World Applied Programming, Vol (3), Issue (2), February 2013.

56-60
ISSN: 2222-2510
2013 WAP journal. www.waprogramming.com

Study of Different Capping Agents Effect on the Structural

and Optical Properties of Mn Doped ZnS Nanostructures
Abbas Rahdar
Department of Physics, Faculty of Science,
University of Zabol,
Zabol, Iran.
a.rahdar@uoz.ac.ir
Abstract: In this work, we report effect of different capping agents on structural and optical properties of Mn
doped ZnS (ZnS:Mn),which were prepared by co-precipitation method using the solution of ZnCl2, Na2S as
sources for zinc and sulfur, respectively and MnCl2 as doping agent ,thioglycerol(TG) ,mercaptoethanol (ME),
sodium hexaetaphosphate (SHMP) as capping agents for control particles size. The optical absorption spectra of
the samples obtained using UV-Vis spectrophotometer shows the blue-shift with decreasing particle size. The
value of band gap energy has been found to be in range 4.07-4.57 eV This behavior is related to size
quantization effect due to the small size of the particles.So-prepared Mn doped ZnS nanoparticles then
characterized by using X-ray diffraction (XRD). The size of the particle is found to be in 2.20-2.67 nm range.
TEM image shows morphology of TG and ME- capped ZnS:Mn nanostructures.
Keywords: ZnS, Sodium Hexametaphosphate, Mercaptoethanol , Thioglycerol,Capping agent

I.

INTRODUCTION

Semiconductors in nanocrystallized form exhibit markedly different electrical, optical and structural properties, as
compared to those in the bulk form. Various methods like solgel, precipita- tion, microemulsion, and chemical vapor
deposition have been reported for the preparation of ZnS nanoparticles [15]. Zinc sulfide (ZnS) is one of the most
important IIVI semiconductor compounds that has been widely used as a key material for some devices such as lightemitting diodes [6], flat-panel displays [6], bio sensors [7], luminescence devices [814] and photonic crystal devices
[15]. The use of ZnS quantum dots in these devices modify or improve their performance .ZnS has two structures:a cubic
form (c-ZnS ) with sphalerite structure and a hexagonal form(h-ZnS) corresponding to wurtzite ,which show a wide band
gap of .53.7 and3.73.9 eV, respectively. ZnS exhibits a wide range of novel structures by controlling the growth rate
along different directions. ZnS quantum dots have been synthesized by many researchers with the aid of capping agents,
and those materials exhibited strong confinement effects. Capping agents are used to arrest the growth of nanoparticles
and to stabilize them from aggregation. They also modify the structural, morphological and optical properties of
nanoparticles. Here, we report on the synthesis and structural and optical properties of water-dispersible Mn doped ZnS
nanoparticles stabilized by different capping agents, which modifies surface of nanoparticles and prevents the growth of
the particles to larger size.
II.

EXPERIMENTAL AND PREPARATION

The Mn doped ZnS (ZnS:Mn) nanostructures were prepared by the chemical co-precipitation method as follows. First,
ZnCl2 Na2S and MnCl2 was dissolved indouble-distilled water with 0. 1 M concentration separately. then obtained
solutions was magnetically stirred for 20 min at room temperature. Afterwards, Na2S (50 ml) solution and MnCl2 (50 ml)
solution was added drop by drop to the ZnCl2 solution under vigorous stirring in an N2 atmosphere separately.next, as
capping agent ,different of capping agents thioglycerol(TG) ,mercaptoethanol(ME) , sodium hexametaphosphate(SHMP)
was dissolved in double-distilled water for 20 min at room temperature. Afterwards, first the capping agents solution
(50 ml) with certain molar concentration(1% ) was added drop by drop to the ZnCl2 solution under vigorous stirring in
an N2 atmosphere separately. After 10 minutes, solution of sodium sulfide was poured drop by drop . The resulting
solution was stirred continuously for 6 hours. In the final step, the white 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.

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Abbas Rahdar, World Applied Programming, Vol (3), No (2), February 2013.

III.

RESULTS AND DISCUSSION

Figure 1 shows the XRD pattern for the capped Mn doped ZnS
thioglycerol,mercaptoethanol,sodium hexametaphos-phate.

nanostructures with capping agents of

Figure 1. XRD spectrum of the capped ZnS:Mn nanostructures with different of capping agents.

It shows three diffraction peaks (2) of 29.3 , 48 and 56.9 degree, respectively. The peaks are identified to originate from
(111), (220) and (311) planes of the cubic (zinc blend) phase of ZnS. The broadening of the diffraction peaks indicates
the nanocrystalline nature of the sample. The peak broadening at lower angle is more meaningful for the calculation of
particle size. The mean crystallite size (D) of nanoparticles was also estimated using the Scherrer formula using (111)
reflection from the XRD pattern as follows:
0 . 9
(1)
D
B cos
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 lattice parameter has been
computed as 6.29 , which is close to the standard value (5.42 ).The optical absorption spectra ofnanoparticles were
measured using a USB-2000 UVVis spectrophotometer. Figure 2 shows the optical absorption spectra of Capped
ZnS:Mn nanostructures with different of capping agents.The absorption edge is observed in the range of 304271 nm.

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Abbas Rahdar, World Applied Programming, Vol (3), No (2), February 2013.

Figure 2. Absorption spectra of the capped ZnS:Mn nanostructures :a (TG-Capped ZnS:Mn) ,b (SHMP-Capped ZnS:Mn) and c (MECapped ZnS:Mn).

Table 1. Absorption edge and optical band gap of the capped ZnS:Mn nanostructures with different capping agents.
Capping agent

Concentration of ZnCl2 ,
Na2S and MnCl2
(molar)

Absorption edge
(nm )

Band-gap
(ev )

Particle Size
(nm)

TG 1.0 %
SHMP 1.0 %

0. 1
0. 1

304
285

4.07
4.35

2.67
2.35

ME 1.0 %

0. 1

271

4.57

2.20

The obtained optical band gap values for different samples are shown in Table 1.So that Absorption spectra of the
capped ZnS:Mn nanostructures with different of capping agents and the table 1 datas shows that The Absorption edge
of Nanocrystallite semiconductors are also sharp,indicating that the synthesized particles have relatively narrow size
distributions as the bulk band-gap of ZnS is 3.6 ev ,it means there is a stong quantum confinement in case of capped
ZnS:Mn Nanoparticles in our case.
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 were determined by Taucs relation [16]:

h 0 ( h Eg )1 2

(2)

Where h, o and Eg are photon energy, a constant and optical band gap of the nanoparticles, respectively. Absorption
coefficient () of the powders at different wavelengths can be calculated from the absorption spectra. Finally, the values
of Eg were determined by extrapolations of the linear regions of the plot of (h )2 versus h .
As seen in Table 1, the values of optical band gap Eg increases with the decrease in Growth time and therefore decrease
particles size that as mentioned earlier is due to quantum confinement effect. Also, the variation of optical band gap with
particle size is shown in Figure 3.
These semi-conductor nanocrystals were then subjected to transmis-sion electron microscopy (TEM, JEOL JEM3010)
for characterization. Figure 4 and 5 shows TEM image of ME-capped ZnS nanocrystals.

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Abbas Rahdar, World Applied Programming, Vol (3), No (2), February 2013.

Figure 3. The variation of optical band gap with particle size.

Figure 4. TEM image of ME- capped ZnS:Mn semi-conductor nanocrystals.

Figure 5. TEM image of TG- capped ZnS:Mn semi-conductor nanocrystals.

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Abbas Rahdar, World Applied Programming, Vol (3), No (2), February 2013.

IV.

CONCLUSION

ZnS:Mn nanostructures, synthesized by chem-ical co-precipitation technique, are in 2.20-2.67 nm diameter range using
the different capping agents.XRD and Optical band gap data have been ob-tained to confirm nano-size of these materials.
XRD patterns shows that the capped ZnS:Mn nanoparticles prepared are in a (FCC) cubical phase. The broad peak of
XRD pattern indicates nanocrystalline behavior of the particles. The Mn doped ZnS nanoparticles, have the band gap
value of 4.07, 4.35,4.57 eV which indicates a blue-shift as compared to the band gap of bulk ZnS (3.6eV), indicating the
quantum confinement in the ZnS nanocrystallites.TEM image shows clearly that the particles almost are spherical.

ACKNOWLEDGEMENTS
The author would like to thank Dr. M. Ali-Ahmad, my dear mother Mrs.M.Asudeh,my hardworking father Mr.H.Rahdar,
Mrs. Heidari Mokarrar, Mrs.F.Rahdar and Mrs.Motahereh Asudeh for their support and assistance with this project.

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