Polymers

 Polymers are known to have good insulating properties. (they are used in electrical and electronic
applications as insulators)

 Polymers are one of the most used materials in the modern world. Their uses and application range from
containers to clothing.

 They are used to coat metal wires to prevent electric shocks.

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 Properties and uses of Polymers
Properties
 Lightness
 Strength
 Flexibility
 Resistance to Corrosion and chemical attack
 Elasticity
 Mouldability
 Ease of handling

Uses
 In space
 Aeronautics
 Electronics
 Non-linear Optics

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 What is conductivity?
Conductivity is the ability of a material to pass an electric current.
In a metal the outer electrons are free to carry charge and the
impedance to flow of charge is mainly due to the electrons
"bumping" in to each other.

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 Conducting Polymer: History
 Alan J. Heeger, Alan G. MacDiarmid and Hideki Shirakawa have changed this view with their discovery
that a polymer, polyacetylene (PA), can be made conductive almost like a metal.
 They found that organic conjugated polymers, exhibits dramatic increase in electrical conductivity on
treatment with oxidizing (electron-accepting) or reducing (electron donating) agents.
 These oxidation and reduction reactions, which induce high conductivity in PA are termed as p-doping
and n-doping.

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 Instability of PA in air
 The discovery of highly conducting PA led to sudden research activity directed towards the study of new
conducting polymeric systems as PA was found to be less stable in air

 PA get oxidized in presence of air forming new covalent bonds in the form of O2 and CO2 interrupting
double bond conjugation.

 Hence less conjugation leads to lowering in conductivity.

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 Example of Conducting Polymers
H
N
N n
n
n
S n H n

Polyacetylene Polyaniline Polythiophene Polypyrrole Polyfluorenes

(PA) (PANI) (PT) (PPy) (PF)

O O

n S n n n
Poly(p-phenylene vinylene) Poly(3,4-ethylenedioxythiophene) Poly(p-phenylene) Poly(p-phenylene
(PPV) (PEDOT) (PPP) ethynylene)
(PPE)

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 Conditions for Electrical Conductivity
 All the previous examples share many structural features like
i. Conjugated backbones
ii. Planarity
iii. Large anisotropy Ratio (i.e. intrachain conductivity is much larger than that of interchain conductivity)

 While the enhanced conductivity can be related to the

i. The alignment of polymer chains
ii. The conjugation length
iii. The doping percentage
iv. The purity of sample

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 Conditions for Electrical Conductivity
 All the previous examples share many structural features like
i. Conjugated backbones
ii. Planarity
iii. Large anisotropy Ratio (i.e. intrachain conductivity is much larger than that of interchain conductivity)

 While the enhanced conductivity can be related to the

i. The alignment of polymer chains
ii. The conjugation length
iii. The doping percentage
iv. The purity of sample

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 Conditions for Electrical Conductivity
(1) The polymer consists of alternating single and double bonds, called conjugated double bonds.
In conjugation, the bonds between the carbon atoms are alternately single and double. Every bond contains
a localised “sigma” (σ) bond which forms a strong chemical bond. In addition, every double bond also
contains a less strongly localised “pi” (π) bond which is weaker.

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 Conditions for Electrical Conductivity
(2) Polymer has to be disturbed - either by removing electrons from (oxidation), or inserting them into
(reduction), the material. (Doping; the role of the dopant is either to remove or to add electrons to the
polymer.)

There are two types of doping:

Oxidation with halogen
Polymer + X (polymer) n+ + Xn-
Reduction with alkali metal
Polymer + M (polymer) n- + Mn+

X= I2, Br2, AsF5……. M = Na, Li……….

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 Doping Process
 The iodine molecule attracts an electron from the polyacetylene chain and becomes I 3-. The
polyacetylene molecule, now positively charged, is termed a radical cation, or polaron.
 The lonely electron of the double bond, from which an electron was removed, can move easily. As a
consequence, the double bond successively moves along the molecule. This movement of charge is
what is actually responsible for electrical conductivity.
 The positive charge, on the other hand, is fixed by electrostatic attraction to the iodide ion, which does
not move so readily.

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 Conductivity Responsible Species
 Earlier increase in conductivity observed was initially thought to result from the formation of unfilled
electronic bands.
 But this assumption was challenged as in PA and PPP, conductivity is associated with spinless charge
carriers not unpaired electrons
 After doping, these polymers are associated with formnation of self-localized excitations such as
solitons, polarons, bypolarons as they move throughout the material freely.
 As a result of doping, strong electron-phonon interactions present in these quasi- one dimensional
polymers.

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 Engineering of small band gap polymers
 The process of doping enhance conductivity but it leads to chemical instability and poor processibility in
them.
 So achieving small band gap without using dopant is a challenging process but can be done by applying
following strategies

1. Substitution/Fusion
2. Ladder polymerization
3. Topological methods
4. Copolymerization
5. Donor-Acceptor polymerization

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Engineering of small band gap polymers

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 Conductivity of typical materials
 Doped polyacetylene is, e.g., comparable to good conductors such as copper and silver, whereas in its
original form it is a semiconductor.

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Conductivity of Polymers

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 Applications of conductive Polymers
Conducting Polymers have many uses. The most documented are as follows:

 anti-static substances for photographic film

 Corrosion Inhibitors
 Compact Capacitors
 Anti Static Coating
 Electromagnetic shielding for computers "Smart Windows"
 Transistors
 Light Emitting Diodes (LEDs)
 Lasers used in flat televisions
 Solar cells
 Displays in mobile telephones and mini-format television screens

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