FULL PAPER

Efficient Photosensitization and High Optical Gain in a Novel

Quantum-Dot-Sensitized Hybrid Photorefractive Nanocomposite at
a Telecommunications Wavelength**
By Kaushik Roy Choudhury, Yudhisthira Sahoo, Seongjin Jang, and Paras N. Prasad*

A high-performance hybrid polymeric photorefractive nanocomposite operating at the telecommunications wavelength of

1.34 lm is presented. The photorefractive nanocomposite is sensitized with PbS nanocrystals synthesized via a hot colloidal
route. Photoconductivity experiments confirm and quantify the photocharge-generation quantum efficiency of the nanocrystals.
A pronounced two-beam coupling effect at the operation wavelength is observed, leading to very high optical gains. Temporal
evolution of the photorefractive growth process is also studied.

1. Introduction makes this class of materials especially attractive. By simply

Media in which information can be encoded, routed, or pro-
cessed by using light are of particular interest for optoelectron-
ic and photonic applications, and, among these, organic materi-
als with photorefractive (PR) properties have recently
attracted remarkable interest. In PR materials, charges photo-
generated by a non-uniform light-intensity pattern are trans-
ported and redistributed in space to produce an internal space±
charge electric field, which, in turn, modulates the refractive in-
dex via molecular reorientations and/or electro-optic effects.
Optical information can then be recorded, erased, read-out,
and rewritten using suitable low-power laser beams. These ver-
satile materials, therefore, have the ability to manipulate light
and are potentially important for optical image processing,
beam clean-up and amplification, high-density holographic
storage, dynamic interferometry, pattern recognition, novelty
filters, and simulation of neural networks.[1±2]
Polymeric PR materials have attracted significant amounts
of research interest in recent times owing to their large optical
nonlinearities, low dielectric constants, design flexibility, ease
of synthesis and processability, and economic viability.[3±12] In
composite polymeric PR materials, the necessary functional-
ities for the realization of the effect are provided by different
components integrated into the composite; it is this aspect that
± suitable organic dyes to photosensitize PR polymeric compos-
[*] Prof. P. N. Prasad, K. Roy Choudhury, Dr. Y. Sahoo, S. Jang
Institute for Lasers, Photonics, and Biophotonics
Departments of Physics and Chemistry
State University of New York at Buffalo
Buffalo, NY 14260 (USA)
E-mail: pnprasad@buffalo.edu
[**] This research was supported in part by a Defense University
Research Initiative on Nanotechnology (DURINT), Contract
No. F496200110358, through the Directorate of Chemistry and Life
Sciences of the Air Force Office of Scientific Research and in part
by a NSF, DMR Solid State and Polymer Chemistry Grant
No. DMR0075867. The authors thank Dr. Jeffrey Winiarz for his ad-
vice at different stages of the project and Dr. Marek Samoc for his
critical review of this manuscript and his valuable comments and
suggestions.
changing the material composition, it is possible, in principle,
to individually optimize the main physical processes that con-
stitute the effect of photorefractivity: photosensitivity, charge
transport, and electro-optic response.[3,12] Thus, one is afforded
a greater control over material parameters than is possible with
inorganic crystals.
With the inception of colloidal routes for nanocrystal synthe-
sis, well-defined particles with pre-tailored sizes and shapes,
compatible with different solvent media, have been available;
consequently, novel means of photosensitizing polymeric com-
posites have been realized.[13±16] Hybrid organic±inorganic ma-
terials are emerging as a new class of electronic and opto-
electronic media for a number of potential technological
applications. Nanocomposites consisting of inorganic quantum
dots and functional polymers have shown promise for PR ap-
plications, light-emitting diodes, and photovoltaic devices.[17±19]
The primary advantage of this method of photosensitization is
the tunability of the bandgap of semiconductor nanocrys-
tals,[20,21] which translates into control over the accessible spec-
tral range of operation. Judicious selection of the materials, in-
cluding narrow-bandgap semiconductors, and successful
engineering of their bandgap via control over the nanocrystal
size permits this approach to be used for ultraviolet and visible,
as well as for applications involving infrared wavelengths. This
helps to overcome the longtime problem of non-availability of
ites at infrared wavelengths for optical communication. De-
spite prior efforts at altering the absorption spectra of recog-
nized organic photosensitizers through functionalization of the
parent chromophore, the observed spectral shifts have been
meager and inadequate.[22±24] In addition to the advantage of
wider spectral coverage with inorganic-semiconductor nano-
crystals, superior photocharge-generation efficiency, U, and en-
hanced mobility, l, may lead to enhanced PR figures of merit.
There have been several reports in recent times, both from our
group[9,25] as well as from others,[26,27] demonstrating the phe-
nomenon of photorefractivity in hybrid inorganic±organic
nanocomposites.

Adv. Funct. Mater. 2005, 15, No. 5, May DOI: 10.1002/adfm.200400396  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 751
 K. Roy Choudhury et al./A Photorefractive Nanocomposite Operating at a Communications Wavelength
FULL PAPER

In this paper, we report efficient photo-

a) b)
sensitization of a polymeric PR composite
at a communication wavelength (1.34 lm,
in this case) by the incorporation of a nar-
row-bandgap semiconductor quantum dot
and, to the best of our knowledge, the first
instance of high optical gain in such a nano-
composite at the concerned wavelengths.
The primary polymeric matrix used is
poly(N-vinylcarbazole) (PVK), well-known
as a medium of transport of photogenerated
charge carriers (holes).[28,29] Inclusion of
N-ethylcarbazole (ECZ) as a plasticizer c) d)
decreased the glass-transition temperature
(Tg) of the composite to below ambient
temperature, allowing for room-tempe-
rature in-situ electric-field poling of the
second-order nonlinear-optical chromo-
phore, 4-(N,N-diethylamino)-b-nitrostyrene
(DEANST). The composite was photosen-
sitized at 1.34 lm through the incorporation
of nanocrystals of lead sulfide (PbS).

Figure 1. TEM images of the PbS nanoparticles after a) 10 min, b) 30 min, c) 45 min, and d) 1 h
2. Results and Discussion of the progress of reaction.

2.1. Fabrication and Characterization of Photosensitizing

Quantum Dots quantitative elemental analysis. However, the clean spectrum
does confirm the absence of any extraneous impurity in the
For PR applications, it is desirable to fabricate a composite sample. Results from powder X-ray diffraction (XRD) of the
in which the sensitizer possesses the smallest bandgap with re- nanocrystals is shown in Figure 2. The XRD pattern confirms
spect to the other components. This allows for operation at an the cubic rock-salt structure of the PbS. The crystalline-domain
optical wavelength which is preferentially absorbed by the sizes of the nanoparticles estimated from Scherrer's equation
photosensitizer, eliminating any background absorption by the D = 0.9k/dcosh, where D represents crystallite size [Š], k the
other components.[3,30] Due to the relatively large Bohr radius wavelength of Cu Ka radiation, and d the corrected half width
of the exciton (20 nm), PbS nanocrystals offer unique access to of the diffraction peak, was found to be 6 nm.
the regime of extreme quantum confinement,[16] with an ab- The absorption spectrum of the composite film is shown in
sorption edge tunable from the bulk value of 0.41 eV to Figure 3. The sample shows an absorption edge starting at
2.32 eV,[31] spanning the entire near-infrared and part of visible
spectrum. In order that the nanocrystalline PbS incorporated
into the PR mixture performs as an efficient photosensitizer at
the desired wavelength of 1.34 lm, it was necessary to ensure
strict control over the final size of the nanocrystals. For our
purpose it was imperative to synthesize nanocrystals with sizes
~ 6±8 nm. The transmission electron microscopy (TEM) images
shown in Figure 1 reveal uniformly sized nanocrystals about
8 nm across. As can be seen from the panels of Figure 1, the
very small nanocrystals (4±5 nm) are formed within the first
10 min, and the growth of the nanocrystals is almost complete
within the first 30 min. Between 30 and 60 min, the nanocrys-
tals maintain an average size of 8 nm. It is found that their sur-
face is well passivated by the surfactant, thus facilitating a
stable dispersion in organic solvents such as toluene or hexane.
An energy-dispersive spectrogram (EDS) of the sample was
obtained (not shown) to determine the presence of impurities.
Since lead and sulfur have their characteristic X-ray emission Figure 2. XRD pattern of PbS nanocrystals depicting a cubic rock-salt
peaks at the same energy, EDS was not helpful in carrying out structure.

752  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.afm-journal.de Adv. Funct. Mater. 2005, 15, No. 5, May
K. Roy Choudhury et al./A Photorefractive Nanocomposite Operating at a Communications Wavelength
1350 nm, close to the wavelength of interest. This occurs as a
result of the quantum confinement effect in the nanocrystals,
as the absorption edge differs markedly from that of bulk PbS
at 3200 nm. Moreover, none of the other components in the
PR mixture displays optical absorption in this range.
Figure 3. Absorption spectrum of the PVK:ECZ:DEANST:PbS composite.
2.2. Photoconductivity
The phenomenon of photorefractivity in polymeric compos-
ites can be realized in materials that simultaneously exhibit
photoconductive and electro-optic- or electric-field-dependent
birefringence properties.[1±3] Photoconductivity at the desired
excitation wavelength allows for the formation of an internal
space±charge electric field through a successive combination of
photogeneration, transport, and trapping of charges. Hence,
the photoconductivity of the composites was checked first. The
photosensitivity Sph (photoconductivity per unit light intensity)
of the PR composite is presented in Figure 4 and was deter-
mined according to the equation
Figure 4. Photosensitivity, Sph, of the nanocrystalline PbS as a function of
the applied electric field, E0.
Adv. Funct. Mater. 2005, 15, No. 5, May http://www.afm-journal.de
FULL PAPER
 Jph
Sph ˆ ˆ (1)
I EI
where r is the photoconductivity, Jph the photocurrent density,
E the applied electric field, and I the illumination intensity of
the beam. Significant photosensitivity is observed at 1.34 lm.
In addition to the photosensitivity, an alternate parameter that
quantifies the photoresponse of the composites is the photo-
charge generation quantum efficiency, U. The electric-field
dependence of U is depicted in Figure 5 and was determined
according to the equation
Figure 5. Photocharge-generation quantum efficiency, U, of the nanocom-
posite at 1.34 lm as a function of applied electric field, E0.
 
Ncc hc
U…E† ˆ ˆ Jph (2)
Nph kead
where Ncc is the number of charge carriers generated per unit
volume, Nph the number of photons absorbed per unit volume
in the sample, h Planck's constant, c the speed of light, a the
absorption co-efficient of the sample, and d the sample thick-
ness. The samples display greatly enhanced photocharge gen-
eration quantum efficiency, U, compared to previously report-
ed results.[25]
2.3. Two-Beam Coupling
A characteristic feature of the PR effect is that the refrac-
tive-index grating created in the medium is spatially shifted
with respect to the light-intensity pattern of the writing
beams.[1±3] This phenomenon results in an asymmetric energy
transfer between beams interfering in the sample. The PR na-
ture of the composite was demonstrated through asymmetric
two-beam coupling (TBC) experiments employing an oblique
geometry[1,3,10] as shown in Figure 6. A typical experimental
measurement verifying effective energy exchange between the
laser beams is illustrated in Figure 7. For this particular run,
the writing beams I1 and I2, with intensities of 140 mW cm±2,
were used, while an external electric field E0 = 64.8 V lm±1 was
applied to a 54 lm thick sample. The external electric field was
turned on at t = 65 s and turned off at t = 220 s.
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Figure 6. The oblique geometry of the TBC experiment. I1 and I2 are writ-
ing beams; I1¢ and I2¢ are the transmitted beams; h1 = 35 and h2 = 55 are
the incident angles with the sample normal N; and HV is a high-voltage
source.
Figure 7. Asymmetric energy exchange between laser beams in the TBC
study of the PVK:ECZ:DEANST:PbS nanocomposite. The external electric
field (64.8 V lm±1) was turned on at t = 65 s and turned off at t = 220 s.
The TBC gain co-efficient C is given in terms of the experi-
mentally determined quantities c0 and b, as
 h    i
1 mechanisms may be present and these can complicate the
Cˆ ln c0 b ln b ‡ 1 c0 (3)
L dynamics of the process. In Figure 9, the time-resolved evolu-
where L= d/cosh is the effective optical path length of the
beam experiencing gain inside the sample, b is the ratio of the
writing beam intensities before entering the sample, and c0 is
the beam-coupling ratio, defined as c = P1/P0, P1 being the in-
tensity of the signal with pump, and P0 being the intensity of
the signal without pump.[1±5,9±11,24±26]
The electric-field dependence of the TBC gain C for the
studied composite is presented in Figure 8. A maximum TBC
gain of 184.5 cm±1 at an applied external electric field of
92.6 V lm±1 was obtained. This, to the best of our knowledge, is
the highest reported gain at this operating wavelength for PR
polymers and is a huge improvement in TBC gain over the PR
response at communication wavelengths reported by our group
previously.[25] From a practical point of view, the optical ampli-
754  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.afm-journal.de
Figure 8. Electric-field, E0, dependence of the TBC gain co-efficient, C, in
the PVK:ECZ:DEANST:PbS nanocomposite at 1.34 lm. The highest gain
recorded was 184.5 cm±1 at 92.6 V lm±1.
fication, C, needs to exceed the absorption loss, a, of the PR
sample. In the present case, the optical absorption of the sand-
wiched sample at 1.34 lm, as determined from the absorption
spectrum (Fig. 3) is a = 69 cm±1, yielding a net gain coefficient,
C±a, of 115 cm±1 at 92.6 V lm±1.
2.4. Dynamics of Grating Build-up
The dynamics of the TBC process is complex. Writing of a
PR hologram in a material involves a succession of steps:
charge generation, migration, and trapping, followed by chro-
mophore reorientation in the electric field. The electric-field
dependence of these various processes is described by different
equations. But all the individual steps, and hence their con-
fluence, are faster at higher electric fields. The evolution of the
growth of the gain in the TBC experiment was studied at differ-
ent applied fields. Gain transients are supposed to be exponen-
tial according to the single carrier model of photorefrac-
tivity.[32] However, in polymers, multiple grating-growth
tion of the transient gain is depicted for a range of applied elec-
tric fields.
The growth data permits a quantitative determination of the
growth time constant associated with this PR composite under
the given experimental conditions. The data was fitted with a
stretched exponential function of the form,
   
 k
c…t† ˆ c0 1 exp t sg (4)
where c0 is the steady-state gain, sg is the time constant, and
the exponent k is a measure of the slowing down of the rate of
increase with time.[24,33,34] This stretched exponential behavior
is common for physical processes involving a distribution of
time constants.[33,35] Polymer composites are inherently highly
Adv. Funct. Mater. 2005, 15, No. 5, May
K. Roy Choudhury et al./A Photorefractive Nanocomposite Operating at a Communications Wavelength
Figure 9. Evolution of the TBC gain transient, c, with time, t, for a range of
applied electric fields.
dispersive systems. The realignment of the dipolar chromo-
phores is controlled by local fields and local environment and
hence it proceeds at different rates. Additionally, charge trans-
port in such nanocomposites has been shown to be disper-
sive.[36] Thus, it is not unreasonable to expect a distribution of
time constants, and consequently, a stretched exponential be-
havior. As is evident from Figure 10, the stretched exponential
function does provide a good fit to the data, especially at
Figure 10. Stretched exponential fit to the growth data at an electric field
of 83.33 lm±1.
moderate to high fields. However, at comparatively low fields,
the data could not be fitted satisfactorily by this function. This
problem has also been encountered in other similar compos-
ites.[23,37] One possible factor responsible for this behavior
maybe that even in dispersive systems certain physical pro-
cesses, like charge transport, tend to become less dispersive
with increasing fields. Consequently, their functional depen-
dence on field changes.[36]
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FULL PAPER
The electric-field dependence of the inverse rise time sg±1
and the value of k are depicted in Figure 11. One observes a
monotonic increase of both parameters with field. An increase
Figure 11. Electric-field, E0, dependence of the inverse risetime, sg±1 (open
squares) and k (filled circles), of the PVK:ECZ:DEANST:PbS nanocompos-
ite at 1.34 lm.
in k indicates a narrowing of the width of distribution of time
constants, although detailed analysis of these dependencies is
much more complicated due to the field dependencies of both
U and l. This will be the subject of our future study with this
composite.
3. Conclusions
Efficient photosensitization of a PR polymeric composite by
semiconductor nanocrystals for operation at the infrared wave-
length of 1.34 lm is demonstrated. The composite material
shows high photocharge generation quantum efficiency. Excel-
lent TBC optical gain of 184.5 cm±1 at 92.6 V lm±1 was accom-
plished; higher than that realized in any similar hybrid PR com-
posite operating at any wavelength. A response time faster
than other hybrid PR nanocomposites is also observed. The
temporal evolution of the PR growth mechanism was studied
and quantified.
4. Experimental
Nanocrystal Synthesis: PbS nanocrystals were produced by reacting
the precursors via a hot colloidal synthetic route, widely adopted for
the preparation of II±VI and III±V semiconductor particles [16]. In a
typical reaction, 1 mmol of lead acetate, 3 mmol of oleic acid, and
5 mL phenyl ether were loaded into a 50 mL three-necked flask set in
a heating mantle. At 100 C, lead acetate was dissolved in the mixture
and an alternate cycle of evacuation and argon flow was maintained for
half an hour. At this time, 0.3 mmol of sulfur dissolved in 2.5 mL oley-
lamine was injected into the flask, whereupon instant reaction yielded
a black color. Subsequently, the temperature was raised to 200 C and
the reaction mixture was constantly stirred at the raised temperature
for another hour. Small aliquots (0.5 mL) were drawn from the reac-
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 K. Roy Choudhury et al./A Photorefractive Nanocomposite Operating at a Communications Wavelength
FULL PAPER
tion mixture at the intervals of 10, 30, 45, and 60 min to monitor the
growth profile with the time of reactions. At the end of the reaction,
the nanocrystals were retrieved by first adding 15 mL of toluene, fol-
lowed by 100 mL of ethanol to the reaction mixture, resulting in com-
plete precipitation. Then the mixture was centrifuged and the collected
precipitate redispersed in toluene.
Sample Preparation: Toluene was used to disperse the PbS nanocrys-
tals by sonication. This was followed by the introduction of DEANST,
ECZ, and PVK. The mixture was then subjected to ultrasonic ªmixingº
until a homogeneous dispersion was achieved. The final prepared mix-
ture had a composition of 48:15:35:2 wt.-% (PVK:ECZ:DEANST:PbS
respectively). For photorefractive experiments, the solution was then
dripped onto an indium tin oxide (ITO)-coated glass substrate with an
etched electrode pattern. The film was allowed to dry slowly at ambient
temperature (for 24 h) and, subsequently, heated to 70 C for 3±4 h,
followed by storage in a vacuum chamber for several hours to ensure
complete solvent evaporation. Next, the film was softened by placing it
on a hot plate (~ 90±100 C) for 30 s, and another ITO-coated glass sub-
strate was pressed on top to produce a sandwich glass±ITO±sample±
ITO±glass geometry, yielding 50±100 lm-thick samples. For photocon-
ductivity measurements, thin films (3±8 lm) were spin-coated onto an
ITO-coated glass substrate from the same sample mixture. The films
were then left in vacuum for several hours to ensure complete removal
of the solvent. Film thickness and integrity of the surface were con-
firmed using an Alfa step profiler. Subsequently, aluminum counter-
electrodes (~ 0.04 cm2) were fabricated via high-vacuum deposition to
form a sandwich device structure. It should be noted that the colloidal
solution of the photosensitizing nanocrystals of PbS as well as the com-
posite photoconductive or photorefractive films are stable without any
perceptible degradation over several weeks and have yielded reproduc-
ible data.
Nanocrystal Characterization: The morphology of the nanocrystal
assembly was studied by TEM. The specimens for TEM were prepared
by drop-casting the nanocrystal dispersion in toluene onto an amor-
phous carbon-coated 300-mesh copper grid, and allowing the solvent to
evaporate. TEM images were acquired with a JEOL model JEM-
100CX microscope at an acceleration voltage of 80 kV. Crystal phases
were identified and crystalline-domain sizes were estimated by (XRD)
using nickel-filtered Cu Ka radiation. Absorption spectra of the sample
in the thin-film geometry were obtained with a Shimazdu 3101 spectro-
photometer.
Photoconductivity: The photoconductivity of the composite was
studied using a simple direct-current (dc) photocurrent technique,
where a dc voltage was applied to the sample, and the current compo-
nent induced by a laser pulse of duration 15 ms from a Lepton Series
Laser (Micro Laser System) operating at 1.34 lm was measured in an
external circuitry. The sample was thermally grounded (to minimize
any thermal effects due to the impingement of laser radiation) via an
aluminum block which is a part of the sample stage.
Photorefractivity: Holographic gratings were written through the in-
tersection of two coherent laser beams from the same laser that was
used in the photoconductivity experiments, the beams being of p-polar-
ization. The writing beams were of approximately equal intensity and
intersected in the sample at incident angles of 35 and 55 (in air) with
respect to the sample normal, respectively, creating an intensity grating
with a periodic spacing, K, of 4.83 lm. An asymmetric energy transfer
between the p-polarized writing beams was observed by monitoring the
intensity of each of the transmitted beams with respect to time using
photodiodes, until steady-state conditions were achieved.
Received: August 31, 2004
Final version: October 13, 2004
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