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 Materials and processes for energy: communicating current research and technological developments (A. Méndez-Vilas, Ed.)
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Metal oxides for photoinduced hydrogen production and dye-sensitized

solar cell applications
A. E. H. Machado*; A. O. T. Patrocinio*; M. D. França; L. M. Santos; K. A. Borges; L. F. Paula
Laboratorio de Fotoquimica – Instituto de Química - Universidade Federal de Uberlandia, Uberlandia, Minas Gerais,
Brazil * aehmachado@gmail.com; otaviopatrocinio@iqufu.ufu.br

The interest on application of metal oxides semiconductors in photocatalysis and in photoelectrochemical devices has
constantly increased. The different fields in which metal oxide-based semiconductors are applied include environmental
remediation, photovoltaics, self-cleaning surfaces and hydrogen production. In the present review, the recent advances on
synthesis and characterization of metal oxides semiconductors are discussed, aiming the application in photocatalytic
systems. Due to the large number of applications and metal oxides reported in the literature, this work will focus on TiO2-
based systems, which is by far the most studied oxide for photocatalysis, and their application in hydrogen evolution and
in new generation solar cells, such as dye-sensitized solar cells (DSCs).

Keywords: metal oxide semiconductors; titanium dioxide; hydrogen evolution; solar cells.

1. Aims and Scope

Currently, the research in renewable energy sources is intense due to the concerns about the global warming and other
environmental issues related to the huge dependence of the global energy matrix on the fossil fuels. The enhancement in
the participation of renewables requires the development of cost effective materials capable to produce fuels or
electricity from solar light as well as from earth abundant green sources.
The goal of the present work is to present the concepts and current research involving the application of metal oxide-
based semiconductors in solar energy conversion. In the first section, the synthetic methodologies for production of
metal oxides with different sizes and shapes are discussed and correlated to their optoelectronic properties. Following
the discussion about morphology and electronic properties of metal oxides, the recent advances in heterogeneous
photocatalytic hydrogen evolution are briefly discussed. Due to size limitations and the very intense research activity in
this topic, we have focused the manuscript on TiO2-based systems, which is the most studied oxide in photocatalysis.
Finally, in the third section, the use of metal oxides thin films in Dye-sensitized solar cells is explored. The role of film
morphology, the deposition method and the oxide electronic properties on the light-to-current conversion efficiency is
discussed based on the recent literature. The advances reported evidence the feasibility of large use application of metal
oxide-based semiconductors in renewable solar energy systems.

2. Synthesis, morphology and electronic properties of semiconductor metal oxides

2.1. Synthesis and morphology

The electronic, optic and photocatalytic properties of metal oxides are strongly dependent on the method of preparation
and treatment conditions which they were submitted [1-2]. In the development of materials for specific applications,
such as photocatalysis, synthetic methods that allow the control of the particle size are desirable. Efforts have been
made towards the development of new synthetic methods or variants of traditional methods, to obtain nanoparticles in a
determined crystalline phase, with controlled size and morphology [2-4].
Semiconductor metal oxides can be prepared by different routes, forming amorphous, crystalline materials, thin
films, nanotubes, etc. [5-7]. These routes can be distinguished according to the phase (gas or liquid) where the synthesis
is performed [8-9]. The most widespread methods in gaseous phase synthesis are the Chemical Vapour Deposition
(CVD) [9] and oxidation under flame [8], the latter employed in the production of the well-known TiO2 P25. The liquid
phase methods are preferable to obtain powders and films and have been largely explored in the literature, especially the
hydrolitic sol-gel methods [10-11] of polymeric precursors [12-13] and also hydro- and solvothermal methods [3, 14-
15].
The sol-gel method provides homogeneous mixtures, yielding films, fibers and gels with high surface area and with
great importance in photocatalytic applications. The method is characterized by a reaction in homogeneous medium
(“sol”) which destabilizes in a controlled manner, forming particles or nanoparticles (“gel”). The term sol-gel is usually
related to a hydrolytic process, that is the reaction of an anhydrous precursor in an aqueous medium [16-17]. The
hydrolytic process involves the binding of HO- ions to the metal from an organic precursor or halide [18-19]. The main
advantage of this method is the possibility to obtain homogeneous systems with a high degree of purity, which can be
calcined at relatively low temperatures, allowing the production of oxides with well-defined properties [14, 20].

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The synthesis via polymeric precursors is a variant of the sol-gel process, where the reaction is non-hydrolytic and
generates a polymer which, after calcination or solvent-based removal of the organic matter, yields the oxide of interest
[21]. It stands out for being an alternative process for obtaining nanometric powders, with controlled particle size, high
purity and chemical homogeneity at relatively low cost, not requiring sophisticated equipments for its application. In a
typical synthesis, a complex is formed between a hydroxycarboxylic acid (usually citric acid) and metallic cations in an
aqueous solution, which is mixed to a polyalcohol (usually ethyleneglycol) being heated (80 to 110ºC) up to obtaining
of a limpid solution. A new heating (150 to 250ºC) causes a condensation reaction with water formation. If the heating
is maintained, a polyesterification reaction will occur, with the elimination of the excess of water associated to the
organic matter, resulting in a solid and with high crystallinity, important for applications in catalysis, sensors, among
others [21].
Homogeneous precipitation has been also applied in the production of photocatalysts due to its versatility [22].
Chlorinated or alcoxides precursors react with a base (sodium or ammonium hydroxide), resulting in metal hydroxides,
which is converted in amorphous oxides by water loss. Under different thermal treatments, selected crystalline phases
can be produced [22-23]. The main disadvantage of this method is the relative difficulty in controlling particle size,
since very fast precipitation tend to occur, causing the formation of very large particles [23]. On the other hand, this
method allows the production of materials with narrow particle size distribution, high crystallinity using lower
temperatures than in solid phase synthesis and with reduced preparation time [24].
An alternative for obtaining crystalline oxides without high temperature thermal treatments is the use of
hydrothermal and solvothermal conditions. The hydrothermal process consists of a heterogeneous reaction in pressured
aqueous medium carried above the room temperature [6, 25-26]. The application of this method tends to reduce the
reaction time and the temperature of synthesis, due to the high pressures applied [27]. The apparatus used in
hydrothermal essays basically consists of a stainless steel reactor coated internally with polytetrafluorethylene (PTFE),
to minimize or eliminate the possibility of chemical attack of the vessel by the solution. The reactor is externally heated
by a tubular furnace. A built-in temperature probe and a pressure probe keep the control of the system, which can
operate at constant temperature and at a pressure of up to 40 atm for long periods [26-27].
The solvothermal process involves reactions under no aqueous medium. In such process the precursor is dissolved in
anhydrous alcohol [6, 14, 28] and heated in a closed reactor at temperatures higher than 150°C, and high pressures.
Under these conditions, the hydroxide ion present in the alcohol partially binds the metal ion, starting a
polycondensation reaction. The steric hindrance by the organic groups favors the formation of nanoparticles. The main
obstacle of this method is the possibility of the presence of organic groups on the surface of the nanoparticles, which
can poison the catalytic sites [6, 23].
In order to improve the synthetic techniques and morphology control to obtain ordered mesostructured materials
with superficial characteristics desirable from the catalytic and photocatalytic point of view [5-6, 25, 29-31], processes
based on the strategy of structural molding via a surfactant, through cooperative automounting involving inorganic
species has been applied [32]. Colloidal systems have been considered very efficient molds in promoting control of
particle size and shape [29-30]. Hierarquical structures can be used as hard molds to host and guide the growth of
aligned and ordered metal and semiconductor 1D nanostructures such as nanowires or nanotubes, with different
morphologies [5, 29-30]. Mesoporous nanowires, for example, are particularly attractive for applications in sensors and
catalytic converters [32].

2.2. Optoelectronic properties

Semiconductors are characterized by two distinct energetic regions, separated by a band gap. The term band gap refers
to the energy difference between the top of the valence band (VB), and the bottom of the conduction band (CB) [22].
The energy required to promote an electron from the VB to the CB can be provided by a phonon (heat) or a photon to
yield a hole (h+) at the VB and an excess of electronic charge in the CB simultaneously, favoring the occurrence of
oxidation and reduction reactions [12, 19]. The efficiency of a photocatalytic process depends on the competition
between the process of formation of electron/hole pairs, the recombination pathways, and the subsequent reactions
[33-34].
Titanium dioxide is the most studied wide band gap metal oxide photocatalyst [35]. In general, it exhibits n-type
semiconductor properties, however, deviations in the stoichiometry of TiO2 can lead to the formation of an extrinsic
semiconductor with p-type features [36-37]. The electrical properties of TiO2 can change depending on environmental
conditions. In view of this, TiO2 as well as other metal oxides, such as ZnO, CuO, among others, have been proposed as
gas sensors [38-40]. In particular TiO2 has been studied as a sensor of oxygen, hydrogen, carbon monoxide and methane
[39]. The gas interacts with defects on the surface of the material, changing its electrical conductivity. This interaction
can be enhanced by doping with transition metals. The insertion of d orbital electronic levels of the dopant tends to
promote changes in the electrical properties of the material with implications on the sensitivity and the operation
regimen of the device [41-42].
Electronic properties of metal oxides, such as the band gap energy, play an important role in heterogeneous
photocatalysis. The three crystalline phases of TiO2 have different photocatalytic activities [43-44]. Anatase and rutile,
to a lesser extent, has been widely employed in the mediation of photocatalytic processes. The anatase, which has the

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largest band gap (3.2 eV) compared with the other two phases, is the most popular polymorph used in photocatalytic
processes [12, 43-44]. Despite being the least studied of the three, the polymorph rutile has been shown to be effective
in promotion of photocatalytic degradation of various substrates, with even higher photocatalytic activity than anatase,
and in some cases than the TiO2 P25 [45-46]. The brookite phase is still not completely explored due to the difficult to
synthesize. Nevertheless, Kandiel, Bahnemann and co-workers in a recent study involving titanium dioxide
nanoparticles consisting of pure anatase, anatase-rich, brookite-rich and pure brookite, have shown that brookite TiO2
exhibits higher photocatalytic activities than anatase, and a comparable activity to that of the anatase-rich nanoparticles
[47]. In a parallel study, Shen and co-workers have observed that anatase-brookite mixtures exhibit higher activity than
pure anatase, and that a mixed-phase TiO2 containing 53.4% brookite and 46.6% anatase shows the highest
photocatalytic activity [48].
For all TiO2 polymorphs, increased photocatalytic activity can be reached by modification of some electronic
properties. Doping and association to photosensitizing dyes are some possibilities to shift the light absorption to the
visible region and/or increase the lifetime of the photoproduced electron-hole pairs [12].

3. Hydrogen production
In the last 150 years, the production and provision of energy, initially based on the burning of wood and coal, have
incorporated petroleum, natural gas, hydroelectric, nuclear energy, and, more recently, renewable sources [49]. Among
renewable energy sources, there is a growing interest for development of clean technologies for the production and use
of H2. However, currently, not more than 5% of the commercial production of hydrogen is from renewable sources,
mainly through the electrolysis of water, while about 95% are essentially derived from fossil fuels [50].
Among the alternatives of generation and use of energy, the use of hydrogen gas seems to be promising due to its
high calorific value and almost null emission of pollutants. There are great expectations for use of hydrogen as energy
input, which is driving a growing market and that moves billions of dollars annually [51-52]. A large part of the efforts
to establish the use of hydrogen as a renewable energy source is based on the development of the fuel cell technology,
aiming to expand its lifetime and minimizing the production costs [53]. The production of hydrogen from renewable
sources still has a high cost, however, ongoing studies are seeking alternatives in order to make this production
commercially competitive. A promising alternative is the use of photocatalysis. In this field, TiO2 stands out because it
is photosensitive, abundant, nontoxic, chemically and photochemically stable in a large range of pH and insoluble in
water [54].
The photocatalytic hydrogen production is based on the reaction between the electronically excited semiconductor
and water. In principle, the decomposition of water into hydrogen and oxygen (Equation 1) can be achieved by a
semiconductor upon light irradiation with energy greater than its band gap [55].
hν  E 1
H 2O ⎯⎯⎯g → H 2 + O2 (1)
2
Thermodynamically, the overall water splitting involves a considerable energy uptake (ΔG = + 238 kJ.mol-1) [56-
57]. For an efficient H2 production, the semiconductor must present a band gap energy in the range between 1.23 eV
(decomposition potential of water in 1000 nm) and 3.0 eV (420 nm). Thus, a “band engineering” is necessary to
produce appropriate semiconductors [14]. The photocatalytic production of H2 is a redox process that involves
photogenerated charge carriers (holes and electrons). Oxidation is promoted by holes in VB, and leads to the formation
of O2(g), while the reduction is promoted by electrons in the CB, and results in the formation of H2(g) (Equations 2 and
3). The electrons and holes act separately, as a reducing and oxidant agents, respectively, on the decomposition of water
to produce hydrogen and oxygen. However, in order to effectively promote water decomposition, it is essential to
minimize the electron-hole recombination [55, 58].
2 e − + 2 H + ⎯ E⎯
BC  E H + / H 2 O
⎯ ⎯⎯→ H 2 (2)
1
2h+ + H2O ⎯E⎯
Bv  EO 2 / H 2 O
⎯⎯⎯→ O2 + 2H + (3)
2
For a large-scale photocatalytic production of hydrogen, it is imperative the use of visible radiation [59]. Therefore,
the development of photocatalysts able to mediate reactions with the use of visible radiation is more than desirable [3,
60]. Once the TiO2 is only able to be photo-excited with UVA radiation (less than 5% of the solar energy received in the
biosphere) [3-4, 12], efforts have been made to introduce changes in the TiO2 or even develop photocatalysts able to use
visible radiation [4, 61-62], which represents about 43% of solar energy incident on the biosphere [12, 63].
Among the different ways to make visible radiation photocatalysis, the association between a semiconductor oxide
and photosensitizing dyes is a viable strategy [59]. In particular, with regard to the photocatalytic hydrogen production
under visible light, Ru and Pt complexes, metalloporphyrins, phthalocyanines, eosin-Y, rhodamine B, Rose Bengal,
merocianines, coumarins, etc., has been used associated to semiconductor oxides [2, 14, 18, 31]. In addition, the bio-
inspired antenna effect, common in polynuclear complexes of Ru(II), has been used to promote an efficient absorption

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of visible radiation [59]. Other alternatives that have been proposed to obtain more efficient photocatalysts for hydrogen
production are: doping with transition metals [14], with non-metals [64-65], associations between different
semiconductor oxides [66], and association between semiconductor oxides with addition of a transition metal [67].
Antony and coworkers [68] studied the hydrogen production using nanocomposites based on TiO2 containing
platinum depositied on the surface in an ethanol-water mixture. It was observed that the highest yields of hydrogen
production (0.03 mol /h/g) were achieved using photocatalysts containing 1.0 to 2.5% m/m of platinum depositied.
Choi and coworkers [69] synthesized TiO2 nanoparticles and nanofibers sensitized with Eosin-Y. Photocatalytic
activities for production of hydrogen by the nanocomposites were compared with and without the addition of Pt to the
surface. In the experimental conditions used in this study, they found that the photocatalytic activity of TiO2 nanofibers
was higher than that of nanoparticles: with one hour of reaction with TiO2 nanofibers 0.21 mmol.g-1 of H2 were
produced, while the nanoparticles yield 0.03 mmol.g-1of H2. When platinum was deposited on the surface of these
nanocomposites, there was a significant increase in the production of hydrogen for both photocatalysts, although the H2
production continued to be higher with the nanofibers: 7.14 mmol.g-1 against 1.92 mmol.g-1of H2 with the nanoparticles
after 1 hour irradiation. The highest photocatalytic efficiency presented by TiO2 nanofibers can be explained by
different factors, including the easier charge transfer in nanofibers, since the particles are directionally arranged.
The Table 1 presents a short summary of some relevant studies that involve the production of hydrogen by
heterogeneous photocatalysis, using TiO2-modified nanocomposites.

Table 1. Some examples of heterogenoeous photocatalysts and experimental conditions for hydrogen production.
Photocatalyst Synthetic Medium Incident H2 Production Refs
method radiation
Cu(OH)2/ TiO2 Hydrothermal CH3OH/H2O UV 14.94 mmol h-1 g-1 [70]
nanotubes precipitation
Pt-CdS/TiO2 Photodeposition Na2S/Na2SO3 Visible light 3.7 mL [71]
Method solution
Pt/hex-CdS/ Precipitation glycerol (30%) solar light- 65 μmol g−1 h−1 [72]
TiO2 method simulating
C-TiO2 Electrochemical - UV–vis light 282 μL h−1 cm−2 [73]
nanotubes anodization
Pt/TiO2 Sol-gel method Propionic acid UV 112.9 μmol min-1 [74]
solution
Fe/TiO2 - glycerol (30%) Visible light 4.9 mL [75]
N-TiO2 Sol-gel method Na2SO4 solution Visible light 28 μmol h-1 [76]
TiO2 Sol-gel method CH3OH/H2O UV 10.74 μmol h-1 [77]
(25%)
TiO2/HTiNbO5 Exfoliation – Diethanolamine UV 219 μmol h-1 [78]
restacking solution (10%)
RhB-Co/TiO2 Impregnation H2O Visible light 227 μmol h-1 [79]
method

In water decomposition, the oxidation of water into oxygen involves four electrons and it is the rate limiting step and
decreases significantly the efficiency of hydrogen evolution. Thus, it is common to use sacrificial oxidizing reagents in
order to maximize the H2 production [80-81]. A great effort has been undertaken to define efficient and low cost
sacrificial agents capable of minimize the recombination of the electron/hole pair [5, 56, 81-82]. Alcohols, such as
ethanol and methanol are commonly used as sacrificial agents [5]. Alternative sacrificial agents have also been reported
[82-83].
Kim and coworkers [82], using TiO2-based photocatalysts modified with anions and transition metals, studied the
degradation of 4-chlorophenol with simultaneous production of hydrogen. They showed that in the conditions under the
TiO2 was modified only with one component (F-TiO2, P-TiO2 or Pt/TiO2), the desired double function was not
observed. When oxides have been modified concurrently with fluor and platinum (F-TiO2/Pt) or with phosphorus and
platinum (P-TiO2/Pt), these photocatalysts were active both in the degradation of organic matter as well as in the
production of hydrogen. In addition, the same researchers found that the photocatalytic efficiency was dependent on
both, the metal deposited and the medium pH. The F-TiO2/Pt, as example, has its application limited to acid pHs. On
the other hand, P-TiO2/Pt exhibited a consistent photoactivity across a wide pH range. They still observed the
occurrence of a synergistic effect between the anions and the metal deposited on the surface of the TiO2, that extends
the interfacial charge transfer and reduces the charge recombination, resulting in an increase of about 20 times in the
production of hydrogen in the presence of 4-chlorophenol, when compared with the TiO2 only with metal deposited.
Slamet and coworkers studied the hydrogen production concomitant with the degradation of glycerol in aqueous
medium using TiO2 nanotubes simultaneously modified with nitrogen and platinum [84]. In order to define the best
condition for the production of hydrogen, it was evaluated the role of glycerol concentration, morphology of TiO2, as
well as the different dopants used. They showed that TiO2 nanotubes produced more hydrogen than the Degussa P25

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TiO2. The analysis by diffuse reflectance spectroscopy showed that the TiO2 doped with nitrogen was more sensitive to
visible light than the similar non-doped, while the Pt-N-TiO2 presented a much higher activity in the production of H2
using UV light, when compared with the other photocatalysts synthesized. The explanation for this fact is possibly the
same presented by Kim and coworkers [82].
The global demand for energy sources economically viable and sustainable is unquestioned. Studies show that the
production of gaseous hydrogen is a possibility, especially considering the use of photocatalytic processes. However,
for a large-scale photocatalytic production, there are many obstaclesto be transposed. On the other hand, the advances
made in recent years show that its large-scale economic production is a mere matter of time.

4. Metal oxide thin films for Dye-sensitized solar cells applications

In some applications of metal oxide-based semiconductors, such as in photoelectrochemical cells, is convenient to
immobilize the particles in a suitable substrate to produce modified photoelectrodes able to perform specific functions
under irradiation. This strategy was successfully employed by Fujishima and Honda to show the UV-light induced
water decomposition by using a TiO2-based photoanode [85]. A second breakthrough in the field was achieved by
O’ Reagan and Gratzel in 1991 by reporting a sensitized mesoscopic TiO2 based photovoltaic solar cell with overall
conversion efficiency higher than 7% [86]. Since them, the so-called Dye-sensitized solar cells, DSCs, have been
studied by several groups around the world [87-92] due to their relatively low production cost and good stability, which
makes the practical application feasible. So far, the overall conversion efficiency has reached up to 12.3% [93].
In DSCs, Figure 1a, the photoanode is comprised by a ~10 μm mesoporous TiO2 film deposited over a transparent
conductive substrate (TCO) and sensitized by an appropriate dye, capable of injecting electrons on TiO2 conduction
band under solar radiation. The photo-oxidized dye is regenerated by a redox pair in the electrolyte, which can be
liquid, quasi-solid or solid [88-89]. The oxidized species in the electrolyte are regenerated at counter electrode. Ideally,
at end of each cycle, no net reaction occurs and the device can work for a long period of time without efficiency losses.
A typical IV curve for a DSC with the main photoelectrochemical parameters are shown in Figure 1b.

(a) (b)

Figure 1. (a) Components of a Dye-sensitized solar cell and (b) the main photoelectrochemical parameters obtained from a curren-
voltage curve.

As a multicomponent system, the physicochemical properties of each constituent influences on the conversion
efficiency [94-95]. Particularly, for the metal oxide semiconductor thin film, it is the nanosized mesoscopic structure the
main factor for the huge increase in the DSC conversion efficiency in comparison to monocrystalline TiO2-based
photoanodes. As pointed out by Grätzel, the incident photon-to-current conversion efficiency of a mesoporous TiO2 thin
film photoanode is c.a. 600 times higher than an electrode employing a single-crystal anatase under same conditions
[96]. The reasons for this great difference is associated to the larger surface area available for dye adsorption on
mesoporous film and the ease charge carrier percolation through the mesoscopic particle network, which is better
described by the random walk model [97-98].
Continuous advances on synthesis of TiO2 nanoparticles, led to the development of photoanodes with different
arrangements including nanotubes, nanorods, among others [99-102]. Several synthetic approaches have been employed
to produce the nanostructures such as, the sol-gel method followed by a hydrothermal treatment [103], electrochemical
routes [104] and microwave-based methods [105]. Despite TiO2 is the preferred oxide for DSC applications due to its
low cost, non-toxicity, inertia and appropriate electronic properties, other oxides have been used as mesoporous layer
such as, ZnO [106], SnO2 [107-108], Nb2O5 [35, 109] and WO3 [110]. Different configurations have been proposed in
the literature, including NiO-based p-type DSCs in which the electron transfer takes place from the valence band of the
semiconductor to the photoexcited dye [91].
It is common in all methodologies proposed in the literature, the seeking after mesoporous layers with high surface
area and nanocrystallinity in order to guarantee good dye adsorption and efficient charge transport. However, the

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control of the recombination losses (dark current) at different interfaces of the photoelectrochemical cell is a critical
point that has to be addressed to production of high efficient devices. In DSC photoanodes, charge recombination can
occur mainly at TiO2/sensitizer, TiO2/electrolyte or TCO/TiO2 interfaces [111-112]. The Figure 2 illustrates the
competitive pathways at different DSC interfaces. The importance of each recombination pathway will depend on the
quality of the materials employed, the processing methodologies and also the operating conditions [98].

Figure 2. Operating principle of a DSC. The green arrows indicate the desired process and the red arrows, the possible
recombination pathways.

Under short circuit conditions, back electron transfer in the TCO/TiO2 interface is negligible as pointed out by
Cameron and Peter [113-115], since the Fermi level in the conductive substrate is close to the redox pair Fermi level. In
this condition, the short circuit photocurrent measured, Isc is given by the Equation 4, in which I0 is the incident photon
flux in Coulomb s-1, Φlh is the light harvesting efficiency, Φcs is the quantum yield for charge separation at TiO2/dye
interface and Φcol is the charge collection efficiency [116-117].

I sc = I0Φlh Φcs Φcol (4)

In equation 4, Φlh is intrinsically connected to the nature of the dye employed in the cell and its surface
concentration. Nevertheless, oxide scattering layers can be used as “light traps” to improve the photon absorption [118].
Φcol is related to the electron diffusion through the TiO2 nanoparticle network, which competes with electron transfer
from the oxide conduction band to the I3- ion or other redox species present in the electrolyte. Since the electron
transport in TiO2 is relatively slow, efficient charge collection requires diffusion lengths at least two times larger than
the film thickness. Detailed discussion about the electron collection efficiency in DSCs have been performed by Peter
[119-120] and more recently by O’Regan and Durrant [98].
Interfacial charge separation efficiency, Φcs, is dependent on the excited state properties of the sensitizer and its
overlap with TiO2 isoenergetic conduction band states. As pointed out by several studies reported in the literature,
efficient sensitizers adsorbed on TiO2 are capable of injecting electrons to conduction band within few ps. Electron
injection dynamics of Ru(II) polypyridyl sensitizers [121-122], Porphyrins [93, 123-124] and organic sensitizers [125-
126] on TiO2 has been fully characterized by time resolved techniques.
Improvements on the photocurrent have been achieved by surface treatment of TiO2 films with TiCl4 solutions,
followed by a sintering step [111, 116, 127]. As a result, an extra TiO2 layer on the order of 1 nm is formed in the
surface of the mesoscopic layer. This treatment have been largely used for production of more efficient devices, but the
causes of the beneficial effect of TiCl4 treatment is still not completely understood. O’Regan and co-workers have
investigated the effect of TiCl4 treatment on DSCs using morphological and transient photocurrent/photovoltage
measurements [116, 127]. It has been found that TiCl4 treatment has important effects on TiO2 surface electric field as
well as some influence in electron transport thorough the mesoporous layer.
Electrolyte composition also plays a role on electron injection efficiency since the presence of cations and organic
species capable of interacting with the oxide surface influences on both, kinetics and thermodynamics of the electron
injection process [117]. Meyer and co-workers have reported detailed kinetic/thermodynamic data on the influence of
cations on DSC dynamics [128-129]. It has been found that the presence of small cations, such as Li+ leads to a positive
shift in the TiO2 acceptor state potentials, similar to the Nernstian shift observed in aqueous medium as function of pH
[130-131]. Therefore, in DSCs with Li+ in the electrolyte, there is a greater driving force for electron injection, which
occurs faster than in neat acetonitrile. As a result, it is observed an increase in the photocurrent. On the other hand,
addition of high concentrations of cations on electrolyte leads to a decrease in photovoltage, since the maximum
potential that can be obtained in a DSC is given by the difference between the TiO2 flatband potential and the redox pair
midpotential. Thus, there is an optimum cation concentration in which both photocurrent and photovoltage are
maximized.

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Grätzel and co-workers have reported the use of relatively small organic molecules, such as tert-4-butylpyridine or
guanidinium, as co-adsorbents in DSCs [95]. These molecules are capable to adsorb on TiO2 surface and reduce the
dark current at TiO2/electrolyte interface, increasing the open circuit voltage (Voc). The presence of co-adsorbents in the
electrolyte results in a negative shift on TiO2 flatband potential and, more importantly, inhibits a close contact between
I3- ions and electrons in TiO2. Consequently, higher overall conversion efficiencies are achieved.
An alternatively strategy to control the dark current at TiO2/electrolyte interface comprises core shell structured
mesoscopic electrodes, in which the TiO2 cores are covered by a thin shell of a metal oxide with more negative
conduction band potential. In this way, the back electron transfer to the electrolyte or the sensitizer is avoided due to
creation of an energy barrier at TiO2/electrolyte interface. Core-shell structures with Al2O3, Nb2O5, ZrO2, SrTiO3 and
ZnO as shell materials have been reported [132].
Under open circuit conditions or on load, another recombination pathway has to be considered. It involves electron
transfer from the conductive substrate (TCO) to the I3- ions [113-114, 133]. At the TCO/TiO2 interface, charge
recombination occurs due to the physical contact between the electrolyte and the TCO surface. The mesoporous
structure of the TiO2 layer allows the percolation of the electrolyte and the electron transfer on the TCO surface
becomes feasible. A possible solution for decrease the dark current at TCO/electrolyte is the introduction of a compact
blocking oxide layer capable of physically prevent the reaction of I3- ions on the electrode surface. Ito and co-workers
have studied the effect of TiCl4 surface treatment of fluorine-doped thin oxide (FTO) conductive glass on DSCs [134].
It has been found a 12% enhancement in the overall conversion efficiency in relation to bare FTO-based DSCs. Hu and
coworkers have shown the influence of different TiO2 porosities on the DSC efficiency, including large modules under
outdoor conditions [135]. Different deposition techniques as well as others wide band gap semiconductors have been
employed to produce efficient blocking layers. Some results found in the literature are listed in the Table 2.
The efficiency of the blocking layers is related to the control of its thickness, homogeneity, reproducibility and low
porosity. The TiCl4 treatment does not allow a precise control of these parameters and more effective results have been
reported by using spray pyrolysis as deposition method [115, 136]. Xia et al. have reported improvements on DSC
performance due to deposition of TiOx [137] or Nb2O5 compact layers on FTO by frequency magnetron sputtering [138-
139]. Other authors have also used other deposition techniques such as pulsed laser deposition [140] and dip coating
[141-142] among others [143-146]. Patrocinio et al have reported efficient layer by layer TiO2 compact films as
blocking layers in DSCs [147]. Layer by layer (LbL) is a versatile and inexpensive technique that has been employed in
several molecular devices with different materials [148]. Production of thin films by LbL allows the control of
morphology and thickness at nanoscale level, along with the possibility to use a large variety of materials, such as
polyelectrolytes, inorganic nanostructures, proteins etc.
For blocking layer applications, LbL films were firstly obtained using positively charged TiO2 nanoparticles as
cations and sodium sulphonated polystyrene, PSS, as a polyanions [147], Figure 3a. It has been found that TiO2/PSS
films are formed by plates of nanoparticles aggregates, in which the negatively charged PSS chains act as “a glue”
holding the positively charge TiO2 particles. The reduced size of oxide nanoparticles are efficiently packed, leading to a
compact morphology. The maintenance of compact morphology after the sintering step depends on the thermal stability
of the polyanions employed [149]. It has been observed that DSCs with LbL films employing PSS or lignosulphonate
(LS) exhibit higher conversion efficiencies than DSCs with TiO2/poly(acrilic acid), PAA, films. This behavior can be
explained by the relatively low thermal stability of PAA at sintering temperature (450 ºC). For TiO2/PAA films, the
high polymer mass loss at 450 ºC leads to disruption of nanoparticle aggregates, resulting in a more porous surface. As
a result, the efficiency of the TiO2/PAA blocking layer decreases.
The organic polyanions in LbL films can be conveniently replaced by inorganic nanoparticles, Figure 3b. A first
example of all inorganic LbL blocking layer was described using TiO2 nanoparticles prepared under alkaline conditions
as anionic species [150]. Some advantages of inorganic materials include the high thermal stability and the reduction of
the deposition times, since thicker films can be obtained with fewer bilayers.

(a) (b)

Figure 3. (a) TiO2 layer- by layer film using positively charged nanoparticles and a polyanions and (b) an all inorganic film
employing negatively and positively charged TiO2 nanoparticles.

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Quantitative analysis of the influence of such a blocking layers in electron recombination reaction at FTO/electrolyte
interface have been performed by open-circuit voltage decay measurements (OCVD), in which photovoltage decay
reflects the decrease of electron concentration at FTO due to recombination losses [112, 115, 142]. As faster is the Voc
decay, higher is the recombination losses. The extent of recombination losses can be quantified by the electron lifetime
(τn) obtained by the equation 5 [151], where kB is the Boltzmann constant, e is the positive elementary charge and T is
the absolute temperature.

(5)

Table 2. Some examples of metal oxide blocking layers applied in DSCs and their respective photoelectrochemical parameters
Blocking layer Deposition Method Voc / V Jsc / ff η/% Relative Ref.
mA cm-2 Increase %*

TiO2 Immersion in TiCl4 0.81 17.6 0.74 10.5 12 [134]

solution
TiO2 Sputtering 0.71 8.4 0.73 4.4 26 [137]
TiO2 Sputtering 0.73 13.9 0.63 6.4 47 [146]
TiO2 Layer-by-Layer 0.73 12.6 0.62 7.3 28 [147]
#
TiO2 Spray Pirolysis 0.81 6.5 0.71 3.8 9 [152]
TiO2 Dip-Coating 0.73 15.4 0.64 7.1 7 [153]
TiO2 Dip Coating 0.69 13.7 0.60 5.6 33.3 [154]
TiO2 Radio Frequency 0.73 12.3 0.65 5.8 20 [155]
TiO2 Pulsed Laser Deposition 0.70 15.1 0.68 7.1 9 [140]
TiO2 Dip Coating 0.70 13.9 0.67 7.6 33 [142]
TiO2 Eletrochemical 0.73 15.8 8.0 9.9 [104]
TiO2 Spin Coating 0.72 1.8 0.68 7.2 31 [156]
ZnO Sputtering 0.77 14.8 0.68 7.8 26 [157]
ZnO Atomic Layer Deposition 0.82 16.3 0.53 7.1 11 [158]
ZnO Spin Coating 0.77 16.6 0.66 8.9 9.6 [159]
ZnO Spin Coating 0.69 15.0 0.65 6.7 15.5 [160]
Nb-doped TiO2 Pulsed Laser Deposition 0.71 16.3 0.66 7.7 18 [140]
Nb2O5 Spray Pyrolysis 0.63 8.1 0.66 3.3 20 [139]
Nb2O5 Sputtering 0.71 9.3 0.68 4.5 28 [161]
* Relative increase calculated from DSCs prepared with bare FTOs under same experimental conditions.
# Solid-electrolyte DSC

Another beneficial effect of metal oxide blocking layers in DSCs is the increase in the photocurrent due to decrease
of the ohmic contact between the mesoporous layer and the FTO substrate. Direct evidence for this effect has been
observed by electrochemical impedance spectroscopy (EIS) [149, 162-163]. Goes and co-workers have shown the linear
dependence of photocurrent on blocking layer thickness, which is related to internal series resistance of the cell [155].
Therefore, it is clear that the selection of the metal oxide, the synthetic method and the thin film deposition technique
in order to control the morphology and the electronic properties are fundamental to the production of high efficiency
DSCs. The research activity in this field is very intense aiming large scale applications and also the development of
other photoelectrochemical devices, such as those for artificial photosynthesis.

5. Final Remarks
In this brief overview we tried to provide the main aspects regard to application of metal oxide semiconductors in solar
energy conversion to fuels (hydrogen evolution) and electricity (dye-sensitized solar cells). There still are several

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challenges to be superposed in the field that involve both fundamental and practical aspects. Nevertheless, this
interesting class of materials can provide effective solutions for the energy issues in the near future.

Acknowledgements The financial support by Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG), Conselho
Nacional de Desenvolvimento Científico e Tecnológico (CNPq), Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
(CAPES) and Rede Mineira de Química (RQ-MG) is gratefully acknowledged.

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