UNIT II - ENERGY CONVERSION MATERIALS

1. Production of metallurgical Grade Silicon

The starting material is pure sand, which is available in plenty on earth's crust. Sand
(SiO2) is heated with carbon in an electric furnace to reduce it according to the reaction:

SiO2 +2C-------------------- Si +2CO

The silicon thus obtained is of 99% purity and is called metallurgical grade silicon. This
has to be purified further to a very low level of impurity content to make it suitable for
use in devices.

2. Semiconductor Grade Silicon

The semiconductor grade silicon has only a fee parts per billion of impurities.
Starting from the metallurgical grade, it can be produced by the zone refining process.
The other common method is a chemical process. The metallurgical grade silicon is
dissolved in HCl :

Si + 3HCl ------------- SiHCl3 + H2

The product trichlorosilane (SiHCl3) is a liquid at room temperature. The fractional

distillation of this liquid removes chlorides of dopants and of other impurities, such as
iron and copper and also SiCl4. A mixture of the purified SiHCl3 and H2 is then
evaporated and passed through a reactor which contains "slim rods" of high purity
silicon. The gaseous mixture now undergoes the reverse reaction:

SiHCl3 + H2 ---------------Si + 3HCI

Solid silicon is deposited on the heated “slim rods”, which grow radially. Rods of
semiconductor-grade, polycrystalline silicon up to 200 mm in diameter and 2-3 m long
can be produced by this process

3. Single Crystal Growth:

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Single crystals of semiconductor grade silicon are grown either by the Czochralski (CZ)
method or by the float zone (FZ) method.
Semiconducting devices like diodes, transistors, solar cells, etc., are made of single crystals of
semiconductor. The crystals have to be perfect single crystals without any defects, the
crystals must be extremely pure. There should not be any impurities other than the one
deliberately added, such as donor and acceptor impurities. One of the standard methods of
growing single crystals of semiconductors is the czochralski technique. The method used for
purifying semiconductors is called the zone refining technique.

Czochralski Technique

The principle of this technique is the growth of crystal by a gradual layer-by –layer
condensation of the melt. The material is melted in a crucible and a small seed crystal is
immersed into the surface of the melt, such that only a small part of the crystal is inside the
me1t. The temperature gradient at the crystal-melt interface is critically maintained such that
at the melt, the temperature is just above the melting point and at the crystal it is just below
the melting point. The seed crystal is gradually pulled upwards maintaining a critical pulling
rate. The temperature at the crystal-melt interface is controlled by the temperature gradient
and the pulling rate of the crystal. As the crystal is pulled, the melt condenses on the crystal
and thus the crystal grows. The schematic diagram of the Czochralski apparatus is shown in
below fig.

The essential parts of the apparatus are:

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 (i) A crucible to hold the melt.
The crucibles are cylindrical shaped and are usually made of carbon. For
GaAs crystals, silica crucible are used.
(ii) Heated to heat the crucible.
The most commonly used heating method is resistance-heating or rf induction-heating.
For resistance heating SiC is used as the heating element
(iii) A seed crystal.
The seed crystal is cut from a previous crystal. When such a crystal is not available,
the growth can be initiated on a thin rod or wire. From the
crystal grown on the rod, a small seed crystal may be cut.
(iv) A crystal holder and a mechanism to raise and rotate the crystal.
(v) A sealed enclosure to maintain suitable atmosphere for crystal growth.

Procedure: Pure material is taken in the crucible and the temperature is raised just above the
melting point. The seed crystal is introduced into the melt by means of a crystal holder. A
small amount of seed material is initially dissolved. The temperature is then adjusted suitably
to promote the growth of the seed crystal and the crystal is gradually withdrawn maintaining
the crystal-melt interface near the surface of the melt. Initially the diameter of the crystal is
large and the crystal may not be perfect. The pulling rate is then increased to reduce the
diameter. This is called necking. At this stage a good single crystal will be formed and then
again by gradually reducing the pulling rate and simultaneously controlling the temperature,
the diameter of the crystal can be increased. The crystal is rotated as it is being pulled, to
promote stirring of the melt and to average out slight temperature gradients.
The atmosphere of crystal growth is controlled by enclosing the unit in an evacuated
chamber. This avoids contamination and oxidation. If necessary the chamber may be filled
with hydrogen or an inert gas such as nitrogen, at suitable pressures to maintain equilibrium
vapour pressure. For GaAs, arsenic atmosphere is used.
By this technique, large single crystals of about 15 cm diameter arid 10 cm length can be
grown. To grow p-type or n-type crystals, the impurities are added to the melt in suitable
proportions.

Zone Refining Technique

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 The zone refining technique is used for purification of semiconducting materials. The
principle used in this technique is that when a solid is partly melted, creating a solid-melt
interface, most of the impurities tend to diffuse towards the liquid phase.
A solid-melt interface is created by melting a small portion or a zone of the material (which
is in the form of a long rod) by means of a short induction heater. The molten zone is swept
from one end of the rod to the other. This causes the impurities to get collected at one end of
the rod, thus leaving the rest of the solid relatively purer. The zone refining apparatus is
schematically shown in below Fig.

The material is taken in the form of a long rod or in a long boat-like crucible. Several
heaters are arranged the length to create a number of moIten zones. The most commonly
used heating method is rf induction heating. The crucible is moved past the heater, making
the molten zones pass through the solid.
When a liquid-solid interface is created, at equilibrium, the impurity has a greater
concentration ill the liquid phase than in the solid phase. A parameter, called the distribution
coefficient is defined as

k = CS/CL

where Cs is the concentration of the impurity in the solid phase and CL is the con-
centration of the impurity in the liquid phase. The distribution coefficient is characteristic of
a given impurity in the solid. For most impurities, k is less than one (0.1-0.00 I). So, if the
molten zone is swept across the solid, the impurity atoms tend to concentrate in the liquid
zone as it passes through the solid. Several passes of the molten zone may be made across
the rod to get good purification. In practice, the solid is passed once through several heaters

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as shown in Fig. 8.6.
Zone refining technique will be more effective if the ratio of the width of the molten zone
to the length of the ' rod is less than 10 %. Purity levels of better than 99.9999% can be
achieved by this technique.
Zone melting: The principle of the zone melting can also be used to grow single crystals.
This is called Zone technique. In this technique, a seed crystal is inserted at the starting end
of the crucible containing a polycrystalline sample. A molten zone is created in the rod at a
distance farther from the end containing the seed. The zone is then backed upto the seed is
wetted; then the zone is slowly moved through the specimen to get a single crystal in the
shape of a rod.

Zone leveling: Zone melting can also be used to get uniform doping of impurities in
semiconducting crystals and the technique is called zone levelling. The crystal is first purified
by zone refining; then a large concentration of the desired impurity is introduced into the
molten zone. If the impurity concentration is large, and the zone is swept through, as many
impurity atoms are trapped during freezing as are removed by melting. This helps in getting a
uniform distribution of the impurities in the crystal.

Floating zone method: In this method the polycrystalline rod is held vertically between two
chucks and a single molten zone is passed from one end of the rod to the other by moving the
heater. The molten zone is held in position between the two solid portions by the surface
tension of the liquid. The advantage of this method is that no crucible is required and thus
crucible contamination is eliminated. Here the diameter of the rod has to be small, so that the
surface tension forces may hold the liquid in position.

SEMICONDUCTOR BASED
PHOTOELECTROCHEMICAL CELLS

1. SOLAR SPECTRUM

Solar energy, as received on the earth’s surface, represents a clean, non-poluting,

abundant and relatively “free” energy. The solar radiation ranges from 200-2000nm in the
electromagnetic spectrum with a distribution shown in Fig.1.1. About 45% of the spectral
energy is distributed in the visible region, about 52% in near IR, about 3% in UV region and
the rest in far IR regions. This spectral distribution of the solar radiation is modified due to

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atmospheric extinction and selective absorption by CO2, O3 and water vapour and scattering
due to clouds, dust and water droplets. Thus, solar radiation reaching the earth is either direct
or diffused depending on the path length and transparency of the atmosphere.

2. DEVICES FOR SOLAR ENERGY CONVERSION

There are various ways of harnessing solar energy. Among the systems converting solar
energy into electrical/chemical energy, the most important ones are:
(1) Photovoltaic cells (p-n junction and Schottky junction, which use solid state
junction),
(2) Photoelectrochemical cells (the Photo assisted electrolysis cells and liquid junction
solar cells) and]
(3) Photo galvanic cells (in which light is absorbed by dye molecules)
(4) Solar thermal
Since these devices are quantum converters, in which a photon is absorbed resulting in an
electron-hole pair or breaking of the chemical bond, these can use only the relatively high
energy photons and considerable portion of the IR radiation cannot be used. The photovoltaic
technology is well-established and very high efficiencies of the order of 26% (on a laboratory
scale) have been realized. In addition, several other techniques exist for the conversion of
solar energy into other forms of energy. (Table 1.1)

3. PHOTOELECTROCHEMICAL (PEC) CELLS

The semiconductor based photo electrochemical (PEC) cells form an important class
of the direct conversion systems. These cells can be classified into two types according to
their application. When the cell is used for the conversion of solar energy into electrical
energy, it is called the Liquid Junction Solar Cell (LJSC). In the second class of cells, namely
the Photoelectrosynthesis (PES) cells, solar energy is converted into chemical energy in the
form of fuels. The most attractive application of the latter class of cells is the Photoassisted
electrolysis is a valuable fuel and energy carrier. It is non-polluting, renewable, inexhaustible
and very flexible with respect to conversion to other forms of energy (like heat via
combustion or electricity via fuel cells). Also, the storage of hydrogen is much easier than the
storage of other forms of energy like heat or electricity. Finally, hydrogen is a valuable basic
chemical feedstock used in large quantities for NH3 synthesis and petroleum refining. The
major breakthrough in the study of Photoelectrochemistry came in the early 1970’s, when

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Fujishima and Honda (1972) demonstrated the potential application of Photoelectrochemical
systems for solar energy conversion and storage. Fujishima and Honda used an n-type TiO2
electrode for the photoelectrodecomposition of water.

4. ADVANTAGES AND DISADVANTAGES OF PHOTOELECTROCHEMICAL

(PEC) CELLS

Photoelectrochemical (PEC) cell is a device in which a photoactive semiconductor

material is in contact with an electrolyte (Fig. 1.2). Irradiation of the SC/electrolyte
junction with light of energy > Eg, the band gap of the semiconductor, produces electron-
hole pairs. The electron-hole pairs are spatially separated (due to the junction potential) to
drive oxidation and reduction reactions in the system.

The major advantages of PEC cells over photovoltaic cells are:

(i) Easy junction formation (mere dipping of the SC electrode in the electrolyte).

(ii) In-situ water electrolysis is possible.

(iii) Efficiencies of polycrystalline bulk and thin film electrodes are comparable to

those of single crystal electrodes.

(iv) Novel reaction products are possible and catalytic effects (Photocatalysis) can be

induced on the SC surfaces.

(v) Particulate systems can be used.

The major advantages of PEC cells is the photocorrosion of the semiconductors (esp.
conventional semiconductors like Si, GaAs, CdS etc.) in strong aqueous electrolytes.

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5.

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5. ENERGETICS OF THE SEMICONDUCTOR/ELECTROLYTE INTERFACE

The photoelectrochemical effect is based on the formation of a semiconductor/electrolyte

junction when a semiconductor is immersed in a suitable electrolyte. The junction is
characterized by a space charge layer (also called as the depletion layer) in the
semiconductor adjacent to the electrolyte. The space charge layer is formed due to the
equilibration of the chemical potentials of the SC and the electrolyte whenever they are
different initially. For semiconductors, the chemical potential is the Fermi level and for
the electrolyte it is the redox potential of the redox couple present in the electrolyte.

When the initial Fermi level of an n-type semiconductor is above the redox potential
of the electrolyte, equilibration of the chemical potentials occurs by the transfer of
electrons from the SC to the electrolyte. This results in a positive space charge layer in the
SC adjacent to the electrolyte (Fig. 1.3). Since the region is depleted of the majority
carriers, it is also called the depletion region or layer. As a result, the conduction and
valence bands in the SC are bent such that a potential barrier is developed which prevents
further transfer of majority carriers to the electrolyte.

For p-type semiconductors having the Fermi level below the redox potential of the
electrolyte, the inverse but analogous situation occurs.

The width of the space charge layer in the semiconductor depends on the carrier
concentration, dielectric constant of the SC. The typical widths vary from 100 A& to
several µm .

A charged layer also exists in the electrolyte – the well-known Helmholtz layer. This layer
consists of charged ions from the electrolyte adsorbed on the SC electrode. The width of
the Helmholtz layer is of the order of a few A& .

6. CLASSIFICATION OF PEC CELLS

A PEC cell consists of a semiconductor in contact with a transparent electrolyte. The

photosensitivity of the cell is mainly determined by the interband transitions of SC. When
light (photons) of energy hv ≥ Eg falls on the SC/electrolyte interface, electron-hole pairs
are produced and these electron-hole pairs are used to carry out electrochemical reactions.
The electric field of the depletion layer enables the effective spatial separation of the

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electron-hole pairs and thus, prevents their recombination. Depending on the nature of the
reactions occurring at the SC and counter electrodes. PEC cells can be classified into two
types.
If the electrochemical reaction at the SC electrode is exactly reversed at the counter
electrode, then the overall composition of the electrolyte remains unchanged and the net
result of the photoprocess is the flow of current in the external circuit. Such a cell, which
is analogous to the solid state photovoltaic cell, is called the Liquid Junction Solar Cell
(LJSC).
e.g., n-CdSe/Na2S+S+NaOH/Pt cell
At the anode: Sx2-+S2-+2h+ ---> Sx+12-
At the cathode: Sx+12-+2e- --- > Sx2-+S2-
If two different reactions occur at the two electrodes of the cell, then the result of the
photoprocess is the storage of energy in the form of chemical energy of the products. The
energy stored is the difference in free energy between the two products. This class of the
PEC cells is called the Photoelectrosynthetic (PES) cells. Photoassisted electrolysis (PAE)
cells fall under this category.
e.g., n-SrTiO3/NaOH/Pt
At the anode : 2OH- + 2h+ --- > 1/2O2 + H2O
-
At the cathode: 2H2O + 2e --- > H2 + 2OH-

Net reaction : H2O --- > H2 + H2O2

Which is nothing but electrolysis of water.

If the energetic are favorable, it is possible to electrolyse water without applied bias, as
has been demonstrated in the case of SrTiO3 (Wrighton et al, 1976a; Mavroides et al,
1976) and Zn2TiO4 (Matsumoto et al, 1986).

7. LIQUID JUNCTION SOLAR CELLS (LJSC)

The simplest LJSC consists of two electrodes (one of them a SC and the other a metal)
dipped in an electrolyte containing a redox couple. Both the electrodes must be inert, i.e.,
the electrode material itself should not take part in the electrochemical reactions. One of
the important requirements for the operation of an LJSC is the presence of depletion layer
at the surface of the SC electrode Fig.1.12 (a). For this, the initial Fermi level of the SC
should be above (in the case of n-type semiconductors) the Eredox.

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76
The non-equilibrium electrons in the valence band produced by illumination with light of
energy hv ≥ Eg are spatially separated by the field in depletion layer (Fig.1.12 (b)). The
minority carriers (h+ in the n-type SC’s) are transferred to the surface where they are used
up for oxidation and the electrons are transferred to the surface where they are used up for
reduction and the electrons are transferred to the bulk, then via the external circuit to the
counter electrode, where they are used up for the reverse reaction (reaction). Thus, the
main difference between a PEC cell and the photovoltaic cell is that in the former the
photogenerated carriers transfer the stored energy from light to chemical species in the
solution whereas in the later, there is no such process.

LJSC’s with p-type SC’s function in a similar fashion. In this case, the condition for
formation of the depletion layer becomes Eredox > EF.SC should be below Eredox initially).
LJSC’s with two Sc electrodes (one of them being n-type and the other p-type) are also
known. In this case,
Voc(max)= E F ( n ) − E F ( p )

For efficient solar energy conversion, the requirements for the electrode materials are:

(1) Band gap should be optimum (see section on efficiency considerations).

(2) The doping level should be optimum so that W> α −1 (W α 1 / N D or1 / N A ) . This is
necessary for good spatial separation of the photogenerated carriers and hence, high
quantum efficiency.
(3) Large values of α . This is usually found for direct band gap SC’s.

The following are the requirements for the redox couple:

(i) The electrolyte should have a value of Eredox so as to give a large value of
E redox − EF ,

(ii) Eredox should be in such a position that the electrode decomposition reactions are
not kinetically favoured,
(iii) The reactions at the two electrodes should be perfectly reversible,
(iv) Solution should have adequate transparency
(v) There should be low ohmic resistance (in order to minimise the internal resistance
of the cell).

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 PEC cells used for water electrolysis consist of a SC electrode in contact with an
electrolyte which contains two redox couples, namely, H+/H2 and O2/H2O. the energetics
of such cells is shown in Fig.1.13 (for an n-type SC).

Since there are two redox couples present, the electrochemical potential can be anywhere
depending upon the initial relative concentration of H2 and O2 in the electrolyte. In (a), the
initial electrochemical potential is arbitrarily drawn just above the O2/H2O redox level. In
the dark (b), the Fermi level of the SC equilibrates with the electrochemical potential of
the electrolyte, producing a band bending.

Upon illumination, the Fermi level of the SC rises towards Vfb, producing a photovoltage,
Vph, Vph can be measured between the SC and the counter electrodes. However, the value
of Vph depends upon the initial Fermi level of the metal counter electrode which in turn
depends on the initial concentrations of H2 and O2 in the electrolyte.
Summarizing, apart from electrode stability, the essential requirements for achieving
photoelectolysis of water are:
(i) The width of the band gap of the SC should exceed the difference between the
electrochemical potentials for the hydrogen and oxygen electrode reactions in
water
(1.23 eV).

ii) The flat band potential for an n-type semiconductor should be more negative than the
hydrogen evolution potential (or, for a p-type semiconductor should be more positive than the
oxygen evolution potential). This is essential for photoelectrolysis without any external bias.

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79
Semiconductor electrodes

• Oxidic semiconductors (OS) such as TiO2, ZrO2, etc. were widely used as electrodes for
photoelectrochemical (PEC) conversion of solar energy, as photocatalysts for
decomposition of toxic pollutants and for preparation of the practically important
catalysts during the last 25 years.

• To improve photochemical properties of the OS at λ. * 400 nm, doping of the OS matrix

with transition metal ions was usually applied.

• It should be mentioned that influence of various metal dopants on the OS properties is

rather well known, whereas peculiarities of their structure are studied poorly.

Structure and Photoelectrochemical Properties of the Doped Polycrystalline TiO2

• The samples of the ceramic polycrystalline TiO2 doped electrodes have been prepared by
elaborate mixing the precise amounts of specially purified TiO2, V2O5, Cr2O3 or Nb2O5
powders, pressed into bricks and heated in air at 1200 °C during 2 h in inert atmosphere
(He).

• Then the stuffs were grinded and treated at 1200 °C during 2 h in inert atmosphere.

• Samples of such a set (V-I) contained in their matrix the uncontrolled amount of oxygen
vacancies.

• The samples of the second set V-2 were additionally treated at 900 0C in air during 2 h to
obviate these vacancies.

• The X -ray-phase analysis showed that all mixtures had the rutile structure.

• The bricks of the modified TiO2 were cut to plates with thickness of 1.0 mm, both faces
were polished.
• The back side was covered by In or Cu using the vacuum-deposition technique, then the
ohmic contact was made.

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• Fig.l presents the photocurrent spectra of poly crystalline Ti1-xVxO2 electrodes at different
x values.

• Similar ones have been obtained for Ti1-xCrxO2 samples.

• Although there is a strong increase of the visible light absorption at x > 0.01. One can
observe tenfold drop of the photocurrent with increasing of x (Fig.2).
• For better understanding the causes of this drop the spatial organization of the doped OS
on a molecular level had been studied.

PHOTOCONDUCTIVE EFFECT

Figure 1 is a schematic diagram of a CdS cell and its operation circuit. An electrode is set at
each end of the photoconductor. In darkness, the photoconductor resistance is very high, and
when a voltage is applied the ammeter shows only a small dark current. This is the CdS
photoconductor's characteristic thermal equilibrium current. When light is incident on this
photoconductor a current (I) flows. Figure 2 shows the current that flows when the amount of
light is increased. Here are the basic principles of the photoconductive effect.

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CONSTRUCTION CHARACTERISTICS OF CDS AND CDSE CELLS
Photosensitive devices can be divided into photovoltaic devices and photo emissive
devices. CdS cells are a type of photoconductive device. They are semiconductor sensors that
utilize the photoconductive effect in which light entering the photoconductive surface reduces
the resistance. A voltage is applied to both ends of a CdS cell and the change in resistance due
to light is output as a current change signal. Despite of small size, the output current per
photoconductive surface area is large enough to drive relays directly. For this reason, CdS
cells are used in a wide variety of fields. Here we will explain briefly the basic operating
principles, fabrication and structure of CdS cells.

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This l/d is an important factor in designing the electrode configuration. In other words
the shorter distance between the electrodes and the greater the electrode length, the
higher the sensitivity and the lower the cell resistance. Thus, the electrode patterns for
high-sensitivity CdS cells consist of many zig-zags.

STRUCTURE

The manufacturing process of the photoconductive layer into the sintered type, single
crystal type and evaporated type can divide CdS cells. Of these different types the sintered
type offers high sensitivity areas, a large mass production effect and relatively superior
production profitability. so AGI uses the sintering film fabrication method.
Here is the process for making sintered CdS cells. Impurities and a fusing agent for
encouraging crystal growth are added to highly pure CdS crystal power and this mixture is
dissolved in water. The resulting solution is applied to CdS ceramic substrate and dried, and
then it is sintered in a high-temperature oven to form multiple crystals. In this way, a thick
layer with the photoconductive effect is formed.
Then, lead terminals are introduced to the CdS substrate and the CdS is packaged
(Figure 4 and photo I shows an example of the structure of a plastic-coated CdS cell.)

CHARACTERISTICS

In the selection of a suitable CdS cell, the characteristics required by the functions of
the circuit in which the CdS cell is to be used are important; in general, there are analog uses
such as light measurement and digital uses such as on-off switching.
Use in digital circuits such as switching requires a fast response and a high ratio between
illuminated resistance and daIk resistance. For illumination and exposure meter and other
devices that measure brightness, the sensitivity, the slope of the
resistance vs. illuminant (gamma), and the spectral response characteristic are important
Therefore, understanding the various characteristics of CdS cells presented below is
important for selecting the night CdS cell for your application.

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SENSITIVITY
i Spectral Response Characteristic
The relative Sensitivity of a CdS cell is dependent on the wavelength of the incident
light. The sensitivity as a function of wavelength is called the spectral response
characteristic. Fundamentally, the maximum sensitivity wavelength (or peak wavelength) for
CdS cell is 515 nm, but by controlling the composition ratio of CdS to CdSe, the maximum
sensitively can be optimized at a wavelength between 515 and 730nm. So, photoconductive
cells with spectral response close to that of the human eye are available. Figure 6 shows
these relationships. In general, CdS Cd (SiDSe), and CdSe cells are all often called i§CdS
cell i. This catalog also uses this terminology.
By using a CdS cell with a spectral response similar to the human eye, it can be widely and
easily used in applications as sensors substituting for the human eye.

Dye sentisized solar cells

General Operating Principles
• Conventional solar cells convert light into electricity by exploiting the photovoltaic effect
that exists at semiconductor junctions. They are thus closely related to transistors and
integrated circuits.
• The semiconductor performs two processes simultaneously: absorption of light, and the
separation of the electric charges ("electrons" and "holes") which are formed as a
consequence of that absorption.

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• However, to avoid the premature recombination of electrons and holes, the
semiconductors employed must be highly pure and defect-free.
• The fabrication of this type of cell presents numerous difficulties, preventing the use of
such devices for electricity production on an industrial scale.

• In contrast, the dye sensitized solar cells work on a different principle, whereby the
processes of light absorption and charge separation are differentiated. Due to their simple
construction, the cells offer hope of a significant reduction in the cost of solar electricity

• Light absorption is performed by a monolayer of dye (S) adsorbed chemically at the

semiconductor surface.

• After having been excited (S*) by a photon of light, the dye - usually a transition metal
complex whose molecular properties are specifically engineered for the task - is able to
transfer an electron to the semiconductor (TiO2) (the process of "injection").

• The electric field inside the bulk material allows extraction of the electron.

• Positive charge is transferred from the dye (S+) to a redox mediator ("interception")
present in the solution with which the cell is filled, and then to the counter electrode.

• Through this last electron transfer, in which the mediator is returned to its reduced state,
the circuit is closed.

• The theoretical maximum voltage that such a device could deliver corresponds to the
difference between the redox potential of the mediator and the Fermi level of the
semiconductor.

• The maximal voltage corresponds to the difference between the redox potential of the
mediator and the Fermi level of the semiconductor.

• Figure 1 presents a cartoon of the make-up of the present generation of dye-sensitized

photoelectrochemical cells based on nanocrystalline films of TiO2.

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Description of Dye sensitized Solar cell
• The solar cell consists of two conducting glass electrodes in a sandwich configuration
with a redox electrolyte separating the two.

• On one of these electrodes a few micron-thick layer of TiO2 is deposited using a colloidal
preparation of monodispersed particles of TiO2.

• The compact layer is porous with a high surface area allowing monomolecular
distribution of dye molecules.

• After appropriate heat treatment to reduce the resistivity of the film, the electrode with the
oxide layer is immersed in the dye solution of interest (typically 2xl0 -4M in alcohol) for
several hours.

• The porous oxide layer acts like a sponge and there is very efficient uptake of the dye,
leading to intense coloration of the film.

• Molar absorbances of 3 and above are readily obtained within the micron-thick layer with
a number of Ru-polypyridyl complexes.

• The dye-coated electrode is then put together with another conducting glass electrode and
the intervening space is filled with an organic electrolyte (generally a nitrile) containing a
redox electrolyte (I-E/EI3-).

• A small amount of Pt (5-10 µglcm2) is deposited to the counter-electrode to catalyze the

cathodic reduction of triiodide to iodide.

• After making provisions for electrical contact with the two electrodes, the assembly is
sealed.

• The absorption of light by a monolayer of dye is always destined to be weak.

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• A respectable photovoltaic efficiency cannot therefore be obtained by the use of a flat
semiconductor surface but rather by use of a porous, nanostructured film of very high
surface roughness.

• When light 'penetrates the photosensitized, semiconductor "sponge", it crosses hundreds

of adsorbed dye monolayers.

• The nanocrystalline structure equally allows a certain spreading of the radiation.

• The end result is a greater absorption of light and its efficient conversion into electricity.

• Despite the heterogeneous nature of the semiconducting material, the diffusion of

electrons in the bulk matter towards the supporting conductor occurs with almost no
energy loss.

• The recombination between the electron which is injected into the conduction band of the
semiconductor, and the hole that remains on the oxidized dye is effectively very slow,
compared to the reduction of the latter by the mediator in solution.

• Furthermore, electron-hole recombination in the semiconductor which seriously affects

the efficiency of classic photovoltaic cells does not occur in this case, due to the fact that
there is no corresponding hole in the valence band for the electron in the conduction band.

• As a result, the efficiency of the cell is not impaired by weak illumination, e.g. under a
cloudy sky, in contrast to what happens with classical systems.

Assembly of the Cell

• Adsorption of the photosensitizer onto nano- structured TiO2 film is performed by simple
immersion in a dye solution.
• The counter electrode is then deposited facing the photoanode and separated by a thin
spacer.
• The gap between the electrodes is then filled with a low-volatility electrolyte (such as a
molten salt) containing the redox mediator.

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• To date, the mediator having given the best efficiency is the iodide-triiodide couple
(I- / I-3).
• The construction is completed by hermetic sealing of the whole assembly.
• No other complicated procedures are necessary and production costs are thus minimized.

The Counter-Electrode

• The counter-electrode is composed of glass covered with a conducting oxide layer.

• A tiny amount of platinum (5-10 mg cm2) is deposited at the surface in order to catalyze
the reduction of mediator (I3 + 2e- - -->3I-)

• A new procedure for platinization developed in our laboratory results in a surface

possessing a remarkable electrocatalytic activity unaffected by the anodic corrosion from
which conventional galvanostatically-deposited and sputtered surfaces suffer.

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