Mater. Res. Express 8 (2021) 045010 https://doi.org/10.

1088/2053-1591/abf474

PAPER

Fabrication of DSSC using doctor blades method incorporating

OPEN ACCESS
polymer electrolytes
RECEIVED
7 January 2021
Shivani Arora Abrol1, Cherry Bhargava1,∗ and Pardeep Kumar Sharma2,∗
REVISED 1
19 March 2021
School of EEE, Lovely Professional University, 144411, India
2
School of PS, Lovely Professional University, 144411, India
ACCEPTED FOR PUBLICATION ∗
Authors to whom any correspondence should be addressed.
1 April 2021
PUBLISHED
E-mail: [email protected] and [email protected]
14 April 2021
Keywords: Dye sensitized solar cell (DSSC), Fill factor, FESEM, FTIR, XRD, TGA

Original content from this

work may be used under
the terms of the Creative Abstract
Commons Attribution 4.0
licence. Amongst various sources of renewable energy, solar energy is becoming prime due to its advantages of
Any further distribution of cleanliness, abundance and low operating cost. Currently, amorphous silicon PV cells are most into
this work must maintain
attribution to the commercialization but to contradict, they have a very high manufacturing cost and due to usage of
author(s) and the title of
the work, journal citation
hazardous materials, they lead to environmental degradation. Hence, they are less preferred now a
and DOI. days. To overcome these complications, Dye sensitized solar cells (DSSC) are replacing customary
cells at a very fast rate. In this research, fabrication of DSSC was done based polymer gel electrolytes
prepared by in situ gelation. The ionic properties of the polymer gel electrolyte were also observed with
the help of various tests performed like FESEM, FTIR, XRD & TGA. FTIR & XRD affirmed the good
electron emission characteristics of the polymer electrolyte. XRD & TGA give amorphous nature and
weight loss indication near 360 °C for cell based on polymer electrolytes. The performance evaluation
of hence fabricated DSSC’s was done in terms of calculating efficiency, fill factor, current density
(short circuit) and photovoltage (open circuit). The efficiency of the cell was found out to be 11.32%
and fill factor came out to be 0.439.

1. Introduction

Power generation is heading towards a revolutionary platform with the introduction of clean and greener modes
such as Dye-sensitized solar cells (DSSCs) which is a generating device finding its utility in all fields due to its easy
availability and economic nature. Dye-sensitized solar cells (DSSCs) belong to the group of thin-film solar cells
which have been under extensive research for more than two decades due to their low cost, simple preparation
methodology, low toxicity, and ease of production. The main objective behind this research work is to fabricate a
Dye Sensitised Solar Cell with enhanced efficiency and with a minimum cost of fabrication along with least
environmental hazards. Furthermore, there has been a huge scope for usage of alternative DSSC materials for
enhancements in incident photo conversion efficiencies (IPCE) (Sharma et al 2018) and a few of such materials
that have been incorporated in this work like organic dyes and polymer gel electrolytes which have resulted in
IPCE of 11.32%. DSSCs are mainly composed of a glass substrates-based semiconductor which is dye
synthesized, with an electrolyte, and an electrode. Its performance is majorly affected by the dye used as a
sensitizer. The various components of a DSSC are its photoanode (TCO conductive glass substrate coated with
TiO2) Photosensitizer Dye (organic dyes), electrolyte (gel-based polymer electrolyte), and a counter electrode
(TCO conductive glass substrate coated with graphite). For the working of a DSSC, the molecules from the
anthocyanin extracted from the dye get adsorbed at the surface of TiO2 nanoparticles. The interface amongst
TiO2 and dye leads to the transfer of electrons from dye fragments to the conductive band of TiO2. These
molecules then obtain photons from sunlight and generate electrons via the oxidation of dye. However, during
extraction of anthocyanin from dyes, suitable extractions and storage parameters are expected to be maintained.
The electrolyte further liberates the redox couple and completes the path of electron flow and hence helps in the
regeneration of the lost dye molecule. Various physical and chemical methods have been developed for the

© 2021 The Author(s). Published by IOP Publishing Ltd

Mater. Res. Express 8 (2021) 045010 S A Abrol et al

Figure 1. Materials and methods required for fabrication of DSSC.

fabrication of DSSCs like chemical vapor deposition (Shinde and Bhosale 2008), hydrothermal (Nagaraju et al
2017), solvothermal (Wahi et al 2006), sol-gel (Bhogaita et al 2016), microwave method (Falk et al 2018), and
Electrophoretic deposition (Abisharani et al 2020), however due to ease of understanding and application,
doctor Blades method is preferred over the other.

2. Materials and methods

2.1. Experimental details

For fabrication of DSSC, different components were prepared namely electrodes with coating of TiO2 and
graphite on them, dye, electrolyte and finally the whole assembly was brought together using Doctor Blades
method. Figure 1 shown below gives the detailed flowchart for the fabrication procedure for the same.
The major components used for assembling the cell and methods of their fabrication have been discussed
separately in the consecutive figures.

2.1.1. Preparation of TiO2

Electrodes play a major role in DSSC assembly. The performance of a DSSC depends on the molecules liberated
from the dye and semiconductor electrodes, as a sensitizer. Basically, three processes occur in a DSSC
simultaneously. Firstly, dye gets absorbed at the TiO2 layer of the electrode, which further interacts with the
Sunlight and liberates an electron from the lower orbit of the atomic structure to the excited state. During this
process, light source photons from sun breach into the DSSC and process of photoexcitation takes place.
Secondly, the diffusion of electrons into the titanium dioxide takes place. To complete the circuit, the electron is
returned to the cell dye and brings it in a normalized state with the use of the electrolyte. The DSSC is called a
sandwiched cell because a pair of TCO glass sheets overlap the layers of dye and electrolytes. Hence, the anode
electrode is layered by TiO2 coating using Doctor Blades method as mentioned in figure 2, which is further
sensitized by the dye and counter electrode is coated by the carbon or graphite coating so as to enhance
electrolyte interaction. TiO2 paste is set by magnetic spinning as mentioned in the flowchart in figure 2 and then
TiO2 layer is applied on FTO by Doctor blade method (Muller et al 2003, Shanian and Savadogo 2006, Jørgensen
et al 2008, Aouaj et al 2009, Baek et al 2010, Sima et al 2010, Yoo et al 2010, Kwak et al 2011, Choi et al 2012,
Mazalan et al 2013, Lalasari et al 2018, Abrol et al 2020b).

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Figure 2. Preparation of TiO2. Materials: (a). FTO coated glass substrate, (b). TiO2 powder, (c). Triton X, Method: (d). Magnetic
stirring of all components (e). Pasting of TiO2 layer on anode using doctor blades method (f). Drying uniformly of the anode on a hot
plate.

Figure 3. Preparation of organic dye. Materials: (a). Onion peels used as raw material for the preparation of the dye. Methods: (b).
Onion peels being immersed in distilled water for fermentation. (c). Dispersed onion and water solution being placed in incubator at
90 °C for 24 h. (d). Final extracted anthocyanin from the solution after filtration to be used as a dye. (e). Extracted dye placed in
incubator.

2.1.2. Preparation of organic dye

Figure 3 shows the preparation of the Dye (Sahare et al 2015, Ammar et al 2019, Abrol and Bhargav 2020). The
sensitized anthocyanin is extracted from preparation of dye using organic substrates like onion peels as shown in
figure 3. It was seen that the absorption level of photons of light rose by its usage as a dye in a DSSC. There are
specific functional groups found present in natural dyes which effectively adsorb on the conducting catalytic
layer of TiO2. It was further understood that the functional groups i.e., the OH group found in molecules of
anthocyanin sensitized dye extracted from these natural organic materials lead to decent absorption properties.
Further, C=O group presence also led to improvement in absorption. An emission peak at 565nm was
observed for anthocyanin from dye extracted using onion peels. (Hao et al 2006, Wu et al 2008, Chen et al 2010,
Chiku et al 2011, Akhtar et al 2013, Kashif et al 2013, Aulakh et al 2015, Senthil et al 2016, Calogero et al 2018,
Zhang et al 2018, Ammar et al 2019, Poosapati et al 2019).

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Figure 4. Preparation of Electrolyte. Materials: (a). Potassium Iodide. (b). Iodide (c). Acetic acid (d). Preparation of liquid electrolyte
by magnetic spinning (e). polymethyl methacrylate (PMMA), (f). tetrahydrofuran (THF), (g). propylene carbonate (PC), (h). ethylene
carbonate (EC) Method: (i). the gelator solution obtained after magnetic stirring at 70 °C till its homogenous, the final electrolyte
looked like a high viscous gel as shown. (j). samples of polymer electrolyte formed (k). In situ gelation done in hot air oven l. samples
(final) of electrolytes.

Table 1. Samples of Gel based electrolytes formed after in situ gelation.

Ratio of Ratio of GPE

Gel based electrolyte LE (%) gelator (%)

Sample A 80% 20%

Sample B 70% 30%
Sample C 60% 40%
Sample D 50% 50%

Sample A (80% liquid electrolyte and 20% polymer electrolyte) gave the
best efficiency (11.32%) when used as an electrolyte for DSSC.

2.1.3. Preparation of electrolyte

The next level of assembling a DSSC involves the preparation of the electrolyte. An electrolyte is considered the
heart of the cell. In between the electrodes, the inner charge carrier transportation is done through electrolyte.
Electrolyte also continuously renews itself as well as the dye. They further improve the stability of DSSCs and
solar to electric conversion efficiencies by maintaining the performance parameters. In the fabrication of
polymer electrolytes based DSSC, gel-based polymer electrolytes were prepared by homogeneously mixing
liquid electrolyte and gelator solution in various ratios as shown in figure 4.
In the fabrication of polymer electrolytes based DSSC, gel-based polymer electrolytes were prepared by
homogeneously mixing liquid electrolyte and gelator solution in various ratios. Four combinations of gel
polymers were created based on in situ gelation with the ratio as shown in table 1 below.
After mixing, electrolytes were placed in an oven at 70 °C for 20 min that is solvent evaporation (in situ
gelation), for the preparation of the final gel-based electrolyte to be used for the fabrication of the cell
(Fenton 1973, Yang and Lin 2002, Lei et al 2008, de Freitas et al. 2009, De Freitas et al 2010, Bella et al 2013, Tsai
et al 2013, Seidalilir et al 2015, Su’ait et al 2015, Wu et al 2015, Ngai et al 2016, Senthil et al 2016, Buraidah et al
2017, Gu et al 2017, Park et al 2017, Sachdeva et al 2018, Teo and Arof 2018, Cho et al 2019, Poosapati et al 2019).

2.1.4. Preparation of counter electrode

The final component for assembling the DSSC is the preparation of the counter electrode by graphite coating as
shown in figure 5 (Baranwal et al 2016).

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Figure 5. Preparation of Counter Electrode. Materials: a. FTO coated glass substrate b. Graphite stick Method: c. Coating of graphite
on glass substrate for formation of anode.

Figure 6. DSSC assembly.

2.2. Cell assembly

The anode, also known as sensitised electrode and cathode that is the counter electrode coated with graphite
were clamped together with clips as shown in figure 6.
A small quantity of electrolyte was seeped in into the cell so as to allow charge transportation between the
electrodes. For increasing the segmental electron mobility and for prevention of the cavities on the photoanode,
the sealed electrodes framing a cell were heated on hotplate for 5 min at 120 °C (Sahare et al 2015).

3. Characterization

Surface morphology of the polymer electrolyte samples was observed using FE-SEM i.e., Scanning Electron
Microscope. The particle size was also examined for a better understanding of weight to emission ratio of the
components of the electrolyte using field emission scanning electron microscopy. Gold coat sputtering was done
to avoid the effects of charging. XRD (x-ray diffractometer) with a range of scanning of 20°/80° with Cu Ka
radiations was done for structural analysis. Intermolecular interactions study between the components of the
sample was done by FT-IR spectroscopy (Abbas et al 2020). FT-IR also explained about the samples functional
groups presence which were recorded in the range of 450–4000cm−1. TGA (Thermo gravimetric analysis)
explicated about the PEG polymer electrolyte samples weight loss at a temperature as high as 360 °C.

4. Results and discussions

The performance and responses of the DSSC fabricated with the usage of natural dye and polymer gel electrolyte
was done. It was seen that the DSSC make the use of the principle that the wide band gap in a semiconductor
helps in sensitising the light (Mazalan et al 2013). Characterisation of the samples help in knowing about the
conductive nature and how the power be obtained over a wide range of temperatures (Ammar et al 2019). In this
work, the electrolytes homogeneity tests were performed to affirm the electrolyte samples properties of
photoconduction & absorption (Singh et al 2015). FE-SEM equipped with Energy Dispersive Spectroscopy

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Figure 7. FE-SEM characteristics results for electrolyte used in DSSC.

(EDAX) helped in observing the penetration level, degree of absorption and elements quantification mapping
for the sample (Chiku et al 2011). The performance of DSSC as a parameter of photon rays’ absorption in their
infra-red zone was observed from FTIR analysis. XRD and TGA depict the structural deformity and rate of
thermal decomposition w.r.t distinct organic weight losses.

4.1. Gold coat sputtered FE-SEM characteristics

Through FE-SEM, the porous nature of the specimen was observed as shown in figure 7 (Chiku et al 2011,
Chiappara et al 2016).
The conducting surfaces microstructure morphology for electrolyte film sample was obtained. In
figure 7(a), PMMA- co- THF- KI2 salt complex with pores were depicted that are responsible for enhanced ionic
conductivity for the electrolytes. The spherical grains in figure 7(b) showed the homogeneous structure
of the sample. The presence 1–10 μm sized pores and dark sections were responsible for increased value of
conductivity. Confirmation of the dissolving of all salts present in the electrolyte sample can be seen in figure 7(c)
(Abrol et al 2020a). The cell gave enhanced conductivity shown be uniformly sized tracks of a measurement of
few micrometres seen from the picture in figures 7(d) and (e). The pores with sizes of the range 50–100 nm in
figure 7(f) showed presence of (EC) plasticizer+(KI2) salt. The component of rich ionic motion can be seen by
the light grey regions of the plasticizer component (Chiappara et al 2016, Pasche et al 2017, Sachdeva et al 2018).

4.2. EDAX characteristics

Energy-dispersive X-ray spectroscopy is an analytical procedure applied for chemical characterization of an
electrolyte sample. It depicts the interface of the source of X-ray excitation and sample. Here, EDAX was done
for identifying the elemental composition of the sample used as electrolyte in the DSSC. By EDAX analysis, it is
possible to determine the distribution of the local elements and also the distinction of the different polymers.
Also, the spatial distribution of different elements present can be seen in the spectrum tables. This further helps
in determining the ionic conductivity as the weight of the conductive elements in the electrolyte can be seen.
In the Electron Image I from figure 8, the Spectrum I gives the weight percentage of elements due to gelator
mainly and C & O were found out to be in the weight percentages 65.48% and 30.18% respectively. This
confirms the presence of ionic conductive elements in the PGE. In the Electron Image II from figure 8 resulted in
the Spectrum II & III which shows the weight percentage of elements present due to liquid electrolytes i.e. K & I.
The above spread of different elements characterized the amorphous spread of the ionic contents (Sachdeva et al
2018).

4.3. FT-IR test analysis

For identifying the ionic bond nature and presence of functional groups in the electrolyte used in fabrication of
the DSSC, Fourier Transform Infrared Spectral (FT-IR) analysis was done. The molecules vibration energy could
be monitored by these analyses. The electrolytes FT-IR spectra can be seen from the graph shown in figure 9
which shows amalgamation filler triiodide with plasticizer EC (ethylene carbonate).

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Figure 8. EDAX characteristics results.

Figure 9. FT-IR characteristics results for electrolyte used in DSSC.

Functional groups were identifiable with the help of FT-IR which were important for recognizing the
properties of ionic conductivity for the prepared electrolyte used for DSSC fabrication. These were depicted by the
power of absorbance of peak obtained in the range 400–4000 cm−1. Strong absorbance band at around
1012 cm−1 confirmed the presence of C-O band, responsible for movement of ions in the prepared electrolyte.
Due to the change in the molecular dipole movement, vibrations are caused and these can absorb more radiations.
With further increase in the dipole movement near 1012 cm−1, absorption is more intense which further supports
the ionic movement in the electrolyte. CH bending vibration of the polymer PMMA is depicted by symmetric
C-O-C stretch of vibrations as shown by the band value 1254 cm−1. CH3–C–O group linking is given by the peak at
610 cm−1. Peak 884 cm−1 confirms the amorphous phase of copolymer. The O-H group was represented by
absorption peak value of 3423 cm−1. Symmetrical starching happening for the C-I2 group can be assigned to a
sturdy absorption peak value of 1705 cm−1. The ionic bonding between the polymer electrolyte group and liquid
electrolyte can be observed from the bending and wagging vibrations of –CI2 of PC-co-THF polymer can be seen at
peaks in between the range of 455 cm−1 to 610 cm−1 (Sakthivel et al 2017, Ridwan et al 2018).

4.4. XRD test analysis

The XRD patters of blended PMMA electrolyte were obtained as shown in figure 10. It is apparent from this
figure that broad bands peaking at 2θ equal to 17°, 29.93° and 38° in the x-ray pattern of PMMA matrix
indicated the samples amorphous nature.
These peaks also prove semi crystalline morphology of electrolyte sample prepared i.e., PMMA- co- THF-
KI2/ PC/ EC. This also indicates that addition of liquid electrolyte improved amorphous nature of the

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Figure 10. XRD characteristics results for electrolyte used in DSSC.

Figure 11. TGA characteristics results for electrolyte used in DSSC.

electrolyte. Further, it is seen that small peaks at 30˚ diffraction that smooth crystalline complex is formed due to
the addition of ionic liquid electrolyte. (Sakthivel et al 2017).

4.5. Thermo gravimetric analysis (TGA)

For explicating the weight loss of the prepared electrolytic sample of the gel polymer-based PEG, TGA (thermo
gravimetric analysis) characteristics test was conducted. The electrolytes weight loss occurs near 360 °C (the
range of scan being fixed in between the 30 °–600 °C) and can be seen in the graph shown in figure 11. The TGA
graph indicated the interaction of ions of liquid electrolyte interacted very well with PEG and maintained the
level of thermal stability and further, inveterate that the polymer electrolyte decomposed near 360 °C
(Abisharani et al 2020).

5. Cell performance

The DSSC was tested under day light and diffused sunlight using multi meter. Luxmeter was used to observe the
intensity of sunlight, a shown in figure 12.

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Figure 12. Luxmeter used to observe intensity of sunlight.

Figure 13. (a). Measurement of various parameters for performance check of DSSC, (b). Mathematical model framed for the DSSC
assembly.

47200 lux was received value of output from the luxmeter under sunlight, which was further changed into
Watt m−2 or mW cm−2 i.e., units of power input as below
Sunlight intensity = 37.288 mW cm-2(0.0079 ´ 47200 lux)
DSSC results for its performance were analysed by building a mathematical model for the fabricated assembly as
shown in figure 13 (Chiba et al 2006). Table 2 shows the measurement of the performance parameters like FF (fill
factor) and η (efficiency) of the cell (Bella et al 2013).
Isc
Jsc = (1)
A

Area of fabricated cell, A=6.25 cm2

155.72
Jsc = = 24.91 mA cm-2
6.25
Current density at load for the fabricated cell,
Im 86.2
Jm = = = 13.792 mA cm-2 (2)
A 6.25
Vm ´ Im 0.3 ´ 0.0862
FF = = = 0.439 (3)
Voc ´ Isc 0.3862 ´ 0.155
Vm=load voltage
Im=load current
Incident Photon Energy conversion efficiency for the fabricated sample of the cell,
Voc ´ Jsc ´ FF
h= ´ 100 (4)
Pin (mWATT / cm2)
0.3862 ´ 24.91 ´ 0.439
h= ´ 100 = 11.32%
37.288

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Table 2. Measured parameters of the DSSC for performance parameters calculations.

Voltage at no Voltage at light (at Current at light (at OC voltage at SC current at Fill fac- Efficiency
10

light [Vo (mV)] load) [Vm (mV)] load) [Im (mA)] Current density at light (at load) [Jm (mA/cm2)] light [Voc (mV)] light [Isc (mA)] SC current density at light [Jsc (mA/cm2)] tor [FF] [η (%)]

150 300 86.2 13.792 386.2 155.72 24.91 0.439 11.32

SC current density of the cell.

S A Abrol et al
Mater. Res. Express 8 (2021) 045010 S A Abrol et al

The performance parameters obtained from the above analysis yielded an efficiency of the sample cell fabricated
to be 11.32% and a fill factor was found out to be 0.439.

6. Conclusion

The process used for the preparation of electrolyte i.e., in situ gelation improved the ionic properties of polymer
electrolytes and hence the DSSC. The maximum efficiency obtained for the DSSC fabricated by using gel-based
polymer electrolytes was 11.32% with a fill factor of 0.439. The homogeneous nature and the perfect blending of
various components in polymer electrolytes was affirmed by characteristic tests namely FE-SEM & FT-IR. The
fabricated cell with the help of gel-based polymer electrolytes gave enhanced ionic conductivity because of the
presence of LE blend. XRD & TGA assured the amorphous nature and easy absorption of light for the cell. The
results hence obtained were found out to be encouraging and can be referred for the fabrication of a
revolutionary economic and eco-friendly dye sensitised solar cells.

ORCID iDs

Cherry Bhargava https://orcid.org/0000-0003-0847-4780

Pardeep Kumar Sharma https://orcid.org/0000-0001-9191-2731

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