Chalcogenide Letters Vol. 9, No. 2, February 2012, p.

67 - 72

STRUCTURAL AND OPTICAL CHARACTERIZATION OF PVA CAPPED

CADMIUM SULPHIDE NANOPARTICLES BY CHEMICAL
COPRECIPITATION METHOD

L. SUJATA DEVIa, K. NOMITA DEVIb*, B. INDRAJIT SHARMAa,

H. NANDAKUMAR SARMAc,
a
Department of Physics, Assam University, Silchar-788011, Assam, India
b
Department of Physics, North Eastern Regional Institute of Science and
Technology (NERIST), Nirjuli, Arunachal Pradesh-791109, India
c
Department of Physics, Manipur University, Canchipur, Imphal-795003, India

CdS nanoparticles have been synthesized by chemical co-precipitation method using PVA
as a capping agent. Structural characterization of the as synthesized CdS nanoparticles
were performed by X-ray diffraction (XRD) study which showed hexagonal structure with
average crystallite size of 11 nm and lattice constants a=4.106 Å, c=6.637 Å. Optical
characterization of nanocrystalline thin films prepared by Vacuum Evaporation Method
from the synthesized powder were done by Photoluminescence spectroscopy and UV-
Visible absorption spectroscopy. UV-Visible absorption spectrum showed blue shift in
absorption edge with respect to bulk CdS. The photoluminescence spectrum of the CdS
film exhibited green emission band with a maximum at 528 nm. Radius of the synthesized
CdS nanoparticle has been evaluated from the absorption spectrum by using the effective
mass approximation formula.

(Received November 28, 2011, Accepted February 6, 2012)

Keywords: Chemical method, CdS nanoparticle, Vacuum evaporation, XRD,

UV-VIS spectrum, Photoluminescence.

1. Introduction

The synthesis of nanoparticle of group II-VI semiconductors in powder form has been a
rapid area of research due to their unique chemical, physical, optical, electrical and transport
properties. Cadmium Sulphide (CdS) is one of the most studied materials among II-VI compounds
due to its potential technological applications in field effect transistors, solar cells, photovoltaic
light emitting diodes, photocatalysis, infrared photoconductor and biological sensors [1-7]. There
are many reports about CdS nanoparticles obtained by different methods and from different
precursors [8-13]. Sizes of the nanoparticles depend strongly upon their preparation condition and
methods [14-16]. Polymer capped nanoparticles composite have been increasingly studied
because of their enhanced optoelectronics and optical properties. Polymer is a good choice as
stabilizer as they can interact with metal ion by complex or ion-pair formation and can be designed
to certain physical properties of semiconductor nanoparticle.
In this paper, we report a simple chemical co-precipitation synthesis method using
polyvinyl alcohol (PVA) as a capping agent. Different techniques of synthesis have been
developed to obtain CdS naopaticles in the solid phase (17), precipitation in the liquid phase (18)
and growth in nanosize micells (19). Although many methods for the synthesis of CdS
nanocrystals have been developed, it is still a challenge to synthesize CdS nanocrystals in the
quantum confinement range.

*
Corresponding author: [email protected]
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2. Experimental

CdS nanoparticles were grown by chemical co-precipitation method using PVA as a

capping agent. All the chemicals reagents used were of analytical grade. The matrix solution were
prepared by adding 0.1 M solution of cadmium sulphate (CdSO4) to an aqueous solution (2%) of
PVA with constant stirring at constant temperature 700C maintained for one and half hour until the
solution became a transparent liquid which indicates the complete dissolution of CdSO4. The pH
of the solution was maintained at around 11 by slowly adding NH4OH solution. Then an equimolar
solution of thiourea (CH4N2S) was added to the matrix solution while stirring constantly at
constant temperature until the solution turned into pale yellow and forms precipitates. The
precipitates were filtered out separately and washed thoroughly with de-ionized water and dried at
60oC. CdS nanocrystalline thin films of thickness ~1.2 µm were prepared by evaporating the
synthesized powder onto glass substrates held at 200 0C from a molybdenum boat in a vacuum of
about 10-5 torr using a vacuum coating system (Make: HINDHIVAC; MODEL:12A4DM). The
glass substrates were cleaned with warm dilute chromic acid, detergent solution, distilled water
and isopropyle alcohol in that order. The substrates were placed directly above the source at a
distance of nearly 12 cm.
The structure and phase of the as synthesized sample were determined by X-ray diffraction
using PAnalytical X-ray diffractometer using Cu-Kα (λ=1.54Å) radiation. Diffraction patterns have
been recorded over the 2θ range of 20o to 70o at the scan rate of 2o/min. The optical absorbance
spectra for CdS films are recorded using Perkin Elmer UV-VIS spectrophotometer (Model:Lamda
35) in the wavelength range 300 nm-900 nm. The measurements were 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 sample are recorded using Perkin Elmer LS 55 with
an excitation light wavelength of 390 nm.

3. Results and discussions

3.1 XRD studies

450

400 (002)

350

300 (101)
Intensity (a.u.)

250 (100)

200
(110)

150 (112)
(103)

100
(102)
50

0
20 30 40 50 60
2 (degree)

Fig. 1: XRD spectrum of as synthesized CdS nanopowder

 69

Fig.1 shows the X-ray diffraction pattern of the as synthesized CdS powder. The XRD
pattern indicates the synthesized CdS powder having a hexagonal phase due to the presence of
(100), (002), (101) reflection planes in the angular region between 20o and 30o. The presence of
(102), (110), (103), (112) also supports the existence of hexagonal phase. In fig 1 all diffraction
peaks can be indexed as the hexagonal CdS with lattice constants a= 4.106 Å, c=6.637 Å which is
very consistent with the values in the standard card (JCPDS 80-006). From the full width at half
maximum (FWHM) of the most intense peak, the particle size has been calculated by using
Scherrer formula [20].
(1)

where K is a constant taken to be 0.94, the wavelength of X-ray used, is the FWHM in
radians of the XRD peak and is the angle of diffraction. The evaluated crystallite size is found to
be 11 nm.

3.2 Absorption Studies

2.0

1.5
Absorbance (a.u.)

1.0

0.5

0.0

300 400 500 600 700 800 900

Wavelength (nm)
Fig. 2. Absorption spectrum of CdS nanoparticles

Fig. 2. Absorption spectrum of CdS nanoparticles

The spectrum which is obtained by absorption of electromagnetic radiation is called

absorption spectra. Fig 2 shows the room temperature optical absorption spectrum of CdS film and
as can be seen from the spectrum the optical absorption excitonic peak is shifted to the lower
wavelength side relative to that of bulk CdS (~530 nm) crystals. This result is in agreement with
the value of the reported literatures. [21, 22]. The energy band gap of the material is calculated
using the Tauc relation [23]
(αh)1/n=A(h-Eg) (2)

where A is a constant and Eg is the band gap of the materials and exponent n depends on the type
of transition. For direct allowed transition n=1/2, indirect allowed transition n=2, direct forbidden
transition n=3/2 and forbidden indirect transition n=3. To determine the possible transitions (αh)2
vs h is plotted and shown in Fig. 3. The value of α is obtained from the relation

α= 2.3026(A/t) (3)
70

where A is the absorption and t is the thickness of the sample. The extrapolation of straight line to
(αh)2=0 gives the value of the energy band gap of the prepared materials. The direct band gap
value of the sample is found to be 2.54 eV and this value is shifted about 0.12 eV compared with
the bulk value (2.42eV) and this could be a consequence of quantum-size effect in the sample.

4 .0 0 E + 0 1 1

3 .0 0 E + 0 1 1
2

2 .0 0 E + 0 1 1
(h)

1 .0 0 E + 0 1 1

0 .0 0 E + 0 0 0
2 .0 2 .2 2 .4 2 .6 2 .8 3 .0 3 .2 3 .4
E n e rg y (h  )

Fig 3. The band gap determination of as prepared CdS thin film

Particle size size can be calculated by the effective mass model that relates the change in
band-gap energy to the radius of the particle [24]

(4)

where is the band-gap energy of the nanoparticle as determined from the UV-Vis
absorbance spectrum; is the band gap of the bulk CdS at room temperature; is the radius
of the nanoparticles, (0.19 me) and (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;
is the Planck’s constant, is the vacuum permitivity and is the high frequency dielectric
constant of CdS (5.7). The average nanoparticle diameter calculated from the absorption spectra by
using the effective mass model is 4.26 nm for the prepared CdS nanoparticles.

3.3 Photoluminescence Studies

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
states within the forbidden gap. The photoluminescence originates from the recombination of
surface states [25]. Fig. 5 shows the photoluminescence emission spectra of CdS nanoparticles thin
film at excitation wavelength 390 nm. The figure shows a high intense peak centered at 528 nm.
The peak corresponding to 528 nm provide green emission band. The green emission band was
associated with the emission due to electronic transition form the conduction band to an acceptor
level due to interstial sulphur (Is) site [26].
 71

0.4

0.3

Emmission Intensity (a.u) 0.2

0.1

0.0

-0.1
450 500 550 600 650 700 750
wavelength (nm)

Fig. 4 Photoluminescence emission spectra of as prepared CdS nanoparticle thin film

4. Conclusion

CdS nanoparticles have been synthesized in the PVA matrix through chemical co-
precipitation method. X-ray diffraction confirms the hexagonal structure and the particle size are
11 nm. UV-visible absorption showed a blue shift indicating quantum confinement of the particle.
PL spectrum exhibits peaks centered at 528 nm because of interstial sulphur sites.

Acknowledgement

We are thankful to the Department of Physics, Manipur University for providing necessary
help in carrying out the experimental work.

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