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Dramatic Enhancements in Toughness
of Polyvinylidene Fluoride
Nanocomposites via Nanoclay-Directed
Crystal Structure and Morphology**
By Deepak Shah, Pralay Maiti, Erica Gunn,
Daniel F. Schmidt, David D. Jiang, Carl A. Batt,
and Emmanuel P. Giannelis*
Addition of nanoclays or other nanoparticles into various
polymers to produce nanocomposites has been extensively
utilized in an attempt to enhance the mechanical, physical,
and thermal properties of polymers. While some interesting
properties have been demonstrated, the resulting nanocom-
posites have yet to realize their full potential. Nanoparticles
in general, and nanoclays in particular, with their nanometer
size, high surface area, and the associated predominance of in-
terfaces in the nanocomposites, can function as structure and
morphology directors, for example stabilizing a metastable or
conventionally inaccessible polymer phase, or introduce new
energy dissipation mechanisms. Thus, what distinguishes
nanoparticles from conventional micrometer-size rigid rein-
forcements is that their role might not be limited to only add-
ing stiffness to the polymer, but also to directing morphology,
as well as introducing new energy-dissipation mechanisms
leading to enhanced toughness in the nanocomposites. Herein
we demonstrate this potential by reporting a remarkable (or-
der of magnitude) increase in toughness with a concurrent in-
crease in stiffness in a poly(vinylidene fluoride) (PVDF)
nanocomposite.
The kinetics of crystallite growth and the details of crystal-
lite morphology of semicrystalline polymers can be affected
by the presence of layered silicates.[1,2] Although some
± changes induced by the nanoparticles as well as their in-
[*] Prof. E. P. Giannelis, Dr. P. Maiti, Dr. E. Gunn,[+]
Dr. D. F. Schmidt,[++] Dr. D. D. Jiang
Department of Material Science and Engineering, Cornell University
Ithaca, NY 14853 (USA)
E-mail: epg2@cornell.edu
Dr. D. Shah
Department of Chemistry and Chemical Biology, Cornell University
Ithaca, NY 14853 (USA)
Prof. C. A. Batt
Department of Food Science, Cornell University
Ithaca, NY 14853 (USA)
[+] Summer research student: Department of Chemistry, Simmons
College, 300 The Fenway, Boston, MA 02115-5898, USA.
[++] Present address: Groupe BASF, Institut de Science et d'IngØnierie
SupramolØculaires (ISIS)/UniversitØ Louis Pasteur (ULP), 8, allØe
Gaspard Monge, F-67083 Strasbourg, France.
[**] We thank Cornell Center for Materials Research (CCMR), AFOSR,
NASA and ONR, for financial support provided for this research
and gratefully acknowledge the use of CCMR-sponsored XRD, and
SEM/TEM facilities, as well as the time and assistance of M. Weath-
ers (XRD) and J. Hunt (TEM/SEM). We thank R. Dieckmann for the
use of his ATR-FTIR facilities, and H. Liu for her time and assistance
in this regard. We also thank E. Reynaud, R. Krishnamoorti,
R. A. Vaia, and A. J. Lovinger for their comments and suggestions.
Adv. Mater. 2004, 16, No. 14, July 19 DOI: 10.1002/adma.200306355
changes in morphology have been described in polymer/nano-
particle hybrids,[3±7] near-total stabilization and control of a
crystalline phase, coupled with dramatic enhancements in
materials properties, has not yet been reported.
PVDF is an important engineering plastic. It is used exten-
sively in the pulp and paper industry due to its resistance to
halogens and acids, in nuclear-waste processing for radiation-,
and hot-acid applications, and in the chemical processing in-
dustry for chemical and high-temperature applications. It is
also used in various device applications, due to its unique
piezoelectric[8±10] and pyroelectric[11] properties. There are five
known crystalline forms or polymorphs of PVDF: a, b, c, d,
and e.[12] The a phase is the most common in melt crystalliza-
tion, and remains the dominant crystalline form versus the b,
and c phases. The c phase does not form except at high
temperatures and pressures. Earlier reports have shown that
the a phase (chain conformationÐtrans-gauche trans-gauche,
tg+tg±) is inactive with respect to piezo- and pyroelectric prop-
erties, while the b form (all trans) exhibits the most activity,
and is thus the focus for electromechanical and electroacous-
tic transducer applications. Thus, the b form has great techno-
logical utility and there have been numerous attempts to sta-
bilize this phase. For example, the b form of the PVDF has
been obtained by careful crystallization from solution,[13] by
melt crystallization at high pressure, by application of a strong
electric field,[14] by molecular epitaxy,[15] and by preparing a
carbon-coated, highly oriented ultrathin film.[16] Earlier re-
ports have indicated the possibility of stabilizing a phase of a
crystalline polymer in the presence of well-dispersed layered
silicates in the polymer matrix. Specifically, increases in the
amount of the c phase in Nylon 6[5±7] and the b phase in
PVDF[3,4] nanocomposites have previously been observed. In
this study we report the first instance of a remarkable order of
magnitude enhancement in the toughness of a nanocomposite
compared to that of the pristine polymer. The enhanced
toughness is attributed to the structural and morphological
creased mobility compared to micrometer size fillers, which
contributes to a new energy dissipation mechanism during de-
formation.
The nanoclays used in this study are sodium montmorillon-
ite (NCMU) and bis(hydroxyethyl)methyltallowammonium
ion-exchanged montmorillonite (NCM). These nanoclays
have a 2-dimensional platelet like geometry and are com-
posed of 1 nm thick layers. Polymer chains can be intercalated
between the layers from solution or a melt when favorable in-
teractions between the polymer chains and the surface of the
inorganic host are present.[17,18] X-ray diffraction (XRD) anal-
ysis shows the formation of such an intercalated PVDF nano-
composite, referred to hereafter as PVDFNCM. A compari-
son of the diffraction patterns of the layered host before and
after intercalation shows an increase in the gallery spacing of
the layered silicates from 1.8 to 2.9 nm in PVDFNCM
(Fig. 1a), while it remains unchanged for the hybrid with the
unmodified layered silicate (PVDFNCU). The transmission
electron microscopy (TEM) image of the nanocomposite
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1173
COMMUNICATIONS

The mechanism by which the change from the a to b phase

a NCM b
PVDFNCM occurs is believed to involve a segmental flip-flop motion,
inversion mode of chain segments, or more probably, a
combination of the two.[20] This change appears to be favored
Intensity / a.u.

in the presence of properly surface-modified layered silicates.

2 4 6 8 10
2θ / deg
Figure 1. a) XRD of organomodified silicate (NCM) and the correspond-
ing nanocomposite (PVDFNCM). b) Bright-field TEM image of the PVDF
nanocomposite (PVDFNCM). The scale bar is 500 nm.
(Fig. 1b) shows good, homogeneous dispersion of the layered
silicates in the PVDF matrix. Stacks of alternating organic/in-
organic layers or tactoids with an average thickness of 100 nm
can be seen.
Clear indications of a change in the crystal structure of the
polymer phase are observed in the XRD traces (Fig. 2a). In
the nanocomposites, the (020), (110), and (111) peaks corre-
sponding to the a phase in pure PVDF disappear and are re-
placed by the (200/110) and (001) peaks corresponding to the
b phase.[16] This change can be observed by the addition of as
little as 2 wt.-% of the surface-modified nanoclay. The peaks
characteristic of the b phase appear with increasing intensity
as the nanoclay type is changed from pristine to surface modi-
fied. Materials based on the pristine layered silicate do not ex-
perience significant changes in crystal structure, and are com-
prised mostly of the a phase, with a weak b peak at 2h = 31.
Changes in the crystal structure are corroborated by Fourier-
transform infrared (FTIR) spectroscopy measurements. The
a-PVDF peaks[19] at 763 and 796 cm±1 can be quite clearly ob-
served for both pure PVDF and for the PVDFNCU. A com-
plete disappearance of these peaks is seen for PVDFNCM. Si-
multaneously, strong b-PVDF peaks at 840 cm±1 and 500 cm±1
are observed in the nanohybrids, indicating a change in the fa-
vored crystalline polymorph (Fig. 2b). Note that the pristine
layered silicate leads to an immiscible hybrid with PVDF due
to a lack of any favorable interaction between the polymer
and the silicate.
A probable mechanism for the stabilization of the b phase
could be due to the matching of the crystal lattice of the nano-
clay with that of the PVDF b phase. From the XRD analysis it
is clear that the levels of both polymer and nanoparticle dis-
persion and interactions dictate the structural conversion of
the a phase to the b phase of PVDF. This idea is further rein-
forced by the fact that hybrids made using spherical amor-
phous silica nanoparticles, both pristine and surface treated,
did not show any changes in the structure and morphology of
the PVDF.
Polarized optical microscopy (POM) and scanning electron
microscopy (SEM) studies have provided further evidence of
the extent and selectivity of the phase transformation induced
in the PVDF matrix. For these studies, thin films (~ 30 lm) of
the pristine polymer and the nanocomposite were crystallized
on a hot stage. Figure 3 shows the SEM and POM (inset) im-
ages of the pure PVDF and the corresponding nanocompos-
ites. The presence of large, isotropic spherulites is evident in
the POM inset (Fig. 3a), whereas the main SEM image shows
the features of a single a-spherulite (average diameter
~ 90 lm) with crystallites of lateral dimensions of the order of
2.5 lm in the pure PVDF. As reported previously, the crystal-
lites show a significant orientation perpendicular to the chain
axis (c-axis),[21] except towards the spherulite centers. It can
also be seen that spherulites are impinging upon each other
after full solidification (inset, Fig. 3b). As mentioned pre-
viously, unmodified layered silicates are immiscible with
PVDF. Accordingly, only a partial disruption of the spheruli-
tic structure is observed in this system, as most of the nano-
particle surface is inaccessible to the polymer matrix due to
nanoparticle aggregation. Nevertheless, the nanoparticle ag-
gregates act as nucleating agents, and as a result the average
spherulite diameter decreases to ~ 3 lm, but the presence of
spherulites is still evident in the POM (Fig. 3b inset). SEM
images (Fig. 3b) indicate that the crystallites are arrested in
the early stages of coalescence, but that the crystalline mor-
phology of the matrix is otherwise similar to that of the pure
PVDF. It is, however, possible to locate a few isolated b crys-

a b
β
10

PVDFNCM PVDFNCM
/1

2000
0
Intensity / a.u.

20

β1
00

PVDFNCU

PVDFNCU
1000
PVDF
11 20 α

α
0

1
α

11
0

Figure 2. a) XRD patterns showing devel-

PVDF opment of the b phase in PVDF nano-
0
10 20 30 40 1000 800 600 composites. b) FTIR curves showing
-1 appearance of the b peak (*) in PVDF
2θ / deg Wavenumber / cm
nanocomposites.

1174  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.advmat.de Adv. Mater. 2004, 16, No. 14, July 19
 COMMUNICATIONS
ordered a crystallites in pristine PVDF to disordered, fiber-
(a) like b crystallites in the presence of surface-modified, layered
silicates. A direct correspondence can be drawn between the
size of the a spherulites and the extent of b phase nucleation,
with the level of nanoscale dispersion and the degree of poly-
mer/nanoclay interactions in the nanocomposite systems. It is
also striking to note that the presence of surface modification
can mean the difference between partial and exclusive b nu-
cleation in the PVDF matrix.
The degree of crystallinity was determined via differential
scanning calorimetry (DSC) at a scan rate of 10 C min±1. The
data obtained showed no changes in either the Tm (the melt-
ing point of the crystalline regions of the semi-crystalline
(b) polymer) or the overall degree of crystallinity for the
PVDFNCM systems, as compared with that of the pure
PVDF. Based on the DSC results, the degree of crystallinity
for the PVDF and PVDFNCM samples was calculated to be
48 % and 49 %, respectively. The melting of the a and b
phases cannot be differentiated from DSC, as their melting
points are known to be within a few degrees of each other.[22]
The thermomechanical properties were studied using dynamic
mechanical analysis (DMA). At room temperature we ob-
serve an increase of 35 % in the storage modulus for the nano-
composite system, as compared to the pure PVDF. In addition
the glass transition at ±40 C remains unchanged for the neat
polymer and the nanocomposite.
(c)
Most rigid fillers produce increases in the modulus of the
composite versus that of the unfilled polymer. However, this
is generally associated with a significant decline in the elonga-
tion at break.[23] We show that the changes in polymer nano-
structure and morphology have a profound impact on the
mechanical response of the PVDF nanocomposites. The prop-
erties of these systems are, to the best of our knowledge,
unique, as these materials show simultaneous increases in
both stiffness and toughness (Fig. 4), leading to a situation

7
6x10

Figure 3. SEM images with POM insets showing crystal morphology of

a) PVDF, b) PVDFNCU, c) PVDFNCM.

tallites in the SEM (Fig. 3b), which give rise to the weak b 4x10
7
Stress / Pa

peak observed in XRD (Fig. 2).

In contrast, the PVDFNCM nanocomposite exhibits dra-
matic differences. It can be observed that the sample lacks bi-
refringence (inset, Fig. 3c). This is due to the random orienta- 2x10
7

tion of the smaller b crystallites, versus the larger, highly

ordered spherulitic structures previously observed. In this PVDF
case, no trace of the a spherulites is observed, either in the PVDFNCU
POM analysis or in the SEM image. It can also be seen that PVDFNCM
0
the fiber-like structures corresponding to the b crystallites 0 50 100 150
(average size ~ 0.6 lm) are quite well-defined and span the
entire observable area, further emphasizing the pronounced Strain / %
transition from the a to the b phase in the presence of the ap-
Figure 4. Stress±strain curves for pure PVDF, PVDFNCU, and PVDFNCM
propriate surface-modified layered silicates. Thus, a distinct showing the dramatic increase in elongation at break for the nanocom-
transition is observed, from large spherulites made of highly posite.

Adv. Mater. 2004, 16, No. 14, July 19 http://www.advmat.de  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1175
COMMUNICATIONS
where the overall properties are enhanced without any corre-
sponding trade offs (toughness here is defined as the area un-
der the stress±strain curve). The Young's modulus increases
from 1.3 to 1.8 GPa, while the elongation at break increases
from 20 % to 140 %, giving the hybrid a toughness ~ 700 %
higher than that of the neat polymer. We have recently found
that further optimization of the processing conditions leads to
an elongation for the nanocomposites of the order of 200±
250 %. With respect to macroscopic behavior during these
tensile tests, neck formation and plastic flow are evident in
the nanocomposites, whereas rapid strain hardening and brit-
tle fracture are observed in the pure polymer. It should be
noted that in the case of pristine and surface-modified silica
as well as the pristine layered silicate, no change in toughness
was observed. This is strongly indicative of the role of disper-
sion and interactions between the matrix and layered nano-
particles in the resulting behavior.
While we cannot test b-PVDF in bulk form due to the diffi-
culties in stabilizing the phase discussed earlier, we have
tested b-PVDF thin film samples prepared by axial stretching.
The films are relatively ductile in the transverse stretching di-
rection but show much lower elongation in the longitudinal
direction, in good agreement with previous studies of b-PVDF
thin films.[24] However, the toughness of these films is about
half of that seen in the nanocomposites. When one considers
that addition of reinforcing elements typically leads to de-
creases in elongation, an additional decrease rather than an
increase is expected for the nanocomposites. Therefore, we
conclude that nanostucturing of the polymer induced by the
nanoparticles as well as the presence of the nanoparticles
themselves and not just the b phase formation are responsible
for the enhanced toughness. Although there is no doubt that
the transformation of the phase/morphology plays a signifi-
cant part in the toughening of the nanocomposite, this is the
first reported instance of such a dramatic improvement in the
toughness of the polymer by dispersing a nanoparticle in the
matrix.
DSC of the samples following mechanical testing shows
slightly increased values of overall crystallinity (PVDF 52 %,
PVDFNCM 53 %), the increase being on the order of ~ 5 %
for both the PVDF and the nanocomposites. Although further
studies are underway to elucidate the exact mechanism re-
sponsible for this behavior, from the data obtained so far it is
quite clear that the dramatic increase in the toughness of
these nanocomposites can only be accounted for by changes
in crystal structure, morphology, and the presence of properly
surface modified layered silicates.
In the case of the PVDF nanocomposites, we postulate that,
in contrast to the neat PVDF, nucleation of the fiber-like b
phase on the faces of individual silicate layers leads to a struc-
ture much more conducive to plastic flow under applied stress.
This might give rise to a more efficient energy-dissipation
mechanism in the nanocomposites, thereby delaying crack for-
mation. In addition, recent molecular-dynamics studies have
suggested that nanocomposites might possess increased
toughness due to the ability of nanoparticles to dissipate ener-
1176  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.advmat.de
gy[25] because of their mobility under applied stress. Nanopar-
ticles and polymer chains have comparable time scales for
motion because of their size similarity. Due to their mobility,
the nanoparticles can act as temporary crosslinks between
polymer chains, providing localized regions of enhanced
strength, which in turn can retard the growth of cracks or cav-
ities. Similarly, energy dissipation might be further enhanced
due to the presence of smaller and hence more mobile b crys-
tallites. Our results show that good nanoscale dispersion,
coupled with favorable polymer±silicate interactions, is criti-
cal for improved toughness. Since the toughness enhancement
is observed in intercalated nanocomposites, nanoclay exfolia-
tion in the polymer matrix might not necessarily be required
to achieve the desired property enhancements.
In conclusion, we report the first ever instance of an order-
of-magnitude increase in the toughness of a polymer, with a
concurrent increase in stiffness, through nanostructural con-
trol. Addition of appropriately surface-modified nanoparticles
into a polymer can control the crystalline phase and morphol-
ogy of the polymer matrix. The enhanced toughness is attrib-
uted to the structural and morphological changes induced by
the nanoparticles, as well as their increased mobility as com-
pared to micrometer-size fillers, which contributes to a new
energy-dissipation mechanism during deformation. This study
provides a new approach for toughening of polymers and in
doing so, points the way towards a novel approach for the de-
sign of new nanocomposite materials.
Experimental
Synthesis of Nanocomposites: PVDF (Kynar 721) was provided by
the Atofina Chemical Co. as a fine powder and used as received. Un-
modified sodium montmorillonite (NCMU) and bis(hydroxyethyl)-
methyltallowammonium ion-exchanged montmorillonite (NCM) were
obtained from Southern Clay Products. A polymer/nanoclay premix
was prepared by combining the 5 wt.-% of nanoclay and PVDF pow-
ders in a speed-mixer. This premixed powder was then melt extruded
using a DSM twin screw microcompounder at a temperature of 200 C
under flowing nitrogen. For tensile testing, standardized dog-bone
specimens were prepared via microinjection of the extruded materials
using a Microinjector at a 240 C barrel temperature and a 95 C mold
temperature, with an injection pressure of 80 psi. In order to ensure a
proper comparison, pure PVDF samples were extruded and microin-
jected in an identical fashion.
Characterization: X-ray diffraction spectra were collected on a
Scintag Inc. h-h diffractometer equipped with an intrinsic germanium
detector system instrument, using a Cu Ka source with a wavelength
of k = 1.54 Š and a scan rate of 2 min±1. Infrared spectra were re-
corded in the reflectance mode between 400 to 1000 cm±1 using a Bru-
ker instruments. Dispersability of the nanoparticles in the matrix was
evaluated using a transmission electron microscope operated at an ac-
celerating voltage of 100 kV. Morphological features of thin films
(30 lm) were also studied using a polarizing optical microscope. The
polarized optical microscope was fitted with a color sensitive plate
that allowed for capture of images that were then developed and ana-
lyzed. Degree of crystallinity and melting temperature were deter-
mined via differential scanning calorimetry, over a temperature range
of ±50 to 200 C at a scan rate of 10 C min±1. Tensile tests were per-
formed on the microinjected dog-bone shaped samples at room tem-
Adv. Mater. 2004, 16, No. 14, July 19

perature, using a tensile tester and a strain rate of 5 mm min±1. Five
samples were tested for each specimen. The results obtained from
these experiments were within 15 % assuring good statistics.
Received: October 24, 2003
Final version: April 8, 2004
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Adv. Mater. 2004, 16, No. 14, July 19 DOI: 10.1002/adma.200400327
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Molecular-Level Insulation: An
Approach to Controlling Interfacial
Charge Transfer**
By Saif A. Haque*, Jong S. Park, Mohan Srinivasarao,
and James R. Durrant
cules on semiconductor surfaces is fundamentally important
for the development of molecular electronic devices, including
solar cells, biological and chemical sensors, and heterosupra-
molecular systems.[1±5] One such area of research attracting
particular interest at present is the functionalization of nano-
crystalline metal oxide films by the adsorption of molecular
dyes. Such functionalized metal oxide films are currently un-
der investigation for device applications ranging from dye-
sensitized solar cells to electrochromic displays. The attach-
ment of molecular dyes to the metal oxide nanoparticles is
typically achieved via acidic groups, such as carboxylates or
sulfonates, covalently attached to the sensitizer dye. Such acid
groups have been shown to form ester-type linkages to metal
oxide electrodes.[6] This attachment strategy is however lim-
ited to the use of dyes with suitable acidic groups, precluding
the use of most commercially available molecular dyes. More-
over such direct covalent attachment can often result in unne-
cessarily strong electronic interactions between the molecular
dye and the metal oxide electrode. This has been particularly
observed for small organic dyes, where direct covalent attach-
ment to the electrode surface as been shown to result in unde-
sirably fast interfacial recombination of photogenerated
charge-separated species,[7,8] limiting practical device applica-
tions.
In this paper we present an alternative strategy to the im-
mobilization of molecular dyes on nanocrystalline TiO2 elec-
trodes. Our strategy is based upon insulated sensitizer dyes, in
which the dye molecule is encapsulated at the molecular level
by a cyclodextrin macrocycle, limiting the interaction between
the TiO2 semiconductor surface and dye molecule and there-
±
[*] Dr. S. A. Haque, Dr. J. R. Durrant
Department of Chemistry, Centre for Electronic Materials and Devices
Imperial College of Science Technology and Medicine
London SW7 2AZ (UK)
E-mail: s.a.haque@imperial.ac.uk
J. S. Park, Dr. M. Srinivasarao
School of Textile and Fiber Engineering and
School of Chemistry and Biochemistry, Georgia Institute of
Technology
Atlanta, GA 30332 (USA)
[**] This work was supported by the Engineering and Physical Sciences
Research Council (EPSRC). M. S. would like to thank a grant
through the National Textile Center grant (Department of
Commerce) and the National Science Foundation (DMR-096240,
CAREER) for financial support. We would also like to thank
Emilio Palomares for helpful discussions and Alex Green for syn-
thesis of the TiO2 nanoparticles. Supporting Information is avail-
able online from Wiley Interscience or from the author.
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1177