CHAPTER ONE

1-INTRODUCTION

Conducting polymers are an exciting new class of electronic

materials, which have attracted an increasing interest since their
discovery in 1977. They many advantages, as compared to the
non-conducting polymers, which is primarily due to their
electronic and optic properties. Also, they have been used in
artificial muscles, fabrication of electronic device, solar energy
.conversion, rechargeable batteries, and sensors

Polymer have long been thought of and applied as insulators.

indeed , not so long ago , any electrical conduction in polymers---
mostly due to loosely bound ions was generally regarded as an
undesirable phenomenon .the emergence of electronically
conducting polymers has resulted In a paradigmatic change in our
thinking and has opened up new vistas in chemistry and physics
.this story began in the 1970s , when , somewhat surprising ,a
new class of polymers possessing high electronic conductivity
( electronically conducting polymers) in the partially oxidation
(or, less frequently ,in the reduced) state was discovered. Three
collaborating scientists, Alan J.Heeger, Alan G.MacDirmid and
Hideki Shirakawa,played a major role in this breakthrough, and
they received the Nobel Prize in Chemistry in 2000 "for the
discovery and development of electronically conductive
polymers"1,

The promise of conducting polymers is to combine the chemical,

mechanical, and processing properties of plastics with the electric
behaviour of metals (and semiconductors), or more generally, to
increase the number of materials so that we can search among
the synthetic metals if a desired property profile is not found in a
natural metal.

WHY WOULD ONE BUY INGREDIENTS FOR CONDUCTIVE POLYMERS?

It seems that the largest value increase will not be in the synthesis of the
conducting polymer but in high-tech processes involving conductive
polymers, or more generally, synthetic metals.

1-1,Conjugated polymers.
Polymer has to imitate a metal, that is, its electrons need to be free to move and not
bound to the atoms .Polyacetylene is the simple stopsible conjugated polymer. It is
obtained by polymerisation of acetylene. 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
localized sigma () bond which forms a strong chemical bond. In addition, every
double bond also contains a less strongly localized pi () bond which is weaker.

1-2, Doping Process

Polymers with loosely held electrons in their backbones are often referred as
conducting polymers. Each atom along the backbone is involved in a bond,
which is much weaker than the bonds that hold the atoms in the polymer chain
together, and they characteristically have a conjugated backbone with a high
degree of -orbital overlap (Breads and Silbey, 1991). Through a process known as
doping, the neutral polymer chain can be oxidized or reduced to become either
positively or negatively charged (Wong et al., 1994). It is well known that
conducting polymers in general are not conductive without doping, and doping of-
conjugated polymers results in a highly conducting state of the polymer. The
doping process includes charge transfer from dopant molecules to polymer chains
within an overall neutral system, and in this process charge carriers, polarons and
bipolarons, are introduced into the conjugated chain. The doping process can be
influenced by factors such as polaron length, chain length, charge transfer to
adjacent molecules and conjugation length "5.
1-3,Electrochemical polymerization
electrochemical synthesis is of particular interest because has many parameters
such as potential, scan rate and supporting electrolyte can be easily controlled to
determine the polymer structure to be obtained"7. Electrochemical doping is
realized by electrochemical oxidation or reduction of the
conjugated polymers on an electrode.
For electrochemical p-doping, the conjugated polymer main chain
is oxidized to lose an electron (gain a hole) accompanying the
doping of counteranions from electrolyte solution:

where A denotes the solution anion, CP+(A) represents the

conducting polymer with the main chain oxidized and counter
anion doped. For electrochemical n-doping, the conjugated
polymer main chain is reduced to gain an electron accompanying
the doping of counteractions from electrolyte solution: "8.

1-4,Application of conducting polymers .

.Shield for computer screen against electromagnetic "Smart" Windows radiation -1

.smart" windows -2

Solar cell -3

Photographic Film -4
Light-emitting diodes -5

Cable Shielding.
Capacitors
Controlled - Release Medicine Systems
Electro - Robotics
Electroehromic Smart-Windows
Electroluminescent Flexible LED's
Electromagnetic Shielding
Electron-Beam Resist
Electrostatic Control
Gas Separation Membranes
Nonlinear Optics
Rechargeable Batteries
Sensors
Synthetic Metals, 55-57 (1993) 3623-3631

CONDUCTIVE POLYMERS: EVALUATION OF INDUSTRIAL APPLICATIONS

S. ROTH

Max-Planck-Institut far Festk0rpefforschung, Heisenbergstrasse 1, D-7000 Stuttgart 80

(Germany)

W. GRAUPNER

Institut flit Festk0rperphysik, Technisehe Unlversit~tt, Petersgasse 16, A-8010 Graz (Austria)

aim
The aim of this chapter is to emphasize the impact of band gap
engineering on the design and synthesis of functional p-
conjugated PTs for advanced applications. aim of much research
has been channeled into understanding the physical mechanisms
underlying their operation, in order to spur the development of
efficient devices. Both the size of the electrode= semiconductor
barrier heights of LEDs, whose simplest structure consists of an
emitting organic
film sandwiched by two electrodes, and the magnitude and
distribution of the electric fields across the
diode structure are recognized to be crucial quantities that govern
device physics and operation of LEDs
[3], as is also the case for photovoltaic cells and other
optoelectronic devices. In this chapter we will
review EA spectroscopy in its use as a powerful experimental
technique with which it has become
possible to gauge the internal electric fields, the energy level
lineup, and the barrier heights on completed
and operational devices.

aim at increased conjugation for increased intrachain transport

while maintaining ordering, i.e.,
crystallinity for interchain charge transfer.

The purpose of this chapter is to illustrate the usefulness of PES

for studying the electronic and
chemical structure of conjugated polymer surfaces and interfaces.
As this handbook deals with all aspects
of conjugated polymers, the background information on
conjugated polymers is kept to a minimum
here. It is further assumed that the reader is familiar with some of
the unique electronic structural issues
in the physics of conjugated polymers, i.e., the concepts of
solitons, polarons, and bipolarons.

Conducting polymers are likely to provide a three-dimensional

electrically conducting structure for this purpose. Conducting
polymers can be reversibly doped and undoped using
electrochemical techniques and are accompanied by significant
changes in electrical and spectroscopic properties. To the extent
that these changes may be linked to bioreceptoranalyte
interactions, these changes, and the extent to which they are
modulated, may be used as signals for the biochemical reaction
Handbook of Conducting Polymers
Third Edition