Conference LIS 2022 @ Kota Jambi, Indonesia.

E-ISSN : 2985-4393

ENG 006 :
Effect of Graphene Incorporate into Anatase Titanium
Dioxide Overlayer on Rutile Nanostructure of Dye-
Sensitized Solar Cells

Azman Talib1
1
Jabatan Kejuruteraan Elektrik,
Politeknik Mersing
azman.talib@tvet.pmj.edu.my
Norazlina Ahmad2
1
Jabatan Kejuruteraan Elektrik,
Politeknik Mersing
norazlina_ahmad@tvet.pmj.edu.my

ABSTRACT. Titanium dioxide gives benefit in solar cell applications due to its morphology and
crystalline structure. It is an affordable compound that could make solar cells more
cost economical than traditional silicon solar cells. In this study, reduced Graphene
Oxide (rGO) nanoparticles solution incorporated into anatase Titanium Dioxide (TiO 2)
solutions, which later overlayer onto rutile TiO2 nanostructure for improving the solar
conversion efficiency of dye-sensitized solar cells (DSSCs). Combination of rGO
added TiO2 nanocomposite mixture volume plays a vital role in improving the efficiency
of DSSCs by minimizing the recombination losses of photo-induced charge carriers.
The optimal performance results have been approved over photovoltaic performance
study in terms of characteristics of open-circuit voltage (Voc), short circuit current
density (Jsc) and solar conversion efficiency (η).

KEYWORDS: anatase; TiO2; FTO; rGO; nanocomposite; DSSCs

1 INTRODUCTION
Titanium Dioxide (TiO2) materials present in three major types in our nature that is
rutile, anatase, and brookite. Since rutile is generally the most stable phase of TiO 2, it is the
disadvantage for the application of DSSC due to the dye not being able to attach properly
on the surface of the structure (Venkatachalam et al., 2007). Anatase is also said to be the
better option for DSSC as it provides higher surface area due to its crystallographic
orientation other than lower recombination rate than rutile for its higher indirect bandgap
(Radeva et al., 2006; Venkatachalam et al., 2007).
To date, a variety of preparation methods have been established for the synthesis of
TiO2, for example, hydrothermal (Ahmad, Mokhtar, et al., 2016), chemical bath deposition
(Dhandayuthapani et al., 2016), spray pyrolysis (Oja et al., 2004) and anodization (Nishanthi
et al., 2014; Sennik et al., 2014). The method used in this experiment is spray pyrolysis
deposition (SPD), which is a physical technique. This technique is one of the most promising
ones since the structure of the apparatus is quite simple, and the method is applicable to
produce thin films on a large scale (Pham et al., 2010). The technique is also known as the
pyrosol technique in which the solution was sprayed onto the substrate deposited as a film.
In other words, when source solutions are atomized, small droplets splash, and vaporize on
the substrate and leave a dry precipitate in which thermal decomposition occurs (Okuya et
al., 2002).
In regards to DSSCs, graphene is commonly employed as a counter electrode (Al-
Rawashdeh et al., 2018), and reduced graphene oxide (rGO)/TiO 2 nanocomposite (NC) is
together used as photoanode for the advance of DSSCs superior performance (Nouri et al.,
2016). TiO2 nanoparticles (NPs) material is the best candidate to form a composite film. The
TiO2 NPs can anchor with rGO and improve the electron transportation rate (Fang et al.,
2012; Shu et al., 2013).

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 Conference LIS 2022 @ Kota Jambi, Indonesia. E-ISSN : 2985-4393

In this article, firstly, the one-step hydrothermal method is demonstrated to synthesis

rutile TiO2 (rTiO2) nanorods/nanoflowers (NRs/NFs) growth on Fluorine-doped SnO2 (FTO)
thin film. Secondly, different solution volume of rGO NPs incorporated into anatase TiO 2
(aTiO2) solution to forms nanocomposite mixture and sprayed onto the rutile TiO 2 NRs/NFs
NS. This experiment has been studied and discussed, and it shows that the growth
mechanism under different relatively dependent parameters has essential impacts on the
morphologies and performance of the structure synthesized.

2 EXPERIMENT DETAILS

2.1 Materials and Methods

2.1.1 Deposition of aTiO2 and rGO/aTiO2 solution onto FTO substrate

Once the hotplate and thin-film temperature became 150°C, 2 mL of rGO/aTiO2/NC_1
was filled into the airbrush tank. Hold the brush nozzle to the FTO substrate 10 cm in the
distance straight up directly above the substrates. The spraying method of the solution
followed from left to right movement until all the NC solutions covered on the rTiO 2_NS thin
film and solution in the airbrush tank is empty and named as rGO/aTiO2/rTiO2_1. The same
spraying method repeated with another three rGO/aTiO 2_NC deposited on three different
rTiO2_NS and denoted as rGO/aTiO2/rTiO2_2, rGO/aTiO2/rTiO2_3 and rGO/aTiO2/rTiO2_4.
A normal as-deposited rTiO2_NS thin film without any rGO addition was used as a reference
cell and named as rTiO2_Ref. After the spraying process is finished, the hotplate heat is
switched off, and all the samples are instantly annealed at 500°C for 3 hours in a furnace
(Ahmad, Soon, et al., 2016)

2.1.2 Characterization Techniques

The crystal structure of the as-synthesized films was inspected by Bruker D8 Advance
X-ray diffraction (XRD). Field emission scanning electron microscopy (FE-SEM, JOEL, JSM-
7600F) was used to inspect the morphology and microstructure of the samples. Photovoltaic
performances of the fabricated DSSCs were assessed by using a computer-programmed
Keithley 2420 Source Meter under the illumination of simulated sunlight (100 mW/cm 2, AM
1.5) and a solar simulator (Oriel, 91160-100091192, Parccell Technologies) was employed
as a light source.

3 RESULTS AND DISCUSSION

3.1 Structural Analysis

The XRD patterns of all rGO/aTiO2/rTiO2 samples and rTiO2_Ref are shown in
Figure 1. The graph provides information on crystalline quality and the orientation of the s
and NS. The NS synthesized for rTiO2_Ref sample approving the establishment of high
purity and stable rutile phase of TiO2 NRs/NFs on FTO. It presented crystalline nature with
diffraction peaks lying at 2θ = 27°, 36°, 41°, 54°, and 56° can be indexed to (110), (101),
(111), (211), and (220) planes. The diffraction data were in upright compliance with JCPDS
files no. 21-1276 (Lin et al., 2014).
All rGO/aTiO2/rTiO2 samples, which contain rGO s amount mixed with aTiO2 s deposited
onto rTiO2 NS, show diffraction peaks combination of both anatase and rutile phase of TiO 2.
Anatase phase (JCPDS 21-1272) from the agreement with the XRD results with few sharp
crystalline peaks appearing at 2θ = 25°, 38°, 48°, 54°, 55°, and 63°. These diffraction peaks
were assigned to the (101), (112), (200), (105), (211), and (204) plane, respectively (Xu et
al., 2010), and no FTO peak were observed.
Broad anatase band peaks 25° present at all rGO/aTiO 2/rTiO2 samples, and it covered the
small intensity peaks of rGO diffraction, which are around 2θ = 25° at (002) plane. It was
owing to the higher crystallinity of TiO2 s as compared with the lower intensity of rGO peaks
(Low et al., 2018).

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Figure 1: XRD patterns of thin film synthesis (a) rGO/aTiO 2/rTiO2_4, (b)
rGO/aTiO2/rTiO2_3, (c) rGO/aTiO2/rTiO2_2, (d) rGO/aTiO2/rTiO2_1 and (e) rTiO2_Ref

3.2 Electrical Properties

The four rGO/aTiO2/rTiO2 samples and rTiO2_Ref thin films’ for DSSCs efficiency are
identified based on the photocurrent-voltage characteristics revealed in Figure 2, simulated
below a replicated solar source at 100 mW/cm2 and 1.5 AM condition. The DSSCs’
performances in details were explained in Table I for all samples of photoanodes. The
rGO/aTiO2/rTiO2 photoanode’s current density (Jsc) of augmented from rTiO 2/aGTiO2_1 to
rTiO2/aGTiO2_4 with 5.56, 6.80, 7.05, and 10.37 current density with the highest conversion
efficiency (η) of 5.72% for 4 mL of rGO s. An increase in Jsc and voltage open circuit (V OC)
trend is the chief contribution to the improvement in DSSCs efficiency. The current produced
in the cell is identified based on the photoelectrons amount produced from the dye molecules
which exposed to visible light.

Figure 2: J-V characteristics of the DSSCs (a) rGO/aTiO2/rTiO2_1, (b) rGO/aTiO2/rTiO2_2,

(c) rGO/aTiO2/rTiO2_3, (d) rGO/aTiO2/rTiO2_4 and (e) rTiO2_Ref
Table 1: Photovoltaic parameters of DSSCs

4 Conclusion
In summary, rGO were successfully incorporated into anatase TiO2 to form NC mixture,
which later deposited onto rutile TiO 2 NS for improving the efficiency of DSSCs. The

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Fill Factor (FF

Voc (V) Jsc (mA/cm2) Efficiency % (η)
%)
rTiO2/aGTiO2_1 0.87 5.56 64.18 3.11

rTiO2/aGTiO2_2 0.85 6.80 66.23 3.84

rTiO2/aGTiO2_3 0.93 7.05 67.32 4.41

rTiO2/aGTiO2_4 0.91 10.37 60.46 5.72

rTiO2_Ref 0.72 4.68 64.32 2.18

structure of the rGO/aTiO2/rTiO2 on the FTO substrate possesses significantly contributes

improvement to help prevent the recombination of electron-holes, thus resulting in good
photocurrent activity. As a result, the DSSCs cell using the rGO composition at photoanode
exhibits greatly improved photovoltaic performance as compared to the normal rutile TiO2
NRs/NFs structure without any rGO addition. Further, the DSSCs fabricated using 4 mL of
rGO volume with 2 mL sprayed on rutile TiO 2 exhibited the best photovoltaic performance
with the highest conversion efficiency of 5.72% and most top current density (Jsc) of 10.37
mA/cm2. This experiment demonstrates the introduction of rGO incorporation into the TiO 2
work as one of a successful method for the photovoltaic performance of DSSCs
improvement.

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