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Porphyrins as excellent dyes for dye-sensitized

Cite this: DOI: 10.1039/c4dt02756f
solar cells: recent developments and insights
Tomohiro Higashinoa and Hiroshi Imahori*a,b

Dye-sensitized solar cells (DSSCs) have attracted much attention as an alternative to silicon-based solar
cells because of their low-cost production and high power conversion efficiency. Among various sensi-
tizers, numerous research activities have been focused on porphyrins due to their strong absorption
bands in the visible region, versatile modifications of their core, and facile tuning of the electronic struc-
tures. In 2005–2007, Officer and Grätzel et al. had achieved a rapid increase in the power conversion
efficiency of porphyrin DSSCs from a few percent to as much as 7%. Encouraged by these pioneering
works, further high-performance porphyrin dyes have been developed in the last decade. These studies
have provided us profound hints for the rational design of sensitizers toward highly efficient DSSCs.
Push–pull structures and/or π-extensions have made porphyrins panchromatic in visible and even near-
infrared regions. Consequently, porphyrin sensitizers have exhibited power conversion efficiencies that
Received 10th September 2014, are comparable to or even higher than those of well-established highly efficient DSSCs based on ruthe-
Accepted 23rd October 2014
nium complexes. So far the power conversion efficiency has increased up to ca. 13% by using a push–pull
DOI: 10.1039/c4dt02756f porphyrin with a cobalt-based redox shuttle. In this perspective, we review the recent developments in
www.rsc.org/dalton the synthetic design of porphyrins for highly efficient DSSCs.

1. Introduction
a
Department of Molecular Engineering, Graduate School of Engineering, In recent years, various environmental issues caused by con-
Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan.
sumption of a large amount of fossil fuel have attracted much
E-mail: [email protected]
b
Institute for Integrated Cell-Material Sciences (WPI-iCeMS), Kyoto University, attention. There is also serious concern that the world’s
Nishikyo-ku, Kyoto 615-8510, Japan limited energy resources will be exhausted in the near future

Tomohiro Higashino was born in Hiroshi Imahori completed his

1986 in Osaka, Japan. He doctorate in organic chemistry
received his BSc (2009) and MSc at Kyoto University. From
(2011) degrees from Kyoto Uni- 1990–1992, he was a post-doc-
versity. He received a PhD degree toral fellow at the Salk Institute
from Kyoto University in 2014 on for Biological Studies, USA. In
the chemistry of expanded por- 1992, he became an Assistant
phyrins with main group Professor, ISIR, Osaka University
elements. In 2013, he joined the and then moved to the Graduate
research group of Professor School of Engineering, Osaka
Imahori as an Assistant Pro- University, as an Associate Pro-
fessor. His current research inter- fessor. Since 2002, he has been a
Tomohiro Higashino ests include the creation of Hiroshi Imahori Professor of Chemistry, Graduate
novel pyrrole-based π-conjugated School of Engineering, Kyoto
materials and their application. University. He has received the JSPS Prize (2006), CSJ Award for
Creative Work (2006), Osaka Science Prize (2007), and NISTEP
Researcher Award (2007). His current interests involve artificial
photosynthesis, organic solar cells, and organic functional
materials.

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because the world is facing a continuous growth in population However, the limited supply and high cost of ruthenium metal
and economy, especially in developing countries. From these may hamper their widespread application. From this point of
points of view, photovoltaics and artificial photosynthesis are view, organic dyes with no metal or inexpensive metal com-
highly desirable technologies because clean solar energy from plexes have been intensively explored owing to their potential
the sun is substantially inexhaustible. low-cost production and facile modulation of their structure
Since the seminal paper was reported by Grätzel and co- and basic properties including HOMO−LUMO levels and
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workers in 1991,1 dye-sensitized solar cells (DSSCs) have drawn absorption profiles.10–13 A number of organic dyes exhibiting a
much attention as an alternative to silicon-based solar cells relatively high cell performance have been reported so far. The
because of their low-cost production and high power conver- best DSSC performance with an η-value of 10.3% was noted
sion efficiency (η).2–18 The schematic illustration of com- when metal-free organic dye C219 was used (Fig. 2).12 Never-
ponents and representative operational principles of DSSCs is theless, the cell performance of organic dye-based DSSCs is
depicted in Fig. 1. The typical DSSC consists of a dye-sensi- still inferior to that of ruthenium dye-based DSSCs. Moreover,
tized photoanode (TiO2) and a platinum counter electrode the realization of η-values more than 15% is suggested for the
sandwiching an electrolyte that contains a redox mediator. commercialization of DSSCs. Therefore, it is crucial to develop
The photocurrent of DSSCs is generated through the following inexpensive organic dyes or metal complexes exhibiting a high
processes. First, the photoexcited dye (S*) upon illumination cell performance.
injects an electron into a conduction band (CB) of TiO2 From the beginning of DSSC history, researchers have
(−0.5 V vs. NHE). Then, the resultant oxidized dye (S•+) is attempted to utilize porphyrins as potential sensitizers for
reduced by redox shuttle, an I− ion or Co2+ complex in the elec- DSSCs by focusing on their intense absorption bands in the
trolyte (dye-regeneration). The injected electrons move through visible region, versatile modifications of their core, and facile
an external circuit to the counter electrode. Finally, the I− ion tuning of the electronic structures.14–19 However, until recently
or Co2+ complex is regenerated by the reduction of an I3− ion the η-values of DSSCs based on typical porphyrin sensitizers
or a Co3+ complex at the surface of the counter electrode, and were much lower than those based on ruthenium sensitizers
the circuit is completed. as a result of the poor light-harvesting ability at around
The cell performance of DSSCs strongly depends on sensi- 500 nm and beyond 600 nm. To overcome this drawback, the
tizers. Until recently ruthenium complexes, such as N3 and introduction of a push–pull structure and/or the elongation of
N719 (Fig. 2), have been the most efficient sensitizers exhibit- porphyrin π-conjugated system are effective means to improve
ing more than a power conversion efficiency (η) of 11%.4–9 the light-harvesting property that would allow us to gain better
matching with solar energy distribution on the earth. Officer
and Grätzel et al. reported a series of meso-tetraphenylporphyr-
ins with a β-oligoalkenyl anchoring group (Fig. 3). In 2005 an
η-value of 5.6% was attained for a DSSC based on GD1.20
Furthermore, in 2007 they found that a Zn-1-based DSSC dis-
played a higher η-value of 7.0%.21 Encouraged by the rapid
increase in the η-value of porphyrin DSSCs from a few percent
to as much as 7%, various porphyrins characterized by a
push–pull structure and/or π-conjugated elongation have been

Fig. 1 Schematic illustration of components and operational principles

of DSSCs. TCO denotes a transparent conducting oxide electrode.

Fig. 2 Representative examples of highly efficient sensitizers for Fig. 3 β-functionalized porphyrin sensitizers reported by Officer and
DSSCs. Grätzel et al.

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synthesized in the last decade. In particular, a class of push– photovoltaic properties. In the cases of the aprotic solvents
pull porphyrins with an electron-donating diarylamino group (i.e., DMF and CH2Cl2) the lower η-value resulted from the low
and an electron-withdrawing carboxyphenylethynyl anchoring surface coverage (Γ) of ZnP on TiO2, whereas in the cases of
group have revealed their remarkable photovoltaic perform- the protic solvents they were involved in the adsorption struc-
ance. For instance, DSSCs based on SM315 and GY50 exhibited tures of the porphyrin on TiO2, yielding the higher η-value.
exceptionally high η-values of ca. 13%.22,23 Recent advances of Moreover, the sensitization time also had a large impact on
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the porphyrin-based DSSCs have been reviewed in several the cell performance. When MeOH was used as the sensiti-
reports.14–19 The detailed mechanistic studies, such as the zation solvent, the η-value was increased with increasing
photophysics, electrical and optical spectroscopy, responsible sensitization time to reach a peak of 4.6% in 1 h and then
for performance enhancement have already been reviewed by gradually decreased to reach a plateau. In accordance with the
Mori and Mozer et al.17 Therefore, we will mainly focus on the η-profile, the Γ-value was increased initially with the sensiti-
development of synthetic design and insights of porphyrin zation time and then leveled off in 1 h. Such a drop of the
structures as excellent dyes for highly efficient DSSCs in this η-value in the longer sensitization time was rationalized by an
perspective. increase in self-quenching of the porphyrin excited singlet
state by porphyrin aggregation with sensitization time.
More importantly, Imahori et al. found a direct correlation
2. Insights for the realization of between the η-value and amplitude of the injected, long-lived
electrons (>10 ns) in CB.25,26 The sensitization conditions have
highly efficient porphyrin DSSCs a strong influence on the rates of electron injection and charge
2.1 Adsorption structures of porphyrin on TiO2 recombination (CR) and the amplitude of the long-lived elec-
Since electron transfer (ET) rates are a function of electronic trons. The ET processes occur through space between the
coupling between the adsorbed dye and the TiO2 surface, the tilted porphyrin and the TiO2 rather than through a bond via
cell performance is influenced by adsorption structures of the the bridge. Thus, the tilt angle of the porphyrin on TiO2,
dye on TiO2. Imahori and co-workers addressed the relation- which is affected greatly by the sensitization solvent and time,
ships between sensitization conditions and cell perform- as well as the type of the bridge, governs the ET kinetics, the
ances.24 For ZnP-sensitized solar cells, the η-value showed a photocurrent, and the resultant cell performance. Overall,
strong dependence on sensitization solvents (Fig. 4). The there was a linear correlation between the tilt angle and
η-value obtained for a sensitization time of 12 h increased η-value, the smaller the tilt angle the higher the cell perform-
from 0.55% to 3.7% in the order: DMF < CH2Cl2 < t-BuOH/ ance (Fig. 5).
MeCN < EtOH < MeOH. This is in sharp contrast with the Similarly, D’Souza et al. probed the effect of dye-orientation
weak solvent dependence of N719-sensitized solar cells on the on TiO2 on the photovoltaic properties of meso-carboxyphenyl-
porphyrins where the carboxy group is attached to the para,
meta or ortho position.27 The cell performance was lowered by
varying the substituted positions from para to ortho, which
reflects the faster CR. These studies indicate that the small tilt
angle of porphyrin dye on TiO2 is favorable for retarding CR as
well as obtaining large a Γ-value. He et al. also evaluated the
cell performance of DSSCs using a series of porphyrin sensi-
tizers with identical anchoring groups.28 The p-carboxyphenyl
group was a better anchoring one than m-carboxyphenyl
because the electron density distribution of the p-carboxyphe-
nyl group in LUMO is higher than that of the m-carboxyphenyl
in LUMO. These studies imply that rational design of a suit-

Fig. 4 (a) Current–voltage characteristics of ZnP-sensitized solar cells

and (b) sensitization time profiles of η-value (●) and of the surface Fig. 5 Schematic representation of the porphyrin adsorption geometry
coverage (Γ) (■). on TiO2.

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able anchoring group and optimization of the sensitization

conditions are essential to achieve a high cell performance.

2.2 Steric effect of substituents

The cell performance depends on the peripheral substituent of
porphyrins. Imahori et al. compared the photovoltaic pro-
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perties of a series of porphyrin sensitizers and found that

meso-phenyl-substituted porphyrin gave a lower η-value of
1.2% than that of meso-mesityl-substituted ZnP (η = 4.6%).24
The bulky mesityl groups may suppress self-quenching by por-
phyrin aggregation, leading to an increase of electron injection
efficiency (ϕinj ). Lin and Diau et al. developed alkoxyphenyl-
substituted porphyrins (LD11 and LD12, Fig. 6).29 The cell
based on ortho-substituted LD12 displayed a superior η-value Fig. 7 Molecular structures of porphyrins bearing HOQ as an anchoring
(7.43%) to that of LD11 (η = 4.78%). Importantly, both short group.
circuit current ( JSC) and open circuit voltage (VOC) of the LD12-
based cell were remarkably higher than those of the LD11-
based cell. They proposed that the long alkoxy chains at the
ortho-positions wrapping the porphyrin core would inhibit the
aggregation on TiO2 and retard CR between the injected elec-
trons and I3− by a blocking effect. Recently, ortho-alkoxyphenyl
groups have been regarded as an indispensable substituent for
achieving highly efficient DSSCs, especially when a cobalt-
based redox shuttle is used in the electrolyte (see section 5.2).
Fig. 8 Molecular structures of porphyrin bearing salicylic acid as an
anchoring group and the reference porphyrin.
2.3 Anchoring groups
In DSSCs, carboxylic acids such as benzoic acid and cyano-
acrylic acid have been the most widely used functional groups stronger resistance toward both the acid and the base.
for attaching sensitizers to metal oxides. However, carboxylic Although the η-value is moderate, the better cell performance
acids are prone to dissociate from the metal oxide surface and durability obtained by the use of HOQ make further
under severe conditions, including exposure to aqueous and assessment worthwhile.
alkaline electrolytes.30 Such detachment of adsorbed dyes Jiang and co-workers used salicylic acid as a tridentate
from TiO2 is undesirable considering the durability of DSSCs anchoring group (Fig. 8).33,34 An η-value (4.55%) of a DSSC
for practical applications. For this reason, novel anchoring based on PESp is twice as large as that (η = 2.26%) with PE1
groups have been exploited, and several anchoring groups possessing benzoic acid as the anchoring group.34 Although
exhibiting promising performance are described here. the tridentate binding mode between salicylic acid and TiO2
He et al. found that 8-hydroxyquinoline (HOQ) is an attrac- remains ambiguous, its mode may enhance the ϕinj-value,
tive candidate to replace the benzoic acid group.31,32 The por- resulting in an increase of the η-value.
phyrin dye bearing the HOQ group as the anchoring one can
adsorb on TiO2. DSSCs with DPZn-HOQ and DPZn-COOH gave
η-values of 3.09% and 1.76%, respectively, under the same con- 3. Push–pull porphyrins
ditions (Fig. 7).32 Co-sensitization of DPZn-HOQ with BET 3.1 meso-Diarylamino porphyrins
increased the η-value by 10%, yielding an η-value of 3.41%. In
In recent years, D–π–A type organic sensitizers, which consist
addition, the HOQ-modified porphyrin dye exhibited a
of an electron-donating group (D), π-spacer (π), and an elec-
tron-withdrawing anchoring group (A), have been widely inves-
tigated owing to their broad and intense absorption spectral
features as well as efficient electron injection due to intramole-
cular charge transfer (CT) character.10–13 One can envision that
porphyrins are attractive as the π-spacer moiety. In this
respect, various push–pull type porphyrins have also been syn-
thesized for DSSCs. Diau, Yeh and co-workers prepared a
variety of zinc porphyrin derivatives with diarylamino group as
the strong electron-donating substituent and carboxyphenyl-
ethynyl group as the electron-withdrawing anchoring substitu-
Fig. 6 Molecular structures of alkoxyphenyl-substituted porphyrins. ent at meso-positions (Fig. 9).35 In 2009, by using YD1 they

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ability was improved with an increasing number of diaryl-

amino groups on the porphyrin. However, DSSCs using trans-
ZnP and cis-ZnP exhibited lower η-values (3.8% and 5.5%) than
that of mono-ZnP (6.5%). Considering that there are weak elec-
tronic couplings between the LUMO of porphyrin and the CB
of TiO2 as a result of smaller electron densities on the anchor-
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ing carboxy groups of trans-ZnP and cis-ZnP, inefficient elec-

tron injection would lower the cell performances. With this in
mind, Imahori et al. replaced one carboxyphenyl group in cis-
ZnP with the more electron-withdrawing carboxyphenylethynyl
group, while another carboxyphenyl group in cis-ZnP was
replaced with the bulky mesityl group to create ZnPBAT
(Fig. 10).39 The absorption of ZnPBAT was broadened and red-
shifted compared to that of ZnPBA without the triple bond in
the electron-withdrawing anchoring group and even to YD2
Fig. 9 Molecular structures of YD0, YD1, and YD2.
with only one diarylamino group. The electron densities of the
anchoring group in the LUMOs of ZnPBAT and YD2 are com-
parable and considerably larger than that of ZnPBA. A DSSC
achieved an η-value of 6.0%, which is higher than that using using ZnPBAT achieved an η-value of 10.1%, which is higher
YD0 (2.4%). Importantly, the cell performance of YD1 was than those using ZnPBA (8.3%) and YD2 (9.1%) under their
comparable to that of N3 (6.1%) under their optimized con- optimized conditions.
ditions. The same group designed YD2, which was modified Multiple electron-withdrawing anchoring groups were also
from YD1, to improve its stability.36 The cell performance of employed to enhance the push–pull character as well as to
YD2 increased to an η-value of 6.8% in comparison with that strengthen the binding of the porphyrin on TiO2. Kim and co-
of YD1. Then, the device fabrication was further optimized in workers synthesized push–pull porphyrins tda-1b-d-Zn and
collaboration with the Grätzel group. In 2010 the η-value using tda-2b-bd-Zn, possessing one and two β-oligo-olefinic substitu-
YD2 was remarkably improved to ca. 11%.37 This report was ents as the electron-withdrawing anchoring groups, respect-
the first example of a DSSC using a porphyrin sensitizer that ively (Fig. 11).40 The doubly functionalized porphyrin tda-2b-
achieved an η-value of more than 10%. bd-Zn exhibited a higher η-value of 7.47% than that of tda-1b-
Introduction of multiple diarylamino groups into a por- d-Zn. The η-value of a DSSC with tda-2b-bd-Zn is comparable
phyrin core is a fascinating methodology to enhance the light- to that with N3 dye (7.68%) under their optimized conditions.
harvesting ability. Imahori and co-workers synthesized a series Kim et al. switched the β-oligo-olefinic anchoring groups to
of zinc porphyrins with different numbers of diarylamino carboxyphenylethynyl substituents to create the corresponding
groups at the meso-positions (Fig. 10).38 The light-harvesting ZnEP1 and ZnEP2.41 To the contrary, a DSSC based on ZnEP1
with one anchoring group exhibited a higher cell performance
(η = 5.9%) than a DSSC based on ZnEP2 with two anchoring

Fig. 10 Molecular structures of porphyrins bearing multiple diaryl-

amino moieties. Fig. 11 Molecular structures of β-functionalized push–pull porphyrins.

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groups (η = 4.0%). It is noteworthy that the lowest-energy was ascribed to the more effective intramolecular CT character
Q-bands of tda-1b-d-Zn and tda-2b-bd-Zn (628 and 650 nm) in LW4. Pizzotti and co-workers presented similar β-disubsti-
are more red-shifted than those of ZnEP1 and ZnEP2 (592 and tuted porphyrins Zn-2 and Zn-3 in which dimethylaminophe-
638 nm). These differences imply that oligo-olefinic substitu- nylethynyl and carboxyphenylethnyl groups are introduced at
ents at β-positions have more effective electronic communi- the β-positions (Fig. 12).44 DSSCs with Zn-2 and Zn-3 revealed
cations with porphyrin core than carboxyphenylethynyl η-values of 4.1% and 4.7%, respectively, which are slightly
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substituents, leading to superior light-harvesting ability and superior to that based on LD13 (η = 3.9%) under their opti-
ϕinj-value. mized conditions. The absorption of β-disubstituted porphyr-
ins Zn-2 and Zn-3 showed less broadening and red-shift than
3.2 Dialkylaminophenylethynyl porphyrins those of meso-disubstituted porphyrins LD13, LD14 and LW4,
suggesting a more effective electronic communication through
The dialkylaminophenylethynyl group has been also used as meso-positions than β-ones.
an electron-donating moiety (Fig. 12). Lin and Diau et al. deve-
loped the meso-disubstituted porphyrin sensitizer LD13 for a
DSSC.42 LD13 displayed red-shifted and broadened absorption 3.3 Triarylamine-substituted porphyrins
in comparison with that of YD2. A DSSC with LD13 attained Triarylamine derivatives have been widely used as an electron-
an η-value of 9.34%. Lin and Diau et al. further modulated the donating moiety in various D–π–A organic dyes.10–13 Porphy-
structure of LD13 to redesign porphyrin dye LD14 bearing four rins bearing a triarylamine moiety have also been reported
alkoxy chains at the ortho-positions of the meso-phenyl rings. (Fig. 13). Kim and co-workers synthesized porphyrin HKK-Por1
This steric congestion around the porphyrin core was intended with a carbazole-containing triphenylamine moiety.45 An
to suppress the dye aggregation on TiO2 as well as reduce CR η-value of 5.0% was noted for the HKK-Por1-sensitized solar
between electrons in the CB of TiO2 and I3− in the electrolyte cell. Hung et al. designed push–pull porphyrin sensitizers pos-
solution.29 In fact, the introduction of alkoxy chains led to a sessing multiple anchoring units.46,47 The 1D–π–3A type
ca. 0.04 V increase of VOC and yielded an η-value of 10.2%. Zn1TPA3A-sensitized solar cell exhibited an η-value of 5.4%,
Liao and Wang et al. prepared the analogous porphyrin LW4, which is lower than that of a Zn1NH3A-sensitized solar cell
possessing thiophene-carboxylic acid instead of benzoic acid (6.1%) where the phenyl groups on the N atom are replaced
as the anchoring group. A DSSC based on LW4 attained a with alkyl chains to suppress the porphyrin aggregation on
slightly improved η-value of 9.53% relative to that of LD14 TiO2.47 Importantly, these porphyrin sensitizers bearing mul-
(9.01%) under their optimized conditions.43 This improvement tiple anchoring groups showed better photostability than the
mono-anchoring analogues.
Compared to other push–pull porphyrins, the DSSCs based
on triarylamine-substituted porphyrins display lower cell per-
formances on account of their inferior light-harvesting ability.
Indeed, the wavelength of the lowest-energy Q-band of
HKK-Por1 is limited to 598 nm. Since the meso-phenyl group is
tilted against the porphyrin plane by ca. 60° due to its steric
hindrance, the electronic communication through the phenyl
group is hampered, resulting in the lower η-values.

Fig. 12 Molecular structures of porphyrins bearing a dialkylaminophe- Fig. 13 Molecular structures of porphyrins bearing a triarylamine
nylethynyl moiety. moiety.

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4. π-Extended porphyrins
4.1 Incorporation of π-chromophores into porphyrins
through conjugated bridges
The extension of porphyrin π-conjugation is an enchanting
strategy to achieve an excellent light-harvesting ability in the
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visible and near infrared (NIR) regions. The effect of the intro-
duction of additional π-chromophores through acetylenic
spacers has been studied. Lin, Diau and co-workers examined
the effect of the systematic introduction of acenes from
benzene to pentacene into a porphyrin core through the conju-
gated bridges.48 With increasing the size of the acenes, the
absorption became broadened and red-shifted. Among these
porphyrins, the anthracene-incorporated porphyrin LAC-3
attained the highest η-value of 5.4% (Fig. 14). This was ration-
alized by charge delocalization between the porphyrin core
and the anthracene group at the HOMO level. Lin and Diau
et al. further tethered a cyclic aromatic moiety at the meso-posi-
tion opposite the anchoring group.49,50 Fluorene-substituted
dye LD22 gave an η value of 8.10%, whereas pyrene-substituted
dye LD4 achieved an η-value of 10.1%. The performance of a
DSSC based on LD4 was superior to that of DSSC based on
N719 (η = 9.27%) under their optimized conditions. Fig. 15 Molecular structures of push–pull porphyrins with π-chromo-
Push–pull porphyrins with a π-chromophore incorporated phore incorporated into the electron-withdrawing anchoring group.
into the electron-withdrawing anchoring group were also
described (Fig. 15). Yeh and Diau et al. synthesized porphyrins
YD11–YD13, bearing a benzene, naphthalene or anthracene
LWP1-sensitized solar cell displayed an η-value of 9.7%, which
ring.51 Anthracene-incorporated YD13 showed the most red-
is slightly inferior to that of a LD14-sensitized solar cell (η =
shifted absorption, but its cell performance (η = 1.9%) was low
10%) under their optimized conditions. The photovoltaic pro-
as a result of its aggregation behavior on TiO2. On the other
perties are strongly dependent on π-chromophores. Introduc-
hand, DSSCs with YD11 and YD12 displayed higher η-values of
tion of the larger π-conjugated chromophore creates a better
6.8% and 6.9%, respectively, which are slightly lower than
light-harvesting ability, but the large π-chromophores often
N719 (η = 7.3%). Wu and Lin et al. designed porphyrin dye
trigger dye-aggregation. VOC-values of DSSCs based on LD22
LWP1 consisting of a combination of LD14 with LAC-3.52 An
and LD4 are smaller than 0.7 V due to their shortened excited
state lifetime and/or facile CR between electrons in TiO2 and
the electrolyte. In contrast, π-chromophore incorporated push–
pull porphyrins YD12 and LWP1 exhibited higher VOC-values
than 0.7 V. Although it is still difficult to predict the lifetime of
the excited singlet state of porphyrins in advance, modulation
of the energy levels and electron density distribution of HOMO
and LUMO as well as inhibition of dye-aggregation by bulky
substituents are prerequisite for further enhancement of cell
performance.

4.2 Fused porphyrins

Peripherally fused aromatic structures are one of the fascinat-
ing strategies to extend π-conjugation and thereby reinforce
the absorption in the NIR region for application to materials
science.53–55 In 2007 Imahori and co-workers reported the
meso-naphthyl fused porphyrin fused-ZnP1 as the first
example of the application of fused porphyrins to DSSCs
(Fig. 16).56,57 The light-harvesting ability was significantly
improved by the fusion. A DSSC with fused-ZnP1 showed an
Fig. 14 Molecular structures of porphyrins linked with π-chromophores η-value of 4.1%, which is higher than a DSSC with non-fused
through conjugated bridges. porphyrin ZnP1 (η = 2.8%) under the same conditions.

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Fig. 16 Molecular structures of naphthalene-fused porphyrins.

Imahori and co-workers also developed a series of quinoxa-

line-fused porphyrins for DSSCs.58–61 The unsymmetrical
π-elongation resulted in a broadened and red-shifted absorp-
tion. Moreover, the electron-withdrawing nature of the qui-
noxaline moiety is anticipated to accelerate electron injection.
A DSSC based on ZnQMA displayed an η-value of 6.3%, which Fig. 19 Molecular structures of fused porphyrin dimers.
is higher than ZnP (η = 4.4%) under the same conditions.58
They further designed imidazole- and quinoxaline-fused por-
trum.62 A DSSC using P3 exhibited a photocurrent generation
phyrin ZnPQI to enhance the push–pull structure (Fig. 17).
onset of ∼1100 nm when using SnO2 as the photoanode.
This push–pull porphyrin ZnPQI showed an improved light-
However, a DSSC based on P3 and standard TiO2 did not show
harvesting ability relative to ZnQMA, leading to a higher
any photocurrent generation in the NIR region (700–1100 nm).
η-value of 6.8%.61
This was explained by the inefficient electron injection from
Other polycyclic aromatic compound-fused porphyrins have
the porphyrin excited singlet state to the CB of TiO2 due to a
also been described (Fig. 18). Anderson and Snaith et al. syn-
lowering of the excited state by the π-extension. Wang and Wu
thesized an anthracene-fused porphyrin dye, which reveals a
et al. reported the synthesis of perylene-fused porphyrins and
dramatic red-shift and broadening of the absorption spec-
their application to DSSCs.63 Perylene-fused porphyrins WW-1
and WW-2 exhibited broader IPCE spectra, extending into the
NIR region up to 1000 nm. Nevertheless, owing to their aggre-
gation tendency and the low levels and short lifetimes of their
excited singlet state, these dyes displayed poor η-values of ca.
1.3% together with low maximum IPCE values of ∼30%. Diau,
Yeh and co-workers prepared the triply fused porphyrin dimer
YDD2 and doubly fused dimer YDD3. These dyes also encoun-
tered a low cell performance for similar reasons (Fig. 19).64
Fig. 17 Molecular structures of quinoxaline-fused porphyrins.
Although these fused porphyrins are potential sensitizers with
panchromatic and a particular NIR response, elaborated mole-
cular design, specifically fine-tuning of the HOMO−LUMO
levels, inhibition of the aggregation, and retention of the
rather long lifetime of the excited state is essential to boost the
cell performance.

4.3 Porphyrin arrays

Various covalent and noncovalent porphyrin arrays have been
studied thanks to their excellent light-harvesting abilities,
inspired by natural photosynthetic systems.65–70 The first
demonstration of the utilization of covalently linked porphyrin
dimers as sensitizers for DSSCs was reported by Officer and co-
workers in 2009 (Fig. 20).71 They designed porphyrin dimers
comprising two porphyrin dyes linked in either a linear anti
(P10) or a 90° syn (P18) fashion. While the enhancement of
light-harvesting ability was small on account of a negligible
interaction between the two porphyrins in the ground state,
Fig. 18 Molecular structures of polycyclic aromatic compound-fused JSC-values of DSSCs with the dimers were higher by up to 10%
porphyrins. than that of DSSCs with the corresponding porphyrin

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coupling. A wide IPCE action spectrum in the Soret and

Q-band regions was attained for a DSSC with the dimeric por-
phyrin. An η-value of 4.2% was noted for the PEG-2b-bd-Zn2-
sensitized solar cell. Diau and Yeh et al. also described the ana-
logous meso–meso linked porphyrin dimer YDD1 for DSSCs. A
DSSC with YDD1 yielded an η-value of 5.23%, which is almost
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comparable to that of the reference porphyrin monomer YD0

(η = 5.14%).64 On the other hand, the meso–meso ethynyl-linked
porphyrin dimer YDD0 exhibited a lower photovoltaic perform-
ance (η = 4.07%) due to dye aggregation, irrespective of the
broad absorption extending to the NIR region.
Segawa and co-workers reported a series of meso–meso
ethynyl-linked porphyrin oligomers (Fig. 22).74–77 They intro-
duced an electron-donating amino moiety at the meso-position
of the porphyrin dimer to strengthen the push–pull character.
A DSSC with DTBC exhibited an η-value of 5.2%.74 This was
attributed to the rather long excited-state lifetime of DTBC. A
gradient of the energy levels in the order of the zinc porphyrin
Fig. 20 Molecular structures of porphyrin dimers reported by Officer
et al.72 and the free base porphyrin in DTBC may facilitate the elec-
tron injection from the excited states. They also synthesized
the ethynyl-linked porphyrin trimer Zn-ZnA-Zn for DSSC. A
monomer under the cell conditions with similar Γ-value. DSSC using Zn-ZnA-Zn showed spectral sensitivities up to
Later, Mozer and Mori et al. optimized the device fabrication 900 nm, whereas the IPCE values were less than 25% on
conditions. An η-value of a DSSC based on P10 reached 5.5%, account of the porphyrin aggregation on TiO2. The η-value of a
which is the highest value among the porphyrin dimer-sensi- DSSC using Zn-ZnA-Zn reached 3.2% under the optimized con-
tized solar cells.72 ditions.76 The η-values of DSSCs based on these porphyrin
Kim et al. presented the meso–meso linked porphyrin arrays remain moderate, since their structural and electronic
dimers as sensitizers for DSSCs (Fig. 21).73 While the HOMO− modification is synthetically difficult in comparison with the
LUMO levels were retained at the levels of the porphyrin corresponding porphyrin monomers. Although ethynyl-linked
monomer, a much broader absorption was induced by exciton porphyrin oligomers reveal a broad absorption extending to
the NIR region, the maximum IPCE values are limited up to
ca. 40%. These low IPCE values probably originate from
insufficient electron injection and an aggregation tendency.
On the other hand, a DSSC using DTBC provided higher IPCE
values of up to ca. 60%. Enhancement of push–pull structures
and a well-designed gradient of the energy levels of hetero-

Fig. 22 Molecular structures of meso–meso ethynyl linked porphyrin

Fig. 21 Molecular structures of meso–meso linked porphyrin dimers. oligomers reported by Segawa et al.

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porphyrin arrays would need more consideration to strengthen

the intramolecular CT character, leading to efficient electron
injection and higher η-value.

5. Further improvement of DSSC

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performance
5.1 Co-sensitization
Co-sensitization is an effective approach to enhance the cell
performance through a combination of two or more different
dyes exhibiting complementary absorption in the visible and
NIR regions (Fig. 23). Dye aggregation on TiO2 may be inhib-
ited by mixing the dyes with different shapes and sizes. Kim
and co-workers reported a DSSC with push–pull porphyrin 2,4-
ZnP-CN-COOH co-sensitized with HC-A1.78–80 While an η-value
of 4.9% was obtained in the absence of a co-sensitizer, a DSSC
with HC-A1 as the co-sensitizer displayed a remarkably
improved η value of 8.4%.79 Co-sensitization not only increases
JSC, but also VOC, because of an enhancement of the light-har-
vesting ability as well as suppression of CR. Yeh and Diau et al.
used a cocktail of YD2-o-C8 (vide infra), CD4, and YDD6 with
different absorption profiles for DSSCs. An η-value of 10.4%
was achieved under the optimized cell conditions.81 The IPCE
values of 75–80% and 40–60% were obtained in spectral
regions of 400–700 nm and 700–800 nm, respectively, giving a
high JSC value of 19.28 mA cm−2. Chen and co-workers applied
a combination of HD18 and PT-C6 to DSSCs.82 Since the phe-
nothiazine molecule PT-C6 can act as both co-adsorbent and
sensitizer upon co-adsorption, the DSSCs displayed an η-value
of 10.1% under their optimized conditions. Xie and co-
workers presented the co-sensitization of XW4 by C1 for
DSSCs.83 An η-value of ca. 8% for a DSSC with only XW4 was
increased to ca. 11% for a DSSC by the co-sensitization. Diau
and Lin et al. demonstrated that LD31 co-sensitized with AN-4
extended the light-harvesting ability up to ca. 800 nm and an
η-value of 10.3% was attained in an iodine-based electrolyte.84
However, since LD31 has already achieved an outstanding
light-harvesting ability, the co-sensitization with AN-4 resulted
in only a 0.3% increase in the η-value compared to that of a
DSSC based on LD31 alone (10.0%).
These excellent works indicate that organic dyes possessing
absorption bands around 500 nm are useful for the co-sensiti-
zation with porphyrin sensitizers that lack intense absorption
around 500 nm. Additionally, relatively rigid and bulky struc-
tures would be favorable for the suppression of dye aggrega-
tions. Interestingly, the η-value of DSSCs using the co-
Fig. 23 Molecular structures of porphyrins and co-sensitizers.
sensitizer alone seems to have no relationships with the
η-values of DSSCs with the corresponding porphyrin sensitizer
together with the co-sensitizer. For instance, DSSCs based on functions, such as efficient light-harvesting around 500 nm,
PT-C6, C1, and HC-A1 attained η-values of 8.2%, 5.7%, and suppression of dye aggregation, and excellent hole-conducting
0.37%,80 respectively. At least co-sensitizers should reveal a character, would be a potential option for improving the cell
high IPCE value at a specific wavelength region that compen- performance of porphyrin DSSCs.
sates the moderate IPCE by porphyrins. Meanwhile, HC-A1 Another concept derives from the use of an energy relay
possesses the hole-conducting function because of a low oxi- with additional photoactive dye in supramolecular assemblies
dation potential. Thus, the use of co-sensitizers with multiple (Fig. 24).85–87 While the electron and energy transfer processes

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the relatively high overpotential of the iodide/triiodide redox

shuttle for dye regeneration. Among these, CoII/IIItris(bipyridyl)
has been studied as a promising candidate.88–91 The cobalt
redox electrolyte can achieve a higher VOC and resultant
η-value, since the potential of the CoII/IIItris(bipyridyl) redox
couple (+0.57 V vs. NHE) is more positive by 0.17 V than that
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of the iodide/triiodide redox couple (+0.40 V vs. NHE) (Fig. 1).

A drawback of the CoII/III redox couple is the fast CR in com-
parison with the iodide/triiodide redox couple. Blocking of
undesirable CR can be attained by the use of bulky substitu-
ents around dyes.90–93 In this regard, a number of porphyrin
dyes bearing long alkoxy chains at the ortho-positions of meso-
phenyl rings have been synthesized for DSSCs with the CoII/III
redox couple. Diau, Yeh, Grätzel and co-workers designed the
porphyrin sensitizer YD2-o-C8, an analog of YD2. An impress-
ive η-value of ca. 12% ( JSC = 17.3 mA cm−2, VOC = 0.965 V, fill
factor (ff ) = 0.71, 99.5 mW cm−2) was attainable by increasing
the conventional VOC (0.7–0.8 V) to ca. 0.96 V when the CoII/III
redox couple was used.94 A cocktail of YD2-o-C8 and comp-
Fig. 24 Supramolecular assemblies of MP216 + MP151 and Zn-4 + A1.
lementary Y123 as a co-sensitizer led to a comparable η-value
of ca. 12% (Fig. 25).
of supramolecular systems have been studied in great detail, Wang and Wu et al. designed porphyrin dyes bearing an
the utilization of supramolecular interactions in solar cells is electron-donating N-annulated perylene (Fig. 26).95 DSSCs
scarce. Ballester, Palomares and co-workers designed the self- based on WW-5 and WW-6 with a CoII/IIItris(bipyridyl) redox
assembled trisporphyrin complex MP216 + MP151.86 The couple showed high η-values of 10.3% and 10.5%, respectively.
pyridyl group of porphyrin MP151 coordinated to the zinc These values were comparable with that of YD2-o-C8 under
atom of porphyrin MP216 adsorbed on a TiO2 surface. The their optimized conditions (η = 10.5%). The lowest-energy
DSSC performance was obtained with a 100% increase in
η-value for the supramolecular trisporphyrin MP216 + MP151
assembly (2.9%), compared to a plane zinc bisporphyrin
MP216 (1.5%). Not only did the improved light-harvesting
ability attain a higher photocurrent generation, but also the
blocking effect of the supramolecular assembly retarded the
CR process. Odobel et al. utilized a borondipyrromethene
(BODIPY) dye bearing an imidazole moiety A1 as a light-har-
vesting antenna for a supramolecular assembly with zinc por-
phyrin dye Zn-4.87 The action spectra clearly displayed that the
Fig. 25 Molecular structures of YD2-o-C8 and Y123.
IPCE value in the 450–550 nm region was strongly enhanced
when the porphyrin dye Zn-4 was connected to the antenna
dye A1. For a DSSC based on this supramolecular array, an
η-value of 4.6% was remarkably higher than that based on Zn-4
alone (3.6%) due to an increase of JSC by 25%. On the other
hand, BODIPY dye lacking the imidazole moiety displayed no
enhancement, highlighting the importance of the supramole-
cular assembly for efficient energy transfer. These approaches
can be extended to other pigments possessing substituents
coordinating to zinc metal, such as a pyridine and imidazole
moiety. To extend this concept and achieve higher cell per-
formances, optimization of additional dyes and supramolecu-
lar architecture is required.

5.2 Cobalt-based redox shuttle

An iodide/triiodide redox couple has been utilized as the most
common electrolyte for DSSCs.88 However, other redox
mediators have been searched for because its VOC is limited by Fig. 26 Molecular structures of WW-5 and WW-6.

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Q-band of WW-6 (672 nm) is significantly more red-shifted 5.3 Effects of aging and light exposure on photovoltaic
than those of SM315 (668 nm) and GY50 (665 nm), indicating performance
the superior light-harvesting ability of WW-6. However, VOC of The effect of light exposure on photovoltaic properties has
WW-6 is relatively low (0.809 V) in spite of using the cobalt been reported for various DSSCs, but the change of cell per-
redox shuttle. This behavior is analogous to that observed for formance in DSSCs upon light exposure is dye-dependent.96–98
π-chromophore-incorporated porphyrins (section 4.1). Namely, In 2011, for the first time Officer and co-workers described the
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N-annulated perylene moiety may induce dye aggregation and/ significant and simultaneous improvement in all photovoltaic
or a fast CR, leading to a lower η-value of ca. 10%. parameters ( JSC, VOC and ff) of DSSCs based on porphyrins.99
Grätzel and co-workers further elaborated the molecular The current–voltage characteristic of DSSC with GD2 was
structure of YD2-o-C8 to create SM315 (Fig. 27).22 A benzothia- measured immediately after cell fabrication and then re-
diazole unit was used in SM315 as a more strongly electron- measured after light exposure (Table 1). After 1 h light exposure,
withdrawing anchoring group. The absorption of SM315 the JSC-value increased by 6% to 13.1 mA cm−2, accompanied by
became broadened and the lowest-energy Q-band was signifi- an additional 6% increase in both VOC and ff, leading to an
cantly red-shifted to 668 nm. A DSSC based on SM315 yielded η-value of 6.2%. In addition, the cells stored in the dark dis-
an η-value of ca. 13% ( JSC = 18.1 mA cm−2, VOC = 0.91 V, ff = played a gradual improvement with time, which was attributed
0.78) without a co-sensitizer. At the same time, Yeh and to the light exposure effect induced during the measurements
Grätzel et al. reported GY50, which is very similar to SM315. A of the photovoltaic performance under illumination.
DSSC based on GY50 displayed an η-value of 12.7% ( JSC = Mori and co-workers evaluated the details of the improve-
18.53 mA cm−2, VOC = 0.885 V, ff = 0.773),23 which is compar- ment by light exposure.100 DSSCs based on a TiO2 film with a
able to the photovoltaic performance of SM315 (Fig. 26). The full coverage of dye exhibited a light exposure effect with 6%
more bulky biphenyl substituent of SM315 is unlikely to be and 5% increases in the JSC and VOC, respectively. On the other
necessary for the suppression of CR. In contrast, the porphyrin hand, when the dye loading was reduced by ∼50%, light
dye GY21 lacking a phenylene spacer in the anchoring group exposure caused enhanced increases in the JSC by 24% and the
gave a remarkably low cell performance (η = 2.52%). This VOC by 6%. These larger increases in the DSSC with the
suggests that a subtle change in the electronic coupling reduced amount of dye suggested the importance of the extra
between the porphyrin and TiO2 has a large impact on the ET space on TiO2. Photovoltage and photocurrent transients were
kinetics at the interface, varying the photovoltaic properties examined for DSSCs prepared using three different electrolyte
greatly (see section 2). compositions: (i) standard, (ii) DMPIm+ (dimethylpropyl-imi-
dazolium)-rich, and (iii) Li+-rich electrolytes. Under light
exposure, Li+ ions were removed from the TiO2 surface and
replaced with DMPIm+ ions. This process was found to
enhance the electron lifetime by decreasing CR with the redox
mediator. They proposed that the light exposure effect was
initiated by the formation of dye cation radicals by light rather
than photoinduced changes in the levels of the semiconductor
surface. Finally, they concluded that the initial limited injec-
tion and fast CR processes arise from the presence of Li+ ions
on the TiO2 surface, and the improved injection and retar-
dation of the fast CR after the light exposure is triggered by the
replacement of Li+ ions with DMPIm+ ions under illumination
(Fig. 28).
Imahori et al. assessed an “aging effect” in which the
η-value is gradually increased to reach a plateau with time.39
Immediately after cell fabrication, DSSCs with YD2, ZnPBA
and ZnPBAT exhibited η-values of 8.1%, 6.2%, and 8.6%,
respectively. After aging for several days under dark condition,
the η-values were improved to 9.1%, 8.3%, and 10.1%, respect-
ively. Palomares and co-workers also found an improvement in

Table 1 Photovoltaic parameters measured before and after light

exposure for DSSCs with GD2

JSC/mA cm−2 VOC/V ff η/%

Fig. 27 Molecular structures of benzothiazole-incorporated porphyrin As prepared 12.43 0.665 0.63 5.2
sensitizers. Light-exposed 13.14 0.705 0.67 6.2

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Table 2 Summary of the light-harvesting spectral region and photovol-

taic performance for the selected porphyrin sensitizers in this
perspective

IPCE
onseta/ JSC/mA
Sensitizer nm cm−2 VOC/V ff η/% Ref.
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Zn-1 740 14.0 0.680 0.74 7.0d 21

YD2 760 18.6 0.77 0.764 11d 37
ZnPBAT 800 19.33 0.719 0.724 10.1 39
LD4 >800 19.63 0.711 0.721 10.1 49
LD14 780 19.17 0.736 0.721 10.2 29
Fig. 28 Schematic representation of light-induced cation exchange.
LD22 800 17.26 0.689 0.681 8.10d 50
LW4 790 17.65 0.75 0.72 9.5 43
LWP1 >800 17.77 0.73 0.75 9.7 52
2,4-ZnP-CN-COOH + 750 15.39 0.739 0.74 8.5 79
HC-A1
YD2-o-C8 + CD4 + 850 19.28 0.753 0.719 10.4 81
YDD6
HD18 + PT-C6 750 19.36 0.735 0.710 10.1 82
XW4 + C1 820 20.15 0.736 0.71 11d 83
LD31 + AN-4 >800 20.27 0.704 0.718 10.3 84
YD2-o-C8 + Y123c 750 17.66 0.935 0.74 12d 94
WW-6b 800 17.69 0.809 0.735 10.5 95
SM315b 800 18.1 0.91 0.78 13d 22
GY50b,c 790 18.53 0.885 0.773 12.7d 23
Fig. 29 Molecular structure of VC-70.
a
Estimated from the corresponding IPCE spectra. b With cobalt-
based redox electrolyte. c 99.5 mW cm−2. d Corrected on a basis of
cell performance with a light exposure effect.101 A DSSC using significant figures.
YD2-o-C8 showed an η-value of 7.6%, but there was little differ-
ence in device performance upon 90 min light soaking (7.4%).
for enhancing the light-harvesting ability. Bulky substituents
On the other hand, with light soaking an η-value of a DSSC
such as ortho-alkoxyphenyl group are vital to suppress the dye
with VC-70 was increased markedly from 5.5% to 7.3%
aggregation as well as CR. Table 2 summarizes the light-har-
(Fig. 29). They proposed that the loose packing of VC-70 on
vesting spectral region and photovoltaic performance for the
TiO2 due to the bulky indoline group facilitated cation
promising porphyrin sensitizers as mentioned in this perspec-
exchange.
tive. It is noteworthy that these porphyrin sensitizers exhibit
efficient photocurrent generation up to 750–800 nm.
It is estimated that by utilizing ∼80% of the incident solar
6. Summary and outlook light up to 900 nm in DSSCs with the I−/I3− redox electrolyte,
JSC = 27 mA cm−2 should be expected.102 Assuming VOC = 0.75 V
In the last decade, extensive efforts have been devoted to the and ff = 0.75, an η-value of 15% can be calculated. Similarly, in
design and synthesis of porphyrin sensitizers for DSSCs. Con- DSSCs with a cobalt redox electrolyte, JSC = 22 mA cm−2 should
sequently, porphyrin sensitizers revealed remarkably high cell be obtained by utilizing ∼80% of the incident solar light up to
performances that are comparable to conventional ruthenium 800 nm.102 Given VOC = 0.9 V and ff = 0.75, an η-value of 15%
sensitizers such as N3 and N719. Specifically, SM315 and can also be estimated. In this respect, the synthesis of por-
GY50-sensitized solar cells exhibited an η-value of ca. 13%, phyrin sensitizers that efficiently absorb sunlight from the
which outperforms that of ruthenium sensitizer-based DSSCs. visible to NIR region to improve the light-harvesting ability is
These remarkable improvements stem from the rather facile an effective approach to achieve higher cell performances.
tuning of HOMO−LUMO levels and the intrinsic intense Besides, optimizations of the dye structure and cell fabrication
absorption bands of porphyrins. Thus, we believe that por- can also increase VOC and ff, leading to an η-value of more
phyrin dyes hold the key to further development of highly than 15%. Therefore, we believe this review would be useful
efficient DSSCs. To realize practical applications of porphyrin- for the rational molecular design and cell fabrications for the
based DSSCs, the following challenges still remain: (i) further further development of highly efficient DSSCs based on por-
improvement of the light-harvesting ability in the visible and phyrin dyes.
NIR regions, (ii) suppression of porphyrin aggregation on TiO2
to reduce undesirable quenching of the excited singlet state,
(iii) optimization of electron injection and inhibition of CR Acknowledgements
processes at the interface by controlling the adsorption struc-
tures on TiO2, (iv) novel redox couples that can increase VOC, This work was supported by ALCA, JST. The authors thank
and (v) long-term stability under illumination. Further explora- Prof. Seigo Ito (University of Hyogo) for the DSSC fabrications and
tion of push–pull structures and/or π-extensions is prerequisite Prof. Villy Sundström (Lund University), Prof. Helge Lemmetyinen,

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