CONDUCTING POLYMERS

INTRODUCTION
Polymers were rigidly regarded as insulators. They were utilized as inactive packaging
and insulating material. This very narrow perspective is rapidly changing as a new class of
polymer known as intrinsically conductive polymer or electroactive polymers are being
discovered.

In 1958, polyacetylene was found to be a semi-conductor with conductivity between 7 X

10-11 to 7 X 10-3 Scm-1, depending upon how the polymer was processed and manipulated.
Exposure of silvery thin film of polyacetylene to halogens increased its conductivity a billion
fold. Undoped, the polymer was silvery, insoluble and intractable, with conductivity similar
to that of semiconductors. When it was weakly oxidised by compounds such as iodine, it
turned a golden colour and its conductivity increased to about 104 Scm-1. In the 1980's,
polyheterocycles were first developed. Polyheterocycles were found to be much more air
stable than polyacetylene, although their conductivities were not so high, typically about 103
Scm-1. By adding various side groups to the polymer backbone, derivatives which were
soluble in various solvents were prepared. Other side groups affected properties such as
their colour and their reactivity to oxidising and reducing agents. A l ogarithmic
conductivity ladder of some of these polymers are shown below.
 It has been found that about a dozen different polymers and polymer derivatives
undergo this transition when doped with a weak oxidation agent or reducing agent. They are
all various conjugated polymers. This early work has led to an understanding of the
mechanisms of charge storage and charge transfer in these systems. All have a highly
conjugated electronic state.

CHARGE STORAGE
One early explanation of conducting polymers used band theory as a method of
conduction. This said that a half filled valence band would be formed from a continuous
delocalized pi-system. This would be an ideal condition for conduction of electricity.
However, it turns out that the polymer can more efficiently lower its energy by bond
alteration (alternating short and long bonds), which introduces a band width of 1.5 eV
making it a high energy gap semiconductor. The polymer is transformed into a conductor by
doping it with either an electron donor or an electron acceptor. This is similar to doping of
silicon based semiconductors where silicon is doped with either arsenic or boron.

The polymer may store charge in two ways. In an oxidation process, it could either lose
an electron from one of the bands or it could localize the charge over a small section of the
chain.

Typical oxidizing dopants used include iodine, arsenic pentafluoride, iron(III) chloride
and NOPF6. A typical reductive dopant is sodium naphthalide.

To understand the conducting mechanism in conducting polymers, let us consider

polyacetylene as an example. On doping, polarons, bipolarons and solitons are produced as
seen in the picture given below. The combination of a charge site and a radical is called a
polaron. This could be either a radical cation or a radical anion. Solitons can be neutral (free
radical), positively charged (carbocation) or negatively charged (carbanion).

When reductive doping is carried out, from a neutral polymer chain, a radical anion
(negative polaron) is generated. Further reduction creates a carbodianion (negative
bipolaron). This is of lower energy than the creation of two distinct polarons. At higher
doping levels, it becomes possible that two polarons combine to form a bipolaron. Thus at
higher doping levels, the polarons are replaced with bipolarons. They further lead to the
formation of soliton pairs due to the delocalization of charge carriers (negative/positive) in
these conjugated systems, where the produced solitons are found to be delocalized over
about 12 CH units. Soliton formation results in the creation of new localized electronic states
that appear in the middle of the energy gap. When sufficient solitons are formed, a new mid
gap band formed which overlaps the CB and VB allowing the electron to follow to create true
metallic conductivity.

The same mechanism can be rewritten by involving the movement of positive charges
with oxidative doping. Nevertheless, reductive doping is less common than oxidative doping.

Step-by-step mechanism in polyacetylene by reductive coupling

CHARGE TRANSPORT
The mechanism of conduction is by movement of charge carriers between localized
sites or between soliton, polaron or bipolaron states. Alternatively, in extrinsically
conducting polymers, where inhomogeneous doping produces metallic island dispersed in an
insulating matrix, the conduction is by movement of charge carriers between highly
conducting domains. Charge transfer between these conducting domains also occurs by
thermally activated hopping or tunneling.

APPLICATIONS
The extended pi-systems of conjugated polymer are highly susceptible to chemical or
electrochemical oxidation or reduction. These alter the electrical and optical properties of
the polymer, and by controlling this oxidation and reduction, it is possible to precisely
control these properties. Since these reactions are often reversible, it is possible to
systematically control the electrical and optical properties with a great deal of precision. It is
even possible to switch from a conducting state to an insulating state.

There are several important applications for these polymers as compiled below in the
table.

Electrostatic materials Molecular electronics

Conducting adhesives Electrical displays
Electromagnetic shielding Chemical biochemical and
thermal sensors
Printed circuit boards Rechargeable batteries and solid
electrolytes
Artificial nerves Drug release systems
Antistatic clothing Optical computers
Piezoceramics Ion exchange membranes
Active electronics (diodes Electromechanical actuators
transistors)
Aircraft structures 'Smart' structures
Switches