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Vertically-aligned nanostructures of ZnO for excitonic solar cells: a review

Irene Gonzalez-Valls and Monica Lira-Cantu*
Received 7th July 2008, Accepted 29th September 2008
First published as an Advance Article on the web 25th November 2008
DOI: 10.1039/b811536b

This work is a brief account of the most recent developments observed in the application of ZnO
nanostructured materials in excitonic solar cells (organic, hybrid and dye sensitized solar cells). Special
emphasis is made to one-dimensional (1D), vertically-aligned nanostructures (nanowires NW,
nanorods NR) of ZnO semiconductor oxide and the extensive research work invested in recent years for
Published on 25 November 2008 on http://pubs.rsc.org | doi:10.1039/B811536B

its application as an electron acceptor material in solar cells. Our aim is to give the reader a broad
overview of this semiconductor oxide and to understand the causes, advantages and disadvantages, for
its application in a well-aligned nanostructure form. We briefly describe the most applied
methodologies for its synthesis as well as the effect on surface area, electron transport and charge
recombination when it is applied as an electron transport material in excitonic solar cells (XSCs). The
importance of low-cost and easy-scalable synthesis techniques, as well as stability issues on these solar
cells are discussed. Finally, we include a brief analysis of the possible future trends for the application of
this interesting semiconductor oxide in XSCs.

Introduction of photons from sunlight produces an exciton, a tightly bound

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electron–hole pair, which must be split for charge generation.

In our need for highly efficient, low cost and CO2-free sources of
energy, the conversion of sunlight into electricity has material-
ized as one of the most encouraging alternatives. Among the
different emerging photovoltaic options, XSCs are promising
candidates for achieving the basic criteria for large scale
commercialization: they are highly efficient devices that employ
low-cost materials and offer the possibility of being fabricated by
large-scale and inexpensive (solution processing) techniques.1,2
The most important examples of XSCs are Organic Solar Cells
(OSC), Hybrid Solar Cells (HSC) and Dye Sensitized Solar Cells
(DSC) and their main difference with respect to conventional
inorganic solar cells (ISC) resides in their photoconversion
mechanism. In ISCs the absorption of light leads to the direct
formation of free electron–hole pairs in the bulk of the material
and the direct production of charge carriers.1,2 In XSCs, the
presence of organic semiconductors implies that the absorption
Centro de Investigacio en Nanociència i Nanotecnologia, CIN2
(CSIC-ICN). Campus UAB, Edifici ETSE 2nd Floor, Bellaterra,
Barcelona, Spain E-08193. E-mail: monica.lira@cin2.es
Exciton dissociation takes place at the interface between the
constituent semiconductors. Thus, XSCs encompass photovol-
taic systems largely dependent on interfacial processes. The reli-
ance on the crystallinity of the materials for photovoltaic
response indicates that while highly crystalline and chemically
pure materials are required for ISCs (e.g. silicon), less pure and
therefore less expensive compounds can be applied in XSCs (e.g.
TiO2).2,3 Although ISCs have the advantage of high efficiency
(
20%) and long lifetime (25 y), state-of-the-art XSCs have
improved enormously in the past few years demonstrating
efficiencies as high as 11.3% and lifetimes of 10 000 h for
DSC4,5,126,158 and about 5–6% efficiency for OSC.5 These prom-
ising results have encouraged many research groups, as well as
industrial partners, to investigate different ways to improve
XSCs performance, especially device efficiency and lifetime.
In this review, an introduction to the application of ZnO
nanostructured electrodes is given, particularly vertically-aligned
nanostructures like nanowires (NW), nanorods (NR), nanotips
or similar. We discuss XSCs where inorganic semiconductor
oxides, such as ZnO, act as the electron transport material, i.e.

Broader context
Excitonic solar cells (organic, hybrid and dye sensitized) are the best examples of efficient and environmental friendly energy-
conversion devices. The possibility of being fabricated by low-cost and easy-scalable solution processing techniques has driven the
technology into the marketplace. Nanostructured materials are key constituents of these solar cells. The improvement in photo-
voltaic efficiency is achievable by the application of advanced structures built at a nanoscale: nanoparticles, nanorods, nanocables,
nanosheets, core-shell, among many others. ZnO has become a promising semiconductor oxide when applied as an electron
transport material. It presents properties closely related to the best semiconductor oxide used up to date, TiO2, but contrary to the
former, it is possible to obtain ZnO in a wide variety of nano-forms by low-cost and scalable synthesis methods. Yet another
breakthrough in ZnO-based photovoltaics seems possible if nanostructures could be obtained in a controlled, well-ordered and
reproducible manner. This review describes the evolution and future potential for the application of nanostructured ZnO in next-
generation excitonic solar cells.

This journal is ª The Royal Society of Chemistry 2009 Energy Environ. Sci., 2009, 2, 19–34 | 19

HSC and DSC but not OSCs.2,6 We summarize the most applied
techniques used for ZnO fabrication and review the advantages
and disadvantages observed during its application. We discuss
the need for higher solar cell stability and the development of
synthesis techniques that are easily scalable and produce well-
aligned, ordered and reproducible nanostructures at the nanosize
scale. Finally, we give a brief description of the possible future
development in XSCs.
Excitonic solar cells: organic (OSC), hybrid (HSC)
and dye sensitized solar cells (DSC)
Classification
Published on 25 November 2008 on http://pubs.rsc.org | doi:10.1039/B811536B
In XSCs the transformation of photons of light into electrical
energy takes place in three basic steps: (1) Photon absorption and
exciton formation, (2) Charge separation or exciton dissociation
and (3) Charge transport. The active materials (donors and
acceptors) required for these processes to take place can be
organic or inorganic semiconductors. If we classify XSCs by the
type of semiconductor material applied, then we can identify
three general types: OSCs, HSCs and DSCs. In OSCs both
materials are purely organic semiconductors, for example the
blend between two conducting organic polymers or a mixture
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between C60 derivative and a conjugated polymer.5,29 In the case
of HSC, the device is characterized for the presence of, at least,
one phase of an inorganic semiconductor (e.g. CdSe, TiO2) and
a second phase of a conducting organic polymer. Although DSC
can be classified also as HSC (due to the application of organic
and inorganic materials), here we consider DSC as a different
type of XSC, due to the presence of a liquid electrolyte.† The
inorganic materials in XSCs can be in any form (nanoparticles,
nanorods, tetrapods, nanosheets, etc).
† Excitonic solar cells can also be classified by the type of n–p junction.
Thus, a bulk-heterojunction solar cell will be the one applying
semiconductor materials (e.g. organic C60 derivatives like PCBM, or
inorganic ZnO or CdSe nanoparticles) in direct physical contact with
a conjugated polymer (see ref. 29). In DSC we find two types of
junctions: a bulk heterojunction made by the TiO2 nanoparticles and the
light-harvesting Dye, and an electrochemical junction between the
Dye/TiO2 electrode and the redox electrolyte (see ref. 3).
Irene Gonzalez-Valls studied
chemistry at the University of
Barcelona where she received
her laureate degree in organic
chemistry in 2006. She obtained
a Masters degree in organic
chemistry at Prof. Roeland J.
M. Nolte’s laboratory (Nether-
lands). She is currently pursuing
PhD studies at the Nanoscience
and Nanotechnology Research
Centre (CIN2, CSIC-ICN).
Her research is devoted to the
synthesis of well-ordered nano-
structured oxides for excitonic
solar cells applying hydrothermal, electrochemical and nano-
fabrication techniques.
20 | Energy Environ. Sci., 2009, 2, 19–34
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The application of organic semiconductors in XSC presents
some drawbacks, like low electronic mobility of, for example,
conducting organic polymers, with values typically around
104cm2V1s1.7 Thus, HSCs have been shown to enhance
performance by the introduction of electron transport and
charge transfer materials.7,8,11 The formation of a donor–
acceptor junction yields a charge-separation state that should
be within the organic semiconductor diffusion length, this is,
about 20 nm.8 To enhance organic solar cell performance
Hegeer and Friend et al., proposed the bulk-heterojunction
concept.9,10 In this concept an intimate mixture in the nanoscale
range between the n-type (C60 derivatives) and p-type (polymer)
materials allows for a large-area donor–acceptor interface for
efficient exciton dissociation.11 The electron is accepted by the
material with greater electron affinity and the hole by the
material with lower ionization potential.12 Conducting organic
polymers act as the hole transport material (HTM) in these
systems, although other organic semiconductors can be applied.
The concept has been extended to other n–p type systems,
where inorganic materials are applied as electron acceptors such
as inorganic semiconductors and semiconductor oxides. These
types of solar cells known as HSC are easily recognized by the
direct physical contact between the electron transport material
(ETM) and the hole transport material (HTM), or the inor-
ganic and organic semiconductors, respectively. In HSC, the
donor and the acceptor semiconductors are found in a direct
physical contact so the exciton dissociation takes place effi-
ciently at the interfaces. Thus, one of the active materials has
the dual function of light-harvesting and charge carrier trans-
port (hole or electron) while the other phase is only responsible
for (the opposite) charge carrier transport. Although a similar
mechanism for exciton dissociation is observed in the DSC,3
there is an important difference. The light-harvesting and
charge transport is carried out by different active materials: in
DSC a Dye is absorbed on the surface of a nanostructured
semiconductor oxide, usually nanoparticles of TiO2, and is
responsible for light absorption. Upon excitation an electron is
injected into the conduction band of the oxide and transported
through the nanoparticle network; an organic hole conductor
(liquid redox electrolyte) is responsible for the regeneration
Dr Monica Lira-Cantu received
her PhD in 1997 at the Institute
of Materials Science of Barce-
lona (ICMAB) working on the
application of hybrid organic–
inorganic materials for lithium
batteries. From 1999 to 2001 she
worked as a research scientist at
ExxonMobil Research & Engi-
neering (USA) and returned to
Spain in 2002. She is currently
a permanent research scientist at
the Nanoscience and Nanotech-
nology Research Center (CIN2,
CSIC-ICN) in Barcelona
(Spain). Her research interests are the synthesis and application of
nanostructured materials for excitonic solar cells and sensors
This journal is ª The Royal Society of Chemistry 2009

of the Dye. The spatial separation between the light-harvesting
compound (Dye) and the charge carrier material in DSC
seems to be the key to their higher efficiency and longer life-
time.13,14 Nevertheless, it is not clear yet the advantages and
disadvantages in terms efficiency and lifetime proposed for this
separation.15
There are many inorganic semiconductors applied as nano-
structured materials for XSCs; semiconductor oxides such as
TiO2,16–24,74,113 Nb2O5,22–25 ZnO,23,25–28,108 SnO2,30 CeO2 or CeO2-
TiO2,23,25 or inorganic semiconductors applied in HSCs; CdSe,31
copper indium disulfide CuInS2,32–35 CuInSe2 and CuInTe2,35
PbS,36–40 GsAs,41,42 PbSe,43 or HgTe nanocrystals,44,46 among
others. As will be explained, ZnO has recently emerged as
Published on 25 November 2008 on http://pubs.rsc.org | doi:10.1039/B811536B
a promising candidate due to its semiconducting properties
which are very similar to the most used semiconductor oxide,
TiO2, but are especially due to the possibility of obtaining ZnO
nanostructures by easy and low-cost techniques.45
Why vertically-aligned nanostructures?
In a HSC where the light-harvesting compound is an organic
semiconductor (e.g. a conducting organic polymer) the applica-
tion of vertically-aligned oxide nanostructures arise from the
need to overcome problems observed at the bulk heterojunction.
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In the former type of heterojunction, an inorganic semiconductor
oxide nanoparticle is dispersed within the conjugated polymer
matrix. The resulting oxide nanoparticle/polymer blend must be
annealed to improve nanoparticle connection and to favor elec-
tron pathway through the electrode. Nevertheless, these devices
are still limited by incomplete exciton dissociation due to the
isolation of some nanoparticles from each other after thermal
treatment. The later eliminates the possibility of efficient electron
transport reducing overall device efficiency. A nanostructured
thin film made of vertical-aligned nanowires provides a higher
interfacial area between the donor and the acceptor material
(polymer/oxide, respectively) with highly-efficient electron
transport pathways. In the case of DSCs, the replacement of the
nanoparticle electrode by vertically-aligned nanostructures has
also emerged as a possible way to obtain faster electron transport
thus improving solar cell efficiency. Moreover, the urge to
replace problematic liquid electrolytes in DSC by solid hole-
conductors with slower kinetics6 impels the application of faster
electron transport materials like the vertically-aligned nano-
structures. Fig. 1 shows a schematic representation of a XSC
applying vertically-aligned ZnO nanostructured electrode. The
hole conductor can be a conducting organic polymer in HSC and
solid-state dye sensitized solar cells (ss-DSC), and a redox liquid
electrolyte in the case of DSC.
Zinc oxide as nanostructures: the basics
Zinc oxide (ZnO) is well-known for its multiple properties; it
exhibits semiconducting, piezoelectric or pyroelectric properties,
among many others. It can be obtained in a wide variety of
nanostructures; nanoparticles, core-shell nanoparticles, tetra-
pods, hierarchical structures, nanoflower, nanosheets, vertically-
aligned nanosheets, nanowires, nanorods, nanotips, nanotubes
or, more recently, branched nanostructures have been reported.47
Thus, it is not surprising to find ZnO in many devices:
This journal is ª The Royal Society of Chemistry 2009
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Fig. 1 Schematic representation of an XSC applying ZnO nanowires as
the electron transport material. In a DSC the ZnO nanowires are loaded
with an adsorbed layer of a light-harvesting Dye and the hole conductor
is typically a liquid electrolyte with a I/I3 redox couple. In a HSC the
hole conductor and light-harvesting compound is a conjugated polymer.
optoelectronics, sensors, biomedical, electrochemical, etc. The
control of its structures at nanosize level provides novel and
enhanced electrical, mechanical, chemical and optical properties
that help us to understand the many processes occurring in new
generation solar cells49 Its development has followed a trend
based on the need to improve efficiency by increasing surface
area (enhancing the interface between semiconductor constitu-
ents), or the application of single-crystalline nanostructures that
are able to reduce electron hopping steps and enhance electron
mobility.48 Large amounts of information and reviews about
ZnO properties, synthesis, characterization and applications are
available in the literature,47–50 so we have limited this section to
a general overview about some of the most interesting aspects
of this oxide, especially those related to its application in solar
cells.
ZnO properties
Despite the fact that TiO2 is the most used semiconductor oxide
in XSCs, ZnO is being intensely investigated because of its
similarities with the former, i.e. it is a wide band gap semi-
conductor oxide (3.37 eV) with a conduction band edge located
at approximately the same level as TiO2. The electron mobility of
ZnO has been proven to be higher than TiO2.51,52 The longer
electron lifetimes observed for ZnO means lower charge recom-
bination which is beneficial for solar cell performance. An
important advantage of ZnO over TiO2 is that it can be
synthesized applying a wide range of synthesis techniques;47–50
to obtain a great variety of different morphologies and nano-
structured electrodes, especially vertically-aligned nano-
strucutres.62 Some of these methodologies have been shown to be
easily scalable and suitable for many substrates,45 which makes
ZnO very attractive for fabricating complete solar cell devices by
applying low-cost solution processing techniques. Surprisingly,
the highest efficiency XSCs applying ZnO have only reached
6–7%53,161 which is less than the 11.3% obtained with the best
DSC applying TiO2.4 Thus it is important to have carefully
control parameters, such as dye or polymer concentration, pH or
sensitization with time, in order to improve solar cell efficiency.
Dye immersion time and ZnO solubility. In DSC, the reasons
for the lower efficiency of XSC applying ZnO are not yet clear
Energy Environ. Sci., 2009, 2, 19–34 | 21
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but it seems to be related to the stability of the oxide surface Synthesis methods: requirements to obtain optimal
and surface area density. In DSC, some authors have reported nanostructures
that, contrary to TiO2, low dye absorption time is required for
The synthesis of 1D ZnO nanostructures have been recently
higher solar cell efficiency60,80,81 which indicates some basic
reviewed for semiconductor oxides in general56 and for ZnO
differences in surface chemistry between these two oxides. Keis
nanostructures in particular.57,58 Nanostructures of ZnO can be
et al. reported the difference between dye-sensitization on TiO2
found as simple nanoparticles or as nanorods, nanobelts,
and ZnO.52 In TiO2 there is strong adsorption of the carboxyl
branched nanorods, nanowires, ultranarrow nanobelts, hierar-
groups to the surface which favors monolayer growth and
chical nanostructures, nanocombs, nansoprings, nanospirals,
usually 20–24 h immersion time needed. In ZnO, however, the
nanorings, core-shell nanostructures, nanocages, nanoflowers,
sensitization process follows more complicated steps: diffusion
among many others.54,56 There are many possible methods of
of the dye, adsorption on the ZnO surface, dissolution of Zn
fabricating ZnO nanomaterials and the observed properties
surface atoms and formation of [Dye–Zn2+] complex.52
depend to a great extent on the preparation conditions. It is also
Moreover, the acidity of the –COOH binding groups from the
Published on 25 November 2008 on http://pubs.rsc.org | doi:10.1039/B811536B

difficult to establish the optimal synthesis methodology for solar

Dye affects the chemical stability of the ZnO, which dissolves
cell applications because the efficiency of a XSC depends on
and precipitates as a [Dye–Zn2+] complex, responsible for the
many aspects and not only on ZnO nanostructure, like thin film
poor electron injection from the Dye.51,52 The formation of this
thickness, nanostructure dimension or surface area and also on
complex has not been observed for TiO2. In ZnO the surface is
overall device preparation such as the polymer or dye applied,
predominantly positively charged at a pH below the point of
back contacts, active area, etc. Up to date, the most attractive
zero charge (pzc) and negatively charged above it. The pH for
synthesis technique for obtaining well-aligned nanostructures of
the dye loading process is usually around 5 but in ZnO
ZnO for photovoltaic applications is the hydrothermal method
proceeds at about 9.52 Other groups have also reported the
(HT). Although more expensive and less straight-forward
effect that ZnO treatments in basic media (KOH) has on the
techniques have been applied, including high-temperature vapor-
absorption–desorption of dye molecules.157,159–161 Problems
phase deposition techniques (physical and chemical vapor-phase
related to the instability of the ZnO surface, in the presence of
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deposition),69 metal organic vapor deposition (MOCVD), chem-

conducting polymers, have not been addressed yet for HSC.
ical vapor deposition (CVD), atomic layer deposition (ALD),
For example, Janssen et al. reported that the stabilization of
among others (see Table 1 and 2).
polymers increases with increasing nanoparticle loading in
In general, the hydrothermal technique is based on a two-step
blends made by polymers/ZnO.116,125 This stabilization is
method involving the coating of a substrate with ZnO nano-
clearly observed when blends are applied and is the basic
particles (seeds) of less than 10 nm in diameter. Every ZnO seed
principle for some devices.155,156 Nevertheless, Krebs et al.
works as a nucleation site for the formation of ZnO nanowires
reported that the application of polymers containing –COOH
under mid-wet conditions.70 The synthesis conditions, like zinc
groups result in the stabilization of the polymer/ZnO nano-
concentration in solution, growth time or growth temperature,
particles, enhancing the lifetime of the solar cell up to
determine the final nanorod dimension and quality. Also, the
hundreds of hours.119 In HSC these studies are very recent and
stability of precursor ZnO seeds (nanoparticles) or the substrates
in-depth research efforts are needed to understand this
to be applied are important factors affecting the final ZnO
behavior.
nanostructures with reproducible results. As an example, Fig. 2
shows a graph of the variation of nanorods length and diameter
Wettability. Another example considers one of the main
depending on the additives added during synthesis. In this case,
problems observed in XSCs when applying high surface area
the authors applied an additive, polyethylenimine (PEI)59 and
electrodes: wettability. The organic semiconductor (dye, poly-
searched for large surface area electrodes so that a higher amount
mer or similar) must penetrate and reach the whole surface area
of Dye absorption can be obtained when applied in a DSC.
of the electron transport oxide for good charge transport, a task
Nanorods as long as 30 mm were observed when PEI additive was
that is sometimes problematic during solar cell fabrication. The
used, without additive the length of the nanorods was not more
possibility of overcoming these problems may be found within
than 5 mm, and their diameters also increased with time (see
the ZnO surface itself, which is known to present high sensi-
Fig. 2). Yet, the longest nanorods, 20–25 mm, show only 1/5 of
tivity towards conditions of humidity or UV irradiation22–24
the surface area of an electrode made of nanoparticles. The best
which affect its interaction with dyes, polymers or other organic
photovoltaic efficiency was not higher than 1.5%, applying
semiconductors.52,54,80,81 Some laboratories have reported
nanorods of 16–17 mm in length and between 120–300 nm in
properties of superhydrophobicity and superhydrophilicity on
diameter.59
ZnO under different conditions. These properties can be
The resulting vertically-aligned nanorods present an aspect
reversibly switched by the alternation of UV irradiation and
similar to those shown in Fig. 3a. In this case, however, the
dark storage. The effect has been reported to be related to the
authors applied chemical bath deposition technique to grow ZnO
interaction between surface photosensitivity and the nano-
nanorods at 95  C, a method closely related to the hydrothermal
structure of the oxide and should be analyzed for its relation to
technique described above. The NRs obtained in this case, had
solar cell activity.55 These sometimes contradictory results,
thinner diameters, about 50 nm, closer in value to the electron
indicate that ZnO presents many other properties, which are
diffusion length (
20 nm) of organic semiconductors. The
still under investigation or not yet analyzed under conditions of
obtained ZnO nanostructures can be characterized by scanning
sunlight irradiation or in the interaction with components of the
electron microscopy (SEM), transmission electron microscopy
solar cell.

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Table 1 Application of vertically-aligned nanostructures of ZnO in dye sensitized solar cells (DSCs). HT: Hydrothermal, SP: Spray Pyrolysis, S:
Sputtering, PCEM: Pulsed Current Electrolysis Method, TM: Template, MOCVD: Metal Organic Vapor Deposition, VD: Vapor Deposition, CVD:
Chemical Vapor Deposition, TD: Thermal Decomposition, ALD: Atomic Layer Deposition, CBD: Chemical Bath Deposition, EQ: Electrochemical
Deposition

Nanorod (NR) or nanowire (NW) dimensions

Synthesis Light intensity Jsc Voc FF h
Ø (nm) L(mm) method Dye (mW/cm2) (mA/cm2) (V) (%) (%) Ref.

150 1.8 MOCVD porphyrin- — — — — 0.1 82

based
3.5 HT + VD N719 100 1.17 0.76 25 0.22 83
8 HT N719 100 1.3 0.67 32 0.3 65
110 4–5 HT N3 23.6 0.49 0.34 45 0.32 84
190 7 HT N719 100 1.5 0.8 40 0.38 85
3.2 MOCVD N719 100 2.04 0.662 41 0.55 86
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70–100 5 CVD N719 100 1.2 0.82 61 0.60 87

500 10 HT N719 100 1.94 0.45 70 0.62 88
60 1 HT + TD Rose bengal 2 0.049 0.55 55 0.7 89
50 4.6 CVD Mercurochrome 100 3.30 0.516 49 0.83 90
130–200 16–17 HT N719 100 5.3–5.85 0.61–0.71 36–38 1.2–1.5 59

150 4.5 ALD + TM N719 90 3.3 0.739 64 1.6 91
150 2.6 HT N719 100 2.88 0.6 54 0.94 93
150 4.0 HT N719 100 3.97 0.59 54 1.27 93
150 5.1 HT N719 100 4.84 0.61 48 1.42 93
150 10.8 HT N719 100 5.37 0.64 49 1.69 93
100–120 14 HT N719 100 6.79 0.54 50 1.7 94
200 11 HT N719 100 5.5 0.65 53 1.9 95
30–70 0.24 HT N3 42 1.02 0.52 39 0.5 96
30–70 0.85 HT N3 42 1.96 0.56 42 1.1 96
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30–70 1.1 HT N3 42 3.46 0.57 38 1.8 96

30–70 1.9 HT N3 42 5.18 0.55 36 2.4 96

Others: Nanoparticles (NP), doped NP, Mixed NP + NW (Mix), Branched NW (b-NW), Nanosheets (NS), Terrace NW (t-NW), Nanotube (NT),
Porous single crystal (PSC).

Synthesis Light Jsc Voc FF h

Structure Dimensions method Dye intensity (mA/cm2) (V) (%) (%) Ref.

b-NR 100 nm NR 20 nm MOCVD N719 100 1.62 0.74 38 0.5 64

branches
t-NR CBD + HT N719 8.0 0.42 27 0.9 104
b-NR MOCVD N719 100 3 1.1 103
Mix 30–300 nm HT Mercurochrome 100 6.28 0.61 62 2.37 99
Mix 30–300 nm NW HT Mercurochrome 100 9.06 0.58 60 3.2 100
15 nm NP
NS N-719 100 13.8 0.56 44 3.3 97
NS Pyrolysis N-719 100 11.2 0.58 3.9 102
NT 210 nm pore ALD + TM N-719 100 3.3 0.73 64 1.6 92
329 nm spacing
NP 20 nm Commercial N-719 100 6.0 0.701 49 1.8 171
NT 11 nm CBD + Pyrolysis N-719 100 12.6 0.67 48 4.1 98
NT 11 nm CBD + Pyrolysis N-719 14 1.5 0.60 72 4.6 98
NP N-719 100 1.3 0.56 68 5 53
TiO2/NR NR: 100 nm L Sol–gel N3 11.4 0.76 50 5.8 105
25 nm W
Pop-corn 100 nm aggregates of Hydrolysis N3 100 18.7 0.63 45.1 5.4 172–173
10–15 nm nanoparticles (6.2)
Doped NP 26–60 nm Sol–gel N-719 10 6.49 0.79 37 6 101
NP 20–30 nm Commercial N-719 100 18.11 0.62 58 6.58 157
PSC — EQ D-149 100 — — — 7.2 159–161

(TEM), high-resolution TEM (HRTEM), powder X-ray
diffraction (XRD), etc. HRTEM analyses demonstrates the
synthesis of a high-crystalline ZnO structure (Fig. 3b) as required
for high electron mobility.48
As can be observed in Table 1 and 2, vertically-aligned
nanostructures of ZnO have been extensively applied in XSCs.
Nevertheless, in terms of vertical and well-ordered alignment, the
current synthesis methodologies applied for their fabrication
produce irreproducible nanostructures with dimensions that are
too far away from ideal electrode characteristics. Synthesis
conditions must be controlled carefully, a minimal change in
synthesis condition or even in the roughness of the underlying
substrate can affect nanorods dimension.61,162 For example,
images in Fig. 4 were obtained with careful control of the
synthesis conditions applied, from concentration of reactants to
growth time and temperature, as well as additives. The only

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Table 2 Some examples of HSC applying ZnO nanostructures as the electron transport material and conducting polymers as the hole transport
material. HT: Hydrothermal, SP: Spray Pyrolysis, S: Sputtering, PCEM: Pulsed Current Electrolysis Method, TM: Template, DF: Dense Film, NP:
Nanoparticles, NR: Nanorods

Type of ZnO
Synthesis Organic Light intensity Jsc Voc FF h
D (nm) L (mm) technique component Substrate (mW/cm2) (mA/cm2) (V) (%) (%) Ref.

NP — — SP, S MEH–PPV ITO 100 50 nA 0.41 — — 109

0.28
Mesoporous/NP — — TM P3HT ITO 100 0.44 0.46 — — 118
NP — — HT P3HT ITO 100 9.55 0.31 42 — 120
P3HT/Perylene
NP — — HT P3MHOCT ITO 100 0.7 0.65 56 0.05 119
NR 110 1.25 HT P3HT + ITO 100 1.73 0.30 38.9 0.20 107
interfacial modifier
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DF — — HT Dye/P3HT ITO 100 0.5 0.22 — 0.03 108

P3HT/P3HT
NP 70/150 — HT Dye/P3HT ITO 100 2.0 0.17 — 0.05 108
P3HT/P3HT
NR 60/100 0.5/1 HT Dye/P3HT ITO 100 3.2 0.22 — 0.20 108
P3HT/P3HT
NP (55%) HT PPAT ITO 100 0.79 0.71 54 0.30 121
NR 100 0.25–0.5 HT P3HT ITO 100 2.2 0.44 56 0.53 110
NP (55%) — — HT PPHT ITO 100 0.38 0.64 54 0.12 122
NP (55%) — — HT Dye/PPHT ITO 100 1.45 0.62 61 0.55 122
NR 50 0.18 PCE P3HT Au-coated ITO 100 0.30 0.335 40 0.04 106
NR 50 0.18 PCE P3HT/TiO2 Au-coated ITO 100 1.96 0.38 39 0.29 106
NR ZnO/TiO2 50 0.18 PCE P3HT/TiO2 Au-coated ITO 100 2.20 0.40 35 0.31 106
NR ZnO/TiO2 50 0.18 PCE P3HT/TiO2–Pyr Au-coated ITO 100 2.67 0.49 45 0.59 106
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NP 4.9 — HT P3HT ITO 100 2.38 0.70 60 0.9 116

NP — — HT P3HT ITO 100 3.5 0.83 50 1.4 114
NP 4–6 — HT MDMO–PPV ITO 85 3.46 0.845 42 1.47 115
NP 4.9 — HT MDMO–PPV ITO 71 2.40 0.814 59 1.6 125
3.9 — 0.80 50
NP 10 — HT P3HT ITO 100 6.1 0.75 52 2.4 163
NR 20–40 0.3 HT P3HT/PCBM ITO 100 9.6 0.57 50 2.7 112

Fig. 3 (a) Cross-section scanning electron microscopy image of ZnO

Fig. 2 Effect of polyethylenimine additive on the dimensions of ZnO
nanorods. C indicate synthesis with PEI and : without PEI.59
difference between the ZnO nanorods in these images is the
distance from the substrate to the bottom of the reaction flask
used during synthesis which was 10 times larger for the nanorods
observed in Fig 4b. NRs with almost the same length were
obtained (500 nm) in both cases, but the surface density and NR
diameter were different in each case.61
Another example is the effect of ambient humidity on the
degree of alignment in ZnO nanorod arrays. Lee, et al, report
that close-packed ZnO nanorod arrays with [001] axis perpen-
dicular to the substrate can be obtained only when seeded at
nanowires arrays on fluor tin oxide (FTO). (b) HRTEM image of indi-
vidual ZnO NW and its corresponding SAED pattern inset.90

20% relative humidity (RH) at room temperature (RT). When
the seeding RH was raised to
60%, the polydispersity in the
diameter and length of the ZnO nanorods increased. Thus, these
authors report an optimal seeding humidity of 30–40% for the
synthesis of ordered ZnO nanorod arrays.162
Table 1 and 2 show the dimensions of vertically-aligned ZnO
nanostructures applied in XSCs (DSCs and HSCs) and the
photovoltaic performance observed in each case. The tables
are arranged by increasing efficiency and for comparison
a few examples of XSCs applying ZnO electrodes made of
colloidal nanoparticles are included. We observed that the
highest solar cell efficiency obtained corresponds to solar cells

24 | Energy Environ. Sci., 2009, 2, 19–34 This journal is ª The Royal Society of Chemistry 2009
 View Online

branched-nanowire network (see Fig. 5c) could, in principle,

benefit even more for both a larger surface area for light-
harvesting compound loading (polymer or Dye) and more
efficient electron transport.64,67–79 In addition, some groups
report that the use of vertical nanostructures may not be optimal
for light-harvesting because some photons can fall on the gap of
adjacent nanorods and the light loss could be significant. In
vertically-aligned ZnO branched nanorods (Fig. 5c) the
improvement could be double: higher surface area and increased
interaction with light, maintaining good electron transport.68
Another possibility based on the porous single crystal concept
described previously159–161 where nanoporosity is in the exact
nanosize range required for dye loading (or re-loading), ensuring
Published on 25 November 2008 on http://pubs.rsc.org | doi:10.1039/B811536B

ideal oxide–dye interaction. Moreover, the nanostructure repre-

Fig. 4 Top view of arrays of vertically-aligned ZnO nanorods synthe-
sized by the hydrothermal method on indium tin oxide (ITO) substrates.45
Distance from the substrate to the bottom of the reaction flask was 10
times larger for (b) with respect to (a). Nanorod diameter: (a)
75 nm and
(b)
150 nm.61
applying ZnO nanorods with very thin diameters (30–70 nm) and
lengths up to 1.9 mm.96 Nevertheless, highest efficiency is still
observed for electrodes made of colloidal nanoparticles, in DSC
the best efficiency is 6% and for HSC 2.4%. An innovative
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sents an up-standing and well-crystalline ZnO nanostructure
which is not completely vertical (See Fig. 5d) thus improving
surface area for charge collection.
Thus a careful design of the nanostructured electrode made of
vertically-aligned nanorods should be made in order to fulfill the
best requirements for the type of solar cell where will be applied.
For example, one of the most problematic issues observed in
XSCs is Dye or polymer infiltration (wettability), a solvent-
soluble Dye could reach the whole surface area of the nano-
structured electrode more easily than a viscous polymer solution

synthesis method developed by Prof. Yoshida’s group has been which has to penetrate into dense packed nanowire network.
applied to obtain porous single crystal ZnO. Although the Research work on wettability of ZnO nanostructures seems to be
obtained ZnO nanostructure is not made from nanowires or missing from the literature.
nanorods of ZnO, the as-prepared material presents inter- The possibility of obtaining highly porous ZnO nanomaterials
connected and vertically-aligned channels of crystalline ZnO. with crystalline structure as already reported, suggests that there
The voids left behind during synthesis present the exact required is room for improvement on solar cell efficiency. Nevertheless, all
nanosize for dye loading. The technique is based on a one-step
electrochemical self-assembly where the oxide is electrodeposited
in the presence of organic dye molecules which are de-loaded
after synthesis to give porous thin films of crystalline ZnO. The
ZnO electrodes prepared by this technique and analyzed in DSCs
resulted in a 7.2% efficiency,161 the highest reported efficiency to
date from applying ZnO in XSCs.159–161 Moreover, the versatility
of the technique permits the fabrication of ZnO thin films at low
temperature and applying flexible substrates.

Surface area and design of ZnO nanostructure.

The key to high efficiency when applying porous single crystal as
described above, is related to the optimal distance obtained
between ZnO and the Dye. Thus, it is not difficult to realize that
in order to overcome all the aforementioned issues and to
obtain maximum photovoltaic performance, vertically-aligned
nanostructured thin films of ZnO must be optimized in 3D by
selecting the height, diameter and spacing between nanorods as
schematically represented in Fig. 6. The ideal nanostructure is
not easy or straightforward to obtain. The fact that electron
diffusion length is in the range of 20 nm suggests that the best
well-aligned nanostructure could have vertical nanostructures of
about 20–40 nm in diameter and space between them of about
40 nm. Thus, a dense array of long and thin single-crystalline
nanowires electrode would be ideal. Besides electrical properties,
the nanostructure of the electrode is of crucial importance Fig. 5 Schematic representation of the possible electron path taking
to obtain higher surface and higher electron transport. Thus place on different nanostructured electrodes made with (a) nanoparticles,
in a more sophisticated nanostructure, a vertically-aligned (b) nanorods, (c) branched nanorods and (d) porous single crystal.

This journal is ª The Royal Society of Chemistry 2009 Energy Environ. Sci., 2009, 2, 19–34 | 25

Fig. 6 Schematic representation of a vertically-aligned electrode where
the height, diameter and spacing between nanorods can be modified
to suit the best properties for electron transport and dye/polymer
absorption.
Published on 25 November 2008 on http://pubs.rsc.org | doi:10.1039/B811536B
the synthesis methods found in the literature to obtain ZnO
nanostructures applied in XSCs show irreproducible results. The
latter means that similar but no identical ZnO nanostructures
can be obtained from synthesis to synthesis. The best reproduc-
ible nanostructures have been observed for synthesis methods
requiring several steps or more elaborated methodologies like the
application of templates or vapor-phase synthesis techniques. A
recent review by M. Zacharias62 describes various growth
processes, with special emphasis on the vapor–liquid–solid (VLS)
process, which offers the possibility for the control of the
positions of the nanostructures in 3D.62 The authors describe
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techniques like vapor–liquid–solid (VLS), vapor–solid (VS),
solution growth (SG), and describe the benefits of applying
nanolithography (NL) techniques like photolithography (PhL),
e-beam lithography (eBL), nanospheres lithography (NSp),
masks and templates based on porous alumina (TM), nano-
imprint lithography (NIL), etc.62 Many of these nanostructures
are obtained on metallic substrates like Au, or on semiconductors
not compatible with XSC configurations but could be adapted to
the application of substrates compatible with XSC components.
Vertically-aligned ZnO nanostructures for high
efficient electron transport
An efficient nanostructured electrode for XSC should present
high electron transport and low recombination rate. The effective
electron diffusion length depends on the application of an
optimal electrode thickness, and is represented by
Ln ¼ (Dntn)1/2
where Dn is the diffusion coefficient for the electron within the
electrode and the tn is the survival time of the electron with
respect to the regenerator (a Dye in a DSC and a polymer in
a XSC).63 Analysis applying the intensity modulated photocur-
rent spectroscopy (IMPS) technique together with the analysis of
photocurrent decay can determine the values of electron diffu-
sion and transport time (td). In both cases the solar cell is illu-
minated with a laser whose intensity is varied as a function of
time and the transient response of the solar cell photoresponse is
measured. The minimum angular frequency observed in the
imaginary plot of modulated photocurrent vs frequency can be
applied to obtain the electron transport time: td ¼ u,min1.63
For electrodes made with colloidal nanoparticles, it has been
observed that charge transport and recombination accelerate
when increasing light intensity and their ratio (td/tn) remains
26 | Energy Environ. Sci., 2009, 2, 19–34
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constant. In the case of vertically aligned electrodes a similar
intensity-dependent behavior was observed for recombination
and the electron transport was observed to be independent of
light. The measured recombination/transport times ratio was
observed to be about 64, or 18 times that observed with the
nanoparticle electrode, as seen in Fig. 7.63 Other interesting
results have been observed when comparing the carrier density of
nanostructured and dense thin film electrodes of ZnO. Some
models demonstrated that ZnO nanowires present high donor
density of 6.2  1019 cm3, and the effect of annealing temper-
ature has been proved to reduce this value by two orders of
magnitude.117
Thus, improving the interfacial processes where exciton
generation and separation take place will translate into higher
solar cell efficiency. Other reports demonstrate that electron
transport in semiconductor oxides made of nanoparticles
proceed by a trap-limited diffusion process due to the random
pathway the electrons must follow through the thin film. The
electron must pass through a series of interparticle hopping
steps, estimated in 103–106 particles, in order to reach the
collection electrode.64,65 Although the electron transport
through a nanoparticle thin film is high, the electron must
overcome several grain boundary and dead ends with a high
probability for recombination before reaching the electrode
current collector.65,66 Despite their slow nature, electron collec-
tion is favored over recombination in DSCs due to the slower
kinetics observed for the liquid electrolyte. Galoppini et al.
analysed electron transport in DSCs by always applying films of
2 mm thickness synthesized by the MOCVD technique and
comparing them with a thin film made of nanoparticles.83
Results demonstrated that the electron transport of the ZnO
nanoparticle electrode was similar to a thin film made of TiO2
nanoparticles (transport time of
10 ms) but the electron
transport increased about 2 orders of magnitude when a thin
film of ZnO vertically-aligned nanowires was used (
30 ms).66,67
The same authors reported the electron mobility for ZnO
thin film, which has been measured to be about 400 cm2 V1 s1,
and electron mobility several orders of magnitude higher for
ZnO nanowires (>20 cm2 V1 s1).66
If we consider that the electron collection efficiency is
a measure of the competition between electron transport and
Fig. 7 Electron lifetime (O) and average transit time (C) over a range
of illumination intensities. h highlight the difference between tn and td
for nanoparticle (:) and nanorod (B) devices.63
This journal is ª The Royal Society of Chemistry 2009

recombination rate, a well-aligned nanostructured semi-
conductor oxide could provide a faster and direct electrical
pathway for the collection of electrons as shown in Fig. 5b. The
latter has been proved by Hupp67 who compared the dynamics
of charge transport and recombination of two ZnO electrodes,
one made by ZnO colloidal nanoparticles and the other as
vertically-aligned nanorods. Fig. 7 shows the dependence of
electron recombination with light intensity for both types of
electrodes.67
Photovoltaic properties of vertically-aligned ZnO
nanostructures in excitonic solar cells
Published on 25 November 2008 on http://pubs.rsc.org | doi:10.1039/B811536B
The properties of vertically-aligned nanostructures has been the
subject of extended research work and several reviews can be
found in the literature.71 Particularly TiO2, as one of the most
widely used semiconductor oxides in Hybrid and Dye sensitized
solar cells, has been recently reviewed.72 Moreover, reviews on
other type of nanowires and nanotubes of different inorganic
semiconductors like ZnO, CdS, CdSe, CdTe, CuO can also be
found.73–76,78
In this section we consider XSCs where sole ZnO nano-
structures are used as the ETM. Thus, XSCs applying ZnO in
addition to other compounds that could enhance electron
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injection (like PCBM, TiO2 or similar) are not included.
Application in dye sensitized solar cells
The first application of ZnO in DSC goes back to 1969 with the
work reported by Gerisher et al. applying a single crystal oxide as
the electrode.76 Since then, several attempts to improve solar cell
efficiency have been observed. In 1980, electrodes made of ZnO
disks were applied in DSC obtaining 2.5% efficiency.77 Currently,
the application of ZnO nanostructured electrodes made of
colloidal nanoparticles has achieved up to 6.58% efficiency,157
Efforts to improve the DSC conversion efficiency by increasing
surface area was made by the application of ZnO nanostructures
like nanoflower (h ¼ 1.9%),95 nanosheets (h ¼ 3.9%),102 hierar-
chically structured (3.5%),146 or its application together with
other oxides as mesoporous SnO2–ZnO (6.34%),131 core–shell
ZnO–TiO2 (9.8%)148 or more recently doped-ZnO nanoparticles
(h ¼ 6%).101 The highest efficiency reported up to date is 7.2%
applying porous single crystal.161 Table 1 summarizes photo-
voltaic properties observed for DSC applying ZnO vertically-
aligned nanostructures (nanorods, nanowires, nanotubes) and
other related structures.
The first principle to consider in relation to efficiency is the size
and spacing of the nanostructures which must be in the range of
the exciton diffusion length, between 5 and 20 nm. Thus the
optimum nanostructure will be the one with a perfectly ordered
array of crystalline ZnO nanowires oriented normal to the elec-
trode surface. The nanowires must also be thin (up to 40 nm in
diameter) and with spacing between them of about 20–40 nm.
The length of the nanowires will define the amount of absorbed
dye within the nanostructure and, as a consequence, the solar cell
efficiency, thus a 10–20 mm nanowire length is desirable.81
Dimensions of vertically-aligned nanowires vary greatly
depending on the synthesis technique used, the later influences to
a great extent the photovoltaic properties of the DSC. We have
This journal is ª The Royal Society of Chemistry 2009
View Online
observed that vertically-aligned nanostructures of ZnO applied
as electron acceptors in DSC are limited to only a few synthesis
methods, hydrothermal, MOCVD, CVD, atomic layer deposi-
tion or a combination of them as seen in Table 1.
From Table 1 we can also extract the different ZnO nanorods
lengths applied by different laboratories. NRs length and
diameter are directly related to the surface area available for Dye
loading which directly affect the solar cell efficiency.90 Baxter and
Aydil et al. carried out a detailed study of the effect of NRs
length and diameter on photovoltaic response.65 The authors
applied hydrothermal techniques using seeded substrates of ZnO
nanoparticles of about 5–10 nm in diameter (the application of
no-seeded substrates results in ZnO NR of larger diameter).
During synthesis the nanorods were grown from ZnO seeded
substrates and the solution was replaced several times to enhance
nanorod growth. Each time the growth solution was changed one
synthesis cycle is completed. Their study revealed a linear growth
of the NRs with the number of cycles. Lengths which varied from
2, 5 or 8 mm were obtained after 2, 4 or 8 four-hour-cycles,
respectively (Fig. 8).
In the case of the diameter, the results indicate an initial linear
diameter growth with number of cycles but the growth was
observed to take place at a slower rate, going from 50 nm up to
150 nm (aspect ratios from 10 to 60), when going from 1 to 8
cycles. As a result of the surface area increase with NR length, the
efficiency observed for DSC with 1 mm length and 50 nm diam-
eter (1 synthesis cycle) was observed to be 0.04% which increased
up to 0.18% for a NR of 8 mm in length and 155 nm in diameter,
as shown in Fig. 9. The best conversion efficiency obtained by the
authors was 0.3%.
Although the photovoltaic performance of DSCs depends on
multiple parameters, the above example demonstrates the
importance of the synthesis technique applied for the fabrication
of the electron transport electrode. To our knowledge, the
highest conversion efficiency obtained to date applying only
vertically-aligned ZnO nanostructures has been reported by Guo
et al.96 The authors applied nanorods of ZnO with diameters
between 30–70 nm and lengths up to 1.9 mm. The authors carried
out a detailed study of synthesis conditions for the ZnO nano-
rods, growth time and temperature, and its influence on DSC
efficiency. Their findings revealed a direct improvement of solar
cell efficiency with increasing NR growth temperature, h ¼ 0.5%
when growth temperature was 40  C, h ¼ 1.1% at 60  C, h ¼
1.8% at 80  C and h ¼ 2.4% at 95  C. The improvement in effi-
ciency was attributed to the length of the ZnO nanorods, that
increased from 240 nm up to 1.9 mm when the temperature was
raised. The latter affects the total amount of dye loading on
the electrode and as a consequence higher amount of photons
can be converted into electrical energy. As we can observe from
Table 1 the NR applied by these authors are especially thin (the
smallest diameter of all), and are closely related to the electron
diffusion length values (10–20 nm) required for efficient exciton
dissociation.
In general, nanowires between 50 nm up to 300 nm average
diameter and from 1 to 16 mm in length have been applied in
DSC, as detailed in Table 1. Although DSC efficiency depends on
different parameters like type of dye, type of electrolyte and
especially the electrode morphology, we observed that solar cell
efficiency is related to the diameter of the nanorods rather than
Energy Environ. Sci., 2009, 2, 19–34 | 27

Published on 25 November 2008 on http://pubs.rsc.org | doi:10.1039/B811536B
Fig. 8 Cross-sectional (upper row) and top view (lower row) SEM images of ZnO nanowire arrays grown for ((a), (d)) one, ((b), (e)) four, and ((c), (f))
eight 4 h synthesis cycles. Scale bars are 2 mm for ((a)–(c)) and 1 mm for ((d)–(f)).65
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Fig. 9 (a) Current density (-) and efficiency (B) as a function of
number of growth cycles. Inset shows open circuit voltage (Voc) in volts
(-) and fill factor (B) vs growth cycles. (b) Roughness factor of the
nanowire arrays as a function of the number of growth cycles. The dotted
line helps to show the sub-linear dependence of the roughness factor on
the number of growth cycles.65
their length. As mentioned before, the ZnO nanostructure most
closely related to the optimal described previously, is probably
the one that Prof. T. Yoshida has been developing for the last
several years.159–161 This nanostructured thin film of ZnO is made
by electrochemical deposition of Zn precursors and the appli-
cation of dyes during the electrochemical synthesis.159–161 In
a recent conference161 the group presented their latest results,
7.2% efficiency of a DSC based on a self-developed dye labeled
D149. The ZnO nanostructure obtained is a porous single crystal
(see Fig. 5d), obtained by the de-adsorption of the dye molecules
28 | Energy Environ. Sci., 2009, 2, 19–34
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from the ZnO–Dye nanomaterial after electrochemical synthesis.
The de-adsorption of the dye permits the formation of nano-
porosity with the exact nanosize required for dye re-loading,
ensuring an ideal oxide–dye interaction.
Application in hybrid solar cells
The first reports of the application of ZnO in XSCs with rela-
tively good efficiencies are very recent and may be attributed to
Prof. J. A. Janssen. This group demonstrated in 2004 that solar
cells applying blends of a conducting organic polymer and ZnO
nanoparticles show efficiencies up to 1.6%.116,125 Recent reports
from this group show an improvement on solar cell performance
obtaining a current density, Jsc, of 6.1 mA cm2, 0.75 V, 0.52 FF,
and 2.4% efficiency,163 the highest efficiency reported to date for
XSCs applying ZnO nanoparticles.
Many efforts to improve efficiency by the optimization of the
nanoparticle/polymer blend or by the application of higher
surface area electrodes (nanoparticles, nanorods, opals of ZnO,
etc) have been observed by many groups. The first report of the
application of ZnO as vertically-aligned nanostructures in HSC
was made in 2006.107,108,111 The ZnO nanostructure was applied in
different configurations: in direct contact with a conducting
organic polymer; as part of TiO2 nanorods or nanowires; or, as
part of a bulk-heterojunction solar cell made with a PCBM–
P3HT blend; in all these systems ZnO has been observed to
improve electron transport.
In HSC, the interest in the application of vertically-aligned
ZnO nanostructures is based on the good performance observed
when applying TiO2 vertically-aligned nanostructures in solar
cells.74 Moreover, it offers the possibility of synthesizing ZnO
nanorods applying a simple hydrothermal method that can be
fabricated on a large scale and, almost, on any substrate.19,45,108
The photovoltaic response observed for HSC applying vertically-
aligned ZnO nanostructures is listed in Table 2. We observed that
the diameter of the ZnO nanorods applied by the different
laboratories are between 80 and 150 nm, the most applied
polymer is P3HT (one of the best and more stable of the
commercially available polymers), the efficiencies reported are
This journal is ª The Royal Society of Chemistry 2009

very similar between laboratories and, to our surprise, are not
higher than 0.5%. Voc is relatively low, never higher than 0.44 V
and, in general, the current density is reported to increase by
four, when compared with devices in a planar configuration or
applying nanoparticles.109,110 In addition, the longer the nanorod
the higher the current density obtained from the solar cell.66
Olson and Ginley et al. studied HSCs applying the configuration
ITO/ZnO NR/P3HT/Ag.66,110,111 The applied ZnO nanorods were
synthesized with lengths between 250 and 500 nm, this increment
in surface area was translated in an improved Jsc which changed
from 1.29 to 2.17 mA cm2. The low external quantum efficiency
(EQE) values observed for the devices was attributed to the
diameter (100 nm) and space between the NR that were not
Published on 25 November 2008 on http://pubs.rsc.org | doi:10.1039/B811536B
optimized to encompass the short electron diffusion length (3–5
nm) of the P3HT polymer. The reason for the low values of Voc
(about 0.3 V) is not clear, the authors relate it to the presence of
mid-gap states on the surface of the ZnO, or to high electron
mobility within the ZnO NR which could increase recombina-
tion. Other results from the same author show the beneficial
effect on Voc when treating the ZnO surface with surfactants at
expense of Jsc.66 A recent report made by Plank and Schmidt-
Mende et al. show the effect of ZnO layer thickness on the Voc
and EQE values.109
The authors show that a thinner layer of ZnO presents an
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improvement in Voc from 0.28 V up to 0.41 V and EQE from 2%
to 7.2% for a 650 nm and 130 nm layer thickness, respectively. In
general, all the published works inform about the importance of
the type of synthesis on photovoltaic performance. The possi-
bility to control the diameter, spacing and length on the ZnO
vertically-aligned nanostructure is a critical issue for all authors.
It is also important to carry out studies on the control of polymer
reorganization and morphology within the ZnO interface, which
can affect the exciton dissociation and the unidirectional flow of
electrons through components of the solar cell.116
All solid-state excitonic solar cells (ss-XSCs) applying ZnO: In
between HSC and DSC.
Recent efforts to eliminate practical problems related to the
liquid electrolyte in DSCs such as leakages, corrosion of elec-
trodes, solvent evaporation, among others,129,130 have resulted in
the development of XSCs in solid or quasi-solid state
Table 3 solid-state Exitonic Solar Cells (ss-XSC) applying ZnO nanostructures as the ETM and dyes as spatial separator between the HTM and ETM.
TCO: Transparent conducting oxide like indium tin oxide, ITO, or fluor tin oxide, FTO. PDI: N,N0 -didodecyl-3,4,9,10-perylene tetracarboxylic diimide.
SAF: Safarine-O dye
From HSC Al/ZnO/PDIdye/(P3HT + ZnOnp)blend/PEDOT/ITO
ss-XSC Al/PPTH : SAFdye : ZnO/ITO
From DSC ITO/ZnOdense/Z907dye/P3HT/PEDOT/Au
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configurations. The ss-DSC concept was first reported around
1995136,145,147 and several compounds have been applied that
include the application of p-type inorganic semiconductors,130
polymer or gel electrolytes,129,132–135 ionic liquids,137–142 ionic
liquid crystals,129,142,143 conducting organic polymers144,151–154 or
redox molecules covalently linked to the dye and the TiO2
forming a triad,123,144,147 and several examples can be found in the
literature. The most relevant are DSC applying TiO2 as ETM
and spiro-OMeTAD or conducting organic polymers as solid-
state HTM that have shown promising conversion efficiencies of
4% and 2.8%, respectively.151–154 The application of ZnO nano-
structures in all solid-state XSCs have emerged from variations
of the HSC or the DSC configurations. In a HSC there is a direct
contact between the oxide and the polymer, thus dye has been
introduced as the separator of HTM and ETM to improve
electron injection and reduce recombination. In DSC configu-
ration is HTM (usually a liquid electrolyte), the one that is
replaced by solid hole conductors. Only a few examples of
ss-XSC applying ZnO were found in the literature and are listed
in Table 3. In these ss-XSCs the highest solar cell efficiencies are
not higher than 0.55% but the research on these solar cells is in
the early stages and more research results are expected in the
following years.
In these few cases, all the authors agree on the beneficial effect
observed on Jsc and whole solar cell performance when the dye is
introduced between the HTM and ETM in a HSC. Nevertheless,
in a DSC the effect is the contrary, replacement of the fast
injection liquid electrolyte by a solid HTM results in a decrease in
solar cell performance.
Stability of excitonic solar cells applying ZnO
Long-term stability tests performed on XSCs have reached
several thousand hours under continuous illumination: from
1000 h up to 20 000 h for DSCs165 and from 4000 h166 to 10 000 h
for OSCs.167,168 Recent publications on the stability test carried
out to XSCs applying ZnO can be found, especially for HSC and
ss-XSCs.
HSC stability. In HSCs, an oxygen release and exchange
mechanism has been recently reported for semiconductor oxides
working in direct contact with light-harvesting and hole
Jsc Voc h FF
(mA/cm2) (V) (%) (%) Ref.
9.55 0.35 — — 120
1.45 0.62 0.55 0.61 122
3.2 0.28 0.2 — 108
Energy Environ. Sci., 2009, 2, 19–34 | 29

conducting polymers.22–24,124–125,127 This mechanism affects the
performance of the solar cell under different atmospheres
due to the semiconductor oxide requirement (‘‘breathing’’) of
oxygen.22–24 The possibility to encapsulate these HSC or, to work
under inert atmospheres is not an option due to the detrimental
effect observed on photovoltaic properties in these environments.
The latter suggests that XSCs applying semiconductor oxides
cannot be applied under inert atmosphere environments, for
example, in space-related applications.
The observed mechanism is linked to the semiconductor itself
and has been observed in systems like ZnO electrodes applied in
HSC made of dense thin films,22–25,128 hybrid nanocomposites
made with nanoparticles124 and more recently on vertically-
Published on 25 November 2008 on http://pubs.rsc.org | doi:10.1039/B811536B
aligned ZnO nanostructured electrodes.66 This behavior is not
exclusive to ZnO, it has also been observed in systems applying
other semiconductor oxides (TiO2, Nb2O5, CeO2, etc22–24) in
different configurations like TiO2/polymer nanocomposites,124
planar oxide/polymer HSC,22–24 and also in nanorods/polymer
devices.124 Some initial reports applying ZnO nanoparticles
indicate the stabilization of the oxide/polymer blend when
increasing ZnO nanoparticle content. Nevertheless, the stabili-
zation applies within ZnO/polymer nanoparticle blends and does
not avoid the photo-oxidation (photobleaching) of the polymer
under long-term irradiation conditions. The latter mechanism
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can not be avoided by the application of UV filters or inert
atmospheres.24 Yet, much effort has been made to understand
degradation mechanisms in XSCs, especially in OSCs22–25,119,168–170
and, very recently, efforts show the initial results of the effect of
semiconductor oxides on organic polymers in HSCs.119 Krebs
et al. has recently reported the long-term stability of a HSC
made of ZnO nanoparticles and the polymer poly-(3-carbox-
ydithiophene) (P3CT). The author modified the planar HSC
configuration of ITO/ZnO/MEH–PPV/Ag22–24 applying ZnO as
dense thin films, to ITO/ZnO/(P3CT–ZnO)blend/PEDOT:PSS/Ag
using ZnO nanoparticles.119 While the lifetime of the first
configuration was limited to only a few minutes (hours), the new
configuration shows a lifetime of up to 500 h, in both cases
without the use of a UV filter. There are many possible expla-
nations for this lifetime improvement, among them are the higher
stability of the polymer used and the electron withdrawing
carboxylic acid groups which is more stable towards oxygen.119
Nevertheless, the time required for the solar cell to exchange
oxygen and degrade the polymer could also be related to the total
active surface area of the oxide. If the latter is true, in a HSC
made of dense thin films of ZnO (about 30 nm thickness) the
exchange of oxygen and the stabilization in the dark would take
place in only a couple of hours,22–24 while in a nanostructured
ZnO thin film made of nanoparticles the stabilization period
could take several days, even months.110
ss-XSC stability. Another possible alternative to overcome the
degradation problem observed in HSCs could be the physical
separation of the electron- and hole-transporting components as
already suggested in published reports.123,124 This separation
could avoid polymer degradation and improve lifetime in HSC
applying semiconductor oxides as is observed in long-lasting
DSCs. But, it could imply the possibility to enhance charge
separation and avoid or retard recombination in this and all
other types of bulk-heterojunction solar cells, as reported
30 | Energy Environ. Sci., 2009, 2, 19–34
View Online
earlier.123,124 The latter has been proven by Ravirajan et al.,108
who fabricated a HSC applying ZnO in three different configu-
rations: flat layer structure, vertically aligned nanorods and as
nanoparticles. The authors applied the polymer in intimate
contact with ZnO, but also added an amphiphilic molecular
interface layer (a dye) in between the ZnO and the polymer. A
transient absorption spectroscopy technique was used to obtain
the photoinduced electron-transfer yield and the charge recom-
bination kinetics. Comparison between the devices, ZnO coated
and uncoated with dye showed that the dye-treated ZnO devices
presented (a) longer lifetime of the hole polarons, (b) improve-
ment of 50% in the charge transfer yield and (c) a slower half-life
by a factor of 4–5. The authors observed an improvement in
charge separation yield attributed to the ‘‘cascade’’ type of
interface applied (ZnO/Dye/polymer) which blocked hole trans-
fer. Another factor is the orientation of the dye, which is believed
to attach its polar side group to the oxide while maintaining its
nonpolar side towards the polymer, improving wettability. A
direct charge transfer between ZnO and P3HT would promote
recombination but it is effectively retarded by the application of
a dye as a spatial separation between the hole and electron
transfer materials. The latter work by Ravirajan et al.108 demon-
strated the beneficial effect of separating the hole and the electron
transport materials, and a few similar XSCs have been published
since.149 The application of a dye (or any other sensitizer) as
a spacer between the hole and electron transport material would
resemble a DSC or more exactly, a solid-state DSC (ss-DSC).
Wang et al.120 carried out stability analyses of a solid-state
XSC of the type Al/P3HT:ZnO:PDI/PEDOT/ITO where ZnO
was used in the form of nanoparticles and the dye PDI was used
to improve photovoltaic performance. As reported previously,108
the light absorption and exciton separation was greatly improved
by the addition of the dye between the HTM and ETM.
Nevertheless, stability analyses with the application of UV filter
did not show any improvement in solar decay behavior.
Initial efforts to understand the effect of the long term stability
of ss-DSCs, applying a Dye/TiO2 electrode as the light-harvest-
ing and electron transfer materials, respectively, and spiro-
OMeTAD as the solid hole conductor, has been very recently
presented by Fabregat-Santiago and Bisquert et al.164 The
reported results show impedance models able to describe the
main electrical parameters that determine the behavior of these
ss-DSC, but more important is the report of the effect of different
atmospheres (argon and air) on the photovoltaic and electrical
properties of the ss-DSC. Initial results show better performance
of the ss-DSC under oxygen-containing atmospheres, as reported
previously for HSC.22–25 The latter implies that the presence of
a dye is not enough for solar cell stability under different
atmospheres as suggested earlier.15 The effect is currently under
investigation by many research groups.
Future trends
ZnO nanostructure and efficiency
Outstanding progress has been observed in recent years on the
synthesis of vertically-aligned nanostructures of ZnO, nanorods,
nanotubes or similar. The improvement in electron transport
applying these nanostructures is a reality and current densities
This journal is ª The Royal Society of Chemistry 2009

Table 4 Highest solar cell efficiencies reported for XSCs applying ZnO
nanostructures
Efficiency (%)
ZnO nanostructure DSC HSC ss-DSC Ref.
Nanorods (NR) 2.4 96
0.53 110
0.20 108
Nanoparticles (NP) 6.58 157
2.4 163
0.55 122
Porous single crystal (PSC) 7.2 161
Published on 25 November 2008 on http://pubs.rsc.org | doi:10.1039/B811536B
have been observed to improve by four when changing from
nanoparticles to vertical nanostructures. The best solar cell
performance applying nanostructures of ZnO in DSC now
reaches 7.2% efficiency when applying vertical nanostructures
made of porous single crystal ZnO, 6.58% when nanoparticles are
used and 2.5% for vertically-aligned nanorods. In the case of
HSC, the highest values are observed when ZnO nanoparticles are
used, only 0.5% efficiency, for vertically-aligned nanostructures
the efficiency is no higher than 0.2%. In the case of ss-XSC the
observed efficiencies are even lower, as shown in Table 3. For
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comparison purposes Table 4 summarizes the best solar cell
efficiencies observed to date for XSCs applying ZnO nano-
structures. These low efficiencies seem to be related to many
factors but especially to problems related to surface area, polymer
infiltration, wettability and slow kinetics, in the case of solid hole
conductors. In order to increase solar cell efficiency the surface
area of the nanostructured ZnO electrode must be enhanced. In
an effort to increase surface area and, at the same time, the
interface between the semiconductor oxide and the corresponding
organic semiconductor (Dye or conducting polymer), vertical
nanostructures, such as branched nanorods or nanosheets, seem
to be promising candidates for high efficiency XSCs. Particularly
ZnO nanostructures, such as the porous single crystals reported
by Yoshida161 (see Table 4), which present most of the charac-
teristics needed for high electron transport and high solar cell
efficiency: high density nanostructure, high surface area, low voids
concentration between the nanostructure, and single-crystalline
structure for electron transport without grain boundaries.
Working mechanisms
More recent developments relate to the application of doped
ZnO materials to enhance light-harvesting properties. For
example, a detailed study on the charge generation mechanism
has been reported when applying Zn1xMgxO (x ¼ 0–0.4).
Findings of new charge generation mechanisms in HSCs were
reported and revealed to be completely different from the exciton
dissociation mechanism observed to date of exciton dissociation
at the interface in XSCs.150 In DSC, on the contrary, ZnO has
been doped with Ga obtaining 6% efficiency, in this case the
device was made by applying ionic liquid electrolytes.101
All-solid-state devices
Finally, a promising research trend is the possibility of devel-
oping XSCs as all-solid-state devices with high efficiencies,
This journal is ª The Royal Society of Chemistry 2009
View Online
avoiding the application of problematic liquid electrolytes, and
applying solution processing techniques for fabrication. We have
identified two main research trends: the first is related to the
application of solid hole conductors to replace the liquid elec-
trolyte in DSC; the second is the application of a light-harvesting
compound (e.g. a dye) between ZnO and the conducting poly-
mer. Although efficiencies as high as 4% have been reported for
ss-DSC applying solid hole conductors, such as spiro-OMeTAD,
or almost 3% when applying conducting polymers,151–154 the
electrode applied was made of TiO2 colloidal nanoparticles and
not ZnO. The application of vertically-aligned nanostructures of
ZnO in all-solid-state DSC is in its very early stages, and could
possibly be attributed to J. Nelson.149 Although encouraging
results have been obtained with these systems and research
efforts seem to be directed towards this type of solar cell, it is
necessary to understand their degradation mechanisms, or to
find new methods for efficiency improvement.
Reproducibility and scalability
ZnO nanostructures can be obtained by relatively easy hydro-
thermal techniques with the possibility of large scale production,
but reproducibility of the nanostructure is still an issue. Tech-
niques based on templates or nanolithography-based synthesis
offer the possibility of reproducibility and the control of nano-
structure dimensions in 3D (space between nanostructure,
height, and thickness or diameter). A general trend seems to be
towards the application of nanofabrication synthesis methods
but the selected technique must be simple enough to avoid or
reduce multi-step processes or the need for special equipment for
the synthesis of ZnO nanostructures.
The development of high efficiency and long lasting XSCs
applying nanostructured ZnO may depend upon an under-
standing of the basic working mechanism behind nanostructured
ZnO and more importantly, its interaction with light-harvesting
organic semiconductors, dyes or polymers.
Conclusions
This work provides a brief overview of the most recent research
developments in the application of ZnO as a nanostructured
material in excitonic solar cells. Vertically-aligned nano-
structures have been exhaustively applied as electron transport
material in DSC and HSC. Its application as vertical nano-
structures goes beyond nanorods, nanotubes or nanowires and
gets immersed into the application of higher surface area
nanostructures, such as branched nanorods, nanosheets, nano-
wiskers or porous single crystals, among many others. The latter
serves two purposes, it introduces a high surface area for higher
interface between the light-harvesting material (dye or polymer)
and increases the probability of photon absorption. Although
many different synthesis techniques can be applied for the
synthesis of ZnO nanostructures, only a few are promising
candidates for low cost, solution processing fabrication and
scalability, particularly the wet-chemical hydrothermal method.
Nevertheless, reproducibility of the alignment and dimensions of
the nanostructures has not been fully accomplished. A synthesis
technique that is able to control the synthesis of these vertically-
aligned nanostructures at the 3D level is required. The synthesis
Energy Environ. Sci., 2009, 2, 19–34 | 31
 View Online

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