Journal of Alloys and Compounds 650 (2015) 381e385

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Synthesis and characterization of nanocrystalline zinc sulphide thin

lms by chemical spray pyrolysis
P.O. Offor a, B.A. Okorie a, F.I. Ezema b, V.S. Aigbodion a, *, C.C. Daniel-Mkpume a,
A.D. Omah a
a
Metallurgical and Materials Engineering Department, University of Nigeria, Nsukka, Nigeria
b
Crystal Growth and Characterization Laboratory, Department of Physics and Astronomy, University of Nigeria, Nsukka, Nigeria

a r t i c l e i n f o a b s t r a c t

Article history: This work reports the structural, morphological and optical properties of zinc sulphide (ZnS) thin lms
Received 28 March 2015 obtained by chemical spray pyrolysis (CSP) technique using zinc chloride as cationic and thiourea as
Received in revised form anionic source with ethylene-diamine tetra acetate (EDTA) complex. The ZnS thin lms were deposited
4 July 2015
on glass substrate at 300
C, 400
C and 450
C. The inuence of the substrate temperatures on the
Accepted 19 July 2015
Available online 21 July 2015
structural, morphological and optical properties was studied. The XRD spectra show that the lm is
nanocrystalline with peak intensity increasing with temperature. The morphology of the lms was seen
by scanning electron microscopy (SEM). The lms dislocation density and micro strain increased with
Keywords:
Spray pyrolysis method
temperature. Optical properties show a high transmittance which increased with temperature.
Zinc sulphide 2015 Elsevier B.V. All rights reserved.
Optical properties
Structural properties

1. Introduction chemical spray pyrolysis technique which was rst investigated by

Zinc sulphide is an important semiconductor material with
energy band gap of Eg 3.65 eV (bulk), which is the highest among
all IIeVI compound semiconductors [1]. The lms formed by wide
band gap IIeVI semiconductors are of considerable interest, as their
emissions cover the technologically attractive blue and green
spectral region [2]. Zinc Sulphide is a semiconductor compound
suitable for a number of optoelectronic devices, such as solar cells,
antireective coatings, electroluminescent displays, optical sensors
[3e6], UV light emitting diodes, blue light emitting diode, emission
at screens etc. [7,8].
Zinc sulphide thin lms have been deposited using various
techniques including sputtering, metalorganic chemical vapour
deposition, molecular beam epitaxy (MBE) and atomic layer
epitaxy. These methods have the disadvantage of requiring
expensive vacuum systems for the deposition [9]. Thin lms of zinc
sulphide have been prepared using various less expensive tech-
niques, such as chemical bath deposition, solution growth, suc-
cessic ionic layer adsorption and reaction, electrodeposition and
* Corresponding author.
E-mail addresses: Peter.offor@unn.edu.ng, peterjoyoffor@yahoo.com (P.O. Offor),
victor.aigbodion@unn.edu.ng, aigbodionv@yahoo.com (V.S. Aigbodion).
Chamberlin and Skarman [10] with the following advantages [11],
(i) simple and continuous operation, (ii) economical (iii) uniform
particle size distribution (iv) controllable size, and (v) controllable
anion and cation concentrations or dopants.
The performance and efciency of thin lm-based devices are
strongly dependent on the structural, electrical and optical prop-
erties of the lm component. For this reason the study of these
properties and the characteristics of the deposited lm are very
important. It helps to optimize the parameters for better device
applications. Moreover, the electrical and optical properties of the
lms are affected by the parameters such as ow rate, substrate
temperature, and concentration of solution etc, as well as the
presence of impurities and defects in the lms [12,13]. Hence,
studies of the inuence of these parameters on surface
morphology, structural and optical properties of deposited thin
lms are considered very important since they are expected to play
very important role in enhancing the efciency of the device.
In the present study, we report the inuence of the substrate
temperature on surface morphology, structural and optical prop-
erties of zinc sulphide thin lms.
Zinc sulphide (Zns) thin lms were prepared using spray gun
perfumed atomizer spray technique onto ultrasonically cleaned
glass substrates at the substrate temperature of 310
C. The aqueous
solution was composed of zinc acetate and thiourea [14]. Zns thin

http://dx.doi.org/10.1016/j.jallcom.2015.07.169
0925-8388/ 2015 Elsevier B.V. All rights reserved.
382 P.O. Offor et al. / Journal of Alloys and Compounds 650 (2015) 381e385
lms on glass substrates were prepared by spray pyrolysis tech-
nique at 220, 250 and 280
C. Aqueous solution of 50 ml containing
zinc acetate dehydrates and thiourea salts of 1:1 M were used [16].
Also Zns thin lms were deposited by chemical spray pyrolysis
(CSP) using mixed aqueous solutions of zinc sulphate and thiourea
at substrate temperature of 500
C [17]. Zns thin lms were also
prepared using zinc chloride and thiourea by spray pyrolysis at
substrate temperature of 400
C [18]. Zns thin lms were suc-
cessfully deposited on glass substrates by CSP method using zinc
acetate and thiourea at substrate temperature range of 300e400
C
[7]. In the same vein Zns thin lms were prepared by CSP using two
mixed aqueous solutions: (a) dehydrated zinc acetate (102M) and
thiourea (4  102 M) in bidistilled water; (b) Zinc chloride
(102 M) and thiourea (4  102M) in bidistilled water. The solu-
tions were sprayed on silica gel substrates heated to 500
C for rst
solution and 450
C for the second [1]. Zns thin lms were prepared
by CSP using zinc chloride, thiourea and drops of hydrochloric acid
on glass substrates heated to a temperature of 350
C [19]. Boron
doped Zns thin lms were deposited on highly clean glass sub-
strates at different temperatures within the substrate temperature
rage (450e550
C) by CSP. The starting materials used were zinc
chloride, thiourea and boric acid [3]. Nanoparticle Zns lms were
deposited on glass substrates by CPS at temperature of (400 5
C).
The lms were annealed at 450, 500, 550 and 600
C. The spraying
solution was prepared by mixing zinc chloride and thiourea as
starting materials [20,21]. Zns thin lms were deposited on the
glass substrates at 350
C by CSP and annealed at 450
C and 550
C.
An aqueous solution of zinc acetate and thiourea were used to
deposit the Zns thin lms [12]. The present study reports the
preparation of zinc sulphide thin lms on glass substrates by a
chemical spray pyrolysis equipment using 0.1 M zinc chloride, 0.1 M
thiourea and 0.01 M ethylene-diamine tetra acetate (EDTA)
Fig. 1. X-ray diffraction of ZnS thin lms at various temperatures.
complex at substrate temperatures of 300
C, 350
C, 400
C and
450
C.
2. Experimental details
Thin lms of zinc sulphide were deposited on glass substrates
(7.5  2.5) cm2 by chemical spray pyrolysis (CSP) equipment
developed in the Department of Metallurgical and Materials Engi-
neering, University of Nigeria, Nsukka. The glass substrates were
washed with detergent, rinsed in water, rinsed in distilled water,
soaked in acetone for 20 min to remove contaminants and rinsed
again in distilled water. After the cleaning process, the substrates
were placed on a tray and dried in a sterilizer (oven). The deposition
process involved the thermal decomposition of an aqueous solution
of zinc salt, thiourea and ethylen-diamine tetra acetate (EDTA. Zinc
chloride (ZnCl2) was used as the of Zn2 ion, thiourea (SC(NH2)2) as
the source of S2 ion and EDTA (C10H16N2O) was added as a com-
plexing agent. Solution containing zinc chloride (ZnCl2), and thio-
urea (SC(NH2)2) of molar concentration 0.1 M and EDTA of molar
concentration 0.01 M were used to prepare zinc sulphide (ZnS) thin
ims. The equation of reaction is as follows:
ZnCl2aq SCNH2 2aq 2H2 O/ZnSs 2NH3aq CO2g
2HClg
(1)
The time interval between two sprays was kept constant at 10 s.
The spray pressure and the spray nozzle to substrate distance were
kept constant at 4 bars and 20 cm respectively. The ZnS thin lms
were deposited on the glass substrates at 300
C, 350
C, 400
C and
450
C respectively.
Structural study was done using EMPYREAN X-ray
 P.O. Offor et al. / Journal of Alloys and Compounds 650 (2015) 381e385 383

Table 1
Variation of interplanar distance, FWHM, hkl, dislocation density and micro strain values with substrate temperature for the ZnS thin lms.


Temperature ( C) 2q d spacing () D ASTM () FWHM (b) (hkl) Standard Lattice Crystalline size(G) Dislocation density (d) Micro strain ()
constant (a) () (nm) (Lines/m2) 1015 102

300 27.04 3.3 3.32 0.055 002 3.8 25.96 1.4839 1.3369
43.86 2.1 1.904 0.058 110 3.8 25.96 1.4839 1.3451
56.26 1.6 3.12 0.060 118 3.8 25.96 1.4839 1.3228
350 28.52 3.1 3.32 0.057 002 3.8 25.12 1.5847 1.3811
61.00 1.5 3.12 0.064 118 3.8 25.12 1.5847 1.3786
400 26.49 3.3 3.16 0.057 008 3.8 23.03 1.8854 1.3871
41.73 2.2 3.20 0.066 102 3.8 23.03 1.8854 1.5418
53.22 1.7 2.93 0.069 104 3.8 23.03 1.8854 1.5423
71.86 1.3 1.904 0.076 110 3.8 23.03 1.8854 1.5385
450 25.64 3.5 3.32 0.077 002 3.8 18.47 2.9313 1.8770

diffractometer system. X-ray diffraction spectra were obtained us-
ing CuKa (l 1.5406 ) radiation. Surface morphology was studied
using JOEL JSM 5900LV scanning electron microscope (SEM, and the
optical properties were measured by Avantes UVeVISeNIR
spectrophotometer.
electronic and optoelectronic devices [25]. The existence of multi-
ple diffraction peaks in the diffraction patterns indicated poly-
crystalline nature with hexagonal structure for the ZnS lms. The
(002) peak has pronounced intensity with temperature. It is highest
at 450
C. The d-values were calculated from the peaks of the X-ray
spectrum using Bragg's relation [18]:

3. Results and discussions

3.1. Structural analysis
All the deposited ZnS lms were white, homogeneous with a
good adherence to the substrate. XRD pattern of the deposited Zinc
sulphide thin lms deposited at 300
C, 350
C, 400
C and 450
C
by spray technique are shown in Fig. 1.
The XRD patterns show the presence of [(002), (110), and (118)],
[(002), and (118)], [(002), (102), (104), and (110)], and [(002)]
reection planes at 300
C, 350
C, 400
C and 450
C respectively.
The x-ray diffraction patterns of all the samples (Fig. 1 (a)e(d))
showed diffraction peaks corresponding to standard d values of ZnS
data card. Some of these peaks exhibited by the samples are broad
peaks. The presence of broad diffraction peaks indicate that the thin
lms deposited on the substrates are of nanosizes [22e24]. Nano-
crystalline thin lm is of signicant interest for a large variety of
2dsinq nl (2)
where n 1, l 1.5406 for CuKa target and q is Bragg's angle. The
grain size (G) of the deposited lms was determined from half
maximum intensity by using Scherer equation [18]:
kl
G (3)
bC0Sq
Where k is constant (0.9 approximately) and b is Full width at half
maximum intensity (FWHM). The amount of the defects in the
deposited material was determined by calculating the dislocation
density [26]. The dislocation density (d), dened as the length of
dislocation lines per unit volume, was estimated using the
following formula [26,27]:

Fig. 2. SEM images of ZnS thin lms at various temperatures (1000).

384 P.O. Offor et al. / Journal of Alloys and Compounds 650 (2015) 381e385
Fig. 3. Transmittance spectra of ZnS thin lms.
1 properties of ZnS lm. ZnS may play an important role in photo-
d (4)
G2
and the micro strain is considered as the presence of defects which
expands or contracts the nearer lattices by producing local strain
close to the defect [26]. The micro strain () can be calculated from
the following formula [26,27]:
bCOSq
(5)
4 Fig. 4 below shows the optical reectance of ZnS lms at
The values of dislocation density and micro strain are shown in
Table 1. The table shows that the values of dislocation density and
micro strain increased with temperature. Also reduction in dislo-
cations can be directly correlated with decrease in micro strain in
the material.
The d values were compared with the standard American So-
ciety for Testing Materials (ASTM) data to conrm the structure of
ZnS as listed in Table 1. The values of the lattice constant and the
grain size of the prepared lm are listed in Table 1.
3.2. Surface morphological analysis
Surface morphology of the samples prepared at 300
C, 350
C,
400
C, and 450
C substrate temperature was studied using
scanning electron microscope (SEM). Fig. 2 shows the SEM images.
The SEM images indicate a uniform lm and continuous coverage of
Fig. 4. Reectance spectra of ZnS thin lms.
the substrate with very at surface. The lms contain cracks and
voids which grow with increase in temperature.
3.3. Optical properties
Fig. 3 below shows the optical transmittance of ZnS lms at
different temperatures in the wavelength range of 300 nme960 nm
. The lms deposited at optimum conditions show transmittance of
values 91% at 450
C, 83% at 400
C, 78% at 350
C and 71% at 300
C.
The optical studies show that the transmittance of the ZnS lms
increases as substrate temperature increases. All the samples of ZnS
lms show very high transmittance in VIS and NIR region and low
transmittance in the UV region. The relatively high transmittance in
the IR regions could be used in glazing applications for space
heating. At 450
C sample of ZnS lms exhibit the highest trans-
mittance of about 91% in NIR region at wavelength of 900 nm. The
lm is actually transmitting and can be used as antireective ma-
terial because of the high optical transmission and anti-reective
voltaic devices. The lm is practically non-absorbing in NIR region.
The samples deposited at 300
C have the least transmittance for
each concentration. The lm show maximum transmittance of 71%
in the NIR region at 900 nm. These results obtained compare
favourably with high transmittance (60e99%) in the visible and
near infrared region obtained by Nadeem and Ahmed [13], 88%
obtained by Krishnamurthi et al. [14], and 95% obtained by Ibiyemi
et al. [15].
different temperatures in the wavelength range of
300 nme960 nm. From the curves reectance increases slowly
within the visible region and is almost constant in the range
690e930 nm. The highest value of reectance is 9.5% at 450
C
while the lowest is 8.1% at 300
C. This concentration is not good for
applications requiring high reectivity like mirrors. From the
curves reectance increases slowly within the visible region and is
almost constant in the range 690e930 nm. The highest value of
reectance is 9.5% at 450
C while the lowest is 8.1% at 300
C. This
concentration is not good for applications requiring high reec-
tivity like mirrors.
It can be seen that the absorbance seem to be nearly constant in
the visible range up to near infra-red. From the studies, it shows
that all the samples of the ZnS lms exhibit high absorbance in UV
regions and low absorbance in the IR regions. In the visible regions,
it absorbs only slightly. The result obtained by Nadeem and Ahmed
[13] and Ibiyemi et al. [15] on the optical absorbance of ZnS thin
lms for wavelength in the infrared region showed that ZnS is
practically non-absorbing in these regions which compares
favourably with the result obtained in this present work.
4. Conclusions
From the results and discussions above the following conclu-
sions can be made:
(1) The zinc sulphide thin lms deposited are polycrystalline in
nature with hexagonal structure.
(2) The lms show high transmittance values ranging from 71%
to 91%.
(3) The XRD peaks of the lms increased with temperature.
(4) The lms dislocation density increased with temperature.
(5) The lms micro strain increased with temperature.
(6) The SEM show smooth and continuous lms.
 P.O. Offor et al. / Journal of Alloys and Compounds 650 (2015) 381e385 385

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