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MattJrials Ckmistry and Physics, I2 (1985) 12 I .
- 128 121
FORMATION OF CuxS THIN FILW THROUGH A CHEMICAL BATH DEPOSITION

PROCESS
E. FATAS, T. GARCIA and C. IIONTEIWYOR
Departamento de Electroquimica
A. MEDINA
Departamento de Geoloqia
E. GARCIA CAMARERO and F. ARJONA
Depatamento de Flisica Aplicada. Un ivers idad AutEjnoma de Madrid.

Cantoblanco, Madrid-34 (Spain).
Received30 April 1984; accepted6 June 1984
ABSTRACT
A method for the preparation of Cu_S thin films through chemi-

cal bath deposition is described. The*films have been formed on
a glass substrate from a bath containing a triethanolamine complex
of copper ions, ammonia and thiourea. The stoichiometry and
optical characteristics of the films have been determined. This
method has been used to form a solar cell through deposition of
Cu.-S on a CdS substrate. The I-V characteristics of the cell are
re$orted.
INTRODUCTION
Current interest in direct energy conversion devices has led

to renewed research into the materials for such devices. The ma-
nufacture of large area solar cells of CdS/CuZS requires an eco-
nomical and simple process for the formation of thin films of CdS
on a conducting base and Cu2S films on the CdS.
The hitherto used methods of manufacturing CuxS layers (vacuum

evaporation, sputtering and spray pyrolysis) cannot be considered
optimal because they involve a high consumption of material and
energy. In addition, only substrates of limited size can be made,
and the control of the stoichiometry of the films is rather poor.
A relatively less common but inexpensive method for the prepara-
tion of large area thin films at low temperature is a chemical
solution growth technique, which has been known for some time for
thin film deposition of such compound semiconductors as CdS, PbSe
and case 11-53.
0254-0584/851$3.30 0 Ekevier Sequoia/P~nted in The Netherlands

122
Copper sulphides are important materials for applications in

large area polycrystalline solar cells, therefore we have under-
taken a study of the deposition of CuxS films by the solution
growth technique. The process involves the application of a
controllable chemical reaction which proceeds at a low rate in
an aqueous solution containing a reducing agent and a source of
sulphide ions.
In this paper we describe the preparation of CuxS films by

decomposition of thiourea in alkaline solutions of a copper salt
with a complexing agent. The optical properties and characteris-
tic of the film are reported. The method is also used to form a
Cu2S hetero-junction on a CdS substrate.
EXPERIMENTAL
For this study, thin films of CuxS were prepared on a glass

substrate by the reaction of thiourea and the triethanolamine
complex of Cu(I1) ions in basic media.
Freshly prepared, twice distilled water as used to prepare

the solutions and to clean the glass slides to be used as substra
tes. These slides were initially cleaned by a detergent solution,
then acetone, then were boiled in doubly distilled water.
To IO ml. of 114copper sulphate and IM sodium acetate solution,

5ml. of 7.40M triethanolamine solution was added. The resulting
solution was stirred until it formed an homogeneous solution. Then
about 3ml. of IM thiourea solution and 6ml. of 13.4M ammonia
solution were added. The resulting solution was made up to 100ml.
with twice distilled water and stirred. The pH was 9.4. The
solutions were prepared with water at 40°C, and the beaker was
placed in a water bath with automatic temperature control. After
few seconds the glass slide was inmersed vertically in the
beaker. Experiments were performed at 40°C.
The films thickness was measured by a mechanical stylus

arrangement (talystep).
The morphology of the deposited film was studied by scanning

electron microcopy (SEM), with a Philips Microprobe system.
123
The stoichiometry of copper sulphide films was determined

electrochemically, using the method proposed by Castel[6] based
on e.m.f. measurements of the cell Cu/Cu 2+aq./CuxS/In. Some
experimental details are given in ref. [7J.
Reflection and transmission measurements were carried out with

a Cary 17D spectrophotometer. The optical constants of the film
were determined following ref. 181.
Van der Pauw's method 193 was used to determine the resistivity
of the copper sulphide samples. Four gold points were left on the
copper sulphide layers, after evaporation, providing good ohmic
contact, and serving as electrodes.
RESULTS AND DISCUSSION
After the substrate had been immersed in the solution for about
an hour, there appeared a dark brown, uniform, adherent, specular
ly reflecting and rather thin (a5002) film of CuxS. Stirring of
the solution during the deposition process led to a non-uniform,
very poor quality film.
The optical absorption spectrum of a CuxS film obtained

without stirring is shown in Fig. 1, as compared with the spectra
Fig. 1. Trahsmittance spectra of CuxS films:(l)evaporation Cu2S;

(2) evaporated CU,.~~ S;(3) chemically grown CuxS.
124
corresponding to evaporated CuxS films. The direct gaps (see Fig.

2) refraction index, composition and resistivity of these films
are given in Table 1.
T0
2
5
-mo
-300
-200
,100
Fig. 2. Determination of direct gap for: (1) evaporated Cu2S;

(2)evaporated CU~,~~ S;(3) chemically grown 0.1,s.
As can be seen, the absorption spectrum of the chemica1l.y grown

film has less simi.Larity to that of evaporated chalcocite and is
more like the curve corresponding to evaporated digenite. The
evaporated digenite and the chemically grown film begin to absorb
between 600 and 75Onm, while the chalcocite curve falls at IOOOnm.
The values of the parameters of Table 1 indicate the similarities
between the chemically ,grown film and the evaporated digenite.
Figs. 3 and 4 show the micrographs of the chemically grown and
evaporated films, respectively. The morphological aspects are very
similar in both cases. The first of two zones which can be seen is
a large, dark and compact zone. The second one consists of white
stains, probably richer in copper.
125
Table I. Direct Gaps, Refraction Index and Composition of CuxS

Films.
Sample E n x 6 P
z::, (500nm) (8) (Qcm)
Chem.grown
film 2.58 3.08 i .a6 450 3x1o-3
Evaporated
chalcocite 1.95 3.30 1.99 2.000 4x1o-2
Evaported
digenite 2.56 4.39 1.89 1.000 9x10-3
Fig. 3. Scanning electron micrograph of Cu2S evaporated film

(x5000).
The analysis of the results obtained shows that the stoichiome

try and characteristics of the chemically grow films are not qui-
te apropiate for the construction of efficient solar cells.
126
Fig. 4. Scanning electron micrograph of CuxS chemical1 .y grown film

(5000).
This led us to improve the stoichiometry by a short circuiting

treatment following the method previously reported [IO].
A CdS/Cu2S hetero-junction was formed by dipping a CdS substra

te supplied by Prof. Dr. H. Bloss (Stuttgart University) into the
corresponding solution, which is indicated in the experimental
section. The resulting hetero-junction was subjected to the short-
circuit treatment mentioned above. Under in illumination intensity
of 90mW/cm2 we found an open circuit voltage of 520mV and a short
circuit current of 2.5m.A./cm‘. The I-V characteristic curve is
shown in Fig. 5.
The interpretation of the chemical process involved in the
formation and growth of the CuxS film requires consideration of a
source of sulphide ions in solution and a weak reducing agent;
both roles being played in this case by thiourea. A possible reac-
tion mechanism based on Kaur's model 111 could result as follows.
127
0 100 300 500 V(mV)
l-
3-
J(mAldm2)
Fig. 5. I-V characteristics of the CdS/CuxS hetero-junction.
The copper complex of TEA and ammonium are formed. Formation

of CuxS on the substrate requires preferential adsorption of at
least one type of the reacting ions. Preferential adsorption of
cu2+ or S= on the glass surface from aqueous solutions is not
known, but OH- ions are adsorbed on hydrophilic surfaces from
aqueous alkaline solutions. This would result in the formation of
2+
CutOH) nuclei on the substrate with the Cu released by the
2+
TEA-Cu complex.
The CUE nuclei stimulate the decomposition of thiourea [II,

which is also oxidized to C2N4S2H6; thus some of the Cu(I1) is
reduced to CutI), and Cu2S is formed with the S= ions originating
from the decomposition of thiourea on the catalytic surface of
CUE.
In this deposition process participating ions are slowly

generated, and the solubility product helps to maintain the
stoichiometry constant for almost any ratio of cations and anions.
As a result of these processes homogeneous phases of compound are
obtained.
Obviously, confirmation of the mechanism and elucidation of the

nature of the nucleation and growing processes require more expe-
rimental work, which is now in progress.
128
REFERENCES
I. Kaur, D.K. Pandya and K.L. Chopra, J. Electrochem. Sot.,

127 (1980) 943.
A. Modal, T.K. Chauduri and P. Pramanik, Solar Energy
Materials, 1 (1983) 431.
N.R. Pavaskar, C.A. Menezes and A.P.B. Sinha. J. Electrochem.
sot., 124 (1977) 74 3.
R.C. Kanthla, D.K. Pandya and K.L. Chopra, J.Electrochem.Soc.,
127 (1980) 277.
G.A. Kitaev and T.P. Sokolova, Russian J. Inorg. Chem. -15
(1970) 167.
E. Caste1 and J. Vedel, Analusis, 2 (1975) 487.
E. Fatas, R. Duo, F. Arjona and E. Garcia-Camarero, Mat. Chem.
Phys. 8 (1983) 203.
--
F. Arjona, E. Garcia-Camarero, R. Duo and E. Fatas, J. Power
Sources, 2 (1983) 41.
J. Van der Pauw, Philips Res. Rep. -13 (1958) 1.
10 E. Garcia-Camarero, F. Arjona and E. Fatas, J. Power Sources,
(in press).

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MattJrials Ckmistry and Physics, I2 (1985) 12 I .

FORMATION OF CuxS THIN FILW THROUGH A CHEMICAL BATH DEPOSITION

E. FATAS, T. GARCIA and C. IIONTEIWYOR

E. GARCIA CAMARERO and F. ARJONA

Depatamento de Flisica Aplicada. Un ivers idad AutEjnoma de Madrid.

A method for the preparation of Cu_S thin films through chemi-

Current interest in direct energy conversion devices has led

The hitherto used methods of manufacturing CuxS layers (vacuum

0254-0584/851$3.30 0 Ekevier Sequoia/P~nted in The Netherlands

Copper sulphides are important materials for applications in

In this paper we describe the preparation of CuxS films by

For this study, thin films of CuxS were prepared on a glass

Freshly prepared, twice distilled water as used to prepare

To IO ml. of 114copper sulphate and IM sodium acetate solution,

The films thickness was measured by a mechanical stylus

The morphology of the deposited film was studied by scanning

The stoichiometry of copper sulphide films was determined

Reflection and transmission measurements were carried out with

RESULTS AND DISCUSSION

The optical absorption spectrum of a CuxS film obtained

Fig. 1. Trahsmittance spectra of CuxS films:(l)evaporation Cu2S;

corresponding to evaporated CuxS films. The direct gaps (see Fig.

Fig. 2. Determination of direct gap for: (1) evaporated Cu2S;

As can be seen, the absorption spectrum of the chemica1l.y grown

Table I. Direct Gaps, Refraction Index and Composition of CuxS

Fig. 3. Scanning electron micrograph of Cu2S evaporated film

The analysis of the results obtained shows that the stoichiome

Fig. 4. Scanning electron micrograph of CuxS chemical1 .y grown film

This led us to improve the stoichiometry by a short circuiting

A CdS/Cu2S hetero-junction was formed by dipping a CdS substra

0 100 300 500 V(mV)

Fig. 5. I-V characteristics of the CdS/CuxS hetero-junction.

The copper complex of TEA and ammonium are formed. Formation

The CUE nuclei stimulate the decomposition of thiourea [II,

In this deposition process participating ions are slowly

Obviously, confirmation of the mechanism and elucidation of the

I. Kaur, D.K. Pandya and K.L. Chopra, J. Electrochem. Sot.,

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