Thin Solid Films 451 – 452 (2004) 86–92

Electrochemical comparative study of titania (anatase, brookite and rutile)

nanoparticles synthesized in aqueous medium
M. Koelscha, S. Cassaignona,*, C. Ta Thanh Minhb, J.-F. Guillemolesb, J.-P. Joliveta
a
` Condensee,
Laboratoire Chimie de la Matiere ´ UMR-CNRS 7574, Universite´ P. et M. Curie, 4 place Jussieu, 75252 Paris Cedex 05, France
b
´
Laboratoire d’Electrochimie et de Chimie Analytique UMR-CNRS 7575, Ecole Nationale Superieure de Chimie de Paris, 11,
rue Pierre et Marie Curie, 75231 Paris Cedex 05, France

Abstract

Titanium oxide TiO2 has found extensive use in a great variety of applications among which electrode materials for dye-
sensitized solar cells. The polymorphs of TiO2, rutile, anatase and brookite exhibit specific physical properties, band gap,
electronic surface states. For many applications the size of particles was an important parameter because it determines the surface
to volume ratio, which greatly influences many properties. TiO2 anatase was the most used phase for photovoltaic applications
and brookite seems potentially interesting. Nanometric particles of the three polymorphs were synthesized in aqueous medium in
order to compare the electronic properties of these materials for photovoltaic devices. No significant difference was observed
between the phases by cyclic voltammetry. The surface and consequently the electrode preparation seemed to be the main
parameter. The measurement of double layer capacitance has shown the film activation initially insulating and strong frequency
dependence. After dye sensitization, it has been observed that at low I2 concentration in solution (with a fixed concentration of
Iy), the open circuit voltage (Voc) was independent of this concentration while above a certain threshold for I2, Voc decreased
logarithmically with the iodine concentration.
䊚 2003 Elsevier B.V. All rights reserved.

Keywords: TiO2; Anatase; Brookite; Rutile; Electrochemistry; Capacitance; Dye-sensitized solar cells; Sensitization

1. Introduction amorphous or to crystalline anatase. The other phases,

Much attention has been focused on the use of the
titanium oxide nanoparticles for various technical appli-
cations, such as electrochromic material w1x, organic
depollutant on window w2x, dielectrics w3x, lithium-ions
batteries w4x and dye-sensitized solar cells (DSSC) w5x.
In all these devices the photoelectrode is of a thin film
of nanoparticulate TiO2. The properties of these films
certainly depend on the phase, morphology and prepa-
ration method that were used, and it is of interest to
investigate what kind of surface is the most suitable for
a given application and therefore which is the property
that makes TiO2 so preferred for all these applications.
TiO2 films can be directly synthesized by a wide
variety of techniques such as chemical vapor deposition
w6x, aerosol pyrolysis w7x, electrodeposition w8,9x and
sol–gel processings w10,11x. Most of them lead to
*Corresponding author. Tel.: q33-1-44-27-30-45; fax: q33-1-44-
27-47-69.
E-mail address: cassai@ccr.jussieu.fr (S. Cassaignon).
rutile or brookite have not been investigated as much.
Another possibility, very versatile, is to form nanopar-
ticles in solution by soft chemistry and to deposit them
on a substrate afterwards. The three polymorphs of
TiO2 can be synthesized by thermolysis of TiCl4 or
TiCl3 in aqueous medium and the control of the precip-
itation conditions (acidity, nature of anions, ionic
strength, titanium concentration, etc.) allows the control
of crystalline structure, size and morphology of particles.
Spheroidal nanoanatase w12x, platelets of pure brookite
with nanometric size w13x and rutile with various shapes
(needle, rod or platelets) w14x were obtained. In this
way, it becomes possible to investigate systematically
the influence of phase and morphology of the particles.
For DSSC, TiO2 anatase is still considered to be the
best candidate, but recently, the first DSSC using brook-
ite as the semiconducting electrode was reported w15x,
with promising results. Owing to the small scale of the
constituents of the thin films, charge carriers in transit
get frequently close to the surface, implying that the

0040-6090/04/$ - see front matter 䊚 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2003.11.150
 M. Koelsch et al. / Thin Solid Films 451 – 452 (2004) 86–92
Fig. 1. TEM photos of TiO2 nanoparticles: (a) anatase (A9); (b) anatase (Alo) (c1) brookite (B17); (d1) rutile (F9); (e1) rutile (Ru4); (f1)
rutile (Ru5).
transport and the charge transfer processes are strongly
related to the electronic surface states. These processes
are then expected to be sensitive to the crystal structure,
size and morphology of the exposed lattice planes as it
was shown w16,17x, as well as to the band gap and to
the flat band potentials w18,19x.
Solar cell photopotential is especially sensitive to the
nature of the semiconductor surface that determines
largely the occurrence of reverse reactions (i.e. recom-
bination). The best actual solar cells work with the I2 y
Iy (or Br2 yBry) couple w20x, because of a slow kinetics
for I2 reduction on SnO2 and specially on TiO2 surfaces
w21x. This process is in competition with the power
generation in the cell that involves fast electron injection
from dye’s LUMO into TiO2’s conduction band and dye
cation regeneration by the redox couple w5x. Therefore,
the open circuit voltage of an illuminated cell is a good
measure also of the surface reactivity with respect to
the redox couple measured against that of the adsorbed
dye.
Here we report on the electrochemical behavior in
aqueous solution of several films of TiO2 (anatase,
brookite and rutile) and the influence of parameters
such as the crystalline structure and the morphology on
the electrochemical response. Double layer capacitance
was measured by impedance spectroscopy to complete
this study and to have an idea of the energetic density
of states (DOS) at the interface. Finally, to compare the
influence of the different reverse reaction on the Voc,
the TiO2 has been sensitized with a dye and the Voc was
measured as a function of the wI2x y wIy x ratio.
87
2. Experimental
For the synthesis of solids, a known volume of
TiCl4 or TiCl3 was added to a hydrochloric acid solution.
The acid concentration was adjusted between 0.5 and 5
mol ly1 or sodium hydroxide has been added to fix the
pH between 1 and 6. These solutions were heated and
aged at 60, 100 or 120 8C over 24 h. Rutile, anatase
and brookite were obtained in various proportions. The
particles were then centrifuged, washed with distilled
water and peptized with nitric acid to obtain stable sols.
The sols were concentrated to get approximately 1
mol ly1 titanium concentrate solutions. Depending on
the synthesis conditions anatase spherical particles (A9)
(⭋s5 nm) and (A10) (⭋s9 nm) w13x, needles with a
size of 300=15 nm2 (Ru5), rod-like with a size of
100=15 nm2 (Ru4) and small rods with a size of 15=5
nm2 rutile nanoparticles (F9) w14x or pure nanometric
brookite platelets (B17) (⭋s9 nm) w12x were obtained
(Fig. 1). BET measurements were made on TiO2 pow-
ders, for anatase (A9) the specific surface was Ss210
m2 gy1, for brookite (B17) Ss117 m2 gy1 and finally
for rutile (Ru4) Ss125 m2 gy1.
Nanostructured TiO2 electrodes were prepared by
depositing the concentrate sol on a conducting fluorine-
doped tin oxide (F-SnO2) glass substrate. The sol was
spread using a glass rod. The films were dried in an
oven at 60 8C for a few minutes and sintered for 30
min at 450 8C. White films of TiO2 were obtained. It
has been verified that the crystalline structure and the
particle size were kept w18x. The surface was homoge-
neous and the films were porous w18x. The thickness
88 M. Koelsch et al. / Thin Solid Films 451 – 452 (2004) 86–92
Fig. 2. Cyclic voltammetry of anatase (A9), brookite (B17) and rutile
(F9) and (Ru5) in H2SO4 pH 3yK2SO4 0.1 M, scan speed 50
mV sy1.
was nearly 10–15 mm for rutile and brookite and thinner
for anatase.
The electrochemical study was realized in a conven-
tional three electrodes cell at room temperature, using
an EGGyPAR 273A potentiostatygalvanostat. The
potential of the working titania electrode (Ss0.125
cm2) was measured vs. a saturated mercurous sulfate
electrode (SME, ESMEs0.658 VySHE). All potentials
are reported against this electrode. The auxiliary elec-
trode was a platinum wire. The electrolyte was an
aqueous solution of H2SO4 pH 3yK2SO4 0.1 M. The
cell was deoxygenated before and during measurements
by argon. Impedance spectra were recorded between
106 and 10y3 Hz using a Perkin Elmer PAR 263A
potentiostatygalvanostat connected to a Solartron 1260
frequency response analyzer. The amplitude of the super-
imposed sinusoidal potential signal was 10 mV.
The sensitization of the films was conducted with
ruthenium 535 (Solaronix) a bipyridile ruthenium deriv-
ative, in dry ethanol for 24 h in the dark. Dark-red films
were obtained. For the measurement of the Voc as a
function of the wI2x y wIy x ratio in solution, the initial
electrolyte solution was a KI 0.2 M pH 3 solution in
water, and additions of I2 in the cell were followed by
measuring the Voc vs. the potential of the auxiliary
electrode.
3. Results and discussion
3.1. Cyclic voltammetry
Fig. 2 shows the reduction of the different films. A
very small cathodic peak is apparent approximately
y0.5 V at pH 3, which increased significantly if a
second scan going at anodic potential (1 V) was
performed (not shown). Because of the large specific
surface of the nanocrystalline electrodes, the surface
states show clearly on the electrodes of TiO2. The
reduction of a nanocrystalline film of titania entails the
injection of electrons, these charge carriers can be
trapped in a energy level localized under the conduction
band. It has been established that this level corresponded
to the energy level of Ti3q, that is one of the identified
surface states of the titania w18,22x. This cathodic peak
was observed to increase after prolonged oxidation of
the films at anodic potentials above 1 V. At more
negative potential this peak is followed by a second one
at y0.8 V and by another large peak (Efy1.2 V) as
the film was becoming black. For some experiments
(not shown) this large peak could be decomposed into
two distinct peaks nearly located at y1.2 and y1.6 V,
respectively. It has been shown by spectroelectrochem-
istry that these peaks corresponded to the reduction of
the surface Ti4q into Ti3q w23x. Finally, at the most
negative potential, approximately y1.8 V, the reduction
of the solvent takes place. This peak corresponded to
the reduction of the Ti4q in the bulk probably accom-
panied by insertion of hydrogen in the materials w24,25x.
When the potential was reversed the reoxidation of the
solvent and of the film was observed. At the most
positive potential, 0.7 V, the electronic surface states,
reduced at y0.5 V, were reoxidized just before the
solvent. No major differences were observed between
different films composed of different phases with similar
particle sizes ((A9), (B17) and (F9)) or of same phase
with different morphology ((Ru5) and (F9)) suggesting
that the phase is not the main parameter influencing the
surface electrochemical behavior, but rather details of
the film processing: difference between different prepa-
rations of the same phase was just as significant.
Possibly the electronic behavior of the outer layer of
the particle is not completely determined by the core
structure one, as would be the case if that outer layer
was somewhat amorphous.
3.2. Double layer capacitance
The Nyquist diagram for titania particles at pH 3 (not
shown) exhibits an evolution of the curves with the
potentials. At the less negative potentials where no peak
was visible on the cyclic voltammetry a semicircle was
observed, whereas when the potential corresponded to
the reduction of the electronic surface states a different
curve appeared. These curves were well-modelized by a
classical equivalent circuit (the double layer capacitance
Cd is in parallel with the polarization resistance Rp
themselves in series with the non-compensated resis-
tance Re) without taking into account effects of the
diffusion. The values of the double layer capacitance
Cd as a function of the potential could be calculated at
high frequencies. Capacitances have been compared for
the three polymorphs of titania in Fig. 3 for three
frequencies (11.7, 1.08 and 204 Hz). No significant
variation between the different phases was observed.
However, it was interesting to notice that whatever the
 M. Koelsch et al. / Thin Solid Films 451 – 452 (2004) 86–92 89

crystalline phase of titania, an abrupt and strong increase

of the capacitance (for 100–1000 times) is visible at a
potential of y0.8 V corresponding to the reduction of
the surface titanium as it has been seen on cyclic
voltammetry. The capacitance of the doped tin oxide
(F-SnO2) alone has also been reported on the graph,
and it is readily apparent that before the reduction of
the electronic surface states the behavior of titania films
and SnO2 were similar. It can be assumed that the
observed limiting phenomenon corresponds to SnO2.
This result confirms that only a capacitive current was
measured on cyclic voltammetry. The interpretation fol-
lows that proposed earlier by Zaban et al. w26x that as
the film is reduced, it becomes conducting and electro-
chemically active. Initially, only SnO2 (and TiO2 close
to it) can participate in electrochemical reactions, as Fig. 4. Mott–Schottky diagram for thin films of anatase (A9), rutile
attested (i) by the value of the capacitance, close from (Ru4) and rookite (B17).
the Helmoltz capacitance of a flat SnO2 film and (ii)
by the Mott–Schottky type behavior of the capacitance deduced. As can be seen in Fig. 3, all the films display
giving a free carrier concentration in the film corre- the same characteristics in the anodic potential range
sponding to that of tin oxide (f1021) and a flat band giving a strong support to the hypothesis that the film
potential of tin oxide close from y0.8 V (Fig. 4) was are not electrically active in this potential range. By

Fig. 3. Double layer capacitance of thin film of titania in H2SO4 pH 3yK2SO4 0.1 M as a function of the potential. (a) Brookite (B17), (b)
anatase (A9) (c) rutile (Ru4).
90 M. Koelsch et al. / Thin Solid Films 451 – 452 (2004) 86–92
comparison of the SnO2 and titania films it is possible
to have an idea of the active surface of the TiO2 films.
Indeed, if one supposes that SnO2 and TiO2 after
reduction are sufficiently conductive, the capacitances
correspond essentially to the Helmoltz capacitances,
therefore the ratio of the capacitances of TiO2 and
SnO2 gives the ratio of the surfaces. For the brookite,
this ratio being approximately 1500, the active surface
can be estimated to Sas190 cm2. This result is in
agreement with the generally accepted value of the
porosity (50%) of a titania thin film of thickness
approximately 15 mm and particles size of 5 nm w27x.
Moreover, the charge passed for the film reduction at
the y0.8 V wave would correspond roughly to the
reduction of all surface Ti atoms.
The influence of the frequency has also been studied.
The increase of the capacitance with the decrease of the
frequency indicates that the capacitance is related to the
electronic surface states of the titania since these species
have a relatively slow reaction rate: when the frequency
is too high, the electrochemical reaction cannot take
place within a cycle and the capacitance response is
lowered.
3.3. Energetics
From the experiments above, the interface energetics
can be tentatively inferred. Both capacitance and voltam-
metric measurements suggest that the respective posi-
tions of the SnO2 and TiO2 conduction bands are not
the same before and after surface reduction as the
charging of the TiO2 induces a shift in its Fermi level.
Fig. 5 presents the energetics diagram. In the ‘oxidized’
state, as the SnO2 is highly doped (to the point of
degeneracy), its conduction band (given by the flat band
potential) must be close to the equilibrium Fermi level
Ef, i.e. at y0.8 V. This is also the position for which
the TiO2 film starts getting reduced, and this level
corresponding to electronic surface states is therefore
pinning Ef in the oxidized film. Upon reduction elec-
tronic surface states are reduced, which causes an Ef
increase with respect to the TiO2 conduction band in
the particles. Interestingly, during reduction the energet-
ics of the film is ‘scanned’ as all the levels of TiO2 are
being reduced in turn. If the voltammetry is conducted
slowly enough, the current is proportional to the number
of states reduced, i.e. to the DOS at the given potential.
Since the standard hydrogen electrode (SHE) can be
placed on the absolute electron energy scale (y4.5 eV
with electron in vacuum as reference), the DOS can be
placed on the electron energy scale. If moreover this
scanning is done irrespective of the distance between
the particle and the electrode, the TiO2 DOS can be
inferred directly from either voltammetry or capaci-
tance–voltage measurements.
3.4. Photosensitization
In the following step, interface energetics was probed
in dye-sensitized cells for different TiO2 phases. More-
over, various statements can be found in the literature
regarding factors affecting the photovoltage (Voc), and
for instance low values of wIyx y wIy 3 x are sometimes
regarded as preferable.
Two models have been proposed: (i) that a low value
of the ratio would tend to increase the interfacial electric
field and therefore increase the photovoltage w28x and
(ii) that a high value of the ratio increases the energy
difference between Eredox and the HOMO of the dye
which would unavoidably hamper the photovoltage by
the same amount w29x unless under illumination the
HOMO of the dye shifts to higher energies with respect
to the redox level. Alternatively, one could suggest that
the photopotential is essentially limited by the recom-
bination of the electrons injected in TiO2 with either the
dye cation (Dq) or the iodine, and that the dye cation
regeneration depends on the Iy concentration. Moreover,
one could argue that a fast Dq regeneration, being the
expression of a quasi equilibrium between the redox
couple with the holes trapped on the Dq specie, this
imposes a shift of the dye and TiO2 levels with respect
to Eredox. This model regards high wIyx y wIy3 x as prefer-
able for the Voc. We note first that the expression for
the redox level with respect to the iodideyiodine con-
centrations is (Eq. (1))
kT wIy
3 x
EsE8q Ln y 3 . (1)
2q wI x
Therefore, previous experiments such as in Ref. w30x at
constant wIyx y wIy
3 x have not been carried out at constant
redox level position but rather for decreasing Eredox.
Experimental results for TiO2 films are reported in
Fig. 5, and show a very characteristic behavior: at low
I2 concentrations, Voc is insensitive to iodine, but
decreases strongly after a certain threshold in concentra-
tion. Clearly, low wIyx y wIy
3 x are detrimental to Voc, and
the first model is inadequate. A good fit to the experi-
mental values can be obtained using the second model,
with some simple assumptions, as explained below. The
photopotential of the cell is that for which the generation
current equals the recombination current, i.e. when
JgensJrec. In such cells, provided the illumination inten-
sity is not too large, generation of photocarriers is
proportional to the absorbable photon flux: JgensKF,
where F is the photon flux. The recombination current
can proceed via either of the two paths (Eqs. (2) and
(3)) (Fig. 6):
eyq1y2Iy
3 ´3y2I
y
(2)
eyqDq´D8 (3)
 M. Koelsch et al. / Thin Solid Films 451 – 452 (2004) 86–92 91

AkT B KF E
Vocs LnC ym q
F (8)
q D K1Nc8)I3 ) qK2Nc8)D ) G

This expression tells us that at low I2 concentration, the

Voc is independent of the I2 concentration while above
a certain threshold for I2, Voc will decrease logarithmi-
cally with the iodine concentration.

4. Conclusion

Nanometric particles of anatase, brookite and rutile

were synthesized in aqueous medium in order to com-
pare the electronic properties of these materials for
photovoltaic devices. No significant difference was
Fig. 5. Energetics diagram for a titania film on F-SnO2 substrate observed between these phases by cyclic voltammetry.
before (a) and after (b) surface reduction with CB: conduction band, The surface and consequently the electrode preparation
VB: valence band and Ef: Fermi level.
seemed to be the main parameter. Although the exposed
faces were not the same, and then the coordination of
the titanium atoms was different (more or less charged
With K1 and K2 being, respectively, the kinetic constant by hydroxylation), the conditions of preparation and
of Eqs. (2) and (3). Therefore, the recombination current especially the deposition of the sol on the substrate were
can be expressed as (Eq. (4)) the determinant factors. Measurement of the double
m
layer capacitance has allowed to show the film activation
JrecsK1nwIy q
3 x qK2nwD x (4) initially insulating and a strong frequency dependence
proving one more time that it was the electronic surface
where n is the electron concentration in TiO2 and m is states, which were implied. Finally, after dye sensitiza-
the reaction order. From the Fermi distribution, n can tion the Voc has been measured as a function of the
be obtained as (Eq. (5)) concentration of the couple I2 yIy and it has been
observed that at low I2 concentration, the Voc was
B
ŽEfnyEc. E independent of this concentration while above a certain
nsNc expC F threshold for I2, Voc decreased logarithmically with the
D kT G
iodine concentration showing a change in the dominant
recombination mechanism at a critical concentration of
B
ŽEfnyEredoxqEredoxyEc8qEc8yEc. E
sNc expC F I2 in the millimolar range.
D kT G
(5)

where Nc is the conduction band DOS and Ec its position

(Ec8 is the conduction band position in the dark, the
position of the redox level being taken as a reference)
Efn is the quasi Fermi level of electrons in TiO2 under
illumination. By definition, qVocsEfnyEredox, moreover,
we make the assumption that the conduction band shift
under illumination is proportional to Voc (Eq. (6)):

B1 E
Ec8yEcsC y1FqVoc (6)
DA G

Thus, n can be expressed as (Eq. (7))

B qV E
nsNc expC F
oc
(7) Fig. 6. Open circuit voltage of a thin film of anatase (A10), rutile
D AkT G
(Ru4) and brookite (B17) sensitized with ruthenium 535 in solution
Iy 0.2 M pH 3y0-I2-0.01 M: reproducibility and comparison with
and therefore Voc can be expressed as (Eq. (8)) the EPFL anatase.
92 M. Koelsch et al. / Thin Solid Films 451 – 452 (2004) 86–92

Acknowledgments w14x M. Koelsch, S. Cassaignon, J.P. Jolivet, in progress.

w15x K.J. Jiang, T. Kitamura, H. Yin, S. Ito, S. Yanagida, Chem.
The authors express their most sincere gratitude to B. Lett. (2002) 872.
w16x A. Zaban, S.T. Aruna, S. Tirosh, B.A. Gregg, Y. Mastai, J.
O’Regan for helping us with some useful experimental
Phys. Chem. B 104 (2000) 1104.
tips. w17x C.J. Barbe,´ F. Arendse, P. Comte, M. Jirousek, F. Lenzmann,
V. Shklover, M. Gratzel, J. Am. Ceram. Soc. 80 (12) (1997)
References 3157.
w18x S. Doherty, D. Fitzmaurice, J. Phys. Chem. 100 (1996) 10732.
w1x T. Ohzuku, T. Hirai, Electrochim. Acta 27 (1982) 1263.
w2x I. Sopyan, S. Murasawa, K. Hashimoto, A. Fujishima, Chem. w19x M. Koelsch, S. Cassaignon, J.F. Guillemoles, J.P. Jolivet, Thin
Lett. 8 (1994) 723. Solid Films 403–404 (2002) 312.
w3x T. Fuyuki, T. Kobayashi, H. Matsumami, J. Electrochem. Soc. w20x K. Hara, T. Horigushi, T. Kinoshita, K. Sayama, H. Arakawa,
135 (1988) 248. Solar Energy Mater. Solar Cells 70 (2) (2001) 151.
¨
w4x L. Kavan, K. Kratochvilova, M. Gratzel, J. Electroanal. Chem. w21x J.S. Salafsky, W.H. Lubberhuizen, E. van Fassen, R.E.I.
394 (1995) 93. Schropp, J. Phys. Chem. B 102 (1998) 766.
¨
w5x B. O’Regan, M. Gratzel, Nature 353 (1991) 737. w22x A. Hagfeld, M. Gratzel,
¨ Chem. Rev. 95 (1995) 49.
w6x G.K. Boschloo, A. Goossens, J. Schoonman, J. Electrochem. w23x M. Koelsch, S. Cassaignon, J.F. Guillemoles, S.A. Bilmes, J.P.
Soc. 144 (4) (1997) 1311. Jolivet, in progress.
¨
w7x L. Kavan, M. Gratzel, Electrochem. Acta 40 (1995) 643. w24x P. Clechet, C. Martele, R. Olier, J.P. Thomas, M. Falavier, J.
¨
w8x L. Kavan, T. Stoto, M. Gratzel, D. Fitzmaurice, V. Shklover, Electrochem. Soc. 130 (8) (1983) 1795.
J. Phys. Chem. 97 (1993) 9493. w25x M.F. Weber, L.C. Chumacher, M.J. Dignam, J. Electrochem.
w9x Y. Lei, L.D. Zhang, J.C. Fan, Chem. Phys. Lett. 338 (2001)
Soc. 129 (9) (1982) 2022.
231.
w26x A. Zaban, A. Meier, B. Gregg, J. Phys. Chem. B 101 (1997)
w10x G.K. Boschloo, D. Fitzmaurice, J. Phys. Chem. B 103 (1999)
7985.
7860.
¨
w11x L. Kavan, M. Gratzel, w27x D. Cahen, G. Hodes, M. Gratzel,
¨ J.F. Guillemoles, I. Ries, J.
J. Rathousky, A. Zukal, J. Electrochem.
Soc. 143 (2) (1996) 394. Phys. Chem. B 104 (2000) 2053.
´
w12x A. Pottier, S. Cassaignon, C. Chaneac, F. Vilain, E. Tronc, J.P. w28x K. Schwarzburg, F. Willig, J. Phys. Chem. B 103 (1999) 5743.
Jolivet, J. Mater. Chem. 13 (2003) 877. w29x G. Smestad, Ph.D. Thesis, EPFL, Lausanne, 1998.
´
w13x A. Pottier, C. Chaneac, E. Tronc, L. Mazerolles, J.P. Jolivet, J. w30x Y. Liu, Hagfeldt, X.R. Xiao, S.E. Lindquist, Solar Energy
Mater. Chem. 11 (2001) 1116. Mater. Solar Cells 55 (1998) 267.