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www.rsc.org/pccp PERSPECTIVE
Adsorption of organic dyes on TiO2 surfaces in dye-sensitized solar cells:
interplay of theory and experiment
Chiara Anselmi, Edoardo Mosconi, Mariachiara Pastore, Enrico Ronca and
Filippo De Angelis*
Received 28th August 2012, Accepted 11th October 2012
DOI: 10.1039/c2cp43006a

First-principles computer simulations can contribute to a deeper understanding of the dye/

semiconductor interface lying at the heart of Dye-sensitized Solar Cells (DSCs). Here, we present
the results of simulation of dye adsorption onto TiO2 surfaces, and of their implications for the
functioning of the corresponding solar cells. We propose an integrated strategy which combines
FT-IR measurements with DFT calculations to individuate the energetically favorable TiO2
adsorption mode of acetic acid, as a meaningful model for realistic organic dyes. Although we
found a sizable variability in the relative stability of the considered adsorption modes with the
model system and the method, a bridged bidentate structure was found to closely match the
FT-IR frequency pattern, also being calculated as the most stable adsorption mode by
calculations in solution. This adsorption mode was found to be the most stable binding also for
realistic organic dyes bearing cyanoacrylic anchoring groups, while for a rhodanine-3-acetic acid
anchoring group, an undissociated monodentate adsorption mode was found to be of comparable
stability. The structural differences induced by the different anchoring groups were related to the
different electron injection/recombination with oxidized dye properties which were experimentally
assessed for the two classes of dyes. A stronger coupling and a possibly faster electron injection
were also calculated for the bridged bidentate mode. We then investigated the adsorption mode
and I2 binding of prototype organic dyes. Car–Parrinello molecular dynamics and geometry
optimizations were performed for two coumarin dyes differing by the length of the p-bridge
separating the donor and acceptor moieties. We related the decreasing distance of the carbonylic
oxygen from the titania to an increased I2 concentration in proximity of the oxide surface, which
might account for the different observed photovoltaic performances. The interplay between
theory/simulation and experiments appears to be the key to further DSCs progress, both
concerning the design of new dye sensitizers and their interaction with the semiconductor and
with the solution environment and/or an electrolyte upon adsorption onto the semiconductor.

1. Introduction
The answer to the growing demand of environmentally
sustainable energy resources at the planetary level might lie
in the ability to capture and utilize solar energy for a sustainable
development on a large scale. In this scenario, dye-sensitized
solar cells (DSCs) represent a particularly promising approach
to the direct conversion of sunlight into electrical energy at low
cost and with high efficiency.1–4
In DSCs, a dye sensitizer absorbs the solar radiation and
transfers the photoexcited electron to a wide band-gap semi-
conductor electrode consisting of a mesoporous oxide layer,
Computational Laboratory for Hybrid/Organic Photovoltaics
(CLHYO), Istituto CNR di Scienze e Tecnologie Molecolari, Via
Elce di Sotto 8, I-06123, Perugia, Italy. E-mail: filippo@thch.unipg.it;
Fax: +39 075 585 5606; Tel: +39 075 585 5523
usually TiO2, composed of nanometer-sized particles. The
charge hole which is concomitantly created in the dye after
excited state charge injection is then transferred to a redox
couple in a liquid electrolyte or to a solid hole conductor
(see Scheme 1).
Of the three main DSCs constituting materials, i.e. the dye,
the semiconductor oxide and the redox shuttle, the chemical
nature and structure of the dye is by far the subject which has
been more vastly investigated, with a general target of increasing
the dye molar extinction coefficient and shifting the dye absorption
towards the near-IR region, thus enhancing the overlap between
the solar emission and the dye absorption spectrum and eventually
achieving higher DSCs photocurrents. A further important
sensitizer’s feature is the matching of ground and excited state
oxidation potentials with the redox shuttle potential and the
semiconductor conduction band, respectively.5,6 These energetic

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Scheme 1 Schematic representation of the charge flow and of the
energy levels of a dye-sensitized solar cell.
requirements rule the DSCs kinetics and are needed to allow
for efficient electron injection into the semiconductor manifold
of unoccupied states and subsequent regeneration of the
oxidized dye.7,8
Ru(II)-polypyridyl complexes have been primarily employed
as dye sensitizers.9–13 The remarkable performance of the N3
dye,9 of its doubly protonated analogue (N719)10 and of the
so-called black dye11,12 had a central role in significantly
advancing the DSCs technology, with solar to electric power
efficiencies exceeding 11%.10,13 In the last few years, a flourishing
family of new generation Ru(II)-dyes have been designed and
synthesized to provide higher molar extinction coefficient or
peculiar supramolecular interactions compared to N719, thus
enhancing the DSCs overall stability and/or efficiency.14–18 Fully
organic sensitizers have been developed as metal-free dyes because
of their increased molar extinction coefficient, compared to
Ru(II)-dyes, spectral tunability and reduced environmental
impact.19,20 When employing the most common I /I3 electrolyte,
organic dyes have delivered very high photovoltaic efficiencies,
exceeding 10%.21,22 Finally, functionalized donor–acceptor Zn(II)-
porphyrins have recently emerged as a new class of sensitizers with
high performance potential, due to the extended absorption
spectrum in the red, up to near IR region.23–25
From the semiconductor side, TiO2 is essentially established
as the most performing metal oxide in DSCs, both in the form
of the commonly employed sintered nanoparticles and nano-
tubes,26,27 although research on alternative oxides such as ZnO
and SnO2 is being actively pursued in various laboratories.28–31
The I /I3 redox couple in an organic solvent has been
considered for many years the standard high-performance
redox shuttle in DSCs,10,13 even if the field has very recently been
revolutionized by Co(II)/Co(III) redox couples, which allowed for
demonstration of photovoltaic efficiency close to 13%.25
As mentioned above, the dye sensitizer plays a crucial role in
efficient DSCs. Apart from the discussed spectral and energetic
requirements, a salient feature of efficient dyes is the presence
of suitable functional groups able to strongly bind to the
semiconducting oxide surface. The anchoring group should
indeed coincide, or be very close, to the dye acceptor moiety,
where unoccupied electronic states are spatially confined. This
promotes electronic coupling between the donor levels of the
excited dye and the delocalized acceptor levels of the semiconductor
conduction band, and helps the charge injection process.32–34
15964 Phys. Chem. Chem. Phys., 2012, 14, 15963–15974
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Also the orientation and packing of adsorbed dyes on the
semiconductor surface strictly depends on the binding motif,
possibly affecting the rate and effectiveness of parasitic
recombination reactions.35–37 Finally, the sensitizer’s anchoring
group should provide stable grafting of the dye onto the semi-
conductor surface, thus leading to long-term device stability.38–40
In an effort to design new and more stable and efficient dyes,
it is then clear how fundamental is to disclose the anchoring
mode showed by the most commonly employed sensitizers
and by the newly designed ones. This understanding could
contribute to individuate and optimize many aspects that
affect the DSCs performance, such as the solvent used for
the sensitization process,41,42 the use of co-adsorbent species,43,44
and the electrolyte composition.45,46 From an experimental
standpoint, information on the dye binding modes at the dye-
sensitized semiconductor interface are conventionally accessed by
vibrational spectroscopy [Fourier Transform Infra Red (FT-IR)
spectroscopy and Surface-Enhance Raman Spectroscopy
(SERS)].47,48 These techniques can provide structural details
about adsorption modes as well as information on the relative
orientation shown by surface-adsorbed molecules. Photoelectron
Spectroscopy (PES) has also been successfully employed to
characterize the dye/oxide interface for a series of organic
dyes.49–52 The analysis of the PES spectra yields information
on the molecular and electronic structures at the interface, along
with basic indications of the dye coverage and of the distance of
selected atoms from the surface. More recently, X-ray reflecto-
metry has also been employed to unravel the orientation of dye
molecules adsorbed onto TiO2 surfaces.53
The anchoring mechanism of the largely employed carboxylic
acid group onto the semiconductor surface can be exemplified
referring to the coordination modes of the carboxylate fragment
(COO ) to metal ions; there are basically three possible coordina-
tion modes, i.e. monodentate, chelated and bridged bidentate
(see Scheme 2).54 An empirical rule, derived by Deacon and
Philips,55 correlates the difference between the asymmetric and
symmetric stretching frequencies (Dnas) of COO to the type of
coordination. If the measured Dnas for the adsorbed species is
larger than that measured for the neat salt, a monodentate
coordination is supposed to take place; otherwise if Dnas is similar
or smaller than that of the corresponding salt, a chelated or a
bridged bidentate adsorption mode is inferred.
Identification of the COO– symmetric and asymmetric
vibrational frequencies is usually possible for simple carboxylic
acids, but often realistic dyes show a plethora of overlapping
absorptions in the 1400–1600 cm 1 range, which hinder identifi-
cation and/or assignment of the diagnostic carboxylic modes.
Along with experimental studies, computer simulations
have contributed to a deeper understanding of the electronic
Scheme 2 Graphical representation of the three possible carboxylate
bonding modes: (a) monodentate ester-like, (b) bidentate chelating,
(c) bidentate bridging.
This journal is c the Owner Societies 2012

structure and optical properties of new dyes and to unravel the
intimate dye–semiconductor interactions characterizing the
crucial DSCs heterointerface.56,57 A number of theoretical
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studies dealing with dye adsorption onto TiO2 have been
published, see ref. 58–77 for a list of few representative
examples, starting from the pivotal work by Vittadini et al.
concerning formic acid adsorption on the TiO2 anatase (101)
surface.77 In some cases, calculations showed that for organic
dyes bearing a carboxylic acid as an anchoring group, the
preferred adsorption mode was bidentate bridging, with one
proton transferred to a nearby surface oxygen, while the
monodentate anchoring is usually predicted to be less stable,
although some dependency of the relative stability of these two
anchoring modes on the employed computational methodology
has been outlined.76 As a matter of fact, different stabilities can
be obtained for the e.g. monodentate or bidentate anchoring
modes depending on the employed level of theory.76
To overcome the individual limitations of experimental and
computational techniques, here we propose an integrated
experimental/computational strategy which combines FT-IR
measurements with DFT computer simulations to individuate
the most energetically favorable adsorption mode for a carboxylic
acid probe, followed by calculation of the IR spectra and
structure validation by comparison with experimental data. In
particular, we focus on the adsorption of prototypical dyes,
exploiting the typical diagnostic symmetric and asymmetric
stretching frequencies of the carboxylic group. Considering the
complexity of the most efficient organic dyes, we chose the
structural simplicity of acetic acid as a meaningful model for
realistic organic dyes. Acetic acid, Scheme 2 with R = Me, offers
the advantage of having the most commonly employed carboxylic
acid group of realistic dyes, coupled to a single methyl group,
substantially simplifying the IR spectrum.
In the first part of our paper, we thus investigate, by means
of combined FT-IR spectroscopy and DFT calculations the
possible anchoring modes onto the TiO2 surface showed by
acetic acid. We consider both monodentate and bidentate
binding modes, evaluating their relative energies at various
levels of theory, along with simulating the IR spectra of the
surface adsorbed species. The FT-IR spectra of acetic acid
vapors as well as of its partly deuterated analogues
(CH3COOD) adsorbed on TiO2 have been measured to build
up a correlation between theoretical and experimental data. In
the second part of the manuscript, we compare the results
obtained for the acetic acid probe in relation to previous
results on the adsorption of realistic organic dyes on TiO2
and the implication of the different adsorption modes for
DSCs functioning, including injection/recombination kinetics
and dye–electrolyte interactions.
2. Models, methods and experimental
2.1 Computational details
The carboxylic group is initially considered to be protonated,
as required by the dye solution charge neutrality. The acidic
proton can then be either transferred to the oxide surface
(both in a bidentate and a monodentate anchoring mode) or
be retained on the dye and possibly interact with a surface
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oxygen via hydrogen-bonding. We considered here two different
monodentate binding modes (M1 and M2) and a bridged
bidentate (BB) anchoring, see Fig. 1. In M1 the –OH group
interacts with a surface oxygen which is not directly bound to
the adsorption-involved Ti atom, while in M2 the interaction is
instead established with the adjoining surface oxygen, see
optimized geometries in Fig. 1.
For the description of the TiO2 semiconductor we used two
different approaches, i.e. a cluster and a periodic model. The
cluster model has the advantage of allowing for straight-
forward use of hybrid exchange–correlation functionals and
continuum solvation models. The periodic approach allows
for a more rigorous description of the surface properties,
which is free from finite-size effects. We use two stoichiometric
(TiO2)n clusters, with n = 38 and 82, which have been
demonstrated to reproduce to a good degree of accuracy the
DOS of periodic TiO2 surfaces.67 The two cluster models are used
to gauge the stability of the various adsorption modes, allowing
for the comparison of hybrid and GGA DFT functionals.
We then resort to a (TiO2)32 periodic slab for comparison
purposes. It was recently shown that TiO2 anatase slabs having
thickness similar to our clusters or periodic models, nicely
reproduce the electronic structure of thicker films.69 In all cases,
our TiO2 models expose the majority (101) surfaces.
Cluster calculations. Geometry optimizations were carried
out in the gas phase with the ADF program package78
employing the PBE exchange–correlation functional79 with a
TZVP(DZVP) basis set for Ti (H, C, N, O, S). We have also
taken into account the solvent role as well as the effect of
calculation level on the relative stability of optimized structures by
performing single point calculations in the gas phase and in water
solution using the B3LYP80 and PBE exchange–correlation func-
tionals together with a large 6-311G** basis set, of comparable
quality to that used for geometry optimizations. Solvation effects
were taken into account by means of the C-PCM solvation
model81 as implemented in Gaussian 03 (G03).82
Periodic calculations. Periodic DFT calculations have been
carried out within the generalized gradient approximation
(GGA) using the PBE exchange–correlation functional. The
Car–Parrinello (CP)83 code was used, as implemented in the
Quantum-Espresso package.84 Electron–ion interactions were
described by ultrasoft pseudopotentials with electrons from O,
N and C 2s, 2p; H 1s; and Ti 3s, 3p, 3d, 4s shells explicitly
included in the calculations. Plane-wave basis set cutoffs for the
smooth part of the wave functions and the augmented density
were 25 and 200 Ry, respectively. The dye molecules were
Fig. 1 Optimized geometrical structures of the investigated adsorp-
tion modes of acetic acid onto the TiO2 surface.
Phys. Chem. Chem. Phys., 2012, 14, 15963–15974 15965

adsorbed on one side only of the slab and the vacuum between
the top of the molecules and the adjacent slab was B7 Å.
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2.2 l-FTIR measurements
All the experimental spectra were recorded using a m-FTIR
instrument consisting of a JASCOs FTIR 4100 spectrometer,
equipped with a liquid nitrogen cooled MCT detector coupled
with an IMV-4000 optical microscope. Measurements were
performed in the transmission mode (through a Cassegrain
16X objective) on a micro diamond cell, scanning an energy
range of 6000–600 cm 1 and with a resolution of 4 cm 1. The
spectra were recorded using 5000 scans; background correc-
tion was adopted by means of a spectrum collected on the
empty micro diamond cell. TiO2, CH3COOH and CH3COOD
with purity >99.5% were all purchased from Aldrich and
used as received. Three samples of TiO2 powder were heated
for 1 h at 500 1C. They were then put in contact, at room
temperature and atmospheric pressure, with vapours of pure
AcOH, d4-AcOH and AcOD respectively. After 20 h a m-FTIR
spectrum of each sample was recorded directly on powders.
3. Results and discussion
3.1 Acetic acid on TiO2
Acetic acid (AcOH) vapors were adsorbed at room temperature
and atmospheric pressure (the standard temperature and pressure
conditions in which DSCs are normally assembled) onto a pre-
heated (500 1C) titania (anatase) nanopowder. After 20 h exposure
a m-FT-IR spectrum was recorded, as shown in Fig. 2.
In the recorded AcOH spectrum, the main signals recognizable
in the wavenumber range of COO– adsorption (apart from that
of residual water at 1630 cm 1) are due to the asymmetric and
symmetric carboxylate stretchings as well as to methyl group
modes (see Table 1).
The frequencies experimentally found for AcOH are referred in
the literature85 to be characteristic of bidentate species, with the
bands at 1558 and 1424 cm 1 due to asymmetrical and symmetrical
COO– stretching, respectively. While a large consensus supports
the asymmetrical carboxylate stretching assignment, the signal
at 1430 cm 1 is in some cases86 referred to dCH3 vibrations
Fig. 2 m-FTIR spectra of AcOH (red) and AcOD (blue) vapors
adsorbed onto the TiO2 surface.
15966 Phys. Chem. Chem. Phys., 2012, 14, 15963–15974
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Table 1 Experimental IR frequencies for AcOH and AcOD
Vibrational modes (cm 1) AcOH AcOD
nas COO 1558 1556
nsym COO 1424 1428
dCH3 1335 1335
(1420–1412 cm 1), whereas other authors85 assigned this
wavenumber range (1433–1426 cm 1) to the symmetric carboxylate
stretching.
To possibly elucidate the involvement of the carboxyl
proton in binding to TiO2 (e.g. in M1 or M2 structures) we
repeated the experiment with the monodeuterated acetic acid
CH3COOD (AcOD) as an adsorber. The measured IR spectrum
(Fig. 2) essentially overlaps with the one already seen for acetic
acid. Both the asymmetric and symmetric carboxylate stretchings
remain localized at the same wavenumbers of AcOH and so
does the signal at about 1330 cm 1. Such similarity between
AcOH and AcOD suggests that probably no H (or D)
belonging to acidic OH (or OD) groups is directly interacting
with the surface-adsorbed carboxylic group, as would be the
case for M1 and M2.
For the interacting AcOH/TiO2 system, we then calculated
the optimized geometries and the relative energies of the M1,
M2 and BB adsorption modes, see Fig. 1 and Tables 2 and 3.
Different calculation levels were employed and the effect of
water solvent on the adsorption stability was also taken into
account on the geometries optimized in vacuo. Considering the
PBE/DZ(TZ)VP level used for geometry optimization on the
cluster-adsorbed systems, at least two structures should be
taken into account in terms of relative energy, i.e. BB and M2.
Our data suggest M2 to be the most stable structure, as
previously found for acetic acid adsorption on the (110)
TiO2 surface in ref. 87. On the same (ADF) optimized cluster
geometries, the relative stabilities calculated by the PBE functional
by ADF, CP and G03 programs in vacuo are totally consistent,
despite the different basis sets (Slater, Gaussian and Plane Waves),
showing a similar description of the dye–TiO2 interaction by all
such computational approaches. M2 is predicted to be the most
stable structure, with BB lying very close in energy and M1 much
higher. B3LYP data in vacuo are consistent with the corresponding
PBE data, suggesting a marginal effect of the functional.
Moving to the water solution environment (e B 78) leads
BB to be calculated as the most stable structure both with
B3LYP and PBE, with M2 and M1 lying, respectively,
1.3 (1.4) and 6.5 (4.2) kcal mol 1 higher in energy with the
B3LYP (PBE) functional. Our results are in line with previous
calculations, showing a sizable sensitivity of the most stable
adsorption mode for carboxylic acids and organic dyes onto
the (101) TiO2 surface to the presence of explicit solvent (water
or acetonitrile) molecules.76,88,89
Surprisingly, a totally different stability order is calculated if
one considers the CP optimized geometries, employing a PBC
TiO2 description (PBE/PWs entries in Table 2), which shows
the M1 adsorption mode to be the most stable structure, in line
with the results of Vittadini et al. on the prototype formic acid
system.77 As it can be noticed, slightly different geometries are
calculated for cluster and periodic approaches, see Table 3,
although the differences seem to be quite small (except the OH
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Table 2 Relative stabilities (kcal mol 1) of the various investigated adsorption modes of AcH on TiO2. Both results obtained with a cluster (CL)
and a periodic (PBC) TiO2 model are reported. PBE/DZ(TZ)VP data were obtained by the ADF code and PBE/PWs by the CP code; PBE/
6-311G*** and B3LYP/6-311G** have been obtained by the Gaussian code
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Geometry optimization Energy evaluation BB M1 M2

CL/ADF PBE/DZ(TZ)VP Vac 0.0 +10.1 4.1
PBE/DZ(TZ)VP PBE/PWs Vac 0.0 +8.9 4.1
PBE/6-311G** Vac 0.0 +7.3 1.6
Solv 0.0 +4.2 +1.4
B3LYP/6-311G** Vac 0.0 +10.8 0.9
Solv 0.0 +6.5 +1.3
PBC/CP PBE/PWs Vac 0.0 12.1 10.8
PBE/PWs

Table 3 Main optimized geometrical parameters (Å) of the investi- three intense signals at 1543, 1432 and 1351 cm 1, to be compared
gated systems on the TiO2 cluster by the ADF program (CL-ADF) to experimental signatures at 1558, 1435 and 1340 cm 1, respec-
and the structure optimized by the CP program in Periodic Boundary
Conditions (PBC-CP). See Fig. 1 for labels
tively. The assignment of the 1543 cm 1 feature to the asymmetric
COO– stretching is straightforward, while the two modes
Structure Geometry Ti1–O1 (Ti1/2–O2) C–O1 C–O2 O1–H H–O3/4 calculated at 1432 and 1351 cm 1 result from the admixture
BB CL-ADF 2.06 (2.16) 1.29 1.26 — 0.98 of the symmetric COO– stretching and of the dCH3 mode.
PBC-CP 2.07 (2.10) 1.30 1.27 — 0.97 Thus a clear assignment of these two features cannot be made,
M1 CL-ADF 2.15 1.25 1.31 1.04 1.55 also considering their inverted intensity pattern compared
PBC-CP 2.15 1.24 1.32 1.02 1.63
M2 CL-ADF 2.06 1.29 1.27 1.31 1.13 to the experiment. We note, however, that the separation
PBC-CP 2.18 1.26 1.32 1.04 1.51

distances in M2) to explain the substantial effect on the

stability order. We have no further data to comment on this
marked difference but, based on the similarity of the energetics
by CP, ADF and G03 at fixed geometry, we speculate that this
effect might be due to a different description of proton
interactions with the TiO2 surface by the CP method rather
than by a cluster vs. periodic TiO2 difference.76
This seems to be confirmed by the different M2 structures
calculated by the ADF and the CP code, whereby ADF
predicts the proton to be transferred to the surface while CP
retains it on the dye (notice the different O1–H and H–O3/4
distances in Table 3).
Considering the large variability of computed stabilities
with the employed geometry optimization method and since
based on the relative energies alone it was not possible to
clearly discriminate among the possible AcOH adsorption
modes (the inherent accuracy of most DFT methods is com-
parable to some of the calculated energy differences), for each
of the considered structures, we calculated the IR vibrational
frequencies at the same PBE/DZ(TZ)VP level of theory used
for geometry optimization. A summary of the main IR peaks
and their assignment is reported in Table 4, while in Fig. 3 we
report a comparison between the experimental and calculated
spectra for BB, M1 and M2.
Looking at the calculated frequencies, the BB adsorption
mode well reproduces the three main spectral features, showing

Table 4 Calculated (unscaled) and experimental IR frequencies for

AcOH adsorbed onto TiO2

Frequencies BB M1 M2 Exp.
Fig. 3 Comparison between the experimental (red) and calculated
nas COO 1543 1614 1748 1558 (blue) IR spectra of AcOH on TiO2 for the BB, M1 and M2 adsorption
nsym COO 1432 1425 1377 1424 modes. The calculated spectra have been rescaled so that the high
dCH3 1351 1335 1416 1335 energy features have the same intensity as the experimental band at
D(nas nsym) 111 189 371 134
1558 cm 1.

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between the asymmetric and symmetric COO stretching found

experimentally is 138 cm 1, reasonably comparing with the
111 cm 1 difference found between the asymmetric stretching
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and the band of mixed character calculated at 1432 cm 1.

Based on the comparison between the experimental and
simulated IR spectra, Fig. 3, the presence of the monodentate
species M1 and M2 (either dissociated or undissociated) can be
ruled out, due to the significant discrepancies found in their IR
spectra compared to the experimental data. The experimental
spectra show no trace of peaks of the characteristic carbonyl
stretching belonging to the M2 adsorption mode (B1760 cm 1).
For M1 the feature at B1550 cm 1 is missing and a new feature
at ca. 1250 cm 1 appears, which is not found experimentally. So
even if the carbonyl stretching (1614 cm 1) was overlapping with Fig. 4 Molecular structures of L0, rh-L0, D5L2A1 and D5L2A3.
the residual water peak (1630 cm 1) this mode can be excluded.
It has to be noted that frequency assignment in these two cases is injected electrons into the TiO2 CB. Low electron lifetime
further complicated by the admixture of several modes, including values, due to high recombination rates, therefore determine
OH modes, so that for M1 and M2 the mode assignments low Voc values.
in Table 2 should be taken with some care, although the We investigated the possible anchoring modes onto the TiO2
listed frequencies are those displaying highest intensity in the surface of the two representative L0 and rh-L0 organic
investigated energy range. dyes,50,93 considering both monodentate and bidentate binding.
Summarizing, our combined experimental and computa- The optimized geometries are reported in Fig. 5, while relative
tional modeling of acetic acid adsorption on TiO2 points at energies of BB, M1 and M2 adsorption modes are reported in
the BB structure as the most likely AcOH adsorption mode, Table 5. The data in Table 5 follow the trend outlined above for
consistent with the calculated energetics in solution. acetic acid adsorption, whereby at the PBE/DZ(TZ)VP/vac
level of theory, M2 is slightly more stable, by 1.5 kcal mol 1,
3.2 Organic dyes on TiO2: electron injection and than the bidentate structure, BB, while the M1 adsorption mode
recombination with the oxidized dye seems to be strongly destabilized (ca. +10 kcal mol 1) with
respect to BB. Single point calculations on the optimized
As mentioned above, investigating the possible anchoring structures in water solution, however, always indicate the
modes of dye sensitizers to the TiO2 surface is of crucial bidentate configuration as the preferred one, giving the stability
importance as the bonding type and the extent of electronic ordering BB > M2 > M1. Although all the three investigated
coupling between the dye excited state and the semiconductor structures would be compatible with the PES data for the
unoccupied states can directly influence the cell performances. related D5L2A1 dye,49 which indicates that the molecule lies
An emblematic case is represented by the D5L2A190,91 and with the donor (TPA) group pointing out from the surface and
D5L2A350 dyes, which we recently investigated.37 The two the acceptor CN group close to the TiO2, our calculated
dyes only differ in the anchoring unit, namely a conjugated stabilities are suggestive of a bidentate coordination mode for
cyanoacrylic acid in the former and non-conjugated rhodanine-3-
acetic acid in the latter (see molecular structures in Fig. 4). The
loss of electron conjugation between the donor-linker moiety and
the anchoring –COOH group passing from the cyanoacrylic to
the rhodanine-3-acetic acid was related to the drastic drop in the
photovoltaic efficiency of D5L2A3 (B2%)50 compared to
D5L2A1 (B6%).90,91 Wiberg et al.92 reported that the two
different sensitizers showed unitary electron injection efficiency
but substantially different rates of charge recombination between
the photo-injected electrons and the oxidized dye, with estimated
losses of 80% and 50% of injected electrons for D5L2A3 and
D5L2A1, respectively, within 1.4 ns.92
Recombination between TiO2-injected electrons and the
oxidized dye or the electrolyte directly influences the charge
density into the semiconductor and thus the open-circuit
voltage of the cell. By definition, at open circuit the flux of
the injected electrons equals that of the recombining electrons,
fixing the Fermi level and thus the output voltage of the
device. The Fermi level is determined by the CB edge potential
and by the electron density into the TiO2, n, which is in turn
proportional to the rate of the electron injection and to the Fig. 5 Optimized structures of the L0 (upper panel) and rh-L0 (lower
electron lifetime, t, namely the average time spent by the panel) dyes on TiO2.

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 View Article Online

Table 5 Relative energies (kcal mol 1) of BB, M1 and M2 adsorption
modes of L0 and rh-L0 on (TiO2)38. From ref. 37. PBE results in water
(Solv* entry) solution were obtained with the 6-311G* basis set
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(approximated here by the dye LUMO) and the TiO2 manifold
of unoccupied states.61 We thus calculated the partial density
of dye unoccupied states (PDOS) for the interacting BB and

Energy evaluation BB M1 M2 M1 adsorption modes of the L0 dye. We recall that according

to the Newns–Anderson model, the entity of the dye LUMO
L0 dye
PBE/DZ(TZ)VP Vac 0.0 +10.9 1.5 broadening when interacting with the semiconductor is an
PBE/6-311G** Vac 0.0 +10.8 +2.6 estimate of the intervening electronic coupling.75,97 The results,
Solv* 0.0 +8.4 +7.4 reported in Fig. 6, clearly show a larger broadening (and
B3LYP/6-311G** Vac 0.0 +14.9 +3.6
Solv 0.0 +10.9 +7.7
asymmetry) for the L0 dye LUMO PDOS adsorbed in the BB
rh-L0 dye than in the M1 mode.
PBE/DZ(TZ)VP Vac 0.0 +7.1 1.9 The dye LUMO broadening, estimated as the full width at
PBE/6-311G** Vac 0.0 +6.7 5.6 half maximum of the Lorentzian distributions75 reported at
Solv* 0.0 +0.4 +5.0
B3LYP/6-311G** Vac 0.0 +8.1 +2.9 the bottom of Fig. 6, is ca. 0.05 eV larger for the BB than for the
Solv 0.0 +0.4 +7.7 M1 adsorption mode, reflecting the stronger dye–semiconductor
interaction characteristic of the BB structure.70

L0 and analogous dyes bearing a cyanoacrylic anchoring

group.65
Similar remarks can be made for rh-L0: at the PBE/
DZ(TZ)VP/vac level of optimization, the bidentate structure
is the most stable adsorption mode. Although small energy
differences are calculated at some levels of theory, these data
indicate on overall that also for this type of dyes the bidentate
coordination is favored, and therefore we conclude that rh-L0
as well as the related D149 and D10236 dyes lie almost flat with
an inclination of about 45 degrees with respect to the TiO2
plane, as also found in previous works.94,95
Differences in the recombination kinetics between TiO2-
injected electrons and the dye cations are strongly dependent,
upon other factors, from the spatial separation of the charge
hole localized on the oxidized dye, which can be assimilated to
the HOMO of the neutral dye, and the TiO2 surface. We recall
indeed that the electronic coupling between the donor (TiO2)
and acceptor (oxidized dye) states can be represented in terms
of an exponential function of the spatial separation r between
the donor and the acceptor. Considering the calculated different
orientation of the L0 and rh-L0 dyes with respect to the TiO2
surface, determined by the different anchoring unit, and recalling
that the dye HOMOs are mainly localized on the donor groups,
a different spatial separation between the dye donor groups and
the TiO2 surfaces can be outlined for L0 and rh-L0. Looking at
the more stable BB structures reported in Fig. 5, the dye donor
group/TiO2 distance can be roughly estimated to be 8–10 Å for
L0 and 6–8 Å for the rh-L0 dye. By extrapolating these data for
the longer D5L2A1 and D5L2A3 dyes examined by Wiberg
et al.,92 we calculate a dye donor group/TiO2 separation of
14–16 Å and 9–11 Å for the two dyes, respectively. These data
are consistent with the measured differences in the recombina-
tion rates, whereby a closer proximity of the charge hole
localized on the dye to the semiconductor surface would lead
to higher recombination rates. Our model is also in agreement
with recent data by Long et al.,96 which showed an increased
recombination rate between injected electrons and the oxidized
sensitizer for the D205 dye, bearing the rhodanine-3-acetic acid,
compared to the C218 dye, having a cyanoacrylic acid group.
It is also interesting to exploit our data for the L0 dye to
check whether the specific dye adsorption mode, i.e. bridged
bidentate vs. monodentate (e.g. BB vs. M1) can induce differ-
ences in the electronic coupling between the dye excited state
3.3 Effect of the dye adsorption mode: recombination with the
electrolyte
Recombination between TiO2-injected electrons and oxidized
species in the electrolyte is a main loss channel in DSCs,
leading to reduced Voc values.98 Despite the accepted knowledge
that the adsorbed dyes act as an isolating layer, keeping the
reduced electrolyte far from the direct contact with the oxide
surface,99–101 some authors102–106 suggested that particular atoms
or chemical groups can also provide binding sites for I2 (I3 ),
increasing its concentration close to the TiO2 surface and thus
accelerating the recombination process. Evidence of stable
Ru-complex–I2 adducts has been reported by Tuikka
et al.,106 which isolated N3–I2 crystals. O’Regan et al.102 found
that the replacement of two oxygen ligand atoms with two
sulfur atoms in a Ru(II)-dye caused a 2-fold increase in the
recombination rate. This was ascribed to the stronger tendency
of ethylthioether compared to ethylether to bind I2. An
extensive investigation on the effects of dye molecular structure
and electrolyte composition on the recombination dynamics has
been reported by Miyashita et al.,103 who examined the photo-
voltaic performances of a series of organic- and Ru(II)-dyes.
These authors consistently found lower electron lifetimes for the
metal-free based DSCs compared to those employing Ru dyes.
The lower Voc values were interpreted as arising from an
increased I3 concentration in the proximity of the oxide surface
yielding higher recombination rates. Interestingly, among
the organic sensitizers, those having alkyl chains and larger
molecular size showed longer lifetimes, possibly due to the
formation of a compact aggregate layer able to protect the
TiO2 surface from the I3 approach.
Various computational investigations on dye–electrolyte
interactions were recently reported,107–113 including a time-
domain ab initio study of charge relaxation and recombination
in dye-sensitized TiO2 by Prezhdo and coworkers.114 To
contribute to the understanding of dye–electrolyte inter-
actions, we recently investigated the adsorption mode of various
prototype organic dyes on TiO2, along with I2 binding to the
various electron-donating sites in the molecule. This was done
for a representative group of sensitizers, selected among those
examined by Miyashita et al.103 Here we discuss results for two
coumarin dyes (NKX2587 and NKX2697), which differ by the
number of thiophene rings in the bridge (one and three,

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Fig. 6 Top: partial density of states (PDOS) calculated for the L0
dye LUMO anchored to TiO2 in a BB (blue) and M1 (red)
adsorption modes. Bottom: Lorentzian broadening of the dye LUMO
PDOS.
respectively), see Fig. 7. In a recent work,104 we have shown that
in the case of two organic dyes containing, respectively, one and
two ethylenedioxythiophene (EDOT) moieties, the O–I2 inter-
action is slightly stronger than the S–I2 one and that, in any
case, both sites might effectively bind iodine, thus accounting
for the accelerated recombination rate measured for the dye
bearing two EDOT groups. This was recently confirmed for the
dyes investigated here, indicating the oxygen atoms as the
preferred binding sites for I2. Moreover carbonylic or car-
boxylic oxygens can also bind positive ions present in the
electrolyte solution, such as Li+, thus favoring the electrostatic
interaction between triiodide anions and the dye. The formation
of dye–I2 or dye–I3 complexes in proximity of the TiO2 surface
can play a crucial role in determining the short lifetimes
measured for certain organic dyes containing oxygen atoms in
the donor and bridge units.104
15970 Phys. Chem. Chem. Phys., 2012, 14, 15963–15974
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Fig. 7 Optimized structures of NKX2587 and NKX2697 adducts
with I2.
Having established the affinity of sulfur, oxygen and nitrogen
atoms in the standalone dyes to bind I2, we moved to model the
dye/semiconductor interface, with relation to the anchoring
modes of the dyes and the effective distances of the iodine
from the TiO2 surface. We thus carried out a Car–Parrinello
molecular dynamics simulation on the NKX2587 dye adsorbed
onto the (TiO2)82 cluster in vacuo, starting with the preferred
dissociative bridged bidentate adsorption mode and thermalizing
the system at 350 K. We notice that the presence of explicit
solvation could possibly alter the adsorbed dye dynamics.59 Also
the rather short simulation time (4.5 ps) is not sufficient to
capture possible slow dye rearrangements but we believe this
time slice to be sufficient to locally sample the potential energy
surface around the calculated minimum energy structure. Our
results showed that the BB adsorption mode was maintained
throughout the simulation time, and that the dye remained on
average perpendicular to the TiO2 surface, without significant
geometrical distortions with respect to the optimized adsorption
geometry at 0 K. Hence no significant change in the average
distance of the I2 binding sites from the surface was observed
compared to the optimized geometry. As shown in Fig. 8, the
variation in the distance of the carbonylic oxygen from the
surface during simulation time of 4.5 ps is about 1 Å, going
from a minimum value of 9.7 to a maximum of 10.8 Å, with an
average value of 10.4 Å.
We also optimized the structure of the O–I2 adduct of TiO2-
adsorbed NKX2587 and, as displayed in Fig. 9, this structure
shows negligible geometrical rearrangements of the O–I2
configuration due to the presence of the substrate: the O–I
distance is predicted to be 2.85 Å compared to the value of
2.84 Å reported in Table 1, the C–I–O angle increases from
1201 to ca. 1501 and the distance from the surface is about
10 Å, as predicted by the Car–Parrinello dynamics.
Therefore, a reasonable approximation of the average distance
of the bonded I2 from the surface oxide can be obtained by
taking the distances from the TiO2 cluster of the various I2
binding sites in the dye@TiO2 optimized structures at 0 K
(Fig. 9). The distance of the I2 possibly bonded by the CN group
is about 5 Å, while the carbonylic oxygens, which are the
predominant binding sites, lie at ca. 10 and 16 Å from the titania
in NKX2587@TiO2 and NKX2696@TiO2 respectively. The
sulfur atoms in NKX2697 are at about 8, 11 and 14 Å from
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Fig. 8 Distance (in Å) of the carbonylic oxygen from the TiO2
surface against the simulation time for the NKX2587@(TiO2)38
system. The average distance (in blue) and the maximum and mini-
mum values (in red) are also reported.
Fig. 9 Optimized molecular structures of the O–I2 adduct of
NKX2587 and NKX2697 adsorbed onto the (TiO2)38 cluster.
the TiO2. The data by Miyashita et al.103 showed that the
NKX2587 sensitized cells had shorter lifetime than those based
on NKX2697. The increase in the distance of the preferred
carbonylic oxygen from the titania going from NKX2587@TiO2
(E10 Å) to NKX2697 (E16 Å) and hence the increased I2
concentration in proximity of the oxide surface might account
for the differences in the lifetime values measured in ref. 103 for
NKX2587-sensitized solar cells compared to those employing the
longer NKX2697 homologous.
4. Conclusions
We have presented a survey of new and recently published
results obtained in the first principles computer simulation of
dye adsorption onto TiO2 surfaces, as models of the hetero-
interface crucial to the functioning of dye-sensitized solar cells
(DSCs). First-principles simulations have contributed to a deeper
understanding of the electronic structure and optical properties
of new dyes and to unravel the intimate dye/semiconductor
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View Article Online
interactions characterizing the DSCs functioning, possibly
contributing to the further development of this important
class of photovoltaic devices.
The dye sensitizer plays a crucial role in efficient DSCs; a
stringent dye characteristic is the presence of suitable anchoring
groups which should provide effective dye adsorption onto the
semiconducting oxide surface. The dye anchoring group promotes
electronic coupling between the donor levels of the excited dye
and the delocalized acceptor levels of the semiconductor conduc-
tion band, and mediates charge injection. Also the orientation
and packing of adsorbed dyes on the semiconductor surface
strictly depends on the binding motif, possibly affecting the rate
and effectiveness of parasitic recombination reactions. Finally, the
sensitizer’s anchoring group should provide stable grafting of the
dye onto the semiconductor surface, thus leading to long-term
device stability. Understanding the dye adsorption mode onto the
semiconductor surfaces could thus contribute to individuate and
optimize many aspects that affect the DSCs performance.
A number of theoretical studies dealing with the adsorption
mode of the most commonly employed carboxylic acid groups
onto TiO2 have been reported to provide such understanding.
In some cases, the preferred adsorption mode was bidentate
bridging, with one proton transferred to a nearby surface
oxygen, while in other cases a monodentate (either dissociative
or undissociated) anchoring was predicted to be favored. Some
dependency of the relative stability of these two anchoring modes
on the employed computational method and the model was
however outlined, which did not allow a conclusive assignment
of the biding motif exhibited by the most performing dyes.
From a different perspective, experimental techniques usually
employed to probe dye surface adsorption (FT-IR, SERS, PES
and X-rays scattering) are often not sufficient to unravel the
atomistic details of the dye–semiconductor binding. As an
example, FT-IR spectroscopy, which is largely employed to
probe the adsorption mode of carboxylic acids on metal oxide
surfaces, usually has to deal with an envelop of overlapping
bands in the diagnostic region of the asymmetric and symmetric
carboxylic stretchings which does not allow a clear distinction
of such bands, thus of the dye adsorption mode.
To overcome the individual limitations of experimental and
computational techniques, here we propose an integrated
experimental/computational strategy which combines FT-IR
measurements with DFT first principles simulations to individuate
the most energetically favorable adsorption mode for a carboxylic
acid probe, followed by calculation of the IR spectra and structure
validation by comparison with experimental data. Considering
the complexity of the most efficient organic dyes, we chose the
structural simplicity of acetic acid as a meaningful model for
realistic organic dyes.
We considered a dissociative bridged bidentate and two
monodentate adsorption modes (either dissociative or non-
dissociative), and calculated their relative stability with
various models and at various levels of theory. As anticipated,
we found a sizable variability in the relative stability of the
three adsorption modes with the model/method, which did not
alone allow us to trace clear conclusions concerning the favored
adsorption mode. We thus measured the FT-IR spectra of AcOH
adsorbed on TiO2 nano-powders and calculated the vibrational
IR frequencies for the three representative adsorption modes.
Phys. Chem. Chem. Phys., 2012, 14, 15963–15974 15971

By comparing the two data sets we identified the bridged
bidentate adsorption mode as the one which most closely
matches the FT-IR frequency pattern, also being calculated
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(although by a few kcal mol 1 only) as the most stable
adsorption mode by cluster calculations in solution.
We then compared the results of the present investigation to
previous data from our lab, obtained for realistic dye sensiti-
zers. Interestingly, the bridged bidentate adsorption mode was
found to be the most stable binding motif also for organic dyes
bearing cyanoacrylic anchoring groups, while in the case of a
rhodanine-3-acetic acid anchoring groups, an undissociated
monodentate adsorption mode was found to be of almost
comparable stability. The two different cyanoacrylic and
rhodanine-3-acetic acid anchoring groups were found to induce
a totally different dye packing on the TiO2 surface, with dye
molecules standing up or lying almost flat compared to the TiO2
surface, respectively. These structural differences were related to
the different electron injection/recombination with oxidized dye
properties which were experimentally assessed for the two
classes of dyes. Furthermore, considering the cyanoacrylic
anchoring mode, a stronger coupling between the dye LUMO
and the TiO2 manifold of unoccupied states was calculated for
the bridged bidentate than for the monodentate adsorption
mode, suggesting a possibly faster electron injection from the
dyes anchored in the bridged bidentate mode.
To contribute to the understanding of dye–electrolyte inter-
actions, we investigated the adsorption mode of various prototype
organic dyes on TiO2, along with I2 binding to the various electron-
donating sites in the molecule. We found that oxygen-containing
groups in the dyes (either EDOT or carbonyl groups) may
constitute sites for I2 binding, thus accounting for the accelerated
recombination rate measured for the dye bearing such groups. By
performing combined Car–Parrinello molecular dynamics and
structural geometry optimizations for two coumarin dyes adsorbed
onto TiO2, differing by the length of the p-bridge separating the
donor and acceptor moieties, we were able to relate the decreasing
distance of the preferred carbonylic oxygen from the titania to an
increased I2 concentration in proximity of the oxide surface, which
might account for the differences in the electron lifetime values
measured for DSCs based on the shorter dye.
In conclusion, we believe that computer simulations based
on a first principles description of dye adsorption modes onto
semiconductor oxides, lying at the heart of DSCs, represent a
powerful tool for unravelling the atomistic feature of the
crucial DSCs interface. This in turn may allow for a detailed
understanding of the factors affecting the efficiency of the basic
charge generations/recombination processes, possibly leading
to improved DSCs photovoltaic performances.
The interplay between theory/simulation and experiments
appears key, in our view, to further DSCs progress, both
concerning the design of new dye sensitizers and the under-
standing of the sensitizers’ interaction with the semiconductor
and with the solution environment and/or the electrolyte upon
being adsorbed onto the semiconductor.
Acknowledgements
We thank FP7-NMP-2009, project 246124 ‘‘SANS’’, FP7-
ENERGY-2010, project 261820 ‘‘ESCORT’’, Istituto Italiano
15972 Phys. Chem. Chem. Phys., 2012, 14, 15963–15974
View Article Online
di Tecnologia, Project Seed 2009 ‘‘HELYOS’’, and Consiglio
Nazionale delle Ricerche, Project ‘‘EFOR’’ for financial support.
The authors thank Paolo Salvatori for helpful discussions.
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