REVI EW

Recent Trends in High Efciency Photo-Electrochemical Solar

Cell Using Dye-Sensitised Photo-Electrodes and Ionic Liquid
Based Redox Electrolytes
Suresh Chandra
Received: 1 January 2011 / Accepted: 8 April 2011 / Published online: 1 March 2012
The National Academy of Sciences, India 2012
Abstract Low cost and long life photovoltaic solar cell is
one of the most viable renewable energy technologies
needed for the future. The development of commercial
solidsolid junction type solar cells (e.g., pn junction
based on semiconductor like Si, GaAs, CdS, CdTe etc.) is
still limited by cost. A new technology of semiconductor-
electrolyte junction viz. Photo-electrochemical solar cells
(PESC) has recently evolved. Dye-sensitization of PESC
photo-electrodes has revolutionized the concept of PESC
and many low cost dye-sensitized solar cells (DSSC)
with fairly high efciency have been reported which has
made them as a safe bet for the future energy needs. This
paper gives an overview of the recent progress made in
DSSC after elucidating the principles and limitations of
earlier PESCs. The future prospects are also discussed.
Keywords Solar cells Photoelectrochemical cells
Dye sensitised solar cells Ionic liquids
Introduction
Direct conversion of solar energy to electrical energy
through the use of photo-voltaic solar cells has been the
strategy followed for more than four decades to develop an
alternate renewable source of energy in order to replace, at
least partly, the fossil fuel based energy systems. Genera-
tion of photovolatage in photovoltaic solar cells involves
the following steps:
(i) Each photon having energy greater than the bandgap
of semiconductor (i.e., hm [E
g
) results in the transfer
or excitation of one valence band electron to the
conduction band, leaving a hole in the valence band.
In other words, such photoexcitation leads to the
generation of electronhole pair:
semi conductor !
hm
e

(ii) Subsequently photo-voltage is generated when these

photogenerated electronhole pairs are separated by
some electric eld built-in within the solar cell.
In general, the built-in eld is produced by some
charge discontinuity or inhomogeneity. The earliest
approach was to have a pn semiconductor junction. It is
well known in semiconductor physics [1] that electrons
diffusing from n-type semiconductor to p-type semicon-
ductor and hole diffusing from p-side to n-side annihilate
near the junction resulting in the formation of depletion
layer consisting of sheaths of positively and negatively
charged atoms on n-side and p-side respectively. This
results in a junction eld. Most earlier developed conven-
tional solar cells were pn junction solar cells. Subse-
quently, many more variants of junction solar cells were
developed like MetalSemiconductor (MS), Metal
OxideSemiconductor (MOS), MetalInsulatorSemi-
conductor (MIS) etc. All these are SolidSolid junction
solar cells. The technology of fabricating such solar cells is
expensive both in terms of actual money as well as power
needed to produce them. Nonetheless, most of the currently
marketed solar cells belong to this category. Finding
alternatives of these solar cells was and still is a challenge.
It is clear from the above discussion that the creation of
depletion layer and junction eld in the conventional solid
solid junction solar cell was as a result of charge transfer
S. Chandra (&)
Physics Department, Banaras Hindu University, Varanasi
221005, India
e-mail: sureshchandra_bhu@yahoo.co.in
1 3
Proc. Natl. Acad. Sci. Sect. A Phys. Sci. (JanuaryMarch 2012) 82(1):519
DOI 10.1007/s40010-012-0001-4
across p and n sides (in pn junction) or across metal and
semiconductor (in MS junction). A different type of
charge transfer can possibly occur from the semiconductor
to liquid electrolyte (consisting of ?ve and -ve ions like
holes/electrons in semiconductors). Such an electrochemi-
cal charge transfer under photo-excitation was visualized
by Fujushima and Honda [2] to split water (electrolysis)
and by Gerisher [3] for producing electricity directly from
solar energy. The formation of junction simply implied
dipping a semiconductor into a liquid electrolyte. This was
the beginning of replacing solid state junction of conven-
tional solar cells by solidliquid electrolyte junction solar
cells. Considering the nature of charge transfer, such solar
cells were termed as photo-electrochemical solar cells
(PESC) [4]. The story of development of PESC is full of
ups and downs. It started with hype in 1970s; sulked in late
1980s when satisfactory solutions to problems like stabil-
ity, photo-corrosion, life and efciency could not be found
out; got an upward kick in 1990s when Gratzels group [5]
in Switzerland suggested the new concept of dye sensiti-
zation of photo electrodes of PESC resulting in high ef-
ciency dye sensitized solar cells (DSSC) which was further
boosted in 2000s when ionic liquids offered a novel route
for obtaining high performance electrolytes for DSSC (see
[6] and references cited there in). The present paper briey
introduces the basic principles, problems and perspectives
of early Photo-electrochemical solar cells followed by an
overview of the recent trends of dye sensitization and use
of ionic liquids in developing long- life, sustainable, ef-
cient and inexpensive photo-electrochemical solar cells.
Photo-electrochemical Solar Cells: Basics
As discussed above, the photo generated charge carriers in
semiconductor junction solar cells are separated by the
eld across the depletion layer. Let us consider the most
common pn junction shown in Fig. 1a. The p-side has
more free holes while n-side has more electrons. So,
electrons from n-side would diffuse towards p-side and
holes will move the other way. At or near the junction, they
may collide and annihilate leaving behind immobile ion-
ized donor and acceptor atoms on the two sides of the
interface. These ionized donors and acceptor atoms result
in a sheath of positive and negative charges separated by a
distance, called as depletion layer. Hence, an electric eld
is created across the depletion layer. The diffusion of
electrons and holes will continue till the junction eld is
large enough to stop such cross-over. At equilibrium, the
Fermi levels on the p-side and n-side align themselves. The
energy level diagram for such a pn junction is shown in
Fig. 1b. On photoexcitation, the photogenerated electron
hole pairs modify the number of electrons and holes near
the junction and hence modify the junction voltage and
current. It may be noted that the energy levels on both
p- and n-sides are bent depending upon the respective
charge carrier concentrations.
Suppose one side of junction in Fig. 1a is replaced by an
electrolyte. This can be attained by dipping the semicon-
ductor into an electrolyte as shown in Fig. 2.
This forms the basis of photo-electrochemical solar cell.
The junction can now be visualized as a semiconductor-
electrolyte junction in which the electronsholes from
semiconductor and ions from electrolyte may try to cross
the junction (as in pn junction) resulting in reduction
oxidation (REDOX) reaction and the formation of deple-
tion layer. To understand this, we will have to study the
potential and charge distributions on the semiconductor
and electrolyte side separately in order to be able to con-
struct the energy level diagram near the junction.
Charge and Potential Distribution on the Electrolyte
and Semiconductor Sides of a PESC
For proper understanding of semiconductor-electrolyte
interface, the charge and potential distributions on both
electrolyte and semiconductor sides have to be understood.
The charge distribution on the electrolyte side of the
interface in a photoelectrochemical solar cell is more
Fig. 1 a Formation of pn junction, b energy level diagram near the
junction
6 Proc. Natl. Acad. Sci. Sect. A Phys. Sci. (JanuaryMarch 2012) 82(1):519
1 3
complicated than that in pn junction. Generally, a dense
layer of ions get stuck to the semiconductor photo electrode
surface (termed as Helmholtz layer) while the ions form a
diffuse layer beyond this (termed as Gouy layer) as shown
in Fig. 3.
Most of the cations and anions in aqueous electrolyte are
solvated by water molecules. The attractive image as
well as dipole induced forces due to the water dipole,
dispersive forces and chemical bonding are collectively
responsible for sticking of the water dipoles to the semi-
conductor electrode surface. Apart from this, partially
desolvated ions also can get stuck to the semiconductor
surface. Some possible manners of sticking of ions to the
semiconductor electrode surface to form the inner dense
layer (Helmholtz layer) are shown in Fig. 4.
The free as well as the solvated cations/anions in the
bulk of the electrolyte beyond the dense layer form a
diffused layer (also termed as Gouy layer) as shown
earlier in Fig. 3. Potential distribution, /
G
(x), in the
Gouy layer can be obtained by solving the Poissons
equation:
d
2
u
G
x
dx
2

q
el
x
=
e
o
e
G
1
where q
el
is the ionic charge in the electrolyte at a distance
x from the junction, e
o
and e
G
are free space and Gouy
layers permittivities, respectively. The charge distribution
for cations and anions can be approximated by Boltzmann
distribution:
q
el
x
X
i
Z
i
eC
o
i
expZ
i
eux=kT 2
where Z
i
is the valence of the ith ion, C
o
i
is the ion con-
centration at x = 0.
Assuming concentration of both the cations and anions
to be same and taking Z
i
= 1, Eq. 1 can easily be solved
for u
G
xwhich is given by
u
G
x u
o
exp[ L
G
x 3
where /
o
is potential at x = 0 and L
G
is Gouy layer
thickness given by the following expression
L
G

e
o
e
G
kT
.
2C
o
e
2
Z
2

1=2
4
Similarly we can get the expression for the potential dis-
tribution onthe semiconductor-side of the semiconductor-
electrolyte interface /
SC
by solving relevant Poissons
equation:
d
2
u
sc
x
dx
2

1
e
o
e
sc
:q
sc
x 5
where e
sc
and q
sc
, respectively, are dielectric constant and
charge density on the semiconductor side given by
q
sc
x eN
D
nx px N
A
6
where N
D
and N
A
are number of ionized donors and
acceptors, n(x) and p(x) are electrons and hole
concentration at different distances (x) from the interfaces.
Assuming exponential variation of n and p with x, the
potential distribution on the semiconductor side can be
obtained as (see [4]):
u
sc
x u
o
L
D
x 7
where L
D
is termed as Debye length given by
L
D

e
o
e
sc
kT
2ne
2

1=2
8
The total interface potential, u
Ga
(galvanic potential) will
be the sum of potential drop across space charge layer in
Fig. 2 Basic photo electrochemical solar cell
Fig. 3 Hypothesized ionic charge distribution on the electrolyte side
of the interface
Proc. Natl. Acad. Sci. Sect. A Phys. Sci. (JanuaryMarch 2012) 82(1):519 7
1 3
semiconductor (u
sc
), dense or Helmholtz layer on the
electrode side (u
H
) and Gouy layer (u
G
):
u
Ga
u
sc
u
H
u
G
An order of magnitude calculation for a typical PESC
shows that [4]
u
sc
: u
H
: u
G
750 : 1 : 1:5
So, u
sc
is only important. This is approximately similar to
metalsemiconductor junction where most of the drop is
known to occur on the semiconductor side. Thus, a PESC
behaves like a MS junction solar cell.
With this background, we are in a position to discuss
the basics of PESC. The four energy levels involved are
conduction and valance bands (E
c
and E
v
) of the semi-
conductor and oxidation and reduction energy levels of
redox specie (Wox and Wred) in the electrolyte. On
illumination of semiconductor, electronhole pair gener-
ation occurs which are separated in the space charge layer
on the semiconductor side with subsequent lowering of
depletion layer barrier. This results in increased number
of holes crossing over to the electrolyte side to be
captured by the reduced ionic species. On short circuiting
(or connecting through a load) the photoelectrode and
counter electrode of the PESC (see Fig. 2), the electrons
are driven via the external circuit towards the metal
counter electrode where it participates in the reduction
reaction of the oxidized species. If the redox couple is
such that the total cathodic ? anodic reactions do not
lead to a net chemical change (DG = 0) and the two
electrodes only serve as a shuttle for the charge
transfer, then the cell is an electrochemical photovoltaic
device or solar cell. If net chemical reaction is taking
place as a result of charge transfer with DG\0 or
DG[0, then such cells are respectively called as pho-
toelectrolysis cell and photocatalytic cells. This paper is
concerned with electrochemical photovoltaic solar cell
(i.e., DG = 0; no net chemical change). It is obvious that
the overall efciency of such solar cells will depend upon
E
c
and E
v
of semiconductor, charge transfer kinetics
between redox electrolyte and semiconductor as well as
counterelectrode.
Fig. 4 The formation of ionic
dense layer on the electrolyte
side of PESC near the
semiconductor electrode a Two
possible orientation of water
dipole. b Solvated ions sticking
in the electrode. c Partially
desolvated ions sticking to the
electrode
8 Proc. Natl. Acad. Sci. Sect. A Phys. Sci. (JanuaryMarch 2012) 82(1):519
1 3
Materials Choice and Problems of Conventional PESC
The materials choice depends mainly upon the following
criteria:
(i) high efciency (g)
(ii) long life (negligible corrosion)
(iii) suitable band gap of the photoelectrode so as to be
able to absorb major portion of solar spectrum and
produce electronhole pair. Further factors like
surface states, recombination, etc. should not reduce
efciency much.
(iv) Compatibility of the electrolyte with the semicon-
ductor to yield fast charge transfer kinetics.
The efciency of solar cell g is dened as:
g
output power
input power (solar energy)
100 %

E
g
R
1
E
g
aENEdE
R
1
0
NEdE
9
where E
g
is the band-gap of semiconductor, N(E) is number
of photons coming from sun having energy E and a(E) is the
fraction of photons absorbed. The photons with energy
greater than E
g
(i.e., hm [E
g
) are only important for solar
energy conversion since only these photons would generate
electronhole pairs. This is why the lower limit of integra-
tion in the numerator of Eq. 9 is E
g
. It is obvious that for
higher g, E
g
and a(E) both must be large which often are self-
contradictory. Considering the energy distribution in ter-
restrial solar spectrum, it is found from Eq. 9 that highest
efciency will be found for E
g
& 1.5 eV. The popular
semiconductor materials in the above range of E
g
are GaAs,
GaP, CdTe, CdSe etc. (see [4] for detailed discussion).
Because of the high promise and potential of PESC, hun-
dreds of studies were reported between 1975 and 1985 using
single crystals, thin lms, electro-deposited thin lms etc. of
GaAs, CdS, CdTe, MoSe
2
etc. Reasonably high efciency
(*7 to 19%) using small area n-GaAs single crystals could
be attained using S
2
=S
2
2
redox electrolyte [7, 8]. Single
crystals of n-CdS E
g
* 2.4 eV with a variety of redox
couple like S
2
=S
2
2
; I

=I
2
; Fe(CN)
3
6
=Fe(CN)
4
6
also
were found to give efciencies in the range 1.56.5% but
were generally unstable [911]. The stable cells had much
lower efciency. Single crystalline CdTe and CdSe
(E
g
& 1.4 and 1.7 eV), whose band-gaps are near to the
optimum values gave higher efciencies as expected [12
17]. Large semiconductor crystals are difcult to prepare
and therefore, thin lm large area PESCs were developed
but their efciencies were considerably less [1820]. Most
physical techniques of thin lm deposition are expensive.
Chandras group [2125] in India tried a cost effective
electrodeposition technique for preparing large area thin
lms of semiconductors and used them to fabricate PESCs.
The efciencies as well as stability of these PESCs were
also less than those of single crystalline PESCs.
The limitation imposed by the band gaps on the ef-
ciency of the solar cell can be partly taken care of by
designing multiple band-gap semiconductor electrolyte
solar cells (for a review see [26]). This concept (Fig. 4) is
equally applicable to the solidsolid junction solar cells
(Fig. 5).
It is well known that higher band gap materials will give
higher photo-potential but low photo-current because the
lower energy photons (which are more abundant in ter-
restrial solar radiation) are not absorbed by the wide band-
gap semiconductors (ht \E
g
) and hence do not contribute
to the photo-current. On the contrary, the low band-gap
semiconductors will give large photocurrent but lower
photovolatage. Therefore, multiple band-gap systems will
provide better matching/utilization of incident solar radia-
tion. Consider a solar cell of four semiconductor photo-
electrodes with different band gaps E
g1
, E
g2
, E
g3
, E
g4
such
that E
g1
[E
g2
[E
g3
[E
g4
. The higher energy part of
solar insolation ht
1
\E
g1
will be absorbed in semicon-
ductor 1 and the lower energy photons will pass to the
semiconductor 2 in the stack where photons whose energy
is more than E
g2
will be absorbed. This process will con-
tinue from one semiconductor to the next in the stack. This
results in better utilization of the whole part of solar
spectrum. Many variants of PESCs based on multi-band
gap structures are designed by Licht [26]. The achievable
theoretical efciencies are predicted to be higher than 30
50% which still remains elusive.
Attempts were made not only to try different band gap
semiconductors in PESC, but some interesting congurations
Fig. 5 Conceptual visualization of utilization of different energy
photons in a stacked multijunction solar cell
Proc. Natl. Acad. Sci. Sect. A Phys. Sci. (JanuaryMarch 2012) 82(1):519 9
1 3
were also tried in which the liquid electrolyte was replaced
by polymer electrolyte. The rst attempt in this direction was
by Skotheims group [27, 28] using PEO-based polymer
electrolytes. The efciency as well as the stability was very
low. The lower efciency was due to lower conductivity as
well as the interfacial contact problem because of web-like
contact (not smooth contact) between polymer electrolyte
lmand the semiconductor due to the shrinkage of the former
[29].
Apart from the low efciency, the more serious problem
in all types of PESCs was the stability and short life of the
cell due to the decomposition of semiconductor surface
(electrochemical corrosion) in contact with the electrolyte.
It may be remarked here that the mobile charges of both
signs from semiconductor (electrons and holes) and elec-
trolyte (cations and anions) participate in the charge
transfer reaction at the semiconductor electrolyte interface.
Consider a compound semiconductor AB. The decom-
position takes place in the following two ways:
(a) Cathodic decomposition: electrons (n) participate in
the reaction like
AB + Z:e

! AB
Z
solv:
10
The more electronegative element B goes as the sol-
vated ion in the electrolyte. The free energy for the
above reduction reaction should exceed the thermo-
dynamic decomposition potential
n
V
D
.
(b) Anodic decomposition: holes (p) participate in the
decomposition reaction
AB + Z:h

! A

solv:
B 11
The more electropositive element A goes as the sol-
vated ion in the electrolyte. The corresponding ther-
modynamic decomposition potential is
p
V
d
.
The electrode decomposition is a thermodynamically as
well as chemically controlled process. The semiconductor
is stable if
p
V
D
[V
redox
[
n
V
D
12
It is unstable, if
V
redox
[
p
V
D
or V
redox
\
n
V
D
13
Sometimes, even when energetics of Eq. 12 predicts
stability, the decomposition occurs due to slow charge
transfer reaction kinetics. Many efforts were made to stop
corrosion in late 1970s and 1980s (see [4]) like surface
decoration by a protective layer, proper choice of redox
electrolyte, use of a fast redox couple, etc. However, the
success was limited. The journey of research efforts for
replacing conventional solidsolid junction (like pn) solar
cells by PESC were found to be heading towards
insurmountable road-block.
It was felt that wide band semiconductors are likely to
be less corrosive (but not good for photo generation of
charge carriers). The photo generation with ht & 1.5 eV
will be ideal, but such semiconductor would corrode if its
charge-transfer reaction at the interface involves electro-
lyte. These are self contradictory and the solution of this
problem eluded till the novel concept of dye-sensitization
of a wide band gap semiconductor (TiO
2
) was propounded
by Gerischer and his group [3] in 1991 giving the dye-
sensitized solar cells (DSSC) described below.
Dye sensitized solar cells (DSSC): working principle
In the rst Dye-Sensitized Solar Cell, ORegan and
Gratzel [5] used TiO
2
sensitized by a ruthenium complex
dye as photoelectrode. The photo excitation took place in
the dye and excited dye transferred the electron to the wide
bandgap nano-TiO
2
. Since the rst report of ORegan and
Gratzel [5], many groups became active worldwide and
numerous cell congurations have been studied. Cost
effective and commercially viable DSSCs with efciency
*10% have already been reported. (see for example
[6, 3033], and references cited therein). The basic design
of DSSC is schematically shown in Fig. 6.
The photoelectrode is usually obtained by forming a thin
layer of nano-TiO
2
paste on to a conducting glass plate
(ITO or FTO). Two most common methods for spreading a
uniform layer of TiO
2
are:
1. Doctor Blade method. In this method the TiO
2
paste
goes between a blade edge and the ITO/FTO substrate.
Fig. 6 Schematic representation of a dye sensitized solar cell
10 Proc. Natl. Acad. Sci. Sect. A Phys. Sci. (JanuaryMarch 2012) 82(1):519
1 3
The lm spreads as blade moves along the substrate.
The thickness is controlled by adjusting the blade edge
height.
2. Conventional Screen Printing technique. The ITO/
TiO
2
assembly as obtained above is subsequently
dipped in the dye solution. The dye molecules cover
most of the TiO
2
particles. This composite assembly
becomes the photoelectrode of DSSC. Some impor-
tant dyes used in DSSC are described later. The
counter electrode could be either sputter coated
platinum on to a glass or metal substrate. A suitable
electrolyte is sandwiched between the counter elec-
trode and the photoelectrode which acts as charge
mediator between them. The photo generated elec-
trons enter the DSSC through the counter electrode
after owing through the external load. The whole
assembly is sealed to make the DSSC leak proof and
mechanically stable. Most commonly used redox
couple is I

=I

3
, though other types have also been
used which are briey described in a later section.
The total charge transfer mechanism in the DSSC is a
multi step phenomenon as shown in Fig. 7 and described
below:
Step 1 Dye (D) absorbs spectral light and goes to the
excited state D*:
TiO
2
=D + hm ! TiO
2
=D* 14
Step 2 The energy levels of chosen dye are such that the
excited dye D* is able to inject electrons from the
excited state rapidly to the conduction band and,
in turn, dye gets oxidized to D
?
:
TiO
2
=D* ! TiO
2
=D

+ e

=TiO
2
15
Step 3 These injected electrons (e
-
), after owing
through the external circuit, return back into the
DSSCsystem through the counter electrode and
reduce the oxidized component of the redox
couple RC]

ox
:
RC]

ox
+ e

=CE ! RC] 16
Step 4 The oxidized dye D
?
gets regenerated to D by
receiving an electron from the reduced
component of the redox couple, i.e., [RC]
TiO
2
=D

+ [RC] ! TiO
2
=RC]

ox
17
After step 4, the complete regeneration of DSSC
(inclusive of TiO
2
, dye and redox couple) has taken place
and the cell is ready for the next cycle of operation. From
the above discussion, it is clear that the over all efciency
of DSSCs heavily rests on the following:
1. Suitable dye sensitizer
2. Proper redox electrolyte
Therefore, much of the recent research is focussed on
these aspects. Some important developments are described
below.
Some important Sensitizer Dyes for DSSC
Dye sensitization is a crucial step in the realization of high
efciency DSSCs. Some of the necessary requirements for
a good dye sensitizer are: (i) broad absorption spectrum,
particularly in the visible range. (ii) suitable ground and
excited energy states compatible with the semi-conductor
electrode energy levels (as well as that of redox mediator)
for efcient energy transfer to and from it as shown in
Fig. 7. (iii) ability to form well contacted interface with the
semi-conductor surface. (iv) should regenerate itself via
electron donation from the redox electrolyte (or from the
hole conductor being used as mediator in a special type
solid state DSSC described later). (v) non-Toxic (vi)
long stability. It should be able to sustain about 10
8
turn-
over cycles corresponding to about 20 years of exposure to
natural light [32].
Most popular dye sensitizers for DSSC are mostly based
on Ruthenium Complexes [6, 31, 3338] shown in Fig. 8,
in particular Dye coded as N
3
dye [cis-di (isothiocyanoto)
bis (2,2
0
bipyridyl-4,4
0
dicaxboxylate) ruthenium (II)]. The
N
3
dye suffers from the drawback that it lacks absorption in
Fig. 7 Schematic representation of energy levels of TiO
2
and dye
along with charge transfer amongst photoexcited dye, TiO
2
, redox
couple mediator and the counter electrode
Proc. Natl. Acad. Sci. Sect. A Phys. Sci. (JanuaryMarch 2012) 82(1):519 11
1 3
the red spectral region. Nonetheless, this still continues to
be one of the best dye sensitizer and many studies are
reported on DSSCs with efciencies in the range 510%
using N
3
dye.
A new ruthenium dye giving DSSCs with efciency
greater than 10% is black dye, coded as N749,[tri(cy-
anoto)2,2
0
,2
00
,ter-pyridyl-4,4
0
,4
00
,tricarboxylate) ruthenium
(II)]. The highest efciency of 11.1% has already been
achieved. Apart from ruthenium charge- transfer com-
plexes, some metal porphyrins like chlorophyll, Zinc
metalloporphyrins, etc. have also been tried. However, the
efciencies of DSSCs obtained for these dyes are much
lower than those of cells which used ruthenium dyes (see
Goncalves et al. [34] and references cited therein).
Many metal free organic dyes like indoline, couma-
rin, polyene, cynanine, perylene, pthalocyanine, etc. have
also been successfully used in DSSC, with efciencies
ranging from 1.5 to 9%. Li et al. [39], recently reported
DSSC using two newly synthesized metal free organic
dyes. These dyes contained thienothiophene or thiophene
segments as pconjugation system (dyes were called as
D-ST and DSS, respectively). The structure of these two
dyes along with some other important organic dyes [34, 39]
are shown in Fig. 9. The advantage of metal free organic
dyes over the Ru-complexes is that they, apart from having
high molar extinction coefcient, can be synthesized in
pure form at lower cost.
Electrolytes for DSSC
Electrolyte is a very critical part of DSSCs since it acts as
a mediator to regenerate the dye at the photoelectrode
through the electronic charge received from the counter
electrode as explained earlier. Many redox couples have
been tried and the following couples have given promising
results:
(i) I

3
=I

: This has so far given the highest efciency and

is most popular. Nearly 90% of studies reported in
literature on DSSCs use this redox system. The
mechanism of electron charge transfer between redox
Fig. 8 Some common
ruthenium complex based dye-
sensitizers for DSSC (i) N-13
(red), (ii) Z-49 (black dye), (iii)
Z-907, (iv) N-719, (v) K-19 and
(vi) K-60
12 Proc. Natl. Acad. Sci. Sect. A Phys. Sci. (JanuaryMarch 2012) 82(1):519
1 3
couple I

=I

3
and the counter electrode as well as
between redox couple and dye is schematically
shown in Fig. 10. The diffusion of I

3
is generally
Grotthus-type charge transport mechanism [40].
(ii) Co(II)/Co(III): This is probably the most promising
new redox system because of some advantages over
Iodide-couple like its non-volatility and non-toxicity
[41, 42], (iii) (SeCN)
2
(SeCN)
-
and (SCN)
2
/(SCN)
-
[43, 44]. (iv) Br

3
=Br

[45]
For efcient charge transfer from or to the redox system,
the redox system should be capable of forming good
interface with the dye as well as with the counter electrode.
The different manners in which it has been achieved are
briey described below.
Traditional Volatile Solvent Based Electrolytes
Most dyes are water sensitive. Therefore, instead of
aqueous solvent, non-aqueous solvents are used. Some of
the common non aqueous solvents used are acctonitrile,
valernitrile, 3-methoxy propionitrile, ethylene carbonate,
propylene carbonate, c-butyrolactone etc. In fact, many
other solvents can also be used so long they show good
redox couple solubility, low volatility, low toxicity and low
viscosity allowing fast diffusion of ions in the electrolyte.
The DSSCs using volatileorganic solvents, inspite of
having high efciency suffer from the problems of long
term stability (solvent evaporates), leakage and sealing
packaging problems. To overcome some of these difcul-
ties, ionic liquids are increasingly being used as solvent.
Ionic Liquid Based Electrolytes
Ionic liquids (IL) are a new class of material [46], which
are self-dissociating and composed of large organic cations
and inorganicorganic anions of varying sizes. This leads
to high ionic conductivity in IL. Apart from high conduc-
tivity, the ILs have low vapour pressure, high thermal and
chemical stability, good solubility for many organicinor-
ganic compounds and large electrochemical window. This
has resulted in their application in many electrochemical
solar cells, including DSSC. Papageorgiou et al. [40] were
the rst to develop a DSSC with ionic liquid 1-methyl-3-
hexyl imidazolium iodide (MHIm). They reported long
Fig. 9 Some important metal
free organic dyes used in DSSC
(i) indolin, (ii) coumarin, (iii)
polyene, (iv) dyes with
thienothiophene and thiophene
segment, D-ST and D-SS
Fig. 10 Mechanism of electron exchange involving redox couple
mediator I
2
/I
3
2
Proc. Natl. Acad. Sci. Sect. A Phys. Sci. (JanuaryMarch 2012) 82(1):519 13
1 3
term stability of this cell. Since then, many 1,3-dialky-
limidazolium cation based ionic liquid have been used.
(See for example [6, 34]). The general molecular structure
of dialkylimidazolium based ionic liquid is given in
Fig. 11.
By changing R
1
and R
2
, one can obtain a variety of ionic
liquids. It may be noted that if the cation of the ionic liquid
is I

; SCN

; SeCN

; (BCN
4

, etc., the ionic liquid as

electrolyte serves dual role of acting as redox couple source
(I

; SCN

, etc.) as well as solvent. The high viscosity of

ILs, coupled with their negligible volatility, reduces the
sealing problem considerably. However, the high viscosity
tends to reduce ion diffusivity and hence, slow charge
transfer for dye regeneration. This decreases the over all
efciency of the DSSCs.
Many approaches have been used for increasing the V
oc
,
J
sc
and the efciency of ionic liquid based DSSCs. Some
of the important approaches adopted are:
(i) Use of low viscosity ionic liquids has been proposed
because it is expected that this will increase the ion
diffusivity which, in turn, will enhance the dye
regeneration rate. Most of the Imidazolium Iodides
have high viscosity. As mentioned earlier, iodides
offer preferred redox system because of its good
charge transfer behaviour. To overcome the dif-
culty posed by the high viscosity of imidazolium
iodides, it has been mixed with low viscosity
imidazolium based ILs with anions other than
iodide (like SCN

; SeCN

; N(CN)

2
; and BF

4
,
etc.) [6, 47] giving binary and ternary mixtures. A
DSSC using a ternary mixture of ionic liquid has
recently been reported with efciency as high as
8.2% [45].
(ii) Some inorganic, e.g., CuI or organic additives, e.g.,
tetra-butylpyridine,N-alkylbenzimidazoles, guanidi-
nium thiocyoanate, etc. have also been tried. (see [6]
and references cited therein). It is believed that the
additive cations are adsorbed to the porous photo-
electrode of TiO
2
shifting the conduction band edge
of the semiconductor.
(iii) Non-imidazolium based ionic liquids have also been
used like sufonium[49], ammonium[50], guanidinium
[51], phosphoniun [52], or tetrahydrothiopheniun [53].
The former four showed low efciencies but for the
latter the efciency seems promising.
(iv) An interesting modication to the DSSCs has been
made in which the solar cell is irradiated both from
the front side (see Fig. 6) as well as from the back
side viz. counterelectrode side. Such a cell has been
termed as Bifacial dye-sensitized solar cell (see
for example [54] and references cited therein). In
front-side alone type DSSCs, most of the radiation
is absorbed in the rst few layers of dye-sensitized
TiO
2
while in bifacial cells, the solar radiation from
rear side also contribute to the photo-effect in the
remaining back portion of TiO
2
photo-electrode
resulting in enhanced efciency. This has been
attained by a minor design change by pressing
porous silica on the counterelectrode side between it
and the electrolyte.
Inspite of the success achieved in developing high ef-
ciency DSSCS using electrolyte containing ILs, the
problem of leakage in cells stored or used for long time
persisted. Two approaches viz. using Ionic gel and Ion-
conducting polymer electrolyte are being extensively
investigated which yield quasi-solid state and all solid state
DSSCs. These are briey described below.
Quasi-solid State DSSCs
Using Ion Gels as Electrolytes
The IL-electrolytes used in DSSCs have been converted
into quasi-solid state ionic gels using two main approaches:
(i) Use of inorganic materials in nano and micron sizes
to produce thickened gel-like composite material is
very common. Many dispersed materials have been
tried like SiO
2
[5557], carbon nano-tubes, carbon
black [58], a-ZrP [59], etc. DSSC efciencies *5 to
6% could be obtained, particularly with SiO
2
nano-
composites.
(ii) The other approach is to use organic gelators. Some
gelators are: (PVP ? different dicarboxylic acids)
[60], PVdF-HFP [61], PEG [62], low molecular
weight gelators [63], natural polysaccharide agarose
[64], cross-linked gelataion agents like NMBI (1-N-
methylbenzimidazole) [65], etc.
In general, the efciency of DSSCs with gel-electrolyte
was less than those having ILs without gelators. This is
understandable because the I

=I

3
diffusion in gels will be
slower than in pure ILs resulting in slower charge transfer
kinetics. A comparison of short circuit current (J
sc
), open
circuit voltage (V
oc
) and efciency (g) for DSSCs using
gelled (obtained by adding by PVDF-HFP) and non-gelled
electrolyte viz. ionic liquid, 1-ethyl-3-methylimidazolium
N
+
N
R
2
X
-
R
1
Fig. 11 Structure of di-alkyl imidazolium cation (and X
-
anion)
based ionic liquid
14 Proc. Natl. Acad. Sci. Sect. A Phys. Sci. (JanuaryMarch 2012) 82(1):519
1 3
bis(triuoromethane sulphonyl)imide, (EMIm-TFSI) ?
[L
i
I ? tetrabutyl pyridinium] is given in Table 1 along
with DSSCs using organic volatile solvent (methoxy-
acetonitrile) instead of IL.
Large area (100 mm 9 100 mm) DSSCs using ion gels
have already been demonstrated which promises their
commercial viability [58, 66].
DSSCs Using Plasticized Polymer Electrolyte
Membrane
As discussed earlier, the polymer electrolytes have been
tried earlier as a replacement of liquid electrolyte in many
studies on conventional PESCs [25, 27, 29]. Similar
modied membranes have been used recently in DSSCs.
Polyethylene oxide (PEO) doped with a variety of
salts have been studied for quite a long time as
Li

; Na

; K

; H

, etc. conductors [6772] for applica-

tion in fuel cells and polymer batteries. Most of these were
conducting through cations as well as anions. The mobil-
ities of iodide anion in PEO ? NH
4
I and SCN
-
in Poly-
ethylene Succinate ? NH
4
SCN systems were so high that,
given proper aggregating sites, they grew into large size
fractals [73, 74]. There are a large number of studies on
polymer electrolytes (see [67] for earlier work). The rele-
vant point with reference to DSSCs is that the anions (like
iodide ions) are also mobile which can be made to act as
charge transfer mediator between the dye and the
counter-electrode.
De Paoli et al. [7579] has reported many studies on
DSSCs using membranes of PEO-based elastomer (viz.
polyethylene oxide-co-epichlorohydrin) doped with
NaI ? I
2
. They have integrated many such cells to fabri-
cate a Solar Module of *8 V. Kang et al. [80] devel-
oped a DSSC with polymer electrolytes obtained by
blending PEO, polysiloxanes and a series of quaternary
ammonium iodides (PS-NQAS). Many plasticizers (e.g.
propylene carbonate, PC; c-butyrolactone, c-BL etc.) were
also added to enhance the conductivities. They reported
efciency of *1.39%. Recently effort has shifted to much
simpler systems like PEO ? (KI ? I
2
), PEO ? (NaI ? I
2
)
etc. containing a variety of ionic liquids to enhance
conductivity as well as to obtain plasticization effect [81
84]. The efciencies attained with all types of polymer
electrolyte based DSSC are still much lower than those
which use gel electrolytes or organic solvent electro-
lytes. However, the exible nature of polymer electrolytes
and associated avoidance of the problem of leakage,
packaging etc. still make them a promising alternative for
long term applications.
All Solid State DSSCs by Replacing Electrolyte with p-
Semiconductor
This is a radical and fundamental departure from the con-
ventional DSSCs. As explained earlier, an electron from
valance band of dye, after photoexcitation, goes to the
conduction band which gets transported through the TiO
2
electrode and subsequently through the external circuit
goes to the counter electrode. To regenerate the dye,
electron transfer from the electrolyte to dye occurs which,
in turn, is regenerated by receiving the electron from the
counter electrode. In the new concept of all solid state
DSSCs, the electrolyte is replaced by p-semiconductor (as
shown in Fig. 12).
The photoexcited dye is regenerated by hole transfer
(from Dye valance band) to the p-semiconductor through
which it hops and ultimately meets the electron from the
counter electrode side. The above mechanism is schemati-
cally given in Fig. 13). However, the p-semiconductors to be
used in such DSSCs have to satisfy some basic criteria viz.
(a) The p-semiconductor should be such that it can be
deposited easily into the porous composite (TiO
2
?
dye) photo electrode by low temperature processes
without removing the dye layer over the TiO
2
.
Table 1 Comparison of dye sensitized solar cell parameters with
iodine couple in normal organic volatile solvent, IL, Ionic gel and
Ionic gel sheet (Matsui et al. [66])
Iodine redox couple solvent J
sc
(mA/cm
2
) V
oc
(mV) g (%)
Volatile 14.6 750 6.7
Ionic liquid 12.1 640 4.5
Gel 9.6 640 3.8
Ion gel sheet 8.0 480 2.4
Fig. 12 Schematic representation of the basic assembly of all solid
state DSSC in which p-semiconductor is responsible for charge
mediation and dye-regeneration
Proc. Natl. Acad. Sci. Sect. A Phys. Sci. (JanuaryMarch 2012) 82(1):519 15
1 3
(b) Since hole transfer from the valance band of dye has
to take place to the p-semiconductor, the valance
band of the semiconductor should lie above the dye
valance band as shown in Fig. 13.
Both inorganic and organic p-semiconductors have been
used. DSSCs using CuI, CuSCN and NiO have been
studied. Tennakone et al. [85] were rst to report the solid
state DSSC using p-CuI. The same group later reported
[86] enhanced efciency for such cells with efciency as
high as 2.6%. The stabilities were low because CuI tends to
be oxidized under illumination. It has been reported that by
incorporating small quantities (1 mM) of thiocyanates like
1-methyl-3-ethylimidazolium thiocyanate [87] or triethy-
lammoniumhydrothiocyanate [88] improves the stability.
Meng et al. [89] using the former additive reported a cell
with efciency *3.8% which was stable for nearly
2 weeks.
Cells using CuSCN [9093] and NiO [94] have also
been reported but the efciency of these cells is still lower
than those using CuI but the stability is comparative or
sometimes even better.
Gratzel et al. [95] was rst to report a DSSC with p-type
organic semiconductor. The material used by them was
OMeTAD [2,2
0
,7,7
0
-tetrakis (N, N-di-p-methoxyphenyl-
amine) 9.9
0
-spiro-biuorene]. They found that efciency
was very low unless it is doped with some ionic salts (say
lithium salts) but it needed co-solvents. Many co-solvents
have been tried [96, 97] to yield cells with efciency of
*3%. Some novel supramolecules have also been reported
[98, 99] which dissolve Li
?
-ions without using co-solvents.
Many other hole transporting materials like PEDOT(Poly-
ethylenedioxythiophene, polyaniline, polypyrrole etc.)
have also been tried but the cells so obtained have com-
paratively low efciency (see [30] and references cited
therein).
In conclusion, the science and technology of DSSC have
come to a stage where it can be stated that DSSCs are a
safe bet as a future replacement of conventional semicon-
ductor junction solar cells because of its low cost, easy
processibility and possibility of scaling up.
Acknowledgments Thanks are due to National Academy of Sci-
ences, India for the award of NASI-Platinum Jubilee Senior Scientist
Fellowship. Thanks are also due to S. K. Chaurasia, M. P. Singh, Y.
L. Verma and Abhishek Kumar Gupta for help in preparing the
manuscript.
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