Journal Pre-proof

Impacts of paste preparation methods on the porous TiO2 nanostructure properties

and naturally dye-sensitized solar cells performance

Javad Salimian, Shahriar Osfouri, Reza Azin, Tahmineh Jalali

PII: S2238-7854(22)00633-0
DOI: https://doi.org/10.1016/j.jmrt.2022.04.134
Reference: JMRTEC 4830

To appear in: Journal of Materials Research and Technology

Received Date: 11 January 2022

Revised Date: 14 April 2022
Accepted Date: 25 April 2022

Please cite this article as: Salimian J, Osfouri S, Azin R, Jalali T, Impacts of paste preparation methods
on the porous TiO2 nanostructure properties and naturally dye-sensitized solar cells performance,
Journal of Materials Research and Technology, https://doi.org/10.1016/j.jmrt.2022.04.134.

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© 2022 The Author(s). Published by Elsevier B.V.

 Impacts of paste preparation methods on the porous TiO2 nanostructure
properties and naturally dye-sensitized solar cells performance

Javad Salimian1, Shahriar Osfouri1,, Reza Azin2, Tahmineh Jalali3

1- Department of Chemical Engineering, Faculty of Petroleum, Gas, and Petrochemical

Engineering, Persian Gulf University, Bushehr, 75169, Iran.
2- Department of Petroleum Engineering, Faculty of Petroleum, Gas, and Petrochemical
Engineering, Persian Gulf University, Bushehr, 75169, Iran.
3- Department of Physics, Faculty of Science, Persian Gulf University, Bushehr, 75169, Iran.

Abstract

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In the last two decades, researchers have attempted to use environmentally friendly pigments
and porous nanostructures as sensitizers and semiconductors in dye-sensitized solar cells

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(DSSCs), respectively. In this study, the pigments were extracted from black plums

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(Syzygium cumini) to increase the biocompatibility of the DSSCs. The UV-vis spectroscopy
of the extracted solution revealed the existence of anthocyanin pigments. The cyclic
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voltammetry measurement showed that the pigment energy levels were suitable for electron
transfer to the TiO2 semiconductor, and the pigment electrochemical properties were also
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comparable with the commercial synthetic pigments. The dynamic light scattering
experiment and zeta potential measurement illustrated that the size and electrostatic potential
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of the pigments were 0.3 nm and ±5 mV, respectively. These data confirmed the potential of
the pigments for the diffusion into the porous structure of the TiO2 semiconductor and
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attraction as a shell layer on its surfaces. Besides, the TiO2 pastes were produced with seven
different methods and characterized using XRD, SEM, and BET experiments. The results
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showed that the morphology, particle size, porosity, and surface area of the produced
nanostructures were different in each method. Finally, the pastes were coated on the glass,
sensitized with the extracted natural pigments, and used in the fabricated DSSCs. The
efficiency of the cells was evaluated in the range of 0.027% to 0.256% using the sun simulator
technique. The results showed that the optimum particle size of the TiO2 semiconductor was
around 25.6 nm which had been formed in the sixth method of the paste preparation.

Keywords: solar cell; sensitizer; natural dye; paste; TiO2

1. Introduction
Dye-sensitized solar cells (DSSCs) are the third-generation solar cells that have received
attention due to their ease of fabrication and environmental-friendly applications [1-3].
DSSCs constitute one type of inexpensive solar cells that are classified as thin-layer solar


Corresponding Author’s E-mail: osfouri@pgu.ac.ir
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cells. As shown in Figure 1, this type of solar cell has three main components of the counter
electrode, electrolyte, and photoanode which include transparent conductive oxide (TCO),
dye as sensitizer, and semiconductor paste. Due to the light absorption by the sensitizers,
photo-excited electrons from dye molecules are injected into the semiconductor film
conduction band. Before flowing back to the counter electrode, electrons diffuse to the TCO
substrate and subsequently to the external circuit. At the same time, the oxidized dye
molecule will be regenerated through the reduction process by the redox pair existing in the
electrolyte.

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Figure 1: Schematic diagram of a typical DSSC

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In DSSCs, the mesoporous metal oxide layer plays a vital role as the key component of
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photoanode, so the efficiency of the cell is highly dependent on its surface and electronic
properties. The semiconductor paste, with its porous structure, provides the surface needed
to absorb the dye molecules and creates a path for the electron diffusion, so that electron
transfer can take place easily. Therefore, its specific surface area, thickness and particle size
have a significant impact on the DSSC photovoltaic performance. Semiconductors such as
titanium dioxide, zinc oxide, tin oxide, niobium oxide, tungsten oxide, strontium oxide, and
nickel oxide are commonly used in photoanode of the DSSCs, where titanium dioxide (TiO2)
is found to be the most promising one [4-17].
TiO2 has shown good performance in solar cells due to its high chemical stability, good
bonding with pigment and suitable band gap (3.20 eV) in the anatase phase [18, 19]. One of
the vital aspects of DSSCs performance is the paste formulation of the TiO2 films and the
subsequent sintering procedure which can be mainly controlled by the paste preparation
process.
TiO2 paste formulation is developed by different precursors and deposition techniques for
various purposes and applications. One of the most popular precursors of producing TiO2

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paste is based on a sol-gel Pechini method which has been used by various researchers [20-
23]. These composition precursors have been developed and reported by different scholars
such as Krasovec et al. [24] and Mashreqi et al. [25]. Another precursor for the production
of TiO2 paste is considering the paste with or without binders. Muliani et al. [26] and Lin et
al. [27] focused to make an optimum performance for flexible DSSC despite low temperature
operation. In one study it was found that by adding a binder to the TiO2 paste mixture for
photoelectrode, and the comparative study between these methods, the paste with a binder
improves the performance of the device. The pastes with the binder are used to produce
flexible cells and are often baked at low temperatures [28-34]. Also, to improve the surface
morphology of the paste and reduce the surface cracking, polymeric materials and acids are
used to both improve the consistency of the paste and to achieve higher efficiency by
increasing the porosity [35-44]. The use of polyethylene glycol and acetic acid has been

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reported by many researchers to modify the surface morphology [45, 46]. Another feature of
DSSCs is the transparency of these cells. In this regard, researchers are looking to make a

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transparent paste to obtain a transparent or semitransparent cell [47, 48]. To improve the

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performance of the transparent paste used in the DSSC, Supriyanto et al. [49] changed the
composition of the materials and achieved the optimal composition.
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The next procedure is the easy paste preparation method. Other researchers [50] used a simple
paste that contains solvent and TiO2 and needs no sophisticated technology. It simply mixes
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these two components to achieve the paste used in the DSSCs. For example, mixing TiO2
with ethanol can provide an inexpensive paste that is easy to make [47]. It is important to
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note that all efforts to modify the structure of the paste have caused changes in properties
such as the specific surface area of the paste and the size of the paste nanoparticles, as well
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as the porosity of the paste. In 2003, Benco et al. examined the effect of three nanoparticles
sizes of 4 nm, 8 nm, and 14 nm in the produced paste on the DSSCs efficiency [51]. They
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concluded that the produced paste with an average particle size of 14 nm had more electron
injection kinetics from pigment to the paste, despite the classical electron transfer theory. In
another attempt, Nakadeh et al. studied the electron diffusion coefficients and electron
recombination lifetime in TiO2 films with average particles diameters of 14 nm, 19 nm, and
32 nm, which increased by increasing the particle size [52, 53]. In 2016, Al-Khafaji et al.
investigated the effect of the paste particle size on the DSSCs efficiency. They showed that
by using three different particles sizes of 10, 38 and 50 nm, the efficiency increases with
decreasing the nanoparticle size [54].
Based on the existing literature, the structure type and particle size of the paste, which were
related to the paste fabrication method, significantly influenced the efficiency and
performance of the DSSCs. Hence, the objective of this research is to fabricate various TiO2
pastes precursors as a photoanode thin film to achieve a more efficient DSSC based on a
natural dye sensitizer. Therefore, the authors used the improved Pechini sol-gel method (P1),
the low temperature method using titanium isopropoxide as the binder (P2), the polymer-
modified paste as the binder (P3), the acid-modified paste as the binder and surface modifier

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(P4), transparent paste (P5), simple method paste (P6), and low temperature method using
titanium isopropoxide as the binder and modified with acid (P7) to make TiO2 paste and the
optimum condition on the performance of DSSCs. The TiO2 pastes were characterized using
several microscopic and spectroscopic techniques, including scanning electron microscopy
(SEM), Brunauer-Emmett-Teller technique (BET) experiment, X-ray diffraction (XRD),
energy-dispersive X-ray (EDX) spectroscopy to analyze morphology, particle size, specific
surface area, phase-type, size, strain of the crystal lattice, and elemental analysis of the pastes,
respectively. In addition, the natural pigments were extracted from black plum fruit using the
solvent extraction method [1]. The optical properties, size, stability, and energy levels of the
pigments were characterized using UV-vis, dynamic light scattering (DLS), zeta potential,
and cyclic voltammetry (CV) techniques, respectively. Finally, the performance of the
assembled DSSCs was evaluated and compared under the sun simulator (100mw/cm2, AM

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1.5G) analysis.

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2. Materials and methods

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2.1 Materials
Ethylene glycol, citric acid, Triton 100-X, ethanol, polyethylene glycol, hydrochloric acid,
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acetic acid, polyvinyl pyrrolidone, titanium isopropoxide (TTIP), acetylacetone, acetone,
butanol, acetonitrile, potassium iodide, and iodine were purchased from Merck chemical
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company, Germany. TiO2 nanoparticles with anatase phase and purity of more than 99.5%
were purchased from Vira carbon nanotubes company, Iran. Double distilled water was used
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as the solvent. The fluorine-doped tin oxide (FTO) conductive glass, sheet resistance
15Ω⁄𝑐𝑚2, platinum paste, and Surlyn foils, 60 μm thick, were purchased from Sharif solar
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company, Iran. Besides, black plums (Syzygium cumini) which were used as the pigment
source were provided from the wild plant of the northern border of the Persian Gulf region.
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2.2 Pigment extraction process

The pigments were extracted from black plums (Syzygium cumini) using the solvent
extraction method. The dried black plums (Syzygium cumini) and the solvent, water, with a
solid to liquid ratio of 1:15 (g/ml) were well mixed at 44 °C in the incubator shaker (FTSKT-
801L, Korea) for 1 h. Then, the solution was centrifuged (Sigma, Model: 2-16P) at 2500 rpm
for 5 min to remove the insoluble material from the dye solution. Finally, the solution was
filtered with Whatman grade 42 filter paper and used without further purification. Figure 2
shows the plants, the extracted pigment, and the dominant chemical structure of the black
plum.

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 Figure 2: Fresh fruit, extracted pigment, and dominant chemical structures of the black plum (Syzygium
cumini)

2.3 The TiO2 paste preparation methods

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In this study, the TiO2 paste was prepared with seven types of precursors including the
Pechini sol-gel method (P1), the low temperature method using a flexible TTIP as a binder

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(P2), the polymer-modified paste as the binder (P3), the acid-modified paste as the binder and

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surface modifier (P4), transparent paste (P5), simple-method paste (P6), and low temperature
method using TTIP as the binder and modified with acid (P7). Because the paste thickness
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on the photoanode will influence the performance of the fabricated DSSCs, all of the
produced pastes were deposited with uniform thickness on the conductive electrode, a glass
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substrate, using the “doctor Blade” method. Pechini sol-gel (P1): In the first method, the
TiO2 paste preparation was due to the polyester-based titanium sol phase synthesis by using
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a precursor molar ratio of 1:6:24 (TTIP: citric acid: ethylene glycol). The sol phase was
prepared by stirring and heating ethylene glycol at 60 °C and adding the TTIP to the solution.
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Finally, the corresponding amount of citric acid was added to the solution, and the
temperature increased to 90 °C. The solution was stirred at this temperature until it turned
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transparent. The TiO2 paste, P1, was prepared by mixing the TiO2 powder and sol phase in
an alumina mortar for 1 h. The molar ratio between the TiO2 powder and TTIP in the paste
formulation was 7:1. The deposit layers were sintered at 450 °C for 1 h [24].
The low temperature method using TTIP as the binder (P2): In the second method, the
ethanolic solution containing 1.4 g of double distilled water and 86.8 g of ethanol was used
as the solvent. To produce the paste, P2, 10 g of TiO2 nanopowder was dispersed into the
solvent using 70 W ultrasonication (Bandelin Sonoplus GM 3100) for 20 min. Then, 1.8 g of
TIPP was added dropwise to the dispersed solution. In the final step, the mixture was kept
under mild stirring for about 5 h to achieve a further homogenized solution. The deposited
films were dried in air for about 15 min, and then heat-treated in a convection oven at 120
°C for 1 h [31].
The polymer-modified paste (P3): In the next method, 0.5 g of TiO2 powder and 0.4 g of PVP
were ground in a solution containing 2 ml of ethanol and 0.3 ml of acetylacetone using an
alumina mortar for 20 min. Then, 0.2 ml of the acetic acid was added to the solution while
stirring the mixture. Finally, 1 ml of the dispersant, Triton X-100, was added, followed by 3

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ml ethanol. After thorough mixing, the solution was concentrated by heating to obtain a
viscous paste, P3. To reduce the surface irregularities, the deposited TiO2 films were air-dried
for approximately 5 min. The films were then heated to 500 ºC in the air for 30 min to remove
the organic loads and facilitate the interconnection of the TiO2 nanoparticles [43].
The acid-modified paste (P4): In the fourth method, 6 g of TiO2 powder was ground in the
mortar with 10 ml of dilute acetic acid (0.87 M). To produce a homogenized solution, the
dilute acetic acid was added to the TiO2 powder in a stepwise process. In each step, 1 ml of
dilute acetic acid was dropped and ground for 2 min. This process continued for 20 min until
the solution turned into a milky white paste, P4. To prevent the re-aggregation of the particles,
0.8 ml acetylacetone was added to the paste. Dilute acetic acid helps to modify the surface
with H+ ions and works as a binding agent. The solution was kept at room temperature for 15
min to equilibrate with the surrounding. After completing the deposition process, the

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substrate was kept to dry for around 10 min. The tape was carefully removed from the glass
without damaging the coated side. Then, the substrate was placed in the furnace for

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calcination. The calcination temperature was set to 450 ºC for 30 min [44].

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Transparent paste (P5): In this method, the TiO2 paste, P5, was prepared by dissolving 1 gr of
TiO2 nanopowder with 1 ml of ethanol and stirring using a magnetic stirrer at 350 rpm. Then,
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the deposited sample was heated with a furnace to a temperature of 450 ºC with a 30 min
holding time [49].
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Simple-method paste (P6): In another attempt, the TiO2 paste, P6, was made by mixing TiO2
nanoparticles with polyethylene glycol binder (1:1 g/g) and deposited on the FTO to prepare
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DSSC photoanode. The prepared TiO2 film was air-dried at 80 ºC for 1 h and treated at 450
ºC for 30 min to eliminate the polymer binder [50].
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Low temperature method using TTIP as the binder and modified with acid (P7): In this last
method, the TiO2 nanopowder was calcined at 450 °C for 2 h and cooled at room temperature.
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Calcined TiO2 powder was mixed with a solution of butanol and HCl (0.01 M) with a molar
ratio of 1:5:3, respectively. Then, 3 mole percent of TTIP, as a binder, was added into the
mixture. The mixture was stirred by a magnetic stirrer for 24 h at 60 °C. The paste, P7, was
deposited, and the films were sintered at a temperature of 120 °C for 4 h [26]. The schematic
of the paste production procedures is illustrated in Figure 3.

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 P1 P2 P3
Titanium Titanium dioxide Acetylacetone
isopropoxide nanopowder
Acetic acid
Ethylene glycol
Triton X-100
Citric acid
Ethanol Ethanol
DI water
PVP

Ultrasonicate

Titanium dioxide

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nanopowder
Titanium

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Titanium
dioxide stirring isopropoxide
nanopowder

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Grinding stirring
Grinding
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P4 P5 P6
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Acetylacetone Ethanol Poly

ethyleneglycol
Acetic acid
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Titanium dioxide Titanium dioxide

Titanium dioxide nanopowder nanopowder
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nanopowder

Grinding
Grinding Grinding

P7
Butanol

HCl
Titanium
Titanium dioxide isopropoxide
nanopowder

Figure 3: Schematic of TiO2 paste preparation

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2.4. DSSC fabrication method
To prepare the working electrode, FTO conductive glasses were first cleaned in a detergent
solution, rinsed with water and ethanol, and then oven-dried at 70˚C. The active area on the
FTO-glass was 0.25 𝑐𝑚2. After the sintering process, the photoanodes were soaked in the
dye solution for 24 h in a dark place. The platinum paste was deposited on the perforated
FTO glass and put at 400 °C to prepare the counter electrode. Then, a dye-sensitized
photoanode and a counter electrode were sandwiched by placing a 60-μm spacer between
both electrodes. Finally, the electrolyte solution, containing 1.5 mM I2 and 7.5 mM KI in 7.5
ml acetonitrile and 2.5 ml ethylene glycol, was injected into the cell through a hole in the
counter electrode. Three cells were fabricated using each paste.

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Figure 4: The fabricated DSSC

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2.5. Characterization methods

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The crystal structure of the produced TiO2 paste was characterized by powder X-ray
diffractometer (Philips PW1730) using "Cu-Kα1" radiation at scattering angles between 20°
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and 80° with increments of 0.05°.s-1. The morphology of the microstructure prepared films
and the particle size of the paste particles were studied using scanning electron microscopy
(SEM, TESCAN Vega3, TESCAN). Besides, the specific surface area of the produced pastes
was measured using the Brunauer-Emmett-Teller technique (BET, ASAP2020,
Micromeritics) at 77 K. The BET method is the standard technique for the estimation of the
mesoporous film pore size distribution and its surface area per gram. Moreover, the EDX test
was performed to determine the elements and compounds in the produced paste (EDX,
TESCAN Vega3, TESCAN).
The optical properties of the extracted dyes were characterized using a UV–vis
spectrophotometer (UviLine9600, SECOMAN). Besides, dynamic light scattering (CiLas,
nano DS) and zeta potential (Zeta compact, CAD) experiments were conducted to
characterize the size distribution and surface charge of the extracted pigments, respectively.
Zeta potential measurement is a technique for evaluating the electric potential of a surface in
a liquid. Zeta potential is an important particle property that can affect the stability of
particles and the adhesion of their cells. To investigate the electrochemical properties of the
extracted pigments, the cyclic voltammetry test was carried out using a modular
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electrochemical workstation (CV, ZAHNER, Zennium). Cyclic voltammetry (CV) is the
most well-known electrochemical technique and is widely used in DSSC research to
characterize dyes, redox mediators, and charge transfer processes at interfaces. By scanning
the voltage and monitoring the current in a forward and a reverse scan, the formal redox
potential, as well as the interface charge transfer rates and the diffusion coefficient, can be
estimated. The CV measurement is used to calculate the highest occupied molecular orbital
(HOMO) and the LUMO energy level of the extracted pigment. Studies have also shown that
the difference in redox levels is proportional to the energy levels of HOMO and LUMO. This
test can detect the band-gap by calculating the numerical differences between the identified
HOMO and LUMO. In this experiment, glassy carbon electrodes were used as a working
electrode, platinum electrode as a counter electrode, and Ag/AgCl electrode as a reference
electrode at a scan rate of 100 mV/s. The supporting electrolyte was 10 ml of 0.1 M KNO 3

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solution. To measure the electrochemical properties of the extracted pigments, two drops of
the dye were dripped on the glassy carbon electrode and waited to dry at room temperature.

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The photovoltaic performance of the produced DSSCs was evaluated using a solar simulator

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(NANOSAT company, Iran) under a light intensity of 100 mW/cm2 at the standard AM 1.5
G conditions.
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3. Results and discussion
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3.1 Pigment characterization

Figure 5 shows the UV-vis absorption spectrum of the extracted pigments. The highest
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absorption was observed near a wavelength of 535 nm, which was very close to the maximum
absorption peak of the anthocyanin pigments [41, 55].
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2.5
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2
Absorbtion

1.5

0.5

0
400 450 500 550 600 650 700 750 800
Wavelenght (nm)

Figure 5: UV-Vis spectroscopy of the extracted pigments from the black plums (Syzygium cumini)

Using the UV-vis data, the extracted percent of anthocyanin, %Ex, from the initial dry-mass
of the black plums (Syzygium cumini) can be calculated as follows:
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 𝑚𝑔 𝐴𝑏𝑠𝜆𝑚𝑎𝑥 × 𝐹𝐷 × 100
%𝐸𝑥 ( ) = 1% (5)
𝑔 𝐸1𝑐𝑚
1%
where 𝐴𝑏𝑠𝜆𝑚𝑎𝑥 , 𝐸1𝑐𝑚 , and FD are the maximum absorbance, molar absorptivity at the
wavelength of 535 nm (98.2), and the dilution factor (0.33), respectively. Based on Equation
(5), the extracted percent of anthocyanin from the black plum is 57 (mg/g), which was less
than blueberries, 280 (mg/g), and more than strawberries, 40 (mg/g) [56, 57].
Figure 6 shows the electrochemical properties of the extracted pigments. Based on the results,
the HOMO and the LUMO energy levels of the pigments were -5.114 eV and -3.912 eV,
respectively. Besides, the band-gap of the extracted pigments was 1.202 eV. The results of
the CV test also showed that the extracted pigment band-gap was lower than that of the TiO2,
3.2 eV, while its LUMO energy level was higher [58]. These characteristics caused a better
excited-electron transfer from the pigment to the TiO2 paste.

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Current (μA)

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-2 -1.5 -1 -0.5 0 0.5 1 1.5
Potential/ V vs. Ag/Agcl

Figure 6: Cyclic voltammograms of the extracted pigments from black plums (Syzygium cumini)

The DLS results are shown in Figure 7. Based on the results, the size of the extracted pigment
particles is around 0.3 nm, which is suitable for binding with the TiO2 pastes.

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 60% 120
a b
50% 100

40% 80
Count (%)

Number
30% 60

20% 40

10% 20

0% 0
-25 -15 -5 5 15 25 0 1 2 3
Zeta potential (mV)

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Size (nm)

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Figure 7: (a): Zeta potential of the extracted pigment from black plums (Syzygium cumini) at pH=5,
(b): Size distribution of the extracted pigments from black plums (Syzygium cumini) at pH=5

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The zeta potential of the extracted pigments is shown in Figure 7. Due to the zeta potential
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distribution in the range of ±5 mV, the pigment tends to aggregate rapidly [59]. The
anthocyanin agglomeration at pH=5 was attributed to its adsorption characteristics. Zeta
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potential negativity caused more pigment to be absorbed into the TiO2 shell. A nucleus with
a positive charge could shift the dipole toward the TiO2 shell, consequently, the band-gap
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moved upward (negatively) and hence it enhanced the open-circuit voltage (Voc) [60, 61].
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3.2 Produced pastes characterization

3.2.1 Surface morphology
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The SEM image of the samples is shown in Figure 8. The results revealed that the coated
photoanodes with the prepared pastes had different surface morphology, and most of the
particles were spherical. Table 1 also shows the average particle size of the different pastes.
Based on the results, the P1, P3, and P6 samples had the smallest particle size than the P2, P4,
P5, and P7 samples.

Table1: Average particle size

Sample name Average particle size (nm)
P1 21.88 ± 0.46
P2 38.09 ± 0.87
P3 28.33 ± 0.54
P4 29.94 ± 0.64
P5 31.48 ± 0.38
P6 25.64 ± 0.36
P7 38.59 ± 1.27

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Figure 8: The SEM images of the produced TiO2 pastes

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Using the SEM technique, a typical cross-sectional image of a coated photoanode with a
paste is shown in Figure 9. The results showed that the thickness of the porous paste layer is
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around 12.4 micrometers, which is a great candidate for the photoanode fabrication of the
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DSSCs.
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Figure 9: The SEM image of a typical photoanode in the fabricated DSSCs

The results confirmed that the layer of TiO2 paste obtained from the Pechini sol-gel method
has a sponge-like structure, which is a prerequisite for achieving a high efficient DSSC [62].
TIPP was found to cause agglomeration of TiO2 particles due to the creation of an extended
TiO2 network among the particles [63]. For this reason, in pastes P2 and P7, the agglomeration
of TiO2 particles and surfaces with less porosity are observed. However, the addition of acid,

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which causes porosity in the structure of the paste, has caused the paste to have P7 relatively
more porosity than the paste P2. The absence of TTIP reduces the accumulation of TiO2
particles and the presence of acid increases the porosity of the paste structure. Acetic acid
can be adsorbed on the surface of TiO2 and prevents each particle from aggregating,
according to Ito et al. [64]. As expected, the presence of PVP in P3 results in a homogeneous
structure without aggregation [43]. On the other hand, the addition of PEG to TiO2 Paste is
well reported to affect the porosity of the TiO2 electrode [36]. As can be seen in Figure 8, P3
and P6 have a homogeneous structure, without cracks and with high porosity. However, the
results showed that the good dispersion of TiO2 in ethanol created a uniform layer with good
porosity for the pigment adsorption.

3.2.2 Specific surface area

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The BET results of all samples shown in Table 2 are in accordance with the SEM results. As
shown, the pastes consisting of the smallest particle size had the biggest surface area. Based

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on the BET results, the samples P1, P3, and P6 had the largest surface area than the other

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samples. The particle size and the surface area of the samples P3, P4, and P5 were close to
each other while the porosity of the P3 sample was more than the other samples. The surface
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area and the porosity of the samples P2 and P7 were drastically less than the other samples.
Thus, it is expected that these pastes do not provide a proper surface for the efficient pigment
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absorption as well as the light-harvesting process. P7, although modified with acid, showed
less porosity and less specific surface area for the pigment absorption. This can be due to a
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higher percentage of TTIP (12% w/w in P7 compared to 2% w/w in P2) in the initial solution,
which causes more agglomeration of TiO2 nanoparticles and reduced porosity.
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Table 2: The measured surface area and porosity of all samples using the BET tests
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Sample name Surface area (m²/g) Porosity

P1 55.30 0.49
P2 11.07 0.26
P3 47.27 0.65
P4 46.34 0.54
P5 45.09 0.61
P6 53.18 0.60
P7 5.52 0.11

3.2.3 Phase characterization and crystallography

The difference between the photo-electrochemical performances of the electrodes in the
DSSCs may be attributed to the microstructures of the TiO2 pastes. Seven typical XRD
spectra of the produced pastes are shown in Figure 10.

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 Intensity(Count)

Anatase
Anatase Anatase Anatase Anatase Anatase
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Anatase Anatase Anatase Anatase Anatase Anatase

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Anatase Anatase Anatase Anatase

Anatase Anatase

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Anatase
a

g
f
b

e
d

Position [°2Theta]
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Anatase Anatase Anatase Anatase Anatase
Anatase Anatase Anatase Anatase Anatase
Anatase Anatase Anatase
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Anatase Anatase Anatase Anatase Anatase Anatase
Anatase
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Anatase Anatase Anatase
Anatase Anatase Anatase Anatase Anatase

Figure 10: The XRD pattern of (a) P1, (b) P2, (c) P3, (d) P4, (e) P5, (f) P6, (g) P7
Anatase Anatase Anatase Anatase Anatase
As shown in Figure 10, all samples contain titanium dioxide in the anatase phase. Based on
the results, the diffraction peak positions 25, 37, 47, 53, 54, 62, 68, 70, and 74 in the P1
sample were indexed to the (101), (004), (112), (200), (105), (211), and (204) crystal planes
of the tetragonal body-centered TiO2, respectively. Besides, the XRD patterns revealed the
anatase phase of the TiO2 in the produced pastes. The diffraction peak positions 25, 37, 48,
53, 55, 62, and 70 in the P2 sample belonged to the TiO2 in the anatase phase. Moreover, it
can be found that the positions of peaks 26, 38, 49, 54, 56, and 63 in the XRD spectra of the
P3 sample belonged to the TiO2 in the anatase phase. The diffraction peak positions 25, 37,
48, 53, 55, 62, and 75 in the P4 sample were attributed to TiO2 in the anatase phase. Besides,
the diffraction peak positions 24, 37, 47, 53, 54, 62, 68, 70, and 75 in the P5 sample as well
as 25, 37, 48, 53, 55, 62, 68, 70 and 75 in the P6 sample belonged to the TiO2 in the anatase

of
phase. Also, the peak positions 25, 37, 48, 55, 62, 70 and 75 in the P7 sample were related to
TiO2 in the anatase phase. However, the results showed that samples P2 and P7, which were

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heated to 120 °C, did not completely crystallize. Different methods of making the paste and

-p
the materials used in each paste have caused the crystal size of the samples to be different
from each other. In the P1, P3, P4, P5 and P6 samples, the main peak around 25.5 corresponded
re
to the anatase (101) crystalline plane, but in P2 and P7, the main peak around 48 corresponded
to the anatase (112) crystalline plane. It should be noted that since all samples were coated
lP

on the glass and then sintered, the courier related to the glass was removed from the other
couriers. The full description of the X-ray diffraction calculations is presented in Appendix
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A, and a summary of the results is shown in Table 3. Based on the XRD results, P2 and P7
samples have different main peak positions as well as lower peak intensities with respect to
ur

the other pastes. These differences are due to the low sintering temperature of these two
samples and as a result, the incomplete crystallization process.
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Table 3: Calculated average crystalline size (nm) using the XRD results
Sample name Scherrer formula Williamson-Hall formula
P1 19.25 21.22
P2 18.64 18.65
P3 22.48 26.45
P4 21.96 23.65
P5 16.67 17.26
P6 20.31 21.22
P7 18.41 19.72

3.2.4 Elemental analysis

To determine the elemental content of the samples, the EDS test was done on different pastes.
The EDX spectrum of the P1 in Figure 11 showed the presence of titanium and oxygen in the

16
composition of the paste. Besides, the presence of gold in the EDX spectra was due to its
property as a resolution enhancer. The other elements attributed to the solvent were fade
during the production and heating process. The results demonstrated the presence of
characteristic peaks of Ti, O, and Au. The peaks at 0.5 keV, 4.5 keV, and 4.9 keV revealed
the existence of Ti in the paste, while the peak at 0.5 keV and 2.2 keV confirmed the presence
of O and Au, respectively. Based on the results, the weight percent of Ti, O, and Au were
44.8%, 43.2%, and 12%, respectively.

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Figure 11: EDX graph of TiO2 paste

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3.3 Efficiency evaluation of the fabricated DSSCs

The efficiency evaluation of the fabricated DSSCs was performed using a sun simulator
under AM 1.5 G standard experiment. All experiments were repeated using three to seven
fabricated cells, and the same results were obtained for each set of the experiments. The I-V
curves of the fabricated DSSCs are shown in Figure 12. The results showed that the fabricated
DSSCs using the P3, P6, and P4 pastes had a higher current density than the other cells, while
the fabricated DSSCs using the P1, P6, and P5 pastes had a higher voltage than the other cells.
As the results show, P3 and P6 in which polymer was used as a binder, showed the highest
current density. It is important to note that the effect of the surface modification with polymer
and acid is observed simultaneously in P3 and has increased the current density. However,
the unmodified polymer method showed a higher voltage. This indicates that the effect of
additives and modifiers such as acids can enhance the current density; however, due to
changes in the electrical properties of nanoparticles, it reduces the cell voltage.

17
 1.2

Current density (mA/Cm2) 1

0.8

0.6

0.4

0.2

0
0 100 200 300 400 500
Voltage (V)

of
P1 P2 P3 P4 P5 P6 P7

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Figure 12: I-V curve of fabricated DSSCs

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On the other hand, it is known that pastes with TTIP as the binder that is sintered at low
temperatures are less efficient. It is clear that in these pastes, the greatest focus has been on
re
the accumulation of nanoparticles to maintain the structure of the paste in flexible substrates,
and this has led to the lack of porosity and space required to absorb pigment which in turn
lP

has reduced the cell performance. “Based on the results, short-circuit current density is
directly related to porosity, particle size, and specific surface area. The higher the specific
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surface area, make more space to load the pigments. The increase in porosity is associated
with decreasing the electron path and as a result, the short-circuit current enhances. On the
ur

other hand, the particle size of the paste can also influence the ability of light scattering or
reflection, the light-harvesting process, and the performance of the fabricated DSSC. The
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smaller TiO2 paste particles have a higher specific surface area for pigment loading and less
light reflection. It is observed that the P1 sample, despite having the highest specific surface
and the smallest particle size as well as less light reflection, is in the fourth position of the
most short-circuit current density. Besides, for the P3 sample with the highest porosity, the
highest short-circuit current has been achieved. Having a high specific surface area and high
porosity in P6 and P4 samples has caused these two TiO2 pastes to be in second and third
places in the most short-circuit current density. Despite having good porosity, the P5 sample
was in the fifth position in the most short-circuit current density due to its inability to create
a suitable specific surface area. These results show that only one geometrical parameter is
not sufficient to obtain the highest amount of short-circuit current density, while particle size,
specific surface area, and porosity should be simultaneously considered for achieving the
best current density. Moreover, particle size and the specific surface area directly influence
the open-circuit voltage. According to the results, the P1 and P6 samples, which have the
highest specific surface area and the smallest particle size, have the highest open-circuit
voltage. However, it is observed that the modification of the paste by acid, which was done

18
on P3 and P4 samples, caused a relative decrease in their voltage and therefore, the P5 sample
voltage enhanced with respect to these two samples.”
The power diagrams of the fabricated DSSCs are shown in Figure 13. Based on the results,
the fabricated DSSCs using the P1, P3, and P6 pastes had the highest power density compared
to the other cells. These efficiency enhancements may be attributed to the increasing hollow
structure of the pastes P1, P3, and P6, using SEM images data and BET results.

250

200
Power density (µw/cm2)

150

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100

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50 re
0
0 50 100 150 200
lP

Number of measured points

P1 P2 P3 P4 P5 P6 P7
Figure 13: Power diagram versus measured point
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A summary of the measured and calculated photovoltaic properties of the fabricated DSSCs
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is shown in Table 4.
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Table 4: Photovoltaic parameters of fabricated DSSCs

DSSC number Paste name ISC )mA/cm2( VOC (V) FF 𝜂 (%)
1 P1 0.504 0.464 0.575 0.134
2 P2 0.204 0.360 0.434 0.031
3 P3 1.105 0.409 0.429 0.194
4 P4 0.637 0.436 0.461 0.128
5 P5 0.433 0.439 0.582 0.111
6 P6 0.932 0.464 0.602 0.256
7 P7 0.138 0.408 0.559 0.027

The results showed that the fabricated DSSCs using the P3 and the P6 pastes had the highest
short-sircuit current density (Isc) and the highest open-sircuit voltage (Voc), respectively.
Also, based on the results, the cell efficiency (𝜂) corresponding to the P1 paste was more than
that of P4, which could be attributed to the higher fill factor (FF) of this cell. Moreover, based
on the XRD results, the lowest values of the cell efficiency of P2 and P7 samples could be
attributed to the incomplete formation of crystals in these two pastes.

19
By combining the SEM, BET, and I-V data, the effects of semiconductor size and surface
area of the produced pastes on the efficiency of the fabricated DSSCs were investigated. The
results are shown in Figure 14. The results showed that the cell efficiency increased by
decreasing the TiO2 size from 38.6 nm to 25.6 nm. With further decreasing the particle size
from 25.6 nm to 21.8 nm, the cell efficiency also decreased drastically. The increasing trend
of the cell efficiency can be attributed to the increased surface area of the pastes in the
photoanode by decreasing the particle size of the pastes, which provided a more active
surface for binding with the pigments and harvesting light [65]. However, the results
demonstrated that the higher specific surface area is not the only factor affecting the
efficiency of the solar cell. Another factor that can be mentioned is the size of the paste
particle which affects the electronic properties of the nanoparticles, and this factor will
change the efficiency of the cell. Moreover, decreasing the cell efficiency by decreasing the

of
size of nanoparticles from the optimum value, around 25 nm, to lower values can be attributed
to the light-scattering properties of the paste particles, the decrease in the conduction band

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density of states in the smaller particles, unfavorable anchoring of the dye on the surface of

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the pastes, longer diffusion length, and a smaller recombination lifetime [51, 52].
re
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Figure 14: The average particle size versus the efficiency of the fabricated cells

4. Conclusions
The UV-vis experiment revealed the existence of anthocyanin pigments in the solution after
the solvent extraction process of the black plums. Using the DLS technique, the pigment size
was measured around 0.3 nm which was suitable for diffusing and adsorbing in the porous
structure of the TiO2 pastes. Besides, the CV measurement showed the HOMO and the
LUMO energy levels, as well as the band-gap of the extracted pigments, were proper for the
electron transfer from the pigments to the TiO2 pastes. Moreover, the LUMO energy level of
the extracted pigments was close to the LUMO energy level of some common synthetic

20
pigments, such as N719 and N749, which showed the capability of using natural pigment
instead of synthetic one in the DSSCs. The pastes were synthesized with seven different
methods and used in the photoanode of the fabricated DSSCs. The crystallography of the
pastes, using X-ray and EDX experiments, illustrated the existence of TiO2 in the anatase
phase in all samples. The SEM images showed the different morphology of the pastes while
most particles in the pastes were spherical with the diameter of 21.88 nm to 38.59 nm. The
characterization tests of the produced pastes were completed by measuring the specific
surface area and the porosity of the pastes using the BET experiments. The BET data
confirmed the SEM results and revealed that the specific surface area of the pastes increased
by decreasing the particle size of the pastes. The sun simulator results showed that the
fabricated DSSC using the paste P6 had the highest efficiency concerning the other cells.
Thus, the sixth method of paste preparation was more effective than the other methods.

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Besides, the results showed that the optimum particle size of TiO2 semiconductor to obtain
the higher cell efficiency was around 25.6 nm.

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Nomenclatures
𝐴𝑏𝑠𝜆𝑚𝑎𝑥 Maximum absorbance of black plum
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AM Air mass
DSSC Dye-sensitized solar cell
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1% Molar absorptivity
𝐸1𝑐𝑚
%Ex Extracted percent of anthocyanin
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FD Dilution factor
FF Fill factor
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FTO Fluorine-doped tin oxide

FWHM Full width at half maximum
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HOMO The highest occupied molecular orbital (eV)

I current (mA/cm2)
K Shape factor (0.9)
L Crystallite size (nm)
LUMO The lowest unoccupied molecular orbital (eV)
P Electrical power (mW)
PVP Polyvinyl pyrrolidone
TTIP Titanium isopropoxide
V Open circuit voltage (V)
Greek symbols
𝛽 Peak broadening
ε Strain induced in the sample
𝜂 Photoelectric conversion efficiency (%)
θ Diffracted angle (°)
λ Wavelength (nm)

21
 Subscripts
max Maximum
S Strain
SC Short-circuit
OC Open-circuit

Data availability
The raw/processed data required to reproduce these findings cannot be shared at this time as
the data also forms part of an ongoing study.

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Appendix A
The broad profile in the X-ray diffraction spectra is due to the instrumental and physical
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factors, such as crystallite size and lattice strains. The crystallite size of the nanoparticles in
the produced pastes can be obtained from Debye-Sherrer's formula [66, 67]:
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𝐾𝜆 (A-1)
𝐿=
𝛽𝐷 𝑐𝑜𝑠𝜃
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where θ, λ, βD, L, and K are diffracted angle, the X-ray wavelength, Full width at half
maximum (FWHM) of the diffracted peak, the crystallite size, and the shape factor. Using
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the Scherrer formula, the calculated crystalline size of the samples P1, P2, P3, P4, P5, P6 and,
P7 are shown in Table A-1 to Table A-7, respectively. Based on the results, the crystallite size
varied from 12.22 nm to 22.05 nm, from 10.66 nm to 27.57 nm, from 13.57 nm to 35.49 nm,
from 13.50 nm to 35.35 nm, from 12.33 nm to 22.74 nm, from 12.23 nm to 29.47 nm, from
12.74 nm 22.77 nm for the samples P1 to P7, respectively. Besides, 25.06o, 26.25o, 25.22°,
24.89° and, 25.17°together with 20.65 nm,20.72 nm, 20.68 nm, 16.53 nm and, 20.68 nm
crystallite size were the main peaks and for the samples P1, P3, P4, P5, and P6, respectively.
On the other hand, 48.06° and 48.14° together with 17.67 nm and 17.68 nm crystallite size
were the main peaks and for the samples P2 and P7, respectively.

Table A-1: Experimental XRD data for sample P1 (anatase phase)

Peak position 2θ (o) FWHM Crystalline size (nm)
25.06 0.394 20.65
37.55 0.492 17.05
47.83 0.394 22.05
53.78 0.689 12.92

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 54.88 0.443 20.20
62.49 0.689 13.48
68.63 0.787 12.22
70.08 0.689 14.08
74.95 0.492 20.34

Table A-2: Experimental XRD data for sample P2 (anatase phase)

Peak position 2θ (o) FWHM Crystalline size (nm)
25.25 0.2952 27.57
37.79 0.7872 10.66
48.06 0.492 17.67
53.74 0.5904 15.08
55.02 0.3936 22.75

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62.76 0.5904 15.76

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70.34 0.5904 16.46

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Table A-3: Experimental XRD data for sample P3 (anatase phase)
Peak position 2θ (o) FWHM Crystalline size )nm)
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26.25 0.3936 20.72
38.83 0.3936 21.40
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49.02 0.246 35.49

54.9 0.5904 15.16
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56.03 0.3936 22.86

63.58 0.6888 13.56
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Table A-4: Experimental XRD data for sample P4 (anatase phase)

Peak position 2θ (o)
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FWHM Crystalline size (nm)

25.22 0.3936 20.68
37.74 0.492 17.06
48.01 0.246 35.35
53.82 0.5904 15.09
55.06 0.3936 22.76
62.73 0.6888 13.50
75.16 0.5904 16.97

Table A-5: Experimental XRD data for sample P5 (anatase phase)

Peak position 2θ (o) FWHM Crystalline size (nm)
24.89 0.492 16.53
37.45 0.5904 14.20
47.85 0.492 17.66
53.80 0.5904 15.08
54.94 0.3936 22.74
62.59 0.5904 15.74

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 68.61 0.5904 16.29

70.21 0.7872 12.33

75.03 0.6888 14.54

Table A-6: Experimental XRD data for sample P6 (anatase phase)

Peak position 2θ (o) FWHM Crystalline size (nm)
25.17 0.3936 20.68
37.74 0.492 17.06
48.13 0.2952 29.47
53.85 0.6888 12.93
55.12 0.492 18.21
62.87 0.5904 15.77

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68.79 0.7872 12.23

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70.34 0.492 19.75
75.01 0.5904 16.96

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Table A-7: Experimental XRD data for sample P7 (anatase phase)
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Peak position 2θ (o) FWHM Crystalline size (nm)
25.28 0.3936 20.68
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37.95 0.5904 14.22

48.14 0.492 17.68
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55.23 0.3936 22.77

62.90 0.492 18.92
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70.46 0.5904 16.47

75.23 0.7872 12.74
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Based on the Williamson-Hall formula, 𝛽𝑐𝑜𝑠𝜃 is linear concerning to 4𝑠𝑖𝑛𝜃 [66, 68-70]:
𝐾𝜆
𝛽𝑐𝑜𝑠𝜃 = + 4𝜀𝑠𝑖𝑛𝜃 (A-2)
𝐿
where ε is the strain induced in the sample due to the crystal imperfection and distortion.
𝛽𝑠
𝜀= (A-3)
4𝑡𝑎𝑛𝜃
Besides, 𝛽 is the sum of size broadening, 𝛽𝐿 , and microstrain broadening, 𝛽𝑆 :
𝛽 = 𝛽𝐿 + 𝛽𝑠 (A-4)
Based on the Williamson-Hall approach, the micro-strain and the crystallite size of the
samples P1 to P7 were calculated and the results are shown in Table A-8 to Table A-14,
respectively. The results show that the micro-strain was in the order of 10-4 for all samples
except P2.

Table A-8: The calculated strain and crystallite size based on the Williamson-Hall approach for sample P1
Peak position 2θ (o) FWHM ε Crystallite size (nm)

30
 25.06 0.394 0.0005 20.65
37.55 0.492 0.0005 17.05
47.83 0.394 0.0005 22.05
53.78 0.689 0.0005 12.92
54.88 0.443 0.0005 20.20
62.49 0.689 0.0005 13.48
68.63 0.787 0.0005 12.22
70.08 0.689 0.0005 14.08
74.95 0.492 0.0005 20.34

Table A-9: The calculated strain and crystallite size based on the Williamson-Hall approach for sample P2
Peak position 2θ (o) FWHM ε Crystallite size (nm)
25.25 0.2952 0.000001 27.58

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37.79 0.7872 0.000001 10.66

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48.06 0.492 0.000001 17.68
53.74 0.5904 0.000001 15.08

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55.02 0.3936 0.000001 22.76
62.76 0.5904 0.000001 15.76
re
70.34 0.5904 0.000001 16.46
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Table A-10: The calculated strain and crystallite size based on the Williamson-Hall approach for sample P3
Peak position 2θ (o) FWHM ε Crystalline size (nm)
na

26.25 0.3936 0.0006 20.72

38.83 0.3936 0.0006 21.40
ur

49.02 0.246 0.0006 35.49

54.90 0.5904 0.0006 15.16
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56.03 0.3936 0.0006 22.86

63.58 0.6888 0.0006 13.56

Table A-11: The calculated strain and crystallite size based on the Williamson-Hall approach for sample P4
Peak position 2θ (o) FWHM ε Crystallite size (nm)
25.22 0.3936 0.0003 21.52
37.74 0.492 0.0003 17.92
48.01 0.246 0.0003 40.37
53.82 0.5904 0.0003 16.03
55.06 0.3936 0.0003 25.04
62.73 0.6888 0.0003 14.38
75.16 0.5904 0.0003 18.65

Table A-12: The calculated strain and crystallite size based on the Williamson-Hall approach for sample P5
Peak position 2θ (o) FWHM ε Crystallite size (nm)
24.89 0.492 0.0002 16.88

31
 37.45 0.5904 0.0002 14.59
47.85 0.492 0.0002 18.42
53.80 0.5904 0.0002 15.70
54.94 0.3936 0.0002 24.21
62.59 0.5904 0.0002 16.52
68.61 0.5904 0.0002 17.20
70.21 0.7872 0.0002 12.86
75.03 0.6888 0.0002 15.32

Table A-13: The calculated strain and crystallite size based on the Williamson-Hall approach for sample P6
Peak position 2θ (o) FWHM ε Crystallite size (nm)
25.17 0.3936 0.0002 21.23
37.74 0.492 0.0002 17.62

of
48.13 0.2952 0.0002 31.67

ro
53.85 0.6888 0.0002 13.39
55.12 0.492 0.0002 19.14

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62.87 0.5904 0.0002 16.55
68.79 0.7872 0.0002 12.73
re
70.34 0.492 0.0002 21.14
75.01 0.5904 0.0002 18.03
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Table A-14: The calculated strain and crystallite size based on the Williamson-Hall approach for sample P7
na

Peak position 2θ (o) FWHM ε Crystallite size (nm)

25.28 0.3936 0.0003 21.52
ur

37.95 0.5904 0.0003 14.82

48.14 0.492 0.0003 18.86
Jo

55.23 0.3936 0.0003 25.06

62.90 0.492 0.0003 20.69
70.46 0.5904 0.0003 17.94
75.23 0.7872 0.0003 13.66

32
Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

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