Conductive polymers

Most commercially produced organic polymers are electrical insulators. Conductive polymers, which are almost always organic, have extended delocalized bonds (often comprised of aromatic units) 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 (see below) the electrical conductivity increases dramatically. Technically almost all known conductive polymers are semiconductors due to the band structure, however so-called zero band gap conductive polymers may behave like metals. The most notable difference between conductive polymers and inorganic semiconductors is the mobility which, until very recently, was dramatically lower in conductive polymers than their inorganic counterparts, though recent advancements in self assembly is closing that gap.

Delocalization can be accomplished by forming a conjugated backbone of continuous overlapping orbitals, for example, alternating single and double carbon-carbon bonds, which leaves a continuous path of overlapping p orbitals. This continuous string of orbitals creates degeneracy in the frontier molecular orbitals (the highest occupied and unoccupied orbitals named HOMO and LUMO respectively) which leads to the filled (electron containing) and unfilled bands (valence and conduction bands respectively) that define a semiconductor. 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, which is far less common) does a conducting polymer become highly conductive. Doping (p or n) generates charge carriers which move in an electric field. Positive charges (holes) and negative charges (electrons) move to opposite electrodes. This movement of charge is what is actually responsible for electrical conductivity.

The chemistry Nobel prize in 2000 was awarded for the discovery and study of conducting polymers.

Contents

Chemistry

Common classes of organic conductive polymers include poly(acetylene)s, poly(pyrrole)s, poly(thiophene)s, poly(aniline)s, and poly(para-phenylene vinylene)s.

Doping

In silicon semiconductors, a few of the silicon atoms are replaced by electron rich (e.g., phosphorus) or or electron-poor (e.g. boron) atoms to create n and p-type semiconductors, respectively. There are two primary methods of doping a conductive polymer, both through an oxidation-reduction (redox) process. The first method, chemical doping, involves exposing a polymer, such as melanin (typically a thin film), to an oxidant (typically iodine or bromine) or reductant (far less common, but typically involves alkali metals). The second is electrochemical doping in which a polymer-coated, working electrode is suspended in an electrolyte solution in which the polymer is insoluble along with separate counter and reference electrodes. A potential difference is created between the electrodes which causes a charge (and the appropriate counter ion from the electrolyte) to enter the polymer in the form of electron addition (n doping) or removal (p doping).

The reason n doping is so much less common is that Earth's atmosphere is oxygen-rich, which creates an oxidizing environment. An electron-rich n doped polymer will react immediately with elemental oxygen to de-dope (re-oxidize to the neutral state) the polymer. Thus, chemical n doping has to be done in an environment of inert gas (e.g., argon). Electrochemical n doping is far more common in research, because it is easier to exclude oxygen from a solvent in a sealed flask; however, there are likely no commercialized n doped conductive polymers.

Conjugation

The extended conjugation of a conductive polymer tends to give rise to fluorescence which has lead to the rapid development of polymer-based light emitting devices (OLEDs) and organic photovoltaic devices.

Properties

The biggest advantage of conductive polymers is processibility. Conductive polymers are also plastics (which are organic polymers) and therefore can combine the mechanical properties (flexibility, toughness, elasticity, etc.) of plastics with the high electrical conductivities of a doped conjugated polymer.

Physics

This increase in conductivity can also be accomplished in a field effect transistor (organic FET or OFET), or by irradiation. Strong coupling can also occur between electrons and phonons (mechanical oscillations, particles of sound) since both are constrained to travel along the polymer backbone.

Applications

In some cases, light emission is observed when a voltage is applied to a thin layer of a conductive organic polymer film. It has led to the development of flat panel displays using OLEDs, solar panels and optical amplifiers.

Conductive polymers are present in most mammal tissues where electrical conduction or transduction from light or sound are necessary, including the skin, eye, inner ear, and brain. Its electronic conductivity seems to be the underlying mechanism for absorption of light, and electron-phonon interactions are exploited in hearing [1] (http://www.organicsemiconductors.com/). See the main article: Melanin.

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