Accepted Manuscript

Review article

Amphiphilic photosensitizers in Dye Sensitized Solar Cells

Sujit Bhand, Sunita Salunke-Gawali

PII: S0020-1693(19)30110-0
DOI: https://doi.org/10.1016/j.ica.2019.118955
Article Number: 118955
Reference: ICA 118955

To appear in: Inorganica Chimica Acta

Received Date: 22 January 2019

Revised Date: 6 June 2019
Accepted Date: 6 June 2019

Please cite this article as: S. Bhand, S. Salunke-Gawali, Amphiphilic photosensitizers in Dye Sensitized Solar Cells,
Inorganica Chimica Acta (2019), doi: https://doi.org/10.1016/j.ica.2019.118955

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Amphiphilic photosensitizers in Dye Sensitized Solar Cells

Sujit Bhand, Sunita Salunke-Gawali*

Department of Chemistry, Savitribai Phule Pune University, Pune 41107, India

Abstract
Dye sensitized solar cells have motivated many researchers to develop various
sensitizers with tailored properties involving anchoring and ancillary ligands. Ancillary
ligands carry favorable light-harvesting abilities and are therefore crucial in determining the
overall power conversion efficiencies.
This review aims to provide insight into the relationship between amphiphilic
sensitizer structure and DSSC properties, which can further guide the function-oriented
design and synthesis of different sensitizers for DSSCs. This review outlines how the new
and rapidly expanding class of amphiphilic photosensitizers metal free as well as ruthenium
complexes. Introduction of amphiphilicity in photosensitizer provides an enhancing in the
performance and stability of DSSCs. These classes of photosensitizer have gained increasing
interest for feasible large-scale commercialization of DSSCs due to their more favorable
light-harvesting abilities and long-term thermal and chemical stabilities compared with other
conventional sensitizers. Therefore, the main idea is to collect data for the researcher to
explore advancement in the design of new amphiphilic sensitizer for DSSCs.

Keywords

Dye Sensitized solar cell, Amphiphilic photosensitizer, Ruthenium complexes, organic

photosensitizers

E-mail: sunitas@chem.unipune.ac.in

Contents

1. Introduction
2. The operational principle of Dye Sensitized Solar Cell(DSSC)
3. Amphiphilic ruthenium complexes in DSSC
3.1 Amphiphilic ruthenium photosensitizers with 4,4’-dialkyl-2,2’-bipyridine
ligands
3.2 Amphiphilic ruthenium photosensitizers with substituted alkoxy bipyridine ligands

1
3.3 Amphiphilic ruthenium photosensitizers with bipyridine ligands with substituted amide
linkage
3.4 Amphiphilic ruthenium photosensitizers containing bipyridine ligands with substituted
thiophene
3.5 Fluorine terpyridine based amphiphilic ruthenium photosensitizers
3.6 Amphiphilic ruthenium-terpyridine photosensitizers containing three thiocyanate ligands
3.7 Amphiphilic ruthenium-terpyridine photosensitizers containing with extended π
conjugated ligands
4. Metal-free amphiphilic photosensitizers
4.1 Monosubstituted triphenylamine based photosensitizers
4.2 Amphiphilic photosensitizers containing tri-substituted triphenylamine bearing alkoxy
groups
4.3 Tri-substituted triphenylamine based amphiphilic photosensitizers
4.4 Metal free amphiphilic photosensitizers containing thiophene ring
4.5 Squaraine based amphiphilic photosensitizers
4.6 Phenoxazine, phenothiazine based amphiphilic photosensitizers
4.7 Carbazole based photosensitizers
5. Conclusion

2
1. Introduction

Energy is one and the most primary component of economic infrastructure and
development of society. It is an essential requirement of the sustained growth of the
community. There is a direct relationship between levels of economic development and per
capita energy consumption. Development needs increment in per capita energy investment or
consumption. As per as sources of energy concern they are differentiated as conventional and
non-conventional sources of energy. First, one conventional source is the primary source of
utilization and satisfying vast need, but they are limited and may be exhaustible shortly. Oil,
natural gas, coal are examples of such conventional source of energy. Apart from
conventional sources of energy, there are non-conventional sources of energy. These are also
called renewable sources of energy. Examples are bioenergy, solar energy, wind energy, and
tidal energy. They are not exhaustive by nature.
Rising prices of oil and gas and their potential shortages have raised uncertainties about
the security of energy supply in the future, which has severe effects on the growth of the
world economy. Increasing the utilization of fossil fuels also causes serious environmental
problems. Hence, there is a must need to use renewable energy sources like solar, wind, tidal,
biomass, and energy from waste material. Out of which solar energy is the most promising
source due to its feature. Solar energy is radiation light and heat from the sun that is
harnessed using a range of ever-evolving technologies such as solar heating, photovoltaics,
solar thermal energy, solar architecture, and artificial photosynthesis.
The earth receives a massive amount of solar radiation from the sun. Considering the
whole spectrum of solar light at the earth's surface is mainly spread across the visible and
near-infrared ranges with a minor part in the near-ultraviolet. Photovoltaics are devices that
convert solar radiation into electricity using semiconductor that exhibit the photovoltaic
effect.

2. The operational principle of Dye Sensitized Solar Cell (DSSC)

Dye sensitized solar cells are currently attracting widespread academic and commercial
interest for the conversion of sunlight into useful electricity because of their low investment
and high efficiency. Over the past decade, considerable progress made in understanding the
working and mechanism of various components of dye-sensitized solar cells. During the past
few years, dye-sensitized solar cells (DSSCs) have attracted widespread interest as a
promising, low-cost alternative to conventional silicon photovoltaic devices.

3
 DSSC is composed of a nanocrystalline mesoporous metal oxide (typically TiO2 and
ZnO) [1] film, thinly coated with a monolayer of a photosensitizer dye, interpenetrated by a
hole-transporting medium, such as an I¯/I3¯ redox liquid-electrolyte or solid state molecular
hole conductor (solid state electrolyte). A schematic representation of the dye-sensitized solar
cell presented in Fig. 1. Following primary steps convert photons (light) to electric current in
DSSC. Firstly the incident photons are absorbed by dye photosensitizers on the conducting
oxide surface. The photosensitizers are excited from the ground state (D) to the excited state
(D∗) see equation (1). The excited electrons injected into the conduction band of the
conducting oxide electrode. These results in the oxidation of the photosensitizer (D+) see
equation (2).
D + hν → D∗ (1)
D∗ → D+ + e− (conducting oxide) (2)

The injected electrons in the conduction band of conducting oxide transported between
mesoporous conducting oxide nanoparticles with diffusion toward the back contact. And the
electrons finally reach the counter electrode through the circuit. The oxidized photosensitizer
species (D+) accepts electrons from the I− ion redox mediator leading to regeneration of the
ground state (D), and the I− is oxidized to the oxidized state, I3−. See equation (3)

D+ + e− → D (3)

The oxidized redox mediator, I3−, diffuses toward the counter electrode and then reduced to I−
ions. See equation (4)

I3− + 2e− → 3I− (4)

The overall efficiency of a DSSC mainly depends upon the four relative energy levels of the
component: the excited state (LUMO) and the ground state (HOMO) of the photosensitizer,
the Fermi level of the conducting oxide electrode and the redox couple potential of the
mediator (I−/I3−) in the electrolyte.

4
 Fig. 1 Mechanism and critical component of DSSC

The durability of DSSC devices is the most crucial problem that precludes the practical
application. Weak strength of DSSC is mainly due to the volatile nature of electrolyte. Recent
research has focused on the use of ionic liquids (ILs) as the electrolytes [2-5], because of
their unique, advantageous properties such as low vapor pressure, non-flammability, high
ionic conductivity and gel-forming properties with polymers [6–9]. However, high viscosity
ionic liquids (ILs) also has a problem serving as mass transport.
The electron collection efficiency at the transparent conductive oxide electrode
directly determines the short circuit current density (JSC) of DSSC. The potential difference
between the Fermi level of electrons in the semiconductor substrate and the redox potential of
the electrolyte gives the open circuit photovoltage (VOC). These two parameters are important
factors determining the DSSC energy conversion efficiency.

The FF is the fill factor at which DSSC operates with the maximum power, which is mainly
related to the total series resistance of the DSSC. Pinc is the input power of incident solar
light.
Recently field succeeded in discriminating the contributions of physical diffusion and
exchange reaction based diffusion of an iodine redox couple to the charge transport processes

5
in 1-ethyl-3-methylimidazolium bis(trifluoromethane sulfonyl) imide (EMImTFSI) by using
an ultra-microelectrode technique [10]. Although numerous studies conducted on suitable
electrolyte for photosensitizer for maximum performance of the cell, only a little attention is
given for suitable photosensitizer for the electrolyte. The orientation order of liquid crystals
near solid surfaces is known to depend on the interactions between the mesogens of liquid
crystals and the solid surfaces. The materials and the orientation near the surface (within nm)
determine the direction of liquid crystals [11-13].
Amphiphilic compounds possess a polar ‘head’ group and non polar ‘tail’ group. With
respect to amphiphilic metal complexes, metal ion and the donor groups of the ligands for
example N,S are the head group while the hydrophobic chains are the tail group.
Amphiphilic sensitizers have several advantages (a) it enhances the binding of the complex
onto the TiO2 surface. (b) The decreased charge on the sensitizer the electrostatic repulsion
and thereby increase the dye loading. (c) The presence of the hydrophobic moiety on the
ligand increases the stability of solar cells toward water-induced desorption. (d) The
oxidation potential of these complexes is shifted, which increases the reversibility of the Ru
(III/II) couple, leading to enhanced stability. This review mainly focuses on amphiphilic
photosensitizers (metal complexes and metal free photosensitizers).
3. Amphiphilic ruthenium complexes in DSSC
Amphiphilic metal complexes are presented in Table 1.
3.1 Amphiphilic ruthenium photosensitizers with 4,4’-dialkyl-2,2’-bipyridine ligands
Studies on DSSCs using cis-dithiocyanatobis(4,4’-dicarboxylic acid-2,2’-bipyridine)-
Ru(II); 1 (N3 dye)(Table 1) is a paradigm in this field [14,15]. A new development for
photosensitizer applied to solar cell comes only from the preparation of amphiphilic
heteroleptic N3 equivalents molecules [16]. Amphiphilic heteroleptic sensitizers have several
advantages compared to the N3 complex, the ground state pKa of the 4,4’-dicarboxy-2,2’-
bipyridine in the amphiphilic heteroleptic complex is higher compared to the N3 that
enhances the binding of the complex onto the TiO2 surface.
Although an extended π-conjugated system may benefit the DSSC efficiency because
of its higher molar extinction coefficient [17] an increment in the size accompanying the
extended π conjugation may also result in lower dye adsorption. It should be attractive to
develop useful simple amphiphilic transition-metal-based sensitizers tolerant toward the
thermal stress and light soaking for future solar cell applications. The importance of the chain
length in photosensitizer is as a spacer between TiO2 and the hole conductor. The dye

6
orientation at the dye-hole-conductor interface highly depends on its chain length.
Considering a certain number of hydrocarbon units, the chains seem to stretch out and
increase the distance between TiO2 and the hole conductor. Recombination between electrons
and holes effectively suppressed by increasing this distance. It assumed that up to a certain
number of methylene units, this distance correlated to the length of the chain.

Grätzel et al. reported alkyl chain containing new sensitizers (2, 3, 4) that yield incident
photon-to-current conversion efficiency values of 80%. These three hydrophobic complexes
(2, 3, 4) as photosensitizers in a nanocrystalline TiO2 based DSSC shown excellent stability
toward water-induced desorption. These kinds of sensitizers operate in the presence of water-
containing electrolytes [16].
The DSSC device with the long alkyl chain containing ruthenium photosensitizer cis-
RuL’L’’(SCN)2 (L’ = 4,4'-dicarboxylic acid-2,2'-bipyridine, L’’ = 4,4'-dinonyl-2,2'-
bipyridine); 5 incompetence with electrolyte a quasi-solid-state polymer gel, gives efficiency
of more than 6% (under AM 1.5, 100 mW cm-2). This photosensitizer is also known as Z907.
Dye plays a role in achieving the high-temperature stability. An ultramicroelectrode
voltammetric measurement confirms that the I−/I3− redox shuttle can perform charge transport
in the polymer gel. The cell sustained heating for 1,000 hrs at 80 °C, maintaining 94% of its
initial performance. The device also showed excellent stability under light soaking at 55°C
for 1,000 hrs in a solar simulator [18].
It has demonstrated that co-grafting an amphiphilic ruthenium dye 5 [19] with
hexadecylmalonic acid onto TiO2 semiconductor nanocrystals remarkably enhanced the
photocurrent, photovoltage and power conversion efficiency of dye-sensitized solar cells.
Long-term stable DSSCs with about 8% power conversion efficiency have fabricated. Co--

7
grafting with hexadecylmalonic acid enhanced parameter like the photocurrent, photovoltage
and overall conversion efficiency considerably to cells containing no hexadecylmalonic acid.
The high light absorption of 6 dye is advantageous compared to the widely used Z907
dye, (NaRu(4-carboxylic acid-4’(-carboxylate)(4,4’(-dinonyl-2,2’(-bipyridine)(NCS)2). The
effective performance of 6 dye-based DSSC explained by electronic absorption, transient
photovoltage decay, and electrochemical impedance measurements. Extending the π-
conjugation of spectator ligands induces an enhanced light harvesting and retards the charge
recombination [20].

Lagref et al. reported [21] amphiphilic photosensitizer 7; as well as other heteroleptic

photosensitizers 8, 9. These photosensitizers yield IPCE values ~80%.
Nazeeruddin and co-worker reported ruthenium polypyridyl sensitizers, 10 and 11,
with conjugated linkers on the anchoring bipyridyl group. This change in linkers responsible
for enhancements in the short-circuit photocurrents in thin film DSSCs as compared with
Z907 dye-sensitized cells due to increased molar extinction coefficients and enhanced
spectral response in the visible light and the near-IR regions [22].
3.2 Amphiphilic ruthenium photosensitizers with substituted alkoxy bipyridine ligands
Instead of a π-conjugated system, simple fluorous amphiphilic dyes, 12, 13 and 14
[23] gives better efficiencies. The hydrophobic polyfluorinated chains in these dyes lead to
higher dye density on TiO2 also suppress dye leaching. The better cell efficiency and dye
durability were observed polyfluorinated dyes as compared to nonfluorinated dyes.
DSSC devices with more than a 10.5% efficiency were reported utilizing high molar
extinction coefficient photosensitizer; 15 (K77) [24] exhibiting long-lasting stability (1000
hrs) under both light stress and thermal stressing has been obtained using the 15
photosensitizer.
3.3 Amphiphilic ruthenium photosensitizers with bipyridine ligands with substituted
amide linkage

8
Grätzel et al. [25] also reported the ruthenium photosensitizer 16 to 19, which passes
amphiphilic moieties. The photocurrent action spectra of the amphiphilic heteroleptic
complexes show full features covering a large part of the visible spectrum. Only
photosensitizer 19 contains straight alkyl chain showed maximum efficiency ~8.5 %.

17

Chou and co-worker reported a novel Ru(II) sensitizer 27 containing the 4,4’-
dioctylamido-2,2’-bipyridine as an ancillary ligand. Power conversion efficiency is 7.25% for
this dye in DSSC devices [26].
The addition of excellent photovoltaic performance of 21 was reported by Largef et
al. over photosensitizer 7. This novel bis amide complex 21 and the possibility to induce self-
organization with hydrogen-bonding recognition groups [21].
3.4 Amphiphilic ruthenium photosensitizers containing bipyridine ligands with
substituted thiophene
The increase in efficiency in solid-state dye-sensitized solar cell (from 2.9% to 4.5%)
of photosensitizer 22 can be attributed to the high molar-extinction coefficient of the
alkylthiophene-containing groups, as well as to augmentation of the charge recombination
lifetime [20].
A novel heteroleptic ruthenium photosensitizer with a high molar extinction
coefficient to considerable enhance in the optical absorptivity of mesoporous titania film. For
this dye (23), the achievement of over 10.5% power conversion efficiencies is very
encouraging in this research area [27].

9
 The significant molar extinction coefficient of ruthenium photosensitizer featuring a
hexylthiothiophene conjugated bipyridine ligand is to enhance the optical absorptivity of
mesoporous titania film remarkably. Photovoltaic parameters of a solvent-free cell based on
the 24 measured under an irradiance of 100 mW cm-2 AM 1.5 G sunlight during successive
full sunshine soaking at 60°C and IPCE efficiency of 11.4% [28].
Heteroleptic ruthenium complex with a high molar extinction coefficient 25, having
an electron-rich hexylthio-terminal chain, has been reported as an efficient sensitizer for
DSSC [29]. With this new photosensitizer, the excellent power conversion efficiency is
11.5% and 4.7% obtained under irradiation of full sunlight (air mass 1.5 global) in
combination with a volatility electrolyte and solid-state hole transporting material,
respectively. The devices with low volatility electrolyte showed excellent stability under
visible light soaking at 60 °C during 1000 h of accelerated tests.
Branched and bulky photosensitizers (26-29) reported by Nazeeruddin et al. [30].
Two types of branched alkyl chains, either 2-methylhex-2-yl or 1,1-dipropylbutyl are used to
design these photosensitizers and their performances in DSSC compared in both series. The
2-methylhex-2-yl substitution pattern was found more efficient in both 26 and 28, which
provides some guidelines for designing Ru-(II) bipyridine dyes for DSSCs. The
photosensitizer; 28 possesses extended, and red-shifted absorption caused by dithiophene
moieties in the ancillary group and 2-methylhex-2-yl substitution logically achieved the
highest conversion of the series (η = 8.5%). The optimization of 28, with dye-soaking and
electrolyte composition, the overall conversion efficiency achieved of 9.1% under AM1.5 G.
A series of heteroleptic ruthenium complexes (30, 31) containing 5,5'-disubstituted-
2,2'-bipyridine ancillary ligands have reported by Wong et al. with spectroscopic and DFT
studies[31]. The different substituent on bipyridine acts as an excellent functional
chromophore to tune the overall properties of the complex. The relationship between the
nature of the ancillary ligand and the DSSC performance of the dye investigated. As
demonstrated by the absorption spectral studies, the increase in conjugation length of the
ancillary ligand results in a lower MLCT energy and a diminished intensity of the transition.
Photosensitizer 31 gave the highest conversion efficiency of 3.00% and among complexes 30,
31 the performance results correlate well with the molar absorption coefficient of the MLCT
band of the dyes and their different light-harvesting ability. These findings suggest that
bipyridine chromophores substituted at the synthetically more accessible 5, 5’- positions open

10
an alternative good class of ancillary ligands over the traditional 4, 4’-disubstituted ones for
use in DSSC research based on the photosensitizing metal polypyridyl core.
Kim et al. reported two ruthenium photosensitizers (32 and 33) those contain fused
dithiophene and unsymmetrical indeno [1,2-b]thiophene unit in the ancillary ligand 32 and
33. The bidentate thiocyanate ligand used to enhance the performance of the dye. The dye
shows the photovoltaic performance as a Jsc 18.60 mA/cm2, Voc 0.72 V, and a fill factor of
0.71, yielding conversion efficiency of 9.54% [32].
Diau et al. [33] reported some heteroleptic ruthenium complexes having fluoro-
substituted and thiophene-based benzimidazole ligands as a core unit for DSSC application.
Out of reported four photosensitizers two (34 and 35) contains carbon alkyl chain in the core
structure. The alkyl chain substituted complexes shows more power conversion efficiencies
than others. Results indicated that the alkyl chain and the thiophene units little affected the
potential but affected the charge recombination in various directions.

3.5 Fluorine terpyridine based amphiphilic ruthenium photosensitizers

The panchromatic photosensitizers 36, 37 and 38 of 4,4’,4’’-tricarboxylic 2,2’:6’,2’’-
terpyridine-ruthenium(II) complexes with one β-diketonato chelating ligand containing
different bulky alkyl chain lengths between C(1)–C(16) developed by Islam et al. [34]. The
photovoltaic data of this photosensitizer showed 7.6% power conversion efficiency under
standard AM 1.5 irradiation (100 mW cm−2). Photosensitizer dye containing bulky alkyl
chain length of C16 (38) is independent, i.e., not showing any enhancement, while bearing
alkyl chains length of C6 (37) showed 10%.
A terpyridyl- ruthenium complex introduced in 2001 [35] by considering, tune the
electronic and optical properties by exchanging one or more of ligands. Its extended
absorption in the near infrared region significantly enhances the overall incident photon to
current conversion efficiency. Thus, DSSCs sensitized with this so-called ‘black dye’; 39,
have a higher short circuit current. The conversion efficiency of 10.4% (1 cm2), is the highest
certified efficiencies so far, which makes this dye as the second most efficient photosensitizer
after N3. The HOMO level of 39 destabilized by introducing three thiocyanate ligands and
the LUMO levels lowered by the presence of 4,4',4''-tricarboxylic acid 2,2',6,2''-terpyridine
ligand. Reducing the HOMO-LUMO gap, the resulting sensitizer shows absorption extending
in the near IR regions. When the sensitizer is chemically bound to the TiO2 surface, the

11
protons of the anchoring group (carboxylic acid) partially transferred to the surface of TiO2
[35].
Chou et al. [36] reported a series of ruthenium photosensitizers 40-43; featuring the
substituting of three NCS groups by 2,6-bis(3-(trifluoromethyl)-5-pyrazolyl)pyridine
derivatives new series of bis-tridentate Ru(II) sensitizers in which a π-conjugated thiophene
pendant group has strategically added onto the dicarboxyterpyridine chelating ligand at the 5-
or 6-position of the terminal pyridyl unit. This pendant group serves as an antenna to harvest
solar energy, increasing the light-harvesting. DSSC devices showed high overall conversion
efficiencies. Photosensitizer 40 showed a Isc of 19.0 mA cm−2, a Voc of 0.71 V, and FF of
0.68, an overall conversion efficiency of 9.21%, which is more than that of the N749 dye
device.
Chou and co-worker [37] also developed new panchromatic Ru(II) sensitizers; 44-47,
that incorporate both 4,4',4''-tricarboxylic-2,2':6,2''-terpyridine and 2,6-bis(5-
pyrazolyl)pyridine ligands; with power conversion efficiencies as high as 10.7%. This
outcome encourager’s thiocyanate free complexes and also tridentate structure avoids
problematic isomerization and simplifying the purification process and offering good product
yield. Chemically, the multidentate coordination, should improve the long-term stability, as
evidenced by the great life span of solar cells fabricated with 45. This modification seems to
show satisfactory sensitization up to 900 nm, and it still possesses major deficiencies. One is
the inferior absorptivity in the visible region, attributed to the lack of effective auxochrome.
The second problem is the presence of three thiocyanate ligands in these dyes, which reduces
the synthetic yield due to coordination isomerism and deteriorate the life of the fabricated cell
units, the reason is the weak Ru-NCS bonding causes dye decomposition.
Ru–terpyridine photosensitizer 48 is a substitution or an electron-donating π -
conjugated 4-methylstyryl group onto the terpyridyl ligands [38]. Photosensitizer 48
exhibited more intense absorption over the whole spectral region compared to black dye
owing to the extended π -conjugation resulting from the 4-methylstyryl moiety. The DSSC
based on the 48 dye achieved a conversion efficiency of 11.1%, which is higher than the
efficiency of the reference cell based on black dye (+ 0.5%) under the same standard AM 1.5
G.
Various alkyl groups containing ruthenium terpyridine complexes (49-52) as
panchromatic sensitizers [39] responses as much higher molar extinction coefficients at 400–
550 nm and gives better DSSC performance in terms of conversion efficiency (ղ = 10.05 for

12
49 and thermal and light stability. Photosensitizer 52 the best among the series of
photosensitizer studies, which gives ISC = 21.6 mA cm-2, VOC = 714 mV, and FF = 0.652,
corresponding to an overall ղ = 10.05 %. This efficiency value is 10.8 % greater than that of
the reference solar cell fabricated employing the well-known black dye.
3.6 Amphiphilic ruthenium-terpyridine photosensitizers containing three thiocyanate
ligands
Chou and co-worker presented tris(thiocyanate) ruthenium(II) sensitizers that possess
a functionalized dicarboxylic terpyridine ligands (53-56)[40]. These complexes not only
show better light-harvesting capabilities relative to that observed for parent N749 in the
shorter wavelength region but also retain the characteristic MLCT transition at about 600 nm,
which is necessary for improving the overall efficiencies of DSSCs changing from parent
photosensitizer 53 to thiophene anchored photosensitizer 54 or EDOT-attached
photosensitizers 55 and 56 was found to induce an increase in VOC as large as 50–70 mV,
indicating that the thiophene (or EDOT) unit and the associated hydrophobic carbon chain, in
part, may inhibit the dark current [40].

3.7 Amphiphilic ruthenium-terpyridine photosensitizers containing with extended π

conjugated ligands
Efficient dyes reported by Jang et al.; photosensitizers 57 and 58 both having
oligophenylenevinylene π-conjugated structure as core backbones for increasing absorbance
and each with one N, N-dibutylamino moiety[41]. Photosensitizer dyes 57, and 58 shows
12% and 17% increment in efficiency for their DSSCs, when contrast to the efficiency
obtainable with N3 dye [41].
Photosensitizers (59-60) featuring alkoxy groups introduced [42]. The purpose of
4,4’- bis((E)-2,5-dimethoxystyryl)-2,2’-bipyridine ligand that contains extended π-
conjugation with substituted methoxy groups is to enhance molar extinction coefficient of the
sensitizers and furthermore to provide directionality in the excited state by tuning the LUMO
level of the ligand with the electron-donating alkoxy groups. The absorption spectra of
complexes (59-60) dominated by the MLCT transitions in the visible region and the lowest
allowed MLCT bands appearing at 400 and 545 nm. DSSC performance exhibited ISC 16.50
mA/cm-2, with a VOC 790 mV and a fill factor of 0.72, corresponding to an overall conversion
efficiency of 9.6%.

13
 Sugihara et al. reported [43] cyclometallated ruthenium (II) complexes,
Ru(tctpy)(C^N)(NCS) (61 and 62), where C^N is a bidentate cyclometallating ligand such as
2-phenylpyridinato or 2-(4-(2-phenylethynyl) phenyl)pyridinato. These compounds act as
light sensitizers with excellent light harvesting properties, particularly in the near-IR region.
Hence are used in DSSCs. A DSSC sensitized with 61 shows a 10% IPCE at 900 nm.
Ruthenium [3+2+1] sensitizers 63 and 64 showed strong absorption over the whole
spectral region [44]. The presence of π-conjugated 4-methylstyryl group is presumed to be
responsible for overcoming the competitive absorption from redox couple. Unsymmetrical
ancillary bipyridine ligand increased the molar extinction coefficient of Ru-complex as well
as decreases the direct recombination with I3-. The DSSC, based on complex 61, exhibited the
high overall conversion efficiency of 5.19%.
Photosensitizers 65, 66 have been designed such that the extra conjugation is between
pyridine and benzene ring. Alkyl and alkoxy group deployed for regulating aggregation and
reducing recombination in the DSSC. The based DSSC constructed which showing solar to
electrical energy conversion efficiency (η) of 8.36% under 1.5 AM sunlight, while the
compared with N719 based DSSC exhibited η-value of 7.2% [45].
Photosensitizer 67 bearings with terpyridine as an anchoring ligand and
tetrabutylammonium as the counter ion and BOC (tertbutyloxycarbonyl) protected bidentate
benzimidazole derivative as an ancillary ligand reported. Photovoltaic performance of this
photosensitizer for DSSCs with iodine triiodide electrolyte showed a JSC of 15.25 mA cm−2, a
VOC of 0.576 V, a FF of 0.691 and overall power conversion efficiency of (η) 6.07% [46].

14
 Table 1 Amphiphilic Ru-based photosensitizers

O OH

OH

O N
N NCS
Ru
NCS
N 10.4 14
HO N

HO O

>6.00 18

2.9 20

6
7.4 21

15
 6.92 22

10
7.45 22

11
6.23% 23

12
6.93% 23

13

16
 6.82% 23

14
SCN NCS
O

N
Ru O
N

N
N
OH 11.05 24

OH
O O

15
7.01 25

16
7.62 25

18

17
 COOOH

HO
N
N COOH
Ru
N 8.86 25
N
HO
NCS
SCN

19

7.25 26

20
7.4 21

21
4.5 20

22

18
 10.53 27

23
8.51 28

24
11.5 29

25
7.5 30

26

19
 6.1 30

27
7.5 30

28
8.0 30

29

20
 3 31

30
2.03 31

31
9.54 32

32
8.70 32

33

21
 9.4 33

34
10 33

35
6.63 34

36
6.82 34

37

22
 7.46 34

38
10.7 35

39
8.80 36

40
9.21 36

41

23
 8.53 36

42
8.05 36

43
9.11 37

44
10.5 37

45

24
 10.7 37

46
10.5 37

47
11.1 38

48

9.14 39

49

25
 9.33 39

50
9.54 39

51
10.05 39

52
8.54 40

26
53
8.04 40

54
9.10 40

55
10.3 40

56

27
 4.6 41

57
4.8 41

58
9.6 42

59

8.4 42

60

28
 2.2 43

61

3.7 43

62
5.19 44

63

29
 4.63 44

64
7.2 45

65
5.77 45

66
6.07 46

67

30
4. Metal-free amphiphilic photosensitizer
Metal free photosensitizer based DSSC has many advantages as well as disadvantages
over conventional silicon as well as ruthenium complexes. Organic photosensitizers are
advanced compounds, in terms of significant molar extinction coefficient, control of
absorption wavelength, simple design, synthesis, and lower cost than ruthenium
photosensitizers. Moreover, the molar extinction coefficient of charge transfer band in metal
free dyes usually are much higher than that of the metal to ligand charge transfer (MLCT)
band in highly efficient ruthenium photosensitizers. However, the significant applications of
organic photosensitizers in the DSSC devices limited because of quite less efficiency than
ruthenium photosensitizers. Apart from this, the performance of organic photosensitizer
based DSSC has also recently improved so it may happen that shortly, those organic
photosensitizers could compete with ruthenium dyes [47-50]. Metal free photosensitizers are
still behind the ruthenium photosensitizer in terms of conversion efficiencies, however
interest has grown for metal free photosensitizers because of the demerit of ruthenium dyes,
for example, the ruthenium metal cost, its complexes required careful monitored synthesis
and tricky purification processes [51-57]. To improve performance of DSSC and its
applicability, it needs to design organic dyes with potential absorption properties with
intramolecular charge separation and should capable to strongly bind to conducting material
for natural percolation or transportation of electron in cell device through nonporous
photoanode [58-61]. Organic material solar cells also have a feature like low cost and
environment-friendly with pollution free nature. Organic materials also play an essential role
in organic photovoltaic devices (OPV) as polymeric conducting materials. Small molecular
photosensitizer attracts more attention in this field. Amphiphilic metal free photosensitizers
are presented in Table 2.
4.1 Monosubstituted triphenylamine based metal free photosensitizers
Marks et al. [62] reported a series of metal-free alkylated tetrathienoacene (TTAR)-based
organic chromophores, (68-70) synthesized for application in DSSCs. Extensively conjugated
TTAR π-bridge incorporated in all three dyes, which response as exhibit high extinction
coefficients (1*105 M-1 cm-1). The branched-alkyl chain in dye 68 promotes enough tilting
and packing distortion on TiO2 in comparison to more ordered monolayers of long linear
alkyls 69 and 70. The branched-alkylated TTAR unit in 68 increases the electron injection
efficiency. Photosensitizer 68 exhibits higher short-circuit current densities and achieved a
high PCE of 11.18%.

31
 Triphenylamine dyes [63] that were containing alkylthio-substituted thiophenes with a
low bandgap as a π-conjugated bridge unit were developed (71 and 72). The effects of the
structural differences in terms of the position, number, and shape of the alkylthio substituent
are in the thiophene bridge on the photophysical properties of the dye, and the photovoltaic
performance of the DSSC reported. Both photosensitizers show promising photo-current
conversion efficiencies.
Thiazole is a common moderate electron-withdrawing heterocycle. Several moieties
based on thiazole have widely introduced into organic semiconductors, with high
performances in organic electronic devices. Sensitizers 73 and 74 contain a thiazolyl unit in
the π-conjugation [64]. The position of the nitrogen atom of the thiazolyl unit is different for
these two dyes. Both photosensitizers contain alkyl chain at the same carbon atom.
The cyclopentadithiophene in 75 and 76 efficiently increase the conjugation length,
exhibiting the CT absorption band at 450 and 460 nm. Wang et al. compared alkoxy- or
fluoro-substitution on the phenyl unit in a triphenylamine based organic sensitizer. Out of
which the alkoxy-substituted 77 shows better performance than difluoro-substituted due to its
broader spectral response [65, 66].
4.2 Amphiphilic photosensitizers containing tri-substituted triphenylamine bearing
alkoxy groups
Fused-ring thiophene compounds (78-81) emerged as an essential building block for
organic photosensitizer dyes in DSSC because of their excellent charge transfer and light-
harvesting phenomenon. The hex-1-en-1-ylbenzene (HEYB) unit introduced in two new
fused-ring thiophene dyes (78 and 81). It observed that of the HEYB unit in arylamine donor
enhances the driving force for dye regeneration and suppressing dye aggregation as well as
reducing the charge recombination in DSSC mechanism. A dye-sensitized solar cell
employing the 78 photosensitizer with cobalt electrolyte exhibits an excellent power
conversion efficiency of 9.75% measured under the 100 mW cm−2 [67].
Suranna et al. reported [68] some -extended metal free photosensitizers for DSSCs
had been designed (82 and 83) to optimize the interactions between the dye/TiO2 layer and
the redox electrolyte. Molecular tailoring performed by i) positioning an alkyl chain onto the
pi-spacer and ii) increasing the bulkiness of the electron donor. Two different alkyl branching
were attached on two positions of the dye to reduce hopping of charge in the device.
Zhu et al. [69] developed a series of metal-free organic photosensitizers (84-88) based
on a robust electron-deficient thiadiazole[3,4-c]pyridine. The insertion of the auxiliary unit

32
thiadiazole[3,4-c]pyridine can effectively tune the energy levels and proven as designing
small band-gap photosensitizers with panchromatic absorption. Authors reported the study of
the impact of various π-conjugated spacers on the absorption properties, electrochemical
properties, and photovoltaic performances. The photosensitizer 87 with a benzene unit
adjacent to the anchoring cyanoacrylic group produces a higher photocurrent and
photovoltage in cell performance, as compared to 84 and 85 with thiophene and n-
hexylthiophene unit adjacent to the anchoring group. Further, the structural optimization of
photosensitizer 86 with containing n-hexylthiophene and a π-conjugated spacer between the
donor and thiadiazole [3,4-c]pyridine, results in the best photovoltaic performance. This
research demonstrates that the long alkyl chains can efficiently improve the cell performance
by suppressing the dye aggregation on TiO2 film surface, enhancing electron injection
efficiency, and retarding charge recombination by shielding the surface of TiO2 from I3- ions.
Tian et al. [70] reported DPP(diketopyrrolopyrrole) -based organic sensitizers (89 and
90) for DSSCs containing methoxy substituted triphenylamine as an electron donor and
cyanoacrylic acid as an electron acceptor and anchoring group. The electron-withdrawing
DPP unit is involved in the p-bridge between the donor and acceptor, indicative of a typical
D–A–π–A configuration. To increase the solubility of the dye in the solvent attachment of
long alkyl chain on lactam nitrogen positions could be used for space to reduce aggregation.
The introduction of long alkyl chains into DPP rings can also inhibit the charge
recombination and increase the electron lifetime.
Tian et al. also developed a series of organic sensitizers 91 to 92 by incorporating a
bithiazole unit into the π-linker [71] carefully modified the electron donor and -bridge by
introducing the methoxy group, phenyl group, and triple bond for tailoring their combination
pattern. DSSCs based on these five dyes exhibit high Voc (745-810 mV) with a moderate
conversion efficiency (in the range of 4.20-5.73%). Apparently, due to their relatively weak
electron-withdrawing character, thiazole and bithiazole-based organic D–A–π–A dyes do not
show full spectral response. All these dyes show the HOMO–LUMO gap more significant
than 2.3 eV, and the charge transfer band shorter than 465 nm. However, it is worth replacing
the thienyl unit with the thiazolyl unit in some dyes.
Pei et al. reported [72] the dithienyl-fused BTD(benzothiadiazole) based dyes 93 and 94
[72]. Their alkyl chains are away from the BTD core, and their absorption properties are
consistent with the alkyl chain effect. The methoxy groups in 94 shift the charge transfer
band to the long wavelength region by 17 nm relative to 93.

33
 Licheng Sun et al. [73] reported a series of organic dyes (95 to 97) with pyridinium as
acceptor had synthesized for HOMO and LUMO energy level tuning. For triphenylamine
based dyes, by substituting the 3-hexylthiophene group with a carbon-carbon double bond as
π-spacer, the bathochromic shift of absorption spectra and higher current density (Jsc) are
achieved. Insertion of the methoxy and n-hexyl into 95 to construct dyes 96 and 97, the
absorption peak is red-shifted compared with that of 95 due to the increase of the electron-
donating ability. The devices fabricated with sensitizers 96 and 97 show higher Jsc and open-
circuit voltage (Voc) than those of the device sensitized by 95, which can be mainly attributed
to the broader incident photon-to-current conversion efficiency (IPCE) response and the
suppression of electron recombination between TiO2 film and electrolyte, respectively.
4.3 Tri-substituted triphenylamine based amphiphilic photosensitizers
Photosensitizer 98 and 99 are two successful examples of molecular optimization with
n-alkyl chains [74]. The induction of long alkyl chains into thiophene π-bridge of dyes 98 and
99 can cause enhancement in the tolerance toward the water in the electrolytes. DSSC of 98
with volatile electrolyte yielded an overall conversion efficiency of 8.6%, whereas the
conversion efficiency of the same sensitizer-based DSSC with a solvent-free ionic-liquid
electrolyte was 7% under AM 1.5 G. Interestingly the 98-based solar cells fabricated using a
solvent-free ionic-liquid electrolyte exhibited excellent stability under light soaking.
Photosensitizers 100-102 are the representative organic dyes with π-phenylene
vinylene units [75]. Photovoltaic properties of dyes 100-102 hugely affected by different
numbers of π-phenylene vinylene units. The maximum power conversion efficiency of the
DSSC based on 102 containing three π-phenylene vinylene units reached 7.0% under AM 1.5
G.
Ko et al. reported [76] the dithienyl-fused BTD based organic sensitizers 103. The
alkyl chains are quite useful in increasing the electron lifetime by preventing the dark current,
improving Voc of the DSSC cell.

4.4 Metal free amphiphilic photosensitizers containing thiophene ring

A donor dithiafulvenyl group is used for constructing of D-π-A type DSSC in metal-
free photosensitizers 104-106 [77]. Dithiafulvenyl as a donor containing sensitizer reported
by Yang et al. with a cyanoacrylic acid acceptor but differing in the spacer phenyl, biphenyl,
and phenyl-thiopheneyl-phenyl π-bridges. A DSSC device based on these dyes gives

34
enhancement performance with the increasing π-bridge length, culminating with η = 8.29%
under standard global AM 1.5 illumination.
Wei-Hong Zhu et al. [78] reported three different donor-free dyes of (107, 108, and 109)
with the main difference of number and location of long alkyl chains designed. The
integrated electron-deficient quinoxaline unit is found to enhance the intramolecular charge
transfer transition and weaken the deprotonation effect on absorption properties, resulting in
an improved light harvesting efficiency.
Jing Li et al. [79] reported five organic D–A–π–A sensitizers 110-114 containing
benzothiadiazole (BTD) or benzotriazole (BTZ) as auxiliary electron withdrawing units.
Although all of these dyes have long alkyl chains grafted on a π-bridge, DSSCs with
photosensitizer containing a BTZ unit displayed higher open circuit voltages (757–829 mV)
than those containing a BTD unit (682–712 mV). It is because the nitrogen-based
heterocyclic group of BTZ can lift the conduction band edge and reduce the charge
recombination that arises from the absence of the sulphur atom. With this modification and
the introduction of alkyl chains on the located nitrogen, DSSCs with one dye containing BTZ
and thieno[3,2-b] thiophene (TT) as the π-spacer (111) showed the highest open circuit
voltage (Voc = 829 mV) [79].
Compared with the traditional D–π–A structure, this D–A–π–A indoline dyes (115 and
116), with the additional incorporated acceptor unit of benzothiadiazole in the π-conjugation,
exhibit a broad photo response, high redox stability, and convenient energy-level tuning. The
attached n-hexyl chains in both dyes are sufficient to suppress charge recombination,
resulting in a decreased dark current and enhanced open-circuit voltage [80].
Several dyes reported [81] possessing n-hexyl alkyl chain terthiophene, (117-118) as an
electron donor and cyanoacrylic acid as the electron acceptor and the suppressed
intermolecular interaction with the presence of n-hexyl chain linked to thiophene gave rise to
an enhanced electron transfer process [81].
A series of new fluorene-bridged organic dyes (119-122) with di-anchoring groups
have synthesized and well characterized [82]. Modified a molecular engineering design
strategy using two organic anchors inhibits the undesirable charge recombination and
sustainable the electron lifetime which gives significant increment conversion efficiency. The
results also explain that the fluorene unit is a promising bridge for an organic di-anchoring
photosensitizer because of the presence of two long alkyl chains which can improve the
solubility of the dyes and suppress the undesirable dye aggregation.

35
4.5 Squaraine based amphiphilic photosensitizers
Nithyanandhan and co-worker [83] developed a new squaraine based dyes with straight
chain alkyl chain in the core structure of photosensitizers; authors monitored the proper
distance between the core electrons accepting part of the photosensitizer. A series of donor-
acceptor−donor−π spacer−acceptor (D−A−D−π−A) unsymmetrical squaraines, 123 to 127
with indoline donor and squaric/cyanoacetic acid acceptor units, were designed for sensitized
solar cells.

4.6 Phenoxazine, phenothiazine based amphiphilic photosensitizers

An efficiency of 5.5% has achieved in a DSSC based on photosensitizer 128. The
photosensitizer containing a cyanoacrylic anchor group has much better DSSC performance
than those dyes containing a rhodanine- 3-acetic acid group [84].
Min Zhang et al. reported phenoxazine (POZ)-based metal free photosensitizers 129.
They successfully demonstrated the enhancement in the conversion efficiencies due to
incorporation alkyl chain [85].
Phenothiazine based dyes 130-131 reported by Sun et al.[73]. These dyes possess
better electron donor ability as compared to triphenylamine photosensitizers 105-107.
4.7 Carbazole based Photosensitizers
Carbazole based sensitizers for DSSC (132, 133) [86] have investigated. The effect of
a π conjugated system of n-hexyl-substituted oligothiophenes on DSSC performance. They
found that the photovoltaic performance of these dyes depended on the molecular structures
in terms of the number and position of n-hexyl chains and the number of thiophene moieties.
n-hexyl chains attached to the thiophene group are responsible for the retardation of charge
recombination, which increases in electron lifetime. The overall conclusion may outcome as
an increase in photovoltage and efficiency of DSSCs were improved with the addition of n-
hexyl chains to the thiophene groups. The Voc (0.69-0.75 V) for DSSCs based on 132 and
133 dyes. A DSSC based on 133 consisting of n-hexyl-substituted quarter-thiophene
produced 8.3% efficiency under simulated AM 1.5 G.
Harima and coworkers [87] have made efforts on structural optimization of
benzofuro[2,3-c]oxazolo[4,5-a]carbazole-type fluorescent dyes (such as 134 and 135) for

36
DSSCs. Authors studied in detail the effect of the position of the carboxyl group on DSSC
performance, and found that despite the lengths of alkyl chains, the electron-withdrawing
group cyanide of the dyes was located close to the semiconductor surface due to the
flexibility of alkyl chains, and a good electron injection yield have achieved between the
cyanide and TiO2 surface.

37
Table 2 Metal free amphiphilic photosensitizers

10.21 62

68

9.02 62

69

7.60 62

70
5.03 63

71
4.24 63

72

38
 6.88 64

73
4.92 64

74
3.69 65

75
4.86 65

76

6.9 66

77

39
 67
7.90

78
67
9.13

79
67
6.66

80
67
7.70

81

40
 9.83 68

82
10.26 68

83
2.86 69

84
3.84 69

85
4.46 69

86
6.30 69

87

41
 1.32 69

88
3.24 70

89
1.45 70

90
5.60 71

91
5.05 71

92
6.04 72

93

42
 4.68 72

94
3.8 73

95
5.6 73

96
6.3 73

97
7.42 74

98

43
 8.60 74

99
5.34
75

100
6.89 75

101
7.02 75

102

44
 6.61 76

103

8.29 77

104

4.18 77

105

3.15 77

106

8.05 78

107

6.64 78

45
108

6.81 78

109

5.65 79

110

6.23 79

111

7.15 79

112

5.20 79

113

46
 5.82 79

114

7.76 80

115

7.23 80

116

2.2 81

117

1.8 81

118
82

47
 R R

N N

S n S
n

HOOC CN NC COOH

119, R=1-octyl, n=1 6.11

120, R=2-ethylheyl, n=1 5.94
121, R=1-octyl, n=2 6.05
122, R=2-ethylhexyl, n=2 5.88
C6H13

O
HO CN N

N C10H21
O
O C8H17
7.01 83

123

5.55 83

124
C6H13
O
CN
HO N
N
S
7.21 83
O O
C10H21
C8H17

125
C6H13 O
O
S
N OH

N CN
O
6.39 83
C10H21 C8H17

126

C12H25
O
CN
N 8.15 83
HO N
S
O C12H25
O
C10H21

127

48
 5.5 84

128

6.6 85

129

7.1 73

130
6.9 73

131

3.7 86

132

49
 8.3 86

133

0.86 87

134

1.0 87

135

5. Conclusion
In this review of amphiphilic ruthenium polypyridyl, photosensitizers along with
metal free photosensitizers in DSSC are described with their essential aspects. Idealized by

50
the natural photosynthesis, Dye-Sensitized Solar cells have become a credible alternative to
solid-state p–n junction devices. Light to current conversion efficiencies over 11% and 15%
have already obtained with single junction and tandem cells, respectively, on the laboratory
scale, with still ample room for further improvisation. Various functionalized metal-free
organic dyes have been designed and exert impressive results. We have systematically
described the different substituents to the organic as well as ruthenium complexes
photosensitizers. This summary on photosensitizer provides extended results in absorption
and conversion efficiencies. Optimization in performance of DSSC device directly related to
every material used in the cell however photosensitizers has its importance.
Acknowledgment
SSG and SB (for fellowship) acknowledges to UPE -Phase II (University with Potential for
Excellence) a scheme of Union Grants Commission (UGC), New Delhi, India

51
References

1. B. O’regan, M. Grätzel, A low-cost, high-efficiency solar cell based on dye-sensitized

colloidal TiO2films Nature 353 (1991) 737-740. DOI: 10.1038/353737a0.
2. J. G. Rowley, B. H. Farnum, S. Ardo, G. J. Meyer, Iodide Chemistry in Dye-Sensitized
Solar Cells: Making and Breaking I−I Bonds for Solar Energy Conversion. J. Phys.
Chem. Lett. 1 (2010) 3132-3140. DOI: 10.1021/jz101311d
3. G. Boschloo, A. Hagfeldt, Characteristics of the Iodide/Triiodide Redox Mediator in
Dye-Sensitized Solar Cells. Acc. Chem. Res. 42 (2009) 1819-1826. DOI:
10.1021/ar900138m
4. B. C. O’Regan, K. Walley, M. Juozapavicius, A. Anderson, F. Matar, Ghaddar, T.;
Zakeeruddin, S. M.; Klein, C.; Durrant, J. R. Structure/Function Relationships in Dyes
for Solar Energy Conversion: A Two-Atom Change in Dye Structure and the
Mechanism for Its Effect on Cell Voltage. J. Am. Chem. Soc. 131 (2009) 3541-3548.
DOI: 10.1021/ja806869x
5. F. Matar, T. H. Ghaddar, K. Walley, T. D. Santos, J. R. Durrant, B. O’Regan, A new
ruthenium polypyridyl dye, TG6, whose performance in dye-sensitized solar cells is
surprisingly close to that of N719, the ‘dye to beat’ for 17 years J. Mater. Chem. 18
(2008) 4246-4253. DOI: 10.1039/b808255c
6. D. Kuang, C. Klein, Z. Zhang, S. Ito, J. E. Moser, S. M. Zakeeruddin, M. Grätzel,
Stable, High-Efficiency Ionic-Liquid-Based Mesoscopic Dye-Sensitized Solar Cells
Small 12 (2007) 2094-2102. DOI: 10.1002/smll.200700211
7. W. Kubo, T. Kitamura, K. Hanabusa, Y. Wada, S. Yanagida, Quasi-solid-state dye-
sensitized solar cells using room temperature molten salts and a low molecular weight
gelator. Chem. Comm. (2002) 374-375. DOI: 10.1039/B110019J
8. R. Kawano, H. Matsui, C. Matsuyama, A. Sato, M. A. Susan, B. H. Tanabe, M.
Watanabe, High performance dye-sensitized solar cells using ionic liquids as their
electrolytes J. Photochem. Photobiol., A 164, (2004) 87-92.
doi:10.1016/j.jphotochem.2003.12.019
9. H. Matsumoto, T. Matsuda, T. Tsuda, R. Hagiwara, Y. Ito, Y. Miyazaki, The
application of room temperature molten salt with low viscosity to the electrolyte for
dye-sensitized solar cell Chem. Lett. 30 (2001) 26-27. DOI: doi.org/10.1246/cl.2001.26

52
10. D. Kuang, P. Wang, S. Ito, S. M. Zakeerudddin, M. Grätzel, Stable Mesoscopic Dye-
Sensitized Solar Cells Based on Tetracyanoborate Ionic Liquid Electrolyte. J. Am.
Chem. Soc. 128 (2006) 7732-7733. DOI: 10.1021/ja061714y
11. C. Li, W. Wang, X. Wang, B. Zhang, Y. Cao, Molecular design of squaraine dyes for
efficient far-red and near-IR sensitization of solar cells, Chem. Lett. 34 (2005) 554-555.
Doi:10.1246/cl.2005.554
12. S. Alex, U. Santhosh, S. Das, Dye sensitization of nanocrystalline Ti02: enhanced
efficiency of unsymmetrical versus symmetrical squaraine dyes. J. Photochem.
Photobiol., A 172 (2005) 65-71. DOI: 10.1016/j.jphotochem.2004.11.005
13. Y. Chen, Z. Zeng, C. Li, W. Wang, X. Wang, B. Zhang, Highly efficient co-sensitization
of nanocrystalline TiO2 electrodes with plural organic dyes. New J. Chem. 29 (2005) 773-
776. DOI: dx.doi.org/10.1039/B502725J
14. M. K. Nazeeruddin, A. Kay, I. Rodicio, R. Humphry-Baker, E. Muller, P. Liska, N.
Vlachopoulos, M. Grätzel, Conversion of light to electricity by cis-X2bis(2,2'-bipyridyl-
4,4'-dicarboxylate)ruthenium(II) charge-transfer sensitizers (X = Cl-, Br-, I-, CN-, and
SCN-) on nanocrystalline titanium dioxide electrodes. J. Am. Chem. Soc. 115 (1993)
6382-6390. DOI: 10.1021/ja00067a063
15. M. K. Nazeeruddin, S. M. Zakeeruddin, R. Humphry-Baker, M. Jirousek, P. Liska, N.
Vlachopoulos, V. Shklover, C. H. Fischer, M. Grätzel, Acid-Base Equilibria of (2,2‘-
Bipyridyl-4,4‘-dicarboxylic acid)ruthenium(II) Complexes and the Effect of
Protonation on Charge-Transfer Sensitization of Nanocrystalline Titania. Inorg. Chem.
38 (1999) 6298-6305. DOI: 10.1021/ic990916a
16. S. M. Zakeeruddin, M. K. Nazeeruddin, R. Humphry-Baker, P. Pechy, P. Quagliotto, C.
Barolo, G. Viscardi, M. Graetzel, Design, Synthesis, and Application of Amphiphilic
Ruthenium Polypyridyl Photosensitizers in Solar Cells Based on Nanocrystalline TiO2
Films. Langmuir 18 (2002) 952-954. DOI: 10.1021/la0110848
17. P. Wang, C. Klein, R. Humphry-Baker, S. M. Zakeeruddin, M. Grätzel, A High Molar
Extinction Coefficient Sensitizer for Stable Dye-Sensitized Solar Cells. J. Am. Chem.
Soc. 127 (2005) 808-809. DOI: 10.1021/ja0436190
18. P. Wang, S. M. Zakeeruddin, J. E. Moser, M. K. Nazeeruddin, T. Sekiguchi, M.
Grätzel, A stable quasi-solid-state dye-sensitized solar cell with an amphiphilic
ruthenium sensitizer and polymer gel electrolyte. Nat. Mater. 2 (2003) 402-407. DOI:
10.1038/nmat904

53
19. P. Wang, S. M. Zakeeruddin, P. Comte, R. Charvet, R. Humphry-Baker, M. Grätzel
Enhance the Performance of Dye-Sensitized Solar Cells by Co-grafting Amphiphilic
Sensitizer and Hexadecylmalonic Acid on TiO2 Nanocrystals. J. Phys. Chem. B, 107
(2003) 51, 14336-14341. DOI: 10.1021/jp0365965
20. M. Wang, S. J. Moon, D. Zhou, F. L. Formal, N. Ha, R. Humphry-Baker, C. Grätzel,
P. Wang, M. S. Zakeeruddin, M. Grätzel, Enhanced‐Light‐Harvesting Amphiphilic
Ruthenium Dye for Efficient Solid‐State Dye‐Sensitized Solar Cells. Adv. Funct.
Mater. 20 (2010) 1821-1826. DOI: 10.1002/adfm.200902396
21. J. J. Lagref, M. K. Nazeeruddin, M. Grätzel, Molecular engineering on semiconductor
surfaces: design, synthesis, and application of new efficient amphiphilic ruthenium
photosensitizers for nanocrystalline TiO2 solar cells. Synthetic Metals 138 (2003) 333–
339. DOI: 10.1016/S0379-6779(03)00034-1
22. S. Jang, J. Yum, C. Klein, K. Kim, P. Wagner, D. Officer, M. Grätzel, and M.K.
Nazeeruddin High Molar Extinction Coefficient Ruthenium Sensitizers for Thin Film
Dye-Sensitized Solar Cells. J. Phys. Chem. C, 113(5) (2009) 1998-2003. DOI:
10.1021/jp8077562
23. N. Lu, J. Shing, W. Tu, Y. Hsu, J. T. Lin, Novel Fluorous Amphiphilic Heteroleptic
Ru-Based Complexes for a Dye-Sensitized Solar Cell: The First Fluorous Bis-
ponytailed Amphiphilic Ru Complexes. Inorg. Chem. 50 (2011) 4289-4294. DOI:
10.1021/ic102192m
24. D. Kuang, C. Klein, S. It, E. M. Jacques, R. Humphry-Baker, N. Evans, F. Duriaux, C.
Grätzel, M. Z. Shaik, M. Grätzel, High‐Efficiency, and Stable Mesoscopic
Dye‐Sensitized Solar Cells Based on a High Molar Extinction Coefficient Ruthenium
Sensitizer and Nonvolatile Electrolyte. Adv. Mater. 19 (2007) 1133-1137. DOI:
10.1002/adma.200602172
25. C. Klein, Md. K. Nazeeruddin, D. Di Censo, P. Liska, and Michael Grätzel
Amphiphilic Ruthenium Sensitizers and Their Applications in Dye-Sensitized Solar
Cells. Inorg. Chem. 43 (2004) 4216-4226. DOI: 10.1021/ic049906m
26. A. J. Hallett, J. E. Jones, Purification-free synthesis of a highly efficient ruthenium dye
complex for dye-sensitized solar cells (DSSCs). Dalton Trans. 40 (2011) 3871-3876.
DOI:10.1039/C0DT01374A
27. F. Gao, Y. Wang, J. Zhang, D. Shi, M. Wang, R. Humphry-Baker, P. Wang, S. M.
Zakeeruddin, M. Grätzel, A new heteroleptic ruthenium sensitizer enhances the

54
 absorptivity of mesoporous titania film for high efficiency dye-sensitized solar cell Chem.
Commun. (2008) 2635-2637. DOI: 10.1039/B802909A
28. Y. Cao, Y. Bai, Q. Yu, Y. Cheng, S. Liu, D. Shi, F. Gao, P. Wang, Dye-Sensitized
Solar Cells with a High Absorptivity Ruthenium Sensitizer Featuring a 2-
(hexylthio)thiophene Conjugated Bipyridine. J. Phys. Chem. C, 113 (2009)15, 6290–
6297. DOI: 10.1021/jp9006872
29. C. Chen, M. Wang, J. Li, N. Pootrakulchote, L. Alibabaei, C. Ngoc-le, J. Decoppet, J.
Tsai, C. Grätzel, C. Wu, S. M. Zakeeruddin, M. Grätzel, Highly Efficient Light-
Harvesting Ruthenium Sensitizer for Thin-Film Dye-Sensitized Solar Cells. ACS Nano,
3, 10 (2009) 3103-3109. DOI: 10.1021/nn900756s
30. M. S. Carballo, M. Urbani, A. Kumar Chandiran, D. G. Rodríguez, P. Vázquez, M.
Grätzel, M. K. Nazeeruddin, T. Torres, Branched and bulky substituted ruthenium
sensitizers for dye-sensitized solar cells. Dalton Trans., 43 (2014) 15085–15091.
DOI:10.1039/C4DT01357C
31. F.R. Dai, W. Wu, Q.W. Wang, H. Tian, W.Y. Wong, Heteroleptic ruthenium
complexes containing uncommon 5,5′-disubstituted-2,2′-bipyridine chromophores for
dye-sensitized solar cells Dalton Trans., 40 (2011) 2314-2323. DOI:
10.1039/C0DT01043J
32. J.J. Kim, K. Lim, H. Choi, S. Fan, M. S. Kang, G. Gao, H. S. Kang, J., Ko, New
Efficient Ruthenium Sensitizers with Unsymmetrical Indeno[1,2-b]thiophene or a
Fused Dithiophene Ligand for Dye-Sensitized Solar Cells. Inorg. Chem. 49, 2010,
8351-8357. DOI: 10.1021/ic1009658
33. W. Huang, H. Wu, P. Lin, E. Diau, Design and Characterization of Heteroleptic
Ruthenium Complexes Containing Benzimidazole Ligands for Dye-Sensitized Solar
Cells: The Effect of Thiophene and Alkyl Substituents on Photovoltaic Performance
J. Phys. Chem. C 117, 2013, 2059-2065. DOI: 10.1021/jp3118693
34. A. Islam, S. P. Singh, M. Yanagida, M. R. Karim, L. Han, Amphiphilic Ruthenium(II)
Terpyridine Sensitizers with Long Alkyl Chain Substituted β-Diketonato Ligands: An
Efficient Coadsorbent-Free Dye-Sensitized Solar Cells Int. J. Photoenergy (2011) 1-7.
DOI: 10.1155/2011/757421
35. M. K. Nazeeruddin, P. Pe´chy, T. Renouard, S. M. Zakeeruddin, R. Humphry-Baker, P.
Comte, P. Liska, L. Cevey, E. Costa, V. Shklover, L. Spiccia, G. B. Deacon, A. B.
Carlo, M. Grätzel, Engineering of Efficient Panchromatic Sensitizers for

55
 Nanocrystalline TiO2-Based Solar Cells. J. Am. Chem. Soc. 123 (2001) 1613-1624.
DOI: 10.1021/ja003299u
36. K. L. Wu, C. H. Li, Y. Chi, J. N. Clifford, L. Cabau, E. Palomares, Y. M. Cheng, H. A.
Pan, P. T. Chou, Dye Molecular Structure Device Open-Circuit Voltage Correlation in
Ru(II) Sensitizers with Heteroleptic Tridentate Chelates for Dye-Sensitized Solar Cells
J. Am. Chem. Soc. 134 (2012) 7488-7496. DOI: 10.1021/ja300828f
37. C. C. Chou, K. L. Wu, Y. Chi, W. P. Hu, S. J. Yu, G. H. Lee, C. L. Lin, P. T. Chou,
Ruthenium(II) Sensitizers with Heteroleptic Tridentate Chelates for Dye‐Sensitized
Solar Cells. Angew. Chem. Int. Ed. 50 (2011) 2054-2058. DOI:
10.1002/anie.201006629
38. Y. Numata, S.P. Singh, A. Islam, M. Iwamura, A. Imai, K. Nozaki, L. Han Enhanced
Light‐Harvesting Capability of a Panchromatic Ru(II) Sensitizer Based on π‐Extended
Terpyridine with a 4‐Methylstylryl Group for Dye‐Sensitized Solar Cells. Adv. Funct.
Mater. 23 (2013) 1817–1823. DOI: 10.1002/adfm.201202504
39. B. S. Chen, K. Chen, Y. H. Hong, W. H. Liu, T. H. Li, C. H. Lai, P. T. Chou, Y. Chi,
G. H. Lee, Neutral, panchromatic Ru(II) terpyridine sensitizers were bearing pyridine
pyrazolate chelates with superior DSSC performance. Chem. Commun., (2009) 5844-
5846. DOI: 10.1039/B914197A
40. S. Han Yang, K. Wu, Y. Chi, Y. Cheng, Pi-Tai Chou, Tris(thiocyanate) Ruthenium(II)
Sensitizers with Functionalized Dicarboxyterpyridine for Dye‐Sensitized Solar Cells.
Angew. Chem. Int. Ed. 50, (2011) 8270 –8274. DOI: 10.1002/anie.201103515
41. S. R. Jang, C. Lee, H. Choi, J. J. Ko, J. Lee, R. Vittal, K. Kim,
Oligophenylenevinylene-Functionalized Ru(II)-bipyridine Sensitizers for Efficient
Dye-Sensitized Nanocrystalline TiO2 Solar Cells. J. Chem. Mater. 18 (2006) 5604-
5608. DOI: 10.1021/cm061447v
42. M. K. Nazeeruddin, E. Baranoff, M. Grätzel, Dye-sensitized solar cells: A brief
overview. Solar Energy 85 (2011) 1172-1178. doi:10.1016/j.solener.2011.01.018
43. T. Funaki, M. Yanagida, N. Onozawa-Komatsuzaki, K. Kasuga, Y. Kawanishi, M.
Kurashige, K. Sayama, H. Sugihara, Synthesis of a new class of cyclometallated
ruthenium(II) complexes and their application in dye-sensitized solar cells. Inorg.
Chem. Commun., 12 (2009) 842-845. DOI: 10.1016/j.inoche.2009.06.030
44. C. P. Kumar, V. Anusha, K. Narayanaswamy, K. Bhanuprakash, A. Islam, L. Han, S. P.
Singh, M. Chandrasekharam, New ruthenium complexes (Ru[3+2+1]) bearing π-

56
 extended 4-methylstyryl terpyridine and unsymmetrical bipyridine ligands for DSSC
applications. Inorganica Chim. Acta. 435 (2015) 46-52. DOI: 10.1016/j.ica.2015.04.038
45. M. Chandrasekharam, T. Suresh, Surya P. Singh, B. Priyanka, K. Bhanuprakash, A.
Islam, L. Han, and M. Lakshmi Kantama, Functionalized styryl bipyridine as a superior
chelate for a ruthenium sensitizer in dye-sensitized solar cells. Dalton Trans., 41 (2012)
8770–8772. DOI: 10.1039/C2DT30688C
46. T. Swetha, S. Niveditha, K. Bhanuprakash, A. Islam, L. Han, I. M. Bedja, R.
Fallahpour, S. P. Singh, New heteroleptic benzimidazole functionalized Ru-sensitizer is
showing the highest efficiency for dye-sensitized solar cells. Inorg Chem Commun. 51
(2015) 61-65. DOI: 10.1016/j.inoche.2014.10.033
47. K. Zhang, W. Zhang, J. Huang, A. Pang, M. S. Won, Metal-free photosensitizers based
on benzodithienothiophene asp-conjugated spacer for dye-sensitized solar cells Org.
Electronics (2017), 42, 275-283. DOI: 10.1016/j.orgel.2016.12.044
48. H. Tian, P. H. Liu, F. S. Meng, E. Q. Gao, S. M. Cai, Wide spectral photosensitization
for SnO2nanoporous electrode with soluble perylene derivatives and cyanine dyes.
Synth. Met., 121 (2001) 1557-1558. DOI: 10.1016/S0379-6779(00)01258-3
49. K. Hara, K. Sayama, H. Arakawa, Y. Ohga, A. Shinpo, S. Suga, A coumarin-derivative
dye-sensitized nanocrystalline TiO2 solar cell was having a high solar-energy conversion
efficiency up to 5.6%Chem. Commun., (2001) 569-570. DOI:10.1039/B010058G
50. K. Hara, M. Kurashige, Y. Dan-oh, C. Kasada, A. Shinpo, S. Suga, K. Sayama, H.
Arakawa, Design of new coumarin dyes having thiophene moieties for highly efficient
organic-dye-sensitized solar cells. New J. Chem., 27 (2003) 783-785.
DOI:10.1039/B300694H
51. K. Hara, T. Sato, R. Katoh, A. Furube, Y. Ohga, A. Shinpo, S. Suga, K. Sayama, H.
Sugihara, H. Arakawa, Molecular Design of Coumarin Dyes for Efficient Dye-
Sensitized Solar Cells. J. Phys. Chem. B, 107 (2003) 597-606. DOI:
10.1021/jp026963x
52. A. Ehret, L. Stuhi, M. T. Spitler, Spectral Sensitization of TiO2 Nanocrystalline
Electrodes with Aggregated Cyanine Dyes. J. Phys. Chem. B. 105 (2001) 9960-9965.
DOI: 10.1021/jp011952+
53. T. Horiuchi, H. Miura, S. Uchida, Highly-efficient metal-free organic dyes for dye-
sensitized solar cells. Chem. Commun., (2003) 3036-3037. DOI:10.1039/B307819A

57
54. T. Horiuchi, H. Miura, K. Sumioka, S. Uchida, High Efficiency of Dye-Sensitized
Solar Cells Based on Metal-Free Indoline Dyes. J. Am. Chem. Soc. 126 (2004) 12218-
12219. DOI: 10.1021/ja0488277.
55. + L. Schmidt-Mende, U. Bach, R. Humphry-Baker, T. Horiuchi, H. Miura, S. Ito, S.
Uchida, M. Grätzel, Organic Dye for Highly Efficient Solid‐State Dye‐Sensitized Solar
Cells. Adv. Mater, 17 (2005) 813-815. DOI: 10.1002/adma.200401410
56. S. Ito, S. M. Zakeeruddin, R. Humphry-Baker, P. Liska, R. Charvet, P. Comte, M. K.
Nazeeruddin, P. Pechy, M. Takata, H. Miura, S. Uchida, M. Grätzel, High‐Efficiency
Organic‐Dye‐ Sensitized Solar Cells Controlled by Nanocrystalline‐TiO2 Electrode
Thickness Adv. Mater, 18 (2006) 1202-1205. DOI: 10.1002/adma.200502540
57. D. Kuang, S. Uchida, R. Humphry-Baker, S. M. Zakeeruddin, M. Grätzel, Organic dye-
sensitized ionic liquid-based solar cells: remarkable enhancement in performance
through the molecular design of indoline sensitizers Angew. Chem., Int. Ed. 47 (2008)
1923-1927. DOI: 10.1002/anie.200705225
58. S. Ito, H. Miura, S. Uchida, M. Takata, K. Sumioka, P. Liska, P. Comte, P. Pechy, M.
Grätzel, High-conversion-efficiency organic dye-sensitized solar cells with a novel indoline
dye. Chem. Commun., (2008) 5194-5196. DOI:10.1039/B809093A
59. S. Hwang, J. H. Lee, C. Park, H. Lee, C. Kim, C. Park, M. H. Lee, W. Lee, J. Park, K.
Kim, N. G. Park, Kim, C. A highly efficient organic sensitizer for dye-sensitized solar
cells. Chem. Commun., (2007) 4887-4889. DOI:10.1039/B709859F
60. D. P. Hagberg, J. H. Yum, H. Lee, F. De Angelis, T. Marinado, K. M. Karlsson, R.
Humphry-Baker, L. Sun, A. Hagfeldt, M. Grätzel, M. K. Nazeeruddin, Molecular
Engineering of Organic Sensitizers for Dye-Sensitized Solar Cell Applications. J. Am.
Chem. Soc., 130 (2008) 6259-6266. DOI: 10.1021/ja800066y
61. W. H. Liu, I. C. Wu, C. H. Lai, P. T. Chou, Y. T. Li, C. L. Chen, Y. Y. Hsu, Y. Chi,
Simple organic molecules were bearing a 3,4-ethylene dioxythiophene linker for
efficient dye-sensitized solar cells. Chem. Commun., (2008) 5152-5154. Doi:
10.1039/b808535h.
62. Y. Ezhumalai, B. Lee, M. Fan, B. Harutyunyan, K. Prabakaran, C. Lee, S. Hsiung
Chang, J. Ni, S. Vegiraju, P. Priyanka, Y. Wu, C. Liu, S. Yau, J. T. Lin, C. Wu, M. J.
Bedzyk, R. P. H. Chang, M. Chen, K. Ho, T. J. Marks, Metal-free branched alkyl
tetrathienoacene (TTAR)-based sensitizers for high-performance dye-sensitized solar cells.
J. Mater. Chem. A, 5 (2017) 12310-12321. DOI:10.1039/C7TA01825H

58
63. C. Sakong, S. Kim, S. Yuk, J. Namgoong, S. Park, M. Ko, D. Kim, K. Hong, J. Kim,
Influence of Solvent and Bridge Structure in Alkylthio-Substituted Triphenylamine
Dyes on the Photovoltaic Properties of Dye-Sensitized Solar Cells. Chem. Asian J.,
2012, 7, 1817 – 1826. DOI: 10.1002/asia.201100814
64. C. Chen, Y. Hsu, H. Chou, K. R. J. Thomas, J. T. Lin, and C. Hsu, Dipolar Compounds
Containing Fluorene and a Heteroaromatic Ring as the Conjugating Bridge for High-
Performance Dye-Sensitized Solar Cells Dipolar Compounds Containing Fluorene and
a Heteroaromatic Ring as the Conjugating Bridge for High-Performance Dye-
Sensitized Solar Cells, Chem.–Eur. J., 2010, 16, 3184–3193. DOI:
10.1002/chem.200903151
65. D. Y. Chen, Y. Y. Hsu, H. C. Hsu, B. S. Chen, Y. T. Lee, H. S. Fu, M. W. Chung, S. H.
Liu, H. C. Chen, Y. Chi and P. T. Chou, Organic dyes with remarkably high
absorptivity; all solid-state dye-sensitized solar cell and role of fluorine substitution.
Chem. Commun., 46 (2010) 5256–5258. DOI: 10.1039/c0cc00808g
66. S. Wang, J. Guo, Y. Deng, J. Zhao, and L. Zhang, Efficient triphenylamine
photosensitizers with alkoxy- or fluorine-substituted phenylene spacer for dye-
sensitized solar cells. J. Mater. Sci., 47 (2012) 1843-1851. DOI 10.1007/s10853-011-
5971-0
67. H. Dong, M. Liang, C. Zhang, Y. Wu, Z. Sun, S. Xue, wisted Fused-Ring Thiophene
Organic Dye-Sensitized Solar Cells J. Phys. Chem. C 120 (2016) 22822−22830. DOI:
10.1021/acs.jpcc.6b06604
68. R. Grisorio, L. Marco, R. Giannuzzi, G. Gigli, G. Suranna, Molecular engineering of
largely π-extended metal-free sensitizers containing benzothiadiazole units:
Approaching 10% efficiency dye-sensitized solar cells using iodine-based electrolytes
Dyes and Pigments (2016) 282-292. DOI: 10.1016/j.dyepig.2016.04.020
69. Y. Hua, J. He, C. Zhang, C. Qin, L. Han, J. Zhao, T. Chen, W. Wong, W. Wong, X.
Zhu, Effects of various π-conjugated spacers in thiadiazole[3,4-c]pyridine-cored
panchromatic organic dyes for dye-sensitized solar cells. J. Mater. Chem. A, 3, (2015)
3103–3112. DOI:10.1039/C4TA05350H
70. S. Y. Qu, W. J. Wu, J. L. Hua, C. Kong, Y. T. Long and H. Tian, New
diketopyrrolopyrrole (DPP) Dyes for Efficient Dye-Sensitized Solar Cells, J. Phys.
Chem. C, 114 (2010)1343–1349. DOI: 10.1021/jp909786k

59
71. J. He, W. Wu, J. Hua, Y. Jiang, S. Qu, J. Li, Y. Long, H. Tian, Bithiazole-bridged dyes
for dye-sensitized solar cells with high open circuit voltage performance. J. Mater.
Chem., 21 (2011) 6054–6062. DOI: 10.1039/c0jm03811c
72. Z. M. Tang, T. Lei, K. J. Jiang, Y. L. Song and J. Pei, Benzothiadiazole contains D-pi-
A conjugated compounds for dye-sensitized solar cells: synthesis, properties, and
photovoltaic performances, Chem. Asian J., 5 (2010) 1911–1917. DOI:
10.1002/asia.201000158
73. M. Cheng, X. Yang, F. Zhang, J. Zhao, L. Sun, Tuning the HOMO and LUMO Energy
Levels of Organic Dyes with N-Carboxomethylpyridinium as Acceptor To Optimize
the Efficiency of Dye-Sensitized Solar Cells. J. Phys. Chem. C 117, (2013) 9076−9083.
DOI: 10.1021/jp311378b
74. H. Choi, C. Baik, S. Kang, J. Ko, M. Kang, M. K. Nazeeruddin, M. Grätzel Highly
efficient and thermally stable organic sensitizers for solvent-free dye-sensitized solar
cells. Angew. Chem. Int. Ed. 2008, 47, 327–330. DOI: 10.1002/anie.200703852
75. C. Kim, H. Choi, S. Kim, C. Baik, K. Song, M. S. Kang, S. O. Kang, J. Ko, Molecular
Engineering of Organic Sensitizers Containing p-Phenylene Vinylene Unit for Dye-
Sensitized Solar Cells. J. Org. Chem. 73 (2008) 7072-7079. DOI: 10.1021/jo8005182
76. J. Kim, H. Choi, J. Lee, M. Kang, K. Song, S. O. Kang and J. Ko, A polymer gel
electrolyte to achieve ≥6% power conversion efficiency with a different organic dye
incorporating a low-band-gap chromophore. J. Mater. Chem., 18 (2008) 5223–5229.
DOI:10.1039/B809376H
77. H. Dong, M. Liang, C. Zhang, Y. Wu, Z. Sun, S. Xue, wisted Fused-Ring Thiophene
Organic Dye-Sensitized Solar Cells J. Phys. Chem. C 120 (2016) 22822−22830. DOI:
10.1021/acs.jpcc.6b06604
78. C. Shen, Y. Wu, W. Zhang, H. Jiang, H. Zhang, E. Li, B. Chen, X. Duan, W. Zhu,
Incorporating quinoxaline unit as the additional acceptor for constructing efficient
donor-free solar cell sensitizers Dyes and Pigments 149 (2018) 65-72. DOI:
10.1016/j.dyepig.2017.09.055
79. X. Hu, S. Cai, G. Tian, X. Li, J. Su, J. Li, Rigid triarylamine-based D–A–π–A structural
organic sensitizers for solar cells: the significant enhancement of open-circuit photovoltage
with a long alkyl group. RSC Adv., 3 (2013) 22544–22553. DOI: 10.1039/C3RA43057J
80. Y. Wu, X. Zhang, W. Li, Z. Wang, H. Tian, W. Zhu, Hexylthiophene-Featured D–A–
π–A Structural Indoline Chromophores for Coadsorbent-Free and Panchromatic Dye-

60
 Sensitized Solar Cells Hexylthiophene-Featured D–A–π–A Structural Indoline
Chromophores for Coadsorbent-Free and Panchromatic Dye-Sensitized Solar Cells,
Adv. Energy Mater. 2, (2012), 149–156. DOI: 10.1002/aenm.201100341
81. Y. Won, Y. Yang, Jae Hong Kim, Jang-Hyun Ryu, Kyung Kon Kim, and Sung Soo
Park, Organic Photosensitizers Based on Terthiophene with Alkyl Chain and Double
Acceptors for Application in Dye-Sensitized Solar Cells, Energy Fuels 24 (2010) 3676–
3681. DOI: 10.1021/ef100429r
82. C. Siu, L. Tien Lin Lee, Po-Yu Ho, P. Majumdar, C. Ho, T. Chen, J. Zhao, H. Lie, W.
Wong, Fluorene-bridged organic dyes with di-anchoring groups for efficient co-
adsorbent-free dye-sensitized solar cells, J. Mater. Chem. C, 2 (2014) 7086–7095. DOI:
10.1039/c4tc00661e
83. Y. Wu, X. Zhang, W. Li, Z. Wang, H. Tian, W. Zhu, Hexylthiophene-Featured D–A–
π–A Structural Indoline Chromophores for Coadsorbent-Free and Panchromatic Dye-
Sensitized Solar Cells Hexylthiophene-Featured D–A–π–A Structural Indoline
Chromophores for Coadsorbent-Free and Panchromatic Dye-Sensitized Solar Cells,
Adv. Energy Mater. 2, (2012), 149–156. DOI: 10.1002/aenm.201100341
84. H. Tian, X. Yang, R. Chen, Y. Pan, L. Li, A. Hagfeldt, L. Sun, Phenothiazine
derivatives for efficient organic dye-sensitized solar cells. Chem. Commun., (2007)
3741-3143. DOI: 10.1039/b707485a
85. P. Li, Y. Cui, C. Song, H. Zhang, A systematic study of phenoxazine-based organic
sensitizers for solar cells Dyes and Pigments 137 (2017) 12-23. DOI:
10.1016/j.dyepig.2016.09.060
86. Z. Wang, N. Koumura, Y. Cui, M. Takahashi, H. Sekiguchi, A. Mori, T. Kubo, A.
Furube, K. Hara, Hexylthiophene-Functionalized Carbazole Dyes for Efficient
Molecular Photovoltaics: Tuning of Solar-Cell Performance by Structural Modification.
Chem. Mater. 20 (2008) 3993–4003. DOI: 10.1021/cm8003276
87. Y. Ooyama, Y. Shimada, Y. Kagawa, Y. Yamada, I. Imae, K. Komaguchi, Y. Harima,
Synthesis of new-type donor–acceptor π-conjugated benzofuro[2,3-c]oxazolo[4,5-
a]carbazole fluorescent dyes and their photovoltaic performances of dye-sensitized
solar cells. Tetrahedron Letters, 48 (2007) 9167–9170. DOI:
10.1016/j.tetlet.2007.10.107

61
88.
89. Sujit Bhand completed his Ph.D. degree under the guidance of Professor Sunita Salunke, in
90. Chemistry at Savitribai Phule Pune University, Pune, Maharashtra, India. He received his Master
91. degree in chemistry in 2013. His research interest is the design and synthesis of new
photosensitizer for dye-sensitized solar cells.

Dr. Sunita Salunke-Gawali is Professor at Department of Chemistry, Savitribai Phule Pune

University since 2008. She did her Ph.D. (1999) at Pune University, further she was Postdoctoral
Research Associate at Laboratoire de Magnétisme et d’Optique, Versailles France (Prof. F. Varret,
2001-2002), Department of Chemistry, IIT Bombay, India (Prof. C.P. Rao, 2002 and 2004),
Universidade do Porto, Portugal, supervised by Prof. Eulália Pereira (2004-2007) and Max-Planck-
Institut für Bioanorganische Chemie, Mülheim an der Ruhr, Germany (Dr. Eckhard Bill, 2007-
2008). Her research interests are coordination and Bioorganic Chemistry of naphthoquinone
ligands, naphthoquinone containing Ruthenium polypyridyl complexes as a photosensitizer for
DSSC, HPLC method development for anticancer drugs and organic tautomers, chemosensors, and
metallosurfactants.

62
Amphiphilic photosensitizers in Dye Sensitized Solar Cells

63
Highlights

 Photosensitizer is important part of DSSC

 Introduction of amphiphilic in photosensitizer increase stability of DSSC devices.
 amphiphilic ruthenium complexes as well as organic photosensitizers are reported
 Total 96 references of amphiphilic compounds are included

64