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Original Article

Effect of poly ethylene glycol (PEG) as surfactant on

cerium doped ZnS nanoparticles

Shanmugam Cholan, Nadana Shanmugam ∗ , Natesan Kannadasan,

Kannadasan Sathishkumar, Kanthasamy Deivam
Department of Physics, Annamalai University, Annamalai Nagar, Chidambaram, India

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

Article history: Cerium-doped nanoparticles capped with different levels of poly ethylene glycol (PEG) have
Received 25 February 2014 been synthesized in aqueous solution by a simple chemical precipitation method. The syn-
Accepted 16 April 2014 thesized particles were characterized by X-ray diffraction (XRD), UV–vis absorption and room
Available online xxx temperature photoluminescence (PL) spectroscopy. The morphology of the products was
studied by field emission scanning electron microscope (FESEM) and confirmed by high reso-
Keywords: lution transmission electron microscopy (HRTEM). The functional groups of the synthesized
Cerium particles were identified by Fourier transform infrared spectroscopy (FT-IR). Photolumine-
Morphology scence studies for the entire investigated samples displayed two emission bands one at UV
Poly ethylene glycol region and the other at visible region. In addition, XRD and high resolution transmission
Cubic phase electron microscope studies showed the formation of cubic ZnS:Ce3+ nanoparticles with an
Energy gap average crystal size of 2.8 nm on 2.5% of PEG capping.
Nanostructure © 2014 Brazilian Metallurgical, Materials and Mining Association. Published by Elsevier
Editora Ltda. All rights reserved.

luminescent materials may open up its usage in optoelectro-

1. Introduction nics such as LEDS and lasers owing to their interesting mag-
netic and electro-optical properties [8–11]. Among different
Researchers have been taking enormous interest to synthe-
doping agents Ce3+ ions have unique optical characteristics
size nanometer-sized semiconductor materials because of
and can be used as an ideal material for visible light-emitting
their size-dependent optical and electric properties. ZnS is
phosphors in display, high-power laser, and light-emitting
a wide band gap II–VI semiconductor with remarkable opti-
diodes [12–15]. Several techniques have been employed so far
cal properties [1–6]. It has found its role as photo catalysis
to prepare doped nanocrystals such as hydrothermal method,
as a result of the rapid generation of electron–hole pairs by
sol-gel method, solid state reaction, auto-combustion, and
photo excitation and the highly negative reduction poten-
chemical precipitation method. In our previous work, ZnS
tials of excited electrons [7]. ZnS doped with optically active

∗
Corresponding author.
E-mail addresses: quantumgosh@rediffmail.com, shankarguru52@gmail.com (N. Shanmugam).
http://dx.doi.org/10.1016/j.jmrt.2014.04.001
2238-7854/© 2014 Brazilian Metallurgical, Materials and Mining Association. Published by Elsevier Editora Ltda. All rights reserved.

Please cite this article in press as: Cholan S, et al. Effect of poly ethylene glycol (PEG) as surfactant on cerium doped ZnS nanoparticles. J Mater
Res Technol. 2014. http://dx.doi.org/10.1016/j.jmrt.2014.04.001
JMRTEC-86; No. of Pages 6
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nanoparticles with different doping concentrations of Ce3+
were synthesized through simple chemical precipitation
method [16]. As per the available literature, there are only few
reports on the polymer assisted synthesis of cerium doped ZnS
nanocrystals. In the present work, we have attempted to syn-
thesize polymer PEG assisted Ce3+ doped ZnS nanoparticles.
2. Materials and methods
2.1. Chemicals
Zinc acetate dihydrate [Zn(CH3 COO)2 ·2H2 O], thiourea
[NH2 CSNH2 ], cerium (III) chloride hepta hydrate [(CeCl3 )·7H2 O]
and polyethylene glycol [HO(C2 H4 O)n H] (PEG, MW : 6000) were
purchased from Merck. All chemicals were used as received
since they were of analytical regent grade with 99% purity.
The glasswares used in this experimental work were acid
washed. Ultrapure water was used for all dilution and sample
preparation.
2.2. Synthesis of Ce3+ doped ZnS nanostructures
For the synthesis of Ce3+ doped ZnS, 3 g (0.35 M) of zinc acetate
in 40 mL of deionized water–ethanol matrix (equal volume)
and 1.5 g (0.39 M) of cerium (III) chloride hepta hydrate in 10 mL
of water were mixed drop by drop. The entire mixture was
stirred magnetically at 80 ◦ C until a homogeneous solution
was obtained. Then, 3 g (1 M) of thiourea in 40 mL of deionized
water–ethanol matrix was added drop by drop to the above
mixture. The entire was stirred magnetically until a white pre-
cipitate was formed. The obtained dispersions were purified
by dialysis against de-ionized water and ethanol several times
to remove impurities. Finally, the product was dried in a hot
air oven at 120 ◦ C for 2 h.
2.3. Synthesis of PEG capped ZnS:Ce3+
In the synthesis process, 0.35 M of zinc acetate and 0.39 M of
cerium (III) chloride hepta hydrate were mixed up drop by
drop. Then different volume percentages (1.25%, 2.5%, 3.75%
and 5%) of PEG were added to the above solution. The mix-
ture was stirred magnetically at 80 ◦ C until a homogeneous
solution was obtained. Then 1 M of thiourea was added drop
by drop to the above mixture and stirred magnetically until a
white precipitate was formed. The precipitate was washed as
discussed above and dried in a hot air oven.
2.4. Characterization of uncapped and PEG capped
ZnS:Ce3+ nanostructures
The X-ray diffraction (XRD) patterns of the powdered sam-
ples were recorded using X’PERT PRO diffractometer with
Cu-K␣ radiation (k = 1.5406 Å). The crystallite size was esti-
mated using the Scherrer equation. The data was collected
with a step size of 0.05◦ and a counting time of 10 s per
step in the 2 range from 10◦ to 80◦ . For recording XRD, the
samples were coated on the glass substrates. The samples
were allowed to dry and then measured in reflection geom-
etry. The optical absorption spectra of all the samples in
Please cite this article in press as: Cholan S, et al. Effect of poly ethylene glycol (PEG) as surfactant on cerium doped ZnS nanoparticles. J Mater
Res Technol. 2014. http://dx.doi.org/10.1016/j.jmrt.2014.04.001
(111) ZnS: Ce3+ (1.5g): PEG (5%)
(220)
(311)
ZnS: Ce3+ (1.5g): PEG (3.75%)
Iintensity (a.u)
ZnS: Ce3+ (1.5g): PEG (2.5%)
ZnS: Ce3+ (1.5g): PEG (1.25%)
ZnS: Ce3+ (1.5g)
10 20 30 40 50 60 70 80
2 theta (deg)
Fig. 1 – XRD patterns of uncapped and various levels of PEG
ZnS:Ce3+ nanoparticles.
deionized water were recorded in the wavelength range of
280–400 nm using LAMBDA 25 PERKIN ELMER spectrometer.
Fluorescence measurements were performed on a VARIAN
spectrophotometer. The FT-IR spectrum was recorded from a
SHIMADZU-8400 with a resolution of 4 cm−1 . Measurements
were performed with pressed pellets which were made using
KBr powder as diluent. The morphology of the product was
observed by a HITACHI S-4700 field emission scanning electron
microscope (FESEM). Energy-dispersive spectrum (EDS) mea-
surement was carried out with the EDS arrangement enclosed
with HITACHI S-4700 FESEM. High-resolution transmission
electron microscopy (HRTEM) analysis was performed using
JEOL 3010 HRTEM to study the morphology and size of the
nanostructures. Samples for HRTEM were prepared by making
a clear dispersion of the nanocrystals in water and putting a
drop of the solution on a carbon-coated copper grid. The solu-
tion was allowed to evaporate leaving behind the nanocrystals
on the carbon grid.
3. Results and discussion
3.1. XRD analysis
The phase characteristics of the products were examined by
powder X-ray diffraction. Fig. 1 shows the XRD patterns of
uncapped and different levels of PEG capped ZnS:Ce3+ . All the
diffraction peaks can be indexed to (1 1 1), (2 2 0) and (3 1 1)
planes of cubic phase of ZnS with lattice parameters compa-
rable to that of JCPDS card No: 05-0566. No diffraction peaks
other than ZnS was noted, indicating high purity of the syn-
thesized products. When compared with uncapped product,
diffraction patterns of capped products were shifted to smaller
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3.5 1 1. ZnS: Ce3+ (1.5g)

1 400
2. ZnS: Ce3+ (1.5g): PEG (1.25%)
3.0 2 3. ZnS: Ce3+ (1.5g): PEG (2.5%)
4
3 4. ZnS: Ce3+ (1.5g): PEG (3.75%)
2.5 1. ZnS: Ce3+(1.5g) 300
5. ZnS: Ce3+ (1.5g): PEG (5%)
2. ZnS: Ce3+(1.5g): PEG (1.25, 3.75 and 5%)
Intensity (a.u)

3. ZnS: Ce3+(1.5g): PEG (2.5%)

Intensity (a.u)
2.0

2 200
1.5
3
1.0 100 5

0.5

0
0.0
300 350 400 300 350 400 450 500 550 600 650 700 750 800

Wavelength (nm) Wavelength (nm)

Fig. 2 – UV–vis absorption spectra of uncapped and Fig. 3 – PL emission spectra of uncapped and different
different concentrations of PEG capped ZnS:Ce3+ . concentrations of PEG capped ZnS:Ce3+ .

Table 1 – The calculated agglomeration number for where, “n” is the agglomeration number, “Na” is Avogadro’s
various concentrations of PEG. number, “Vm” is the molar volume of ZnS in cm3 mol−1 , and r
Polymer concentration Nanoparticle Agglomeration is the nanoparticle radius. The calculated agglomeration num-
in volume percentage radius (r) number (n) bers for various concentrations of PEG are given in Table 1.
From the table, the lowest value of agglomeration number is
1.25 3.63 5022
predicted for the 2.5% of PEG addition confirming its optimum
2.50 1.8 612
3.75 4.22 7890
capping level.
5 4.32 8465
3.2. UV–vis absorption spectra

angle side. Broadening of the XRD peaks indicates the forma-

The UV–vis absorption spectra of uncapped and PEG capped
tion of nanocrystals.
ZnS:Ce3+ are shown in Fig. 2. As shown, the uncapped sam-
From the X-ray diffraction peak widths, the diameter of
ple has an absorption maximum at 298 nm with a band gap of
the nanocrystals was estimated through Scherrer formula [17].
4.15 eV. From the figure, it is also noted that the peak position
The estimated particle sizes are 22, 7.27, 3.6, 8.45 and 8.65 nm
for uncapped and nanocrystals capped with 1.25%, 2.5%, 3.75%
and 5% of PEG, respectively. When compared with uncapped
ZnS: Ce3+(1.5g): PEG(5%)
products, all the capped particles show reduced size as a result
of capping.
The mechanism behind the formation of size reduced par-
ticle is explained as follows. After introducing polymer into the
reaction mixture, Zn2+ ions form a complex with PEG, resulting ZnS: Ce3+(1.5g): PEG(3.75%)

in particle capping upon nucleation. Upon titration of thiourea

into preformed Zn–PEG complex, a competition between the
Transmittance (%)

sulfide and PEG is introduced. Further, the reaction proceeds

ZnS: Ce3+(1.5g): PEG(2.5%)
to form a link with S2− at the Zn–PEG complex. By using appro-
priate amounts of PEG and thiourea, the conditions described
here allow efficient incorporation of the sulfide into Zn–PEG
complex to form nanocrystals. During the process, the intro- ZnS: Ce3+(1.5g): PEG(1.25%)
duction of PEG not only stabilized the small particles but
also inhibited their agglomeration. The nanoparticle forma-
tion takes place due to agglomeration of the primary particles,
which in this case is the single ZnS unit. Agglomeration num- ZnS: Ce3+(1.5g)

ber specifies the number of primary particles or molecules

contained in a single nanoparticle of a given size [18]. By
considering that the nanoparticles are spherical in shape, par-
ticle agglomeration number was calculated from the following 4000 3600 3200 2800 2400 2000 1600 1200 800 400
expression [19,20]: Wavenumber (cm-1)

4Nar3 Fig. 4 – FT-IR spectra of uncapped and various levels of PEG

n=
3Vm carped ZnS:Ce3+ .

Please cite this article in press as: Cholan S, et al. Effect of poly ethylene glycol (PEG) as surfactant on cerium doped ZnS nanoparticles. J Mater
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Fig. 5 – FESEM images of (a) uncapped ZnS:Ce3+ , (b) PEG capped ZnS:Ce3+ , and (c) EDS pattern of PEG capped Zns:Ce3+
nanocrystals.

has no change with respect to the capping concentrations.
However, on 2.5% of PEG capping, the absorption edge was
blue shifted to 293 nm with a band gap of 4.22 eV as a result
of quantum confinement effect. Quantum confinement effect
occurs in the case of the nanoparticles when the particle size
becomes comparable with or smaller than the exciton Bohr
radius. It is natural that the quantum confinement effect does
occur in 2.5% of PEG capped samples because the diameter of
the 2.5% capped ZnS:Ce3+ nanoparticle is 3.6 nm (from XRD).
This value is less than the Bohr excitonic diameter of ZnS,
which is around 5.5 nm.
samples showed two distinct emission spectral bands, one in
the UV region and the other centered in the visible region, as
a result of 5d→4f transitions of cerium [17]. Jung, et al. [21]
observed similar type of UV and visible bands for ZnS:Ce3+ .
Occasionally, on transition metal ion doping ZnS may exhibit
emission bands in the UV and visible regions. Such optical
emission was obtained by Murugadoss et al., on surfactant
assisted Mn2+ doped ZnS nanocrystals [8].
3.4. Functional group analysis

To evaluate the functional groups of the synthesized products,

3.3. Photoluminescence studies
Fig. 3 shows the Photoluminescence spectra of the products
recorded at room temperature upon excitation at 290 nm. The
PL spectra of the uncapped and various levels of PEG capped
FT-IR analyses were made. The IR spectra of the uncapped
and various levels of PEG capped nanoparticles are shown in
Fig. 4. All the samples exhibit a broad absorption band in the
range of 3330–3400 cm−1 due to stretching vibration of O H. As
shown in Fig. 4, PEG capped samples show absorption bands at

Please cite this article in press as: Cholan S, et al. Effect of poly ethylene glycol (PEG) as surfactant on cerium doped ZnS nanoparticles. J Mater
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Fig. 6 – HRTEM images of (a) uncapped ZnS:Ce3+ , (b) PEG capped ZnS:Ce3+ , and (c) PEG capped ZnS:Ce3+ SEAD patterns.

2920 cm−1 due to CH asymmetric stretching vibrations. The particles with an average diameter of 5 nm, which is good
absorption band positioned at around 2860 cm−1 is resulted agreement with the calculated results from XRD patterns.
from characteristic peak of PEG. The decrease in absorption The selected area electron diffraction (SAED) pattern in Fig. 6c
intensity of characteristic peak of PEG is noted at the concen- indicates that these nanospheres are of high crystallinity. The
tration of 2.5% which proves its optimum level of capping. The three inside track diffraction rings correspond to the (1 1 1),
band centered at 1247 cm−1 originates from C O C bands of (2 2 0) and (3 1 1) reflections of cubic ZnS, respectively, which
PEG [22]. It is well known that PEG has ether oxygen in its is fully consistent with the XRD results.
chain, and can interact with metal ions at the molecular level.
The broad peak positioned at 1102 cm−1 is due to ether link-
age [22]. A spectral band appearing at around 660 cm−1 can be 4. Conclusion
ascribed to ZnS vibration.
On 2.5% of PEG capping, this ZnS vibration has been shifted In conclusion, we have synthesized different sized ZnS:Ce3+ by
to a new position 670 cm−1 with enhanced intensity of absorp- a simple chemical precipitation method using different levels
tion, indicating the formation of homogeneously distributed of PEG. The particle size determined from XRD line broadening
smaller sized ZnS:Ce3+ . show that the size depends on the concentration of capping
agent. Among the different concentrations, 2.5% of PEG cap-
ping yields smaller sized particles. Optical and morphological
3.5. Morphology studies
measurements of the products have been carried out to know
the effect of capping on the synthesized particles. Increase of
The FESEM image of uncapped ZnS:Ce3+ in Fig. 5a shows the
PL intensity ratio on 2.5% of PEG capping shows that energy
flower-like nanostructure consisted of nanorods with diame-
transfer mechanism from capping layers to photoluminesce-
ter of 26 nm and length up to 130 nm. The FESEM images in
nce centers is more pronounced. FESEM and HRTEM studies
Fig. 5(b and c) show that ZnS:Ce3+ nanocrystals obtained with
of PEG (2.5%) capped particles show a considerable effect on
2.5% of PEG consist of spherical nanoparticles with diameters
the morphology and size distribution of the obtained products.
about 50 nm, and some rod-like structure with average width
Considering the above factors, 2.5% of PEG as a capping agent
100 nm and length 1 ␮m. FESEM data demonstrated that PEG
is optimum for the preparation of cerium doped ZnS nanopar-
addition has a considerable effect on the morphology and size
ticles in order to control the size of the particle and also for
distribution of the obtained material. To know the elemental
modern optoelectronic technology and other industrial appli-
composition of the PEG assisted ZnS:Ce3+ , the EDS analysis
cations.
was carried out and the result is shown in Fig. 5d. As seen
in the EDS spectrum, well-defined peaks of Zn, S and Ce were
predicted, indicating that the synthesized products are cerium
Conflicts of interest
doped ZnS.
The morphology and structure of the products were char-
The authors declare no conflicts of interest.
acterized in further detail by HRTEM and SAED. The HRTEM
image of the uncapped product is shown in Fig. 6a. From
the figure, it is observed that ZnS nanocrystals doped with references
cerium composed of uniform nanorods with average diam-
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Res Technol. 2014. http://dx.doi.org/10.1016/j.jmrt.2014.04.001
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