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CONDUCTIVE POLYMERS

AN INTRODUCTORY STUDY

PRESENTED BY
UJWALA HUJURI
M.TECH 2ND SEM
CIPET, LUCKNOW
INTRODUCTION

Polymers are commonly known to have good insulating properties.They


are used to coat metal wires to prevent electric shocks.However, the
discovery of electrical and optical activities in one class of polymers,viz.,
conductive polymers, resulted in the development of one of today’s
exciting areas of condensed matter science.These materials have
attracted academic & industrial research groups, not only because of
their theoretically interesting properties, but also because of their
technologically promising future.
WHAT IS CONDUCTIVITY ?

The conductivity refers to that property which renders the materials to


be classified as coductors, semi-conductors or insulators. It depends on
the no. of charge carriers (no. of electrons) in the material & their
mobility. e.g., in a metal it is assumed that all outer electrons are free to
carry charge & the impedance to flow of charge is mainly due to the
electrons bumping in to each other. Insulators, however have tightly
bound electrons so that nearly no electron flow occurs, so they offer
high resistance to charge flow.So, for conductance free electrons are
needed.
CONDUCTIVITY OF DIFFERNENT MATERIALS
WHAT ARE CONDUCTIVE POLYMERS ?

Conductive polymers, best described as electro-active polymers,


comprise groups of materials, conductive plastics, inherently conductive
polymers (ICPs) & very highly specialized polymers with both electrical
and / or optical (electro-optic) properties.Conductive polymers, which
are almost always organic, have conjugated unsaturations which are
extended delocalized bonds that creates a band structure similar to
silicon.When charge carriers ( from the addition or removal of electrons)
are introduced into the conduction or valence bands, the electrical
conductivity increases dramatically.
SOME IMPORTANT POINTS

Conductivity is possible above the glass transition temperature,


where the polymer molecules are free to move. The free volume also
provides room for the ions to move.
The ionic conductivity possesses a diffusive liquid-like behaviour in
addition to the hopping-type behaviour characteristic of an electron in a
disordered solid.
The conductivity is somewhat lower than that of a doped semi-
conductor.
High conductivities are achievable by using “comb” polymers that
can readily transport charge.
Zero band gap conductive polymers may behave like metals.
MECHANISM

Delocalization can be accomplished by forming a conjugated backbone of


continuous overlapping orbitals (e.g., alternating single and double C-C
bonds) which leaves a continuous path of overlapping p-orbitals. This
continuous string of orbitals creates degeneracy in the frontier molecular
orbitals which leads to the filled (electron containing) & unfilled bands
(valence and conduction bands resply.) that define a semi- conductor.As
synthesized, conductive polymers exhibit very low conductivities. It is not
until an electron is removed from the valence band (p-doping) or added to
the conduction band (n-doping) does a conducting polymer becomes highl
conductive. Doping (p or n) generates charge carriers which move in an
electric field. Positive charges ( holes) & negative charges (electrons)
move to opposite electrodes. This movement of charge is what is actually
responsible for electrical conductivity.
DIFFERENT MECHANISMS

There are three principal mechanisms whereby a polymer may exhibit


electrical conductivity.
Metallic or other conducting particles may be incorporated into a non-
conducting polymer.
The polymer may contain ions derived from small-molecule
impurities, such as fragments of polymerization catalysts,from ionizable
groups along the chain or from salts specially introduced to provide
conductivity for a specific use.
The polymer may exhibit electronic conductivity associated with the
motion of electrons (more strictly, particle-like excitations of various
kinds) along the polymer chains.
EXAMPLES

Polyacetylene
Poly(paraphenylene)
Poly(phenylenesulphide)
Polypyrroles & Polythiophenes
High-Temperature polymers
Polyaniline
Polyacetylene copolymers
Composites of conducting polymers
WHAT IS DOPING ?

In silicon semi-conductors, a few of the silicon atoms are replaced by


electron rich e.g., phosphorous or electron poor e.g., boron atoms to create
n- and p- type semi-conductors respectively. This method of incorporating
impurity atoms to create holes and electrons is known as doping.This
increases conductivity.
DOPING TECHNIQUES
Chemical doping: It involves exposing the polymer (typically a thin
film), to an oxidant (typically iodine or bromine) or reductant (alkali
metals) either in the vapour e.g., I 2 or liquid phase e.g., I 2 in hexane.
Electrochemical doping: Here, a polymer coated working electrode is
suspended in an electrolyte solution in which the polymer is insoluble
along with separate counter & reference electrodes. A potential
difference is created between the electrodes which cause charge to enter
the polymer in the form of electron addition (n- doping) or removal (p-
doping).e.g., LiClO4 in THF.
Ion implantation:Polymers can become conducting by implanting ions
in the polymer’s lattice, forming covalent bonds by use of proper ion
beams.
Photochemical doping:This is done by treating the polymer with the
dopane species, which are initially inert towards the materials followed
by uv irradiation.
FEATURES

The extended conjugation of a conductive polymer tends to give rise to


fluorescence which has led to the rapid development of polymer-based
light emitting diodes (OLED) and organic photovoltaic devices.
As conductive polymers are also plastics, and therefore can combine
the mechanical properties (flexibility, toughness,elasticity, etc) of plastics
with the high electrical conductivities of a doped conjugated polymer.
APPLICATIONS
Electrostatic materials
Conductive adhesives
Electromagnetic shielding
PCBs
Artificial nerves
Piezoceramics
Aircraft structures
Electrical displays
Chemical, biochemical, thermal sensors
Corrosion-inhibitors
Smart structures & Switches
STABILITY & STABILIZATION OF PRISTINE & DOPED
POLYMERS
Polyphenylene, Poly(phenylenesulfide), & ladder chain
heterocyclic polymers are quite stable in air. They are also stable at
higher temperature(T>2000 C)
Pristine Polyacetylene reacts with oxygen & moisture
comparatively rapidly in ambient atmosphere.It also degrades when
annealed at temp. below 2000 C.
The stability of the doped polymers, whether related to air, heat, or
dopant diffusion, depends upon the stability of the complex formed
between the chain & doping species.
Air stability:
1. Pristine Polyacetylene films- It becomes brittle & conductivity
decreases.
2.Doped Polyacetylene: p- type films are relatively more stable than
parent polyacetylene films& oxidized more slowly, n-type films are
oxidized immediately when exposed to air.
Thermal stability:
1.Pristine Polyacetylene: At T>2000 C, the films start to decompose. At
T> 4200 C,thermal decomposition as well as 63% wt. loss occur.
2.Doped Polyacetylene: The degradation of the doped polymer occurs
at lower temp. than that for the parent films.
STABILIZATION TECHNIQUES
Polyacetylene needs to be stabilzed so that its tremendous potential can
be used in technological applications.
1.Doping-
Chemical doping- When the dopant is an acceptor , the structure can
be stable in air for few months.
Ion implantation- Due to the covalent bonding between the implanted
ions & the polymer backbone, conductive polymers obtained by this
technique is more stable than when it is chemically doped.
2. Plastification-
Composites consisting of polymerizing acetylene into the protecting
polymer.
Composites of two coducting polymers, one of which is air-stable.
Surface protection
Copolymerization
3. Antioxidizing agents
4. Water stabilization
5. Stabilization of n- doped polymers by crown ethers
FUTURE TECHNOLOGICAL APPLICATIONS
Technology developments and printed circuits :-
Developing a versatile platform technolgy to improve
performance in organic electronic devices
Analysing advanced electronics such as OLED & printed organic
electronics
Application potential of ORGACON transparent conducting
screen-printing inks.
Latest innovations in polyaniline-based products for ESD
protection & other applications:-
Examining new coating materials & inks.
Masterbatches for melt processing.
Examining the use of conjugated polymer materials for photo-
voltaics.
Utilising High volume manufacturing techniques to produce
inherently conducting polymers.
Conductive polymer based devices, e.g., all polymer transistors
(OFET), flexible OLED for decorative uses, printable temperature
indicators, ICP- PAPER INDICATOR.
CONCLUSION

During the past decade, conductive organic polymers have become


the focus of intensive research and development. While interest in
conducting polymers stems from their non-classical elecro-optic
properties as well as their potential technological applications, some
of the factors limiting their use are their intractability and instability
in ambient environment. Therefore, research has extended towards
solving these problems & progress has recently been made in that
direction. So, if all the properties are harnessed properly, conductive
polymers will prove to be one of the most fascinating discovery of
the recent times.
THANK YOU