Dye Sensitized Solar Cells: Structure and Working

Introduction
Considering the ever-increasing energy needs of modern world, the diminishing conventional
fossil-based sources of energy would need to be switched to sustainable and renewable sources.
In this regard, there are few options to look into, which include, wind, tidal, hydro, biomass,
atomic and solar energy. Solar cells/photovoltaic cells provide an efficient route to utilize the
ample solar energy. Among the various categories of solar cells, the dye-sensitized solar cells
(DSSC) are utmost promising options for sunlight harvesting due to their low cost and
environmental begin nature. Invented by Brian O’Regan and Michael Grätzel DSSCs are thin
film solar cells with simple manufacturing procedures and good light-harvesting efficiency.
The fundamental difference between the DSSC and the conventional solar cell is that, in DSSCs
photo anode is made up of layer of dye adsorbed on the porous surface of a semiconductor
oxide. The dye serves the task of light absorption and injects the electrons into the conduction
band of the metal oxide semiconductor.
Components of DSSCs
The DSSC cell generally consists of a set of layers of different components, including ITO or
FTO glass substrate, transparent semiconducting metal oxide nanoparticles (usually TiO2),
dye-sensitizer (organic or metallo-dye),electrolyte(I-/I-3orCoII/Co III complexes), and counter
electrode (Platinum of carbon based)
ITO/FTO glass Substrate
DSSCs are generally fabricated with using the substrates which are transparent as well
as conductive. The substrate provides a support-base for the semiconducting oxide, it is
essential that the support-base should be transparent to allow the efficient passage of sunlight
to the dye-sensitized semiconducting oxide. Higher electrical conductivity of the support-base
is also desired to promote the efficient charge transfer. Typically, fluorine tin oxide (FTO,
SnO2:F) or indium tinoxide (ITO, In2O3:Sn) coated soda lime glass plates are used as substrates
in DSSCs. Generally, ITO glass plates have about 80% of transmittance and sheet resistance of
18 Ω/cm2, whereas, FTO glass plates exhibit about 75% transmittanceand have sheet resistance
of 8.5Ω/cm2.
Nano Semiconducting Metal Oxide Electrode
Semiconducting metal oxides with wide band gaps (3 – 3.8eV), mainly, TiO2, ZnO, SnO2,
and Nb2O5are used in the DSSCs. TiO2 nanoparticles are the best choice due to their non-toxic
nature, cost-effectiveness and easy availability. Due to the large surface area provided by their
porous structure, dye molecules can strongly get attached onTiO2 surface.
Dyes/Sensitizers
Dyes or sensitizers aid in the light harvesting and hence govern the photoelectric conversion
efficiency of the solar cell. The ideal sensitizer should absorb the broad spectrum of solar light,
tightly bind to the semiconductor oxide surface and efficiently inject the photoexcited electrons
to the conduction band of the semiconductor (negative LUMO than the conduction band).
Other important requirements for the ideal dye are that, the dye should have high redox
potential so that, regeneration can be achieved quickly by the electron donation from the
electrolyte (positive HOMO than the redox potential of the electrolyte). Further the dye
molecule should be thermally stable and durable.
There are mainly three class of dyes/sensitizers known, natural dyes, metal complex dyes and
synthetic metal-free dyes. Natural dyes are the colored compounds extracted from plants
(mostly flavonoids). They are attractive due to their environmental friendliness but the tedious
extraction and purification processes and lower stability and poorer efficiency are the
drawbacks of these dyes [5]. Figure 1 shows the structures of natural dye molecules extracted
from Cassia fistula

.
Figure 1 : Major components of the natural dye extract obtained from Cassia fistula
Metal complex dyes provide great advantage due to the synergy between the ligand molecules
and metal center. Strong and broad absorptions in solar spectrum due to the intra-ligand and
MLCT (metal to ligand charge transfer) electron transitions make them ideal photosensitizers.
Presence of anchoring groups in the ligands can help to strongly bind to the semiconductor and
ease the electron injection. Polypyridyl ruthenium complexes lead this class due to their higher
efficiency and stability.

Figure 2: Some of highly successful polypyridyl ruthenium dyes in DSSC applications (TBA
= Tetra butyl ammonium)
However, the synthetic difficulties, economic and environmental concerns associated with
ruthenium-based dyes have prompted the development of other transition metal complex dyes
based on zinc, copper and iron Figure 3 shows some successful non-ruthenium metal complex
dyes used in DSSC applications.

Figure 3: Some successful non-ruthenium metal complex dyes used in DSSC applications

Metal free synthetic organic dyes have also been used in DSSC applications. Owing to their
easy synthetic protocols and tunability they are receiving much attention. However, overall
efficiency of these sensitizers is inferior to the metallo-dyes and entail further strategic
developments.

Electrolyte/Redox Mediator
Electrolyte/redox mediator supplies the electrons to the dye molecules, when the dye molecule
injects the electrons into the conduction band of the metal oxide semiconductor, it gets oxidized
and then comes back to the normal reduced form by accepting electrons from the redox
mediator. Thus, lifetime of the DSSC strongly depends on the stability and efficiency of the
electrolyte. For the best performance, the electrolyte should have high electrical conductivity
and possess good contact with the dye-sensitized metal oxide semiconductor (anode) and the
counter electrode (cathode). Liquid electrolytes based on the I3-/I-redox couple are found to
be more successful electrolytes, recently there is an increasing interest in the development of
cobalt-based electrolytes, quasi-solid-state electrolytes and solid-state electrolytes, which offer
long time stability.
Counter Electrode/Cathode

Counter electrode/cathode regenerates the electrolyte. After transferring the electron to the dye
molecule (oxidation), the electrolyte diffuses towards the counter electrode/cathode and
receives the electrons from the external circuit (reduction). Platinum and graphite-based
materials have been extensively used as counter electrodes in DSSC applications.
Working Mechanism of DSSC
Working mechanism of DSSCs is slightly different from the conventional solar cells. It
involves the following steps.
Step 1: Dye molecules coated on the metal oxide semiconductor absorb wide spectrum of the
sunlight. And upon absorption of sunlight the electrons of dye molecule get excited.
Step 2: The exited electrons of the dye molecule are injected into the conduction band of the
metal oxide semiconductor.
Step 3: These electrons will diffuse through metal oxide and finally reach counter electrode
through the circuit.
Step 4: The oxidized dye molecules will get the electrons from the redox mediator/electrolyte
and come back to their original (reduced) form.
Step 5: The oxidized electrolyte species diffuse towards the counter electrode and get reduced.
And this cycle continues to produce the current. It is important to note that, the overall
performance a DSSC depends on the energy levels of these four components: the ground state
(HOMO – Highest Occupied Molecular Orbital) and exited state of the dye molecules (LUMO
– Lowest Unoccupied Molecular Orbital), the band-gap of the metal oxide semiconductor and
the redox potential of the electrolyte.General components and working mechanism of typical
DSSC are depicted in Picture 3.

Picture 3: General components and working oftypical DSSC(Reproduced from reference [12]
with permission)