Eddie Nahúm Armendáriz-Mireles1

Photocurrent generation by dye-sensitized Enrique Rocha-Rangel2

solar cells using natural pigments Frida Caballero-Rico1
José Alberto Ramı́rez-de-León1
∗
Manuel Vázquez3

1 Knowledge Management Center, Autonomous University of Tamaulipas,

Victoria, Tamaulipas, México
2 Department of Manufacturing of Advanced Materials, Polytechnic
University of Victoria, Victoria, Tamaulipas, México
3 Department of Analytical Chemistry, Faculty of Veterinary Science,
University of Santiago de Compostela, Lugo, Spain

Abstract
The development of photovoltaic panels has improved the
conversion of solar radiation into electrical energy. This paper
deals with the electrical and thermal characteristics (voltage,
current, and temperature) of photovoltaic solar cells sensitized
with natural pigments (dye-sensitized solar cell, DSSC) based
on a titanium dioxide semiconductor. Several natural pigments
(blackberry, beets, eggplant skin, spinach, flame tree flower,
their sensitizing effect on titanium dioxide. The results showed
the great potential of natural pigments for use in solar cells.
The best results were obtained with the blackberry pigment,
reaching a value of 7.1 mA current, open-circuit voltage (Voc )
of 0.72 V in 2 cm2 , and fill factor (ff) of 0.51 in the DSSC. This
performance is well above than that currently offers by actual
cells. 
C 2015 International Union of Biochemistry and Molecular Biology,

papaya leaf, and grass extracts) were evaluated to determine Inc. Volume 00, Number 0, Pages 1–6, 2015

Keywords: sensitized, solar cell, electrical characterization, DSSC, natural

pigment, TiO2 semiconductor

1. Introduction the first solar cell, using selenium as a dielectric material.

Energy efficiency was only 1%. The continuous development
In the past few decades, clean technologies have been de-
of photovoltaic panels has improved the conversion of solar
veloped for producing energy, replacing gradually traditional
radiation into electrical energy [5]. Nowadays, this technology
methods of generating energy from nonrenewable resources
has greater importance than others for energy generation.
(oil, natural gas, and coal) by other renewable resources (wind,
Additionally, monitoring is essential for optimal performance.
hydro, and solar) [1]. Nowadays, the use of renewable and
The principle of operation of a solar cell is based on a light-
sustainable natural resources has become a global energy pri-
sensitive material absorbing solar energy and converting it
ority. Solar energy is considered as a source of endless energy.
into electrochemical energy [6]. Solar cells have been classified
Therefore, the use of this radiation has led to the development
by their evolution, according to their temporal development,
of new devices for such purposes [2].
technology, and energy efficiency:
The photovoltaic effect was first discovered by Becquerel
in 1839, when he observed an increase in current in one of
the electrodes of an electrolytic cell connected to two platinum
plates exposed to sunlight [3, 4]. In 1883, Charles Fritts built r First-generation cells: These are based on monocrystalline
silicon wafers, with limited theoretical efficiency and high
cost.
Abbreviations: DSSC, dye-sensitized solar cell; EU, European Union; ff, fill r Second-generation cells: These are thin-film panels, poly-
factor; TiO2 , titanium dioxide..
∗ Address
crystalline and amorphous silicon, with limited theoretical
for correspondence: M. Vázquez (PhD), Department of Analytical
efficiency and low cost.
Chemistry, Faculty of Veterinary Science, University of Santiago de r Third-generation cells: These are sensitized and organic
Compostela, Lugo 27002, Spain. Phone: +34 982822420;
Fax: +34 982822420; e-mail: manuel.vazquez@usc.es. panels. This technology is in a testing stage. Several strate-
Received 2 September 2015; accepted 8 October 2015 gies have being applied to achieve substantial efficiency
DOI: 10.1002/bab.1449 gains [7]. One such strategy is manufacturing multifunc-
Published online in Wiley Online Library tional cells, thermoelectric cells, dye-sensitized solar cells
(wileyonlinelibrary.com) (DSSCs), or cells built with organic materials [8, 9].

1

Sensitized by natural coloring cells are third-generation
solar cells. They are known as DSSC or Grätzel type, in honor
of their inventor. These cells have great economic potential due
to the low price of raw materials and labor input required to
manufacture, compared to silicon-based solar cells [10].
The processes of light absorption and electron transfer
in DSSC cells are performed separately, which means lower
manufacturing costs [11]. Their development has been of great
interest because their operation imitates natural photosynthe-
sis. In 2012, a study of the properties of spinach to generate
electricity combining a photosynthetic plant protein with a sili-
con semiconductor was published. This type of cell was called
biohybrid [12]. In a natural dye-sensitized cell, the pigment is
responsible for capturing sunlight. This pigment in combina-
tion with a nanocrystalline titanium dioxide semiconductor and
an electrolyte is the main part of this double solar energy
capture.
In natural sensitizers, purely organic dyes with good
photovoltaic performance are clean and low-cost sources for
DSSC, although their efficiency is much lower than industrial
requirements [13]. Most leaves of green plants are rich in
chlorophyll and the application of such natural colorant has
been investigated frequently in many related studies [14].
The working ranges of DSSC are as follows:
(1) Titanium dioxide: Absorbs less than or equal to 400 nm in
the spectrum.
(2) Silicon: Absorbs from 300 to 1100 nm in the spectrum.
(3) Gallium nitride: Absorb wavelengths that are less than
silicon.
Solar panels made from the materials described above
depend on manufacturing processes that employ not clean
energy. Silicon and gallium arsenide have to be extracted
from the earth’s crust and then they are transformed through
different processes to place them on the panel, not to mention
the polluting waste from companies that manufacture the
panels.
In 2010, it was estimated that the European Union
(EU) would generate more than 7,000 tons of solar waste.
It is estimated that in 2020–2025 there will be a signif-
icant increase in waste, since the first large-scale pho-
tovoltaic plants date from the 1990s (http://www.belt.es/
noticiasmdb/home2 noticias.asp?id = 9817). It is expected
that an estimated 130,000 tons of this type of waste will be
produced by 2030 [2]. Therefore, even in this technology-clean
operation, it is required to minimize the environmental impact
and if during the process there are better returns, the task will
have been accomplished. The aim would be to have a clean
technology from manufacturers for disposal of wastes.
The process of converting sunlight into electricity takes
place in DSSC based on the sensitizing of a semiconductor.
Therefore, numerous inorganic, organic, and hybrid dyes have
been used as sensitizers in DSSC. Among synthetic inorganic
dyes, a ruthenium compound was effectively used as molecular
2 Photocurrent Generation by DSSCs Using Natural Pigments
Biotechnology and
Applied Biochemistry
sensitizer in DSSC with high efficiency of up to 11–12%.
However, the ruthenium compounds are expensive, even less
abundant, and carcinogenic. Therefore, natural dyes are of
great interest for use as sensitizers in DSSC [3, 15].
The objective of this study was to characterize electrical
and thermal DSSC by several natural dyes based on titanium
dioxide (TiO2 ) as a semiconductor using a data acquisition
system designed to monitor the variables voltage, current,
and temperature to assess the efficiency of the cells and to
determine the most efficient dye.
2. Materials and Methods
Solar cells were manufactured, characterized, and monitored
based on a process called “artificial photosynthesis” using
solar cells produced with simple materials: paste TiO2 , dyes
chlorophyll and anthocyanin (natural pigments), electrolyte
(iodine [I2 ] and potassium iodide, KI), and conductive glass [16].
We focused on this type of solar cell to understand the behavior
of chlorophyll and anthocyanin, which are present in plants
and fruit, respectively, and their relationship to the transfer
of electrons. One of the main reasons for this relationship is
the anchor property of pigment (chlorophyll and anthocyanin)
with the semiconductor. The characterization of the DSSC and
a common silicon cell was presented through electrical and
thermal readings of variables, such as the open-circuit voltage
(VOC ), short circuit current (ISC ), and the cell temperature (TCEL ).
The LabVIEW platform (National Instruments Corporation,
Austin, TX, USA) was used to characterize both environmental
conditions through which monitoring and data acquisition
were performed to analyze the efficient use of the solar cells for
power generation. The characterization of the solar panels was
conducted by developing an integrated circuit whose purpose
was the conversion of parameters such as voltage, current,
and temperature, which are suitable to be read. The electrical
signals were processed using the computer with LabVIEW
software in which data were stored and statistical analysis was
carried out.
Two pieces of glass working functioning as electrodes were
used for the construction of the DSSC; on the surface of the
glass, a thin film of graphite was deposited to make them
conductive. The redox couple KI/I dissolved in ethylene glycol
was used as an electron conducting means. Natural pigments
were used as solar energy absorbers and eventually nanosized
TiO2 particles were used as a medium where the coloring
(chlorophyll and anthocyanin) is anchored.
During the first study, photosynthetic pigments based
on anthocyanin present in blackberries, beets, beetroot, and
eggplant skin were tested. The extraction of natural pigments
from the materials used was as follows. An aliquot of 10 g of
the selected substance was weighed on an analytical balance,
and then each sample was ground in a porcelain mortar and a
mallet of the same material. Each crushed sample was mixed
with 50 mL of distilled water at room temperature in a dark
room. Solid wastes from the solution were filtered through a
 (A) Electric diagram obtained using LabVIEW, from
FIG. 1 the National Instruments Corporation, software
that is used for lectures and the acquisition of
experimental data. (B) Graphic interface obtained
using the LabVIEW software that is used for
lectures and the acquisition of experimental data.
filter paper to acquire a pure natural pigment solution. Then,
extracts of blackberry, beets, eggplant skin, and beetroot were
mixed with ethylene glycol in a volume ratio of 1:1 to serve as
a blend of natural pigments [17].
For the extraction of chlorophyll from green plants such
as spinach, flame tree flower, papaya leaf, and grass, 10 g of
each plant was separately mixed with 200 mL of distilled water.
They were heated for 20 Min to extract chlorophyll through
hydraulic indirect heating in boiling water. Solid waste in the
solution was filtered through a filter paper to obtain a solution
of pure natural pigments. Then, the extracted fluids were
mixed in the ratio of 1:1 to serve as a natural pigment [15].
The following materials, tools, and equipment were used to
characterize and monitor the manufacturing of the solar cells:
conductive glasses Rs < 10  (Delta Technologies Limited,
Loveland, CO, USA), electrolyte iodine KI in ethylene glycol,
Degussa P25 titanium dioxide, graphite powder (Solaronix SA,
Aubonne, Switzerland), a variable resistor (potentiometer) of
500  (Fluke Inc, Everett, WA, USA), a digital multimeter card
(NI cDAQ-9184, NI-9211, NI-9215) for the platform LabVIEW,
computer, and temperature gauge NI USB-TC01 thermocouple
type ”J” (National Instruments Corporation, Austin, TX, USA).
The artificial light source was a halogen lamp, 100 W heat
source (heat gun), nitric acid (10 mL with deionized water, pH
3–4) (Quimica Noreste, Monterrey, Mexico), security materials
(latex gloves and glasses), and other accessories (clamps,
containers, and spoons). Blackberry, beets, eggplant skin,
beetroots, spinach leaves, flame tree flower, papaya leaf, and
grass extracts were used as natural pigments.
3. Results and Discussion
The DSSC was tested under the following real conditions: (1)
the shade; (2) sunlight. An initial experiment was conducted
to determine the influence of sunlight in the process of light
Biotechnology and Applied Biochemistry
absorption and electron transfer in the cells. In addition, it
was used to show how photosynthesis is mimicked. In another
experiment, DSSC was tested using artificial light produced
by a halogen lamp. The cells were tested under controlled
conditions to determine the standard curve as shown in the
literature [17].
Parameters such as voltage, temperature, and irradiation
were recorded remotely as signals to be read from data
acquisition card (NI cDAQ-9184, NI-9211, NI-9215; National
Instruments Corporation) and therefore using a computer
with the LabVIEW software (Fig. 1A). A graphic interface was
created to control and store data, as shown in Fig. 1B.
The results of experimental parameters were analyzed
using the current flow behavior and the amount of voltage
with respect to temperature of the DSSC cell. The maximum
values of current and voltage generated by the photovoltaic
panel standard were recorded between 13:00 and 14:00, the
time when the sun is highest in the sky and perpendicular
to the photovoltaic panels. At this point, the cell reached a
temperature of 47 ◦ C. This may relate to the voltage generated
immediately with the presence of the sun regardless of its
position relative to the photovoltaic panels and the transmitted
radiation. Meanwhile, power is highly dependent on the relative
position of the sun to the photovoltaic panels and the radiation
transmitted by the generated voltage decreases. The behavior
was similar to that found in the literature [18].
In Fig. 2, it can be seen that the voltage is higher with
blackberry than with the other pigments. This can be due to
the high anthocyanin levels. Figure 3 shows the measurements
of voltage and current (V × I) for the DSSC. Current is plotted
in short circuit, Isc , and open-circuit voltage, Voc . The DSSC of
blackberry illuminated with artificial light based on halogen
light reproduces conditions similar to sunlight radiation. The
curve shown in Figure 3 compares very well with that reported
in the literature [19].
3
 Biotechnology and
Applied Biochemistry

Photovoltaic performance parameters in solar cells

TABLE 1 sensitized with natural pigment obtained in this work

Open-circuit Photo current

photo voltage density Fill factor
Dye (Voc , V) (Jsc , mA cm2 ) (ff)

Blackberry 0.72 7.10 0.51

Spinach 0.53 0.41 0.53

Flame tree flower 0.50 0.55 0.53

Pawpaw leaf 0.44 0.60 0.53

Voltage, temperature, and irradiation under solar Skin of eggplant 0.38 1.60 0.40
FIG. 2 light generated by DSSC manufactured with
natural pigments.
Beet 0.32 0.67 0.52

Beetroot 0.29 0.32 0.40

Grass 0.20 0.30 0.40

The efficiencies ranging from 0.6% to 2.6% using a mixture

The curve of V–I of the DSSC manufactured with
FIG. 3
blackberry pigment under artificial light.
To make a comparative analysis of the anthocyanin present
in some plants and fruits, DSSC with natural pigments such as
blackberries, beets, eggplant skin, and beet was characterized
by making voltage measurements (Fig. 2). The tendency of
the pigments is to decrease their efficiency as temperature
increases by the heat produced by the 100-W halogen bulb.
However, there are chemical factors that determine the antho-
cyanin stability during processing and storage when subjected
to temperatures above 75 ◦ C, as reported in the literature [20].
Table 1 shows the results of our work using different
natural pigments to understand the behavior of chlorophyll
and anthocyanin in plants and fruits and their relationship
to the transfer of electrons. One of the main reasons for this
relationship is the anchor property of anthocyanin with the
semiconductor.
The results in Table 2 show the parameters obtained in
studies by other researchers, which address various natural
sensitizers (rose bengal, eosin Y, skin of jabotica, fluorescein
sodium, blueberry, black rice, spinach, ipomoea, flame tree
flower, pawpaw leaf, mulberry, skin of eggplant, sicilian or-
ange). These studies showed values of 0.72 V for rose bengal
and 0.59 V for the blackberries sample.
of xanthophyll and chlorophyll were due to energy transfer
of pigment mixed with cosensitized TiO2 [13]. The use of
chlorophyll pigments from granada leaf, mulberry extracts,
and mixture of chlorophyll and anthocyanin ranged from
0.55% to 0.72% [21]. Anthocyanin extracts of jabotica showed
a successful conversion of visible light into electricity [22]. In
a natural pigment extracted from black rice, the VOC ranged
from 0.551 to 0.412 V. The extract of black rice showed a
photosensitized effect, which is due to the interaction between
the carbonyl and hydroxyl of the molecule of anthocyanin and
the surface of TiO2 [14]. Red sicilian orange juice and extract
of purple eggplant shells as natural DSSC sensitizers yielded
0.66% and VOC = 0.325 V [23]. The efficiency and stability of
the devices based on natural sensitizers such as blackberry and
blueberry and skin jabotica were investigated by Kimpa et al.
[24]. The performance using blackberry was 0.52%, and it was
0.61% using blueberry.
Natural pigments from the flame tree flower, papaya leaf,
and mixtures were used as sensitizers for DSSCs [25]. The
photoelectrochemical performance of the color extract of the
flame tree flower showed an open-circuit voltage (VOC ) of
0.50 V, a fill factor (ff) of 0.588, and a conversion efficiency of
0.20%. The conversion efficiency of the DSSC prepared with
papaya leaf extract was 0.20%, with 0.50 V VOC and 0.605 ff.
The conversion efficiency of the pigment mixture of the flame
tree flower and papaya leaf was 0.27%, with 0.518 V VOC and
0.69 ff.
It was observed in the conversion efficiencies that both
the short-circuit current density and fill factor of the cells are
improved using the mixed pigments. DSSC manufactured using
rose bengal pigments for sensitization of TiO2 nanocrystals
yielded a VOC = 0.89 V and ff = 0.53 [26,27].

4 Photocurrent Generation by DSSCs Using Natural Pigments

 Photovoltaic performance parameters in solar cells sensitized with natural pigment reported in the literature
TABLE 2

Open-circuit photo Photo current Fill factor

Dye voltage (Voc , V) density (Jsc , mA cm2 ) (ff) Reference

Rose bengal 0.72 8.73 0.44 [25]

Eosin Y 0.69 6.10 0.42 [12]

Skin of jabotica 0.66 2.60 0.62 [21]

Fluorescein sodium 0.65 3.65 0.38 [12]

Blueberry 0.59 1.00 0.61 [23]

Black rice 0.55 1.14 0.52 [13]

Spinach 0.55 0.46 0.51 [20]

Ipomoea 0.54 0.91 0.56 [20]

Flame tree flower 0.50 0.67 0.58 [24]

Pawpaw leaf 0.50 0.64 0.60 [24]

Mulberry 0.49 6.10 0.52 [23]

Skin of eggplant 0.35 3.40 0.40 [22]

Sicilian orange 0.34 3.84 0.50 [22]

In our work, the manufacture of DSSC based on blackberry 4. Conclusions

juice improved the conversion of solar radiation into electricity
The prototype developed demonstrates that it is possible
through a conductor of titanium dioxide. It yielded voltage up to
to obtain the output voltage levels of the DSSCs through
0.72 V and an efficiency of 0.51%. This situation is attributed to
a variation in its construction using blackberry pigments,
the high concentrations of anthocyanin combined with graphite
since the output voltage levels at 0.72 V in 2 cm2 is well
in a liquid form, which acts as the conveyor of electrons that are
above currently offered by the DSSCs in the presence of a
generated by the process of photosynthesis, producing output
semiconductor. In these experiments, natural conversion of
that is well above currently offered by DSSC as mentioned
light is used to show improvement in efficiency with the
above.
combination of the anthocyanin present in blackberry. These
During the first phase of experimentation, it was directly
results show the potential of research to get better results
confirmed that it is possible to measure the voltage using
without the need of semiconductors. It is also important
natural pigments with these equipments such as the voltmeter
to advance in DSSC prototypes without semiconductors for
or virtual laboratory. During this stage, natural pigments of
the development of a cell that can compete with the silicon
green plants from spinach, flame tree flower, papaya leaf,
cell.
and grass were selected as sensitizers for the preparation
of DSSC. These green plants have the natural mechanism of
converting solar energy into electrons (chlorophyll). Berries,
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6 Photocurrent Generation by DSSCs Using Natural Pigments