Current Opinion in Colloid & Interface Science 17 (2012) 124–131

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Current Opinion in Colloid & Interface Science

journal homepage: www.elsevier.com/locate/cocis

Electron transport in nanostructured metal-oxide semiconductors

Juan A. Anta
Área de Química Física, Universidad Pablo de Olavide, Sevilla, Spain

a r t i c l e i n f o a b s t r a c t

Article history: Nanostructured films of metal-oxide semiconductors are the focus of intensive research nowadays due to
Received 21 February 2012 their applications in the current quest for new sources of clean energy. Metal-oxides like TiO2 and ZnO can
Accepted 22 February 2012 be used to make efficient photoanodes for photoelectrochemical solar cells and nanostructured substrates
Available online 3 March 2012
for photocatalytic production of non-polluting fuels. In these applications electron transport through the
nanostructure is crucial to achieve a good photon-to-electron quantum efficiency. In this paper the current
Keywords:
Nanostructured semiconductors
knowledge of the electron transport mechanisms that take place in these systems is reviewed, highlighting
Charge transport the influence of energy and morphological disorder on the efficacy of the transport process. A special connec-
Solar cells tion is made between the specificity of the electron transport in these systems and their applications in solar
Photocatalysis cells and photocatalytic devices.
Random walk numerical simulation © 2012 Elsevier Ltd. All rights reserved.

1. Introduction contact. In nanostructured photocatalysts, electrons (holes) should be

New concepts in photovoltaics, photocatalysis and energy storage,
attracting extraordinary interest from researchers and technologists
nowadays, are based on the unique properties of nanostructured ma-
terials [1,2 •,3]. The decisive advantage of a nanostructured morpholo-
gy is that it provides a high surface to volume ratio while maintaining
some of the basic properties of the bulk material and adding new ex-
citing ones. For example, due to quantum confinement, they present
specific features like peculiar optical and electronic properties [4].
Morphology in the nanoscale is a key issue in next generation solar
cells such as dye-sensitized solar cells [5–7 •], hybrid solar cells [8]
and extremely-thin-absorber solar cells [9,10], where the high surface
area ensures a large concentration of the light absorber material (i.e.,
the dye or the inorganic sensitizer) leading to good light harvesting
and an intimate contact with the electron and hole transporter material.
In nanostructured photocatalytic films the high surface area provides
many active sites for the heterogeneous reactions that take place on
the surface of the semiconductor so that a decent final product yield
can be achieved. Advances in these topics are crucial in modern science
and technology due to environmental and economic reasons, including
the development of solar cells [3], and the production of hydrogen [11]
and hydrocarbon fuels by carbon-neutral processes [12 •] (artificial
photosynthesis).
The good performance of photoelectrochemical and optoelectronic
devices based on nanostructured semiconductors rely on efficient charge
separation. For instance, in a good performing solar cell the generation of
excitons in the semiconductor or in the semiconductor/sensitizer inter-
face is correlated to an efficient collection of charges in the external
E-mail address: anta@upo.es.
transferred rapidly to external oxidants (reductants) to guarantee that
the photochemical process takes place efficiently. In a battery or a super-
capacitor, a large accumulation of charge should be achieved with re-
spect to small variations of applied voltage for efficient energy storage.
In all these applications the Holy Grail is to overcome the limitation
posed by the Second Law of Thermodynamics, i.e. the natural energy
dissipation that follows an excitation (either absorption of photons or
the application of an external voltage). This dissipation occurs by thermal
losses of the charge carriers (by transferring energy to the crystalline
lattice) but also by recombination of electrons and holes. In both cases,
transport plays a decisive role because only the charge carriers than
can be extracted from the active material would lead to the production
of useful electrical work. In this regard, the quest of modern nanotech-
nologists is very similar to that of the engineers of the 19th century,
who looked for the perpetuum mobile of the second kind fighting entropy,
pursuing the maximum free energy production.
Electron transport in nanostructured semiconductors shows key
differences with respect to their bulk counterparts. These differences
are narrowly linked to the presence of disorder in the material. The
main consequence of disorder in the electronic structure of the material
is the appearance of localized states. This is well-known since the classic
works of Anderson [13] and Mott [14]. The existence of localized states
implies the existence of anomalous electron transport properties, as dem-
onstrated in the seminal work of Scher and Montroll [15]. Although all
these pioneering investigations focused on amorphous, non-crystalline
semiconductors, the fact is that very similar features are characteristic
of nanocrystalline materials as well. The breaking of the crystalline sym-
metry brings forward the appearance of defects in the lattice, either at
grain boundaries or at interfaces, where dangling bonds and interactions
with chemical species present in an embedding electrolyte or another
semiconductor are produced. Defects in a lattice imply localized states

1359-0294/$ – see front matter © 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.cocis.2012.02.003
 J.A. Anta / Current Opinion in Colloid & Interface Science 17 (2012) 124–131
for electrons and holes. The classical picture of band theory with a con-
duction band and a valence band should then be reformulated in a disor-
dered semiconductor. Localized states can act as “traps” for electrons and
holes that influence transport, and/or recombination centers that reduce
the efficient collection of charges. Defect states can also act as dopants,
with either a donor or an acceptor character, and convert an intrinsic
semiconductor in an n-type or a p-type semiconductor. We refer the
reader to several excellent books [16,17] for a general view of all these
topics.
In this article the current state of the art as regards electron trans-
port in metal-oxide nanostructured semiconductors is reviewed, but
with especial attention to technological applications such as solar and
photoelectrochemical cells. It must be stressed out that the suggestive
applications of metal-oxide semiconductors in dye-sensitized solar
cells and related devices [2•,5] have fueled an extraordinary research
effort to study electron transport mechanisms in materials such a
nanostructured TiO2 in contact with an redox-active electrolyte. This
is a typical example where technological applications have motivated
intense theoretical research. In this respect, the proper understanding
of the electronic processes goes normally behind the most spectacular
empirical advances. For this reason many points are still obscure and
subject to different, sometimes contradictory interpretations. In any
case, and due to their technological applications, electron transport in
nanostructured metal-oxide semiconductors is nowadays much more
studied than in other disordered semiconductors. Furthermore, the
vast majority of the electron transport studies are carried out in practi-
cal, functioning devices, dye-sensitized solar cells in most of the cases,
due to the extraordinary interest that this topic is drawing in the recent
literature (in this respect it is recommended to read Ref. [18 ••] for a crit-
ical discussion of the course that research on dye-sensitized solar cells is
taking nowadays). Despite of that, many of these specific studies pro-
vide in fact interesting insights to the mechanisms of electron transport
in nanostructured metal-oxides in particular and in disordered inorganic
semiconductors in general.
Here the focus will be on transport in the long time scale and at
long distances, where the morphological and energy disorder of the
material plays a fundamental role. Hence, we will not address quantum
(atomistic) effects such as Coulomb blockades or resonant tunneling
[19,20]. We would not, either, review reports that discuss transport of
free (conduction band) electrons, in the short-time scale, probed by
techniques such as time-resolved terahertz spectroscopy [21,22••].
This is an important clarification, because materials that have attracted
much attention recently (like nanostructured ZnO) [1] are believed to
be very adequate for applications where a fast transport is required.
However, this belief is based on the fact that bulk electron transport mo-
bilities in the bare material are very large in comparison with another
metal-oxide semiconductors. The reality is that electron diffusion coeffi-
cients in nanostructured morphologies show a similar behavior and have
similar values, regardless of the actual material of which the device is
made. In this review it will be shown that this is a consequence of the
disorder that is characteristic of nanostructured materials. In summary,
charge transport will be discussed in the colloidal domain, where many
of the afore-mentioned technological applications are developed. The
influence on electron transport of morphological properties such as
porosity and grain size will also be analyzed, as well as the effect of an
applied electrochemical potential. The adequate understanding of these
effects helps to make progress to improve charge collection in practical
devices.
2. The mechanism of electron transport in metal-oxide
nanostructured materials
2.1. A general mechanism of electron transport
As mentioned in the introduction, the electronic structure of
nanostructured materials is characterized by the presence of localized
125
states. Henceforth, we will call these localized states “traps”, since
they effectively act as potential wells for electrons and holes in the
material. The location and energetics of these traps will determine
the electron transport in the material. For simplicity we will refer in
the following to electron transport as this is the most discussed case.
However, it must be born in mind that transport of holes obeys in
fact the same rules. The use of p-type nanostructured metal-oxides
has become increasingly important in recent times [23,24].
Two main empirical observations are characteristic of the electron
transport in metal-oxide nanostructured semiconductors: first, mea-
sured diffusion coefficients lie several orders of magnitude below bulk
(single crystal) values; second, diffusion coefficients and electron mo-
bilities are density-dependent, with larger values found when the elec-
tron concentration is increased, either by illumination or by application
of an external voltage. Both are well-known facts that are still reported
routinely in the recent literature [22••,25•,26••,27•]. For instance Tiwana
and coworkers [22••] carried out a comprehensive study of the electron
transport properties of three nanostructured metal oxides (TiO2, ZnO
and SnO2) in dye-sensitized solar cells. They found very similar values
for the electron diffusion coefficient in the long time and the long length
scale (what they called the “device” diffusion coefficient, not to be con-
fused with the “terahertz” mobility, which is essentially a conduction
band transport). Values of 1.110− 4 cm2/s, 4.3 10− 4 cm2/s and
7.3 10 − 5 cm2/s were reported for TiO2, ZnO and SnO2, respectively,
which are between 2 and 5 orders of magnitude below the bulk values.
Also recently, Guillén et al. [28•] studied electron transport by Intensity
Modulated Photocurrent Spectroscopy in nanostructured ZnO dye sensi-
tized solar cells. In this paper increasing values of the electron diffusion
coefficients with respect to illumination are reported, with values in
the range 10− 6–10− 4 cm2/s. Hsiao et al. [27•] used the same technique
to identify two transport times in nanocrystalline TiO2 films with nega-
tive dependence with respect to illumination intensity.
The microscopic mechanism behind these experimental observa-
tions is still subject to debate, especially as regards its implications in
nanostructured solar cells and photocatalytic devices [7•,27 •,29•,30••].
However, the fact that diffusion is much slower than in single crystals
is a clear evidence that electron traps limit the mobility of free carriers
in nanostructured materials. The dependence of the electron diffusion
coefficient on electrochemical bias suggests that the transport process
follows special rules, in which electron–electron interactions play an
important role.
Electron transport in disordered semiconductors occurs by thermal
activation and/or electron tunneling. Thermal activation implies the ex-
citation of an electron to a conduction band (more strictly speaking
when studying a disordered semiconductor: a mobility edge) or to
another trap of a higher energy. Tunneling arises from direct transfer
mediated by the electronic overlap of the wave functions of both
traps. The most simple model that incorporates these two mechanisms
is the popular Miller-Abrahams hopping formula [31]
" #
rij Ej −Ei
ν ij ¼ ν 0 exp −2 − if Ej > Ei
α 2kB T
" hopp # ð1Þ
rij
ν ij ¼ ν0 exp −2 if Ej b Ei
α hopp
where νij is the average hopping rate, ν0 is the attempt-to-jump frequen-
cy, rij is the distance between the traps, αhopp is the localization radius
for hopping, kB is the Boltzmann constant, T is the absolute temperature,
and Ei and Ej are the energies of the target and the starting traps, respec-
tively. The Miller-Abrahams formula contains in a single expression two
important physical features: (1) hops to nearer traps are more likely
(with a probability that decreases exponentially with distance) and
(2) hops uphill in energy depend on the energy difference according
to a thermal Boltzmann factor. An additional term should be included
in Eq. (1) if there is a local electric-field present in the system, because
126 J.A. Anta / Current Opinion in Colloid & Interface Science 17 (2012) 124–131
this would make the trap to vary its energy along the field direction.
However, nanostructured metal-oxide semiconductors are normally
highly doped. In addition, in practical devices they are used as elec-
trodes immersed in high ionic strength electrolytes. These features
imply that band bending is normally negligible (at least for nanoparticles
of tenths of nanometers in size) so that electric fields do no contribute
significantly to the electron transport process. Why electrical fields can
be ignored in nanostructured solar cells has elegantly been discussed
recently [32••].
Eq. (1) shows that disorder enters the transport mechanism in
two ways: via the spatial location of the traps and via the energy of
those traps. In fact, both factors are related as the energy of the localized
states depends on their surroundings so that a spatial disorder would
also induce a dispersion of trap energies. Fig. 1 illustrates how energy
and spatial disorder influence the transport of electrons in a nanostruc-
tured film. Electron transport takes place by a combination of percola-
tion through a network of sites and thermal accessibility to energy
states. Hence, morphological parameters such as porosity, surface area
and grain size will have an impact on the electron diffusion coefficient,
but also the energetic properties, like the distribution of trap energies or
the position of the electron quasi-Fermi level (i.e. the electron concen-
tration) will play a role. In fact both kinds of disorder act in a correlated
way.
2.2. Numerical simulation of electron transport and the trap-filling effect
To tackle the problem of the energy and morphological disorder
from the theoretical point of view, specific numerical tools are
required. Random Walk Numerical Simulation (RWNS) is in fact a
very useful technique to study charge transport in nanostructured
materials and devices [33 •]. RWNS is a Monte Carlo method that
evaluate hopping times between neighboring traps with randomly
distributed values of energy and location. The reason why RWNS is
an interesting technique is that it can incorporate explicitly a specific
mechanism of charge transport coupled with a particular morphology
and energy distribution, so that diffusion coefficients and mobilities
can be extracted from, say, “first-principles”. However, the fact that
it is a simulation method with a time adaptive step makes it possible
to study transport and associated processes like, for instance, recom-
bination, in the long time and spatial scale, non-accessible to quan-
tum ab initio methods.
The Miller-Abrahams model, although originally devised for
amorphous semiconductors, and well accepted to study organic semi-
conductors nowadays [34,35], describes actually quite well electron
Fig. 1. Illustration of the electron transport mechanism in nanostructured semiconductors.
transport properties in semiconductor metal-oxide nanostructured
electrodes. This has been demonstrated recently by implementing
Miller-Abrahams hopping rates in a RWNS calculation, and taking
into account explicitly a finite concentration of electrons [36 ••]. In
Fig. 2 experimental data for the electron diffusion coefficient in TiO2
nanostructures sensitized with CdSe/CdS quantum dots is presented
[26 ••]. As mentioned above, the diffusion coefficient increases expo-
nentially with applied voltage. This effect can be reproduced (Fig. 2)
by RWNS calculations in a random network of traps, with energies
distributed according to an exponential distribution, and a finite con-
centration of electrons. This is implemented in the numerical simula-
tion by assuming that each trap cannot be occupied by more than one
electron. The enhancement of the diffusion rate is a consequence of
the progressive filling of the available traps in the system and provides
a nice explanation of why the electron diffusion coefficient in nano-
structured metal-oxides is observed to increase when the material is
electrochemically biased (either by applying an external voltage or by
optical excitation).
The increase of the diffusion coefficient with the electron concen-
tration is a manifestation of the so-called trap-filling effect: as more
electrons are added to the system, traps of lower energy become filled
and force mobile electrons to hop between shallow traps. As transport
is thermally activated, electrons move on the hole more rapidly when
the Fermi level is raised and deep traps are occupied. Although
described in previous literature [37], this effect is thoroughly used
to explain recent experiments where electron dynamics is affected by
the degree of illumination or the concentration of dopants [38–40].
The slow diffusion in nanocrystalline materials (as compared with the
single crystal) and the trap-filling effect has traditionally been
explained by the multiple-trapping (MT) model [41]. In this model,
transport is assumed to occur via extended states combined with a suc-
cession of trapping and detrapping events in localized states. The MT
model predicts that an increase in electron concentration accelerates
diffusion since the resulting quasi-Fermi level will be closer in energy
to the transport state causing in this way an increase of the detrapping
rate. If the distribution of trap energies is exponential the Fermi level
dependence of the diffusion coefficient and the conductivity is also
exponential.
Although the MT and the Miller-Abrahams hopping models are
treated as alternative transport models (with a preference for the former
due to its simplicity: there is no spatial dependence), the fact is that
the MT model can be considered a special case of hopping when an
exponential distribution of trap energies can be assumed for the
semiconductor. Exponential distributions are in fact ubiquitous in
 J.A. Anta / Current Opinion in Colloid & Interface Science 17 (2012) 124–131
Fig. 2. Left: Electron diffusion coefficient obtained by Electrochemical Impedance Spectroscopy in nanostructured TiO2 solar cells sensitized with CdS/CdSe Quantum Dots. Adapted
by permission from Ref. [26••] Copyright 2010 American Chemical Society. Right: Electron diffusion coefficient as obtained from RWNS calculations with Miller-Abrahams hopping
rates at varying electron concentrations in an exponential distribution of trap energies. Adapted by permission from Ref. [36••] Royal Society of Chemistry.
disordered semiconductors [42 •,43,44,45 ••,46]. The exponential trap
distribution g(E) can be expressed as
 
αN t α ðEc −EÞ
g ðEÞ ¼ exp −
kB T kB T
where Ec is the energy of the transport level (conduction band), Nt is
the total trap density and α is a parameter that reflects the average
energy of the distribution of trap states below the conduction band.
Commonly the trap parameter is related to temperature via α = T/T0
where T0 is the characteristic temperature of the distribution.
Probably, the most clear evidence of the existence of an exponen-
tial distribution is the measurement of the accumulated charge or the
capacitance of a nanocrystalline film as a function of applied voltage.
Both are commonly found to vary exponentially with Fermi level
[42 •,45 ••,28 •]. However, the origin of the exponential functionality is
still not clear [7 •,47]. It is known that the distribution as a whole
can be displaced to lower or higher energies depending on the sur-
roundings, like the embedding electrolyte [48 •]. But the exponential
dependence and even the value of the characteristic temperature is
found to be in all cases in the 900–1500 K range [42 •], even for mate-
rials of different compositions [46,28 •]. However, differences can be
observed when one compares different morphologies. For instance
Mohammadpour et al. [45 ••] extracted the accumulated charge density
for nanoparticulate and nanotubular TiO2 films and found a quite dis-
tinct concentration of traps and voltage dependence for both kinds of
substrates. Martinson et al. [49 ••] observed much larger characteristic
temperatures (as compared to nanoparticles) for ZnO nanotubes.
As indicated above, the fact that the distribution of trap energies is
exponential implies that the MT and the Miller-Abrahams hopping
model lead to equivalent results. Eq. (2) with high characteristic tem-
peratures (normally values of around T0 ~ 1000 K are reported) means
that deep traps are most likely surrounded by shallow traps. Hence,
the most likely hop for a trapped electron is by thermal activation
to a trap of larger energy. As the probability of hopping arises from
a combination of spatial and energy factors, it is found that there
exists an optimum value of the energy of the target trap through
which most of the hops take place. This is the transport energy concept
widely discussed in the classic literature of amorphous semiconduc-
tors [16]. González-Vazquez and coworkers [36 ••] studied the validity
of this approximation in disordered semiconductors with exponential
distribution of trap energies by RWNS calculations with Miller Abrahams
hopping rates. These authors observed that most of the hops occurred in
a well defined energy interval, especially when “round trip” hops,
127
which do not contribute to actual transport, are removed (see Fig. 3).
This optimum energy is the transport energy and can be considered as
the transport level of the MT model. Furthermore, the transport energy
is found to be density dependent, with larger values found when the
ð2Þ
Fermi level is raised. This displacement does not alter the fact that the
diffusion coefficient increases exponentially with Fermi level (Fig. 2),
as observed in the experiments. Hence MT and hopping are in fact indis-
tinguishable from each other in view of the main trends observed in
experiments.
2.3. The influence of morphological disorder on electron transport
Although less studied from the theoretical point of view, morpho-
logical features have a clear impact on the effectiveness of electron
transport. This is attracting considerable attention in the recent liter-
ature, especially in connection with the use of aligned nanostructures,
also called one-dimensional (1D), like nanotubes and nanowires
[50 •]. In general faster transport is found for 1D nanostructures
[45 ••,49 ••,51 •] although the real advantage is in fact an increase of
the electron lifetime [52 •,53], as discussed in the next section. The ad-
vantage of using 1D nanostructures relies on providing a more direct
pact towards the collecting substrate. In reality, it is not necessary to
have perfectly crystalline and vertically aligned nanostructures to ob-
tain better transport properties (regardless how nice they like in a
SEM image). The strategy of perfect ordering introduces indeed addi-
tional complications like a reduction of the surface area (required for
better light harvesting or catalytic activity) or the practical difficulty
of preparing and handling these nanostructures. On the contrary, a
preferential direction towards the collecting substrate or a better con-
nectivity between the nanoparticles constituting the conducting film
may be enough. For instance, very recently Liou and coworkers [54 ••]
reported a reduction of ~50% in the electron transit time when a prefer-
ential direction is induced in the system via an electrophoretic deposi-
tion method (see Fig. 4). Phadke et al. [55 ••] also found an increase of
the electron diffusion coefficient in TiO2 nanostructured films from
3.6 10 − 4 to 4.4 10− 4 cm2/s when a template method is used to improve
the interconnection between the TiO2 nanoparticles.
These recent results show clearly that the connectivity of the nano-
particles constituting a nanostructured electrode is a critical factor for
good electron transport. In this connection, probably the parameter
that allows for a better experimental control is the porosity of the nano-
structure. Bearing this in mind Ansari-Rad et al. [56 ••] managed to
separate the trap-filling effect and the morphological influence of the
porosity by performing RWNS at constant Fermi level. These authors
128 J.A. Anta / Current Opinion in Colloid & Interface Science 17 (2012) 124–131

Fig. 3. Left: Illustration of the transport energy concept. Right: Total and “corrected” (without “round trip” hops) histograms of hopping energies as obtained from RWNS simulations.
Adapted by permission from Ref. [36••] Royal Society of Chemistry.

reproduced with this methodology (see Fig. 4) the well-known reduc- recombination event. For the case of linear recombination kinetics [30••]
tion of the diffusion coefficient with increasing porosity, say this is shown to be equal to

δ 1=2
D∝jðP−P c Þj ð3Þ Ln ¼ ðDn τ rec Þ ð4Þ

where δ is the conductivity exponent and Pc is the percolation threshold,
for which, ideally, transport to the long length scale is not possible. It is
found that the conductivity exponent predicted by percolation theory
(i.e. δ=1.5) is only partially reproduced by the simulations when the
electron diffusion is assumed to occur via electron traps located in the
bulk of the nanoparticles (volume diffusion), rather than in their surface
(surface diffusion). On the other hand, the percolation threshold is found
to be close to a 78% in both cases.
3. A key parameter: the electron diffusion length
3.1. Definition of diffusion length and the compensation effect
In applications where good collection of charges is required, elec-
tron transport cannot be unlinked from loss processes like charge
transfer with external electron acceptors (recombination). The elec-
tron collection efficiency has typically been discussed in the current
literature in terms of the diffusion length, which represents the average
distance that an electron can travel in the material before undergoing a
where Dn is the electron diffusion coefficient and τrec is the recombina-
tion time constant, also known as lifetime. As discussed in detail by
Bisquert and Mora-Seró [30••] if the recombination kinetics is not linear
on free electron density, Eq. (4) is then used to define a “small perturba-
tion” diffusion length, which is still useful to diagnose the collection
efficiency in an electron collecting device.
We have discussed in Section 2 the acceleration of diffusion upon
increase of electron concentration. This behavior of the transport
properties would naively lead to the conclusion that electron collec-
tion is more efficient at conditions of high electrochemical bias. For
instance, a solar cell or a photocatalytic device based on a nanostruc-
tured semiconductor would show a better performance at conditions
of high illumination because transport of electrons is faster. However,
the fact is that the lifetime is also a density-dependent magnitude, that
becomes progressively shorter as the Fermi level is raised. Hence, an in-
crease of the electron concentration will accelerate transport but also
recombination. As the density dependence is in fact very similar, the
opposite behavior of both magnitudes leads to a diffusion length that
remains approximately constant upon Fermi level variation.

Fig. 4. Left: Electron transport time in nanostructured TiO2 films as obtained from Intensity Modulated Photocurrent Spectroscopy Experiments. Results for a film obtained by a
standard method (PC) and by electrophoretic deposition (EPD) that improves connectivity are shown. Adapted by permission from Ref. [54••] Copyright 2011 American Chemical
Society Right: electron diffusion coefficient as obtained from RWNS simulations at constant Fermi level and different porosities. Results for diffusion via bulk (“volume”) and “surface”
states are shown. The solid lines stand for fittings to Eq. (3). Adapted by permission from Ref. [56••] Copyright 2011 American Chemical Society.
 J.A. Anta / Current Opinion in Colloid & Interface Science 17 (2012) 124–131 129

In Fig. 5 recent experimental data for the electron diffusion length
in TiO2-based dye-sensitized solar cells is presented. The correct de-
termination of the electron diffusion length in this kind of systems
has been controversial in recent times [29•,30 ••,57 ••]. However a careful
control of the experimental conditions provides reliable results (specifi-
cally, one has to make sure that the perturbation of the electrochemical
bias in the experiment is small so that the assumptions under which
Eq. (4) is valid are hold in the measurement). These data are in fact
very useful to assess the real electron collection efficiency of practical de-
vices. The electron diffusion length is found to be constant or increases
slowly with applied voltage or illumination, depending on the composi-
tion of the embedding electrolyte used in the measurement. As indicated
above, this is a consequence of the compensation effect between faster
transport and faster recombination.
There are two interpretations of this compensation effect in the
literature. In the dynamic interpretation the reduction of the electron
lifetime with Fermi level is a consequence of faster transport. As elec-
trons move more rapidly it is more likely that they reach recombination
centers, thus accelerating the recombination kinetics [58]. In this inter-
pretation, the recombination process is viewed as a chemical reaction
whose rate is limited by the diffusion of the reactants. Alternatively,
the static interpretation is closely related to the scenario described by
the MT model [42•]. In this interpretation it is assumed that trapped
and free electrons maintain a common equilibrium, defined by the
same Fermi level. If only electrons that are free can move and recom-
bine, a raise of the Fermi level accelerates simultaneously and by the
same amount the diffusion rate and the recombination rate, hence
keeping constant the diffusion length. Gonzalez-Vazquez et al. [59••] an-
alyzed these two views by performing RWNS calculations that included
a constant probability of recombination for moving electrons. The nu-
merical simulation makes is possible to extract the electron lifetime
and the electron diffusion length by monitoring the survival times of
the electrons before recombination and the distance traveled between
recombination events. The obtained results showed that diffusion coef-
ficient and lifetime follow indeed equal but opposite dependences with
Fermi level, and that the diffusion length remains constant (Fig. 5).
Careful analysis of the experimental data shows that, in many cases,
the diffusion length is not strictly constant but it tends to increase with
Fermi level, as observed, for instance in Fig. 5. The reason for this behavior
has been attributed to non-linear features in the recombination kinetics
[30••]. However, the molecular origin of these non-linear features remains
unclear. A likely explanation is that surface states may play an important
role in the recombination mechanism. On the other hand, the voltage
dependence is found to change when the embedding electrolyte changes
its composition (see Fig. 5), suggesting that the relative energy positions
of the semiconductor traps and the electron acceptors in the electrolyte
determine the probability of charge transfer to electron acceptors.
3.2. Morphology and collection efficiency
Not only energetics is a determining factor in the behavior of the
diffusion length, but also the morphology of the semiconductor material.
As mentioned above, 1-D nanostructures have been proposed as a
powerful alternative to improve the charge collection efficiency of pho-
tovoltaic and photocatalytic devices [50•]. However, the fact is that re-
cord efficiencies has never been obtained with ordered nanostructures.
On the contrary, disordered nanostructured films are always the choice
in best performing devices. It has to be stressed that there is a consider-
able confusion in the recent literature in this respect, because it is clum-
sily assumed that just by using nanotubes or nanowires one would
enhance the efficiency. This conclusion is popularly supported by com-
paring transport and efficiency data with reference samples which are
not optimized. The observed improvement is then just taken as a gener-
al result, when in fact it should be taken with reserve.
In a recent paper, the issue of the real benefit of using 1-D nanostruc-
tures has been addressed from the theoretical point of view [60••]. To do
so, RWNS calculations are carried out on a packing of nanospheres
where a “columnar” ordering is imposed (see Fig. 6). A Lambert–Beer
electron generation profile is also implemented, to reproduce the typi-
cal light absorption that takes place in a nanostructured photoelectrode,
as well as a constant probability of recombination, which determines a
value of the electron diffusion length. The collection efficiency of
carriers in an external surface (defined as the number of collected elec-
trons divided by the total number or generated electrons) is then com-
puted, and compared with the efficiency of the “isotropic” sample.
As expected, an improvement in the collection efficiency is detected
when columnar order is present in the sample, but only if the recombi-
nation rate is neither too low nor too high. Specifically, it is found that
only if the electron diffusion length is of the same order of magnitude
as the light absorption length, carrier collection is improved. On the
contrary, a fast recombining system or a slow recombination rate
would never need an ordering of the nanostructure to improve the effi-
ciency. This latter situation is the most important one: normally best
performing devices have already good electron collection (long

Fig. 5. Left: Electron diffusion length (Ln) versus photovoltage in dye-sensitized nanostructured TiO2 films as obtained from Impedance Spectroscopy (squares) and analysis of
quantum efficiency data (circles). Red and orange symbols correspond to samples with a small and a large concentration of lithium ions in the electrolyte, respectively. Adapted
by permission from Ref. [57••] Copyright 2010 American Chemical Society. Right: Diffusion coefficient, lifetime and diffusion length for moving electrons in RWNS simulations in
a random network of traps as a function of Fermi level position. Adapted by permission from Ref. [59••] Copyright 2010 American Chemical Society.
130 J.A. Anta / Current Opinion in Colloid & Interface Science 17 (2012) 124–131
Fig. 6. Left: Packing of nanospheres with (right image) and without (left image) a columnar order induced in the system by the application of a sinusoidal potential (shown in red).
Right: Improvement ratio in the electron collection efficiency between the “columnar” and the “isotropic” sample as obtained from RWNS calculations for different values of the
recombination probability (reflected in varying values of the electron diffusion length Ln) and a light absortion length of 3.3 μm. Adapted by permission from Ref. [60••] Copyright
2012 American Chemical Society.
diffusion lengths). Therefore, there is no benefit in working with or-
dered systems in those cases. This obvious fact (although normally ig-
nored) explains why record efficiencies have never been reported
with structures like nanowires and nanotubes in spite of the evident im-
provement in electron transport.
However, in view of this conclusion, it can be argued that in systems
with a relatively fast recombination, working with ordered nanostruc-
tures would still be beneficial. However, the recent advances demon-
strate that the most significant improvements in performance are
always obtained by optimizing the light absorption and/or the recom-
bination rate [61•,62], instead of using ordered nanostructures. This
reality is further accentuated by the fact that fabrication of ordered
nanostructures is commonly tricky, and that the surface area (needed
for efficient dye absorption or catalytic conversion) is generally
lower. An intermediate strategy consist in introducing just a partial
ordering in the system, as predicted by the simulations of Ref. [60••].
In this regard, the works of Liou et al. [54••] and Phadke et al. [55••],
where a shorter collection time was obtained by improving the mor-
phological characteristics of the film, confirm this prediction. In the
field of the photocatalytic applications, Lana-Villareal and coworkers
[63•] achieved a significant improvement of the photoelectrochemical
efficiency by introducing nanowire-like particles in the photoelectrode.
4. Conclusions and outlook
The exceptional research efforts devoted recently to study light
harvesting devices based on nanostructured metal-oxide films have
led to a better understanding of the mechanisms of electron transport
in disordered semiconductors. Transport of charge is limited by
trapping-detrapping processes in which both energy and morpholog-
ical disorder play a role. Furthermore, in these devices, the electron
transport is strongly coupled with charge transfer to external electron
acceptors (recombination). This coupling determines the collection
efficiency of the device, which is the parameter to optimize for efficient
production of energy, either electrical (in a solar cell) or chemical (in a
photocatalytic device). The theoretical study of electron transport and
electron collection in nanostructured materials requires specific numer-
ical tools like Random Walk Numerical Simulation. With the use of these
techniques, recent reports have helped to understand the ambivalent
effect of the trapping effects in the electron transport (by accelerating
transport and recombination, by a similar but not equal amount), and
the role of parameters such as porosity and morphological order in the
transport efficacy of nanostructured metal-oxide films. As regards the
latter, the relative benefit of nanostructures such as nanowires and nano-
tubes has been critically discussed.
Although the basic mechanisms behind electron transport in
nanostructured metal-oxide materials are relatively well understood
nowadays, there are still several issues that need further investigation.
Hence, one can pose the following questions: (1) What is the nature
of the traps and what is the origin of the exponential distribution of
trap energies that all experiments so clearly reveal? (2) What is the
origin of the non-linearity observed in the recombination kinetics and
what is the role, if any, that electron transport plays in it? (3) Are there
any other factors affecting transport apart from trapping/detrapping
and percolation? The answers to these and other questions will provide
a double benefit. On the one hand we will get a better insight to charge
transport in disordered media. On the other hand, the quest for better
efficiencies in solar cells and related devices will be supported by a
fundamental understanding of the electron transport processes that
determine their functioning.
Acknowledgments
We thank the Ministerio de Ciencia e Innovación of Spain for fund-
ing under project HOPE CSD2007-00007 (Consolider-Ingenio 2010)
and CTQ2009-10477, and Junta de Andalucía under projects P06-
FQM-01869, P07-FQM-02595 and P07-FQM-02600. I would also like
to thank my collaborators, especially J. Pablo González Vazquez and
Dr. Morales-Flórez. I would also like to thank “Little Bug” for a critical
read of the manuscript.
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