World Applied Programming, Vol (3), Issue (3), March 2013.

108-112
ISSN: 2222-2510
2013 WAP journal. www.waprogramming.com

Effect of Reaction Tempreture on ME Capped ZnS

Nanoparticles: Structural and Optical Characterization
Abbas Rahdar

Fereshteh Izadpanah

Department of Physics, Faculty of

Science, University of Zabol, Zabol, Iran.
a.rahdar@uoz.ac.ir

Department of Physics, Faculty of Science,

University of Ker-man, Kerman, Iran.

Abstract: In this work, we report effect of reaction tempreture on structural and optical properties of
nanocrystalline ZnS particle with mercaptoethanol as a stabilizer, which have been synthesized by coprecipitation method. The structural properties of ZnS nanoparticles have been characterized by X-ray
diffraction (XRD) analysis. The XRD patterns show fcc structure in nanoparticles. The optical size calculated
from the Brus equation has been found in the range of 2.79-2.67 nm with the increase in tempreture of reaction.
We also found that optical band gap (Eg) increases with the increase in tempreture of reaction using UV-Vis
spectrophotometer. This behavior is related to size quantization effect due to the small size of the particles.TEM
image shows morphology .
Keywords: ZnS nanoparticles, Brus equation ,reaction, Capping agent, Optical band gap

I.

INTRODUCTION

A burst of research activities has been emerged in the synthesis and characterization of semiconductor nanoparticles for
size dependent optical properties, because they find great applications in photonic and biophotonics [1-2]. The size
dependence of the bandgap is the most identified aspect of quantum confinement in semiconductors;the bandgap
increases as the size of the particles decreases. When the dimensions of nanocrystalline particles approach the exciton
Bohr radius, a blue shift in energy is observed due to the quantum confinement phenomenon .The effective mass model
is commonly used to study the size dependence of optical properties of quantum dots (QD) system [3].The tunability of
the properties of nanoparticles by controlling their size may provide an advantage in formulating new composite
materials with optimized properties for various applications.However, applications would be restricted due to different
nonradiative relaxations pathways. One of the most important nanoradiative pathways is surface related defects.To
overcome the above mentioned difficulties, organic and inorganic capping agents are used to passivate the free quantum
dots. Various wet chemical methods have been developed for the synthesis of sulphide nanoparticles[4-9]. To control the
growth of the nanoparticles,organic stabilizers (polymers) e.g. polyethylene oxide (PEO), poly(N-vinyl-2 Pyrrolidone,
PVP), polyvinylcarbazole (PVK) are added during the wet-chemical synthesis for capping the surface of the particles
([10-12].
Zinc sulfide (ZnS) is a semiconductor material, which has a band gap of 3.70 eV [13] and is an ideal material for studies
of variation in discrete gap energy due to the reduction of physical dimensions into nanoscale regime. Research over past
several years revealed that ZnS particles are potential to be implemented as cathode-ray tube, luminescent materials in
flat panel displays and IR windows [14-15]. There have been extensive reports in the past few years demonstrating the
systematic exploration of growing ZnS nanoparticles with a narrow size distribution in the surfactant system. So in the
present paper, we tried to find the structural and optical properties of ZnS nanoparticles with 2-Mercaptoethanol as
capping agent by the chemical co-precipitation method that was magnetically stirred for different temperatures were
studied.

II.

MATERIALS AND EXPERIMENTAL PROCEDURE

Zinc chloride (ZnCl2), sodium sulfide (Na2S) as source materials, mercaptoethanol as capping agent for control particles
size and doubledistilled water as dispersing solvent were used to prepare ME Capped ZnS nanoparticles .
The ME Capped ZnS nanoparticles were prepared by the chemical co-precipitation method at different temperatures as
follows. First, Zinc chloride sodium sulfide was dissolved indouble-distilled water with 0.1 M concentration separately.

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Abbas Rahdar and Fereshteh Izadpanah. World Applied Programming, Vol (3), No (3), March 2013.

then obtained solutions was magnetically stirred for 20 min . Afterwards, Na2S (50 ml) solution was added drop by drop
to the ZnCl2 solution under vigorous stirring in an N2 atmosphere separately. Then, an appropriate amount (50 ml) of
ME (0.01 M) was added to the reaction medium to control the particle size of ME Capped ZnS.
M .E

(1)

ZnCl 2 Na 2 S ZnS 2 NaCl

the resulting solution titrated to pH 9 with 2 M NaOH and then was magnetically stirred for 20 min. The stirring speed
was same for all samples. The nanoparticles were collected by centrifugation at 2000 rpm for 10 minutes. In the final
step, the obtained precipitate was filtered and dried at room temperature to remove both water and organic capping and
other byproducts formed during the reaction process. After sufficient drying, the precipitate was crushed to fine powder
with the help of mortar and pestle. It is necessary to mention that different sample of nanoparticles has been obtained at
different temperatures namely ME-capped ZnS (A) , (B) and (C) as the amount of tempreture of used for reaction
medium in the preparation is 15, 25 and 35 respectively. The synthesis process of ZnS nanoparticles by the
coprecipitation method is summarized in a flow chart shown in Fig. 1.

Fig. 1. The flow chart of preparation ME-capped ZnS nanoparticles by chemical co-precipitation method.

III.

RESULTS AND DISCUSSION

The X-ray diffraction (XRD) patterns of the ME-capped ZnS (A) and (C) nanoparticles are depicted in Fig. 2 and
o

Fig. 3respectively .The spectrum presents three broaden peaks at about 29.2 , 48.1 and 57.3 in 2, which correspond
to the Miller index of the reflecting planes for (111), (220) and (311).

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Abbas Rahdar and Fereshteh Izadpanah. World Applied Programming, Vol (3), No (3), March 2013.

Fig. 2. XRD pattern of ME-capped ZnS (A) nanoparticles.

The broadening of the diffraction peaks suggests that the dimensions of the nanoparticles are very small.

Fig. 3. XRD pattern of ME-capped ZnS (C) nanoparticles.

The peak broadening at lower angle is more meaningful for the calculation of particle size. The average size (D) of
nanoparticles was also estimated using the Scherrer formula (Scherrer 1918) using (111) reflection from the XRD pattern
as follows:
D=

0.9
,
B cos

(2)

Where , B, and are the X-ray wavelength of the radiation used (K(Cu) = 0.154056 nm), the full width at half
maximum (FWHM) of the diffraction peak and the Bragg diffraction angle, respectively. The values of Average
crystallite size obtained from XRD (Scherrer formula ) for different tempretures are listed in Table 1.
The absorption spectra of the different samples are shown in Table 1. The absorption edge is observed in the range of
320280 nm, which is blue shifted compared to bulk ZnS (345 nm). Fig. 4. Shows Absorption spectra of of ME-capped
ZnS (C) nanoparticles.

Fig. 4. Absorption spectra of of ME-capped ZnS (C) nanoparticles.

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Abbas Rahdar and Fereshteh Izadpanah. World Applied Programming, Vol (3), No (3), March 2013.

The absorption spectrum of ME-capped ZnS nanoparticles synthesized at 35 c temperature is shown in Fig. 4. It
shows an excitonic absorption peak at 302 nm (4.10 eV). There is a clear blue shift of band gap with respect to bulk ZnS,
since band gap of bulk ZnS with cubic structure is 3.6 eV (345 nm). This is due to the modification of valence and
conduction bands by quantum confinement effects. Even though the nanocrystallites exhibit bulk like crystal structure,
they are too small to have bulk like electronic wave functions. Applying the confinement effects, the optical band gap
energy of nanocrystallites is given by Brus equation (Brus, 1986):
Eg (nano) g (bulk)

22 1
1 1.8e2

2R2 me mh R

(3)

where Eg(bulk) in eV is the bandgap energy of bulk, me and mh are electron and hole effective masses and R in
nm is the particle size.For cubic ZnS, Eg=3.6 eV, me=0.34 mo and mh=0.23 mo, mo is the free electron rest mass and =8.76
is the permittivity of the sample (Landolt., 1987). Taking the band gap of synthesized nanoparticles as 4.10 eV,the
substitutionin Eq. (3) gives the particle optical size as 2.67 nm. The discrepancy with XRD (2.50 nm).
Table 1. Calculated size of ZnS nanoparticles from Scherrer formula and Brus equation.
Samples

amount of
Tempreture of used for
reaction medium (c)

Optical Size (nm)

Average crystallite size (nm)

Absorption Edge (nm)

Optical band gap (eV)

ME-capped
ZnS (B)

25

2.79

2.72

315

3.93

ME-capped
ZnS (C)

35

2.67

2.35

302

4.10

The obtained direct optical band gap values for different samples are shown in Table 1. It is necessary to mention that
the optical direct band gap values of the ZnS nanoparticles can be determine by Taucs relation (Tauc, 1966; Liu et al.,
2006):

h 0 ( h Eg )1 2

(4)

Where h, o and Eg are photon energy, a constant and optical band gap of the nanoparticles, respectively. Absorption
coefficient () of the nanoparticles at different wavelengths can be calculated from the absorption spectra. Finally, the
values of Eg can be determine by extrapolations of the linear regions of the plot of (h )2 versus h .
ME-capped ZnS nanoparticles were then subjected to transmission electron microscopy (TEM,JEOLJEM3010) for
characterization. Fig. 4shows TEM image of ME-capped ZnS Semiconductor nanocrystals.

Fig. 4. TEM image of ME-capped ZnS (C) nanoparticles .

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Abbas Rahdar and Fereshteh Izadpanah. World Applied Programming, Vol (3), No (3), March 2013.

IV.

CONCLUSIONS

It is possible to produce ZnS nanoparticles using mercaptoethanol as a capping agent in order to control the particle size
using a simple chemical method. XRD and optical band gap data have been obtained to confirm nano-size of these
materials. The cubic structure of the synthesized nanoparticles has been observed using XRD studies .It is also observed
that the particle size depends on reaction tempreture . The optical band gap and optical size values of ZnS nanoparticles
have changed from 3.93 to 4.10 eV and 2.79 to 2.67 nm by increasing tempreture of reaction respectively. These values
exhibit a blue shift in Eg which is related to the size decrease of the particles and to the quantum confinement limit
reaching of nanoparticles.The yellowish green emission band at 476 nm for the ME-Capped ZnS nanoparticles is most
likely due to the self - activated defect centres formed by the zinc va-cancy inside the lattice.TEM image shows clearly
that the particles almost are spherical.

ACKNOWLEDGEMENT
The authors would like to thank Mr. A. Rahdar, Mr. R, Hakimi-Pooya, Mrs. M. Asudeh, Mr. H. Rahdar and Mrs. Heidari
Mokarrar for their support and assistance with this project.
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