Проводящие органические полимеры и области их применения

Organic polymers that conduct electricity
bulk applications of conductive polymers

Conductive polymers or, more precisely, intrinsically conducting polymers (ICPs) are organic polymers that conduct electricity. Such compounds may have metallic conductivity or can be semiconductors. The main advantage of conductive polymers is that they are easy to process, mainly by dispersion. Conductive polymers are generally not thermoplastics, i. e., they are not thermoformable. But, like insulating polymers, they are organic materials. They can offer high electrical conductivity but do not show similar mechanical properties to other commercially available polymers. The electrical properties can be fine tuned using the methods of organic synthesis and by advanced dispersion techniques. The first highly conductive organic compounds were the charge transfer complexes. In the 1950s, researchers reported that polycyclic aromatic compounds formed semi conducting charge transfer complex salts with halogens. In the early 1970s, researchers demonstrated salts of tetrathiafulvalene show almost metallic conductivity, while superconductivity was demonstrated in 1980. Broad research on charge transfer salts continues today. While these compounds were technically not polymers, this indicated that organic compounds can carry current. While organic conductors were previously intermittently discussed, the field was particularly energized by the prediction of superconductivity following the discovery of BCS theory. In 1963 Australians B. A. Bolto, D. E. Weiss, and coworkers reported derivatives of polypyrrole with resistivities as low as 1 ohm·cm. Refs. and cite multiple reports of similar high conductivity oxidized polyacetylenes. With the notable exception of charge transfer complexes (some of which are even superconductors), organic molecules were previously considered insulators or at best weakly conducting semiconductors. Subsequently, DeSurville and coworkers reported high conductivity in a polyaniline. Likewise, in 1980, Diaz and Logan reported films of polyaniline that can serve as electrodes. While mostly operating in the quantum realm of less than 100 nanometers, "molecular" electronic processes can collectively manifest on a macro scale. Examples include quantum tunneling, negative resistance, phonon assisted hopping and polarons. In 1977, Alan J. Heeger, Alan MacDiarmid and Hideki Shirakawa reported similar high conductivity in oxidized iodine doped polyacetylene. For this research, they were awarded the 2000 Nobel Prize in Chemistry "for the discovery and development of conductive polymers." Polyacetylene itself did not find practical applications, but drew the attention of scientists and encouraged the rapid growth of the field.

Linear backbone "polymer blacks" (polyacetylene, polypyrrole, polyindole and polyaniline) and their copolymers are the main class of conductive polymers. Poly(p phenylene vinylene) (PPV) and its soluble derivatives have emerged as the prototypical electroluminescent semiconducting polymers. Today, poly(3 alkylthiophenes) are the archetypical materials for solar cells and transistors. and constant voltage. The advantage of Electro (co)polymerization are the high purity of products. But the method can only synthesize a few products at a time.

The conductivity of such polymers is the result of several processes. For example, in traditional polymers such as polyethylenes, the valence electrons are bound in sp3 hybridized covalent bonds. Such "sigma bonding electrons" have low mobility and do not contribute to the electrical conductivity of the material. However, in conjugated materials, the situation is completely different. Conducting polymers have backbones of contiguous sp2 hybridized carbon centers. One valence electron on each center resides in a pz orbital, which is orthogonal to the other three sigma bonds. All the pz orbitals combine with each other to a molecule wide delocalized set of orbitals. The electrons in these delocalized orbitals have high mobility when the material is "doped" by oxidation, which removes some of these delocalized electrons. Thus, the conjugated p orbitals form a one dimensional electronic band, and the electrons within this band become mobile when it is partially emptied. The band structures of conductive polymers can easily be calculated with a tight binding model. In principle, these same materials can be doped by reduction, which adds electrons to an otherwise unfilled band. In practice, most organic conductors are doped oxidatively to give p type materials. The redox doping of organic conductors is analogous to the doping of silicon semiconductors, whereby a small fraction of silicon atoms are replaced by electron rich, e. g., phosphorus, or electron poor, e. g., boron, atoms to create n type and p type semiconductors, respectively. Although typically "doping" conductive polymers involves oxidizing or reducing the material, conductive organic polymers associated with a protic solvent may also be "self doped." Undoped conjugated polymers are semiconductors or insulators. In such compounds, the energy gap can be > 2 eV, which is too great for thermally activated conduction. Therefore, undoped conjugated polymers, such as polythiophenes, polyacetylenes only have a low electrical conductivity of around 10−10 to 10−8 S/cm. Even at a very low level of doping (< 1%), electrical conductivity increases several orders of magnitude up to values of around 0.1 S/cm. Subsequent doping of the conducting polymers will result in a saturation of the conductivity at values around 0.1–10 kS/cm (10–1000 S/m) for different polymers. Highest values reported up to now are for the conductivity of stretch oriented polyacetylene with confirmed values of about 80 kS/cm (8 MS/m). Although the pi electrons in polyacetylene are delocalized along the chain, pristine polyacetylene is not a metal. Polyacetylene has alternating single and double bonds which have lengths of 1.44 and 1.36 Å, respectively. Upon doping, the bond alteration is diminished in conductivity increases. Non doping increases in conductivity can also be accomplished in a field effect transistor (organic FET or OFET) and by irradiation. Some materials also exhibit negative differential resistance and voltage controlled "switching" analogous to that seen in inorganic amorphous semiconductors. Despite intensive research, the relationship between morphology, chain structure and conductivity is still poorly understood. which are largely amorphous.

Conductive polymers show promise in antistatic materials flexible transparent displays, electromagnetic shielding and possibly replacement for the popular transparent conductor indium tin oxide. Another use is for microwave absorbent coatings, particularly radar absorptive coatings on stealth aircraft. Conducting polymers are rapidly gaining attraction in new applications with increasingly processable materials with better electrical and physical properties and lower costs. The new nano structured forms of conducting polymers particularly, augment this field with their higher surface area and better dispersability. Research reports showed that nanostructured conducting polymers in the form of nanofibers and nanosponges, showed significantly improved capacitance values as compared to their non nanostructured counterparts. With the availability of stable and reproducible dispersions, PEDOT and polyaniline have gained some large scale applications. While PEDOT (poly(3,4 ethylenedioxythiophene)) is mainly used in antistatic applications and as a transparent conductive layer in form of PEDOT:PSS dispersions (PSS=polystyrene sulfonic acid), polyaniline is widely used for printed circuit board manufacturing – in the final finish, for protecting copper from corrosion and preventing its solderability. Moreover, Polyindole is also starting to gain attention for various applications due to its high redox activity, thermal stability,

Electroluminescence is light emission stimulated by electric current. In organic compounds, electroluminescence has been known since the early 1950s, when Bernanose and coworkers first produced electroluminescence in crystalline thin films of acridine orange and quinacrine. In 1960, researchers at Dow Chemical developed AC driven electroluminescent cells using doping. In some cases, similar light emission is observed when a voltage is applied to a thin layer of a conductive organic polymer film. While electroluminescence was originally mostly of academic interest, the increased conductivity of modern conductive polymers means enough power can be put through the device at low voltages to generate practical amounts of light. This property has led to the development of flat panel displays using organic LEDs, solar panels, and optical amplifiers.

Since most conductive polymers require oxidative doping, the properties of the resulting state are crucial. Such materials are salt like (polymer salt), which makes them less soluble in organic solvents and water and hence harder to process. Furthermore, the charged organic backbone is often unstable towards atmospheric moisture. Improving processability for many polymers requires the introduction of solubilizing substituents, which can further complicate the synthesis. Experimental and theoretical thermodynamical evidence suggests that conductive polymers may even be completely and principally insoluble so that they can only be processed by dispersion. The Organic Electronics Association is an international platform to promote applications of organic semiconductors. Conductive polymer products with embedded and improved electromagnetic interference (EMI) and electrostatic discharge (ESD) protection have led to both prototypes and products. For example, Polymer Electronics Research Center at University of Auckland is developing a range of novel DNA sensor technologies based on conducting polymers, photoluminescent polymers and inorganic nanocrystals (quantum dots) for simple, rapid and sensitive gene detection. Typical conductive polymers must be "doped" to produce high conductivity. As of 2001, there remains to be discovered an organic polymer that is intrinsically electrically conducting. Recently (as of 2020), researchers from IMDEA Nanoscience Institute reported experimental demonstration of the rational engineering of 1D polymers that are located near the quantum phase transition from the topologically trivial to non trivial class, thus featuring a narrow bandgap.