Journal of Materials Science: Materials in Electronics

https://doi.org/10.1007/s10854-019-00929-6

REVIEW

Electrochemical studies of tin oxide based-dye-sensitized solar cells

(DSSC): a review
S. N. F. Zainudin1 · H. Abdullah1 · M. Markom2

Received: 14 August 2018 / Accepted: 13 February 2019

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

Abstract
Tin oxide ­(SnO2) is a promising candidate for dye-sensitized solar cell (DSSC) application due to its wide band gap, high
stability and high electron conductivity. Despite of its remarkable benefits, a detailed discussion on electron transfer mecha-
nism inside S­ nO2-based DSSC is still needed. Electrochemical impedance spectroscopy (EIS) analysis have been widely
employed to understand the electron transport processes and performance of DSSC by correlating the impedance spectrum
with its equivalent circuit model. The scope of this review provides an insight overview on the photovoltaic potential of S
­ nO2
as photoanode in DSSC application followed by a detailed review on the application of EIS analysis in morphologically
modified ­SnO2-based DSSC and hybrid structure of ­SnO2-based DSSC.

1 Introduction manufacturing cost and high-power conversion efficiencies

Sunlight is the most abundant and reliable energy source for
renewable energy and thus the concept for energy conver-
sion was initiated by the studies of photovoltaics effect for
almost two centuries [1]. The concept for energy conver-
sion from solar to electrical energy was initialized to over-
come the disadvantages of the photovoltaic devices based
on the p–n junction diode [2]. The basic concept of solar
cell is explained by the excitation of electrons from solar
irradiation and collected at the anode. The electron is then
re-injected with energy below Fermi level, EF from the cath-
ode into the cell. Thus, the solar cell is designed by which
the charges cannot be transferred from collection site (high
energy) to the injection site to avoid losses of energy of the
excited electron as described schematically in Fig. 1 [1].
Dye-sensitized solar cells (DSSC) is a third generation
of solar cell. It had gained a lot of interest owing to its low
* H. Abdullah
huda.abdullah@ukm.edu.my
1 corresponds to the difference between the Fermi level of the
Center of Advanced Electronic and Communication
Engineering (PAKET), Faculty of Engineering and Built
Environment, Universiti Kebangsaan Malaysia,
43600 Bangi, Selangor, Malaysia
2
Research Center for Sustainable Process Technology
(CESPRO), Faculty of Engineering and Built Environment,
Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor,
Malaysia
[3]. DSSC generally consists of four main parts which are
working electrode (anode), dye-sensitizer, redox electrolyte
and counter-electrode (cathode). All of which are sand-
wiched together between two transparent conducting glass
substrates typically consists of either indium-doped tin oxide
(ITO) or fluorine-doped tin oxide (FTO) based glass sub-
strates [4, 5]. The mechanism of electron transfer in DSSC
is initiated by the photoexcitation of dye molecules that is
adsorbed on tin oxide which acts as a semiconductor metal
oxide (MO) as shown schematically in Fig. 2. The photoex-
citation results with the injection of electrons into the con-
duction band of tin oxide. The rate of electron injection is
correlated with the coupling of the dye excited-state LUMO
orbital and relative energies of the state [6]. These electrons
may be recombined with the oxide of the dye sensitizers or
redox electrolyte. The excited state of the dye sensitizer is
converted back to its original state by the donation of elec-
trons from the electrolyte. The iodide is regenerated in turn
by the reduction of triiodide at the counter electrode and
the circuit being completed via electron migration through
the external load. The voltage generated under illumination
electron in the MO and the redox potential of the electro-
lyte. Therefore, the electron collection efficiency in DSSCs
is determined by the competition between transport of elec-
tron in the MO and recombination of electrons with ­I3− ions
in the electrolyte [2, 4, 7, 8]. The mechanism of the tin oxide
sensitization is presented by Fig. 3.

13
Vol.:(0123456789)

Fig. 1  General mechanism of solar cell [1]
Generally, a high-efficient photo electrode for DSSCs
should possess advantageous features of fast electron trans-
port, slow interfacial electron recombination, and effective
light absorption [10]. Incorporation of different promising
materials was found to enhanced dye absorption, charge
collection efficiency, charge transfer dynamics and optical
scattering [11]. The open-circuit photovoltage (Voc) is deter-
mined by the potential difference between the Fermi energy
level of the photoanode and the redox potential of the elec-
trolyte under illumination. The decay of Voc may be caused
by the downward shifting of conduction band or due to the
back reaction of photo-generated electrons in the oxide thin
film to the oxidized species in the dye or electrolyte [12, 13].
The correlation of Voc with back-reaction current is shown
in the following Eq. (2) [14]:
[ ]
kB T jph + jo
Voc = ln (1)
q𝛽 jo
Based on Eq. (1), Voc depends logarithmically on the inverse
concentration of I­ 3− and increases with incident photo flux
Fig. 2  Schematic representation
of electron transfer mechanism
in DSSC [4]
13
Journal of Materials Science: Materials in Electronics
[15]. Thus, efficiency can be improved by minimizing the
back reaction at photoanode/dye/electrolyte interface.
Meanwhile, the short-circuit photocurrent density (Jsc)
is mainly determined by the forward photocurrent density
subtracts backward current density. Short-circuit photo-
current density, J sc is also influenced by the amount of
photoexcited electrons, recombination rate of interface
dye/photoanode or photoanode/electrolyte and redox of
­I−/I3− in electrolyte [16]. Therefore, Jsc can be improved
by the enlargement of surface area and long diffusion
length. Fill factor, FF is governed by the series resistance
of the device and the electron recombination loss at the
oxide/dye/electrolyte interface [14].
Electrochemical impedance spectroscopy (EIS) is a
very useful tool to understand the electron transport mech-
anism and processes such as recombination and re-gen-
eration that occurred in the internal system of DSSC. In
spite of the low performance of ­SnO2 in DSSC application,
there is very limited studies concerning on the application
of EIS analysis to model the electron transport behaviour
in the S ­ nO 2-based DSSC. Understanding the electron
behaviour is essential to allow researchers to identify the
detrimental factors affecting the photo-conversion perfor-
mance of the cell. In this review, we aim to give an insight
on the potential of ­S nO 2 being the non-expensive and
abundant photoanode material as a promising candidate
in DSSC application. The correlation between the pho-
tovoltaic parameters of DSSC (Voc, Jsc, FF and PCE) and
the parameters obtained by EIS analysis such as charge
transport resistance (Rct), transport resistance (Rt), chemi-
cal capacitance (Cµ), effective electron lifetime (τeff), effec-
tive electron chemical diffusion coefficient (Deff), effective
rate constant for recombination (k eff), effective electron
diffusion length of the photoanode (Ln) and finite Warburg
impedance in the electrolyte (ZD) were discussed.
Journal of Materials Science: Materials in Electronics
Fig. 3  Energy level diagram of DSSC based ­SnO2 which is described
by the charge injection from the dye excited state, Ru(II)* to conduc-
tion band (CB) of oxide and the dye regeneration by the reduction of
­I− ions of the electrolyte [9]
2 Tin oxide as photoanode in DSSC
The n-type semiconductor of S ­ nO2 is a promising alterna-
tive candidate to T­ iO2 owing to its high electron mobility
(100–200 cm2/V s) [17] and wide band gap (3.62 eV), which
indicates a faster transport of photo-generated electrons and
more excellent long-term stability of electrons [18]. Moreo-
ver, the low isoelectric points and positive conduction-band
edge of ­SnO2 facilitate the formation of a surface dipole
layer toward ­SnO2 when coated with other materials like
­TiO2 and ZnO [7] and facilitates high efficient electron
injections from the adsorbed dye molecules [19]. With
these advantages, it has been extensively utilized in many
applications, including supercapacitor [20–22], gas sensing
[23–26], dye-sensitized solar cells [27–30] and lithium ion
batteries [31–33].
However, Tennakone et al. [34] reported the occurrence
of inherent fast recombination process and poor fill factor
of ­SnO2 particles as photoanode in DSSC. This phenom-
enon can be ascribed by the high recombination of elec-
trons with acceptors during transit to the back contact [35,
36]. Green et al. [37] explained that the major drawback
was due to the positive shift of 300 mV of conduction band
edge of ­SnO2 which results in fast electron recombination
and low electron trapping density. The intrinsic defects in
­SnO2 generally related by the formation of tin interstitial and
oxygen vacancy. The formation of oxygen vacancies is most
likely to occur due to lower formation energy compared to
tin interstitial which lead to the reduction of S ­ n4+ to S
­ n2+.
The presence of this non-stoichiometric defects is caused
by the insertion of O interstitials into tetrahedral and octa-
hedral sites of S ­ nO2. The presence of O interstitial tends to
form peroxide ions [38], which may acts as a trap sites for
recombination to occur. In contrast, Porte et al. [39] dem-
onstrated that by controlling the environment parameters
such as temperature and pressure deposition, the formation
of tin interstitials is more likely to occur compared to oxygen
vacancies.
In addition, the high back electron transfer rate is cor-
related with the low open-circuit voltage (Voc) which most
likely occurs due to the low intrinsic value of the conduction
band (CB) energy level [40] and the higher rate of electron
interception by the redox electrolyte [41]. Doping S ­ nO2 with
other n-type material will lead to an excess of oxygen vacan-
cies and further reduce the band gap. Meanwhile, doping
­SnO2 with p-type material will shift the Fermi energy level
towards valence band and further widen the band gap. Due to
the formation of oxygen vacancies which is close to the top
valence band of tin oxide (about 1 eV) [42], the presence of
dopants with rich electrons will increase the oxygen vacan-
cies and shifts the Fermi energy level towards the conduction
band and narrows the band gap as the valence band moves
upwards. Boumeddienne et al. [43] observed a significant
structural relaxation and modification of the charge around
Sb in Sb-doped ­SnO2 (1 1 0) surfaces. Sb doping introduces
occupied surface states of hybridized 5 s and 5p orbitals of
Sb atoms and the substitution of Sn with Sb improves the
surface conductivity due to the role of Sb which acts as a
donor as well as acceptor centre at the surface. The reduction
in the surface band bending and accumulation layer width
with the increase of surface electron concentration is appar-
ent as the bulk Fermi level moves to higher energies in the
conduction band. Li et al. [44] supported that disparity of
Jsc can be ascribed to the difference of light-harvesting capa-
bility and charge transport and recombination of photoan-
odes which is related to the morphology of the film. Studies
showed an improved performance of DSSC with increase Jsc
results with higher surface roughness factor which implied
higher dye loading and consequently higher light harvesting
efficiency and high current densities [45]. Aponsu et al. [46]
incorporated Au as a dopant in S ­ nO2 based photoanode with
various concentration of Au. ­SnO2 sample with concentra-
tion of Au of 0.0014 wt% showed a highest efficiency at
PCE ~ 3.9% (Table 1). The enhancement is described by the
shift of conduction band edge of S ­ nO2 to a higher level upon
in contact with Au nanoparticles. Shalan et al. [40] employed
­Ni2+ and Z ­ n2+ ions as a dopant in S ­ nO2 nanoparticles and
they observed that Zn and Ni doped ­SnO2 exhibited a higher
power conversion efficiencies (PCE ~ 4.2% and PCE ~ 3.6%,
respectively) than that of bare S ­ nO2 (PCE ~ 3.2%) as shown
in Table 1. The elevation of Fermi level with the presence
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 Journal of Materials Science: Materials in Electronics

Table 1  Comparison of Sample Dye Jsc (mA/cm2) V oc (V) FF 𝜼 (%)

photovoltaic properties of ­SnO2-
based DSSCs SnO2 [48] Eclipta alba 0.82 0.40 0.54 0.29
La–SnO2 [48] Eclipta alba 1.03 0.48 0.68 0.34
La–Cu–SnO2 [48] Eclipta alba 1.27 1.30 0.53 0.37
SnO2 [48] Cocinia indica 0.70 0.54 0.61 0.26
La–SnO2 [48] Cocinia indica 0.82 0.54 0.54 0.29
La–Cu–SnO2 [48] Cocinia indica 1.01 0.56 0.57 0.31
Ti0.7Sn0.3O2 [49] D131 9.03 0.64 0.66 3.81
Ti0.7Sn0.3O2 [49] N719 8.79 0.64 0.66 3.61
Ti0.7Sn0.3O2 [49] D131 + N719 (1:1) 10.49 0.65 0.66 4.46
CaCO3-coated ­SnO2 [50] N719 11.40 0.68 0.69 5.40
SnO2 [50] N719 11.90 0.35 0.41 1.70
SnO2 HNS [10] N719 8.50 0.50 0.36 1.51
SnO2 HNS–TiO2 [10] N719 18.29 0.74 0.48 6.54
SnO2 HNS–TiO2 P25 [10] N719 11.38 0.77 0.61 5.38
BaSnO2 [51] N719 0.50 0.51 0.41 0.12
SnO2/Zn2SnO4 HMS [44] N719 10.98 0.59 0.73 4.72
SnO2/Zn2SnO4 MS [44] N719 7.22 0.57 0.74 3.05
SnO2 MS [44] N719 5.32 0.41 0.63 1.38
SnO2 [52] N719 4.95 0.40 0.33 0.70
TiO2–SnO2 [52] N719 11.52 0.59 0.57 3.82
TiO2/SnO2 (~ 10 nm) [53] N719 12.59 0.73 0.69 6.35
TiO2/SnO2 (~ 18 nm) [53] N719 13.66 0.74 0.72 6.33
TiO2 rod/SnO2 MS (0.06 g) [54] N719 6.23 0.78 0.59 2.09
TiO2 rod/SnO2 MS (0.12 g) [54] N719 6.48 0.73 0.59 2.12
TiO2 rod/SnO2 MS (0.18 g) [54] N719 6.93 0.72 0.53 2.26
Ni/Sn [30] N719 10.00 0.64 0.689 4.42
SnO2 [51] N719 5.66 0.15 0.34 0.28
Zn-doped ­SnO2 [51] N719 2.85 0.71 0.63 1.29
SnO2 [46] Indoline 149 9.20 0.52 0.49 2.40
Au-doped ­SnO2 (0.9 × 10−3) [46] Indoline 149 9.70 0.60 0.58 3.40
Au-doped ­SnO2 (1.4 × 10−3) [46] Indoline 149 10.10 0.61 0.63 3.90
Au-doped ­SnO2 (1.9 × 10−3) [46] Indoline 149 6.30 0.60 0.66 2.50
Au-doped ­SnO2 (2.4 × 10−3) [46] Indoline 149 2.90 0.59 0.70 1.20
SnO2 nps [55] N719 3.20 0.37 0.32 0.37
SnO2 nanorod [55] N719 5.50 0.44 0.59 1.40
SnO2 [56] N719 8.63 0.40 0.40 1.37
SnO2–TiO2 (15%) [56] N719 7.09 0.57 0.70 2.80
SnO2–TiO2 (40%) [56] N719 0.34 0.67 0.61 0.14
SnO2–TiO2 (70%) [56] N719 3.02 0.78 0.73 1.71
SnO2 [57] Rose Bengal 16.91 0.69 0.51 5.73
ZnO–SnO2 [57] Rose Bengal 15.93 0.65 0.47 4.72
ZnO/SnO2 nanoneedle [19] N719 9.80 0.59 0.57 4.71
SnO2 [40] N719 6.85 0.68 0.70 3.20
Ni-doped ­SnO2 [40] N719 7.61 0.69 0.69 3.60
Zn-doped ­SnO2 [40] N719 8.57 0.76 0.67 4.20
SnO2 [58] N719 8.30 0.43 0.39 1.38
SnO2/ZnO [58] N719 10.22 0.65 0.48 3.18
SnO2/MgO [58] N719 15.90 0.69 0.48 5.25
SnO2/CaCO3 [58] N719 16.07 0.72 0.45 5.17
SnO2/ZrO2 [58] N719 12.96 0.69 0.47 3.96
SnO2/TiO2 nps [59] N719 13.17 0.43 0.43 2.37

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Journal of Materials Science: Materials in Electronics

Table 1  (continued) Sample Dye Jsc (mA/cm2) V oc (V) FF 𝜼 (%)

SnO2/TiO2 TTIP [59] N719 11.13 0.64 0.67 4.74

ZnO/SnO2 (3%) [28] N719 1.44 0.59 0.65 0.55
ZnO/SnO2 (4%) [28] N719 2.09 0.57 0.67 0.80
ZnO/SnO2 (5%) [28] N719 1.62 0.59 0.68 0.66
Bare ­SnO2 nanotubes [45] N719 7.99 0.49 0.27 1.06
TiO2/SnO2 nanotubes [45] N719 9.91 0.68 0.49 3.47
TiO2/SnO2 (60 nm) [60] N719 14.51 0.79 0.67 7.92
TiO2/SnO2 (120 nm) [60] N719 15.84 0.82 0.65 8.38
SnO2 [61] N719 0.50 0.55 0.62 0.17
Zn2SO4 [61] N719 1.60 0.71 0.43 0.48
Sn–ZnO [62] N719 5.10 0.79 0.45 1.82
Zn2SO4 [51] N719 1.99 0.67 0.67 0.90
Zn2SO4/SnO2 [51] N719 2.85 0.71 0.63 1.29
SnO2 [51] N719 5.66 0.15 0.34 0.28
SnO2 nps [63] N719 7.49 0.47 0.48 1.66
SnO2 nanograin [63] N719 8.09 0.60 0.61 2.98
SnO2–ZnO nanograin [63] N719 8.70 0.65 0.70 3.96
Sn-doped ZnO (5.5 wt%) [29] N719 9.18 0.64 0.65 3.79
SnO2 [64] Erythrosin 0.76 0.21 0.40 0.06
SnO2 [36] N3 11.2 0.25 0.26 0.74
SnO2/TiO2 [36] N3 20.1 0.39 0.27 2.08
SnO2/TiO2/Al2O3 [36] N3 21.9 0.44 0.30 2.85

on Zn and Ni was due to the following: (i) the enhance band
bending to lower the density of empty trap states, (ii) the
minimization of trap density and (iii) the reduction of light
intensity which alleviates the decay of light to energy con-
version efficiency. Similar result was obtained by Li et al.
[47] with four times increase of conversion efficiency of Zn-
doped ­SnO2 (PCE ~ 4.15%) over bare ­SnO2 (PCE ~ 1.13%).
Wang et al. [28] observed an improvement of conversion
efficiency of ZnO based DSSC upon addition of Sn. In their
results, ZnO with 4% Sn showed a highest power conversion
efficiency (PCE ~ 0.80%) with Jsc of 2.09 mA/cm2, Voc of
0.57 V and a fill factor (FF) of 66.9% due to high amount
of dye adsorption.
Surface modification of ­SnO2 nanoparticles have been
proposed to minimize the interfacial problems [40]. The
introduction of coating layer with a higher band gap metal
oxide than ­SnO2 such as MgO, ­ZrO2, ­SiO2, ­Nb2O5 could
develop a fast redox shuttle, while the presence of coat-
ing layer insulator such as C ­ aCO3 and A ­ l2O3 could pas-
sivate the tin oxide surface states and effectively impede
the charge recombination to redox electrolyte [52, 58, 65].
The choice of metal oxide is constrained by energy levels
of the dye with respect to the conduction band edge and
the efficiency of electron transfer from the dye to the semi-
conductor ­SnO2 [2]. For example, Lee et al. [66] observed
that ZnO–SnO2 nanocomposite thin film exhibit excellent
electronic conduction properties due to the unique electronic
structure of amorphous nanocomposite coupled with two
heavy-metal Zn and Sn cations having spherically symmet-
ric s-orbitals. Another studies on the incorporation of ­SnO2
with ­Zn2SnO4 revealed the efficient separation of photo-
generated electron–hole pairs due to the lower conduction
band of ­SnO2 compared to ­Zn2SnO4 [44]. Meanwhile, Li
et al. [51] reported a significant improvement of conversion
efficiency (PCE ~ 1.29%) of ­Zn2SO4/SnO2 over bare ­Zn2SO4
(PCE ~ 0.90%) and ­SnO2 (PCE ~ 0.28%) based DSSC. This
results is explained by the properties of conduction band
edge of Z ­ n2SO4, which is more negative than that of S ­ nO2
thus shifted to a more negative value [61]. The presence
of ­Zn2SO4 also enhance the dye adsorption due to its high
isoelectric point. A higher dye absorption with the presence
of coating layer occurred due to the enhancement of light
scattering ability [41]. Liu et al. [36] emphasizes the role of
the interface between T ­ iO2, ­SnO2 and ­Al2O3 on the transfer
of photo-generated electrons in ­Al2O3-coated ­SnO2/TiO2
photoanode. In this mechanism, photo-generated electrons
tunnelled trough ­Al2O3 layer to the conduction band of ­TiO2
from excited dye and rapidly transfer to the conduction band
of ­SnO2. The presence of A ­ l2O3 layer suppress the recom-
bination of the electrons on T ­ iO2 conduction and holes in
the electrolyte or the oxidized dye. T ­ iO2 compact layer also
act as a blocking layer to prevent the backflow of electron
from FTO to S ­ nO2 film due to the higher conduction band of
­TiO2 compared to ­SnO2. Wang et al. incorporates a bilayer

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 Journal of Materials Science: Materials in Electronics

­SnO2/TiO2–ZnO nanoplates ternary heterostructures in

DSSC system. They observed an improvement of efficiency
(PCE ~ 6.37%) with the addition of ­SnO2 blocking layer.

3 Modelling of electron transport in ­SnO2

based DSSC

The behaviour of electron transport in dye-sensitized solar

cells (DSSC) can be described as diffusion, hopping, tun-
neling, and a trap–detrap mechanism [67]. The kinetic
behaviour of trap and de-trap mechanism of charges in
homogenous system contributes different capacitive and
resistive element of faradaic impedance [68]. The forma-
tion of the resistive element occurs as a result of formation
of depletion layer due to the increase in the carrier density
that pushes the Fermi level into the band gap of photoanode Fig. 4  Nyquist plot of EIS spectra of S
­ nO2-based DSSC [60]
[69, 70]. Impedance terms are utilized as a measurement
of the ability of the system to impede the flow of electri-
impedance diffusion in electrolyte (Warburg element, WS)
cal current which ascribed by the ratio of a time-dependent
[75].
voltage and time-dependent current as expressed by Eq. (3)
A transmission line equivalent circuit model is devel-
and Eq. (4), respectively [71]. The impedance (Z) of an elec-
oped to estimate the electron recombination resistance
trochemical cell is evaluated at various frequencies ( 𝜔 ) by
and transport resistance through the multilayers in DSSC
schematic presentation of Nyquist plot (Z′ vs. -Z″) and Bode
[76]. This estimation is useful to determine the effective
plot |Z|(𝜔) , 𝜙(𝜔) , where Z′ is the real part (Zreal = Z0 cos∅) ,
electron diffusion length, Ln , effective electron diffusion
Z″ is the imaginary part (Zimag = Z0 sin∅) , |Z| is the modulus
coefficient within photoanode layer, Deff and effective
and 𝜙 is the phase of Z [72].
electron lifetime 𝜏eff  . The lifetime of electrons ( 𝜏eff )can be
V(t) = Voc cos (𝜔t) (2) estimated from the maximum of angular frequency ( 𝜔max )
( ) of the impedance semicircle at middle frequencies as in
I(t) = V0 cos 𝜔t − � (3) the following Eq. (7) [68]:
where V0 and I0 are the amplitudes of voltage and current
1 1
signals, respectively, and 𝜔 is the radial frequency in radi- 𝜏eff = = (4)
𝜔max 2𝜋fmax
ans per second [71]. The impedance spectrum or so called
as Nyquist plot is obtained by electrochemical impedance where fmax is the maximum frequency at the peak of the
spectra (EIS) analysis. The Nyquist plot describes the elec- intermediate semi-circle. The effective diffusion coeffi-
tron transport processes involves in DSSC system due to (i) cient, Deff and diffusion length, Ln of electrons across the
electron diffusion through photoanode and ionic diffusion in ­SnO2 photoanode layer can be evaluated by Eqs. (5) and (6),
the electrolyte solution (for frequencies lower than 1 Hz); (ii) accordingly [75].
charge transfer and surface states of the porous network of
photoanode thin film and recombination at the photoanode/ Rct L2
electrolyte interface (between 1 Hz and 1 kHz); and (iii)
Deff =
Rt 𝜏eff (5)
charge transfer at counter electrode/electrolyte interfaces
(above 1 kHz) [14, 73, 74]. The Nyquist plot of impedance
( )1∕2
spectrum for dye-sensitized solar cell generally consist of Rct
three semicircles, which are fitted by a transmission line Ln = L (6)
Rt
equivalent circuit. Figure 4 shows an example of Nyquist
plot of ­SnO2-based DSSC. The high frequency semicircle where L is the thickness of ­SnO2 photoanode layer. An effi-
can be attributed to a charge transfer resistance (Rct) and cient charge collection is determined by the longer charge
Helmholtz capacitance of counter electrode. The middle fre- diffusion length compared to the thickness of the photoanode
quency semicircle represents the recombination resistance layer ( Ln > L ) [77]. Suitable equivalent circuit is proposed
(Rt) at photoanode/electrolyte interface and the capacitance based on the behavior of the impedance and capacitance
of photoanode. The low frequency semicircle represents the

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Journal of Materials Science: Materials in Electronics

represented by the semicircles obtained from the impedance
spectrum of Nyquist plot. As shown in Fig. 5a, the equiva-
lent circuit for ­SnO2-based DSSC system is modeled as a
simple columnar structure that represents the penetration of
dye into the pores of the mesoporous ­SnO2 layer. The paral-
lel circuit of Rr and C𝜇 describe the charge transfer resistance
related to the recombination of charges at S ­ nO2/electrolyte
interface and chemical capacitance of ­SnO2 as a results of
the change of electron density as a function of Fermi level,
respectively [65]. Meanwhile, the parallel combination of
RTCO and CTCO localized at the end of the pore represent
the charge transfer resistance and double layer capacitance
at TCO/electrolyte interface [78]. The equivalent circuit of
Fig. 5a can be simplified to Fig. 5b when the potential is
closed to open circuit condition. Therefore, only one semi-
circle can be observed in the impedance spectrum within the
medium frequency range [77]. However, when the potential
is close to the potential of conduction band of ­SnO2, the

(a)
SnO2 particles with adsorbed
dye on the surface

Electrolyte in
Electrolyte within the pores of between the
SnO2 particles electrodes

SnO2 particles with adsorbed Counter

FTO dye on the surface electrode

(b) Rs rt rt rt rt rt

rct cµ rct cµ rct cµ rct cµ

RTCO RPt
Zd(sol)

CTCO
CPt

Rs Rt
(c)

RTCO Rct Cµ RPt

Zd(sol)

CTCO
CPt
Rr RPt
(d)
Rs Zd(sol)

Cµ CPt

Fig. 5  a Typical representation of ­SnO2-based DSSC system consists Simplified equivalent circuit when the applied potential near to the
of penetrated electrolyte solution into the pores of ­SnO2 particles. b open circuit. d Simplified equivalent circuit when the applied poten-
Transmission line equivalent circuit model of S ­ nO2-based DSSC. c tial is near to conduction band of ­SnO2

13
 Journal of Materials Science: Materials in Electronics

equivalent circuit will be a serial connection of Rs, Zd(sol) charge transfer resistance than the recombination resistance,
and parallel combinations of Rr and Cµ, and Rpt and Cpt Rt > Rr , or equivalently 𝜔d > 𝜔k , and the line is converted to
(Fig. 5c), which will result with a capacitive vertical line in a semicircle as the frequency decreases [80]. This behaviour
the impedance spectrum [65]. It is crucial to obtain a high can be interpreted by the following expression [82]:
Rct in order to allow the charge carriers to accommodate in At high frequencies (𝜔∕𝜔d ),
the Cµ of the cell, and hence, increases the Fermi level of the
( )1∕2
photoanode [4]. The total series resistant, Rs proportionally 𝜔
influenced the short-circuit current, Jsc according to the fol- Z = Rt i . (9)
𝜔d
lowing Eq. (4), [60]:
{ ( ( )) } ( ) and at low frequencies, the semicircle is displaced to the
q V + IRs V + IRs right by the quantity of Rt ∕3 , thus gives the following
I = Iph − Io exp −1 −
nkT Rsh impedance expression:
(7) Rr R
Adachi et al. [79], derived an impedance model of DSSC Z= + t (10)
1 + i𝜔∕𝜔k 3
based on the diffusion-recombination model and continuity
equations proposed by Bisquert et al. [80] and Kern et al. Constant phase element (CPE) is normally applied to rep-
[81] as given in the following expression: resent equivalent circuit for DSSC system to ascribed the
distribution of reactivity or non-homogeneity of a system.
( )1 [( )1 ( )] 2
1

Rt Rr 2 𝜔k 2
i𝜔 Therefore, the impedance of CPE is expressed as follows
Z= coth 1+ (8) [83]:
1 + i𝜔∕𝜔k 𝜔d 𝜔k
/[ ]
Z = 1 𝜏(j𝜔)p (11)
where 𝜔d = Dn ∕L2 = 1∕Rt C𝜇 is the frequency of diffusion in where 𝜏 is characteristic time constant for the distribution of
finite layer, 𝜔k = 1∕Rr C𝜇 is the rate constant
√ for recombina- reactivity of the system. Table 2 summarized the values of
tion, 𝜔 is the angular frequency and i = −1 [82]. Bisquert resistances and other parameters obtained from EIS analysis
et al. [80] proposed that the formation of a straight tilted of ­SnO2-based DSSC.
line at the high frequency region correlated with the higher

Table 2  Comparison of photoelectrochemical properties of S

­ nO2-based DSSCs
SnO2-based DSSC Photovoltaic properties Photoelectrochemical properties
Jsc Voc FF 𝜂 Rs Rk Rt Rct C𝜇 teff Keff Deff Ln
(mA/cm2) (V) (%) (Ω) (Ω) (Ω) (Ω) (µF) (ms) (/s) (cm2/s) (µm)

SnO2 nps [84] 2.84 0.385 0.44 0.48 – 118.5 – 9.87 – 10.04 – –
SnO2 nanoflowers [84] 1.50 0.525 0.50 0.32 – 381.5 – 9.48 – 12.65 – –
SnO2/Li–ZnO [84] 4.40 0.670 0.69 2.02 – 69.33 – 9.01 – 6.33 – –
SnO2 [85] 1.83 0.75 0.53 0.72 29 84 15 28 17 – – –
ZnO–SnO2 (3%) [28] 1.44 0.59 0.65 0.55 2.3 162.1 13.6 – – – – –
ZnO-SnO2 (4%) [28] 2.09 0.57 0.67 0.80 2.2 107.4 9.4 – – – – –
ZnO–SnO2 (5%) [28] 1.62 0.59 0.68 0.66 2.6 113.0 13.4 – – – – –
SnO2 120 nm [60] 13.30 0.83 0.69 6.10 10.35 18.42 8.7 6.39 0.94 – – –
SnO2 60 nm [60] 8.80 0.87 0.72 5.60 11.0 18.43 9.3 6.48 0.96 – – –
SnO2 [41] 7.62 0.38 0.50 1.43 16.8 87.74 – 17.94 – – – –
TiO2-coated ­SnO2 [41] 14.70 0.74 0.56 6.05 15.18 332.69 – 16.66 – – – –
SnO2 [45] 7.99 0.49 0.27 1.06 – 145 – – – 12.89 11.90 1.71 14.72
TiO2-SnO2 [45] 9.91 0.68 0.49 3.47 – 165 – – – 18.91 8.39 2.89 23.31
SnO2 nanorod [55] 5.50 0.435 0.59 1.40 – 119 – 0.68 – 28.3 35.3 6.17 × 10− 5 –
SnO2 nps [55] 3.20 0.365 0.32 0.37 – 46.76 – 1.77 – 1.3 725.7 19.17 × 10− 5 –
SnO2/Zn2SnO4 NW-HMS [44] 10.98 0.59 0.73 4.73 – 39.7 – – – 19 – – –
SnO2/Zn2SnO4 NW [44] 7.22 0.57 0.74 3.05 – 61.3 – – – 12 – – –
SnO2 MS nanorod [44] 5.32 0.41 0.63 1.38 – 143.8 – – – 8.08 – – –
TiO2–SnO2 [52] 11.52 0.59 0.57 3.82 – – – – – 15.6 – – –

13
Journal of Materials Science: Materials in Electronics

4 Electron transport studies of ­SnO2‑based

DSSC

4.1 Morphological modifications

Various morphology of ­S nO 2-based photoanode have

been fabricated ranging from 1-dimensional (1-D) such
as nanorod, nanotubes and nanowires to 3-dimensional
(3-D) nature such as nanospheres, nanoflowers to a more
complex structure such as hollow microspheres (HMS) as
shown in Fig. 6, to minimize the formation of dark current
and improve the DSSC photovoltaic performances. Wijer-
atne et al. [55] explained a morphological-dependent per-
formance by the comparison of ­SnO2 nanorod and ­SnO2
nanoparticles through EIS analysis and transmission line
equivalent circuit as shown in Fig. 7. The middle semicircle
arc for ­SnO2 nanorod is larger than that of SnO2 nanopar-
ticles, which describes a lower charge recombination pres-
ence in S ­ nO2 nanorod. The 1-D nature of S ­ nO2 nanorod
Fig. 7  Comparison of EIS analysis of (a) nanorod ­SnO2 and (b) nan-
provides a direct conductive pathway for electrons injected oparticles ­SnO2 (SNP) based DSSC and its equivalent circuit [55]

Fig. 6  Various modified morphologies of ­SnO2 fabricated to enhance the performance of DSSCs a urchin-like ­SnO2 [41], b nanorod ­SnO2 [55],
c nanochain hollow microspheres S
­ nO2 [54] and d nanoflowers S ­ nO2 [84]

13

from sensitized dye, reduced the charge transfer resistance,
Rct and increase the electron lifetime 𝜏eff  . In their studies,
despite of the low Deff  , they observed a longer electron life-
time for S­ nO2 nanorod ( 𝜏eff = 28.3 ms) compared to ­SnO2
nanoparticles 𝜏eff = (1.3 ms) which resulted by the low Rct .
Meanwhile, Rui et al. [86] reported a correlation between
the length of S­ nO2 nanorod with charge transfer resistance
in DSSC system. They observed a reduced charge transfer
resistance, Rct with the increase length of ­SnO2 nanorod
which is explained by the accelerated charge transportation.
In spite of the 1-D nature of S ­ nO2 nanorod that provide a
direct conduction channel, the formation of surface electrical
field is another factor that supported this phenomenon as the
presence of electrical field confines the electron towards the
central zone and impede the back transfer, thus reduce elec-
tron recombination. The effect of ­SnO2 nanorod is further
enhanced by the formation of a more complex structure of
­SnO2 nanorods as reported by Qi et al. [87] that compares
the photovoltaic performance of S ­ nO2 nanoflowers and S­ nO2
nanoparticles by EIS analysis. S ­ nO2 nanoflower that com-
prises of multiple ­S( nO2 nanorods showed) a lower charge
transfer (resistance Rct =) 32.33 ohm and longer electron
(lifetime 𝜏eff = 15.91 ms compared)to S ­ nO2 nanoparticles
Rct = 222.76 ohm, 𝜏eff = 7.37 ms due to a better inter-
connection pathway for electron transportation.
Hollow spheres is another alternative of structure modi-
fication which acts as a light entrapment that are able to
provide multiple scattering of the light to enhance the
photocatalytic effect in the solar cell [88]. The improved
dye adsorbing capacity of the photoanodes also have been
reported due to the large surface area of the hollow spheres
structure [44]. Ma et al. [54] reported a remarkable improve-
ment of light reflectance and scattering by introducing S ­ nO2
hollow microspheres (HMS) on T ­ iO2 nanorod layer as a pho-
toanode in DSSC due to the reflection of confined incident
light within the S
­ nO2 network inside the HMS. The presence
of ­SnO2 hollow microspheres improved the efficiency due to
the reduced charge transfer resistance and interfacial charge
recombination, faster diffusion constants and enhanced
light absorption [89]. This phenomenon is supported by the
increment of fill factor (FF) which represent high electron
mobility within ­SnO2 network. As deduced from the data,
the increment of Jsc by the light scattering effect is corre-
lated well with the high Rct and longer electron lifetimes as
described previously. The lowering value of Voc could be
resulted from the effect of band gap energy when Fermi level
is shifted closer to the redox potential. However, the results
reported by Chen et al. [10] is in contradiction to the previ-
ous seminal works where they observed an increased cell’s
performance accompanied by the increase of both Voc and Jsc
which was described by the formation of surface dipole layer
toward ­SnO2 that accelerates the forward electrons transfer
and suppresses the back recombination. Li et al. [11] studied
13
Journal of Materials Science: Materials in Electronics
the effect of incorporation of different morphologies of com-
plex ­Zn2SO4 on S ­ nO2 based DSSC. The photo-conversion
efficiency obtained by S ­ nO2/Zn2SO4 NW-HMS is higher
(PCE ~ 4.72%) compared to ­SnO2/Zn2SO4 NW and ­SnO2
MS nanorod which is 3.05% and 1.38%, respectively. This
result is significantly related to the effects of electron life-
time by which ­SnO2/Zn2SO4 NW-HMS obtained a longer
electron lifetime ( 𝜏eff ~ 19 ms) compared to S ­ nO2/Zn2SO4
NW and ­SnO2 MS nanorod.
4.2 Structural modifications
Other than morphological modification of the photoan-
ode, the addition of other wide band gap metal oxide into
­SnO2-based photoanode is an alternative way to alter the
band gap and inhibit the back transfer of electrons from
­SnO2 to the redox electrolyte ­(I3−) and further improve the
power conversion efficiency (PCE) of ­SnO2-based DSSC.
Modifications was made to ­SnO2-based photoanode by dop-
ing with wide band gap metal oxide such as ZnO [28], NiO
[40] and ­TiO2 [90]. Wang et al. [28] fitted a simple equiva-
lent circuit to describe the effects of ­SnO2 as a dopant in
ZnO-based DSSC. They obtained two semicircles as shown
by the Nyquist plot and modelled the mechanism accord-
ingly through a simple equivalent circuit (Fig.  8). The
enhanced photovoltaic performance by ZnO doping is in
agreement with the low charge transfer resistance, Rct at the
photoanode/electrolyte interface in ­SnO2-based DSSC. The
photovoltaic properties such as Jsc and Voc were improved
significantly after doping with S
­ nO2 due to the increased dye
adsorption. The increase of dye adsorption was correlated
to the formation of smaller particles size which increase the
surface area for dye adsorption and light harvesting [19].
The high Jsc was reflected by the high charge transfer resist-
ance at electrolyte/counter electrode interface and lower
Fig. 8  Electrochemical impedance spectra of ZnO and S
­ nO2-doped
ZnO-based DSSC and its equivalent circuit
Journal of Materials Science: Materials in Electronics
charge transfer resistance at the photoanode layer which
signifies the inhibition of electron recombination in the cell.
The introduction of dopant in ­SnO2 based photoanode not
only widen the band gap but also increases the amount of
dye adsorption on the photoanode surfaces.
The introduction of the insulating layer is a good approach
to increase the band gap energy as well as light scattering, in
order to enhance the efficiency of S ­ nO2-based photoanode.
Bhattacharjee et al. [84] reported an improved photovoltaic
performance of DSSC by the presence of additional insu-
lating layer of Li-doped ZnO nanoparticles on ­SnO2-based
photoanode. Even though it showed a low electron lifetime,
𝜏eff  , the high PCE obtained is explained by the reduced
charge transfer resistance between the photoanode/FTO
interfaces due to the presence of Li-doped ZnO as a blocking
layer that shift the redox potential and promotes an efficient
electron transport across the DSSC. Meanwhile, Amit Thapa
et al. [41] employed a layer of T ­ iO2 on S
­ nO2 based DSSC
and they observed an increase of photo-conversion efficiency
(PCE ~ 6.05%), Jsc  ~ 14.7 mA/cm2, Voc  ~ 0.74 V with the
decrease of resistances ( Rct ~ 15.18 Ω and Rct  ~ 16.7 Ω)
compared to bare ­SnO2 which confirms the slower charge
transport in ­SnO2 due to lower interparticle electron mobility
in ­SnO2 film (Fig. 9). The high charge recombination resist-
ance of T ­ iO2 coated S
­ nO2 proved the successful surface pas-
sivation of ­SnO2 by ­TiO2 layer which led to slower recombi-
nation rate compared to the other photoanodes. The presence
of ­SnO2 in ­TiO2 based photoanodes promoted an electronic
semiconductor feature [90] due to the position of conduc-
tion band edge of ­SnO2 that is lower than ­TiO2, thus effec-
tively transfer the injected electron from the dye adsorbed
on ­TiO2 to S ­ nO2 [91]. Gu et al. [52] demonstrated a reduced
arcs of the semicircles of EIS spectra (Fig. 10) when they
coated ­SnO2 on ­TiO2 based photoanode as compared to bare
Fig. 9  Electrochemical impedance spectra of ­SnO2 and ­TiO2-coated
­SnO2-based DSSC and its equivalent circuit [41]
Fig. 10  Electrochemical impedance spectra of DSSC-based ­
TiO2,
­ iO2–SnO2 (TSN) and S
T ­ nO2 [52]
­ iO2 due to an increase of electron recombination losses to
T
electrolyte in ­TiO2–SnO2 based DSSC which reflected by
the higher Jsc , FF and PCE of the cell. However, the larger
arcs of semicircles of ­TiO2-SnO2 based DSSC compared
to ­SnO2 based DSSC implied the increase in charge trans-
fer resistance on the electrolyte/photoanode interface. This
result is in agreement with Basu et al. [92]. In their study,
­SnO2 photoanode is treated with T ­ iO2 and T
­ iCl4 which act
as a blocking layer to prevent recombination of charges. The
presence of ­TiO2 blocking layer successfully enhanced the
PCE of the cell as a result of reduced charge recombination
at the FTO/electrolyte interface.
5 Conclusion
In summary, tin oxide (­SnO2) is a promising and reli-
able candidate as a photoanode in dye-sensitized solar cell
(DSSC) application due to its low cost, abundant source,
wide band gap, high stability and high electron mobil-
ity. However, the high back-electron transfer rate of S ­ nO2
is related to its low value of conduction band edge which
accelerates the recombination of electrons and impedes
the electron trapping density. It is crucial to understand the
electron transfer behaviour inside the DSSC which can ( be )
analysed by EIS analysis. In spite (of electron
) lifetime 𝜏eff  ,
and electron( diffusion
) coefficient, Deff  , the charge transfer
resistance, Rct is the most significant factor that reflect the
charge recombination inside the cell. Challenges in reducing
the Rct have been overcome through structural modifications
and incorporation of S ­ nO2 with other metal oxides to tune
the band gap and electron mobility of ­SnO2-based photoan-
ode. Morphological modification also an effective strategy
to improve the effectiveness of charge transfer through the
13

role of the structure itself or by increasing the surface area
and interconnectivity between particles. The future trend in
morphological modification is more towards the formation
of a complex structure from basic structure such as S ­ nO2
nanorod which directly channel the electron and reduce the
back-transfer rate due to its 1-D nature. The formation of
­SnO2 hollow structure such as hollow microspheres (HMS)
and hollow nanofiber (HNF) also captured great interest
due to its efficient role in tuning the light scattering which
indirectly affect the charge injection in DSSC mechanism
without the need for any additional insulating or blocking
layer. Another common issue with S ­ nO2-based DSSC is the
disappearance of the third semicircle arc in Nyquist plot
which can be explained by the low viscosity of electrolyte.
Thus, the utilization of a more viscous electrolyte such as gel
electrolyte can greatly improve this phenomenon. Therefore,
it can be deduced that the strategies to improve the perfor-
mance of S ­ nO2-based DSSC does not only limited to the
photoanode, but also towards other components of DSSC
such as dye, electrolyte and counter electrode.
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