UNIT- 4

Polymers and Composites for Flexible Electronics

Stretchable and Wearable Microelectronics:

Stretchable and wearable microelectronics are a growing field of technology that creates
lightweight, flexible devices for monitoring and interaction by conforming to the body, similar to
skin. These devices integrate sensors, displays, and circuits onto substrates that can withstand
stretching and bending, enabling applications like smart clothing, electronic skins, and advanced
health monitors. This approach replaces rigid traditional electronics with devices that are more
comfortable and can collect real-time physiological data non-invasively.
Stretchable substrates: Materials like polydimethylsiloxane (PDMS) with a low modulus are
used as the base for these circuits, as they are soft and can stretch over 40% without failure.
Conductive materials: Metals like gold and silver, carbon nanotubes, or graphene are embedded
in the stretchable substrate to form the functional circuits.
Stretchable components: Researchers have developed intrinsically stretchable diodes,
transistors, and antennas that can operate at high frequencies, crucial for wireless capabilities.
Flexible displays: These are integrated into smart textiles and electronic skins to provide real-
time feedback directly on the user's body.

Applications
Healthcare: Continuous, remote patient monitoring for a wide range of physiological parameters
like heart rate, blood oxygenation, and blood pressure.
Smart textiles: Integrating sensors and displays into clothing to create smart garments that can
monitor activity, vitals, or even provide adaptive camouflage.
Human-machine interfaces: Creating "electronic skins" that can act as sensors or provide
feedback on the body, and developing wireless devices for seamless interaction.
Personal and environmental monitoring: Creating personal wearable gadgets and, in other
sectors, using similar technology for agricultural sensors to monitor crop conditions like
temperature and moisture.

Introduction of Lithography
Lithography is a core microfabrication technique used to transfer geometric patterns onto a
substrate, which then serves as a template for subsequent processes like patterned material
deposition or etching. In the case of patterned copper deposition, the technique most commonly
uses an additive process like electroplating in conjunction with photolithography, often referred
to as the Damascene process in semiconductor manufacturing.
Basic Principles
The fundamental principle of lithography is to create a three-dimensional relief image in a
photosensitive polymer (photoresist) using a mask and an energy source (e.g., UV light, electron
 beam). The key steps involve changing the solubility of the resist material upon exposure to
radiation.
Positive Photoresist: The areas exposed to radiation become more soluble and are removed
during development.
Negative Photoresist: The areas exposed to radiation become less soluble (e.g., through cross-
linking) and the unexposed areas are removed during development.

The resulting patterned resist layer acts as a stencil, allowing the underlying substrate to be
selectively modified in the exposed or unexposed regions.

Working of Lithography for Micro-patterned Copper Deposition

For patterned copper deposition, an additive process is typically used. The lithography creates a
mold or template into which the copper is deposited, often by electroplating or electroless
deposition.
The general sequence of steps is as follows:
1. Substrate Preparation: The substrate (e.g., a silicon wafer with an insulating layer) is cleaned
to ensure good adhesion of subsequent layers. An adhesion promoter (like HMDS
(HexaMethylDiSilazane)) may be applied.
2. Seed Layer Deposition: A thin, uniform conductive seed layer (often copper itself, or
sometimes a barrier/adhesion layer like titanium or tantalum followed by copper) is deposited
over the entire substrate using techniques such as sputtering or chemical vapor deposition
(CVD).
3. Photoresist Coating: A layer of photoresist (typically a thick, negative-tone resist for creating
the deep trenches needed for copper interconnects) is applied to the seed layer, usually via spin
coating, and soft-baked to remove excess solvent.
4. Exposure and Development: A photomask containing the desired pattern is placed over the
resist, which is then exposed to a light source (e.g., UV light). The exposed areas are then
developed away, leaving a pattern of open trenches in the photoresist layer that exposes the
underlying seed layer in specific areas.
5. Copper Deposition: The entire wafer is then placed in an electroplating bath (e.g., a copper
sulfate solution). The exposed seed layer acts as the electrode, allowing copper to selectively
grow within the trenches of the photoresist pattern and over the top, filling the open areas.
6. Resist Strip (Lift-off/Planarization): The remaining photoresist is stripped away (lift-off
process) using a chemical solvent, which also removes the excess copper deposited on top of the
resist, leaving only the desired copper pattern directly on the substrate. For global planarization,
chemical mechanical polishing (CMP) may be used to remove the excess metal and resist from
the top surface.
This method allows for the creation of precise, high-aspect-ratio copper interconnects essential
for modern microelectronics
 Polydimethylsiloxane
Polydimethylsiloxane is a polymer whose monomer is dichlorodimethylsilane. Generally, PDMS
is produced via a chain-growth polymerization reaction involving hydrolysis and condensation
reactions. This polymer is known to be a thermoplastic polymer, i.e. it softens upon heating and
can, therefore, be remolded.
Synthesis:

H2O

→ →
-H2O

Dichlorodimethylsilane Polydimethylsiloxane
Properties
• Its elastomeric nature,
• High flexibility,
• Biocompatibility,
• Chemical inertness,
• Hydrophobicity, and transparency

Applications of PDMS
• Biomedical: Its biocompatibility and inertness make it ideal for use in medical devices,
implants, contact lenses, and microfluidic devices for biological research and diagnostics.
• Microtechnology: It is extensively used in microelectromechanical systems (MEMS),
microfluidics, and sensors due to its precise fabrication properties and mechanical
versatility.
• Coatings and sealants: Its flexibility, water repellency, and stability allow it to be used
as a component in sealants (caulk), lubricants, and coatings for various surfaces.
• Contaminant remediation: PDMS sponges, synthesized from sugar templates, can be
used for the selective absorption of oil and organic pollutants from water due to their
hydrophobic/oleophilic properties.

Applications of PDMS (polydimethylsiloxane) for e-skin

PDMS is used in e-skin applications for creating flexible, stretchable, and transparent sensors
that can detect pressure, temperature, and human movement
• Flexible substrates: PDMS serves as a flexible and stretchable base for mounting other
electronic components, enabling wearable and skin-mountable devices.
• Pressure sensors: It is used to create high-sensitivity pressure sensors that can detect
very light pressures and track human movements like gait and posture.
• Temperature sensors: PDMS nanostructures can be engineered into self-powered
temperature sensors that use the triboelectric effect to convert mechanical motion into
electrical signals, with the output signal changing based on temperature.
• Microfluidic channels: PDMS is used to create microchannels filled with materials like
liquid metal, which can function as stretchable and highly sensitive tactile sensors for e-
skin.
• Protective and encapsulating layers: A thin layer of PDMS can be used to encapsulate
and protect the underlying electronic components of an e-skin, ensuring durability and
function.
• Multifunctional e-skin: By integrating different materials and microstructures, PDMS-
based e-skins can be designed to monitor multiple physiological signals simultaneously,
such as pressure and temperature, for health monitoring and human-computer
interactions.
Radio Frequency Identification applications:
• Traditional RFID tags are often rigid and prone to damage when bent or twisted. PDMS
enables the creation of flexible and wearable RFID tags for applications such as
healthcare monitoring, logistics, and body area networks.
• Stretchable composites: When combined with conductive materials like carbon
nanotubes, PDMS forms stretchable and conductive composites that can function as
antenna elements. This allows the development of truly conformable and wearable RFID
tags.
• PDMS is an excellent dielectric isolator that can be used to protect fragile electronic
components, like RFID chips, from mechanical shock and environmental elements such
as moisture.
Polymer

Introduction:
A polymer is a large molecule, or macro-molecule, composed of many repeated sub units. The
term "polymer" derived from the ancient Greek word meaning "many, much"and meros,
meaning "parts, and refers to a molecule whose structure is composed of multiple repeating
units, from which originates a characteristic of high relative molecular mass and attendant
properties. Because of their broad range of properties, both synthetic and natural polymers play
an essential and ubiquitous role in everyday life. Polymers range from familiar synthetic plastics
such as polystyrene to natural biopolymers such as DNA and proteins that are fundamental to
biological structure and function. Polymers, both natural and synthetic, are created via
polymerization of many small molecules, known as monomers. Their consequently large
molecular mass relative to small molecule compounds produces unique physical properties,
including toughness, viscoelasticity, and a tendency to form glasses and semicrystalline
structures rather than crystals.

Definition of polymers: A polymer is a large molecule of high molecular weight obtained by the
chemical interaction of many small molecules of low molecular weight of one or more type. The
process of manufacture of a polymer is called the polymerization.
Monomers: Small molecules of low molecular weight, which combine to give a polymer, are
called monomers.

Degree of polymerization: The number of monomers used in the process is called degree of
polymerization.

Functionality: The total number of functional groups or bonding sites present in a monomer
molecule is called the functionality of the monomer.
Polymerization: Is the process of conversion of low molecular weight substances into high
molecular weight substances with or without the elimination of by products such as HCl, H2O,
NH3 etc.
Synthesis of Polyacetylene
It is prepared by polymerization of acetylene under low pressure (6 - 7atm) in presence of
triethyl aluminium and titanium tetrachloride (Ziegler – Natta catalyst) initiator or catalyst at a
temperature of 333K – 343K.
The reaction is given below –

Conduction mechanism of polyacetylene

The conduction mechanism of polyacetylene relies on doping to introduce mobile charge
carriers, such as polarons and bipolarons (for p-type) or solitons (for n-type), along its
conjugated π-electron backbone. This doping creates a charge-transfer complex between the
polymer and the dopant, allowing these charge carriers to delocalize and move along the chain
under an applied electric field, mimicking a metal by enabling electron flow.
 Molecular Weight of Polymer
“Molecular weight of a polymer is defined as sum of the atomic weight of each of the atoms in
the molecules, which is present in the polymer”.
This distribution of molecular weights is caused by the statistical nature of the polymerization
process e.g. methane (CH4) molecules have the same molecular weight (16), but all polyethylene
do not have the same molecular weight because the statistical distribution of molecular weight
may be different for the different grade of the polyethylene and the degree of polymerization
may also be different.

Number Average Weight(Mn¯)

The number average molecular weight is mass obtained when total mass of all the molecules of
the sample is divided by total number of molecules.

Mn¯ = ∑niMi
∑ni
w =Total weight, n=Total number of particles,
n1M1 + n2M2 + ….
n1 + n2 + ------
(Where n1, n2---etc are number of particles having mass M1, M2 etc.)

Weight Average Molecular Weight (Mw¯)

The weight average molecular weight is mass obtained when sum of the products of total mass of
groups of molecules of the sample is divided by total mass of all molecules.

Mw¯ = ∑niM2i
∑niMi
2 2
= n1 M1 + n2 M 2 + ------ (Since W1 = n1m1)
n1 M1 + n2 M2 +-----

Numerical Problems on Polymers

1. A polymer sample contains 2, 3 and 4 molecules having molecular weights 2 x 103, 3 x 103 and 4
x 103 respectively. Solve for the number average and weight average molecular weights of the
polymer.
Mn¯ = n1 M1 + n2 M2 + ------
n1 + n2+ …..
=2(2x103)+3(3x103)+4(4x104)= 3.22x103
2+3+4

Mw¯ = n1 M12 + n2 M22 + ------

n1 M1 + n2 M2 +-----
 2( 2x103)2+3(3x103)2+4(4x104)2 = 3.41x103
2( 2x103)+3(3x103)+4(4x104)

2. A polymer sample has population as follows: 5 molecules of molecular mass each= 2000; 4
molecules of molecular mass each = 3000; 3 molecules of molecular mass each = 4000. Solve
for its number average and weight average molecular weights.
Mn¯ = n1 M1 + n2 M2 + ------
n1 + n2 + -
= 5( 2x103)+4(3x103)+3(4x103) = 2833.3
5+4+3

Mw¯ = n1 M12 + n2 M22 + ------

n1 M1 + n2 M2 +-----
5( 2x103)2+4(3x103)2+3(4x103)2 = 3058.82
5( 2x103)+4(3x103)+3(4x103)
3. Solve for Mn and Mw of a polymer which consists of 35% molecules having molecular mass
25000, 35% molecules having molecular mass 20000 and the remaining molecules having
molecular mass 10000.
Mn¯ = n1 M1 + n2 M2 + ------
n1 + n2+ ------

= 35x25000+35x20000+30x10000 = 18750
100
Mw¯ = n1 M122 + n2 M2 + ------
n1 M1 + n2 M2 +-----
35x(25000)2+35x(20000)2+30x(10000)2 = 20733
35x25000+35x20000+30x10000

4. Solve for number average and weight average molecular weights of a polymer consisting of 150
molecules with molecular mass 102g/mol, 200 molecules with molecular mass 103 g/mol and
350 molecules with molecular mass 105g/mol.
Mn¯ = n1 M1 + n2 M2 + ------
n1 + n2+ -
=150x102+200x103+350x105 =50307
150+200+350

Mw¯ = n1 M12 + n2 M2 2 + ------

n1 M1 + n2 M2 +-----
150(102)2+200(103)2+350(105)2 = 99395.18
150x102+200x103+350x105
 Polyvinylidene Fluoride (PVDF)
Synthesis: PVDF is produced via a radical polymerization of monomers of vinylidene
difluoride. Even though PVDF has alternating -CH2 and -CF2 groups it is still a homopolymer
because it consists of just one repeating monomer unit.

Properties of Polyvinylidene Fluoride (PVDF)

It is a semi-crystalline fluoropolymer known for its exceptional resistance to chemicals,
• PVDF exhibits excellent mechanical strength and toughness,
• Good Thermal properties-PVDF can withstand a wide range of temperatures while
maintaining its structural integrity.
• Unique electrical properties- PVDF's electrical characteristics are crucial for its use in
sensors and actuators.

PVDF offers several advantages over other materials for E-nose applications:
• High β-phase content: High piezoelectric and ferroelectric properties in the β-phase
ensure a strong, measurable electrical signal in response to chemical stimuli.
• Chemical stability: As a fluoropolymer, PVDF is highly resistant to a wide range of
corrosive chemicals, solvents, and UV radiation, ensuring sensor longevity.
• Flexibility and scalability: Its processability allows for the fabrication of flexible and
miniaturized sensors, which are ideal for integration into portable E-nose devices.
• Composite formulation: PVDF's compatibility with various nanomaterials allows for
the creation of composites with tunable properties, enabling the design of highly sensitive
and selective sensor arrays.
Polymer Composites:
A polymer composite is a material made of at least two constituent materials with different
physical or chemical properties, where at least one is a polymer. These materials are strategically
combined to create a product with superior properties and performance that surpasses the
individual components. A typical polymer composite consists of a polymer matrix that holds
dispersed filler or reinforcing materials, such as fibers or particles.
Fibers
Introduction
Fibers are like tiny little rods or tubes - much longer than they are wide. Fibers can be natural -
from plant or animals, or synthetic - made by people. Fiber is a natural or artificial substance that
is significantly longer than it is wide. Fibers are often used in the manufacture of other materials.
The strongest engineering materials often incorporate fibers, for example carbon fiber and ultra-
high-molecular-weight polyethylene.
Synthetic fibers can often be produced very cheaply and in large amounts compared to natural
fibers, but for clothing natural fibers can give some benefits, such as comfort, over their synthetic
counterparts.
Kevlar:
KEVLAR is one of the most important man-made organic fibers ever developed. Because of its
unique combination of properties, KEVLAR is used today in a wide variety of industrial
applications. KEVLAR para-aramid fiber possesses a remarkable combination of properties that
has led to its adoption in a variety of end uses since its commercial introduction in the early
1970s.

Synthesis: It is prepared by condensation polymerization between aromatic dichloride and

aromatic diamines with continuous elimination of HCl.

Properties of Kelvar
• High tensile strength at low weight
• Low elongation to break
• High modulus (structural rigidity)
• Low electrical conductivity
• High chemical resistance
• High toughness (work-to-break)
• Excellent dimensional stability
• High cut resistance
• Flame resistant, self-extinguishing
Smart electronic devices applications
• Wearable electronics and e-textiles: Lightweight and flexible KFRP, particularly when
combined with graphene, can be used to create e-textiles for smart clothing. These can
include integrated health-monitoring sensors, flexible displays, and flexible batteries or
supercapacitors.
• Flexible and conformable sensors: By embedding conductive KFRP with nanoparticles,
strain, pressure, and temperature sensors can be fabricated. These can be integrated into
 structures for real-time health monitoring or used in prosthetics to provide a sense of
touch.
• Flexible energy storage: Modified KFRP can act as a substrate for flexible batteries and
supercapacitors, providing high strength and thermal stability for wearable power
sources.
• Flexible circuit boards: KFRP can serve as a robust and lightweight alternative to
traditional rigid circuit boards for use in bendable smartphones, portable devices, and
aerospace applications.
• EMI shielding: The conductive properties of modified KFRP composites allow them to
be used as a shield against electromagnetic interference (EMI), protecting sensitive
electronic components.
• Aerospace and automotive electronics: KFRP's high strength-to-weight ratio and
ability to be fabricated into complex shapes make it ideal for structural electronics in
aircraft and vehicles, where embedded sensors and circuits can monitor performance and
fatigue.