Optical Materials 110 (2020) 110441

Contents lists available at ScienceDirect

Optical Materials
journal homepage: http://www.elsevier.com/locate/optmat

Performance evaluation of natural native dyes as photosensitizer in

dye-sensitized solar cells
Tahmineh Jalali a, *, Parisa Arkian a, Malihe Golshan b, Mandana Jalali c, Shahriar Osfouri b
a
Department of Physics, Persian Gulf University, 7516913817, Bushehr, Iran
b
Department of Chemical Engineering, Faculty of Petroleum, Gas and Petrochemical Engineering, Persian Gulf University, 7516913817, Bushehr, Iran
c
General and Theoretical Electrical Engineering (ATE), Faculty of Engineering, University of Duisburg-Essen, And CENIDE—Center for Nanointegration Duisburg-Essen,
47048, Duisburg, Germany

A R T I C L E I N F O A B S T R A C T

Keywords: In this paper, the efficacy of wild natural dyes as the sensitizer was investigated for the fabrication of natural dye-
Dye-sensitized solar cell sensitized solar cells (DSSCs). The natural pigments were extracted from Crocus sativus (Saffron), Allium cepa L
Crocus sativus (red onion), Malva sylvestris (Mallow), and Oregano (Origanum vulgare) using solvent extraction method. Based
Malva sylvestris
on the UV–vis results, the extracted solutions have been shown to contain anthocyanin or chlorophylls pigments,
Allium cepa L
Origanum vulgare
which are excellent pigments required for the charge-carriers generation in the energy harvesting process from
Natural dye sensitizer the sunlight. The efficacy of all sensitizers has been evaluated using the cyclic voltammetry and current-voltage
Photoelectrochemical open circuit experiments of the fabricated DSSCs. The photovoltaic performance of DSSCs in terms of efficiency,
current, voltage, and filling factors was performed under standard illumination of AM 1.5G having an irradiance
of 100mWcm− 2 . The results showed that the photoelectric conversion efficiency of the fabricated DSSCs were
nearly less than 2%, while the open-circuit voltage and short-circuit current density were from 0.43 to 0.55 V and
0.45–0.54 mAcm-2, respectively. The appropriate LUMO energy level and the band-gap of these extracted dyes
would enable them to become efficient sensitizer for utilizing in fabricated DSSCs. Therefore, due to the existence
of carbonyl and hydroxyl groups in dye’s chemical structures, it enable them to bind to the TiO2 layer, conse­
quently, improve the electron transfer, and enhance the energy conversion efficiency of the fabricated DSSC.

1. Introduction couple electrons in the electrolyte [13,18], and finally, the electron
could transfer via the external load in the circuit [11,12,18], and it also
Nanotechnology has an impact on the design, fabrication, and entering into the metal oxide semiconductor conduction band (counter
characterization of several new materials for recent opportunities to electrode) again, while regenerate the electrolyte catalyst.
provide sustainable energy [1]. Nowadays, dye-sensitized solar cells Dye sensitivities act as an important role in the DSSCs performance
(DSSCs) as a third-generation and alternative of conventional solar cells [3–5,19]. Various types of dyes, such as organic (natural dye: chloro­
have been investigated, due to the easy fabrication, low-cost production, phyll a & b, carotenoids, xanthophylls, carotenoids, anthocyanins, and
and eco-friendly operation [2–4]. The DSSCs (Graetzel cells) are using betalains) [13, 14] and inorganic dye (Ruthenium, safranin, …) were
synthetic or natural dyes as a light-harvesting elements [2–7]. The entire utilized in DSSCs [20–24]. At the moment, inorganic dyes like Ruthe­
sunlight conversion into electricity occurs by three components of DSSC, nium were recognized as the most considerable dye for the DSSCs
including the electron transport semiconductor (wide band-gap) [8–12], fabrication with great efficiency [22,25]. Nevertheless, these kinds of
the light-absorber (natural or synthetic dye as a sensitizer) [13–15], and dye are quite expensive (Ru is rare metal), toxic nature, and difficult in
the hole transport electrolyte (redox couple) [16–18]. As shown in their purification [20]. Recently, natural dyes have extensively investi­
Fig. 1, the overall DSSC process is summarized as follows: At first, the gated due to their large absorption in the visible spectrum, abundance in
dye photoexcitation could transfer an electron into the metal oxide nature, easy sample preparation, low production cost, and
semiconductor conduction band (generally TiO2 , SnO2 and ZnO) [8–10]. eco-friendliness [26–28]. In spite of the availability and subsequently
Afterward, the oxidized dye molecules would regenerate from the redox low cost of the natural dyes, they mostly do not harvest energy

* Corresponding author.
E-mail address: jalali@pgu.ac.ir (T. Jalali).

https://doi.org/10.1016/j.optmat.2020.110441
Received 6 July 2020; Received in revised form 13 September 2020; Accepted 14 September 2020
Available online 1 October 2020
0925-3467/© 2020 Elsevier B.V. All rights reserved.
T. Jalali et al. Optical Materials 110 (2020) 110441

and their effectiveness on the fabricated DSSCs was presented. Then,

characterization techniques were accomplished to study the absorption
and electrochemical properties of extracted dyes using UV–visible
spectroscopy and cyclic voltammetry, respectively. Moreover, to eval­
uate the effectiveness of each dye, the extracted dyes were utilized as
sensitizers for DSSCs fabrication. In the last step, the photovoltaic per­
formance, such as η, Voc , Isc , and FF of the fabricated DSSCs was calcu­
lated by the current-voltage characteristic (I-V) curves.

2. DSSCS operation process

2.1. Governing kinetics and efficacy evaluation

Interaction of light to DSSCs leads to a sequence of reactions in the

cell. These electron migration kinetic data, which occur at the semi­
conductor oxide, dye, and electrolyte interface, were described in brief
as follows:
Anode:

S + hν→S* Absorption (1)

Fig. 1. Schematic of a DSSC sensitized with the extracted dyes.
S∗ → S+ + e−cb (TiO2 ) Electron injection (2)

conversion efficiencies of over 2% [26–30]. Natural dyes as chemical

2S+ + 3I − →2S + I3− Regeneration (3)
compounds play a vital role in all living organisms’ growth [26,27].
Plants are one kind of the main producer of dyes, which were catego­ Cathode:
rized into four groups, including chlorophylls a&b, anthocyanins, fla­
I3− + 2e− (Pt)→3I − (4)
vonoids, and carotenoids, consistent with their bio-synthesis basis and
common structure [31–37]. The natural dyes were extracted from Electron loss reactions take place in the DSSCs, which compete with
roselle, blue pea flowers, Safflower, algae, fruits, and so on have been the reactions (1)–(4). The photo-injected electrons collection efficiency
investigated as sensitizers in DSSCs, which has electric conversion effi­ at the photoanode back contact was slowed down by two main recom­
ciencies less than 2% [31,33,34]. Nevertheless, some of them are shown bination processes, transferring back electron, and capturing electron
efficiencies of more than 2% [28,30,38]. The optical properties of the from the TiO2 conduction band by the oxidized redox.
natural dyes are different due to variations in their chemical structures.
S+ + e−cb (TiO2 ) → S + TiO2 (5)
The anthocyanin molecule dye contains carbonyl and hydroxyl groups,
which bounded to the porous semiconductor oxide layer surface and
I3− + 2e−cb (TiO2 ) → 3I − + TiO2 (6)
helps electron migration from the anthocyanin molecule to the semi­
conductor oxide conduction band [14]. Natural carotenoids have been S → hν + S ∗ (7)
used in DSSCs, with the highest efficiency of around 2.6% [27]. By
cockatail of carotenoids in combination with chlorophyll derivatives, The overall conversion sunlight to the electricity in a DSSC (η) can be
the efficiency enhanced up to 4.2% [27,37]. Comparison between dyes obtained by multiplying the absorbance efficiency (ηabs ), electron in­
indicated that regarding performance as well as cost, some DSSCs with jection efficiency (ηinj ), and the charge collection efficiency (ηcoll ):
natural dyes are capable of attaining significantly better results than
η = ηabs ηinj ηcoll (8)
DSSCs with Ru-based dye, the efficiency enhanced up to 14.3% [24,39,
40]. Ghann et al. sensitized NDSSCs using the dyes extracted from The absorbance efficiency, as well as the electron injection effi­
pomegranate and berry fruits. It has been found that using pomegranate ciency, are directly concerning the selected dye of the DSSCs. Besides,
dye extract containing anthocyanin, the efficency of NDSSC reached to the charge collection efficiency was related to the injection of electrons
2.0%. This enhanced efficiency had attributed to the high concentration to the TCO glass substrate. The contribution of each term on the overall
of anthocyanin present in pomegranate dye, the use of graphite as the efficiency of the DSSC reveals the crucial role of dye on the performance
counter electrode, and TiCl4 treatment of the photo-anode [41]. Gol­ of the cell. On the other hand, the overall efficiency (η) of the DSSCs can
shan et al. optimized the dye extraction conditions using RSM and found be calculated based on the experimental data of the maximum power out
that the microwave-assisted Malva verticillata DSSC had the highest (Pmax ) generated by the DSSCs and incident power (Pin ) [40]:
efficiency of 1.702% [37]. Maiaugree et al. achieved a relatively high
DSSC efficiency of 2.63% using carbonized mangosteen peel and η = Pmax / Pin = (Jsc Voc FF) / Pin (9)
mangosteen peel dye extract as a natural counter electrode and a
where JSC , (VOC ), and FF are photo-current density measured at short
photosensitizer, respectively [42].
circuit, open circuit photovoltage, and fill factor, respectively. All the
While all DSSC components are under investigation for better per­
data were determined using Current-voltage characteristics curves. In
formance, we concentrated the research on the use of natural dyes as the
the I-V diagram, the maximum current for a DSSC was indicated, which
most crucial light-harvesting elements in the DSSCs. In this work, the
converts incident photons underneath the absorption onset wavelength
photoanode and counter electrode materials are TiO2 , semiconductor
into electric current.
oxide, and platinized conducting glass, respectively. The highest fabri­
cation cost of DSSCs was recognized to the dyes; therefore, the wild
regional plants for dye extraction could be an excellent candidate to 2.2. The dye structure
decrease the fabrication cost. The potential of dye extraction from four
native plants Crocus sativus (Saffron), Allium cepa L (red onion), Malva The dye produced by pigments is due to the specific structure of the
sylvestris (Mallow), and Oregano (Origanum vulgare) was evaluated chromophore molecule, which causes the electron to transfer from the
outer orbitals to a higher orbital by absorbing the energy in the visible

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T. Jalali et al. Optical Materials 110 (2020) 110441

region [43]. In nature, flowers, leaves, and fruits with different colors vibrational band centered at 3433 cm− 1 was ascribed to the O-H
have various dyes that can be extracted and employed for DSSC fabri­ stretching. Chlorophyll has two main functional groups, -OH and
cation. Natural colorants with pigmentary molecules have hydroxyl and –COOH, that bind chemically weak with TiO2 nanoparticles. The peak of
carbonyl groups in their structure [44]. For instance, the plants and their Oregano in the region 600-1750 cm− 1 is nearly similar extracts due to
chemical structures used in this study for the fabricated DSSCs are containing chlorophyll molecules, and the main differences are in peak
shown in Fig. 2. intensities. The bands 1070 cm− 1 , and 1112 cm− 1 were assigned to
The FTIR spectra of the extracted dye from Crocus sativus(Saffron), stretching vibration C-O, and 1253 cm− 1 was attributed to carbonyl
Malva verticillata (Mallow), Allium cepa L(red onion), Oregano (Orig­ groups, C-O, O-H, and 1591 cm− 1 was attributed to N-H bending vibra­
anum vulgare) are shown in Fig. 3. The dye structure of saffron petal has tions and C-C stretching [50,51]. These modes help in binding the dye
various C = Oand OH groups, and capable of anchoring to the and the TiO2 layer, which causes the energy conversion efficiency
TiO2 nanoparticle. Based on the FTIR results, the presence of the hy­
enhancement [41]. The peak at 1639 cm− 1 of Red Onion L is ascribed to
droxyl group in the saffron petal extract molecular structure can be
the vibrational modes of C=O stretching [52]. Besides, the peaks at 1033
bound to the surface of the TiO2 layer. The 3365 cm− 1 peak was attrib­
and 1037 cm− 1 were assigned to the C-O-C stretching band. For the lower
uted to the OH stretching vibration [45–48]. Furthermore, the peaks at
frequencies, the peak at 3467 cm− 1 , and 3444 cm− 1 were assigned to N-H
2862, 2946 cm− 1 , and 1033 cm− 1 were attributed to the CH stretching
and O-H stretching, while the peak at 2933 cm− 1 was assigned to CH2
mode and CO vibration, respectively [48]. Moreover, Malva verticillata
antisymmetric stretch [53,54]. Red Onion L chemical structure pos­
chemical structure possesses carbonyl and hydroxyl groups in chloro­
sesses carbonyl and hydroxyl groups in anthocyanin molecules, and the
phyll molecules, which can help to bind the dye to the TiO2 surface [37].
advantage of anthocyanin is the binding of these groups to the surface of
The absorption bands at 2923 cm− 1 and 2810 cm− 1 were assigned to sp3
TiO2 film. Therefore, electrons migration can happen from the antho­
C-H stretching, at 1631 cm− 1 was for carbonyl group (C=O), and the cyanin molecule to the TiO2 conduction band [32,45]. In the end, the
absorption band at 1734 cm− 1 was due to CO stretching [49]. The broad wide absorption peak of these dye in the visible frequency range

Fig. 2. Plants, powder, powder in aqueous solution, and dominant chemical structures of: (a) Crocus sativus(Saffron), (b) Malva verticillata (Mallow), (c) Allium
cepa L(red onion), (d) Oregano (Origanum vulgare).

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T. Jalali et al. Optical Materials 110 (2020) 110441

Fig. 3. FTIR of Plants: Crocus sativus(Saffron), Malva verticillata (Mallow), Allium cepa L(red onion), Oregano (Origanum vulgare).

designates that the dye molecules absorb the TiO2 nanoparticles. The plant, Allium cepa L (red onion), and wild plants, Malva verticillata
binding natural dye molecule on TiO2 nanoparticle compared to RU dyes (Mallow), as well as Oregano (Origanum vulgare), were collected from a
possess a poor absorption which, leads to lower efficiency. Due to the local farm and a region in the north border of Persian Gulf region,
high surface area of TiO2 nanoparticle, the dye can be bound to it and respectively. Fresh saffron flowers were collected from a farm in the
consequently can be responsible for electron transfer. Therefore, lower Ghaenat area (Iran).
efficiency attributed to a lack of strong bonds between the dye molecule
and TiO2 , which electron can be injected from excited dye to
TiO2 molecule [55]. For most metal complex dyes such as N719, a 3.2. Methods
carboxyl group is an effective anchor, which dyes bind to the
TiO2 nanoparticle surface. These carboxylic groups can bind to the hy­ The saffron petals were separated, dried in a dark and naturally
droxyl group of TiO2 nanoparticle and improve the coupling effect and ventilated room at the room temperature to provide the good quality
fast electron-transport rate [55]. Moreover, chlorophyll, b-carotene, and anthocyanin [45,48,56]. The other fresh plants were first washed,
anthocyanin possess lower stability than N719, which leads to lower oven-dried at 42∘ C, and powdered. To extract the dye, 1 gr of samples
efficiency. Natural dye has a characteristic low Voc , which can be was dissolved in 20 ml of the solvent. The solvent extraction was per­
elucidated by the electron/dye recombination and the mostly acidic dye formed in an incubator shaker apparatus (FTSKT-801L, Korea). After
absorption environment. These interface of TiO2 /dye/electrolyte leads this process, the extracts were separated by centrifuge (Sigma, Model:
the resistance and consequently, short circuit current is reduced. 2-16P) at 2500 rpm for 5 min. The solid fibers were filtered out from the
Therefore, natural dye materials with a carboxyl group, are indispens­ solution by filter papers and achieved a pure and clear natural dye so­
able to improve DSSC efficiency. These natural dyes possess low fill lution. These natural dyes extracts were also stored at a cold and dark
factors, which can be explained as high resistance for the electron place to characterize as a sensitizer and fabricate the DSSC. To fabricate
transport in TCO substrate, large electrolyte thickness, and the poor the DSSCs, the FTO glass has been used as the working electrode. The
quality of the Pt layer. Another reason for the calculated low fill factor conductive glass substrate must first be washed in a detergent solution,
for the photoanode electrode can be probably attributed to the electron rinsed with water and ethanol, and then oven-dried at 70∘ C. Afterward,
recombination kinetics. Higher recombination reactions, lower the FTO-glass coated with sequential layers of the TiO2 transparent layer and
electron density in the TiO2 nanoparticles, which lead to lower the TiO2 scattering layer with the active area 0.5 × 0.5cm2 and
open-circuit voltage. 50μmthickness using doctor blade technique. The TiO2 electrode was
gradually heated at 325∘ Cand then sintered at 500∘ Cfor 30 min. After
3. Materials and methods cooling the electrode, the film immersed in the extracted dye solution
for 24 h in the dark at room temperature. To prepare the counter elec­
3.1. Materials trode, the platinum was coated on the FTO glass and then heated at
450∘ Cfor 15 min.
The Fluorine-doped tin oxide (FTO) conductive glass (resistance The working and counter electrodes were sandwiched using spacer
3.75Ω), transparent anatase TiO2 paste (20–25 nm), reflector rutile adhesive for sealing. The electrolyte solution was prepared by dissolving
TiO2 paste coated with SiO2 , platinum paste, Cis-bis (isothiocyanato) bis 2.07 gr of KI and 0.19 gr of iodine in 25 ml of ethylene glycol. An
(2.20 bipyridyl 4.40 dicarboxylato) Ru(II) (N719), redox electrolyte solution, including iodide/triiodide, was injected into the
(I− /I− 3 )electrolyte solution were purchased from the Solarsharif com­ cell, and a spacer adhesive closes the cavity. To estimate the natural dye
pany. Besides, the Surlyn foil (60 μmthick) was purchased from the quality, the extracted dye was analyzed using a UV–Vis spectropho­
Solarinix company. Ethanol (99.9%), Acetone, and Hydrogen Chloride tometer (UviLine9600, SECOMAN). To analyze the electrochemical
were prepared from Merck chemical company. The clean and fresh behavior of the extracted dyes, cyclic voltammetry (CV, ZAHNER,
Zennium) was carried out. These measurements were performed with a

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T. Jalali et al. Optical Materials 110 (2020) 110441

three electrodes system composed of a platinum counter electrode, a inject in the TiO2 layer. Saffron and Oregano have a smaller and larger
glassy carbon working electrode, and Ag/AgCl reference electrode with band-gap, respectively.
a 100 mVs scan rate, and the electrolyte was 10 ml of 0.1 M KNO3 solution.
The reversible process of oxidation and reduction of dye propose
The electrode preparation for this analysis carried out by putting two charge migration, as well as, the low band-gap of TiO2 makes it possible
drops of dyes on to the glassy carbon electrode and dried it at room for the injection of both carriers efficiently from the electrode. Optical
temperature, then immersing the prepared electrode in the electrolyte absorption and cyclic voltammetry results showed that all extracted dye
[57]. The UV–Vis absorption spectra and reduction onset of CV curve and their derivatives possess adequate band-gap with high electron af­
were used to calculate the lowest unoccupied and highest occupied finity (LUMO level ∼ − 3.6eV)) and high positive oxidation potential.
molecular orbital (LUMO and HOMO) energy levels of the extracted These properties indicate that these dyes are situated candidates as an
dyes by the Tauc relation [58,59]. Moreover, Photovoltaic characteris­ acceptor for DSSCs. Using cyclic voltammetry, the results revealed that
tics performance were carried out to find the DSSCs performance, using tuning the dyes band-gap the more the quantity of oxygen-containing
a solar simulator (Solar Cell Simulator IIIS-200+, Nanosat CO., Iran) functional groups can raise dyes catalytic activity and conducted the
having an irradiance of 100 W/m2 at the standard condition of AM 1.5G. charge transfer at the interface, and consequently, low resistance delays
All the experiments were done at room temperature and repeated three electronic transport within the TiO2 layer. Moreover, the DSSCs can
times. absorb efficiently sunlight because of suitable natural dyes band-gap,
accordingly enabling the electron excitation and migration process for
4. Results and discussion increasing efficiency sunlight conversion of the electricity.
Fabricated photoanodes and assembled DSSCs with extracted dyes
The optical absorption spectrum of natural extract dyes was char­ and photocathode were shown in Fig. 6. The characteristic of the cor­
acterized using a UV–Visible spectrometer. The UV–vis spectroscopy responding voltage current is accomplished, and the optical current is
results of the extracted dyes in the ethanol were shown in Fig. 4. Mallow defined as the increase in the flow under AM1.5G light illumination at
extracted dyes possess two notable peaks: The first one is around 470 nm 100 W/m2 intensity from a solar simulator. This indicates the production
(blue light), and the second one at 665 nm (red light). Both peaks relate of free carriers by absorbing lightIsc photons. The phenomenon of optical
to the combination of chlorophyll [20]. For the second pigments were current consists of the process of absorbing light photons in the deple­
extracted from the Saffron dye, the peaks observed around 325 nm tion layer and producing charge carriers.
(violate light), and 470 nm (red light), which both peaks correspond to Photovoltaic parameters (open and short circuit currents) for all
the anthocyanins. Besides, the results showed that the extracted pig­ DSSCs were plotted in Fig. 7. The calculated information (η, Voc , and FF)
ments from the Oregano dye reveal two peaks around 320 nm (violate from I-V curves and the performance of all fabricated DSSCs were
light), and 420 nm (red light). These peaks relate to the combination of summarized in Table 2. The Ru complex N719, synthetic sensitizer, was
chlorophyll a and b and derivatives. The wide region from 310 nm to selected as a reference DSSC [37]. According to the calculated results,
370 nm (violate to blue light) for the Red Onion dye and the peaks the Voc and the Isc , were varied from 0.43 to 0.55 V and 0.45–0.54 mA,
correspond to the anthocyanin. These peaks could increase the charge respectively. Based on the photovoltaic results in Table 2, it was found
transfer reaction under sunlight illumination in the fabricated DSSC. The out DSSC using Red Onion dyes has higher Voc , Isc , and consequently, η
absorption peaks are generally spread in the visible wavelength range compared to DSSCs sensitized with other extracted dyes. Therefore, a
(400–900 nm). It is pointed out that all the absorption spectra of the higher LUMO energy level of the extracted dyes than the conduction
extracted dyes possess the double peaks, which can efficiently absorb the band energy level of the TiO2 layer, where relatively suitable band-gap of
sunlight. the extracted dyes enhance their efficiency for the fabricated DSSCs.
The electrochemical properties of these extracted dyes were inves­ Besides, it appears that the Voc of Red Onion L-DSSC is comparable to
tigated using cyclic voltammetry technique. Cyclic voltammograms of that of the reference DSSC that used the N719 dye as a sensitizer [59].
the extracted dyes were depicted in Fig. 5. These measurements were Overall, based on the results, the photovoltaic parameters (η, Voc , Isc , and
analyzed to define the LUMO and HOMO energy levels of the extracted FF) of all DSSCs were more than corresponding DSSCs fabricated using
dyes. These results, including the LUMO and HOMO energy levels and dyes extracted with ordinary solvent extraction method. The maximum
energy band-gap of all extracted dyes were summarized in Table 1. The energy conversion efficiency of fabricated NDSSCs is as follows: Mallow,
TiO2 conduction band nearly − 4.3 eV is reported [37]. It is obvious that Saffron, Oregano, and Red Onion. Due to low-cost harvesting of Red
the LUMO energy of the extracted dyes is appropriately higher than the Onion, Oregano, Malva verticillata, and Saffron as well as dye extrac­
TiO2 conduction band. Therefore, the electrons are capable to easily tion, compatibility with the environment, low toxicity, and comparable

Fig. 4. Comparison of UV–vis absorption spectra of the extracted dyes from a) Crocus sativus (Saffron) b) Malva verticillata (Mallow) c) Allium cepa L(red onion), d)
Oregano (Origanum vulgare) e)N719.

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T. Jalali et al. Optical Materials 110 (2020) 110441

Fig. 5. Cyclic voltammograms of: (a) Crocus sativus (Saffron), (b) Malva verticillata (Mallow), (c) Allium cepa L(red onion), (d) Oregano.

energy conversion efficiency of its DSSC with the reference cell, they are
Table 1
suitable candidates for substitution with synthetic dyes.
Photoelectrical parameters, LUMO, HOMO and bandgap energies of the natural
Due to carbonyl and hydroxyl groups in the chemical structures of
dyes.
the extracted dyes from Malva verticillata, It binds to the TiO2 layer of
Dyes LUMO(ev) HOMO(ev) Bandgap(ev)
the photoanode and facilitates the electrons migration from the excited
Saffron − 3.64 − 6.04 2.40 dyes to the semiconductor conduction band. The conjugation between
Mallow − 3.70 − 6.49 2.79 the sensitizer and the TiO2 layer considerably leads to an enhancement
Red Onion L 3.69 6.49 2.80
energy conversion efficiency of the fabricated DSSCs. Similarly, the
− −
Oregano − 3.64 − 6.24 2.60
existence of carbonyl groups in chemical structures of Red Onion dyes,
as well as Oregano dyes, enable them to bind with the TiO2 layer and
improve electrons migration as well. Besides, the existence of

Fig. 6. Photoanode and Assembled DSSCs with extracted Dyes and photocathode.

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T. Jalali et al. Optical Materials 110 (2020) 110441

Fig. 7. Photocurrent -voltage characteristics of a DSSC. The photosensitizer was the extracted dyes from Mallow, Red Onion, Oregano, Saffron, and Reference
N719 [59].

and 0.45–0.54 mA, respectively. The Oregano-DSSC had the highest

Table 2
energy conversion efficiency of 1.9% while its Voc was less than that of
Summary of the I-V characteristics curve solar cell’s performance.
reference DSSC containing standard dye N719. This outstanding
DSSC dye ISC (mA /cm2 ) VOC (v) FF (%) Efficiency (%)) photovoltaic performance was assigned to the dyes concentration,
Reference N719 [59] 19.3 0.71 50.00 6.85 photocatalytic activity as well as the optical activity stated by UV–vis
Saffron 2.48 0.43 48.04 0.51 and CV measurements. The pigment structure, anchoring group (which
Mallow 2.16 0.49 42.65 0.45 attaches with TiO2 ), and stability are responsible for this lower effi­
Red Onion L 2.12 0.55 46.66 0.54 ciency than N719. The suitable LUMO energy level, as well as the band-
Oregano 2.48 0.43 47.82 0.51
gap, of the extracted pigments, illustrated them as the efficient sensitizer
for utilizing in fabricated DSSCs. Moreover, due to the existence of
anthocyanin in the Saffron was extended π conjugation, the positive carbonyl and hydroxyl groups in the chemical structure of the extracted
charge and free OH groups in the delphinidin structure of anthocyanin, pigments, it enables them to bind to the TiO2 layer, as a result, improve
and allowed the dye to absorb visible sunlight. Increasing dye-TiO2 the electron migration, as well as, enhance the energy conversion effi­
binding intensity decreases required excitation energy at a higher ciency of the fabricated DSSC. The proper energy level and the geo­
wavelength due to decreasing the band-gap of the semiconductor-dye metric connection between the natural sensitizer and the TiO2 layer
complex. Accordance with the results, the photovoltaic parameters (η, confirm that these natural dyes are excellent alternatives to the expen­
Voc , Isc , and FF) of all DSSCs were acceptable compared to the previous sive Ru-sensitizers. As a result, due to the low-cost, eco-friendly, and
natural dyes based DSSCs [52], The best energy conversion efficiency of technical efficacy of the extracted pigments, these plants are good
the fabricated DSSCs are sorted descending as follows: Mallow, Saffron, candidates for the development of DSSCs production on an industrial
Oregano, and Red Onion. Owing to the low-cost of Red Onion, Oregano, scale.
Mallow, and Saffron, as well as easy dye extraction, low toxicity, envi­
ronmentally friendly, and satisfactory energy conversion efficiency of CRediT author statement
the fabricated DSSC with the natural dyes and reference cell, they are
suitable candidates for substitution with synthetic dyes. Tahmineh Jalali: Supervised the research, conception of the proj­
ect, design of methodology and experimental protocol, analysis, drafting
5. Conclusion the manuscript, designed the figures, revising it critically for important
intellectual content. Parisa Arkian: performed some of the measure­
In this work, the extracted pigments from the wild and native natural ments and characterization, data collection, analysis, drafting the
plants such as Crocus sativus (Saffron), Allium cepa L (red onion), Malva manuscript. Maliheh Golshan: performed some of the measurements
sylvestris (Mallow), and Oregano (Origanum vulgare) were used as and characterization, data collection, analysis, drafting the manuscript.
photosensitizers to increase the biocompatibility of the DSSCs. The Mandana Jalali: design of methodology and experimental protocol,
UV–vis results showed that the extracted pigments are containing supervising the fabrications, drafting the manuscript. Shahriar Osfouri:
anthocyanin and chlorophylls, where they are very excellent light- analysis, drafting the manuscript, revising it critically for important
harvesting pigments and effective for charge generation carriers from intellectual content.
sunlight. The performance of extracted dyes as photosensitizer has been
evaluated using cyclic voltammetry and current-voltage open circuit of Declaration of competing interest
the fabricated DSSCs. The results showed that similar to the most DSSCs
that had used natural pigments as a sensitizer; the photoelectric con­ The authors declare that they have no known competing financial
version efficiencies were less than 2%. Moreover, open-circuit voltage interests or personal relationships that could have appeared to influence
and short-circuit current density obtained in a range from 0.43 to 0.55 V the work reported in this paper.

6. Nomenclatures

List of symbols
CV Cyclic voltametry
DSSCs dye-sensitized solar cells
FF fill factor
FTO Fluorine-doped tin oxide

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T. Jalali et al. Optical Materials 110 (2020) 110441

HOMO the highest occupied molecular orbital

I current (mA)
LUMO the lowest unoccupied molecular orbital
P electrical power (mW)
UV–Vis Ultraviolet–Visible
V voltage (V)

Greek letters
η Efficiency
λ Wavelength

Subscript
Cb conduction band
inj injection
In Incident
Mp maximum power
Oc open circuit
Sc short circuit
Max Maximum

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