J Mater Sci: Mater Electron (2017) 28:6628–6634
DOI 10.1007/s10854-017-6353-4
Structural and optical properties of cadmium sulfide thin films
on flexible polymer substrates by chemical spray pyrolysis
technique
M. G. Faraj1,2 · M. Z. Pakhuruddin3 · P. Taboada1 
Received: 23 November 2016 / Accepted: 4 January 2017 / Published online: 19 January 2017
© Springer Science+Business Media New York 2017
Abstract  Cadmium sulfide (CdS) films were depos-
ited on polymide (PI) plastic substrate by chemical spray
pyrolysis technique at substrate temperature in the range
(300–375 °C) in 25 °C steps. The effects of substrate tem-
perature on the structural and optical properties of the films
were studied.Characterization of structural properties was
carried out by X-ray diffraction (XRD). The XRD results
confirmed proper phase formation of the CdS structure.
These also revealed that the CdS films have a hexagonal
structure and the crystallite size increased with increas-
ing film temperature.The root mean square roughness of
the films was measured by atomic force microscopy. This
quantity increased as the film temperature did.The optical
transmission measurements by UV–Vis spectrophotometer
determined the energy gap of the CdS films on the PI plas-
tic substrate. The optical band gap values of CdS thin films
slightly increased as the film temperature did, and it was
found to be in the range of 2.42–2.48 eV.
* M. G. Faraj
mohammad.ghaffar@koyauniversity.org
1
Grupo de Física de Coloides y Polímeros, Departamento de
Física de la MateriaCondensada, Universidad de Santiago de
Compostela, 15782 Santiago de Compostela, Spain
2
Department of Physics, Faculty of Science and Health,
Koya University, Daniel Mitterrand Boulevard,
Koya KOY45 AB64, Kurdistan Region, Iraq
3
Nano‑Optoelectronics Research and Technology Laboratory,
School of Physics, UniversitiSains Malaysia, 11800 Penang,
Malaysia
13
Vol:.(1234567890)
1 Introduction
CdS is a II–VI compound semiconductor consisting of cad-
mium, from group II, and sulfur, from group VI, of theperi-
odic table of elements. CdS is naturally an n-type material
with an energy band gap of 2.42 eV at room temperature,
so it has been used as a window material together with sev-
eral semiconductors, such as CdTe, ­Cu2S, ­CuInSe2 and InP
in thin-film solar cells, with 14–16% efficiency [1–4]. CdS
is an important and useful material for optoelectronic appli-
cations. Thin films of CdS have been prepared through var-
ious physical and chemical thin-film deposition techniques,
such aselectro deposition [5], chemical bath deposition [6],
spray deposition [7], femtosecond pulsed laser deposition
[8], molecular beam epitaxy [9], successive ironic layer
adsorption and reaction [10], screen printing [11], close
spaced sublimation [12], radio frequency (RF) sputtering
[13], metal organic chemical vapor deposition [14], pulsed-
laser deposition [15] and thermal evaporation [16]. Among
the aforementioned techniques, spray technique is really
advantageous as a consequence of its low-cost and suitabil-
ity for forming large area thin-films [17].
Research on CdS deposition on flexible polymeric sub-
strates such as polyimide (PI) is gaining immense interests
due to their flexibility, light-weight, low-cost, high tem-
perature resistance (typically up to 400 °C processing tem-
perature), low coefficient of thermal expansion (CTE), low
moisture uptake and high moisture release characteristics,
itsexcellent electrical properties and also increased voltage
endurance [18]. Due to its superior properties, PI has found
applications as substrates in flexible thin-film solar cells,
flexible printed circuits and high density interconnects [19,
20].
In this work, CdS thin-films were deposited on PI sub-
strate by chemical spray pyrolysis at different substrate
J Mater Sci: Mater Electron (2017) 28:6628–6634 6629
temperatures (300, 325, 350 and 375 °C). The influence
of the substrate temperature on the structural and optical
properties of the CdS films was then studied. The ulti-
mate aim of this investigation is to use PI as a substrate
for thin-film solar cells with chemical spray pyrolysis
technique.
2 Experimental procedure
2.1 Substrates cleaning
In this experiment, PI plastic from DuPontCorporation
was used as substrate.The PI substrate was cleaned by
alcohol for 10  min to remove contamination. After the
cleaning process, the substrate was rinsed with distilled
water (DI water). The sample was then dried with nitro-
gen ­(N2) gas.
2.2 Materials
The materials used in the preparation of CdS thin films
include cadmium chloride ((CdCl2), 99.99%), and thiou-
rea (CS ­(NH2)2) ≥ 99.0%, from Sigma–Aldrich and used
as received.
Fig. 1  Experimental set-up of spraying apparatus (right), and layout of enlarged spraying glass nozzle (left)
2.3 Preparation of CdS solutions
Aqueous solutions of cadmium chloride ­(CdCl2) and thio-
urea (CS ­(NH2)2) with molarities of 0.1  M and appropri-
ate volumes were mixed with DI water by using a magnetic
stirrer for 30 min. Then the solution of cadmium chloride
and thiourea are mixed to obtain the cadmium sulfide
(CdS) and ammonium chloride (­NH4Cl) according to the
reaction equation [21–23]:
CdCl2 + CS(NH2 )2 + 3H2 O → CdS + 2NH4 Cl + CO2 ↑ +H2 O
The resulting solution was sprayed onto PI substrate by
chemical spray pyrolysis technique at different substrate
temperatures (300–375 °C) in 25 °C steps and the ammo-
nium chloride ­(NH4Cl) dissolved by heating into ammo-
nia gas and hydrogen chloride gas, as seen in the reaction
equation [23].
CdS + 2NH4 Cl + H2 O ���→
Δ
� CdS(s) + 2NH3 ↑ + 2 HCL ↑
The description of the experimental set-up of the CSP
system is shown in Fig.  1. In order to get uniform thin
films, the height of the spraying nozzle and the rate of
spray process were kept constant during the deposition pro-
cess at 35 cm and 5 ml/min respectively.Compressed air at
a pressure of 6 N/cm2 was used as a carrier gas. The thick-
nesses of the CdS on the PI substrates were of the order
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6630
of 200 nm, measured with an optical reflectometer (Model:
Filmetrics F20). The structural properties of the prepared
CdS thin films have been investigated using a high reso-
lution X-ray diffractometer system (Model: Panalytical
Empyrean) with ­CuKα radiation (λ) of 0.154 nm at 40 kV
and 45  mA. The surface morphology of the CdS films
were studied by atomicforce microscope (AFM) (Model:
ULTRA1Objective model). Optical properties of the CdS
thin films were characterized with aultraviolet-visible (UV)
spectrophotometer (Model: U-2000 HITACHI).Photolumi-
nescence (PL) was recorded using a JobineYvon HR 800
UV system at an excitation wavelength of 325 nm.
3 Results and discussion
3.1 Structural properties
XRD patterns of CdS thin films deposited on PI plastic sub-
strateatdifferent substrate temperatures (300, 325, 350 and
375 °C) are shown in Fig. 2. The main peak corresponding
to the PI plastic substrate was observed at an 2θ angle of
22.08°; as seen in Fig. 2.This result agrees with previously
reported data [24]. All CdS films had hexagonal structure
in agreement with standard XRD data, JCPD6-314 [25].
The XRD patterns of all the CdS films showed a sharp
(002) peak at 2θ = 26.523° along with a minor peak of cor-
responding to the (110) plane at 2θ = 43.805°. The intense
peak along the (002) plane in every films indicates that
these are highly oriented along the c-axis. The results con-
firm the proper phase formation of the CdS films. XRD pat-
terns show a clear dependent of the peaks intensity on the
Fig. 2  XRD patterns of CdS films at substrate temperatures of a
300 °C, b 325 °C, c 350 °C, and d 375 °C
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J Mater Sci: Mater Electron (2017) 28:6628–6634
substrate temperature of the deposited films. It is observed
that the increase of the substrate temperature increases the
diffraction peak intensity of the (002) plane, as observed in
Fig. 2. This behavior agrees with previous reports [26].
The relative change of full width at half maximum
(FWHM) for the (002) plane is shown in Fig. 3. The maxi-
mum peak value at 300 °C indicates enhanced crystallinity
of the deposited CdS thin film. This result is in good agree-
ment with previously reported data [23].
From the XRD results, the crystallite size (D) of the CdS
films was determined using Scherrer’s formula as the fol-
lowing [27]:
0.9𝜆
D= (1)
𝛽cos𝜃
where β is the full width at half maximum (FWHM) of the
peak corrected for instrumental broadening, λ is the wave-
length of the X-ray, 1.5406 Å and θ is the peak position.
Based on the line width of the (002) diffraction peak,
the crystallite sizes calculated for as-deposited CdS films
were 28.6–82.78 nm at different temperatures ranging from
300 to 375 °C in 25 °C steps. For the CdS films deposited
at 300 °C, the crystallite size was calculated to be 28.6 nm,
while for the other films, the crystallite size increased from
34.7 to 82.78  nm with increasing temperature, as shown
in Fig.  4. It was observed that the increase of the sub-
strate temperature increase the diffraction peak intensity of
(002) plane which resulted in increase in crystallite size of
the films. This behavior is a consequence of the decrease
in density of nucleation centers as the substrate tempera-
ture increases. Under this condition, smaller numbers of
nucleation centers start to grow, resulting in larger grains
Fig. 3  Variation of FWHM of preferential orientation (002) of CdS
films with substrate temperature
J Mater Sci: Mater Electron (2017) 28:6628–6634 6631
Fig. 4  Crystallite size as a function of substrate temperatures
in agreement with previous reports using other deposition
techniques [28].
AFM images of CdS thin films deposited on PI plastic
substrate are shown in Fig. 5. The RMS surface roughness
of the films was 2.47, 3.88, 4.85 and 7.08 nm for films at
temperature in the range of (300–375 °C) in 25 °C steps,
as seen in Fig. 6. It should be noted that the RMS surface
roughness slightly increases with increasing substrate tem-
perature [29].
Fig. 5  AFM images of CdS
films deposited on PI substrate
with different substrate tem-
peratures a 300 °C, b 325 °C, c
350 °C and d 375 °C
3.2 Optical properties
Figure 7 shows the variation of theoptical transmission as a
function of wavelength (300–1000 nm region) for the films
deposited at different substrate temperatures. All the CdS
films show more than 60% transmission for wavelengths
longer than 500  nm.The transmissions of the CdS films
increases with increased the substrate temperature. An
increase in substrate temperature improved the transmis-
sion of the CdS films. This improvement can be attributed
to either the decrease in thickness or the improvement in
perfection and stoichiometry of the films. Similar transmis-
sion profiles of CdS films have been previously reported
[30, 31]. At 375 °C, the transmission is the highest, with
values exceeding 80% above 500 nm wavelength. The high
values of optical transmission are crucial when using the
CdS film as a window layer in thin-film solar cells. A high-
transmission window layer allows maximum incident light
to reach the active layer of the solar cell for creation of
electron–hole pairs.
The optical band gap ­(Eg) was determined by analyzing
the optical data with the expression for the optical absorb-
ance (α) and the photon energy (hν) using Tauc’s equation
32.
(𝛼h𝜈) = k (h𝜈 − Eg )n (2)
where n = ½ for allowed direct transition (for a direct
band gap semiconductor),and k is a constant. The energy
band gap was then estimated from the straight line of the
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6632
Fig. 6  Variation of the RMS roughness of CdS films with different
substrate temperatures
Fig. 7  Transmittance ofCdSfilms sprayed at different substrate tem-
peratures (in 300–1000 nm wavelength region)
2
plot (αhν) vs. photon energy for CdS thin films as shown
in Fig.  8. Extrapolation of the linear portion of the graph
to the energy axis at α = 0 gives the band gap energy ­(Eg),
which lies in the range of 2.42–2.48 eV. From this, the opti-
cal band gap values of CdS thin films is found to slightly
increase as the film temperature increases [30].
Figures 9 and 10 shows reflectance and refractive index
curves as a function of wavelength (in 400–1000 nm wave-
length region) for the CdS films deposited at different sub-
strate temperatures, respectively.From the measured reflec-
tance (R) curve, refractive index (n) of the CdS films is
derived using the following equation [33]:
13
J Mater Sci: Mater Electron (2017) 28:6628–6634
Fig. 8  Plot of (αhν)2 of as a function of photon energy forCdS thin
filmsdeposited on PI substrate at different substrate temperatures
Fig. 9  Reflectance of CdS thin films at different substrate tempera-
tures
1 + (R)1�2
n= (3)
1 − (R)1�2
where n is the refractive index of a CdS film, and R is its-
surface reflectance. Both R and n reduced rapidly to almost
constant values at long wavelengths (above 550  nm).At
the highest substrate temperature (375 °C), the reflectance
showed itslowest value (compared to the other substrate
temperatures), about 9% at 600  nm. The wide band gap,
high optical transparency and low reflectance (less than
20% in the visible range) for the deposited CdS films on
PI plastic substrate make them suitable as a window layer
in thin-film solar cells. Photoluminescence spectra of CdS
J Mater Sci: Mater Electron (2017) 28:6628–6634 6633
Fig. 10  Refractive Index of CdS thin films at different substrate tem-
peratures
Fig. 11  PL spectra of CdS thin films at different substrate tempera-
tures
thin films at different substrate temperatures are shown in
Fig.  11. These are found to exhibit an emission peak at
about 510 nm (2.43 eV) at a temperature of 300 °C, which
is ascribed to the band-to-band transition. The emission
band present at510nm is known as the green emission band
of CdS [34]. For the other films, the PL intensity decreases
with increasing film temperature. As indicated, the photo
luminescence intensity depends strongly on the deposi-
tion temperature. Similar observations have been found in
other studies [35, 36]. For the CdS film at a temperature
300 °C, Eg was found to be 2.43 eV, while for other films,
­Eg increased from 2.44 to 2.48 eVwith increasing film tem-
perature. These valuesare similar to thoseobtained from the
optical transmissionstudies previously depicted in Fig. 8.
4 Conclusions
CdS films were prepared by chemical spray pyrolysis
technique using a solution of cadmium chloride and thio-
urea.CdS films were deposited on PI substrate at varied
temperature (300–375 °C). Good quality, adherent, uni-
form and pine-hole free CdS thin films were obtained.
The XRD patterns confirmed proper phase formation of
the CdS. Substrate temperatures during deposition were
found to have influenced the phase and preferred orienta-
tion of the films. The film prepared at the lowest temper-
ature (300 °C) was found to have the least crystallinity,
which then increased at higher substrate temperatures.
The RMSroughness of the films increased as the film
temperatures increased. All the films showed more than
60% transmission for wavelengths longer than 500  nm.
This wide band gap, high optical transparencyand low
reflectance (less than 20%) in the visible range observed
in the deposited CdS films on PI plastic substrate make
them a suitable candidate as a window layer in thin-film
solar cells.
Acknowledgements  The author M. G. Faraj would like to thank
Koya University and Ministry of Higher Education of Kurdistan
Region for the permission given to carry out his research activities
abroad. P. T. thanks MINECO for project MAT2016-80266R.
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