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ELECTROCHEMICAL MATERIALS SCIENCE

UNIT IV ADVANCED FUNCTIONAL MATERIALS

• Thin film metallic glasses-preparation-properties
and applications- smart materials-piezoelectric
materials-thermoelectric materials-self-cleaning
materials-chromogenic materials-solar cells-
single crystalline silicon solar cells- amorphous
silicon solar cells- thin film polycrystalline solar
cells-photoelectrochemical cells- Dye-sensitized
solar cells - perovskite solar cells-supercapacitors.

Basics of Photovoltaics

Ref.: K. L. Chopra S. R. Das “Thin Films Solar Cells”

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Why Solar Energy?

• Solar energy – clean, abundant & economical
• Captured & converted into useful forms
• Solar thermal conversion
• Solar electricity – Photovoltaic (PV) & Photoelectrochemical
(PEC) cells
• PV cells – Si – 5 - 47% efficiencies
• Dye sensitized TiO2 – 14% efficiency
• Perovskite solar cells (2013 onwards) – 26%*

N. Armaroli, V. Balzani, Angew. Chem. Int. Ed.,45 (2006) 2.

*NREL best research-cell efficiencies 3

Solar Energy Conversion

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Solar Energy Conversion

Solar Energy Conversion Strategies

Fuel
Light
Electricity

Fuels Electricity

CO2 SC
e
Sugar
O2 H2 sc SC
H2O
O2

Photosynthesis Semiconductor/ Photovoltaics

Liquid Junctions
Three technology approaches for converting sunlight to stored energy.

N.S. Lewis, MRS Bull., 32 (2007) 808 5

Solar Fuels
Natural Photosynthesis Artificial Photosynthesis

A very simplified sketch representing key processes
in natural photosynthesis: solar light harvesting by
pigments, energy transfer to the reaction center,
charge separation, production of carbohydrates and
oxygen
D donor, A acceptor, P photosensitizer.
A very simplified sketch representing key processes
in artificial photosynthesis: solar light harvesting by
molecular antennas, energy transfer to a reaction
center, charge separation, water splitting with
production of hydrogen and oxygen on the two sides
of a membrane

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N. Armaroli, V. Balzani, Angew. Chem. Int. Ed.,45 (2006) 2.

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Solar Energy Conversion

The production of 20 TW of power, the world’s mid-century projected demand,

would require covering 0.16 % of Earth’s land (red squares) with 10% -efficient
solar panels (courtesy of Prof. Nathan Lewis, Caltech, Pasadena).

20 TW of power – nearly twice the world’s consumption rate of fossil energy

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N. Armaroli, V. Balzani, Angew. Chem. Int. Ed.,45 (2006) 2.

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Why Semiconductors?

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Moss-Burnstein shift

In heavily doped semiconductors, the absorption edge lies

at much shorter wavelengths as compared to the intrinsic case (undoped)
This effect is known as Moss-Burnstein shift. 13

Photovoltaic Device
Photovoltaic device comprises
(i) an absorber
(ii) a junction region or converter
(iii)a collector

Junction
Three types:
(i) p (or) n homojunction
(ii) Heterojunction
(iii) Metal/Semiconductor (MS) or
Conductor(Metal)/insulator/semiconductor (CIS or MIS)
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Ref: Physics, XII std., CBSE

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Junctions in the Dark

Junction
p (or) n homojunction – one semiconductor with two regions of
different conductivity (n- or p- type)
Junction forms at the place where the conductivity changes from
one type to the other
Depending on the variation in the impurity concentration
(i) Abrupt homojunction
(ii) Graded homojunction

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Graded
Abrupt

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Forward biased Reverse biased

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Regions
(1) generation-recombination
(2) diffusion current
(3) high-injection
(4) series resistance effect
(5) reverse leakage current 21

Heterojunction

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Metal-Insulator-Semiconductor Metal-Semiconductor

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Junction under Light

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Short-circuit current (Isc) – current that flows through the junction

Under illumination at zero applied bias. In ideal case (when Rs and Rsh
are zero), Isc is equal to the light-generated current IL and proportional
to the incident number of photons (illumination intensity)

Open-circuit voltage (Voc) – voltage through the device at zero current

Voc = (1/A)ln[(Isc+Is)+1]

A = q/nkT

Power output – The output power is given by

P = IV = IsV[exp(AV)-1]-IscV

Condition for maximum power can be obtained by setting P/V = 0

Pm = VmIm
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Fill factor (FF) – Fill factor FF is defined as

FF = VmIm/VocIsc

FF measures the squareness of the I-V curve

Efficiency () – The efficiency of a solar cell in converting light into

Useful power is given by
 = VmIm/Pin

Pin = input power 𝑃 = 𝐴 ∫ 𝐹   𝑑

where At = total device area

F() = number of photons per square cm per sec per unit bandwidth
incident on the device at wavelength 
hc/ = energy associated with each photon

 = (VocIscFF/Pin)x100% 26

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Dye Sensitized Solar Cell (DSSC)

DSSC – Grätzel Cell 31

Dye Sensitized Solar Cell (DSSC)

First report by Michael Grätzel – Nature 1991

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Dye Sensitized Solar Cell (DSSC)

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M. Grätzel, Prog. Photovolt. Res. Appl. 8 (2000) 171.

M. Grätzel, Inorg. Chem. 44 (2005) 6841. 34

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RuL3 cis-RuL2(NCS)2 RuL(NCS)3

L = 2,2-bipyridyl-4,4-dicarboxylic acid

L = 2,2,2-terpyridyl-4,4,4-tricarboxylic acid

Ru dye - MLCT

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Fill factor (FF) measures the ideality of the device

Ratio of maximum power output to the product VOC and JSC

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Impedance Spectroscopy

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CdSe Quantum Dot

in UV light

in ambient light

Particle Size

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Quantum Dot Solar Cells

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Quantum Dot Solar Cells

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Perovskite Solar Cells

Perovskite, mineral, CaTiO3, Russia
Named by Gustav Rose in 1839 in honor of Count Lev Alekseevich Perovski (1792-1856)
Perovskite structure compounds – AIBVO3, AIIBIVO3, AIIIBIIIO3
Applications – Catalysis, Magnetism, Dielectric, Optical, Electronic,…..Solar

BaTiO3

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ABX3
A = CH3NH3
B = Sn, Pb, Bi
X = I, Br

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Perovskite Solar Cells

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Semiconductor-Electrolyte
Interface

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n-type
semiconductor

p-type
semiconductor

Before contact After contact

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ND = donor density
W = depletion layer width

W = 10 – 1000 nm
Helmholtz layer width = 0.4 – 0.6 nm
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Mott-Schottky Relation

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Mott-Schottky Relation

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Mott-Schottky Relation

Mott-Schottky plots of TiO2 coated FTO electrode in 3M aqueous KCl

solution at 1 kHz frequency. The pH was adjusted with 1M HCl and 1M
KOH.

Courtesy: K. S. Anuratha, PA, CECRI

M. D. Ward, J. R. White, A. J. Bard, J. Am. Chem. Soc. 105 (1983) 27.61

Photoelectrochemical Cell (PEC)

 Photovoltaic cell – can produce electricity

 Photoelectrolytic cell – using incident photons causes a chemical reaction
eg. – Hydrogen production by photoelectrolysis of water

 Photoanode (n-type Semiconductor) + Metal cathode

 Photoanode (n-type Semiconductor) + Photocathode (p-type Semiconductor)
 Metal anode + Photocathode (p-type Semiconductor)

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Photoelectrochemical Water Splitting

Fujishima & Honda – 1972, Photoelectrochemical (PEC) splitting of water
A. Fujishima, K. Honda, Nature, 238 (1972) 37.

C. Jiang, S. J. A. Moniz, A. Wang, T. Zhang, J. Tang, Chem. Soc. Rev. 46 (2017) 4645.

Photoelectrochemical Cell (PEC)

Device configurations
Type I – Single light absorber
Type II – Heterojunction photoelectrode
Type III – Wired PEC tandem cell
Type IV – Wireless PEC tandem cell
Type V – PV-PEC tandem cell
Type VI – PV-Electrolyzer cell

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C. Jiang, S. J. A. Moniz, A. Wang, T. Zhang, J. Tang, Chem. Soc. Rev. 46 (2017) 4645.

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Photoelectrochemical Cell (PEC)

C. Jiang, S. J. A. Moniz, A. Wang, T. Zhang, J. Tang, Chem. Soc. Rev. 46 (2017) 4645.

CO2 reduction into methanol & valuable products

using PEC

S.K. Kuk et al., Angew. Chem. Int. Ed. 56 (2017) 3827.

Mott-Schottky Relation

Mott-Schottky plots of TiO2 coated FTO electrode in 3M aqueous KCl

solution at 1 kHz frequency. The pH was adjusted with 1M HCl and 1M
KOH.

M. D. Ward, J. R. White, A. J. Bard, J. Am. Chem. Soc. 105 (1983) 27.66

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Continuity Equations

n/t = Gn – Un + (1/e).Jn

p/t = Gp – Up + (1/e).Jp
where Gn & Gp in cm-1s-1 = electron and hole generation rate due to external influences
such as optical excitation with photons or impact ionization under large electric fields
Un = electron recombination rate in p-type semiconductor (minority carrier)
Up = hole recombination rate in n-type semiconductor (minority carrier)

For optical excitation, the generation rate is

G(x) = 0exp(-x)
 0 = the number of photons (cm-2s-1)
 = the absorption coefficient which is a function of wavelength 74

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The recombination can happen by three

processes:
1. Band to band recombination
2. Single level recombination
3. Multiple level recombination

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Minority carrier lifetime

Under low-injection conditions, i.e., n = p<n or p, the majority carriers

U = (pn – pn0)/p

where p = equilibrium minority carrier concentration, pn = p + pno

p = minority carrier lifetime

n-type semiconductor, p = 1/pthNt

p-type semiconductor, n = 1/nthNt

where p and n = hole and electron capture cross-section, respectively

th = carrier thermal velocity (3kT/m*)1/2
Nt = trap density
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Spectral response – the photocurrent collected at each wavelength relative to the

number of photons incident on the surface at that wavelength.

Measurement of wavelength dependence of the photocurrent

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