Materials Letters 58 (2004) 1223 – 1226

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Strong quantum confinement effects in polymer-based PbS

nanostructures prepared by ion-exchange method
K. Suresh Babu a, C. Vijayan b,*, R. Devanathan a,1
a
Department of Metallurgical Engineering, Indian Institute of Technology Madras, Chennai 600 036, India
b
Department of Physics, Indian Institute of Technology Madras, Chennai 600 036, India
Received 17 June 2003; received in revised form 1 September 2003; accepted 7 September 2003

Abstract

Nanostructures of narrow band-gap semiconductiors such as PbS provide a large scope for band-gap engineering as strong quantum
confinement effects can alter the bulk band-gap value all the way from 0.41 to 2.3 eV, rendering the material transparent in most of the visible
range of the electromagnetic spectrum. This paper discusses the preparation and characterization of polymer-based PbS nanostructures
showing large characteristic blue shift in optical absorption. Enhancement in electrical resistivity is observed as a result of quantum
confinement. This material is found to exhibit strong thermal lens effects, which is utilized to achieve optical limiting at low laser power levels.
D 2003 Elsevier B.V. All rights reserved.

Keywords: Lead sulfide; Nanomaterials; Quantum confinement; Semiconductors

1. Introduction Semiconductor nanocrystals in a transparent matrix have

Semiconductor nanocrystallites are known to exhibit
unique size-dependent optical properties, which render them
attractive from the viewpoint of integrated photonic devices.
Quantum confinement effects are particularly important if
the crystallite dimension is less than a critical size known as
the exciton Bohr radius of the material [1,2]. Controlled
variation of nanocrystallites size results in remarkable
changes in properties from molecular to bulk. Also, by
doping polymers or glasses with these small semiconductor
clusters and utilizing their large resonant third-order optical
nonlinearity, new composite photonic materials can be
prepared. Efforts are on to develop novel types of nano-
materials with large scope for band-gap engineering in a
form easily adaptable for device applications. Lead sulfide
being a narrow band-gap material offers large tunability.
Band gap of PbS can be varied in a wide range, up to 2.3 eV,
from the bulk value of 0.41 eV, by changing the mean cluster
size of the nanoclusters [3].
* Corresponding author. Tel.: +91-044-22578686; fax: +91-044-
22570509.
E-mail address: cvijayan@iitm.ac.in (C. Vijayan).
1
Currently at Pacific Northwest National Laboratory, Richland, WA
99352, USA.
attracted recent interest due to their potential in applications
in nonlinear optics such as photonic switching [4]. Organic
materials such as polymers [5,6] and inorganic materials
such as glasses [7– 10] have been used as host matrices for
semiconductor nanostructures. There are several aspects of
recent interest on polymer-based nanostructures such as
their stability, dopant – host interactions, surface effects
and nature of quantum confinement which continue to be
open issues. It is essential to systematically address these
issues not only for understanding the electronic processes,
but also for their realizing their full potential applications.
Earlier work from our laboratory on polymer-based CdS
nanoclusters in the regime of strong confinement had
resulted in new findings on exciton confinement effects on
optical absorption and fluorescence, photoacoustic response
[11,12], acoustic and optical phonon confinement effects
[13] and enhanced optical nonlinearity [14] in polymer-
based CdS nanostructures. This paper presents some recent
results on preparation and characterization of PbS quantum
dots in Nafion polymer within the regime of strong quantum
confinement. We also report on the observation of optical
nonlinear properties and enhanced electrical resistivity in
these quantum dots. To the best of our information, these are
the first results on band-gap engineering of polymer-based
PbS nanostructures prepared by an ion-exchange method.

0167-577X/$ - see front matter D 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2003.09.012
1224 K.S. Babu et al. / Materials Letters 58 (2004) 1223–1226
2. Experimental details
The host matrix for the PbS quantum dots in the present
work is Nafion, a cation-exchange polymer available com-
mercially in the form of transparent sheets. These sheets
have good mechanical strength, chemical inertness and
temperature stability and are widely used in humidity
sensors and proton exchange membrane in fuel cells. Nafion
contains nanopores in its structure, which facilitate easy
formation of nanoclusters. It consists of a fluorocarbon
backbone and an interconnected ionic cluster [15,16].
Nafion 117 films of thickness 18 Am are cleaned in
boiling nitric acid and then repeatedly washed with boiling
water until the pH of the water bath becomes neutral. The
dried films are immersed in a 0.1 M lead acetate trihydrate
solution for varying amounts of time and ultrasonically
agitated to clean the surface. Samples designated A, B and
C are obtained after immersion times of 24, 12 and 1 h,
respectively. After ammonia passivation, films are finally
exposed to hydrogen sulfide gas and dried under vacuum. X-
ray diffraction (XRD) is carried out using Shimadzu Hori-
zontal Diffractometer using Cu-Ka radiation (k = 1.5418 Å),
in the step-scan mode with a step width of 0.02j (2h) and 10-
s counting time so as to improve the signal-to-noise ratio.
Optical absorption spectra of the sample are recorded on a
Hitachi U-3400 Spectrophotometer and conductance mea-
sured at room temperature using HP 4192A LF impedance
analyzer. Z scan experiments are done using the convention-
al geometry [17] with a helium neon laser at 20 mW as the
source. The optical limiting set up consisted of a converging
lens to focus the beam to a spot size of about 20 Am. The
sample is placed at the focal point so that the nonlinear
absorption is maximum and defocusing occurs at a lower
threshold. The light coming out is collected through an
aperture and made to fall on a photodetector. As the intensity
of light increases, defocusing occurs expanding the beam so
that the amount of light passing through the aperture
decreases, protecting the sensor.
3. Results and discussion
The XRD pattern for bulk PbS and representative sam-
ples A and B containing PbS quantum dots are shown in
Fig. 1 along with that of Nafion. The diffraction peaks
correspond to cubic rock salt structure of PbS (JCPDS file
No. 5-592) with the lattice parameter of 5.92 Å. The mean
nanocluster diameter of the sample A is found to be 15 nm
(using Scherrer formula) [18]. For other samples (with
presumably smaller cluster sizes), signal-to-noise ratios are
rather poor in the XRD pattern in spite of slow scanning and
no detailed size analysis could be attempted with these data.
Fig. 2 shows the optical absorption spectra of samples A,
B and C. The maximum wavelength limit of the instrument
used is 2600 nm and a bulk PbS sample would be opaque in
this range. However, all the quantum dot samples show
Fig. 1. XRD pattern of (a) bulk PbS, (b) sample A, (c) sample B, (d) Nafion.
optical absorption cut-off much shifted from the bulk value
of 3020 nm (corresponding to band gap of 0.41 eV)
signifying quantum confinement. From the tight binding
approximation model [1], the mean cluster diameter can be
calculated and is found to be 13 nm for sample A, 8 nm for
sample B and 3 nm for sample C. Accordingly, the samples
show different colors ranging from light yellow to brownish
red. The calculated sizes are also in the range of the rough
estimates made from line broadening in XRD. A quantita-
tive comparison, however, is not attempted in view of the
poor signal-to-noise ratio in XRD.
Fig. 3 shows the variation of ac resistivity of the pure
Nafion as well as Nafion incorporated with nanostructures.
Samples A and B, with mean nanoparticle sizes 13 and 8 nm,
respectively, show almost similar values of resistivity at
high frequencies. However, sample C, with mean cluster
size 3 nm shows an increase in resistivity compared to the
other samples. An enhancement in the resistivity in the case
of very small cluster sizes has been reported earlier in the
case of CdS nanoclusters embedded in Nafion [19].
Electrical conduction in Nafion membrane is known to
be by way of the Grothus mechanism of proton transport
[20], brought about by the motion of hydrogen ions in the
sulphonic groups assisted by water molecules in the pores of
the polymer. The ion-exchange process during the formation
of PbS nanoclusters in Nafion membrane initially causes the
hydrogen ions of Nafion to be replaced by less mobile lead
ions. Later during the reaction with hydrogen sulfide,
several of these lead ions form PbS molecules and in the
process get released from the sulphonic groups. These lead
ions are probably replaced by hydrogen ions. This effect is
larger in the case of clusters of larger diameter, as a larger
number of lead ions would have replaced hydrogen ions
 K.S. Babu et al. / Materials Letters 58 (2004) 1223–1226
Fig. 2. Optical absorption spectra of samples A to C.
initially during formation. Consequently, a larger numbers
of lead ions would get replaced by hydrogen ions in the
sulphonic groups during the formation of larger PbS clus-
ters, leading to an enhanced conductivity and hence lower
resistivity in comparison with samples having smaller nano-
sclusters. The effective increase in the ratio of surface area
to volume in the case of smaller clusters also could be a
contributing factor. The possibility of other contributions to
the mechanism of proton transport depending on the actual
size of the embedded nanostructures cannot be ruled out and
the embedded PbS nanoclusters could also play a role.
Proton transport in these materials can be fully understood
only though more detailed and systematic measurements on
the size dependence of conductivity in a wide size range of
nanoclusters and further work is in progress in this direction.
Thermal lens effect was observed on passing a low
power cw helium –neon laser beam through sample C and
Fig. 3. Electrical resistivity for samples A, B, C and Nafion.
1225
Fig. 4. Closed z scan trace of sample C.
is studied using the z scan geometry. Fig. 4 shows the z scan
trace obtained. The prefocal peak and post focal valley are
indicative of the formation of a negative lens, which leads to
self-defocusing. This is utilized in the optical limiting set up
using which the transmitted optical intensity from the
sample is measured as a function of the incident input
intensity. The result is depicted in Fig. 5.
In both z scan and optical limiting experiments, a laser
beam is passed through the sample, and hence, the sample is
required to be sufficiently transparent to allow a beam of
detectable intensity to pass through the sample. This is
possible in semiconductor nanostructures only if the optical
cut-off is sufficiently blue-shifted from the wavelength of
the laser wavelength used, 632 nm in the present work. The
optical absorption spectra (Fig. 1) show that samples A and
B are opaque at the laser wavelength. It was not possible to
Fig. 5. Optical limiting in PbS – Nafion for sample C.
1226 K.S. Babu et al. / Materials Letters 58 (2004) 1223–1226
pass the laser beam through these samples and hence z scan
and the optical limiting experiments could not be performed
with these samples. The laser wavelength falls in the tail end
of optical absorption cut off in the case of sample C, making
it possible for the beam to pass through.
The defocusing nature of the sample is dependent on the
aperture size and the focal length of the condensing lens
used in the optical module. The threshold for limiting is
found to be 6 mW. The output remains constant at about 4
mW even when the input is close to 8 mW. Earlier work on
CdS [14] had indicated that nonlinearity observed is large in
the regime of strong quantum confinement where the
particle size is much smaller than the exciton Bohr diameter.
The nonlinearity being probed here is of thermal origin as
the source used is a low power cw laser. Further experiments
are underway using high power laser pulses in the nano-
second and picosecond regime to probe nonthermal contri-
butions to nonlinearity in these samples and also to
investigate systematically the effect of nanoparticle size on
the nonlinearity.
In summary, PbS quantum dots in the regime of strong
quantum confinement are synthesized and stabilized in
Nafion polymer with a wide range of cluster sizes, by a
simple room temperature ion-exchange technique. The sig-
nature blue shift observed in optical absorption spectra of the
samples is quite large compared to the bulk value, in
agreement with the predictions of the tight binding approx-
imation. An increase in electrical resisitivity is obtained in the
case of films with extremely small PbS nanoparticles. Tem-
perature dependence of the refractive index in these materials
leads to self-defocusing effect as measured from the z scan
experiment. This is utilized to demonstrate the use of the
material for optical limiting applications at low powers.
Acknowledgements
The authors acknowledge the help provided by Ms.
Kaladevi Sendhil in the z scan and optical limiting
experiments, financial assistance from Government of India
and the valuable suggestions provided by the reviewer of the
paper.
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