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Emerging molecular design strategies of unsymmetrical phthalocyanines for

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RSC Advances
REVIEW

Emerging molecular design strategies of

unsymmetrical phthalocyanines for dye-sensitized
Cite this: RSC Adv., 2014, 4, 6970
solar cell applications
Varun Kumar Singh, Ravi Kumar Kanaparthi and Lingamallu Giribabu*

Received 17th September 2013
Accepted 14th November 2013
DOI: 10.1039/c3ra45170d
www.rsc.org/advances
In recent years, dye-sensitized solar cells (DSSCs) have emerged as one of the possible solutions for the
global energy crisis. Among the various components of DSSCs, the sensitizer, which harvests solar
energy and injects electrons in to the semiconductor layer, plays a crucial role in achieving high
efficiency and durability of the cell. To date ruthenium(II) sensitizers exhibit high efficiencies (>11.5%), but
they are not so suitable for roof-top/commercial applications mainly because of their limited harvesting
capability, expensive ruthenium metal and low durability. In this context, various sensitizers which
include porphyrins, phthalocyanines and metal-free organic dye sensitizers have been developed and
some of them were found to exhibit enhanced efficiencies compared to classical ruthenium(II)
sensitizers. Man-made tetrapyrrolic systems, phthalocyanines (Pcs) have also been studied significantly
because of their unique thermal and electronic properties in the red and near-IR regions. Over the years,
the efficiency of Pc-based DSSC has improved to 6.1% by synthesizing various Pc derivatives and
optimizing fabrication parameters. However, in the present review article, only the recent developments
in Pc-based DSSCs have been documented in detail. This review also emphasizes different molecular
engineering approaches that the researchers developed for achieving higher efficiency.

Inorganic & Physical Chemistry Division, CSIR-Indian Institute of Chemical
Technology and CSIR-Network Institutes for Solar Energy (CSIR-NISE), Tarnaka,
Hyderabad 500007, India. E-mail: giribabu@iict.res.in; Fax: +91-40-27160921
1. Introduction
Meeting the world's growing energy demand is one of the most
signicant challenges in modern human society. Today, a major
share of energy produced for mankind comes from fossil fuels.
While the fossil fuels are declining with a greater rate,

Varun Kumar Singh was born in Ravi Kumar Kanaparthi was

Delhi in 1984. He completed his
undergraduate studies (B. Sc.,
Chemistry) at Delhi University
in 2005. Then he obtained his
Masters degree (materials
chemistry) from Jamia Millia
Islamia University in 2007. At
present he is pursuing a Ph.D. at
CSIR-IICT under the guidance of
Dr L. Giribabu of Inorganic and
Physical Chemistry Division. His
research interests are tetrapyr-
roles such as porphyrins, phthalocyanines, corroles and related
macromolecules for dye-sensitized solar cell applications and
photophysical properties of electron donor–acceptor systems.
born in Yelavarru, a village near
Tenali, in 1982. Aer his
undergraduate studies (B. Sc.) at
S. V. R. M. College, he joined the
School of Chemistry, University
of Hyderabad and received
M. Sc. (Chemistry) and Ph.D.
degrees in 2005 and 2011,
respectively. Subsequently, he
moved to CSIR-Indian Institute
of Chemical Technology, Hyder-
abad, India as a Post-Doctoral
Fellow working with Dr L. Giribabu. Currently he is an assistant
professor at Kerala Central University. His research interests are
broad absorbing sensitizers for dye-sensitized solar cells, photo-
voltaic and optoelectronic devices, and electron and energy
transfer reactions.

6970 | RSC Adv., 2014, 4, 6970–6984 This journal is © The Royal Society of Chemistry 2014
Review
greenhouse gases (SO2, CO2, NO2 etc.) are increasing as a result
of fossil fuels and causing severe global warming. So, there is a
great demand and urgency for new technologies that are
economically feasible and environmental friendly. Among the
many renewable energy sources, solar energy is the best for
electrical power generation as it is abundant, clean, and viable.
Therefore, if we could accomplish harvesting merely a tiny
fraction of the solar energy that reaches the planet earth, we
would solve many of our problems not only in energy, but also
global, environmental and political issues.
A solar cell is a device that directly converts light energy into
electrical energy and it works on the photovoltaic effect. The
rst practical photovoltaic cell was developed in 1954 at Bell
Laboratories based on elemental silicon with 6% efficiency.1
Since then, a great variety of photovoltaic devices have been
developed and some of them are already proven to show good
power conversion efficiency. As a whole, solar cells are broadly
categorized into three generations.2–4 The rst two generations
are mainly based on crystalline and multi-crystalline silicon
(c-Si), amorphous silicon (a-Si), Cd–Te, Ga–As and CIGS etc. The
materials that are associated with the rst two generations of
solar cells are either hazardous or not cost effective. In order to
overcome the drawbacks of rst and second generation solar
cells, scientists have developed excitonic solar cells, tandem
solar cells etc., which are categorized as third-generation solar
cells. The excitonic solar cells are broadly divided into nano-
crystalline, dye-sensitized solar cells (DSSCs) and organic/poly-
mer solar cells.
Dye-sensitized solar cells are the most promising alternative
to conventional solar cells emerging dramatically in recent
years. These DSSCs work under entirely different principles
compared to the conventional solar cells and their mechanism
is close to natural photosynthesis. Unlike the conventional solar
cells (silicon p–n junction cells), in DSSCs interfacial processes
play a vital role. Conventional solar cells are also known as
minor carrier devices in which their efficiency is determined by
Lingamallu Giribabu was born in
1969. He received his Ph.D.
degree in chemistry from Univer-
sity of Hyderabad under the
supervision of the late Professor
Bhaskar G. Maiya in 2000.
Subsequently, he moved to
Central Queens Land University,
Australia and University of
Houston, USA for postdoctoral
assignments. He has worked as a
senior scientist in Indian Insti-
tute of Chemical Technology
since 2003. He is national co-ordinator of the dye-sensitized solar
cells area of CSIR-TAPSUN programme. His research interests
include development of new sensitizers for dye-sensitized solar cells,
donor–acceptor systems, non-linear optical properties based on
tetrapyrrolic systems and photoelectrochemistry of
macromolecules.
This journal is © The Royal Society of Chemistry 2014
RSC Advances
the ability of photogenerated minor carriers (for example elec-
trons in a p-type material) to escape from one side of the device
before recombination with the major carriers. Thus, the minor
carriers' properties such as lifetime and diffusion length are
essential parameters of the device. Even though the interfaces
are important in these p–n junction devices, the charge carrier
processes of photogeneration, separation and recombination
occur primarily in bulk material which determines the ultimate
power conversion efficiency. Therefore, bulk semiconductor
properties such as crystallinity and chemical purity oen
control the efficiency of conventional solar cells and unfortu-
nately optimizing these properties is more expensive and
arduous. On the other hand, DSSCs belong to major carrier
devices in which electrons are found exclusively in one phase
and holes in another phase. Charge carriers are generated at the
interface between the electron-conducting and hole-conducting
phases via exciton dissociation. In other words, all important
charge carrier processes like photogeneration, separation and
recombination occur primarily or exclusively at the interface.
Henceforth, the interfaces properties are of paramount impor-
tant and bulk properties are less critical. As a result, the
investigated materials do not need to be highly pure which
apparently reduces the cost of overall device fabrication. These
differences between DSSCs and p–n junction solar cells provide
an opportunity to work on various essential requirements of the
DSSCs for better understanding and improving the present
state of art and perhaps for these reasons it is believed that
among many research areas, the study of DSSCs is a fruitful
topic.
O'Regan and Gratzel were the rst to report the DSSC
concept in 1991 with a remarkable efficiency of 7.1% based on
natural photosynthesis.5 Over the last twenty years, the DSSCs
efficiency improved further and recently it has reached 12.3%.6
Among many other components of DSSC devices, the sensitizer
is known to play a crucial role in achieving high efficiency and
durability of the device. Extensively studied sensitizers are Ru(II)
polypyridyl complexes with the general structure ML2(X)2 where
L stands for 2,2-bipyridyl-4,40 -dicarboxylic acid, M is Ru, and X
represents thiocyanate (–NCS). In fact, the ruthenium complex
cis-RuL2(NCS)2, N3 dye has become a paradigm of heteroge-
neous charge-transfer sensitizers for mesoporous DSSCs.7 The
high-energy conversion efficiency of this dye is generally
attributed to the ultra-fast electron injection from dye to the
TiO2 conduction band and a much slower reverse process. A
number of modications have been made in order to further
improve the efficiency and durability of the device.8–12 Even
though ruthenium(II) complexes are found to be good in terms
of power conversion efficiency, they have certain drawbacks:
ruthenium sensitizers are very expensive due to the rarity of the
metal, several difficult synthetic protocols, lack of absorption
and lower molar extinction coefficients in the red region of the
absorption spectrum oen limit their broad utility in the
manufacturing of prototype DSSCs panels and thereby
commercialization of the technology. In order to overcome
these problems, a great variety of alternative sensitizers has
been studied for the last two decades based on non-ruthenium
metal complexes, metal-free organic sensitizers, tetrapyrrolic
RSC Adv., 2014, 4, 6970–6984 | 6971
RSC Advances Review

compounds which include porphyrins, phthalocyanines and

corroles etc.13–28 The present review’s emphasis is mainly on
recent developments and emerging trends of Pc-based sensi-
tizers for DSSC applications. Although few review articles have
appeared on Pcs and their application in solar cells, for last two
years, several research papers have been published in the
literature which shows their importance in the DSSCs research.
Therefore, we reect to document these recent emerging trends
in such a way that this article enables the scientic community
to understand the current state of art and how to improve the
power conversion efficiency of the phthalocyanine sensitizers
further.

2. Working principle
The basic working principle and essential requirements of
DCCS are well documented in the literature.29–31 The DSSC is
composed of a dye/sensitizer anchored to nanocrystalline Fig. 2 Molecular structures of symmetrical phthalocyanine dyes.
mesoporous TiO2 lm on conducting glass (working electrode),
electrolyte, spacer in between two electrodes, platinum (Pt)
sputtered conducting glass (counter electrode) and a cell
the sensitizer, Fermi level of TiO2 (located near the conduction
sealant. Fig. 1 presents a schematic energy diagram of a DSSC
band level) and the redox potential of the redox couple (I/I3)
and working principle. The dye photosensitizer anchored to the
in the electrolyte solution. The photocurrent generated from the
TiO2 absorbs incident photon ux and is excited from the
DSSC is determined by the energy difference between the
ground state owing to its MLCT transition. Then the excited dye
HOMO and LUMO of the photosensitizer corresponding to
injects electrons into the conduction band of TiO2 and results in
the band gap of the semiconductor, TiO2. The smaller the
oxidation of the sensitizer. The injected electrons in the
HOMO–LUMO gap, the larger the photocurrent generation
conduction band of the TiO2 lm are transported through the
because of utilization of the long-wavelength region of the solar
surface or the interconnected TiO2 nanoparticles by diffusion
radiation. The LUMO of photosensitizer must be sufficiently
towards the back contact (conducting FTO glass) and conse-
negative with respect to the conduction band of TiO2 in order to
quently they reach the counter electrode through external load.
inject electrons effectively. In addition, substantial electronic
The oxidized photosensitizer is regenerated by accepting
coupling between the LUMO and the conduction band of TiO2 is
electrons from the redox couple (e.g. I/I3 in acetonitrile). I
also essential for effective electron injection thus to improve the
ion regenerates the dye photosensitizer to its ground state by
overall DSSC efficiency.
giving one electron and is apparently itself oxidized to I3 ion.
Then the oxidized I3 ion diffuses to the counter electrode
(Pt-coated FTO glass plate) and is reduced back to I ion. The
DSSC performance is predominantly judged based on four
3. Symmetrical phthalocyanine
energy levels: ground state (HOMO) and excited state (LUMO) of sensitizers
Phthalocyanines are tetrapyrrolic cyclic aromatic (18-p electron)
organic molecules, demonstrated as potential candidates for

Fig. 3 Molecular structures of symmetrical phthalocyanine dyes 5 and

Fig. 1 Energy levels and basic working principle of a typical DSSC. 6.

6972 | RSC Adv., 2014, 4, 6970–6984 This journal is © The Royal Society of Chemistry 2014
Review
Fig. 4 Molecular engineering strategies of phthalocyanines.
Fig. 5 Molecular structures of axial substituted phthalocyanines dyes.
several practical applications that include optoelectronic, pho-
tocatalysis, chemical sensors, photodynamic therapy and pho-
todegradation of organic pollutants etc. owing to their unique
optical and electronic properties.32–37 In general, phthalocya-
nines are well characterized by an intense Soret-band
(350 nm) and Q-band (650–700 nm) with molar absorptivity
(3) values that exceed 105 L mol1 cm1, which will be inter-
esting features for solar-cell applications. Pcs exhibit good
absorption in the red and/or near-IR region of the solar spec-
trum and they can be tuned to be transparent over a large region
of the visible spectrum, thereby enabling the possibility of using
This journal is © The Royal Society of Chemistry 2014
RSC Advances
Fig. 6 Molecular structures of axial substituted phthalocyanine
sensitizers.
them as “photovoltaic windows”: a red/near-IR absorbing
photovoltaic cell. In place of a window, one can place this
photovoltaic window which allows visible light to enter a
building while harvesting the red/near IR part of solar energy.
Moreover, with this kind of photovoltaic window, solar heating
of buildings can be reduced or avoided completely. The thermal
and electronic properties of Pcs are suitable for the sensitization
of wide band-gap semiconductor oxides such as TiO2, SnO2 etc.
The optical, thermal and physical properties of Pcs can be tuned
by introducing various substituents at peripheral and non-
peripheral positions as well as by introducing various metals at
RSC Adv., 2014, 4, 6970–6984 | 6973
RSC Advances
Fig. 7 Molecular structures of unsymmetrical phthalocyanines.
Fig. 8 Molecular structures of unsymmetrical tert-butyl phthalocya-
nines with different anchoring groups.
its central cavity. However, the Pcs oen exhibit low power
conversion efficiencies due to poor solubility in common
organic solvents, aggregation due to the planar Pc macrocycle
and lack of electron directionality in its excited state. In 1999,
for the rst time, Nazeeruddin et al. reported zinc(II) (Dye 1 and
3) and aluminium(III) (Dye 2 and 4) symmetrical Pcs bearing
carboxylic acid and sulfonic acid anchoring groups to facilitate
proper adsorption on to the TiO2 surface (Fig. 2).38 Among these
dyes the zinc(II) tetracarboxy phthalocyanine showed maximum
overall power conversion efficiency of 1% and the IPCE values
are between 10% and 45%.The low efficiencies of these Pcs were
attributed to deactivation of the excited Pc because of their high
aggregation originated from the planar conguration. Since
then many efforts appeared in the literature which deal with
reducing the aggregation and thereby increasing the efficiency.
Aranyos et al. have reported a series of Pcs with aryl groups
connected at the peripheral positions of the Pcs.39 Interestingly,
6974 | RSC Adv., 2014, 4, 6970–6984
Review
Fig. 9 Molecular structures of unsymmetrical tert-butyl phthalocya-
nines with different anchoring groups.
Fig. 10 Molecular structures of unsymmetrical phthalocyanines
bearing different anchoring groups.
even though these Pcs sensitizers do not have any anchoring
group they have shown reasonable IPCE values, 4–9%.
A few hyper-branched zinc(II) phthalocyanines have also
been synthesized and nearly 67% IPCE was observed, but their
overall power conversion efficiencies are still restricted to 1%.40
The main reason for the low performance of these Pc-based
DSSC was found to be due to aggregation which promotes non-
radiative deactivation of the dye excited states in aggregates.
Later He et al.41 reported a zinc(II) phthalocyanine bearing
tyrosine substituents (Dye 5) in order to increase solubility and
to reduce aggregation at the semiconductor surface (Fig. 3).
However, this dye showed merely 0.54% efficiency with an IPCE
of 24%, attributed to the fast recombination of injected
This journal is © The Royal Society of Chemistry 2014
Review RSC Advances

Table 1 Photovoltaic data of various phthalocyaninesa

Sensitizer IPCEb (%) Jscb (mA cm2) Vocb (V) FFb hb (%)

Dye 1 43 5.40 0.416 — 1.00

Dye 2 13 1.10 0.466 — 0.42
Dye 3 30 0.48 0.453 — 0.77
Dye 4 10 0.60 0.382 — 0.14
Dye 5 24 2.25 0.360 0.670 0.54
Dye 6 —c 6.94 0.940 0.630 4.10e
Dye 7 60 —d —d —d —d
Dye 8 21 3.15 0.360 0.540 0.61
Dye 9 45 2.61 0.340 0.650 0.58
Dye 10 —c — — — 0.20
Fig. 11 Molecular structures of unsymmetrical phthalocyanines Dye 11 25 6.56 0.360 0.38 0.90
bearing organic chromophores. Dye 12 80 19 0.460 0.51 4.50
Dye 13 75 6.5 0.635 0.743 3.05
Dye 14 25 2.81 0.525 0.764 1.13
Dye15 80 7.60 0.617 0.75 3.52
Dye 16 47 5.63 0.557 0.75 2.35
Dye 17 9 0.90 0.55 0.72 0.40
Dye 18 56 4.80 0.61 0.74 2.20
Dye 19 65 6.80 0.613 0.74 3.10
Dye 20 16 1.44 0.611 0.75 0.67
Dye 21 65 9.37 0.605 0.725 4.10
Dye 22 75 7.37 0.609 0.74 3.28
Dye 23 50 5.88 0.587 0.75 2.55
Dye 24 55 6.80 0.576 0.69 2.64
Dye 25 67 9.15 0.600 0.72 3.96
Dye 26 40 6.86 0.584 0.72 2.87
Dye 27 70 7.01 0.610 0.73 3.26
Dye 28 21 3.70 0.520 0.73 1.40
Dye 29 36 7.07 0.563 0.75 2.97
Dye 30 85 7.67 0.559 0.76 3.24
Dye 31 40 5.25 0.541 0.73 2.07
Dye 32 40 4.96 0.543 0.74 1.98
Dye 33 50 4.8 0.58 0.77 2.10
Dye 34 86 10.4 0.63 0.70 4.60
Dye 35 85 1.31 0.585 0.76 6.13
Dye 36 50 8.77 0.584 0.71 3.63
Dye 37 65 12.8 0.61 0.68 5.30
Dye 38 82 13.7 0.613 0.70 5.90
Dye 39 —c 3.26 0.604 0.67 1.07
Dye 40 —c 2.33 0.504 0.75 0.89
Fig. 12 Molecular structures of sterically crowded unsymmetrical
phthalocyanine dyes.
a
Redox electrolyte is I/I3 in volatile organic solvent. b IPCE: Incident
photon to current conversion efficiency; Jsc: current density; Voc: open
circuit voltage; FF : Fill factor; h : Efficiency. c IPCE not reported.
d
Photovoltaic data not reported. e Counter electrode is PEDOT:PSS,
otherwise Pt counter electrode.
electrons and insufficient steric hindrance of the tyrosine
moiety. In another study, myristic acid was employed as a
co-adsorbent of aluminium(III) tetraphenoxy phthalocyanine the HNO3-treated photo-electrode retards back electron transfer
hydroxide for the sensitization of nanocrystalline TiO2.42,43 It at the interface with electrolyte and increases the amount of
was found that the co-adsorbent showed a dramatic decrease in dye. In a recent work, Jin and co-workers have reported zinc(II)
the aggregation of Pc on the nanocrystalline surface and as a phthalocyanine with eight octacarboxylic acid anchoring sites.
result the test cell efficiency was improved. Balaraju et al.44 have Although the aggregation is reduced, the DSSC device was not
used iron tetrasulfonic acid phthalocyanine (Dye 6) sensitizer found be efficient.45
and the corresponding device has shown an overall conversion In order to further improve the efficiency one has to mini-
efficiency of 4.1% by employing a PEDOT:PSS-coated FTO mize the aggregation of a Pc macrocycle through molecular
counter electrode instead of the usual Pt counter electrode and engineering. There are two methods to minimize the aggrega-
dilute HNO3 treatment of TiO2. The increase in power conver- tion of phthalocyanine macrocycles. One is the substitution of
sion efficiency of the DSSC based on nitric acid treatment for anchoring or aromatic groups at axial position(s) of the resident
the photo-electrode is mainly attributed to the increase in metal ion of the phthalocyanine. A second method is intro-
photocurrent. A comparative photovoltaic investigation of duction of bulky substituents as well as anchoring groups at
DSSCs using HCl-treated TiO2 photo-electrode indicates that peripheral positions i.e., ‘push–pull’ concept (Fig. 4).

This journal is © The Royal Society of Chemistry 2014 RSC Adv., 2014, 4, 6970–6984 | 6975
RSC Advances
Fig. 13 Molecular structures of sterically crowded unsymmetrical
phthalocyanine dyes.
Fig. 14 Molecular structures of the co-sensitizers employed with the
phthalocyanine sensitizers.
Fig. 15 Schematic representation of the DSSC with energy relay dye.
4. Axially substituted phthalocyanines
Nazeeruddin and co-workers tried to overcome the aggregation
problem by synthesizing axially substituted Pcs and reported
ruthenium(II) phthalocyanine sensitizer, Dye 746 bearing bis(3,4-
dicarboxy)pyridine as anchoring groups (Fig. 5). The sensitizer 7
had shown a promising 60% IPCE in the near IR region,
6976 | RSC Adv., 2014, 4, 6970–6984
Review
Fig. 16 Molecular structures of PTCDI, DCM and Rhodamine B.
Fig. 17 Molecular structures of BL315 and BL302.
however its overall efficiency was not impressive due to
desorption of sensitizer molecules on the TiO2 surface because
of weak the coordinating ability of the Ru(II) metal with the
pyridine ligand. Yanagisawa et al. have compared the sensiti-
zation properties of an axially substituted anchoring phthalo-
cyanine with that of peripherally substituted phthalocyanines
under identical test cell conditions.47 The axial substituted
sensitizer, Dye 8 has shown better efficiency (0.61%) than the
peripherally substituted counterpart sensitizer Dye 9 (0.58%)
and the decreased efficiency was attributed to reduced stability
of adsorbed Pcs on the TiO2 surface. As the axially substituted
Pcs are showing somewhat better efficiencies (owing to their
reduced aggregation and near-IR region absorption) Durrant,
Morandiera et al. have studied interfacial electron transfer
dynamics. They demonstrated that ultra-fast electron transfer
rates are not required for efficient electron injection yield.
Aerward Morandeira et al. studied the effect of co-adsorbents
on the device performance of axially substituted ruthenium(II)
phthalocyanies in order to understand the DSSC device physical
aspects. The effect of lithium cation (Li+) and co-adsorbent
chenodeoxycholic acid (CHENO) was studied systematically.48
From the previous studies it is known that the addition of Li+ is
expected to lower the conduction band edge of TiO2 and
decrease the photovoltage as well. However, an optimum
concentration of Li+ increases the electron injection yield and
photocurrent of the DSSC device. Interestingly, it was observed
that Ru-phthalocyanine sensitizers showed a remarkable
decrease in the aggregation compared to symmetrical phtha-
locyanines sensitizers reported till that time. On the other hand,
the co-adsorbent CHENO has also shown a signicant effect on
the device performance. The CHENO hinders the formation of
aggregates and thereby enhances the electron injection yield
and ultimately increases the photocurrent response. Moreover,
it is also found that recombination (dye cations with the elec-
trons in TiO2) becomes slower and regeneration of the dye
This journal is © The Royal Society of Chemistry 2014
Review
cations by the redox electrolyte is faster which apparently
enhanced the photocurrent. The reduced recombination can
also due to increased hole–electron (phthalocyanine ring–TiO2
surface) distance because of the unique geometry of CHENO
which helps it to stand straight on the TiO2 surface thereby
slowing down the dye cation–electron recombination.
Torres and co-workers have utilized the axial position of
titanium(IV) phthalocyanines, (Dye 10) for DSSC applications
(Fig. 6).49 Unlike Gratzel and co-workers, they have connected
anchoring carboxy catechol at the axial position. By using
covalent bonds, desorption from the surface of nanocrystalline
TiO2 can be minimized. The solution absorption spectrum of
Dye 10 exhibits an intense Q-band (lmax ¼ 702 nm, 3 ¼ 135 000
dm3 mol1 cm1) and the dye is strongly adsorbed on to the
TiO2 surface. However, its photovoltaic properties (IPCE ¼ 19%
and h ¼ 0.2%) are not impressive due to poor electron injection
from the LUMO of the phthalocyanine to the TiO2 conduction
band. Axially substituted Pcs such as Si(IV) phthalocyanines
have also been reported and tested for their applicability in
DSSCs. In this context, it is worthwhile to discuss a recent paper
by Sellinger and Gratzel in which Dye 11 and Dye 12 have been
shown to be very good candidates for DSSCs.50 The silicon
naphthalo–phthalocyanine hybrid sensitizer, Dye 12 showed
excellent light harvesting efficiency (IPCE ¼ 80%) and high
photocurrent density of 19 mA cm2. Bulky tert-butyl substitu-
ents were added to the core periphery in order to avoid aggre-
gation and trihexylsiloxy groups were introduced as
coordinating ligands to the silicon center. The sensitizer Dye 12
has shown a Jsc of 19 mA cm2, open circuit voltage, Voc ¼
0.46 V, ll factor (FF) ¼ 0.51 and overall efficiency of 4.5% under
standard irradiation conditions. But, the sensitizer Dye 11 has
shown a lower efficiency of 0.9% which was attributed to
insufficient driving forces for electron injection into the
conduction band of TiO2 and regeneration of the oxidized dye
by the redox electrolyte. Although there are a few other Si(IV)
phthalocyanines in the literature, their photovoltaic behaviour
is not efficient.
5. Unsymmetrical phthalocyanine
sensitizers for DSSCs
Based on many reports, symmetrical Pcs have indeed been
shown to be potential sensitizers for DSSC applications.
Although their synthesis and purication are not a matter of
concern, the majority of them are inefficient in achieving high
power conversion efficiencies mainly due to poor solubility in
common organic solvents, aggregation and lack of direction-
ality in the excited state. Hence, it was realized that in order to
improve efficiency, one has to modify the molecular structure of
the existing symmetrical Pcs. By placing appropriate substitu-
ents on the Pcs, one can tune desired properties such as solu-
bility and aggregation. Moreover, it is indeed possible to break
the symmetry of Pcs by placing two different functional groups
on the molecule. This can be achieved by mixed condensation
of different substituted phthalonitriles and desired the Pc can
be synthesized in such a way that it should have an acid
This journal is © The Royal Society of Chemistry 2014
RSC Advances
substituent at one of the isoindoline units for better binding
with the TiO2 surface. For their potential applications as
photosensitizers, the other three isoindoline units can be
functionalized with different substituents to make them more
soluble, facilitate ease of purication and hinder aggregation
which has an undesirable effect in its DSSC application. Then
the obtained precursors are reacted together and the resulting
products can be carefully puried by column chromatography.
In 2004, Yanagisawa and co-workers reported two unsym-
metrical phthalocyanines with different metal ions at the
phthalocyanine's central cavity.51 The zinc-Pc-based sensitizer
showed an overall conversion efficiency of 0.03% whereas Ru(II)
phthalocyanine sensitizer showed 0.4% efficiency. The low
efficiency of these phthalocyanines was attributed to the
rupture in the conjugation between the macrocycle and the
anchoring group which resulted in poor electron injection from
the excited state of the phthalocyanine to the TiO2 conduction
band. Later, in order to further improve the efficiency of DSSC
devices, unsymmetrical phthalocyanines have been designed
and developed based on the “push–pull” molecular architecture.
The rst breakthrough appeared in 2007 by Giribabu and co-
workers in which they reported a very interesting unsymmet-
rical phthalocyanine sensitizer (Dye 13) which gave the highest
overall conversion efficiency of 3.05% using the iodide–triio-
dide electrolyte (Fig. 7).52–54 The Dye 13 sensitizer was designed
in such a way that it has three bulky tert-butyl groups to increase
solubility and to decrease aggregation. The tert-butyl group also
acts as an electron-releasing (push) group and the succinic acid
group serves as an electron-withdrawing group (pull) to anchor
with the TiO2 surface. The Dye 13 sensitizer showed an excellent
IPCE of 75% and its high efficiency was attributed to the excited
state directionality thereby providing efficient electron injec-
tion. By using a durable redox electrolyte (high boiling point
solvents such as g-butyrolactone) the Dye 13 sensitizer showed
2% conversion efficiency and the device was found to be stable
for at least 1000 hours.54 The Dye 13 sensitizer gives an IPCE of
43% and overall conversion efficiency of 0.87% by using solid-
state organic hole transporter 2,20 ,7,70 -tetrakis(N,N-di-p-
methoxyphenylamine)-9,90 -spirobiuorene (spiro-MeOTAD)
instead of liquid electrolyte. Subsequently, Giribabu and co-
workers53 have designed and synthesized a stronger “push–pull”
derivative Dye 14 and its photovoltaic performance was
compared with Dye 13. The new sensitizer Dye 14 possesses six
donor butoxy groups at the a-position due to which the
absorption spectrum shied by 10 nm compared to Dye 13.
But, unfortunately, Dye 14 sensitizer gives only 1.13% overall
efficiency and 25% IPCE. The prime reason for the low efficiency
was poor electron injection quantum yield which also resulted
in the decreased Jsc value.
In another study by Torres and co-workers, Dye 13 was
redesigned having only one carboxylic acid group instead of two
acid anchoring groups. The DSSC device fabricated using Dye
15 sensitizer showed improved overall efficiency of 3.5% under
standard irradiation conditions and the IPCE value at the
Q-band absorption maxima was found to be 80%.55 The reason
for enhanced efficiency of Dye 15 is that the anchoring group
directly attached to the phthalocyanine macrocycle, which did
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RSC Advances
not break the aromaticity as was the case in Dye 13. Later,
Giribabu and co-workers reported Dye 1656 sensitizer by rede-
signing the parent sensitizer Dye 13 based on the “push–pull”
architecture and extended the p-conjugation concept. Malonic
acid is the anchoring group in Dye 16. Although, the sensitizer
Dye 16 exhibited better light harvesting ability (broader
absorption) compared to the parent sensitizer, the overall
conversion efficiency (2.35%) was not improved as expected;
under similar test cell conditions Dye 13 has shown a conver-
sion efficiency of 2.80%. The reason is that the IPCE of Dye 16
was only 47%, whereas Dye 13 has shown 71%.
Despite the fact that several researchers are working on the
development of phthalocyanine-based sensitizers, the efficiency
has reached little higher than 3% under standard conditions.
These sensitizers are highly attractive candidates because of
their high absorption coefficients but still their efficiencies are
not enough for commercialization. Therefore, a great deal of
research still needs to be done for understanding the device
physics and performance of the unsymmetrical sensitizers.
6. Molecular design optimization:
study based on unsymmetrical tert-
butyl phthalocyanines
Although in many studies co-adsorbents have been employed as
aggregation controllers in DSSC devices none of them have
proven helpful in improving the 3% efficiency. So, in later
studies of electron injection, recombination lifetime of sensi-
tizers has become a major concern in achieving high efficiency.
In this context, a few studies by Torres and coworkers57 on
unsymmetrical Pcs sensitizers for DSSC applications are note-
worthy to mention at this point of discussion. For example, they
have designed and synthesized unsymmetrical zinc-phthalocy-
anines based on the “push–pull” molecular arrangement in
which bulky tert-butyl donor groups and carboxylic acid
anchoring group are linked to the core phthalocyanine ring
through different spacers. The DSSC devices fabricated with
these “push–pull” phthalocyanines reveal that the nature of the
spacer unit and distance between the phthalocyanine core and
the anchoring group play a signicant role in determining the
efficiency of the device. It was found that Dye 15 (without a
spacer unit) has the highest overall power conversion efficiency
(h ¼ 3.52%) compared to Dye 17 (h ¼ 0.4%) possessing a exible
and unconjugated pentoxy group spacer (Fig. 8). Dye 20 pos-
sessing a phenoxy spacer has also shown merely 0.67%
conversion efficiency. Based on the results, it was proposed that
the loss of directionality in the excited state led to poor electron
coupling of the donor with titanium 3d-orbitals and thus shows
remarkably low efficiencies. Further it was found that due to the
exible and non-directional nature of the oxygen linker (pentoxy
and phenoxy), there is a possibility that the sensitizer might not
be able to stand straight on the TiO2 surface. However, on other
hand Dye 18 and Dye 19 have shown comparable efficiencies
with Dye 15. Even though Dye 18 shows faster recombination
dynamics (compared to the other sensitizers), it showed better
6978 | RSC Adv., 2014, 4, 6970–6984
Review
efficiency (h ¼ 2.2%) because of its high electron injection yield
owing to improved directionality in the excited state.
In another study, they demonstrated the effect of the
anchoring group on the stability of DSSC and the device
performance.58,59 Pc Dye 21 was designed to possess two
carboxylic acid anchoring groups in order to improve direc-
tionality in the excited state and its efficiency in the presence of
volatile and non-volatile electrolytes was compared with Dye 15
(Fig. 9). Dye 21 has shown improved conversion efficiencies of h
¼ 3.33% and h ¼ 4.10% in the presence of volatile and non-
volatile electrolytes, respectively. Broad absorption and
enhanced photocurrent response of Dye 21 are the governing
factors for its higher efficiency. This major breakthrough a
couple of years aer the Dye 15 report had further sparked many
researchers to design and synthesize Dye 22, Dye 23, Dye 24, Dye
25 and Dye 26 sensitizers (by modifying anchoring groups) in
order to explore the factors governing injection efficiency and
the device performance has been compared with the parent Dye
15. When a double bond was incorporated between the donor
macrocycle and the anchoring carboxylic acid (Dye 22), a small
decrease in IPCE was observed and the overall conversion effi-
ciency dropped down to h ¼ 3.28%. Then in Dye 23 and Dye 24,
the cyanoacrylic acid group was used as the anchoring group.
These sensitizers showed inferior device performance
compared to the parent dye. In Dye 23, a lower Jsc of 5.88 mA
cm2, Voc of 587 mV and h ¼ 2.55% was observed. The extended
conjugation between phthalocyanine and cyanoacrylic acid (Dye
24) was also not helpful in achieving better efficiency ( Jsc ¼
6.80 mA cm2, Voc ¼ 576 mV and h ¼ 2.64%). However,
improved photovoltaic behaviour was observed in case of Dye 25
sensitizers in which cyanoacrylic acid anchoring group was
replaced with a malonic acid anchoring group. Enhanced
photocurrent response ( Jsc of 9.15 mA cm2) and a slight
decrease in the photovoltage were observed. The decrease in
photovoltage response was attributed to low electron lifetime
and an increase in the number of carboxylic groups. The DSSC
device has shown overall conversion efficiency of 3.96% which
is higher than the Dye 15 sensitizer. However, when the
conjugation was extended between the malonic acid anchoring
group and the macrocycle in Dye 26, a sudden breakdown in the
Jsc ¼ 6.86 mA cm2, Voc ¼ 584 mV and thus overall conversion
efficiency 2.87% was observed. It was concluded that the
sensitizers bearing malonic acid anchoring group could
possibly be the choice of anchoring group for future designs.
The efficiencies exhibited by all the sensitizers revealed the
signicant involvement of high order directionality in the
excited state of the dye which is a prerequisite for good elec-
tronic coupling between the excited state of the dye and the
titanium 3d-orbitals.
Nazeeruddin, Torres et al. examined the effect of an ethynyl
spacer between the carboxylic acid anchoring group and the
phthalocyanine. It is expected that due to rigid planar spacer,
the phthalocyanine core will be perpendicular and closer to the
TiO2 surface which enhances the electronic coupling between
the dye and Ti-3d orbital. In order to understand the ethynyl
effect, Dye 27 and Dye 28 have been designed and synthesized
(Fig. 10).60 While Dye 27 gives a 3.26% overall conversion
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Review
efficiency (IPCE ¼ 68%), Dye 28 exhibits only 1% efficiency
(IPCE ¼ 22%). The higher efficiency with one carboxyethynyl
spacer was attributed to the longer electron lifetime and higher
short circuit current density. However, the drop in the efficiency
on introduction of an additional carboxyethynyl spacer was due
to the reduced Jsc owing to low driving force for charge injection
from excited dye into the TiO2 conduction band.
Gratzel and co-workers61 have synthesized two new phtha-
locyanine sensitizers Dye 29 and Dye 30 by employing a phos-
phinic acid anchoring group and their photovoltaic properties
were compared with Dye 15. It was observed that Dye 29 has
shown a lower IPCE of 36%, attributed to the poor adsorption of
Dye 29 on mesoporous semiconductor lm. It was found that
the phosphinic acid anchoring groups enhance long term
photostability of the dye compared to the carboxylic acid
anchoring group. However, their overall efficiencies were found
to be slightly lower because of the decrease in the dye adsorp-
tion on the semiconductor surface. However, the sensitizers,
Dye 29 and Dye 30 have shown superior conversion efficiency to
Dye 15 in the presence of co-adsorbent, CDCA.
The phthalocyanines have high absorption coefficients in
the near-IR (NIR) region. However, they lack absorption in the
400–600 nm region. So, by synthesizing panchromatic
(absorption in the UV-Vis region) Pc sensitizers one can indeed
improve their efficiencies even further.62 For this reason, Torres
and Nazeeruddin have developed conjugated panchromatic
sensitizers by covalently attaching an organic chromophore at
three positions which has absorption in the complimentary
region with the Pc core and the carboxylic acid group used for
anchoring on to the TiO2 nanoparticles.63 In Dye 31, the
peripheral positions are substituted with triarylamine-termi-
nated bisthiophene units and in Dye 32, hexylbisthiophene
units are attached (Fig. 11). Unfortunately, both the sensitizers
have shown only 40% IPCE and 3% overall conversion effi-
ciency by using a co-adsorbent. The reduced efficiencies of
these dyes have been assigned to the aggregation and poor
electron injection efficiencies.
7. Sterically crowded unsymmetrical
phthalocyanine sensitizers
The peripheral substitution of phthalocyanines is one of the
promising ways to reduce planarity and thus aggregation and it
is possible to manipulate the physicochemical properties as
well. Several researchers have reported phthalocyanines with
long alkyl chains or bulky substituents to suppress the inter-
molecular interaction and thereby aggregation.64–66 The most
viable way of suppressing aggregation is to have bulky substit-
uents at adjacent positions like b,b0 -positions of the phthalo-
cyanine periphery. In fact a similar strategy has also been used
before in designing various phthalocyanine sensitizers. For
example, the good photovoltaic behaviour of Dye 13 and Dye 15
was due to a signicant decrease in aggregation and enhanced
directionality in the excited state owing to the presence of bulky
tert-butyl groups at the periphery of the phthalocyanine. It was
found that these dyes have performed even better in the
This journal is © The Royal Society of Chemistry 2014
RSC Advances
presence of co-adsorbents like CDCA which demonstrates that
there is adequate room for reducing the aggregation tendency
of these molecules. For the rst time Imahori and coworkers
reported a substituted phthalocyanine (b,b0 -position) synthe-
sized for DSSCs applications.63 They synthesized free base and
zinc phthalocyanines with 4-tert-butylphenyl substituents
covalently attached at six b,b0 -positions of the phthalocyanines
and benzoic acid anchoring groups at the other two b,b0 -posi-
tions. But the zinc phthalocyanine sensitized cell displayed
poor power conversion efficiency of 0.57% (Jsc ¼ 1.47 mA cm2;
Voc ¼ 0.54 V; FF ¼ 0.71) and 4.9% IPCE. The free base coun-
terpart of the same substituted phthalocyanine sensitizer has
shown even lower power conversion efficiency. Moreover, it was
observed that the these sensitizer did not show any change in
device performance even in the presence of the CDCA co-
adsorbent which indeed proved the ability of such a molecular
design (bulky alkyl substitutions at b,b0 -positions) to reduce
aggregation. Poor photovoltaic performance of these sensitizers
was attributed to the small driving force for electron injection
from the LUMO of free base/zinc phthalocyanines to TiO2 and
lack of proper electronic coupling between the dye excited state
and the TiO2 conduction band.
Later Mori et al. designed a promising “push–pull” phthalo-
cyanine sensitizer demonstrating the importance of three
dimensional (3D) enlargement of the phthalocyanine molecular
structure to suppress the aggregation completely. Three new
sensitizers Dye 18, Dye 33 and Dye 34 were synthesized and their
aggregation reducing order is Dye 34 > Dye 33 > Dye 18
(Fig. 12).67 The Dye 34 sensitizer showed a maximum IPCE of
78%, high Jsc of 10.4 mA cm2 and record overall conversion
efficiency of 4.6%. Completely suppressed aggregation,
improved electron injection yield and increased directional
electron-transfer behaviour were found to be the primary
reasons for the record efficiency of Dye 34. In an another study,
Bisquert et al.68 have studied the electron transfer dynamics
based on two sterically hindered phthalocyanines (Zn(II) and
free base) and compared their results with the benchmark N719
dye. These phthalocyanines possess electron-donating tert-
octylphenoxy groups and the electron-withdrawing acid anhy-
dride group served as an anchoring group. Both the sensitizers
have shown lower efficiencies when compared to N719 dye.
However, relatively zinc phthalocyanine gave slightly lower
efficiency than that of free base phthalocyanine, attributed to
the higher number of protons in free base phthalocyanine
interacting with the semiconductor surface which lowers the
conduction band edge. It was concluded that increasing the
injection yield and liing the energy levels of the phthalocya-
nine could help in improving the DSSC efficiency. The photo-
voltaic data of all phthalocyanines are summarized in Table 1.
In another study by following a similar structural design to
Dye 34, Ragoussi and co-workers60 replaced the benzoic acid
anchoring group with a carboxyethynyl anchoring group and
reported Dye 35 and Dye 36. The two dyes differed only in the
number of carboxyethynyl groups. Dye 35 with one ethynyl
spacer group has shown h ¼ 6.1% conversion efficiency, the
highest efficiency reported so far using phthalocyanines and the
IPCE also reached more than 85% at 700 nm. On the other
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RSC Advances
hand, Dye 36 has shown h ¼ 3.54% and 55% IPCE. The high Voc
of Dye 35 was attributed to the enhanced electron lifetime and
decreased aggregation. On the other hand, the decreased effi-
ciency of Dye 36 (compared to Dye 35) was due to its low
injection efficiency, evident from the LUMO level (calculated
using electrochemical techniques) of the Dye 36. These results
suggests that the ethynyl group is the most optimal bridge
between the Pc-core and the carboxylic anchoring group which
provides good electronic coupling between the Pc and TiO2.
However, the presence of two ethynyl spacer anchoring groups
was found to decrease the efficiency mainly due to the
decreased driving force for electron injection from the excited
dye into the TiO2 conduction band.
Mori, Kimura and co-workers have further explored the
molecular design strategy based on 3D-enlargement by
substituting methoxy groups at the peripheral positions and
reported Dye 3769 and Dye 38 (Fig. 13).70 Dye 37 has better
solubility and electron donation ability to the phthalocyanine
core. The sensitizer Dye 37 differed only by a methoxy group on
the peripheral diphenylphenol moiety compared to Dye 34.
While the aromatic substituent in these two dyes were kept
constant to optimize the electronic linker structure, in Dye 38 a
different adsorption site (compared to Dye 37) had been intro-
duced with a vision to improve the electronic coupling with
TiO2. The sensitizer Dye 37 has shown high photocurrent
response, IPCE of 72% and 5.3% conversion efficiency. It was
found that the better electron donating ability of methoxy
groups in 2,6-diphenyl-4-methoxyphenoxy of Dye 37 helped to
increase injection yield and thus enhanced overall conversion
efficiency. The structural optimization was carried out by
replacing the bulky 2,6-diphenyl-4-methoxyphenoxy groups
with 2,6-diisopropylphenoxy groups in Dye 38 to facilitate close
packing of dye molecules on the TiO2 surface which is reected
in its photovoltaic properties. The Dye 38 showed an improved
power conversion efficiency of 5.9% (Jsc ¼ 13.7 mA cm2, Voc ¼
0.613 V, FF ¼ 0.70) when compared to Dye 37. Based on charge
separation and injection efficiency, it was suggested a direct
link from the carboxylic acid group to the phthalocyanine core
was the appropriate choice in designing new sensitizers.
Molecular modeling studies conrmed that the undesirable
orientation of Dye 37 on TiO2 was the main reason for low
adsorption density and a decreased efficiency. This study
further revealed that the speculation “greater the steric
hindrance, greater will be the efficiency” (keeping the anchoring
group same) may not always be correct. The efficiencies greatly
depend on the adsorption density of dye on the TiO2 surface as
well.
Recently, Giribabu, Filippo, Nazeeruddin and co-workers
have reported new sterically hindered phthalocyanines based
on methoxy substituents having different patterns.71 The
sensitizer Dye 39 possess 3,4-dimethoxyphenyl substituents at
the b-positions while Dye 40 has 2,6-dimethoxyphenoxy
substituents as electron donors. However, with Dye 39 only
1.07% power conversion efficiency has been achieved due to
lack of directionality in the excited state. Unfortunately, the
sensitizer Dye 40 which was supposed to show better efficiency
than that of Dye 39 because of decreased aggregation due to
6980 | RSC Adv., 2014, 4, 6970–6984
Review
comparatively hindered structure had indeed shown even lower
efficiency (0.89%). On the basis of theoretical calculations, it
was stated that the charge delocalization of the LUMO extends
to only one of the carboxylic anchoring groups, which may
decrease charge regeneration. Very recently, Giribabu and co-
workers have designed an unsymmetrical zinc(II) phthalocya-
nine with tert-butylthiophenyl groups at the non-peripheral
positions.72 Due to substitution at the non-peripheral positions
the phthalocyanine has strongly red shied absorption
centered at 750 nm; the absorption in the near-infrared region
can help to harvest a greater number of photons and thereby
increase the cell efficiency. However, it was observed that this
sensitizer could harvest a very limited amount of solar energy
and the cell showed 0.40% efficiency.
8. Co-sensitization effects in
unsymmetrical phthalocyanine based
DSSCs
Over the years, photovoltaic performance of phthalocyanines
has improved quite signicantly and in fact they have been
shown to be one of the alternative sensitizers for commercial-
izing DSSC technology. This came true only aer nding proper
solutions for reducing aggregation and enhancing the direc-
tionality in the dye excited state. However, there has been
limited work on the improvement of phthalocyanine absorption
in the 400–550 nm region, where the molar absorption coeffi-
cient of the phthalocyanine is minimal. Co-sensitization is a
convincing way to enhance the device performance through a
combination of two or more dyes with complimentary absorp-
tions characteristics on the semiconductor lms. For this
purpose, the dyes have to be chosen in such a way that they
should broaden the absorption, which essentially enhances the
harvesting ability thus charge transfer efficiency and to reduce
the back transfer of electrons from the interconnected semi-
conductor oxide nanoparticle material to the sensitizing dye.
The co-sensitization strategy has been reported before
employing ruthenium complex,73,74 metal-free organic dyes75,76
and porphyrin systems77,78 to show enhanced photovoltaic
performance compared to their single dye systems.
The rst phthalocyanine–organic dye co-sensitization system
for dye solar cell application was reported in 2007 by Torres and
co-workers.55 They demonstrated the enhanced photovoltaic
response of Dye 15 co-sensitized with a reported organic dye
JK279,80 and observed enhanced device performance, Jsc ¼ 16.20
mA cm2, Voc ¼ 0.66 V, FF ¼ 0.72 and h ¼ 7.74% compared to
the individual phthalocyanine dye (3.5%) and JK2 (7.08%)
(Fig. 14). The photoresponse of the cocktail system has reached
up to 700 nm with incident photon to current conversion effi-
ciency of 72% at 690 nm. The increased performance of the
cocktail sensitizer was related to the high molar extinction
coefficient of the dyes which would provide sufficient space on
the semiconductor surface to allow absorption of another dye
having complimentary absorption.
In 2012, Mori and co-workers69 co-sensitized Dye 37 with two
organic dyes, D10281,82 and D13183 resulting in an enhanced
This journal is © The Royal Society of Chemistry 2014
Review
photovoltaic performance of the cocktail sensitizer. The DSSC
device fabricated from cocktail sensitizer Dye 37/D102 exhibited
17% enhancement in the Jsc value while Dye 37/D131 cocktail
sensitizer showed 28% enhancement in the Jsc compared to Dye
37 DSSC devices. An impressive IPCE of 80% even aer co-
sensitization showed the capability of good electron injection of
the cocktail sensitizers. There was no decrease noticed in the
IPCE value in the near-IR region which also points towards zero
interaction between the two dyes. The Jsc of 15.3 mA cm2, Voc of
0.63 V, FF of 0.64 corresponding to an overall efficiency of 6.2%
was achieved with the Dye 37/D131 system while the Dye
37/D102 cocktail system has shown Jsc of 13.9 mA cm2, Voc of
0.625 V, FF of 0.64 giving conversion efficiency h ¼ 5.6%. The
authors proposed that the bulky substituents not only reduced
the aggregation but were also very effective in inhibiting the
interaction between the two complimentary dyes because of an
increase in the distance between their molecular frameworks.
9. Energy relay dyes: a strategy to
increase the light harvesting ability of
phthalocyanine dyes
To have an efficient cocktail sensitizer based on the co-sensiti-
zation phenomena, it is necessary that the constituent dyes
should adsorb strongly on the TiO2 surface, transfer charge
efficiently into the TiO2, and be effective at regeneration84 and
charge injection.85–88 However, so far there have been limited
dyes which exhibit all these characteristics. Moreover, the co-
sensitization methodology has a constraint regarding the
number of anchoring sites on the TiO2 surface that are available
for the dye attachment. In this context, recently, long range
energy transfer has been employed to increase the light har-
vesting ability in DSSCs (Fig. 15).89–91
Recently, Cid et al. have reported an energy relay dye using a
highly uorescent chromophore, PTCDI, dissolved in electrolyte
and tested using Dye 15 (Fig. 16).55 A 28% increase in the
photocurrent response was observed due to the increase in
external quantum efficiency from the 400–600 nm region giving
a total 26% increase in the power conversion efficiency.
However, no change in open circuit potential and ll factor of
the relay device was found. The device efficiency was found to be
2.55% and 3.21% in the absence and presence of PTCDI,
respectively.92 In another work by Hardin and others,93 the
energy relay dye 4-(dicyanomethylene)-2-methyl-6-(4-dimethy-
laminostyryl)-4H-pyran (DCM) was used with Dye 15 and the
overall power conversion efficiency increased from 3.5% to
4.5%. In this study extremely high average excitation transfer
efficiency (>96%) with transparent TiO2 lms was demon-
strated. However, the external quantum efficiency of the relay
dye was limited to 40% in the optimized device due to low
absorption of the relay dye. They have further showed that the
energy relay dyes should have a high molar absorption coeffi-
cient and very good solubility in the electrolyte to achieve an
optimum DSSC architecture.
In a demonstration of the enhancement in the photovoltaic
performance of a DSSC device using energy relay dyes,
This journal is © The Royal Society of Chemistry 2014
RSC Advances
tetra-tert-butyl zinc(II) phthalocyanine has been dissolved in the
electrolyte of a ruthenium polypyridine complex acceptor,
unbound with no direct chemical bond or covalent linker,
achieving four-fold increase in the quantum yield for red
photons in dye-sensitized nanowire array solar cells.94 The close
packed nanoarray architecture was proven to be essential to
ensure special Forster Resonance Energy Transfer (FRET)
between the donor and the acceptors. In an effort to increase
panchromatic response, which is essential to enhance the light
harvesting capability thereby solar conversion efficiency,
recently multiple energy relay dyes (with complementary
absorption characteristics) in the electrolyte has been demon-
strated. Two dyes DCM and Rhodamine B with complementary
absorption have been used with Dye 15 and high excitation
transfer efficiency with 35% increase in the photovoltaic
performance has been achieved. Fluorescence resonance energy
transfer from both relay dyes to the sensitizing dye was found to
be the dominant mechanism for increased light harvesting
system; however, the need to design energy relay dyes which are
more inert to quenching by the electrolyte was also
highlighted.95
Very recently, two energy relay dyes BL302 and BL315 have
been used together with Dye 15 with a 65% increase in the
efficiency of the DSSC device (Fig. 17).96 The excitation transfer
efficiency was limited to 70% only, which is low compared to the
previously reported energy relay dyes. The majority of the losses
in excitation transfer efficiency were found to be due to energy
transfer to the deabsorbed sensitizing dyes and static quench-
ing of the energy relay dye by complex formation. These studies
further suggested that the energy relay dyes have fundamentally
different function mechanism and design rules than the
sensitizing dyes; this architecture greatly expands the range of
dyes that can be used in DSSCs. Still better understanding of the
energy relay dye design rules is anticipated to use them for
complimentary light harvesting systems in record devices.
10. Conclusions
Considering their optical and electrochemical properties,
phthalocyanines have been successfully tested in various prac-
tical DSSC applications. In the recent years, the potential of
phthalocyanines in dye-sensitized solar cells has been widely
explored. Various design strategies yielded stable, near-infrared
absorbing, less aggregating phthalocyanines with high internal
quantum efficiencies and moreover the directionality of the
electron ow in the excited state has also been improved.
However, new molecular design strategies for the construction
of highly efficient devices are still essential and a profound
understanding of the morphology of phthalocyanine sensitizers
is indeed necessary in order to control their photophysical
properties. On the other hand, the use of energy relay dyes has
emerged as a new concept for increasing the light harvesting
using these sensitizers through FRET in dye-sensitized solar
cells. Though the energy relay dyes have paved the way to new
Pc-based cocktail systems for DSSCs, still greater understanding
of the energy loss mechanisms in such systems is required.
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RSC Advances
Acknowledgements
VKS thanks to CSIR for a senior research fellowship. LG thanks
CSIR-NISE and Department of Science & Technology (DST),
Government of India for nancial support to carry out this work
under two major projects DST-EU (‘ESCORT’) and DST-UK
(‘APEX’) and also CSIR-TAPSUN programme.
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