1.

Introduction
As the global population continues to increase, the resulting energy demands have escalated,
along with concerns about greenhouse gas emissions and climate change. These have greatly
motivated researchers worldwide to search for alternative and clean methods of energy
production. Among the various renewable energy sources, solar energy offers abundant, silent
and eco-friendly power that has enormous potential for meeting the global energy consumption
demands [1, 2]. Photovoltaics (PV) provide an opportunity to affordably convert this abundant
and clean energy source into electrical energy.

Of the PV technologies, crystalline silicon (Si)-based PV systems have dominated the global PV
market over the past five decades. This is largely because of their beneficial features such as
efficient electricity generation under full sunlight, good photovoltaic performance stability in all
climatic conditions, as well as the maturity around their research and development (R&D)
activities and associated material value chain. Nevertheless, there are several drawbacks
associated with Si-based PV systems, including their energy intensive production processes, poor
aesthetics, and low photovoltaic performance in low light intensities. Together these have limited
their widespread use in building integrated photovoltaics (BIPV), portable electronics and indoor
applications [2–5].

In contrast to traditional PV technologies, third-generation photovoltaic technologies such as

dye-sensitized solar cells have been developed using low-cost and abundant materials with facile
and scalable fabrication methods. Currently, their lower solar-to-electrical energy conversion
efficiency and photovoltaic performance stability has prevented them from successfully
competing with the existing commercial PV technologies for bulk electricity generation outdoors
[6, 7].

However, their capability to be manufactured as thin and lightweight flexible solar modules [8,
9] make them ideal for portable electronics [10]. Similarly, their high efficiency under dim light
which outperforms other existing technologies at typical indoor conditions makes them
promising for ambient energy harvesting for the wireless sensors used in the internet of things
devices [5,10–12].
Over the last 20 years there has been extensive academic and, increasingly, commercial interest
in this technology. This was initiated by the report by O’Regan and Gratzel in 1991 of an
efficient photovoltaic device based on a mesoporous, nanocrystalline titania electrode sensitized
to visible light by the adsorption of a ruthenium bipyridyl dye in the presence of an iodide/iodine
redox electrolyte [13]. Over this period, there has been great progress in the materials
composition of such devices not only to enhance device efficiency, but also to improve stability
and processability and to reduce production costs. These materials advances have been reviewed
extensively elsewhere [14-20]. In parallel with these materials advances, great progress has been
made at understanding the science of the processes underlying device performance [21-25].

2. Device Composition of DSSCs

DSSC’s basic components involve a sensitizer, working electrode (photoanode), a counter

electrode (CE), and an electrolyte. Semiconductor nanostructures are used for the development
of photoanode. Indium tin oxide (ITO) or fluorine-doped tin oxide (FTO) coated sheets with
small resistance and with visible-light transmission (400–700 nm) of >80%, allowing electron
injection and transmission is being used as a transparent conductive oxide (TCO) glass substrate
sheet [27]. A photoanode separates and transfers the photogenerated electrons in the dye
sensitizer towards the collecting electrode [28]. To explore materials for efficient photoanodes,
several metal oxides are used as photoanode like TiO2, SnO2, ZnO2, In2O3, CeO3, and NbO3,
etc. [29]. An ideal photoanode for DSSCs should meet the requirements of faster electronic
transport, high specific surface area, and less interfacial electron recombination [30]. Ruthenium-
bipyridyl based dyes like N719, N3, and black dye-sensitized titanium dioxide (TiO2) nano-
structured materials have been the most effective photoanode products for many years, and have
subjugated the immensely efficient DSSCs [31,32]. Platinum (Pt) coated TCO is commonly
utilized as a CE as it has been the most productive combination for CE. Since, Pt costs too much,
discovering an alternative cost-effective material is extremely important to substitute the Pt in
CE. Carbon-based materials like graphene sheets, amorphous carbon, and carbon nanotubes are
potent substitutes as these materials have favourable properties as Pt-free counter electrodes [33,
34]. A typical DSSC comprises of a liquid electrolyte having a redox iodide/triiodide mediator
and a Pt CE [26].
3. Working principle of DSSC

The details of the operating principle of the dye-sensitized solar cell are given in Fig.1. The
photoexcitation of the metal-to-ligand charge transfer (MLCT) of the adsorbed sensitizer (Eq.1)
leads to injection of electrons into the conduction band of the oxide (Eq.2). The oxidized dye is
subsequently reduced by electron donation from an electrolyte containing the iodide/triiodide
redox system (Eq.3). The injected electron flows through the semiconductor network to arrive at
the back contact and then through the external load to the counter electrode. At the counter
electrode, reduction of triiodide in turn regenerate iodide (Eq. 4), which completes the circuit
With a closed external circuit and under illumination, the device then constitutes a photovoltaic
energy conversion system, which is regenerative and stable. However, there are undesirable
reactions, which are that the injected electrons may recombine either with oxidized sensitizer
(Eq.5) or with the oxidized redox couple at the TiO 2 surface (Eq.6), resulting in losses in the cell
efficiency.

S (adsorbed on TiO2) + hv → S∗ (adsorbed on TiO2) (1)

S∗ (adsorbed on TiO2) → S+ (adsorbed on TiO2) + e- (injected) (2)

S+ (adsorbed on TiO2) + 3/2 I- → S+ (adsorbed on TiO2) + ½ I-3 (3)

I-3 + 2e- (cathode) → 3I- (cathode) (4)

S+ (adsorbed onTiO2) + e- (TiO2) → S+ (adsorbed on TiO2) (5)

I-3 + 2e-(TiO2) → 3I- (anode) (6)

At the heart of the system is a mesoporous oxide layer composed of nanometer-sizedparticles,

which have been sintered together to allow electronic conduction to take place. The material of
choice has been TiO2 (anatase) although alternative wide band gap oxides such as ZnO, SnO 2
and Nb2O5 have also been investigated [10]. Attached to the surface of the nanocrystalline film is
a monolayer of a sensitizer. The high surface area of the mesoporous metal oxide film is critical
to efficient device performance as it allows strong absorption of solar irradiation to be achieved
by only a monolayer of adsorbed sensitizer [11]. The use of a dye monolayer avoids any
requirement for excited state (or “exciton”) diffusion to the dye/metal oxide interface. It also
avoids the acceleration in non-radiative excited state decay to ground state that is often
associated with thicker molecular films. The use of a mesoporous film results in a dramatic
enhancement of the interfacial surface area by more than 1000-fold for a 10mm thick film. This
leads to high visible light absorbance from the monolayer of adsorbed dye [12].

Fig. 1. Schematic diagram of a dye-sensitized solar cell.

4. Electron transfer dynamics

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