Record Review

DOI: 10.1002/tcr.201500007

THE
CHEMICAL
Efficiency Records in Mesoscopic
RECORD Dye-Sensitized Solar Cells
Josep Albero, Pedro Atienzar, Avelino Corma, and Hermenegildo Garcia*[a]
[a]
Instituto Universitario de Tecnologa Qumica (CSIC-UPV), Univ. Politecnica de Valencia,
Avda. de los Narajos s/n, Valencia 46022 (Spain), E-mail: hgarcia@qim.upv.es

Received: January 21, 2015

Published online: July 17, 2015

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ABSTRACT: The aim of the present review article is to show the progress achieved in the
efficiency of dye-sensitized solar cells (DSSCs) by evolution in the structure and composition of
the dye. After an initial brief description of DSSCs and the operating mechanism the major part of
the present article is organized according to the type of dye, trying to show the logic in the
variation of the dye structure in order to achieve strong binding on the surface of the layer of
nanoparticulate TiO2, efficient interfacial electron injection between the excited dye and the
semiconductor, and minimization of the unwanted dark current processes. Besides metal
complexes, including polypyridyls and nitrogenated macro rings, organic dyes and inorganic light
harvesters such as quantum dots and perovskites have also been included in the review. The last
section summarizes the current state of the art and provides an overview on future developments in
the field.

Keywords: dyes/pigments photovoltaic devices semiconductors sensitizers solar cells

Josep Albero was born in 1980. He
obtained his Chemical Engineering
degree from the Jaume I University of
Castellon (Spain) in 2005. Later he
obtained his M.Sc. degree from Rovira I
Virgili University in 2009. He worked on
the synthesis and characterization of
nanocrystalline semiconductor quantum dots for photovol-
taic applications during his Ph.D. in the group of E. Palo-
mares at ICIQ. Afterwards he joined the H. Garca group at
ITQ as a postdoctoral fellow. His research interests are the
charge transfer reactions in nanostructured materials and
their applications in renewable energies.
Pedro Atienzar obtained his Ph.D.
(2007) from the Instituto de Tecnologia
Qumica (UPV-CSIC) at the Universi-
dad Politecnica de Valencia under the
supervision of Prof. Hermenegildo
Garca. Afterwards he joined the group of
Prof. Jenny Nelson in the Department of
Physics at Imperial College London, where he worked as a
postdoctoral fellow (20072009) in the field of hybrid and
polymeric photovoltaic devices. Currently he holds a
Ramon y Cajal research contract at the Instituto de
Tecnologa Qumica. His major research interest is the devel-
opment of photoactive materials and devices applied to
renewable energies. He has co-authored over 50 peer-
reviewed papers.
Avelino Corma was born in Moncofar
(Spain) in 1951. He studied chemistry at
the Universidad de Valencia (1967
1973) and received his Ph.D. from the
Universidad Complutense de Madrid in
1976. He was a postdoctoral worker in
the Department of Chemical Engineer-
ing at Queens University (Canada, 19771979). He has
been Director of the Instituto de Tecnologa Qumica (UPV-
CSIC) at the Universidad Politecnica de Valencia. His cur-
rent research field is catalysis, covering aspects of synthesis,
characterization and reactivity in acidbase and redox cataly-
sis. Avelino Corma is co-author of more than 700 articles
and 100 patents on these subjects. In 2014 he was awarded
with the Principe de Asturias Prize of Science.
Hermenegildo Garca is Full Professor at
the Instituto de Tecnologa Qumica of
the Technical University of Valencia, a
joint center of the Technical University of
Valencia and the Spanish National
Research Council, and Honorary
Adjunct Professor at the Center of Excel-
lence in Advanced Materials Research of King Abdulaziz
University. He made a postdoctoral stay at the University of
Reading with Prof. Andrew Gilbert and several sabbatical
leaves in the group of Prof. J. C. Scaiano at the University of
Ottawa. Prof. Garca has been active in the field of heteroge-
neous catalysis, working with porous catalysts and nanopar-
ticles, and has published over 550 papers and filed over 25
patents. Prof. Garca holds a Doctor Honoris Causa from the
University of Bucharest and was the recipient of the 2011
Janssen-Cilag Award given by the Spanish Royal Society of
Chemistry and the 2008 Alpha Gold Award of the Spanish
Society of Glass and Ceramics.

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1. Introduction
The increasing energy demand and the concern about green-
house gas emissions have motivated during the last decades an
increasing interest in the production and storage of efficient,
renewable and cheap energy and fuels.[1] Solar energy is the
most promising renewable primary energy source, with several
ways in which sunlight can be used, such as artificial photosyn-
thesis[2] and light-to-electric energy conversion.[3]
Photovoltaic devices based on highly crystalline silicon are
nowadays close to achieving the maximum theoretical effi-
ciency limit (31%) determined by Shockley and Queisser[4]
and they are at present dominating the commercial market.[5] Scheme 1. Components of a DSSC. FTO: transparent conductive working
Nevertheless, their elevated production cost, mainly due to the and counter electrodes. TiO2: n-type semiconductor in the working electrode.
Platinum layer: catalyst in the counter electrode. Dye: light harvester. Electro-
high and prolonged temperatures required to achieve large and lyte: hole-transporter material.
ultrapure silicon single crystals, has promoted the search for
alternative cheaper materials for use in photovoltaics.
A second solar cell generation based on thin-film (1 mm breakthrough (7%) in the field using mesoporous films of
thickness) semiconductor materials such as cadmium telluride TiO2 nanoparticles with controlled size.[13] Since then, all
(CdTe), copper indium gallium selenide (CIGS) or amor- efforts have been focused on achieving more efficient and
phous silicon appeared to overcome the high cost of silicon long-term stable DSSCs through the rational design of sensi-
solar panels.[6] These semiconductor thin films allow the use of tizers and electrolytes.
less material, as well as decreasing manufacturing process costs. In this review, we report DSSC efficiency evolution since
Although the fabrication costs were considerably reduced, the the seminal paper of ORegan and Gratzel, paying attention to
efficiencies of such solar cells (for single junctions) were lower the most relevant items that have contributed to efficiency pro-
than crystalline silicon. Moreover, some concerns were raised gress. The aim is not to cover all the existing literature, but to
regarding the use of hazardous toxic materials in the solar cells. offer an overview of how the efficiency has been increased by
The third generation of photovoltaic cells is being inten- sensitizer design. Progress in the long-term stability of DSSCs
sively researched from a variety of materials and architectures through the use of nonliquid electrolytes will also be com-
with the aim of reducing production costs as well as exceeding mented upon.
the Shockley and Queisser efficiency limit.[7] Mesoscopic dye-
sensitized solar cells (DSSCs) are currently one of the most effi-
cient third-generation solar cells. Most of the materials 2. Dye-Sensitized Solar Cells
employed in DSSCs are abundant and low cost, and the devi- DSSCs are considered to be low-cost photovoltaic cells because
ces can be easily fabricated using conventional roll-to-roll tech- of their simple preparation and the inexpensive and abundant
niques, even on flexible substrates. They are semitransparent, materials employed in their fabrication. They are also called
which offers a wide variety of applications, and it has further-
photoelectrochemical cells[14] because, in contrast to other
more been demonstrated that DSSCs can operate even under
photovoltaic devices, the photoinduced charge generation and
diffuse light, in contrast to the other semiconductor-based
charge transport processes take place in different materials. In
photovoltaic devices.[8] All of these properties and the exten-
the following section we will describe the typical materials
sive development of mesoscopic DSSCs have led to this tech-
employed in their fabrication as well as the device architecture,
nology coming very close to commercial application for low-
operating principle and the main factors that limit the device
consuming electronics,[9] building-integrated photovol-
efficiency.
taics,[10] or even small modules.[11]
The development of DSSCs started in the last decades of 2.1. Materials
the twentieth century when semiconducting metal oxide films
with a very smooth surface were sensitized with dye mono- DSSCs may be prepared from a variety of materials, but we
layers, inspired by the work from Desilvestro et al.[12] The will focus on the ones that provide better performance in com-
reduced surface area of the inorganic films, mainly, as well as plete devices. As shown in Scheme 1, DSSCs are basically com-
other factors such as the use of unsuitable aqueous electrolytes posed of a dye-sensitized metal oxide layer sandwiched
and light harvesters, led to power conversion efficiencies lower between two electrodes, of which at least one is transparent,
than 1%.[13] In 1991, ORegan and Gratzel made an efficiency that constitute the working and counter electrode, with an

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electrolyte filling all empty spaces between the working and
counter electrodes.
The transparent conductive electrodes (TCEs) usually
employed are based on a nicrometric film of doped oxide semi-
conductors (In2O3, SnO2 or ZnO) supported on glass. Suita-
ble TCEs for DSSCs must maintain electrical and optical
properties upon heating up to temperatures close to 5008C, at
which metal oxide layers are sintered. The most utilized TCE
in DSSCs is SnO2:F (FTO) and others include In2O3:Sn,
SnO2:Sb and ZnO:Al, mainly due to their thermal resistance,
high conductivity (Rs<10 X/sq) and transmission properties
(optical transparency >80% for visible light).[15] Another
promising alternative to doped metal oxides is graphene-based
electrodes, due to their large specific area and electronic prop-
erties.[15,16] DSSCs have also been built on flexible sub-
strates.[17] Commercial applications have actually already been
reported using a metallic Ti foil as a flexible TCE. Other sub-
strates based on stainless steel or ZnO nanowires have also
been explored.[17]
The working electrode is completed by adding an n-type
semiconductor layer on top of the FTO, although p-type semi-
conductors have been explored too.[18] TiO2 has been the
most widely used metal oxide, although other semiconductors
have also been tested (ZnO, SnO2). Despite the fact that ZnO
and SnO2 show higher carrier mobilities than TiO2, the ana-
tase phase of this semiconductor has been demonstrated to
provide the best efficiencies in such photovoltaic devices.[19] It
has been determined that the amount and energy of trap states
in pure anatase TiO2 nanocrystals provide efficient electron
transport to the metal contact.[20] Moreover, the nanocrystal-
line structure of TiO2 film has been found crucial for the effi-
cient performance of DSSCs. A wide range of nanostructures
have been tested with the aim of improving the charge collec-
tion, such as nanotubes,[21] nanorods,[22] and inverse opals.[23]
However, anatase nanocrystalline particles with an average size
of 1520 nm have been demonstrated to be among the most
convenient for efficient device operation since they easily form
mesoscopic films which optimize the dye load per unit area,
allow electrolyte infiltration through their pores, and slow
down recombination events.[13,24]
The nanoparticle layer may be completed with larger
TiO2 nanoparticles (200400 nm) deposited on top of the
small ones in order to reflect back unharvested light. This scat-
ter layer has been reported to increase the device current den-
sity (JOC  34 mA/cm2) because of the reabsorption of lost
photons, especially in the near-infrared part of the
spectrum.[25]
The sensitizer has probably been the most investigated
material in DSSCs in the last decades. The possibility to opti-
mize cell light harvesting just by changing one single func-
tional group in a molecule opened many lines of research for
synthetic chemists trying to design panchromatic dyes with
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absorptions able to overlap the solar spectrum.[26] Dyes must
satisfy some conditions besides wide absorption range. For
instance, they must contain anchoring groups capable to attach
and inject electrons to the TiO2 surface, they must possess cor-
rect energy levels (HOMOLUMO) matching with the redox
potential of the TiO2 conduction band, and they must also be
stable in contact with the different species forming the electro-
lyte under continuous light irradiation. The dyes may be classi-
fied essentially into organometallic or metal-free organic
molecules. The most reported organometallic molecules are
ruthenium complexes,[27] although porphyrins[28] and phtha-
locyanines[29] with various metal centers have also been fre-
quently used. The metal-free dyes cover a wide variety of
molecules such as indolines, coumarins, squarines, free-base
porphyrins and phthalocyanines, perylenes, and donorp-
bridgeacceptor complexes.[26,30] Nonetheless, as we will dis-
cuss later, other sensitizers based on inorganic materials have
been explored as well.[31]
The electrolyte is responsible for dye regeneration and
hole transport in DSSCs. Electrolytes usually consist of a redox
couple with different additives dissolved in an organic solvent.
The redox couple must accomplish long-term and fast cycling
and exhibit suitable thermodynamics to provide efficient dye
regeneration and maximum open-circuit voltage (VOC) in the
device. The solvent, on the other hand, must show low volatil-
ity for long-term cell stability but proper wettability to fill all
pores in the mesoporous film. The most employed redox cou-
ple is iodide/triiodide (I2/I32), although Br2/Br32, sulfur/
polysulfide (Sn22/nS22), and metal-based molecules such as
cobalt complexes (CoII/CoIII) have also been explored.[32]
The additives in the electrolyte play a key role to enhance
photovoltaic performance. They are expected to modify the
charge on the TiO2 surface, shifting the conduction band and
blocking the recombination events.[33] Some of the most
employed additives that are able to tune the semiconductor
conduction band are nitrogen-containing heterocyclic com-
pounds such as tert-butylpyridine or cationic salts such as
LiClO4. Guanidinium thiocyanate has been extensively used
to reduce dark current losses, enhancing device efficiency.[32]
The most common solvents reported in liquid electrolytes
have been water, ethanol, acetonitrile, propionitrile, valeroni-
trile, and ethylene carbonate, among others. However, for effi-
cient and stable devices solvent mixes have been proposed, for
instance acetonitrile/valeronitrile (85:15, v/v). Nonvolatile
electrolytes have been extensively studied. Although the cell
efficiencies using these electrolytes are still lower than cells
with liquid electrolytes, they have been demonstrated to pro-
vide long-term stability to the devices.[32,34]
The counter electrode is also composed of FTO usually
coated with a thin layer of Pt, whose role is to catalyze the
reduction of the oxidized redox species. The main function of
the counter electrode is to collect the charges from the hole-
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Scheme 2. Flux diagram representing all charge transfer processes taking place
in a DSSC, with an indication of the time scale on which they occur.
transporting material. Pt is the most preferred catalyst due to
its good electrocatalytic activity towards I32 reduction; how-
ever, when different redox couples are employed other catalysts
might be more suitable.[35] Different materials have been pro-
posed instead of noble metal particles as catalysts in DSSC
counter electrodes for economic reasons. Of these, carbon-
based materials such as carbon black, graphene, carbon nano-
tubes and polymeric composites have been widely
investigated.[35,36]
2.2. Device Operating Principle
As mentioned before, DSSCs are considered photoelectro-
chemical cells,[37] and all of the charge transfer processes are
summarized in Scheme 2. The first process taking place in a
DSSC is the photosensitizer photon absorption (1). Upon
light excitation one electron from the ground state of the dye is
promoted to the excited states. These electrons must be subse-
quently injected into the semiconductor conduction band (2),
leaving the photosensitizer in its oxidized state. The electrons
are transported up to the counter electrode through the exter-
nal circuit (3), producing a net electrical current. At the coun-
ter electrode, the electrons must reduce the oxidized species in
the electrolyte. Finally, the reduced redox couple regenerates
the oxidized dye (4), closing the circuit and keeping the system
cycling continuously. Some undesirable reactions may take
place as well, including the back electron transfer from the
TiO2 conduction band to the dye oxidized state (5) and the
recombination between the electron in the conduction band
and oxidized species in the electrolyte, also named dark
current (6). The DSSC operating mechanism is based on the
reversible reactions summarized in Scheme 3.
The overall device efficiency depends on a kinetic compe-
tition between charge injection, regeneration and recombina-
tion.[38] It is defined by the photocurrent density measured at
short circuit (JSC), the open-circuit voltage (VOC) and the
device fill factor (FF) at a certain incident light intensity (IS),
as indicated in Equation (1):
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Scheme 3. Possible reactions taking place in a DSSC. The numbers
correspond to those indicated in Scheme 2. S 5 sensitizer.
g JSC  VOC  FF =IS (1)
The higher the injection yields, the higher the JSC. This
parameter depends directly on the sensitizer absorption spec-
trum, molar extinction coefficient and thermodynamics. The
VOC depends on the electrolyte redox potential and the metal
oxide conduction band as well as the dark current rate. The FF is
defined as the ratio of the maximum power to the product of the
VOC and JSC, and is a parameter that reflects the yield of internal
losses; the higher the FF, the lower the recombination.[37]
2.3. Limiting Factors
In DSSCs the main limiting factor is the recombination of
charges, which takes place at the TiO2 interface between elec-
trons and holes. The main loss mechanisms have been found
to be the recombination of the photoinjected electrons in the
semiconductor with the oxidized dye and with the oxidized
species of the redox electrolyte (dark current).[26b,39]
These recombination mechanisms have been widely stud-
ied and different strategies have been proposed in order to
minimize these losses. For instance, the dye molecular struc-
ture can play a key role in reducing dark current. The dye can
act as a barrier, forming compact layers between the electrolyte
and the TiO2 surface.[39b] It has also been reported that thin
amorphous layers of Al2O3 deposited between the TiO2 sur-
face and the adsorbed dyes can reduce recombination losses
without detrimental effect on the electron injection.[40]
Another factor controlling device performance has been
recently reported to be the tilt angle between the main plane of
the dye and the TiO2 surface. It has been observed that the
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O O
N
N N
O Ru
O C N design has been the synthesis of more stable dyes under long-
N
N N
CN
Ru
N N CN
O N
C
O N
Ru
N N
O Due to the broad range of molecular sensitizers, in the fol-
O N
Scheme 4. Structure of the trimeric Ru complex.
orientation of the dye on the TiO2 surface affects the electron
injection and recombination, limiting the device efficiency.[41]
3. Developments in Molecular Photosensitizers
Since the seminal paper of ORegan and Gratzel,[13] many
efforts have been made to increase the DSSC efficiency with
the aim of achieving values comparable to silicon-based photo-
voltaic technology. In that work, the breakthrough came from
the utilization of transparent mesoporous TiO2 films, increas-
ing the film inner surface area per cm2 of geometric surface by
a factor of 780 and thus increasing the sensitizer loading.
Moreover, selecting a suitable sensitizer, which harvested light
from 750 nm to the UV part of the spectrum, and electrolyte
composition pumped the device efficiency up to 7.12% under
simulated AM1.5 solar light.[13]
Although many attempts to improve the metal oxide layer
morphology have been made, none of the proposed nanostruc-
tures so far have been clearly demonstrated to exceed the per-
formance of the 1520 nm anatase nanoparticle layers.
However, the trimeric ruthenium complex RuL2(m-
(CN)Ru(CN)L0 2)2 (Scheme 4), where L is 2,20 -bipyridine-
4,40 -dicarboxylic acid and L0 is 2,20 -bipyridine, employed as
sensitizer[42] has been the entry point for the development of
new dyes able to further improve the overall device efficiency.
The rational design of new sensitizers has mainly explored two
directions: (i) enhancing the light-harvesting efficiency by
increasing the dye molar extinction coefficient, and (ii) extend-
ing the light absorption up to the near-infrared part of the
spectrum. In both cases the aim was the synthesis of a dye that
efficiently overlaps the solar spectrum.
It is worthwhile to note that the sensitizer energy levels need
to be aligned with the redox potential of the electrolyte and, there-
fore, modification of the electrolyte composition or even the
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redox couple has generally accompanied any change in the dye
employed, in order to optimize the overall device efficiency, as
will be commented upon in more detail in the following sections.
A third line of research that has been explored in sensitizer
term operation conditions. The presence of residual water or
other oxidant species in the electrolyte composition has a detri-
mental effect on the device performance, especially for the
molecular sensitizers, desorbing or even degrading the dyes,
enhancing loss mechanisms that eventually decrease the overall
device efficiency.[43]
lowing we have distinguished between dyes containing metallic
elements and metal-free sensitizers.
3.1. Metal Complexes as Sensitizers
Mononuclear and polynuclear metal complexes have been
widely explored as sensitizers in DSSCs, not only polypyridyl
complexes with metal ions such as RuII,[26a,44] OsII,[45] PtII,[46]
ReI,[47] CuI,[48] and FeII,[49] but also ZnII, RuII, TiIV, SiIV, FeII,
HfIV and ZrIV porphyrins[26b,c,28], and phthalocyanines.[26c,29]
Although the most efficient DSSC so far was fabricated with a
ZnII porphyrin, the most employed dyes have been the RuII
polypyridyl complexes due to their unique redox and photo-
physical properties.[44b] The tunable photophysical and photo-
chemical properties arise from the metal-to-ligand charge
transfer (MLCT) process, specifically the broad absorption in
the visible region and the stability in the oxidized state. These
tunable photoelectrochemical properties may be engineered by
the sequential modification of different ligands (typically
bipyridines or terpyridines modified with various groups such
as alkyl, aryl heterocycle, carboxylate, etc.), which changes the
energies of the MLCT, making these compounds very conven-
ient as light harvesters in DSSCs.[26c,44b]
The ability of the RuII polypyridyl complexes to sensitize
wide band-gap semiconductors and the photoinduced charge
transfer reactions between them has been extensively stud-
ied.[12,50] However, the ORegan and Gratzel paper initiated
intensive synthetic effort in order to obtain panchromatic Ru
complexes capable of increasing the overall device efficiency.
In 1993, Gratzel et al. reported a series of bipyridyl RuII
complexes using different halogenated, cyanide and thiocya-
nate ligands. One of these, cis-bis(isothiocyanato)-bis(2,20 -
bipyridyl-4,40 -dicarboxylato)ruthenium(II), named N3,[51]
has been for many years considered a reference dye in DSSCs
(Scheme 5). The use of two thiocyanate groups instead of other
ligands produced a red shift in the spectral response up to
800 nm, increasing the JSC up to 17 mA/cm2 and achieving
10% solar-to-electric energy conversion efficiency.[51] Several
years later, in 1999, a study of the N3 deprotonation effect on
the DSSC performance allowed the authors to find that the
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reversible Ru(II)/(III) state was shifted negatively 290 mV
from the fully deprotonated to the fully protonated form
(N3), with a shift of almost 600 mV to the diprotonated form,
named N719[52] (Scheme 5). The DSSC power conversion
efficiency using N719 as active material has reached, after puri-
fication and device optimization, 11.2%.[53] Devices using N3
presented slightly higher JSC values; however, the double pro-
tonation in N719 produced photovoltage enhancement
(130 mV), resulting in an improved overall device
efficiency.[52]
A different approach consisted of the use of the trithiocya-
nato-ruthenium(II) terpyridyl complex, named N749 or black
dye (Scheme 5) in 1997.[54] The inclusion of one thiocyanate
group more than N3 extended the light absorption further
into the near-infrared (NIR) part of the spectrum, up to
920 nm. The power conversion efficiency using this dye as
active material and optimized electrolyte (I32/I2) composition
was 11.1%,[54] and it was considered to be the sensitizer with
the widest light-harvesting ability for many years. Only a few
sensitizers have been able to exceed the 20.9 mA/cm2 gener-
ated by N749, whose electric current generation is almost
100% over the wavelength range from 400 to 700 nm and
whose light-harvesting capability extends up to 920 nm.[54]
The N749 sensitizer demonstrated that thiocyanate
groups were able to extend the light absorption into the NIR.
However, these ligands have been shown to be weakly coordi-
nated, exhibiting poor stability. The search for new ligands
able to extend the light absorption as well as increase the molar
extinction coefficient and that demonstrate improved stability
has been intensively pursued.
In 2002, a systematic study of Ru sensitizers with trans-
dithiocyanate and trans-dichloro moieties combined with dif-
ferent bipyridine and quaterpyridine ligands with benzimida-
zole, phenyl or carbonyl groups was reported.[55] The use of
trans-dichloro groups led to red-shifted absorption spectra. In
addition, complexes containing phenyl and diphenyl substitu-
ents on quaterpyridine ligands presented increased molar
extinction coefficients due to their improved p-conjugated
donoracceptor characteristics. This enhancement of harvested
light results in JSC values of up to 18 mA/cm2 with a reduction
in thickness of the TiO2 layer (from 18 to 12 mm), which also
benefits the VOC due to a reduced dark current.[55]
The relatively limited durability has been an important
drawback of DSSCs for commercial applications. One of the
main problems has been the composition of the liquid electro-
lytes, which contained low-boiling-point organic solvents and
promoted desorption of the attached dyes and subsequent
photodegradation of the desorbed molecules. For that reason,
ionic liquids with high viscosity as well as solvent mixtures
(low and high boiling points) have been incorporated into the
electrolyte composition in order to solve the leakage of organic
solvent.[56] On the other hand, the design of Ru complexes
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incorporating hydrophobic moieties was investigated. In
2003, a heteroleptic amphiphilic Ru(II) complex named Z907
(Scheme 5) was reported to exhibit remarkable long-term sta-
bility with about 8% power conversion efficiency.[57] The
function of the hydrophobic alkyl chains was to reduce dye
desorption due to residual water as well as to increase affinity
for gel electrolytes composed of ionic liquids in a polymer gel.
Another important consequence of the incorporation of the
long alkyl chains together with the use of co-grafted molecules
(i.e., hexadecylmalonic acid) was the formation of a blended,
well-packed monolayer that provides an effective insulating bar-
rier for dark current losses.[57] Another strategy to reduce charge
recombination events through the molecular design was reported
to be addition of a secondary electron-donor moiety, N,N-(di-p-
anisylamino)phenoxymethyl to a [Ru(dcdpy)2(NCS)2] com-
plex.[58] This functional group provided physical separation
between the holes and electrons in the TiO2 surface, increasing
the lifetime of the oxidized molecule.[58]
Although these amphiphilic dyes presented improved sta-
bility, lower efficiencies than the analogous N719 were obtained
due to the lower molar extinction coefficients. This fact led to
the development of new amphiphilic dyes with extended p-
conjugated systems in the bipyridine groups. This increase in
the conjugation length promoted red shift of the MLCT and
higher molar extinction coefficients while maintaining the long-
term stability characteristics. One of these molecules containing
both hydrophobic and conjugated moieties was reported in
2004, and it was named Z910 (cis-dithiocyanato-(2,20 -bipyr-
idyl-4,40 -dicarboxylate)-[4,40 -bis(3-methoxystyryl)-2,20 -bipyr-
idyl]-Ru(II), Scheme 5).[59] Using this dye, a red shift of
20 nm compared with Z907 was obtained as well as a higher
molar extinction coefficient than N719. The power conversion
efficiency under the AM1.5 solar spectrum at one sun was
10.2%, which was higher than Z907 and N719 if the Z910
optimum conditions (TiO2 thickness and electrolyte composi-
tion) were applied to the three dyes.[59]
Similar strategies have been reported in the use of long-
term stable amphiphilic heteroleptic polypyridyl Ru complexes
with high molar extinction coefficients. For instance, the K19
dye was reported in 2005 (Scheme 5).[60] In photovoltaic devi-
ces this dye showed thermostable properties with a high molar
extinction coefficient. This complex was very similar to Z910
but with 4,40 -bis(m-hexyloxystyryl)22,20 -bipyridyl moieties
instead of the 4,40 -bis(3-methoxystyryl)22,20 -bipyridyl
groups. A molar extinction coefficient of 18.2 3 103 M21
cm21 was reported, which is higher than those of N719 (14 3
103 M21 cm21) and Z910 (17 3 103 M21 cm21).[60] The
K19 dye has shown a power conversion efficiency of only
7%; however, the K77 dye (Scheme 5), whose structure is
very similar to K19 after replacement of the p-hexyloxystyryl
unit by 3-tert-butyloxyphenyl(ethenyl), led to a reported effi-
ciency of 10.5%.[61]
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Scheme 5. Structures of selected Ru complexes for use in DSSCs.

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Another approach to increase the conjugation in the ancil-
lary ligands has been the use of thiophene groups. The substi-
tution of the typical bipyridine ligands by alkylthiophene
groups (CYC-B1) was reported in 2006 (Scheme 5), and a
power conversion efficiency of 8.54% was obtained.[62] In this
case, the polythiophene moiety is more electron rich than, for
example, the phenylenevinylene ones, and the sulfur atoms
provide aromatic stability to the polyacetylene chains while
preserving electrical properties.[62] Moreover, the thiophene
groups are well known because of their easy functionalization,
opening up new synthetic opportunities to incorporate differ-
ent functional groups to tune the dye photophysical properties.
In fact, CYC-B1 was later modified to CYC-B11 (Scheme 5),
which incorporates an electron-rich terminal hexylthio group
on the thiophene chains.[63] This modification provided an
improved molar extinction coefficient (2 3 104 M21 cm21),
increasing the power conversion efficiency from 8.54% for
CYC-B1 to 11.5% for CYC-B11.
As mentioned before, the increase in molar extinction
coefficient (by ca. 14%) in addition to enhanced light harvest-
ing allow a decrease in the TiO2 thickness, avoiding dark cur-
rent leakages and consequently leading to an increase in the
VOC. The addition of both characteristics promoted the overall
efficiency enhancement.[63]
There are more examples in the literature where the intro-
duction of one single atom modifies the electronic transitions
of the Ru complexes, increasing the molar extinction coeffi-
cients and shifting the absorption spectra to the NIR. This is
the case for amphiphilic heteroleptic Ru(II) sensitizers C101
and C106 (Scheme 5), with reported efficiencies of 11% and
11.4%, respectively.[64]
Besides the molecular engineering employed to obtain
panchromatic and efficient light harvesters with Ru polypyr-
idyl complexes, other kinds of metal-coordinated molecules
have been explored for DSSC applications. Some of the first
examples of Ru-free sensitizers that researchers investigated
were chlorophylls and porphyrins, probably attracted by their
role in natural photosynthesis.[65] In particular, the porphyrin
structure is based on macrocycles with electronic delocaliza-
tion, which provides strong absorptions between 400 and
500 nm as well as between 600 and 750 nm. The characteristic
absorption bands of porphyrins have been widely studied and
they are known as the Soret band (400500 nm) and the Q
band (550750 nm). These characteristic porphyrin bands
may also be tuned through the appropriate introduction of
functional groups and, therefore, porphyrin derivatives are also
suitable panchromatic sensitizers for DSSCs.
Since the pioneering charge transfer studies between zinc
tetrakis(4-carboxyphenyl)porphyrin (ZnTCPP, Scheme 6) and
TiO2,[66] many porphyrin structures have been proposed.
Although it has been demonstrated that the kinetics of charge
injection and recombination are very similar to those of Ru
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polypyridyl complexes, the search for suitable structures has
aimed to avoid the main drawbacks of porphyrins, which are
molecular aggregation phenomena on the TiO2 surface and
poor electronic interaction between the porphyrin core and the
anchor linkers (mainly carboxylates). The aggregation issue
has been typically addressed by the use of co-adsorbates, which
provide a physical separation between molecules, or the use of
long alkyl chains as in the case of the Ru complexes. The latter
drawback has been addressed by breaking the porphyrin sym-
metry, for instance, by employing the zinc b-substituted styryl-
carboxylic acid tetraphenyl porphyrin series (ZnTXPSCA,
Scheme 6).[67] By using this sensitizer with this single-anchor
linker, cell efficiencies of 4.2% have been demonstrated. This
substitution in the b-position led to a red shift in the Q band.
The use of xylyl instead of phenyl groups promoted 4.8%.[67]
These achievements meant new synthetic opportunities to
optimize these sensitizers, both in terms of the conjugation of
the functional groups as well as the carboxylic anchor, creating
donoracceptor moieties in these molecules.
In 2005, a series of tetraphenyl zinc porphyrin sensitizers
with different modifications of the anchor group were reported,
such as the addition of cyano groups or the replacement with
benzenedicarboxylic acids. It was found that the addition of the
cyano group to the carboxylic moiety to give cyano-3-(20 -
(50 ,100 ,150 ,200 -tetraphenylporphyrinato zinc(II))yl)-acrylic acid
(Zn3, Scheme 6) had two consequences: (i) a red shift in the
visible spectrum; and (ii) physical separation between the elec-
tronic density from the molecule core and the linker substituent,
favoring the electron transfer to the TiO2 conduction band. All
these improvements provided a power conversion efficiency of
5.6% using the Zn3 dye.[68]
Later, in 2007, a series of Zn porphyrins with overall effi-
ciencies over 5% were reported. In these porphyrins, the
malonic acid anchor group was fixed and the peripheral func-
tional groups were modified from phenyl to methylphenyl,
ethylphenyl, butylphenyl, octylphenyl and dimethylphenyl
groups, obtaining with the 4-methylphenyl groups the best
cell efficiency of 7.1%.[69] The similarity in the HOMO
LUMO transitions of the various molecules indicated that
the efficiency differences arose from the electronic effects
derived from the small modifications of the phenyl
substituents.
All these studies led to the milestone achieved recently
with the combination, on the one hand, of the development of
the donoracceptor moieties concept in Zn porphyrins, which
makes them able to absorb light in the complete visible spec-
trum, besides the use of long-chain alkoxy groups, which had
already been demonstrated to improve dye stability and block
device dark current losses, and, on the other hand, the use of
cobalt polypyridyl based redox pairs, which minimize energy
losses between the energy of the dye HOMO and the electro-
lyte redox potential, maximizing the VOC. In this way, the Zn
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HOOC

N
N
Zn
N
COOH N
N
N
Zn
N
N
HOOC

ZnTCPP COOH ZnTXPSCA HO O

COOH

C8H17
O

N C8H17
N O
N Zn
N
Zn O N
C8H17 N
N
N
O
N C8H17
C6H13
NC
Zn3 COOH YD2-o-C8 C6H13

COOH

N
S
N

C8H17
O
C8H17
N O
N OH
Zn
O N O
N
C8H17
O
N N
C8H17 N
Zn
O N
N
C6H13 O
C6H13
O
C6H13 O
SM315 C6H13 TT1
Scheme 6. Structures of some of the best-performing porphyrins and phthalocyanines.

porphyrin YD2-o-C8 (Scheme 6) achieved 11.9% efficiency,[70]
demonstrating a potential of almost 1 V (965 mV) and
a remarkable current density of 17.5 mA/cm2 when CoII/III tris
(bipyridyl) complex was used as redox pair in the electrolyte
composition. The device performance using the same sensitizer
was only 7.6% when I2/I32 was used.[70] The cobalt complex
not only improved the VOC (ca. 193 mV) due to the fine tuning
of the energetic levels, but also increased the JSC (ca. 2.3 mA/
cm2) due to the reduced dark current losses. In this sense, the
long alkoxy groups in the Zn porphyrin are more effective with
the Co polypyridyl complexes, which are bulkier compounds
compared to the I2/I32 redox pair, in order to impede the elec-
trolyte approaching the TiO2 surface.[70]
Therefore, although the utilization of Co complexes as
redox pairs had already been investigated, new research ave-
nues were opened up by molecular engineering and the use of

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cobalt-based electrolytes in efficient and robust DSSCs.
Actually, many reports have appeared since then comparing
not only Zn porphyrins, but also Ru polypyridyl complexes,
when CoII/III and I2/I32 are employed as the redox pairs.[71]
Recently, another Zn porphyrin named SM315, using
CoII/III as redox pair, has demonstrated an impressive 13%
overall power conversion efficiency.[72] In this molecule, the
core of the YD2-o-C8 dye is preserved and the similar donor
moiety bis(20 ,40 -bis(hexyloxy)-1,10 -biphenyl-4-yl)amine is
used, but a benzothiadiazole moiety has been incorporated as
the acceptor/anchor group. The incorporation of the benzo-
thiadiazole moiety produced a broadening of the Soret and Q
bands, increasing the light harvesting in the regions between
500 and 600 nm and up to 800 nm, where porphyrin absorp-
tion is usually low. This enhancement in light harvesting con-
sequently gave an improved JSC (18.1 mA/cm2) over YD2-o-
C8 and comparable VOC (0.91 V). This panchromatic sensi-
tizer has to date the record efficiency at full-sun illumination of
13%.[72]
The utilization of Co complexes as redox pairs in electro-
lytes is nowadays attracting much attention, not only in por-
phyrin sensitizers, but also with Ru polypyridyl complexes in
order to combine the optimized VOC from Co electrolytes and
the high JSC obtained from extended light harvesting in the
NIR of Ru polypyridyl complexes, which have demonstrated
higher light absorption in the NIR than Zn porphyrins, as in
the case of N749. It has been demonstrated that the substitu-
tion of thiocyanates by cyclometalated bi- or tridentate ligands
is very convenient for the use of these dyes with Co electrolytes,
and at the same time provides panchromatic dyes with long-
term stability.[73] The power conversion efficiency of
thiocyanate-free Ru sensitizers is still below 10%. However,
the promising light harvesting in the NIR part of the solar
spectrum that these dyes offer, exceeding 20 mA/cm2, and the
near 1 V potential that Co electrolytes provide to the devices
could in the near future lead to the achievement of the power
conversion efficiencies that other technologies have shown.
Another group of metalated molecules that have attracted
much attention as sensitizers in DSSCs are phthalocyanines.
For instance, in 2009, a group of unsymmetrical zinc phthalo-
cyanines was reported using various carboxylic anchoring
groups having different spacers.[74] As it was commented upon
in the case of porphyrin dyes, the different anchor groups pro-
duced a red shift in the visible spectrum. Moreover, the differ-
ent spacers had an effect not only on the distance from the
TiO2 surface but also on the molecular orientation, which led
to differences in the electron injection and recombination
kinetics and, therefore, in the overall efficiencies.[74] Although
these molecules have been reported to exhibit modest efficien-
cies when compared with Ru polypyridyl complexes and Zn
porphyrins (3.5% obtained using TT1, Scheme 6),[74] they
have been widely investigated due to their impressive molar
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THE CHEMICAL RECORD
extinction coefficients in the NIR absorption region, especially
when they are combined with other molecules with comple-
mentary absorbance.
Indeed, it is not unusual to find the combination of two
or more dyes in DSSCs. The use of dye cocktails has also been
investigated in DSSCs, especially the combination of meta-
lated complexes and metal-free molecules because of the com-
plementary optical properties that each type of molecule may
offer. It is well known that metal-free dyes have high molar
extinction coefficients in the visible part of the spectrum and,
as commented upon earlier, some Ru complexes can extend
light harvesting up to the NIR part of the spectrum
(900 nm), and porphyrins and phthalocyanines have optical
windows between 500 and 600 nm; therefore, their combina-
tion could lead to panchromatic light harvesting.
Although examples of dye cocktails for DSSCs had
already been reported, a study was published in 2007 where
the efficiency of the dye combination exceeded the efficiencies
obtained with those dyes separately.[75] The combination of
the Zn phthalocyanine TT1, with an intense absorption
between 550 and 750 nm, and the metal-free dye JK-2, which
exhibits excellent light harvesting in the visible region, covering
the spectral window that TT1 leaves free, resulted in a cell with
an overall efficiency of 7.74%.[75] Under similar conditions,
the cell efficiency obtained using only JK-2 was 7.08% and
TT1 3.5%; therefore, the higher overall efficiency of the cell
using the dye cocktail was attributed to the complementary
light absorption of each dye. In a similar approach, the co-
sensitization of TiO2 nanoparticles using N749 and the
organic dye 3-carboxymethyl-5-[3-(4-sulfobutyl)-2(3H)-ben-
zothiazolylidene]-2-thioxo-4-thiazolidinone, sodium salt
(NK3705),[76] which provided strong absorption between 300
and 500 nm, was reported. A dye bilayer structure was
obtained in two separate steps, under pressurized CO2 condi-
tions. The power conversion efficiency using the bilayer con-
figuration was 9.16%, while N749 and NK3705 produced
7.28% and 1.85%, respectively, using in all cases the same con-
ditions.[76] In this case, the light harvesting from 600 to
900 nm comes from the Ru complex and the organic dye
increases the current density in the UVvis part of the spec-
trum. One year later, 11% efficiency was achieved just by mix-
ing N749 and the indoline dye D131.[77]
There are examples where three dyes have been sequen-
tially employed to sensitize TiO2 nanoparticles. One of these
examples was the use of a column chromatography methodol-
ogy to adsorb N719, N749 and the organic dye 2-cyano-3-(5-
(4-ethoxyphenyl)thiophen-2-yl)acrylic acid (P5) in a mesopo-
rous TiO2 film.[78] Although the overall efficiency was <5%,
the sequential deposition of these three dyes was
demonstrated.
Zn porphyrins have also been employed in co-
sensitization. For instance, the YD2-o-C8 dye (Scheme 6) was
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Scheme 7. Structures of some of the best organic dyes for DSSCs.

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Scheme 7. (Continued).

co-sensitized with the organic dye Y123 (Scheme 7), whose 3.2. Metal-Free Sensitizers
maximum absorption is located at approximately 550 nm,
Dye molecules have a fundamental role in DSSCs, independ-
conveniently covering the spectral window that YD2-o-C8
ently of their structure or composition. These molecular dyes
leaves.[70] The power conversion efficiency of this co-sensitized
must fulfill a series of demands to provide not only optimum
DSSC was 12.3%. Recently, other studies of co-sensitizing Zn
device performance parameters with a high extinction coeffi-
porphyrins and organic dyes have been reported.[79] In all of
cient in as much of the solar spectrum as possible, but also
these cases the idea is to fill up the absorption valleys of Zn
photostability and thermal stability. Low-cost, large-scale pro-
porphyrins with the organic dyes. For instance, a series of Zn
duction is also desirable, simplifying synthetic routes and puri-
porphyrins with different donor groups and a series of organic
fication steps. Metal complexes have demonstrated
dyes with different acceptor moieties were synthesized and
outstanding performance in complete devices with light har-
tested in co-sensitized DSSCs. The combination of the Zn
vesting in the entire visible and part of the NIR spectrum in
porphyrin XW4 with a bis(ortho-alkoxy) group in the donor
many cases. Nevertheless, metal complexes do not completely
moiety and the organic dye XS3 with a thiophenyl cyanoa-
accomplish all of these requirements. Metal complexes are
crylic acid moiety produced cells with 10.75% efficiency.[79]

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expensive, not only because of the use of costly metals such as
Ru, but also due to their multistep synthesis and the need for
complex purification methods.[30d] In addition, the molar
extinction coefficients of these complexes are usually much
lower than those of metal-free organic molecules (usually one
order of magnitude lower). For these reasons, organic dyes
have been proposed as good candidates to overcome the draw-
backs of the metal complexes. The most important advantages
of organic dyes are the lower cost of large-scale production due
to their easier synthesis, higher molar extinction coefficient
when compared with metal complexes, and the lack of
dynamic exchange of ligands as for metalorganic bonds.[30a]
All these advantages make metal-free organic dyes very conven-
ient as sensitizers in DSSCs. In addition, organic dyes can be
designed by molecular engineering to tune their physicochemi-
cal properties. In contrast, metal-free sensitizers present some
drawbacks, which are responsible for the lower power conver-
sion efficiency compared with metal complexes. These are
mainly the narrower absorption spectra, the increased recom-
bination dynamics as a consequence of surface aggregation
phenomena, and in some cases low thermal and photostabili-
ty.[26c] Nonetheless, the easier preparation and the tunability
with a broad range of functional groups allow numerous possi-
bilities with the hope to overcome these drawbacks.
Among the first metal-free organic sensitizers studied in
DSSCs were coumarin dyes. Although fast electron injection
kinetics were demonstrated (<1 ps) for a coumarin dye
(C343, Scheme 7), the cell efficiency was below 1%.[80]
Despite this poor conversion, coumarin dyes became promis-
ing sensitizers due to their intense absorption in the visible
region and their convenient HOMOLUMO positions. This
coumarin dye was later optimized through introduction of
vinylene groups in between the anchor group (cyanoacrylic
acid) and the dye core, leading to a power conversion efficiency
of 5.2%.[81] It was also found that further increase in the num-
ber of vinylene moieties was detrimental to the overall effi-
ciency, due to an increased dye aggregation.[81]
Heteroanthracene dyes are another example of organic
dyes used in the early studies. These dyes include xanthenes,
phenothiazines and phenoxazines.[82] However, initially they
provided modest cell efficiencies as a consequence of their nar-
row absorption in the visible region and instability issues.
Squarines have also been commonly used for DSSC sensitiza-
tion. Similarly to Zn porphyrins, these molecules exhibit
intense and sharp absorption bands in the visible and NIR
regions. However, in the first studies, the efficiency of complete
devices employing these dyes was between 0.7 and 2.2%.[83]
This low efficiency was attributed to a high aggregation, lack
of influence of directionality in the excited states and poor
thermal and photostability. The aggregation in the charge
injection and recombination was studied in 2007[84] using a
symmetrical squarine molecule (Msqb, Scheme 7). It was
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found that the presence of dye aggregates on the TiO2 surface
decreases the yield of charge injection as well as slows down the
regeneration process using liquid electrolyte. Therefore, the
use of co-adsorbent molecules such as 3a,7a-dihydroxy-5b-
cholic acid was found to be necessary to decrease aggregation
in squarines as well as in other metal-free sensitizers. Although
it has been studied whether the use of co-adsorbents reduces
light harvesting since they compete with the dye for TiO2 sur-
face area, the enhancement in VOC and fill factor produced an
improvement in the overall device efficiency, and additives
were included in the majority of DSSCs using metal-free sensi-
tizers. In fact, the use of co-adsorbents and the design of new
asymmetric squarines led to an efficiency increase of up to
4.5% by using these dyes.[85]
Other molecules that have also been shown to exhibit
aggregation are merocyanines. In addition to the aforemen-
tioned use of co-adsorbents, other strategies to avoid aggrega-
tion have been explored. The use of dioctyl sodium
sulfosuccinate (AOT) with the merocyanine MC540 was stud-
ied in 1999 (Scheme 7).[86] The dye incorporation in these
micelles allowed dye deposition as organized assemblies, con-
trolling aggregation of the adsorbed MC540 on the TiO2 sur-
face. In a different approach, the systematic synthesis of
merocyanines containing alkyl chains with different lengths
led to the observation of the formation of J-aggregates instead
of H-aggregates, promoting a red shift in the absorption spec-
tra and leading to cell efficiencies of 4.5% in 2002.[87]
Perylene dyes have also been proposed as good candidates
for DSSCs. They present high molar extinction coefficients in
the visible range (105 M21 cm21) and they had already been
commercialized as colorful pigments. The first reports employ-
ing perylene dyes as sensitizers reported efficiencies below
2%.[88] The maximum power conversion efficiency obtained
using perylenes was reported in 2008 (6.8%),[89] although
their use has been more focused on exploring the effects of dye
structural modifications on the device performance.
Indole dyes can be synthesized through simple routes,
achieving good power conversion efficiencies. One of the first
examples applying an indole dye in a DSSC reported a 6.1%
efficiency in 2003.[90] Subsequently, a series of indole mole-
cules, introducing among others a rhodanine framework into
the molecular structure (D149, Scheme 7), produced a red
shift in the absorption spectra, and as a consequence, an
impressive 8% device efficiency.[91] Further device optimiza-
tion by reducing TiO2 layer thickness, employing an ionic-
liquid-based electrolyte and adding chenodeoxycholic acid as
co-adsorbent produced in 2006 an optimized cell efficiency of
9%.[92] In 2008, in order to avoid aggregation, besides addi-
tion of optimized amounts of chenodeoxycholic acid, the
indole D149 dye structure was modified by adding n-octyl
substituents to the rhodanine moiety (D205, Scheme 7), lead-
ing to a device efficiency as high as 9.5%.[93]
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Although the power conversion efficiencies of these
organic dyes became close to the Ru complexes at this point,
the main progress arose from the indole structure modification
through introduction of several functional groups with elec-
tron donor or acceptor properties, as in the rhodanine case.
This molecular optimization has produced similar effects in
DSSC efficiency using not only indole dyes, but also coumar-
ins, squarines and perylenes, among others, as parts of more
complex molecules. One of the main differences between the
modified molecules and their original structures is their direc-
tionality in the excited states. For instance, in D149 the phenyl
moieties on one side of the molecule push the electron density
to the rhodanine moiety, located close to the TiO2 surface, and
the rhodanine electron-withdrawing character pulls this elec-
tron density towards the carboxylic acid.
The synthesis of organic molecules with electron-
donating and electron-withdrawing moieties (pushpull mole-
cules) has been explored as well by Yanagida and co-workers
since 2004.[94] They synthesized a series of oligoene dyes with
different aminophenyl-substituted groups as electron donors,
obtaining efficiencies up to 6.6%. Later, in 2006, Sun and
Hagfeldt actuated the DpA molecule design.[95] This has
been considered one of the biggest advances in metal-free
organic sensitizer synthesis for DSSC applications. These types
of molecules are based on three main components: an electron
donor moiety (D), a linker or p bridge (p) and an electron
acceptor moiety (A). Upon light excitation, the D must push
from its excited state electron density to the p-conjugated sys-
tem, leaving the holes far from the TiO2 surface but close to
the redox pair. The use of a linker between D and A promotes
efficient intramolecular charge separation between D and A
after light excitation. Eventually, the A moiety, which usually
contains the anchor group, pulls this electron density towards
the TiO2 surface.[30a]
Many donor groups have been tested in DpA sensi-
tizers. Arakawa et al. synthesized a series of molecules contain-
ing N,N-dimethylaniline as D, polyenes of different lengths as
p bridge and cyanoacrylic acid as A.[96] The dye NKX-2569
(Scheme 7) with two dimethylaminophenyl groups as D and
the longest polyene chain provided a cell efficiency of 6.8% in
the presence of deoxycholic acid.[97]
In a similar approach, a series of sensitizers were reported
using coumarin as donor moiety, different oligothiophenes as
p bridge and the typical cyanoacrylic acid as acceptor. In this
study, a power conversion efficiency of 7.4% was reported
when the dye NKX-2677 (Scheme 7) with two thiophenes was
used, due to the optimized LUMO position, which provides
ultrafast electron-injection kinetics.[98] However, NKX-2677
showed poor light-harvesting ability in the NIR and this dye
was modified through incorporation of one vinylene unit
between the thiophene moieties in the p bridge. This new dye,
named NKX-2700 (Scheme 7), demonstrated higher photo-
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THE CHEMICAL RECORD
current than NKX-2677 due to a red shift in the absorption
spectrum, and upon addition of an appropriate amount of
deoxycholic acid a power conversion efficiency of 8.2% was
achieved.[99] It has also been reported that the introduction of
one or more cyano groups into the p bridge improves the light
absorption in the NIR. Thus, by using this approach, NKX-
2883 (Scheme 7) showed a power conversion efficiency of
7.6%.[100]
Other examples of donor units in DpA systems have
been reported. For instance, a series of dyes were synthesized in
2006 based on a carbazole moiety as D with different n-hexyl-
substituted oligothiophenes as linkers.[101] The MK-2 dye
(Scheme 7) showed the best efficiency (7.7%), due on one
hand to the extended p conjugation, which provided wider
light harvesting than other congeners, and on the other hand,
the presence of the n-hexyl groups, which avoided aggregation
and reduced device dark current. Further device optimization
using the same dye was achieved in 2008,[102] when 8.3% was
reported. The n-hexyl groups made unnecessary the addition
of a high concentration of co-adsorbents in this case, increasing
the amount of molecular dyes adsorbed on the semiconductor
surface and consequently also increasing the current density
and fill factor. Moreover, the reduction of dark current pro-
vided enhanced open-circuit voltage. A power conversion effi-
ciency of 8.1% was later demonstrated by introduction of a
hexyloxyphenyl group on the carbazole moiety of MK-2. This
new dye (MK-14, Scheme 7) showed increased electron life-
time and, therefore, higher VOC. The improved VOC was due
to a more efficient blocking effect, not only avoiding aggrega-
tion, but also dark current. As we have already mentioned,
amphiphilic groups like alkyl chains are able to reduce dark
current by providing a higher coverage of the TiO2
surface.[103]
In this sense, Sun et al. investigated the evolution of the
spectral response of a series of dyes incorporating in the triphe-
nylamine D moiety p-dimethylamine and/or p,o-butoxy
groups, with a thiophene as p bridge and cyanoacrylic acid as
A.[104] Although the dye D-29 (Scheme 7) with p-dimethyl-
amine moieties showed wider light absorption, the most effi-
cient devices were prepared with the dye D-35 (Scheme 7)
with p,o-butoxy groups (6%).[104] Again the alkyl chains pro-
vided better blocking of the electrolyte for the TiO2 surface,
while still avoiding molecular aggregation. As a consequence,
the electron lifetime using D-35 was longer than with the
others, leading to improved VOC.
The introduction of a second triphenylamine with
methoxy groups increased the power conversion efficiency of
one of these dyes (D-11, Scheme 7) up to 7.2%.[105] It was
found that the methoxy groups promoted a red shift in the
absorption spectrum. The second triphenylamine enhanced
light harvesting in the visible region as well as disfavored
recombination kinetics. Identical efficiency but improved
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photostability was demonstrated by using the dye D21L6
(Scheme 7).[106] This dye has a similar structure to D-35 but
with two hexyloxy groups in the triphenylamine D group and
two thiophene groups as linker.
One interesting example of a D moiety involved the
replacement of the typical triphenylamine by a bis(dimethyl-
fluorenyl)amino group. In addition, instead of the thienyl, the
p bridge was based on dithienothiophene.[107] With this mole-
cule (C-203, Scheme 7) a power conversion efficiency of 8%
was demonstrated with considerably good stability. The bis(di-
methylfluorenyl)amino moiety as D group was also tested in
the JK-1 and JK-2 dyes (Scheme 7).[108] In this case the linkers
were one thiophene for JK-1 and two thiophenes for JK-2,
leading to cell efficiencies of 7.2% and 8%, respectively. The
sequential incorporation of thiophenes in the conjugated sys-
tem increased the light harvesting in the visible part of the
spectrum. Actually, the dye (JK-46) with the same D group
but three n-hexylthiophene groups as linker led to a power
conversion efficiency of 8.6%.[109] In a similar way, the sensi-
tizer C-218 (Scheme 7) with dihexylcyclopentadithiophene as
p bridge demonstrated 8.95% efficiency due to the high molar
extinction coefficient that this unit promoted.[110] Neverthe-
less, the TA-St-CA dye (Scheme 7) containing just a phenyle-
nevinylene moiety as p bridge led to a cell efficiency of
9.1%.[111]
Other units for the p bridge have been explored besides
the polyenes and thiophenes. For instance, in the dye LJ1
(Scheme 7), thiophene was replaced with a 3,4-ethylenediox-
ythiophene (EDOT) moiety as the p linker, with the triphe-
nylamine maintained as D and the cyanoacrylic acid as
A.[112] Comparing the same dye with a thiophene (L1) and
LJ1, the power conversion efficiency increased from 5.2% to
7.3%, which was mainly due to the improved spectral
response. The extent of the p bridge has also been explored.
Wang and co-workers compared the utilization of one (C-
206) or two (C-211) thienothiophene groups as linker with a
dihexyloxy-substituted triphenylamine D group (Scheme
7).[113] This second unit promoted an enhancement in the
molar extinction coefficient of the molecule, leading to a cell
efficiency of 8%. Afterwards, a different study reported 9.8%
efficiency using the dye C-217 (Scheme 7), which possesses a
binary p-conjugated spacer, where an electron-rich EDOT
unit is connected to the dihexyloxy-substituted triphenyl-
amine D moiety to lift up the HOMO energy, while a conju-
gated thienothiophene unit is linked to the cyanoacrylic acid
A moiety to lower the LUMO energy.[114] This substitution
produced a red shift in the absorption spectrum that, com-
bined with the good molar extinction coefficient demon-
strated by thienothiophene moieties, explains the high
efficiencies reached with this dye.
Finally, following on from this reasoning, the dye C-219
(Scheme 7) was synthesized in 2010, leading to the best effi-
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ciency using a metal-free sensitizer, 10.3%.[115] In this dye, the
binary p-conjugated spacer was composed of an EDOT unit
conjugated with the D moiety and a dihexyl-substituted
dithienosilole conjugated with the A moiety. C-219 exhibits
higher molar extinction coefficient and comparable light-
harvesting efficiency to the Ru complex Z907.
Since then, more sophisticated structures have emerged in
order to exceed 10% efficiency using metal-free sensitizers.
The incorporation of binary p-conjugated spacers to the Dp
A systems gave rise to more complex structures such as DD
pA, DApA and DpAA.[30b]
For instance, the metal-free sensitizers JK-68 and JK-69
(Scheme 7) have been considered as DApA molecules,
where D is bis(dimethylfluorenyl)amino, the first A group is
thiophene (JK-68) or n-hexylthiophene (JK-69), the second A
group is the cyanoacrylic acid anchor group, and the p bridge
is a benzothiadiazole moiety.[116] Again, the amphiphilic hexyl
groups had a beneficial effect on recombination kinetics, lead-
ing to efficiencies of 7.5% and 8.2%, respectively, for devices
employing JK-68 and JK-69.[116]
A study including a benzothiadiazole as secondary A, with
thiophene or phenylene as different p bridges and indole or tri-
phenylamine as different D groups, has been reported.[117]
The introduction of the indole group on the one hand, and the
incorporation of a thiophene group as secondary A on the
other hand, led to a reduction in the gap between the HOMO
and LUMO levels. As a consequence, the molecule WS-2 with
this configuration presented extended light absorption com-
pared to other combinations, and the highest overall efficiency
of 8.7%.[117] Later, sensitizer WS-9 (Scheme 7) incorporating
n-hexyl-substituted thiophene groups exhibited an improved
efficiency of 9%.[118] This modification produced a blue shift
in the absorption spectrum relative to WS-2, but the amphi-
philic groups reduced dark current, improving VOC, as men-
tioned earlier.
Examples with DDpA systems have also been
reported. In addition to a triphenylamine, Tan et al. explored
carbazole, fluorene and spirobifluorene as secondary donors,
facilitating electron-donating ability and shifting the light
absorption to the NIR.[119] It was found that the highest effi-
ciency of 7% was achieved with the carbazole group. Simi-
larly, Gratzel et al. reported 9.1% cell efficiency using dye JK-
113 (Scheme 7).[120] This dye possesses thienothiophene and
vinylene donors and an additional thienothiophene as linker.
This configuration provided an excellent molar extinction
coefficient to this dye.
Although the acceptor moiety has received comparatively
little attention, some studies have appeared recently employing
sensitizers with a DpAA structure. Bauerle et al. synthe-
sized a metal-free dye with triphenylamine as D, oligothio-
phene as p bridge and the double acceptor benzothiadiazole/
cyanoacrylic acid, studying the effect of the introduction of a
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Scheme 8. Pictorial illustration of a QDSSC and an ideal energy diagram
with QDs of different size.
phenyl group between them.[121] They found that the inser-
tion of this phenyl ring into the dye improved the cell effi-
ciency from 1.24% to 8.21%.[121] The addition of this phenyl
group blocks back electron transfer after charge injection,
reducing recombination by fivefold. More recently, a series of
metal-free sensitizers with two anchor groups were investi-
gated.[122] Usually, dyes with two anchoring groups displayed
improved photocurrents but lower photovoltages due to effi-
cient dark current. However, the introduction of thienyl sub-
stituents between the linker and the anchor groups in dye DA-
2 (Scheme 7) produced a reduction in dark current, and, con-
sequently, cell efficiencies of 7.87% in the presence of cheno-
deoxycholic acid were achieved.[122]
As reported for metal complex sensitizers, the use of redox
pairs other than I2/I32 has been explored for metal-free dyes as
well. Wang et al. reported DpA sensitizers with 2,6-bis(thien-
2-yl)24,4-dihexyl-4H-cyclopenta[2,1-b:3,4-b0 ]dithiophene (C-
229, Scheme 7) and 2,7-bis(thien-2-yl)29,9-dihexylfluorene
(C-228) linkers.[123] The use of the thiophene moiety instead of
fluorene led to a red shift in the absorption spectrum, increasing
the JSC. Moreover, the use of the CoII/CoIII redox pair rather
than I2/I32 led to an improved VOC and cell efficiencies up to
9.4% using C-229 dye.[123] A similar dye named Y123 (Scheme
7), which also contains dihexylcyclopentadithiophene as the p
bridge but has a dihexyloxybiphenyl-containing D moiety, dem-
onstrated 9.6% efficiency in DSSCs in the presence of the CoII/
CoIII redox pair.[124]
This dye has been used in combination with the Zn por-
phyrin YD2-o-C8 dye, as mentioned earlier.[70] In addition,
the combination of two metal-free organic dyes in co-
sensitized DSSCs has also been reported. For instance, dyes
FNE46 and FNE53 were used in co-sensitized solar cells to
obtain 8% overall efficiency.[125]
Another class of organic dyes that have been proposed for
low-cost large-scale production for DSSC applications are nat-
ural dyes.[126] These natural products are known because of
their low cost, attainability, abundance and environmental
friendliness. They may be extracted from flower petals, leaves,
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fruits, vegetables or bark. Although the power conversion effi-
ciencies of these dyes have been reported to be much lower
than those of the synthetic ones, they are still appealing sensi-
tizers for commercial applications of DSSCs.
4. Other Sensitizers
Since the late 1990s, DSSCs have achieved efficiencies higher
than 10% by means of sensitizer molecular engineering, opti-
mizing dye light harvesting, minimizing recombination events
and improving dye long-term stability. However, DSSCs still
present instability issues and some difficulties in achieving
strong broadband light harvesting using a single dye.
Inorganic semiconductors have been presented as good can-
didates to overcome the molecular sensitizer drawbacks. Narrow
band-gap semiconductor materials exhibit continuous light
absorption in the major part of the solar spectrum due to strong
absorption of photons with energies larger than their band gap
and they have demonstrated excellent thermal and photostability.
The main types of inorganic semiconductors employed as
sensitizers have been quantum dots, extremely thin absorbers
and the special case of perovskites. In the following sections we
will discuss the main characteristics of these inorganic sensi-
tizers relating to their progress in device efficiency.
4.1. Quantum Dot Sensitized Solar Cells (QDSSCs)
Quantum dots (QDs) are inorganic semiconductor nanopar-
ticles with spatial confinement of the photogenerated charge
carriers. This quantum confinement provides unique optical
and electronic properties. The main advantages in the use of
QDs are the tunable energy gap, possibility of multiple exciton
generation, high photostability, elevated molar extinction coef-
ficient and low-cost production.[31,127] The device working
principle and structure are very similar to DSSCs, but with
replacement of the molecular dyes by QDs (Scheme 8). More-
over, there are several possible methodologies to sensitize the
semiconductor metal oxides with QDs: successive ionic layer
adsorption and reaction (SILAR), chemical bath deposition
(CBD), ex situ fabricated colloidal QDs attached by molecular
linkers (LA) or simply their direct adsorption (DA), and elec-
trophoretic methods (EP).[31]
One of the first examples of a QDSSC was reported in
1990,[128] where CdS quantum dots were prepared by SILAR.
Although the device IV characteristics were measured under
monochromatic light at 460 nm and an incident light power
of 867 mW/m2, a promising 175 mA/m2 and 395 mV were
obtained. Since then, numerous inorganic QDs have been
tested as sensitizers (CdS, CdSe, PbS, PbSe, CdTe, InP, Ag2S,
Sb2S3, Bi2S3, and CuInS2)[129] using the various possible dep-
osition methodologies. However, it was since 2008 that a rapid
increase in the number of publications and improvements in
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Scheme 9. Pictorial illustration of an ETA DSSC configuration.
the efficiency records were reported.[130] This breakthrough
arose from the understanding that, while in DSSCs a standard
configuration can be applied to a wide variety of sensitizers, in
the case of QDSSCs the inorganic semiconductor light har-
vester and its deposition method dictate the requirements of
the other device components.[131] Actually, the typical I2/I32
redox couple affords good DSSC efficiencies with the majority
of molecular sensitizers; however, in the presence of chalcoge-
nide semiconductor QDs it promotes corrosion. Instead of the
usual I2/I32, other redox couples have been proposed, such as
CoII/III or polysulfide. Although polysulfide-based electrolytes
have shown the best efficiencies, high charge transfer resistance
has been demonstrated when the typical Pt-coated counter
electrode is used. Therefore, alternative counter electrode cata-
lysts have been proposed (i.e., Cu2S). The knowledge of all
these new parameters, different from those of conventional
DSSCs, has promoted the fast growth of QDSSCs in the last
years, leading to record efficiencies close to 7%.[132] Further
understanding of the main operating mechanism of these devi-
ces is needed in order to overcome the current DSSC
efficiencies.[133]
4.2. Extremely Thin Absorber Solar Cells (ETA DSSCs)
The motivation for the use of extremely thin absorbers (ETAs)
comes from the need for high extinction coefficient materials
and the need to improve the DSSC stability issues related with
the use of liquid electrolytes. Great efforts have been dedicated
to developing the so-called solid-state DSSC. However, the
use of solid-state electrolytes with molecular sensitizers is still
far from showing comparable efficiencies to their liquid elec-
trolyte counterparts. Therefore, a solar cell technology based
on the use of thin semiconductor materials was proposed by
Siebentritt et al.,[134] inspired by the pioneering work of Vogel
et al. (Scheme 9).[128]
The main differences of ETA DSSCs with respect to
thin-film technology (second generation) arise from their
working principles.[135] In the case of thin-film solar cells
the semiconductor material must absorb a large portion of
the incident photons in layers of 25 mm thick, where
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charges are photogenerated, and these charges must travel
through these layers to reach the contacts. Therefore, high-
quality materials are required in order to obtain large carrier
diffusion length and achieve good efficiencies. However, in
ETA DSSCs (third generation), the ETA function is only
light harvesting, and the charge transport role is performed
by n-type wide band-gap semiconductor materials (TiO2,
ZnO) and hole transport materials (CuCNS, spiro-OMe-
TAD).[136] Therefore, the absorber layer relaxes the require-
ments of material quality. Low-cost chemical synthesis
methods can be employed and the optimization of the light
harvester can focus on superior light absorption, leaving the
optimization of transport properties for other materials.
The aim of ETA DSSCs is to produce low-cost solar cells
with comparable efficiencies to those of thin-film
technology.[137]
In the first examples of ETA DSSCs the absorber materials
were composed of semiconductors made of Se or CdTe, lead-
ing to efficiencies around 1%.[138] The efficiency progress in
ETA DSSCs increased rapidly from 2007 through the applica-
tion of Sb2S3 as sensitizer over mesoporous TiO2 layers and
CuSCN as hole transporter.[139] Device efficiencies up to 4.1%
were achieved by using this configuration. Nevertheless,
CuSCN presented several limitations due to the difficulty of
this material to completely fill the pores of the mesoporous
TiO2 layer, sensitivity to its gaseous environment and lack of
reproducibility. Three years later, further efficiency progress
was achieved by employing organic semiconductors as the hole
conductors, such as the semiconducting polymers poly(3-hex-
ylthiophene) (P3HT) and poly(2,6-(4,4-bis(2-ethylhexyl)-
4H-cyclopenta[2,1-b;3,4-b0 ]dithiophene)-alt-4,7-(2,1,3-ben-
zothiadiazole)) (PCPDTBT, Scheme 10), instead of the inor-
ganic ones. ETA DSSC efficiency achieved 5.1%[140] and
6.2%[141] by using these polymers as hole conductors. How-
ever, the ETA DSSC record efficiency of 6.3% was achieved
using a blend of the semiconducting polymer PCPDTBT with
the fullerene derivative PCBM as hole transport layer.[142]
Further understanding of the working mechanism of ETA
DSSCs is still needed, since only a few reports have been pub-
lished addressing the fundamental interfacial charge transfer
reactions that take place between the different semiconductor
materials.[143]
4.3. Perovskite Solar Cells
For the past 20 years, hybrid perovskites, and in particular
those containing metal halides of the fourth main group
(Ge21, Sn21, Pb21), have received interest due to their good
optoelectronic properties and potential for device fabrica-
tion.[144] Recently, they have attracted considerable attention
because of their excellent light-harvesting characteristics, high
efficiency in DSSCs, low cost and easy production. These types
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Scheme 10. Structures of the semiconducting polymers P3HT and
PCPDTBT.
of perovskites are organometal trihalides, and currently the
most commonly employed is CH3NH3PbI3. The chemical
structure is ABX3, where A 5 alkali, B 5 Ge, Sn, Pb, and
X 5 halide (Cl, Br, I, or their mixed halides). Mechanistically,
lead halide perovskite is a semiconductor material that may
both work as a light absorber and show very efficient ambipo-
lar transporting behavior for both types of charge carriers.
However, a comprehensive understanding of the operating
mechanism of this photovoltaic system is still required for the
further improvement of this photoactive material (Scheme
11).[145] It is worth noting that in perovskite solar cells the
organometal trihalide, besides acting as light harvester, plays a
second role as charge carrier. Due to this dual role, the perov-
skite solar cell cannot be strictly considered as a photoelectro-
chemical solar cell, since the light harvester is also transporting
charges. The above properties make possible two main config-
urations, one based on the classical DSSC with a mesoporous
metal oxide layer that can act as electron transporter and/or
scaffold, and the planar heterojunction, where a thin film of
perovskite is sandwiched between p- and n-type selective
charge-extracting contacts (see Scheme 11). Nevertheless, con-
sidering the impressive efficiency record that devices based on
perovskites have shown in a short period of time, it is of inter-
est to include a brief comment on them in the present review.
In 2009 appeared the first perovskite DSSC by Miyasaka
et al., which displayed an efficiency of 3.8% using the perovskite
as sensitizer and liquid electrolyte.[146] This opened the door for
the application of this perovskite in the field of solar cells. This
efficiency was improved in 2011 by optimizing the preparation
conditions and an efficiency of 6.54% was reached.[147] A break-
through appeared in 2012 using these organometal trihalides in
solid-state DSSCs, in which submicrometer mesoporous TiO2
film adsorbed with the perovskite CH3NH3PbI3 exhibited an
efficiency of 9.7% under one-sun illumination.[148] Currently,
the maximum efficiency officially achieved using this type of
semiconductor is 20.1%, which was obtained by researchers at
the Korean Research Institute of Chemical Technology (KRICT).
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Scheme 11. Different architectures of perovskite solar cells.
5. Electrolytes
5.1. Liquid Electrolytes
The electrolyte used in DSSCs has a strong influence on the pho-
tovoltaic performance. In fact, before the appearance of the hybrid
organometal halide perovskites, the maximum efficiency of a
DSSC had been achieved using liquid electrolytes based on organic
solvents. The liquid phase should be responsible for the diffusion
and the dissolution of the redox couple. The desired properties of
the solvents are high dielectric constant and low viscosity. The
most common solvents used for DSSCs are acetonitrile, propylene
carbonate, 3-methoxypropionitrile, ethylene carbonate and N-
methylpyrrolidine. However, liquid electrolytes present several
problems such as leakage, evaporation, dye desorption and corro-
sion of the counter electrode. These limit the long-term stability of
DSSCs. The highest conversion efficiency obtained in DSSCs,
13.1%, was achieved using acetonitrile-based electrolytes.[72] This
high efficiency was mainly due to the low viscosity and the solubil-
ity of the salts and additives. Much effort has been made to use less
volatile solvents in order to prolong the operating life of DSSCs,
like using 3-methoxypropionitrile with its high boiling point,
although the final efficiency was slightly reduced.
5.2. Quasi-Solid-State Electrolytes
In order to solve the problem of evaporation of liquid electro-
lytes, quasi-solid-state electrolytes have been developed using
ionic liquids, nanopowders or polymers. They form a three-
dimensional matrix by using a suitable gelator, which retains the
liquid and disfavors the evaporation process. The main problem
of the ionic liquids based on imidazolium salts is their high vis-
cosity, which limits the diffusion of the redox couple (I2/I32)
and diminishes the device performance. The first use of ionic
liquids in DSSCs was in 1996 by Papageorgiou et al.,[149] who
demonstrated that they are attractive candidates for photoelectro-
chemical solar cells with improved stability. Afterwards, several
works appeared using different types of ionic liquids, leading to
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Scheme 12. Charge transport processes taking place in ssDSSCs.
efficiencies over 8%. For instance, ionic liquids based on the
SeCN/(SeCN)3 redox couple gave an efficiency of 7.5%,[150]
1-ethyl-3-methylimidazolium tetracyanoborate gave an efficiency
of 7%,[151] and a binary electrolyte composed of 1-propyl-3-
methylimidazolium iodide and 1-ethyl-3-methylimidazolium
tricyanomethanide gave an efficiency of 7.4%.[152] However,
most of them still exhibited limited stability. In 2008 a new con-
cept appeared, using eutectic melts of mixtures of ionic liquids
without liquid electrolyte, leading to excellent device stability
and an efficiency of 8.2%,[153] which is so far the maximum effi-
ciency achieved using ionic liquids.
On the other hand, polymer gel electrolytes can be classi-
fied as thermo-reversible (thermoplastic) via physical gelling or
thermo-irreversible (thermosetting) by chemical bonding or
covalent cross-linking. The conductivity of the polymer gel
will depend on the molecular weight and morphology of the
polymer because of the different mobility of charges in the
amorphous and crystalline domains of the gel. One of the
most commonly used thermoplastic gelators is poly(vinylidene
fluoride-co-hexafluoropropylene) (PVDF-HFP), which has
been used to reach efficiencies over 7%.[154] An example of a
thermosetting gel is poly(acrylic acid)poly(ethylene glycol)
(PAA-PEG), which is stable and increases the performance of
the device. To date, the highest efficiency obtained by this
approach is 10.5%, using poly(acrylonitrile-co-vinyl acetate)
(PAN-VA).[155]
Another approach consists of the solidification of the liq-
uid electrolyte by addition of nanopowders such as SiO2,
Al2O3, ZrO2 or carbon. At a certain weight concentration, the
electrolyte becomes a viscous paste. In addition, the surfaces of
these nanoparticles can also participate in the charge transport
mechanism. The performance of the cells fabricated by nano-
powder gel is comparable to that of liquid electrolytes.[156158]
However, quasi-solid-state electrolytes still have problems
from solvent leakage and require suitable sealing. Also, device
performance depends on the working temperature, because
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this parameter can produce phase transformation from a gel
state to a solution state. It appears that completely solid-state
electrolytes are more interesting in terms of stability and future
commercialization.
5.3. Solid Electrolytes
Solid-state DSSCs (ssDSSCs) have been extensively investi-
gated in order to replace the liquid electrolyte. Solid electro-
lytes include inorganic and organic hole-transporter p-type
materials (HTMs). The operating mechanism of ssDSSCs is
slightly different from conventional DSSCs with liquid elec-
trolytes. The processes of sensitizer excitation, electron injec-
tion and dye regeneration are the same as in DSSCs with
liquid electrolytes. The difference is that the hole transfer takes
place between the dye and the HTM, and the holes are trans-
ported via hopping to the counter electrode. Scheme 12 illus-
trates the operation of ssDSSCs using HTMs. With this
configuration the band gap structure of the p-type material
must be compatible with the HOMO level of the dye for
regeneration. The ideal HTM should have a valence band with
an energy that is slightly above the HOMO level of the dye.
One of the main disadvantages of I2/I32-based electro-
lytes is that they are chemically very aggressive. In contrast,
most of the HTMs are chemically less aggressive and eliminate
the problem of solvent evaporation; however, a number of
other problems are encountered, for instance pore filling of the
mesoporous TiO2 layer. In addition, hole mobility is slower
than in a liquid electrolyte and the recombination rate of elec-
trons in the conduction band is higher for HTMs.
Inorganic HTMs that have been employed include CuI,
CuBr, CuSCN and CsSnI3. The use of CuI as a HTM in
ssDSSCs was first demonstrated by Tennakone et al., with a
power conversion efficiency over 4.7%.[159] CuSCN was
reported as an alternative with improved stability, but still with
limited efficiency (around 2%).[160] CuI and CuSCN have
also been used as HTMs in hybrid perovskite solar cells, lead-
ing to efficiencies of 6.0%[161] and 12.4%,[162] respectively. In
addition, CsSnI3 is another promising inorganic HTM, due to
its high mobility and low-cost processing. Recently, a cell using
CsSnI3 yielded a photon conversion efficiency of up to
10.2%.[163]
In general, these copper-based materials have a good con-
ductivity, which facilitates their hole-transporting properties.
However, they have some limitations due to their stability and
fast crystallization reducing the degree of infiltration.
Recently, the use of other inorganic HTMs with good effi-
ciency has been demonstrated in systems consisting of a meso-
scopic nickel oxide layer acting as an efficient hole-collecting
contact, leading to a power conversion efficiency of 9.51%.[164]
Organic HTMs have advantages over inorganic HTMs
because of their theoretical low cost and easy deposition. The
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Scheme 13. Structure of the HTM spiro-OMeTAD.
most commonly used are 2,20 ,7,70 -tetrakis(N,N-di-4-methoxy-
phenylamino)-9,90 - spirobifluorene (spiro-OMeTAD, Scheme
13),[165] P3HT,[166] and poly(triarylamine) derivatives.[167]
However, spiro-OMeTAD is at present the material that
gives better power efficiency in ssDSSCs. This material was
introduced in 1998 by Gratzel et al. with an initial power effi-
ciency of 0.74%.[165] Several consecutive improvements have
increased the efficiency. In 2001, the efficiency was increased
up to 2.56% by a combination of 4-tert-butylpyridine and lith-
ium bis(trifluoromethanesulfonyl)imide acting to inhibit
charge recombination at the interface.[168]
The use of dyes with high absorption coefficients such as
C104 and C220 increased the power efficiency to 4.6%[169]
and 6%.[170] A value of 7.2% was achieved in 2011 using a
cobalt compound for doping of spiro-OMeTAD.[171] As indi-
cated above, the breakthrough for ssDSSCs was with the appli-
cation of the hybrid perovskites, to reach an efficiency of 9.7%
using organometal halides (CH3NH3PbI3).[148] During this
time, a study with perovskite as light absorber and Al2O3 mes-
oporous film reached an efficiency of 10.9% due to the con-
finement of the photoexcited electrons within the
perovskite.[172] An efficiency of 12.3% was reported using
CH3NH3PbI3 and poly(triarylamine) as HTM.[167] The high-
est efficiency in 2013 was 15.0%, using the sequential deposi-
tion method for the formation of the perovskite.[173] This
efficiency value beats the dye-sensitized record of 13.1% using
porphyrin sensitizer (SM375 dye).[72] Another improvement
recently appeared that consisted of modifying spiro-OMeTAD
by changing the positions of the two methoxy substituents,
leading to an energy conversion efficiency of 16.7%.[174]
In November 2014 the certified efficiency record was
20.1%, which was achieved by KRICTresearchers. Also, during
the same period of time, an efficiency of about 24% was claimed
at the WCPEC-6 conference but without certification.
In addition, other efficient organic HTMs have been used
with success, such as a tetrathiafulvalene derivative (TTF-1),
P3HT, and PCPDTBT, with efficiencies of 11.03%, 12.4%
and 6.3%, respectively.[142,166,175]
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There are some other examples that use perovskites as
the photoactive material, but with Pb replaced by other met-
als. The device with better efficiency has a composition of
CsSnI2.95F0.05 doped with SnF2 and also used a ruthenium
complex dye to achieve an efficiency of 10.2%, as reported by
the group at Northwestern University led by Mercouri
Kanatzidis.[163]
It should be mentioned that ssDSSCs and particularly
perovskite-based solar cells are currently a hot topic in this
area. The maximum efficiency is changing continuously, and
in only a few years the efficiency has increased from 3% to over
20%. Perovskites are attractive materials that can be in solution
at low processing temperatures. However, some issues remain
to be solved, such as the operating mechanisms of the cell and
the long-term stability for commercial applications.
6. Conclusions and Future Prospects
In the last decades, progress in DSSC efficiency has been
mainly driven by the synthesis and optimization of sensitizers
and electrolytes. The rational design of sensitizer organic dyes
has spearheaded the main efficiency progress in the last part of
the 20th and the beginning of the 21st centuries. It has been
only in the last decade that inorganic sensitizers have become a
good choice for DSSCs. Finally, the inorganic perovskite-
based sensitizers have held the leading role in efficiency break-
through during the last decade and the main improvements in
the next years are expected to derive from intense research on
perovskites rather than from the development of novel dyes.
An efficiency record summary of the different sensitizers
exposed in this work is presented in Scheme 14.
As it has been shown in the previous pages, the two main
strategies followed by researchers in order to improve dye per-
formance in DSSCs have consisted of increasing the molar
extinction coefficient to absorb more light and extending the
light-harvesting wavelength range up to the NIR. Moreover,
the improvements in light harvesting have been accompanied
by the correct choice of redox pair and the appropriate selec-
tion of additives in the electrolyte composition. This has
resulted in an increase of the overall efficiency, not only by
selective alignment of energy levels, but also by reducing
recombination events. Furthermore, sensitizer engineering has
allowed the achievement of sensitizers with not only high effi-
ciencies but also long-term stability. These efficient and robust
sensitizers in combination with the solid or quasi-solid electro-
lytes open up the opportunity to produce in the near future
commercial products based on this technology.
However, in order to realize this expectation, the target of
obtaining reproducible modules able to convert light into elec-
tric current at efficiencies similar to or higher than silicon panels
(20%) is still needed. To accomplish this target a new
823
Record Review
Scheme 14. Summary of the main efficiency records obtained with the
various sensitizers in the last 25 years. Please note that some of the presented
efficiency values have not been certified by independent institutions. However,
they show the trends over the last decades for the Gratzel cells with different
light harvesters and the perovskite solar cells. A list of certified device
efficiencies can be found in reference [176].
breakthrough will be necessary through the combination of sev-
eral factors, including sensitizers able to completely harvest the
solar spectrum, electrolytes that perfectly align their redox prop-
erties with the sensitizer potentials, devices that can be kept
operational over the long term, and suitable electrodes able to
extract all photogenerated charges with as low losses as possible.
Acknowledgements
Financial support by the Spanish Ministry of Economy and
Competitiveness (Severo Ochoa and CTQ2012-32315) and
Generalidad Valenciana (Promoteo 2013/014) is gratefully
acknowledged. P.A. and J.A. thank the Spanish Ministry of
Economy and Competitiveness for Ramon y Cajal and Severo
Ochoa research associate contracts, respectively.
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