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Simulation and modelling of charge transport in dye-sensitized solar cells based on carbon
nano-tube electrodes
View the table of contents for this issue, or go to the journal homepage for more
2013 Phys. Scr. 87 035703
(http://iopscience.iop.org/1402-4896/87/3/035703)
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Phys. Scr. 87 (2013) 035703 (11pp) doi:10.1088/0031-8949/87/03/035703
Simulation and modelling of charge
transport in dye-sensitized solar cells
based on carbon nano-tube electrodes
Yahia Gacemi
1
, Ali Cheknane
1
and Hikmat S Hilal
2
1
Laboratoire des Semiconducteurs et Mat eriaux Fonctionnels, Universit e Amar Telidji de Laghouat,
Laghouat Algeria
2
SSERL, Chemistry, An-Najah National University, PO Box 7, Nablus, Palestine
E-mail: cheknanali@yahoo.com
Received 19 June 2012
Accepted for publication 18 January 2013
Published 13 February 2013
Online at stacks.iop.org/PhysScr/87/035703
Abstract
For a better understanding of the mechanisms of dye-sensitized solar cells (DSSCs), based on
carbon nano-tube (CNT) electrodes, a phenomenological model is proposed. For modelling
purposes, the meso-scopic porous CNT electrode is considered as a homogeneous
nano-crystalline structure with thickness L. The CNT electrode is covered with light-absorbing
dye molecules, and interpenetrated by the tri-iodide (I

/I

3
) redox couple. A simulation
platform, designed to study coupled charge transport in such cells, is presented here. The work
aims at formulating a mathematical model that describes charge transfer and charge transport
within the porous CNT window electrode. The model is based on a pseudo-homogeneous
active layer using driftdiffusion transport equations for free electron and ion transport. Based
on solving the continuity equation for electrons, the model uses the numerical nite difference
method. The numerical solution of the continuity equation produces currentvoltage curves
that t the diode equation with an ideality factor of unity. The calculated currentvoltage (JV)
characteristics of the illuminated idealized DSSCs (100 mWcm
2
, AM1.5), and the different
series resistances of the transparent conductor oxide (TCO) layer were introduced into the
idealized simulated photo JV characteristics. The results obtained are presented and
discussed in this paper. Thus, for a series resistance of 4 of the TCO layer, the conversion
efciency () was 7.49% for the CNT-based cell, compared with 6.11% for the TiO
2
-based
cell. Two recombination kinetic models are used, the electron transport kinetics within the
nano-structured CNT lm, or the electron transfer rate across the CNTelectrolyte interface.
The simulations indicate that both electron and ion transport properties should be considered
when modelling CNT-based DSSCs and other similar systems. Unlike conventional
polycrystalline solar cells which exhibit carrier recombination, which limits their efciency,
the CNT matrix (in CNT-based cells) serves as the conductor for majority carriers and
prevents recombination. This is because of special conductivity and visiblenear-infrared
transparency of the CNT. Charge transfer mechanisms within the porous CNT matrix and at
the semiconductordyeelectrolyte interfaces are described in this paper.
PACS numbers: 78.20.Bh, 78.56.a
(Some gures may appear in colour only in the online journal)
1. Introduction
The dye-sensitized solar cell (DSSC) is a third-generation
photovoltaic device, with high prospects for use in low-cost
photo-conversion technology in the future. DSSCs are
photo-electrochemical cells involving photoactive electrodes
based on meso-porous nano-structured metal oxide (typically
TiO
2
or ZnO) lms [12].
Numerical modelling of solar cells helps us to understand
the principles of the photo-conversion process and to
0031-8949/13/035703+11$33.00 Printed in the UK & the USA 1 2013 The Royal Swedish Academy of Sciences
Phys. Scr. 87 (2013) 035703 Y Gacemi et al
design devices with higher efciencies. Since their advent
in 1991 [3], DSSCs based on sensitized nano-structured
meso-porous metal oxides are among the most promising
third-generation devices. Such DSSCs have very high
photo-conversion efciencies, with values of up to 11.1%
under 1 sun, AM1.5G illumination [4]. In particular,
the DSSC using TiNCCB (1:1, mass ratio)/Ti electrode
presents an energy conversion efciency of 7.92%, which
is higher than that (6.59%) of the device using the Pt/FTO
(uorine-doped tin oxide) electrode measured under the same
test conditions [5].
The performance of a DSSC is based on the combination
of good visible light harvesting, efcient charge separation,
relatively fast transport and low recombination rate. An
efcient combination is achieved by interpenetrating an
electron-conducting material with a hole-conducting
medium at the nano-scale. In a typical DSSC [6] the
electron-conducting material is a meso-porous semiconductor
oxide such as TiO
2
or ZnO, whereas the ion transport occurs
in the electrolyte solution.
The dynamic competition between electron transport
and recombination determines the electron diffusion length
[4, 79]. To achieve high quantum efciencies under short-
circuit conditions, the electron diffusion length should
be larger than the thickness of the metal oxide lm.
Electron transport in meso-porous oxide lms, impregnated
with high electrolyte concentrations, is believed to occur
mainly by diffusion [10, 11]. Diffusion exhibits anomalous
features, such as extremely slow transport, as compared
with mono-crystalline electrodes with diffusion coefcients
depending on light intensity [12, 13].
Carbon nano-tube (CNT)-based photovoltaic devices
are based on window CNT electrodes. The carriers are
transported inside the conduction band of the stable
semiconductor to the charge collector at the interface.
On the other hand, titania nano-tube array-based DSSCs
degrade under illumination, which limits their lifetime and
stability. This shows the CNTs future prospects to function
as very stable photo-electrodes [14]. In addition to their
stability [14, 15], CNT lms exhibit excellent conductivity
and good transparency in both the visible and near-infrared
regions. Thus, CNT-based solar cells deserve more theoretical
and experimental investigations.
For a better understanding of the basic working
mechanisms of DSSCs, a phenomenological model was
proposed. For modelling purposes, the mesoscopic porous
structure, consisting of TiO
2
nano-particles, covered with
light-absorbing dye molecules and interpenetrated by the
I

/I

3
redox mediator was considered to be a homogeneous
nanocrystalline structure of uniform thickness [16].
In this work, we investigate, for the rst time, charge
transport processes in dye-sensitized CNT-based solar cells.
The study is based on solving the continuity equation.
Numerical solution involves two steps. (i) spatial and temporal
discretization of equations describing the transfer processes
for ion and electron transfer. As a result of discretization,
the initial set of differential equations, with the corresponding
boundary conditions, is reduced to a set of generally nonlinear
difference equations. (ii) Solving a set of difference equations
using the nite difference method (FDM). An approximate
solution can thus be reached.
In the rst part of our approach, we have presented
the development of equations and procedure. We have
taken into account the time-dependent parameters. Thereafter,
in the second stage, our calculation was performed
under steady-state conditions in order to provide guidance
on transient performance, such as the currentvoltage
characteristic, where we can determine the performance
parameters of the cell as: the short-circuit current (J
SC
),
open-circuit potential (V
OC
) and ll factor (FF). Nevertheless,
more detailed properties cannot be extracted from steady-state
measurements and so dynamic techniques should be
considered. These techniques allow the interpretation of the
kinetics, mainly characterized by diffusion coefcients and
lifetime of the different carriers. One of the most powerful
characterization techniques of DSSCs involving transient
probing is electrochemical impedance spectroscopy [16]. That
task is the subject of our future activity.
2. Development and simulation of the DSSC model
A solar cell is largely governed by the relative rates
of several charge transfer steps. It is assumed that the
active layer, as described below, is electrically modelled
as a one-dimensional pseudo-homogeneous layer, along the
x-direction. The majority carriers are photo-generated free
electrons, injected in nano-porous CNT, iodide and tri-iodide
ions in the electrolyte. The structure of the DSSC is rst
divided into two different regions: the active layer and the bulk
electrolyte layer.
It is necessary to understand all the electronic processes
taking place at the CNT nano-particle level [17]. Models
were proposed for the internal structure of the DSSC,
where electrons ow from an Ru complex (N3) dye
to the nano-porous CNT electrode, and then to the
transparent conduction oxide (TCO) electrode [16, 18].
One model [16] proposed the following sequence of
charge-transport processes: (i) electron excitation, (ii) electron
injection from the dye lowest unoccupied molecular orbital
(LUMO) to the CNT conduction band, (iii) regeneration of the
dye, (iv) tri-iodide reduction to iodide at the counter-electrode,
(v) excited-state decay to the ground state, (vi) recombination
of the injected electrons with the oxidized dye and (vii)
recombination of the injected electrons with tri-iodide ions.
The cell open-circuit photo-voltage (V
OC
) corresponds to
the difference between the CNT Fermi level (E
F
) and the
electrolyte redox potential (E
redox
).
In addition to the forward electron transfer and transport
processes, the model also illustrates several competing
electron loss pathways, including [16]
S + hv S

, electron excitation in the dye molecule, (1)

S

S
+
+e

CB
, electron injection into the conduction band CB,
(2)
S
+
+
3
2
I

1
2
I

3
+ S, dye regeneration, (3)
I

3
+2e

CE
3I

, electrolyte regeneration at the counter

electrode CE, (4)
2
Phys. Scr. 87 (2013) 035703 Y Gacemi et al
S

S, fall to ground state, (5)

S
+
+e

CB
S

, regeneration of dye by injected electrons,

(6)
I

3
+2e

CB
3I

, recombination of injected electrons with I

3
,
(7)
where S is the dye sensitizer; S

is the electronically excited

dye sensitizer; S
+
is the oxidized dye sensitizer; and O/R is
the redox couple (e.g. I

3
/I

).
In order to capture as much solar radiation as possible,
the dye must have a wider absorption spectrum. The dye
LUMO must energetically lie above the conduction band
edge of the semiconductor to allow electron injection into
the nano-porous CNT, before it can fall back to its ground
state (reaction (5)) [17, 19]. On the other hand, the dye
HOMO must have a more positive (lower) potential than
E
redox
. To prevent recombination of the injected electrons
with the oxidized dye (reaction (6)), hole transfer to the
redox couple must be extremely fast. The electrolyte in
turn conducts the holes to the counter-electrode, where the
redox couple itself is regenerated. As V
OC
corresponds to
the difference between the E
redox
and the CNT Fermi level,
the former must be as positive as possible to guarantee
higher photo-voltages. The over-voltage for reduction of
the species in the counter-electrode must be small, since it
represents a loss in the photo-voltage of the cell. To enhance
charge-transfer at the counter-electrode, a charge-transfer
catalyst, such as platinum particles, is commonly used [16].
The over-voltage at the semiconductordye interface must be
high, since the dark current caused by electron back transfer
to the electrolyte lowers the number of electrons available for
the photocurrent (reaction (7)).
2.1. Electrical model for charge transport
2.1.1. Charge transport in nanocrystalline CNT lms
(continuity equation for electrons). The electron diffusion
through the nano-structured CNT lm, with variable
generation and recombination terms using appropriate
boundary conditions, is evaluated. By illuminating the
working electrode, electrons are injected in the system,
resulting in an electron density build-up in the lm that
is a function of position and time. Electrons are allowed
to diffuse towards the working electrode, which in turn
behaves as a collecting interface. The continuity equation is
nally solved by linear geometry, i.e. only the x-coordinate
is considered [20]. The x denotes the location within the
cell, where x =0 indicates the TCOCNT interface at the
front electrode. The x =d indicates the interface between the
electrolyte and Pt-TCO where d represents the thickness of
the simulated cell; and n
c
is the density of free electrons in the
conduction band. Hence, the following differential equation
is solved:
D
e

2
n
e
(x, t )
x
2
+ G(x)
n
e
(x, t ) n
eq

e
=
n
e
(x, t )
t
, (8)
where D
e
is diffusion coefcient for electrons (m
2
s
1
); and
G(x) is the generation rate at distance x, n
e
(x, t ) is the total
density of electrons (cm
3
) as a function of time (t) and
distance (x) from the working electrode [16], and n
eq
is the
carrier density of electrons at equilibrium in the dark.
Equation (8) is solved by FDM using the lax scheme
[20, 21] and with the following two boundary conditions:
_

_
x =0, q D
e

n
e
x

x=0
= J
cell
,
x =d,
n
e
x

x=d
=0,
(9)
where q is elementary charge of the electron (1.6 10
19
C),
and J
cell
is short-circuit current density of the cell.
Considering that for t =0 the cell is in the dark at
equilibrium:
t =0, n
e
(x, 0) =n
eq
, (10)
where t is exposure time in seconds.
The generations could be simplied in integral
form (equation (11)), where () denotes the absorption
coefcient, n
inj
is the electron injection efciency, () the
incident photon ux, and the wavelength:
G(x) =
inj
_

max

min
()()e
()x
d. (11)
Generation rates are integrated in the wavelength range
from 300 (
min
) to 800 nm (
max
), where the DSSC is
active [22], while on the other hand, they could also be a result
of the optical simulator. At open circuit only recombination
currents ow inside the cell. Electrons recombine with
tri-iodide ions in the electrolyte, or enter the front TCO layer
and recombine from there [23]. The electron transportation
(recombination) to the tri-iodide species follows rst-order
kinetics as [16, 22]
R
e
(x) =
n
e
(x, t ) n
eq

e
, (12)
where R
e
(x) is the rate of electron combination as a function
of x, and
e
is electron lifetime (s) determined by back reaction
with redox couple I

/I

3
.
The dark equilibrium carrier density n
eq
corresponds
to the matching between the Fermi level in the CNT
and the E
redox
. When the Fermi level is aligned with
electrolyte potential (i.e. kept constant, because electrolyte
concentrations are almost constant and their potential is nearly
constant) this indicates that the carrier density is constant.
Fermi level is affected by majority carrier density.
2.1.2. Charge transport in redox species (continuity equation
for redox species). The oxidation of iodide ions and the
reduction of tri-iodide occur inside the electrolyte species
present in the interstitial space within the CNT nano-particles.
Taking into account the stoichiometry of reactions (3) and
(4), the terms of generation and recombination of tri-iodide
and iodide species must be affected by the corresponding
3
Phys. Scr. 87 (2013) 035703 Y Gacemi et al
coefcients (1/2) and (3/2), respectively:
_

_
D
I

2
n
I

3
(x, t )
x
2
+
1
2
p
_
G(x)
n
e
(x, t )n
eq

n
e
(x, t )
t
_
=
n
I

3
(x, t )
t
,
D
I

2
n
I
(x, t )
x
2

3
2
p
_
G(x)
n
e
(x, t )n
eq

n
e
(x, t )
t
_
=
n
I
(x, t )
t
,
(13)
where D

I 3
and D

I
are diffusion coefcients for ions I

3
and
I

, respectively; n

I 3
and n

I
are concentrations for I

and I

ions, respectively (m
3
); and
p
is CNT lm porosity.
In a non-steady state, the accumulated electrons do not
participate in the redox reactions and must thus be discounted
from the ion generation term [16]

n
e
(x, t )
t
. ,, .
electron accumulation
. (14)
At time t =0, initial concentrations of the electrolyte
species are assumed:
t =0, n
I

3
(x, 0) =n
init
I

3
, n
I
(x, 0) =n
init
I
. (15)
At the TCOCNT interface only the photo-injected
electrons ow. The net ux of I

and I

3
ions is zero, thus
x =0,
n
I

3
(0, t )
x
=0;
n
I
(0, t )
x
=0. (16)
The total amount of the redox species contained in
the CNT nano-pores remains constant during the DSSC
operation. This may be described as [24]
x =d,
_
d
0
n
I

3
(x) dx =n
ini
I

3
d;
_
d
0
n
I
(x) dx =n
ini
I
d.
(17)
In this study, the approximate equations of
n
I

3
(x, t ), n
I

3
(x, t ) and n
e
(x, t ) are estimated using the
FDM.
3. Numerical solutions of difference equations for
various types of boundary conditions
3.1. Numerical solutions for electron transport in the CNT
electrode
The platform, the so-called slice here, involves a number
of sub-models. The sub-models describe the structure of the
electrode, the generation of electrons and the contacts. They
also describe the electron and ion mass transport processes,
and the electron transfer reactions between the redox couple
(I

/I

3
) and the oxidized dye molecules [25].
In addition to transporting charge between respective
interfaces, the electrolyte also inuences electron transport
within the nano-porous CNT [2528]. The electrolyte has
both redox and screening properties. Screening is directly
coupled to the ionic ability to charge-compensate electrons in
the nano-structured semiconductor.
The cell is treated as a one-dimensional effective medium
whose thickness, d, is divided into a number of slices, x
N
. The
-
+
-
-
+
+
+
-
+
I
-
I
-
3
x1 x0 x2
xi-1
xi xN xN-1
x
Figure 1. Description of the DSSC by the slice model, and
illustration of the multiple-trapping model of transport (left) and the
geometry used for solving the continuity equation (right). The cell is
assumed to be a one-dimensional medium whose thickness, d, is
divided into a number of slices, x
N
, where the length of each slice is
x
i
= x
i
x
i 1
=x.
length of an individual slice is expressed as x
i
= x
i
x
i 1
=
x. The relation is expressed as
d =
x
N

i =1
x(i ). (18)
A sequence of slices is referred to as a region. A slice
includes a generation region, an electron transport region and
an electrolyte transport region. Figure 1 shows a schematic
slice structure model corresponding to a DSSC. In the
multiple trapping (MT) models, electron transport is assumed
to occur via an extended state E
c
. Furthermore, in the present
numerical model, the recombination processes of electrons
with tri-iodide ions and dye cations may occur in the cell
under operation.
In solving equation (8), for charge transport, the FDM
will be used. For the sake of simplicity, it is assumed
that the mesh with nodes in points 1, . . ., i, . . ., N is
homogeneous. Thus, x
i
= x
i
x
i 1
=x =constant. The
node with subscript 1 is located at the electrode surface, and
the node with subscript N is located at the outer boundary of
the diffusion layer.
D
e
n
e
|
k
i +1
2 n
e
|
k
i
+ n
e
|
k
i 1
x
2
+

f

k
i
=
n
e
|
k
i
n
e
|
k1
i
t
for i =1, . . . , N 1, (19a)
with

k
i
= G|
k
i

n
e
|
k
i
n
eq

e
. (19b)
In the inner nodes of the mesh, for the spatial
discretization of equations (19a) and (19b) of CNT electrode
transfer, the central differences are used. Therefore

D
e
x
2
n
e

k
1
+
_
2
D
e
x
2
+
1
t
_
n
e

k
2
=
1
t
n
e

k1
1
+

f

k
1
+
D
e
x
2
n
e
(0, t
k
)

D
e
x
2
n
e

k
1
+
_
2
D
e
x
2
+
1
t
_
n
e

k
2

D
e
x
2
n
e

k1
3
4
Phys. Scr. 87 (2013) 035703 Y Gacemi et al
=
1
t
n
e

k1
2
+

f

k
2

. . . =. . .

D
e
x
2
n
e

k
i
+
_
2
D
e
x
2
+
1
t
_
n
e

k
i +1

D
e
x
2
n
e

k1
i
=
1
t
n
e

k1
i
+

f

k
i

. . . =. . .

D
e
x
2
n
e

k
N2
+
_
2
D
e
x
2
+
1
t
_
n
e
|
k
N1
=
1
t
n
e

k1
N1
+

f

k
N1
+
D
e
x
2
n
e
(d, t
k
), (20)
k designates the point order of the node in the mesh, and
should not be confused with the Boltzmann constant which
is denoted as k
B
elsewhere.
3.2. Numerical solutions for ion transport in the electrolyte
In the uni-dimensional case, for the approximation of the
theory of equations (13), ion transfer in dimensionless form
can be written as
_

_
D
I

3
n
I

k
i +1
2 n
I

k
i
+ n
I

k
i 1
x
2
+ a

f

k
i
=
n
I

k
i
n
I

k1
i
t
+ a
n
e
|
k
i
n
e
|
k1
i
t
,
D
I

n
I

k
i +1
2 n
I

k
i
+ n
I

k
i 1
x
2
+

b

f

k
i
=
n
I

k
i
n
I

k1
i
t
+

b
n
e

k
i
n
e

k1
i
t
,
D
e
n
e

k
i +1
2 n
e

k
i
+ n
e

k
i 1
x
2
+

f

k
i
=
n
e

k
i
n
e

k1
i
t
,
_

_
D
I

3
n
I

k
i +1
2 n
I

k
i
+ n
I

k
i 1
x
2
+ a

f

k
i
=
n
I

k
i
n
I

k1
i
t
+ a
n
e

k
i
n
e

k1
i
t
,
D
I

n
I

k
i +1
2 n
I

k
i
+ n
I

k
i 1
x
2
+

b

f

k
i
=
n
I

k
i
n
I

k1
i
t
+

b
n
e

k
i
n
e

k1
i
t
.
(21)
In the inner nodes of the mesh, for the spatial
discretization of equations of electrolyte species transfer (21),
the central differences are used. Thus
_

_
_
2
D
I

3
x
2
+
1
t
_
n
I

k
1
+
a
t
n
e

k
1

D
I

3
x
2
n
I

k
2
=
1
t
_
n
I

k1
1
+ an
e

k1
1
_
+ a

f

k
1
+
D
I

3
x
2
n
I

3
_
0, t
k
_
,
_
2
D
I

x
2
+
1
t
_
n
I

k
1
+

b
t
n
e

k
1

D
I

x
2
n
I

k
21
1
t
_
n
I

k1
1
+

bn
e

k1
1
_
+

b.

k
1
+
D
I

3
x
2
n
I

_
0, t
k
_
,

. . . =. . .

D
I

3
x
2
n
I

k
i 1
+
_
2
D
I

3
x
2
+
1
t
_
n
I

k
i
+
a
t
n
e

k
i

D
I

3
x
2
n
I

k
i +1
=
1
t
_
n
I

k1
i
+ an
e

k1
i
_
+ a

f

k
i
,

D
I

x
2
n
I

k
i 1
+
_
2
D
I

x
2
+
1
t
_
n
I

k
i
+

b
t
n
e

k
i

D
I

x
2
n
I

k
i +1
=
1
t
_
n
I

k1
i
+

bn
e

k1
i
_
+

b

f

k
i
,

. . . =. . .

D
I

3
x
2
n
I

k
N2
+
_
2
D
I

3
x
2
+
1
t
_
n
I

k
N1
+
a
t
n
e

k
N1
=
1
t
_
n
I

k1
i
+ an
e

k1
i
_
+ a

f

k
N1
+
D
I

3
x
2
n
I

3
_
d, t
k
_
,

D
I

x
2
n
I

k
N2
+
_
2
D
I

x
2
+
1
t
_
n
I

k
N1
+

b
t
n
e

k
N1
=
1
t
_
n
I

k1
i
+

b n
e

k1
i
_
+

b

f

k
N1
+
D
I

3
x
2
n
I

_
d, t
k
_
(22)
with
a =
1
2
p
, (23a)

b =
3
2
p
. (23b)
4. Numerical model for electron conductivity in
nano-structured CNT semiconductors
The measured capacitance, which is believed to be a chemical
type in nature as shown below, is affected by a number
of parameters, as shown in gure 1 [29, 30]. Process (B)
indicates polarization at the transparent conducting substrate
(TCS)electrolyte interface, and (C) indicates the Helmholtz
layer at the oxideelectrolyte interface. The former effect is
important when the electron density in the semiconductor
5
Phys. Scr. 87 (2013) 035703 Y Gacemi et al
Figure 2. Schematics of the capacitive contributions in a DSSC:
(A) Chemical capacitance due to increasing chemical potential
(concentration) of electrons in the CNT phase, obtained when the
electrode potential, V, displaces the electron Fermi level, E
Fn
, with
respect to the lower edge of the conduction band, E
c
, in the
semiconductor nanoparticles. (B) Electrostatic capacitance of the
Helmholtz layer (and semiconductor band-bending) at the interface
between the exposed surface of the transparent conducting oxide
substrate and the electrolyte. (C) Electrostatic capacitance at the
Helmholtz layer at the oxideelectrolyte interface.
is low [31] and the latter when the density is very high
with semiconductor band unpinning. Both contributions can
be thought of as ordinary electrostatic capacitors, where the
charges in two highly conducting plates sustain an electrical
eld in between.
In the intermediate range of Fermi level variation, a
different kind of capacitive effect is found, as shown in section
(A) of gure 2. The semiconductor bands are pinned, and
the charge accumulation is related to the displacement of the
Fermi level position with respect to the conduction band edge.
This means variation of the chemical potential of electrons as

n
=
n
. Hence, the increment of charge (both electronic
and ionic) occurs inside the nano-structured electrode with no
concomitant electrical eld variation therein. This is because
the electrical eld is shielded near the TCS [31]. Therefore,
free energy storage in the capacitor is due to chemical rather
than electrostatic energy. Therefore, it is a chemical capacitor
rather than an electrostatic one. The chemical capacitance
((A) in gure 2) is a major feature in CNT nano-structured
electrodes. Besides, the chemical capacitance is a concept
of crucial signicance for solar cell applications, because it
properly describes the splitting of Fermi levels caused by
excitation of carriers in the light absorber material [30, 32,
33]. Considering the variation of the electron density upon a
change in local chemical potential in a DSSC, the chemical
capacitance occurs. Two components in equation (24) may be
distinguished [34]. The rst is related to the free conduction
band electrons.
C
(cb)
ch
=q
2
n
c
k
B
T
=q
2
n
c

n
, (24)
where C
(cb)
ch
is the chemical capacitance in the conduction
band; n
c
is the conduction band electron density; k
B
is the
Boltzmann constant and T is the temperature (K).
To analyse these questions a relatively simple kinetic
model is outlined for diffusion, trapping and interfacial
charge transfer of electron carriers in a nano-structured
semiconductor permeated with a redox electrolyte. We will
use the MT model for transport and charge transfer illustrated
earlier [1618]. This model is adapted to nano-structured
semiconductors from a wide experience on disordered
semiconductors.
In the context of the MT model, the electron transport is
carried out by a single kind of state, the extended states of the
conduction band. Carriers trapped in localized states do not
contribute to the dc conductivity until they are released again.
The kinetic transport equations are stated in the MT model for
a single kind of trap, involving the equations of conservation
for free and trapped electrons [30]:
n
c
t
=
J
e
x
n
c
[1 f
L
] + f
L
, (25)
where J
e
is the electron ux and f
L
is the fractional occupancy
(n
L
= N
L
f
L
, where N
L
is the density of traps); is the
symmetry coefcient; and is the rate constant for electron
thermal release from the trap to the conduction band.
As explained before, diffusive transport of electrons
within the CNT lm towards the TCO is considered. Equation
(26) relates the electron ux, J
e
, at any position x to the
gradient of electron concentration across the CNT layer, n
e
,
by means of the electron diffusion coefcient, D
e
in Ficks
law [22, 30]
J
e
=D
e
n
c
x
. (26)
The rate constant for electron capture is determined by the
thermal velocity of free electrons, , the electron capture cross
section of the trap, s
n
, and the overall density of traps, N
L
, as
= N
L
s
n
, (27)
where N
L
is the total density of localized sites.
The rate constant for electron thermal release from
the trap to the conduction band, , is described by the
ShockleyReadHall statistics
= N
c
exp [(E
c
E
L
)/k
B
T] , (28)
where E
c
is the lower band edge energy, E
L
is the energy
of the localized state in the band gap and N
c
is the effective
density of conduction band states. The occupancies, f
L
, in the
two kinds of states are given explicitly by
f
L
=
1
1 +e
(E
L

n
)/k
B
T
. (29)
Note that, in equation (29), the Fermi level
n
can be
maintained at a value different from the redox potential in
solution, E
redox
[30].
In the one-dimensional case, considering the
approximation of the theory of equations, electron
conductivity transfer in dimensionless form can be written as
follows:
n
c
|
k
i
n
c
|
k1
i
t
= D
e
n
c
|
k
i +1
2 n
c
|
k
i
+ n
c
|
k
i 1
x
2
[1 f
L
] n
c
|
k
i
+ for i =1, . . . , M 1. (30)
In the inner nodes of the mesh, for the spatial discretization
of equations (30) of electronic conductivity CNT transfer, the
6
Phys. Scr. 87 (2013) 035703 Y Gacemi et al
Table 1. Simulator input parameters.
Parameter Value Reference
A
C
0.158 cm
2
[16]

e
23.6 ms [16]
D
e
(electrode TiO
2
) 1.10 10
4
cm
2
s
1
[16]

e
(electrode CNT) 10
8
cm
2
V
1
s
1
[14]
D
e
(electrode CNT)
k.T
e

e
[14]
D
I
8.5 10
6
cm
2
s
1
[23]
D
I

3
8.5 10
6
cm
2
s
1
[23]
N
CB
1.0 10
21
cm
3
[16]

inj
0.90 [16]
() 1000 cm
1
[16]

p
5% [37]
() 1.0 10
17
cm
2
s
1
[38]
m
e
5.6 m
e
[23]
Resistivity (CNT) (300 K) 0.1 cm [14]
T 298 K
E
CB
E
redox
0.93 eV [16]
n
0
I

3
2.71 0
20
cm
3
[23]
n
0
I

3
3.01 10
19
cm
3
[23]
n
0
e
10 10
10
cm
3
[23]
central differences are used. Therefore
_
_
_
_
_
_
_
_
r r 0 . 0 0
r r r . 0 0
0 r r r . 0
. . . . . .
0 0 0 . r r
r r
_

_
_
_
_
_
_
_
_
_
n
c
|
k
1
n
c
|
k
2
n
c
|
k
3
.
n
c
|
k
M2
n
c
|
k
M1
_

_
=
_
_
_
_
_
_
_
_
n
c
|
k1
1
+n
c
_
0, t
k
_
+t
n
c
|
k1
2
+t
n
c
|
k1
3
+t
.
n
c
|
k1
M2
+t
n
c
|
k1
M1
+n
c
_
M, t
k
_
+t
_

_
. (31)
Another important quantity for many applications is the
electron conductivity, which can be simulated in the steady
state as reported elsewhere. Using equation (24), the
conductivity related to the electron diffusion process,
n
, can
be obtained from the generalized Einstein relation where
n
is the chemical potential of electrons [30, 34] as

n
=q
2
n
c

n
D
0
=C
(cb)
ch
D
0
, (32)
where D
0
is the constant diffusion coefcient for free
electrons.
5. Results and discussion
In order to validate the present numerical model, the
simulation results are compared with the numerical results
in the literature, particularly with TiO
2
-based DSSC
performance results reported by Andrade et al [16]. All input
parameters used in the simulation are shown in table 1.
Figure 3 compares the evolution of the transient electron
density prole obtained from the present simulation with the
numerical results of the FDM. The plot shows that as the
electron density distribution increases, the diffusion of the
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x 10
-4
0
1
2
3
4
5
x 10
17
x [cm]
n
e
-

[
c
m
-
3
]


CNT-based solar cell (our approach)
TiO
2
-based solar cell Ref [16]
Figure 3. The distribution of the electrons within the simulated
1 10
4
cm thick active layer in CNT- and TiO
2
-based DSSCs.
tri-iodide towards the electrode becomes more limiting. This
is primarily due to their low initial concentration, with the
limited density of 4.6 10
17
cm
2
obtained for this case. The
plot shows very good agreement with the numerical results
obtained from FDM which forms the basis of the present
model. Parametric studies based on the validated model are
discussed here. Figure 3 shows the evolution of the electron
density proles under short-circuit conditions before reaching
the steady-state condition.
The electron density proles during the rst micrometers
of the TiO
2
and CNT lm steadily increase, becoming
more at afterwards. The active layer, presented by
the nite difference method, is electrically modelled
as a one-dimensional pseudo-homogeneous layer. The
electro-active charge carriers included in the model are
photo-generated free electrons (injected in nano-porous
CNT), iodide and tri-iodide ions in the electrolyte. The
structure of the DSSC is rst divided into two different
regions: the active layer (a mixture of electrolyte and
nano-pores covered with dye which is treated as the
pseudo-homogeneous layer) and the bulk electrolyte layer.
Figures 35 show the distribution of the electrons, iodide
and tri-iodide ions within the simulated 1 10
4
cm-thick
active layer of DSSC under the short-circuit operation
conditions. Figure 3 shows that the electron concentration
distribution is much smaller under short-circuit conditions,
since most of electrons reach the front contact. The rst few
micrometres of the CNT contribute most to the total J
SC
,
while electrons generated deeper in the active layer partly
recombine with tri-iodide ions. Therefore under short-circuit
conditions, the electron concentration almost equals zero
at the front contact and monotonically increases along the
positive x-direction. I

ions are normally generated at the

counter-electrode. Therefore, the concentration of I

ions
monotonically decreases with decreasing x, gure 4. The role
of iodide is to restore the positively charged photo-excited
dye into its ground state. Consequently, under short-circuit
conditions, the concentration of I

ions is smallest near the

working electrode.
On the other hand, iodide could also be formed
by a recombination process, especially under open-circuit
conditions. Therefore, the concentration of I

ions becomes
7
Phys. Scr. 87 (2013) 035703 Y Gacemi et al
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x 10
-4
3
3.5
4
4.5
5
5.5
6
6.5
x 10
19
x [cm]

n

io
d
id
e

[
c
m
-
3
]

Figure 4. The distribution of the iodide ions within the simulated
1 10
4
cm thick active layer of the DSSC.
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x 10
-4
1.6
1.8
2
2.2
2.4
2.6
2.8
x 10
19
x [cm]
n

t
r
i-
io
d
id
e

[
c
m
-
3
]
Figure 5. The distribution of the tri-iodide ions within the
simulated 1 10
4
cm thick active layer of the DSSC.
higher near the counter-electrode. The opposite is true for
tri-iodide ions, which are formed at the working electrode
and then diffuse towards the counter-electrode, as shown in
gure 5. At the counter-electrode interface, the tri-iodide
ions may recombine with free electrons. Therefore the
concentration of tri-iodide ions monotonically decreases with
increasing x.
The conductivity distribution proles for CNT and
TiO
2
electrodes were studied. Conductivity prole results
for CNT and TiO
2
electrodes are shown in gures 6
and 7, respectively. The conductivity values were calculated
by equations (31) and (32), using the nite-difference
method simulation of the standard DSSC conguration.
For the CNT case, gure 6 indicates that the conductivity
of the semiconductor lm varies over more than eight
orders of magnitude, up to a maximum of 4.4 10
4
(
1
cm
1
) due to electron accumulation. As the electron
concentration accumulates, at voltages less positive than
the open-circuit voltage, an increase in conductivity is
observed.
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x 10
-3
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
x 10
-4
x [cm]
s
i
g
m
a
s
c

[
o
h
m
-
1
.
c
m
-
1
]
Electron Conductivity in Nanoporous CNT
Figure 6. Evolution of electron conductivity in nano-porous CNT.
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x 10
-3
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
x 10
-4
x [cm]
s
i
g
m
a
s
c

[
o
h
m
-
1
.
c
m
-
1
]
Electron Conductivity in Nanoporous TiO
2
Figure 7. Evolution of electron conductivity in nano-porous TiO
2
.
It can be concluded that Ohmic contributions to the total
current resulting from internal resistances, conductivity and
diffusion affect the current in regions of larger positive or
negative voltages. No signicant similar inuence appears
under short-circuit current conditions. Interfacial reactions,
dye coverage and total dye concentration do affect the
short-circuit current. In the case of the interfacial rate
constants, it appears that the total current is more inuenced
by the injection rate and electron returning rate than by any
other interfacial reaction.
The distribution of the currentvoltage (JV)
characteristics for DSSC having different series resistances
(A
C
is the cell area, see table 1) can now be discussed. Under
short-circuit conditions, the (total) electron density, at the
working electrode (x =0) and at zero time, is considered
to be equal to the electron density at zero photovoltage,
n
0
=n(x =0, V =0, t =0) =n(x =0, V =0, t ). Under
short-circuit conditions, electrons are easily extracted
as a photocurrent and none of them is drawn to the
counter-electrode directly. Therefore, the boundary conditions
8
Phys. Scr. 87 (2013) 035703 Y Gacemi et al
are
n(0) =n
0
=
_

E
c
f
L
(E)N(E) dE (33)
and
_
dn
e
dx
_
x=d
=0. (34)
The short-circuit current density J
SC
can thus be obtained
as
J
SC
=
_
qL()[L() cosh(d/L) +sinh(d/L)
+L()exp (dx)]
_
(1 L
2
()
2
) cosh(d/L)
, (35)
where q is the charge of an electron; L is the electron diffusion
length that equals

D
e
; and d is the thin lm thickness
[35, 36].
Cells with an external resistive load can be modelled if
an appropriate functionality for the electron density at the
working electrode is taken into account. In the presence of
an applied voltage or under higher illumination intensity, the
electron density in the lm increases. Here, we compute the
electron density as a function of voltage at x =0, n
e
(V), as
follows:
n
e
=n
0
exp (e V/k
B
T), (36)
where is a parameter that reects the average depth of
the distribution of the trap state energy below the conduction
band.
For each dened external current density the cell
voltage is calculated using equation (37), where V denotes
the cells voltage and E
R
(d) the redox potential at the
counter-electrode. The E
n
F
(0) is the Fermi level of the CNT
at the TCOCNT interface (x =0), which is determined from
the concentration of free electrons at the TCOCNT interface,
n
e
(0), equation (38). The N
CB
is the effective density of states
in the CNT conduction band (equation (39)), where m

e
is the
effective electron mass and h is Plancks constant [22, 23]:
V =
1
e
_
E
n
F
(0) E
R
(d)
_
, (37)
E
n
F
(0) = E
CB
+k
B
T ln
n
e
(0)
N
CB
, (38)
N
CB
=2
_
2m

e
k
B
T
h
2
_
3/2
. (39)
The presented model, which was implemented in a
thin lm solar cell simulator [1, 23], permits the steady-
state simulation of the complete JV characteristics,
depth-dependent concentration of electro-active spices and
their current densities in a DSSC. The numerical solution
of the continuity equation (equation (8)), in combination
with equations (36) and (37), and the boundary conditions,
produces currentvoltage curves that t the diode equation
with an ideality factor of unity. Thus, the solar cell
behaves as an ideal diode at different series resistances. The
calculated JV characteristics of illuminated TiO
2
-DSSC [16]
and CNT-DSSC-based solar cells (100 mWcm
2
, AM
1.5
) for
different series resistances of TCO layer were introduced into
the idealized simulated photo JV characteristics. The results
are presented in gures 8 and 9.
0 100 200 300 400 500 600 700 800
0
2
4
6
8
10
12
V [mV]
J

[
m
A
.
c
m
-
2
]
currentvoltage characteristic
Rs = 0 ohm
Rs = 4 ohm
Rs = 8 ohm
Figure 8. Calculated photo JV characteristics for
TiO
2
-DSSC-based solar cells with different series resistances of the
TCO layer using the input parameters of [16].
0 100 200 300 400 500 600 700
0
2
4
6
8
10
12
14
16
18
V [mV]
J

[
m
A
.
c
m
-
2
]
currentvoltage characteristic
Rs = 0 ohm
Rs = 4 ohm
Rs = 8 ohm
Figure 9. Calculated photo JV characteristics for
CNT-DSSC-based solar cell having different series resistances (our
approach).
Based on simulation results in a simple electrical
model the calculated short-circuit current density (J
SC
) is
18.8 mAcm
2
for CNT-based DSSC, compared with the values
for TiO
2
-based based DSSC which are generally about
12.2 mAcm
2
. The calculated open-circuit voltage (V
OC
) is
700 mV for CNT-based DSSC, which is less than the V
OC
for TiO
2
-based DSSC. The FF was 69.30% for CNT-based
DSSC, when the idealized cell without TCO resistance
was simulated (R
S
=0 ). The conversion efciency of
simulation results in a CNT-based solar cell without additional
series resistance was 8.29%, compared with 7.02% for
the TiO
2
-based counterpart. The difference is in agreement
with expectations since the material parameters used in
simulation are not optimized yet. Performance parameters
for the two cell types are summarized in table 2 (entry 1).
Unlike polycrystalline-based solar cells which exhibit carrier
electronhole recombination, which limits their efciency, the
CNT matrix (in CNT-based cells) serves as the conductor
for majority carriers and prevents such a recombination. That
9
Phys. Scr. 87 (2013) 035703 Y Gacemi et al
Table 2. Performance parameters of simulated DSSC having different series resistances for CNT- and TiO
2
-based systems.
J
SC
(mAcm
2
) V
OC
(mV) FF (%) (%)
CNT-based TiO
2
-based CNT-based TiO
2
-based CNT-based TiO
2
-based CNT-based TiO
2
-based
DSSC DSSC DSSC DSSC DSSC DSC DSSC DSSC
R
S
() (our approach) ([16]) (our approach) ([16]) (our approach) ([16]) (our approach) ([16])
0 18.8 12.2 700 740 69.30 68.91 8.29 7.02
4 18.8 12.2 700 740 62.68 62.95 7.49 6.11
8 18.8 12.2 700 740 54.25 60.16 6.49 5.70
is because of special conductivity and visible-near infrared
transparency of the CNT.
Different series resistances were then introduced into the
idealized simulated photo JV characteristics for CNT-based
DSSC. The results are again shown in gures 8 and 9 and
are summarized in table 2 (entries 23). As expected, the
J
SC
and V
OC
values did not change for either cell. In the
CNT-based cell, the FF decreased from 69.30 to 62.68%
when R
S
=4 was added, and to 54.25% when R
S
=8
was added. Consequently, the initial conversion efciency was
reduced from 8.29% to 7.49 and 6.49% when R
S
=4 and 8
were added, respectively. The TiO
2
-based cell also exhibited
lowering in values of FF and conversion efciency by adding
series resistances, as shown in table 2.
6. Conclusion
A mathematical model for a new type of photovoltaic solar
cell based on dye-sensitized CT electrodes is discussed. In
contrast to conventional solar cells, where light absorption
is due to band gap excitation of the semiconductor itself,
the CNT with its wide band gap is transparent in the visible
spectrum. While the efciency of conventional polycrystalline
solar cells is limited by charge carrier recombination at grain
boundaries, bulk defects and impurities, the CNT serves only
as the conductor for majority carriers (injected electrons),
so that electronhole recombination in the semiconductor is
absent. The unique characteristics of carbon lms as window
electrodes are due to their excellent conductivity and good
transparency in both visible and near-infrared regions.
The model describes charge transfer and charge transport
within the porous CNT electrode of the DSSC.
Charge transfer at the semiconductordyeelectrolyte
interface within a DSSC is also described. The model is based
on solving the continuity equation for electrons, using the
numerical nite difference method. The equations were used
to describe the charge transport within the electrolyte lled
pores and the porous semiconductor.
Acknowledgments
YG and AC acknowledge Universit e Amar Telidji de
Laghouat, Alg erie, for nancial support. HSH acknowledges
the Al-Maqdisi Project for help.
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