J. Pure Appl. & Ind. Phys. Vol.

2 (3A), 360-364 (2012)

Optical Properties of Bulk ZnS:Mn and ZnS:Mn

Nanoparticles
RAVI SHARMA1, D.P. BISEN2, LATA WANZARI2, ISHWAR2
and USHA SHUKLA3
1

Department of Physics,
Arts and Commerce Girls College, Raipur-492001,C.G., INDIA.
2
S.O.S. Physics and Astrophysics,
Pt. Ravi Shankar Shukla University, Raipur, C.G., INDIA.
3
Department of Physis,
Amity University Lakhnow Campus, Lakhnow, U.P., INDIA.
ABSTRACT
The present paper reports the chemical route synthesis and
characterization of ZnS:Mn nanocrystals with mercaptoethanol
(ME) as the capping agent. The particle size of such nanocrystals
was measured using XRD and SEM pattern and it was found to be
in the range 2nm - 6nm. The absorption spectra showed blue shift
for the synthesized samples as compared to bulk. The
photoluminescence spectra shows two peaks for the ZnS:Mn
nanoparticles. The first peak was at around 420 nm and the second
peak was found at 598nm.
Keywords: Nanocrystals; XRD, photoluminescence, optical
absorption spectra and ZnS:Mn.

INTRODUCTION
Nanoparticles are of great scientific
interest as they are effectively a bridge
between bulk materials and atomic or
molecular structures. A bulk material should
have constant physical properties regardless
of its size, but at the nano-scale this is often
not the case. Size-dependent properties are
observed such as quantum confinement in
semiconductor particles, surface plasmon
resonance in some metal particles1.

Nanoparticles have a very high surface to

volume ratio. This provides a tremendous
driving force for diffusion, especially at
elevated temperatures. The large surface
area to volume ratio also reduces the
incipient
melting
temperature
of
nanoparticles2.
Nanomaterials are not simply another
step in the miniaturization of materials. They
often require very different production
approaches. The two main approaches which
are used to synthesize the nanoparticles in

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Ravi Sharma, et al., J. Pure Appl. & Ind. Phys. Vol.2 (3A), 360-364 (2012)

nanotechnology are "top-down" approach

and the "bottom-up" approach. The top
down approach involve milling or attrition,
cutting, grinding and etching and
volatilization of a solid followed by
condensation of the volatilized components.
In the "bottom-up" approach, nanoparticles
fabrication involves condensation of atoms
or molecular entities in a gas phase or in
solution.
The synthesis of semiconductor
nanoparticles in colloidal solutions has
attracted many researchers3-5. Synthesis of
nanophosphors is generally done by
chemical methods. Under chemical methods,
different routes such as colloidal, capping,
cluster formation, sol-gel, electrochemical
etc., are being followed. Physical methods
widely used are molecular beam epitaxy,
ionized cluster beam, liquid metal ion
source, consolidation, sputtering and gas
aggregation of monomers are much
sophisticated. Chemical precipitation in
presence of capping agents, reaction in
micro emulsions, sol gel reaction and auto
combustion are commonly used techniques
for synthesis of nanophosphors.
In this work ZnS : Mn nanocrystals
were prepared by chemical route technique
and mercaptoethanol (ME) was used as
capping agent. The effect of particle size on
optical absorption spectra and the
photoluminescence spectra was investigated.
XRD and SEM studies of the samples were
also made.
EXPERIMENTAL
A "bottom-up" approach, chemical
route is used in the present investigation.
The powder of ZnS nanocrystals were

prepared by using chemical deposition

technique described by Khosravi6. For
synthesis, the 1M aqueous solution of ZnCl2
and 1M aqueous solution of Na2S were
mixed in the presence of mercaptoethenol
(C2H5OSH) solution. MnCl2 solution was
added to the above solution in ratio 99:1,
while stirring the solution continuously. The
obtained precipitate was washed thoroughly
three to four times in double distilled water
and then separated by centrifuge at 3500
rpm, and finally air dried. Samples with
different concentration of mercaptoethanol
were prepared.
All the samples were characterized at
Inter University Consortium (IUC) Indore.
For Scanning Electron Microscope (SEM),
JSM5600 LV was used. The morphologies
and sizes of the mercaptoethanol capped
ZnS:Mn were determined by X-ray
diffraction studies with Cu K radiation
(=1.5418 ). XRD data were collected over
the range 200-700 at room temperature.X-ray
diffraction patterns have been obtained by
Rigaku
Rotating
Anode
(H-3R)
diffractometer. The particle size was
calculated using the Debye-Scherrer
formula.
Absorption spectra of the samples
prepared with various concentrations of Mn
was recorded with the help of UV-Visible
spectrometer (SHIMADZU).
The PL measurement was performed
on the synthesized samples of ZnS:Mn using
a Shimadzu Spectroflurophotometer RF
5301PC.
RESULTS AND DISCUSSION

and

The XRD spectra of bulk ZnS:Mn

synthesized ZnS: Mn particles are

Journal of Pure Applied and Industrial Physics Vol.2, Issue 3A, 1 July, 2012, Pages (286-402)

Ravi Sharma, et al., J. Pure Appl. & Ind. Phys. Vol.2 (3A), 360-364 (2012)
shown in Figure 1. Figure (Y) shows the
XRD pattern of bulk crystals of ZnS: Mn
and figure (X) shows the XRD pattern of a
sample of ZnS: Mn nanoparticle. There are
some important differences between the
diffraction patterns of nano and bulk
materials. It can be very clearly seen from
the figures (X) that the XRD pattern shows
broadening in the peak. Nanomaterials have
small particle size and this causes
broadening in their diffraction peak. The
broadening of the peak is due to a small
number of crystal planes. This broadening in
turn causes a loss of intensity in the signal of
their diffraction patterns. Strain factors as
well as broadening due to the instrument
could also contribute to the broadening of
the peaks. Bulk materials, on the contrary,

362

have sharp, narrow and high-intensity peaks.

The sharp peaks of the bulk particles show
that it is highly crystalline and the particles
are in the micron size. The three diffraction
peaks positions corresponds to the lattice
planes of (1 1 1), (2 2 0) and (3 1 1)
matching the zinc blende (sphalerite) ZnS
crystal structure (JCPDS 5-566). The XRD
pattern of the synthesized nano ZnS:Mn
particles resembles that of the bulk particles.
The size of the particles has been computed
from the width of first peak using Debye
Scherrer formula7. The grain size of the
sample were determined to be in the range
2-6 nm from the full width at half maximum
of the most intense peak making use of the
Scherrer's equation.

Fig.1 XRD spectra of bulk ZnS:Mn and synthesized nano ZnS: Mn

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Ravi Sharma, et al., J. Pure Appl. & Ind. Phys. Vol.2 (3A), 360-364 (2012)

Fig. 2 SEM photograph nano ZnS:Mn

Fig.3 Absorption Spectra of Bulk and nano ZnS:Mn

Figure 4 PL spectrum of ZnS:Mn (Bulk)and ZnS:Mn (nano)

A typical SEM image of ZnS

nanocrystals is shown in Fig.2. It can be
seen that some of the particles were highly
agglomerated. The particle sizes obtained
from SEM images are found to be in the
range of 5nm to 10nm.

Figure 3 shows the absorption spectra

of the bulk ZnS:Mn and ZnS:Mn
nanoparticle. The optical absorption spectra
of the samples are in the range of 400 nm200 nm. It was found that the spectra are
featureless and no absorption occurs in the

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Ravi Sharma, et al., J. Pure Appl. & Ind. Phys. Vol.2 (3A), 360-364 (2012)
visible region (800 nm-390 nm). Absorption
edge was obtained at shorter wavelength.
The characteristic absorption peak due to
ZnS nanoparticles appears in the wavelength
range 250-340 nm and this peaks position
reflects the band gap of the material. For the
ZnS:Mn nanoparticle an absorption peak
appears at around 300 nm. This peak is blueshifted from the absorption peak of bulk
ZnS:Mn at 340nm.
Figure 4 shows the PL spectrum of
ZnS:Mn (Bulk) and ZnS:Mn nanoparticles.
The spectrum of ZnS: Mn nanoparticles
show two peaks. First peak is a broad peak
with less intensity at 420 nm and second
narrow peak with high intensity at 598 nm
which corresponds to the characteristic
4
T16A1 transition of Mn ions. The peak
intensity at 420 nm associated with band gap
emission of ZnS was observed very less in
the case of Bulk ZnS:Mn. The intensity of
the second peak was also found less as
compared to the ZnS: Mn nanoparticles.
CONCLUSIONS
The ZnS:Mn nanoparticles were
successfully synthesized by the chemical
route technique, with ME as a capping
agent. SEM images show the agglomeration
of nanocrystals and therefore larger size of
nanoparticles were observed. XRD pattern
shows that the nanoparticles are in zinc

364

blend phase. The absorption peak is fairly

blue-shifted from the absorption edge of the
bulk. The particle size measured from the
optical absorption spectra and XRD was
found to be around 4nm-6nm. The PL
spectrum showed that the synthesized
nanoparticle has more intense peak as
compared to the bulk. The PL spectra show
two peaks, first at ~ 420nm and second at
598nm. The first peak is due to sulphur
vacancies and second peak is due to Mn2+
ions.
REFERENCES
1. National Nanotechnology Initiative
(http://www.nano.gov). (2000).
2. www.evidenttech.com/quantum-dotsexplained/quantum-dot-glossary. Html.
3. Zang Jinxin, Zhao Gaoling, Han
Gaorong, Front. Chem. China, 2 (1), 98,
(2007).
4. M. Azad Malik, Paul OBrien and N.
Revaprasadu, J. Mater. Chem., Vol.11,
2382, (2001).
5. S.Shrivastava and B. Verma, Cryst. Res.
Technol. 42, 5, 466, (2007).
6. A. A. Khosravi, M. Kundu, G. S.
Shekhawat, R. R. Gupta, A. K. Sharma,
P. D. Vyas, S. K. Kulkarni, Appl. Phys.
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Journal of Pure Applied and Industrial Physics Vol.2, Issue 3A, 1 July, 2012, Pages (286-402)