Quantum Dot Sensitized Solar Cells

1. Introduction
As the modern world requires alternating energy sources with the rapid
depletion of fossil fuels and the imminent threats of global warming, several
technologies are currently working on developing a reliable, cost-effective, and
environmental-friendly energy source. Many renewable energy sources such as wind
energy, tidal energy, hydro-electrical and geothermal energies are currently being
used as alternative sources of energy and the generation of energy by the direct
conversion of sunlight into electricity using photovoltaic (PV) cells has been one of
the most promising among them. But the greatest challenges when developing new
types of advanced materials have been the development of new materials, which are
robust and inexpensive and have the desired electrical and optical properties while
giving the capability of ease of fabrication, higher efficiencies to the PVs. Since the
first generation, silicon-based PV cells have been dominating the solar energy
industry because of the robustness and the cheaper price of silicon. But all the silicon-
based PV cells are currently limited to an efficiency of 33.7% and it hugely affects the
amount of energy that can be supplied to the current demand. The Shockley−Queisser
limit, which is the thermodynamic limit of light conversion efficiency is also at
around 32.9% for a cell of the single junction. Due to such reasons, solar energy still
haven been able to use as the primary source of energy rather than used as an
additional supply.

Solar power used as additional supply to main power line

To overcome this limitation many attempts are being carried out resulting in the
advancement of the third and fourth generation of solar cells. Some of those
advancements are the solar cell family of photoelectrochemical solar cells (PESC).
They include technologies such as dye-sensitized solar cells (DSSCs) and quantum
dot (QD)- sensitized solar cells (QDSSCs). Those technologies are currently showing
promising advancements in the terms of high conversion efficiency and low-cost
fabrication. Among those two, QDSSC has the most attention as the quantum dot
technology has many advantages when used as sensitizers such as their large
absorption coefficient, absorption spectrum tunability, hot electron injection,
multiplication, etc. With those advantages, those solar cells have been able to achieve
higher efficiencies such as 44.7%.

The first DSSC was introduced in 1991 along with optically active sensitizing
material. When considering the making of DSSCs, they consist of two electrodes, a
sensitized photo-anode, and a counter electrode with appropriate electrolyte. A
transparent conductive substrate, usually Fluorine doped tin oxide – FTO or Indium
doped tin oxide – ITO or PET-ITO, is used for making the sensitized photo-anode by
depositing a wide bandgap semiconductor material over it. Then an optically active
sensitized dye layer is deposited over it. The dye-based on Ru was used to achieve
higher efficiencies and lower costs. Along with liquid electrolytes based on iodide-
triiodide (I -–I3-), platinum (Pt) is used as a common counter electrode in DSSC.
DSSC is usually preferable over conventional p-n junction solar cells because that
they do not require very pure and defect-free semiconductors. But their efficiencies
are limited due to some reasons such as absorption spectrum performance of the dye,
breakdown of the dye, and the low thermal and long-term stability.

2. Quantum dot semiconductor solar cells (QDSSCs)

So after some time, the dye was replaced by quantum dots, which are light-
absorbing materials. Hence the design of QDSSC was introduced. These QDs consist
of some unique characteristics related to optoelectronics such as size-dependent
tunable energy band gap, carrier multiplication, etc. And to increase the overall
performance of solar cells, those unique characteristics are optimized. Also, the
QDSSC is capable of absorbing a wide range of solar radiation wavelengths from UV
to infrared.

QDSSCs

QDSSC is widely used in the field of photovoltaic (PV)s in different configurations.

Those are designed based on the form of QD Schottky junction solar cell, QD hetero-
junction solar cell, QD hybrid polymer solar cell, QD sensitized solar cell (QDSSC),
QD & Dye co-sensitized solar cell, QD rainbow solar cell, etc. QDSSCs have
surpassed the other forms and have emerged as a promising technology in the field of
PVs.
When considering the making of DSSCs, they consist of two electrodes, a sensitized
photo-anode, and a counter electrode with appropriate electrolyte. And the sensitized
photo-anode is made by depositing a wide band-gap semiconductor over a transparent
conductive substrate (Fluorine doped tin oxide – FTO or Indium doped tin oxide –
ITO or PET-ITO) and then depositing a layer of optically active sensitized dye over it.
Platinum (Pt) is a common counter electrode in DSSC, using an iodide-triiodide (I –I3)
based liquid electrolyte. Although DSSCs are preferable to conventional p-n junction
solar cells in that they do not require a very pure and defect-free semiconductor, their
efficiency is restricted due to dye absorption spectrum performance, dye breakdown,
and low thermal and long-term stability.

3. Working principles

Most of the QDSSCs includes wide-band-gap semiconductor which is usually

TiO2, Semiconductor nanocrystals that have narrow bandgaps, a redox electrolyte
solution along a counter electrode. The electrons are injected into the wide-bandgap
semiconductor conduction band when the semiconductor nanocrystals are excited.
Then the electrons are diffuse to the front contact and the holes are sent to the
electrolyte for the process of regeneration occurs at the counter electrode.

To excite and form electron and hole pairs, the QDs must be irradiated with sunlight
having energy equal to its bandgap energy. Different chemical processes occur during
charge separation and transit

Here, the letters e and h stand for electron and hole, respectively.

Following the above process, the transportation of chargers at wide bandgap (WBG)
SC/QD interface as follows.

Here, Red and Ox denote the reduction and oxidation of electrolytes respectively.
Also, the size of the QD is the parameter that determines the separation of charges at
the WBG SC/QD interface. The reduction of the size of QD results in the
improvement of electron transport.
 Working of (a) DSSC and (b) QDSSC

4. Fabrication techniques

When it comes to the fabrication technologies of QDSSC, many

improvements have been done to improve solar cell performance. And the most
popular synthesis methods which are being used for QDSSC for semiconductors thin-
film coated electrodes, QD layer deposition, and counter electrode preparation are as
follows.
For the preparation of semiconductor coated electrode, many thin film deposition
techniques such as doctor blading, screen printing, etc. Are being used. They create a
layer of wide bandgap semiconductor, usually TiO2, ZnO, and SnO2, over a
conductive substrate mainly FTO or ITO glass.

4.1. Doctor blading

In doctor blading an appropriate ratio of an organic binder such as ethylcellulose, a
surfactant, usually terpineol, a solvent such as ethanol, is used to create a thick and
viscous paste of evenly dispersed nanocrystals of semiconductor. This paste is then
applied to a specific portion of the substrate’s conducting surface. This specific area is
usually marked with scotch tape or a mask. Then a sharp blade is used to create a
homogeneous coating of semiconductors by distributing the paste over the electrode.
Drying of the thin film process is done at the ambient temperature before using the
high temperature for the annealing process. The quality of the thin film is determined
by the composition of the paste, speed and the angle of the blade, and the annealing
temperature, etc. Also masking using multilayer scotch tape helps to regulate the
thickness of the thin films.

4.2. Screen printing

But in screen printing, a huge amount of thin films of the same quality can be
produced at the same time. It is mainly used in the commercial fabrication of
conventional silicon solar cells. In the most basic type of screen printing technique, a
mask with a mesh type structure is used on the conductive surface of the substrate.
Using the same way as in the doctor blade method, a paste is made and pasted on the
mesh of the mask to fill the open areas of the mesh. Then a machine-operated
squeegee is dragged across the substrate to force the paste through the open areas of
the mesh. Then the mask is removed after ejecting the remaining paste off the
electrode’s surface. Here also drying and the annealing process is done similar to the
doctor blade method.

4.3. Other methods

As for the other methods, spluttering, spray pyrolysis, electro-spinning, and atomic
layer deposition are used to get the varied structural and morphological qualities while
improving the thin film quality. Sometimes a combination of two techniques is used
in instances such as the fabrication of one-dimensional nanostructures, such as
nanorods and nanotubes. Usually, spin coating or sputtering techniques deposit the
seed layer on the substrate while hydrothermal techniques to assist in growing one-
dimensional nanostructures on semiconductors are used on such occasions.

Usually, screen printing is the most suited process to fabricate photoanode with
mesoporous spherical shape while spin coating or spray pyrolysis is used for seed
layer deposition. The hydrothermal process is most suited for processes such as
creating vertical one-dimensional or hierarchical structures.

5. QD sensitizing layer
And in the preparation of the QD sensitizing layer, the in-situ method or the
ex-situ methods are used to deposit the QD layer on a semiconductor coated electrode.
In-situ methods are often used as a manufacturing process in QDSSC technologies as
they are simple and low cost. Which makes them an ideal choice for large-scale
manufacturing. There are two processes which mainly used in in-situ QD deposition
namely, chemical bath deposition (CBD) and sequential ionic layer absorption and
reaction (SILAR).

5.1. In-situ methods

The CBD process is a simple, repeatable, and cost-effective method for

producing high-quality compounds semiconductor metal halides, and chalcogenide
thin films. This method can be used on both metallic and non-metallic substrates. Due
to past researches, the CBD process is now able to generate films with good structural,
optical, and electrical characteristics similar to those generated by other advanced thin
film deposition methods.
In this method, desired chemicals are precipitated slowly by using their ions in a
reaction bath solution.

The sequential ionic layer absorption and reaction method is mostly used for thin film
deposition of large-area thin films because of its economical, easy, and convenient
capabilities. It primarily depends on processes of absorption and reaction of ions from
solutions. Also to avoid homogeneous precipitation in the solution, washing with
deionized water in between each immersion is done.

The growth mechanism consists of three main phases. First, the compound’s most
strongly adsorbed ions which have been grown by the substrate while immersed in a
solution of one of its cationic precursors were specifically adsorbed. Then the excess
solution which still adheres to the substrate is water rinsed. And finally, chemical
reactions occur between the adsorbed cations and anions. Factors such as optimization
of precursor concentrations, pH of the solutions, adsorption, reaction and washing
times, etc. determine the quality of the thin films.

5.2. Ex-situ methods

When depositing ex-situ grown QDs, the size and the form of the
monodisperse QDs are adjusted by synthesizing using organic capping ligands. After
the production, the QDs are removed from the additional organic ligands. Next, they
are dissolved in an organic solvent and then connected the TiO2 electrodes. In order
to address the issue of not bonding between the layers of QDs and mesoporous TiO2,
mercapto-carboxylic acid is used as a bifunctional molecular linker. In the dipping
process of electrode in mercapto-carboxylic acid ligands, the change in surface of
TiO2 occurs. This process is known as the dip coating. This allows the carboxylic
acid groups to be bonded with TiO2 surface. Then this modified TiO2 electrode is
submerged in the QDs solution which allows the QDs to diffuse into the pores and the
binding the QDs with TiO2 surface is done by the mercapto groups using partial
ligand exchange.
Another method of depositing particles on TiO2 surface is the electrophoretic QD
deposition process.

6. Further development of QDSSCs

High performance QDSSCs are being developed with a significant progress in

the recent years. Increasing the efficiencies of light to electric power conversion have
been a main focus on those researches. Increase of efficiencies about 5-7 % have been
achieved by some researchers. When compared to DSSCs, this is a giant leap forward.
But in order to achieve such efficiencies while implementing them commercially,
further research and developments have to be done. There are some important areas
that need to be considered when developing the QDSSCs further. Those areas mainly
consist of materials and interfaces needed for QDSSCs.
 Main interfaces or the material of QDSSC

6.1.Sensitizer Materials
When it comes to the semiconductor sensitizer materials in QDSSCs, most widely
used materials are CdS and CdSe. That is due to the reasons such as their harvesting
ability sun’s spectrum’s several regions and their good charge separation properties.
This is the process of hole removal with the use of electron injection into wide band
gap oxide and redox electrolyte. Based on the numerous studies done in recent years,
the possibility of using sensitizer materials such as QD sensitizers have been
improved rapidly. It has resulted a rapid growth of QDSSC conversion related
efficiencies too. Those boost in performanes were done making canges to the
semiconductor materials such as CdS or CdSe structures.

6.2. Triple junction

When it comes to the triple junction, the mechanisms of charge transfer process
occurs between nanostructured TiO2, the sensitizing QDs, and the aqueous polysulfide
electrolyte. They produce complex interfaces which enables the charge transfer
processes which heavily affects the overall performance of QDSSCs. Charge injection
and recombination processes and modifying the photocurrent and photovoltage of the
solar cell are mainly impacted by the energy level distribution of the materials which
forms the triple junction. There are numerous ways to tune the band edges of TiO2
with regard to the redox electrolyte in QDSSCs, as they can in conventional DSSCs.
This is often done by the alteration of pH levels of the solution which finally result in
change of the surface environment of the TiO2, or modification of electrolyte by
injecting additives, or attaching molecular dipoles.

Recombination losses are also can be reduced in the triple junction. This is done by
the use of semiconductor quantum rods (QR). The semiconductor quantum rods are
used to replace the QD particles which are typically used at the TiO2/QDs/electrolyte
triple junction. By this method, the photogenerated charges are efficiently separated
by the rodlike particles which have a high aspect ratio. Because of that the holes
diffuse to one end of the particle while the electrons diffuse to the other.

6.3. Redox electrolyte

When it comes to the redox electrolyte, one of the primary problems in the field of
QDSSCs have been the creation of an effective electrolyte solution of rapidly
transferring electrons to regenerate oxidized QD sensitizers. Also this solution should
maintain a long term stability in usual working conditions. In ordinary DSSCs the I-
/I3- redox couple is used and it is well known for its good performance. But when it
used with the QDSSCs, the inorganic semiconductor QDs are heavily corroded by the
iodine. This results in deterioration of the photoactive electrode function rapidly. So
the polysulfide redox couple which is in aqueous solution is used instead. And by far
it has been the most favoured electrolyte for the cells of this types. The polysulfide
electrolyte usually results in high oxidized QD regeneration rates but it also has a low
cell Voc when compared to a standard DSSC. The energy difference between the
fermi level and the electrolyte redox potential is taken to determine the Voc of a
QDSSC. So the highest theoretical solar cell Voc which can be achieved is highly
restricted by the negative redox potentials by its intrinsic polysulfide characteristics.
So the current researches on developing new forms of liquid electrolytes have been to
overcome such restrictions. But this should be done retaining the stability of the QDs
as well as increasing the Voc by having a higher positive redox potential

6.4. Counter electrode

When focussing on the counter electrode, the best performance of QDSSCs can be get
by discharging electrons quickly at the counter electrode. As the polysulfide
electrolyte was used to improve the photoanode stability in liquid junction QDSSCs,
they also result in lower power conversion efficiencies when compared with DSSCs.
Also Pt is used as a counter electrode because of the highly catalytic behaviour over a
wide range of reactions regarding electrochemical processes, such as the reduction of
I-/I3- redox couple in DSSCs. But the problem with platinum counter electrodes is the
lower performance when they are used with polysulfied electrolyte. Because of such
problems, development of alternative counter electrodes have been a focus in may
researches. There have been researches on developing such counter electrode material
which can efficiently catalyze the polysulfied reaction process while also being able
to be stable in electrolyte solution. CoS, Cu2S are such counter electrodes which
discovered to be able to have a greater catalytic characteristics than platinum.

6.5. Other methods

Other than the above mentioned, the active layer thickness is also a parameter which
can impact the overall performance of a solar cell. In QD deposition, a photoanode
which is too thin will not be able to provide enough specific area for the process of
deposition. Also a photoanode which is too thick will not be able to transport
electrons effectively. The increase of the wide band gap semiconductor thin film
depth also result in the decrease of amount of deposited QDs. So when the thickness
rises of the thin film, the QD size will also grow. So the active layer thickness can be
optimized. Some experiments have demonstrated that a solar cell with optimum
thickness of 10 micrometers of TiO2 thin film have a highest efficiency of 3.26%.
Also a higher efficiency of 4.09% have been achieved in a porous ZnO nanostructure
CDS/CdSe QDSSC combined with CuS counter electrode by altering the duration of
the QD deposition.

7. Advantages and disadvantages of QDSSCs

As the QDSSCs still need to be optimized in order to have them available in

commercial use, they have many advantages and some disadvantages when using.

7.1. Advantages of QDSSCs

When considering about the advantages and benefits of using QDSSCs, they have a
good power to weight ratio which enables the miniaturization. They also have a
higher efficiencies and current studies suggest that they can be further optimized.
They also have a smaller mass and require less space compared to other cells, and
they are said to have a good adaptability. Because of their versatility, they can be used
in entire structures such as windows rather than only using as rooftops.

7.2. Disadvantages of QDSSCs

And the drawbacks of quantum dot solar cells as follows. The CdSe material which is
used in QDSSC are extremely toxic and hazardous in nature. So they need to be
handled with care and this may complicate things when QDSSCs are implemented in
residential structures. Another drawback is that they degrades faster in wet and UV
environments.

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