Thin Solid Films 500 (2006) 4 8

www.elsevier.com/locate/tsf

Review

Effect of pH on the properties of ZnS thin films grown

by chemical bath deposition
T. Ben Nasr a,*, N. Kamoun a, M. Kanzari b, R. Bennaceur a
a
Laboratoire de Physique de la Matie`re Condensee, Faculte des Sciences de Tunis (2092) El Manar, Tunisia
b
Laboratoire de Photovoltaque et des Materiaux Semi-conducteurs, Ecole Nationale dIngenieurs de Tunis, Tunis El Manar, Tunisia

Received 7 April 2005; received in revised form 16 September 2005; accepted 14 November 2005
Available online 20 December 2005

Abstract

Zinc sulphide thin films have been deposited on glass substrates using the chemical bath deposition technique. The depositions were carried
out in the pH range of 10 to 11.5. Structure of these films was characterized by X-ray diffraction and scanning electron microscopy. Optical
properties were studied by spectrophotometric measurements. Influence of the increased pH value on structural and optical properties is described
and discussed in terms of transmission improvement in the visible range. Transmission spectra indicate a high transmission coefficient (70%).
The direct band gap energy is found to be about 3.67 eV for the films prepared at pH equal to 11.5.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Zinc sulphide; Chemical bath deposition; Structural, morphological and optical properties

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2. Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.1. Structural and morphological properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2. Optical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

1. Introduction
Zinc sulphide (ZnS) is an important II VI semiconducting
material with a wide direct band gap of 3.65 eV in the bulk [1].
It has potential applications in optoelectronic devices such as
blue light emitting diodes [2], electroluminescent devices and
photovoltaic cells [3]. In thin film solar cells based on
CuGaIn(S,Se)2 absorbers, a CdS buffer layer is generally
required in order to obtain high conversion efficiency.
However, there are toxic hazards with respect to the production
and use of the CdS layer. Therefore research in developing Cd-
* Corresponding author. Tel.: +216 98524797; fax: +216 71885073.
E-mail address: tarek.ben-nasr@laposte.net (T. Ben Nasr).
0040-6090/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2005.11.030
free buffer layers has been encouraged. This has lead to the
investigation of ZnS as a buffer layer in ZnO / ZnS / CuInS2
devices [4]. ZnS has a wider energy band gap than CdS, which
results in the transmission of more high-energy photons to the
junction, and to the enhancement of the blue response of the
photovoltaic cells. Several techniques such as thermal evapo-
ration [5], molecular beam epitaxy [6], metal-organic vapor
phase epitaxy [7], chemical vapor deposition [8], spray
pyrolysis [9], and chemical bath deposition (CBD) [10] have
been used to produce ZnS thin films. Among them, chemical
bath deposition is well known as a prevalent low-temperature
aqueous technique for depositing large area of semiconductor
thin films, the simplest and the most economical one. The CBD
process uses a controlled chemical reaction to achieve thin film
 T. Ben Nasr et al. / Thin Solid Films 500 (2006) 4 8
deposition by precipitation. In most of the experimental
approaches, substrates are immersed in an alkaline solution
containing the chalcogenide source, the metal ion, the added
base and a complexing agent. In CBD spontaneous reaction is
possible from the liquid phase, whereas in spray pyrolysis
technique the reaction takes place from the vapour phase at
much higher temperature (300 600 -C). Using CBD method, a
large number of binary compound semiconductors such as
CdS, CdSe, PbS, ZnS have been deposited as thin films.
Chemical bath deposition of ZnS thin films using NH3 and
hydrazine (N2H4) as complexing agents has been reported by
Dona and Herrero [11].
In the present work, we report the chemical bath deposition
of ZnS thin films and their characterization. The effect of pH
on structural, morphological and optical properties of these
films is investigated with the objective to optimize the
conditions of the deposition process.
2. Experiments
ZnS thin films can be prepared from decomposition of
thiourea in an alkaline solution containing a zinc salt and a
suitable complexing agent which allows to obtain a soluble
species of Zn2+ in this medium. One of these complexing
agents is NH3, following the reaction [12]:
ZnNH3 2 2
4 T4NH3 Zn :
ZnCl2 is used as the Zn2+ source, and thiourea supplies S2
ions through hydrolysis in alkaline medium [11]:
SCNH2 2 OH TSH CH2 N2 H2 O
SH OH TS2 H2 O:
Complex and sulphide ions migrate to the substrate surface,
where they react to form ZnS [13]:
ZnNH3 2 2
4 S TZnS 4NH3
During ZnS film deposition according to the above reaction,
the formation of Zn(OH)2 occurs as a competitive process in
the bath. NH3 is a source of OH ions through the following
reaction:
NH3 H2 OTNH4 OH :
Hydrazine is a usual complementary complexing agent for
the chemical bath deposition of ZnS. It improves homogeneity,
and specularity of the layer, as well as its growth rate.
Hydrazine could potentially act as a bridging ligand and may
facilitate surface binding.
ZnS thin films are prepared by CBD method on glass
substrates. The chemical bath is an aqueous solution of zinc
chloride (ZnCl2: 0.077 mol L 1), thiourea (SC (NH2)2: 0.071
mol L 1), ammonia (NH3: 1.39 mol L 1) and hydrazine
((NH2)2: 2.29 mol L 1). All samples reported here correspond
to 3 h deposition time at a bath temperature of 90 -C. The film
deposition is carried out with the same bath basic composition.
5
600
Thickness (nm)
500
400
300
10.0 10.5 11.0 11.5
pH
Fig. 1. Thickness of ZnS thin films deposited at different pH of the chemical
bath for a constant dipping time of 3 h.
Hydrochloride acid solution is added to the chemical bath to
adjust the pH from 10 to 11.5 under the control of a pH meter.
Layer thickness is estimated by the double weight method using
an ultraprecision balance. Fig. 1 shows the variation of ZnS film
thickness as a function of the pH value. The thickness increases
from 320 to 600 nm when the pH decreases respectively from
11.5 to 10.
X-ray diffraction (XRD) spectra are recorded with an
automated Bruker D8 advance X-ray diffractometer with CuKa
radiations (40 kV and 30 mA) with 2u ranging from 20- to 60-.
Scanning electron microscopy images are carried out using a
Cambridge S360 microscope operating at acceleration voltage
of 20 kV. The optical properties are studied with a UV-VIS-
NIR spectrophotometer (Shimadzu UV-3101PC).
3. Results and discussion
3.1. Structural and morphological properties
Zinc sulphide exists in sphalerite, cubic and hexagonal
forms. The cubic form is stable at room temperature, while
the less dense hexagonal form (wurtzite) is stable above 1020
-C at atmospheric pressure [14]. However, some authors have
observed hexagonal structure for ZnS films obtained by CBD
[15]. XRD measurements are performed to follow the change
of layer crystallinity induced by the pH of the chemical bath.
Fig. 2 shows the diffraction patterns of polycrystalline ZnS
films deposited at different pH ranging from 10 to 11.5. The
broad hump in the 2u range of 20 30- is due to the glass
substrate. At pH = 11.5 no diffraction peak is discernable (Fig.
2a), which indicates highly disordered layer. Broad peaks
corresponding to improved crystallinity start to appear, while
the pH decreases from 11.5 to 10. Two main peaks can be
observed at the diffraction angles of 28.8- and 47.7- on the
XRD spectrum obtained on the ZnS films prepared at pH 10
(Fig. 2d). These two peaks are assigned to both cubic and
hexagonal phases of the planes (111)cub/(002)hex and (220)cub/
(110)hex. The other characteristic peaks of (100), (101), (102),
6 T. Ben Nasr et al. / Thin Solid Films 500 (2006) 4 8

transmission spectra of ZnS thin films obtained at different pH

(111)cub/(002)hex
are displayed in Fig. 4. The broad cut off towards short
wavelengths indicates the onset of intrinsic inter-band absorp-
tion in the ZnS. An increase of the transmission values over the
whole spectral range is observed with increasing pH values. In
the transparency region, transmission is the largest (T 55
71%) at pH = 11.5. At pH = 10.99 and pH = 10.31 transmission
is 60% in the near infrared region and 35 48% in the
visible region. At pH = 10 transmission varies from 20 to 46%.
However there is no detectable variation of the short
Intensity (Arb. Unit)

(220)cub/(110)hex
(d) wavelength absorption edge with the pH. The decrease of
the transmission coefficient with decreasing pH can be
interpreted by an increase of the film thickness as reported
(c) in Fig. 1. Films grown at pH = 10 appear to have the best
crystallinity but also the smallest transmission in the transpar-
ency region. In Fig. 4d one notices the presence of interference
fringes which confirm that, the ZnS film thickness is almost
(b) constant at pH = 10.
In fact, the effect of pH on the transmission spectra is
related to the growth conditions. An increase of the pH leads

(a)
A

20 30 40 50 60
2 (deg.)

Fig. 2. X-ray diffraction patterns of ZnS thin films deposited on glass substrates
at different solution pH, (a): 11.5, (b): 10.99, (c): 10.31 and (d): 10.

(103) and (200) planes of hexagonal are not present in all

spectra. Therefore, it can be concluded that we have prepared
ZnS films having cubic structure (h-ZnS) whatever the tested
pH. For a comparison, see J. M. Dona and J. Vidal [11,12]
who obtained amorphous or poorly crystalline ZnS thin films
by CBD method. Applying the Scherrer formula [16] to the
(111) diffraction peak of spectrum 2d the average crystallite
size is found to be about 14.8 nm. 1 m
SEM brings microscopic information of the surface B
structure and roughness. In this work, it appears to be a
helpful technique to specify the growth mode via the study of
a surface roughness, and to determine the effect of the pH on
the film morphology. Fig. 3 shows surface topography of ZnS
layers obtained at two different pH. Semispherical grains are
uniformly distributed at the surface. A slight increase of the
grain size follows the pH decreasing but does not improve the
surface roughness. Concerning the nucleation stage film
growth proceeds by nucleation of crystallites, then forming
grains which coalesce to cover the entire substrate surface and
to show a dense structure. These results are consistent with
previous reports [17].

3.2. Optical properties

Transmission measurements are performed at normal Fig. 3. SEM images of ZnS thin films grown at different solution pH, (A): 10,
incidence over a large spectral range (300 to 1800 nm). The (B): 11.5.
 T. Ben Nasr et al. / Thin Solid Films 500 (2006) 4 8 7

80 Table 1
a Band gap values of the ZnS thin films for different pH of the chemical bath
ZnS films prepared using Optical band gap (T0.02 eV)
b
60 c pH 11.50 3.67
Transmission (%)

pH 10.99 3.81
d pH 10.31 3.88
pH 10.00 3.78
40

Based on the optical transmission measurements, the

20 square of absorption coefficient (a 2) is plotted as a function
of photon energy (hm) in Fig. 5. It can be seen that the films
have a steep optical absorption feature, indicating good
homogeneity in the shape and size of the grains as well as
0
400 800 1200 1600 2000 low defect density near the band edge. a 2 varies almost
Wavelength (nm) linearly with hm above the band gap energy (Eg). Thus, the
following equation can be applied for a direct inter-band
Fig. 4. Optical transmission spectra of ZnS thin films deposited at different transition [18]:
pH of the chemical bath, (a): 11.5, (b): 10.99, (c): 10.31 and (d): 10.

to more OH ions in the solution, which tend to combine a2 Ahm  Eg

readily with zinc without leaving enough zinc for ZnS growth
on the substrate. In other words, slow growth rates keep
enough Zn in the solution on the form of Zn(OH)2. This result
is also indicated by thickness measurements which show
thinner layer at greater pH (Fig. 1). To summarize, for the
same deposition time, films grown at low growth rate
(pH = 11.5) are thinner and have lower absorption, whereas,
films grown at higher growth rate (pH = 10) are thicker and
have higher absorption.
15
pH = 11.55
pH = 10.99
pH = 10.31
pH = 10
where A is a constant. The band gap energy is obtained by
extrapolating the linear portion of the plot to the crossing
with hm axis. Determined band gap energies are listed in
Table 1. At pH = 11.5, Eg equals 3.67 eV and it is close to
the band gap of bulk ZnS (3.65 eV) [1]. However, the film
with the best crystalline structure, according to the XRD
pattern (Fig. 2), has band gap energy equal to 3.78 eV. One
would expect that a more ordered structure will have a band
gap closer to the single crystal value. This shift may be due
to the CBD technique. Band gap energy varies from 3.67 to
3.88 eV, which closely agree with the values reported for
ZnS thin films obtained by CBD [11,19] and by metal
organic vapour phase epitaxy (MOVPE) [20].
4. Conclusion

10
Zinc sulphide thin films are prepared on glass substrates
by the CBD technique. There is a good agreement between
()2 (x 109 cm-2)

XRD, SEM, and optical results. These studies show that the
pH contributes noticeably to the growth and to the structure
of deposited films. It is particularly observed that the best
crystallinity of the ZnS thin films is obtained at pH = 10. The
decreasing of the pH value from 10.99 to 10 is related with
the increasing of the (111) diffraction peak intensity. The
5
optical transmission coefficient is found to increase when the
pH increases from 10 to 11.5. This may be interpreted by the
decrease of the film thickness. ZnS film prepared with pH
11.5 shows a high transmission coefficient (70%) and a
wide band gap of 3.67 eV. From these studies we are able to
optimize the process in order to produce the layer suitable
for optical window in solar cells. For example, in the solar
0
cell ZnS/CuInS2 that we are still investigating, CuInS2 is the
2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2
absorber material which will be grown by spray pyrolysis
h (eV) technique [21]. Annealing at high temperature under nitrogen
Fig. 5. (a 2) versus (hm) plots of ZnS thin films for different pH of the chemical gaz or in vacuum is under investigation in order to improve
bath. the crystallinity of these films.
8 T. Ben Nasr et al. / Thin Solid Films 500 (2006) 4 8
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