Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

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Renewable and Sustainable Energy Reviews

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

Nano-structured TiO2/ZnO nanocomposite for dye-sensitized solar cells

application: A review
⁎
Bibha Boroa, B. Gogoia, , B.M. Rajbongshib, A. Ramchiarya
a
Department of Energy, Tezpur University, Tezpur 784028, Assam, India
b
Department of Chemical Engineering, IIT Delhi, India

A R T I C L E I N F O A BS T RAC T

Keywords: Dye-sensitized solar cell (DSSC), the third generation photovoltaic technology is most promising alternative
Dye sensitized solar cells photovoltaic technology due to low-cost, stable electrical generation, good temperature stability, non-toxic
TiO2/ZnO emission during manufacturing, rapid efficiency enhancement and wider flexibility in design. The present study
Nanocomposite reviews the advanced techniques and research trends of ZnO compotization with TiO2 in different nano-
Nanostructure
structures. Performance efficiency gap between the conventional silicon solar cell and DSSC is an intensely
Photo-anode
promoted area of research. It results in an efficient photoanode which further leads to the improvement in
Solar cells
DSSC. Their performance is further enhanced using engineered nanostructured metal oxide photoanode. The
study emphasizes on nano-compotization of conventional titanium dioxide with other metal oxide in different
structures. It is one of the active research technologies for efficient DSSC. Comparative performance study
shows that three dimensional and hybrid nanostructured TiO2/ZnO nanocomposite such as nanodonuts,
nanoflower and 3D hierarchical heterostructure have better performance. Their open circuit voltage, short
circuit current, fill factor and efficiency lies in the range of 0.76–0.82 V, 3.24–16.70 mA/cm2, 0.17–0.69% and
0.51–9% respectively. Thus they result in rapid electron transfer rate, slower charge recombination rate and
higher surface area.

1. Introduction b. Nanocomposite of metal oxide through efficient charge separation

Solar energy is a gift of nature to the living beings of the planet
Earth. Since ancient days, it is being used in different forms and
applications. Its knowledge and applications are growing linearly with
development of technology. One of the promising solar energy harnes-
sing techniques is the use of photovoltaic systems (PVs) [1]. It was in
the year 1991, when Micheal Gratzel and Brian O’Regan made a
remarkable development of Dye Sensitized Solar Cells (DSCCs). They
have exceptional qualities of high photo-conversion efficiency, low-
cost, flexibility and fine-tuned materials [2–6]. Since then DSCCs have
drawn the attention of many researchers from the field of photo voltaic
technologies. Its performance is measured in terms of photo-conver-
sion efficiency, which in turn is dependent on rate of electron transfer.
They are reported to be affected with change in crystallinity, morphol-
ogy and surface area of the semiconductor [6]. Moreover the perfor-
mance of DSCCs has been reported to be enhanced with:
a. Doping and/or sensitization to increase the absorption of solar light
[7–10]
e.g. Al2O3/TiO2 [11], MgO/TiO2 [12], ZnO/Al2O3 [13], TiO2/ZnO
[14], ZnO/SnO2 [15].
c. Multi-structured semiconductor metal oxide for effective path for
electron transport and higher surface area for dye absorption [16,17]
In addition to the conversion efficiency, for utilization and better
commercialization of DSSCs good stability and easy fabrication also
plays a vital role in its selection [18]. Amongst the above mentioned
enhancement techniques, using composites of metal oxides has made
its largest impact and is advantageous over bare use of n-type metal
oxide semiconductors. The prime reason is the formation of hetero-
junction structures. These structures can be different forms and
possess the property of reducing the probability of photo-generated
electron-hole recombination to a great extent. Nanocomposite materi-
als constitute a good number of advantages like they are simple to
manufacture, benign and low fabrication cost [19]. Researchers on the
other hand are trying their best in finding the best combination of the
nanomaterials for enhancing the properties and the performance of
DSSCs using nanocomposite materials. Kanmani et al. reported core/

⁎
Corresponding author.
E-mail addresses: bibha@tezu.ernet.in (B. Boro), biswa27@tezu.ernet.in (B. Gogoi), bijumani2010@gmail.com (B.M. Rajbongshi), onjalu@gmail.com (A. Ramchiary).

http://dx.doi.org/10.1016/j.rser.2017.06.035
Received 20 January 2016; Received in revised form 24 May 2017; Accepted 9 June 2017
1364-0321/ © 2017 Elsevier Ltd. All rights reserved.

Please cite this article as: Boro, B., Renewable and Sustainable Energy Reviews (2017), http://dx.doi.org/10.1016/j.rser.2017.06.035
B. Boro et al.
shell TiO2/ZnO nanomaterials composites significantly improves the
open circuit voltage (Voc) compared to the bare TiO2 [20]. Similarly,
Jung et al. found that MgO coated TiO2 nanoparticles increases the
maximum conversion efficiency by 45% as compared to uncoated TiO2
electrode [21]. Improvement of performance and physicochemical
properties of DSSCs has been studied with the incorporation of
multi-walled carbon nanotube (MWCNT) into TiO2 based electrode
[22]. Lim et al. has demonstrated gold-silver (Au-Ag) incorporated
TiO2 photoanode where the conversion efficiency has been enhanced.
The enhancement in the efficiency has been attributed due to the
synergistic effect between the Au and Ag, and their surface plasmon
resonance effect, that improved the optical absorption and interfacial
charge transfer by minimizing the charge recombination process [23].
An extensive study has been carried out by the researchers using
different composite nanomaterials for DSSCs. Amongst all the compo-
sites of doping and sensitizing of metal oxides, TiO2/ZnO has emerged
as an excellent composite for DSSCs. The use of TiO2 is favorable due to
its abundance and the properties of high surface area, high dye
adsorption capability, high chemical stability and longer electron
lifetime [6]. It has remarkable optical and electrical properties, low
production cost and can be tuned for various physical properties [15].
Whereas, ZnO has the properties of swift carrier mobility, can be
synthesized easily, non-toxic and nano-crystalline particles for better
dye absorption [18–21,24]. Therefore, reports support the use of ZnO
in DSSCs for better photo conversion [25,26]. Both TiO2 and ZnO, has
been reported to occupy the top tally of photo conversion efficient
materials. But due to higher band gap of 3.2 eV and 3.37 eV for TiO2
and ZnO respectively, the effectiveness of photo-conversion is low.
Nanoparticles of ZnO comprises higher electron mobility than TiO2 but
the chemical stability of ZnO in acidic condition is low [26,27]. This
results in low power conversion efficiency (PCE) of solely ZnO
nanoparticles based DSSCs as compared to TiO2. To overcome these
drawbacks of ZnO, various strategies have been reported such as
coating, decorated, composites sensitization with other semiconductors
[27–29]. This fact has driven the intention to avail the swift electron
mobility and high chemical stability of the semiconductors through
composition of both the material for improved performance.
It is observed that integration of TiO2 with ZnO uses the high
reactivity potential of TiO2 and the high electron mobility of ZnO,
which improves the process of electron-hole transfer between the
corresponding conduction and valence bands [30]. Moreover, compo-
site of ZnO/TiO2 electrodes in DSSCs facilitates charge carrier separa-
tion and can enhance cell performance [31]. Park et al. synthesized
ZnO type shell TiO2 core for DSSCs [32]. Moreover, due to the size-
tunable physicochemical properties and high activities TiO2 and ZnO
semiconducting nanomaterials together have shown significant effects
on surface morphologies, dye absorption, stable, electronic and photo-
electrochemical properties in the field of solar cells [33,34]. Yao et al.
has presented a density-controlled ZnO-TiO2 core shell nanorod arrays
photoanode for DSSCs. Using of density-controlled ZnO-TiO2 core
shell nanorod arrays photoanode has provided better diffusion path
from ZnO nanorod arrays, reduced recombination losses and moreover
improved the performance of DSSCs than the conventional TiO2 [35].
Rajkumar et al. have synthesized TiO2:ZnO nanocomposites and used
as electrode in DSSCs. 4% increase in efficiency has been observed than
TiO2 nanoparticle electrode. The use of ZnO has formed energy barrier
at electrolyte/electrode interface leading to reduction in recombination
rate and increased cell performance [36].
The combination is further enhanced with the formation of various
heterogenic nanostructures in forms of nanoparticles (NPs), nanocom-
posites (NCs), nanotubes (NTs), nanobelts (NBs), nanodonuts (NDs),
nanorods (NRs), nanowires (NWs), hybrid nanostructures such as
NW/NT, NP/NW etc. [37,38]. These nanosize materials have peculiar
properties that could not be expected in bulk phase [39]. With increase
in involvement of research their synthesis in a controlled and repro-
ducible way has become possible with better investigation of their
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Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx
properties. It has been reported that, the optical and electrical proper-
ties are dependent on the morphology and phases of nanostructures
[40,41]. Nanosize semiconductors are useful material for photo active
systems such as DSSCs [42–46]. For this purpose various nanosize
photoanode materials have been synthesized having different nano
morphologies with the aim of improving the dye adsorption and
enhancing light absorption in DSSCs [47]. Among different nanos-
tructures the one-dimensional (1D) and three dimensional (3D)
nanostructures have attracted considerable attention in terms of its
application to DSSCs. They have improved the charge collection
efficiency i.e, faster electron transport and slower recombination rate
[48]. Li et al. has successfully prepared translucent TiO2 nanowires/
nanotubes using two-step anodization method for the use of solar cells
[49]. Highly-ordered TiO2 nanotube arrays have been successfully used
in DSSCs by Mor et al. [50]. Similarly, Martinson et al. used high
surface area ZnO nanotube in DSSCs [51]. In this regard important role
has been taken by proper choice of synthesis and processing parameter
to control the resulting TiO2/ZnO composite properties [29]. Literature
reports the preparation of TiO2/ZnO nanostructure systems for DSSCs
use by various techniques like sol-gel [52], hydrothermal method [53],
Chemical Vapor Deposition (CVD) [54], etc.
The present study, therefore focusses in reviewing one of the
promising metal oxide composites i.e. TiO2/ZnO and its potential in
the field of developing nanostructures. The study provides a detailed
layout and comparative analysis between various reported nanostruc-
tures of TiO2/ZnO composite. This will enable to have a better overview
of the potentials and areas of development in metal oxide composite
DSSCs.
2. TiO2/ZnO nanocomposite as photoanode in different
nanostructures
Study of DSSCs, a third generation photovoltaic technology, has
literally grown exponentially over the past two decades. But even then,
its application is still in laboratory scale. Works on DSSCs is based on
nanotechnology, which targets safe manufacturing with abundant raw
materials [55,56]. DSSCs has the advantages of low-cost materials and
manufacturing, stable electrical generation even under weak and
indoor lighting, good temperature stability, no toxic emission in
manufacturing, potential for rapid efficiency enhancement, wide flex-
ibility in design (colors and patterns) [57–59]. Besides its many
applications and advantages DSSCs has been facing issues of reliability
for practical application and further improvements in electricity
generation performance [60,61]. Inclusion of nanostructured and
composite materials in DSSCs has increased the potential and success
rate by many folds. Composite material is a combination of two or more
materials. Because of its high catalytic activity nanocomposites are
popular for DSSCs [62]. They have the potential to change the
dimension of the structure of pristine nanomaterials to nanowires,
nanotubes, nanobelts, nanotips etc. This resulted in improved surface
area and electron diffusion length [63].
With development in research and technology TiO2/ZnO composite
material and nanostructures has evolved as one of the favorable choice
for DSSCs because of their low-cost preparation methods, environ-
mental friendliness and good efficiency [64,65]. Even though a lot of
work has been done in this field but review of the status and
comparative study between various nanostructures is lacking. Studies
in this field will enable to find out the regions to be focused. Therefore
the present work reviews the development of TiO2/ZnO composite
nanostructures to identify the needed areas of research.
The nanostructures of TiO2/ZnO composite is broadly categorized
into (a) One-dimensional (1D) nanostructure, (b) Two-dimensional
(2D) nanostructure, (c) Three-dimensional (3D) nanostructure and (d)
Hybrid nanostructure. A detailed study of these nanostructures has
been done in Sections 2.1–2.4. All these nanostructures TiO2/ZnO
composite photoanode nanomaterials show different characteristics as
B. Boro et al. Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

Table 1
Characteristics of DSSCs with different structures of TiO2/ZnO nanomaterials.

Nanostructures/ Materials Voc Jsc FF η (%) Ref.

Nanocomsites (V) (mA/cm2) (%)

Nanorods TiO2 doped with different size ZnO nanrods 0.76 11.4 0.50 5.8 [52]

Nanotubes Coaxial TiO2/ZnO nanotube arrays 0.65 7.28 0.60 2.8 [75]
ZnO/TiO2 nanotube arrays 0.895 5.96 0.704 3.75 [76]
ZnO-decorated TiO2 nanotubes 0.72 6.77 65.11 3.17 [77]
ZnO nanotube arrays coated with TiO2 nanoparticles 0.94 6.97 0.60 3.94 [31]

Nanowires ZnO nanowires arrays coated with thin shell of anatase TiO2 0.78–0.82 4.0–4.5 0.58–0.6 2.25 [13]
TiO2-coated ZnO nanowires arrays 0.788 12.2 0.587 5.65 [79]
Nanofibres TiO2/ZnO core-sheath nanofibers films 0.75 11.3 0.61 5.17 [80]

Nanocomposites TiO2 coated ZnO 0.770 8.78 0.724 4.89 [26]

ZnO coated TiO2 nanoparticles 0.72 0.49 0.69 1.21 [81]
ZnO coated TiO2 0.75 13.46 0.654 6.62 [82]
Nanodonuts TiO2/ZnO nanodonuts 0.78 16.70 0.69 9.00 [89]

Nanoflower ZnO nanoflowers/TiO2 nanocomposite 0.82 6.14 0.56 2.82 [90]

amorphous/crystalline TiO2 over the ZnO nanoflowers/nanorods 0.76 6.303 0.60 3.1 [91]
ZnO nanoflowers converted into TiO2 flower-like cluster 0.76 7.96 0.453 2.73 [93]
3D hierarchical heterostructure 1D ZnO nanorods deposited on 2D TiO2 nanosheet 0.8 3.24 0.17 0.51 [92]

shown in Table 1, when used for DSSCs.
2.1. One-dimensional nanostructures of TiO2/ZnO composite
Amongst different types of nanostructured materials one-dimen-
sional (1D) nanostructure are promising elements for DSSC due to
several performances and processing benefits [66]. Such nanostruc-
tures has the property to enhance the electron transport properties due
to directional smooth electron mobility. It therefore accelerates the
electron transport and lowers the recombination probability [67]. In
addition its geometry offers a large surface area which in turn increases
the performance of DSSCs [68]. Moreover, its large size also con-
tributes to the light scattering effect which enhances the light adsorp-
tion of dye molecule [69]. They have been developed using various
techniques in the forms of nanotubes, nanorods, nanowires etc. of TiO2
and ZnO. Their use in DSSCs is a promising solution to replace the
nanoparticle film, which provides a direct pathway for collection of
charges generated throughout the device [70–74]. It is supported by
the use of high surface area ZnO nanotube which has been successfully
synthesized and used in DSSCs [51]. Pang et al. doped TiO2 based
DSSC with different sizes of ZnO nanorods. They have reported an
increase of 15% in power conversion efficiency on addition of 1% of
ZnO nanorods in weight. This was 1–3 orders of magnitude of carrier
diffusion rate faster than in the TiO2 electrode [52].
Another form of 1D nanostructure is the nanotubes. Xie et al.
prepared coaxial TiO2/ZnO nanotube arrays by electrochemical meth-
od. They have reported the success in deposition of ZnO layer inside
the original TiO2 pores. ZnO layer is composed of very small ZnO
nanoparticles which gave rough and nanoporous inner layers. It is
favorable for dye loading and electrolyte transport. Using this photo-
anode 2.8% energy conversion efficiency was achieved which was 40%
higher compared to pure TiO2 NTs as photoanode [75]. In another
study, Liu et al. introduced ZnO into TiO2 nanotube arrays with
average pore diameter of 83 nm and length of 14 µm. It is a result of
electrodeposition technique and is supported on Ti substrate (photo-
anode electrode). On investigating the results it was found that
conversion efficiency has doubled on depositing ZnO with deposition
time of 60 min on TiO2 nanotubes compared to bare TiO2 nanotubes
[76]. In a similar study, Lee et al. has also reported the synthesis of
ZnO-decorated TiO2 nanotubes for DSSCs shows higher efficiency
compared to TiO2 counterpart NTs. They have achieved higher surface
area, increased amount of dye loading and improved electron lifetime
in the system [77]. Yang et al. prepared ZnO nanotube arrays coated
with TiO2 paste using Doctor Blade method with an active area of 0.15
× 10−4 m2. The structure shows efficient electron transport and large
amount of dye loading exhibiting better performance than pure ZnO
nanotubes. An efficiency of 3.94% is reported to be increased, about
twice the efficiency of pure ZnO nanotubes cell. It also enhanced the
open circuit voltage (VOC) and short circuit current (JSC) [31].
Investigations prove that nanotube based DSSCs has the potential to
improve the photo-conversion efficiencies of DSSCs to a great extent.
The process of transport or recombination is affected with change in
density and location of structural defects, crystallinity and the compo-
sition of redox electrolyte [78].
Law et al. constructed DSSCs based on ZnO nanowire arrays, coated
with thin shell of anatase TiO2 by atomic layer deposition. Titania
shells of 10–25 nm thickness caused increase in VOC and Fill Factor
(FF). This results in improvement of overall conversion efficiency up to
2.25% under air mass (AM) 1.5 [13]. Xu et al. fabricated solid-state
DSSCs using multilayer TiO2-coated ZnO nanowire arrays as photo-
anodes and spiroOMeTAD as solid-state Hole Transporting Materials
(HTM). Multistep HTM filling procedure increases the electron re-
combination lifetime and reduces the series resistance resulting 5.65%
increase in efficiency [79].
In addition to the above Du et al. prepared TiO2/ZnO core-sheath
nanofibers (NFs) films for the use of DSSCs using coaxial electrospin-
ning technique. The film shows better dye loading capacity and
efficiency of 5.17% which is 16% larger than TiO2 NFs film based
DSSCs [80]. Sakai et al. studied the performance of DSSCs using
porous ZnO, TiO2 and TiO2 coated ZnO photoelectrodes with dyes
N719 and D149. It was found that D149 sensitized TiO2 coated ZnO
has shifted conduction band and shows the highest efficiency of 4.89%
under 1000 Wm−2 irradiation [26]. Kim et al. modified the surface of
TiO2 nanoparticles by coating with a layer of ZnO, thickness of
~0.5 nm. It facilitates the reduction in recombination of electron and
increases conversion efficiency from 0.71% to 1.21% under a light
intensity of 200 Wm−2 [81]. Chou et al. investigated ZnO-coated TiO2
electrodes with various concentration of ZnO, with variation in
duration of dipping and dye loading over TiO2 film. With seven layers
of dipping and 10.7 µm of film thickness, it shows the highest
conversion efficiency of 6.62% w.r.t conventional DSSCs with a TiO2
electrode of 5.54% [82].

3
B. Boro et al.
2.2. Two dimensional TiO2/ZnO composite nanostructures
Recently, several researchers have reported using two-dimensional
(2D) nanostructure nanomaterials like branched nanowire, na-
nosheets, nanofilms etc. for DSSCs [83,84]. Suh et al. successfully
used branched structure of ZnO for DSSCs [85]. 2D TiO2 nanosheets
were also been used for DSSCs which showed good performance
compared to naked TiO2 nanoparticles due to its comparable dye
adsorption amount and light-scattering capability [86]. Meng et al. also
synthesized 2D ZnO nanosheet for DSSCs [87]. The 2D nanostructures
possess many low dimensional characteristics with unique shape-
dependent characteristics that differ from bulk properties. They are
subsequently utilized as the key components of nanodevices [66]. But
the use of 2D nanostructure of TiO2/ZnO composite for dye-sensitized
solar cells is not popular because of its low photo-conversion efficien-
cies.
2.3. Three dimensional TiO2/ZnO composite nanostructures
During the development of DSSCs, porous photoanodes shows
superior photovoltaic properties due to their high dye absorption,
large pore volume, superior light scattering and good optical transpar-
ency [88]. Such properties are seen in three-dimensional (3D) nanos-
tructured materials. Li et al. synthesized novel sponge like TiO2/ZnO
nanodonuts by electrospray method. The results indicates a large pore
volume, higher dye absorption, better light scattering, more efficient
electron transport and electron penetration properties. Also energy
conversion efficiency of 9% is obtained which is 44.4% higher than
DSSCs based on P25 particles. This is relatively higher than other TiO2/
ZnO morphologies as well [89]. Liu et al. synthesized ZnO nanoflowers
using low temperature solution phase method. ZnO nanoflowers/TiO2
nanocomposite photoanode was made using doctor blade technique
having a film thickness of about 10 µm. Mass ratio of 25:75 of ZnO/
TiO2 gave the best conversion efficiency which was increased by about
1.5 times compared to pure TiO2 DSSCs [90]. Prabakar et al. intro-
duced a new architecture device of high surface area 3D photoanode for
DSSCs. They reported success in growing ZnO semiconductor nanorods
(NRs) and nanoflowers (NFs) fluorine doped tin oxide (FTO) coated
glass substrates by solution method. They subsequently deposited
amorphous/crystalline TiO2 over the ZnO electrode. This structure
enhanced electron transport and decreased the rate of recombination
[91]. Zheng et al. prepared a 3D hierarchical heterostructure, consist-
ing of CdS sensitized 1D ZnO nanorods deposited on 2D TiO2
nanosheet using solution-process method. The developed structure
improved the absorption, enhanced photoelectric performance and
efficiency of light harvesting [92]. Xin et al. prepared ZnO nanoflowers
converted it into TiO2 flower-like cluster. They used the Chemical Bath
Deposition (CBD) method by immersing the former into (NH4)2TiF6
and boric acid (H3BO3) solution. Thus the conversion efficiency
increases from 1.16% to 2.73%. Report shows that flower-like struc-
tures has a fast electron transit time and charge collection efficiency
was nearly 100% [93].
2.4. Hybrid TiO2/ZnO composite nanostructures
Apart from the use of TiO2/ZnO composite nanostructures for
DSSCs some hybrid structures with a combination of different nanos-
tructures have been studied for DSSCs. Recently DSSCs of 13% PCE at
full sun illumination has been fabricated utilizing the [Co(bpy)3]2+/3+
redox couple (which is a redox mediator) and porphyrin dye (SM315 a
green dye) over TiO2 film. It attributes to better light harvesting in both
visible and near-infrared [94]. Feng et al. have successfully synthesized
TiO2/ZnO hybrid heterostructured arrays (TiO2 nanowire/ZnO nanor-
od or TiO2 nanowire/ZnO nanosheet). They proved to be excellent
nanomaterials for superior quality solar cells [95]. Zheng et al. have
combined TiO2 structure with nanotube arrays and nanoparticles by
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Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx
controlling the thermal annealing condition of the electrochemically
anodized TiO2 nanotube arrays. This results in high surface area, good
conductivity. This in turn is helpful for efficient electron transfer and
diffusion of the electrolyte in DSSC resulting in 5.75% power conver-
sion efficiency (PCE) [96]. Zhao et al. synthesized ZnO/TiO2 hybrid
structure to form nano-sculptured foxtail-like patterns for DSSCs that
showed good electron transport capability, improved charge injection
and transport, reduced recombination and increased surface area that
improved the PCE from 0.3% to 1.8% [97].
Comparing the performance of different TiO2/ZnO nanostructures
used for DSSCs it is observed that superior performance owing to more
rapid electron transfer, slower charge recombination and higher
efficiency could be seen on DSSCs using one dimensional structure
(nanotubes, nanorods and nanowires). The best DSSCs involve TiO2
mesoporous nanoparticles [98].
3. Challenges and future work
Commercialization of DSSCs faces major challenges in the fabrica-
tion, poor performance and stability [99]. Its parts can be broadly
classified into anodes, dyes, electrolytes and counter electrodes which
are the areas for materials development [100]. Well optimization of
these components will lead to maximize the PCE of DSSCs. In order to
make significant improvement in the system, at least one of compo-
nents has to be altered [101].
Photoanode is one of the major components of the DSSCs which
determines the performance of the devices. Photoanode material is
composed of semiconductor metal oxides or nanostructured semicon-
ductor films which acts as the backbone of DSSCs [102]. Photoanode
supports sensitizer and transport photo-excited electrons from exciter
to external circuit, which requires large surface area and ensures
electron collection efficiency [103,104]. In order to enhance these
properties nanoparticles of different forms and structure, different
materials has been researched. Though TiO2 proved to be the efficient
material for DSSCs, the fast recombination rate, long term stability,
weakly bound dye molecules and limited photo response of TiO2 has
hindered its commercialization [36,105]. While using titanate nano-
tubes complexity and cost of the process makes it less attractive from
the perspective of commercialization [106]. Giannouli et al. has studied
the performance of TiO2 and ZnO DSSCs and put forward the low
efficiency and low stability of these cells compared to silicon based
solar cells which hinder their commercialization [107]. New materials
like perovskite are coming into focus. Since 2009, organolead halide
perovskites are being used for solar cells [108]. After the first efficient
solid-state perovskite solar cells has been made in mid-2012, since
then rapid progress has been made in terms of efficiencies. The highest
verified lab determined efficiencies is over 19% [109–112].
In addition to photoanodes, dyes also play a major role in
enhancing the PCE of solar cells by absorbing photons flux. Different
kinds of dye molecule are being developed and used in DSSCs. Most
common ones are ruthenium metal complexes, porphyrin and phtha-
locyanine systems, metal free organic dye molecules, squaraine dyes,
amine-free dyes, natural dyes etc. [113–115].
Electrolytes act as charge carriers that collects electron at the
cathode and transport electrons back to the dye molecules. In order to
improve the performance of DSSCs dyes plays a vital role. Most
popularly used electrolyte is the iodide/triiodide (I-/I3-) redox couple
which is a liquid electrolyte. The liquid electrolytes possess the
problems of leaking toxic solvent, evaporation of volatile ions and
increase in internal resistance. Therefore other electrolytes e.g. solid-
state electrolytes, quasi-solid state electrolytes have been developed
that increases the stability of the system [116–118].
Counter electrode acts as a catalyst to the redox couples regenera-
tion and electron collector from the external circuit. For efficient
performance, the counter electrode materials should possess good
electrical conductivity. Platinum, carbon materials, carbon nanotubes,
B. Boro et al.
polymers, transition metals can be used as counter electrode. In
addition, carbides, nitrides, oxides, sulfides etc. and multiple com-
pounds and composite materials, which show similar properties of
platinum, are also used as counter electrodes [119–121]. Moreover, for
novel strategies for high energy conversion efficiency, factors playing
vital role are (a) solar radiation, (b) minimization of system degrada-
tion rate that is related to long-term stability of the system and most
importantly (c) the reduction in the cost of the system [122]. These
factors need further investigation which will increase the economic
viability of DSSC based photovoltaic system.
4. Conclusion
It is well supported by various literatures that the properties of
higher surface roughness, porosity, crystallinity, structure and mor-
phology of semiconductor films are desirable to determine cell perfor-
mance. The present review shows that TiO2/ZnO has successfully been
used as photoanode in DSSCs in different forms of nanostructures. The
TiO2/ZnO nanocomposite shows the characteristics of higher surface
area and ability to inject photo-induced electrons effectively from the
dye to the semiconductor. Their inclusion as photoanode in DSSCs has
influenced its photovoltaic performance. Amongst all the nanostruc-
tures 1D, 3D and hybrid structures show better performance. The 1D
structures have the advantages of better performance with processing
benefits. Whereas 3D structures along with hybrid structures because
of their porous characteristics and high surface area shows better
performance. Although a lot of development is taking place in research
level but their commercialization still requires a number of improve-
ments.
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