M~~etia~

Chemistly
and Physt'cs,
27 (1991)
1-43

REVIEW

CHEBII~L DEl?aSITIIcsJ
OFMEmL CXAtCOGENIDE THIN FILMS

C. D. LWHANDE
Department of Physics, Shivajj. University, Kolhapur 416 004 (India)

I. Introduction .............................................. 2
2 Theoretical background .................................... 4
3 Deposition of metal chalcogenide thin films ............... 13
4 Conclusions ............................................... 37
5 References ................................................ 38

ABSTRACT

~&al cbalcogenide thin fflm preparation by chemical deposition

is currently attracting considerable attention as it is relatively
fnexpensiva, simple and convenient for large area deposition. H
variety of substxatee such as insulators, s%miconductors or metals
can be us%d since it is a low t%mp%ratur% process which avoids
oxidation or corrosion of metallic substrates. It is a slow process
which facilftat%s better orientation of crystallites with improved
grain structure, Depending upan the deposition condftions, film
growth can take place by ian-byion condensation of the materials
cm the substratas or by adsorption of the colloidal particles frcm
the solutiu3 Onto a substrate, Using this llrethod
thin films of
grasps II-VI, IV-VX, V-VI, I-III-VI etc. have been deposited,

In this review article, the theoretical background of ch%#xical

deposition is dsscribed fn detail. A Survey of binary and ternary
metal chalcogcaaida thin films is given with respect to their prepa-
rativa parant%ters,structural, optical and electrical properties.
Such films have been used in solar sslective coatings, solar carts01
photoconductors,solid state and pbotoelectrochemFca1 solar cells.

0254-0584/91/$3.50 OElsevier
SequoiaiPrinted
inThe Netherlands
2

1 INTROWCTIQN

The range of thzn film application is very large and

extends from micrometer dots in microelectronics to coatings of
several square meters on wlndow glasses. Polycrystalline films
of metals and oxides were the first films which found industrial
applications,mainly in the field of optical devices and eleo-
trOniCS * Polycrystallinesemiconducting thin films have found
widespread indUStrfdl applications [1,2]. Canpound srmiconduc-
tors like Sb2s3 and Sb2Se3 are used in the vidicon television
pick up tube and CdS and CdSe films in photoconductorsand
Solar cells, The III-VI canpound films especially IaAs and InSb
have been used in galvanunagneticdevices, while PbS, &$z and
HgS thin films have been used as IR detectors. Rapid progress
in thin film devices has helped for ICs of monolithic and
hybride microelectronics.

Dictated by considerations of simplicity, economics end

input energy, large area thin films necessarily have to be
deposited by chemical techniques. Electrodeposition,anodizaticm
electroconversion,electrophoresis,electroless, spray pyrolysis,
dip growth and chemical deposition are sane of the chemical
techniques for the growth of thin films fras the liquid phase
C3,43. Of these techniques, chemical deposition (also known as
solution growth, controlled precipitation, electroless plating
or chemical bath deposition), is presently attracting conside-
rable attention as it is relatively inexpensive, simple and
convenient for large area depositions, It does not require
sophisticated instrumentationlike vacuum systems end other
expensive equipment. It can be carried out in a glass beaker
and a hot plate and a stirrer are the equipment needed. The
starting chemicals are commonly available and cheap materials,
 With chemical depositions a large number of substrates can

be coated in a single run with a proper jig design. Unlike in

electrodeposition, electrical can&activity of tne substrate is

not a necessary requirement in chemical deposition. Hence, any

insoluble surface to which the soluticn has free access will be

a suitable substrate for deposition. The low temperature depo-

sition avoids oxidation or corrosion of metallic substrates.

Chemical deposition results in pinhole free and uniform deposits

as the solutron fran which these are deposited alwys remains

in touch with the substrates, Stoichianetric deposits are easily

obtained since the basic building blocks are ions instead of

atans. Tne preparative parameters are easily controllable and

better orientation and improved grain structure can be obtained.

The process of precipation of a substance from the solution

onto a Substrate depends mainly on the formation of a nucleus

and subsequent growth of a film. The concept of nucleaticm in

solution is that the clusters of molecules formed undergo rapid

decomposition and particles canbine to grow up to a certain

thickness of the film, Depending upon the deposition conditions,

such as the bath temperature, stirring, rate, pH, solution

concentration etc., the film growth ean take place by ion-by-ion

condensation of the materials or by adsorption of colloidal

particals from the solution on the substrate.

Using chemical deposition, a number of binaries, such as

MS, CdSe, Bi2S3, BiZSeg, Pbs, PbSe, Ag2S, TlSe, MoS2, urSe~$

ZnS, SnSq, etc. and ternaries such as CuInS2, CuZnSe 2. CdnS,

PbHgS, cdebse, etc. have been depazited as thin films.

In this review article, a survey of thin film chemical

depositicn of chslcogenide semiconductors is given. Ihe theore

tica. aspects of chemical deposition are discussed. Binary and

ternary chalcogenide semiconductor deposition and their physical

and chemical properties are discussed.

 4

2 TH~OKtiTICHL
[Link]
2.1 Solubilitv and Ionic Product

When a sparingly soluble salt AB is placed in water, a

saturated solution containing A and B ions in cantact with the
undissolved solid hB is obtained and an equilibrium is establi-
shed between the solid phase and the ions in the solution. Thus
AB (s) =A+ B 2.1

Applying law of mass action to this equilibrium

C
'A+ . B-
1. -
2.2

=AB(s)

Where CA+ , CB- and &are ccmcentrations of A, B andAB in the

solution respectively.

Tne ccncentration of a pure solid phase is a constant

number, &

Cm (5) = aconstant-K

C C
A* B-
K= 2.3
t
K

or rac’ = c c 2.4
A+ B-

AS K andK' are constants, the product KK’ is also constant,

say KS, therefore eqn, 2.4 bE%XXtlt3S

KS f c x c 2.5
A+ B-

The constant KS is called as the solubility product and the

expression C X C is called as the ionic prodluct.
A* B-
Z2 PreclxxLtate fornation in.,,.,,the
[Link]
6

seed particles are present. In case of an ionic solid the

process involves deposition of cations and anions on

appropriate sites.

( .4B In +A++B - ( AB In+1 2.7

2.8

where n is the minimum number of A and B ions that must canbine

in order to yield the stable particle ( A B 1,. 'Ihe rate of

growth is directly proportional to the supersaturation :

Rate of grwth = Ko'A (Q - S) 2.9

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

constant that is characteristic of the particular precipitate.

If the supersaturation is maintained at a low level throughout

the precipitation, the relatively few nuclei formed will grow

to qive a small number of large particles. With high supersatu-

ration, many more nuclei are formed initially and nucleation

may occure throughout the entire precipitation process. As a

result there are many more centres upon which the growth

process can take place, none of the particles can becane very

large and a colloidal suspension is formed.

The colloidal suspension consists of finely divided solid

particles in a liquid phase with diameters of 0.01 to [Link].

Under sane circumstances, colloidal particles can cane together

and adhere to one another and the resulting solid is called a

colloidal precipitate and the process by which it is formed

is termed coagulation or agglomeration. Colloidal particles

when agglomerated have guite different properties frCnI a

crystalline solid since the particles are arranged irregularly.

2.3 Controlled nrecivitation in the solution

The degree of supersaturation can be reduced by the slow,

dropwise addition of the reagent and by the use of dilute

soluticns of both the ions to be precipitated and the reagent.

In precipitation frcauhanogenous solution the precipitating

agent is chemically generated in the solution. Local reagent

excesses does not occur because the precipitating agent appears

slowly and hanogeneously throughout the entire solution; the

relative supersaturation is thus kept low.

Urea is often employed for the homogenous generation of

hydroxide ion. The reactian can be expressed by the equation:

( H2N ) 2C0 + 2H20 = C02+ 2NH+ + 20H- 2.10

This reaction proce&ds slowly at tm@ratures just below the

boiling point and typically 1 to 2 hours are needed to produce

sufficient reagent for the canpletion of a precipitation.

Haaogenous precipitation of crystalline precipitates also

results in marked increase in crystal size as well as imprwe-

ment in purity.

Controlled precipitation can be obtained when a solution

reacts with reacting gases like NH3 or H2S [8-111. When a

gas is bubbled through the bulk of the solution, precipitation

is obtained while if the solutiai is slowly exposed to the gas

a thin solid film is obtained. 'Ihe thickness and quality of

films can be cantrolled by optimizing the preparative para-

meters. A typical reaction involved in precipitation of CdS

film by reaction of H2S gas with CdSOq solution is as follow:

cdSo4 + H2S - Cds + H2S04 2.11

2.4 Growth of thin films bv the bulk orecioitation of solution

Thin films of metal chalcogenides are obtained by the

bulk precipitation of solution. The reaction of a metal solution

takes place with an aqueous solution of a canpound capable of

giving chalcogenide ions under suitable conditions. Thiourea,

8

thioacetamide or sodium selenosulphate are the canmonly used

canpounds which furnish sulphur or selenium ions respectively

by hydrolysis in alkaline media [12-151.

As representative of the procedure, the deposition of CdSe

is considered [12]. Appropriate amounts of cadmium salt and

ammonia solutions are mixed together and the desired pH is

adjusted. To this, sodium selenusulphate is added and substrates

are dipped in the solution which is heated to the desired tempe-

rature with ccntinous stirring of the solution. The overall

chemical reaction is as follows :

CdCH3(COOH]2 + Na2SeS03 + NaOH+CdSe + 2CH3C08 + H+

+ 3 Na+ + SOi- 2.11

The films are grown by the ion by ion or the cluster by cluster

mechanism depending upon the preparative ccnditicns. Ihe reac-

tion mechanism and growth kinetics of CdSe film formation is

proposed as :

Sodium selenium sulphate (Na2SeS03] hydrolyzes in alkaline

solution to give Se2- ions according to

Na2SeS03 + G-I--+ Na2S04 + HSe- 2.12

HSe'- + CX-I- ---+ 2-

H20 + Se 2.13

In the presence of cadmium ions (Cd29 in the solution, CdSe

will be formed if the ionic product of Cd'+ and Se 2- exceeds

the solubility product of CdSe.

Cd2+ + Se* W CdSe 2.14

To control the number of ians and hence rate of reactian, the

metal icns, M are taken in the form of a fairly stable canplex

The canplex dissociates to give the coatrolled number of M2+

ions which then combine with Se*,icns to form CdSe.

 9

In the present case, ammonia hydrolyzes in water to give GI-

according to

NH3 + Ii20 & NH; -I-

m- 2.15

with hydrolysis cciwtant Khyd= 1.8 x 1O-5

wfienammonia solution is added to Cd salt solution, Cd(QQ2

starts prepfpitating when the solubflity prockwt (SP) of
Gd(CEi?2is exceeded i,e,

cd*2 +2a
-- - GdKw2

with sp = [Cdf2] [#H-2] = 2.2 x lo-l4 2.16

The Gd(CIi)2precipitate dissolves in excess ammonia soluticm

2+
to form the ccmrplexcadmium tetra-ammine icy Gd(NH4 ) 2.17

The stability constant of Cd (NH3)r, pK = 7.12, t.e,

LCd2+] Em3 1 -8
1. 7.56 x Pz!O 2.18
[Cd (NH,),2']

Conversion to logarithmic concentrations and elimination of

pCCd2+] fran eqns. (2.16) and (2,17) leads to

PH = 10.73 + 1/2 p[Gd (NH3)2+] - 2 p [wi3]

4

Xf excess ammonia is added to dissolve the Gd(CW2 precipitate,

then p [cd (NH~):+] can be approximate& by PC salt, hence

pti' 10.73 f 112 pCsdtt - 2 p (NH~);

fa the present case, pGsalt = - lcq (4.8 x 10 02) = 1.3

therefore, pH = Il.38 - 2 p [NH33 2.19

10

13.5

-
---
T-L
‘1
T
12.5

31
o- --Y
11.5 ,-_
I

10.5
-0.45 -03 -035 0

Puw3 I-

Pig. 1, A plot Of pH s J+H$ UShg SF. 2.19.

Equation (2,191, when plotted, is a straight line A as shown

in Pig. 1, Points lying cn the line and in region I represent

a homogeneous system consisting of stabie Cd(NH3)42t ClXQh?X

in equilibrium with Cd'+ ions. In region II, Which can be

reached by the addition of an alkali to the ~[Link], cOndid

tions for the spCmtane<us formaticn Cd(CW2 exists0 that the

points lying in the region II represent a heterogeneous system

ccnsisting of the ccmplex Cd(rTH$~ and a solid phase of

Cd(W2 simultaneously in equilibrium with Cd ions. cdSe films

have been obtained in the region II for [Link] correspmd-

ing to three points on the line A. In the heterogeneous system

of Cdw2 and Cd(B?HS],2+, the region enclosed by the two

dotted lines B'and C represents conditicns for obtaining

films of measurable thickness.

Similar types of icn-by-icm growth reacti- mechanisms

have been proposed for PbSe, Cds, Ybs and HgS 115,ISl.
nccording to Lundin and Kiteav[14]nucleation on substrates

takes place by adsorption of the colloidal particles and

growth takes place as a result of surface coagulation of these
particles, resulting in thin and adherent films. This is
Known as icluster-by-cluster*grcwth of a film.
!thegrowth of Sane chalcogenide thin films fran acidic
baths using Na2S203 as a sulphur scurce has been reported
[17-191. For example, the reaction mechanism for SnS2 deposition
is proposed as follt%s :
Na2S203 is a reducing agent by virtue of the half cell reaction
as

2 "2OJ2 - S40z2 + 2e' 2.20

In the acidic medium, the dissociation of Na2S2S3 takes

place :
-2
'2'3 + 2.21
H+.---, HSO; + s

Ihe released electrons from (2.20) react with sulphur

released fran t2.21) as :

S + 2 e' -----+ s-2 2.22

and fomtation of:SnS2 takes place as

SXP + 2 sm2 ----+ SnS 2.23

2

2.5 Effect of nreaarative parameters

2.5.1 -
Effect of ti

The reaction rate and the rate of deposition depend on

the supersaturation: the lower the supersaturation, the slower
the formation 0fMX. If the ccncentraticn of OH-ion in the

solutim is higher, the M ian ccslcantration

will be lower and
the reaction rate will be slow. With an increase in pH as the
M lon ccncentration decreases, the rate of formation of Mx is
12

decreased. At a certain PI-I,the c~centration of&lions

decreases to a level such that the iCni.c product of M and X

becanes less than the solubility product of MX and a film

will be formed.

2.5.2 Effect

'Ihemetal ion cancentration decreases with increase in

concentration of canplexing ions. Consequently, the rate of

reaction and hence precipitation is reduced leading to a

larger terminal thickness of the film.

2.5.3 Effect of temnerature

'Ihe dissociation of the canplex and the anion of the

canpound ( X compound 1 depends on the temperature. At higher

temperatures, the dissociation is greater and gives higher

concentrations of M and X ions which result in higher rates

of deposition.

The thickness increases or decreases with increase in

the bath temperature depending on the conditions under which

films are prepared. At low pH values, supersaturation is

high even at low temperature and increases further with

increasing temperature. This results in formation of precipitation

and consequently lower thickness is obtained. Athigh pH

values, precipitation is limited due to the low supersatura-

tion and most of the product is formed on the substrate

surface. Further the thermal dissociation of canplex and

anion caapound is increased at higher temperatures so that

more M and X ions are available for MX formation and &us

higher thickness is obtained.

2.5.4 Effect of anion~ccauoound ( X cawound ) concentration

meincrease in X canoound concenuation leads to an

 13

increase in X ion concentration and a film of MX with larger

thickness is obtained. However, above a certain concentration

when rate of reaction becomes high and [Link] also

becanes important leading to a lesser amount of MX on the

Substrate and hence lower thickness,

2.5.5 Effect of substrate

Film formation can take place only under certain ccndi-

tions &, either under optimum ccmditions for MX formation

Ol? when the Substrate has special properties facilitating

for format&cm of Single crystal films. The second ccpldition

favours the formation because when the lattice of the deposited

material matcheS well with that of the substrate the free

energy change is smaller, thereby facilitating nucleation.

2.5.6 Effect of doninq

Impurities in the starting materials can be incorporated

into the films only if the impurities form insoluble chalcc+

genides under the same ccnditicns of deposition and provided

their corresponding ionic product is greater than the

Solubility product, The doping effects film thickness and

properties,

3 DEPDSITICN OF METAL ~LC~~~I~~ FILMS

3.1 Metal Sulnhide Films

3.1.1 Cadmium Sufphide (Cc%)

CdS films have been deposited by using cadmium Salt and

thiourea in a hot (30-W°C) alkaline medium bath by a number

Of workers [12,16,22-431. fn general, equfmolar cadmium salt

and thiourea and NHqU-i solutions in the appropriate volume

ratio are mixed together. 'Ihe substrates are suspended fran

14

a shaft in a reaction cell and rotated continously by a motor

at a ccnstant temperature of 80 to 90°C. After 3O-40 mins,,

yellow-redLish CdS films have been obtained. The overall

chemical reaction, for example is as follows :

NH&H
CdCl2 + iNH2) CS -CdS +CH&+ 2H++ 2Cr 3.1.1

Kaur et al. [16]have studied the kinetics of growth of

Cd.5 fran alkaline solution. Main results are (i) films prepared

in the presence of Cd(W2 in the solution are very adherent,

physically coherent and specularly reflecting, (ii) vigorous

stirring of the solution decreases the powdery nature and

increases auhesion and (iii) in general the higher the

depositian rate, the lower is the terminal thickness. ft has

been established that the growth of film takes place either

by ion-by-ion condensation of Cd+2 and S* ions or by adsorp

tion of colloidal particles of CdS formed in the solutiQ1,

depending on the various deposition parameters and the method

of preparation. As deposited, CdS films exist as a mixed

phase (wurtzite and zinc blende) and films are polycrystaAline

El219 !Phermoelectrfc power measurement showed that CdS films

are n- type. The optical bandgap of CdS films is 2.40 ev,

The substrates used were stainless steel, tin oxide coated

glass, titanium and glass. The pH was between 8 to 12.

Cadmium ions have been complexed as Cd(NI-13)+2[12,16,21,

22]., [Cd(CN)4] +2 [21] and [Cd(TEA)+2] [23,24]. Mondal et al.

1233 using TEA ccanple~d Cd. ions, have reported film growth

at room temperature (3OOC). The bath ws prepared by stirring

cadmium acetate and a solution of TEA. To it, ammonia and

thiourea [Link] were added. After about 18 hours, the

substrates were covered with orangeyellow CdS deposits.

 15

At 30°C, the rate of growth was slow and the terminal thick-

ness was 3 microns after 18 hours, while at 50°C, the growth

rate was higher and the terminal thickness was 1.7 microns in

13 hours. It was found that the increase in temperature,

increased the rate of grmth of CdS but decreased terminal

thiCKrlesS. The TEA excess addition resulted into reduction of

film thickness. 'Ihe reaction mechanism with TE.+ ccmplexed

Cd+2 ions is

[Cd(TEA)+2] + (NH2)2CS + 2cH -CdS + TEA

+ (NH~) 2co + H20 3.1.2

CdS films of very high photoconductivity ( p / d>9)

and a resistivity of 10-l ohm cm were prepared by adjusting

molar ratios of Cd+2 to thiourea between 1 : 0.5 : to 0.25 by

Nair [Link] 1291. They reported that the films with equimolar

ratios were found to be inferior. Thickness on glass substrates

was In the 0.3 to 0.4 micron range. The films were prepared

at 75OC using TEA as a canplexing agent. The sizes of the

single crystallites vary considerably with the bath tempera-

ture. The dark conductivity was 2 X 10' ohm--' cm and activa-

tion energy was > 1 eV. The films showed a photoconductivity

decay time of 13 hours/decade.

Nair and Nair [28] carried out a deposition directly under

sunlight with intensity of 600 iJ/m2. They used 1 M thiourea

and Cd acetate. The roan temperature was 23OC. During the

initial phase of depositia, there was a darkening of the

bath, which increased the solar radiation absorption of the

bath. Ihe resulting photothermal ccaversion in the bath

elevates the bath temperature and thereby increases the

depositicm rate. Good quality films of 0.5 u&iron thickness

have been obtained in l-2 hours as compared to 15 hours
16

required for the depcxsitionunder ambient. [Link] ah-d

excellent optoelectronicpraperties,
A number of d0pants have heen added to CdS films,
Bharadwajet al. (241prepared doped films by the addition of
CuI and AlCl3 in the reacticw bath, Sahu and Chandra 1251 and
shikalgar and Pawar [29] prepared Li doped Cds films. Sahu
end Cnandra [ZS] added Li203 (la-5 N)in to the loath,The
optical bandgap of CdS:Li films was 2.35 eV and the resistivity
of the films was lower. Shfkalgar and Pawar [ZS] added 0.1%
by weight fithum salt to the bath. XRD showed that CdStLi
films are polycrystallineand contain a mixture of 90% of
B cubic and lOXhexagonal forms of CdS. Further optical
properties of these films were studied in detail.
Bargale et-al,1303 prepared Na daped cds fflms to &ding
sodium sulphate ( 1 wt% ) to a bath, The films became less

crystalline when sodium was added. 'R'kenWelect?Ac p0wer

measurement showed that CdS:Na films ware n-type. 'Ihermoelec-
tric power and conductivity experiments showed that Na acts
as an acceptor and defect levels are shall0u. ~h#t~~~c~vity
properties of CdS:Na indicated pinning of the fermi level at
high excitation level.
Pavaskar et.a1.[12] prepared Cds:Cu films by addition
of a copper salt ( CM, 0.1% by weight 1 to the bath. It was
found that addition of cations like As, Cu, In, Zn etc. to the
deposition Mth makes the films [Link] density 0f
states was of the order of 10K,,2O cm3/eV by field effect
measurement. The carrier density was 1014 craw3end mobility
was 5 aa2/V+ec.
Warad et.&. [323 prepared CdS:Bi films by additicm Of
bismuth nitrate (0.1 to 5 wt%) in to bath. The thi&n~S Of

c&s:ai films increased with doping level and attained maximum

 17

at 2 wt% Bi doping. The bandgap decreased to 2.2 eV fran

2.4 eV. The thermoelectric power, mobility and conductivity

were higher for Bi doped CdS films. The (photo)electrochemical

characterization of films has been carried out. Lokhande and

Pawar [34-361 prepared CdS:Al films by audition of A12(S04j3

to bath (0.1 wt%). The crystallinity was improved with CdS:KL

films. The surface state density was 1017 cmq3 eV-I. Pawar &
a. [37] prepared CdS:In and Deshmukh et al. [39] prepared
CdS:As films and their structural and electrical characteriz-
ations are reported. Indium doping was reported to be 0.01 wt
%.
Recently Lokhande [44] has reported on CdS film deposition

fran an aciaic bath using sodium thiosulyhate as a sulphur

source. Eguimolar CdS04 and Na2S203 solutions were mixed

together and the bath was heated to 85'C for 15 - 20 mins.

The pH of the bath was 2 - 3. After 20 mins. yellowish CdS

films were deposited ato glass, titanium and tin oxide coated

glass substrates. A short heat treatment at 150°C improved

adherance of the films. The chemical mechanism is similar to

SnS2 depositicn. Addition of EDTA was found to be beneficial

Film thickness wes between 0.1 - 0.15 micron. Roan temperature

resistivity was lo3 - lo4 ohm cm-l. The optical bandgap was

2.55 eV.

3.1.2 Zinc Sulohide (Z&1

Chemical deposition of zinc sulphide thin films hav been

carried out by Biswas et al. [45] and many workers while

preparing solid solution ternary sulphide films [46,47].

Biswas et al. [45] deposited ZnS films from alkaline medium

using TEA as a ccanplexing agent. Equal volumes of 1 M zinc

chloride, 7.4 M TEA and 7.5 M NaC+i solution were mixed

together and 2 ml of hydrasine hydrate (80%) was added

18

followed by 10 ml of 1 M thioutea solution. After 16 hours,

glass substrates were covered with ZnS films. At 55OC bath

temperature, the rate of growth is higher and terminal thick-

ness is 0.1 micron after 8 hours, while at room temperature,

rate of growtn is slow and terminal thickness is 0.2 micron

after 24 hOurS. The p&i value was optimised.

The XRD showed that 2n.S films are of wurtzite form. ‘l&he

optical bandgap on a quartz substrate was 3.68 %V. The optical

bandgap from photocurrent spectra was estimated to be 3.66 eV.

The thermoelectric1 power measurement showed that films are

n- type in nature.

3.1.3 Lead Sulphide (PbS)

Cnemical ueposition of PbS fran alkaline medium has been

reported, Acharya and Bose (481 mixed lead acetate, thiourea

and mrrnonia solutions. Hithin a minute, the SOlutiOn COiOur

changed to brown. Glass slides were used as the substrates.

The thickness of Pb9 films was of a few tenths of micra=& in

1 hour at temperature 30°C. The XRD showed that films are

polycrystalline without any preferred orientatian. The

activation energy in the high temperature region was 0.16 ev

and in low temperature region was 0.04 ev, The photoconductivity

decay time was lo4 sec. Similarly Nair and Nair f493 have

deposited PbS films at 29OC from a bath Containing Pb+2 ions

and thiourea in the 1:3 molar ratio. Reddy et a&. [50] have pre-

paredPbs ontin oxide coated gLass and zn0 substrates.

3.1.4 Cooner Sulohfde (Cu&

chemical deposition of CuxS films fran uncanplexed and

complexed baths has been reported [51-541. Fatas et al+. (533

and Pramanik et al. [52] used TEA as a complexing agent.
 19

Fatas et al. [531 have mixed lM CuSO4, 1M sodium acetate and

7.4 M TEA solutions and added 1M thiourea with the pH maintained

at 9.4 and experiments were performed at 40°C. In an hour, a

dark brown film of 500 2 thickness was obtained. The optical

bandgap was 2.58 eV and resistivity was 3~10~~ ohm-cm. Tne

film canposition was Cul 8S. The stirring of the solution led
.
to a nonuniform and very poor quality film. Pramanik et al. [52]

have mixed 0.15 M CdS04, 7.4 M TEA and 14M ammonia anu to this

10.5M digol was mixed. Deep brown colcured films of thickness

between 0.26 to 0.42 micrcm were deposited in 10 hours deposi-

tion time. The XRD showed that films are amorphous and film

canposition was Cule8S. The optical bandgap was estimated to

be 2.28 eV. It was reported that with temperature, initial

growth rate increases but 'terminal thickness is smaller.

Varkey [54] has reported CuxS deposition using WTA as a

canplexing agent into the bath formed with CuCl, Nacl and

hydroxylamine hydrochloride solutions. The alkaline pH>lO

values were obtained by addition of NaGH solution. The sub-

strates used were glass, iron, steel, Al pl and C. The films

on Al had voids. Gravimetric analyses showed that the stoichic-

metry range was 1.83Cx<1.85. 'Ihe optical bandgap was 1.45 eV.

'iheresistivit:i of as deposited films was 10v4 to 10'3 ohm--an

and changed to 10B2 to 10-l ohm-cm after air annealing. The

film thickness was 3 to 5 microns. Cadmium doping and annealing

in N2 was found to minimize fluctuation in the electrical

properties of these films with temperature.

3.1.5 Silver SulDhide WaJi)

Chemical deposition of silver sulphide films fran alkaline

as well as from acidic medium baths have been carried out.

Mangalam et al. [55,56] carried out Ag2S deposition from
20

alkaline medium using thiourea as a sulphur source. For this,

glass substrates were immersed in a beaker cantaining water

and stirred ccntinously. Aqueous solution (10 ml of 0.5~)

silver nitrate was added, followed by (2.5 ml of 1.5M) thiourea.

Aft=r 15 mins. adherent deposits of matt-grey Aq2S were formed.

The film thickness was 3-6 micron. The films are n- type in

nature. Dhumure and Lokhande [57] deposited Ag2S films in the

temperature range of 8 to 55'C and canplexing Ag ions with EDT&

(15 ml of 20mM). It was found that the films deposited at 8OC

bath temperature and ccmglexeci with &NW are of better quality.

The roan temperature resistivity was 2 x 10 3 ohm cm -1 . The film

thickness was increased with EDTA audition from 0.19 to 0.52

micron. The XRD showed that films are amorphous in nature. The

plots of (am vs h3 gave 'Eg' equal to 0.8eV.

Dhumure and Lokhande [58] have reported Ag2S depositiol

fran an acidic medium using thioacetamide. A 15 ml of [Link]

silver nitrate and 15 ml of 0.5M thioactamide sOluti~s were

mixed. The bath temperature was varied fran 8 to 55OC and EDTA

(15 ml of 29 mM) was used as a canplexing agent. The film

thickness was 3 to 3.5 micron. The electrical resistivity

was 8.2 x lo4 ohm cm-l. The activation energy is 0.1 eV. With

EDTA, film thickness was decreased. The optical Wndgap was

+3 +'3
0.8 eV. Dopants used were Bi '3, Sb'3, In . Ca , Cd+2, 'fh+*

Hg+2 and Au+~. Of these oily Au" and lig+2 were suitable

dopants for photoconducting properties 1553

3.1.6 Arsenic trisulphide (As2S3)

Chemical deposition of As2S3 films fran acidic and alkaline

media have been reported by Lokhande [59]. The As+~ ions were

canplexed with EDTA andNa 2S 203 solution was added to it. The

pH of the solution was adjusted with dilute HCl to between 2-3.

The deposition was carried out at roan temperature for 12

hours. For the alkaline medium, Nash solution was used to

change the pH of the Asq3 ccmplexed solution. Tine EDTA

canplexed alkaline medium films were found to be superior to

other films. The optical bandgap of As2S3 films was estimated

to be 1.82 ev. The electrical resistivity was of the order of

lo3 - 10 4 ohm cm-1

3.1.7 Tin monosulohide (SnS)

Deposition of SnS fran alkaline medium has been reported

by Pramanik et al. [60].lhe 0.1 Sn'2 solution was prepared by

titrating SnC12: 2 H20 and glacial acetic acid and heating to

+2 , TEA and ammonia solutions
373 K for sane time. To this Sn

were added successively and thioacetamide solution was mixed.

The solution gradually turned brown. In about 2 hours, glass

slides were covered with deep brown deposits.

The XRD showed that SnS films are amorphous in nature.

The Optical bandgap was estimated to be 1.51 ev. The films

are photoconducting and thermoelectric power measurement

showed that SnS films are n- type in nature.

3.1.8 Manaanese sulohide &nS]

Pramanik et al. [61] have carriediout chemical aeposition

of MnS films frcan a TEH cunplexed alkaline bath. lM Mn acetate

solution and 7.4 TEA and lM NH4Cl were mixed together and the

solution was stirred well so that a clear homogencns solution

was formed. To it, 0.2 ml of hydrazine hydrate (85%) was added

followed by 15 ml of lM thioacetamide solution. The resulting

solution was stirred well and after 1.5 hours, the slide was

Covered with a thin pinkqrey deposit. The XRD of as deposited

MnS films showed an amorphous nature while the MnS powder

22

hzsted at 773 K for 6 to 7 hours in an inert atmpsphere showed

a crystalline nature. The plots of (ahY)1/2 Vs (hY) showed

'Eg' equal to 3.25 eV. Thermoelectric power measurement showed

tiat MnS films are p type. Roan temperature resistivity was

lo5 ohrt+cm and activation energy was 1.5 eV. The terminal

thickness was 0.26 micron for 8 hours deposition, The reaction

for MnS deposition is proposed as :

N2H4
Mn(T&1)+2 + NH4Cl + Ui3CSNH2 + MnS + TEA + CH3CCNH2
21°C
+ H20
3.1.3
The filrma were deposited by the ion-by-ion condensation

process.

3.1.9 Cobalt sulnhide (COS)

Cobalt sulphide films have been deposited fran alkaline

medium using thioacetamide by Basu and Pramanik 1621. 10 ml

of 0.25M cobalt (II) chloride solution was mixed with 16 ml

of 7.4M TN and 3 ml of 14M NH4CH were added successively

with stirring. Then thioacetamide (10.4 ml of 0.25M) s~lutico

was added and volume was made to 50 ml, After 6 to 7 hours,

the sliaes was covered with a thin black deposit. The reaction

is as follows :
t=25Oc
Co(TW)+2 + CH3CSNH2 + 2d+ O2 - CoS + TEA* CH3CO NH2

+ H20 3.1.4

The film thickness was between 0.02 to 0.07 micron. 'Ihe

XRD showed that CoS films are polycrystalline in nature. !the

plots of (o()%v, hY gave 'Eg' equal to 0.62 ev. Thermoelectric

power measurement showed that CoS films are p- type. Electrical

4 &&l_ /l at room temperature. With
conductivity was 10

temperature the initial deposition rate increased but however

the terminal thickness decreased which suggested that film

growth is ion-by-ion condensation.

3.1.10 Nickel SulDhide (NiS)

Chemical deposition of nickel sulphide frcm an alkaline

medium using thioacetamide has been carried out by Pramanik

and Biswas [63] . For this, 10 ml of 0.8M nickel sulphate

solution was taken in a 100 ml beaker to which 15 ml of 7.4M

TU and 35 ml of 14M ammonia were added successively. Then

with stirring 0.8M thioacetamide so1utica-1was added. After

4 hours, the slide was covered with a black deposit. The film

thickness was between 0.03 to 0.09 micron. The chemical

reaction for NiS depositian is :

3o"c
Ni(TEA)+2 CH3CSNH2 +2CIi- ~Nj.s + G-13Cl;rjH
2
+ TEi+ +H20 3.1.5

The XKD showed that NiS films are polycrystalline in

nature. The plots of(ahv)2 vs hY gave 'Egg equal to 0.35 eV.

The NiS films were p type semiconductors as indicated by

thenn~electric power measurement. Tne roan temperature

-1
resistivityiwas 10 ohm cm

3.1.11 Bismuth Sulnhide (Big3)

Chemical deposition of Bi2S3 has been carried out fran

alkaline and acidic baths using thiourea, thioacetamide and

sodium thioeulphate as the sulphur sources [17,64-691.

Pramanik and Bhattacharya [64]have deposited Bi2S3 films

using thiourea fran an alkaline medium. A 20 ml of Bi+3

canplexed with TEA was mixed with lM thiourea and l7M NH4CH.

The bath was heated to 100 - llO°C for 40 mins and kept at

roan temperature for 40 mins. The pH was 8. The film thickness

was 0.05 to 0.1 micron. The XRD showed that films are amorphous

in nature and SEM showed that they contain a randcan distribu-

24

tion of small crystallites, ffhe optical bandgap Mas estimated

to be 1.47 eV and electrical resistivity was 10 to 30 x 106

ohm-cm. Later on Bhattacharya and Pramanik [65] added the

following observations in the Bi2S3 deposition process. The

eflrect of pH and solution preparation was critical. when

bismuth solution is freshly prepared and the deposition

mixture heated in an oil bath at 120°C, the Bi2S3 takes up a

brown color at pH = 9.29. If the solution is kept at 120°C

for a total of 30 mins, the pH changes to 9.54. The solution

is then allowed to cool down for 4 hours. The depositicm of

very uniform thin films of 0.05 micrcm is obtained. If bismuth

solution is prepared 4 - 6 hours before the films are thicker

(0.1 to 0.25 micron) and uniform, but if the solution is

prepared for greater than 24 hours, films are not adherent to

the substrate. Such films are n- type and carrier concentration

was 2.6 x 1014 per cm3 and mobility was 0.07 cm2/V+Sec. fran

Hall effect measurements.

Acharya et al. [66] modified the above procedure. They

triturated bismuth nitrabei with distilled water and no

canplexing agent was added.

Biswas et al. [67] have used thioacetamide as a sulphur

source. Bismuth nitrate was triturated with TEA and then

distilled water was added. As deposited films are amorphous

and the optical bandgap was 1.7 eV. 'Ihermoelectric power

measurement showed that films are p Yype. 'IheSEM showed

that the film is an aggregrate of islands with overgrowth

scattered. The reaction for deposition of Bi2S3 is proposed

as follows :

2 Bi(TEA)+3 + 3 CH3CSNH2 + 6 Cl-l + Bi2S3 +

+ 3H20 + 3CH3CCNH2+ 2 TEA 3.1.6

 Lokhande et al. [17,69] have prepared Bi2S3 films in

alkaline and acidic media using Sodium thicsulphate as d

sulphur source. EDTA was used to canplex Bi+3 ions, Equimolar

E&+3 and Na2S203 were mixed together and pH was maintained

between 2 to 3 at room temperature, For the alkaline medium,

the pW of the Ei canplex was raised to alkaline by aodition

of dilute Name The films from alkaline medium were more

uniform. The optical bandyap was estimated to be 1.54 2V.

The electrical resistivity was between lo5 - IO7 ohm cm-1

3.1.12 Antimcmv Sulnhide (Sbg3)

Thin films of Sb2S3 have been deposited from acidic and

alkaline media using ha2S2Q3 as a sulphur source 1591. A 100 mM

solution of Sb203 was prepared and .EDm was used for ccmpfex-

ing Sbi3 ions. To it, 100 mM NaZS203 solution was added. The

w of the bath was 2 to 3, The deposition was carried cut cm

a glass substrate at room temperature for about 12 hours. For

deposition from an alkaline medium, the pH of ELM caplexed

+3
Sb solution was raised from 8 to 10 by addition of 0.5 M NaOH

solution. The Sb S
films with the alkaline bath were uniform
23
and conpact. The film thickness was between 0,3 and G.4 microns,

The optical bandgsp of films from the EGTA complexed bath was

decreased to 1.82 from 1.97 eV. The resistivity of EDT-A

cmplexed alkaline bath - grown films is lower than from

acidic baths. The activation energies were 0.27 and 0.05 eV

in high and low temperature regions respectively.

3.1.13 nolvbdenum sulphide (MoS$

Pramanik and Bhattacharya [13f have chemically deposited

molybdenum sulphide films from an alkaline bath using thioace-

tamide as a sulphur source, For this, 10 ml of 5% ammonium

26

molybdate solution was mixed with 15 ml of 13.4M ammonia

solution and 10 ml of 20% sodium dithionite solution. The

resulting solution was stirred and 15 ml of 1M thioacetamide

solution was added to it. The bath was heated to 90°C for 30

mins and then the beaker was kept at room temperature for 5

hours. The slide was covered with a yellowish brown deposit.

The chemical reaction for MoS2 is proposed as :

CH3CSNH2 + OH- A CH3CONH2 + S-2

MO?; + Na2S204 + S-2, + H20 + Na2S04 + SO2 3.1.7

MoS2

The thickness of the films was between 0.5 to 0.6 micron.

At low concentration of ammonia or sodium dithionite, the

terminal thicknesses of the films were less but increased and

dropped again with higher concentrations. The XRD pattern

showed that MoS2 films are amorphous. The plots (hhv ) I'2 E

hv gave @Eg* equal to 1.17 eV. Thermoelectric power showed

that films are n- type. The electrical resistivity of MoS2

films was lo4 ohm cm-l

3.1.14 Tin disulnhide tSnS2)

The films of SnS2 have been chemically deposited fran

an acidic bath using Na2S203 as a sulphur source, onto glass

tin oxide coated glass and titanium substrates [70]. The Sn +4

solution was prepared by dissolving tin in c~[Link]. TO it,

Na2S203 solution was added and substrates were introduced.

Within 1 hour, yelloG-golden coloured films were obtained.

Large area films (%50 an') have been prepared. The increase

in pH > 2 resulted into thinner films. Similarly increase in

temperature resulted in thinner films and rapid yellowish

pr,ecipitation in the solution. 'Ihe BID showed that films are

amorphous in nature. 'Ihe optical bandgap @Eg' was estimated

to be 2.35 ev which corresponds to the W structure of SnS2

 27

films. The resistivity was of the order of lo3 - lo4 ohm-an.

'Ihe films are of n- type and showed photovoltaic activity.

3.1.15 Cadmium - Zinc sulnhide (CdZnS)

Thin films of Cdl-x ZnxS (X = 0.2, 0.4, 0.6 and 0.8) were

deposited on quartz substrates [46, 711. The solutions of 1M

CdCl2, 1M ZnCl2 and 4M ammonia were used as basic ingredients.

The substrates were kept steady for 3 hours in the stirred

solution; Thin, adherent and specularly reflecting alloyed tilms

were formed at 80 + 2OC and at pH equal to 10.

Film thickness of alloyed films of different Zinc conpo-

sitions was measured and found to decrease with the increase

in Zinc composition, XRD showed that films are polycrystalline

and hexagonal in lattice structure. These films were used in

PEC cells.

Sharma et al.[46] have proposed the following reaction :

NH4CH
(i--x) cdC12 + ~znci~ + tN~212C.S > Cdl_xZnxS + CH2N2+2H+
+2c1-
3.1.8

3.1,16 Lead - Cadmium Sulphide WbCds)

Films of Pb l_xCdxS have been deposited by Nayak et al.

[71], Nayak and Acharya [72] and Reddy et al. [73]. Aqueous

solutions of lead acetate, thiourea and cadmium acetate were

mixed and NH4Cfi was added. The pH of the mixture was maintained

at 10. A good quality film was deposited at rocm temperature

for 45 mins. Thickness of Pb l_xCdxS films decreased with

increasing temperature. XRD showed that Pbl_xCdxS exists in

the cubic phase and the lattice constants are found to be

attributed to interestitials. The lattice constants have been

found to vary linearly with at % of Cds.

28

SEM studies showed that at lower Cd concentration the

Pbl_xCdxS films maintain a reasonably smooth surface but at
an x value 7 0.27, the appearance of hamispherical blobs is
ObSWXeti which suggests that beyond 0.27, scme Cd ions are

rejected from the lattice and sit on the surface to picx up

lead and sulphur ions from the solution forming blobs of

3.1.17 Lead Mercurv Sulohide IPbHuSI

Thin films of Pbl_x Hg xS were grown on glass substrates by

chemical reaction of aquetiw solutions of Lead acetate,
thio~r@a and marcury (II) chloride [47,74]. A film grown at
a temperature of less than 4S°C exhibits a single phase
f.c.c. structure,
?&e solution growth technique allowed the incorporation

of both phases ( o<a_nd&Iphase) of HgS into the PbS lattice

up to 33% Hg. The two alloy phases were stabilized by choosing
appropriate grcwtb conditions. The lattice parameter and the
optical bandgap of the f,c,c. alloy of Pb5 with A-HgS increase
with increasing Hg concentration in the films, The alloy of
PbS with )3-HgShas an f.c,c. structure, but its lattice para-
meter and optical bandgap decrease with increasing Hg ccncen-
tration, By changing the canposition upto 33% Hg, the 'Eg' was
varied over a wide range from 0.2 to 1.2 eV.
The proposed reaction for Pbl,xHgxS film -for's@timiS
(l-x)Pb(CH3000)2+ x(HgCl2) + (NH2)~ __j) Pbl_&QxS +

+ cqNsJ,+ 2(1-x)cH3cOO-+ 2x6.4 2H+ 3.1.9

_

*
er Indrum Sulnhxde iCZxL&a2)
3.1.18 &C!om~

Stoichi0iuetricthin films of CulkaS2have been deposited

by Padam and Rao [75]. Solutions of 0.M CuC12s2.5 "20, O.!M
 29

InC13, 0.5M thiourea, O,SM TEA and 13.4M ammonia were mixed

together. Glass substrates were kept with stirring. Films

deposited at 80°C without stirring were nonuniform. Substrates

used were glass, MO, Si, quartz and conducting glass. 'Ihe
grain size and canposition depend on the substrate material.
-1
The electrical resistivity was 0.1 to 100 ohm cm . The films

were p- type. The TED and XRD showed that films are single

phase with chalcopyrite structure.

3.2 Metal Selenide

_- Films

3.2.1 Cadmium Selenide (CdSe)

Chemical deposition of CdSe has been carried cut by a

number of workers [15,28,76-781. Kainthla et al. [15] prepared

the reaction mixture from 0.5M cadmium acetate, 7M ammonia

solution, 5M KCH and 0.125M sodium selenosulphate solution.

The substrates were single crystals of Ge and Si, gl;ss, mica

and copper. The effect of bath parameters and the nature of

the substrates on the rate of deposition and terminal thick-

ness has been established. With temperature, deposition rate

and terminal thickness were increased. CdSe films were poly-

crystalline (cubic and hexagonal. A growth kinetics has been

proposed where CdSe film formation takes place by recombination

of ions on the substrate surface via a nucleation and growth

process.

Baudreal and Rauh [76] have modified the above process.

The solution mixture was heated rapidly in a stoppered glass

container with a 90°C ccnstant temperature bath. Thesubstrates

were Ti and stainless steel and were soaked in a suspension

of Cd(W2 for 5 mins at 50°C. It was found that the role of

the ammonia addition was critical in setting good quality

reproducible CdSe films.

30

Mondal et al. [23] used TEA as a complexing agent to get

room temperature deposition. lH Cd-acetate and 7.4M Tti

solution and 0.45M sodium selenosulphate were added. The

pH was 10. The excess TEA addition reduced the thickness of

Cdse films. 'IheXRD, optical absorption and photoccnductivity

measurements have been used for CdSe formatian confirmation.

The reaction of CdSe preparation is proposed as :

Cd(TEA)+Z + Na2SeSO3 + 2oii CdSe + TEA + Na2S04 + H20

3.2.1

3.2.2 zinc Selenide (SnSe)

ZnSe films from an alkaline bath have been deposited by

Pramanik and Biswas [79]. For this 1M ZnC12 solution was mixed

with 7.4H TEA, 7.5M NaCii and 14M ammonia solution. To this,

80% hydrasine hydrate and 0.4M sodium selenoeulphate solutions

were added. The temperature of the oil bath was 1OO'C. After

lhourdeposition time, the film thickness on theglass

substrate was between 0.05 to 0.12 microns.

The XRD showed that ZnSe films are polycrystalline in

nature. The optical bandgap was estimated to be 2.63 eV.

Thermoelectric power measurement showed that films are n-type

in nature. The electrical resistivity was lo4 - lo5 ohm-an.

The plSe films were found to be photoconducting in nature.

3.2.3 Lead Selenide (PbSe)

Qlemical depositi- of Pbse thin films has been carried

out by a number or workers. Wlner and Watts [SO] reported a

method which involved the reaction of lead acetate witi

selenourea in aqueous soluti0n. Prior to carrying out this

reaction a very thin film of PbS was deposited cn thesurface

to be coated. This fine depositia furnishes the nuclei which

act as a seeding layer for the growth of microcrystalline

PbSe, The reaction was slow and about an hour was required for

the deposition of a sufficiently thick layer of H?Se. Photo-

conductive cells were formed with tiese films, %%in films of

poLycrystalXine 115,81-851, amorphous 1861 and microcrystalline

1871 PbSe have been formed. Pol_vcrystafline films of PbSe

using selanourea or its dexivativtW and sodium selenosulphate

[15,84,85] have been reported. Sarma et al. [SS] have reported

PbSe formation frcm lead nfizrate, NaW, thiourea and sodium

[Link].

Polypcrystalline PbSe films have been prepared by Zingaro

and Skovlin f82I. 0,lM lead citrate, 7.9 NH4C%i solutions were

mixed. O,LM DMS containing [Link] sodium sulphite was added to

it, The best fflms ware produced from so1utAon.s having a pH

of 9.8. Smooth films were deposited after 30 mins. of reaction,

The glass slides placed in gold sulfide solutions prior to

deposition gave best results,

~orph~s PbSe deposition has been reported by Biro et al.

i861. For this lead acetate solution was carrplexed with sodium

citrate and the prS was adjusted with NH4M. 0.l.M lead canplex

and 0,3M sudium selenasulphate were mAxed and to this 0,3M

sodium thiosulphate solution ~8 added, Thin films of PbSe

were deposited 013 glass seeratas after 18 to 24 hours at

roan temperature, The citrate bath had a good stability, both

acidic and alkaline Na$%& cartroll& the pre~~pi~~~ in

solution. Zhe amorphous growth is attributed to I> the low

temperature of the substrate, 21 the increased deposition rata

and 3) the virteous structure of the substrate. The amorphous

phase had its photorespcase maximum at 1.1 micron, pitis

beat& at 35OOC showed a crystalline pnase-
32

3.2.4 Thallium Se-de (TiW

TiSe films have been chanically deposited onto glass

substrates by Mangalam et al. [891 and Bhattacharya and Pramanik

[511. Mangalam et al. [89] mixed 0.5M thallous acetate and

sodium selenosulphate. A mixture of 40% NaM solution and

hydratine was added gradually to the above solution. After

15 mins., shining dark grey mirror films were obtained. Films

were 3-4 microns thick. The hot probe method showed that films

are p type. Gold and silver gave ohmic contacts to TiSe films.

The characteristics of TiSe such as spectral response, effect

of dopants and structure were studied. The optical 'Eg' was

found to be 0.8 eV.

Bhattacharya and Pramanik [511 used thallium sulphate

solution to which TEA and NH OH were added. After additicn of

sodium selenosulphate, uniform films cm glass substrates were

obtained. The films thickness was 0.3 - 0.5 micron. Ihe films

were polycrystalline in nature. The electrical resistivity

was of the order of 1O'ohmcm -? The mobility was 0.25 V-Cm2eV

and carrier ccncentration was 8.5 x 10lg cm3. The 'Egr was

estimated to be 1.12 eV.

3.2.5 Cobalt Selenide (CoSe)

Cobalt selenide films have been deposited fran an alkaline

medium by Pramanik [go]. For this, 0.4M cobalt (IL) chloride

solution was mixed with TEA, followed by successive additions

of NaCXi and 80% hydrasine hydrate solutions. TO this. 0.4M

sodium selenosulphate solution was added. The deposition Was

carried cut at 100°C for 1.5 hours. The slides wsfe CoiTered

with a deep brownish deposit. xBD showed that films are

amorphous in nature. The optical bandgap was estimated to be

0.4 oV. Thermoelectric peer measurement showed that the fil...s

are p- type. The proposed reaction is as follows :

N2H4
CO(TEA)+~ +Na2Se203 2oH F CoSe + Na SO + TBA
373 K 2 4
+ H20
3.2.2

3.2.6 Nickel Selenide (NiSe)

Deposition of NiSe fran an alkaline medium has been

reported by Pramanik and Biswas'L631. 0.4M nickel sulphate

solution was mixed with 7.4M TW, 14M ammonia and 5M NaQI

solution. 80% hydrazine hydrate and 0.4M Na2SeSC3 solution

were added successively. After about 50 mins., the slide was

covered with a dark deposit. The thickness of the film was

0.06 to 0.25 microns. XRD showed that the NiSe films are poly-

crystalline in nature. TEP measurement showed that films are

p type. The optical bandgap was estimated to he 0.23 eV. The

electr ical resistivity was lo2 ohm cm. The reaction mechanism

for deposition of NiSe is as follow :

N2H4
Ni(TEA)+2 + Na2SeS03 + 2CXi- _ NiSe + Na2S04 + TEA
303 K
+ H20 3.2.3

3.2.7 Conner Selenide (C&e)

Padam [911 has reported on Cul_xSe (x = 0.1) films fran

an alkaline medium. Solutions of 0.5M CuC12:2.5 H20, 0.5M

Na2SeS03, 7.4M TEA and 13M NH40H solutions were mixed together.

The pH of the resulting solution was 10. The deposition mixture

Was heated from 90 to 95OC and stirred magnetically for 30 mins.

'Ihe thickness of CuSe films was 2-3 microns. The SBM showed

that the films are hanogenous with average grain size of the

order of 0.7 micron. The XRD showed the cubic form of CusxSe.
34

The optical bandgap was estimated to be 1.2 eV, The films were
p- type in nature and with electrical resistivity of 0.1 to
2 x 10m2 ohm cm-'.

3.2.8 Molybdenum Selenide (MoSe2)

Framanik and Bhattacharya 1131 have reported deposition

of M&e2 films fran an alkaline medium. For this 5% ammonium
molybdate solution and 20% a~~~~ acetate and 2 ml glacial
acetate acid were mixed, followed by 20% sodium dithionite
solution, Sodium selenosulphatesolution was used as a selenium
source. Zhe resulting solution was h8ated to 90°C with constant
stirring for 30 mins, and then kept at rocm temperature for
5 hours. The chemical reaction for the deposition of MaSe2 is
follows :
Na2SeS03 + 2 LB- W Na2S04 + SO2 f i-I24

-2 w M&e2 * NaZSOg + SO2

sYG2+ i?+S204 + MOO* 3.2.4

Lt was observed that at low concentrations Of ammonia or

sodium dithionite, the terminal thickness or t&s films was 1SSS.

‘Ihe maximum film thickness was 0.5 t0 0.6 miCr0IL The XRD
showed that the MaSe2 films are polycrystallinein nature. The
'Eg' was estimat8d to be 1.14 eV. The 'IZPmeasurement showed
films are n- type in nature. The resistivity of film Was
IO4 ohmtcm-'

3.2.9 Tin Selenide (SnSe)

The SnSe films fran an alkaline medium have been deposited

by Pramanik and Bhattacharya [921. For this, 2M Snc12:M20
soluticn was mixed with 7.4M !LW, 2.5M NaCH and 0.5% polyvinyl
pyrtillidone(PVP). The resulting soluticm was stirred well and
0,2M Na2S&003 solution was added, After deposition for abcut
4 hours, the glass slides were covered with SnSe films. The

PVP was optimised as 0,15 ml of 0.5% which crjetsabsorbed on

the surface of the substrates and facilitate the formation of

hanogenous thin films. The chemical reaction is :

Sn (TEA)+2 + SeS03 + 2ai- pVp) SnSe + TEA + Na2So4

300 K
+ Ii20 3.2.5

The as-deposited films were amorpheus. The 'Eg' was

estimated to be 0.95 eV. The TEP measurement showed that films

are n-type. The thickness of the snSe film ~a.5 Ck 0.4 micron.

3.2.10 Bismuth Selenide (Bi2Se3)

Pramanik et al. I931 have reported on chemical deposition

of i3i2Se3 films. Bi nitrate was triturated with Tfi and mixed

with 0.65M NH4W and sodium selenosulphate solution. me solu-

tion was kept at 30% for 2 hours. The films of 0 to 0.2 micron

thickness were obtained, When hydrazine hydrate was added to

the bath, a metallic luster was obtained with reduced deposition

time. The pH was kept between 9.8 to 10. If the pH value is

more than 10, the deposition rate is too slow to obtain a tnin

film. There was no effect of bismuth solution aging cm the

Bi2Se3 films 1651.

XBD showed BIZSe3 formation and SEM showed that films

contained randan distribution Of small crystallites. The *Eg'

was 1.15 to 1.03 ev. The films were ijhotocanductive in nature.

The films deposited with hydratine hydrate showed the low

resistance of 4.5 x 10L ohm-an.

32.11 Antimcnv Selenide (Sb,Se3)

For Sb2Se3 films 25 gm. Of potassium antimgly tartarate

were dissolved in water to get a saturated solutfcat of PotaSsim
antimany tartarate [94]. To this, ti and NH4W were added and

the solution was stirred. Na2SeS03 was used as aseleniuasoorce.

The deposition was carried out at 30°C for 10 hours cnto glass

substrates. The film thlckneris was 0.9 to 1.2 micron. XRD

showed that the films are amorphous in nature. The optical

badgap was estimated to be 1.88 %V, The electrical resistivity

was lo7 ohm-cm, The SEM studies showed randandistribution of

small crystallites for tne films. The Sb2Se3 film canposition

was in the stoichianetric ratio.

3.2.12 CoonerIndium Selenide (CuInSe2f

Chemical deposition of CuInSe2 is based on the slow

reaction between a conplexed solution with both Inf3and &

and Na2SeSO3 [95-1001. Bhattacharya [95] used the deposition

+3
mixture of 0.05 In , 0.5M C!u+ and 0.314MaZSeS03. To this,

0.04% TEA and ammonia was added . The film thickness was

between 200 to 300 2 cnto glass and SnO2:F coated glass at

rocm temperature. The films were polycrystalline with grain

size of 0.08 micron. The 'Eg @ was estimated to be 1.08 ev.

Padam [96] has prepared stoichianetric CuInSe2 films from

the deposition mixture of CuCl, Na2SeS03, IEA and NH4CH solu-

tions, The pH of the resulting mixture was NlO. The deposition

mixture was stirred for 30 mins. at different temperatures.

The films deposited at SO'C were Cul 011nSe2,02 and the thick-
.
ness was 2 to 3 microns. XRD showed that films are chalcopyrite

with extra lines of C&Se, The grain size was between 0.4 to

1.5 microns and grains were spherical and randanly orieslted,

-1
The film resistlvity was 0.08 to 0.09 ohm cm . The films from

the 90°C bath had the canposItian Cul .011nSel.8~~ The film

thickness was 1.3 to 1.5 microns and films were single phase
chalccpyrite, tie grains were elliptical and oriented al-g I1121-
 37

The grain size was 0.2 to 0.3 micron and resistivity was 50

to 0.2 ohnrcm, All films were p type and 'Eg' was 0.98 eV.

Gara--et a1.[37] mixed Na2SeSC3 solution with a canplex

of tetraamine copper and indium citrate. The solution tempera-

ture was 40°C for 14 hours. Uniform films of CuInSe2 were

obtained on glass and quartz substrates at the rate of 30 2

per min. The as-deposited films were annealed at 520°C t0

give stable and reproducible results. A stoichicmetric film

annealed at 520°C had a 'Eg' of about 1.15 eV. The films

annealed were p- type in nature and electrical resistivity

3
was lo ohnrcm. 'Ihe effect of annealing in air, vacuum and

In and Se vapour has been studied by Sharma et al. [98] and

Shanna and Garg [99].

3.2.13 CadmiumLeaWelenide (Cdl_xPb&Se)

Cdl_xPbxSe films have been prepared by Shanna et al. [47I.

The proposed reaction is :

T
(~-x)P~(CH~COO)~ + xCd(CH3COO)2 + Na SeS03 + NaC%i a
2

+ PblqCdxSe + 2CH3COz +H+ + Na++ SO;;"

3.2.6

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

reaction rate in order to avoid excessive precipitation in the

reaction bath.

4 CONCLUSIONS

chemical deposition is a simple inexpensive and ccmvenient

method for large area depositicn. Using this method, 3 large

number of metal chalccgenides (sulphides and selenides) have

been deposited. 'Ihephysical and chemical properties of such

semiconductors are canparable with the semiconductor Prepared

38

by other methods. Such films have been used in devices such

as solar cells, photoconductors, detectors, solar selective

coatings etc.

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