ARTICLE IN PRESS

Journal of Luminescence 130 (2010) 660–665

Contents lists available at ScienceDirect

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-

red windows [11,12]. Doped materials show different type of
In recent years, semiconducting nanoclusters have drawn luminescent properties which are strongly depended on the type
significant attention due to their unique optical, electrical and of dopant ions. These dopant impurities play an important role in
chemical properties originating from their small size [1]. When changing the electronic structure and transition probabilities of
size of these particles is comparable to their corresponding the host material. There are several reports on the photolumines-
Bohr exciton radius, they exhibit quantum confinement effect cence properties of ZnS nanostructures doped by various types of
with significant blue shift in absorption spectra [2,3] and high impurities like Cu2 + , Mn2 + , Co2 + , Ni2 + , rare earth and transition
surface-to-volume ratio. Because of this, their surface consist elements etc. [13–17]. In doped ZnS nanocrystals, impurity ion
large number of atoms and lead to high surface reactivity. A occupies the Zn lattice site and behaves as a trap site for electron
way to remove all these states is a process known as a and holes. The electrons are excited from the ZnS valence band to
‘passivation’ or ‘capping’, which consists of bonding of surface conduction band by absorbing the energy equal or greater than
atoms to different materials (called passivating or capping their band gap energy. Subsequent relaxation of these photo-
agents) to prevent particle–particle interaction. Sol–gel synth- excited electrons to some surface states or levels is followed by
esis, embedding the particles in a polymer matrix, electro- radiative decay enabling the luminescence in visible region.
deposition, sonochemical synthesis, are certain synthesis However, two different kinds of ions present simultaneously in
routes which are used to obtain nanoparticles with a narrow a host material produce fluorescence which is completely
size distribution [4–9]. In addition to this, the nanoparticles are different from the emission due to single ion and this property
also having high thermal stability, increased quantum effi- is very beneficial for white light generation [18–20].
ciency for luminescence and radiative lifetime shortening with In the present paper, we firstly report the synthesis of double
decreasing particle size [1]. ion (Mn2 + and Cd2 + ) doped ZnS luminescent quantum dots at
Among the II–VI compound semiconductor nanomaterials, ZnS ambient temperature by chemical co-precipitation method.
is an important material having direct and wide band gap Nanoparticles were stabilized with Methaacrylic Acid (MAA)
(3.67 eV). It is widely used in flat panel displays [10], optical 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
n photoluminescence property due to presence of two different
Corresponding author at: Physics Department, University of Allahabad,
Allahabad- 211002, India. Tel: + 91 532 2460993. ion species in the same lattice. Here, PL studies exhibited red
E-mail address: lkumarau@gmail.com (L. Kumar). 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 Fig. 2. Transmission Electron Microscopy (TEM) image of Cd–Mn co-doped ZnS
sample which shows the uniform distribution of particles.
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. 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
3. Results and discussion (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
Crystallinity, size and phase of particles were characterized by constant gives the strong evidence for the incorporation of dopant
XRD as shown in Fig. 1. Peak positions indicate the formation ion into the host matrix which is also confirmed by PL spectra.
of zinc blend crystal structure with three most preferred Size and morphology of co-doped ZnS nanoparticles analyzed
orientations [1 1 1], [2 2 0] and [3 1 1]. No observable impurity by TEM is represented in Fig. 2. Image reveals that the nano-
phases in the spectra, indicating the formation of pure cubic phase crystals are spherical in shape with the size of 4–8 nm, which is
of ZnS only while broadening of the diffraction peaks show the slightly larger than the size estimated by the Scherrer formula
formation of nanosized particles. The average nanocrystallite size calculations based on XRD pattern. Discrepancy between TEM and
are calculated from full width at half maximum (b) of XRD peaks XRD results divulge that prepared particles are polycrystalline in
using Debye–Scherrer’s formula [21] nature.
In order to confirm the presence of Mn2 + and Cd2 + ions in the
0:9l
D¼ ð1Þ material, we perform the EDAX study of co-doped sample.
b cosy According to EDAX spectra as shown in Fig. 3, it is clear that the
Where l is the wavelength of incident X-ray (1.54 Å) and y is the final product contains strong atomic percentage of Zn (27.86%)
Bragg’s angle. From the calculations, the average diameter of the and S (17.90%) as compared to Mn2 + and Cd2 + ions due to
particles is 2.0 nm. Fitted value (using software JADE 6.0) of 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

Fig. 5(a) shows the room temperature normalized Photo-
mne and mnh are the effective masses of the electron and hole,
luminescence (PL) spectra of ZnS:Cd2 + , ZnS:Mn2 + and ZnS:Cd2 + ,
respectively. First term in the above equation represents the
Mn2 + samples whereas multi peak Gaussian fitting of co-doped
kinetic energy of both electron and hole, second term corresponds
sample is depicted in Fig. 5(b) that suggests the presence of six
to the Coulomb interaction and the last one is attributed to the
emission bands with peak positions at 433, 454, 486, 520, 580 and
correlation between two particles. For ZnS nanocrystals, the first
644 nm. For the sake of convenience, we are using sample A,
order approximation gives the good relation between the particle
sample B and sample C nomenclature for the Cd2 + -doped ZnS,
radius (r) and band gap (Eg) [26],
Mn2 + -doped ZnS and co-doped ZnS nanocrystals, respectively.
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi The smallest wavelength peak  433 nm, present in all the three
0:32  2:9 ðEg  3:49Þ
rðEg Þ ¼ ð3Þ samples corresponds to the ‘‘self activated’’ blue emission (near
2ð3:50  Eg Þ
band edge emission) which is due to the radiative transition from
Obtained value of particle size is about 4.0 nm using average the sulfur vacancies (i.e. Vs -Valance Band) [27]. The presence of
band gap of 3.9 eV (318 nm) for all the spectra and it matches well sulfur deficiency is also confirmed by EDAX study of co-doped
with the values obtained from TEM. 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 from Cd ions related defect states (E - De) present in between the
[28,29] or due to recombination of Cd2 + ions as an impurity band gap. Luminescence characteristics of ZnS:Mn2 + has been
centre [30]. From XRD measurements, it is clear that Cd ions are extensively studied by several groups [15,31–33]. Bhargava et al.
doped into lattice sites and do not exist as separate species [34] reported that in Mn2 + -doped ZnS nanoparticles, very strong
(i.e. CdS) in both Cd-doped and co-doped samples. So, the intense hybridization occurs between the sp levels of Zn and d levels of
peak at 520 nm in sample A and C corresponds to the transition Mn2 + ions and it results the crystal field splitting of Mn2 + levels in
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664 M. Mall, L. Kumar / Journal of Luminescence 130 (2010) 660–665

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 nanoparticles with size ranging from 4 to 8 nm. Mn2 + -doped
excited electrons from conduction band (CB) to Mn2 + levels and ZnS nanoparticles contains orange emission while a green
further transition between 4T1 to 6A1 leads the orange emission. emission band is found in case of ZnS:Cd2 + nanoparticles. In
Hence the peaks at around 580 nm in sample B and C are related contrast to single-ion doped crystals, co-doped material exhibits
to Mn impurity ions in ZnS. Due to approximately same ionic radii red shift in photoluminescence spectrum. Transition between
as of Zn2 + ion (0.78 Å), Mn2 + ions can be easily incorporated into composite energy level of the two metal ions composite centre,
the Zn matrix in comparison to Cd2 + ions (0.92 Å) and so results in gives the luminescence from a different origin.
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 - Acknowledgements
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 We thank Department of Science and Technology, India for
appears in spectra of co-doped sample that cannot be observed funding the Nanophosphor Application Centre project under
in single ion (either Mn or Cd) doped materials. Similar red IRHPA in collaboration with Nanocrystal Technology, New York.
emission with slight blue shifting (637 nm) is reported for ZnS 1D One of the authors (M.M.) gratefully acknowledges to Dr. A. C.
nanostructure co-doped with the same two dopant ions [18]. Pandey (P.I. Nanophosphor Application Centre, University of
Schematic diagram present in Fig. 6 indicates the different Allahabad) for providing facilities for synthesis and XRD, UV–vis
transitions which are responsible for above mentioned and PL measurements of samples. We would also like to thank
emissions peaks. Mechanism of red luminescence in ZnS Dr. Dinesh Srivastava, BARC, Mumbai, for TEM and Mr. Vipin
nanoparticles co-doped with Mn and Cd ions can be described Chawla at IIT Roorke for EDAX characterizations.
as follows: In ZnS nanomaterials, with excitation wavelength
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