IJSTE - International Journal of Science Technology & Engineering | Volume 2 | Issue 11 | May 2016

ISSN (online): 2349-784X

Synthesis and Luminescence Properties of Ni

Doped ZnS Nanoparticles
B. Hariprasad Reddy
Research Scholar
Department of Physics
Sri Venkateswara University, Tirupati, 517502, India.

G. S. Harish
Research Scholar
Department of Physics
Sri Venkateswara University, Tirupati, 517502, India.

P. Sreedhara Reddy
Professor
Department of Physics
Sri Venkateswara University, Tirupati, 517502, India.

Abstract
In this paper we discussed cost effective chemical co-precipitation method for preparing water soluble Ni doped ZnS nanoparticles
and studied the effect of dopant concentration on the structural, morphological, compositional and photo luminescence properties
using X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), energy dispersive analysis of X-rays
(EDAX) and photo luminescence studies. Broadened XRD peaks confirmed the formation of nano-sized ZnS: Ni nanoparticles
with cubic structure at different capping agent concentrations. SEM and EDAX analysis showed surface morphology and effective
elemental composition of prepared nanoparticles. The Raman peak observed at 344 cm-1 can be assigned as the LO mode of cubic
ZnS. Ni doped ZnS nanoparticles and showed broad emission ranging from 440-520 nm. The Photo Luminescence intensity of
ZnS: Ni Nanoparticles is enhanced by the incorporation of Ni ions.
Keywords: chemical co-precipitation, nanoparticles, photoluminescence, scanning electron microscopy, X-ray diffraction
________________________________________________________________________________________________________
I.

INTRODUCTION

The nano-sized materials have found many novel applications and are attracted great interest due to enhanced mechanical, optical,
opto-electronic and magnetic properties of nanocomposite. IIVI semiconducting nanoparticles have attracted great interest due to
their unique structural, optical and electronic properties which arise due to their large surface to volume ratio [1-5]. ZnS
nanoparticles doped with Ni2+ have been obtained by chemical co-precipitation from homogeneous solutions of zinc and nickel
salt compounds with S2- as precipitating anion formed by decomposition of sodium sulfide. Average particle size and structural
analysis of the doped and pure ZnS nanoparticles were observed by X-ray diffraction analysis. Enhanced luminescence properties
were observed in photoluminescence spectra of ZnS nanoparticles doped with Ni2+. Composition analysis and surface morphology
information were obtained from EDS and SEM analysis respectively. Raman studies showed the absence of impurities and effective
doping of Ni2+ ions into ZnS.
II. EXPERIMENTAL AND CHARACTERIZATION TECHNIQUES
All the chemicals were of analytical reagent grade and were used without any further purification. The samples were prepared by
chemical co-precipitation method using pure zinc acetate, nickel chloride and sodium sulfide. Appropriate amounts of Zn(ac)2 and
NiCl2. 6H2O were dissolved in 50ml distilled water. To this solution, 50ml of sodium sulfide solution is added drop wise under
constant stirring until to get fine precipitate of Ni doped ZnS nanoparticles. After the completion of the reaction, products were
collected and thoroughly washed for several times with distilled water and ethanol, Ni doped ZnS nanoparticles were subjected to
various characterization studies. The X-ray diffraction patterns of the samples were collected on a Seifert 3003 TT X- Ray
diffractometer with the Cu K radiation (=1.5405A). Elemental composition of the prepared samples were analyzed through
EDS using Oxford Inca Penta FeTX3 EDS instrument attached to Carl Zeiss EVO MA 15 Scanning Electron Microscope.
Photoluminescence spectra of the present Nano powders have been recorded using a Horiba-Fluorolog-3 (Model FL3-22)
spectrofluorometric at room temperature (300 K). Raman Spectroscopic studies of the as prepared samples were carried out using
LabRam HR800 Raman Spectrometer.

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III. RESULTS AND DISCUSSION

Elemental Analysis:
Chemical composition analysis of all samples was done by EDS technique. In order to analyze the amount of Ni content and
distribution in doped ZnS this technique is much useful. Fig.1 (a), (b), (c) and (d) shows EDS spectra of Pure ZnS, Zn1-xNixS
(x=0.02,0.04, 0.06) nanoparticles respectively. EDS spectra of the samples confirmed that the amount of Zn, S and Ni were close
to the nominal (target) values.

(a)

(b
)

(c)

(d
)

Fig. 1: EDS spectra of (a) Pure ZnS nanoparticles, (b) Zn 1-xNixS, x= 0.02, (c) Zn1-xNixS, x= 0.04 and (d) Zn1-xNixS, x= 0.06 nanoparticles

Morphological Studies:
The surface morphology is studied by Scanning Electron Microscope (SEM), by observing the top and cross-sectional views of
the sample. The surface morphologies of the Pure ZnS, Zn1-xNixS (x=0.02, 0.04, 0.06), nanoparticles were shown in fig. 2 (a), (b),
(c) and (d) respectively. It is noticed that in the doped samples the agglomerated particles appear to be nearly spherical with the
distribution becoming nearly homogeneous.

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Synthesis and Luminescence Properties of Ni Doped ZnS Nanoparticles

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Fig. 2: SEM image of (a) Pure ZnS nanoparticles, (b) Zn1-xNixS, x= 0.02, (c) Zn1-xNixS, x= 0.04 and (d) Zn1-xNixS, x= 0.06 nanoparticles

Structural Analysis:
According to Fig. 3 shows the XRD patterns of pure ZnS, Zn1-xS: Nix (x=0.02, 0.04, 0.06). The three diffraction peaks in the XRD
patterns for all four products (Figure 3) were indexed as the (1 1 1), (2 2 0) and (3 1 1) crystal planes of cubic ZnS, although the
three diffraction peaks were slightly shifted to higher angles with increasing Ni concentration. This indicated that Zn 1xNixS
nanoparticles were successfully synthesized.
The average particle size calculated by Debye Scherrers equation [a] for ZnS: Ni nanoparticles lie in the range of 8-10 nm.

-------------------[a]
Where, D is the average particle size and hkl is full width at half maximum of XRD peak expressed in radians and is the
position of the diffraction peak

Fig. 3: XRD patterns of Pure ZnS, Zn1-xNixS, x= 0.02, 0.04 and 0.06

Photoluminescence Studies:
The room temperature PL spectra of pure ZnS, Zn1-xS: Nix (x=0.02,0.04, 0.06) nanoparticles are shown in fig. 3.4. The excitation
wavelength is 320nm. For pure ZnS nanoparticles a broad emission peak is observed at around 450nm [6]. Ni doped ZnS
nanoparticles showed broad emission ranging from 440-520nm. P.Yang, et.al observed emission peaks of ZnS: Ni nanocrystals at
520nm [7] and R. Mohan et al.[8] reported emission peak centered at 425 nm. Ni doped ZnS nanoparticles showed broad emission
peak at around 440 nm, which may be due radiative recombination of sulfur vacancies and ZnS host lattice. In this study with
incorporation of Ni2+ ions a broad emission ranging from blue region to green region is observed. The Photo Luminescence
intensity of ZnS: Ni Nanoparticles is enhanced by the incorporation of Ni 2+ ions as in fig. 4.

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Synthesis and Luminescence Properties of Ni Doped ZnS Nanoparticles

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Fig. 4: PL spectra of Pure ZnS, Zn1-xNixS, x= 0.02, 0.04 and 0.06

Raman Spectroscopy:
Fig.5 shows the typical Raman scattering data to the pure ZnS and at different concentration of Ni (2, 4 and 6 at.%). For bulk cubic
ZnS, the Raman peaks were observed near 271 and 352 cm-1 corresponding to transverse optical (TO) and longitudinal optical
(LO) modes respectively [11].
S. Kumar et al.,[12] reported broadening of the Raman peaks and their shifting towards lower energy as compared to the bulk
values. As the carrier concentration in the semiconductor increases, the frequency of L+ mode increases from bulk LO mode
frequency and the frequency of L- mode increases from zero to TO mode frequency. Hence the peak at 258 cm-1 observed in the
present sample can be attributed to the TO mode. The Raman peak observed at 344 cm-1 can be assigned as the LO mode of cubic
ZnS. The shifting of Raman peaks towards lower energy may due to quantum confinement effect. No other impurity peaks were
observed which supports the effective doping of Ni into ZnS.

Fig. 5: Raman spectra of Pure ZnS, Zn1-xNixS, x= 0.02, 0.04 and 0.06

IV. CONCLUSION
Undoped and Ni doped ZnS nanoparticles were successfully synthesized through facile chemical co-precipitation method. The assynthesized nanoparticles were subjected to chemical analysis (EDAX) and the estimated compositions were compliance with that
of the starting compositions. XRD studies demonstrated that Ni doped ZnS nanoparticles were in cubic zincblende crystal structure
with an average particle size of the order of 8-10 nm. No other impurity peaks were observed in Raman spectroscopic studies
which supports the effective doping of Ni into ZnS. Photoluminescence measurements revealed that Ni doped ZnS nanoparticles
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Synthesis and Luminescence Properties of Ni Doped ZnS Nanoparticles

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showed the emission intensity increased with increasing Ni content up to 4 at.% Ni and thereafter it decreased and the emission
wavelength was slightly shifted to higher wavelengths and broadened with Ni content.
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