™Unit II - Energy Conversion Materials

™Photovoltaics: Principle of photovoltaics – materials for

photovoltaic cells- Silicon – band structure – various forms of
silicon: single crystal – films : CVD, MOCVD – alternate
photovoltaic materials : silicon substitutes – efficiency in energy
conversion : chemistry involved.

™Photoelectrochemical cells (PEC): Liquid junction solar

cells; Photo assisted electrochemical cells - Phenomenon at
semiconductor-electrolyte interface.

™Semiconductor Electrodes & devices: Compound

semiconductors – CdS, CdSe – Electronic properties (band
gap). Dye sensitized solar cells (Gratzel cells)
1
Energy Conversion Materials
 Important
• In India….. Energy
+
• Coal – 51 % (92 billion metric tons of coal CO 2
deposits are still available.)
CO 2
• Anthracite is a soft coal but very efficient.
CO 2
• Oil – 36 % (24 billion barrels of oil is being
consumed in the world/ year) CO 2

• Gas – 9 % CO 2

• Hydrothermal – 2 % CO 2 CO 2

• Nuclear – 2 %

Positive Carbon Approach

 Other sources??
• Hydrogen fuel
• Solar cells – Negative carbon approach
• Biofuels – Neutral carbon approach
• e.g. Ethanol is getting produced.
 *Butanol – is just like petrol….
Can we make this easily?

• Cellulose Butanol!!!!???
(Food) Is this possible?
 Solar cells
• Portugal – 62 MWp (out put)
with 2520 solar panels in 320 acres.
• Where is the place for efficient solar
conversion?
Ans: Deserts…..
Satellites, Highways

• SOFC
The solar spectrum

oAbout 46% of the
spectral energy
is distributed in
the visible region
oAbout 49% in
near IR 

oAbout 3% in UV
region and rest (2%)   
in far IR region

7
oPetroleum based fuels will be available for next 50 yr only!
oSolar Based energy/alternate fuels: Huge and endless
oBecause
o Abundant
o Non-polluting
o Free of cost
o Clean

8
 Solar energy conversion devices
Methods of tapping solar energy
A. Photosynthesis B. Water heaters C. Photovoltaic cells D. Chemical routes
Plants Flat plate, tube p/n Si, Si, GaAs
(Visible light ) (IR radiation) (Visible light)
η = 2-4% η = 12-26%

™D2: PEC cells

™D1: Biomimetism
™ Mimicking
™ Photosynthesis
™ via chemicals
™b.
a. LJSC Photoelectrosynthesis
™ (PES) cells
™ (i) Sc/Elect/M ™(i) Photoassisted
™ η= 13-14% ™ electrolysis cells
™ η= 13.3%
™ (ii) Photogalvanic
™(ii) Photoassisted
™ electrosynthesis
cells
™ M/Elect/M ™ cells
™ η= 0.01% ™ eg. CO2 CH3OH
™
™
N2 NH39
 ™Photovoltaics &
™Photoelectrochemical cells (PEC) 10
 Terminology
o In  semiconductor  physics,  the depletion  region,  also 
called depletion layer, depletion zone, junction region or 
the space charge region, is an insulating region within a 
conductive,  doped  semiconductor  material  where  the 
mobile charge carriers have diffused away, or have been 
forced away by an electric field. 

o The  only  elements  left  in  the  depletion  region  are 

ionized donor or acceptor impurities.
o The Fermi level is an energy pertaining to electrons in a 
semiconductor. 

11
12
13
™Introduction to depletion layer pn junction:
•If one side of crystal pure semiconductor Si(silicon) or
Ge(Germanium) is doped with acceptor impurity atoms and
the other side is doped with donor impurity atoms, a PN
junction is formed. P region has high concentration of holes
and N region contains large number of electrons.

•In this region, on the left side of the junction, the acceptor
atoms become negative ions and on the right side of the
junction, the donor atoms become positive ions.

•The potential barrier is approximately 0.7V for a silicon PN

junction and 0.3V for germanium PN junction. 14
 Photovoltaic cells 
™ A  solar  cell  is  a  device  that  converts  the  energy  of  sunlight 
directly into electricity by the photovoltaic effect. 
™ The  photovoltaic  effect  involves  creation  of  a  voltage  (or  a 
corresponding electric current) in a material upon exposure 
to electro‐magnetic radiation. 
™ Though  the  photovoltaic  effect is  directly  related  to  the 
photoelectric effect, the two processes are different.
™ In  the  photoelectric  effect  electrons  are  ejected  from  a 
material's  surface  upon  exposure  to  radiation  of  sufficient 
energy. 

15
•System converts light energy to electricity

•Applications in Aerospace & Satellite etc

16
 Demerits of Conventional Solar Cells
™ In the case of silicon, the majority of visible light from red to violet has
enough energy for photo excitation. Unfortunately this also means that the
higher energy photons, at the blue and violet end of the spectrum, have
more than enough energy to cross the band gap; although some of this
extra energy is transferred into the electrons, the vast majority of it is
wasted as heat.
™ Another issue is that in order to have a reasonable chance of capturing
a photon in the n-type layer it has to be fairly thick. This also increases the
chance that a freshly-ejected electron will meet up with a previously-
created hole in the material before reaching the p-n junction.
™By far the biggest problem with the conventional approach is cost; solar
cells require a relatively thick layer of doped silicon in order to have
reasonable photon capture rates, and silicon processing is expensive.
(Fabrication).
 Why Silicon
™Silicon is a very common element abundant
in nature 
(It is the main element in sand and quartz)

™ Silicon is considered as the most suitable
material for solar energy conversion
because of
1. Most abundance (~ 28% by mass) after oxygen
2. Optimum band gap of 1.23 eV at 300K
3. Cost effectiveness
4. Interestingly, silicon has a greater density in a
liquid state than a solid state.
18
19
20
Crystal Structure of Silicon
™The crystal structure, or atomic arrangement, of any material has a great
deal to do with its electrical properties. When analyzing the physical
structure of any material, we can speak of its existing in a crystalline, a
polycrystalline or an amorphous form.

In its crystalline form, a material is characterized by an ordered array of component

atoms. This array is repetitive with displacement through the material sample.

Where a polycrystalline material is concerned, the object is composed of a

number of sub-sections, each of which is crystalline in form. These subsections,
however, are independently oriented so that at their interfaces the atomic order
and regularity undergo sharp discontinuities.

The final category, the amorphous material, displays no atomic regularity of

arrangement on any macroscopic scale.
™ Photovoltaic cells made from polycrystalline materials are less
expensive to construct per unit area than single crystal solar cells
(both in terms of finance and in terms of energy).

™However, they are less efficient and often more sensitive to changes
in ambient conditions-both undesirable attributes.
 Production of Silicon

1. Metallurgical Grade Silicon:
SiO2 +2C               Si +2CO

™ Sand (SiO2) is heated with carbon in an electric furnace 
to reduce it.

™ The  silicon  thus  obtained  is  99%  pure  and  is  called 
metallurgical grade silicon.

™ This is purified further to reduce levels of impurities to 
make it suitable for use in devices.

24
™An arc causes them
to melt at
approximately 1800°C.
™SiO2 + 2C ------------
Si + 2CO )
™The liquid silicon
collected at the bottom
of the crucible (melting
point 1415°C) can then
be drawn off. Its
purity is
approximately 98%.
This is called
metallurgic-grade
silicon (MG-Si) and a
large quantity is used in
the iron and
aluminium industries.
™As the energy consumed by this process is very high
More than 500,000
tonnes are
at 14 kWhkg, production takes place in areas of the
manufactured per year
world where excess hydroelectric power is available (e.g.
worldwide.
Noway, Canada).
25
2. Semiconductor Grade Silicon (by chemical method):
Si + 3HCl SiHCl3 + H2
™ The product trichlorosilane (SiHCl3) is liquid at room temperature. 
• Since trichlorosilane is a liquid at temperatures below 30°C it can easily 
be separated from hydrogen.

™ It  is  fractionally  distilled  to  remove  chlorides  of  dopants and  of  other 
impurities, such as iron and copper and also SiCl4.

SiHCl3 + H2 Si + 3HCl

™ A mixture of purified SiHCl3 and H2 is evaporated and passed through a 

reactor which  contains  "slim  rods"  of  high  purity  silicon  (200  mm 
diameter and 2‐3 m long rod can be produced).

™ Solid silicon is deposited on the heated “slim rods”. 
™ The impurity level is needed less than 10-10% 26
™Preparation of
Polycrystalline
Silicon

27
¾A thin silicon rod (in this case u-shaped) is electrically heated to a temperature of
approximately 1350°C. A mixture of hydrogen (which must also be high-purity) and
trichlorosilane is introduced into the reactor vessel. Trichlorosilane is reduced to
silicon on the hot surface of the silicon, which deposits itself on the rod surface.
™Thus, high-purity polycrystalline silicon is produced in a continuous process to rod
diameters up to 30 cm and rod lengths up to approximately 2 m.
Additional Information (for understanding and not for exam purpose)
More recently another process has been developed, based upon similar
chemical principles. In a type of fluidized-bed reactor, silicon is deposited on
the surface of fine silicon balls using silane created in situ. The silicon powder
manufactured in this manner with a particle size of some tenths of a millimetre
can be used either in the CZ pulling process or for the direct manufacture of
silicon foil.

28
29
™The puller is located within an enclosure flushed with inert gas. At the lower end
a single crystal seed is again melted onto the polycrystalline rod by induction heating.
After melting, a region of liquid silicon is propelled upwards by the vertical movement
of the induction coil whilst being rotated.
™When the silicon cools, it solidifies in single crystal form. The desired doping is
achieved by the addition of a suitable dopant in gaseous form (e.g. phosphine PH3 or
diborane B2H6) to the inert gas. One advantage of this process is the additional
cleaning of the crystal. Impurities (in particular metallic impurities) possess a very low
segregation coefficient), i.e. their solubility in liquid silicon is some orders of
magnitude higher than in solids. Thus these substances are largely carried with the
fluid zone and transported to the upper end of the crystal. This process makes it
possible - particularly with repeated pulling - to achieve very perfect crystals of high
purity and thus - if desired - high resistivity.

30
 ™2PH3 + 4O2 →P2O5 +3H2O
™Si + O2 → SiO2
™SiO2 + P2O5 → NaAl3PSiO8 (Phosphorous Silicate glass)

™POCl3 + SiO2 → NaAl3PSiO8 + Cl2

™Cl2 + Metal → volatile metal chloride

End of Additional Information (for understanding and not for exam

purpose)

31
 Single crystal growth of silicon  Czochralski Technique
™ Essential parts of the
™Sealed evacuated
™chamber
apparatus are:
™ A crucible to hold the
melt (made of C or Si
for GaAs)

™ Heater to heat the

crucible

™ A seed crystal

™ A crystal holder and a

mechanism to raise and
rotate the crystal and for
necking

™ A sealed enclosure to
maintain suitable
atmosphere for crystal
growth.
32
The principle of this technique is growth of single crystal by a gradual layer‐by‐
layer condensation of the melt.
Large single crystals of about 15 cm diameter and 10 cm length can
be grown.
2. Semiconductor Grade Silicon (by Zone refining technique):

™A parameter, called the distribution coefficient is defined as k = CS/CL

™For most impurities, k is less than one (0.1-0.001).

• 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.
34
 3. Thin-Film Deposition

Chemical Vapor Deposition

 What is CVD?
• Chemical Vapor Deposition is the formation of a non-volatile solid
film on a substrate by the reaction of vapor phase chemicals
(reactants) that contain the required constituents.

• The reactant gases are introducedinto a reaction chamber and are

decomposed and reacted at a heated surface to form the thin film.

• Deposited films range from metals tosemiconductors to insulators.

• Many different films can be deposited: elements and compounds,

crystalline, polycrystalline, and amorphous. Most films can be
deposited from several different precursor systems.

• High temperatures and low pressures are the most common process
conditions, but are not necessary.

• All CVD involves using an energy source to break reactant gases

into reactive species for deposition.
• In a typical CVD process, reactant gases (often diluted in a carrier
gas) at room temperature enter the reaction chamber.

• The gas mixture is heated as it approaches the deposition surface,

heated using radiation or placed upon a heated substrate.

• Depending on the process and operating conditions, the reactant

gases may undergo homogeneous chemical reactions in the vapor
phase before striking the surface.

• Near the surface thermal, momentum, and chemical concentration

boundary layers form as the gas stream heats, slows down due to
viscous drag, and the chemical composition changes.

• Heterogeneous reactions of the sourcegases or reactive intermediate

species (formed from homogeneous pyrolysis) occur at the deposition
surface forming the deposited material.

• Gaseous reaction by-products are ht en transported out of the reaction

chamber.
In every case, CVD processes must:

™provide a volatile precursor containing the constituents of the film

™ transport that precursor to the deposition surface

™encourage or avoid reactions in the gas phase

™encourage surface reactions that form the film

™and do it rapidly, reproducibly, and uniformly for industrial

applications.
 ™3.7.2 Chemical Vapor Deposition
(CVD)
Pressure sensor Resistance-heated furnace
Quartz tube
Trap
To exhaust
Si Wafers

Pump
Source
gases
Gas control
system
™CVD
 Chemical Vapor Deposition (CVD)

™Thin film is formed from gas phase components.

 ™Steps involved in a CVD process (schematic)

1. Transport of reactants by forced convection to the deposition region.

2. Transport of reactants by diffusion from the main gas stream through

the boundary layer to the wafer surface.

3. Adsorption of reactants on the wafer surface.

4. Surface processes, including chemical decomposition or reaction,

surface migration to attachment sites, site incorporation, and other
surface reactions.

5. Desorption of byproducts from the surface.

6. Transport of byproducts by diffusion through the boundary layer and

back to the main gas stream.

7. Transport of byproducts by forced convection away from the

deposition region.
Advantages:
• high growth rates possible
• can deposit materials which are hard to evaporate
• good reproducibility
• can grow epitaxial films

Disadvantages:
• high temperatures
• complex processes
• toxic and corrosiveby-product gasses
 Metal-Organic Chemical Vapor Deposition
(MOCVD)
• Example reaction:
Ga(CH3)3 + AsH3 →→
(Trimethyl gallium gas) (Arsine gas)
3CH4 + GaAs
(Methane gas) (on the substrate)
• The reaction occurs in asealed container
(reactor)
• NOTE!! Arsine gas is highly toxic & highly flammable!
Trimethyl gallium gas is highly toxic!! Methane gas is highly
explosive!
 MOCVD

™Dopants are introduced in precisely controlled amounts!

™This technique allow crystals to be deposited on a substrate one

monolayer at a time with great precision.

™This technique is also very useful for artificial crystal structures such as
“superlattices” and “quantum wells”.

™ Useful for lab experiments & for mass production

™Some thin film solar cells made of other semiconductor materials,
i.e.
¾Cells made of amorphous silicon (a-Si).
¾Cells made of semiconducting compounds e.g. gallium-arsenide (GaAs)
and cadmium-telluride (CdTe).
¾Cells made of copper-indium-diselenide (CIS).

™Metal Insulator Semiconductor (MIS) Technology

‰ At 100-fold concentration of Sun an increase in efficiency of 20%

relatively is achieved.
‰In 1980 Khemthong et al. increased this value to over 20% (at 40 suns).
‰ In 1977 Burgess et al. introduced a cell with what was at the time a high
efficiency of 15% at 50-fold solar radiation.
48
 Cells made of amorphous silicon (a-Si) (Eg=1.7eV
¾ Amorphous materials - glass is a typical example - differ from crystalline
structures primarily because the strict periodicity of the lattice is not present.
¾Normal selection rules for crystal do not apply. In particular, the
absorption of light occurs directly.
¾ Amorphous silicon [a-Si] - a compound of silicon and hydrogen - has this
characteristic.
¾ In 1977 first solar cell made of a-Si had efficiency of 2% and now ~ 20%
¾The critical problem of a-Si solar cells is their stability (Disadvantage)
¾The most probable explanation is that the recombination of light
generated charge carriers causes weak silicon-hydrogen bonds to be
broken in the amorphous material, thus creating additional defects, which
lower the collective efficiency and increase serial resistance.
49
 ™Degradation affects fill factor and
short circuit current, but not open
circuit voltage

™TCO= Transparent conductive oxide

™ITO= Indium Tin Oxide

™Advantage: One decisive advantage of the a-Si cell is that

the necessary serial connection of cells can take place
50
simultaneously during manufacture.
 Gallium-Arsenide Solar Cells (Eg=1.42 eV)
¾The semiconductor material GaAs has won widespread approval in
Electronics after its discovery in 1950.
¾Current applications are mainly in the field of optoelectronics, such as
diodes and laser.
¾ Alo.85Gao.15As (Eg=1.9 eV) Efficiency >22%

Advantages: It promises an almost optimal adaptation to solar radiation.

Further advantages are:
‰ GaAs is also a direct semiconductor and therefore up to 90% of the
sunlight is absorbed in a film thickness of 2 µm.
‰The temperature dependency of efficiency in a GaAs solar cell is only one-
third of that of silicon due to the higher energy gap.
‰GaAs solar cells have a much lower sensitivity to cosmic radiation than do
Si solar cells.
‰ This binary semiconductor can be easily transformed into a ternary
semiconductor by the addition of elements from the third or fifth group of the
periodic table. This means that semiconductors with larger band gaps can be
produced, which can then act as a window layer, or with smaller band gaps
51
for tandem solar cells.
ƒThe highest efficiency yet of 25% under
AM1.5 conditions, or with the same cell,
29% at 100 suns
ƒ Using GaAs as substrate is highly costly.
ƒ Ge is considered, because thermal
expansion mismatch of only 0.27% and
therefore permits a relatively fault free
precipitation of GaAs.
ƒ Silicon would be very desirable as a
substrate material for reasons of
cost and better heat conductivity,
but has an expansion mismatch of
approximately 4%. 52
Disadvantages:
1)One is the very high price of the GaAs cell, if it has to be built on a GaAs
substrate.
2)The second is a problem with acceptability since Ga and As are toxic
substances.

53
 Cadmium-Telluride Solar Cells (Eg=1.45 eV)
ƒ CdTe is a direct semiconductor and therefore sunlight is totally absorbed
in a layer of a few µm thickness. This also means that recombination on
the surface must be prevented.
ƒ The best laboratory cells have achieved efficiencies of 10-14%.
¾ Solar cells made of this material possess high stability.
¾ The question of acceptability is just as critical as for GaAs, since
cadmium is poisonous and its hazardous nature both in production and in
accidents must be carefully considered.

54
 Copper-Indium-Diselenide Solar Cells (Eg= 1.0 eV)
¾ Chalcopyrite semiconductor, the copper-indium-diselenide (CuInS2) cell
has been the most highly acclaimed as early as 1978.
¾High efficiencies were being achieved for these thin film cells with no
degradation.
¾The CuInS2 layer itself is polycrystalline, so the influences of grain
boundaries and electronic states which exist in them strongly influence the
characteristics of photocurrent and open circuit voltage. In addition, low
defect densities are decisive for the very high efficiency of > 15%

Disadvantages:
ƒWith a band gap of approximately 1 eV, CuInS2 is somewhat unfavourable.
ƒIf In is completely replaced with Ga, i.e. the structure is CuGaS2 the band
gap achieved is approximately 1.7 eV. It is thus possible to achieve the
optimal band gap of 1.4 eV.

Note 1: Some researchers have tried to replace Sulphur by Selenium, but

not encouraging. CuInSe2
Note 2: other materials for cost reduction, energy saving, high efficiency
and high stability 55
 Photoelectrochemical cells
™Photoelectrochemical (PEC) cell is a device in which a 
photoactive  semiconductor  material  is  in  contact 
with an electrolyte . 
™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.

1
 Classification of Photoelectrochemical cells
™PEC cells are Classified into two types according to 
their application. 

1.  Liquid Junction Solar Cell (LJSC) –
This  cell  is  used  to  convert  solar  energy  into 
electrical energy

2. Photoelectrosynthesis (PES) cells –
In this class of cells, solar energy is converted into 
chemical energy in the form of fuels.

2
 Conditions for Efficient Solar Energy Conversion –
Electrodes 

™ The requirements for the electrode materials are:

(1) Band gap (Eg) should be optimum

(2) The doping level should be optimum, so that there will be a 
good  spatial  separation  of  the  photo‐generated  carriers 
and hence, high quantum efficiency.
(3) Should have large values of absorption co‐efficient (α). This 
is usually found for direct band gap SC’s.

3
 Conditions for Efficient Solar Energy Conversion – Redox
couple 
The following are the requirements for the redox couple:
(i)     The electrolyte should have a value of Eredox while Eredox‐EF = +ve
(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).

™Splitting water, or photoelectrolysis, is one form of artificial

photosynthesis that converts water into protons (and eventually
hydrogen) and oxygen using sunlight. 4
 Energetic of the Semiconductor / electrolyte interface
(phenomenon at SC-electrolyte interphase)

PEC effect is based on the formation of a SC/electrolyte interface junction

n-SC (majority of e-s carriers; holes are minority carriers)

Condition A: n-SC before contact with solution in dark

ECB ECB – conduction band energy

O EF – Fermi level (chem. Potential)
EF
E redox R energy (probability of ½ occupied level)
Eg
Energy (E)

O – Oxidant; R – Reductant (Redox)

EVB
Eg – Band gap energy
Bulk-SC Surface-SC EVB – Valance band energy
-Metal (SC)- - electrolyte SC- Semiconductor
+ redox-

(Note: n-Semiconductor (SC) is due excess conduction band e-s; extrinsic)

5
 Photoelectrochemical effect at  
semiconductor ‐ redox electrolyte interface.
a) On contact the Fermi level of the n‐type semiconductor equilibrates 
with that of the metal and with the redox couple of the electrolyte.

b)   After  charge  (electron)  transfer,  a  band  bending is  established  as  in 
the case of the previous solid‐state junctions, with establishment of 
the depletion zone.

c)    Under  light,  photoelectrons  enter  the  conduction  band;  the  band 
bending  is  reduced  and  a  photovoltage is  generated  between  the 
semiconductor Fermi level and the redox potential of the electrolyte 
‐ equivalent to the potential of the metal counter‐electrode. 

d) Minority carriers ‐ holes ‐ are then available for an oxidation reaction 

with  the  electrolyte  at  the  Semiconductor  photoanode.  A  reduction  
6
reaction takes place at the cathodic counter electrode.
 ™Major advantages of PEC cells over photovoltaic cells

™ Easy junction formation (mere dipping of the SC

electrode in the electrolyte).
™ In-situ water electrolysis is possible.
™ Efficiencies of polycrystalline bulk and thin film
electrodes are comparable to those of single crystal
electrodes.
™ Novel reaction products are possible and catalytic
effects (Photocatalysis) can be induced on the SC
surfaces.
™ Particulate systems can be used.
7
¾For semiconductors with large bandgaps (>2 eV), current flow is
dominated by the band that has an energy closest to the redox couple,
at least at potentials near equilibrium.
¾Significant current contributions from both bands are more likely for small
bandgap materials and at large applied potential biases.
¾ The net cathodic current in Figure 3a can result from electron transfer from
the conduction band to an oxidized molecule or by injection of a hole from the
molecule into the valence band.
¾ At more negative applied potentials for n-type semiconductors (positive
potentials for p-type), majority carriers accumulate at the surface and current
flow resembles processes observed at metal electrodes.
¾ When EF is positive of Em for n-type electrodes (negative of ECB for p-
type), conditions of extreme depletion or carrier inversion exist. Current
flow is usually irreproducible in these situations and likely to be dominated by
8
tunneling processes or band-edge movement.
¾ Anodic current for n-type materials since it is caused by valence band
holes that are driven to the interface by the field in the space charge
region. Cathodic photocurrents resulting from conduction band electrons
are observed at p-type semiconductors.

¾ When an SEI is illuminated with light that causes generation of minority

carriers, the populations of electrons and holes near the interface are
changed. This change is often represented by a flattening of the
semiconductor bands,

¾Quasi-Fermi level near the surface that more accurately reflects the
increased concentration of minority carriers. This quasi-Fermi level will be
closer to the valence band for n-type materials and closer to the
9
conduction band for p-type.
10
11
 ™Energetic of LJSC
™LJSC cell:
™n-SC/ electrolyte+Redox/ Metal

Counter electrode -
+
EC bulk -
B
O e-
EF
hv>E R
g

EV +
B
n-SC Electrolyte Metal
+Redox
-ASN- 12
Regenerative photoelectrochemical cells

13
 Mechanism of Liquid Junction Solar Cells
™ 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 electro‐ chemical 
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. 

™ For this, the initial Fermi level of the SC should be above (in 
the case of n‐type semiconductors) the Eredox.

14
 Working of  LJSC

™ The  non‐equilibrium  electrons  in  the  valence  band  are 

produced by illumination of light with energy hν ≥ Eg. 

™ 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 

™ 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 (reduction). 

15
PEC commercial unit
LJSC cell:

n-SC/ electrolyte+Redox/ Metal

+ -
n-CdS / S2- + S + NaOH / Pt

Anode: Sx2- + S2- + 2h+ ⎯→ Sx+12-

Cathode: Sx+12- + 2e- ⎯→ Sx2- + S2-

(*Note:
.Net change in the reaction is nil
.Sx is polymorphic form of sulphur
x = 7 or 8) 16
 ™Liquid Junction Solar Cell (LJSC)

Cell : n‐CdS / Na2S + S + NaOH / Pt

At the anode: 
Sx2‐ + S2‐ + 2h+ ‐‐‐> Sx+12‐
At the cathode: 
Sx+12‐ + 2e‐ ‐‐‐ > Sx2‐ + S2‐

Net reaction : Nil
17
Energetics of LJSC

18
Energetics of LJSC

19
 Condition B: n-SC after Condition C: n-SC after
contact with solution in dark contact with solution in light

∆φ
e-s
EC EC bulk -
B O B O
EF EredoxR EF R
Eg hv>E
g surface

EVB EVB +
Solution hole Solution
-ASN- -ASN-

Condition C: p-SC after EC - surface Note: p-SC due to

O valence holes
contact with solution in light B
R
∆φ = potential of the surface hv>E In p-SC, holes are
with respect to bulk EF the major carriers;
g
EVB e-s minor carriers
+
Towards Bulk p-SC Solution
20
-ASN-
 ™Photo‐assisted electrolysis (PAE) cells
™SrTiO3 (Wrighton et al, 1976; Mavroides et al, 1976) and
™Zn2TiO4 (Matsumoto et al, 1986)

Cell : n‐SrTiO3 / NaOH / Pt

At the anode : (O2/H2O system)

2OH‐ + 2h+ ½ O2 + H2O

At the cathode: (H+/H2 system)

2H2O (= 2OH‐ + 2H+) + 2e‐ H2 +  2OH‐

Net reaction :    H2O          H2 + ½ O2
21
Photochemical cells used for the photoassisted electrolysis (PAE) 
of H2O

22
Energetics of PAE Cell
Energy band 
representation of the 
operation of Photo 
Assisted Electrolysis
(PAE) cell
(a) in dark, after  
equilibration
(b)  under illumination 
without applied bias
(c)  under illumination
with applied bias to 
effect electrolysis
23
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.

24
 Dye Sensitization ‐ Grätzel cell
1. Sunlight energy (photon of light) passes through the titanium dioxide layer 
and  strikes  electrons  within  the  adsorbed  dye  molecules.  Electrons  gain 
this energy and become excited because they have the extra energy. 
2. The  excited  electrons  escape  the  dye  molecules  and  become  free 
electrons.  These  free  electrons  move  through  the  titanium  dioxide  and 
accumulate at the ‐ve plate (dyed TiO2 plate). 
3. The  free  electrons  then  start  to  flow  through  the  external  circuit  to 
produce an electric current. This electric current powers the light bulb. 
4.    To  complete  the  circuit,  the  dye  is  regenerated.  The  dye  regains  its  lost 
electrons from the iodide electrolyte. Iodide (I‐) ions are oxidised (loss of 2 
electrons) to  tri‐iodide (I3‐). The  free  electrons  on the  graphite plate  then 
reduce  the  tri‐iodide  molecules  back  to  their  iodide  state.  The  dye 
molecules are then ready for the next excitation/oxid/red cycle. 25
 Photoelectrochemical processes in a dye‐sensitized solar
cell.
Conducting
glass TiO2 Dye Electrolyte Cathode

Injection S*
-0.5
Maximum
Voltage
0 hν
E vs
NHE Red Mediator Ox
(V ) 0.5
Diffusion

1.0
+
S S
/
- -
e e

™In  a  molecular  system  such  as  the  dye,  the  gap  between  the  highest 
occupied  molecular  orbital  and  the  lowest  unoccupied  level  (HOMO‐
LUMO gap) is analogous to the conduction band ‐ valence band gap in a 
semiconductor. 26
 The Grätzel Cell 

Upper Plate :
Dye coated TiO2
Plate (-Ve)

Lower Plate :
Graphite coated
conductor (+Ve)

By Hermetic sealing

Prepared Grätzel cell

27
28
Description of the Dye Sensitized Solar Cell:

Anode (conducting glass/TiO2/S //adsorbed + electrolyte-Redox // Metal (cathode,

Pt)
Under light (hv): (Energetic/ electron-transfer mechanism)

hv TiO2
So S* S+ + TiO2 (e-) (electron-transfer/injection step) on Anode

Red/Ox
S+ So (Regeneration Step) on Cathode

Thus e- flow through the circuit under the illumination → electrical energy
from solar energy

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

the cathodic reduction of triiodide to iodide
29
 Construction of Grätzel cell
o In Grätzel cell a range of organic dyes are used.
o Examples: ruthenium-Polypyridine, Indoline dye & metal free organic dye.
o These dyes are extractable from simple foods such as hibiscus tea, tinned
summer fruits, blackberries.

Construction:
o Two transparent glass plates are perforated on one side with a transparent
thin layer of a conducting material.
o Onto the conducting sides, one plate is coated with graphite and the other
plate is coated with titanium dioxide (TiO2).
o A dye is then adsorbed onto the TiO2 layer by immersing the plate into a
dye solution of 10-4M in alcohol for 10 min. (approx.)
o The plates are then carefully sandwiched together and secured using a
paper clip.
o To complete the cell a drop of iodide electrolyte is added between the
plates.
o Figure shows a Grätzel cell prepared from hibiscus tea.
o The upper plate is the TiO2 plate, dyed with hibiscus tea and the lower plate
is coated with graphite.
30
 Working Principle of Grätzel Cell
o Sunlight energy passes through the titanium
dioxide layer and strikes electrons within the
adsorbed dye molecules. 
o Electrons gain this energy and become excited 
o The excited electrons escape from the dye 
molecules to become free electrons. 
o These free electrons move through theTiO2 and 
accumulate at the –ve plate (dyed TiO2 plate). 
o The free electrons then start to flow through the 
external circuit to produce an electric current. 
o This electric current powers the light bulb. 
o To complete the circuit, the dye is regenerated. 
o The dye regains its lost electrons from the iodide
electrolyte. 
o Iodide (I‐) ions are oxidised to tri‐iodide (I3‐). 
o The free electrons at the graphite plate then reduce
the tri‐iodide molecules back to their  iodide state. 
o The dye molecules are then ready for the next
excitation/oxidation/reduction cycle. 
31
™Ru 2,2-bipyridyle-4,4’-dicarboxylate and

cis-dithiocyanotobis(2,2’-bipyridyl-4,4’-dicarboxylate)-Ru(II) were

used and these can absorb solar light up to 650nm (1.9 eV) and 775

nm (1.6 eV), respectively.

 Oxidic Semiconductor (OS) electrodes
™ Oxidic semiconductors (OS) such as TiO2, ZrO2, etc. are being widely used 
as electrodes for
a) photoelectrochemical (PEC) conversion of solar energy
b) as photocatalysts for decomposition of toxic pollutants 
and 
c) for preparation of the practically important catalysts
for 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 peculiarity of their structure 
are studied poorly.

33
Photoelectrochemical properties of doped TiO2

™Fig. 1 presents the photocurrent 
Spectra of polycrystalline 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. there is a  tenfold (Fig. 1)
drop of the photocurrent with 
increasing of x (Fig. 2).
™For better understanding of the 
causes of this drop the Spatial 
organization of the doped OS on 
a molecular level has been studied.                          
34
35
36
UV-Vis absorbance response of V2O5 doped TiO2 (Ti1-
xVxO2)
10 UV Visible

Photo/Intensity x= 0.005 (before doping)

x = 0.05 M of V2O5 in
TiO2
(after doping/
Shift to visible region)

λ/nm
200 300 400 500 -ASN-

Doping of V2O5 shift the absorption band from UV to Visible

region.

Similar observation with SrTiO3 system also (dopent = Sr) .

37
 Photoconductivity
™ In  certain  materials,  there  is  an  increase  in  electrical 
conductivity  which  results  from  increase  in  the  number  of  free 
charge carriers generated when photons are absorbed. 
™ Note: The  photons  must  have  quantum  energy  sufficient  to 
overcome the band‐gap in the material in question.
™ Electrode configuration depends on (I/d α sensitivity)
¾l (length of electrode)/d (distance between electrodes)
¾High l/d value will be if l is bigger and d is shorter 
¾Leads to lower cell resistance and higher sensitivity

38
 Photoconductive Effect
CdS or CdSe based Systems A. Photoconductive effect device (in Dark)

The SC-materials act as a strong electronic-

conductor under photo-light illumination CdS or CdSe
0 conductiving holder
At a fixed voltage applied (bias) to both
ends of a CdS (Cadmium sulphide) or CdSe Ammeter (A) Biased potential (V)
(Cadmium selenide) under illuminated
condition, effective current transfer within B. Photoconductive effect device (In light)

the circuit was observed (Figure B). Solar light (hv)

i.e. Semiconductor (SC) Conductor

CdS or CdSe
(With reduced resistance) conductiving holder

Ammeter Biased potential (V)

CdS photoconductor's characteristic ASN

thermal equilibrium current 39

 Basic principles of the photoconductive effect
™ Directly  beneath  the  conduction  band  of  the  CdS crystal  is  a  donor  level 
and  there  is  an  acceptor  level  above  the  valence  band.  In  darkness,  the 
electrons  and  holes  in  each  level  are  almost  crammed  in  place  in the 
crystal and the photoconductor is at high resistance.
™ When light illuminates the CdS crystal and is absorbed by the crystal, the 
electrons  in  the  valence  band  are  excited  into  the  conduction  band.  This 
creates  pairs  of  free  holes  in  the  valence  band  and  free  electrons  in  the 
conduction band, increasing the conductance.
™ Furthermore, near the valence band is a separate acceptor level that can 
capture free electrons only with difficulty, but captures  free holes  easily. 
This lowers the recombination probability of the electrons and holes and 
increases  the  number  for  electrons  in  the  conduction  band  for  N‐type 
conductance.

40
 Cadmium Sulphide (CdS) Cell
™The processes of making the photoconductive layer 
a) sintered type   
b) single crystal type
c) evaporated type 

™ Sintered type offers high sensitivity, a large mass production effect
and relatively superior production profitability. 
™ Impurities and a fusing agent for encouraging crystal growth are
added to highly pure CdS crystal powder and this mixture is
dissolved in water. 
™ The resulting solution is applied to CdS ceramic substrate and
dried.
™ Then it is sintered in a high‐temperature oven to form multiple
crystals. 
™ Thus, a thick layer with the photoconductive effect is formed.
™ Then, lead terminals are introduced to the CdS substrate and the
CdS is packaged. 41
CdS Cell

42
Working process of CdS cells

43
 Spectral response of CdS Cells
™ The relative Sensitivity of a CdS cell depends on the wavelength of
the incident light. 
™ The sensitivity as a function of wavelength is called the spectral
response characteristic.
™ 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. 
™ By using a CdS cell with a spectral response similar to the human
eye, it can be widely and easily be used in applications as sensors
44
substituting for the human eye.
 Spectral Response Characteristics of CdS cell

™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.  45
46
CdS cells Vs Human Eye

™CdS > 515nm

™CdSSe> 620nm
™CdSe> 715nm
47
Examples of CdS cell configurations

48
Plastic coated CdS cells

49