Module III: Advanced Materials

By

Dr. Bhavna Vyas

 Polymers in day-today life

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Polymers: Large molecule with high M.W. composed of many repeated
subunits (Monomer)
(Poly - many & mer – parts or units) PE, PVC, Nylons
Natural polymers - wood, rubber, cotton, wood, leather, silk etc
Synthetic polymers – PE, PS, PP, PVC etc

Monomers: Small molecule with low M.W. &

at least two reactive positions
(building block of polymer)
E.g.: Ethylene Vinyl Chloride, propylene
repeat repeat repeat
unit unit unit

H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH3H CH3H CH3
Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP)
Functionality – number of reactive sites
Monomer – Polyfunctional -unsaturation or functional group
1) Bifunctional monomer – 2 reactive sites - linear polymer
eg: Ethylene, VC(unsaturation), Adipic acid (functional group)
2) Trifunctional monomer -3 reactive sites - branched (short or long)
eg: Phenol (unsaturation), glycerol (functional group)
3) Higher functionality monomer – Tetrafunctional (4), 5,or more reactive
sites - crosslinked polymer respectively
eg: Acetylene, urea, butadiene etc

Degree of Polymerization (DP) - number of monomeric units in

polymer molecule. Denoted by ‘n’
Higher the DP, greater is the molecular weight, greater is the strength with
more complex structure of Polymer.
M = n* Mo
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Tacticity in Polymers: Arrangement of side groups on C-C chain

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 Glass TransitionTemperature (Tg)
Tg - Temperature below which polymers exist as hard
and brittle (glassy state) and above which they exist
as soft and elastic i.e. viscoelastic (rubbery state)
Tm - Temperature below which polymers exist in visco-
elastic state and above which they exist in visco-fluid
state
Molecular & Segmental motions based on KE
1) Below Tg: No movements of molcules at all
2) Between Tg & Tm: Only segmental
3) Above Tm: molecular & segmental both motions

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Introduction, preparation, properties and applications:
1. Engineering Thermoplastic : Polycarbonate
2. Conducting polymer : Polyacetylene
3. Polymer Composites : Fiber reinforced plastics – Glass
fiber and carbon fiber reinforced polymer composites
4. Nanomaterials: Graphene
5. Nanomaterials: Carbon Nanotube (CNT)
6. Semi-Conducting Nanomaterials: Quantum Dot (QD)
7. Organic Semiconductor Memory Material:
p-type memory material - Pentacene
n-type memory material - Perfluoropentacene
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Engineering Thermoplastic

Polycarbonate (PC)
 Engineering Thermoplastic
Few examples where metals or glasses are
replaced by polymeric materials:
What is so special about this
polymeric materials???

Engg. Thermoplastic
 Engineering Thermoplastic
All these products/ materials (shown above and others
as well like covers/bodies of cell phones, laptops,
computers, sockets of plugs, switches, CD/DVD, etc. )
are examples of Engineering Thermoplastics.

Engineering Thermoplastics is a group of polymeric

materials synthesized from thermoplastic like
Polyethylene, Polystyrene, Polypropylene,
Polycarbonate, etc.

Engineering Thermoplastics are the polymeric materials

having outstanding (or we can say having specific)
properties
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when compared.
© Bhavna Vyas 11
 Engineering Thermoplastic

Engineering Thermoplastics are the polymeric materials

having outstanding (or we can say having specific)
properties when compared.
It may be:
➢ High Impact and/or mechanical strength

➢ High Thermal stability

➢ Excellent chemical resistance

➢ Light Weight

➢ Readily moldable into various shapes

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 Engineering Thermoplastic
Polycarbonate – An Engineering Thermoplastic
➢ It is a thermoplastic polyester having functional
group linked together by carbonate group molecular
chain
Molecular Structure of Polycarbonate:

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 Engineering Thermoplastic:
Polycarbonate
Polycarbonate – Structure

Or

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 Engineering Thermoplastic:
Polycarbonate(Lexan, Merlon)
Traditional Synthesis of Polycarbonate by
polycondensation: Using Bisphenol A and Phosgene
and Methylene dichloride is used as a solvent in the
process.

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 Engineering Thermoplastic:
Polycarbonate
Greener Pathway of Polycarbonate Synthesis: Asahi
Chemicals, Japan developed green synthesis of
Polycarbonate to overcome the disadvantages of traditional
synthesis: In this synthesis process, Bisphenol A and
Diphenyl Carbonate are mixed in molten state.

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 Properties of Polycarbonate
• Has high impact strength
• High tensile strength over wide temp. range
• Highly Transparent plastic (@90% light
transmittance and refractive index 1.58)
• Soluble in organic solvents, alkali
• Has Good Heat and Flame resistance
• Low combustibility and High Melting Point
Tm=230-250 0C and Tg =145 0C;
• Good thermal stability
• Limited Chemical and Scratch resistance
• 12-12-2024
Not resistant to UV © Bhavna Vyas 18
 Applications of Polycarbonate
• As insulator in electronics
(Can be used for making industrial plugs, sockets,
covers of cell phones, laptops etc.)
• Used as housing for hair drier bodies, cameras
• Used as bullet proof material vests
• Used to manufacture domestic ware(transparent food
container), helmets, covers of vehicle light
• Handles of screwdriver, for pliers
• To manufacture CD’s, DVD and for housing of
apparatus, Used for substitute for glass in Constru.
• Used for UV thin eye lenses, sunglasses,
Scuba/swimming gogles, visors in helmets, head lamp
lenses in vehicles, windscreens for vehicles etc.
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 Engineering Thermoplastic : Polycarbonate (PC)

SAMPLE QUESTIONS:

1) Differentiate between properties of commodity and engineering

thermoplastics and give one example of each type (3 differences -3M, 1

example of each type -1M)

2) What are engineering thermoplastics? What advantages do they have over

common thermoplastics? (Definition – 1M, advantages – 2 M)

3) Give the structure, properties and applications of

polycarbonate.(structure -1M, 2 properties-1M, 2 applications – 1M)

4) Give reasons for why Polycarbonate is used for making (a) safety goggles;

(b) bullet proof glass; ( c) roofing sheets; (d) CD/DVD (1 M each)

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 Conducting Polymers
Eg.: Polyacetylene:

Polythiopene:

Polypyrrole:

Polyaniline

Structural Requirement:
1) Planar & highly crystalline,
2) Linear
3) Presence of conjugation (free mobile electrons)
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 Conducting Polymers
Eg.: Polyacetylene, Polythiopene, Polypyrole, Polyaniline,

Structural Requirement:
1) Planar & highly crystalline,
2) Linear
3) Presence of conjugation (free mobile electrons)
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 Conducting Polymers:
A polymer which can conduct
electricity

Intrinsically Conducting Extrinsically Conducting

Polymer: Extensive Polymer: Owe their
conjugation in the conductivity due to the
backbone responsible for presence of externally
conductance added ingredients in them
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 Intrinsically
Conducting
Polymer

Conducting Doped
polymers having conducting
conjugation polymers
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b) Doped Conducting polymers
Conductivity of polymers having conjugation can be increased
easily as compared to conventional polymers, as they have low
ioniztion potential and high electron affinities

Conductivities can be increased by creating positive or

negative charge on the polymer backbone by oxidiation or
reduction. The process is referred as Doping by analogy with
semiconductor technology

Doping: Polymer has to be disturbed - either by removing

electrons from (oxidation), or inserting them into (reduction)
into the material.
There are two types of doping:
p-doping: Oxidation with halogen
(positive charge developed on polymer)
n-doping: Reduction with alkali metal
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(negative charge ©developed
Bhavna Vyas
on polymer) 25
 Doping Reactions of Intrinsic
Conducting Polymers
2(CH)x + 3 I2 = 2 (CH)x+ I3-
Polyacetylene Iodine p-Doped polyecetylene

(CH)x + FeCI3 = 2 (CH)x+ FeCI4- + FeCI2

Polyacetylene p-Doped polyecetylene

(CH)x + Na = (CH)x- Na+

Polyacetylene Sodium p-Doped polyecetylene

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Doped conducting polymers: The conducting polymers obtained by
exposing the polymer to a charged transfer agent in either gas phase or in
solution are called doped conducting polymers.
Doping is the process by which conductivity of the polymers may be
increased by creating negative or positive charge on the polymer backbone
by oxidation or reduction. Doping may be of two types:
(A) p-Doping : It is done by oxidation process. In this process, the
conducting polymer is treated with a Lewis acid.
2(CH)x + 3 I2 = 2 (CH)x+ I3-
Polyacetylene Iodine p-Doped polyecetylene
(B) n-Doping : It is done by reduction process. In this process, the
conducting polymer is treated with a Lewis base.
(CH)x + B = (CH)-x B+
Polyacetylene Lewis base n-Doped polyacetylene
Advantages of intrinsically conducting polymers :
(i) Their conductivity
(ii) Their ability to store a charge.
(iii) Their ability to undergo ion exchange.
(iv) They can absorb visible light to give coloured products. (v) They are
transparent to X-rays.

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 Extrinsically
Conducting
Polymers

Conducting Blended
Element Filled Conducting
polymers polymers
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Extrinsically conducting polymers :

Those conducting polymers which owe their conductivity due to the presence
of externally added ingredients in them are called extrinsically conducting
polymers. They are of two types :

(i) Conductive element filled polymers : In this type, polymer acts as a

binder to hold the conducting elements together in solid entity.

(The minimum concentration of the conductive filler, which is added to let the
polymer start conducting is called the percolation threshold). Imp. Charactert.
(a) They possess good bulk conductivity.
(b) They are cheaper.
(c) They are light in weight.
(d) They are mechanically durable and strong.
(e) They are easily processable in different forms, shapes and sizes
(ii) Blended conducting polymers: These types of polymers are obtained by
blending a conventional polymer with a conducting polymer either physically
or chemically. Such polymers can be easily processed and possess better
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physical, chemical and mechanical properties.
Applications of conducting polymers:
1. In Rechargeable Batteries
2. As antistatic material,
3. For preparation of ion exchangers
4. In Optical filters
5. Sensors for pH, O2, SO2, NH3, Glucose
6. In electronics (LED)
7. In Photovoltic cells
8. Telecommuniction systems Solar cell
9. In microelectronic devices
10. Molecular switches
[Link] biomedical applications, controlled
reléase of drugs
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 Conducting polymer : Polyacetylene
SAMPLE QUESTIONS:

1) What is the structural requirement for a polymer to show conductive

property? Give example of a conducting polymer. ( main chain

conjugation with structure – 2M, doping -1M)

2) Give the structure of cis- and trans-polyacetylene. Which has higher

conductance? (2 structures -2M, explanation-1M)

3) Give the structure of polyacetylene. Give one example each of p- and n-

dopant.( structure -1M, 2examples – 2 M)

4) Give the structure, properties and applications of polyacetylene.( (3M)

structure -1M, properties-1M, 2 applications – 1M)

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 Polymer Composites
Polymer based material (matrix phase) & Reinforcing material
(dispersion phase) put together to form composites with
defined interface to obtain specific properties
Essential constituents of Polymer Composite:
Polymer Matrix Phase:
Commercial Thermoplastics (ABS, PE, PP) & Thermoset resins
(polyesters, epoxy resin and phenolic resins) gives a
continuous body constituent, surrounding the other phases
and gives a bulk form to the composite
Objectives (Functions) of Polymer Matrix:
1) To bind the reinforcing particles or fibres strongly
2) Acts as a medium for distribution of external applied load to
reinforcement
3) Keeps proper orientation of reinforcing fibres for high
strength
4) To prevent cracks propagation due to its plasticity & softness
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 Polymer Composites
Reinforced / Dispersion Matrix Phase:
These are the structural constituents like fibres, sheets, particles which
are embedded in matrix phase

Fibres - Long thin filaments of Glass, Carbon, aramides are added to

give high tensile strength, high stiffness and low density

Particulates - Small metallic or nonmetallic particles are added to

increase surface hardness, abrasion resistance and strength, reduces
the cost and carry major portion of the applied load

Types of Polymer Composites:

1) Particles Reinforced Composites / Particulate Composites,

2) Structural Composites : Lamellar sheets/ sandwitched panels
3) Fibre Reinforced Composites

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 Polymer Composites

Schematic representations of the various geometrical and spatial

characteristics of particles of the dispersed phase that may influence the
properties of composites:

(a) concentration, (b) size, (c) shape, (d) distribution, and (e) orientation.
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(From: Richard A. Flinn and Paul K. Trojan, Engineering Materials and Their Applications)
Types of Polymer Composites:
1) Particle Fiber Composite:
Metal powders & oxides, Carbon black, silica (Dispersed
phase or reinforcing phase)

2) Structural composites:
Laminar Composites – Lamellar Sheets (high Strength)or
panels with proper orientation are stacked & cemented
together with resin. Eg. Plywood
Sandwitched Panels – 2 strong outer sheets separated
by a layer of less dense material (core) Face Material can
be FRP whereas core can be synthetic rubber, foamed
polymer. Eg. Aircraft wings, boat hulls, roof floors, walls

3) Fibre reinforced composites:

It is a Composite material made of a polymer matrix
reinforced with fibres (dispersed phase)
Commonly used Fibres - Glass, Carbon, Aramid, Al,
asbestos, paper, wood© fibres
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 Polymer Composites
Based on the form of reinforcement, common composite materials can be
classified as follows:
Particles as the reinforcement
Fibers as the reinforcement (Particulate composites)
(Fibrous Composites)

Random fiber (short fiber) Continuous fiber (long fiber)

reinforced composites reinforced composites

Flat flakes as the reinforcement Fillers as the reinforcement

(Flake composites) (Filler composites)

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 Schematic representations of
(a) continuous and aligned,
(b) discontinuous and aligned, and
(c) discontinuous and randomly oriented fiber- reinforced composites.
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 The stacking of successive oriented,
fiber-reinforced layers for a
laminar composite

Schematic diagram showing

the cross section of a
sandwich panel.
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 Fiber Reinforced Plastics (FRP)
• Fibre-reinforced plastic (FRP):
They are composites that contain fibre in the dispersed phase.
The design goals of fibre reinforced composites often include
high-strength and stiffness on a weight basis.

• Glass-reinforced plastics (GRP): Most commonly used

Popularly known as ‘fibreglass’, made of plastic material
reinforced by fine glass fibres in the dispersed phase.

Properties:
➢ Dimensional stability: Glass fibre exhibits dimensional stability.
It does not stretch or shrink on exposure to extremely high or low
temperatures.
➢ Moisture resistance Glass fibres do not absorb moisture.
➢ High strength: Possess high strength-to-weight ratio. Useful for
applications where high strength and minimum weight is required.
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 Fiber Reinforced Plastics (FRP)

Properties:

➢ Fire resistance: Being inorganic in nature, glass fibre does not

burn or support combustion.
➢ Chemical resistance: Chemically inert. However, they are
affected by hydrofluoric acid, hot phosphoric acids and strong
alkaline substances.
➢ Electrical properties: Have low dielectric constant. Glass fibres
are excellent materials for electrical insulation.

Characteristics Properties of FRP depends on:

1) Nature of orientation, concentration, length and
distribution of fibers
2) Nature of Polymer matrix
3) Strength of interfacial bond between fibre phase and polymer
matrix phase
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 Fiber Reinforced Plastics (FRP)

Glass FRP: High Tensile strength and impact resistance, Lower

densities, Excellent resistance to corrosion and chemicals
(Used in automobiles to reduce weight and used as its parts,
storage tanks, plastic pipes, industrial flooring etc.)

Limitations: Deteriorates at high temp,

Do not possess desired stiffness and
Rigidity cannot be used as structural components

Carbon FRP: High elastic modulus, High temperature and

corrosion resistance (Used as structural components like wings,
body for aircrafts and helicopters)

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Properties of FRP:
• High tensile strength
• High thermal stability
• High Stiffness and lower density
• High dimension stability
• Better abrasion resistance
• Better toughness and impact strength
• Low coefficient of expansion
• Low cost of production

Applications of FRP:
• Automobile bodies, chasis parts, vehicle components
• Boats body, propeller shafts
• Parts of aircrafts
• Sport goods, musical instruments, toys etc
• High speed machinery parts, PCB, bodies of refrigerators,
coolers, cabins for offices, windows, doors

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 Applications of FRPs

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Nanomaterial Introduction :
Definition
Nanomaterials are defined as a set of substances
where at least one dimension is less than
approximately 100 nanometers

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 Nanodimensional Structures
What are nano dimensional Structures?
• When one or more of the dimensions of a solid are
reduced significantly, its physicochemical characteristics
notably depart from those of the bulk solid.
• With reduction in size, novel electrical, mechanical,
chemical, magnetic, and optical properties can be
introduced. The resulting structure is then called a low-
dimensional structure (or system).
• Nanostructures constitute a bridge
between molecules and bulk materials.

• Suitable control of the properties and

responses of nanostructures can lead to
new devices and technologies.

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 12-12-2024 © Bhavna Vyas 48
Source: [Link]
Nanomaterials: Classification
Classification based on:
◆ Origin

◆ Composition

◆ Dimensions

Classification based on Origin:

➢ Natural
➢ Artificial

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Nanomaterials: Classification
Classification based on Composition:

➢ Organic: Carbon based nanomaterials (Graphene,

CNT), Nanobiomaterials, Dendrimers/Polymers

➢ Inorganic: Metals, Metal Oxide, Semiconductors

(QD)

➢ Nanocomposites: Organic/Inorganic

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Nanomaterials: Classification
Classification based on Dimensions:

➢ Three-dimensional (3D) structure or Bulk

nanostructure

➢ Two-dimensional (2D) structure or Quantum wells

➢ One-dimensional (1D) structure or Quantum wires

➢ Zero-dimensional (0D) structure or Quantum Dots

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Nanomaterials: Classification

Dimensionality refers to the

number of degrees of freedom in
the particle momentum rather than
particle confinement direction
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 Nanomaterials: Graphene
▪ Structure: Dimensionality, Details of Carbon atoms

arrangement and bonding, Figure (sheet) required

▪ Properties: Chemical, Physical or Mechanical, Electrical

property (electronics) and optical property, thermal

conductivity etc.

▪ Applications: Potential uses based on different properties

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 Nanomaterial: Graphene
➢ One of the most promising nanomaterial
➢ Discovery of Graphene: In 2004 by Andre Geim and
Konstantin Novoselov
➢ Single atom-thick layer of tightly bonded Carbon
atoms, arranged in flat hexagonal honeycomb like
lattice structure
➢ Monolayer Graphene can be viewed as an
individual plane of Carbon stoms extracted from
Graphite, hence building block
for other Graphitic materials
WONDER Material
12-12-2024 © Bhavna Vyas 54
 Structure of Graphene
➢ Dimensionality: 2D structure
(atomic
thickness: 0.345 nm)
➢ All Carbon
atoms are sp 2
hybridized

12-12-2024 © Bhavna Vyas 55

Source of Image: [Link]
 Key Properties of Graphene

➢ Physical Properties: Atomic thickness, strength,

toughness, surface area, impermeability, thermal

Conductivity

➢ Chemical Properties: Reactivity

➢ Electrical Properties: Electron mobility

➢ Optical Properties: Transparency

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 Physical Properties of Graphene
• One of the thinnest (only one carbon atom
thick ~0.34 nm)
• Flexible material; most stretchable crystal
(stretch upto 20%-25% of initial size w/o
breaking it)
• Toughest 2D material: Harder than either
steel ( 200 times stronger than steel ) or
diamond of the same dimensions

• High tensile strength

( of over 1 Tpa)

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 Physical Properties of Graphene
• Lightweight; it weighs just 0.77 mg/m 2

• Highest surface area to Volume ratio, since single 2D

sheet

• Highly impermeable (even He atoms cannot go through it)

• Perfect thermal conductor: Conducts heat in all directions - it

is an isotropic conductor

• The measured thermal conductivity of Graphene is in the range

of 3000 to 5000 W/m/K at room temperature which is among
the highest of any other known material

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Chemical Properties of Graphene
• An inert material and does not readily react with
other atoms (Even though all of graphene’s atoms are
exposed to the environment).
• However, “absorb” different atoms and molecules. This
can lead to changes in the electronic properties.

• Ca n also be functionalized by various chemical

groups, which c an result in different materials s u c h a s
graphene oxide or fluorinated graphene
(functionalized with fluorine).

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Electrical Properties of Graphene
• High electrical current density (million times that of
copper) and intrinsic mobility (100 times that of silicon)
• Lower resistivity than any other known material
at room temperature, including silver.
• There are also some methods to turn it into a
superconductor ( carry electricity with 100% efficiency)
• Although graphene, the fastest and most efficient
conductor, it cannot be readily used to make transistors
as it does not have a bandgap.
• There are several methods to open a
bandgap that are in existence and
some
12-12-2024that are under development
© Bhavna Vyas 60
 Optical Properties of Graphene
• Extremely thin, but still a visible material, as it absorbs
about 2.3% of white light (which is quite a lot for a 2D
material) i.e. 98% of visible light passes through
graphene, making it transparent

• Combine this with graphene’s amazing electronic

properties, and it turns out that graphene can
theoretically be used to make very efficient solar cells

• In addition, absorbing 2.3% of

visible light still makes graphene
very much transparent to the
human eye, which may have
various uses. E.g.: Used to make
transparent
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 Potential Uses of Graphene
Water Filtration Systems: For purification of water a s it
allows water to pa ss , but not other liquids and gases
Touch Screens in Devices: Transparency and
conductivity of graphene can be us ed in displays and
touchscreens, however more expensive to produce than
currently us ed indium tin oxide

In Electronic Devices: Touted a s

Siliocon’s successor and has
been used to make very fast
transistors. However, its
conductivity cannot be switched
off a s Silicon can.
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 Potential Uses of Graphene
Sensors :Graphene as sensor is ultrasensitive as every atom
is exposed to it’s surrounding allowing it to sense changes in
the surrounding. For e.g.
➢ To produce Smart food Packaging that detects atmospheric
changes caused by decaying food.
➢ To protect the crops as Farmers would be able to monitor the
existence of any harmful gases and determine ideal areas for
growth of certain crops depending on atmospheric conditions
➢ To monitor stresses and strains in constructional components
➢ To detect biological agents like drugs in our body
➢ To detect light and used in camera
It is Multifunctional material and allows
To create
12-12-2024
micrometer sized sensor
© Bhavna Vyas 63
 Potential Uses of Graphene
Drug delivery in Medical field:

➢ Several biomedical applications are being explored for

graphene, including drug delivery, cancer therapy, etc.

However, its toxicity profile must be investigated before

clinical use
Energy Storage & Composites:
➢ Used in normal batteries and supercapacitors a s a
Substitute for graphite that can
store more energy, charge faster

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 Graphene Products
Head You Tek Graphene Instinct Tennis Racquet (In 2013 )
Uses Graphene coating on the shaft to make it stronger
and better controlled racket
Huawei’s Mate 20 X smartphone uses Graphene film cooling
technology for heat management purpose
Cardea uses a graphene based biosensors and AGILE system
which allows for real time detection of small molecules which
offer faster sample processing, greater accuracy, portability and
cost savings
Ford used Graphene reinforced foam
covers for noisy components in its
2019 F-150 and Mushtang cars
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Nanomaterials: Carbon Nanotube

▪ Structure: Dimensionality, Details of Carbon atoms

arrangement and bonding, Figure (sheet) required

▪ Properties: Chemical, Physical or Mechanical, Electrical

property (electronics) and optical property, thermal

conductivity etc.

▪ Applications: Potential uses based on different properties

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 Structure of Carbon Nanotube

➢ Tubular form of carbon with diameter as small

as 0.5 to 1 nm and Length: few nm to microns.
➢ Dimensionality: 1D
(but configurationally equivalent to
2D graphene sheet rolled into a tube)
➢ All Carbon atoms are sp2 hybridized
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 Types: Carbon NanoTubes

• Single Wall CNT (SWCNT): One-atom

thick single tube
• Multi-Wall CNT (MWCNT): Buildup of
a12-12-2024
number of concentric tubes
© Bhavna Vyas 68
Based on the arrangement of Carbon atoms,
Carbon Nanotubes are further classified as:

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 Properties: Carbon Nanotubes
➢ High Electrical Conductivity
➢ Very High Tensile Strength (Higher than steel and Kevlar)
➢ Highly Flexible- can be bent considerably without damage
➢ High Thermal Conductivity
➢ Light weight
➢ Highly Absorbent
➢ High Aspect Ratio
(length = ~1000 x diameter)
➢ Low Thermal Expansion Coefficient
➢ Very Elastic ~18% elongation to failure

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 Electrical Properties of CNT
High Electrical properties:
Electrical Conductivity in nanotubes is based on the degree of
chirality – i.e. the degree of twist and size of the diameter of the
actual nanotube - which results in actually extremely
conductive (making it suitable as an interconnect on an
integrated circuit) or non-conductive (making it suitable as the
basis for semi-conductors) nanotube.
➢ Electron transport occurs only along
the axis of the tube.
➢ Single walled nanotubes can route
electrical signals at speeds up to 10 GHz
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 Thermal Properties of CNT

High Thermal Conductivity:

The strength of the atomic bonds in carbon
nanotubes allows them to withstand high temperatures
Very good thermal conductors.
● When compared to copper wires, which are commonly
used as thermal conductors, the carbon nanotubes can
transmit over 15 times the amount of W/m K
● The thermal conductivity of CNT
depends on the temperature of tube
and the outside environment
12-12-2024 © Bhavna Vyas 72
Synthesis of Carbon Nanotubes
Carbon nanotubes can be synthesized by:
• Arc Discharge method
• Laser Ablation
• Chemical Vapour Deposition (CVD)
➢ CVD has the highest potential for mass production of CNT
It can produce bulk amounts of defect-free CNTs at
relatively low temperatures.
➢ Arc Discharge method: Used to
synthesize CNTs in small quantities
➢ Laser Ablation

12-12-2024 © Bhavna Vyas 73

Applications of Carbon Nanotubes
Drug delivery:
CNT-Promising Drug Delivery Carrier
➢ Carbon nanotubes present the opportunity to work with
effective structures that have high drug loading
capacities and good cell penetration qualities
➢ Carbon nanotubes function with a larger inner
volume to be used as the drug container, large aspect
ratios for numerous
functionalization attachments,
and the ability to be readily taken
up by the cell
12-12-2024 © Bhavna Vyas 74
Applications of Carbon Nanotubes
Waste-water treatment:

➢ CNTs have a very large surface area (e.g.,~ 500 m2 per

gram of nanotube) that gives them a high capacity to
retain the pollutants
➢ Can also be Used as air filtration
Solar cells:
➢ Due to their strong UV/Vis-NIR
absorption characteristics,
SWNTs are a potential candidates
` for use in solar panels.
12-12-2024 © Bhavna Vyas 75
Applications of Carbon Nanotubes
Catalysts Support:
➢ CNTs provides an opportunity for Catalyst supports
because large surface area and ability to attach any
chemical species to their sidewalls (Functionalization)

Composites and Adhesives/Coatings:

➢ CNT Ceramic Reinforced Composite
➢ Used as adhesives of different
stiffness by varying the
concentration of CNTs
12-12-2024 © Bhavna Vyas 76
Applications of Carbon Nanotubes
Electronics Field:

➢ SWNT ropes are the most conductive carbon fibers known

➢ SWNT can be used as High performance and thin film
Field Effect Transistors (CNT based sensors) are wide
used to detect gases such as greenhouse gases in
environmental applications
➢ Bucky paper thin tube can be used as Heat Sink for
chipboards

.
12-12-2024 © Bhavna Vyas 77
Applications of Carbon Nanotubes
Used in various fields:
1) Medical field
2) Filtration Units
3) Structural materials
4) Textiles (Fabric and Fibers)
5) Plastic
6) Energy Storage
7) Composites etc.

12-12-2024 © Bhavna Vyas 78

 Nanomaterials: Quantum Dots
▪ Introduction: Definition, Common QD materials (group)

Dimensionality,

▪ General Feature: Effect of Interaction of UV light with

different sizes, Band gap tuning by size (splitting of energy

levels due to size/composition)

▪ Properties: Electronic and Optical

▪ Applications: Uses in Different domains

12-12-2024 © Bhavna Vyas 79

 Nanomaterials: Quantum Dots
▪ Definition: Quantum dots (QDs) are often referred to
very tiny man-made semiconductor nanoparticles/nano
structures whose sizes are normally not more than 10
nanometers (2-10nm), that exhibit 3-dimensional
quantum confinement, which leads to many unique
optical and transport properties

▪ QDs have ability to absorb the light and then emit a light
of specific λ with the release of energy
(Broadly, Quantum confinement means restricting the motion of
randomly moving electrons in very small particle to a specific
discrete
12-12-2024
energy levels rather than a quasi continuum of energy
© Bhavna Vyas 80
 Nanomaterials: Quantum Dots

▪ Dimensionality: 0-dimensional nanostructure

Degree of freedom of particle momentum is zero while

motion of electron-hole pair is confined/restricted in all 3

spatial dimensions

Examples: Typically, QD composed of the elements of

periodic groups II-VI, III-V and IV-VI materials like CdSe,

CdS2, InSe, PbSe, InP, GaAs, CdSe/ZnS etc.

12-12-2024 © Bhavna Vyas 81
 Types of Quantum Dots
Quantum Dots can be classified based on their composition
and structure:
▪ Core Type QD: Single component material with uniform
composition like Chalcogenides (selenides,sulfides or
telurides) of metals like Cd, Pb or Zn
▪ Core Shell QD: Particles of one material embedded in
other, e.g. QD with CdSe in the core and ZnS in the shell
▪ Alloyed QD: Alloying together two semiconductor with
different composition

12-12-2024 © Bhavna Vyas 82

General Feature of Quantum Dots
• When illuminated by UV light, some of the electrons receive
enough energy to break free from the atoms.
• This capability allows them to move around the nanoparticle,
creating a conductance band in which electrons are free to
move through a material and conduct electricity. When these
electrons drop back into the outer orbit around the atom (the
valence band), they emit light.
• The color of that light depends on the energy difference
between the conductance band and the valence band
• A majority of QDs have the ability to emit light of specific
wavelengths if excited by light or electricity.

12-12-2024 © Bhavna Vyas 83

 Absorption and emission occur at specific
wavelengths, which are related to QD size.

12-12-2024 © Bhavna Vyas 84

Source: [Link]
 Properties of Quantum Dots
• QDs properties can be determined by their size, shape,
composition and structure.
• QDs show color glow when illuminated by UV light of
specific λ
Typically, smaller QDs (e.g., radius of 2~3 nm) emit
shorter wavelengths generating colors such as violet,
blue or green. While bigger QDs (e.g., radius of
5~6 nm) emit longer wavelengths generating colors like
yellow, orange or red.

12-12-2024 © Bhavna Vyas 85

Quantum Size Effect: Splitting of energy levels in QD
Source: [Link]/

Energy levels become discrete, and energy becomes larger

compared to bulk of same material
Semiconductor band gap increases with decrease in size
of the nanocrystal
12-12-2024 © Bhavna Vyas 86
 Properties of Quantum Dots
• Smaller QDs have a large bandgap
• Absorbance and luminescence spectrums are blue
shifted with decreasing particle size
• QDs are bandgap tunable by size/composition
which means optical and electrical properties
can be engineered to meet specific applications

12-12-2024 © Bhavna Vyas 87

Emission of different color of light by tuning the composition

Photoluminescence of alloyed CdSxSe1-x/ZnS quantum dots of

6nm diameter. The material emits different color of light by tuning
the composition

12-12-2024 © Bhavna Vyas 88

Source: [Link]/
Potential Uses of Quantum Dots
QDs find variety of applications in different domains:

➢ BioImaging

➢ LEDs

➢ Solar Cells

➢ Dyes

➢ Miniature Lasers communication devices

➢ TV/Electronic devices Displays etc.

12-12-2024 © Bhavna Vyas 89

Potential Uses of Quantum Dots
BioImaging:

➢ QDs are coated with hydrophilic polymers and also be

conjugated to obtain multifunctionality. They can be

linked with biological agents such as antibodies,

peptides, oligonucleotides, inhibitor molecules etc.

E.g. QDs can be used in cancer detection.

Detection of tumor in human body,

Multicolor Imaging of the tumor
tissue by QDs in live ©animals
12-12-2024 Bhavna Vyas 90
 Potential Uses of Quantum Dots
BioImaging:
➢ In-vivo imaging poses problems with the clearance of
the particles from body.
(Toxicity and hazards effects needs to be evaluated
thoroughly)
➢ QDs of different colors are used for imaging multiple
target simultaneously.
CdSe/ZnS QDs used to
image cancer cells
Source: [Link]

Gao, Xiaohu. "In

vivo cancer
targeting and
imaging with."
Nature
12-12-2024 Biotechnology
© Bhavna Vyas 91
 Potential Uses of Quantum Dots

➢ Light Emitting Diodes:

Quantum dot light emitting diodes (QD-LED) and ‘QD-
White LED’ are very useful for displays in electronic devices
QD-LED displays can render colors very accurately and
use much less power than traditional displays.
Quantum-dot-based LEDs emission wavelength can be
easily tuned by changing the size of the quantum dots

12-12-2024 © Bhavna Vyas 92

Potential Uses of Quantum Dots
Solar Cells:

➢ Quantum dot (QD) solar cells have the potential to

increase the maximum conversion of efficiency of solar

photon conversion up to about 66% by utilizing hot

photogenerated carriers to produce higher photovoltages

or higher photocurrents

➢ Cost effective
➢ Cu-InSe sulfide QD–nontoxic than QDs containing
Pb/Cd
12-12-2024 © Bhavna Vyas 93
Potential Uses of Quantum Dots
Alternative to traditional Dyes:
➢ Quantum dots are an attractive alternative to
traditional organic dyes because of their high quantum
yield (brighter emission) and photostability.
➢ The quantum yield of some QDs is 20 times greater
than traditional organic fluorophores

12-12-2024 © Bhavna Vyas 94

 Organic Semiconductor Memory Materials
Memory Materials ??

Remember and revert to a previous state when exposed to a specific external stimulus.

Semiconductor Memory Materials ??

Refer to materials used to store data in electronic devices, leveraging their ability to

maintain different states (like charge or magnetic orientation) to represent binary

information (0s and 1s).

Organic Semiconductor Memory Materials ??

Based on organic compounds that can store and retrieve data by exploiting the

electrical, optical, or magnetic properties of organic molecules or polymers.

Lightweight, flexible, and low-cost used in memory devices suitable for emerging

technologies
12-12-2024 like wearable electronics,©flexible
Bhavna Vyasdisplays, and the Internet of Things
95(IoT)
Organic Semiconductor Memory Materials
Characteristics of Organic Semiconductors
• Lightweight and Flexible: Suitable for wearable and flexible devices.

• Solution-Processable: Enables low-cost, large-area fabrication.

• Tunability: Properties can be tailored through chemical modifications.

• Environmental Sensitivity: Requires encapsulation to protect against oxygen

and moisture.

Examples of Common Organic Semiconductors:

Pentacene (C22H14)

Perfluoroentacene (C 22F14)

Fullerenes (e.g., C₆₀ and C₇₀)

Rubrene (C42H28)

Polyfluorene (PFO)
12-12-2024 © Bhavna Vyas 96
Organic Semiconductor Memory Materials
Structural Characteristics of p type Pentacene
• Pentacene molecules have a planar structure with five linearly fused aromatic
rings, enabling strong π-π stacking.

• This molecular arrangement promotes efficient charge transport.

• Chemical Formula: C22H14

12-12-2024 © Bhavna Vyas 97

 Properties of p type Pentacene
Electrical Properties: Pentacene is a p-type semiconductor, meaning it

predominantly conducts via holes (positive charge carriers).

➢ Hole Mobility: Among the highest for organic semiconductors, reaching values

up to 3 cm²/V·s under optimized conditions, crucial for efficient charge

transport.

➢ Ionization Energy: ~5.0 eV, suitable for hole injection and conduction in

memory devices.

➢ Charge Retention: When combined with charge-trapping or ferroelectric

layers, pentacene provides stable, non-volatile data storage.

Optical Properties

➢ Strong absorption in the visible spectrum, which can contribute to

photoinduced
12-12-2024 memory effects in specific device designs.
© Bhavna Vyas 98
 Properties of p type Pentacene
Morphological Properties:

➢ Forms highly crystalline thin films with π-π stacking, ensuring efficient charge

transport.

➢ Films can be deposited via vacuum sublimation or solution processing, allowing

for versatile fabrication methods.

Environmental Sensitivity:

➢ Prone to degradation from oxygen, moisture, and UV light, requiring

encapsulation to ensure long-term device stability.

Flexibility and Processability

➢ Compatible with flexible substrates and low-temperature processing, making it

suitable for bendable and wearable electronics.

12-12-2024 © Bhavna Vyas 99
 Applications of Pentacene in Memory Devices
Pentacene in Memory Devices

• Pentacene serves as the active layer in organic memory devices,

particularly in organic field-effect transistors (OFETs) and organic
thin-film transistors (OTFTs). It interacts with other materials to
provide memory functionalities such as non-volatile data storage.

1. Non-Volatile Memory: Used in organic flash memory where stored

information persists without power.

2. Flexible Electronics: Thin films of pentacene are compatible with

flexible substrates, making them suitable for wearable electronics.

3. Low-Cost, Large-Area Devices: Enables scalable production of

memory devices for IoT and low-cost consumer electronics.

12-12-2024 © Bhavna Vyas 101
Organic Semiconductor Memory Materials
Structural Characteristics of n type Perfluoropentacene (PFP)

• Consists of five linearly fused benzene rings, similar to pentacene, n-type

organic semiconductor derived from pentacene by replacing all hydrogen
atoms with fluorine atoms, which are highly electronegative.

• The planar structure facilitates π-π stacking in the solid state, crucial for
charge transport.

• This substitution significantly alters

the electronic structure, making PFP

suitable for electron transport in

organic electronic devices

• Chemical Formula: C22F14

12-12-2024 © Bhavna Vyas 102

Organic Semiconductor Memory Materials
Key Modifications Due to Fluorination:
• Increased Electron Affinity: The electronegative fluorine atoms lower the
LUMO (Lowest Unoccupied Molecular Orbital) energy level, enabling efficient
electron transport.

• Hydrophobicity: Fluorination increases resistance to moisture, improving

environmental stability.

• Crystal Packing: The molecular packing density is altered due to fluorine’s

influence, enhancing charge transport properties.

12-12-2024 © Bhavna Vyas 103

 Properties of n type Perfluoropentacene (PFP)
1. Electronic Properties:

1. Electron Affinity: High (~4.0–4.5 eV), making it an excellent electron

acceptor for n-type conductivity.

2. Charge Mobility: Moderate to high electron mobility, depending on film

quality and deposition techniques.

3. Energy Levels: The substitution with fluorine lowers the HOMO and
LUMO energy levels, favoring electron conduction.

2. Optical Properties: Strong absorption in the visible spectrum, enabling

potential applications in light-sensitive devices. Red-shifted absorption
compared to pentacene due to fluorination.

3. Thermal Stability: More thermally stable than pentacene, making it suitable

for high-temperature applications.

4. Environmental Stability: Superior to pentacene in resisting oxidation and

degradation, thanks to the protective fluorine atoms.

5. Mechanical Properties: Retains flexibility and compatibility with thin-film

12-12-2024 © Bhavna Vyas 104
deposition methods, similar to other organic semiconductors.
 Applications of n type Perfluoropentacene (PFP)
1. Organic Field-Effect Transistors (OFETs):

1. Acts as the active layer for electron transport.

2. Used in low-power, flexible electronics.

2. Organic Photovoltaics (OPVs):

1. Serves as an electron acceptor material in donor-acceptor systems.

2. Enhances charge separation and transport efficiency in solar cells.

3. Organic Light-Emitting Diodes (OLEDs): Functions as an electron-transport

layer (ETL), complementing p-type materials like pentacene.

4. Memory Devices: Utilized in organic resistive memory (ORM) and charge-

trapping memory architectures. Non-volatile memory applications benefit from
its stability and electron affinity.

5. Chemical Sensors: Sensitive to specific gases or analytes due to its n-type

behavior, making it ideal for environmental monitoring.

6. Flexible and Wearable Electronics: Compatible with flexible substrates,

enabling
12-12-2024 applications in wearable©devices
Bhavna Vyasand smart textiles. 105
 Thanks!!!

12-12-2024 © Bhavna Vyas 106