Current Applied Physics 12 (2012) 238e246

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Current Applied Physics

journal homepage: www.elsevier.com/locate/cap

Analysis of electron recombination in dye-sensitized solar cell

Miha Filipi

c*, Marko Berginc, Franc Smole, Marko Topi

c
University of Ljubljana, Faculty of Electrical Engineering, Tr
za
ska 25, SI-1000 Ljubljana, Slovenia

a r t i c l e i n f o a b s t r a c t

Article history: A steady-state numerical model of dye-sensitized solar cell is based on continuity and transport equa-
Received 12 January 2011 tions for electrons, iodide and triiodide ions. The cell model consists of an active layer, where photo-
Received in revised form voltaic effect including diffusion of electrons in mesoporous TiO2 and ions in electrolyte takes place, and
7 June 2011
a bulk electrolyte layer, where only ions diffuse. Exponential distribution of trap states in TiO2 and
Accepted 13 June 2011
Gaussian distributions of energy levels in the electrolyte within active layer are included in modeling of
Available online 21 June 2011
the recombination dynamics, according to Shockley-Read-Hall statistics and Marcus-Gerischer electron
transfer theory. Recombinations at the front contact and a voltage drop at the platinum covered back
Keywords:
Dye-sensitized solar cell
contact are included in the model. Simulation results are compared with the measured currentevoltage
Electron recombinations characteristics at different light intensities. In particular, light intensity dependence of open circuit
Numerical model voltage is studied over 4 decades. Optimization of cell efficiency regarding active layer and electrolyte
layer thickness is carried out. Simulation results show that best efficiency is achieved when electrolyte
layer thickness is minimized as much as possible and that active layer thickness is traded off with respect
to recombination rates and/or diffusion limited current determined with the selection of the electrolyte.
Ó 2011 Elsevier B.V. All rights reserved.

1. Introduction
Dye-sensitized solar cell (DSSC) based on dyed mesoporous
semiconductor surrounded with electrolyte or other hole con-
ducting media is a promising device for efficient, low-cost, stable
and sustainable solar energy conversion. Current record efficiencies
for laboratory scale DSSC are above 12% [1]. To further increase
efficiency, the parameters that influence cell performance need to
be optimized. Numerical simulations based on models that
describe physical and chemical processes that govern DSSC oper-
ation are useful in finding the optimal cell design.
Södergren et al. [2] developed analytical model based on
diffusion of electrons in TiO2. Papageorgiou et al. [3] included
diffusion of electrolyte species and effects of porosity of meso-
porous film. Ferber et al. presented numerical models treating
electrolyte permeated dye covered TiO2 as quasi-homogeneous
medium [4] as well as a 2D model with simplified TiO2 structure
[5]. Effects of monoenergetic trap states in the band gap were
considered by Usami and Ozaki [6]. Nelson and Chandler [7] used
continuous-time random walk simulations to describe electron
transport. Lee et al. [8] developed closed-form model with detailed
description of interface reactions. Layer of bulk electrolyte was
studied by Oda et al. [9]. Penny et al. developed detailed interfacial
* Corresponding author. Tel.: þ386 1 4768 276; fax: þ386 1 4264 630.
E-mail address: miha.filipic@fe.uni-lj.si (M. Filipi

c).
reaction model [10] and applied it to anodic half cell of DSSC [11].
Chen et al. [12] modeled the effects of partial shading of DSSC on its
performance. Villanueva-cab et al. [13,14] presented models based
on continuity equation for electrons and considered trapping
effects as well as different recombination dynamics. Recently
Barnes et al. developed a time dependant numerical model of
a complete DSSC [15]. In our previous work [16] we focused on
optical modeling of DSSC.
Our model includes both the active layer and the bulk electro-
lyte layer in the DSSC. Effects of transparent conductive oxide (TCO)
at the front contact and platinum at the back contact are considered
when currentevoltage characteristics are calculated. Recombina-
tions are assumed to be affected by an exponential distribution of
trap states in the band gap of TiO2. Shockley-Read-Hall (SRH)
statistics [17] are applied to determine trapping and detrapping
rates and Marcus-Gerischer (MG) theory [18e20] is considered
when determining electron transfer rate between the semi-
conductor and ions in the electrolyte.
2. Implemented models
2.1. Basic device operation and device structure
First step of energy conversion in DSSC is incident light
absorption by a monolayer of dye molecules covering mesoporous
semiconductor, usually TiO2. After absorption dye molecules inject
electrons from their excited states into TiO2 conduction band. In

1567-1739/$ e see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cap.2011.06.011
 M. Filipi
c et al. / Current Applied Physics 12 (2012) 238e246 239

TiO2 the electrons travel mainly by diffusion to the front TCO

contact. Following the injection the dye is regenerated by iodide 1 djA;i
 ¼ Gi  R i ; (3)
ions, which themselves are oxidized to triiodide ions. Ions of the q dx
iodide and triiodide diffuse between dye molecules and platinum
where jA,i are current densities in the active layer, Gi are the
covered back TCO contact. Platinum acts as efficient catalyst in the
generation rates and Ri are the recombination rates of the corre-
electron transfer at the back contact where triiodide ions are
sponding particles represented by index i ¼ e, I, I3 and q is the
reduced to iodide ions. Loss mechanisms of DSSC include recom-
elementary charge. We assume there are no electrons in the bulk
bination of electrons with triiodide ions at the uncovered surface of
electrolyte, therefore generations or recombinations do not occur,
TiO2 or front TCO that electrolyte reaches and dye cations.
and the continuity equations are
We model DSSC as consisting of two layers shown in Fig. 1. First
layer is the active layer (0 < x  D in Fig. 1), where light absorption 1 djB;i
takes place and conduction band electrons diffuse to the front TCO  ¼ 0; (4)
q dx
contact. Electric field of electrons is assumed to be effectively
screened by cations in the electrolyte, and the drift component of where jB,i are current densities in the bulk electrolyte layer. Diffu-
electron transport is neglected in the model. Active layer is sion is considered to be the main transport process in the DSSC and
modeled as pseudo homogeneous mixture of TiO2/dye/electrolyte, current densities in the active layer are described by transport
where generation and recombination of particles takes place. equations
Second layer is the bulk electrolyte layer (D < x  L in Fig. 1), where
only ion diffusion is present. dnA;i
jA;i ¼ qDA;i ; (5)
dx
where DA,i are the diffusion coefficients of corresponding charge
2.2. Model equations
carriers and nA,i are their densities in the active layer. In the bulk
electrolyte layer we have
Basic model framework is based on work by Ferber et al. [4].
Injection of excited state electrons into TiO2 conduction band (ps dnB;i
range) and dye regeneration (ns range) are fast reactions [21], jB;i ¼ qDB;i ; (6)
dx
therefore we assume that each absorption of a photon is simulta-
neous with electron injection and dye regeneration according to where DB,i are diffusion coefficients of ions in the bulk electrolyte
chemical reaction layer. Eq. (6) applies only to iodide and triiodide ions (i ¼ I, I3 )
since no free electrons are present (nB,e ¼ 0, jB,e ¼ 0) in the bulk
3I  /I3 þ 2e : (1) electrolyte layer.

We neglect recombinations of electrons with oxidized dye

2.3. Boundary conditions
molecules, since regeneration of the dye from iodide ions is
assumed to be more efficient. Under these assumptions the net
In order to get a unique solution to the system of differential
generation (Ge  Re) of two electrons is accompanied by net
equations, a set of boundary conditions is required. Electron density
generation of one triiodide ion and net recombination of three
at the front contact nA,e(0) is determined by the applied voltage
iodide ions [4,9]
[4,13]. The voltage is defined as the difference between electro-
1
 1
 chemical potentials, identified as the quasi-Fermi level of electrons
ðGe  Re Þ ¼ GI3  RI3 ¼ RI  GI : (2) EF(0) at the front contact and the redox potential Eredox(L) at the
2 3
back contact
We model DSSC using continuity equations for the particles
involved in the cell operation, namely electrons e, iodide ions I and qU ¼ EF ð0Þ  Eredox ðLÞ: (7)
triiodide ions I3 at steady-state and in one dimension. In the active
Redox potential (physical energy scale) for the reaction in Eq. (1)
layer photons are absorbed and the continuity equations are
is calculated according to the Nernst equation
!
0 kT nI ðLÞ=nst
Eredox ðLÞ ¼ Eredox  ln
3 3 ; (8)
2
nI ðLÞ=nst
0
where Eredox is standard redox potential measured at concentration
nst (1 M). Electron concentration at the front contact determines
the quasi-Fermi level

nA;e ð0Þ
EF ð0Þ ¼ ECB þ kTln ; (9)
NCB
where NCB is the effective concentration of conduction band states
in TiO2, ECB is the edge of TiO2 conduction band, k is the Boltzmann
constant, and T is temperature. Using Eqs. (7e9) we can express
electron concentration at the front contact in terms of applied
voltage.
At the end of active layer (x ¼ D) electrons cannot leave the
mesoporous TiO2 and their current density is zero
Fig. 1. DSSC structure with active layer (0 < x  D) and bulk electrolyte layer
(D < x  L). jA;e ðDÞ ¼ 0: (10)
240 M. Filipi
c et al. / Current Applied Physics 12 (2012) 238e246

At the front contact some of the electrons that already left TiO2
recombine with triiodide ions through the TCO. Taking into account
reaction (1) the recombination current jTCO (see Section 2.5)
determines the value of triiodide and iodide current densities at the
front contact

3
jA;I ð0Þ ¼  j ; (11)
2 TCO

1
jA;I3 ð0Þ ¼ j : (12)
2 TCO
Densities of iodide and triiodide ions in the active layer are
dependent on porosity p of TiO2, and jump discontinuously at the
border of active layer and bulk electrolyte, where TiO2 does not
occupy any volume (i ¼ I, I3 )

nA;i ðDÞ ¼ p$nB;i ðDÞ: (13)

Current densities of ions at the border remain continuous

(i ¼ I, I3 )

jA;i ðDÞ ¼ jB;i ðDÞ: (14)

Total number of particles present in the cell remains constant

and we describe the conservation of iodine nuclei and electrons by
two integral boundary conditions *
Fig. 2. Recombination paths in DSSC Edye 0
is excided dye state, Edye is ground dye state,
ECB is conduction band edge, Eox is most probable energy of oxidized ions, Ered is most
ZD  ZL   probable energy of reduced ions, Eredox is standard redox potential and l is reorgan-
0

1 1 izational energy.
nA;I3 þ nA;I dx þ nB;I3 þ nB;I dx
3 3
0 D
   
1 1 In order to obtain the difference GeRe we need to know at what
¼ n0;I3 þ n0;I pD þ n0;I3 þ n0;I ðL  DÞ; (15)
3 3 rates the transitions shown in Fig. 2 occur. Rate of transition (a) is
determined by the optical generation rate GL of conduction band
ZD  ZL   electrons and is calculated with optical simulator SunShine [16,24].
1 1 1 Trapping and detrapping rates (b and c) of conduction band elec-
nA;e þ nA;I dx þ nB;I dx
2 3 3 trons are calculated according to Shockley-Read-Hall recombina-
0 D
  tion statistics [17]. Electron transfers rates between the
1 1 1 semiconductor and ions in the electrolyte (d, e and f) are modeled
¼ n þ p n0;I D þ n0;I ðL  DÞ; (16)
2 0;e 3 3 according to Marcus-Gerischer theory (MG) [18e20].
where n0,i are equilibrium concentrations of involved particles Electrons in the conduction band can be trapped by an expo-
(i ¼ e, I, I3 ). nential distribution of localized states in the band gap, from where
they can be thermally released back to the conduction band, or they
can recombine with the triiodide ions in the electrolyte. Expo-
nential distribution of trap states is assumed, although generally
2.4. Generation and recombination rates any distribution of trap states can be included:

Interfacial electron transfer reactions are assumed to consist of  

aNt aðE  Ecb Þ
a single electron step, and effects of iodine radicals [22,23] in gðEÞ ¼ exp ; (17)
electron transfer process are neglected. We need to determine
kT kT
generation and recombination terms only for electrons, since where E is energy of the trap below the conduction band, a is
generations and recombinations of iodide and triiodide ions taking a parameter that determines the decline of the trap distribution,
place in the active layer are obtained by Eq. (2). Relevant energy and Nt is the density of traps. Trapping from the conduction band to
levels and possible recombination paths for electrons are shown in the trap states is determined by
0
Fig. 2 where Edye *
is ground dye state, Edye is excited dye state, Eox is
most probable energy level of oxidized (triiodide) ions, and Ered is
dRSRH;e ðEÞ ¼ ktrap nA;e gðEÞð1  f ðEÞÞdE; (18)
most probable energy level of reduced (iodide) ions. Transition (a)
is the simultaneous photon absorption, electron injection and dye where ktrap is the rate of trapping, and f(E) is occupancy function of
regeneration. Once electrons are present in the conduction band trap states. The term g(E)(1  f(E)) represents the density of
they can be trapped (b) and released (c) from a distribution of trap unoccupied trap states per unit energy. The thermal release of
states in the semiconductor band gap. Transition (d) shows trapped electrons back to the conduction band is determined by
recombinations of conduction band electrons with the oxidized
redox ions. Electrons trapped in the semiconductor band gap can dGSRH;e ðEÞ ¼ krelease gðEÞf ðEÞdE; (19)
also recombine with triiodide which is represented by transition
(e). Transition (f) corresponds to injection of electrons from reduced where krelease determines the probability of thermal release, and
ions into the trap states in the semiconductor band gap. g(E)f(E) represents density of occupied trap states per unit energy.
 M. Filipi
c et al. / Current Applied Physics 12 (2012) 238e246 241

In thermal equilibrium the trapping and detrapping rates have to ZECB

be equal, and the occupancy function is described by the Fer- RMG;e ¼ kox ðEÞgðEÞf ðEÞdE; (32)
mieDirac function [19]. From this a connection between ktrap and
EVB
krelease can be deduced [17]

krelease ¼ n1 ðEÞ$ktrap ; (20) ZECB

GMG;e ¼ kred ðEÞgðEÞð1  f ðEÞÞdE; (33)
 
E  ECB EVB
n1 ðEÞ ¼ NCB exp : (21)
kT
where EVB is the edge valence band of TiO2. Electrons at conduction
The MG theory states that the rates of isoenergetic electron band can also directly recombine with the triiodide ions. Only
transfer between semiconductor and the electrolyte depend on the electron transfers at the energy of the bottom of conduction band
densities of unoccupied (Dox) and occupied electronic states (Dred) are considered and no integration is necessary
at the energy level where electron transfer occurs [19,20]
! RCB;e ¼ nA;e kox ðECB Þ: (34)
nA;I3 ðE  Eox Þ2
Dox ðEÞ ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffi exp  ; (22) Generation and recombination rates of conduction band elec-
4plkT 4lkT trons are determined by transitions (a, b, c and d) in Fig. 2, and by
summation of corresponding rates we get generation and recom-
!
nA;I ðE  Ered Þ2 bination terms for electrons
Dred ðEÞ ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffi exp  ; (23)
4plkT 4lkT Ge  Re ¼ GL þ GSRH;e  RSRH;e  RCB;e : (35)
where l is reorganizational energy, Eox ¼ þ l, and
0
Eredox
0
Ered ¼ Eredox  l (see Fig. 2). The recombination of trapped elec-
trons in TiO2 with triiodide ions in electrolyte is defined as
2.5. Front and back contact
dRMG;e ðEÞ ¼ kox ðEÞgðEÞf ðEÞdE; (24)

where kox(E) includes Gaussian distribution of energy levels of Besides active and bulk electrolyte layer the front and back
oxidized ions and ket determines the rate of electron transfer. contacts also affect the cell operation. Back contact must allow for
fast electron transfer to triiodide ions so they can be reduced to
kox ðEÞ ¼ 2kT$ket $Dox ðEÞ: (25) iodide ions that are able to regenerate dye molecules. If this elec-
tron transfer is not fast enough, the voltage drop at this contact
Injection rate from iodide ions into TiO2 band gap states is becomes significant. To increase the rate of electron transfer the
back contact is covered by a layer of catalyst, usually platinum.
dGMG;e ðEÞ ¼ kred ðEÞgðEÞð1  f ðEÞÞdE; (26)
Since the TiO2 structure is mesoporous, the electrolyte pene-
where kred(E) includes Gaussian distribution of energy levels of trates the pores and reaches the front TCO. Electrons that have
reduced ions already reached the front contact can recombine with triiodide
electrons present at the TCO layer [25]. TCO layer is a highly doped
kred ðEÞ ¼ 2kT$ket $Dred ðEÞ: (27) semiconductor and acts like a metal, therefore we can apply But-
lereVolmer equation that describes current density jk dependence
At steady-state the density of trapped electrons in the band gap
on applied voltage Uk at a metal/electrolyte interface
does not change, and the same amount of electrons that enters
(dRSRH,e, dGMG,e) the trap states must leave (dGSRH,e, dRMG,e) them     
ð1  bk ÞUk bU
jk ¼ ak jk;0 exp q  exp q k k ; (36)
df kT kT
gðEÞ ¼ dRSRH;e  dGSRH;e  dRMG;e þ dGMG;e ¼ 0: (28)
dt where jk,0 is the exchange current density, bk is symmetry factor
By inserting Eqs. (18, 19, 24 and 26) into Eq. (28) and solving for f and ak determines the effective area of the contact surface reached
we get a steady-state occupation function by the electrolyte. Index k represents different contacts, namely
k ¼ TCO at the front contact and k ¼ Pt at the back contact.
ktrap nA;e þ kred ðEÞ At the back contact UPt equals the voltage applied to the whole
f ðEÞ ¼   : (29)
ktrap nA;e þ n1 ðEÞ þ kox ðEÞ þ kred ðEÞ cell, and surface of platinum contact is assumed to be flat, therefore
aPt ¼ 1. At the front contact the UTCO is determined by the difference
Eqs. (18, 19, 24 and 26) give expressions for electron transitions between the quasi-Fermi level of TCO and the redox potential in
at a fixed energy level. In order to get total contributions from all electrolyte at the front contact. Quasi-Fermi level of TCO is assumed
energy levels these equations have to be integrated through the to be the same as in the TiO2 at the front contact
band gap
qUTCO ¼ EF ð0Þ  Eredox ð0Þ: (37)
ZECB
Eredox(0) is calculated using Eq. (8) but with concentrations
RSRH;e ¼ ktrap nA;e gðEÞð1  f ðEÞÞdE; (30) present at the front contact which results in a small value for UTCO
EVB even when the cell is in short circuit. Only parts of the TCO that are
not covered by the TiO2 are in contact with the electrolyte, there-
fore aTCO < 1. In our case we assume that aTCO is the same as TiO2
ZECB porosity (aTCO ¼ p).
In order to get good agreement with measured currentevoltage
GSRH;e ¼ krelease gðEÞf ðEÞdE; (31)
characteristics, resistances of the TCO layers along with other
EVB possible shunting effects are included as the series Rs and parallel
242 M. Filipi
c et al. / Current Applied Physics 12 (2012) 238e246

Rp resistances in the equivalent circuit of the cell presented in Ref.

[4]. Approximation of series resistance is calculated using 1D
distributed series resistance model shown in Fig. 3
 
1 T1
Rs ¼ 2RTCO þ T2 ; (38)
W 2
where RTCO is sheet resistance of TCO, W is the active layer width, T1
is the length of TCO where current is extracted and T2 is length of
TCO where no current is extracted. Sheet resistance of TCO is 8 U/,
(TCO30-8 from Solaronix), and dimensions of the cell are
W ¼ 8 mm, T1 ¼ 7 mm, T2 ¼ 7 mm, which yields a value of 21 U that
is close to the value of Rs ¼ 19.6 U used to fit the measurement
results.

3. Results and discussion

3.1. Currentevoltage characteristics

Using the presented model the currentevoltage characteristics

under different illumination intensity conditions are simulated.
Simulation results are compared with measured currentevoltage
characteristics of an ionic-liquid based DSSC with D ¼ 13 mm thick Fig. 4. Measured and simulated currentevoltage characteristics of DSSC under
TiO2 active layer and L  D ¼ 9 mm thick bulk electrolyte layer (see different illumination intensities.

Experimental section in Ref. [16]) for 1, 0.5, 0.25 and 0.1 sun (AM1.5)
light intensity in Fig. 4. Besides the varied parameter cell is
measured under standard test conditions (STC: 25  C, AM1.5,
100 mW/cm2). Same input parameters listed in Table 1 are used for
all light intensities.
3.2. Light intensity dependence of open circuit voltage
Fig. 5 shows the light intensity (GL) dependence of open circuit
voltage (UOC). The UOC(GL) characteristic was measured using
a white light emitting diode (LED Bridgelux BXRA-C0603) at cell
temperature of 25  C. Lower light intensities were obtained with
neutral density filters, by increasing the distance between LED and
measured DSSC and/or by decreasing the current supply through
the LED. At lower light intensities special care was taken to elimi-
nate stray light. The UOC(GL) measurements were performed in the
range of four orders of magnitude, starting at 1 sun and reduced
down to 104 sun (from 100 down to 0.01 mW/cm2) (note: the
100 mW/cm2 AM1.5 spectrum in the wavelength range between
300 and 800 nm corresponds to approximately 1.8  1013 photons/
s/cm2).
Measurement shows three distinct regions of UOC(GL) with
different slopes. In order to get good agreement of measurement
and simulation results in the lowest light intensity region (light
intensity < 2  103 sun) a single level (monoenergetic) trap states
had to be included in TiO2 band gap at energy level
Emono ¼ 4.35 eV (0.15 eV above Eredox 0 ) with concentration of
17 3
Nmono ¼ 1.5  10 cm . This deep level of trap states influences
mainly the shape of UOC(GL) in the lowest light intensity region,
while the UOC(GL) shape is not affected in higher light intensity
regions since the trap states become filled. In the second low
intensity region (2  103 sun < light intensity < 2  102 sun)
UOC(GL) is determined by recombinations through exponential
distribution of traps and exchange with ions in electrolyte. Slope in
this region is affected mainly by trap distribution parameter a and
electrolyte reorganizational energy l. Trap concentration Nt and
recombination rate constants ket and ktrap determine where regions
with different slopes start and end but do not influence the slope.
Reorganizational energy l also influences recombination factor for
conduction band electrons (Eqs. (34) and (25)). Increase of l
increases Eox and widens the Gaussian distribution of triiodide ions
and consequently increases recombinations through conduction

Fig. 3. Series resistance model of TCO.

 M. Filipi
c et al. / Current Applied Physics 12 (2012) 238e246 243

Table 1 59 mV/decade [26] which does not agree with the measured slope
Input parameters of the model. of 92 mV/decade. A better fit is obtained if we include the effect of
Parameter Symbol Value recombinations through TCO layer (full line in Fig. 5) with
Electron transfer rate ket 5  1018 cm3/s jTCO,0 ¼ 104 mA/cm2 and bTCO ¼ 0.65 (see Eq. (36)), but this would
Trapping rate ktrap 4  1011 cm3/s suggest that UOC(GL) in the third region is determined mainly by
Reorganizational energy l 0.3 eV recombinations through uncovered TCO at the front contact and
Electron diffusion constant De 3.8  104 cm2/s
not by conduction band recombinations. Another possibility of
Iodide diffusion constant DA;I ; DB;I 2.5  107 cm2/s
Triiodide diffusion constant DA;I3 ; DB;I3 2.5  107 cm2/s influencing the slope in the third region is to include nonlinear
Initial iodide concentration n0I 2.3  1021 cm3 recombination from TiO2 conduction band [27,28]
Initial triiodide concentration n0I 1.2  1020 cm3
3
g
Conduction band ECB 3.6 eV RCB;e ¼ nA;e knonlin ; (39)
Standard redox potential 0
Eredox 4.5 eV
Valence band EVB 6.8 eV
where knonlin is recombination constant for the case of nonlinear
Conduction band effective density of states NCB 3.3  1020 cm3
Total trap concentration Nt 5  1018 cm3
recombinations and g is the exponent that influences the slope of
Trap distribution parameter a 0.24 UOC(GL) [26]. With Eq. (39) good fit in the third region can be
Monoenergetic trap concentration Nmono 1.5  1017 cm3 achieved (not shown in Fig. 5; g ¼ 0.65,
Energy level of monoenergetic trap states Emono 4.35 eV knonlin ¼ 1.5  106 cm3(1g) s1), but it does not give us insight in
Porosity p 0.5
the recombination mechanism.
Series resistance RS 19.6 U
Parallel resistance RP 3.6 kU In the inset of Fig. 5 the measured efficiency of the cell with
Cell area A 0.56 cm2 varying light intensity is shown. Maximum efficiency is measured
Active layer thickness D 13 mm at 0.25 sun light intensity. At light intensities above 0.25 sun the
Electrolyte layer thickness LD 9 mm efficiency decreases due to serial resistance losses and a decrease in
Front contact TCO exchange current density jTCO,0 104 mA/cm2
Back contact Pt exchange current density jPt,0 80 mA/cm2
fill factor. Below 0.25 sun light intensity a decrease of UOC causes
TCO symmetry parameter bTCO 0.65 a fall in the efficiency of the cell.
Pt symmetry parameter bPt 0.5
3.3. Electron densities
band. Increasing l therefore increases the slope of UOC(GL) in the
second region and shifts the start of the third region to lower light Fig. 6 shows a profile of electron density in the active layer at
intensities. short and open circuit for different illumination intensities. At short
In the normal range of light intensities during daylight outdoors circuit the electrons are effectively collected at the front contact,
or indoors (third region e light intensity > 2  102 sun) UOC(GL) is and their concentration is decreasing toward the contact. At open
determined by recombinations through conduction band of TiO2 circuit only recombination currents flow inside the cell. Electrons
(dashed line in Fig. 5). Since the iodide and triiodide ion concen- recombine with triiodide ions in the electrolyte, or enter the front
trations in active layer are higher than electron concentrations the TCO layer and recombine from there. Since at open circuit no
variation of Eredox with light intensity is negligible and does not current flows out of the cell, the current of electrons is compen-
affect the UOC(GL) (variation of Eredox with light intensity is dis- sated by current of triiodide and iodide ions in the electrolyte. At
cussed in the last paragraph of this chapter). For conduction band open circuit UTCO is higher than at short circuit and recombination
recombinations in the third region the slope for constant Eredox is current jTCO cannot be neglected. This recombination current
density causes the electron concentration to start decreasing near
the front contact. In our case (jTCO,0 ¼ 104 mA/cm2 and bTCO ¼ 0.65)
it is a rather small decrease as can be seen in Fig. 6 for open circuit
conditions in the region 0 < x < 1 mm.

Fig. 5. Simulated and measured light intensity dependence of UOC. In the light
intensity region >2  102 sun, simulations with and without front contact recom- Fig. 6. Short circuit and open circuit electron densities under different illumination
binations show different slopes. The inset shows the measured efficiency of the cell conditions. In the region <1 mm a decrease of open circuit concentrations is observed,
with varying light intensity. caused by front TCO/electrolyte contact recombinations.
244 M. Filipi
c et al. / Current Applied Physics 12 (2012) 238e246

3.4. Occupation function

Occupation function f along with trap distribution g determines

the density of trapped electrons in TiO2, which in turn affects
generation and recombination rates. Fig. 7 shows the occupancy of
trap states in the semiconductor band gap which depends only on
the ratio of ket/ktrap. This ratio determines the dominant
process that is changing the trapped electrons density. The
values used to simulate the occupation function are fixed at
nA;I ¼ 2.3  1021 cm3, nA;I3 ¼ 1.2  1020 cm3, nA,e ¼ 4  1018 cm3
roughly corresponding to open circuit conditions in the measured
cell. Other values are taken from Table 1. For high values of ratio
(ket [ ktrap) the dominant process is exchange of electrons
between trap states in the semiconductor and ions in the electro-
lyte. For low values (ket  ktrap) the dominant process is trapping/
detrapping between traps states and conduction band of TiO2. Near
the conduction band the occupation is low due to high detrapping
rate. Below the standard redox level at 4.5 eV (vacuum level
energy scale) the trap states are almost full because injection from
the electrolyte to the semiconductor is dominant. Between the
conduction band and redox potential the occupancy function
depends on the ratio between exchange with the conduction band Fig. 8. Shockley-Read-Hall recombination and generation rates between trap states
and exchange with the electrolyte. For value l ¼ 0.3 eV the most and conduction band of TiO2 for different values of ket and ktrap.
probable energy level of triiodide ions Eox lies at 4.2 eV where
occupation function quickly decreases with increasing ket/ktrap detrapping is effective and reduction in number of trapped elec-
ratio. 0
trons at energies above Eredox with increasing ket reduces GSRH for
low values of ktrap when occupation of relevant energy states is low.
3.5. Electron generation and recombination rates through trap For higher values of ktrap decrease of GSRH with rising ket is less
states pronounced since more trap states are occupied.
Fig. 9 presents the effect of ket and ktrap on the exchange of
Fig. 8 presents the effects of ket and ktrap on trapping and electrons with the electrolyte. With increasing ket it is expected that
detrapping rates calculated using Eqs. (30) and (31). Trapping rate RMG and GMG will also increase. Rate of increase is dependent on f
RSRH is not influenced much by ket because it depends on electron and therefore also on ktrap. Inserting Eqs. (25) and (27) into Eq. (29)
concentration in conduction band and unoccupied trap states in the we see that for high ktrap and low ket and also for high ket and low


band gap, but is independent of the energy of the trap state. ktrap f is almost independent of ket dkdf
z0 . For high values of ktrap
et
Occupation function changes mostly around Eox, and this is only
RMG increases with ket with a slope of 1 (logelog plot). This corre-
small part of the all available states in the band gap, so the effect on
sponds to high occupancy where change in ket does not influence f
RSRH is small. On the other hand, releasing from the trap states is
much and the increase of RMG is mainly due to increase of ket (Eqs.
most influential near the conduction band according to factor n1(E)
0 (25) and (32)) and not because of change in f. For low values of ktrap
in Eq. (21). Occupation function changes mostly above Eredox , where
and high values of ket RMG also increases with a slope of 1 but this

Fig. 7. Occupation function for different ratios of ket/ktrap for fixed electron and ion Fig. 9. Marcus-Gerischer recombination and generation rates between trap states in
concentrations corresponding to open circuit conditions. TiO2 and electrolyte for different values of ket and ktrap.
 M. Filipi
c et al. / Current Applied Physics 12 (2012) 238e246 245

time because the occupancy of trap states is low and also not
df
influenced much by ket. For medium values of ktrap dk s0 and slope
et

of RMG is affected by change in f and is less than 1. Injections of

electrons from electrolyte to semiconductor GMG also increase with
ket. For high values of ket the slope of GMG is influenced by changing
f and is higher than 1. For low values of ktrap and high ket exchange
between trap states and electrolyte becomes dominant electron
exchange mechanism. Since we are at steady-state electron
concentration does not change with time and with RSRH and GSRH
small enough RMG and GMG become equal.

3.6. Effects of front and back contact on currentevoltage

characteristic

Currentevoltage characteristics are simulated using parameters

in Table 1 without applying external series and parallel resistances.
Fig. 10 shows the effects of recombinations through the front TCO
contact. At short circuit there is only a small voltage drop between
the front TCO contact and the redox level in the electrolyte.
Although the cell is in short circuit the difference EF(0)  Eredox(0) is
calculated to be 40 mV at 1 sun. With increasing voltage difference
the recombination current increases, and a decrease in the open Fig. 11. Effects of back contact Pt exchange current density jPt,0 on currentevoltage
circuit voltage and the fill factor is present. Higher values of jTCO,0 characteristic.
mean that the kinetics of electron exchange between TCO and
electrolyte are faster and higher recombination current will flow
for the same voltage difference. Efficiencies of the modeled DSSC under STC for electrolyte layer
Effects of jPt,0 are shown in Fig. 11. At open circuit no current thicknesses (LD) of 0, 2, 9, 15 and 30 mm as a function of active
flows through the platinized TCO contact and therefore no voltage layer thickness are presented in Fig. 12. Parameters used in the
drop is present. With increasing current, the voltage drop also simulation are the same as in Table 1. The STC efficiency of the
increases, and the maximum power point (MPP) of the cur- measured cell (L ¼ 22 mm, D ¼ 13 mm) is also plotted in Fig. 12 for
rentevoltage characteristic shifts toward lower values, conse- reference. With increasing active layer thickness amount of absor-
quently fill factor is reduced. For higher values of jPt,0 the voltage bed photons increases therefore generation rate increases.
drop at the back contact becomes less significant, and the shift of Recombinations increase because area where electron transfer
MPP is less pronounced. takes place also increases with active layer thickness and compe-
tition between net generations and net recombinations determines
optimal cell thickness after which cell efficiency starts to decrease.
3.7. Optimization of active and electrolyte layer thickness
Electrolyte layer thickness determines the diffusion limited current
density and the amount of light absorbed in the electrolyte [16,29].
The presented model is used to determine the efficiency of DSSC
as a function of the active layer and electrolyte layer thickness.

Fig. 12. Dependence of STC efficiency on active layer thickness for bulk electrolyte
Fig. 10. Effects of recombinations between front contact TCO and electrolyte on cur- layers (L e D) of 0, 2, 9, 15 and 30 mm. Crosses mark the points of highest efficiency.
rentevoltage characteristic for various front contact TCO exchange current densities jTCO,0. Efficiency of measured cell is shown for reference.
246 M. Filipi
c et al. / Current Applied Physics 12 (2012) 238e246
Plots in Fig. 12 clearly show that highest efficiency can be obtained
by minimizing the electrolyte layer thickness. For 0, 2 and 9 mm
thicknesses the diffusion limited current is higher than current
generated by light and does not influence cell efficiency. For 15 mm
thicknesses diffusion limited current is lower and limits the photo-
generated current when active layer is thick enough to generate
currents comparable to the diffusion limited current. This effect is
even more pronounced for 30 mm electrolyte layer thickness where
diffusion limited current is lowest. For 15 and 30 mm electrolyte
layer thickness current becomes diffusion limited for active layers
thicker than 20 and 10 mm, respectively. Simulation results there-
fore show that optimum active layer thickness is a trade-off
between light harvesting on one side and recombination rates at
the uncovered TiO2 surface and/or diffusion limited current deter-
mined with the diffusion properties of ions in the actual electrolyte
on the other side. Our cell is not far from optimal active layer
thickness for given 9 mm electrolyte layer. According to the results
of the simulation, increasing active layer thickness of our DSSC to
18 mm and decreasing bulk electrolyte layer to 2 mm would further
increase the cell efficiency for an absolute value of 0.3%.
4. Conclusion
The model of the DSSC based on continuity and transport
equations in the active as well as the bulk electrolyte layer including
series resistance of contacting layers is presented. Trapping/
detrapping processes and electron exchange between semi-
conductor and electrolyte is considered when determining recom-
bination rates. Generation and recombination rates are calculated
and influence of trapping and detrapping probabilities on recom-
bination rates are evaluated. Simulated currentevoltage character-
istics and light intensity dependence of open circuit voltage show
good agreement with measured data. Recombinations of electrons
through the front TCO contact are analyzed, and their effect on the
currentevoltage characteristic and electron concentration in the
cell is shown. As an application of the presented model optimization
of cell efficiency with varying active layer thickness is carried out
and optimal thickness is found to be 18 mm for the measured cell.
Simulations show that optimal active layer thickness and efficiency
of the cell increase for thinner electrolyte layers.
Acknowledgments
The authors are grateful for the funding by the Slovenian
Research Agency (P2-0197). The authors would like to thank the
DSSC team of LPVO for providing the DSSC samples.
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