Thin Solid Films 417 (2002) 51–56

Preparation and characterization of CdS and Cu2S nanoparticley

polyaniline composite films
R.L.N. Chandrakanthi*, M.A. Careem
Department of Physics, University of Peradeniya, Peradeniya, Sri Lanka

Abstract

Composites consisting of conducting polymers and nanosized semiconductor particles are scientifically and technologically
attractive because of their unique electronic and optical properties. These properties were found to depend on the size of the
embedded particles. In this study such nanocomposites with polyaniline (PANI) conducting polymers are reported. The results
have shown that CdS and Cu2S nanocrystals can be successfully incorporated into a polyaniline matrix and their particle sizes
can be controlled by adjusting the concentration of the additives. Photovoltaic devices with CdSyPANI systems of various CdS
concentrations were fabricated and their performance were investigated. The short circuit current (ISC ) and open circuit voltage
(VOC) of these devices were found to increase with the concentration of CdS in the polymer matrix. The use of nanocrystals
allows great flexibility in controlling the performance of the devices by changing the size, concentration and the material of the
nanocrystals.
䊚 2002 Elsevier Science B.V. All rights reserved.

Keywords: Polyaniline; Cadmium sulfide; Copper sulfide; Nanocomposites

1. Introduction conductor. The new route is based on metal trifluoro-

Polyaniline (PANI) is a highly promising material for
electronic applications due to its combination of electri-
cal conductivity and environmental stability w1–3x. It is
expected that the incorporation of inorganic semicon-
ducting nanoparticles in PANI matrices results in mate-
rials with modified properties which are again of interest
for their electronic properties w4–6x. In addition the
large internal interface area in nanocomposites enables
an efficient separation of photo-induced charges which
is important for photovoltaic applications w7,8x.
However, PANI itself is difficult to process, since it
decomposes prior to melting and is insoluble in common
solvents except strong acids and N-methylpyrrolidone
(NMP). This severely restricts the fabrication of nano-
composites in the usual way, i.e. via polymer solution
or melt. Therefore, we have developed a new preparation
method for nanocomposites of PANI and CdS as an
n-type and, for comparison, Cu2S as a p-type semi-
*Corresponding author. Fax: q94-8388018.
E-mail address:
nayana@physics.pdn.ac.lk (R.L.N. Chandrakanthi).
methansulfonates as NMP-soluble precursors for the in
situ preparation of metal sulfides.
2. Experimental details
Emeraldine base form (EB) of polyaniline (dried
under a dynamic vacuum of 10y3 mbar for 24 h
prior to use), was dissolved in (NMP) to achieve a final
concentration of 0.004 gyml. Synthesis of
Cd(CF3SO3)2 crystals was done by using
wCd(OH)2.xH2Ox and trifluoromethanesulfonic acid.
Solution of Cd(CF3SO3)2 (0.05 gyml) was made by
dissolving in NMP. The above two solutions were mixed
together and a solution containing NMP and Li2S (0.003
gyml) was added under vigorous stirring. Various weight
ratios of CdS to PANI (rCdy 0.2–5) were prepared by
changing the amount of Cd(CF3SO3)2 and Li2S.
The analogous procedure was used to prepare Cu2Sy
PANI complex. Here wCu(CH3CN)4 xCF3 SO3 (0.1 gyml)
solution was used instead of Cd(CF3SO3) solution.
Metal contents were determined by atomic absorption

0040-6090/02/$ - see front matter 䊚 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 4 0 - 6 0 9 0 Ž 0 2 . 0 0 6 0 0 - 4
52 R.L.N. Chandrakanthi, M.A. Careem / Thin Solid Films 417 (2002) 51–56
Fig. 1. FTIR spectra of various concentrations of CdS on CdSyPANI powders.
spectroscopy performed by the analytical service of the
¨
Laboratory of Inorganic Chemistry of ETH Zurich (for
Cd and Cu analysis in nanocomposites, powders were
dissolved in 0.1 M HNO3 to yield ;5 ppm Cdy or Cu
in the solution). Powder X-ray diffraction patterns for
the above samples were obtained with monochromatized
Cu (Ka) radiation (ls1.542) with a Seimens diffrac-
tometer. Polymer nanocomposites-KBr pellets were used
to obtain FTIR absorption spectra which were recorded
on a Bruker IFS 66v. A Perkin–Elmer Lambda 900
spectrometer was used to collect the absorption spectra
in the wavelength range of 280–900 nm with a scan
speed of typically 375 nm miny1.
3. Results and discussion
3.1. CdSyPANI nanocomposites
FTIR spectra of PANI-EB and CdS-treated PANI are
shown in Fig. 1. It should be noted that PANI samples
prepared from NMP solutions always contain consider-
able amounts of NMP, which cannot be simply removed,
e.g. by heating or drying in vacuum w9x. As a conse-
quence, all nanocomposites prepared here contain NMP,
which is also evident from infrared (IR) spectra.
The signal at 1164 cmy1 has been assigned to a mode
of N_Q_N stretching and 1140 cmy1 is a
vibrational mode w10x. This band is formed in doping
reactions. Also, this band is very intense and broad.
This may be attributed to the existence of the positive
charge and distribution of the dihedral angle between
benzenoid and quinoid rings. Furthermore, the aromatic
ring deformation band in the region of 1000–500
cmy1 is enhanced with increasing CdS concentration.
Therefore, FTIR spectra show a good evidence for the
incorporation of CdS in PANI matrix.
The UV-VIS absorption spectrum of the emeraldine
base form of PANI in NMP revealed absorption maxima
at 637 nm and 340 nm, originating from the charge-
transfer-excitation-like transition from the highest occu-
pied energy level to the lowest unoccupied energy level
and the p–p* transition, respectively w11x. Solutions
containing in situ-prepared CdS and PANI in NMP,
obtained with various CdS-PANI weight ratios (rCd)
between 0.18 and 4.7, also show the two distinctive
absorption bands mentioned above for PANI. With
 R.L.N. Chandrakanthi, M.A. Careem / Thin Solid Films 417 (2002) 51–56
Fig. 2. Absorption spectra of various concentrations of CdS in CdSyPANI. (—) freshly prepared samples and (---) measured after 7 days.
increasing CdS content (with respect to PANI), however,
the peak at 340 nm became less pronounced since the
absorption of colloidal CdS overlaps with that of PANI.
At 637 nm, the contribution of CdS to the absorption is
expected to be negligible even at the highest CdS-PANI
ratios applied here. Indeed, in freshly prepared solutions,
the peak at 637 nm was not affected significantly by
the presence of CdS. We should, however, note that a
hypsochromic shift was observed for solutions kept for
several days in ambient light or in the dark but not for
PANI solutions themselves. For example, the absorption
maximum of a sample with rCds2.0 shifted after 7 days
exposure to ambient light by approximately 30 nm to
lower wavelengths. The shifts were similar for the
samples kept in light and in the dark, and they were
more pronounced the higher the CdS-PANI ratio. The
spectral changes could indicate a partial oxidation of
the emeraldine base to the pernigraniline form of PANI
or a degradation process (Fig. 2).
X-Ray diffraction (XRD) patterns of CdS-PANI nan-
ocomposites show broad peaks at 2u values of 278 and
ca. 478 with a shoulder at approximately 538 (Fig. 3),
analogous to the reported patterns of other CdS-polymer
nanocomposites w12x. These signals have been attributed
to the (111), (220) and (311) planes of CdS. An
additional signal at 258 in the pattern of the PANI-CdS
nanocomposites, which overlaps with the peak at 278,
is assigned to PANI since a signal at this position is
also visible in XRD patterns of pristine PANI. The
53
particle size estimated with Scherrer’s equation from the
line width in XRD patterns yielded values of 1–2 nm.
These sizes agree with the fact that the particles could
hardly be detected by transmission electron microscopy
(TEM).
3.2. Cu2S-PANI nanocomposites
In the UV-VIS spectra of Cu2SyPANI solutions in
NMP, the absorption maximum in the visible wavelength
range of the emeraldine base is shifted to shorter
wavelengths, as evident from Fig. 4 where the absorption
maximum in the presence of Cu2S appears at 592 nm
(at a weight ratio of Cu2S and PANI, rCu, of 0.23)
instead of 637 nm for the pristine PANI solution. As a
consequence, the color of the originally blue PANI
solutions moved towards purple. The shift in the absorp-
tion maximum became more pronounced after 24 h (Fig.
4), when the absorption maximum decreased to 542 nm,
corresponding to lmax of PANI in its pernigraniline
form. The changes in the optical spectra with time and
the concomittant processes had to be considered if
practical applications of such materials are envisaged.
As in the case of the CdSyPANI nanocomposites,
Cu2SyPANI were obtained by coprecipitation upon addi-
tion of ethanol to the NMP solutions. A slightly purple
or blue color in the filtered solution indicated that the
components did not precipitate quantitatively. The purple
54 R.L.N. Chandrakanthi, M.A. Careem / Thin Solid Films 417 (2002) 51–56

Fig. 3. XRD patterns of pristine PANI powder and CdSyPANI nanocomposites.

color most likely arises from a superposition of the are reported at 2u values of 22, 25 and 388 w13x. In
colors of colloidal Cu2S and PANI. Cu2SyPANI samples with rCus0.23 and 2.3, these peaks
The main absorption peaks of Cu2S in XRD patterns appeared extremely broad (Fig. 5). A much sharper

Fig. 4. Absorption spectra of various concentrations of Cu2S in Cu2SyPANI. (—) freshly prepared samples and (---) measured after 24 h.
 R.L.N. Chandrakanthi, M.A. Careem / Thin Solid Films 417 (2002) 51–56 55

Fig. 5. XRD patterns of Cu2SyPANI nanocomposites.

signal at 258 is attributed to PANI. From the broad
peaks in XRD patterns we estimate the diameters of the
Cu2S particles to be at a maximum of 5 nm, in
agreement with TEM images where the particles are not
unambiguously resolved.
The I–V curves were obtained in the dark and under
tungsten-halogen lamp illumination with incident power
100 mWycm2 w14x. The devices studied comprised a
layer of CdSyPANI composite between CdO and Al and
CdOyC60 (fullerene) and Al. Comparing the I–V behav-
ior, formation of Shotty contact between polymer- nan-
ocomposite layer and Al contact can be assumed. In the
case of pure PANI this Shottky barrier height is probably
small, increasing significantly with CdS nanoparticles,
hence providing much higher rectification and improving
the photovaltaic effect. Moreover, the more nanoparticle
concentration in the matrix, the higher the Shottky
barrier is, and the larger the photovoltaic effect is (Fig.
6).
With CdS, it is energetically favorable for the electron
transfer from the polymer to nanocrystal. Alternatively,
if the exciton is created on the nanocrystal, or transfers
onto the nanoparticle by Forster transfer, the hole can
subsequently transfer to the polymer, again producing a
charge separated state with an electron on the nanopar-
ticle and a hole on the polymer. The use of CdS allows

Fig. 6. TEM picture of Cu2SyPANI (a) rCus2.3 and (b) rCus1.4

56 R.L.N. Chandrakanthi, M.A. Careem / Thin Solid Films 417 (2002) 51–56
great flexibility in controlling the performance of pho-
tovoltaic devices, since both the electronic energy levels
and morphology of composites may be altered by
changing nanocrystal size and concentration.
4. Conclusion
CdSyPANI and Cu2SyPANI nanocomposites have
been synthesized using a new chemical method. The
results have shown that CdS and Cu2S can be success-
fully incorporated into polyaniline matrix and their
particle sizes can be varied by changing their concentra-
tion. Stability and aging of nanocomposites in solutions
were also investigated. Photovolatic devices with CdSy
PANI were fabricated and tested. Both short-circuit
currents and open circuit voltages of the devices were
found to increase with the concentration of CdS in the
polymer matrix.
Acknowledgments
Authors wish to thank Prof. Dr Paul Smith and Prof.
Dr Walter Caseri for their guidance throughout this
work. First author acknowledges Swiss Federal Govern-
ment Scholarship commission (ESKAS) for financial
support.
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