulphide and mixed sulphide thin lm coatings nd
extensive use in a number of electronic devices such as
photoconductors, thin lm transistors, photodetectors, electroluminescent cells and photovoltaic devices including
photoelectrochemical solar cells [242244]. A large variety
of deposition technology and their hybrids have been utilized for producing these lms. IIVI group compounds
have a prominent place in this respect as their high efciency, high optical absorbance and direct band gaps corresponding to a wide solar spectrum. Films of Pb1xCdxS have
been deposited many workers [242244].
3.4.9. Copper bismuth disulphide (CuBiS2)

The CuBiS2 system shows rectication characteristics at
the metal point contact and usually crystalline in chalcopyrite structure with peculiar non-linear optical properties.
Sutrave et al. [256] deposited CuBiS2 thin lms by using
copper sulphate, bismuth nitrate and thiourea as a Cu2,
Bi3 and S2 ion sources, respectively.
3.4.6. Mercury cadmium sulphide (HgCdS)

Solid solutions/alloys of IIVI semiconductors, particularly chalcogenides, because of their special characteristics
such as direct transitions, high coefcient of absorption,
relatively higher band gap and low cost for materials production have found suitable in the detection of IR radiation,
in photoconductive and photovoltaic cells and in other
optoelectronic devices. Deshmukh et al. [245,246] have
prepared HgxCd1xS thin lms from an alkaline medium
using thiourea as S2 ion source.
3.4.7. Cadmium zinc sulphide (CdZnS)
Cadmium sulphide together with Cu2S forms the well
known CdS/Cu2S solar cell. The low efciency of CdS/Cu2S
solar cell has been attributed to the mismatching of lattice
constants and electron afnities of the two components.
The addition of zinc into CdS has been tried to match
lattice constant and electron afnity in Cd1xZnxS/Cu2S
solar cells. Increase in Voc without affecting ll factor
and short circuit current has been obtained. The optimal
value of x is found to be in the range of 0.2 to 0.3. Thin lms
of Cd1xZnxS by chemical methods have been reported
[234,247252].
3.4.8. Lead mercury sulphide (PbHgS)
The spectral response of an IR detector can be modied
by varying its optical bandgap and/or the position of an
impurity band in the gap. This objective is commonly
achieved by preparing ternary alloy of suitable compound
semiconductors. Lead sulphide is used for near IR spectral
response towards longer wavelengths. It is necessary to alloy
PbS with a suitable low band gap semiconductor so as to
decrease its optical gap [254]. Because of its favourable
3.4.10. Cadmium chromium sulphide (CdCr2S4)

CdCr2S4 is one of the ferromagnetic semiconductors.
Lade et al. [257] have deposited CdCr2S4 thin lms from
aqueous medium using cadmium chloride, chromic acid and
thioacetamide solutions. Recently, Mane et al. [258] have
deposited CdCr2S4 thin lms onto glass substrate using
equal volume method.
3.4.11. Mercury chromium sulphide (HgCr2S4)
Mane et al. [258] and Gadhave et al [259] have deposited
HgCr2S4 thin lms by using HgCl2, CrO3 and Na2S2SO3
from aqueous medium onto glass substrates and proposed
reaction mechanism for the formation of the lms as
Hg2 2Cr3 4S2 ! HgCr2 S4
(13)
3.4.12. Copper chromium sulphide (CuCr2S4)

Chemical deposition of CuCr2S4 has been carried out
from aqueous acidic bath [260]. CuCr2S4 is a dilute magnetic semiconducting material.
3.4.13. Cadmium lead selenide (CdPbSe)
Sharma et al. [261] have been proposed a reaction
mechanism for the formation of CdPbSe thin lms. The
proposed reaction is as
1 xPbCH3 COO2 xCdCH3 COO2 Na2 SeSO3
Tsc K
NaOH ! Pb1x CdSe 2CH3 COO H Na

SO2
4
(14)
Trisodium citrate (Tsc) was used for efficient control of the

reaction rate in order to avoid excessive precipitation in the
reaction bath.
3.4.14. Copper indium diselenide (CuInSe2)
The reported conversion efciency (11.0%) and excellent
stability with a (Cd, ZnS/CuInSe2) thin lm solar cell [262]
has made the ternary thin lm polycrystalline semiconduc-
28
tor, CuInSe2 a strong candidate for photovoltaic devices.

The optical properties of such lms are gaining importance
in view of the intensive interest in the optoelectronic properties. Thin lms of CuInSe2 with varying copper and selenium contents have been reported by chemical deposition
method by many researchers [262270]. The structure of the
lms depends on the Cu:In ratio and annealing temperature.
3.4.15. Cadmium zinc selenide (CdZnSe)
Pseudo-binary semiconductors have attracted much interest in recent years because of their various applications in
photovoltaics. The opto-electronic properties of
Cd1xZnxSe make it suitable for application in radiation
detectors and laser screen materials in project colour TV.
Sharma and Garg [271] have prepared Cd1xZnxSe thin
lms using solutions of sodium sulphate, cadmium chloride,
zinc chloride and ammonia with 0x0.9.
4. Conclusions
In the present review article, we have described the
chemical bath deposition of metal chalcogenide thin lms.
This method is simple, inexpensive, convenient for large
area deposition and capable of yielding good quality thin
lms. The data presented in the tabular form indicate that the
lm formation could be carried out onto various substrates.
The physical and chemical properties of such semiconductors are comparable with the semiconductors prepared by
other methods. The devices such as solar cells, photoconductors, detectors, solar selective coatings etc. made from
such lms show the promise of the method in modern thin
lm technology.
Acknowledgements
Authors are very much thankful to Mr. S.S. Bellad for his
help in typing this manuscript neatly and to arrange data in
tabular form in a systematic way and to the University
Grants Commission, New Delhi, India for the nancial
assistance through the project UGC-DRS (SAP 19992004).
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Chemical Deposition Method For Metal Chalcogenide Thin Films

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Chemical Deposition Method For Metal Chalcogenide Thin Films

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Materials Chemistry and Physics 65 (2000) 131

Chemical deposition method for metal chalcogenide thin lms

interface techniques are well known [17]. Chemical bath

equipments like hot plate with magnetic stirrer is needed.

Applying law of mass action,

where CA, CB and CAB are concentrations of A, B and

Since K and K are constants, the products of KK is also

The constant Ks is called solubility product (SP) and (CA

where a is the surface area of the exposed solid and Ko is a

2.2. Experimental details

these can be related to the relative supersaturation of the

where n is the number of A and B required for giving

Fig. 1. Experimental set up of chemical bath deposition.

continuous from room temperature, while in some cases, it is

aqueous solutions of thiourea and silver nitrate, over a wide

Metal sulphide thin films

Yellow-reddish coloured films of CdS were obtained.

Li2O3 (105) doped 1 M

Na doped CdS films by adding

Cu doped CdS films by adding

Bi doped CdS films by adding

Al doped CdS films by addition

From XRD studies, CdS films were polycrystalline and

Cds films of yellowish colour were observed. Adherent was [30]

Glass, Ti, FTO

Considerable enhancement was observed in photovoltaic

0.5 M cadmium acetate2 M

Glass, SnO2 coated250 min

For pH<9, yield larger crystalline size and pH>12 fine

Films were nanocrystalline, n-type and photoactive in

The growth mode was influenced by molar ratio. On film

Zinc sulphide (ZnS)

The Cds films were deposited by keeping stainless steel in

Glass and quartz

Growth rate of ZnS films depends upon the bath temperature

0.20 ZnCl24.0 M hydrazine

EDS showed films are microcrystalline with cubic structure.

The optical bandgap was 3.73.8. eV

The optical bandgap was 3.64.0 eV

Glass, FTO coated10 min

Non-uniform and powdery films were obtained. The

Mercury sulphide (HgS)

0.05 M HgCl20.1 M Na2S2O3

FTO coated glass

Films were polycrystalline with hexagonal structure, reddish

increase from 3080A

Manganese sulphide (MnS)

Bismuth trisulphide (Bi2S3)

Films were n-type and photoconductive

At lower temperature, films were uniform polycrystalline

Used as storage electrode with CdSe in photoelectrochemical

MnS films showed amorphous nature with pink-gray colour.

Films were amorphous with indirect bandgap equal to

Films were amorphous with random distribution of small

The effect of pH on solution precipitation was critical. Films

Silver sulphide (Ag2S)

5 ml (100 mM) BiCl35 ml

Films were po1ycrystalline with optical band gap, equal to

Films were uniform and adhesive with bandgap

0.025 M potassium antimony

Methanolic solutions of Sb3

Antimony trisulphide (Sb2S3)

Films were amorphous and precipitate was polycrystalline.