Journal of Materials Science: Materials in Electronics

https://doi.org/10.1007/s10854-019-02584-3

Photoanode annealing effect on charge transport in dye‑sensitized

solar cell
Waqas Pervez1 · Syeda Ramsha Ali1

Received: 9 July 2019 / Accepted: 13 November 2019

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Abstract
Solar energy is an abundantly available form of clean and renewable energy resource that can be used to generate electricity
using many different photovoltaic technologies. Dye-sensitized solar cells (DSSCs) have attracted attention of researchers
due to their low cost and easy fabrication processes, when compared to conventional silicon-based photovoltaic devices.
Performance enhancement of DSSCs continues to be the subject of recent research. In this work, FTO/TiO2/N719/elec-
trolyte/Pt-type conventional DSSCs were fabricated with and without heat treatment of the FTO/TiO2 photoanode before
sensitization and Pt counter electrode. Results of the photovoltaic and impedance spectroscopic measurements are reported
and discussed. The photovoltaic data reveals relatively higher performance of the cell made after heat treatments of the
photoanode and the counter electrodes. The objective of this research is to study the reason for high performance obtained
employing the annealed photoanode. The overall power conversion efficiency and short-circuit current density of the device
made after heat treatment are observed higher than the one without heat treatment by 165% and 206%, respectively. The
impedance spectroscopic studies also confirmed high performance of the cell made after the heat treatments.

1 Introduction photons by the sensitizer adsorbed of the surface of T ­ iO2

Among the new emerging photovoltaic technologies, next-
generation dye-sensitized solar cells (DSSCs) have attracted
considerable attention because of their ease of manufactur-
ing, different colors, potential for building integrated pho-
tovoltaics and clean source of renewable energy [1–6]. The
development and optimization of different components of
the DSSC technology has been the subject of a number of
papers and review articles [6–21].
A conventional dye-sensitized solar cell contains five
components including a glass coated with transparent
conductive oxide, semiconducting oxide film, a sensitizer
adsorbed onto the surface of the semiconducting oxide
film, an electrolyte containing a redox couple, and a coun-
ter electrode capable of regenerating the redox mediator
[7]. The components of a conventional DSSC, its energy-
level diagram and working principle is shown in Fig. 1. The
first step of the DSSC operation involves the absorption of
* Waqas Pervez
waqaspervez847@gmail.com
1
Faculty of Engineering Sciences, Ghulam Ishaq Khan
Institute of Engineering Sciences and Technology, Topi,
Swabi, Khyber Pakhtunkhwa 23640, Pakistan
nanoparticles, resulting in the photo excitation of electrons
from lowest unoccupied molecular orbital (LUMO) to high-
est occupied molecular orbital (HOMO) of the dye. From
HOMO, the excited electrons are injected into the CB of
the titania, leaving the sensitizer in the oxidized state. The
injected electrons reach the counter electrode after passing
through the network of titania nanoparticles, Fluorine-doped
tin oxide (FTO) and external load, reducing the redox couple
and result in the sensitizer’s regeneration.
The effect of annealing temperatures on the optimization
of photoanode and other components of the DSSC for the
enhancement of its performance continues to be the subject
of recent research [6, 22–28]. In most of the earlier researches,
photovoltaic and electrochemical impedance spectroscopy
(EIS) studies were undertaken. In this paper, photovoltaic
and frequency-dependent capacitance–voltage and resist-
ance–voltage measurements, also known as electrical imped-
ance spectra (IS) are reported. This study may be very useful
to probe the charge transport mechanism and other solar cell
aspects such as doping density, trap states and carrier mobil-
ity [29–32]. To correctly explain the reasons of photovoltaic
performance enhancement of DSSCs and optimize their com-
ponents requires a better understanding of the charge transport
mechanisms and electrical properties of the devices.

13
Vol.:(0123456789)

Fig. 1  Working principle of DSSC
In this work, effects of annealing on the photovoltaic per-
formance of the FTO/TiO2/N719/electrolyte/Pt-type conven-
tional DSSC are reported. The cells were fabricated with
and without heat treatment of the FTO/TiO2 photoanode
before sensitization and Pt counter electrode. Photovoltaic
and impedance spectroscopic investigations were carried out
under the radiance of 100 mW ­cm−2 (AM 1.5) and under
dark, respectively. Comparison of photovoltaic and imped-
ance spectroscopic data revealed much higher performance
of the cell made after heat treatment of the photoanode and
provided deep insight into the properties of the devices.
2 Experimental details
2.1 Materials
The materials used for the fabrication of DSSC devices were
purchased from Solarnix Switzerland. The components and
materials included mesoporous titania coated on FTO glass
on an area of 0.36 cm2, N719 dye, counter electrodes, gas-
kets, and electrolyte. The other materials and solvents were
purchased from Sigma-Aldrich.
Details on preparing the T ­ iO2 working electrodes were
reported in our previous work [33]. ­TiO2 mesoporous elec-
trode consists of two layers, thickness of transparent layer of
titania is 11.5 μm and the other one a scattering titania layer
is almost 3.7-μm thick, second layer lies exactly above the
first layer. The platinum-coated FTO with a hole was used
as counter electrode.
2.2 Fabrication of FTO/TiO2/N719/electrolyte/
Pt‑type DSSC without heat treatment (D1)
and with heat treatment (D2)
Device (D1) fabrication is quite simple as compared to the
device (D2). The mesoporous titania electrode without heat
treatment was dipped in 0.5 mM solution of N719 dye in
13
Journal of Materials Science: Materials in Electronics
anhydrous ethanol and then allowed to stain for about 16 h.
Immediately after taking out from the dye, the stained T ­ iO2
photoanode was rinsed thoroughly with ethanol and dried in
nitrogen gas. Then, a portion of 60 μm thick Meltonix 1170-60
PF spot gasket was positioned on the upper side of anode over
the titania area, a conductive side of Pt counter electrode was
placed over the gasket and heated up to 100 C ̊ to ensure per-
fect sealing. The counter electrode was also not heated. After
sealing, through the drilled hole, an iodide-based electrolyte of
tri-iodide in acetonitrile (Solarnix, AN-50) was injected in the
counter electrode. The hole was then sealed with the Meltonix
spot sealing and the glass spot cap. To avoid photo-bleaching
of the dye molecules prior to electrolyte injection, all assembly
works were performed in a dark room. Active area of the cell
was 0.36 cm2. In the fabrication of D2, the same fabrication
method was used as described for the D1, except, the titania
and counter electrodes were heated at 450 °C.
2.3 UV–Visible, photovoltaic and impedance
characterization
The UV–Visible absorption spectrum of N719 dye solution
was recorded on a Perkin-Elmer Lambda 19 spectrometer. The
photovoltaic parameters and impedance spectra of the fabri-
cated cells were measured using Kiethely 4200-SCS equipped
with a digital capacitance meter (model 4210-CVU under dark
and AM 1.5 simulated illuminations (OAI Tri SOL, AM1.5G
Class AAA, USA). The power was set to 100 mW cm−2 using
Newport Oriel PV reference cell system (Model 91150V).
Impedance spectra were studied applying a 30 mV AC signal
from 1 kHz to 10 MHz.
3 Results and discussion
3.1 Photovoltaic performance
The current density versus voltage (J–V) characteristics of the
DSSCs fabricated without and with heat treatment of the pho-
toanode before sensitization and the counter electrode, meas-
ured under 1 Sun illumination are compared in Fig. 2. The
characteristic photovoltaic parameters required for comparison
of the cells can be obtained from these curves. The values of
series and shunt resistances can be determined from the slopes
of J–V curve at J = 0 and V = 0, respectively.
dV ||
Rs = (1)
dJ ||J=0
dV ||
Rsh = (2)
dJ ||V=0
Journal of Materials Science: Materials in Electronics
16
Without heat treatment
With heat treatment
)
-2
12
Current Density mA.cm
(
8 for the photogenerated current, decrease in RSh decrease the
4 3.2 Impedance spectroscopy of FTO/TiO2/N719/
0
0 200 400 600
Voltage (mV)
Fig. 2  J–V curves recorded under AM 1.5 illumination
(100 mW cm−2) for DSSCs fabricated without and with heat treat-
ment
The important photovoltaic parameters of the cells are
determined and given in Fig. 2. J–V curves recorded under
AM 1.5 illumination (100 mW cm−2) for DSSCs fabricated
without and with heat treatment. As can be observed from
Fig. 2 and Table 1, the cell fabricated using heat treatment
of both the FTO/TiO2 and FTO/Pt electrodes at 450 °C has
exhibited better performance and provided a power conver-
sion efficiency (η) of 5.41% with high-short-circuit photo-
current density (Jsc) 13.15 mA/cm2 and high FF of 61%.
Under the same conditions, the device fabricated without
heat treatment of the electrodes showed relatively lower val-
ues of η and Jsc. Its power conversion efficiency and short-
circuit photocurrent density are 2.04%, and 4.30 mA/cm−2,
respectively. The overall power conversion efficiency and
short-circuit current density device made after heat treat-
ment are observed higher than the one without heat treat-
ment by 165% and 206%, respectively. The higher perfor-
mance of DSSC made after heat treatment of the electrodes
can be attributed, due to increase in a number of reaction
sites hence surface area of the film increased, also the con-
tamination decreases in the film at higher temperature [34].
Current–voltage characteristics of DSSCs majorly
depends upon Rs and RSh [34]. Contact resistance, Charge
transferring in semiconductor, resistance in the electrodes
and bulk resistance contribute to Rs of the cell. Higher the
Table 1  Comparison of the parameters of the DSSCs using N719 as sensitizer without and with heat treatment of the FTO/TiO2 and FTO/Pt-
based photoanode and counter
Heat treatment Jsc (mA cm−2)
Without 4.30
With 13.15
Rs lower will be the fill factor, which decreases the maxi-
mum power output, hence an important factor to optimize
the performance of the cell. On the other hand, RSh is due to
the recombination of electrons in the semiconductor/electro-
lyte/dye interface because of crystal defects in semiconduc-
tor material [35, 36]. RSh also provides an alternative path
power loss in the solar cell.
electrolyte/Pt‑type DSSCs
800
Currently, many researchers around the globe are trying for
synthesis and optimizing, the different elements of DSSCs
[5]. Impedance spectroscopy is one of the most appropri-
ate techniques used to study the quality and properties of
DSSC. To critically analyze the electrical behavior of the
cell, important phenomena such as the insight of charge
transport mechanism, processes occurring inside DSSC,
the effect of the aging process on the performance of the
cell, optimization of the device and finally the modeling of
the device must be taken into consideration. Modeling of
the cell is to replace the cell with an equivalent circuit hav-
ing different electrical components, these components can
be related to the chemical and physical processes occurring
inside the device. These models can be parallel or series
[32]. Impedance spectroscopy is used to study the electri-
cal properties of the DSSCs fabricated without and with
heat treatment using N719 dyes. The data obtained can be
utilized for the comparison of the performance of the solar
cell, to know exactly about component’s interface and how
it affects the performance of the solar cell, to test the models
already exist and to optimize the fabrication of device to
enhance the performance of the cell.
3.2.1 Capacitance–voltage (Cp–V) characteristics
Impedance spectroscopy (IS) is carried out to analyze the
device capacitance (Cp) performance as a function of the
applied bias voltage (V) at different frequencies for the
device without heating and with heating, respectively. Fig-
ure 3 shows the capacitance versus voltage graph studied at
various frequencies. It is clear from the graph that capaci-
tance depends on voltage and frequency. At lower frequen-
cies, when the voltage is swept from range − 1.0 to + 1.0 V
Voc (mV) FF (%) η (%) RSh (kΩ) Rs (Ω)
700 67.88 2.04 13.3 55.56
670 61.45 5.41 6.2 38.4
13
 Journal of Materials Science: Materials in Electronics

the value of capacitance shift towards higher values such
that it arrives at a maximum value after that it start decreas-
ing. However, at higher frequencies, the capacitance value
decreases, approaches near to zero and one can see a decline
in the portion of negative capacitance. Such trend of the
capacitance value in which it goes from positive to nega-
tive capacitance value is according to the earlier reported
studies on DSSCs [35, 36]. As the mentioned behavior of
capacitance is assigned to the electron ejection from the
FTO electrode back into mesoporous ­TiO2 [35].
3.2.2 Resistance–voltage (Rs–V) and capacitance–voltage
(Cs–V) characteristics
limitation due to minority carriers concentration, parame-
ters related to charge transport, charge blocking due to slow
injection or extraction at contacts etc. [30]. Capacitance
peak is observed as we reach higher potentials which have
been assigned to localized states of sub-bandgap because of
the surface defects, in effect decreasing the efficiency of the
cell [35]. When the frequency is low and forward voltage is
high the impedance spectra exhibit chemical capacitance and
recombination resistance [2, 29], compared in Figs. 3 and 4.
These figures clearly show the trend, and their variation is
confirming the higher performance of the device with heat
treatment in the N719 dye.

The Rs–V and Cs–V graphs for the devices without heat-
ing and device with heating are compared in Figs. 4 and 5,
respectively. It can be depicted clearly that at low applied
bias, the resistance and the capacitance remain unchanged,
but as applied bias increases, peaks are observed in graphs of
Rs–V and Cs–V. Dependence of impedance spectra on volt-
age and frequency is due to interfaces, traps, states density,
4 Conclusions
In conclusion, we have studied optical absorption spectra of
dye (N719) using UV–VIS spectroscopy. UV–VIS helped us
to understand the light absorption spectra. Two peaks appear
at 378 and 578 nm, which refer to UV and visible region
of the spectrum, respectively. Two devices are fabricated

Fig. 3  Cp–V curves recorded at (a) (b)

different frequencies in the dark 180 10 kHz 160 10 kHz
for a without heating and b with 20 kHz 20 kHz
160 30kHz
140
heating 30 kHz

140 120
120
100
CP (nF)

CP (nF)

100
80
80
60
60
40
40
20
20
0
-1.0 -0.5 0.0 0.5 1.0 -1.0 -0.5 0.0 0.5 1.0
Voltage (V) Voltage (V)

Fig. 4  Rs–V curves recorded at (a) (b)

different frequencies in the dark 45
for a without heating and b with 10 kHz 13 10 kHz
20 kHz 20 kHz
heating 30 kHz
30 kHz 12

11
R S (Ω )

40 10
R S (Ω )

7
35 6

-1.0 -0.5 0.0 0.5 1.0 -1.0 -0.5 0.0 0.5 1.0
Voltage (V) Voltage (V)

13
Journal of Materials Science: Materials in Electronics
Fig. 5  Cs–V curves recorded at (a)
different frequencies in the dark 3.5
for a without heating and b with 10 kHz
20 kHz
heating 3.0 30 kHz
2.5
Cs ( µ F)
2.0
1.5
1.0
0.5
-1.0 -0.5
Voltage (V)
named as D1 without heating and D2 with heating. The
photovoltaic and impedance spectroscopy are carried out
under an AM 1.5 and illumination intensity 100 mW cm−2.
The device D1 and D2 showed power conversion efficiency
(PCE) of 2.0 and 5.4%, respectively. These results indicated
that D2 shows higher PCE due to increase in number of
reaction sites which increases the surface area of the film.
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