ARTICLE IN PRESS

Journal of Luminescence 130 (2010) 660–665

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Journal of Luminescence
journal homepage: www.elsevier.com/locate/jlumin

Optical studies of Cd2 + and Mn2 + Co-doped ZnS nanocrystals

Monika Mall a, Lokendra Kumar a,b,n
a
Physics Department, University of Allahabad, Allahabad- 211002, India
b
Nanophosphor Application Centre, University of Allahabad, Allahabad- 211002, India

a r t i c l e in f o a b s t r a c t

Article history: We report the structural and optical properties of co-doped ZnS nanocrystals synthesized by chemical
Received 26 May 2009 co-precipitation method using Methacrylic Acid (MAA) as a capping agent. XRD patterns confirm
Received in revised form the zinc blend structure of the samples. As calculated by the Debye–Scherrer formula and TEM
27 October 2009
image, the mean nanocluster diameter of the sample is ranging between 4–8 nm. EDAX analysis of
Accepted 5 November 2009
co-doped sample confirms the presence of Mn2 + and Cd2 + ions in addition to the sulfur deficiencies.
Available online 13 November 2009
Optical characterizations of both doped and co-doped samples are carried out by UV–vis and
Keywords: Photoluminescence (PL) spectroscopy. We observed the coexistence of two metal ions and their effect
II–VI semiconductors on the luminescence properties (i.e. red emission) of the host material. The mechanism of energy
Quantum confinement effect
transfer for the emissions are tried to discuss.
Nanoparticles
& 2009 Elsevier B.V. All rights reserved.
Co-doping
Photoluminescence

1. Introduction coatings, photoconductors, electroluminescent devices and infra-

In recent years, semiconducting nanoclusters have drawn
significant attention due to their unique optical, electrical and
chemical properties originating from their small size [1]. When
size of these particles is comparable to their corresponding
Bohr exciton radius, they exhibit quantum confinement effect
with significant blue shift in absorption spectra [2,3] and high
surface-to-volume ratio. Because of this, their surface consist
large number of atoms and lead to high surface reactivity. A
way to remove all these states is a process known as a
‘passivation’ or ‘capping’, which consists of bonding of surface
atoms to different materials (called passivating or capping
agents) to prevent particle–particle interaction. Sol–gel synth-
esis, embedding the particles in a polymer matrix, electro-
deposition, sonochemical synthesis, are certain synthesis
routes which are used to obtain nanoparticles with a narrow
size distribution [4–9]. In addition to this, the nanoparticles are
also having high thermal stability, increased quantum effi-
ciency for luminescence and radiative lifetime shortening with
decreasing particle size [1].
Among the II–VI compound semiconductor nanomaterials, ZnS
is an important material having direct and wide band gap
(3.67 eV). It is widely used in flat panel displays [10], optical
n photoluminescence property due to presence of two different
Corresponding author at: Physics Department, University of Allahabad,
Allahabad- 211002, India. Tel: + 91 532 2460993.
E-mail address: lkumarau@gmail.com (L. Kumar).
red windows [11,12]. Doped materials show different type of
luminescent properties which are strongly depended on the type
of dopant ions. These dopant impurities play an important role in
changing the electronic structure and transition probabilities of
the host material. There are several reports on the photolumines-
cence properties of ZnS nanostructures doped by various types of
impurities like Cu2 + , Mn2 + , Co2 + , Ni2 + , rare earth and transition
elements etc. [13–17]. In doped ZnS nanocrystals, impurity ion
occupies the Zn lattice site and behaves as a trap site for electron
and holes. The electrons are excited from the ZnS valence band to
conduction band by absorbing the energy equal or greater than
their band gap energy. Subsequent relaxation of these photo-
excited electrons to some surface states or levels is followed by
radiative decay enabling the luminescence in visible region.
However, two different kinds of ions present simultaneously in
a host material produce fluorescence which is completely
different from the emission due to single ion and this property
is very beneficial for white light generation [18–20].
In the present paper, we firstly report the synthesis of double
ion (Mn2 + and Cd2 + ) doped ZnS luminescent quantum dots at
ambient temperature by chemical co-precipitation method.
Nanoparticles were stabilized with Methaacrylic Acid (MAA)
reagent and detailed analytical investigations of structure, shape
and composition of the samples were performed using XRD, TEM
and EDAX respectively. Co-doped nanocrystals show an excellent
ion species in the same lattice. Here, PL studies exhibited red
emission in as synthesized co-doped nanoparticles.

0022-2313/$ - see front matter & 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jlumin.2009.11.012
 ARTICLE IN PRESS
M. Mall, L. Kumar / Journal of Luminescence 130 (2010) 660–665 661

2. Experimental section

2.1. Chemicals

Zinc acetate dihydrate (Zn(CH3COO)2  2H2O), Magnous acetate

(Mn(CH3COO)2), Cadmium Acetate dehydrate (Cd(CH3COO)2 
2H2O), Sodium sulphide (Na2S) and Methaacrylic Acid (MAA) are
used as a reagent. All chemicals were purchased from Merck India
Limited and used as received without further purification.

2.2. Sample preparation

In a typical synthesis of co-doped ZnS nanocrystals, 25 ml

ethanolic solution of 0.01 M zinc acetate was mixed with 0.2 mM
Cd acetate solution and stirred well. After that, 0.1 mM co-doping
ion (mangnous acetate) was added to the above solution. Drop
wise addition of 0.01 M Na2S immediately formed a deep whitish
solution of co-doped ZnS:Cd2 + ,Mn2 + . Obtained solution was
stirred vigorously up to half an hour and then 0.01 M solution
of MAA was mixed to prevent the further growth of nanocrystals.
Resulting white precipitate was centrifuged and washed with
alcohol and double distilled water in sequence. Subsequently, Fig. 1. X-ray diffraction (XRD) patterns of bare ZnS, ZnS:Cd 2%, ZnS:Mn 1% and
ZnS:Cd 2%, Mn 1% nanocrystals.
the precipitate was dried at 60 1C in vacuum oven, to obtain the
ZnS:Cd2 + ,Mn2 + nanoparticles in powder form. To understand the
effect of co-doping, three different samples were also prepared
using single dopant ions (Cd2 + and Mn2 + ) and without doping. The
whole reaction process was carried out at room temperature with
constant stirring.

2.3. Instrumentation

To investigate the structural and optical properties, the

samples were characterized by X-Ray Diffraction (XRD), Trans-
mission Electron Microscopy (TEM), Energy Dispersive Analysis
by X-ray (EDAX), UV–vis absorption (UV–vis) spectrometer and
Photoluminescence (PL) spectrometer. X-ray diffraction (XRD)
patterns were obtained by Rigaku D/max-2200PC diffractometer
operated at 40 kV/20 mA using Cu Ka radiation (wavelength
1.5406 Å) in the range from 20 to 701 on 2y scale. TEM experiment
was performed on JEOL 2000 FX system, using an accelerating
voltage of 160 KV with magnification of X30 K while EDAX
pattern was collected by FEI Quanta 200. Optical absorption
measurements were carried out using Perkin Elmer Lamda-35
UV–vis spectrometer ranging from 250 to 550 nm. PL spectra of
the samples were recorded with Perkin Elmer LS-55 photolumi-
nescence spectrophotometer with 325 nm excitation wavelength.
3. Results and discussion
Crystallinity, size and phase of particles were characterized by
XRD as shown in Fig. 1. Peak positions indicate the formation
of zinc blend crystal structure with three most preferred
orientations [1 1 1], [2 2 0] and [3 1 1]. No observable impurity
phases in the spectra, indicating the formation of pure cubic phase
of ZnS only while broadening of the diffraction peaks show the
formation of nanosized particles. The average nanocrystallite size
are calculated from full width at half maximum (b) of XRD peaks
using Debye–Scherrer’s formula [21]
0:9l
D¼ ð1Þ
b cosy
Where l is the wavelength of incident X-ray (1.54 Å) and y is the
Bragg’s angle. From the calculations, the average diameter of the
particles is 2.0 nm. Fitted value (using software JADE 6.0) of
Fig. 2. Transmission Electron Microscopy (TEM) image of Cd–Mn co-doped ZnS
sample which shows the uniform distribution of particles.
interplaner spacing (d111) is about 3.114 and 3.132 Å for undoped
and ZnS:Cd 2%, Mn 1% samples, respectively. The substitution
of the Zn2 + ions (r2Zn+ = 0.78 Å) with the higher radius Mn2 + ions
(rMn2 + = 0.80 Å) and Cd2 + ions (rCd2 + = 0.92 Å) results a small
increase (  0.5%) in lattice constant of ZnS. This increased lattice
constant gives the strong evidence for the incorporation of dopant
ion into the host matrix which is also confirmed by PL spectra.
Size and morphology of co-doped ZnS nanoparticles analyzed
by TEM is represented in Fig. 2. Image reveals that the nano-
crystals are spherical in shape with the size of 4–8 nm, which is
slightly larger than the size estimated by the Scherrer formula
calculations based on XRD pattern. Discrepancy between TEM and
XRD results divulge that prepared particles are polycrystalline in
nature.
In order to confirm the presence of Mn2 + and Cd2 + ions in the
material, we perform the EDAX study of co-doped sample.
According to EDAX spectra as shown in Fig. 3, it is clear that the
final product contains strong atomic percentage of Zn (27.86%)
and S (17.90%) as compared to Mn2 + and Cd2 + ions due to
the small doping concentration. Additional signals like carbon
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662 M. Mall, L. Kumar / Journal of Luminescence 130 (2010) 660–665

Fig. 3. Energy dispersive X-ray spectra (EDAX) of co-doped ZnS sample. It shows the presence of Mn and Cd in ZnS nanoparticles.

and oxygen are showing the presence of capping agent (CH2 =

C(CH3)COOH).
UV–vis absorption spectra of doped and co-doped samples
along with the undoped sample are shown in the Fig. 4. Broad
and less symmetric absorption peaks are observed at 318 nm that
are effectively blue shifted as compared to the bulk band gap
wavelength (338 nm). It is clearly shown in Fig. 4 that the
absorption edges are approximately same for all the samples and
does not show any shifting with doping. This result may be come
due to effective small percentage of dopants. Blue shifting in
excitonic absorption peak is attributed to the quantum size effect
[22], whereas the broadening and asymmetricity are due to the
wide size distribution of synthesized particles as also shown in
TEM results. Different size of particles give number of excitonic
peaks that appear at different energies and overlapping of these
peaks produces a broadening in absorption spectra [23]. It is well
known that band gap shifting in nanoregime is based on the
theoretical effective mass approximation model with the particle
in a box approach and defined as [24,25]
! 0 1
p2 h 1 1 1:8e2 0:25e4 @ 1 1A Fig. 4. UV–vis absorption spectra of (a) undoped ZnS, (b) Mn-doped ZnS,
DEg ¼ þ   þ ð2Þ
2m0 r 2 me mh 4pe0 er r 8p2 e20 e2r h m1 m1 (c) Cd-doped ZnS and (d) Cd, Mn co-doped ZnS quantum dots.
e h

Where r is the particle radius, e is the dielectric constant and

mne and mnh are the effective masses of the electron and hole,
respectively. First term in the above equation represents the
kinetic energy of both electron and hole, second term corresponds
to the Coulomb interaction and the last one is attributed to the
correlation between two particles. For ZnS nanocrystals, the first
order approximation gives the good relation between the particle
radius (r) and band gap (Eg) [26],
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
0:32  2:9 ðEg  3:49Þ
rðEg Þ ¼
2ð3:50  Eg Þ
Obtained value of particle size is about 4.0 nm using average
band gap of 3.9 eV (318 nm) for all the spectra and it matches well
with the values obtained from TEM.
Fig. 5(a) shows the room temperature normalized Photo-
luminescence (PL) spectra of ZnS:Cd2 + , ZnS:Mn2 + and ZnS:Cd2 + ,
Mn2 + samples whereas multi peak Gaussian fitting of co-doped
sample is depicted in Fig. 5(b) that suggests the presence of six
emission bands with peak positions at 433, 454, 486, 520, 580 and
644 nm. For the sake of convenience, we are using sample A,
sample B and sample C nomenclature for the Cd2 + -doped ZnS,
Mn2 + -doped ZnS and co-doped ZnS nanocrystals, respectively.
The smallest wavelength peak  433 nm, present in all the three
ð3Þ samples corresponds to the ‘‘self activated’’ blue emission (near
band edge emission) which is due to the radiative transition from
the sulfur vacancies (i.e. Vs -Valance Band) [27]. The presence of
sulfur deficiency is also confirmed by EDAX study of co-doped
sample. Well-defined Cd ion related green emission is attributed
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M. Mall, L. Kumar / Journal of Luminescence 130 (2010) 660–665 663

Fig. 5. (a) Room temperature PL spectra of (A) ZnS:Cd2 + 2%, (B) ZnS:Mn2 + 1% and (C) ZnS:Cd2 + 2%, Mn2 + 1% nanoparticles. (b) Gaussian fitted PL spectra of ZnS co-doped
with Cd 2% and Mn 1% to determine the exact peak position.

either from direct band-to-band recombination in CdS particles
[28,29] or due to recombination of Cd2 + ions as an impurity
centre [30]. From XRD measurements, it is clear that Cd ions are
doped into lattice sites and do not exist as separate species
(i.e. CdS) in both Cd-doped and co-doped samples. So, the intense
peak at 520 nm in sample A and C corresponds to the transition
from Cd ions related defect states (E - De) present in between the
band gap. Luminescence characteristics of ZnS:Mn2 + has been
extensively studied by several groups [15,31–33]. Bhargava et al.
[34] reported that in Mn2 + -doped ZnS nanoparticles, very strong
hybridization occurs between the sp levels of Zn and d levels of
Mn2 + ions and it results the crystal field splitting of Mn2 + levels in
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Fig. 6. Schematic energy level diagram showing possible emissions between different levels of co-doped ZnS nanoparticles.
between the bands of host material. Subsequent transfer of
excited electrons from conduction band (CB) to Mn2 + levels and
further transition between 4T1 to 6A1 leads the orange emission.
Hence the peaks at around 580 nm in sample B and C are related
to Mn impurity ions in ZnS. Due to approximately same ionic radii
as of Zn2 + ion (0.78 Å), Mn2 + ions can be easily incorporated into
the Zn matrix in comparison to Cd2 + ions (0.92 Å) and so results in
the high-intensity luminescence peak. Emission band centered at
486 nm present in sample A and C is may be associated with the
luminescence arising from the transition Vs - De whereas Vs -
6
A1 gives the 454 emission band obtained only in sample C. In
addition to all these, a new red emission peak (644 nm) also
appears in spectra of co-doped sample that cannot be observed
in single ion (either Mn or Cd) doped materials. Similar red
emission with slight blue shifting (637 nm) is reported for ZnS 1D
nanostructure co-doped with the same two dopant ions [18].
Schematic diagram present in Fig. 6 indicates the different
transitions which are responsible for above mentioned
emissions peaks. Mechanism of red luminescence in ZnS
nanoparticles co-doped with Mn and Cd ions can be described
as follows: In ZnS nanomaterials, with excitation wavelength
325 nm electrons are excited from valence band (VB) to
conduction band. These photo-excited electrons are successively
relax to the surface states or levels induced by doping ions and
produce a broad emission after recombining radiatively with the
holes. In co-doped sample, simultaneous doping of Mn and Cd
exhibits the combination of luminescence centers (i.e. 4T1 and 6A1
levels of Mn ion in addition to E and De levels of Cd ion) between
the band gap. Photo-excited electrons present in conduction band
relax down to E and 4T1 levels followed by radiative transition
between E - De (emission of  520 nm wavelength), 4T1 - 6A1
(emission of 580 nm wavelength) and 4T1 - De (emission
of  644 nm wavelength) levels. This red emission comes only
due to transition that occurs between Mn (4T1) and Cd (De) levels.
In absence of Cd2 + ions, energy will be directly transferred
between splitted levels of Mn2 + ion by emitting characteristic
luminescence of ZnS:Mn.
4. Conclusion
Cd2 + and Mn2 + co-doped ZnS nanoparticles are successfully
synthesized by chemical co-precipitation method. XRD, TEM
analysis and absorption spectra confirm the formation of
nanoparticles with size ranging from 4 to 8 nm. Mn2 + -doped
ZnS nanoparticles contains orange emission while a green
emission band is found in case of ZnS:Cd2 + nanoparticles. In
contrast to single-ion doped crystals, co-doped material exhibits
red shift in photoluminescence spectrum. Transition between
composite energy level of the two metal ions composite centre,
gives the luminescence from a different origin.
Acknowledgements
We thank Department of Science and Technology, India for
funding the Nanophosphor Application Centre project under
IRHPA in collaboration with Nanocrystal Technology, New York.
One of the authors (M.M.) gratefully acknowledges to Dr. A. C.
Pandey (P.I. Nanophosphor Application Centre, University of
Allahabad) for providing facilities for synthesis and XRD, UV–vis
and PL measurements of samples. We would also like to thank
Dr. Dinesh Srivastava, BARC, Mumbai, for TEM and Mr. Vipin
Chawla at IIT Roorke for EDAX characterizations.
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