Applied Energy 115 (2014) 216–225

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Biophotovoltaics: Natural pigments in dye-sensitized solar cells

Hubert Hug a,⇑, Michael Bader a,b, Peter Mair a, Thilo Glatzel c
a
DSM Nutritional Products Ltd., NIC-RD/HN, Wurmisweg 576, CH-4303 Kaiseraugst, Switzerland
b
University of Applied Sciences Northwestern Switzerland, Gründenstrasse 40, CH-4132 Muttenz, Switzerland
c
Department of Physics, University of Basel, Klingelbergstrasse 82, CH-4056 Basel, Switzerland

h i g h l i g h t s

 Natural pigments are photosensitizers in dye-sensitized solar cells (DSSCs).

 Efficiency is still lower compared to synthetic pigments.
 The use of natural pigments such as carotenoids and polyphenols is cheap.
 General advantages of DSSCs are flexibility, color and transparency.
 Usage under diffuse light and therefore, indoor applications are possible.

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

Article history: Dye-sensitized solar cells (DSSCs) which are also called Graetzel cells are a novel type of solar cells. Their
Received 12 April 2013 advantages are mainly low cost production, low energy payback time, flexibility, performance also at dif-
Received in revised form 25 September 2013 fuse light and multicolor options. DSSCs become more and more interesting since a huge variety of dyes
Accepted 30 October 2013
including also natural dyes can be used as light harvesting elements which provide the charge carriers. A
Available online 28 November 2013
wide band gap semiconductor like TiO2 is used for charge separation and transport. Such a DSSC contains
similarities to the photosynthetic apparatus. Therefore, we summarize current available knowledge on
Keywords:
natural dyes that have been used in DSSCs which should provide reasonable light harvesting efficiency,
Dye-sensitized solar cell
Carotenoids
sustainability, low cost and easy waste management. Promising natural compounds are carotenoids,
Polyphenols polyphenols and chlorophylls.
Chlorophylls Ó 2013 The Authors. Published by Elsevier Ltd. Open access under CC BY-NC-ND license.
Low-cost solar cell

1. Introduction membrane to the other side where it is captured by an electron

acceptor. This attractive model which was suggested for the first
The idea of using the reactions of photosynthesis to convert sun time to directly convert sun light into electric energy by using
light into electrical power appeared already by Melvin Calvin be- membranes and pigments quickly became textbook knowledge
fore 1974 [1]. The model was a photo-electrochemical cell based [2]. At the same time, Melvin Calvin also suggested a model for
on a synthetic membrane where carotenoids were used as a wire photochemical hydrogen production. Again, the model was based
inside the membrane. After absorption of a light quantum by a sen- on the photosynthetic electron transport system [1]. Later it was
sitizer molecule localized at one side of the membrane, an electron directly shown that after illumination electrons are transferred
is transferred to a carotenoid and then diffuses through the from canthaxanthin, an accessory carotenoid of the photosynthetic
system, to chlorophyll a, the electron collector system [3].
A similar approach has been taken in parallel in physical and
chemical sciences [4]. Sun light is used to excite electrons of pig-
ments, mainly metal complexes, into a higher energy level which
are then transferred to the conduction band of a wide bandgap
Abbreviations: DSSCs, dye-sensitized solar cells; TCO, transparent conductive semiconductor. Compared to the well-known silicon devices, such
oxide; ITO, indium tin oxide; FTO, fluorine doped tin oxide; FF, fill factor; Ru,
ruthenium; Pt, platinum; Zn, zinc; Co, cobalt; I, iodine; Cs, caesium; Sn, tin; Ti,
dye-sensitized solar cells (DSSCs) cells are belonging to the emerg-
titanium. ing third-generation photovoltaic concept and use synthetic or nat-
⇑ Corresponding author. Tel.: +41 (0)61 815 8486; fax: +41 (0)61 815 8740. ural dyes as light harvesting pigments [5,6]. They are also called
E-mail address: hubert.hug@dsm.com (H. Hug). Graetzel cells named after their publication in 1991 [7].

0306-2619 Ó 2013 The Authors. Published by Elsevier Ltd. Open access under CC BY-NC-ND license.
http://dx.doi.org/10.1016/j.apenergy.2013.10.055
 H. Hug et al. / Applied Energy 115 (2014) 216–225 217

Conventional solar cells require a relatively thick and defect- and the load (any electrical device). The oxidized pigment S+ is re-
free layer of expensive silicon in order to have reasonable photon stored by electron transfer from the electrolyte. A widely used li-
capture and recombination rates. The light conversion efficiency quid electrolyte is the iodide–triiodide (I =I
3 ) redox system in an
of crystalline silicon solar cells is in the order of 25%; a DSSC cur- organic solvent which penetrates into the nanoporous structure.
rently reaches approximately 12.3% with a Zn-porphyrin and a I reduces the positively charged pigment whereby I 3 ions are
Co-based electrolyte [8,9]. However, for DSSCs the potential to formed which diffuse to the cathode. The inner surface of the cath-
achieve production costs below 0.5 $ per watt peak of solar elec- ode contains either graphite or platinum particles as catalyst.
tricity are reasonable [10]. There, I 
3 is reduced to I and the cycle is finished [17].
Major advantages of DSSCs are the large flexibility in shape, col- The ideal energetic pathway of an electron in a DSSC is shown in
or, transparency, and performance also under diffuse light [6,11]. Fig. 2. The maximal obtainable voltage (DV) is the difference be-
DSSCs could be integrated into large varieties of products, e.g. hand tween the Fermi level of the conduction band of TiO2 and the redox
bags or clothing, indoor applications, and building-integrated potential of the redox couple (I =I
3 ).
photovoltaics such as roll-able devices for walls of buildings or A DSSC can be characterised with an IV-diagram where the cor-
windows [12,13]. But many components of a DSSC remain to be responding current (I) at rising voltage (V) is plotted (Fig. 3). At a
optimized. We focus on the identification and usage of natural pig- bias of 0 V the short circuit current (ISC) is measured and when
ments as light harvesting elements in DSSCs. Natural pigments as the current reaches 0 A the open circuit voltage (VOC) is defined.
photosensitizers in DSSCs have the potential to reach similar per- The maximum power output (Pmax) generated by a DSSC is reached
formances and stability as known from dyes based on metal when the product of the current and the voltage is maximal. With
complexes. the equation below, the maximum power is calculated. The corre-
sponding factors are called current at maximal power (Imp) and
voltage at maximal power (Vmp).
2. General composition, function and parameters of DSSCs
Pmax ¼ Imp  V mp
A DSSC is composed of two electrodes at least one of them
transparent for light in the visible range [14]. In most cases glass Often, the current density (J) [mA/cm2] instead of the current (I)
[mA] is stated to allow a better comparison between measure-
covered with a transparent conductive oxide (TCO) material usu-
ally indium tin oxide (ITO) or fluorine doped tin oxide (FTO) is ments of different solar cells. Therefore, the ISC and Imp become
JSC and Jmp, respectively, whereby JSC and Jmp are independent from
used. A basic DSSC setup is shown in Fig. 1. On the conductive sur-
face (15 O/h with a transmission of >80% from 400 to 700 nm) of the photoactive area.
How efficient a solar cell can convert the power of the incident
the anode a nanoporous wide band gap semiconductor is depos-
light into electricity is, beside its life time stability, in the center of
ited. Its nanocrystalline structure (nanoparticle size 20–50 nm) en-
interest. The solar energy to electricity conversion efficiency (g) is
hances the surface area by nearly a factor of 1000 while at the
calculated with the following equation:
same time minimizing the optical absorption. This is usually the
anatase modification of titanium(IV) oxide (TiO2) which contains g ¼ Pmax =P in ¼ Imp  V mp =Pin ¼ ISC  V OC  FF=Pin
excess free electrons and is therefore an negative (n)-type semi-
The incident power (Pin) is the irradiance illuminated on the
conductor [15]. The light absorbing dye pigment is attached to
DSSCs. Pin has to be measured beforehand. The efficiency is be-
the TiO2 surface and should assemble an electrically homogeneous
tween 0% and 100%.
dipole layer [16]. Photoexcitation of the pigment from the ground
Besides ISC, VOC and g also the fill factor (FF) belongs to the four
state S to the excited state S leads to the injection of an electron
key performance parameters of a solar cell [5]. The fill factor is a
into the conduction band of TiO2. This electron diffuses through
value between 0 and 1 that describes the shape of the IV-curve,
the nanoporous TiO2 and finally passes through the TCO layer
where a high value indicates a more preferable rectangular shape
described by the following equation [6]:
FF ¼ Imp  V mp =ISC  V OC
To compare different solar cell concepts and devices a standard
light spectrum (AM1.5) and measurement conditions (homoge-
neous illumination of 100 mW/cm2 at 23 °C) are defined.
First experiments were performed mainly with dyes based on
ruthenium (Ru) complexes e. g. N719 (di-tetrabutylammonium
cis-bis(isothiocyanato)bis(2,20 -bipyridyl-4,40 -cicarboxylato) ruthe-
nium(II)) [18]. Later the use of metal-free synthetic dyes such as
indoline dyes was introduced [19]. However, the overall electro-
chemical configuration, like composition of the electrolyte or the
layer thicknesses, has to be adopted to obtain optimal efficiency
of the DSSCs.
The basic principle of a DSSC with natural dyes is to exchange
the above-mentioned synthetic dyes of the set-up of DSSCs with
natural ones. Developing and optimizing materials for organic so-
lar cells is generally not yet rational, but rather empirical. The rea-
Fig. 1. Schematic setup of a DSSC. The photoanode and counter-electrode are based
on fluorine-doped tin oxide (FTO) coated glass. The illumination (hm) of a DSSC son for this is that multiple parameters have to be taken into
with a liquid electrolyte containing I =I
3 initiates a cascade of reactions which lead
account when new types of materials and dyes are designed for or-
to an electrical current. Photons excite the dye molecule in the ground state (S) to ganic solar cells. The photovoltaic cell’s efficiency does not only de-
its electronically excited state (S). The electronically excited dye molecule injects pend on the pigment’s molecular structure, but also strongly on
then an electron (e) into the conduction band of the semiconductor TiO2. The
oxidized dye (S+) is reduced by iodide (I). The generated tri-iodide (I
solid-state properties, such as morphology, self-assembly and
3 ) is reduced
at the cathode by the catalyst platinum (Pt) to I which completes the cycle. The aggregation of the dye molecules. In the case of DSSCs even more
overall result is the direct conversion of light into electricity. parameters have an influence on the efficiency such as the type
218 H. Hug et al. / Applied Energy 115 (2014) 216–225

Fig. 2. Simple energy level diagram with electron transfer processes of a DSSC with liquid electrolyte. The maximal voltage (DV) achievable with a DSSC is defined as the
difference of the redox potential of the electrolyte’s redox couple (I =I
3 ) and the Fermi level of the semiconductor’s conduction band. DV is equal to the open circuit voltage
(VOC). The gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the dye (S) influences its light absorption
properties, which means the efficiency of getting electronically excited, oxidised and reduced and moreover, the spectral absorption range. However, other chemical structure
characteristics of the dye and the binding between the dye and the TiO2 also crucially influence the solar energy to electricity efficiency (g) of a DSSC. V vs. NHE means that
the redox potential is relative to the redox potential of the normal hydrogen electrode (NHE).

Fig. 3. Photocurrent-voltage characteristics of a DSSC. The photosensitizer was the

ruthenium (Ru) complex dye N719. The liquid electrolyte contained the redox
couple I =I
3 . Similar curves are obtained with natural photosensitizers.

of the photoelectrode, the dye’s anchoring group and the electro-

lyte with the respective redox couple. Hence, the optimal design
of organic dyes regarding to an enhancement of the DSSCs’ perfor-
mance can only be derived from approximate trends. In general,
the design of a photosensitizer consists of a donor–acceptor–
substituted p-conjugated bridge. The acceptor part is the dye’s
anchoring group which is attached to the TiO2 (Fig. 4a) [20]. Up
to now mainly electrolytes known from DSSCs with synthetic dyes
are used for DSSCs with natural dyes [21].
Dye-cocktails or co-sensitization could yield higher efficiencies
if the absorption spectra of the different dyes do not overlap too
much in order to extend the overall absorption spectrum. How-
ever, limitations could be in a lower TiO2 surface area for a partic-
ular dye or intermolecular interactions between the different dyes
which may result in lower electron injection efficiency [22]. Fig. 4. (a) Donor-p-acceptor structure principle of an organic dye in DSSCs with
TiO2 photoanodes. (b) Possible binding modes of a COOH-group to TiO2.

3. Natural pigments used in DSSCs

the absorption in the visible or near-infrared regions of the solar
Based on the results with Ru-complexes also a variety of metal– spectrum and the binding to the semiconductor TiO2 [24]. The
organic dyes such as Zn-porphyrin derivatives have been tested functional group necessary to interact with the TiO2 surface is a
[23]. Prerequisites for photosensitizers to function in DSSCs are carboxylic or other peripheral acidic anchoring group [6,25]. The
 H. Hug et al. / Applied Energy 115 (2014) 216–225 219

Table 1
Natural dyes used in DSSCs.

Plant source Structure or structural class Photoactive Jsc Voc g/FF Remark Reference
area (cm2) (mA/cm2) (mV)
Black rice Anthocyanin 1 1.142 551 na/0.52 Fractionated extract [38]
Erythrina Variegata Carotenoid, Chlorophyll 1 0.776 484 na/0.55 Fractionated extract [38]
Rosa xanthina Anthocyanin 1 0.637 492 na/0.52 Fractionated extract [38]
Kelp Chlorophyll 1 0.433 441 na/0.62 Fractionated extract [38]
Capsicum Carotenoid 1 0.225 412 na/0.63 Fractionated extract [38]
Begonia 0.2 0.63 537 0.24/0.72 Extract [40]
Rhododendron 0.2 1.61 585 0.57/0.61 Extract [40]
Perilla 0.2 1.36 522 0.5/0.70 Extract [40]
Mangosteen pericarp 0.2 2.69 686 1.17/0.63 Extract [40]
Mangosteen pericarp a-Mangostin/b-mangostin 0.2 2.55 621 0.92/0.58 Fractionated extract [40]
Mangosteen pericarp Rutin 0.2 2.92 611 1.12/0.63 Fractionated extract [40]
Hibiscus sabdariffa L. Cyanidin-3-glycosides/delphinidin- – 1.63 404 0.37/0.57 Aqueous extract [78]
3-glycoside
Beta vulgaris rubra Betalains 0.5 9.5 425 1.7/0.37 Aqueous extract [79]
Rhoeo spathacea Stearn – – 10.9 496 1.5/0.27 Ethanol extracts, aqueous [80]
electrolyte
Bixa orellana L. Bixin 0.5 1.1 570 0.37/0.59 Fractionated extract [81]
Spinach Modified chlorophyll/neoxanthin – 11.8 550 3.9/0.60 Isolated compounds [37]
Spinach Modified chlorophyll/violaxanthin – 11.4 540 3.7/0.61 Isolated compounds [37]
Spinach Modified chlorophyll/lutein – 12.5 540 4.0/0.59 Isolated compounds [37,37]
n.a. Modified chlorophyll/b-carotene – 13.7 530 4.2/0.58 Isolated compounds [37]
Chaste tree fruit – – 1.06x 390 na/0.48 Extract [82]
Mulberry – – 0.86x 422 na/0.43 Extract [82]
Cabbage-palm fruit – – 0.37x 442 na/0.61 Extract [82]
Calafate fruit Delphinidin – 0.96 520 na/0.56 Aqueous extract [83]
Jaboticaba skin Peonidin – 2.6 660 na/0.62 Ethanolic extract [83]
Gardenia fruit Crocetin/ 1.0 2.84 430 0.56/0.46 Isolated compounds [84]
crocin 0.45 580 0.16/0.60
Red Sicilian orange ‘‘Moro’’ Cyanin 0.5–1.0 3.84 340 0.66/0.50 Fruit juice [85]
Eggplant skin Nasunin 0.5–1.0 3.40 350 0.48/0.40 Ethanolic extract [85]
Prickly pear Betaxanthin 1.0 8.8 389 2.06/0.60 Acidified juice [16]
Tradescantia Zebrina Antocyanin – 0.63 350 0.23/0.55 Ethanolic extract [86]
Kapok Antocyanin/carotenoid – 0.87 360 0.3/0.49 Ethanolic extract [86]
Pitaya Not reported – 0.5 330 0.17/0.52 Ethanolic extract [86]
Canarium odontophyllum Antocyanin – 2.45 385 0.59/0.62 Ethanolic extract [87]
Ixora sp. Antocyanin – 6.26 351 0.96/0.44 Ethanolic extract [87]
C. odontophyllum + Ixora sp. Antocyanin – 6.26 384 1.13/0.47 Mixed ethanolic extract [87]
C. odontophyllum + Ixora sp. Antocyanin – 9.80 343 1.55/0.46 Ethanolic extracts in [87]
consecutive layers
Rhododendron sp. Antocyanin 0.27 0.85 544 0.33/0.72 Ethanolic extract [88]

n.a. = not applicable x = current not normalized to cell area.

TiO2 binding moiety of large p-aromatic molecules is very often a to be able to shift the electrons through the anchoring group into
carboxylic group [26]. the conduction band of the semiconductor. The color of dyes also
There are several possible chemical functional groups that are depends on such delocalized p electrons.
able to bind the dye to the TiO2. The best anchoring groups for me- Over 80 metal-free organic dyes that can be prepared by cheap-
tal oxides are phosphonic acids followed by carboxylic acids and er methods have been described [20]. The highest g was 9.5% with
their derivatives, such as acid chlorides, amides, esters or carboxyl- a novel indoline dye [29]. A special method for the modification of
ate salts [25]. The carboxylic group is the most frequently used the TiO2 layer with the metal-free organic dye D102 has recently
anchoring group. been reported to result in a significant increase of g [30].
In order to form bonds, the dye’s binding groups react with sur- Natural dyes as photosensitizers for DSSCs are very attractive
face hydroxyl groups of the metal oxide. In the case of phosphonic because they are of low cost, abundant in supply, and sustainable.
acids or carboxylic acids, a reversible binding with high equilib- An early proof that carotenoids can function as photosensitizers in
rium binding constants is established between the photosensitizer DSSCs was with 80 -apo-b-caroten-80 -oic acid bound to TiO2. A pho-
and TiO2. In basic conditions (usually pH P 9) the dyes are easily tocurrent stable for 1 h under continuous radiation was measured
desorbed again. There are several binding modes between the and an ordered monolayer structure of the TiO2-bound carotenoid
TiO2 and a dye molecule with at least one carboxylic group (COOH) has been suggested [31]. Since then, carotenoids have already been
(Fig. 4b) [25,27,28]. Which mode of chemisorption between TiO2 successfully used in DSSCs [32–34]. The highest g with single
and COOH is prevalent depends on the dye’s structure, its anchor- carotenoids was 2.6% [35]. The optimal length of carotenoids con-
ing groups, the pH, and the metal oxide’s preparation [25]. sists of seven conjugated p bounds [36]. By using carotenoids in
The interaction of TiO2 with cyanin, an anthocyanidine, is via combination with chlorophyll derivatives g can be increased to
the hydroxyl-ketone tautomer of cyanin [24]. The main issues up to 4.2% [37]. This increase is probably due to similarities to
which have to be taken into account are an appropriate anchoring photosynthesis.
of the molecules while allowing a fast and energetically optimized Several extracts have been discovered as efficient photosensi-
charge transfer. The p electrons of the carboxylic group should be tizers. The effect of a black rice extract has been attributed to an
in resonance with the p electrons of the polyene backbone in order anthocyanin with an o-hydroxychinon moiety [38]. A different
220 H. Hug et al. / Applied Energy 115 (2014) 216–225

Table 2
Chemical structures of natural dye classes.

Name Chemical structure

Bixin

Crocetin

Crocin

Betaxanthin

Betalains

Delphinidin (an anthocyanidin)

Cyanidin (an anthocyanidin)

Cyanin (an anthocyanin)

 H. Hug et al. / Applied Energy 115 (2014) 216–225 221

Table 2 (continued)

Name Chemical structure

Nasunin (an anthocyanin)

Peonidin (an anthocyanidin)

a-Mangostin

b-mangostin

Chlorophyll a

Rutin (a flavonol glycoside)

(continued on next page)

222 H. Hug et al. / Applied Energy 115 (2014) 216–225

Table 2 (continued)

Name Chemical structure

Methyl-3-carboxy-3-devinylpyropheophorbide (a
modified chlorophyll)

Neoxanthin

Violaxanthin

Lutein

b-Carotene

study showed that amongst 20 plant extracts a mangosteen peri- might be the solution. However, the development of concepts and
carp extract showed the highest efficiency g of 1.17%. The active solutions for an easy-to-handle exchange of the dye in such devices
component has been described as rutin [39]. An overall compari- is still required.
son identified an extract of Rhoeo spathacea with an efficiency g For Zinc oxide (ZnO) as semiconductor it has been shown by a
of 1.49% as attractive source amongst others [40]. The glycosides computational Discrete Fourier Transform study that the caroten-
of anthocyanidins, the anthocyanins, seem to be more efficient oid retinoic acid would be most efficient compared to other natural
than the anthocyanidins. An explanation could be the better solu- carotenoids, e.g. crocetin and bixin [43]. But ZnO has mainly been
bility in H2O. Nevertheless, the interaction of cyanidin with TiO2 describes as interlayers in bulk heterojunction solar cells [44].
particles for the use in DSSCs was suggested already in 2007 [41].
The natural dyes used so far in DSSCs are summarized in Table 1. 4. Improvements of future DSSCs
Data are often obtained under different conditions and device set-
ups by different authors and therefore, they are in some cases dif- The most efficient dyes are synthetic and therefore, still petro-
ficult to compare directly. The photosensitizers belong to different leum based. Some of them even require limited heavy metals as ac-
chemical classes, which contain mainly carotenoids, betalains, tive centers what makes the recycling more difficult. Carotenoids,
flavonoids, or chlorophylls (Table 2). A high g of 2.06% was ob- chlorophylls, anthocyanins or other natural dyes as photosensitiz-
tained with an extract of Sicilian prickly pear [21]. Promising nat- ers are sustainable and are available in large amounts. However,
ural carotenoids are crocetin or bixin. efficient and fast extraction methods for purification are necessary.
Stability of natural photosensitizers in DSSCs is debated. To pro- The pigments of DSSCs degrade when exposed to ultraviolet
tect natural photosensitizers from degradation DSSCs are assem- radiation in combination with oxygen. A UV protection foil consist-
bled under an inert atmosphere [42]. The stability of ing of UV filters or UV absorbing luminescent chromophores
anthocyanins and betalains when protected from direct sunlight (which emit at longer wavelengths) can be applied on the outside
is more than one year [21]. An alternative approach to this issue of the anode. Inside the DSSCs antioxidants could be added to pro-
of depleting dyes is mimicking nature: an annual exchange of dyes tect the pigments from oxidation.
 H. Hug et al. / Applied Energy 115 (2014) 216–225 223

Foliage trees replace their leaves every year. Therefore, in foli- [58]. Another promising approach to replace the Pt coated elec-
age trees the stability of the photo conversion system is less than trode with a similar g are porous carbon plates as a conductive
one year. Silicon-based solar cells are guaranteed to last for substrate with vertically oriented ordered mesoporous carbon
25 years. This time might not be easily reached by solar cells with films as the catalytic layer [59].
natural pigments for light harvesting. Possible solutions would be The I =I
3 redox system has been replaced with a more efficient
to replenish the pigments every year. This is only feasible when system based on cobalt complexes [10,60]. With this electrolyte an
it is cheap and easy to handle. Another possibility would be lowest efficiency g of 12.3% was reached which is the highest g of a DSSC
price foil solar cells that can be removed from the wall or roof as a obtained so far [61,62]. Another suggestion for the replacement of
whole. the I =I
3 electrolyte is a new heteroleptic copper(I) complex with a
The currently most efficient Graetzel cells are still slightly phosphonic acid anchoring ligand [63].
less efficient in comparison to standard silicon-based solar cells. A further goal is to make both electrodes photoactive. Such cell
But as a result of the light absorption mechanism of the pig- types are called double junction hybrid DSSCs. All natural pigments
ments, DSSCs work even in low-light conditions. Therefore, described here inject electrons into n-type semiconductors like
DSSCs are able to work under cloudy skies and indirect sunlight, TiO2 at the photoanode after light absorption. Recently, positive
whereas inorganic semiconductor-based photovoltaic cells would (p)-type semiconductors like nickel(II) oxide (NiO) or copper(I)
suffer a cut-off at some lower limit of illumination. Since the thiocyanate (CuSCN) that transport positive holes have been re-
cut-off of DSSCs is so low, they are even proposed for indoor ported [6,20]. Pigments working with such p-type semiconductors
use, collecting energy for small devices from the light inside must be able to take electrons from the p-type semiconductor
buildings [45]. upon excitation with light. The electron is then transferred to the
The major disadvantage of the conventional DSSC design is the electrolyte which is currently again the I =I
3 redox system. Prereq-
use of the liquid electrolyte, which requires an appropriate encap- uisites of such dyes working with p-type semiconductors are that
sulation against leakage and contamination. Furthermore, at high the highest occupied molecular orbital (HOMO) of the dye must
temperatures, stability problems have to be addressed. High tem- be below the valence band of the p-type semiconductor and that
peratures cause the liquid to expand what stresses the sealing of the lowest unoccupied molecular orbital (LUMO) must be higher
the DSSCs. Another major drawback of the electrolyte solution than that of the redox potential of the electrolyte. The photosensi-
are volatile organic solvents requiring again a careful sealing. This, tizer at the anode attached to an n-type semiconductor, e.g. carote-
along with the fact that the solvents permeate plastics, has not al- noids, absorbs light in the blue range of the spectrum and a
lowed a large-scale outdoor application yet. photosensitizer attached to a p-type semiconductor at the cathode
Antireflective (AR) coating exists for conventional photovolta- should absorb red light and transmit positive holes into the semi-
ics. However, the processes have to be adjusted to flexible DSSCs conductor [6]. In such a way the utilizable light spectrum is consid-
since sintering is done at temperatures too high for polymers erably broadened what should increase g significantly.
and the AR coatings are not flexible yet. To apply AR coatings on Using a solid state electrolyte system improves the stability of a
DSSCs, conductive polymers with higher melting temperatures, DSSC and facilitates its fabrication. But g of solid state devices is
e.g. based on graphene [46], are already in use [47]. lower compared to g of DSSCs with a liquid electrolyte [23]. How-
UV filters may be used since carotenoids and other (natural) ever, solid-state mesoscopic perovskite-sensitized solar cells yield-
dyes are sensitive to UV-light. Tetraethylorthosilicate has been de- ing a g of over 15% have been described recently [64–66]. Another
scribed to decrease UV degradation of Beta vulgaris pigments in promising new type of an all-solid-state, inorganic DSSC that con-
DSSCs [48]. sisted of the p-type direct bandgap semiconductor CsSnI3 and n-
Several different improvements and modifications of the TiO2 type nano-porous TiO2 with the dye N719 showed an g of 10.2%
semiconductor have been described. It has been claimed that [67,68].
TiO2 with a dispersion of nanosized copper (Cu) that is embedded A successful attempt to maximize the surface area and thereby
in an inert carbon shell could increase the efficiency g compared to to increase the efficiency g of DSSCs was the arrangement of single
pure TiO2 by at least 23% [49]. An increase of the TiO2 surface area DSSCs like needles around a branch of a pine tree to capture sun
with well-aligned hierarchical TiO2 tubular macro-channel arrays, light from all directions [69]. The anode was composed of a spiral
obtained by hydrothermal synthesis, resulted in an improvement Ti wire (without TCO) coated with TiO2 to which the Ru dye N719
of g of approximately 0.8% [50]. Furthermore, an increase of the was attached. The anode was wrapped around a cathode which
particle size of TiO2 in the light scattering layer leads to an consisted of either a straight Pt or Ti wire coated with a Pt film.
enhancement of g of approximately 5% [51]. Bamboo-type TiO2 The whole composition was placed inside a glass tube filled with
nanotubes improved g due to higher dye loading by a factor of I =I
3 redox couple electrolyte. Several such 3D-DSSCs were ar-
1.4 [52]. The addition of carbon black to the dye alizarin yellow ranged in series-parallel connections to simulate a pine tree. Effi-
and TiO2 enhanced the conductive band of nano-TiO2 and thereby ciencies g were above 3%.
increased the short-circuit current [53]. TiO2 submicro-rings could A future big advantage for the usage of natural pigments for
help in synthesizing TiO2 directly onto TCO [54]. Infrared rapid DSSCs is the possibility of recombinant expression and therefore,
thermal annealing reduced the sintering of TiO2 from hours to min- large scale production of such dyes. The genes coding for the en-
utes [55]. zymes which are involved in the synthesis of the pigments can
An increase of g with the Ru based dye N719 was obtained be expressed in microorganisms, either in the wild-type form or
when copper phthalocyanine constituted an additional shell to with mutations that lead to a modified product [70–74].
the TiO2-dye complex. Due to cascade charge transfer this increase Single-walled carbon nanotubes show high electron mobility
was 41.08% [56]. but cannot be used as such in DSSCs. Therefore, modified single-
Pt, the catalyst used for the counter electrode, has a limited nat- walled carbon nanotubes are required. An M13 phage that ex-
ural availability and high costs. Therefore, DSSCs with a more effi- presses a pVIII major coat protein with a peptide insert binding
cient Pt cathode have been prepared by homogeneous deposition to single-walled carbon nanotubes -TiO2 nanocrystals has been se-
employing ethylene glycol with a promising improvement of g lected from a phage library [75]. Such nanocomposites were used
[57]. In a different approach, Pt coated cathodes were replaced as photoanodes in DSSCs which may increase stability of large
by hierarchical micro/nano-structured cobalt sulphide spindles modules. The efficiency g with the Ru-complex dye N719 was
with g very close to that of the DSSCs with Pt containing electrodes 10.6%.
224 H. Hug et al. / Applied Energy 115 (2014) 216–225

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