International Journal of ChemTech Research
CODEN (USA): IJCRGG ISSN: 0974-4290
Vol.8, No.2, pp 655-660, 2015
Characterization of Zinc Sulphide Thin Film Prepared by
Electrodeposition Method
Ikhioya I. L.
Department of Physics and Industrial Physics, Nnamdi Azikiwe University, Awka,
Anambra State, Nigeria.
Abstract: Zinc sulphide (ZnS) thin films have been successfully deposited on a glass
substrate Indium Tin oxide (ITO) by electrodeposition technique. The absorbance was
measured using M501 UV-visible spectrophotometer in the wavelength range of 300-900nm.
Zinc sulphide (ZnS) Thin films were investigated at room temperature. XRD analysis showed
that the Zinc sulphide (ZnS) Thin films, so deposited, exhibit hexagonal (wurtzite) structure
with a preferred orientation along (002) plane.
Keywords: ZnS, Thin Films, Electrodeposition, Electrical, Structural and Optical Properties.
Introduction
Zinc sulphide (ZnS) is a II-VI compound semiconductor it is widely applied in the optoelectronic
applications consisting of light emitting diodes with short wavelength, electroluminescent devices, and solar
cells. For the photovoltaic applications, ZnS thin film is also transparent in all wavelengths of solar spectrum
and has high absorption for the wavelength. ZnS has become a promising material in many applications; it is
suitable for red, blue and green light, thin film transistors, infrared coating material, photoelectrochemistry,
laser screens, n type window layer thin film herterojunction, photodetector, ultrasonic transducers. Many
techniques including sputtering [1,2], molecular beam epitaxy [3], pulsed laser deposition [4], chemical vapor
deposition [5], successive ionic layer adsorption and reaction [6], spray pyrolysis [7], and chemical bath
deposition (CBD) [1, 8] have been proposed to fabricate the ZnS thin films. In electrodeposition method, to
prepare thin films substrates are immersed into separately placed cationic and anionic precursors and precipitate
formation in the solution, i.e. wastage of the material was thus avoided. Also, electrodeposition can be used to
deposit compound materials on a variety of substrates such as insulators, semiconductors and metals.
Electrodeposition method and its potential application for large area deposition make it very attractive; Easy
control on film thickness by adjusting number of deposition cycles is the beauty of this method. In this study,
the electrodeposition method was performed to prepare the ZnS Thin films.
Experimental Procedure
ZnS thin films were prepared on the glass substrates Indium Tin Oxide (ITO) by electrodeposition
method. The substrates were cleaned ultrasonically by detergent solution, acetone, and deionized water,
respectively, to ensure the complete cleanness. The reaction bath for the deposition of Zinc Sulphide
(ZnS) was composed of four electrolyte Zinc Chloride (ZnCl 2), hydrated Sodium Sulphide (Na2S.H2O),
Potassium tetraoxosulphate VI (K2SO4) and Tetraoxosulphate VI acid (H2SO4). The growth of ZnS films
were determined with respect to the different bath parameters which includes time of deposition and
substrate for the deposition, the concentration and the PH of the solution were kept constant throughout
the experiment. The PH value was maintained at 2.5 while the concentration of the compounds were
maintained as prepared i.e 0.1M ZnCl2, 0.1M Na2S.H2O, 0.01M K2SO4, and 0.1M H2SO4 with the
following reactions;
Ikhioya I. L./Int.J. ChemTech Res. 2015,8(2),pp 655-660. 656
ZnCl2(aq) + Na2S.H2O(aq) → ZnS(s) + 2NaCl(aq) + H2O (1)
25cm3 each of ZnCl2 and Na2S.H2O was measured into100cm3 beaker using burette. 5.00cm3 of K2SO4
was measured into the same 100cm3 beaker containing ZnCl2 and Na2S.H2O respectively to serve as the inert
electrolyte which helps to dissociate the Zn from the ZnCl 2 and S from the Na2S.H2O to form the required ZnS
film on the substrate and the solutionwas acidified with 5.00cm3 of dilute H2SO4 which serves to adjust the
PH value. The entire mixture was stirred with the glass rod to achieve uniformity.
In each of the reaction baths prepared, a glass substrate and carbon electrode were connected to a DC
power supply source and the voltage was maintained at 5V for different time intervals.
Table1. Variation of Parameters ZnS Thin films
Slide Volume Volume of Volume of Volume of Voltage Time
No. of H2SO4 K2SO4 (cm3) Zn(NO3)2.6H2O Na2S.6H2O (V) (minutes)
(cm3) (cm3) (cm3)
A 5.00 5.00 25.00 25.00 5.00 5.00
B 5.00 5.00 25.00 25.00 5.00 7.00
C 5.00 5.00 25.00 25.00 5.00 9.00
D 5.00 5.00 25.00 25.00 5.00 11.00
Electrical Properties
ZnS thin films are known to be of n-type conductivity. The resistivity of the films is droped from 2.5 ×
10 to 1.5 × 108
8
. The low resistivity for the buffer layers in solar cells helps to improve the
conversion efficiency. However, the resistivity should not be too low due to the inevitable defects in solar cells
fabricated during the actual production process. Those defects can cause short circuit, furthermore, it can drop
the open circuit voltage (Voc) and fill factor (FF). However, the buffer layer with high resistivity can effectively
overcome those problems caused by defects. As a result, the ZnS thin film with 1.6 × 10 8
resistivity is quit suitable for a buffer layer in solar cell. One method which is based on the capacitance and
applied potential measurement is called Mott-Schottky relationship [9] for confirming electrical properties of
semiconductor materials. The Mott-Schottky relationship can be described as follows;
1/C2 = B X [2/ (εεθℓNDℓA2)][EFB – (Kt/ℓ)] (2)
Where ɛ is the dielectric constant of the semiconductor, A is the surface area of the
semiconductor/electrolyte barrier, ND is the carrier density of the semiconductor, EFB is the flat band potential of
the semiconductor, e is the electric charge and ɛ0 is the permittivity of the vacuum. For an n-type
semiconductor, B is 1. For a p-type semiconductor, B is −1. Therefore, the conduction type, carrier
concentration and flat band potential can be estimated by the Mott- Schottky relationship [9].
Table2. Electrical properties of ZnS films
Slides Thickness, t Resistivity, ℓ Conductivity, σ
( (
A 246 2.5x 3.6x
B 256 2.4x 3.7x
C 254 2.4x 3.7x
D 276 1.6x 2.0x
Structural Properties
All the deposited ZnS films were white, homogeneous with a good adherence to the substrate.
Generally, ZnS material has the hexagonal, wurtzite type or cubic, zinc blende type structure. X-ray diffraction
(XRD) technique is used to determine the crystallite size, orientation, lattice constants, phase of the crystal
Ikhioya I. L./Int.J. ChemTech Res. 2015,8(2),pp 655-660. 657
and structure of ZnS particles. Figure 1 shows the XRD pattern of the deposited ZnS thin films on ITO
conducting glass substrate surface showing crystalline structure with some sharp diffraction peaks.
The peaks corresponding to each plane were identified and indexed to hexagonal (wurtzite) structure.
Four sharp peaks were observed in the diffractogram at around 2 values of 16.04 , 26.92 , 33.53
and 59.00 corresponding to(002), (100), (101) and (004) plane of ZnS and has its highest peak at maximum
intensity of 37.9 at around 16.04 corresponding to (002) plane of hexagonal ZnS respectively. From XRD,
it is evident that the obtained ZnS has a hexagonal phase. The presence of broad peaks in XRD implies
presence of thin films which shows that the preferential orientation of ZnS lies along (002) plane of hexagonal
ZnS respectively. The rough structures in the graph showed the presence of noise from the diffractometer. The
average crystallite size is calculated using Debye Scherer formula
D= (3)
The average crystallite size from the calculation was found to be 0.152nm. Details pertaining to the crystallite
size calculation is given in table 4.1
The FWHM of the XRD peaks may also contain contributions from lattice strain. Therefore, the average
strain of the ZnS thin films is calculated using Stokes-Wilson equation
= (4)
The average strain from the calculation was found to be 3.147.
The dislocation density ( ) which represents the amount of defects in the sample is calculated using the
relation
= (5)
The inter-planar spacing known as d-spacing is calculated using the relation dhkl by calculating values
from the peaks of the X-ray spectrum using Bragg’s relation
dhkl = (6)
The lattice parameter is calculated according to the relation
a = d( 2+k2+l2) (7)
Figure 1: X-ray Diffraction pattern of ZnS
Ikhioya I. L./Int.J. ChemTech Res. 2015,8(2),pp 655-660. 658
Table3. Structural parameters of ZnS films
density×1
)
standard
2 (degr
Dislocati
measure
constant
FWHM
Sample
Lattice
d( A)
d( A)
size d(
Micro
Grain
strain
Hkl
ee)
020
on
d
A 002 16.04 5.52 5.53 3.82 0.78 1.77 0.319 1.401
100 19.97 4.44 4.45 7.82 0.18 0.860 1.109
101 20.06 4.42 4.43 1.00 1.40 0.510 1.420
103 20.43 4.34 4.37 0.66 2.11 0.225 0.927
004 21.18 4.19 4.20 0.65 2.14 0.218 0.880
Absorbance Of The Deposited ZnS Films
The optical absorption spectral of ZnS nanoparticles is shown in figure 2. These spectral reveal
that the films grown under the same parametric conditions at room temperature and at varying deposition
time of 5mins, 7mins, 9mins and 11mins for slides A, B, C and D have low absorbance in the visible and
near infrared region. However, absorbance of the films was found to be high in the ultraviolet region
with peak around 360nm which is in accordance with the result obtained in [10] reported that the enhanced
absorption is observed in the neighborhood of ⋋ = 360nm. From the graph, it was observed that slide A
and slide B are relatively constant, slide C has low absorbance in the visible and near infrared region
of about 1.3% and high absorbance of about 1.5% in the ultraviolet region while slide D has a different
trend to the other slides having a low absorbance in the ultraviolet region of about 1.1% and a high
absorbance in the infrared region of about 1.5%. The overall observation shows that the absorbance is
high and increases with deposition time. This high absorbance in the UV region makes ZnS useful in
p-n junction formation of solar cells with other suitable thin film materials for photovoltaic applications,
while the low absorption of ZnS in the infrared makes it useful for window coatings in cold temperate
regions of the world.
Figure2. Plot of absorbance as a function of wavelength of incident radiation
Transmittance Of The Deposited ZnS Films
The transmittance spectral (%) of the ZnS film is shown in figure 3 the transmittance spectral
reveals transmission of above 0.95% in the infrared region and transmission of about 0.63% in the ultraviolet
region for slide B. It was observed that slide A and slide C are relatively constant while slide D has a low
transmittance in the near infrared and visible region of about 0.03% and a high transmittance in the ultraviolet
region of about 0.26%. The general observation show that the overall films demonstrate more than 60%
transmittance at wavelength longer than 400nm which is comparable with the values for the ZnS thin films
deposited in [11] using SILAR method. Below 400nm, there is a sharp fall in the transmittance spectral of the
films, which is due to the strong absorbance of the films. Films of low transmittance in the infrared region is
used in window coatings in hotter regions of the world like Nigeria while films with high transmittance in
the ultraviolet region is useful in photosynthetic coatings because they exhibit selective transmittance of
photosynthetic active radiation (PAR) and also used as reflector and dielectric filter.
Ikhioya I. L./Int.J. ChemTech Res. 2015,8(2),pp 655-660. 659
Figure 3 Plot of transmittance as a function of wavelength of incident radiation
Conclusion
It has been illustrated in this work that electrodeposition (ED) method was used to deposit
semiconductor ZnS films. The X-ray diffraction (XRD) confirmed the hexagonal crystalline structure of
ZnS with an average crystallite size of 0.152nm as calculated using the Debye Scherrer’s equation. The
deposited film showed polycrystalline structure. The effect of substrate on the deposited film show the
presence of broad peaks indicating the presence of Thin films. The film has its highest peak around 16.04 at
a maximum intensity of 37.9 which gave the preferential orientation of (002) hexagonal phase respectively
using the scattering selection rules.
The electrodeposition technique is one of the fastest, easiest and simplest method of growing adherent
thin films as the thickness of the coating may berelatively controlled. The disadvantage associated with the
electrodeposition ethod is that it is very expensive as the cost of purchasing the required apparatus is
relatively high and not found everywhere except in special places.
Another disadvantage is that the electrodeposition method requires constant supply of power and
in the case of power failure as part of what we experience today in our country would need the back up of
an alternative energy resource (for instance, fuel) to supply power for the deposition process which requires
cost.
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