Advanced Materials Research Vol.

665 (2013) pp 341-346

Online available since 2013/Feb/13 at www.scientific.net
© (2013) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.665.341

SYNTHESIS, STRUCTURAL AND OPTICAL CHARACTERIZATION OF

PVA CAPPED CADMIUM SULPHIDE NANOCRYSTALLINE FILMS BY
CHEMICAL BATH DEPOSITION METHOD
L. Sujata Devi 1, K. Nomita Devi2*, B. Indrajit Sharma1
and H. Nandakumar Sarma2
1
Department of Physics, Assam University, Silchar-788011, Assam, India
2
Department of Physics, Manipur University, Canchipur, Imphal- 795003, India
Corresponding author: *nomita_k@rediffmail.com

Keywords: Chemical bath deposition, CdS nanocrystalline films, XRD, UV-visible,

photoluminescence.

Abstract: Nanocrystalline CdS thin films were deposited on glass substrate by chemical bath
deposition method using Cadmium Sulphate and Thiourea as Cd+2 and S-2 ion sources for different
molarities i.e. 0.1 M, 0.2 M and 0.3 M. The crystallite size and lattice parameters for each sample
were determined from X-Ray diffraction data using Scherrer’s formula. The value of the crystallite
size was found to be within the range 14.7 nm-11.4 nm. The optical characterization was done by
UV-Visible and photoluminescence spectroscopy. The optical band gap of the films was determined
from the transmittance spectra. It was observed that when the molarity increases, the average
crystallite size decreases and the band gap energy of the prepared films increases.
Photoluminescence studies showed a prominent peak at around 530 nm. The radius of the
nanocrystalline films had been evaluated from the absorption spectrum by using effective mass
approximation formula.

Introduction
The synthesis of chalcogenide thin films of group II-VI semiconductors are important
because of their non-linear optical properties [1,2], luminescent properties [3,4], quantum size effect
[5,6] and other important physical and chemical properties [7]. Cadmium Sulphide is a wide energy
band gap semiconductor with Eg=2.42 eV in bulk and is a very important technological
semiconductor material which has been studied for decades. There are many reports about CdS
nanocrystalline films obtained by different processes and from different precursors such as Thermal
Evaporation [8], RF Sputtering [9], Spray Pyrolysis [10] and Chemical Bath Deposition Method
[11]. Sizes of the nanocrystalline films depend strongly upon their preparation condition and
processes. Among the various processes, Chemical Bath Deposition (CBD) has been used as an
important route for the synthesis of CdS nanocrystalline films because CBD process is a simple and
an inexpensive process to obtain homogenous, hard, adherent and transparent films.
In this study, we are reporting the preparation of CdS nanocrystalline films by taking
different molarities on glass substrate by CBD process.

Experimental details
CdS nanocrystalline films had been deposited on the glass substrate by CBD method in
PVA matrix. PVA being good solute to multiple phase system provides uniform gaps that are very
close to each other and distribute in the form of an array. The reagents used for the deposition were
Cadmium Sulphate (CdSO4), Thiourea (CS(NH2)2) and 25% of ammonia solution. All the chemical
reagents used were of analytical grade. The matrix solutions were prepared by adding the 0.1 M, 0.2
M, 0.3 M of Cadmium Sulphate (CdSO4) to an aqueous solution (2%) of PVA with constant
stirring at constant temperature (~60oC) maintained for one and half hour until the solution became
a transparent liquid with the complete dissolution of Cadmium Sulphate. The pH of the solution

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342 Condensed Matter and Materials Physics

was maintained at around 11 by slowly adding 25% of ammonia solution. Then an equimolar
solution of Thiourea was added to the matrix solution while stirring constantly at constant
temperature. After that, the glass slides were immersed into the solution bath for 60 minute
deposition time. The preparation of CBD CdS nanocrystalline films were based on the slow release
of Cd+2 and S-2 ions in the solution bath. The Cd+2 ions are given by the dissociation of complex
species called Tetraamino-Cadmium [Cd(NH3)4]+2. The S-2 ions are obtained by the decomposition
of Thiourea (CS(NH2)2) in an alkaline solution and react with Tetraamino-Cadmium [Cd(NH3)4]+2
to form CdS nanocrystalline films. After the deposition, the glass substrates were removed from the
chemical bath, cleaned thoroughly in distilled water and air-dried at room temperature. The CdS
nanocrystalline films formed on the substrate are optically transparent, adherent, homogenous and
yellowish in colour.

Characterization of thin films

The structure and phase of the CdS nanocrystalline films were determined by X-ray
diffraction using PAnalytical X-ray diffractometer using Cu-Kα (α=1.54 Å) radiation. Diffraction
patterns had been recorded over the 2θ range of 20o to 80o at the scan rate of 2o/min. The optical
absorbance spectra for CdS nanocrystalline films were recorded by using Perkin Elmer UV-VIS
Spectrophotometer (Model: Lambda 35) in the wavelength range 200 nm-800 nm. The
measurement was done in the wavelength scanning mode at room temperature in the normal
incidence and using uncoated glass slides as the reference. Photoluminescence spectra of the films
were recorded using Perkin Elmer LS 55 with an excitation wavelength of 390 nm.

Results and discussion

Structural
Fig. 1 shows the X-ray diffraction pattern of CdS nanocrystalline films at different concentration
i.e. 0.1 M, 0.2 M and 0.3 M. The XRD pattern of the synthesized CdS nanocrystalline films shows
cubic phase (Zinc blende) and are well matched with the ICDD card no. 01-75-0581. The calculated
lattice parameters are a=b=c= 5.765 Å, 5.762 Å, 5.72 Å for 0.1 M, 0.2 M and 0.3 M respectively.
With increase in concentration, the peak position of the films are observed to be shifted to higher
diffraction angle suggesting lattice contraction with respect to bulk which is expected to occur
because of higher surface to volume ratio [12]. From the full width at half maximum (FWHM) of
the most intense peak, the size of the particle has been calculated by using Debye Scherrer formula
[13]

Kλ
D= (1)
β 2θ cos θ

where θ is the Bragg angle and λ is the X-ray wavelength . Here K=0.94 is a constant and β2θ is
the FWHM in radians of the XRD peak. The calculated crystallite sizes are found to be 14.7 nm for
0.1 M, 13.3nm for 0.2 M and 11.4nm for 0.3 M.
 Advanced Materials Research Vol. 665 343

(2 1 )
1
0)
(1

1)
)
)

20

1
00

(3
(2
(2
--0.3M

Relative Intensity (arb. unit)

--0.2M

--0.1M

20 40 60 80

2θ (d eg re e)
Figure 1. XRD patterns of CdS nanocrystalline films at different molarities

Optical properties
The spectrum which is obtained by the absorption of electromagnetic radiation is known
as absorption spectrum. When the electrons from the valence band absorb some energy, the
electrons are excited to the conduction band. This excitation energy should be greater than or equal
to the energy band gap of the material. For the excitation less than the band gap, energy is
transmitted and hence energy band gap can be determined from the transmittance spectra. Fig. 2
shows the transmittance spectra of CdS nanocrystalline films in the UV-Visible range for the three
different molarities. From the figure, it can be seen that the transmittance increases slightly with the
increase in molarity and shows the fundamental absorption edge in the range 464nm to 491 nm. The
most direct way of extracting the optical band gap from the figure is to simply determine the
wavelength at which the extrapolation of the base line and the absorption edge cross [14]. Using
this method, the calculated energy band gap for the different molarities are 2.66 eV, 2.59 eV and
2.51 eV and these values are shifted compared with the bulk value and this can be a consequence of
a size quantization effect on the film. As expected the reduction in particle size gives a shift in the
optical band gap of the films.
344 Condensed Matter and Materials Physics

90

80

70

Transmittance (T%)
60

50

40

30

20 0.3 M
0.2 M
10 0.1 M

0
300 400 500 600 700 800
Wavelength (nm)

Figure 2: Transmittance spectra of CdS nanocrystalline films at different molarities

From the band gap information, the sizes of the CdS nanocrystalline films are calculated by
using the effective mass approximation (EMA) method and which is given by the relation
h  1 1  1.8e 2
Eg nano = Eg bulk +  * + *  − (2)
8r 2  me mh  4πεε 0 r
where Egnano is the band gap energy of the nanocrystalline films as determined from the
transmittance spectra; Egbulk is the band gap of the bulk CdS at room temperature; r is the radius of
the nanoparticle, me* (0.19 me) and mh* (0.8 me) are the effective masses of the conduction band
electron and valence band hole in CdS in units of electron mass, e is the electronic charge, h is the
planck’s constant, ε 0 is the vacuum permittivity and ε is the high frequency dielectric constant of
CdS (5.9). The average nanoparticle diameter calculated from the transmittance spectra by using the
effective mass model are 4.4 nm, 3.8 nm and 3.4 nm for the prepared CdS nanocrystalline films.
The variation of the particle size and energy band gap of CdS nanocrystalline films are illustrated in
table 1.

Table 1: Variation of particle size and energy band gap for CdS nanocrystalline films

Molar FWHM Å Particle Energy Blueshift Particle

concentration 2θ(Deg.) a=b=c size(nm) band gap size from
from XRD (Eg eV) (eV) EMA (nm)

0.1 M 0.66 5.77 14.7 2.51 0.09 4.4

0.2 M 0.72 5.76 13.3 2.59 0.17 3.8

0.3M 0.84 5.72 11.4 2.66 0.24 3.4

 Advanced Materials Research Vol. 665 345

Photoluminescence
The photoluminescence spectra of CdS nanocrystalline films in PVA matrix are shown in
fig. 3.

12

0.3 M
10

0.2 M
8
Intensity (A.U)

0.1 M
6

400 450 500 550 600 650 700

Wavelength (nm)

Figure 3: Photoluminescence spectra of CdS nanocrystalline films at different molarities

The spectra were recorded using Perkin Elmer LS 55 with an excitation light wavelength 390 nm.
Generally, photoluminescence is a process in which an electron excited by monochromatic photon
beam of certain energy undergoes radiative recombination either at valence band or at surface state
within the forbidden gap. The figure shows a high intense and broad peak centered at 530 nm which
corresponds to green emission band. This is mainly due to the interstial sulphur (Is) which causes
the electron transmission from the conduction band to an acceptor level [15].

Conclusions
CdS nanocrystalline films have been successfully synthesized by CBD method in PVA
matrix. X-Ray diffraction pattern confirms the cubic phase of the synthesized films. The crystallite
size as calculated from Scherer’s formula and using EMA decreases with in increase in molarity.
UV-VIS absorption spectrum clearly shows an increase in band gap as the molarities increases
which supports the formation of nanocrystallites. Therefore, it shows that the CdS nanocrystalline
films exhibit strong quantum confinement effect as the optical band gap increases significantly from
2.51 eV to 2.66 eV as compared to bulk value 2.42 eV. PL spectrum exhibits a high intense and
broad peak due to the presence of trapped states.

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Condensed Matter and Materials Physics
10.4028/www.scientific.net/AMR.665

Synthesis, Structural and Optical Characterization of PVA Capped Cadmium Sulphide

Nanocrystalline Films by Chemical Bath Deposition Method
10.4028/www.scientific.net/AMR.665.341