ZnO-TiO2 nanocomposite core-shell

ZnO−TiO2 Nanocomposite Films for High Light Harvesting Efficiency
and Fast Electron Transport in Dye-Sensitized Solar Cells
Venkata Manthina,†,§
Juan Pablo Correa Baena,†,§
Guangliang Liu,‡,§
and Alexander G. Agrios*,†,§
†
Department of Civil & Environmental Engineering, University of Connecticut, Unit 3037, 261 Glenbrook Rd, Storrs, Connecticut
06269, United States
‡
Department of Chemical, Materials & Biomolecular Engineering, University of Connecticut, Unit 3222, 191 Auditorium Rd, Storrs,
Connecticut 06269, United States
§
Center for Clean Energy Engineering, University of Connecticut, 44 Weaver Rd, Storrs, Connecticut 06269, United States
ABSTRACT: Electron transport and recombination are the
essential processes that determine the charge collection
efficiency in dye-sensitized solar cells (DSSC). While nearly
100% of charges are collected in well-built ordinary DSSCs,
this value can be sharply reduced by the use of redox couples
other than iodide/triiodide due to fast electron recombination.
To compensate, structures capable of fast electron transport
are needed. Nanorod arrays that have this attribute tend to
suffer from low surface area, resulting in low dye loading and
reduced light harvesting. We have therefore developed a novel
nanocomposite structure consisting of zinc oxide (ZnO)
nanorods coated with titanium dioxide (TiO2) nanoparticles using an electrostatic layer-by-layer (LbL) deposition technique.
The titanium dioxide nanoparticle coating can add an order of magnitude of surface area and is compatible with known high-
performance dyes. This composite nanostructure has been designed to take advantage of the improved electron transport along
the nanorods and surface area provided by the nanoparticles, yielding good charge collection and light harvesting. Transient
measurements indicate that the composite film can transport electrons at least 100 times faster than a nanoparticulate TiO2 film.
In tests using ferrocene/ferrocenium as a model alternative redox couple with fast recombination, current−voltage measurements
indicate that the ZnO−TiO2 hybrid films generate much higher currents than conventional TiO2 nanoparticulate films. However,
not all charges successfully transfer from TiO2 to ZnO due to an energy barrier between the materials.
■ INTRODUCTION
Dye-sensitized solar cells (DSSCs)1
are low-cost alternatives to
silicon photovoltaics. The conventional DSSC consists of two
sandwiched pieces of conducting glass, one of them coated with
a mesoporous layer of nanoparticulate TiO2 with a self-
assembled monolayer of chemisorbed dye molecules, filled with
an electrolyte for dye regeneration. The dye is a transition-
metal complex or organic chromophore that harvests sunlight
by absorbing strongly in the visible region of the solar
spectrum. The principal photovoltaic losses in the DSSC are
due to incomplete light harvesting, recombination of the
photoinjected electrons with the electrolyte, and the over-
potential required for dye regeneration. Ruthenium complex
dyes like N719, N3, and “black dye” exhibit high efficiency with
the I−
/I3
−
redox couple, but there is little room for
improvement in light harvesting in the visible range.
In DSSCs, the I−
/I3
−
redox couple limits the overall
efficiency due to the high overpotential (ca. 0.5 V) for dye
regeneration by I−
. This is believed to be due to the complex
multielectron mechanism of the I−
/I3
−
redox couple involving
the radicals diiodide (I2
•−
) and atomic iodine (I•
).2
The effect
is that the dye HOMO level must be about 0.5 V more positive
than the I−
/I3
−
redox level. Since the voltage output of the cell
is the difference between the redox level and the quasi-Fermi
level in the semiconductor, this 0.5 V is lost. An alternative
redox electrolyte that could regenerate the sensitizer from a
potential closer to its HOMO would result in higher cell
voltage and efficiency, if all else were held equal. Unfortunately,
alternatives (such as iron or cobalt complexes) tend to
recombine rapidly with conduction-band electrons, reducing
the quasi-Fermi level and resulting in no benefit.
There have been important recent advances in using
specialized dyes to slow recombination with electrolytes
based on ferrocene or cobalt bipyridyl complexes.3−5
Our
approach is to utilize novel semiconductor structures to attain
fast electron transport in order to improve charge collection
efficiency. The combination of these approaches will maximize
solar cell performance. In particular, by providing some
tolerance of accelerated recombination, structures for fast
electron transport enable the use of standard dyes such as
N719, which are more facile products than the specialized dyes
Received: May 12, 2012
Revised: September 22, 2012
Published: October 2, 2012
Article
pubs.acs.org/JPCC
© 2012 American Chemical Society 23864 dx.doi.org/10.1021/jp304622d | J. Phys. Chem. C 2012, 116, 23864−23870

mentioned above, which tend to be large and difficult to
synthesize.
Electron transport in DSSCs is slow, due to trapping of the
electrons in the grain boundaries and the relatively long and
tortuous path of the electron to the fluorine-doped tin oxide
(FTO).6,7
In a 10 μm thick film an electron visits about 106
nanoparticles on average before reaching the FTO surface.8
The resulting slow transport is adequate in the presence of
iodide/triiodide, since its recombination kinetics are slow, but
inadequate when using an alternative redox couple with faster
recombination.
Fast electron transport can be achieved by developing 1-D
nanostructures like nanotubes, nanorods, and nanowires of
metal oxides. ZnO is a highly favorable material for application
in DSSCs, since it can be grown in monocrystalline nanorods
using facile methods, its electron mobility is high,9
and its band
edge energies are very close to those of TiO2.10
ZnO is the
metal oxide with the second highest efficiency achieved in
DSSCs.11−13
ZnO nanorods can be synthesized on various
substrates in situ by procedures such as chemical bath
deposition,14,15
electrodeposition,16−18
and chemical vapor
deposition,19,20
and in DSSCs they can transport electrons
more than an order of magnitude faster than a TiO2
nanoparticulate film.21
However, the main disadvantage of
nanorods is their lower surface area than a nanoparticle film for
adsorption of light-harvesting molecules. In addition, dyes
partially dissolve the ZnO, forming a deleterious Zn2+
−dye
surface complex.22
Previous efforts to circumvent these shortcomings have
tended to either boost the surface area of the ZnO, e.g. by
adding ZnO nanoparticles23
or secondary nanorods,24
or to
improve dye performance via, for example, a protective
conformal TiO2 encapsulation of ZnO.25
To create a structure
with both fast electron transport and high surface area, we
developed a hybrid photoanode consisting of ZnO nanorods
coated with TiO2 nanoparticles using facile wet-chemical
methods. ZnO nanorods were grown by chemical bath
deposition (CBD), a low-temperature catalyst-free process
suitable for industrial applications. TiO2 nanoparticles were
coated uniformly over the nanorods by electrostatic layer-by-
layer (LbL) deposition. The LbL technique is based on
exposing a substrate sequentially to cationic and anionic
substances, which form successive bilayers by electrostatic
attraction. The TiO2 nanoparticles greatly increase the total
surface area and provide a superior surface for dye attachment
compared to ZnO, while the nanorods can provide fast
transport of electrons from TiO2 to the conducting substrate.
In addition, the structure includes wide open channels that are
helpful for mass transport of redox species and for filling with
solid hole-transporting materials in solid-state DSSC devices.
Despite the simplicity and attractiveness of this structure and
fabrication method, it has not been done previously, although
Wang et al. added a thin layer of 5-nm TiO2 particles to ZnO
nanorods by sputtering.26
In this work, we compared hybrid films to ZnO nanorod-
only films and TiO2 nanoparticle-only films in terms of dye
loading and device performance. For the latter measure we
compared DSSC devices using two different redox couples:
iodide/triiodide (I−
/I3
−
) and ferrocene/ferrocenium (Fc/Fc+
).
We have chosen the latter as a model alternative redox couple
with fast recombination kinetics. Our tests with Fc/Fc+
show
that these hybrid photoanodes can collect more injected
electrons than a conventional TiO2 nanoparticle film with
equivalent dye loading.
■ EXPERIMENTAL METHODS
Reagents and Materials. Except where noted, all
chemicals were purchased from Sigma-Aldrich and were ACS
grade or better. N719 was purchased from Dyesol. SnO2:F glass
(FTO, transmission >80% in the visible spectrum; sheet
resistance 8 Ω/□) was purchased from Hartford Glass Co.
Electrode Fabrication. ZnO nanorods were synthesized by
a two-step chemical bath deposition (CBD) technique.27
The
nanorods were optimized for subsequent TiO2 deposition using
a modified seed layer technique that will be the subject of a
future publication. Slides of borosilicate glass with a conducting
SnO2:F (FTO) layer were cut into 25 × 50 mm pieces and
cleaned by 10 min sonication in a detergent solution (5% RBS-
25 in water) followed by ethanol. The clean FTO substrates
were coated with the seed layer and then heated at 350 °C on a
titanium hot plate for 30 min. CBD was followed by immersion
in an aqueous solution of 50 mM zinc nitrate hexahydrate, 50
mM hexamethylenetetramine, and 6 mM polyethyleneimine.
The seeded substrates were placed at an angle of 60° from
horizontal in a 100-mL glass bottle with the seeds facing the
bottom of the bottle and held in an oven at 90 °C for 24 h.
TiO2 nanoparticles were synthesized by hydrolysis of
titanium tetraisopropoxide as previously described.28,29
Electro-
static layer-by-layer (LbL) deposition was accomplished by
immersing a substrate alternately in a cationic 1 g/L polymer
solution (PDAC, polydiallyldimethyl ammonium chloride, 70
kDa) in water and in an aqueous suspension of anionic TiO2
particles with intermediate rinsing and drying steps, using a
dipping robot (DR-3, Riegler & Kirstein GmbH).29
All
solutions contained 5 mM triethylamine (resulting in a pH
near 11) to maintain negative particle surface charge. For
deposition on bare FTO, the dipping time in the TiO2
suspension was 5 min. When coating nanorods, the dipping
time was 30 min to allow penetration of the channels between
the rods. LbL was followed by sintering at 500 °C to remove
polymer layers.
Surface/Structure Characterization. The morphology of
ZnO nanorods and TiO2 nanoparticles was investigated by
scanning electron microscopy (FEI Quanta FEG250 SEM in
high vacuum mode). The ZnO nanorods and TiO2 nano-
particles were additionally characterized by X-ray powder
diffraction (XRD) using a Bruker D8 Advance X-ray
diffractometer using Cu Kα radiation (λ = 0.154 178 nm) at
a scanning rate of 0.04° s−1
in the 2θ range from 10° to 90°.
The XRD data were analyzed using the Debye−Scherrer
equation to determine the TiO2 crystallite size.
Sensitization. After sintering, films were allowed to cool to
100 °C and then immediately immersed in 0.3 mM N719 in
ethanol. After 12 h they were removed, rinsed in acetonitrile,
and dried in air. To measure the amount of N719 dye adsorbed
by a film, a dyed and twice-rinsed 4.5 cm ×2.5 cm electrode was
placed in 3 mL of 0.1 M NaOH in water. As the solvent volume
was not sufficient to immerse the electrode, solvent was
repeatedly pipetted over the electrode. After repetitions, the
dye was visibly completely desorbed from the electrode. The
spectrum of the desorbed dye was measured in a 1-cm quartz
cuvette using a Varian Cary 50 spectrophotometer. The
literature peak extinction coefficient of N719 (1.43 × 104
M−1
cm−1
) in ethanol30
was used to obtain the corrected
value in basified water. The molar extinction coefficient for
The Journal of Physical Chemistry C Article
dx.doi.org/10.1021/jp304622d | J. Phys. Chem. C 2012, 116, 23864−2387023865

N719 in water with 0.1 M NaOH was found to be 1.65 × 104
M−1
cm−1
. This value was used to quantify the amount of
desorbed dye.
Solar Cell Assembly. Each sensitized electrode was sealed
against a counter electrode on a hot plate at 120 °C using a hot-
melt plastic frame (Solaronix, Meltonix 1170, 25 μm thick), by
applying light pressure with a glass rod. The assembled cell was
filled with electrolyte through two holes in the counter
electrode. The holes were then sealed using hot-melt plastic
and a thin glass cover slide. The exposed conducting glass leads
of each electrode were coated with copper tape (3M) for
improved electrical conductivity.
Electrolyte Composition. Minimal electrolyte recipes
were used to exclude complications due to interactions with
the various additives that are commonly used. Iodide/triiodide
(I−
/I3
−
) electrolyte was prepared with 0.5 M tetrabutylammo-
nium iodide and 0.05 M iodine (I2) in 3-methoxypropionitrile.
The ferrocene/ferrocenium (Fc/Fc+
) electrolyte contained 0.1
M ferrocene and 0.05 M ferrocenium hexafluorophosphate
(Aldrich) in 3-methoxypropionitrile. The Fc/Fc+
electrolyte
was prepared fresh and deoxygenated by bubbling nitrogen 10
min prior to cell fabrication to minimize reaction of ferrocene
with oxygen.31
Transient Measurements. Measurements of electron
transport time were made using a set of National Instruments
components in a PXIe chassis capable of high-resolution analog
voltage output and digitized input. A square-wave modulation
was applied to a white-light LED that was used to illuminate a
DSSC. The modulation amplitude produced a <10% change in
DSSC current, which is linear with light intensity. The DSSC
was operated in series with a 65-Ω resistor and the voltage
across this resistor was measured. The current is determined by
I = V/R. We refer to this as a “quasi-short-circuit” mode, as the
small voltages measured (<20 mV) were close to the short-
circuit condition, compared to open circuit voltages of
hundreds of millivolts. At least 50 transients were averaged
for noise reduction.
Solar Cell Characterization. Current−voltage (J−V)
measurements were made using a Keithley 2400 source/
meter controlled by a PC, while irradiating at 100 mW/cm2
(1
sun) with AM 1.5G simulated sunlight produced by a solar
simulator (Newport 91160), calibrated against a silicon
reference cell with KG5 filter (PV Measurements, Inc., Boulder,
CO). The DSSC active area was 1 cm2
.
■ RESULTS AND DISCUSSION
ZnO Nanorods. ZnO nanorods were fabricated on FTO. A
typical example is shown in Figure 1, having nanorod
dimensions of about 5 μm length and 600 nm diameter and
a number density of 1.2 × 108
rods per cm2
of FTO after 24 h
deposition. The XRD data (Figure 2a) show that the nanorods
grew as crystalline ZnO with the hexagonal wurtzite structure
[space group P63mc (186); a = 0.3249 nm, c = 0.5206 nm].
The data are in agreement with the Joint Committee on
Powder Diffraction Standards (JCPDS) card for ZnO (JCPDS
070-8070). The prominence of the peak assigned to the (002)
plane of ZnO is consistent with predominant ZnO growth
along the c-axis, perpendicular to the substrate, giving the
nanorod morphology.
ZnO−TiO2 Hybrid Films. TiO2 nanoparticles were
synthesized by an autoclave hydrolysis method and ultimately
dispersed in water. On the basis of a Scherrer analysis of the
(010) peak at 26° of an X-ray powder diffraction pattern (not
Figure 1. SEM images of ZnO nanorods in top view (a) and cross
section (b). Scale bar: 1 μm.
Figure 2. X-ray diffraction pattern of (a) ZnO nanorods and (b) ZnO
nanorods coated with TiO2 nanoparticles, on a fluorine-doped tin
oxide substrate. Z and A denote wurtzite ZnO and anatase TiO2,
respectively.

shown), the crystallite size of the TiO2 nanoparticles was found
to be 16 nm, and only the anatase phase was observed. Particle
size is generally similar to crystallite size for this synthesis
method.32
LbL deposition was used to deposit these nano-
particles over ZnO nanorods. Initial trials used a TiO2
deposition time of 5 min per LbL cycle. XRD spectra for
these samples (Figure 2b) have added peaks indicating the
anatase phase of TiO2, while retaining the same ZnO wurtzite
peaks, indicating that the ZnO nanorod crystal structures were
not affected by the deposition and sintering.
Scanning electron micrographs showing the results of
different numbers of LbL layers of TiO2 are shown in Figure
3. The first layer of TiO2 coats the nanorods well, with
successive layers increasing the TiO2 film thickness while a
conformal coating is maintained. However, cross-sectional
images (not shown) revealed that the TiO2 particles did not
reach the bottom of the nanorods. We therefore lengthened the
TiO2 dipping time to 30 min in each LbL cycle. With this
modification, the TiO2 nanoparticles completely penetrate the
nanorod film and evenly coat all surfaces. An example using
three layers is shown in top view and in cross section, in Figure
4.
Dye Loading. If small spheres form a monolayer with
simple square packing over a large cylinder of area A (not
considering the end faces), the added area will be πA. This
implies that three monolayers would increase the surface area
by about an order of magnitude. Dye desorption measurements
(Figure 5) following sensitization with N719 showed that a
ZnO nanorod array (Z) adsorbed 3.5 nmol of dye/cm2
of
geometric film area, whereas a nanorod array coated with three
layers of TiO2 nanoparticles (ZT) adsorbed 13.9 nmol/cm2
, for
a difference of nearly a factor of 4. That this is less than the
factor of ∼10 calculated above is not surprising given the
approximation of square packing and the fact that an LbL film
has considerable porosity.29
We found that 30 layers of TiO2
deposited on a flat FTO substrate had a dye loading
comparable to that of the ZT hybrid film. Therefore, 30-layer
TiO2 films (T) were used in the device performance
experiments for comparison with the composite films. The
thickness of the 30-layer TiO2 film is approximately 0.6 μm as
measured by scanning electron microscopy (not shown). LbL
TiO2 films have similar morphology to doctor-bladed TiO2
films29
and similar performance in DSSCs when deposited at
comparable thickness.33
For reference, a dye loading for a
typical 10-μm film would be ca. 100 nmol/cm2
.34,35
Electron Transport. Figure 6a shows representative current
transients at quasi-short-circuit conditions for Z, ZT, and T
films. Each transient is well-fit by a single exponential decay of
Figure 3. SEM images of ZnO nanorods coated with zero (a), one (b),
three (c), or five (d) layers of TiO2 with 5-min immersion periods.
Scale bar: 1 μm.
Figure 4. ZnO nanorods coated with three layers of TiO2
nanoparticles using 30-min dipping times shown in top view (a) and
cross section (b). Scale bar: 1 μm.
Figure 5. Uptake of N719 by a ZnO nanorod array (Z), a nanorod
array coated with three layers of TiO2 nanoparticles (ZT), and film of
30 layers of TiO2 nanoparticles (T), all on FTO.

the form y = y0 + A exp(−t/τtr), where τtr is the characteristic
time for electron transport. The fitted time constants τtr over a
range of light intensities are plotted against the corresponding
short-circuit current density JSC in Figure 6b. For TiO2, the
power-law decrease of τtr with increasing JSC is typical of DSSCs
and is well-described by a trapping−detrapping model.36
Time
constants for the other samples are relatively constant at about
0.29 ms for ZnO nanorods and 0.46 ms for ZnO nanorods
coated with TiO2 nanoparticles. The invariability of τtr with JSC
for the Z and ZT samples strongly suggests that a limit of the
measurement has been reached, most likely due to an RC time
based on the resistance of the cell and resistor connected in
series and the capacitance of the semiconductor/electrolyte
interface.21
These time constants should therefore be taken as
an upper limit on the electron transport time of the ZnO
nanorod-based materials. Since the RC time may differ for
different samples, the results shown in Figure 6b cannot
differentiate between the τtr value of Z and ZT films, but they
do demonstrate that electron transport in these samples is at
least 2 orders of magnitude faster than transport through
nanoparticulate TiO2.
Device Performance. Figure 7a compares the current−
voltage characteristics of the DSSCs made from the three
different films in a conventional iodide/triiodide electrolyte.
Each trace represents the mean of triplicate measurements, and
the dotted lines indicate one standard deviation from the mean
at each voltage. The ZT hybrid film strongly outperforms the Z
film, indicating that the higher surface area and dye loading of
the ZT film translate into higher photocurrents. Under these
conditions, the TiO2-only film T outperforms both Z and ZT,
which is to be expected since TiO2 nanoparticles are known to
give the best performance of any material when recombination
rates are low.
The benefit of the hybrid structure is revealed when using
ferrocene/ferrocenium as a model alternative redox couple with
high recombination rates (Figure 7b). We focus here on the
changes in the short circuit current (JSC), as these report on the
electron collection efficiency. We note that faster electron
transport can improve JSC due to higher electron collection
efficiency, but it cannot improve the open-circuit voltage (VOC)
since no electron transport occurs at open circuit. Values of JSC
extracted from Figure 7 are compared in Figure 8. The rapid
Figure 6. (a) Transients for decay of quasi-short-circuit current in
response to square-wave modulation of light intensity, with single-
exponential fits. The inset shows TiO2 transient at a longer time scale.
(b) Fitted electron transport time constants versus quasi-short-circuit
current for T, ZT, and Z films.
Figure 7. Current−voltage (J−V) characteristics for solar cells using
ZT, Z, and T films and electrolyte based on (a) I−
/I3
−
or (b) Fc/Fc+
,
under illumination with 100 mW/cm2
AM1.5G simulated sunlight.
Solid and dotted lines show mean ± SD for triplicate samples. The
inset in part b magnifies the T trace.
Figure 8. Short circuit current of DSSCs constructed with I−
/I3
−
and
Fc/Fc+
electrolyte using Z, ZT (hybrid), and T films under
illumination with 100 mW/cm2
AM1.5G simulated sunlight.

scavenging of conduction band electrons by Fc+
almost
completely short-circuits a cell with a conventional TiO2
nanoparticulate film (T), resulting in a barely visible J−V
trace with a short-circuit current of only 16 μA/cm2
. A ZnO
nanorod film (Z) has much better performance, with JSC = 0.72
mA/cm2
. The hybrid film ZT has the best short circuit current
(0.93 mA/cm2
) due to its higher surface area and dye loading.
The difference in performance here is smaller than with I−
/I3
−
,
which we attribute to (1) recombination of electrons from the
TiO2 with the Fc+
during the time between electron injection
and electron transfer from TiO2 to the ZnO, and/or (2)
impeded electron transfer from the TiO2 into the ZnO, as will
be discussed below. The surprising result that the Z film obtains
a higher current in an Fc/Fc+
electrolyte than in an I−
/I3
−
electrolyte may be the result of corrosion of ZnO by the latter
electrolyte,37
which we have observed in SEM images (not
shown) of ZnO nanorods before and after exposure to I−
/I3
−
.
Energy Barrier. Transfer of electrons from the TiO2
nanoparticles to the ZnO nanorods must be downhill in
energy. Assuming that electron transfer occurs between the
conduction bands of the two materials and that electrons are
rapidly thermalized within the conduction bands, this requires
that the conduction band minimum (CBM) of ZnO lie at a
more positive potential than that of TiO2. The conduction band
edges of ZnO and TiO2 would be expected to lie quite close to
each other in energy, and the relative difference between the
two is difficult to predict. As an indirect measure of this band
edge offset, we measured current−voltage curves in the dark
and in the absence of dye. The measured “dark current” is due
entirely to recombination at the semiconductor/electrolyte
interface.
In this measurement, electrons flow from the FTO into the
semiconductor and reduce triiodide to iodide, which is opposite
in sense to a photocurrent at voltages below VOC. As TiO2
nanoparticles are added to ZnO nanorods, if the CBM of ZnO
is more negative than that of TiO2, then electrons should
transfer easily from ZnO into TiO2, and the added surface area
provided by the TiO2 nanoparticles should increase the dark
current. On the other hand, if TiO2 has the more negative
CBM, electron transfer into TiO2 should be impeded, and the
TiO2 should reduce the dark current by reducing the ZnO
surface area that is in contact with the electrolyte. The result
shown in Figure 9a is that the ZT film has more dark current
than the Z film, which is consistent with ZnO having the more
negative CBM. The dark current from ZT is close to that of a
TiO2-only film (T) of comparable surface area, based on the
above dye desorption measurements. We note that some of the
differences seen in Figure 9 may reflect different reactivities of
ZnO and TiO2 toward I3
−
, as suggested by the longer electron
lifetime observed in ZnO.9
For the reverse experiment, we grew short (1-μm) ZnO
nanorods on a TiO2 film by adding two layers of a standard
seed layer (drop-coating 5 mM zinc acetate in ethanol, allowing
to evaporate, and heating at 350 °C) to a TiO2 film followed by
immersion in a ZnO CBD solution (the same as for the longer
rods) at 90 °C for 4 h (Figure 10). This TZ hybrid film should
have more dark current than a plain T film if and only if ZnO
has the more positive CBM. On the contrary, the addition of
ZnO significantly reduces the dark current (Figure 9b). Both
sets of results, then, are consistent with a more negative CBM
for ZnO, which would tend to pose a barrier to the desired
electron transfer from TiO2 to ZnO (Figure 11). Given the
good TiO2 coverage in the ZT films (see Figure 4), it is likely
that electrons photoinjected into TiO2 can travel to the
conducting glass substrate along a purely TiO2 path on the
outside of the nanorod. This allows high current in ZT samples
in an I−
/I3
−
electrolyte, where electron diffusion lengths38
are
much longer than the nanorods in these samples (about 5 μm).
However, in the presence of Fc/Fc+
, recombination claims
many of these electrons, reducing the benefit of the TiO2
nanoparticulate coating. The fact that ZT still outperforms Z
(and T) in a Fc/Fc+
electrolyte suggests that some electrons are
able to transfer from TiO2 to ZnO, perhaps due to a small
energy barrier that can be thermally overcome by a fraction of
the conduction band electrons at room temperature, resulting
in slow transfer kinetics. Our laboratory is currently at work on
strategies to eliminate this energy barrier.
Figure 9. Dark currents of dye-free films: (a) Z, ZT, and T and (b) TZ
and T.
Figure 10. ZnO nanorods (1 μm) grown atop a 30-layer LbL TiO2
nanoparticulate film. Scale bar: 1 μm.

■ CONCLUSION
We have successfully synthesized a composite nanostructure
consisting of ZnO nanorods coated with TiO2 nanoparticles,
using facile wet-chemical methods. A coating of three
monolayers of TiO2 nanoparticles increased the dye uptake
of the film by a factor of 4 compared to ZnO nanorods only.
Although a TiO2-only film of similar dye loading outperforms
the ZnO−TiO2 film with I−
/I3
−
electrolyte, the nanocomposite
film dramatically outperforms the TiO2 film when using the
fast-recombining Fc/Fc+
electrolyte and modestly outperforms
the ZnO nanorod-only film. Transfer of electrons from the
TiO2 to the ZnO is impeded by an energy barrier, as the
conduction band minimum of ZnO lies at a slightly more
negative potential than that of TiO2, and more work is needed
to remove this barrier. This nanocomposite photoanode points
to a class of structures that can provide both fast transport and
high surface area, enabling DSSCs that are tolerant of
electrolytes with higher recombination rates than are found
with the conventional iodide/triiodide couple.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: agrios@engr.uconn.edu.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was funded by the University of Connecticut
Research Foundation. The authors thank Dr. Teresa Lana-
Villarreal for providing preliminary samples of ZnO nanorods.
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Figure 11. Energy level schematic of the ZT hybrid film showing the
energetics of the individual components used in the cell.

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