Review

pubs.acs.org/CR

Titanium Dioxide Nanomaterials for Photovoltaic Applications

Yu Bai,†,‡ Iván Mora-Seró,§ Filippo De Angelis,∥ Juan Bisquert,§ and Peng Wang*,†
†
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences,
Changchun 130022, China
‡
Institute of Chemistry and Energy Material Innovation, Academy of Fundamental Interdisciplinary Sciences, Harbin Institute of
Technology, Harbin 150080, China
§
Photovoltaic and Optoelectronic Devices Group, Departament de Física, Universitat Jaume I, 12071 Castelló, Spain
∥
Istituto CNR di Scienze e Tecnologie Molecolari, c/o Dipartimento di Chimica, Università di Perugia, via Elce di Sotto 8, I-06123
Perugia, Italy
Biographies AC
Acknowledgments AD
References AD

1. INTRODUCTION: PROPERTIES OF TIO2

NANOMATERIALS
The continuous increase of the world’s population, together
with the substantial development of industry has brought about
imperious demand for larger energy consumption. At present,
most of the energy production is made from the combustion of
fuels, such as oil, natural gas, and coal. However, the depletion
of fossil resources, the commensurate increase in noxious gas
CONTENTS emissions, and the other associated environmental pollutions
have put forward an urgent demand for developing sustainable
1. Introduction: Properties of TiO2 Nanomaterials A energy technologies. Among all of the renewable energy
2. Application in Dye-Sensitized Solar Cells (DSCs) B technologies, including hydro, solar, wind, geothermal heat, and
2.1. Fundamentals of DSCs B biomass, photovoltaic (PV) technology which converts solar
2.2. Interaction of Sensitizers with TiO2 C energy into electricity is expected to be the most promising
2.2.1. Anchoring of Sensitizers on TiO2 Surface C strategy for sustainable energy supply. Solar photovoltaics is
2.2.2. Influence of Sensitizer Adsorption Be- now, regarded as the third most important renewable energy
havior E source in terms of globally installed capacity and by the end of
2.3. Interaction of Coadsorbents with TiO2 H 2012 the world’s cumulative solar PV capacity has passed the
2.4. Interaction of Electrolytes with TiO2 I 100 GW milestone.
2.5. Electrons Transport and Recombination in So far, the solid-state junction devices based on silicon
TiO2 Electrodes K material have dominated PV solar energy converters. However,
2.6. Nanostructured TiO2 Electrodes for DSCs N the light-induced degradation of silicon materials limits the
3. Application in Polymer-Inorganic Hybrid Solar device stability while the relatively high cost of PV electricity
Cells Q production hinders its effective competition with fossil energy.
3.1. Fundamentals of Polymer-Inorganic Hybrid One attractive alternative to crystalline silicon PV devices is
Solar Cells Q cells made from mesoscopic inorganic semiconductors, which
3.2. Devices Based on Nanoporous TiO2 R can be easily prepared and offer the prospect of very low cost
3.3. Devices Based on Polymer-TiO2 Blends T fabrication. In these devices, the inorganic semiconductors
3.4. Devices Based on Nanorods and Nanotubes V mainly function as electron acceptor and provide direct or
4. Application in Quantum Dot-Sensitized Solar tortuous path for electron transport while in some cases they
Cells (QDSCs) W may also act as the scaffold for the adsorption of light
4.1. Fundamentals of QDSCs W harvesters. Of the many semiconductor metal oxides, TiO2
4.2. Surface Treatments in QDSCs X nanomaterial appears to be a distinguishing candidate because
4.3. Nanostructured TiO2 Electrodes for QDSCs Z of its high chemical and optical stability, nontoxicity, low cost,
5. Application in Inorganic Solid-State Solar Cells Z and corrosion resistance. There are four commonly known
6. Application in Perovskite Solar Cells AA
7. Concluding Remarks AB
Author Information AC Special Issue: 2014 Titanium Dioxide Nanomaterials
Corresponding Author AC Received: October 25, 2013
Notes AC

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polymorphs of TiO2 found in nature, i.e., anatase (tetragonal), (e.g., organic molecules, ions, and inorganic materials) and on
rutile (tetragonal), brookite (orthorhombic), and TiO2 (B) the interactions of TiO2 materials with the environment. The
(monoclinic).1,2 Besides, two additional high-pressure forms surface modification not only affects the interfacial energy offset
have been synthesized from the rutile phase including TiO2 (II) but also has significant impact on the charge separation,
with a PbO2 structure3 and TiO2 (H) with a hollandite transport, and recombination processes. In recent years, the
structure.4 Rutile TiO2 has a tetragonal crystal structure and ever increasing growth of research activities in nanoscience and
contains six atoms per unit cell as shown in Figure 1.5 Rutile is nanotechnology continually brings on new physical and
chemical properties of TiO2 nanomaterials and provides new
opportunities for the development of TiO2-based solar cells.
We believe that a new and comprehensive review of TiO2
nanomaterials for PV application would promote further
research of PV field and develop efforts to tackle the ever
increasing global energy challenge.
For the present paper, we aim to offer a brief review on the
application of titanium dioxide nanomaterials in photovoltaic
devices, including dye-sensitized solar cells, polymer-inorganic
hybrid solar cells, quantum dot-sensitized solar cells, inorganic
solid-state solar cells and perovskite solar cells. In each section,
a short introduction is given, including the configuration and
the working principle of the solar cell. Besides addressing the
benefits of using nanostructured TiO2 materials, more emphasis
is given to the modulation of properties and the charge transfer
kinetics at the TiO2 interface in these devices. We summarize
the important findings and select examples representing recent
research progress and hope that this writing will provide reader
comprehensive overview of the application of titanium dioxide
nanomaterials in renewable energy technology research.

2. APPLICATION IN DYE-SENSITIZED SOLAR CELLS

Figure 1. Representations of the TiO2 anatase and rutile forms. (DSCS)
Reprinted with permission from ref 5. Copyright 2003 Elsevier.
2.1. Fundamentals of DSCs
the most thermodynamically stable polymorph of TiO2 at all One important application of TiO2 nanomaterials in PV fields is
temperatures, exhibiting lower total free energy than metastable DSCs. Photoelectrochemical solar cells based on sensitized
phases of anatase and brookite. Anatase TiO2 has a crystalline metal oxides were initially studied by Gerischer and co-
structure that corresponds to the tetragonal system but the workers.7 In 1991, O’Regan and Grätzel8 reported the first
distortion of the TiO6 octahedron is slightly larger for the breakthrough by taking advantage of the large surface area
anatase phase. The anatase structure is preferred over other within a mesoporous TiO2 film, and at present the power
polymorphs for solar cell applications because of its potentially conversion efficiency (PCE) of up to 12.3% has been achieved
higher conduction band edge energy and lower recombination based on a liquid cobalt(II/III)-based electrolyte and a
rate of electron−hole pairs.6 porphyrin sensitizer.9 At the heart of the device is the
The physical and chemical properties of TiO2 nanocrystals mesoporous metal oxide layer composed of a network of
are affected not only by the intrinsic electronic structure, but TiO2 nanoparticles (NPs) which have been sintered together to
also by their size, shape, organization, and surface properties. establish electronic conduction. This mesoporous titania
Interesting morphologies and properties have recently attracted architecture has been proved to provide a 100-fold enhance-
considerable attention and many nanostructured TiO 2 ment in surface area per micrometer thickness when compared
materials, such as nanotubes, nanorods, nanofibers, nanosheets, with a flat film, thus providing larger accessible surface area for
and interconnected architectures, have been fabricated and sensitizer adsorption. A schematic representation of the DSC is
applied in PV devices. Generally, it is crucial to maximize the shown in Figure 2. Photoexcitation of the dye molecule leads to
specific surface area of TiO2 so as to facilitate the reaction at the
interface between TiO2 and the interacting media. Besides large
surface area, the TiO2 nanomaterials should also feature high
electron mobility so that electrons injected in the TiO2 can be
collected effectively. As defects in the TiO2 nanomaterials may
act as electron traps and exist in grain boundaries at the
contacts between nanosize particles, the use of a network
structure consisting of TiO2 single-crystal-like nanowires
instead of TiO2 nanoparticles is expected to induce a great
improvement for rapid electron transportation. However, such
proposition is not proven yet and the nanoparticulate TiO2
continues to provide optimal results in PV devices, despite the
presence of disorder. Besides, the properties of TiO2 also Figure 2. Operating principle and energy level scheme of dye-
strongly relay on the modifications of the TiO2 material host sensitized solar cells.

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Figure 3. Schematic representation of monodentate (M1), dissociative monodentate (M2), bridged bidentate (BB), and bridged chelated (CB)
adsorption modes for a carboxylic acid on the (101) TiO2 surface. Reprinted with permission from ref 22. Copyright 2012 Royal Society of
Chemistry.

electron transfer from the dye’s excited state into the The primary dye−TiO2 interactions are mediated by the dye
conduction band (CB) of the TiO2, leaving the dye in its adsorption mode on the semiconductor surface. A crucial
oxidized state.10−13 Electrons injected in the TiO2 are collected characteristic for efficient dyes is the presence of suitable
at the conducting glass surface through transport across the functional groups which can strongly bind to the surface of
disordered network of TiO2 NPs. The oxidized dye is semiconducting metal oxides. To ensure ultrafast electron
regenerated by electron donation (usually iodide ions, I−) in injection, the anchoring group should coincide or be very close
the electrolyte that is infiltrated into the porous films and the (conjugated) to the dye acceptor unit, where the photoexcited
generated triiodide ions (I3−) are reduced at the counter electrons are spatially confined. This promotes electronic
electrode. In addition to these forward electron transfer and coupling between the donor levels of the excited dye and the
transport processes, there are also several competing loss delocalized acceptor levels of the semiconductor CB, assisting
pathways, including the excited-state decay of dye molecules, the charge injection process.14 The orientation and packing of
charge recombination of injected electrons with dye cations and adsorbed dyes on the semiconductor surface are strictly
with oxidative species in the electrolyte. dependent upon the binding motif and affect the rate and
In DSCs, the working process can be regarded as a effectiveness of parasitic recombination reactions.15,16 More-
competition of these forward and loss pathways. Besides the over, the sensitizer’s anchoring group should provide stable
physical and chemical properties of TiO2 nanocrystal itself, the grafting of the dye onto the semiconductor surface, thus leading
interaction of TiO2 with surrounding environment such as to long-term device stability.17−19 The main information
sensitizers and electrolytes also has significantly impact on the available on dye anchoring on the TiO2 surface is reviewed in
section 2.2.1, while the implications of dye−TiO2 interactions
TiO2/dye/electrolyte interfacial properties, charge transfer
on the DSCs operational mechanism are reviewed in section
kinetics, and thus the PV performance. In recent years,
2.2.2.
extensive efforts have been taken to investigate the interfacial
2.2.1. Anchoring of Sensitizers on TiO2 Surface. The
interactions and the correlated charge transfer processes. These anchoring mechanism of the largely employed carboxylic acid
researches give people intrinsic understanding of the charge group to the TiO2 surface can be exemplified referring to the
transfer in DSCs and provide clues for further improving device coordination modes of the carboxylate fragment (COO−) to
performance by interfacial engineering. metal ions. There are basically three typical coordination
2.2. Interaction of Sensitizers with TiO2 schemes, including monodentate chelating, bidentate chelating,
Dye-TiO2 interactions rule the primary charge generation event and bidentate bridging.20 An empirical rule, derived by Deacon
in DSCs, i.e. electron injection from the dye excited state into and Philips,21 correlates the difference between the asymmetric
the CB of the TiO2, and thus exert a direct influence on the and symmetric IR stretching frequencies (Δνas) of COO− to
the type of coordination: if Δνas for the adsorbed species is
short-circuit photocurrent density (Jsc). The opposite process,
larger than that measured for the neat salt a monodentate
i.e., the parasitic recombination between injected electrons and
coordination (either M1 or M2 in Figure 3) is hypothesized;22
oxidized dyes, which occurs after the electron injection, is also
if Δνas is comparable or smaller than that of the corresponding
entirely dependent upon the dye−TiO2 interactions. This
salt, a bidentate (either bridged bidentate BB or chelating
process may affect the Jsc and, by reducing the electron density bidentate CB in Figure 3) bonding mode is hypothesized.
in the TiO2, the open-circuit voltage (Voc). Dye−TiO2 Thus, the disappearance of the carbonyl stretching of the free
interactions also lead to shifts in the energy of the TiO2 CB, dye and the appearance of the carboxylate symmetric and
thus directly affecting the Voc as well as indirectly influencing asymmetric stretching in the 1300−1650 cm−1 region, are a
the kinetics of electron injection and recombination by shifting diagnostic for dye adsorption mode. However, realistic dyes
the semiconductor CB energy levels. often show a plethora of overlapping absorptions in the
The formation of a compact dye monolayer on the TiO2 interesting range, which may hinder a precise identification
surface can insulate the TiO2 surface from approach of the and/or assignment of the diagnostic carboxylic modes. Most IR
electrolyte and suppress the recombination between injected spectral assignments for dyes on TiO2 are thus based on the
electrons and oxidized species in the electrolyte. As the dye may comparison between experimental data and DFT-calculated IR
also constitute a binding site for oxidized species in the spectra. These techniques give structural details about the
electrolyte, the location of these binding sites and the dye adsorption modes and provide information on the relative
adsorption mode further shed light into reasons of the vastly orientation of the molecules anchored onto the oxide surface.
different efficiencies for very similar dyes. As such, an The binding mode of the prototypical [Ru(NCS)2(dcbpy)2]
understanding of dye−TiO2 interactions from an in-depth dye (known as N3) on TiO2 was investigated by Shklover et
and atomistic perspective is important to the full exploitation al.23 Based on structural analyses, various dye adsorption modes
and optimization of DSCs. were modeled and corresponding surface area occupations were
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estimated. It was concluded that binding via two or three

carboxylic groups would be favored over a single anchoring,
while binding via four carboxylic groups was impeded by
planarity of the TiO2 surface. The adsorption mode of the
doubly protonated N3 dye (also known as N719) was further
investigated by DFT calculation by De Angelis et al.,24 while
the electronic properties of the N3/TiO2 interface were
previously investigated at the DFT level by Persson et al.,25
using a model geometry. Binding of the N719 dye on TiO2 was
found to occur in a dissociative fashion, involving carboxylic
groups residing on different bipyridine ligands.24 De Angelis et
al.26 performed ab initio molecular dynamics simulations and
suggested that N719 adsorbed onto the TiO2 surface via three
anchoring carboxylic groups out of the four dye carboxylic
groups (Figure 4). The simulation of the tetrabutyl ammonium

Figure 4. Optimized geometrical structure of the N719 dye adsorbed

on TiO2 along with its two TBA counterions. Reprinted with
permission from ref 26. Copyright 2010 American Chemical Society. Figure 5. (a) Different possible orientations and coordination patterns
of the stable 2-fold and 3-fold anchored dyes bound to the anatase
(101) surface. (b) The experimental IR spectrum of the N3 dye
(TBA) counterion position revealed one strongly bound TBA, adsorbed on anatase nanocrystals in EtOH (black) and the computed
which was close to the TiO2 surface, and one loosely bound IR spectrum (red) for the fully protonated configuration I1 on the
TBA, suggesting a partial negative charge for the N719- anatase (101) surface. Reprinted with permission from ref 27.
adsorbed dye. Copyright 2010 American Chemical Society.
The anchoring of the N3 dye as a function of protonation of
the carboxylic groups was investigated by Schiffmann et al.27 by basis of the calculated adsorption energies, it is impossible to
combining IR experiments and DFT calculations. It was identify a single adsorbed structure, while it seems that several
demonstrated that the dye binding mode on TiO2 can be configurations with similar stabilities may coexist or convert
significantly affected by the initial dye protonation. When four into one another.
protons was considered in the system, the most stable The photoelectron spectroscopy (PES) can provide
adsorption mode was calculated to occur via three anchoring information on the molecular and electronic structures at the
carboxylic groups (G in Figure 5a), in agreement with the three dye/TiO2 interface, along with basic indications of the dye
anchoring adsorption mode proposed in ref 26. When no coverage and of the distance of selected atoms from the
protons were considered, the most stable adsorption mode was surface.30−34 Also the measurement of the adsorbed dye
shown to correspond to binding via two carboxylic groups monolayer depth compared to the molecular dimensions can
residing on different bipyridine ligands (I2 in Figure 5a), closely give qualitative information about the angle formed by the main
resembling the one previously suggested in ref 24. axis of the adsorbed dyes with respect to the TiO2 surface. By
Despite the calculated dye adsorption energetics, Schiffmann measuring the ratio between the 1s peaks of the nitrogen atoms
et al.27 suggested that solvent molecules could displace one of the triphenylamine (TPA) donor and of the cyanoacrylic
carboxylic group, favoring two-anchoring modes. This is also acid acceptor in typical push−pull organic dyes, Rensmo and
supported by the similarity between the DFT-calculated IR co-workers30 successfully estimated the relative distance of the
spectrum of N3 adsorbed on mesoporous TiO2 and the dye atoms from the surface. As shown in Figure 6a, the N1s
experimental one (Figure 5b). Labat et al.28 also found that N3 core level is originated by two signals separated by 1.3 eV,
dye binded to TiO2 surface via two carboxylic groups residing arising from the TPA nitrogen (399.8 eV) and the cyano group
on different bipyridine ligands although they did not consider (CN) nitrogen (398.5 eV) atoms. The intensity ratio of the two
three anchoring structures. Martsinovich et al.29 investigated signals measured at different photon energies is clearly
the N3 dye adsorption on the rutile (110) surface rather than suggestive of a dye orientation with the TPA moiety pointing
on the anatase (101) surface as from previous studies. On the away from the surface, while the CN group is close to the TiO2
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recombination between injected electrons and oxidized dye

molecules, and recombination between injected electrons and
oxidized species in the electrolyte. The effect of dye adsorption
on the electronic properties of TiO2 is also briefly reviewed.
A large number of theoretical investigations have been
specifically devoted to the effect of the dye anchoring and
spacer groups on determining the efficiency of the electron
injection and the minimization of parasitic recombination
processes.16,41−52 The effect of the anchoring group on the
electron injection dynamics in dye-sensitized semiconductor
surfaces was pioneered by Persson and co-workers in a series of
papers.25,41−44 These researchers exploited the News-Ander-
sson model framework to estimate the lifetime of an electron
initially residing on the dye LUMO when it comes into contact
with the manifold of unoccupied semiconductor states. The
main finding of these studies is that a conjugated anchoring
group, e.g., a perylene dye featuring a double bond connecting
the donor and acceptor moieties, exhibits a much stronger
interfacial coupling and a shorter electron injection time than
the same system with a non conjugated anchoring group. These
results are in excellent agreement with the time-resolved
spectroscopic results by Szarko et al.,53 who found a sizable
dye-semiconductor coupling for the conjugated perylene dye, as
signaled by the broader and partly unstructured steady-state
absorption spectrum measured for the dye anchored to the
semiconductor compared to the dye in solution.
An interesting contribution to the “anchoring group” issue
came from the Troisi group,52 who systematically investigated
Figure 6. (a) N1s core level spectra of D5 adsorbed onto
the electron injection time for different dyes. They set up a new
nanostructured TiO2 measured at three different photon energies. computational strategy, which allows one to compute the
Reprinted with permission from ref 30. Copyright 2010 American injection time by simply investigating the TiO2/anchoring
Chemical Society. (b) and (c) Optimized molecular structures of the group interface, without needing to compute the entire dye-
more stable BB adsorption modes for the L0 and rh-L0 dyes. semiconductor system. The authors investigated a series of
Reprinted with permission from ref 16. Copyright 2011 Royal Society possible anchoring groups (as shown in Figure 7) in
of Chemistry.

surface. Pastore et al.16 investigated the adsorption mode of two

dyes (L0 and rh-L0) on TiO2 as models of the systems having
TPA donor groups and cyanoacrylic and rhodanine-3-acetic
acid acceptor moieties. As illustrated in Figure 6b,c, structural
optimization of the dye adsorbed on TiO2 models revealed a
preference for the bridged bidentate adsorption mode in both
cases, although different binding modes were quite close in
energy for the rh-L0 dye. The mostly employed cyanoacrylic
acid anchoring group induces a perpendicular dye orientation
with respect to the TiO2 surface for the cyanoacrylic acid L0
dye, while the rh-L0 dye, bearing a rhodanine-3-acetic acid
acceptor, forms an angle of ∼40° with the average TiO2 plane.
Besides, the techniques of X-ray reflectometry (XRR),35 X- Figure 7. (a−o) Molecules with model anchoring groups studied in ref
ray photoelectron spectroscopy (XPS),36−39 and neutral impact 48. Reprinted with permission from ref 52. Copyright 2012 American
collision ion scattering spectroscopy (NICISS)40 are also Chemical Society.
applied to unravel the orientation, morphology, and thickness
of dye molecules adsorbed on the titania surface. The combination with a perylene donor moiety. The authors
implications of different dye adsorption modes on the investigated the attachment chemistry and computed the
photovoltaic performances are discussed in the next section. binding energies of 15 different anchoring groups on both
2.2.2. Influence of Sensitizer Adsorption Behavior. anatase (101) and rutile (110) surfaces. Based on periodic DFT
Understanding the adsorption behavior of sensitizers on the calculations, most of the groups were found to have multiple
TiO2 surface, such as dye orientation and molecular packing is stable adsorption modes, with a total of 35 adsorption modes
important for obtaining valuable insight into the charge transfer on anatase (101) and 26 adsorption modes on rutile (110). For
processes occurring in DSCs. In this section, we will shortly each anchoring group and observed adsorption geometry, the
review the effect of dye interaction with TiO2 in the authors computed the electron injection time for a perylene
fundamental operational DSC processes, i.e., electron injection molecule bearing the selected group on anatase (101) and rutile
from the dye excited state into the TiO2 unoccupied states, (110). Based on this data, various interesting alternatives to the
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most common carboxylic or phosphonic acid anchoring are cases, the assemblies of sensitizers on titania surface are
spotted out by this computational investigation, such as proposed to form a blocking layer, thus inhibiting the charge
acetylacetone (c) and hydroxamic acid (d) anchors, which recombination and benefiting the Voc. Wang and co-workers
both display good computed binding and injection character- measured the thickness of dye assemblies on titania by
istics. For a given dye and/or anchoring group, it is also found employing the XPS technique and found that there was a
that the dissociative bridged bidentate adsorption mode induces positive correlation between the electron lifetime and molecular
a higher interfacial coupling and a shorter electron injection coating thickness.37−39 The thicker molecular coating on titania
times than the monodentate adsorption. For the N3 dye on the induces longer tunneling distance between titania electrons and
TiO2 rutile (110) surface, Martsinovich et al.29 found that the oxidative species and consequently offers longer electron
injection time significantly shortened for the bridged bidentate lifetimes of the mesoporous titania film. XPS measurements
adsorption modes as well as by increasing the number of reveal that the branched sensitizers are likely to form thicker
sensitizer carboxylic groups anchoring to TiO2. coatings on titania surface, presumably because they tend to
To discuss the impact of dye adsorption mode on the anchor on the surface of titania with a relatively smaller tilt
recombination reactions54,55 it is worthwhile to recall that the angle with respect to the substrate normal.37,38 These thick
kinetics of recombination between the injected electrons and molecule coatings effectively hinder the leakage of electrons
the oxidized dye are strongly dependent upon the electron and make a decisive contribution to the improved photovoltage
density in the conduction band/trap states, electrolyte as well as the higher charge collection efficiency. Besides the
composition56−58 as well as the spatial separation of the charge thickness of dye coatings, the internal structure of self-
hole localized on the oxidized dye, which can be assimilated to assembling sensitizer layers is of crucial important to the
the HOMO of the neutral dye, and the TiO2 surface.59 Solely charge transfer process in the device. The sensitizers with three-
on the basis of the discussed results, that is of the different dimensional (3D) steric encumbrance are likely to form
charge injection mechanisms, it is not straightforward to powerful porous photoactive layers on the surface of TiO2
hypothesize a different location of the injected electrons as one nanocrystals.63,66 Although this kind of assemblies may exhibit
should take into account the complex dynamics of the thinner compact layer thickness, it can significantly hinder the
delocalization of the electrons into the oxide bulk as well as charge recombination if the resultant micropores are smaller
their relaxation pathways to the CB edge.60 One can however than the oxidative species in the electrolyte.63
speculate that for those dyes featuring weak electronic coupling Recently, two organic sensitizers (C257 and C258, as shown
with the semiconductor CB, such as for the rh-L0 dye in Figure in Figure 8a) with cyclopentadithiophene-benzothiadiazole
6c, the prevalence of a nonadiabatic electron injection unite as the chromophoric core have been synthesized and
mechanism implies an exponential dependence of the electron applied in DSCs in conjunction with a cobalt electrolyte.64
transfer rate upon the dye donor/semiconductor acceptor Solar cells based on C258 sensitizer exhibit relatively low
states; that is, the electronic coupling is determined by the incident photon-to-current efficiency (IPCE) height and Voc as
tunneling probability, with the associated exponential decay. It compared with the C257-based cell and this inferior photo-
can therefore be conceived that a high probability of electron voltaic performance is attributed to the fast charge recombi-
injection would correspond to semiconductor CB states nation of photogenerated titania electrons with the oxidized
localized close to the dye LUMO, i.e. CB states localized at dye molecules and/or Co(III)−bpy ions in the electrolyte.
the semiconductor surface rather than within the bulk, from Contrary to the above-mentioned results, XPS measurement
which a faster recombination with oxidized dyes can be showed that there was not a positive correlation between the
expected. One can furthermore elaborate that the different dye layer thickness and the electron lifetime (Figure 8b). This
orientation of the dyes with respect to the TiO2 surface, phenomenon was explained by the postulation that the C258
determined by the possibly different anchoring unit, results in a sensitizer formed an organic layer with more penetration
different dye HOMO/TiO2 CB separation even considering the channels (Figure 8c), allowing the Co(III)−bpy ions to
same nature of the CB states involved in the electron injection penetrate and thus to be in proximity with the surface of
for the L0 and rh-L0 dyes. Looking at the bidentate structures titania. In the development of low energy gaps of organic dyes,
reported in Figure 6b,c, and considering the TPA donor unity, it is quite common to meet the aggregation induced carrier
the dye HOMO/TiO2 distance can be roughly estimated to be photogeneration troubles. Good dye-bath solvent, in which the
8−10 Å for L0 and 6−8 Å for the rh-L0 dye. By extrapolating interactions between dye segments and solvent molecules are
this data for the longer D5L2A1 and D5L2A3 dyes examined energetically favorable, can prevent the aggregation of dye
by Wiberg et al.,15 a dye HOMO/TiO2 separation of 14−16 molecules on the surface of titania,38,39,67−69 thus improving the
and 9−11 Å for the two dyes is calculated respectively. This electron and hole injection yields in the device. However, the
data might account for the measured differences in the application of a good solvent also diminishes dye loading
recombination rates, whereby a closer proximity of the hole amount and brings forth some pinhole defects in the dye layer
localized on the dye to the semiconductor surface would lead to on the titania surface (Figure 9a). These defects may act as
higher recombination rates.61 A similar argument, i.e., the penetration channels for ions in the electrolyte, speeding up the
different distance of the dye HOMO from the TiO2 surface, interfacial charge recombination and deteriorating the photo-
was also exploited to explain the different recombination voltaic performance of DSCs.
kinetics of the ruthenium C101 dye on TiO2 anatase To obtain optimized molecular assemblies on titania surface,
nanoparticles with preferential (101) and (001) facets.62 the molecules, which feature a high capacity of considerably
While the origins of the inhibited recombination dynamics slowing down the interfacial charge recombination, are used for
can be rather complicated and are still not well understood, pinhole defect filling (Figure 9a). Recently, three fillers have
recent exploratory researches provide us some information on been tested by measuring the dark currents and it was found
the association between the electron recombination kinetics that filler III featured the strongest ability of controlling the
and molecular assemblies on titania surface.37−39,63−65 In most interfacial charge recombination (Figure 9b,c).66 The filler III
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Figure 8. (a) Molecule structures of the C257 and C258 dyes. (b)
Signal intensities of the Ti2p3/2 and Ti2p1/2 photoelectrons emitted
from the bare and dye-grafted mesoporous titania films. The inset
shows the electron lifetime for the C257 and C258 grafted titania
films. (c) Schematic of the self-assembled dye layer of C257 and C258 Figure 9. (a) Pictorial illustration for self-organized molecules on
on titania surface. Reprinted with permission from ref 64. Copyright titania with dyes dissolved in a good solvent (upper) and pinhole
2013 Royal Society of Chemistry. defect filling with a suitable filler (bottom). (b) Molecular structures of
three pinhole defect fillers. (c) J−V characteristics in the dark for cells
employing the bare and grafted titania films with fillers I−III in
combination with a Co−phen electrolyte. Reprinted with permission
grafted on the titania surface forms the molecule layer with the from ref 66. Copyright 2013 Royal Society of Chemistry.
largest thickness and smallest mass density than the other two
fillers, implying that the molecule with a bulkier 3D character
tends to form a thicker coating layer with a larger porosity. The and hold significance for further surface engineering to
close relation between the filler layer thickness and the optimized charge transfer kinetics.
recombination hindering ability of fillers further confirms that The energetics of the TiO2 CB are known to depend on
the resulting porous but thick coating can strongly restrain the several factors, such as the local pH,70−72 the concentration of
charge recombination through elongating the electron tunnel- potential determining ions,72,73 and the nature of the electrolyte
ling distance. Taking advantage of the dark current controlling solvent.73,74 However, the role of surface adsorbed molecules in
power, the filler III was cografted with C258 dye to remove the determining the TiO2 CB energetics is much less clear.16,75−80
penetration channels for the Co(III)−bpy ions.64 As shown in Some researcheres investigated the correlation between the dye
Figure 10, the device performance was greatly improved due to protonation state and the DSCs performance,76−78 showing
enhanced Voc and Jsc, achieving an unprecedented PCE of that dyes carrying a higher number of protons led to higher Jsc
11.2% for DSCs with metal-free organic dyes under AM 1.5 full but lower Voc. An interesting correlation between the dipole
sunlight. These findings suggest the importance of sensitizer- moment of coadsorbing species, mainly substituted benzoic
titania interfacial microstructure upon charge recombination acids, and the corresponding Voc was observed by Rühle et al.,79
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density of the bipyridine groups and the d states found in TiO2,

because the electronic structure around the pyridine structures
was slightly modified after dye adsorption as revealed by the
carbon K-edge X-ray absorption near-edge structure spectra.
For the dye coated TiO2, the Ti 2p spectrum was slightly
shifted to lower binding energy compared to the uncoated
TiO2, indicating that the adsorption of the dye on TiO2 led to a
change of the surface dipole and/or a movement of the Fermi
level position in the band gap. This picture is also in line with
earlier DFT calculations for N3/N719 on TiO2,77,84 which
clearly showed a strong admixture of dye/semiconductor states.
2.3. Interaction of Coadsorbents with TiO2
Dye aggregation, a common phenomenon upon adsorption of
dye molecules to TiO2 surface,85−88 is generally considered as
an undesired phenomenon in DSCs. The aggregation leads to
deactivation of dye excited state via quenching processes and
provokes losses of absorbed photons in the device. Prohibition
Figure 10. (a) Photocurrent action spectra and (b) J−V curves of cells of aggregation by coadsorption of dye molecules with
made with C258 and via cografting C258 with filler III. Reprinted with nonchromophoric adsorbates is recognized as an effective
permission from ref 64. Copyright 2013 Royal Society of Chemistry. method to improve the device efficiency.89−94 Generally, the
cografting of coadsorbents increases the electron injection yield
who pointed out a linear relation between the dye coverage and results in improved device photocurrent, although the
(N), the molecular dipole moment (μ), the component normal competitive adsorption between coadsorbents and sensitizers
to the surface (θ is the molecule tilting angle) and the potential may lead to reduced dye coverage.87,92,93,95,96 However in some
shift (ΔV) at the interface cases, the effect of coadsorbent is more complex and can be
Nμ cos θ closely related with the sensitizer structure. In research based
ΔV = on Ru-phthalocyanines sensitizer, which was developed to
εε0 (1) minimize the formation of aggregates, the coadsorbent
where ε is the dielectric constant of the monolayer and ε0 is the (chenodeoxycholic acid, CHENO) was reported to dramati-
dielectric permittivity of vacuum. cally enhance the photocurrent without lowering the photo-
Study on solid-state DSCs has clearly shown an over 100 mV voltage.94 The similarity of the normalized transient absorption
TiO2 CB shift between a heteroleptic ruthenium dye and an traces indicated that CHENO did not affect the electron
organic dye, and this phenomenon is interpreted in terms of a injection dynamics of the Ru-phthalocyanines sensitized TiO2,
dipole-induced TiO2 CB shift in opposite direction.81 Such and therefore the electron injection quantum yield. Further
shifts are generally more difficult to be observed in DSCs based photophysical measurements showed that the slower recombi-
on a liquid electrolyte,82 in which the high ion strength and the nation of dye cations with the TiO2 electrons and faster
effect of thermal motion hinder the role of interface dipoles. regeneration of dye cations by the electrolyte were responsible
When a dye binds to a semiconductor surface, two effects might for the enhanced photocurrent.
be at work: (i) the electrostatic (EL) effect, due to the dye In addition to photocurrent, cografting of coadsorbents with
dipole moment, and (ii) the effect of the charge transfer (CT) sensitizers also benefits photovoltage of DSCs.91,92,96−99 This
between the dye and the semiconductor which may accompany effect can be attributed to a negative shift of the conduction
the dye-semiconductor bond formation. Ronca et al.83 recently band edge and/or the suppression of recombination of the
employed charge displacement analysis to investigate the injected electrons with the redox electrolyte. Neale et al.98
influence of the adsorption of several prototypical organic systematically investigated the basic physical processes by
dyes and coadsorbents on TiO2 models, quantifying and which CHENO affected Voc and found that adding CHENO
rationalizing the effects of EL and CT contributions to the shifted the TiO2 CB to negative potentials by ∼80 mV. In their
TiO2 CB energetics. It was found that the CT effect research, the usage of adsorbent also increased the rate of
contributed a large fraction of the calculated CB shift, and recombination by a factor of 5, indicating that the net
the CT contribution was subtly modulated by the dye donor enhancement of photovoltage of ∼40 mV was the result of
groups. For undissociated monodentate dye adsorption, a CT both band edge movement and recombination. While the
of ca. 0.10−0.15 electrons was calculated for a dye coverage of reduced recombination is often attributed to the shielding of
∼1 molecule nm−2, inducing a CB shift of 0.02−0.06 eV. The recombination centers on TiO2,96,97 the coassembly of
EL contribution to the total CB shift was nicely correlated with sensitizers and coadsorbents are also proposed to form compact
the electrostatic potential generated by the adsorbed dye. monolayer on TiO2, preventing oxidized species (I3−) from
The electronic properties of N719 adsorbed onto anatase approaching TiO2 surface.92,99 The organic molecule, 3,4,5-
were recently investigated by using X-ray absorption spectros- tris(dodecyloxy)benzoic acid (DOA, which features three
copy (XAS) and XPS techniques.36 It was reported that hydrocarbon chains, were adsorbed together with the Z907
adsorption of dye molecules can induce additional electronic dye to form a monolayer in a solid-state DSC. Coadsorption of
states between dye molecules and TiO2 surface. The electronic DOA permits preparation of a denser interlayer between hole-
interactions between dye molecules and TiO2 were proposed transporting material (HTM) layer and the TiO2 surface, thus
not only to occur through the covalent bonding of the effectively preventing charge recombination between photo-
anchoring groups but also through the aromatic electron induced electrons and HTM. The photocurrent of the device is
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increased by two times due to the suppressed electron electrical impedance spectroscopy (EIS) results, the Li+ ion was
recombination at the TiO2/HTM interface. calculated to evoke a downward shift of the conduction band
2.4. Interaction of Electrolytes with TiO2 edge by 390 meV as compared with dimethylimidazolium,
providing strong evidence for the proposed band edge
The electrolyte is a key component in DSCs. It functions as the movement modulated photovoltage shrinkage upon addition
HTM and regenerates dye molecules at the photoelectrode. As of Li+ ions. Besides, the specific adsorption of cations also
the electrolyte interacts with both TiO2 nanomaterials and influences both the interception of photoinjected electrons by
sensitizers, the ions, additives as well as the solvent in the I3− and the electron transport, thus affecting the charge
electrolyte dramatically influence the thermodynamic and collection across the TiO2 film.103,105−110
kinetic properties at the TiO2/dye/electrolyte interfaces. 4-tert-Butylpyridine (TBP), which was initially applied in
O’Regan and Grätzel8 first reported the cation-dependent DSCs by Grätzel et al. in 1993,111 is a typical additive in highly
photoelectrochemical behavior for DSCs. They found that the efficient electrolyte. The presence of TBP in electrolyte induces
IPCE at 520 nm can be raised from 68% to 84% upon replacing significant improvement in Voc primarily through uplifting of
the tetrapropylammonium iodide electrolyte with the lithium the titania conduction band edge. Moreover, the adsorption of
iodide one. Meyer and co-workers100 studied the impact of TBP on TiO2, which is believed to blocking the approach of
cations on the excited-state deactivation of surface adsorbed triiodide to the TiO2 surface and/or removing adsorbed iodine
ruthenium polypyridyl complexes and convincingly demon- from the surface, can also reduce the electron recombination
strated that the presence of lithium cation (Li+) increased the across the TiO2/electrolyte interface, thus positively influencing
quantum yield for interfacial electron injection. Further studies the photovoltage of the device.112−114 Hagfeldt and co-
based on different sensitizers and electrolytes have achieved workers113 investigated the effect of TBP in the DSCs and
similar results and the electron injection dynamics is proven to found that the photovoltage enhancement upon addition of
be strongly dependent upon the nature and concentrations of TBP could be attributed to the shift of the TiO2 band edge
cations in the electrolyte.61,101−106 The influence of cations on toward negative potentials (responsible for 60% of the voltage
electron injection dynamics is generally attributed to their increase) and to an increase of the electron lifetime
interaction with TiO2, and therefore the influence on the TiO2 (responsible for 40% of the voltage increase). They concluded
surface states. The commonly used Li+ ion is known to be that the action of TBP was both at the semiconductor/
potential determining for metal oxide electrodes and the electrolyte interface, where it affected the surface charge, and in
specific adsorption of Li+ on TiO2 leads to positive shift of the the electrolyte, where it formed a complex with iodine. In fact,
conduction band edge (deeper in the energy scale, with respect the precise effect of TBP on photovoltaic parameter is not
to electron in vacuum).61,101,102,105 Although the existence of immutable and it is closely related with the properties of the
electronic interaction between dye molecules and Li+ ions may sensitizer and the TiO2/dye/electrolyte interfaces. Recently, the
result in reduced excited-state redox potential of the influence of TBP upon the interfacial energetics and kinetics in
sensitizer,101,103 the remarkable positive shift of the titania organic DSCs was investigated based on two push−pull organic
conduction band edge tends to impel favorable energy dyes C218 and D205.115 It was revealed that an increment of
alignment at the TiO2/dye interface, thus increasing the TBP in electrolyte brought forth comparable elevations of
thermodynamic driving force for electron injection. Further to titania conduction band edge for DSCs with C218 and D205.
the enhanced photocurrent due to more efficient electron Interestingly, TBP at a higher concentration, while significantly
injection, another prevailing observed phenomenon is the retarded triiodide interception of photoinjected electrons for
decline of photovoltage upon introducing Li+ ions. This effect is the C218-based cell, had induced significantly accelerated
generally attributed to the Li+-induced positive shift of the CB, recombination reaction at a given free electron density for the
and the photovoltage deterioration is found to be closely D205-based cell. This abnormal observation was suggested to
related to the Li+ ion concentration in the electrolyte.104,106,107 be caused by the bracing of the low-lying D205 molecules or by
Recently, Wang and co-workers103 investigated the influence of the increased thermodynamic driving force for electron
cations on the electrical characteristics of DSCs and derived a recombination.
detail profile of the distribution of surface states in mesoporous Compared with the relatively large number of studies
titania film (Figure 11). Based on quantitative modeling of focusing on the importance of TBP in cell performance, the
microscopic interaction between TBP and TiO2 is less
elucidated. Shi et al.116 suggested, on the basis of in situ
Raman spectroscopy, that some incompletely coordinated
titanium atoms can bind TBP molecules by forming Ti ← N
bonds. By employing a periodic DFT method with full
geometry optimization, Kusama et al.80 investigated the
adsorption of TBP on the TiO2 anatase (101), (100), and
(001) surfaces and found that the adsorption of TBP on any
surface negatively shifted the TiO2 Fermi level (Figure 12).
However, further XPS study gave different results,117 and
indicated that the density of oxygen vacancies on anatase (100)
surface did not change upon TBP adsorption. They concluded
that the adsorption of TBP on anatase (100) surface did not
have any significant effect on the surface band bending and the
Figure 11. Distribution of density of states of cells with LiI and DMII major role of TBP was to protect the TiO2 surface from
based electrolytes. Reprinted with permission from ref 103. Copyright adsorption of ionic components in the electrolyte. Although
2010 Royal Society of Chemistry. giving clues for better understanding of the interaction between
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Figure 12. Geometry-optimized structures of TBP adsorbed on a TiO2

anatase (a) (101), (b) (100), and (c) (001) surface. Reprinted with
permission from ref 80. Copyright 2008 American Chemical Society.

TBP and TiO2, this result only represents an ideal situation. As

the nanostructured TiO2 in DSCs is not made from (100)
oriented crystallites, further work is still needed to clarify the
realistic situation in DSCs.
Apart from the pronounced effects of ions and additives in
the electrolytes, the organic solvents in the electrolytes also
have great influence on the photophysical properties of the
Figure 13. (a) Mulliken charge distributions of TCB (left) and DCA
DSCs. A number of researches employing different solvents (right) calculated at B3LYP level. Reprinted with permission from ref
revealed that the solvents with large donor number enhanced 124. Copyright 2010 Royal Society of Chemistry. (b) Schematic
the photovoltage while reducing the photocurrent of the presentation of the dipole effect on the conduction band edge.
device.118−121 The increase of the solvent’s donor number is Reprinted with permission from ref 125. Copyright 2011 American
proposed to cause extended coverage of the semiconductor Chemical Society.
surface by solvent molecules, leading to a negative shift of the
TiO2 conduction band edge. Besides the solvent’s donor
number, the conduction band edge of the TiO2 can also be
affected by the dipole moment of the solvent. Hao and co- 13b, the adsorption of dicyanamide anion on TiO2 surface
workers122 reported the significant solvent dipole moment forms a dipole pointing from electrolyte toward titania,
modulated conduction band edge displacement of the TiO2 prompting conduction band edge elevation as compared with
electrodes and this effect was responsible for the observed tetracyanoborate anion.125 Recently, the attenuated total
variable driving force for electron injection and the interfacial reflection infrared spectroscopy (ATR-IR) has been applied
charge recombination. to investigate the interactions of anions with TiO2.126
Although the highest PCE of 12.3% has been achieved with Compared to 1-ethyl-3-methylimidazolium tetracyanoborate
DSCs based on a porphyrin sensitizer, the utilization of a highly (EMITCB) IL, there is a significant blue shift of the CN
volatile organic solvent presents a momentous challenge in stretching frequency for the EMIDCA in the presence of TiO2
consideration of a robust electrolyte encapsulation for future NPs (Figure 14a,b), implying that EMIDCA interacts more
large-scale DSC application. Ionic liquids (ILs) have been strongly with TiO2 NPs. Femtosecond transient absorption
actively pursued as an attractive solution to the evaporation of measurements indicates relatively higher electron injection
organic solvent in traditional electrolyte. However, the efficiency in the case of EMITCB environment (Figure 14c)
relatively low fluidity has largely limited the mass transport of and this phenomenon is consistent with previous results.124,125
redox species and thus the cell performance. As the viscosity of Grätzel and co-workers127,128 reported the application of
ILs is strongly correlated to the interaction between the cobalt(III) complexes as p-type dopants for spiro-MeOTAD.
cationic and anionic components, mixing high-viscosity iodide These cobalt(III) complexes were shown to be beneficial for
ILs with low-viscosity ILs with noniodide anions has been controlling the charge transport properties of spiro-MeOTAD.
proved to be an effective approach to constructing relatively Moreover, the properties of the cobalt(III) dopants can be
high-fluidity ionic liquid electrolytes and, as a consequence, to easily adjusted by the modification of the organic ligands and/
reduce transport limitation problem in the device. The ionic or the counterion.128 The solid-state DSC with organic D-π-A
liquid 1-ethyl-3-methylimidazolium dicyanamide (EMIDCA), molecule Y123 as the sensitizer and tris(2-(1H-pyrazol-1-
which features relatively low viscosity, has been utilized in yl)pyridine)cobalt(III) doped spiro-MeOTAD as the HTM
junction with iodide melts to fabricate an over 8% efficiency exhibited a record PCE of 7.2% under standard test conditions.
DSC.105 A number of researches showed that the dicyanamide Besides cobalt(III) complexes, recent research shown that
anion can passivate the surface states of TiO2, inducing higher protic ionic liquids, used as a source of H+, were also effective
photovoltage and lower photocurrent.123−126 Quantum calcu- dopants for small molecule organic semiconductors.129 The
lations revealed that the CN nitrogen atom carried more protic ionic liquids promote single electron oxidation, thus
negative charge than the central nitrogen (Figure 13a), thus was increasing the hole concentration and reducing the charge
more favorable for adsorption on titania.124 As shown in Figure transport resistance in the hole transporting layer.
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Figure 15. (a) Mesoporous structure of thickness L that forms the

electron transport materials in a DSC. It is formed by interconnected
particles that allow the transport of electrons via extended states, as
indicated in the energy diagram. (b) The potential V at the substrate
fixes the electron Fermi level at the edge of the nanostructured
semiconductor, with respect to the Fermi level of the hole conductor.
The localized states in the bandgap trap and release the diffusing
electrons. Injected electrons at the contact have a probability to diffuse
and recombine by charge transfer to the holes species, so that the
effective penetration in the layer is governed by the diffusion length Ln.
Figure 14. ν(CN) stretching frequencies of (a) EMITCB and (b) It is shown a case in which the diffusion length is longer than film
EMIDCA ILs with and without TiO2 film. (c) Femtosecond time thickness. (c) Electronic energy disorder is well described by an
profile of N719/TiO2 in different IL environments with excitation exponential density of states that decreases from the edge of the CB to
wavelength of 532 nm and probe wavelength of 800 nm. Reprinted the center of the gap. The surface states have a strong influence in
with permission from ref 126. Copyright 2012 American Chemical electron transfer to the acceptor species, that constitute recombination
Society. in a DSC.

2.5. Electrons Transport and Recombination in TiO2 where q is elementary charge, EFn is the Fermi level of electrons
Electrodes in the metal oxide, and Eredox is the redox potential in the
The operation of DSCs consists in electron transfer from a electrolyte, or hole Fermi level in the case of solid HTMs.
sensitizer to the TiO2 electron conductor network, followed by The TiO2 phase formed by well-connected anatase NPs can
transport of electrons to the collector of conducting substrate, be considered as a homogeneous medium in which electrons
avoiding recombination along the way. The accumulation of undergo a number of processes, indicated in Figure 15b. A
electrons in TiO2 is the origin of photovoltage, and the flow of main process is the transport of electrons in the extended states
electrons results in the photocurrent. Therefore, there has been of the CB (or mobility edge), where the concentration of free
enormous interest in a detailed understanding of the electronic electrons nc is defined as
steps in the metal oxide semiconductor, which control the nc = nc0eqV / kBT (3)
observed transport and recombination features.130,131 Nano-
crystalline TiO2 used in DSCs normally consists of anatase Here kBT is thermal energy and nc0 is an equilibrium
particles of the order of 20 nm size sintered on top of concentration in the effective density of states of the
conducting glass to form a rigid framework with high internal conduction band Nc. In a steady state situation, the traps
surface area, as shown in Figure 15a. The voltage V is defined remain at equilibrium occupation and the main effect governing
by the expression transport is the displacement of electrons in the CB. The
conductivity σn is a main parameter of the solar cell, as in
qV = E Fn(x = 0) − Eredox (2) practice it works in steady state conditions. σn determines a
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series resistance that should be removed if it is too large with The capacitive behavior of nanoparticulate TiO2 films has
respect to other resistances in the device. The expression of the been widely studied.160,161 The main feature is an exponential
electron conductivity associated to free carrier transport is132 bandtail that enters the gap of the semiconductor, with effective
DOS
q2D0
σn = nc NL
kBT (4) g (E) = exp[(E − Ec)/kBT0]
kBT0 (7)
Here D0 is the free electron diffusion coefficient. Therefore the
conductivity dependence on voltage shows a simple exponential Here T0 is a parameter with temperature units that determines
dependence on voltage with a slope (kBT)−1 due to Boltzmann the depth of the distribution, that is alternatively expressed as a
distribution function of electrons in the CB. This result has coefficient α = T/T0. Representative examples of the chemical
been observed in high quality measurements using the capacitance of a range of DSCs are shown in Figure 16.144 It is
transport resistance of impedance spectroscopy;133−135 how-
ever, it should be noticed that under illumination other effects
play a role and some quantities are displaced form the ideal
dependence.136
Since early work,137 it was recognized that localized states
have a large influence in kinetic processes in DSCs. TiO2 NPs
show a large number of localized states in the bandgap, with
total number NL, and number density nL. These localized states
are able to capture electrons, and later eject them back to the
transport level. Traps below EFn are almost fully occupied,
hence inactive for trapping events, while traps above the Fermi
level are nearly empty. Therefore, the probability of electron
capture is strongly determined by the position of EFn. A
localized state at energy Et releases electrons at a rate τt−1 = Figure 16. Chemical capacitance and recombination resistance of a
βnNce(Et−Ec)/kBT, where βn is the time constant for electron collection of DSCs with different dyes and electrolytes as described in
capture, which is independent of trap depth. Since τt increases represented vs the potential VF in which series resistance contribution
exponentially with the depth of the state in the bandgap, the has been removed. Reprinted with permission from ref 144. Copyright
slowest trap is the deepest unoccupied trap. This fact is the 2011 Royal Society of Chemistry.
cause that many quantities in DSC measurement are observed
to depend exponentially on the Fermi level, as will be further
justified later. The effect of traps is dominant whenever a
transient effect is induced, in which the position of the Fermi observed that the exponential shape is well obeyed. A
level is modified, with the correspondent need for traps release. noteworthy feature is the horizontal displacement of the
In contrast to DC conductivity, several kinetic coefficients of a exponential DOS along the voltage axis. This feature is due to
DSC are strongly influenced by traps, and an understanding of the displacement of the CB level Ec with respect to redox
such effects is critically important for a useful interpretation of energy level Eredox, caused by surface conditions at the
the experimental results.138−141 semiconductor/electrolyte interface. These features can be
Traps, especially surface states, also become a dominant determined and taken into account by combined measurement
aspect of the recombination of electrons in a DSC, that is a of capacitance, transport resistance Rtr, and recombination
charge transfer to the electrolyte or hole conductor, as shown in resistance Rrec in impedance spectroscopy.162
Figure 15c. These phenomena have been widely studied using The origin of the exponential DOS in anatase TiO2 has not
small perturbation techniques such as impedance spectrosco- yet been conclusively established. The DOS resembles that of
py,135,142−144 intensity modulated photocurrent and photo- standard disordered amorphous semiconductors,163,164 and it is
voltage spectroscopies,145−149 electron lifetime by time usually attributed to structural disorder. It should be pointed
transient decays,150,151 and also by stochastic numerical out that electrons in TiO2 show strong polaronic features. The
simulation.152−158 self-trapping effect causes a strong Stokes shift between light
The specific density of localized states (DOS) in the bandgap absorption and emission that is well observed at low
of TiO2, g(E), that is outlined in Figure 15b,c, can be temperatures. While excitation by a photon is a vertical
established by capacitance techniques that provide the chemical transition that takes place above the anatase bandgap value of
capacitance, that is defined as follows159 3.2 eV, photoluminescence occurs from the self-trapped state
and has a maximum at 2.3 eV.165,166 The difference is associated
dn with the stabilization of the electron−lattice system in the
cμ = q2
dE Fn (5) excited state. Self-trapped excitons in TiO2 also produce the
Urbach tails observed in absorption measurements. 167
It corresponds to a capacitance per unit volume. Using the Quantum mechanical calculations168 indicate that the electron
approximation of the zero-temperature limit of the Fermi becomes self-trapped at a Ti lattice site (Ti4+), which then
function, i.e., a step function at E = EFn separating occupied becomes formally Ti3+, with an energy gain (trapping energy)
from unoccupied states, it can be shown that the capacitance of associated with the polaronic distortion ΔEtrap = 0.23 eV, while
localized states takes the form139 the self-trapping energy of a hole is 0.74 eV. Recent DFT
cμL = q2g (E Fn) calculations suggest that disorder is not really a necessary
(6)
requirement to explain the DOS features of small anatase NPs,
Thus cμ provides a direct reading of the DOS at the Fermi level. which can be also caused by under-coordinated 4-fold
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coordinated surface Ti atoms mainly lying at the (100) edges

found at the intersections between (101) surfaces.169
In principle it appears extremely complex to calculate the
relevant kinetic coefficients such as electron diffusion coefficient
Dn, and electron lifetime τn, in the presence of many and
energy-distributed localized states that are indicated in Figure
15. However the model is greatly simplified by a condition that
actually removes the kinetic equation for the traps.170 If the
trapping kinetics is fast (with respect to time scale of the
transient measurement) we may assume that the traps follow
the equilibrium relation with the free carriers
∂nL ∂n ∂n
= L c
∂t ∂nc ∂t (8)
This assumption is termed the quasistatic approximation and
it was introduced to account for the properties of measured
time constants in DSCs.138,156,170 Since eq 8 is well obeyed by
ordinary DSCs, the following results can be demonstra-
ted.141,156 The chemical diffusion coefficient of the electrons
has the form
⎛ ∂nL ⎞−1
Dn = ⎜ ⎟ D0
⎝ ∂nc ⎠ (9)
A calculation of the trapping factor ∂nL/∂nc provides the
following result
Nc ⎡ E − Ec ⎤
Dn = α −1 exp⎢(1 − α) Fn ⎥D0
NL ⎣ kBT ⎦ (10)
A representative set of measurements of DSCs with different
types of hole conductors is shown in Figure 17a. The horizontal
axis shows the electron conductivity, which removes the CB
shift for the different types of DSCs. It is observed that Dn
shows a nearly universal behavior that follows well eq 10.
The description of the electron lifetime requires additional
steps. It is necessary to first define the free carrier lifetime
τf,156,171 in terms of the recombination rate Un
⎛ ∂U ⎞−1
τf = ⎜ n ⎟
⎝ ∂nc ⎠n (11)
c̅

that corresponds to the surface charge transfer events indicated Figure 17. Representation of several magnitudes for diffusion-
in Figure 15c. In addition, the measured lifetime is also recombination in DSCs, as a function of electron conductivity, (a)
influenced by prior trapping and release events, as also shown diffusion coefficient, (b) lifetime, and (c) diffusion length, of electrons
in the nanocrystalline TiO2 for several DSCs, measured in dark
in Figure 15c. The electron lifetime is defined with respect to
conditions, with different holes transport material: L for liquid
total carrier density electrolyte, IL for ionic liquid electrolyte, and Ometad for solid hole
⎛ ∂U ⎞−1 conductor. Efficiencies of the different samples are 4% for Ometad, 5%
τn = ⎜ n ⎟ for L1, 7% for IL, 10% for L2, and 11% for L3. Reprinted with
⎝ ∂n ⎠n (12) permission from ref 179. Copyright 2009 American Chemical Society.
̅
171
In the model of Figure 15c the lifetime takes the form
⎛ ∂n ⎞
τn = ⎜ L ⎟τf from eq 14 that the free carrier lifetime depends on the voltage
⎝ ∂nc ⎠ (13) as follows
that includes the trapping factor. A phenomenological model nc01 − β ⎡ qV ⎤
that gives good results in many cases is the following:135,172 τf = exp⎢(1 − β) ⎥
βk rec ⎣ kBT ⎦ (15)
β β
Un = k rec(nc − nc0 ) (14) thus the lifetime has the expression 171

This last model can be explained by combining the T nL0 ⎡ qV ⎤

transference through an exponential distribution of traps, with τn = exp⎢ (α − β ) ⎥
the Marcus model for electron transfer.55,135,141,171,173 It follows T0 nc0 β βk rec ⎣ kBT ⎦ (16)

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The results of measurements of τn are shown in Figure 17b. compared with that of the anatase film. The detailed synthesis
It should be noticed that τn decreases upon increasing voltage, procedure for TiO2 film to realize DSCs with PCE over 10%
but this dependence is an effect of the trapping factor ∂nL/∂nc, was published by Grätzel’s group.181 For state-of-the-art DSCs,
that introduces the dependence (α − 1)V in the exponent. In the employed mesoporous TiO2 films are comprised of double
fact the free carrier lifetime τf increases with voltage as shown in functional layers including a light-absorbing layer composed of
eq 15. 20 nm sized anatase particles and a light-scattering overlayer
In the operation of the solar cell, the transport of composed of 200−400 nm sized anatase particles. This bilayer
photogenerated electrons competes with recombination events structure increases the light scattering effect and facilitates the
and determines the collection efficiency of the solar cell.174,175 light harvesting of DSCs. Besides the bilayer architecture,
The diffusion length Ln can be broadly defined as the average multilayered TiO2 nanostructured films are also reported by
distance that injected carriers travel from x = 0 before several groups.182−186 These multilayered films are proved to
disappearing from the diffusing medium, as suggested in Figure be beneficial to the light harvesting and/or the charge
15b. If Ln is longer than the film thickness L, then most of the collection in the device. Recently, Diau’s group184 reported
carriers photoinjected along the TiO2 have a large chance to be the fabrication of multilayered TiO2 films with additional layers
collected at the substrate, and the collection efficiency will be of nanorods inserted between the transparent and the scattering
nearly unity. The relationship of the diffusion length to the film layers as shown in Figure 18. The corresponding DSC based on
thickness can be determined by the ratio of the recombination Z907 sensitizer exhibited significantly enhanced light-harvesting
resistance to the transport resistance as follows:142 and electron transport capability, achieving an improved PCE
of ∼10%.
R rec ⎛ L ⎞2
= ⎜ n⎟
R tr ⎝L⎠ (17)
In the diffusion-recombination model the diffusion length is
given by
Ln = Dnτn (18)
This standard result has been shown to be valid for nonlinear
recombination combined with multiple trapping transport,
provided that carrier density is nearly uniform.176 In multiple
trapping model the trapping factors in eqs 9 and 13 compensate
in the diffusion length.138 This feature, the disappearance of the
trapping factors, is a characteristic of steady state quantities as
remarked above for the electron conductivity. Nevertheless, it
has been recognized that the electron diffusion length in a DSC
is dependent on the Fermi level.172 If the free carrier lifetime
shows some dependence with the potential, then the diffusion Figure 18. Schematic demonstration of the structural design for the
length varies with voltage, according to TiO2 multilayer film. NP, SL, NR and LR refer to nanoparticles,
scattering layer and TiO2 nanorods of ∼150 and ∼500 nm,
Ln = D0τf (19) respectively. Reprinted with permission from ref 184. Copyright
Using the free carrier lifetime of the nonlinear β- 2013 American Chemical Society.
recombination model, eq 15, it is found that the diffusion
length increases with the voltage, and this feature, is often
observed in experimental results, as shown in Figure Although these kinds of nanoparticle films have been
17c.138,139,171,177−179 regarded as a paradigm of porous photoelectrode for use in
DSCs, a variety of nanostructures has been tested thus far.
2.6. Nanostructured TiO2 Electrodes for DSCs These studies are motivated by the expectation that 3D packed
The nanocrystalline morphology of the TiO2 film is critical for particle network of TiO2 which are normally used for DSCs
the efficient operation of DSCs. The major breakthrough for provides a tortuous pathway for electron transport, thus
DSCs in 1991 was realized by using the mesoporous TiO2 increasing the possibility of charge recombination and
electrode with a high internal surface area to support the deteriorating the charge collection efficiency of the device. As
monolayer of a sensitizer,8 which immensely improved the light one-dimensional (1D) nanostructures are expected to provide
harvesting capability as well as the photocurrent of the device. direct pathways for charge transport and improve the charge
In DSCs, anatase is considered as the preferred structure collection efficiency of the DSCs, the research has been largely
because it features a larger bandgap and higher conduction promoted toward photoanodes constructed from ordered 1D
band edge energy as compared with rutile. The higher nanostructures such as, nanotubes (NTs),187−195 nanorods
conduction band edge energy of anatase is expected to induce (NRs),196−200 nanowires201−205 etc.
higher EFn and thus Voc in DSCs at the same conduction band NTs are thought to be superior to other 1D nanostructures
electron concentration. Moreover, a comparative study of as their hollow structure can provide larger surface area than
rutile- and anatase-based DSCs reveals that the short-circuit that of nanowires or NRs. In most cases, the self-organized
photocurrent of the rutile-based cell is about 30% lower than TiO2 NT layers are formed by anodic oxidation of a Ti-metal
that of the anatase-based cell.180 The low photocurrent of the sheet in ethylene glycol electrolytes in presence of fluoride ions.
rutile film is ascribled to a reduced amount of adsorbed dye, However, the obtained TiO2 NT arrays are not always highly
which is caused by a smaller surface area per unit volume ordered because the tube upper parts may collapse and form
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bundles or needle-like structures due to the chemical etching transport, which shortens the transport pathway, lessens the
effect in the fluoride electrolyte.206,207 These intertube contacts exposure of electrons to traps, and enables overall faster
lengthen electron transport pathway from the expected one transport. Besides, the bundle-free NTs are also able to provide
dimension to a combination of one and three dimensions, thus an enlarged internal surface area accessible to dye molecules,
adversely affecting the charge transport in NT films. Recently, leading to dramatically increased Jsc for the device. By
the synthesis of bundle-free NT films has been presented by employing a hybrid anodic method, with initial potentiostatic
Frank and co-workers by employing a combinative technique of anodization followed by galvanostatic anodization, Diau’s group
cleaning with ethanol and drying in supercritical CO2.191 In successfully synthezised long titania NT arrays in a much
usual condition of cleaning with water and then drying in air, shorter anodization period.193 The DSCs based on these NT
there are evident NT bundles, microcracks, and an overlayer films showed systematically improved cell performance depend-
which covers the ends of NT channels (Figure 19a). The ing on tube length, exhibiting the highest PCE of 7.6% at a tube
length of ∼30 μm.
As TiO2 NT arrays are commonly grown on opaque titanium
foils or sheets,189,208 the derived devices typically adopt a back-
side illumination geometry. However, this configuration is a less
than optimal approach for achieving high efficiency because the
incident light could be dramatically attenuated due to the light
reflecting effect of the counter electrode and light absorbing
effect of the electrolyte.209 Besides, in back-side illumination
configuration, most photoelectrons are generated near the
outermost regions of the NT film. These electrons have to
travel longer distance before being collected at the fluorine-
doped tin oxide-coated (FTO) glass substrate, thus inducing
higher carrier loss due to electron recombination with oxidizing
species in the electrolyte.210 To overcome these drawbacks,
attempts have been taken to prepare the titania NT on FTO
glass substrate and fabricate cells with front-illumination
configuration.188,192,211−214 One feasible option to realizing
the front-side illumination geometry is to directly grow titania
NT on FTO glass substrate.213,214 In this case, transparent
TiO2 NT/FTO glass is prepared via anodic oxidation of
titanium thin film that is previously sputtered onto FTO
conductive glass. Another method for fabrication of transparent
NTs on FTO glass involves detaching self-standing TiO2 NT
membranes from Ti subtracts and then fixing them on FTO
glass by a bonding interlayer.188,194,211,212 This methodology is
simple and low-cost, and devices prepared with this method
have reached the highest efficiency of 7.6%.188
Besides those 1D TiO2 electrodes, 3D nanostructures have
exhibited significant potential to obtain efficient devices. The
3D nanostructured photoelectrodes not only provide enlarged
surface area to improve the light trapping effect, but also show
excellent capability in achieving highly effective charge
transport and collection. Diau and co-workers215 reported the
synthesis of octahedron-like anatase TiO2 single crystals with
particle sizes in the range of 30−400 nm by employing a simple
two-step sol/hydrothermal method, in which the first step was
the preparation of a suitable titanium tetraisopropoxide
(TTIP)/triethanolamine (TEOA)/diethylamine (DEA) sol at
a basic condition and the second step involved a hydrothermal
Figure 19. SEM images of NT films that were cleaned with (a) water treatment at varied temperature and duration. In this approach,
and then air-dried (b) ethanol and then scCO 2 -dried. (c) the TEOA was used as a chelating agent to retard the hydrolysis
Corresponding transport time constants for DSCs incorporating and the base DEA played bifunctional roles as both a catalyst
different NT films. Reprinted with permission from ref 191. Copyright and a controller of shape for the crystal growth. Measurement
2007 American Chemical Society. of N719-sensitized solar cell with octahedron-like anatase TiO2
single crystals of ∼30 nm as active layer and ∼300 nm as
application of ethanol and drying in supercritical CO2 induces scattering layer revealed a PCE of 10.2%, which was superior to
decreased surface tension, and consequently eliminates the NT that of 9.6% for the NP-based reference device. The improved
bundling and microcrack formation (Figure 19b). As shown in performace was attributed to the more rapid electron transport
Figure 19c, the electron transport in the bundle-free NT film is and negative TiO2 CB edge. Recently, mesoporous single
two times faster than in its conventional NT counterpart. This crystals (MSC) anatase TiO2 was synthesized through a
is because the supercritical CO2 drying process reduces the method of crystal seeding in a sacrificial guiding template.216
formation of clusters of bundled NTs, thus promoting 1D A silica template with an external volume of ∼1% of the overall
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reaction volume was first seeded by pretreatment in a solution greater than that of the best low-temperature all-solid-state
of TiCl4 and then removed by selective etching in aqueous device.
NaOH to recover the mesoporous TiO2 crystal product, As in solid-state DSCs, the charge recombination rate can be
obtaining a near unity yield of clearly faceted single crystals of 2 orders of magnitude faster and electron diffusion length is
anatase TiO2 as shown in Figure 20. The MSC TiO2 film about 1 order of magnitude lower than that in liquid
electrolyte-based DSCs.147,179,217,218 The relatively low electron
collection efficiency combined with incomplete filling of the
mesoporous TiO2 films with HTM limits the photoanode
thickness to less than 3 μm, which is not the optimized
thickness to achieve effective light absorption with the currently
available sensitizers. Tétreault et al.219 presented a novel solid-
state DSC based on a 3D fibrous network of anatase self-
assembled from fused single-crystal NRs. As shown in Figure
21, the nanowires first self-assemble in two dimensions parallel

Figure 21. (a) HRTEM image of the 3D fibrous network of single-

crystalline anatase nanowires. (b) Oriented self-assembly of the NRs
into the 3D fibrous network. (c) HRTEM image showing the
continuous [001] crystal orientation across two NRs. (d) Continuous
(101) crystal plane and spacing across the junction. Reprinted with
permission from ref 219. Copyright 2010 American Chemical Society.
Figure 20. (a) Schematic of MSC nucleation and growth within a
mesoporous template. (b) Fully mesoporous TiO2 grown by seeded to the FTO grass substrate and then undergo a transformation
nucleation in the bulk of the silica template. (c) Electron diffraction
Laue pattern collected from a complete mesoporous crystal assigned to
into chain-like assembly of truncated anatase NRs during the
anatase TiO2 with [001] beam incidence. (d) Mobility dependence on subsequent thermal decomposition process. Compared to
photoinduced charge density for MSC and NP films measured via conventional films based on anatase NPs, the 3D network of
transient mobility spectroscopy. Reprinted with permission from ref NRs exhibits a wide pore size distribution composed of large
216. Copyright 2013 Nature Publishing Group. mesopores (10−50 nm) and macropores (50−120 nm),
resulting in 25% reduction of its surface area as compared
with traditional NP-based electrode. However, the relatively
low dye loading in the 3D network film is partly compensated
features specific free surface similar to equivalent-sized NPs, by significant light scattering effect and the large anisotropy of
providing highly accessible surfaces for dye adsorption as well the nanowires lead to low packing density, allowing for efficient
as effective light adsorption. Besides, the conductivity and infiltration of the HTM into this 3D network films. The DSC
electron mobility of MSCs are significantly higher than that of based on the 3D network of NRs presents a significantly higher
conventional NP films. And more importantly, the MSC films conductivity, shorter transport time, and longer electron
can be prepared in a relative low temperature (below 150 °C), lifetime over a wide range of applied potential as compared
thus decreasing fabrication cost and making the use of flexible to its NP counterpart, resulting in improved collection
substrates possible. Applying this low-temperature MSC TiO2 efficiency. The relatively high roughness factor, significant
films in solid-state DSCs yielded a PCE of 3%, which was vastly light scattering combined with facilitated electron collection
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lead to a relatively high PCE of 4.9% for solid-state DSCs. The which is more appropriate for successful dye adsorption. As
3D hierarchical nanostructured TiO2 films are also widely shown in Figure 23, the periodic line patterns deposited on the
investigated as photoanodes for DSCs in recent years.220−226 surface of photoanode can boost the optical path length across
These 3D hierarchical photoelectrodes promote light scattering a broad wavelength range of incident light by reflecting the light
and the dye loading of the electrodes simultaneously, to back to the photoelectrode, thus leading to more effective light
enhance the light harvesting capability of the device. Moreover, absorption. Further comparison of the reflection behavior
the charge transport and collection capability of the resulting indicates effective light trapping from the 400 to 1000 nm
cells are thought to be improved upon utilizing these 3D wavelength range for the nanopatterned sample, providing
hierarchical photoelectrodes. strong evidence for the improved light harvesting ability of this
In DSCs, an important approach to boosting efficiency is to newly developed electrode. The application of nanopatterns in
increase the path length of light by enhancing light scattering in solid-state DSCs has resulted in approximately 40% and 33%
TiO2 films. While the small size of TiO2 NPs makes enhancement of Jsc and PCE, respectively, achieving a high
conventional nanocrystalline TiO2 films almost transparent, efficiency of 7.03%.
mixing light scattered large particles or covering a scattering One important strategy for improving electron collection is
layer onto the nanocrystalline film has been perceived as an the utilization of metal oxides with high electron mobility, such
effective strategy to improve light absorption. The inverted as ZnO229−232 and SnO2233 as porous semiconductor materials
TiO2 photonic crystals (PCs), which consist of self-assembled for DSC photoanode. Despite enhanced electron transport, the
monodispersed spherical particles, has exhibited significant reported device efficiencies based on these materials are much
potential to obtain efficient light harvesting within a specific lower than that of TiO2 mainly because of the severe
wavelength based on their intrinsic periodic structure. More- recombination when the high mobility material is in direct
over, large porosity structures of the inverted TiO2 PCs have contact with the sensitizer and/or the electrolyte. Conse-
enabled good infiltration for high-viscosity electrolytes. To quently, the development of core-sell structured photoanodes
realize the PC-coupled DSCs that feature enhanced photo- with both high electron mobilities and reduced recombination
current over a large spectral region, a double layered rates has emerged as a promising approach to enhancing the
photoanode integrates a high surface mesoporous underlayer performance of DSCs. A novel bottom-up 3D host−
TiO2 with an optically active TiO2 PC overlayer is fabricated as passivation−guest (H−P−G) photoanode was recently re-
illustrated in Figure 22.227 The significantly improved IPCE of ported for achieving highly efficient electron transport and
charge extraction.234 This H−P−G structure employs high
electron mobility materials, such as aluminum-doped ZnO (Al/
ZnO) or SnO2 as hosts to facilitate the electron transport in
photoanode. As shown in Figure 24, the dispersion of
polystyrene spheres is first doctor bladed on a FTO glass
substrate to attain a large-area highly light scattering disordered
template and then heated and infiltrated with 90 nm of Al/
ZnO, SnO2, or TiO2 by atomic layer deposition. The high-
mobility oxide backbone is then coated with a dense layer of
TiO2 (passivation layer) to hinder the electron recombination
between electrons in the oxide backbone and I3− in the
electrolyte. TiO2 nanocrystals, which are called guest, are
further infiltrated the macroporous inverse transparent
Figure 22. (a) Schematic of the DSC based on double layer conductive oxide backbone in order to increase the surface
photoanode. (b) SEM cross section image of FTO/nanocrystals-
TiO2/PC-TiO2 electrode. Reprinted with permission from ref 227.
area for dye loading. As shown in Figure 25, this 3D open
Copyright 2012 Royal Society of Chemistry. structure exhibits effective pore connectively and enables
conformal coating of dense TiO2 on the 3D host. J−V
characterization of DSC revealed that the electrodes with SnO2
PC DSC indicates that the PC top layer is electrically and Al/ZnO as host exhibited higher Jsc and Voc as compared
connected and contributes to light harvesting over the entire with the TiO2 host counterpart. This phenomenon is regarded
spectrum. Further increasing the thickness of PC-TiO2 top as the consequence of the relatively high electron mobility in
layer from 14 to 20 μm led to a boosted efficiency of 8.2% and the Al/ZnO and SnO2 hosts. Moreover, an improvement in
this enhancement can be explained by effective electrolyte photovoltage of up to 110 mV was obtained for the Al/ZnO
infiltration and improved absorption in a specific spectral host photoanode, indicating the successful suppression of
region owing to the PC effect. charge recombination with the H−P−G structure.
Recently, a simple, fast, and universal nanopatterning
methodology has been developed by Kim et al. for boosting 3. APPLICATION IN POLYMER-INORGANIC HYBRID
the light harvesting efficiency of DSCs.228 A TiO2 layer of ∼10 SOLAR CELLS
μm prepared with an acidic paste was first casted on the FTO
glass substrate and then covered with the second thin layer 3.1. Fundamentals of Polymer-Inorganic Hybrid Solar Cells
made from neutral TiO2 paste. The elastomeric polydimethyl- Recent research on polymer-inorganic hybrid solar cells has
siloxane nanostamp was then manually placed on the neutral generated a promising approach for cost-effective and large-
paste-coated photoelectrode with proper pressure to obtain the scale solar energy conversion. This kind of solar cell combines
nanopatterned photoanode. In this procedure, the application the advantages of inorganic semiconductors, such as high
of neutral paste is crucial, because the patterned photoelectrode electron mobility and stability, with the processing flexibility
prepared with a neutral TiO2 paste has a hydrophilic nature, offered by conjugated polymers. In these devices, light is
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Figure 23. (a) Schematic representation of the light trapping on the nanopatterned TiO2 layer. (b) The reflection behaviors of the compact, flat, and
nanopatterned TiO2 layers. (c) J−V curves and (d) IPCE spectra of DSCs with and without a nanopattern on mesoporous TiO2 photoelectrodes.
Reprinted with permission from ref 228. Copyright 2012 Wiley-VCH.

Figure 25. (a) SEM cross sectional view of a disordered TiO2

passivated 3D Al/ZnO backbone. (b) Top-view of the 3D Al/ZnO
after top surface removal by reactive ion etching and template removal
by annealing. (c) High-magnification micrograph of the TiO2 covered
3D Al/ZnO host. (d) High-magnification micrograph of the 3D Al/
ZnO coated with thin film of dense TiO2. (e) Complete photoanode
after infiltration and calcination of the TiO2 NP paste. Reprinted with
permission from ref 234. Copyright 2011 American Chemical Society.

exciton diffusion length. By constructing bulk or dispersed

heterojunction cells, the donor and acceptor are separated at
Figure 24. Schematic representation of the synthesis method for a 3D nanoscale and the exciton can reach the interface before
host−guest photoanode of DSC. Reprinted with permission from ref undergoing deactivation.
234. Copyright 2011 American Chemical Society. In this section, we mainly address recent advances of bulk
and dispersed structures and provide progress in morphology
control and interface engineering. For more reviews of
absorbed by the polymer and creates excitons. The generated
polymer-inorganic hybrid devices see refs 237−241.
excitons dissociate into separate charges in the vicinity of the
hybrid interface and then inject free holes and electrons into 3.2. Devices Based on Nanoporous TiO2
the polymer and the inorganic semiconductor. Following The nanoporous TiO2 layers, which have been commonly used
charge separation, the electrons and holes travel through the in DSCs, are combined with conjugated polymers to fabricate
direct or percolating pathway and finally are extracted by the bulk heterojunction solar cells in the past decade.242−248 The
relevant electrodes to generate photocurrent. As the diffusion first study reported the bulk heterojunction devices based on
length of excitons in many polymer films is typically less than TiO2 films by sintering isotropic, colloidal TiO2 NPs into a
10 nm,235,236 high photocurrent quantum efficiency requires a connected thin film.242 Further study proposed mesoporous
high probability of exciton generated within the distance of titania films with pore size less than 10 nm to fabricate
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nanoporous TiO2 hybrid solar cells in conjunction with

conjugated polymer poly-3-hexylthiophene (P3HT).243 The
small pore size results in sufficient exciton dissociation and the
interconnected TiO2 particles provide continuous pathways for
electrons transport, yielding a remarkable efficiency of 1.5%.
In nanostructured polymer-inorganic hybrid solar cells, the
surface engineering of the TiO2 nanocrystal film is an important
approach for improving the device performance. Modification
of the TiO2 surface with organic molecules has been reported
to induce dipole at the polymer/TiO2 interface.246,249,250
Consequently, the energy offset at the polymer/TiO2 interface
and thus the Voc can be tuned by employing interfacial
molecules with various dipoles. Besides influencing the energy
alignment at the donor/acceptor interface, the interfacial
molecules can also modify the physical and chemical properties
of the interface, thus blocking or mediating forward charge
transfer or reducing back charge recombination.246,247,250 In
bilayer devices, the improvement of device performance upon
interfacial molecule modification can be mainly attributed to
the optimized polymer/TiO2 interface, because the absorption
of monolayer molecules is negligible. However, in nano-
structured polymer-inorganic hybrid solar cells, dye molecules
used for interface modification can also act as light harvester,
contributing to light absorption and charge generation. In 2009,
Ramakrishna and co-workers244 reported a highly efficient
hybrid device based on mesoporous TiO2 films, in which the
metal-free organic dye (D102) and the ruthenium dye (N719)
were used to modify the TiO2 NP surface. In their work, the
surface treatment of dye-modified TiO2 films by using lithium
bis(trifluoromethylsulfonyl)imide (Li(CF3SO2)2N) and TBP
prior to the deposition of the P3HT layer resulted in a nearly
60-fold improvement of device efficiency for D102-based
devices, achieving a high efficiency of 2.63% under AM 1.5
full sunlight. In contrast, almost no enhancement was obtained
with the treatment for N719-based devices. The effect of TBP
and lithium salt treatment on device performance is strongly Figure 26. (a) “Dye-regenerating” and ‘‘electron-mediating’’ mecha-
dependent upon the nature of the dye, and this effect is nisms for the dye-modified P3HT-TiO2 hybrid solar cells. (b) HOMO
attributed to the variation of the energy level of the sensitizers and LUMO energy levels of N719 and D102 on TiO2 films in different
conditions. (c) The corresponding IPCE of different devices. Devices
as illustrated in Figure 26b. As the N719 sensitizer possesses a A and C are based on N719 dye and devices B and D are based on
lower LUMO level than that of P3HT, the electron transport is D102 dye. Devices A and B are fabricated without Li salt and TBP
facilitated from the LUMO of P3HT to the CB of TiO2. treatment, while the dye modified TiO2 films in devices C and D are
Therefore, the N719 molecule at the hybrid interface acts as an treated by Li salt and TBP prior to P3HT deposition. Reprinted with
energy funnel to improve the electron injection efficiency and permission from ref 244. Copyright 2009 Wiley-VCH.
this procedure is referred to as the ‘‘electron-mediating’’
mechanism. In this case, almost no variation of energy level ation efficiency of P3HT excitons. An impressive efficiency of
and thus no improvement are obtained by Li salt and TBP 2.87% was achieved based on the WL4-modified cell.
treatment. For D102 modifier, the surface treatment leads to In the above-mentioned research, the main role of the
obvious downward movement of both HOMO and LUMO interfacial modification interlayer is to control the energy offset
energy levels, inducing both ‘‘dye regenerating’’ and ‘‘electron- at the polymer/TiO2 interface and influences the charge
mediating’’ mechanisms in the device. As shown in Figure 26c, separation as well as recombination process in hybrid solar
the device based on D102 with Li salt and TBP treatment cells. However, it remains a great challenge to clearly track the
exhibits the highest IPCE value of ∼40% at around 480 nm. effects of intermolecular processes at the mesoscopic level.
The surface modification effect of nanoporous TiO2 with a class Canesi et al.247 reported a step-change improvement in the
of conjugated cyanoacrylic acids (WL-1 to WL-4) were device efficiency through engineering of the hybrid interface by
systematically studied by Yu et al.246 The utilization of 4-mercaptopyridine (4-MP). The presence of 4-MP interlayer
cyanoacrylic acid as a terminal anchoring group increases the facilitates the exciton splitting and hampers the electron back
electron affinity in regions close to titania surface, posing a transfer, leading to a significant improvement of the device
positive effect on Jsc. Moreover, the generated molecular dipole performance. Besides, the migration of polymer on the TiO2/4-
directing away from the titania surface induces the increment of MP substrate is easier since the local charges are smaller and
Voc. The LUMO of interfacial molecules can be tuned by the corresponding electrostatic energy landscape is smoother in
lengthening the conjugation length or adopting a donor− the presence of 4-MP. The relatively diffusibility mobility of
acceptor structure, which may significantly affect the dissoci- polymer on the TiO2/4-MP substrate not only leads to
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relatively large polymer/substrate interface area but also affects Chen’s group252,253 also demonstrated the enhancement of
its final morphology. When 4-MP is used to functionalize the device performance by using interfacial modifications on the
TiO2 surface, the substrate results atomically flat, with much TiO2 NR surface, which improved compatibility between the
smaller atomic partial charges in the external thiol groups. polymer and TiO2 NRs, facilitated charge separation and
Therefore, the backbone of P3HT is planar on the surface and suppressed back recombination at the interfaces of P3HT-TiO2
the alkyl chains are aligned along the thiol rows as shown in NR hybrids. The original OA ligand on the surface of the TiO2
Figure 27. The induced morphological order at the interface NR is removed with three different kinds of ligand molecules of
consequently leads to a strong improvement in charge anthracene-9-carboxylic acid (ACA), tetracarboxy phthalocya-
generation and a decrease in recombination losses. nine copper(II) (CuPc-dye), and cis-bis(4,4-dicarboxy-2,2-
bipyridine)dithiocyanato ruthenium(II) (N3-dye) as shown in
Figure 28a. After the interfacial engineering between P3HT and
TiO2 NRs, both the Jsc and Voc are improved, achieving the
highest efficiency of 2.2% by replacing OA with the N3-dye
molecule (Figure 28b). The attachment of effective interfacial
molecules on the surface of TiO2 NRs can improve the
compatibility between the polymer and TiO2 NRs, facilitating
charge separation in the device. In addition, the back
recombination at the interfaces of P3HT-TiO2 NR hybrids is
also suppressed as revealed by the transient Voc decay
measurements (Figure 28c). The enhanced charge separation
efficiency and reduced interfacial recombination are related to
the significant improvement in Jsc. Moreover, the reduced
charge recombination rate may lead to increased electron and
hole concentrations at interfaces, increasing the difference
between the quasi-Fermi levels of electrons and holes,
accounting for the observed increase in Voc upon interface
Figure 27. Side and top views of (a) TiO2/P3HT interface and (b) the modifications. First-principles calculations indicated that the
TiO2/P3HT interface modified with 4-MP by model potential variation in the recombination rate at the polymer/TiO2 NR
molecular dynamics simulations at room temperature. Reprinted interfaces modified with different interfacial molecules was
with permission from ref 247. Copyright 2012 Royal Society of likely to stem from the variation of stereohindrance effect
Chemistry. associated with different molecular structures. Although
removing the insulating ligands on nanocrystals surface with
effective interfacial molecules has been proved to be an
3.3. Devices Based on Polymer-TiO2 Blends attractive approach to achieving high performance, the
consequent aggregation of nanocrystals tends to hinder further
By blending TiO2 NPs with conjugated polymers, the hybrid
efficiency improvement.
active layer can be processed from solution in a single step.
Besides properties of organic/inorganic interface, the
Contrary to the incomplete infiltration of porous TiO2 layers by
morphological organization of the donor−acceptor blends is
conjugated polymers, this procedure guarantees an improved
another parameter affecting the photocarrier dynamics of the
TiO2-polymer compatibility at the interface. In bulk hetero-
active layers and thus the photovoltaic performance. The
junction solar cells, obtaining optimized morphology with large
donor/acceptor interface area for efficient charge separation control of blend morphology is recognized as an important
and bicontinuous percolating pathway for effective charge approach to improving the self-organization and phase
transport is important. separation. Kwong et al.255 found that good solvent for
Typically, nanocrystals are synthesized chemically from P3HT with lower vapor pressure such as xylene led to better
solution using specific surfactants, such as trioctylphosphine mixing of TiO2 and P3HT. The resulting morphology featured
oxide (TOPO)251 or oleic acid (OA)252 in order to disperse the large number of small domains, yielding large interface and
hydrophilic NPs in common apolar solvents used to dissolve improved exciton dissociation.
the conjugated polymers. However, the presence of an A simple approach was recently developed by using mixed
insulating ligand at the particle surface may hamper the charge solvent to control the morphology of P3HT-TiO2 NR hybrid
separation at the donor/acceptor interface and reduce electron bulk heterojunction solar cells.256 The transmission electron
hopping rates between particles. Replacing the organic ligand at microscopy (TEM) image (Figure 29) indicates that TiO2 NRs
the nanocrystals surface is recognized as a sensible strategy to tends to aggregate into domains in the presence of chloroform
overcome this problem.251−254 Bouclé et al.251 reported the solvent. By using mixed solvent consisting of pyridine,
enhancement of device performance through partial replace- dichloromethane, and chloroform, optimized nanoscale mor-
ment of the insulating TOPO ligands on the TiO2 NR surface phology with relatively uniform dispersion of TiO2 NR in the
with the ruthenium dye Z907. The charge separation yield at hybrid film was obtained. The presence of pyridine in the
the P3HT/TiO2 interface is improved, and this effect is solvent induces the aggregation of P3HT into nanostructured
associated with the 3-fold increase of the device PCE under network and facilitates the dispersion of NRs in the hybrid
simulated solar illumination. However, the charge trapping solution, leading to the formation of morphology with well-
within or between the NRs limits charge transport, resulting in distributed TiO2 NRs embedded in highly crystalline polymer
poor photocurrent as well as low efficiency (0.07%) after the domains. This bicontinuous phase-separated morphology can
ligand exchange. significantly improve the charge separation, transport, and
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Figure 29. TEM image of P3HT-TiO2 hybrid films spun from (a)
chloroform and (b) mixed solvents containing pyridine. Schematic
representations of the films spun from (c) chloroform and (d) mixed
solvent. Reprinted with permission from ref 256. Copyright 2010
American Chemical Society.

with the nanocrystal shapes.257−259 The 3D morphological

organization of TiO2 nanocrystals in P3HT was analyzed by
using electron tomography based on scanning transmission
electron microscopy using high-angle annular dark-field
(STEM-HAADF) electron imaging.257 As shown in Figure
30, the TiO2 NPs are more homogeneously dispersed in P3HT,
while TiO2 NRs are found to induce significant phase
separation with distinct TiO2 NR rich clusters separated by
P3HT domains. The 3D bulk heterojunction morphologies
clearly indicate that the anisotropic TiO2 NRs can largely
decrease the number of junctions of a connective network, thus
reducing the probability of interparticle hopping. Besides, the
elongated TiO2 NRs with preferred orientations angled toward
the plane of the film are more likely to form a connective
network between two electrodes as compared to the isotropic
TiO2 NPs. Despite more efficient exciton dissociation in the
P3HT-TiO2 NP hybrid due to relatively high intermixing, the
presence of anisotropic TiO2 NRs enables the establishment of
a favorable 3D morphology, leading to relatively low
recombination rate as well as more efficient and balanced
transport of carriers in the device. The nanocrystal dimension-
ality also has significant impacts on the nanoscale morphology
of polymers in P3HT-TiO2 nanocrystal bulk heterojunc-
Figure 28. (a) Schematic representations of P3HT-TiO2 NR hybrid tions.258,259 As compared to P3HT-TiO2 NP hybrids, the
after interface modification and chemical structures of different
interfacial molecules of ACA, CuPc-dye, and N3-dye. (b) J−V curves
elongated and anisotropic TiO2 NRs with preferred orienta-
of the P3HT-TiO2 NR hybrid solar cells with different interface tions angled toward the plane of the film can promote the
ligands. (c) The corresponding charge recombination rate constant of formation of increased vertical-stacking of P3HT crystallites,
these devices. Reprinted with permission from ref 253. Copyright 2009 providing a more effective hole transport perpendicular to the
American Chemical Society. substrate. Besides, the TiO2 NRs are found to effectively
promote the polymer crystallinity while minimizing the number
of electron hopping events required for transporting electrons,
recombination kinetics, inducing significant enhanced photo- thereby facilitating electron/hole transport in the devices.
current and photovoltage. Figure 31 displays the simulated 3D morphologies of P3HT-
In polymer−inorganic hybrid solar cells, nanoscale phase TiO2 NP and NR blends prepared at a blending ratio of 1:1.
distribution of the donor−acceptor blends are also correlated Relatively to NPs, the NRs provide a better balance between
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electron transport and exciton dissociation by promoting

polymer crystallinity and minimizing the number of inter-
nanocrystal junctions, while maintaining a reasonably high
specific interface area for efficient exciton dissociation. These
studies provide the possibility of the nanoscale morphology
control of polymer−inorganic nanocrystal bulk heterojunction
blends via tuning the nanocrystal shapes.
3.4. Devices Based on Nanorods and Nanotubes
During the past years, the application of 1D TiO 2
nanostructures has generated remarkable scientific inter-
est.260−262 In these devices, the conjugated polymers are
infiltrated into the free space of the ordered nanostructures to
form the hybrid active layers. The device architectures feature
ordered assemblies and provide direct pathways for charge
transport.
The first example of such devices is composed of vertical
aligned TiO2 NRs prepared by sol−gel process in an anodized
alumina template with P3HT as the hole-conducting
polymer.260 The corresponding device shows efficiency of
0.512%, about 4-fold improvement over planar control device.
Recently, Wu’s group261,262 reported hybrid solar cells
consisting of the rutile TiO2 NR arrays as shown in Figure
32a,b. They demonstrated that the incorporation of D149 or
Z907 molecular interlayers can provide an appropriate band
alignment at the P3HT/TiO2 interface, thus improving the
light trapping in the device. In addition to act as the
photocurrent contributor, the dye molecules can also boost
the compatibility and thus assisting the charge separation at the
hybrid interface. The attachment of dye molecules imparts an
effective recombination barrier at the P3HT/TiO2 NRs
interface, which can significantly enhance the electron lifetime
in the TiO2 NRs. 3D rutile TiO2 nanodendrite arrays developed
Figure 30. STEM-HAADF tomography images of (a) P3HT-TiO2 from TiO2 NR arrays are further utilized to fabricated device in
NPs and (b) P3HT-TiO2 NRs hybrid films respectively. The insets conjunction with P3HT.239 As illustrated in Figure 32c,d, the
also show the 3D distribution of TiO2 NPs or NRs along the thickness nanodendrite array structure not only provides direct and
direction. Reprinted with permission from ref 257. Copyright 2011 ordered electron transport pathways as the 1D TiO2 NR array
American Chemical Society.
does but also makes much larger surface area available for

Figure 31. Coarse-grained molecular dynamics (CGMD) simulated 3D morphologies of P3HT-TiO2 NPs (upper panel) and NRs (lower panel)
blends; P3HT chains and nanocrystals are colored red and blue, respectively. Reprinted with permission from ref 259. Copyright 2012 Royal Society
of Chemistry.

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Figure 32. Top view and cross-sectional view (inset) SEM images of
(a) the TiO2 NR array and (c) the TiO2 nanodendrite array.
Schematic of (b) the D149-modified TiO2 NR array-P3HT and (d)
the D149-modified TiO2 nanodendrite array-P3HT hybrid solar cells.
Panels a and b are reprinted with permission from ref 261. Copyright
2012 American Chemical Society. Panels c and d are reprinted with
permission from ref 262. Copyright 2012 American Chemical Society.

charge separation. Benefiting from the enlarged interface area, a

considerably enhanced charge separation was observed and a
notable efficiency of 3.12% was achieved for the D149
modified-TiO2 nanodendrite array-P3HT hybrid solar cell as
compared to the 2.63% of its NR counterpart.
Although both sensitizer and polymer may contribute to the
photocurrent generation in this kind of device, the sensitizer is
advised to have a minimum spectral overlap with that of the
P3HT to guarantee effective transmission of the high energy
photons. Grimes and co-workers263 demonstrated a hybrid
device structure comprised of TiO2 NT arrays, which were Figure 33. (a) Depiction of the nanostructured P3HT/SQ-1 dye/
TiO2 NT array hybrid solar cell. (b) Representation of energy level
sensitized with unsymmetrical squaraine dye (SQ-1) and positions and charge transfer processes of the corresponding device.
uniformly infiltrated with P3HT as shown in Figure 33. The (c) Optical absorption spectra of the P3HT/TiO2 and SQ-1 dye/TiO2
vertically oriented TiO2 NT arrays with pore size of 20−35 nm hybrid. Reprinted with permission from ref 263. Copyright 2009
provide large surface area for efficient charge generation and American Chemical Society.
facilitate the P3HT infiltration within the tubes. In this
configuration, the SQ-1 dye is used to absorb in the red and 4. APPLICATION IN QUANTUM DOT-SENSITIZED
near-IR portion of solar photons while P3HT is employed for SOLAR CELLS (QDSCS)
harvesting the higher energy photons. The complementary
absorption bands of these two materials make them appropriate 4.1. Fundamentals of QDSCs
for an extended spectrum solar cell. Consequently, the device In recent years, sensitization of metal oxide layers with
exhibited a significant enhancement of performance, achieving quantum dots (QDs), such as CdS,266,267 CdSe,268−273
an efficiency of 3.8% in AM 1.5 full sunlight. PbS,274−279 Bi2S3,280,281 and InP,282 has drawn significant
Although the ordered heterojunction provides a direct path attention for promising photovoltaic devices. As compared with
facilitating electron transport to the collecting electrode, the sensitizers widely employed in DSCs, the band gap of QDs can
poor mobility in the polymer and the resulting recombination be tuned through control of the nanoparticle size, allowing one
of holes with electrons may also hinder further improvement of to adjust both visible response and the energetics at the
device performance. A strategy toward achieving high efficiency interfaces of the QD with the surrounding media. Moreover,
of nanostructured hybrid solar cell is to incorporate both the relatively high extinction coefficients of QDs can improve
ordered heterojunction architectures and bulk heterojunctions the light harvesting ability of the photoanode and increase the
by forming a double heterojunction device to provide two overall efficiency of the device. The formation of multiple
interfaces for charge transfer. Grimes et al.264,265 reported a excitons upon the absorption of a single photon in QDs
double heterojunction polymer solar cells, in which a blend of increases the thermodynamic efficiency limit of the device,
P3HT and [6,6]-phenyl-C71-butyric acid methyl ester making QDSCs extraordinarily attractive alternative for photo-
(PCBM) was infiltrated into the transparent NT array films. voltaic applications.283−287
In this configuration, both the P3HT/TiO2 and P3HT/PCBM The operation mechanism of QDSCs is similar to that of
interfaces provide heterojunctions for charge separation and the DSCs, considering QDs in some cases as a simple alternative
resulting device shows a PCE of 4.1% under AM 1.5 full dye.271,283,287−290 But surface states in QDs, not present in
sunlight. molecular dyes, introduce a significant difference between both
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light absorbers. The difference has to be taken into account as CdSe are passivated by the formation of ZnS layer on its
surface states can affect the injection and recombination surface, the surface trapping of photoexcited electrons and
processes.288,291,292 While the application of QDs as light holes in the QDs is effectively suppressed. Upon ZnS
harvester dates back to the 1990s,280,282,293,294 it has only been modification, the photoexcited electrons are injected more
in recent years when QDSCs have attracted intensive attention. efficiently from CdSe QDs to the TiO2 CB. Since the ZnS
Chemical bath deposition (CBD)295 and succesive ionic layer features a larger band gap than CdSe, the ZnS coating can
absorption and reaction (SILAR) methods296 are commonly further create a potential barrier at the CdSe/electrolyte
used by the QDSC community for the direct deposition of interface. As a result, the electron recombination from the CdSe
QDs onto TiO2 surface. The in situ synthesis of QDs on TiO2 QDs to the electrolyte is inhibited by application of ZnS surface
surface leads to efficient charge injection from the QD into the coatings over CdSe QDs. The QDSCs with ZnS modified
TiO2 material. Meanwhile, these methods ensure a high QD photoanode exhibited significantly improved Jsc, Voc, and PCE,
loading of photoanodes and consequently high photocurrents, obtaining an optimum efficiency of 2.02% under the AM 1.5
although the obtained QDs may feature a broad size full sunlight.
distribution and low crystalline quality.297 Presynthesized In addition to ZnS, the passivation of CdS QDSCs with a
monodisperse QDs, on the other hand, are usually connected thin layer of TiO2 also greatly improves the performance and
through linker molecules to the nanostructured TiO2 or photostability of the solar cells.307 The TiO2 coating passivates
deposited directly without linker molecules onto the TiO2 the CdS QD surface by decreasing the trap density and
surface. However, the electron injection from the QDs to the prevents its direct contact with the redox electrolyte. As the
TiO2 is generally less efficient compared to directly deposited conduction band edge of the amorphous TiO2 shell is located
QDs. In addition, the high QD loading is difficult to attain with closer to the vacuum level compared to its nanocrystalline
colloidal QDs297 that need bifunctional molecular linkers298,299 counterpart, the TiO2 coating can be considered as a potential
or especially designed direct adsorption methods.300 Never- barrier at the nanocrystalline TiO2/electrolyte interface for
theless, very recently Zhang and co-workers272,301,302 developed electron transfer from the nanocrystalline TiO2 core into the
a sensitization method with colloidal QDs, consisting in a electrolyte. Therefore, all five possible recombination paths in
capping ligand exchange followed by electrode sensitization the uncoated system are blocked through the amorphous TiO2
that produced photoanodes with a high colloidal QD loading. coating as shown in Figure 34. The relatively higher conduction
This process has allowed the recent preparation of highly band edge of the amorphous TiO2 shell also induces a barrier at
efficient devices with 6.36% PCE based on CdSexTe1−x alloyed the CdS/electrolyte interface, thus hindering the electron
QDs.302 Further development employing core−shell QDs that injection from the excited CdS QDs into electrolyte. In
utilize the charge transfer (exciplex) state has considerably addition, the amorphous TiO2 coating protects the CdS QDs
improved the light absorption of QDs to longer wavelength.303 from the attack of the corrosive I−/I3− redox couple, allowing
The resulting CdTe/CdSe QD based regenerative sandwich the use of highly efficient iodide-based electrolyte in QDSCs.
solar cells produced the highest efficiency of this kind of solar
cells, achieving 6.76% (Jsc = 19.59 mA cm−2, Voc = 606 mV, FF
= 0.569) under AM 1.5 full sunlight.
4.2. Surface Treatments in QDSCs
Although the employment of QDs as light harvesters has
offered the potential to prepare solar cells with excellent
performance, the obtained efficiencies of QDSCs still lag
behind those of DSCs. One reason for the rather moderate
conversion efficiency of QDSCs is the existence of surface traps
on the QDs, which act as recombination centers and increase
trap mediated recombination in the device.291,304 Besides, the
charge recombination between the electrons in the TiO2 and
the HTMs also constitutes an important electron loss path. As a
relatively large fraction of the TiO2 surface is in direct contact
with the HTM in QDSCs, the probability of the recombination
between separated electrons and holes is higher than in
DSCs.305 A common route for passivating surface states and
reducing internal charge recombination in QDSCs involves the
application of a thin layer coating of wide band gap materials.293
Besides, as most QDs suffer from photodegradation in
corrosive electrolytes, passivation of the QDs surface with
inorganic coatings can also enable the use of the I−/I3−
containing electrolyte.306,307 The inorganic coatings can be
deposited in a conformal and continuous fashion onto TiO2 Figure 34. (a) Schematic drawing of the uncoated CdS sensitized
TiO2 electrode showing five different recombination paths. (b)
electrodes, and it is shown that the semiconductor coating can
Recombination paths of an exited electron in the CdS QD. (c)
improve not only the stability but also the efficiency of Recombination of electrons from the TiO2 with a hole in a CdS
QDSCs.273,306−312 surface state or in the electrolyte. (d) Schematic drawing of the CdS
Shen and co-workers309 demonstrated that the surface sensitized mesoporous TiO2 electrode with amorphous TiO2 coating.
modification of QDs by ZnS coating enormously improved Reprinted with permission from ref 307. Copyright 2009 American
the performance of the CdSe QDSCs. As the surface states of Chemical Society.

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The obtained device with TiO2 protective shell and the I−/I3−
electrolyte exhibited a significant improvement of all cell
parameters, obtaining a PCE of 1.24%. In addition, this TiO2
coating is recently used also as an anchoring base for a second
sensitizer to construct the new bisensitizer layer cell.313 The
new configuration allows both the electron injection from the
outer absorber and fast hole extraction from the inner
sensitizing layer, leading to a 250% increase in efficiency
compared to a QD monolayer cell.
Although the coating of wide band gap materials over
photoanode can passivate the surface states and suppress the
charge recombination in the device, a thick passivation layer
may also hinder the hole tunneling and result in poor charge
transfer. Therefore, effective control of the TiO2 layer thickness
is crucial for further device performance optimization. Atomic
layer deposition (ALD) technique, which can ultrafinely control
the coating thickness, was recently employed to prepare an
ultrathin protection layer of TiO2 on the surface of CdS
QDSCs.306 It was found that the ALD-TiO2 layer slowed down
charge recombination and protected the QDs from the
photocorrosion of the I−/I3− electrolyte. Systematic inves-
tigation of QDSCs with different TiO2 coating thicknesses
indicated that ∼2 nm ALD-TiO2 layer can best promote solar
cell efficiency by balancing the protection effect and the charge
transfer efficiency. The correspondent CdS QDSC obtained a
power efficiency of 1.41% and stability of 20 min under full sun
illumination.
In QDSCs, the recombination processes occur in parallel at
the TiO2/QDs/electrolyte triple junction constitute one of the
major limitations for further photovoltaic improvement. While
the electron recombination from the TiO2 or QDs to the
electrolyte are commonly inhibited by application of surface
coatings over QDs, few researches address the recombination at
the TiO2/QDs interface. Recently, the charge recombination at
the TiO2/QDs/electrolyte triple junction was investigated by
isolating the different interfaces of the photoanode with respect
to the electrolyte (Figure 35a).311 As shown in Figure 35b, the
Jsc exhibits moderate enhancement when intermediate MgO
coating is applied on the mesoporous films prior to CdSe
deposition or when the MgO coating is used after CdSe QD
deposition. For CdSe QDSCs employing both intermediate and
upper coatings, the Jsc significantly increased from 9.3 to 12.4
mA cm−2, while the photovoltage remained nearly unchanged.
The electron lifetimes derived from transient photovoltage
measurements showed that the solar cell with both coatings Figure 35. (a) Schematic drawing of QDSCs showing the four
exhibited the longest electron lifetime while the devices with different types of photoanode. Corresponding (b) J−V characteristics
the upper or intermediate coatings featured moderate electron and (c) transport time constants for QDSCs incorporating different
lifetime (Figure 35c). The measured electron lifetime is in photoanodes. Reprinted with permission from ref 311. Copyright 2013
Royal Society of Chemistry.
excellent agreement with the photocurrents of different cells,
indicating that the high photocurrents obtained for the coated
electrodes originated from suppressed charge recombination. introducing specific additives to the electrolyte or HTM. It
Moreover, the greatly enhanced photocurrent and the was demonstrated that the self-assembly monolayer of an
prolonged electron lifetime of QDSCs with both coatings appropriate molecule onto the TiO2 surface can induce a local
reveal that the recombination occurs at the TiO2/QDs interface dipole field and thereby tailoring an energy alignment
is as important as the other interfaces in the TiO2/QDs/ displacement at the TiO2/QD/electrolyte (or HTM) inter-
electrolyte triple junction. By using double layer MgO coating faces.308,314,315 The modification of CdS QD surface by using
prior and after CdSe QDs deposition, the charge recombination benzenethiol derivatives with a negative dipole upward shifts
is largely suppressed and more than 20% improvement in cell the energy level of the QDs, while a positive dipole causes a
efficiency is achieved. downward movement of the QD energy level.314 In addition,
Besides increasing recombination resistance by surface molecular dipole treatment constitutes an additional energy
modification with inorganic coatings, the band alignment at barrier for recombination, thus hindering the leakage of
the TiO2/QDs/electrolyte interfaces and the corresponding electrons in the device.308,315 Through appropriate surface
charge transfer processes can also be optimized through modification of CdSe sensitized electrodes with conformal ZnS
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coating and 4-methoxybenzenethiol molecule, both the electron TiO2 and CIS layers to control the interfacial properties.329,335
injection and recombination processes can be optimized, As the CBs of In2S3 and CIS are close together and have an
achieving ∼600% enhancement of the efficiency for CdSe offset of about 1 eV when compared to the conduction band
QDSSCs.308 energy of anatase TiO2, the photogenerated electrons can be
4.3. Nanostructured TiO2 Electrodes for QDSCs easily transferred across the CIS/In2S3 interface to the TiO2.
Moreover, the recombination of conduction band electrons of
In conventional TiO2 NP-based QDSCs, electrons have to TiO2 with valence band holes in CIS can be limited due to the
travel through a 3D network of NPs and the undesirable loss of expanded spatial distance of CIS and TiO2 (Figure 36). As the
electrons at grain boundaries impedes effective electron
collection to the electrode. To address this problem, 1D
nanostructured TiO2 has been exploited to increase the
electron mobility and charge collection effi-
ciency.266,267,269,316−318 Comparisons between photoelectro-
chemical behavior of NT array and NP-based QDSCs reveal
that the NT array photoanode exhibits relatively high IPCE
owing to both the increased efficiency of charge separation and
the facilitated electron transport through TiO2 NTs.269 The
electronic coupling between QDs and TiO2 NT was
investigated by using hybrid DFT approach.319 It was found
that the adsorbate states were introduced in the band gap of the
TiO2 NT upon adsorption of CdS QDs on the TiO2 NT
surface and the electron was transferred from the sulfur atoms
of the CdS QDs to the CB of the TiO2 upon adsorption of
visible light. The photoexcited electrons could transport along
the cylindrical ultrathin wall of the TiO2 NT through titanium
dx2−y2 and dz2 orbits, and the TiO2 NT offers a 1D directional
pathway for electron transport across the substrate. Besides
TiO2 NT arrays, the TiO2 fibers has also been investigated for
the QDSC applications.320−323 TiO2 fibers can be produced in
a easy way,320 and with the appropriated surface treatments Figure 36. Energy-band diagram of a TCO/TiO2/Al2O3/In2S3/CIS
have shown an enormous potential for the development of high solar cell. Reprinted with permission from ref 329. Copyright 2004
Wiley-VCH.
performance QDSCs, especially for the high Voc obtained with
this structures.321
Mesoporous inverse opal (IO) TiO2 has been proposed as a deposition of sulfide absorber layers on TiO2 leads to surface
novel approach to improving the performance of QDSCs, due states in the forbidden gap of TiO2, a thin buffer layer of Al2O3
to the fact that its large interconnected pores facilitate the is further used to passivate the surface and improved the
infiltration of both light harvesters and hole transporting photovoltaic performance of the device.
material throughout the TiO2 film. This structure can also In addition to the interfacial properties, the TiO2 film
enhance the absorbance of QDs to achieve efficient light nanostructure, particularly the TiO2 particle size and layer
harvesting due to the slowing of group velocity of photon at the thickness also have great influence on the photovoltaic
wavelength near the photonic band gap.324−327 Diguna et performance.332,333 The device efficiency was enhanced
al.324,325 reported the application of TiO2 IO in QDSCs and the dramatically with increasing particle size, from 0.2% for the 9
conversion efficiency was significantly improved with surface nm TiO2 nanoparticles to 2.8% for the 300 nm counterpart.332
modification of ZnS and fluoride ions. It was shown that larger TiO2 particles led to better
photovoltaic performance due to decreased charge transport
resistance. Furthermore, the larger TiO2 particles may also lead
5. APPLICATION IN INORGANIC SOLID-STATE SOLAR to enhanced photon absorption and decreased carrier-migration
CELLS distance owing to enhanced light trapping and better
The concept of inorganic solid-state solar cells is similar to the infiltration of the CIS overlayer into the TiO2 matrix, thus
solid-state DSCs, in which the TiO2 extracts photoexcited secondarily improving the device performance.
electrons generated in the absorber layer while the sensitizers Besides CIS, another sensitizer material that attracts huge
are replaced by an extremely thin layer of semiconductor such interest is Sb2S3. There are several examples of inorganic solid-
as CuInS2,328−335 CdTe,336−338 or Sb2S3.339−344 The inorganic state solar cells based on nanostructured TiO2 sensitized with
solid-state solar cells have the advantage of enhanced light Sb2S3 employing different HTMs such as CuSCN,339−341
harvesting and are desirable to obviate leakage, sealing, and conducting polymers,342,343 and organic blend.344 Sb2S3-based
degradation concerns in conventional DSCs. cells prepared with nanostructured TiO2 was compared with
The inorganic solid-state solar cells based on interpenetrating analogous device with flat configuration.343 It was found that
networks of TiO2 and CuInS2 (CIS) is a relatively recent decreasing the effective surface area toward the limit of flat
inorganic-based design in this field.328−335 Compared to a samples increased the Voc while providing a significant
planar device, this configuration significantly shortens the photocurrent. This Voc enhancement is attributed to the
average carrier diffusion length, thus improving the collection reduction of the recombination rate. However, the reduction of
efficiency and providing device with a higher tolerance to the the surface area impedes the screening and results in increased
presence of impurities. In the TiO2−CIS inorganic solid-state hole-transport resistance, thus adversely affecting the cell fill
solar cells, an In2S3 buffer layer is typically required between the factor. Therefore, an optimized TiO2 structure has to balance
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between the reduced recombination with the need of effective HTM. While similar hole transfer from lead iodide perovskite
surface area for increasing the light absorption and screening to spiro-MeOTAD is observed for this system, the photoexcited
effect. electrons are not injected into Al2O3 due to the mismatch in
energy level between the CB of Al2O3 and lead iodide
6. APPLICATION IN PEROVSKITE SOLAR CELLS perovskite. In this case, the Al2O3 acts only as a “scaffold” and
Some lead iodide perovskites, which feature direct band gap, the perovskite layer functions not only as light harvester but
large absorption coefficient, and high carrier mobility, have also as n-type component, transporting electrons out of the
attracted attention as a new class of light harvesters in device (Figure 38). Small-perturbation transient photocurrent
heterojunction solar cells.345−355 The optical and electronic decay measurements revealed shorter electron transport
properties of perovskites can be tuned to a great extent by lifetime through the perovskite phase than through the TiO2,
controlling the distance and the electronic coupling between indicating that the perovskite exhibited superior electron
the inorganic sheets according to the structure of the organic transport property than TiO2. A noteworthy feature of the
component employed. In just a few years, this newly developed Al2O3-based devices is their superior Voc over that of TiO2-
device has made a series of remarkable progresses and achieved based devices. It is assumed that for mesoporous TiO2 the
an unprecedented PCE of 15.4% under AM 1.5 full sunlight.356 electrons are trapped mainly in TiO2 surface states and the
Miyasaka et al.357 have pioneered the photovoltaic function electron quasi-Fermi level locates far from the CB while for
of CH3NH3PbI3 and CH3NH3PbBr3 perovskites self-organized Al2O3-based devices, in which the electrons are forced to reside
on TiO2 as n-type semiconductors and obtained an efficiency of in the perovskite, the electron quasi-Fermi level is lifted for the
3.8% in combination with iodide-based electrolyte. Further same charge density. As the Voc is directly related to the
optimization of the CH3NH3PbI3 solution concentration and splitting of hole and electron quasi-Fermi levels, this upward
postannealing temperature yields optimized PCE of 6.54%, movement of the electron quasi-Fermi level leads to enhanced
which is almost two times higher than that of a conventional photovoltage for Al2O3-based device. Although giving an
N719-based cell.358 Unfortunately, a rapid degradation of understandable explanation to the interesting phenomenon,
performance is observed due to the dissolution of the this view is not consistent with subsequent results of Bisquert
perovskite in iodide-containing liquid electrolyte. As the and co-worker.361 As will be mentioned below, the study of
(CH3NH3)PbI3 perovskite features higher absorption coef- Bisquert et al. indicated that charge accumulated mainly in
ficient than conventional sensitizers in DSCs, it is sensible to CH3NH3PbI3 perovskite, no matter it was coated on TiO2 or
use perovskite in solid-state cell where much thinner TiO2 layer on an insulator material (ZrO2). While further work is still
is employed than in liquid junction devices. needed to clarify the origin of the enhanced photovoltage, the
A solid-state solar cell employing (CH3NH3)PbI3 as light morphology and surface state variations of lead iodide
harvester and spiro-MeOTAD as hole-conductor has been perovskites on different metal oxides may also contribute to
reported by Park’s and Grätzel’s groups,359 where a PCE of the different photovoltaic performance. Snaith et al.362 further
9.7% was achieved based on a very thin TiO2 film (∼0.5 μm). reported efficient perovskite (CH3NH3PbI3−xClx)-polymer
The valence band energy and conduction band energy of hybrid solar cells with the highest efficiency of 11.7% by
(CH3NH3)PbI3 were estimated to be −5.43 and −3.93 eV using a mesoporous titania film functionalized with the
below vacuum, guaranteeing well aligned band positions for fullerene (C60SAM) self-assembled monolayer. While the
charge separation (Figure 37b). Further femtosecond transient photoexcitations in both the perovskite and the polymer
P3HT undergo very efficient electron transfer to the C60SAM,
the presence of C60SAM inhibits further electron transfer into
the TiO2 mesostructure due to energy level misalignment and
poor electronic coupling. In this case, the electrons are trapped
on the C60SAM molecules, through which they can be mediated
into the perovskite CB and then transport across the perovskite
absorber. Since the existence of sub-bandgap states on TiO2,
the inhibition of electron transfer into the TiO2 can reduce the
chemical capacitance in the device, thus moving the electron
quasi-Fermi level closer to the perovskite CB at certain charge
density.
Figure 37. (a) Structure of CH3NH3PbX3 (X = I, Br) perovskites. Besides light harvesting and electron transportation, the hole-
Reprinted with permission from ref 351. Copyright 2013 Royal Society transport ability of perovskite is also revealed in several
of Chemistry. (b) Schematic energy level diagram of TiO2/ publications.363,364 A layered sandwich-type architecture based
CH3NH3PbI3/spiro-MeOTAD junction. Reprinted with permission
on a bicontinuous 3D nanocomposite of mesoporous TiO2 in
from ref 359. Copyright 2012 Nature Publishing Group.
combination with CH3NH3PbI3 perovskite and polytriaryl-
amine (PTAA) was introduced by Grätzel et al.364 As the high-
absorption studies demonstrated that the excited state of the molecular-weight polymer PTAA cannot easily infiltrate into
(CH3NH3)PbI3 perovskite can be reductively quenched by mesoporous TiO2 as the small molecular HTMs, the device
spiro-MeOTAD, confirming the charge separation to proceed based on PTAA forms a pillared structure (Figure 39). In this
via hole injection from the excited (CH3NH3)PbI3 into the architecture, the CH3NH3PbI3 perovskite acts both as light
spiro-MeOTAD followed by electron transfer to the meso- harvester and hole conductor. The small CH 3 NH 3 PbI 3
scopic TiO2 film. crystalline domains, which densely forms on top of the
In 2013, Snaith et al.360 reported the application of mesoporous TiO2 and the bicontinuous structure of the
CH3NH3PbI2Cl as a light harvester for mesocopic Al2O3 TiO2/CH3NH3PbI3 nanocomposite ensure effective extraction
films and obtained 10.9% PCE with spiro-MeOTAD as of the charge carriers, while the large interfacial area between
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Figure 38. Schematic illustrating the charge transfer and charge transport in a perovskite thin-absorber solar cells based on TiO2 and Al2O3.
Reprinted with permission from ref 360. Copyright 2012 AAAS.

the CH3NH3PbI3 and PTAA assists in hole extraction to the OMeTAD, the performance of the fabricated solar cell was
gold electrode. The application of PTAA is recognized as a key effectively improved, achiving a PCE of 10.4% under standard
factor for obtaining excellent performance and the correspond- solar conditions.
ing device yields a PCE of 12.0% under AM 1.5 full sunlight. Although the working principle of perovskite thin-absorber
Generally, the CH3NH3PbX3 (X = Br, I) perovskites are solar cells is still not well understood, the tentative researches
deposited onto mesoporous metal oxide films by simulta- imply that this kind of cell do not work as conventional
neously dissolving PbX2 and CH3NH3X in a common solvent. photovoltaic devices.355,360,363,364 Bisquert and co-workers361
However, the uncontrolled precipitation of the perovskite investigated the mechanism of carrier accumulation in perov-
produces large morphological variations, resulting in a wide- skite thin-absorber solar cells by means of EIS. By measuring
spread of photovoltaic performance in the resulting devices. the capacitance extracted from EIS measurements for both
Recently, a sequential deposition method for the formation of nanostructured TiO2 and ZrO2 electrodes, significant higher
CH3NH3PbI3 within the porous TiO2 film has been reported capacitances were observed for samples with perovskite, despite
by Grätzel’s group.365 In their research, the PbI2 was first the large difference from the electrical point view between TiO2
introduced from solution into a nanoporous TiO2 film and and ZrO2. This phenomenon indicates that the charge
subsequently transformed into the perovskite by exposing it to accumulation mainly occurs in light-absorbing materials,
a solution of CH3NH3I. Based on this technique, an CH3NH3PbI3 perovskite in nanostructured devices. In this
unprecedented PCE of 15% has been achieved and the respect, the distribution of surface states on perovskite may
reproducibility of device performance is greatly improved. As have significant impact on the photovoltage of the device,
the diffusion lengths in CH3NH3PbI3−xClx were determined to although there is not a clear recognition of photovoltage origins
be greater than 1 μm, which was an order of magnitude greater in these devices until now. Besides, whether the charge
than the absorption depth, the nanostructuring is not necessary recombination is intensified by the accumulation of electrons in
to achieve high efficiencies with these specific perovskite thin- perovskite materials and the intrinsic principles for its high
absorber solar cells.366 Based on the simplest planar efficiency remain an open question to be answered in the
configuration incorporating vapor-deposited CH3NH3PbI3−xClx future.
perovskite as the absorbing layer, a high efficiency of 15.4% was
achieved under the AM 1.5 full sunlight.356 Zhang et al.367 7. CONCLUDING REMARKS
successfully developed a strategy for incorporating core−shell Over the past decades, titanium dioxide nanomaterials have
Au@SiO2 nanoparticles into organometal halide perovskite been intensively studied for their application in solar to
solar cells to reduce the exciton binding energy of perovskite electricity conversion because of their compatibility with
absorber, and hence enhancing the generation of free charge modern technologies. The continuous breakthroughs in the
carriers. Moreover, the cobalt(III) complex (FK209) was synthesis and modifications of titanium dioxide nanomaterials
introduced as a p-dopant to improve the charge transport have brought novel properties and applications in the
properties of spiro-MeOTAD.368 Due to the reduced carrier photovoltaic filed with improved performance. Besides, newly
recombination and decreased Fermi level of HTM upon the developed devices based on a novel concept have largely
addition of FK209 and the synergistic effect between the expanded the application range of titanium dioxide and also
cobalt(III) complex and LiTFSI in conjunction with spiro- raised new requirements for titanium dioxide properties. In this
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properties of titanium dioxide interface can be modulated

through the interaction between TiO2 and the surrounding
elements, including light harvesters, charge transport materials,
additives as well as interfacial modifiers. By rational modulation
of the intrinsic and interfacial properties of the TiO2
nanomaterials, people have made great progress in controlling
the light harvesting, energy distribution, charge separation,
charge transfer and transport properties in the devices and have
greatly boosted the performance of the devices. Besides these
fundamental achievements, more effort should be taken to
develop large scale preparation technique for high quality, low
cost titanium dioxide nanomaterials and transformative
technology so as to realize the marketing economically viable
solar panels with wide application prospect.
Recently, perovskites have attracted great attention as a new
class of light harvesters for mesososcopic solar cells. This newly
emerged solar cell has made remarkable progresses and
achieved an impressive PCE of 15.4% in just a few years.
Although the full device stability over a broad range of
conditions remains to be proved, lead iodide perovskites have
opened up a new era for developing efficient and low-cost solar
cells. It is believed that future research efforts on new materials
and key interfaces will make the titania-based solar cells as a
new PV energy source.

AUTHOR INFORMATION
Corresponding Author
*E-mail: [email protected].
Notes
The authors declare no competing financial interest.
Biographies

Figure 39. (a) SEM cross-sectional image, (b) SEM surface image, and
(c) architectural schematic of the inorganic−organic hybrid hetero-
junction solar cell consisting of CH3NH3PbI3-coated mesoporous
TiO2 film as well as PTAA hole conductor. Reprinted with permission
from ref 364. Copyright 2013 Nature Publishing Group.

review, the major advances of applying titanium dioxide

nanomaterials to photovoltaics have been discussed, including
the dye-sensitized solar cells, polymer-inorganic hybrid solar
cells, quantum dot-sensitized solar cells, inorganic solid-state
solar cells, and perovskite solar cells. These steady progresses Yu Bai obtained her Ph.D. in Chemistry from the Chinese Academy of
have demonstrated that TiO2 nanomaterials play an important
role in the search for efficient and low cost photovoltaic Sciences in 2011 and is now a professor at Harbin Institute of
technologies. In these photovoltaic devices, the charge transfer Technology. Her research interest focuses on interfacial physical
process is intimately associated with the properties of titanium chemistries of dye-sensitized solar cells as well as novel inorganic
dioxide nanomaterials as well as the titanium dioxide interface.
nanostructures and hole-transport materials for energy storage and
While the unique physical and chemical properties of titanium
dioxide nanomaterials can be controlled through modulation of conversion. She has received the 2009 GUCAS-BHP Billiton award
nanocrystal structure, size, shape, and organization, the and the 2012 CAS president special award.

AC dx.doi.org/10.1021/cr400606n | Chem. Rev. XXXX, XXX, XXX−XXX

Chemical Reviews Review

Juan Bisquert is a professor of Applied Physics at Universitat Jaume I

de Castelló. His main topics of interest are dye and quantum dot-
Iván Mora-Seró obtained his Ph.D. in Physics from the Universitat de sensitized solar cells, organic solar cells, and solar fuel production. He
has developed the application of measurement techniques and physical
València in 2004. Currently, he is an associate professor at the
modeling that relate the device operation with the elementary steps
Department of Applied Physics, Universitat Jaume I de Castelló, and is that take place at the nanoscale dimension: charge transfer, carrier
transport, chemical reaction, etc., especially in the field of impedance
leading the quantum dot and semiconductor research line of the spectroscopy, as well as general device models. He is currently a senior
photovoltaic and optoelectronic devices group. His recent research has editor of the Journal of Physical Chemistry and a member of the
Editorial Boards of Energy and Environmental Science and ChemElec-
largely focused on new concepts for photovoltaic conversion based on troChem.
nanoscaled devices and semiconductor materials following two main
lines: quantum dot solar cells, with especial attention to sensitized
devices, and lead halide perovskite solar cells.

Peng Wang obtained his Ph.D. in 2001 from Changchun Institute of

Applied Chemsitry, Chinese Academy of Sciences. He then worked as
a postdoctoral fellow at Swiss Federal Institute of Technology,
University of Cambridge, and University of California, Santa Barbara.
He is now a professor of chemistry at Changchun Institute of Applied
Filippo De Angelis is a senior research scientist and deputy director at Chemistry, Chinese Academy of Sciences. His research interest centers
the CNR Institute of Molecular Sciences and Technology, in Perugia, on material innovation, device engineering, and in-depth under-
standing of the charge and energy transfer processes for efficient
Italy. He is the founder and coleader of the Computational Laboratory photovoltaic devices. He has received several awards, including the
2009 CAS-Bayer Young Scientist Award, the 2012 CSS-RSC Young
for Hybrid/Organic Photovoltaics. He is an expert in the development
Chemist Award, and the 2013 Young Scientist Award of CAS.
and application of quantum chemical methods to the study of the
structural, electronic, and optical properties of complex systems ACKNOWLEDGMENTS
Y.B. and P.W. thank the National Science Foundation of China
including transition metals. His main research interest is in the field of
(Nos. 51203036, 51125015, and 91233206) and the National
hybrid/organic photovoltaics, employing DFT, ab initio molecular 973 Program (2011CBA00702) for financial support. F.D.A.
thanks CNR-EFOR and FP7-ENERGY-2010 “ESCORT”
dynamics, and TDDFT methods to investigate the electronic structure (261920) for financial support.
of materials and interfaces. He is the 2007 recipient of the Raffaello
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