Luminescence Studies of Nanoparticle / Polymer Nano-

Composites
1
Pooja Chouksey, 2M. Tiwari, 3B. P. Chandra
1
GD- Rungta College of Engineering &Technology, Bhilai (C.G.), India
2
RSR- Rungta College of Engineering &Technology, Bhilai (C.G.), India
3
Disha Institute of Management and Technology, Raipur (C.G.) India

Abstract- CdS/PVK nanocomposites have been successfully prepared using chemical method. First PVK was dissolved in
DMF and appropriate amount of cadimium acetate was added to it; then H 2S is passed to obtain CdS-PVK composites.
The films were prepared by spreading CdS-PVK solution on clean glass plate. The dried films were taken out of the glass
plate and their characterized by (XRD and AFM) were studied. AFM image have shown a typical morphology of
CdS/PVK composite films and the particle size are obtained 43.3, 53.3, 64.3 and 94 nm for 1, 2, 10 and 20% respectively.
This XRD studies that peaks at 2 values of 26.54 0, 43.940, and 520 matching the (111), (220) and (311) crystalline planes
of cubic, indicated the formation of CdS. The Electroluminescence (EL) and Photoluminescence (PL) of CdS nanocrystal-
PVK composites has been studied for varies CdS loading 0, 10, 20, 30 and 40%. The PL spectra that the PL peak occurs
at about 465, 470, 488 and 498 nm for 10, 20, 30 and 40% CdS/PVK nanocomposite samples, respectively and other peak
is obtained in 440 nm that is denoted by in PVK peak. The band gap energy of the CdS nanoparticles in CdS/PVK was
estimated to be 2.66 eV, 2.63 eV, 2.54 eV and 2.48 eV for 10, 20, 30 and 40% CdS/PVK nanocomposite samples,
respectively. For EL studies, cells were prepared by CdS-PVK composite films on a portion of SnO2 coated conducting
glass plate and taking aluminium foil as second electrode. It is observed from the characteristics that the current varies
linearly with the voltage, whereas the EL intensity varies non-linearly with increasing voltage. At a particular frequency,
the EL emission starts at a threshold voltage and then increases rapidly with increasing voltage. The threshold voltage
increases with the frequency of the applied electric field.

Keywords- Characterizations, Photoluminescence and Electroluminescence

I. INTRODUCTION II. EXPERIMENTAL

In recent years nanocrystalline thin films of
different II-VI compound semiconductors have been
widely synthesized and studied. Nanocrystalline thin
films are also polycrystalline in nature but with sizes of
crystallites of the color of a few nanometers. Many
properties of nanocrystalline materials are found to
deviate from these of coarse grained polycrystalline
materials with the same average chemical composition.
These deviations result from dimensionality of
nanometer sized grains and numerous interfaces
between adjacent crystallites [1]. Khanna et al [2] have
reported that the careful preparation of CdS
nanoparticles in DMF with metal rich surface can be
considered responsible for stable light emission. CdS
particles could be synthesized in the polymers so that
the film can be cast directly, thus avoiding the loading
of the particles via multistage. This desire has prompted
us to extend the synthetic methodology to
functionalized and non-functionalized polymers.
Polymers are considered a good choice as matrix
materials for such purpose due to their long time
stability and because they possess flexible
reprocessability [3]. Firth et al. have been reported the
production and luminescent properties of CdSe and CdS
nanoparticle-polymer composites [4]. He et al. studies
that the photoluminescence spectra of pure PVK and the
as-prepared CdS/PVK nanocomposites [5]. The
electroluminescent properties from hybrid structures
consisting of conjugated polymer layer (PVK, PPV) as
evident from reports from the fields of molecular cell
biology, medical diagnostics and targeted therapeutics
[6]. The present paper report the Luminescence Studies
of Nanoparticle/Polymer Nano-compoiste.
Published in International Journal of Advanced Engineering & Application, Jan 2011 Issue
For preparing CdS/PVK composite, 0.4g PVK was
dissolved in 5ml DMF by heating upto 600 c. After the
addition to appropriate quantity of cadmium acetate to
this solution, so that CdS loading in polymer could be
10, 20, 30 and 40%, the resulting solution was stirred for
about 30 min, and then concentrated. The solution was
taken in flask and degassed for 15 minutes by supplying
nitrogen gas. To this clear solution of cadmium acetate
and PVK, H2S gas was passed for a few seconds the
solution was turned yellow instantly and stirring at room
temperature; the H2S gas was flushed out with nitrogen
the reaction is below
PVK + Cd(CH3COO)2 + H2S PVK/CdS +
2CH3COOH
The dense liquid was then transferred on the glass
slides and conducting glass plates and was dried in oven
for several hours to obtain PL, EL and characterization
clear films of CdS/PVK nanocomposite thin film.
AFM observations were carried out by using
DIAFM-4 at IUC Indore. X-ray diffraction patterns
have been obtained by Rigaku Rotating Anode (H-3R)
diffractometer with irradiation from K line of copper (
= 1.5418 ). The photoluminescence spectra of
CdS/PVK nanocomposite were obtained using Cary
Eclipse Fluorescence Spectrophotometer from DUE
University Delhi.
For preparing the EL cell a mica sheet having a
small window was placed on CdS/PVK nanocomposite
film on the conducting glass plate. Aluminum foil along
with conducting gel was pressed over the
nanocomposite film through the window on mica sheet
in a proper way. This foil acted as second electrode and
thus the EL cell was fabricated. For the
electroluminescence studies, the EL cell was connected
106
to an ac EL power supply. The cell was placed at the
slit of PMT (photomultiplier tube), which was
connected to a high voltage power supply and to a pico-
ammeter. Thus, the pico-ammeter recorded the output
of the PMT. The variation in EL brightness with
increasing applied voltage across the thin film of
CdS/PVK nanocomposite was studied. The EL intensity
of the nanocomposite film was measured at different
input frequencies. The dependence of light intensity on
the current-voltage characteristics of EL cell was
measured
The photoluminescence was excited by 400 nm
light. It can be shows from Fig. 2 the PL spectra, the PL
peak occurs at about 465, 470, 488 and 498 nm for 10,
20, 30 and 40% CdS/PVK nanocomposite samples,
respectively and other peak is obtained in 440 nm that is
denoted by in PVK peak. The band gap energy of the
CdS nanoparticles in CdS/PVK was estimated to be 2.66
eV, 2.63 eV, 2.54 eV and 2.48 eV for 10, 20, 30 and
40% CdS/PVK nanocomposite samples, respectively.

III. RESULTS
Fig.1 shows that the XRD peaks at 2 values of
26.540, 43.940 and 520, matching the (111), (220) and
(311) crystalline planes of cubic, indicated the
formation of CdS. This showed that CdS particles
formed in pyridine and polymer media under the
microwave irradiation still retained good crystallinity.
The broad nature of the XRD peaks could be attributed
to the nano-crystaline nature of the CdS particle.

Fig.3: PL spectra for CdS/PVK nanocomposite at various

concentrations of CdS in PVK.

TABLE -I

S. Sample Concentr Area Surface Rough Size

No ation m ness in nm

in (%) Rms (Rq) in nm

1 CdS/PVK- I 2% 11 4.471 55.3

2 CdS/PVK-II 10% 11 4.325 64.3

3 CdS/PVK-III 20% 11 4.087 94

The wavelength and photon energy at the PL peaks

Fig.1: XRD graph for different concentrations of CdS/PVK for various samples are given in Table II. It can be seen
nanocomposite that the average particle size of CdS increasing in
increases the CdS in PVK, a blue shift observed in the
The AFM images have shown in Fig. 2 a typical emission profile.
morphology of CdS/PVK nanocomposite films. The
results indicate that increasing the concentration of CdS TABLE-II
in PVK, the roughness is decreases and particle size Sample % of PL emission Peak
increases as shown in table I. CdS in
PVK Wavelength Energy

CdS/PVK-I 10 465 nm 2.66 eV

CdS/PVK-II 20 470 nm 2.63 eV
CdS/PVK-III 30 488 nm 2.54 eV
CdS/PVK-IV 40 498 nm 2.48 eV

For luminescence studies, the EL cell is connected

Fig.2: AFM images of different concentration
to ac EL power supply. The EL cell is placed at the slit
of PMT (Photomultiplier tube), which is connected to
high voltage power supply and to Picoammeter, which
can record the output of the PMT. The set up for EL
studies is shown in Fig 4.

Published in International Journal of Advanced Engineering & Application, Jan 2011 Issue 107
 Fig. 6 plot of Log (B) versus 1/V of CdS/PVK composite

Fig. 4: Set up for EL Measurement

It is observed from the characteristics that the

current varies linearly where as EL intensity varies non-
linearly with increasing voltage. At a particular
frequency emission starts at a threshold voltage. EL
emission starts at a lower threshold voltage for higher
concentration of CdS in PVK and increases rapidly with
increasing voltage shows in Fig.5. Fig. 6 shows the
graph between logarithm of EL brightness and 1/V for
different frequencies for a particular concentration of
CdS. It is clear that the plot is a straight line with
negative slopes. The brightness-concentration
characteristics as shown in Fig.7 shows that at a
particular frequency and voltage EL intensity of the
composite increases with concentration of CdS Fig.7 Concentration-brightness characteristics
nanoparticles in PVK polymer and attains saturation at
more than 30% CdS concentrations. The results on the IV. DISCUSSION
EL of CdS-PVK composites are discussed and The most direct way of extracting the band gap is
explained on the basis of electron acceleration collision to simply determine the photon energy at which there is
mechanism. a sudden increase in absorption. The optical band gap of
the nanocomposite samples were calculated from the
Characterstics of CdS/PVK (20%) nanocomposite absorption edge using the following formula
hc
180 0.09 Eg = .. (1)
160 0.08
BRIGHTNESS (in a.u.)

CURRENT (in m.a.)

140 0.07 where h is the Plancks Constant, c is the velocity of

120 0.06 light and is the wavelength at which sudden increase
100 0.05 in absorption occurs.
80 0.04 He et al. (2003) have reported that the
60 0.03 photoluminescence spectra of pure PVK and the as-
40 0.02 prepared CdS/PVK nanocomposites. For pure PVK,
20 0.01 which was obtained by free- radical polymerization
0 0 based on AIBN initiator, the photoluminescence peak
0 50 100 150 200 250 300 was narrow with only one emission maximum at 377
nm (exc = 350 nm) attributed to the excimer emission
VOLTAGE (in Volt)
of PVK. The photoluminescence from the CdS/PVK
Fig.5 Voltage-brightness and voltage-current characteristics
nanocomposites displayed two emission peaks at 374
and 530 nm, corresponding to the emission from pure
PVK and pure CdS. Bulk CdS was reported to have a

Published in International Journal of Advanced Engineering & Application, Jan 2011 Issue 108
broad emission band with the emission maximum in the
500700-nm region due to recombination from surface
defects (predominantly sulfur vacancies) [7-8].
It has been found that the EL brightness increases
with the increase in applied voltage. Thornton [9] has
shown that the current-voltage characteristics of
electroluminescent materials follow the normal relation
for forward biased diode rectifier, which establishes the
existence of the rectifying barrier. The width of
Schottky barrier (d) varies with the square root of
applied voltage (V) across the CdS/PVK films and
follows the relation
d = ( V/2 N0)1/2 (2)
where is the dielectric constant of the embedding
medium and N0 is the charge carrier density.
Although a number of empirical and theoretical
relations have been proposed [10], the relation for the
voltage dependence of the EL brightness or emission
intensity from the CdS/PVK EL cell may be given by
B = B0 exp (-b/V) (3)
where B0 and b are constants, which depend on
temperature and frequency of the applied voltage and
also on the size of the EL cell [11].
V. CONCLUSIONS
In the thin films of CdS nanoparticle-polyvinyl
carbazole (PVK) composite prepared by chemical
method, the EL starts after a particular voltage and then
it tends to increase rapidly with increasing voltage. For
a fixed voltage, the EL brightness initially increases
Published in International Journal of Advanced Engineering & Application, Jan 2011 Issue
linearly with the frequency of the applied voltage and
then nonlinearly occurs at higher frequencies. The EL
brightness of CdS nanoparticle composite initially
increases with the concentration of CdS and then tends
to attain a saturation value for higher concentration of
CdS. The high voltage EL in nanoparticle CdS films is
caused by the acceleration-collision mechanism. The
studies have indicated that in the CdS/PVK composites,
CdS crystals are of nanometer size. The size of the
nanoparticle is found to increase by increasing the
concentration of CdS in the composites.
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