Renewable and Sustainable Energy Reviews (xxxx) xxxx–xxxx

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Renewable and Sustainable Energy Reviews

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

An overview of the Challenges in the commercialization of dye sensitized

solar cells
⁎ ⁎
Samaneh Mozaffaria, , Mohammad Reza Nateghib, , Mahmood Borhani Zarandic
a
Faculty of Science, Gonbad Kavous University, P.O. Box 163, Gonbad, Iran
b
Department of chemistry, Yazd Branch, Islamic Azad University, Yazd, Iran
c
Department of Physics, Yazd University, P.O. Box 97175-615, Yazd, Iran

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

Keywords: Dye sensitized solar cells (DSSCs) are a type of photovoltaic device that have received widespread attention in
Solar energy recent years. In comparison with silicon photovoltaic cells, DSSCs exhibit some specific advantages including
Dye sensitized solar cell easy fabrication procedures, low manufacturing cost and compatibility with flexible substrates. In spite of the
Efficiency advantages mentioned, from the industrial point of view, the efficiency and the long term stability of the DSSCs
Stability
system have been subject of concern during the past years of development of this technology. In order to solve
Degradation
these problems, numerous research efforts have been devoted to the engineering and manufacturing of devices
that could meet the standards of the photovoltaic cells market for various applications, but the low efficiency
and stability have remained as the major challenges in development of DSSCs over the past 25 year. This review
focuses on the obstacles and restrictions in the fabrication and commercialization of DSSCs. Losses-in-potential
as a limiting efficiency and degradation processes are discussed and external effective factors on the stability of
DSSC such as thermal and light soaking stresses, environmental conditions and issues related to the sealing
have been investigated in detail. Also, commercial photovoltaic technology of DSSCs in term of efficiency,
stability and lifetime is compared to the different types of photovoltaic solar cells. Results indicate that despite
the many attractive features of this technology, the transition from laboratory to industry and outdoor
applications has been hampered by a number of issues.

1. Introduction devices is based on the charge separation at an interface of two

The growth of world population along with industrial developments
would be an enormous challenge in meeting the rising energy demand
in the near future [1]. As depicted in Fig. 1, the projections of world
energy demand by the US Energy Information Administration forecasts
a total growth from the present 14 TW towards 25–30 TW in 2050 [2].
Besides the demand of energy, the combustion exhaust of fossil fuels
has resulted in the environmental pollution and greenhouse effect.
Thus, with respect to the ecological problems, the limited availability of
fossil fuels, special focus is necessary on renewable energy sources to
contribute significantly to the energy supply of the world [1,3].
Renewable energy sources, such as photovoltaic (PV), hydropower,
wind, solar thermal and biomass, have the potential to meet the rising
energy demand, and are expected to play an essential role in moving
the world to a more safe, reliable and sustainable energy system [4].
Most of the aforementioned forms of renewable energy are based on
solar energy. However, photovoltaic cells are the only devices that
directly convert sunlight to electrical energy [4]. Mechanism of PV
materials with different work function or semiconductor-metal (schott-
ky) junction [5]. Solar cells can be divided into various categories
depending on their materials, working principles and production
techniques [6,7]. The first commercialized generation of PV devices is
fabricated by crystalline silicon as active material. This type of
photovoltaic cells is currently dominant in the market due to the high
efficiency (η) of up to 25%. However, the silicon-based PV devices
involve employment of high purity silicon single crystals that are
manufactured by very extremely expensive processes. Thus, the high
cost of the first generation PV devices severely restricts their wide-
spread applications in the future [8]. The second generation of PV
devices is also referred to as thin film solar cells. Amorphous silicon,
copper indium gallium selenide, gallium arsenide and cadmium tell-
uride are the most commonly used materials. The thin film technology
allows the second generation PV devices to use less material in
fabrication of a solar cell, which significantly reduces the production
cost in comparison with the first generation devices. However, the
efficiency of thin film solar cells is lower than that of the solar cells,

⁎
Corresponding authors.
E-mail addresses: mozaffari.samaneh@gmail.com (S. Mozaffari), mnateghi@iauyazd.ac.ir (M.R. Nateghi).

http://dx.doi.org/10.1016/j.rser.2016.12.096
Received 19 November 2015; Received in revised form 22 December 2016; Accepted 23 December 2016
1364-0321/ © 2016 Elsevier Ltd. All rights reserved.

Please cite this article as: Mozaffari, S., Renewable and Sustainable Energy Reviews (2016), http://dx.doi.org/10.1016/j.rser.2016.12.096
S. Mozaffari et al.
Fig. 1. Projections of world energy demand by the US Energy Information
Administration [2].
ranging between 10–20%. Moreover, the scarcity and toxicity of the
materials being used have been the two major disadvantages for thin
film solar cells from a large-scale production point of view [9,10].
The development of PV technology has focused on the “Golden
Triangle” issues, i.e, increasing photo-electric conversion efficiency,
enhancing long term stability, and decreasing device cost [11,12]. The
third generation PV cell technology differs from the first and second
generation technologies by looking ahead to optimize the energy
conversion efficiency and notably decrease costs [13]. Most of the
third generation solar cells are still in the research step including
organic solar cells (η≈11%), quantum dots solar cells (η≈10%), dye-
sensitized solar cells (η≈13%), and perovskite sensitized solar cells
(η≈22%) [14,15].
DSSCs are promising PV devices due to easy manufacturing, low
cost materials and advantages related to transparency, color choice and
mechanical flexibility [16–19]. The major challenge in the commercia-
lization of DSSCs is the low photo-electric conversion efficiency and
stability of the cells [19]. The maximum achievable theoretical effi-
ciency of the conversion energy has been estimated to be 32% for DSSC
[20]; however, the highest efficiency has been reported so far is only
13% [15]. Extensive efforts have been carried out to understand the
parameters that adjust the performance of DSSC in order to improve its
efficiency. Numerous attempts have already been made to optimize the
redox couple [21] and dye absorbance [22], modify semiconductor with
a wide band gap as working electrode [23,24] and develop counter
electrode (CE) [25]. However, the slow progress and the difficulty
relating to the scale-up processes have fostered the idea that DSSCs
have not fulfilled their promise [26].
Besides enhancing the performance of DSSCs, the materials cost is
another significant issue that needs to be addressed in the future work.
Typically, DSSCs are composed of a mesoporous TiO2 nanocrystal
electrode on a transparent conductive oxide (TCO) substrate, ruthe-
nium-based dyes (Ru), platinum (Pt) on the TCO substrate as a counter
electrode and I-/I3- electrolyte [27]. O’Regan and Gratzel fabricated a
DSSC with an unbeatable record of the highest η using arrays of
nanoparticles photoanode made up of mesoporous TiO2. However,
TiO2 in DSSCs generally requires sintering at 500 °C to improve the
electronic contact, which makes them relatively expensive and limits
substrate choice and monolithic device architectures [28]. As the most
popular sensitizer for DSSCs, Ru(II) polypyridyl dyes show excellent
efficiency as a result of their suitable energy levels with respect to TiO2
photoanodes and I-/I3- electrolyte, broad light absorption range from
ultraviolet to near-infrared light and high molecular stability. Despite
their great potential, Ru-based sensitizers suffer from issues related to
the toxicity, high costs and limited availability of the starting material,
thus making them unsuitable for a widespread application in cost-
effective and environment friendly DSSC systems [29,30]. Moreover,
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Renewable and Sustainable Energy Reviews (xxxx) xxxx–xxxx
the development of new CEs is a main research area of investigation to
improve the efficiency of DSSCs. Typically, Platinum is a superior
catalyst used as counter electrode [6,7], but it is one of the expensive
components in DSSC and the commercial mass production of DSSCs
need a large amount of platinum which is not abundantly available
[24]. Another important factor in the production cost of DSSCs is the
use of TCOs such as indium or fluorine doped tin oxide (ITO or FTO).
These substrates are thick, rigid and heavy. Moreover, they constitute ∼
17% of the total material cost. Thus, the high cost of these materials is
an obstacle and a preventive factor in the commercialization of DSSCs
[19,31].
The stability of DSSCs is also an important aspect for their
commercialization. DSSCs should be able to endure 108 turnovers
corresponding to a 20 year exposure to sunlight without apparent
degradation [32]. The evaluation of the lifetime of DSSCs is a difficult
task because it depends on the specific degradation mechanisms [33].
The leakage of liquid electrolyte, corrosion of the Pt CE by the redox
couple (I-/I3-), electrolyte bleaching and the detachment of the
adsorbed dye on the surface of TiO2 have been investigated as some
of the vital factors limiting the long term stability of the DSSC [34,35].
By using the solid state electrolytes, the DSSCs show good long term
stability. As a result of poor interfacial electrolyte/electrode contacts
and low conductivity, the efficiency of this kind of DSSCs is less (Before
that the perovskite solar cells are introduced) than that of cells
containing liquid electrolyte [36].
This review focuses on the major challenges which prevent the
commercial production of DSSCs. Operation principles and compo-
nents of dye sensitized solar cells are summarized and losses-in-
potential as the efficiency limiting main factor is discussed. Also,
important degradation processes such as dye desorption, decreasing
the triiodide concentration, degradation of the counter electrode, effect
of humidity and issues related to the sealing are described in details.
Moreover, performance and stability of the DSSCs utilizing various
types of electrolytes (ionic liquids, gel and solid state electrolytes) are
reviewed. Finally, commercial photovoltaic technology of DSSCs in
term of efficiency, stability and lifetime is compared to the different
types of photovoltaic solar cells especially with the perovskite solar
cells. Studies show that despite the exponential growth in research
effort over the past 25 years, enhancement in the efficiency and long
stability of the DSSCs are not considerable.
2. Operation principles
Dye sensitized solar cell is a photovoltaic device which consists of a
photoanode, a counter electrode and an electrolyte solution [37]. A
schematic illustration of the structure of DSSC is shown in Fig. 2 [38].
The photoanode is consisting of a semiconductor layer such as TiO2
Fig. 2. Schematic of dye-sensitized solar cells [38].
S. Mozaffari et al.
deposited on a TCO, a flexible polymer substrate or metal foil. The
semiconductor layer is sensitized with a monolayer of a dye which
typically is Ru complexs. Dye molecules absorb photons from sunlight
in the visible region and generate excited electrons. These electrons are
injected into the conduction band of semiconductor and penetrate
through the nanocrystalline TiO2. Fig. 2 indicates the external circuit
and electron transfer toward the counter electrode. The CE is com-
posed of a platinum layer, deposited on another TCO substrate. The
photoanode and counter electrode interval is filled with an electrolyte
solution. Usually I-/I3- dissolved in acetonitrile is used that transports
electron from the counter electrode to sensitizing dye. The excited dye
molecules are reduced to their original state when they receive electron
from I- ions in the electrolyte solution [38,39].
3. Measurements
The conversion efficiencies of the DSSCs are calculated from the
short circuit current density (Jsc), open circuit voltage (Voc), fill factor
(ff) and the intensity of the incident light (Pin) according to the
following equations [40,41].
VOC. JSC. ff
η (%)= × 100
Pin (1)
Vmax .Jmax .
ff =
VOC. JSC (2)
In theory, VOC is determined by the energy difference between the
Fermi level of the semiconductor (nanocrystalline TiO2) and the redox
mediator potential (I-/I3-) in the electrolyte (Fig. 3) [10]. However, the
empirical observations show Voc for various sensitizers is smaller than
the theoretical value. This is generally due to the competition between
charge recombination pathways and electron transfers. Thus, knowl-
edge of competitive reaction mechanism is vital for the improvement of
the energy conversion efficiency of the cells [42,43].
4. Maximum DSSC power-conversion efficiency
The maximum theoretical η (Shockley-Queisser limit) of a single-
junction PV is around 32% [10,44]. For inorganic photovoltaic cells,
the main deviation from this limit is through the loss-in-potential,
which can be defined as the difference between the Voc and the optical
band gap of the photoactive semiconductor. For example, the record
Fig. 3. Energy level and device operation of DSSCs [10].
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Renewable and Sustainable Energy Reviews (xxxx) xxxx–xxxx
30% efficient silicon PVs has a loss-in-potential of around 400 mV,
whereas the record 28% efficient gallium arsenide PVs shows a loss-in-
potential of 300 mV [8]. In contrast to inorganic solar cells, DSSCs
require relatively large over-potentials to drive electron injection into
the conductive band of TiO2 and regenerate the oxidized dye (Fig. 3).
Typically, a potential difference between the lowest unoccupied mole-
cular orbital (LUMO) level of the dye and the conduction band of TiO2
is required for fast electron injection. Theoretical calculations show
that this value is approximately 150 mV for dye sensitized solar cells
[45]. Moreover, regeneration of a ruthenium metal complex dye with
I-/I3- redox couple has a loss around 600 mV so that, more than
300 mV is directly related to the reaction within the iodide electrolyte.
Therefore, it is estimated that the loss-in-potential for the Ru complex/
iodide system is 750 mV, which limits the maximum conversion
efficiency to 13.8% [46,47].
There are two main ways in which the efficiency of a DSSC can be
improved: extending the light-harvesting region into the near-infrared,
and lowering the redox potential of the electrolyte to increase VOC.
4.1. Light harvesting
To achieve high power conversion efficiency based on I-/I3- redox
coupling system which is competitive with conventional silicon solar
cells, the sensitized dye must absorb as much as 80% of the solar
spectrum with the wavelength between 350 and 900 nm [48].
Conventional Ru based dyes such as N3, N719, Z907 and C106 that
have fairly broad absorption spectra (Δλ≈350 nm) exhibit a relatively
broad absorption spectrum which is advantageous; however their
molar extinction coefficients (5000-20 000 M-1 cm-1) are low.
Therefore it is difficult to improve the η of the device using these dyes
[48,49]. Organic dyes have been intensively investigated to replace Ru
complexes as sensitizers for DSSCs. They generally have considerably
higher molar extinction coefficients (50,000–200,000 M-1 cm–1) than
Ru-based complexes, but typically have narrower spectral band widths
(Δλ≈100–250 nm) and emission lifetimes of their excited state are
shorter than those of metal complexes [50,51]. A large number of
organic dyes, most of which are designed with a donor-π spacer-
acceptor (D-π-A) structure, have been investigated for utilization in
DSSCs (Fig. 4) [52]. Such organic dyes generally consist of electron-
rich moieties (e.g. carbazoles, triarylamines and indulines) as donor
parts,π-conjugated groups (e.g. thiophenes, polyenes and benzothia-
S. Mozaffari et al.
Fig. 4. Design structure of metal-free organic dyes [52].
diazole) as π-spacer parts and electron-withdrawing units (e.g. rhoda-
mines, cyanoacrylic acid and pyridines) as acceptor parts [27]. In many
cases, the HOMOs of a D-π-A system are delocalized over the π-
conjugated system in configurations centering on the donor side, and
the LUMOs are mainly delocalized on the acceptor side. Yang et al.
synthesized organic sensitizers based on a phenothiazine framework
containing single and double electron acceptors with thiophene bridge
for DSSCs [53]. The optimized geometries were determined with
density functional theory (DFT) calculations to estimate the photo-
voltaic properties of the dyes in the design stage and the effect of the
anchoring groups on the efficiency of DSSCs was investigated. The
DSSCs based on the double electron acceptors exhibited a better
current density (11.6 mA cm-2) due to the higher molar extinction
coefficient and red-shifted light absorption compared to the DSSCs
based on single electron acceptor (10.2 mA cm-2) and the conventional
N3 Ru dye (10.4 mA cm-2). Contrarily, the larger amount of protonated
carboxylic groups in the double-anchoring organic dye led to a lower
Voc because of the positive shift in the Fermi level of TiO2[53]. To date,
the best conversion efficiency of DSSCs using D-π-A type organic dyes
is about 13% [54]. The narrow absorption bands, adverse dye
aggregation and instability are a major problem for further improve-
ments in metal-free organic dye sensitizers [55]. Moreover, laboratory
development of D-π-A dyes mostly invokes a trial-and-error procedure
which requires extensive materials and synthesis process, so that their
use is restricted in the manufacturing of DSSCs [56]. Tandem DSSCs
were developed to supplement insufficient absorption of single dye
[57,58]. The tandem solar cells consist of several subcell with different
band gap stacked together. Each subcell converts only a particular
region of the incident solar spectrum close to its band gap. Usually, the
front cell is designed to absorb photons in the UV–visible region (280–
700 nm) and lower cells absorb photons in the visible-NIR region
(400–900 nm) of the solar spectrum [59]. First reported a tandem
structured DSSC based on two completed cells using N719 dye as a
front cell and black dye as a bottom cell was reported by Wataru et al.
[60]. The electrode of the front cell is generally highly transparent, and
it is made up of TiO2 nanoparticles, which allow most of the non-
absorbed wavelengths by N719 dye, penetrate through the front cell
and to be absorbed by the black dye at the bottom cell [61]. Hironori
et al. designed a series-connected tandem DSSC (in series tandem cells,
total Jsc is close to the Jsc of the each subcell, while the Voc is equal to
the sum of the Voc generated by both sub cells) with optimized dye
combination (NKX-2677, N719, NK-6037, and black dye). The best
performance (η=10.4%, Voc=1.45 v and Jsc=10.8 mA cm-2) obtained
for tandem DSSC consisting of an N719 front cell and a black dye
bottom cell [62]. In order to improve the efficiency of the cell, the band
gap of the absorbing materials needs to be optimized to fulfill the
current matching condition [63]. Sobus et al. calculatedfor the DSSC
using iodide-electrolyte, the optimum absorption onsets of the sensi-
tizers in the first and second unit of tandem PV system are 660 nm and
930 nm, respectively. The maximum available efficiency of such
tandem configuration is 20%, much more than the current laboratory
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Renewable and Sustainable Energy Reviews (xxxx) xxxx–xxxx
record for single DSSC (η=13%) [64]. However, despite several
attempts at different constructions of tandem DSSCs, the obtained
efficiencies for these devices are still lower than the single DSSCs in
laboratory scale [65,66]. The main reason is poor performance in terms
of incident photo-to-current conversion efficiency (IPCE). IPCE de-
pends on quantum yields and light harvesting efficiency of three partial
charge separation processes in DSSC (dye recombination, electron
injection and charge collection) [17], and its low values indicate that at
least one of these components of IPCE is remarkably less than 100%.
Moreover, the absorption band of dyes used for tandem solar cells is far
from optimum absorption onsets obtained using theoretical calculation
[67]. Co-sensitization using two or multiple dyes with complementary
absorption spectra has been demonstrated to increase light absorption
of DSSCs. Many co-sensitization systems have been used as sensitizers
in DSSCs, such as Ru complex co-sensitized with an organic dye
[68,69], porphyrin or phthalocyanine co-sensitized with an organic dye
[70,71], and organic dye co-sensitized with another organic dye
[72,73]. However, interactions between dyes and undesirable compe-
titive adsorption can easily cause a decrease in the efficiency of DSSCs
[73,74].
4.2. Redox couples as influencing factors on open circuit voltages
Since Voc of DSSCs is highly dependent on the electrochemical
potential of redox mediator, many redox mediators have been studied
in the DSSCs. Although I-/I3-redox couple have been indicated to show
remarkable performance in DSSCs, there are several negative features
limiting its further application. Iodine has a relatively high vapor
pressure, which makes it challenging for device encapsulation; iodine is
extremely corrosive to many sealing materials, especially metals
(silver/copper) in large scale modules and limits long term stability
of the DSSC; the I3- ion and other possible polyiodides (such as I5-, I7-,
and I9-) absorb part of the visible light around 430 nm and reduce the
photocurrent and the conversion efficiency of the devices; the mis-
match (about 0.8 V) between the redox potential of a typical sensitizer
(ΔEredox≈1.1 V vs. NHE) and that of I-/I3- (ΔEredox≈0.35 V vs. NHE)
causes a loss in VOC for DSSCs [21,75]. According to Marcus theory, a
driving force of 0.2–0.3 eV should be sufficient for outer sphere single-
electron-transfer reactions to ascertain a fast dye regeneration rate,
opening up the opportunity to increase the VOC [76]. This beneficial
effect has been observed when the I-/I3- redox couple was replaced by
solid state hole conductors or new cobalt complexes [14,15,77,78].
Various types of the iodine/iodide free redox couples were tested in the
DSSCs. For example, the bromide/tribromide couple has a more
positive redox potential (about 1.1 V vs. NHE) in comparison to the
iodide/triiodide couple (about 0.35 V vs. NHE). It seems that electro-
lytes containing the Br-/Br3- redox system can greatly improve the
photovoltage of the DSSCs. The research results confirmed that the
DSSCs with an eosin Y and several Ru polypyridyl dyes and Br-/
Br3-electrolyte had higher VOC values than that of the DSSCs with I-/I3-
electrolyte but showed lower JSC and ff values [79]. The decreased ff
and Jsc are correlated with the decreased conductivity of the electrolyte
containing Br-/Br3- and the insufficient driving force for dye regenera-
tion respectively [79]. From an energy level point of view, design of
dyes that HOMO and LUMO levels match the redox potential of Br-/
Br3- is difficult and limits the use of this redox couple in the electrolytes
[21]. Interhalogen redox systems, such as I-/I2Br−and I-/IBr2-, have
been studied in various solvents in combination with Ru based
sensitizing dyes [80]. It was shown by mass and Raman spectroscopy
that there is complex equilibrium between the different electrochemi-
cally active species in organic solvents. Overally, light-to-electricity
conversion efficiencies up to 6.4%, 5.0%, and 2.4% at 1000 W m-2 AM
1.5 illumination were achieved using electrolytes based on interhalogen
ionic salts with glutaronitrile, γ-butyrolactone and native ionic liquids
as solvents, respectively. Complex equilibrium between various inter-
halogen anions in the electrolyte solution limits the full characteriza-
S. Mozaffari et al.
tion of redox couple [78]. Pseudo-halogen redox couples, SeCN-/
(SeCN)3- and SCN-/(SCN)3-, have been studied as redox mediators
for DSSCs. The redox potentials of these two redox couples are 0.43
and 0.19 V more positive than that of I-/I3- redox couple, respectively
[81]. The application of selenocianate-based redox couple SeCN-/
(SeCN)2 in liquid electrolyte-based DSSC was introduced by Oskam
et al., by using acetonitrile as solvent and N3 as sensitizer [81]. The
sunlight conversion efficiency values were not reported, but the IPCE
was low (20%) that it can attribute to the inefficient dye regeneration
by the SeCN- ions. Afterward, Gratzel et al. prepared a selenocianate-
based low viscosity IL (i.e., 1-ethyl-3-methylimidazolium selenocya-
nate), which led to outstanding efficiency (8.3%), demonstrating that
pseudohalogens are a valid alternative to the iodine-based couple [82].
Although pseudohalogen redox can reach a high efficiency, the poor
stability under light soaking and prolonged thermal stress limits its
development of the redox couple in the DSSCs [83,84]. An excellent
choice for an alternative redox couple is the ferrocene/ferrocenium
hexafluorophosphate (Fc/Fc+) couple (it is an IUPAC-recommended
reference redox couple). This non-corrosive mediator exhibits well-
defined electrochemistry that is commercially available on a large scale
and has a more desirable redox potential than I-/I3- redox couple
(0.62 V cf. 0.35 V vs. NHE), which should result in a higher VOC.
Moreover, dye regeneration by Fc is a simple one-electron transfer
reaction so that, it does not involve the formation of high-energy
intermediate radical species or reformation of chemical bonds. These
promising features have led to attempts to use ferrocene as a redox
couple in DSSCs, but the resulting devices have exhibited low efficien-
cies (η < 0.4%) [18]. This discrepancy may be explained in terms of the
fast reduction in the rate of back electron transfer from the TiO2/dye/
electrolyte interfaces to the ferrocenium in the electrolyte [85]. Organic
redox disulfide/thiolate (T-/T2) was successfully used as a redox couple
in DSSCs. Wang et al. reported an efficiency of 6.4% with the Ru-based
Z907-Na as sensitizing dye and T-/T2-based electrolyte containing 4-
tert-butylpyridine and LiClO4 [85]. It is notable that despite promising
results obtained for new sulfide-based redox couples, the long term
stability of these cells still needs to be improved. Studies show that the
η drops below 20% of the initial value within one week after the devices
are subjected to standard light soaking conditions at 60 °C and full
sunlight due to a drop of all photovoltaic parameters Jsc, Voc and ff
[86]. Also, since the redox potential of T-/T2 is close to that of I-/I3-, it
cannot be expected further improvement in DSSC voltage [21]. The
best DSSC result achieved so far is 13% by using Cobalt (II/III) based
redox species with tert-butyl pyridine (TBP), and LiClO4 in acetonitrile
and zinc-porphyrin sensitizer (SM315). However, compared to effi-
ciency of silicon photovoltaic cell, this efficiency is not sufficient for
cost-effective commercial production of DSSCs. Moreover, the slow
diffusion of bulky Co(II/III) complex into semiconductor films and the
fast recombination of injected electrons with the oxidized redox species
along with the short term stability have limited its use as the electrolyte
Fig. 5. Electrolyte color change during the soaking test. Left: initial color; right: final color [75].
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Renewable and Sustainable Energy Reviews (xxxx) xxxx–xxxx
[55,87].
In addition to the above attempts, many strategies have been used
to enhance the performance of the DSSCs. Design of nanostructured
semiconductors with effective architectures to achieve high dye load-
ing, fast charge transport rate from the dye to the conduction band of
semiconductor, photoanodes modification for suppression of the back
reaction of the injected electrons from dye to the electrolyte [88], the
utilization of additives in the electrolyte [89], the optimization of the
counter electrode [90], improvement in mechanical connections be-
tween working and counter electrodes [91], and the use of light-
scattering layers [92] are some of these efforts. However, despite the
extensive research during the past 25 years, the maximum electrical
conversion efficiency of DSSCs is 13%, which is much lower than that of
the silicon solar cells [15].
5. Degradation and stability of DSSCs
The stability of DSSC can be divided into external and internal
stability factors [93]. For external stability, the fundamental factors are
thermal and light soaking stresses which a PV cell may experience. The
typical methods to test the stability of the DSSC are thermal stress test
at different temperatures (20–80 °C), light intensity soaking test
(1000 W m-2 equivalent to 1 Sun) [93] or combined thermal and light
soaking tests [94] partly adopted from the established silicon-based PV
technology. These stresses subsequently affect properties of DCCS such
as leakage of electrolyte, thermal stability of dye molecules, mechanical
stability i.e. the detachment of nanoparticles from the photoanode
surface and electrocatalytic activity of the electrolyte/CE interface [95].
Here, we discuss some of the important degradation processes when a
cell is exposed to the stress tests.
5.1. Electrolyte degradation
The electrolyte is one of the most crucial components in DSSCs; it is
responsible for the inner charge carrier transport between electrodes
and continually regenerates the dye. The electrolyte has a great
influence on the long term stability and light-to-electric conversion
efficiency of the devices. In terms of the cell efficiency, the most
commonly used electrolyte is the iodide/triiodide redox couple in an
organic matrix, generally acetonitrile. Experimental studies indicated
that the main reasons for the gradual degradation in performance of
DSSCs are related to changes in the electrolyte and in the TiO2/
electrolyte interface [96–98]. Thus, the correct choice of solvent,
electrolyte additives and redox couple concentrations are critical for
reaching long term stability [99,100]. Most often the degradation of I-/
I3- based electrolytes is related to the loss of I3- which results in
changes from a yellow to a colorless liquid, referred to as bleaching
(Fig. 5) [75,101,102]. The decrease of the I3- concentration increases
the series resistance due to the increased electrolyte diffusion resis-
S. Mozaffari et al.
tance which leads to a lower ff. Moreover, the loss of I3- can reduce the
short circuit current density because of mass transport limitations and
also increases the back recombination rates at the TiO2/electrolyte
interface which may lead to a lower Voc [95,103].
The bleaching phenomenon is mainly linked to the exposure of the
cell to UV illumination which causes direct band gap excitation of the
TiO2 [104,105]. It was found that photogenerated holes in the TiO2
valence band may be quenched by the iodide ions in the electrolyte and
reduce the concentration of I3− [104]. Furthermore, electrolyte bleach-
ing was also reported resulting in the high temperatures (T > 50 °C)
under one Sun illumination even in the absence of UV light and under
both indoor and outdoor ageing conditions in the presence of UV filter
with a cut-off wavelength at 397 nm [105,106]. Also, active oxygen
species (such as hydroxyl groups and OH radicals), water or other
impurities in the electrolyte and sublimation of iodine due to inade-
quate sealing barriers are the other factors in the I3- depletion
mechanisms [107].
5.2. Degradation of the counter electrode
Requirements of a material to be used as a counter electrode in
DSSC is to have a low charge transfer resistance, optimum thickness,
high surface area, porous nature good adhesivity to the transparent
conducting oxide, high reflectance of transmitted light, good electro-
chemical stability in the electrolyte and high exchange current density
[108]. Pt has been widely used as the CE, because of the superior
electrocatalytic ability and high conductivity for I-/I3- redox reaction
[109]. However, as a noble precious metal, platinum is one of the most
expensive materials in a DSSC (about $50,000/kg) [110,111]. Also, the
decomposition process of platinum chloride on FTO requires a high
temperature more than 400 °C that is not applicable for most flexible
plastic substrates [113]. It has been mentioned that Pt might not be
stable long periods of time due to the change of its electrocatalytic
properties (such as the valence state of platinum) and chemical
dissolution in the electrolyte containing an I-/I3- redox couple [113].
Hauch et al. found that the charge transfer resistance of Pt CE was
increased when the platinum electrodes were stored in air for some
months, due to the influence of atmospheric gases [114]. Wang et al.
used x-ray photoelectron spectroscopy analysis to investigate the
stability of Pt electrodes. It was found that the valence state of Pt alter
from 0 to +2 and +4, during the thermal sealing process of the cells
[115]. Degradation of the catalytic activity of the Pt counter electrode
has a negative influence on the cell performance as a result of
increasing the charge transfer resistance in counter electrode/electro-
lyte interfaces [116]. Moreover, dissolution of platinum in electrolyte
and adsorption on the photoanode film would enhance the recombina-
tion of electrons from TiO2 CE to I3- in electrolyte (dark current) and
reduces the open circuit voltage and the fill factor of the DSSCs
[108,114,117].
Carbon materials are emerging candidate material that can replace
Pt owing to electronic conductivity, high specific area, high mechanical
strength, thermal stability and electrochemical stability [118,119].
Imoto et al. used active carbon, a type of amorphous carbon with a
diamond structure, as a CE catalyst in DSSC. The DSSC using activated
carbon CE showed PCE of 3.89% that was lower than that of the DSSC
using Pt-CE (4.30%) [120]. Carbon nanotube (CNT) fibrous CEs were
fabricated by coating CNT paste and spraying CNT suspension solution
on Ti wires. Fluorine tin oxide was used on CNT layer to improve the
adherence of the CNT layer on Ti substrate for sprayed samples. The
catalytic characters of CNT fibrous CEs were carefully investigated by
electrochemical impedance technique and current-voltage measure-
ment. The catalytic activity of CNT films enhanced with CNT loading
amount as the results of the increasing inner surface area of CNT films.
Both of the fibrous-DSSCs with CNT CEs prepared by coating and
spraying methods (spraying time was 1000 s) indicated efficiency of
4.14% and 4.18% respectively, which were comparable to that of a cell
6
Renewable and Sustainable Energy Reviews (xxxx) xxxx–xxxx
with a typical Pt CE (5.05%) [121].
Several authors showed the correlation between the physical and
chemical properties of graphene and its electrochemical activities in
terms of its charge transfer resistance [122,123]. Mayhew et al.
fabricated a DSSC using functionalized graphene flakes with oxygen-
containing sites as CE. High electrocatalytic activity obtained and the
efficiency of the DSSC reached 5.0%, close to that of the DSSC with a
typical Pt CE (5.5%) [124]. However, the efficiency of a cell with a
carbon-based counter electrode is still lower than that of a cell
fabricated by Pt-based counter electrode. This may be attributed to
the defects on the surface of the carbon materials and the purification
during the synthesis process, which is detrimental to their electrical
conductivity and electrocatalytic ability [125]. Also, the poor stability of
carbon materials, caused by their poor adhesion to the substrate is a
crucial issue in their practical applications [126].
Up to now, so many kinds of metal compounds containing carbides,
sulfides, nitrides, phosphides, oxides, tellurides and selenides have
been used in DSSCs as counter electrode to replace the expensive Pt
counter electrode because of their promising application in low-cost
and large-scale DSSCs [127,128]. Lee et al. prepared mesoporous
tungsten carbide (WC) with polymer-derived (PD) and microwave-
assisted (MW) methods and then used them in DSSCs as CE catalysts.
The WC counter electrodes were typically fabricated by coating the WC
paste on FTO glass substrate followed by heat treatment at 250 °C for
1 h in air. The DSSCs based on these CEs showed η values of 6.61 (WC-
PD) and 7.01% (WC-MW), which were lower than that of the DSSCs
using Pt CE (8.23%). This can be attributed to the large particle size
and low surface area of the mesoporous carbides compared to the Pt
nanoparticles [129]. Vanadium nitride (VN) peas and cubes were also
synthesized by regulating the molar ratio of the starting materials
(urea/VOCl3) via the urea-metal chloride route. The VN compounds
were subsequently introduced into DSSCs as CE catalysts for the
regeneration of organic (T2/T-) and traditional I-/I3- redox couples.
The cyclic voltammetry, electrochemical impedance spectroscopy and
tafel polarization curve results proved that the catalytic activity of the
prepared VN was significantly affected by particle shape and particle
size. The VN peas showed the highest catalytic activity and the best
efficiency (7.29%) obtained for DSSC-based on VN peas counter
electrode with I-/I3- electrolyte [130]. Although most of the metal
compounds and their derivatives showed high conductivity and elec-
trocatalytic activity, the synthesis process of metal compounds con-
sume a large amount of energy. Therefore, developing new synthesis
routes with low energy consumption is a main problem to be resolved
for the metal compound CE in DSSCs [131].
6. Effect of humidity
DSSCs are usually fabricated under normal atmospheric conditions.
Thus, the presence of water is inevitable during the fabrication of
DSSCs. It has been shown by Wei et al. that the stability of DSSCs with
the hydrophilic dyes such as N719, N3 and N749 is significantly
affected by the air humidity and oxygen during the cell assembly [132].
Even the presence of as low as 5–10% air humidity during cell
preparation results in a 20% loss of photocurrent due to the dissolution
of dye from the surface of TiO2 [133]. This problem can be solved using
a hydrophobic dye (MK2, Z907 and TG6) that is immobilized on the
surface of TiO2 without dissolution in water solvent [133]. Kato et al.
studied long term stability of monolithically connected DSSCs under
outdoor working conditions and concluded that the decrease of I3- in
the electrolyte due to the irreversible reaction between I3- and water is
the cause of the degradation in the DSSCs [96]. Extensive studies have
reported the water infiltration in the DSSC leads to degraded organic
solvent-based electrolytes due to the formation of iodate (IO3-) instead
of triiodide and detachment of the adsorbed dye through the linking of
water molecules to TiO2 nanoparticle surface [134].
S. Mozaffari et al.
7. Sealants and encapsulation
The performance challenge to get DSSC to practical applications is
mainly associated with its instability during long term operations
[33,135]. This instability has been attributed to the volatility of the
solvent present in the electrolyte solution. In addition, the intrusion of
water and oxygen, effects caused by ultraviolet radiation and tempera-
ture changes harm operation of DSSC [33,136]. Therefore, there is an
essential requirement for a good sealing material to cope the above
mentioned challenges.
Glass frit is often used on the edges of the glass based DSSC to seal
the electrolyte [135,136]. The sealant also acts as a spacer to retain the
counter electrode from touching the photoanode [137]. It has good
chemical stability and can be deposited on the photoanode by screen
printing. However, it require a high temperature sintering at about
600 °C so that, it can be used basically only in DSSCs deposited on glass
and cannot be implemented on low temperature roll-to-roll process
[135].
A typical low temperature solution is the use of thermoplastic films
such as Surlyn and Bynel. Ikegami et al. prepared a rubber-like flexible
seal by applying hot melt (Surlyn) at 120 °C for plastic modules. The
initial photovoltaic performance was maintained for 220 h when
exposed to a high temperature (55 °C) [136]. In practice, Surlyn films
have low softening temperatures and therefore the cells sealed with
them can handle temperatures only below 60 °C which is too low for
outdoor applications [138].
8. Development of DSSC electrolyte
The use of a liquid electrolyte causes practical problems of leakages
and its volatilization, corrosion of the platinum secondary electrode,
desorption and photodegradation of the dye, precipitation of salts at
low temperature and ineffective sealing of DSSCs for long term
applications in solar modules. All of these disadvantages restrict the
commercial applications of DSSCs. Therefore, many efforts have been
made to replace the liquid electrolytes with the ionic liquids (ILs),
polymer gels and solid-state electrolytes [139,140].
8.1. Ionic liquids
Ionic liquids have emerged as promising alternative electrolyte
solvents in DSSCs over the past several years. Ionic liquids are organic
salts with melting points near room temperature, consisting of organic
cations with various anions [141]. ILs possess some unique properties,
such as good ionic conductivity, high chemical and thermal stability,
non-flammability and most significantly, almost negligible vapor
pressure. These attractive properties identify ILs as interesting alter-
native electrolyte solvents in DSSCs [16,142]. A large number of
imidazolium-based ILs incorporating various anions, such as iodide,
thiocyanate, interhalogens, bis (trifluoro-methylsulfonyl) imide, sele-
nocyanate, dicyanamide, tricyanomethide and tetracyanoborate, have
been synthesized and extensively investigated as electrolyte solvents in
DSSCs [143,144]. For example, Kuang et al. used binary ionic liquid (1-
propyl-3-methyl-imidazolium iodide (PMII) and 1-ethyl-3-methyl-imi-
dazolium tetracyanoborate (EMIB(CN)4)) electrolyte in combination
with a new high molar extinction coefficient ruthenium complex (K77)
in the fabrication of DSSC. Photovoltaic performance, charge transport
and electron lifetime on the composition of the binary ionic liquid
electrolyte with different ratios of PMII/EMIB(CN)4 were investigate
by electrochemical impedance and photovoltage transient technique. A
conversion efficiency of 7.6% obtained under illumination with a
simulated solar light of 100 mW cm−2 and devices exhibited acceptable
stability at 80 °C under visible light soaking test for 1000 h [145]. High
conductivity eutectic melts composed of solid imidazolium iodides have
also been introduced as electrolyte solvents in DSCs. Up to date, the
highest overall conversion efficiency (8.2%) has been achieved for IL-
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Renewable and Sustainable Energy Reviews (xxxx) xxxx–xxxx
based electrolytes using a binary iodide eutectic melts as iodide source
in 1-ethyl-3-methylimidazolium tetracyanoborate, in combination with
I-/I3- redox couple [84]. Several other non-imidazolium based ILs have
also been studied as electrolyte solvents in DSSCs, including phospho-
nium, sulfonium, guanidinium, tetrahydrothiophenium, ammonium,
pyrrolidinium with various anions [146–148]. However, the high
viscosities are the main disadvantages for the ILs, which result in low
ion mobility in the electrolytes and consequently lower DSSC device
efficiencies in comparison to organic solvent-based electrolytes [149].
8.2. Polymer gel electrolyte
The combination of polymers and redox couples is commonly used
as polymer gel electrolytes [150,151]. Various kinds of gel electrolytes
have been reported with polymers such as polyacrylonitrile, poly (vinyl
chloride) (PVC), poly (methylmethacrylate), polyvinyl pyrrolidone and
polyethylene glycol [152,153]. The conductivity of the polymer gel
electrolytes depends on the morphology and the molecular weight of
the polymers in the electrolyte. To decrease the degree of crystallinity
of the polymer at ambient temperature and increase the ionic mobility,
it is necessary to introduce a certain degree of disorder in the structure.
This can be achieved by using blends of different polymers, copolymers
or cross-linked networks, which can either reduce the crystallinity of
the polymer or lower the glass transition temperature. Also, it is
possible to introduce a third component in the system, which can act as
a plasticizer to increase the ionic conductivity [154]. Hu et al. prepared
a composite polymer electrolyte based on poly (ethylene oxide)/
poly(vinylidene fluoride-hexafluoropropylene) and the mixture of
hydroxyethyl methylacrylate (HEMA) and ethylene glycol (EG) as
plasticizer. The effect of plastisizer concentration on conductivity and
photoelectric performance of composite DSSC was investigated. The
olefinic bonds in HEMA and hydroxyl bonds in EG provide strong
molecular polarity to effectively reduce the crystallinity of the polymer
electrolyte, thus improve the ionic conductivity of the composite. The
conversion efficiency of the DSSC with 0.15 g of plasticizer reached
6.46%, which was 6% higher than that of the cell with original polymer
electrolyte (6.11%) [155]. A cross-linked gel polymer electrolyte
composed of poly (ethylene oxide-co-2-(2-methoxyethoxy) ethyl glyci-
dyl ether-co-allyl glycidyl ether), γ-butyrolactone, LiI and I2, mixed
with MWCNT was applied in DSSCs by Nogueira et al. Due to its
nature, the terpolymer was chemically cross-linked during DSSC
assembly to give rise to quasi-solid state solar cells. The highest
photocurrent (8.74 mA cm-2) achieved by DSSC based on the cross-
linked gel polymer electrolyte compared to DSSC based on non cross-
linked gel polymer electrolytes (7.93 mA cm-2) [156]. Although, the
corresponding efficiency of DSSCs based on polymer gel electrolytes
has reached 8–9%; however, because of their thermodynamic instabil-
ity under high temperatures, polymer gel electrolytes still suffer from
solvent leakage. Thus, they require careful sealing treatment when used
at elevated temperatures [151,157,158].
8.3. Solid state electrolytes
Solid state electrolytes, including inorganic p-type semiconductors
or various hole transporting materials (HTMs) have been investigated
as hole acceptors to replace liquid electrolytes [158]. Several inorganic
p-type semiconductor based on cooper compound materials (CuI,
CuSCN), CsSnI3, Cs2SnI3Br3 and organic polymer materials (poly (3-
hexylthiophene) (P3HT), poly (3,4-ethylenedioxythiophene) (PEDOT)
and 2,20,7,70-tetrakis (N,N-di-4-methoxyphenylamino)−9,90-spirobi-
fluorene (spiroMeOTAD)) have been successfully used in solid state
DSSCs [158,159]. The first solar cell of this type was reported in 1995
using CuI as a hole conductor with an efficiency of 2.4% by Tennakone
[160]. Although CuI has high hole mobility, but fast crystallization
rates result in poor filling into photoanode films. Triethylamine
hydrothiocyanate and 1-methy-3-ethylimidazolium thiocyanate (mol-
S. Mozaffari et al.
ten salts) have been used to control the crystallization of CuI crystals. A
slightly increased efficiency (η=3.0%) was observed in DSSC cells
equipped with these inhibitors when compared with the efficiency
(η=2.9%) of DSSC containing only HTMs [158]. Spiro-MeOTAD is
much better than other types of organic HTMs [161,162]. It indicates a
work function of about 4.9 eV and a hole mobility of 10-4 cm2 V-1 s-1.
The first reports on spiroMeOTAD appeared in 1998, and the conver-
sion efficiency of its devices has increased dramatically since less than
1% to over 5% [163]. High production cost and low hole mobility
inhibit the application of spiroMeOTAD in solid state DSSCs. High
conductivity for effective hole transfer and good diffusion of HTMs into
photoanode electrode are key issues for solid state electrolytes in
DSSCs [164].
9. DSSC cost
The ultimate goal of any photovoltaic technology is to achieve a
cost-per-watt level that could compete against conventional fossil fuel
technologies. In the past decade, silicon based solar cells have devel-
oped rapidly and their production cost have been decreased from about
4.00 US$ W-1 to around 0.66 US$ W-1. The module η has increased to
10% and life time guarantees to 25 years. However, the electricity
generation cost is much higher than that of conventional fossil fuel
technologies [10].
Given the fact that the cost of silicon-based solar cells has
continuously decreased during these years, the superiority of tradi-
tional liquid state DSSCs in cost has almost disappeared. Gratzel et al.
calculated the cost of traditional sandwich structure DSSC (90–116 US
$ m-2) based on the forecasted future materials costs [34]. To obtain a
cost of 0.66 US$ W-1 comparable to silicon solar cells, the module
efficiency should be 13.6–17.6%. Up to now, the maximum efficiency
has been reported about 8.2% for a DSSC module [165]. Major
contributions (50–60%) to the manufacturing cost of dye sensitized
module arise primarily from dyes, counter electrode and substrates
while almost 27% of the cost is related to the sealing process. As
suggested by Hashmi et al., a significant decrement of price is possible
by replacing some of the expensive components, i.e. replacing FTO by
stainless steel, titanium (Ti) and nickel (Ni) sheets can save up to 80%
of the substrate cost (9% of the total cost) [38]. Moreover, although
DSSCs based on the solid state offer less sealing difficulties than liquid
electrolyte-DSSCs, they are still vulnerable to moisture and oxygen
penetration. Furthermore, the efficiency of this kind of DSSC is lower
compared to DSSCs based on the liquid electrolyte [19,166].
10. Comparison of photovoltaic cells
DSSCs are promising due to their low cost fabrication compared to
the first and second generation PVs; however, their efficiency is much
lower than commercially available silicon and thin film solar modules.
Although efficiency up to ~13% was reported in DSSCs, the certified
value is ~11.9% for devices built on rigid substrates FTO and ~7.6% for
devices built on flexible substrates (Polyethylene terephthalate (PET)/
ITO) [167]. In view of the commercial applications, solar modules
outdoor stability is crucial besides their efficiency. For example, silicon
(η~10%) and thin film (η~6.8%) modules with efficiency much lower
than the certified value of dye sensitized modules (η~8.2%) are
available in the market owing to their remarkably higher lifetime
(~20 years for thin film modules) [168]. Although DSSCs have shown
significant stability in indoor accelerated testing, the life time of liquid
electrolyte-based DSSCs is far lower in outdoor working condition due
to their high volatility [169,170]. Alternatively, solid state DSSCs have
been developed in order to overcome some of the issues related to the
liquid electrolyte. Future research on solid state DSSCs to be dedicated
to solve their primary issues such as poor pore filling (infiltration of
HTM into nanocrystal semiconductor) and inferior hole mobility in
these devices [168]. A breakthrough in the third generation solar cells
8
Renewable and Sustainable Energy Reviews (xxxx) xxxx–xxxx
is the emergence of perovskite sensitized solar cells which employ an
organic-inorganic hybrid perovskite absorber (generally CH3NH3PbX3,
X=Cl, Br or I) on a very thin metal oxide layer [171,172]. Although
perovskite sensitized solar cells initially emerged as a class of DSSCs,
they are likely to be considered a new class of solar cells. The confirmed
efficiency as high as ~20% was reported in perovskite sensitized solar
cells which is a five-time increment in just seven years since its first
report [173]. The replacement of Pb with some non-toxic materials
may presumably increase its market acceptability [173,174]. Results on
the scalable fabrication of perovskite sensitized solar cells have recently
been reported across the globe with efficiency up to 8.7% [175,176].
Long term stability is a major challenge for commercialization of
perovskite sensitized solar cells. The water-solubility of the organic
constituent of the absorber materials makes devices very prone to fast
degradation in moist environments [177]. Encapsulating the perovskite
absorber with polymer-functionalized single-walled carbon nanotubes
has been demonstrated to successfully restrict the immediate degrada-
tion of the material when exposed to moist ambient conditions at
elevated temperatures [177]. Nevertheless, as yet there are no studies
on the long term stability and the comprehensive encapsulation
techniques for this type of photovoltaic.
11. Stability of dye and provskite solar cells
For dye and provskite technology to be commercially successful,
their long term performance under the working conditions such as high
temperature, humidity, and continuous light illumination have to be
ensured [19]. Among the third generation solar cells, perovskite solar
cells are the newest technology and have the highest efficiency, while
DSSCs are closest to commercialization with several companies produ-
cing the DSSC materials and modules [178]. However, both of these
photovoltaic cells share a concern about lifetime and stability.
Although, DSSC efficiency has not exhibited significant progress over
the past 25 year, but there are many commercial developers of
materials and technology working on various aspects of module
DSSCs [178]. Initial products are aimed towards indoor and portable
applications such as chargers, flexible water proof bags, wireless
keyboards and etc. [19]. According to market projections by
IDTechEx, global DSSC market was worth US$ 49.6 million in 2014
and is expected to reach US$ 130 million by 2022, growing at a CAGR
of 12.4% from 2014 to 2022. Growing DSSC demand in portable
charging owing to its ability to provide optimum wattage in these
applications is anticipated to drive the market over the forecast period
[179]. A huge market for module DSSCs is represented by building
integrated photovoltaic, where devices can be incorporated into big
installations worth hundreds of millions of dollars globally.
Development work is ongoing by various industrial companies
(Solaronix and Dyesol) to produce prototypes and demonstrators for
integration in applications such as bus shelters, roofing and building
facades, including semi-transparent windows [19,180]. However, de-
spite good performance of module DSSCs under a wide range of
lighting condition and diversity in appearance, integration in buildings
requires very challenging lifetimes of over 20 years. Outdoor stability
testing is reported stability 2.5 years for module DSSC that it is much
less compared to the 20 years [180,181]. Thus, stability improvements
in DSSC are still desirable for wider range of applications.
Since the perovskite solar cells are newest technology, the present
researches in perovskite solar cells mainly focus on the high perfor-
mance and study about the stability of perovskite solar cells is often
ignored [182]. In order to the application of perovskite solar cells in
industry, the issue of the degradation and stability of the device should
be considered [182]. In the initial report on the perovskite solar cells,
stable performance in ambient and without encapsulation was reported
for a period of 500 h [183,184]. Good stability (over 1000 h) with
storage in the dark and in inert atmosphere was also reported for
perovskite devices [185–187]. However, in other reports less promis-
S. Mozaffari et al.
Table 1
Important characteristics of DSSCs and perovskite solar cells [178].
Perovskite solar cell Dye sensitized solar
cell
NRELa certified record PCE 22% 11.9%
large area modules scarce report demonstrated
sensitivity of moistur high moderate
stability over 1000 h dark, low humidity store in air
atmosphere
outdoor testing results no available available
commercialization in development yes
a competitor for the first generation photovoltaic cells.
National Renewable Energy Laboratory.
ing stability was obtained. For example, it was reported that devices
stored in dry air or nitrogen retain 80% of the initial performance after
24 h and 20% after 6 days, while those stored in ambient air retain less
than 20% after 24 h [188]. Furthermore, the degradation of encapsu-
lated perovskite solar cells was studied under illumination at different
temperatures and relative humidity levels, and it was found that ageing
at high temperature and humidity resulted in the decomposition of the
perovskite layer (MAPbI3), as a result of reaction with H2O, and the
subsequent reaction of hydroiodic acid, formed during MAPbI3 decom-
position with the silver back contact electrode layer. Improved en-
capsulation techniques could improve the stability, but it was found
that the degradation at elevated temperature and humidity was still
significant [188]. Promising strategies for improving the stability of the
perovskite solar cells is carbon-based electrodes, developing material
modifications to improve stability, and introducing interfacial and/or
barrier layers [189]. It should be noted, carbon based electrodes have
lower conductivity compared to metals (silver, gold and aluminum) and
thus would not be suitable for large area devices. The deposition of
metal grids and/or multilayer electrodes containing metal and carbon
would be necessary to overcome this problem [178]. Although, there is
a commercial company working on perovskite solar cell modules
(Oxford Photovoltaics which is a spin-off company of Oxford
University), however lifetime under outdoor conditions for these cells
is still uncertain [19]. Important characteristics of DSSCs and per-
ovskite solar cells are compared in Table 1[178].
12. Conclusions
Converting solar energy into electricity as a clean and renewable
energy resource is very important to solve the environmental pollution
problems and energy crisis induced by the consumption of fossil fuels
[1]. In recent years, dye sensitized solar cells made from low cost
materials with environmentally friendly characteristics have shown
great potential as alternatives to traditional silicon photovoltaics [16].
However, the commercialization of DSSCs is still being postponed by
their relatively lower efficiency and long term stability for outdoor
conditions [15,33]. Following the research reports on nanocrystalline
DSSCs in 1991, numerous research attempts have been made to further
improve the energy conversion efficiency for practical applications
[57]. Unfortunately, the certified value of efficiency is still under 12%
even though thousands of research papers have been published in the
past 25 years [19]. Although some papers have reported the theoretical
efficiency as ca. 32%, there are few chances to reach this efficiency
because the energetic loss in DSSCs is not fully taken into account [27].
Along with efficiency, the long term stability of the DSSCs has been
issue of concern during the past years of this technology development.
The major disadvantage to the DSSC design is the use of the liquid
electrolyte. Lifetime of DSSCs based on liquid electrolyte is far lower in
outdoor conditions due to their leakages and high volatilization [139].
Alternatively, ionic liquid, polymer and solid state electrolytes have
been developed in order to overcome some of the issues related to the
liquid electrolyte. However, the efficiency of this kind of DSSCs is less
than those made of liquid electrolyte [36]. For DSSC technology to be
9
Renewable and Sustainable Energy Reviews (xxxx) xxxx–xxxx
commercially successful, their long term stability under the working
conditions such as high temperature, continuous light illumination and
humidity must be ensured [33]. Commercial deployment of DSSCs
requires device performance without a significant degradation for > 10
years, especially when its contenders, i.e., silicon photovoltaic perform
~25 years with greater than 80% of original η maintained [19]. The
DSSC is potentially vulnerable to various kinds of degradations when
placed under stresses. Up to now, the maximum outdoor ageing test of
DSSCs is reported for 2.5 years that is much less compared to the
silicon photovoltaic [181]. The results show that DSSCs with the slow
progress in efficiency improvement and stability cannot be a serious
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