4688 Langmuir 2000, 16, 4688-4694

Studies of the Adsorption Process of Ru Complexes in

Nanoporous ZnO Electrodes
Karin Keis,† Jan Lindgren,‡ Sten-Eric Lindquist,† and Anders Hagfeldt*,†
Department of Physical Chemistry, Uppsala University, Box 532, S-751 21 Uppsala, Sweden,
and Department of Inorganic Chemistry, Uppsala University, Ångström Laboratory, Box 538,
S-751 21 Uppsala, Sweden

Received September 27, 1999. In Final Form: January 31, 2000

Nanostructured ZnO films consisting of 150-nm sized particles were dye-sensitized with different
ruthenium complexes. Incident photon-to-current conversion efficiencies (IPCE) were found to be dependent
on dye concentration and on residence time of the ZnO film in the dye solution. Results obtained using
infrared and Raman spectroscopies together with traditional two-electrode measurements using a sandwich-
type cell gave evidence of dye agglomeration in the nanostructured ZnO film. Possible reasons for the
agglomeration process in ZnO films are discussed.

Introduction
Photon-to-current conversion properties of numerous
semiconducting nanostructured thin film electrodes have
been reported; for examples, TiO2,1 SnO2,2 Fe2O3,3 ZnO,4
CdS, and CdSe.5 Systems based on TiO2 are the most
extensively studied and, at present, the most promising
for photoelectrochemical systems.6 However, other metal
oxides, like ZnO with a band gap similar to that of TiO2,
could be an alternative material for solar cell applications.
Several attempts have been made to use ZnO in photo-
electrochemical solar cells. Dye-sensitized semiconducting
single-crystal ZnO electrodes were studied by Gerischer
and Tributsch as early as 1969.7,8 In 1980, a 2.5%
monochromatic energy conversion efficiency at 562 nm
was reported by Matsumura et al.9 In the following years
many different dyes were tried for photosensitization of
ZnO electrodes e.g.; chlorophyll,10 phthalocyanides,11 rose-
bengal,9,12 and Cu(I)13,14 and Ru(II)15-complexes. In 1994,
Redmond et al. achieved an incident photon-to-current
conversion efficiency (IPCE) of 13% at 520 nm and an
overall light-to-electric energy conversion efficiency of
* To whom correspondence should be addressed.
† Department of Physical Chemistry.
‡ Department of Inorganic Chemistry.
(1) Hagfeldt, A.; Björksten, U.; Lindquist, S.-E. Sol. Energy Mater.
Sol. Cells 1992, 27, 293.
(2) Bedja, I.; Hotchandani, S.; Kamat, P. V. J. Phys. Chem. 1994, 98,
4133.
(3) Björksten, U.; Moser, J.; Grätzel, M. Chem. Mater. 1994, 6, 858.
(4) Holler, P.; Weller, H. J. Phys. Chem. 1995, 99, 14096.
(5) Hodes, G.; Howell, D. J.; Peter, L. J. Electrochem. Soc. 1992, 139,
3136.
(6) O’Regan, B.; Grätzel, M. Nature 1991, 353, 737.
(7) Gerischer, H.; Tributsch, H. Ber. Bunsen-Ges. Phys. Chem. 1969,
73, 251.
(8) Gerischer, H.; Tributsch, H. Ber. Bunsen-Ges. Phys. Chem. 1969,
73, 850.
(9) Matsumura, M.; Matsudaira, S.; Tsubomura, H. Ind. Eng. Chem.
Prod. Res. Dev. 1980, 19, 415.
(10) Miyasaka, T.; Watanabe, T.; Fujishima, A.; Honda, K. J. Am.
Chem. Soc. 1978, 100, 6657.
(11) Minami, N.; Watanabe, T.; Fujishima, A.; Honda, K. Ber.
Bunsesn-Ges. Phys. Chem. 1979, 83, 476.
(12) Kokado, H.; Nayama, T.; Inoue, E. J. Phys. Chem. Solids 1974,
35, 1169.
(13) Alonso-Vante, N.; Ern., V.; Chartier, P. Nouveau Journal de
Chemie 1983, 7, 1, 3.
(14) Alonso-Vante, N.; Nierengarten, J. F.; Sauvage, J. P. J. Chem.
Soc., Dalton Trans. 1994, 1649.
(15) Bedja, I.; Kamat, P.; Hua, X.; Lappin, G.; Hotchandani, S.
Langmuir 1997, 13, 2398.
0.4%.16 They concluded that the low efficiency was due to
a reduced uptake of the dye and low quantum yield for
charge injection.
Recent results from our laboratory showed that bare
nanostructured ZnO films with 150-nm sized spherical
particles have excellent electron transport properties,
yielding an IPCE value of 90% at 360 nm.17 Thus, it was
shown that ZnO is a possible candidate for highly efficient
dye-sensitized solar cells. However, compared with dye-
sensitized TiO2 solar cells with overall light-to-electric
energy conversion efficiencies of up to 10%, moderate
efficiencies of 2% were obtained for ZnO samples sensitized
in 0.5 mM ethanolic Ru-based dye solution.18
In this paper, the ZnO/dye systems are studied in more
detail. Information about binding modes is obtained from
infrared (IR) and Raman spectroscopies. These results
are then used to interpret the photoelectrochemical output
from solar cell experiments.
Experimental Section
The synthesis of ZnO powder and preparation of colloidal
dispersion are described elsewhere.17 The electrodes were
prepared by spreading out the viscous dispersion of ZnO onto
transparent conducting glass sheets (Libbey Owens Ford,
fluorine-doped SnO2 glass with a sheet resistance of 8 Ω/square).
Using adhesive tape (Scotch brand) as a frame and spacer, a
layer was formed by raking off the excess of the colloidal solution
with a glass rod. Based on preliminary sintering temperature
studies, the samples were sintered at 400 °C in air for 30 min
to form a nanostructured film electrode. ZnO films used in our
experiments consist of 150-nm sized particles forming a highly
porous structure, shown in Figure 1. Thickness of films were
determined by profilometry (Tencor Alpha Step) and were
typically 8-10 µm.
Four different dyes were used for the sensitization of ZnO
electrodes. Two dyes were purchased from Solaronix (Lausanne,
Switzerland): cis-bis(isothiocyanato)-bis(2,2′bipyridyl-4,4′dicar-
boxylato) ruthenium (II) complex (hereafter denoted by N3) and
cis-bis(isothiocyanato)bis(2,2′bipyridyl-4,4′dicarboxylato) ruthe-
nium (II) bis-tetrabutylammonium (hereafter denoted by N719).
The synthesis of the third dye, [bis-(2,2′bipyridyl)] [4-(2-lithium
carboxylate ethyl)-4′methyl-2,2′-bipyridine] ruthenium bis-
(16) Redmond, G.; Fitzmaurice, D.; Grätzel, M. Chem. Mater. 1994,
6, 686.
(17) Keis, K.; Vayssieres, L.; Rensmo, H.; Lindquist, S.-E.; Hagfeldt,
A. J. Electrochem. Soc., submitted for publication.
(18) Rensmo, H.; Keis, K.; Lindström, H.; Södergren, S.; Solbrand,
A.; Hagfeldt, A.; Lindquist S.-E. J. Phys. Chem. B. 1997, 101, 14, 2598.

10.1021/la9912702 CCC: $19.00 © 2000 American Chemical Society

Published on Web 04/07/2000
Absorption of Ru Complexes in ZnO Electrodes
Figure 1. SEM picture of nanostructured ZnO electrode. The
bar corresponds to 1 µm.
hexafluorophosphate (hereafter denoted by C1), is described by
Aranyos et al.19 The fourth dye was trans-[2,6-bis(methyl-
benzimidazol-2-yl)-pyridine](2,2′-bipyridyl-4-phosphonic acid)
ruthenium(II) chloride and is denoted as P1 below. The electrodes
were immersed in a room-temperature ethanolic dye solution
while still being warm at ∼80 °C. The concentrations of used dye
solutions are indicated later, and the “sensitizing time” is defined
as the residence time of the electrode in the dye solution. After
the dye-bath, the excess solution on the electrode surface was
gently dried with tissue paper (Kleenex). The films were then
dried in air before measurement.
The TiO2 colloidal solution was prepared by hydrolysis of
titanium tetraisopropoxide.6 The electrode preparation and dye-
sensitization procedure (0.5 mM N3 dye in ethanol, 24 h in dye-
bath) were similar to those for ZnO electrodes.
In the two-electrode measurements, a sandwich-type solar
cell was constructed by gently squeezing together the dye-
sensitized ZnO electrode with a platinized conducting glass using
a spring. The electrolyte solution, 0.5 M LiI and 50 mM I2 in
3-metoxypropionitrile, was attracted into the cavities of the ZnO
electrode by capillary forces. The working electrode was il-
luminated through its substrate by a 450 W xenon lamp together
with an 80-mm water filter. The IPCE values were determined
at 20-nm intervals between 400 and 800 nm. The results were
not corrected for intensity losses due to light absorption and
reflection by the glass support.
The overall light-to-electric energy conversion efficiency
measurements were performed with a Light Drive 1000 as a
light source (embodying a microwave-powered sulfur plasma).
The lamp simulates the visible part of the solar spectrum rather
well. There are, however, very low intensities in the ultraviolet
(UV) and IR ranges. The light intensity was typically 60 W/m2,
measured by a pyranometer. The active electrode area was
typically 0.5 cm2.
Reflection measurements were performed with an integrating
sphere using a Cary 2000 spectrophotometer.
Fourier transform infrared (FT-IR) spectral measurements
were performed on dye-sensitized ZnO and TiO2 samples (1.5 ×
2 cm2) and on powdered Zn2+/dye complex in Nujol mull between
CaF2 windows. A Digilab-Biorad FTS-45 FT-IR spectrometer
covering the range 400-4400 cm-1 with a resolution of 2 cm-1
was used for the measurements. Reflection-absorption spectra
were recorded using a reflectance unit (Seagull, Harrick Scientific
Corp.) with incidence and reflectance angles of 45°. Sixteen scans
were averaged in all cases. Baseline corrections were made, and
if necessary, water vapor bands were subtracted. The Renishaw
System 1000 micro-Raman spectrometer equipped with a 514-
nm Argon laser (25 mW) and a 780-nm diode laser (20 mW) with
2 cm-1 resolution was used in recording the Raman spectra. No
useful Raman spectra from the 780-nm laser could be registered,
(19) Aranyos, V.; Grennberg, H.; Tingry, S.; Lindquist, S.-E.; Hagfeldt,
A. Sol. Energy Mater. Sol. Cells, in press.
Langmuir, Vol. 16, No. 10, 2000 4689
Figure 2. IPCE at 520 nm versus sensitizing time obtained
from 2-electrode measurement with nanostructured ZnO
electrodes with thicknesses of 10 µm. Dependence was studied
in three different N3 concentrations: 0.5, 0.25, and 0.125 mM.
whereas strong bands using the 514-nm laser were obtained.
This difference is due to the resonance Raman effect (i.e., an
electronic transfer at 520 nm). Therefore, vibrational transitions
are expected mainly from the aromatic system, which is directly
bonded to the ruthenium ion.
Results
In Figure 1 we show a scanning electron microscopy
(SEM) picture of the nanostructured ZnO electrode used
in our measurements. The ∼150-nm sized particles form
a highly porous structure of the film. The structural and
photoelectrochemical characterization of this material is
described elsewhere.17
Two-Electrode Measurements with Sandwich-
Type Cells. Figure 2 shows IPCE values at 520 nm for
ZnO electrodes with a film thickness of 10 µm plotted
against sensitizing time in three different N3 concentra-
tions. Contrary to the very slow dye uptake of ZnO
electrodes (> 24h) reported in the previous literature,16
we observed a very fast dye uptake (minutes to a few
hours) that is comparable to that of nanostructured films
of TiO2. The strong dark red color indicates that the dye
is adsorbed homogeneously through the ZnO nanoporous
film in a few minutes using dye solutions with 0.5 mM
concentration. However, after the initial rapid increase,
the IPCE values decreased when electrodes were left in
the dye-bath for longer times. Corresponding changes in
the action spectra are shown in Figure 3. To follow the
IPCE dependence on sensitizing time in more detail, we
used solutions with lower dye concentrations. Measuring
the IPCE for ZnO electrodes sensitized for only a few hours
in 0.25 and 0.125 mM dye solutions, efficiencies of ∼30%
were obtained. Because it was observed that these films
were still white close to the conducting glass substrate,
we concluded that the dye molecules were not fully
penetrating the films in this time range. Using the same
concentrations but longer sensitization times, we observed
that the films were colored all the way to the back contact.
All used dye concentrations gave a maximum IPCE value
after a certain sensitizing time (Figure 2). We noticed
that by decreasing the dye concentration, it took a longer
time to reach the maximum efficiency. The maximum
IPCE of ∼50% (at 520 nm) was obtained by using a 0.125
mM ethanolic N3 solution for 7 h. It is important to note
4690 Langmuir, Vol. 16, No. 10, 2000 Keis et al.

Figure 3. IPCE action spectra for ZnO electrodes with different

sensitizing times in 0.5 mM N3 solution. Note that the values
for 2 h sensitization time refer to the right-hand axis, whereas
the other curves refer to the left-hand axis.

that different series of measurements gave slightly

different IPCE values, whereas the IPCE dependence on
sensitizing time was always observed (similar to Figure
2).
In Figure 4A, the IPCE action spectra of ZnO/N719 is
shown. The effect of sensitizing time on efficiency is similar
to that of the N3. The IPCE decreased with longer times
in the dye solution. Also, the maximum around 520 nm
flattened out for both dyes (Figures 3, 4A). The situation
was different when the 0.5 mM Pl and C1 solutions were
used. In the case of P1, there was no or little effect of the
sensitizing time on the IPCE values (Figure 4B). In Figure
4C, a slight increase in IPCE with sensitizing time was
observed for C1. Because this increase was slow and did
not reach a maximum within the time of the experiment
(24 h), we suggest that for this dye (with only one carboxylic
group) it takes a comparatively longer time to fill all sites
with a monolayer of the dye. The IPCE values at short
wavelengths (λ < 420 nm, Figures 4A, B, C) are mainly
due to band-gap excitation of ZnO.
Current-Voltage Characteristics. When ZnO elec-
trodes were sensitized in 0.5 mM N719, the short circuit
current (Isc) decreased with longer sensitization time
(Figure 5). A similar behavior was observed with the N3
(not presented here). The highest Isc (6.7‚10-4 A/cm2) was
obtained with shortest sensitization time (2 min) and the
lowest Isc (2.2‚10-4 A/cm2) was obtained with the longest
sensitization time (24 h). The open-circuit voltage (Voc)
varied in the range of the experimental error and could
be considered constant with an average value of 0.48 V
(Figure 6). A highest overall light-to-electric energy
conversion efficiency of 2.1% was obtained with the
electrodes sensitized with N719 for the shortest time (2
min in dye-bath).
In the case of the P1 and C1 dyes, both the short-circuit
currents and open-circuit voltages were unaffected by the
sensitizing time, varying within the experimental error.
The Isc varied between 2.0‚10-4 and 2.5‚10-4 A/cm2, with
Voc being 0.2 V, for P1. For C1, the Isc was between 1.2‚10-4 Figure 4. IPCE action spectra for ZnO electrodes. Effect of
and 1.8‚10-4 A/cm2 and Voc was ∼0.26 V (Figures 5 and sensitizing time in following solutions: (A) 0.5 mM N719; (B)
6). 0.5 mM P1; and (C) 0.5 mM C1.
Optical Measurements. In the optical measurements with increasing sensitizing time. The absorption curves
we observed an overall decreased reflection from electrodes in Figure 7 give the approximate upper limit for absorption
Absorption of Ru Complexes in ZnO Electrodes
Figure 5. The short circuit current density versus sensitizing
time for ZnO sensitized with 0.5 mM N719, C1, and P1 solutions.
Light intensity of 60 W/m2.
Figure 6. The open circuit voltage versus sensitizing time for
ZnO sensitized with 0.5 mM N719, C1, and P1 solutions. Light
intensity of 60 W/m2.
and were calculated by neglecting the transmission. The
absorption maximum at ∼510 nm widened to shorter
wavelengths when the sensitizing time was increased.
Additionally, we observed a change in the shape of the
curve; that is, the absorption increased more quickly
around 650 and 450 nm with increased sensitizing time
compared with other parts of the spectrum.
IR and Raman Spectra. IR spectra for a ZnO/N3
system are shown in Figure 8A. The thiocyanate ligand
at 2100 cm-1 was N-bounded in agreement with the
literature.20,21 Absorptions at 1728, 1610, and at 1378 cm-1
correspond to a carbonyl stretching vibration from carboxyl
groups and an asymmetric and symmetric C-O stretching
vibration from carboxylate groups, respectively. In the
case of TiO2, these three absorption bands have about
equal intensities, whereas in the case of ZnO, the
absorption bands from the carboxylate groups dominate.
(20) Murakoshi, K.; Kano, G.; Yanagida, S.; Miyazaki, H.; Matsumoto,
M.; Murasawa, S. J. Electroanal. Chem. 1995, 396, 27.
(21) Kohle, O.; Ruile, S.; Grätzel M. Inorg. Chem. 1996, 35, 16, 4779.
Langmuir, Vol. 16, No. 10, 2000 4691
Figure 7. Absorption spectra for ZnO electrodes with different
sensitizing times in 0.5 mM N3.
Moreover, in the case of ZnO, the absorption bands
increased with increasing sensitizing time, except for the
carbonyl band, which was practically unchanged. This
behavior was observed for both the N3 and the N719 dyes
anchored to ZnO films (Figures 8A and 8B). For ZnO/
N719, we observed no carbonyl absorption bands (Figure
8B). In Figure 8C we show the IR spectra for ZnO
sensitized with C1. Only the absorption bands from the
carboxylate group appear, broadened and slightly shifted
compared with the other dyes. There was no change in
the spectra with increasing sensitizing time, except for a
slight increase in absorbance, indicating a somewhat
larger amount of the dye on the surface. In Figure 9, the
IR spectrum of a red precipitate formed by mixing a low
concentration of Zn2+ ions (zinc nitrate) in ethanol with
a N3 solution is shown (see Discussion).
In Figure 10A, Raman spectra for the ZnO/N3 system
are presented. At longer wavenumbers, the vibration
bands from mainly aromatic groups of the dye are
observed. We notice that for longer sensitizing time, the
ZnO vibrational band at 450 cm-1 disappears. In the case
of the ZnO/P1 system, the ZnO vibrational band is seen
even with the longest (24 h) sensitizing time (Figure 10B).
Discussion
The theoretical incident monochromatic photon-to-
current conversion efficiency is given by the expression:
φ(λ) ) LHE(λ) φinj ηc
where LHE(λ) is the monochromatic light harvesting
efficiency, φinj is the quantum yield for charge carrier
injection, and ηc is the efficiency of collecting the injected
charge at the back-contact. To get the correct φ(λ) values,
corrections for losses of light in the glass, back-contact,
and different interfaces must be made. To understand
why φ(λ) values of the studied dye-sensitized ZnO solar
cells are significantly smaller than those of systems based
on nanostructured TiO2 , the differences in those three
terms for the two materials need to be considered.
In a previous work, we found the ηc to be as efficient in
ZnO as for TiO2.17 Several authors have concluded that
low-light-harvesting efficiency is due to poor porosity or
thin ZnO films.15,16 Bedja et al. concluded that the weak
interaction in the ZnO/dye surface results in a poor uptake
4692 Langmuir, Vol. 16, No. 10, 2000
Figure 8. IR spectra of ZnO electrodes sensitized in (A) 0.5
mM N3, (B) 0.5 mM N719, and (C) 0.5 mM C1 solutions for
different times. The spectrum for TiO2 electrodes sensitized in
0.5 mM N3 solution for 24 h is shown in Figure 8A. Spectra are
offset from zero absorbance for clarity.
Keis et al.
Figure 9. IR spectrum of the Zn2+/N3 complex in Nujol mull
between CaF2 windows. Nujol bands have been subtracted.
of dye.15 However, from our data we can conclude that the
light-harvesting efficiency for ZnO is similar to that of
systems based on TiO2. The last parameter to consider is
φinj, which may be assumed to be equal for ZnO and TiO2
because the energetics are similar. For the TiO2/N3 system,
φinj is normally observed to be unity. Redmond et al.
explained the low efficiencies for the ZnO/N3 system to
be due to adsorption of dye molecules in a manner that
they do not efficiently inject an electron into the semi-
conductor upon being photoexcited.16 Recent studies of
electron injection dynamics in dye-sensitized ZnO films
showed the presence of multiexponential injection kinetics
with much slower injection times, thus being different
from TiO2.22 Therefore, it seems that the lower efficiencies
in case of ZnO compared with TiO2 can be attributed to
the parameter φinj. Possible reasons for this will now be
presented on the bases of our experimental observations.
The discussion will proceed by considering the following
processes: (a) diffusion of dye into the ZnO nanostructure,
(b) adsorption of the dye to the ZnO surface, and (c)
formation of dye agglomerates in the pores of the ZnO
film.
If it is assumed that only dye molecules in direct contact
with the ZnO surface can inject electrons and contribute
to the photocurrent, we see from our experiment that the
transport and adsorption of the dye to the ZnO -
depending on the concentration - proceeds over minutes
to hours (Figure 2). We noted that the film at the early
stages of the process remained uncolored in a zone close
to the back-contact. The initial increase in IPCE in all
curves in Figure 2 is clearly due to an increase of the
interfacial concentration of effectively injecting dye mol-
ecules. The dye molecules are first adsorbed in the outer
part of the film and, as they penetrate deeper into the
film, the IPCE increases. The flux of dye molecules toward
the back-contact is driven by the concentration gradient
of dye in the solution. If the adsorption is followed by a
desorption of the dye, we have to consider the equilibrium
between dye molecules in solution and dyes adsorbed at
the surface.
When the first monolayer of N3 or N719 is formed in
the outer part of the film, it is ready to proceed to step (c)
(22) Asbury J. B.; Wang Y. Q.; Lian T. J. Phys. Chem. B. 1999, 103,
32, 6643.
Absorption of Ru Complexes in ZnO Electrodes
Figure 10. Raman spectra of ZnO electrodes sensitized in (A)
0.5 mM N3 and (B) 0.5 mM P1 solutions for different times. The
spectrum for P1 powder is presented in Figure 10B.
in our aforementioned scheme. After longer sensitizing
times, in particular at high dye concentrations, the amount
of dye in the ZnO films increases tremendously, resulting
in a broad absorption spectrum with high absorbances
even for wavelengths with relatively low extinction
coefficients (see Figure 7). This result means that after
a complete surface coverage, extra dye molecules are
accumulated in the film. These extra dye molecules do
not inject electrons but are rather shielding the dye
molecules in direct contact with ZnO from absorbing light.
This shielding lowers the overall φinj and explains the
decrease in IPCE values (see Figure 3). The accumulation
of dye molecules in the pores of ZnO also explains the
observed spectral changes presented in Figure 3. The
maximum in the action spectra widens because the filter-
effect is larger to wavelengths with relatively high
extinction coefficients. We also note that Khazraji et al.
have observed similar changes in the photocurrent action
spectra and absorption spectra when sensitizing TiO2 with
monomeric and aggregate forms of Merocyanine 540.23
(23) Khazraji, A. C.; Hotchandani, S.; Das, S.; Kamat, P. V. J. Phys.
Chem. B 1999, 103, 4693-4700.
Langmuir, Vol. 16, No. 10, 2000 4693
Depending on the rate of the different processes (a)-
(c), the outer part on the electrode may well be in the
process of accumulating dye agglomerates in the pores
when the first dye molecules are reaching the interface
between the back-contact and the ZnO film. Thus, the
latter part is on the way to increasing the efficiency,
whereas the former is in a phase of decreasing the
efficiency. The results in Figures 2 and 3 are consistent
with such processes. The IPCE at 520 nm goes through
an optimum. The increase is due to the increasing number
of effectively injecting dye molecules. The decrease is due
to the light absorbed in the noninjecting agglomerated
dye molecules. The time at which the optimal efficiency
appears at each concentration will depend on the dynamics
of the different competing processes.
In the following we will discuss the adsorption and
accumulation of the dye in the nanostructured ZnO film
in more detail. We propose that the mechanism of dye
agglomeration is due to dissolved Zn2+ ions binding to dye
molecules, forming a complex that stays inside the matrix
of the particles. There is much evidence supporting this
mechanism. First, in a beaker, a solution with a low
concentration of Zn2+ ions in ethanol was mixed with a
N3 solution. After 24 h, a colorless ethanolic solution with
a red precipitate in the bottom was formed. An IR spectrum
of the red precipitate (shown in Figure 9) shows two broad
bands, centered at 1630 and 1370 cm-1 corresponding to
an asymmetric and symmetric C-O stretching vibration
from a carboxylate ion, indicating that all protons in the
dye molecule have been exchanged for Zn2+. Another
indication of the existence of such a complex is that in the
Raman spectra the ZnO band disappears after longer
sensitization times due to covering of the complexes on
the ZnO surface (Figure 10A). The large increase of the
carboxylate bands in the IR data of the sensitized ZnO
electrodes also indicates a situation with all four car-
boxylate groups bonded to Zn2+ ions. The detailed structure
of the formed Zn2+/dye agglomerate can, however, not be
deduced from our data. All these observations indicate
the presence of dye agglomerates in the ZnO/dye system.
From the literature we also note reports on complex
formation between ZnO and different sensitizers due to
the dissolution of zinc ions from the surface. In 1973,
Baumeler et al. studied ZnO/dye complexes using 1-(2′hy-
droxy-4′-X-5′-Y-phenylazo)-2-naphthol, where X and Y
stands for different ligands.24 It was shown that the formed
complexes contain zinc that was originally on the particle
surfaces. Furthermore, the formation of tail-like complexes
have been shown by electron microscopy by Brändli et
al.25
Interestingly we notice that in the ZnO/C1 and ZnO/P1
systems there is negligible or no formation of the Zn2+/
dye complex. The initial increase in IPCE with time
corresponds to the filling of adsorption sites with dye
molecules (Figure 4B and 4C). At equilibrium conditions,
there is no additional dye uptake. In the corresponding
IR and Raman spectra, there are no observable changes
present. The results indicate that protons play an im-
portant role in the exchange reaction with Zn2+ in ZnO.
The fewer protons in the dye molecule, the more sup-
pressed is the dissolution of Zn2+ ions from the surface of
the ZnO.
The formation of dye agglomerates does not take place
in the case of TiO2 electrodes but are apparently extremely
important in the case of ZnO. There are many possible
(24) Baumeler, R.; Rys, P.; Zollinger, H. Helv. Chimica Acta 1973,
56, 251, 2451.
(25) Brändli, R.; Rys, P.; Zollinger, H.; Oswald, H. R.; Schweizer, F.
Helv. Chim. Acta 1970, 53, 130, 1133.
4694 Langmuir, Vol. 16, No. 10, 2000
reasons why the dissolution process is not observed in the
case of the TiO2/dye system. One reason is the difference
in surface chemical properties of these two metal oxides.
The pH of point of zero charge (pzc) lies at ∼5 for TiO2 and
at ∼9 for ZnO. The acid-base properties of colloidal ZnO
and TiO2 particles have been studied by Bahnemann.26 It
was shown that titration with acid leads to the dissolution
of the ZnO colloid already below pH 7.4 and the titration
with base gave a maximum coagulation rate at the pHpzc
due to surface electroneutrality. A difference in interaction
between dye molecules and these two metal oxides can be
demonstrated using a simple experiment. By mixing 0.5
g of ZnO powder with 10 mL of 0.5 mM N3 ethanolic
solution, we observed, after 24 h, a colorless solution with
all dye molecules forming a precipitate on the surface of
the ZnO powder. The corresponding experiment with
mixing the TiO2 powder with N3 solution resulted in a
red-colored solution with no formation of dye precipitate.
Some additional information about the nature of the
surface binding between the dye and ZnO can be obtained
from IR spectral data. In an investigation of ruthenium-
(II)bipyridyl dicarboxylic acid as a photosensitizer to TiO2
it was concluded that carboxylate groups are attached via
bridged coordination to the titanium ions.27,28 This con-
clusion was based on a comparison of the spectra of
adsorbed species with carboxylate ions in solution. In
particular, the wavenumber difference between the an-
tisymmetric and symmetric carboxylate stretching bands
of 230 and 244 cm-1 were observed for the TiO2/N3 and
the TiO2/N719 systems, respectively.28 A chelation situ-
ation would result in a substantially smaller wavenumber
difference and unidentade complexes in a larger wave-
number difference compared with the corresponding
carboxylate species in solution. In the present IR spectra
of the ZnO/N3 system, the spacing between the carboxylate
stretching bands was 228 and 248 cm-1 for the ZnO/N719
system, which may indicate a similar binding to that of
TiO2. Additionally, the IR spectra for ZnO/N719 indicate
that the binding to the ZnO surface involves two proto-
nated groups of the dye, which become deprotonated. From
theoretical investigations of the adsorption and reaction
(26) Bahnemann, D. W. Israel J. Chem. 1993, 33, 115.
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Keis et al.
of formic acid on the ZnO(101h 0) surface, the bridging
structure has been found to be energetically the most
favorable and stable geometry.29,30 Additionally, the
abstraction of acidic hydrogen by the basic surface oxygen
to form surface hydroxyl groups was observed.
Conclusions
In this paper we show the importance of the dye
sensitization process in nanostructured ZnO electrodes.
The sensitization process depends on parameters such as
dye composition and concentration and sensitizing time.
Our results give evidence for dye agglomeration in the
ZnO nanostructured electrodes. The process is irreversible,
and the formed complex is not easily removed from the
film. The agglomeration is due to the dissolution of Zn2+
ions from ZnO in which protons from the carboxylic groups
of the dye are active. The dissolution of the Zn2+ ions are
explained by low local pH at the surface of ZnO. In a second
step, the Zn2+ ions initiate a formation of Zn2+/dye
complexes that agglomerate in the pores of the ZnO matrix.
Optimization of the sensitization process to obtain efficient
dye-sensitized ZnO mesoscopic electrodes for solar energy
conversion should therefore be performed in basic solutions
or with dyes that have no acid protons in their structure
but still will attach to the ZnO particles so that effective
electron injection can take place. Further work in these
directions is in progress in our laboratory.
Acknowledgment. This work has been supported
by the Swedish Research Council for Engineering
Sciences (TFR), Swedish Natural Science Research
Council (NFR), Strategic Foundation for Environmental
Research (MISTRA), and Swedish National Energy Ad-
ministration. We thank Viviane Aranyos and Helena
Grennberg for kindly supplying us with the C1-dye and
Oliver Kohle for the P1-dye. Mårten Edwards is gratefully
acknowledged for his help with optical measurements.
We also thank Petter Persson, Gunnar Westin, and Karin
Westermark for helpful discussions.
LA9912702
(29) Nakatsuji, H.; Yoshimoto, M.; Umemura, Y., Takagi, S.; Hada,
M. J. Phys. Chem. 1996, 100, 694.
(30) Persson, P.; Ojamäe, L. Chem. Phys. Lett., in press.