3/13/2025

Module-II (CSE/DS/AI)

Materials for Electronic Applications

Dr. Harisankar A
Department of Basic Science
Bishop Jerome Institute
Kollam

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Nano is 10-9 m

Nanometer

• A nanometer is
one billionth of a
meter
• 1 nm = 10-9 m
• Human hair
(diameter) is
approximately
30,000 - 2,00,000
nm

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• Nano = dwarf

• Atleast 1-dimension less than 100 nm

• At nanoscale- unique optical, magnetic, electronic, mechanical properties

• Lot of applications

• Nanoparticles that are naturally occurring (eg; volcanic ash, soot from forest fires)
or are the incidental byproducts of combustion processes (eg; welding, diesel
engines) are usually physically and chemically heterogeneous and often termed
ultrafine particles.

Nanomaterials in nature

Proteins, haemoglobin Body of yeast, bacteria

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Bright colors in peacock, butterfly

History and Origin

Lycurgus chalice: 4th Century A.D
• Appears green in reflected light
• Translucent red when light shown
directly through it
• 70 nm particles of Ag and Au
• Now in British Museum
• In 1857, Michael Faraday introduced
‘colloidal gold’
samples to the Royal Society

• Gold-silver alloy colloids being used as

Coloring agents for stained glass windows
in the Sainte Chapelle in Paris, decades
before the physics behind their optical
properties were first described.

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• In 1958, ‘There’s plenty of room

at the bottom’

• Manipulation at the level of

atoms and molecules

• Coined the term Nano in 1974 by

NorioTaniguchi of the University
of Tokyo

Richard P. Feynman

Property changes when converted to

nanoscale
Macroscale Nanoscale

opaque 1.Copper Transparent

insoluble 2. Au Soluble

golden colour Deep red to black

3. Au
stable Combustible
4. Al
free flowing Sticky fluid
5. H20

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Classification of nanomaterials
• Based on dimension

1.Zero dimensional (0-D) 2.One dimensional (1-D)

Here all the three dimensions are in the nanometric range
Here one of the dimensions is outside the
eg; Nano particles. nanometric range and the other two are within
the range
eg: Nano wires, fibers and tubes.

nanospheres

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3.Two dimensional(2-D) 4.Three(3-D) dimensional

Here 3 dimensions outside nm range
Here 2 dimensions outside nm range Bundles of nano wires and tubes,
multinano layers.

nanofilm

nanocoating

Bundles of nanowires

Classification of nanomaterials
• Based on materials
fullerene

1. Carbon based Nanomaterials Carbon nanotube

These are defined as materials in which the nanocomponent is pure carbon

eg; Carbon nano tubes (CNT), wires, spheres (fullerenes) and graphene.

2, Metal Based nanomaterials

Metal-based nanomaterials are materials made of metallic nanoparticles
like gold, silver, metal oxides, etc.

For example, Titanium dioxide (TiO2).

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3. Nanocomposites
v Composite nanomaterials contain a mixture of simple nanoparticles or compounds
such as nanosized clays within a bulk material.
v The nanoparticles give better physical, mechanical, and or chemical properties to
the initial bulk material.
Battery of high output power- Used as anodes (Si-C) in Li ion battery
Uses - Sensors
Speed up healing process of bones

5. Nanopolymers / Dendrimers
v Dendrimers are nanosized polymers built from branched units.
v These are tree-like molecules with defined cavities.
v They can be functionalized at the surface and can hide molecules in their cavities.
v A direct application of dendrimers is for drug delivery.
v Properties controlled by surface groups
v Low viscosity, high solubility, high reactivity
v Used in – drug targeting, sensors, might be a blood subsitute

4. Biological nanomaterials

v These nanomaterials are of biological origin and are used for nanotechnological
applications.

v The important feátures of these particles are i) self assembly properties and
ii) specific molecular recognition

v eg; DNA nano particles, nanostructured peptides.

v Various self assembled peptide structures can be designed to release

compounds under specific conditions and are used in drug delivery systems.

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Preparation of Nanomaterials
1. Hydrolysis – Nanoparticles of metal oxides can be prepared by
the hydrolysis of its alkoxide solutions under controlled
conditions.
ie. Preparation of Silica (SiO2), titania (TiO2), alumina (Al2O3).

It can be done using Sol-gel method (a type of hydrolysis)

Sol- Colloidal solution made of solid particles
Gel- solid macromolecule immersed in a solvent
Sol gel method involves the phase transformation of sol (liquid) into
a gel state by changing pH or other factors.

heat
Metal hydrolysis polycondensation low pressure Dried
Sol Gel
alkoxide Change pH gel

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Ø The sol-gel method is based on the phase transformation of a sol into a gel.
Ø A sol is colloidal system of nano-solid particles dispersed in a liquid.
Ø A gel is colloidal system in which liquid droplets are dispersed in a network of solid nanoparticles.
Ø Hydrolysis of metallic alkoxides or metal salts can give a sol at a suitable temperature and pH.
Ø The sol contains many other impurities.
Ø Inorder to remove impurities sol is transformed into a gel by changing the pH or other factors.
Ø The gel can be purified by filtration and washing with suitable solvents.
Ø The purified gel on drying give solid nanoparticle.
Ø For example aluminium oxide nano particles are obtained by hydrolysis of aluminium alkoxide by sol-gel
technique.

Al(OR)3 + 3H20 Al(OH)3 + 3ROH

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Eg. Preparation of silica nanoparticles

a) Hydrolysis (fast)
Suspension in ethanol
Si (OC2H5)4 + H2O Si (OH)4 + Ethanol
Tetra ethyl orthosilicate Silicon tetra hydroxide

b) Polycondensation (slow)
Suspension in ethanol
Si (OH)4 nano- SiO2 + 2 H2O
pH = 11-12 (NH3)

Hydrothermal synthesis
• Solvent (Water) at particular pressure (1 to 10000 atm) and temp
( 100 to 1000 oC) interacts with materials.
• Synthesis done at supercritical temperature of water (374 oC)
• Can synthesize
- thin films, bulk powders, single crystals, nanocrystals
-1D, 2D, 3D nano materials
- Thermodynamically stable novel materials

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Reduction method

Nanoparticles of Au and Ag can be prepared by-

a) reducing respective solutions using reducing agents
b) Neutral metal particles aggregate to form nano-particles
c) stabilised by adding capping agents

eg: Preparing gold nanoparticles

HAuCl4 + Na3C6H5O7 C6H5O7 + HCl + 3NaCl + Au
Chloroauric Trisodium
acid citrate

under controlled temp. and press. neutral gold particles aggregate to form
gold nanoparticles. It is stabilised using thiols as capping agents.

Preparation of Silver nano particles (Reduction)

ü 60 mL of 1 mM AgNO3 solution is taken in a beaker.

ü It is covered with a watch glass and heated in hot plate.
ü The solution is then stirred using a magnetic stirrer.
ü On boiling the solution, 6ml of 10 mM of Trisodium citrate is added
dropwise, about one drop per second.
ü The beaker is then closed and kept for some time till the colour of the
solution changed to a light golden colour.
ü Then it is allowed to cool.
ü The solvent can be removed by freeze-drying.

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Preparing Molybdenum nanoparticles by reduction

MoCl3 + 3NaBH4 Mo + 3NaCl + 3BH3 + 3/2 H2

Molybdenum Sodium
chloride in borohydride
toluene
solution

Electro-reduction method

Eg- Cu nanoparticles preparation

Electrolysis is done on the copper plating bath with acidified

CuSO4 solution, Cu nanoparticles are formed as spongy
layers at cathode.

Physical and Chemical Properties

1, Size and Shape
• Size: Nanoparticles typically range from 1 to 100 nm in diameter. This small size gives them a high surface
area relative to their volume, influencing many of their physical properties.
• Shape: Nanoparticles can have various shapes, including spherical, cylindrical, rod-shaped, and irregular
forms. The shape influences how the particles interact with light, heat, and other materials.

2, Surface Area
Due to their small size, nanoparticles have an extremely high surface area-to-volume ratio. This is one of the
most significant physical properties and is responsible for their enhanced reactivity, strength, and other
behaviors compared to bulk materials.

3, Surface Energy
The high surface area results in increased surface energy, making nanoparticles highly reactive. This is
particularly important in catalysis, drug delivery, and other applications where surface interactions are key.

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4, Mechanical Properties
Nanoparticles can have increased strength and hardness due to the reduced number of defects . For
instance, carbon nanotubes exhibit exceptional tensile strength and are being explored in composite
materials and light-weight construction.
Elasticity: Nanoparticles can also exhibit different elastic properties, including increased stiffness in some
cases, depending on their size and material composition.

5, Chemical Reactivity
The high surface area and energy of nanoparticles lead to increased chemical reactivity. This makes
nanoparticles useful as catalysts or in drug delivery systems, where controlled release and interaction with
other substances are needed.
The surface can also be functionalized with different molecules to tailor the reactivity and solubility of the
nanoparticle.

6, Electrical Properties
Nanoparticles can exhibit unique electrical behaviors due to quantum effects. For instance, metal
nanoparticles can show changes in their electrical conductivity when the particle size is reduced.
Carbon-based nanoparticles like carbon nanotubes and graphene exhibit high electrical conductivity and
are used in applications like sensors, energy storage devices (e.g., supercapacitors), and flexible electronics.

7, Optical Properties
Ø Absorption and Scattering: Nanoparticles can interact with light in unique ways. For example, metal
nanoparticles (like gold or silver) exhibit surface plasmon resonance (SPR), where the electrons on the
nanoparticle surface oscillate in resonance with incident light. This leads to strong absorption and scattering
of light at specific wavelengths.
Ø Quantum Dots: Semiconductor nanoparticles, or quantum dots, can exhibit quantum confinement effects,
where their electronic properties are dependent on their size. This leads to size-tunable optical absorption
and fluorescence, which is useful for imaging and sensing applications.

8, Thermal Properties
Ø Thermal Conductivity: Nanoparticles may have different thermal conductivity compared to their bulk
counterparts. For example, some nanoparticles can exhibit enhanced thermal conductivity, which can be
useful in heat dissipation applications.
Ø Melting Point: Nanoparticles often have lower melting points than bulk materials due to the increased
proportion of atoms or molecules at the surface, which are less tightly bound compared to those in the
interior.

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9. Color and Transparency

Nanoparticles can appear transparent or exhibit specific colors depending on their size and the
material. This property is notably observed in colloidal gold or silver nanoparticles, where their size-
dependent plasmon resonance causes vivid colors, a phenomenon used in sensors and diagnostics.

10. Solubility and Dispersibility

The solubility and dispersibility of nanoparticles depend on their surface chemistry. Functional
groups can be added to nanoparticles to increase their compatibility with solvents, leading to
improved dispersal in liquids, which is important in fields such as drug delivery and coatings.

11. Quantum Effects

At the nanoscale, quantum effects become significant. These include changes in electronic, optical,
and magnetic properties due to quantum confinement (as seen in quantum dots or nanoscale
semiconductors). In these materials, the behavior of electrons becomes discrete, leading to
phenomena like quantum tunneling and discreet energy levels.

Applications of Nanoparticles
1, Single nanosized magnetic particles are mono-domains. Magnetic nano-composites have
been used for mechanical force transfer (ferrofluids), for high density information storage and
magnetic refrigeration.

2, Nanostructured metal-oxide thin films are receiving a growing attention for the realisation
of gas sensors (NOx, CO, CO2, CH4, and aromatic hydrocarbons).

3, Nanostructured metal-oxide thin films are receiving a growing attention for the realisation
of gas sensors (NOx, CO, CO2, CH4 and aromatic hydrocarbons).

4, Carbon nanotube based transistors are used for miniaturizing electronic devices.

5, Carbon nanotube are used for making paper batteries.

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6, A mixture of carbon nanotubes and fullerenes is used for making solar cells.

7, Microcrystalline TiO2 is an insulator, whereas nano-crystalline TiO2 is a semiconductor.

Its Band gap can be tuned by controlling the size of nano-particle. Nano TiO2 can be use
for making dye sensitised solar cells.

8,Nanoparticles are used in the fight against tumours, nanostructured and

functionalised surfaces and membranes improved diagnosis and more targeted use of
active agents; neuro active implants.

9, Nano Cadmium telluride exhibit different colour depending upon its size. It can be
used for dyeing fabrics, such nano colourants never fades.

10, Nanostructured semiconductors are used as window layers in solar cells.

Graphene
• Graphene is a 2-dimensional crystalline
allotrope of carbon whereas graphite is 3-
dimensional allotrope of carbon.

• Single layer of carbon atoms, tightly bound in a

hexagonal honey comb lattice
Honey Comb like lattice of Graphene
• Graphene is defined as "the two-dimensional
mono-layer of carbon atoms, which is the v Each hexagonal ring comprises of three strong in-plane
sigma bonds, with a bond length of 0.142 nm, and a Pz
basic building block of graphitic materials orbitals perpendicular to the plane.
(i.e. fullerenes nanotube, graphite)".
v These orbitals hybridize together to form two half-filled
• In graphene the carbon atoms are sp² bands of free-moving electrons, π and π*, which are
responsible for most of graphene's notable electronic
hybridized and are arranged in hexagonal properties.

fashion.

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• It is considered to be one of the most promising materials of the century.

• It gained world wide attention due to its extraordinary charge transport,
thermal, optical, and mechanical properties.
• It is considered to the lightest, thinnest, strongest material that conducts
heat and elec tricity.
• It is stronger than diamond and ten times more conducting than copper.

Nobel Prize in Physics 2010 was awarded to Andre Geim and Konstantin
Novoselov for the ground breaking experiments regarding graphene.

Preparation of Graphene
1. Mechanical exfoliation method (such as Scotch tape method): Encompasses the repeated
peeling off layers of graphite using adhesive tape. This was the method employed by Geim and
Novoselov.

2. Chemical vapor deposition: Involves the deposition of carbon atoms onto a substrate (like
copper) in the presence of a carbon-containing precursor gas such as methane.

3. Thermal decomposition on SiC: Silicon carbide substrate is heated under ultra-high vaccuum
which results in the sublimation of silicon atoms and deposition of carbon atoms to form
graphene layers on the SiC surface.

4. Graphene oxide reduction method: Graphite oxide, obtained from graphite, is chemically
treated to exfoliate into graphene oxide (GO), which is then reduced to graphene.

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Properties of Graphene
• Conducts electricity much more times than copper- electrons are
able to flow through graphene more easily than copper

• Strongest material ever discovered

• Harder than diamond and 200 times harder than steel

• Stretches like rubber- it is stretchable upto its 20% of initial length

• Very light 0.77 mg/m2 ; 1m2 paper is 1000 times heavier than
graphene

• The thermal conductivity is much higher than all other allotropes of

carbon

Properties of Graphene
q Electrical conductivity: Graphene has high electrical conductivity. Graphene, being two dimensional material shows
Quantum Hall effect. They behave as massless relativistic particles (Dirac fermions) which allows the electron speed
comparable to light. They have high electron mobility compared to metals.

q Mechanical strength and elasticity: They possess high elastic modulus and strength. It is 200 times stronger than steel.
Graphene is highly is flexible and can be stretched by up to 20% of its original length without undergoing structural damage.

q Thermal Conductivity: Graphene exhibits excellent thermal conductivity and is highly efficient for heat dissipitation and
thermal management applications.

q Optical: Graphene absorbs only 2.3% of incident light over a broad wavelength range and hence makes it suitable for
applications in transparent electrodes for displays, solar cells, touch Screens etc.

q Surface area: It has high surface area due to its single-atom thickness and hence useful for applications in energy storage
devices.

q Graphene is chemically inert, stable and biocompatible also.

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Graphenes- Applications

1. Electronics:
(a) Due to its lower resistance and higher transparency, graphene-based thin flms can be used in touch screens, which is
found to be superior than indium tin oxide.
(b) Smaller size transistors can be developed using graphene which shows better performance.
2. Energy storage:
(a) Graphene incorporated lithium-ion batteries have longer life span, faster charging time and higher capacity.
(b) It can improve the efficiency of hydrogen fuel cell by lowering fuel cross over (fuel permeating through the electrolyte or
membrane to the opposite side of the fuel cell).
(c) Graphene is used in supercapacitors to provide high energy density.
3. Biomedical:
(a) Suitably functionalized graphene can be used to carry chemotherapy drugs to cancer cells.
(b) Graphene-based biosensors are highly sensitive when detecting DNA, ATP, dopamine etc.

4. Composites and coating:

(a) By combining graphene with paint, a unique graphene coating is formed which will effectively
prevent rusting.
(b) Graphene in the carbon-fibre coating of aircraft's wing resists impact better and consumes less fuel.
(c) Graphene-based composites and coatings could play a significant role in improving sports equipment
for skiing, cycling etc.

5. Environmental
(a) Graphene based membranes can purify water in a more efticient, cheaper and environmental friendly
way.
(b) lt can be used in filters and coatings to remove pollutants and toxins from the air.

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Graphenes- Applications
1. Paint industry – used in advanced paints to reduce corrosion and to
increase energy efficiency

2. Aircraft techniques and vehicles – due to light weight, high tensile

strength, and hardness, it can be used in aircrafts and cars

3. Optical electronics - high electrical conductivity and high transparency

make it candidate for transparent conducting electrode

4. Energy storage devices – high surface area to mass ratio, it is used as

conductive plates of supercapacitors - used to produce supercapacitors
with greater energy storage density

Graphenes- Other Applications

1. Graphene nano ribbons

2. IR detectors

3. Piezoelectric materials

4. Composite materials

5. Liquid cells in electron microscopy

6. Optical modulators

7. Thermal management materials

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Carbon nanotube

Formed by rolling a sheet of graphene

Graphene- one atom thick planar sheet of SP2 bonded C-
atoms

ü Carbon nanotubes (CNTs) are allotropes of carbon with cylindrical nanostructures.

ü They are conceptually graphene sheet rolled into a tube.
ü CNTs were discovered in l991 by the Japanese electron microscopist Sumio lijima who was studying the material
deposited on cathode during the arc-evaporation synthesis of fullerenes.
ü There are different methods available for the synthesis of CNTs with different structure and morphology.
ü Arc-discharge method, laser ablation/evaporation method, chemical vapor deposition method etc. are the
commonly used methods for the synthesis of CNTs.
ü Carbon nanotubes are one-dimensional nano particles with diameter measuring 1-50 nm and are generally only
a few micrometres in length.
ü They are molecular scale tubes and are nanoscopic hollow fibres of pure carbon.
ü It is 10 times thinner than human hair. They are characterised by high tensile strength and according to structure
are conductive or semiconductive.
ü CNTs are at least 100 times stronger than steel, but only one-sixth as dense.
ü In addition, they conduct heat and electricity far better than copper.

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Classification of CNTs

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ü There are two types of CNTs namely single-walled (SWCNT, one tube) and multi-walled (MWCNT, several concentric tubes).

ü Both of these are typically a few nanometres in diameter and several micrometres to centimetres long.

ü SWCNT can be visualized as rolled-up tubular shell of graphene sheet.

ü Based on the variations arising from the specific orientation and rolling of graphene sheets, SWCNTs are classified into three

- armchair, zigzag, and chiral.

ü Armchair nanotubes exhibit a symmetrical arrangement where the rolling axis aligns with the hexagonal lattice of graphene,

resulting in equal edge lengths.

ü Zigzag nanotubes, on the other hand, are formed when the rolling axis is along the zigzag pattern of the graphene lattice,

leading to edges that consist solely of zigzag lines.

ü Chiral nanotubes are characterized by a rolling axis that is oriented at an angle to the graphene lattice, resulting in unequal

edge lengths and a helical structure.

ü The optoelectronic properties of carbon nanotubes vary significantly with molecular structure and diameter of

the tube.

ü MWCNT is a stack of graphene sheets rolled up into concentric cylinders.

ü There are three different models proposed for MWCNT namely Russian doll model, Parchment model and

mixed model.

ü In Russian doll model, sheets of graphene are arranged into concentric cylinders whereas in Parchment model

single graphene sheet is rolled around itself, similar to a scroll of parchment.

ü Mixed model is a mixture of both Russian doll and Parchment model.

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Properties of Carbon Nanotubes

1, Strength and hardness:
They are the strongest and stiffest materíals.
Single walled nanotubes (SWNTS) are used for synthesizíng super-hard material, by compressing it at room temperature.
High strength could be attributed to the covalent sp bonds formed between the individual carbon atoms.
They can withstand a pressure upto 24 GPa without deformation.
Multi walled nanotubes (MWNT) without inter connected inner shells exhibit telescoping property.
2, Electrical conductivity:
Their electrical conductivity is better than metals.
Electron travelling through a CNT behaves like a wave travelling through smooth channel- Ballistic Transport.
MWNTs with interconnected inner shells show superconductivity with relatívely high temperatures.
3, Thermal conductivity:
Their thermal conductivity also is better than metals.
All nanotubes are expected to be very good thermal conductors along the tube but good insulators laterally to the tube axís-
Ballistíc Conduction.
The thermal stability of carbon nanotubes is found to be upto 2800°C in vacuum and about 750°C in air.

Applications
• Used as strengthening materials
• Used for drug delivery
• Coating nanotube-silicon increase capacity of Li-ion battery
• Mixture of C-nanotubes and fullerenes used as solar cells. electrons trapped
inside fullerenes+ sunlight = electrons start to flow giving current
• Making Ultra capacitors- providing large surface to store electrical charge
• Electrical circuits: Nanotube based transistors have been made that operates at
room temperature. Carbon nanotubes are used for miniaturizing electronic
devices.

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• Energy storage: Due to high surface area, optimised electrical and thermal properties
they are widely employed in energy storage applications.

(a) Paper Batteries: A paper battery is a battery engineered to use a paper-thin sheet of
cellulose infused with aligned carbon nanotubes. It gives a steady power output. This batery
also functions as a super-capacitor which give a quick explode of high energy.

(b) Solar Cells: CNT-fullerene hybrid solar cell is formed by a mixture of carbon nan otubes
and fullerenes. Electrons trapped inside fullerenes are excited by sunlight leading to the flow
of this electrons, which produce the current. CNT acts as the conductive pathway.

(c) They are used for making ultra-capacitors which provide a large surface to store
electrical charge

• Aerospace and automotive industry: Due to easier molding, high

strength, stiffness, and reduced weight, CNT polymer composites are
prefered for aerospace and automotive applications.

• Research is also being carried out to assess the ability of CNTs for the
storage of hydrogen.

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Carbon Quantum dots (CQDs)

q Carbon quantum dots are zero-dimensional small carbon nano particle. A typical QD has a diameter in the range of 2 -
10 nm

q It consists of ultra-fine, distributed, quasi-spherical carbon nanoparticles with size less than 10 nm

q Recently they have attained much attention due to their good solubility and strong luminescence properties.

q CODs are found to be much more superior than traditional semiconductor quantum dots due to its

q Lower molecular weight

q Reduced toxicity

q Ease of surface functionalisation

q Cost effectiveness

q Exceptional fluorescence stability

q Tunable emission wavelength

q Strong biocompatibiity

q QDs have properties combined between bulk semiconductors and atoms.

q Carbon quantum dot was first discovered by Xu et al. in 2004 accidentally during the purification of single-
walled carbon nanotubes via electrophoresis.

q It can be synthesised using two main methods: 'top-down' and 'bottom-up'.

q The top-down approach involves breaking down large carbon structures into small CQDs using techniques like
chemical oxidation, laser ablation, arc discharge, and electrochemical synthesis.
q The bottom-up method involves building CQDs from small carbon molecules through processes like
hydrothermal synthesis, microwave assisted synthesis, and pyrolysis, which allows control over their size and
shape.
q Synthesised particles can be purified using electrophoresis, centrifugation, dialysis, column chromatography
etc.

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Quantum dots - Properties

ü QDs band gap tunable by size – means that their optical and
electrical properties can be engineered to meet specific applications

ü Absorption and emission occurred at specific wavelength, depends

on the size – their fluorescence behaviour can be tuned

ü CQDs shows absorption mainly in the UV region which can extent to

the visible region also.

ü They exhibit strong fluorescence, photoluminescence and

chemiluminescence which makes them useful in imaging and
sensing applications.

ü CQDs show excellent Photostability and biocompatible with less

toxicity than other QDs.

ü Hence they are used for medicinal and Biological applications.

Applications of Carbon Quantum Dots

1, Biomedical:
(a) Due to its fluorescence property, better biocompatibility and low biotoxicity they are employed in fluorescent bioimaging.
(b) CQDs are used as biosensor carriers because of their solubility in water, tunable excitation property, excellent
biocompatibility and photostability. CQDs-based biosensors can visually monitor various substances including glucose, copper,
phosphate, iron, potassium, and nucleic acids.
(c) They are used in drug delivery systems also.
2. Optoelectronics:
(a) CQDs have shown potential in enhancing the performance of DSCs due to their stable light absorption properties,
photostability and low cost. By creating CQD bridged dye/semiconductor complex systems, CQDs improve the photoelectric
conversion efficiency significantly.
(b) CQD-based hybrids have been identified as excellent materials for supercapacitors. CQD-RuO, hybrid show remarkable
electrochemical performance.
3. Lighting: Due to their stable light emitting, low cost and eco-friendliness they are used as LED materials. Switchable
electroluminescence behaviour makes it useful for developing colourful LEDs.

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Fullerenes/Buckminster fullerene
Discovered by Kroto &
Smalley in 1985

• Allotrope of Carbon as hollow sphere, ellipsoid etc- C60,

C70
• Spherical fullerenes- buckyballs
• Cylindrical fullerenes- buckytubes

ü Fullerenes are zero-dimensional, hollow, closed cage nanoparticles made of carbon atoms.
ü The discovery of fullerenes in 1985 by Curl, Kroto, and Smalley culminated in their Nobel Prize in 1996.
ü Fullerenes, or Buckminster fullerene are named after Richard Buckminster Fuller the architect and designer of the
geodesic dome and are sometimes called bucky balls.
ü Fullerene molecules are denoted based on the number of carbon atoms in the spherical carbon ball.
ü The smallest fullerene was reported with twenty carbon atoms as C20 followed by C24 and C28 analogues.
ü Each fullerene generally contains 12 pentagonal and (n/2-10) hexagonal rings, where n >20.
ü C60 fullerene, known as the Buckminster fullerene is the primarily discovered and most widely studied form of fullerene.
ü In 1990, a technique to produce larger quantities of C60 was developed by heating graphite rods in a helium atmosphere.
ü The sooty material formed by condensation of vaporized carbon consists of mainly C60 with smaller quantity of C70
(rugby ball shape) sand traces of fullerenes consisting of even number of carbon atoms up to 350 or above.
ü It is composed of fused pentagonal and hexagonal carbon rings. It contains 12 five membered rings (12 x 5= 60 atoms) and
20 six membered rings. possess a perfect icosahedral symmetry.
ü The geometry is same as that of soccer football

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ü Fullerenes are stable, but not totally unreactive.

ü The sp2 hybridized carbon atoms, which are at their energy minimum in planar graphite, must be bent to form

the closed sphere or tube, which produces angle strain.

ü The characteristic reaction of fullerenes is electrophilic addition at 6,6-double bonds, which reduces angle

strain by changing sp² hybridized carbons into sp3 hybridized ones.

ü The change in hybridized orbitals causes the bond angles to decrease from about 1200 in the sp² orbitals to

about 109.5° in the sp3 orbitals.

ü This decrease in bond angles allows for the bonds to bend less when closing the sphere or tube, and thus, the

molecule becomes more stable.

Properties of Fullerene
Physical:
ü Fullerenes are extremely strong molecules, able to resist great pressures - they will bounce back to their original shape
afer being subject to over 3,000 atmospheres.
ü This property makes fullerenes become harder than steel and diamond.
ü An interesting experiment shows that Fullerenes can withstand collisions of up to 15,000 mph against stainless steel,
merely bouncing back and keeping their shapes.
ü This experiment demonstrates the high stability of the molecule.
Solubility:
ü Fullerenes are sparingly soluble in many solvents.
ü Common solvents for the fullerenes include aromatics, such as toluene, and others like carbon disulfide.
ü Solutions of pure buckminster fullerene have a deep purple color.
ü Solutions of C70 are a reddish brown.
ü The higher fullerenes C76 to C84 have a variety of colors.

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Electrical:
Fullerenes are normally electrical insulators, but when crystallized with alkali metals, the resultant compound can be
conducting or even superconducting.

Light absorption:
Fullerenes absorb strongly in the UV and moderately in the visible regions of the spectrum.

Chemical:
The carbon atoms within a Fullerene molecule are sp² and sp3 hybridized.
Out of which the sp² carbons are responsible for the considerably angle strain presented within the molecule.
C60 and C70 exhibit the capacity to be reversibly reduced.

Applications of Fullerenes
1. Coatings and lubricant:
a) Fullerenes are used for making durable, high-performance coatings that resist wear and corrosion.
b) Fullerenes are used as miniature "ball bearings' to lubricate surfaces. C60 can be used used as excellent microscopic ball
bearings, lubricant and catalyst.
2. Biomedical:
(a) Fullerenes can be used to deliver drugs to specific cells or tissues due to their ability to form stable complexes with various
molecules.
(b) Fullerenes can be used as contrast agents in imaging techniques such as MRI or ultrasound.
3. Energy storage:
(a) Fullerenes and their derivatives are employed energy storage devices due to their electrical conductivity and stability.
(b) They can be used to store hydrogen.
4. Environmental:
(a) Used in water treatment for the removal of pollutants and contaminants.
(b) Used in sensors for detecting environmental toxins and pollutants

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Dye sensitised Solar Cells

Dye sensitised solar cells (DSSC)

v Dye-Sensitized Solar Cells (DSSCs) are a type of solar cell that use organic dyes to absorb sunlight and convert it into
electricity.
v Unlike conventional silicon-based solar cells, DSSCs are made from inexpensive materials, which makes them a more
cost-effective option for solar energy.
v These cells are typically used in low-power applications but offer advantages such as flexibility, transparency, and ease
of production.

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A DSSC mainly consists of a substrate, transparent conductive oxide layer (TCO), semiconductor metal oxide nano particle,
organic / inorganic dye, electrolyte and counter electrode.

1, Substrate substrate

It is generally made up of glass or flexible transparent plastic, TCO is coated on the substrate.

2, Transparent conductive oxide (TCO)

Thin film of Indium Tin Oxide (ITO) or Fluorine doped Tin Oxide (FTO) acts as TCO.

3, Semiconductor metal oxide nano particles

v Semiconducting metal oxides with high surface area and wide band gaps are used in DSSCs.
v TiO2 is the commonly used metal oxide.
v Other metal oxide like ZnO and SnO, are also used.

4, Dye/photo sensitiser:
v Surface of the metal oxide particle is coated with dye molecules.
v These dye molecules are responsible for absorbing sunlight and inject the photoexcited electrons to the conduction band
of the semiconductor.
v Dye-sensitized metal oxide semiconductor acts as the anode.
v Ruthenium-based complexes and organic dyes are commonly used.
v Natural dyes extracted from plants can also be used as photo sensitiser.

5, Electrolyte
v Redox couple iodide/triiodide solution is used as the electrolyte.
v Electrolyte should have good contact with the dye-sensitized metal oxide semiconductor and the counter electrode.

6, Counter electrode
v Platinum or graphite-based materials are employed as the counter electrodes, which acts as the cathode.
v It facilitates the reduction of the oxidized dye molecules and completes the electrical circuit.

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Working Principle
The working of a DSSC can be explained in several steps:

1, Light Absorption:
Sunlight strikes the dye molecules on the photoanode, where the dye absorbs photons from the light.

2, Excitation of Dye:
The absorption of light excites electrons in the dye molecules, moving them from the ground state to an excited state.

3, Electron Injection into TiO₂:

The excited electrons are injected into the TiO₂ layer, where they travel toward the external circuit.

4, Electron Transport:
The electrons move through the TiO₂ layer to the conducting layer and then to the external circuit, generating electricity.

5, Regeneration of Dye:
After the dye loses an electron, it is in a charged state. The electrolyte (e.g., iodide ions) donates electrons back to the
dye, restoring it to its ground state.

6, Flow of Electrons:
The electrons flow through the external circuit, performing work, before returning to the counter electrode, where the
process is completed.

Advantages of DSSC
v The fabrication of DSSCs is simpler processes compared to conventional silicon solar cells
v They are light weight which can be advantageous for applications on vehicles and portable devices.
v They are flexible in shape, and size and hence can be implemented on windows, terraces, facades, etc.
v Natural pigments and organic dyes can be employed makes them more sustainable, ecofriendly and affordable.

Applications of DSSC

v DSSCs are mainly used for sunlight harvesting.

v Since they can be used in window, facades etc., they can generate power while maintain ing aesthetic appearance.
v They can be used in portable solar chargers for electronic devices, such as smartphones and tablets due to its lightweight.
v They can be integrated into the fabric of bags and backpacks, enabling them to charge electronic devices while on the go.
This feature makes them particularly popular among hikers and travellers who need a portable and convenient power
source.
v DSSC can be used to power illuminated signs and displays in locations where access to electricity is limited or costly.

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Supercapacitor
1. Supercapacitors or ultra capacitors are energy storage devices having high-capacity, with a capacitance value much
higher than solid-state capacitors but with lower voltage limits.
2. Both capacitors and batteries are energy storage devices.

A capacitor contains two metal plates separated by a diclectric material whereas a super capacitor generaly consists of
electrodes, electrolyte, separator and collector.

Electrode:

v Materials with good conductivity and high stability like porous active carbon coating are generally used as the electrode

material.

v Carbon based nanoparticles (eg. carbon nano tubes, graphene, carbon quantum dots etc.), metal oxide nanoparticles,

nanowires, quantum dots, conducting polymer-based composites etc. are used as the electrode material in

supercapacitors.

v Nanomaterials enhances the performance of the supercapacitors by increasing the capacitance, energy density, and

cycling stability of the supercapacitors

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Electrolyte:
v Capacity of the capacitor depends mainly on the dielectric constant of the electrolyte.
v Either solid or liquid can be used as the electrolyte.
v For commercial application solid electrolytes are preferred since they are leak-free and possess high ionic conductivity.
Generally, a solvent mixed with conductive salts such as tetraalkylammonium or lithium salts acts as the solid
electrolyte.
v Sulphuric acid, KOH solution etc can act as the liquid electrolyte.
Separator:
v Electrolyte membranes will act as the separator.
v It prevents short-circuiting between the electrodes but allows the electrolyte ions to pass through.
v Polymer-based and paper based are found to be durable and economical.
Collector:
v Electrons are collected at the collector.
v Carbon fibre, metal like Al, Pt, Cu, Ni ete. are the commonly used collectors.
v Binders, such as polyvinylidene fluoride (PVDF) and poly acrylonitrile (PAN), act as adhesives to hold the active material
and current collectors together.

Advantages of Superconductor
q Longer cycling time and higher service life compared to the battery.
q High efficiency, higher charging rates and high power density.
q Low resistance which enables them to produce high load currents.
q Small sizes and lightweight which makes them easily installed in small areas.
q Environment friendly.
Disadvantages of supercapacitor
q Higher self discharge rate.
q Amount of energy stored per unit weight is considerably lower compared to batteries.
q Low voltage limits which demand serial connections to produce high voltage.
Applications of supercapacitors
q Used in hybrid buses in combination with the battery to increase battery life and decrease the size.
q Used in implantable devices and health monitoring devices to supply power.
q Used in solar-powered road and farming devices, street light portable traffic light system, wireless security camera etc.
q Used in wind turbines to supply power to the pitch control of blade.
q Memory devices in laptops, smartphones, tablets etc., are developed using supercapacitors.

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Organic Light Emitting Diode (OLED)

v OLED is organic ight emitting diodes.
v OLEDs are advanced form of LED lighting, made from conducting polymers.
v It is a solid state semiconductor device that is 100 to 500 nanometers thick.
v OLEDS gives a panel of light over a surface area, not a pinpoint lighting.
v It can be used as coating on foil or plastic.

Advantages
v OLEDs generate good quality light colour.
v They are also available in a range of different colours, making them versatile.
v They are dimmable which makes them suitable for use as ambient lighting.
v They are cold lighting sources because they do not generate any heat.
v They have greater efficiency levels than halogen and incandescent lights.
v They are small, light, thin and flexible.

OLED Structure

A typical organic light emitting diode (OLED) structure consisting of the fol lowing five parts

1. Substrate (clear plastic, glass, foil) supports the OLED.

2. Anode, adds electron holes (removes electrons) when a current flows through the device [indium titanium oxide (ITiO), Au,

LiF]

3. A hole transport layer (HTL), This is the conducting polymer layer that Iransport holes from anode. Example-Polyaniline,

Poly (p-phenylene vinylene) (PFPV).

4. An electron transport layer (ETL), This is the emissive layer made of an organic molecule or polymer where light is made

(different one from the conducting layer). Example: poly fluorine.

5. A metallic cathode (Ca, Ag etc) injects electrons when a current flows through the device.

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OLED Structure

glass substrate

Working
v Electronic charges are transported and injected into the polymer from the electrodes (electrons from the cathode, and
holes from the anode).
v The electrons and holes capture each other' through electrostatic interaction.
v Radiative recombination of electron and hole generates light.
v The wavelength of this emitted light depends on the band gap of the polymer used.

Advantages
v The plastic, organic layers of an OLED are thinner, lighter
v More flexibleble than the crystalline layers in an LED or LCD.
v OLEDs are brighter than LEDs.
v OLEDs do not require backlighting, they consume much less power than LCDs.
v OLEDs are easier to produce and can be made to larger and thinner sizes.
v OLEDs produce their own light, so they have a much wider viewing range.

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Disadvantages
v Limited lifetime of organic materials, so OLED displays are not durable.
v Organic materials can easily be damaged by water intrusion into the displays.

v Applications
Major applications of OLED technology are
v OLED TV.
v Mobile phones with OLED screens.
v Smart watch with OLED screens
v Roll top Laptop.

Fire Retardent Polymers

v Fire retardant polymers are materials that are specifically designed to prevent or slow the spread of fire.
v These polymers are typically enhanced by incorporating fire retardant additives that either modify the polymer’s behavior
under heat or interact with the flame to suppress combustion.
v The fire retardants can be classified as halogenated (containing halogens like chlorine or bromine) and non-halogenated
(not containing halogens).
v Both types have their advantages and disadvantages in terms of fire resistance, toxicity, and environmental impact.
Halogenated Fire Retardant Polymers
q Halogenated fire retardants include elements like bromine or chlorine, which are added to polymers to reduce their
flammability.
q These compounds work by releasing halogenated gases when heated, which inhibit combustion.
q However, the use of halogenated fire retardants can lead to toxic byproducts (such as dioxins) when exposed to high heat.
Non-Halogenated Fire Retardent Polymers
q Non-halogenated fire retardant polymers do not contain halogen elements like chlorine or bromine. Instead, they rely on
phosphorus, nitrogen, or inorganic compounds (like aluminum or magnesium hydroxide) to provide fire resistance.

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Examples for fire retardent halogenated polymers

Examples for fire retardent non-halogenated polymers

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Examples for fire retardent halogenated compounds

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