Dye-Sensitized Solar Cells (DSSCs)

reengineering using TiO2 with natural dye

(anthocyanin)
Cite as: AIP Conference Proceedings 1788, 030104 (2017); https://doi.org/10.1063/1.4968357
Published Online: 03 January 2017

Rohmat Subodro, Budi Kristiawan, Ari Handono Ramelan, Sayekti Wahyuningsih, Hanik Munawaroh,
Qonita Awliya Hanif, and Liya Nikmatul Maula Zulfa Saputri

ARTICLES YOU MAY BE INTERESTED IN

Fabrication and characterization dye sensitized solar cell (DSSC) based on TiO2/SnO2
composite
AIP Conference Proceedings 1788, 030062 (2017); https://doi.org/10.1063/1.4968315

Influence of electrolyte proportion on the performance of dye-sensitized solar cells

AIP Advances 7, 105219 (2017); https://doi.org/10.1063/1.5000564

Performance enhancement of dye-sensitized solar cells (DSSCs) using a natural sensitizer

AIP Conference Proceedings 1788, 030123 (2017); https://doi.org/10.1063/1.4968376

AIP Conference Proceedings 1788, 030104 (2017); https://doi.org/10.1063/1.4968357 1788, 030104

© 2016 Author(s).
 Dye-Sensitized Solar Cells (DSSCs) Reengineering Using
TiO2 with Natural Dye (Anthocyanin)
Rohmat Subodro1, 4, b), Budi Kristiawan1, Ari Handono Ramelan2, a),
Sayekti Wahyuningsih3, Hanik Munawaroh3, Qonita Awliya Hanif3 and Liya
Nikmatul Maula Zulfa Saputri3

1
Department of Mechanical Engineering, Sebelas Maret University, Surakarta, Indonesia
2
Department of Physics, Sebelas Maret University, Surakarta, Indonesia
3
Department of Chemistry, Sebelas Maret University, Surakarta, Indonesia
4
Department of Mechanical Engineering, Nahdlatul Ulama University, Surakarta, Indonesia
a)
Corresponding author: aramelan@mipa.uns.ac.id
b)
rohmadsubodro@yahoo.com

Abstract. This research on Dye-Sensitized Solar Cells (DSSCs) reengineering was carried out using TiO2 with natural
dye (anthocyanin). The fabrication of active carbon layer/TiO2 DSSC solar cell was based on natural dye containing
anthocyanins such as mangosteen peel, red rose flower, black glutinous rice, and purple eggplant peel. DSSC was
prepared with TiO2 thin layer doped with active carbon; Natural dye was analyzed using UV-Vis and TiO2 was
analyzed using X-ray diffractometer (XRD), meanwhile scanning electron microscope (SEM) was used to obtain the
size of the crystal. Keithley instrument test was carried out to find out I-V characteristics indicating that the highest
efficiency occurred in DSSCs solar cell with 24-hour soaking with mangosteen peel 0.00047%.

INTRODUCTION
The material of solar cell available commercially is currently based on inorganic silicon semi-conductor in
which the process of preparing solar cell produces environment-unfriendly waste [1]. The high demand for
silicon material of solar cell application purpose will increase in the next decade thereby its price will increase
dramatically. For that reason, the organic solar cell has a very promising and cost-efficient alternative for
photovoltaic production [2]. The type of solar cell is known as a dye-sensitized solar cell (DSSC) and has
attracted considerable attention in past several years. DSSC is a unique set converting visible light into
electricity based on sensitization of semiconductor’s band gap [3]. The performance of DSSC is particularly
dependent on the dye used as a sensitizer. The efficiency of solar cell made of the organic cell is only 0.04% for
the four types of solar cells. The limited ability of solar cell made of organic material is its low ability to absorb
red light spectrum. The property of the organic material has high flexibility level because it allows for preparing a
flexible solar cell [4].
Light absorption is carried out by dye molecule, and charge separation is conducted using organic
semiconductor made of nanocrystal with wide band gap. Semiconductor with wide band gap will contain more
electrons flowing from valence to conduction band. They result in photocatalyst room reaction and absorption
with dye so that the spectrum has wider base [5]. DSSC has consisted of three main components called work
electrode, a counter electrode and electrolyte solution [6]. Work electrode is generally made of a transparent
conductive oxide (TCO) substrate glass. This electrode has conductive surface growing out of thin semiconductor
layer. The working principle of DSSC adopted photosynthesis process on green plant converting sunlight into
solar energy [3]. The most important factor determining TiO2 sensitivity to light is morphological characteristics

International Conference on Engineering, Science and Nanotechnology 2016 (ICESNANO 2016)

AIP Conf. Proc. 1788, 030104-1–030104-8; doi: 10.1063/1.4968357
Published by AIP Publishing. 978-0-7354-1452-5/$30.00

030104-1
of variables. These variables include particle size, crystal structure, and crystallinity of TiO2 material in which
these factors affect the performance of DSSC [7].
DSSC is a solar cell that can convert photon energy into electricity energy [8]. It is created by sandwich
structure in which there are four components of DSSC including ITO (indium tin oxide), FTO (fluorine tin oxide),
and TCO (transparent conductive oxide) glass types, There is transparent conductive glass functioning as
substrate, TiO2 as semiconductor material, natural dye as electron donor, and electrolyte as electron transfer [9].
This research efficiency DSSC result with natural dye still low in value about 0.37% [10], 0.027% [11], 0.00463
[12], 0.3029% [13].

INTRODUCTION
The method used in this research was slip casting. The factors affecting the research include varying dye used,
electrolyte produced, FTO used, TiO2 used and counter-electrode used.

TiO2 Powder Synthesis

The procedure of preparing TiO2 powder was conducted using the sol-gel method in which 6 g Pluronic F-127
was mixed with 76 ml ethanol 96% and then heated using hotplate at 5 rpm stirred for 30 minutes (Solution
Ethanol + Pluronic F-127). Pour 3.5 ml TiCl4 and stirred using magnetic stirrer at 5 rpm for 30 minutes; the
product of stirring was a solution (ethanol + pluronic F-127 + TiCl4) that was originally yellow, smoky, and
thickening into clear yellow solution and less thickness. After the smoke was cleared, the solution (ethanol +
Pluronic + TiCl4 ) was covered using aluminum foil (ethanol + pluronic + TiCl4) and then it was put into the
oven. After that step, the aluminum foil was opened, and the solution was poured into pyrex beaker glass, and
then it was put into the oven at 40°C for 6 x 24 hours. After six days, TiO2 gel would be created, and the gel
was calcinated using hearth at 700°C for 4 hours. Four hours later furnace was taken in the form of clear white
TiO2 powder [5].

Preparing TiO2 Pasta

TiO2 would be stored with thick layer technique produced previously in shaped TiO2 pasta. The manufacturing
procedure process was as follows: dissolve 3.5 g TiO2 into 15 ml ethanol 70%, and then stirred it with a stirrer at
500 rpm for 30 minutes, until the solution was homogeneous.

Dye Preparation
The dye was prepared by grinding mangosteen peel, glutinous rice, purple eggplant peel, red rose, and
seed mortar and then adding solution and stirred with a magnetic stirrer; the solid form would be filtered using
sieve and dye was stored in the Bottle.

Electrolyte Preparation
The electrolyte solution was prepared from 0.8 g KI (potassium iodine). 10 ml PEG (polyethylene glycol) was
dissolved, and 0.127 g iodine (I2) was added. Materials 1 and 2 were mixed using glass stirrer until the solution
was homogeneous.

030104-2
 Counter-Electrode Preparation
To obtain carbon source, active carbon was used by dissolving 3.5 g active carbon and adding it into 15
ml ethanol 70% and then stirred it at 500 rpm for 30 minutes, until the solution was homogeneous. The carbon
electrode was mounted onto FTO.

Testing Method
The crystal structure and size of TiO2 powder, determine with a test were conducted using X-ray
diffractometer (XRD) to find out the morphological structure of SEM nano-particle TiO2 by examining Scanning
Electron Microscope (SEM), the absorption of natural dye was analyzed using UV-VIS spectrometer with U-1800
spectrophotometer instrument. Test electrolyte with El-Kahfi-100 IV-meter, Keithley 2602A instrument test
and current-voltage characterization (I-V) were used.

Fabrication of DSSC
The construction of solar cell used was a sandwich system in the following order: a working electrode was
layered with spacer dye or keyword solution protector – electrolyte – counter electrode. The spacer was used
aiming to prevent the lack of DSSC cell [1]. After each of DSSC components has been prepared successfully, a
solar cell was created with the following procedures. FTO glass was cut in 2.5 × 3.8 cm dimension, and it was
measured for its resistance. Finally, the conductive area was created in 1 cm × 1 cm dimension on sandwich
structure, as substrate and superstrate, one of which was TiO2 into which light enters and counter-electrode were
layered with carbon electrode catalyst. To minimize production cost massively, the cells can be deposited
directly between glasses with large surface width as illustrated. Cellophane tape serves as TiO2 pasta thickness
regulator. TiO2 past and carbon electrode were prepared, mixed with a magnetic stirrer for 10 minutes, and
cleaned using an ultrasonic cleaner for 10 minutes so that the solution became homogeneous. TiO2 layer on FTO
and carbon electrode was also layered with FTO couple and then the FTO glass was calcinated in 300 ᵒC
temperature. Next, the FTO glass was marinated in the following solvents (mangosteen peel, black glutinous
rice, purple eggplant peel, red rose flower). The point on I-V curve yielding maximum current and voltage
was called maximum power point (Max). Another important characteristic of the solar cell was filling factor (FF)
as the following equation [2].

(1)

The maximum power of solar cell was stated by

(2)

So, the efficiency of solar cell was stated as the power yielded from cell (PMAX) divided by entering
light power (P LIGHT)
(3)

030104-3
 RESULTS AND DISCUSSION

XRD Characterization

Figure 1 shows the diffractogram pattern from the synthesis of TiO2. The sharp points indicate the forming of a
material with high crystallinity. The points formed in TiO2 are included in the anatase phase which by JCPDS
No 861167. From the diffractogram, it can be seen that dominant point is at 2θ: 25,32; 37,86 and 48,06. The
anatase phase has a higher photoactive ability compared to the rutile [14]. It is caused by the larger surface area
of the anatase compared to the rutile’s so that the per-unit active sides of the anatase is bigger. With the
anatase phase, it is possible that the DSSC efficiency production can be increased.

FIGURE 1. The Diffractogram Pattern of TiO2

SEM Characterization
The morphology study was analyzed with Scanning Electron Microscopy (SEM), and the synthesis of
TiO2 is shown in Figure 2. It can be seen that there were no agglomerations in the produced particles and the
particle distribution is uneven. The morphology of TiO2 was then analyzed with Image J software to determine
the average particle size. From the calculation, the average particle size was 78.34205 nm. The calibration with
ImageJ shows that the threshold and outline gave an uneven particle distribution description.

A B C
FIGURE 2. Morphology and TiO2 material (a) SEM images TiO2, (b) Threshold, (c) Outline only.

030104-4
 UV-VIS Characterization
Dye material used was dye solution made of extracts of mangosteen peel, rose flower, black glutinous rice,
and purple eggplant peel. The dyes were characterized with the UV-Visible Spectrophotometer to find out the
light absorption by the anthocyanin in each dye. The absorbance spectrum was measured in between the
wavelength range of 400 nm and 800 nm. The absorbance spectrum characterization result showed that the
absorption spectrums of the dye solvents ranged fairly wide in between 440 nm and 589 nm with the maximum
wavelength of 525 nm. The climax of the anthocyanin is in the wavelength of 520 nm. This data indicate that
the extracts contain anthocyanin [13]. With the absorption ability in the UV-Vis wavelength range, it can be
concluded that it is possible for the four natural extracts to be used as the natural dyes in maximizing the DSSC
performance.

The Electrolyte Conductivity and Current-Voltage Measurement

The electrolyte conductivity was measured by using El- khahfi-100 IV-Meter. From the measurement, the
conductivity of the electrolyte is at 5.18 x 10-4Ω-1m-1. Meanwhile. Keithley 2602A Instrument Test was used to
characterize current-voltage (I-V). The characterization of current-voltage (I-V) is a method to find out the
performance of Dye- Sensitized Solar Cells, the extent to which DSSC can convert light into I-V
measurement electricity energy conducted in dark condition covered with aluminum foil layer and in bright
condition under halogen lamp irradiation with the intensity of 1000 W/m2.
In the process of fabricating DSSC, the sandwich structure was used in which TiO2 layered work
electrode was soaked into four natural dyes: mangosteen peel, black glutinous rice, red rose flower and purple
eggplant peel with varying times for 12, 24 and 48 hours. After that, the fabricated DSSC was tested for its
electricity property to find out its current, voltage, and efficiency using I-V meter Keithley 2602A.

TABLE1.Soakingfor12 hours
Dye Isc (A) Voc Imax (A) Vmax Pmax(W) η (%)
Mangosteen peel 0.0000463 0.01008 0.00004.6 0.01008 0.000004 0.00047
2 3 2 7
Black glutinous rice 0.0000176 0.02499 0.000017 0.00994 0.0000001 0.000175
Red rose flower 0.0000457 0.02504 0.000045 0.00997 0.0000004 0.00046
Purple eggplant peel 0.0000025 0.01000 0.000002 0.01000 0.0000002 0.00026

Table 1 shows that in the treatment with soaking for 12 hours, the largest efficiency obtained is 0.00047%
with Isc 0.0000463 Ampere, Voc 0.010082 Volt in mangosteen peel, followed with 0.00046% with Isc
0.0000457 Ampere, Voc 0.025046 Volt in red rose flower, 0.000175% with Isc 0.0000457 Ampere, Voc
0.025046 Volt, in black glutinous rice, and the lowest one 0.00026% with Isc 0.00000255 Ampere, Voc
0.010009 Volt in purple eggplant. The result shows that in 12 hour soaking, the solar cell with eggplant skin
extract gave the least efficiency. This is because the eggplant skin extract contain a low number of antosianin
which made the dye absorption not efficient. The I-V curve of 12 hours soaking is demonstrated in Figure 3.

TABLE 2. Soaking for 24 hours

Dye Isc (A) Voc (V) Imax (A) Vmax (V) Pmax(W) η (%)
Mangosteen peel 0.0000787 0.15999 0.000442 0.15999 0.0000071 0.0071
Black glutinous 0.0000392 0.02501 0.0000229 0.02501 0.00000052 0.000572
Red rose flower 0.0000195 0.040034 0.0000307 0.040034 0.0000122 0.00122
Purple eggplant 0.00000888 0.01004 0.00000888 0.01004 0.0000000892 0.0000892
l
Table 2 shows that in the treatment with soaking for 24 hours, the largest efficiency obtained is 0.0071% with
Isc 0.0000787 Ampere , Voc 0.15999 in mangosteen peel, followed with 0.00122 Ampere with Isc 0.0000195
Ampere, Voc 0.040034 Volt, in red rose flower 0.000572% with Isc 0.0000392 Ampere, Voc 0.02501
Volt, in black glutinous rice, and the lowest one 0.0000892% with Isc 0.00000888 Ampere, Voc 0.01004 Volt

030104-5
in purple eggplant In the 24 hours soaking test, the solar cell efficiency was increased compared to the 12 hours
marination test. This indicates the soaking process affect the efficiency of the solar cell. The I-V curve of 24
hours soaking is depicted in Fig. 4.

FIGURE 3. Chart of soaking for 12 hours

FIGURE 4. Chart of soaking for 24 hours.

TABLE 3. Soaking for 48 hours

Dye Isc (A) Voc (V) Imax (A) Vmax (V) Pmax(W) η (%)
Mangosteen peel 0.0000369 0.115055 0.0000395 0.040181 0.000000159 0.00159
Black glutinous rice 0.0000422 0.025005 4.22 x 10 -5 0.010349 0.000000437 0.000437
Red rose flower 0.000023 0.040032 0.0000453 0.025026 0.00000113 0.00113
Purple eggplant peel 0.00000212 0.009981 0.00000212 0.009981 0.0000000211 0.0000211

030104-6
 Table 3 shows that in the treatment with soaking for 48 hours, the largest efficiency obtained is 0.0015%
with Isc 0.0000369 Ampere , Voc 0.115055 Volt in mangosteen peel, followed with 0.00113 with Isc 0.000023
Ampere, Voc 0.040032 Volt in red rose flower, 0.000437% with Isc 0.0000422 Ampere, Voc 0.025005
Volt, in black glutinous rice, and the lowest one 0.0000211% with Isc 0.00000212 Ampere, Voc 0.009981
Volt in purple eggplant Compared to the solar cell with 24 hours soaking, DSSC with 48 hours soaking
has a decreased efficiency. The I-V curve of 24 hours soaking is shown in Fig. 5.

FIGURE 5. Chart of soaking for 48 hours.

From the data above, it can be concluded that the soaking process affects the efficiency of the solar cell. The
optimum efficiency of a solar cell with extraction dye is achieved with 24 hours soaking process. This is because
in 12 hours soaking the dye was not absorbed completely and in 48 hours soaking the dye was oxidized as
anthocyanin has an easily oxidized properties [15]. Moreover, the solar cell with mangosteen rind extract dye has
the highest efficiency in every soaking treatment. This is because of the high level of anthocyanin in mangosteen
rind extract.

CONCLUSIONS
TiO2 coating as a semiconductor system Dye sensitized Solar Cell (DSSC) has been conducted in the
experimental study. TiO2 material used for coating is anatase phase that has a homogeneous surface
morphology, Fabrication of DSSC uses natural dyes mangosteen peel, black glutinous rice, red roses flower
and purple eggplant peel. The dye used in this work gives the absorbance at 400-550 nm. In DSSC system
the working electrode has been coated with TiO2 soaking with four natural dyes for 12, 24 and 48 hours.
The counter electrode is active carbon which serves as a catalyst in accelerating the redox reaction with the
electrolyte. The test results on the performance of the DSSC 12 hournsoaking provide the highest efficiency
in dye mangosteen with a value of 0.00047%, and the highest efficiency is mangosteen 0.0071% at 24-hour
soaking. For 48 hours soaking four dyes give a decrease in the efficiency and obtain the highest efficiency for
the mangosteen is 0.00159%.

030104-7
 REFERENCES
1. Y. S. Chen, J. N. Lee, S. Y. Tsai and C. C. Ting, Mater. Sci. Forum 594, 324 - 330 (2008).
2. M. Hamadanian, J. J. Ghomi, M. Hosseinpour, R. Masoomi and V. Jabbari, Mater. Sci. Semicond. Process 27,
733-739 (2014).
3. M. Grätzel, J. Photochem. Photobiol. C, 145-153 (2003).
4. Eren, E. C. Gok, B. N. Seyhan, N. N. Maslakci and A. U. Oksus, Asian J. Chem 3745, 27-10 (2015).
5. B. Yuliarto, W. Septina, K. Fuadi, F. Fanani, and L. Muliani, Mater. Sci. Eng (2010).
6. B. O. Reagen and M. Gratzel, Nature Publishing Group A Low-Cost, “High-Efficiency Solar Cell Based on
Dye-Sensitized Colloidal Ti0 (2) Films,” Nature (Nature Publishing Group, Institute of Physical Chemistry,
Swiss Federal institute of teknology, Switzerland, 1991), pp. 737 (1991).
7. Y. Xiao, J. Wu, G. Yue, J. Lin, M. Huang, L. Fan and Z. Lan, J. Power Sources, 197-202 (2012).
8. H. Zhou, L. Wu, Y. Gao, Y and T. Ma, Photochem. Photobiol. A 219(2), 188-194,(2011).
9. C.Y. Liao, S. T. Wang, F. C. Chang, H. P. Wang, H. P. Lin, J. Phys. Chem. Solids 75(1), 38-41 (2014).
10. K. Wongcharee, V. Meeyoo and S. Chavadej, Solar Energy Materials and Solar Cells 91(7), 566-571 (2007).
11. E.M. Abdou, H.S. Hafez, E. Bakir and M.S.A. A.Mottaleb, Spectrochim. Acta, Part A 115, 202-207 (2013).
12. D. Krisdiyanto, S. Khuzaifah, K. Khamidinal,and E. Sedyadi, Pure Appl. Chem, 4(1), 17-24 (2015).
13. H. Munawaroh, L. N. M. Z. Saputri, Q. A. Hanif, R. Hidayat and S. Wahyuningsih, “The co-pigmentation of
anthocyanin isolated from mangosteen pericarp (Garcinia Mangostana L.) as Natural Dye for Dye-Sensitized
Solar Cells (DSSC),” In: IOP Conference Series: Materials Science and Engineering (IOP Publishing, 2016),
pp. 012061.
14. D. O. Scanlon, C. W. Dunnill, J. Buckeridge, S. A. Shevlin,A. J. Logsdail, S. M. Woodley and G.W. Watson,
Nature materials 12(9), 798-801 (2013).
15. A. Setiawan, I. Fatayati, and H. Aliah,. J. Phys. Chem. 12(1), 77-82 (2016).

030104-8