Self-doping

Polyaniline (PANI) can be formed by electrochemical oxidation of aniline in aqueous acid, or by polymerization of aniline using an aqueous solution of ammonium thiosulfate and hydrochloric acid. This polymer is finding increasing use as a "transparent electrode" in semiconducting devices. To improve processibiHty, a large number of substituted polyanilines have been prepared. The sulfonated form of PANI is water soluble, and can be prepared by treatment of PANI with fuming sulfuric acid (31). A variety of other soluble substituted AJ-alkylsulfonic acid self-doped derivatives have been synthesized that possess moderate conductivity and allow facile preparation of spincoated thin films (32). 

Significant variations in the properties of polypyrrole [30604-81-0] ate controlled by the electrolyte used in the polymerization. Monoanionic, multianionic, and polyelectrolyte dopants have been studied extensively (61—67). Properties can also be controlled by polymerization of substituted pyrrole monomers, with substitution being at either the 3 position (5) (68—71) or on the nitrogen (6) (72—75). An interesting approach has been to substitute the monomer with a group terminated by an ion, which can then act as the dopant in the oxidized form of the polymer forming a so-called self-doped system such as the one shown in (7) (76—80). 

IV. SELF-DOPED POLYMERS, POLYMERIC COMPOSITES, AND HYBRID MATERIALS... 

When the substituent is an ionic chain [Fig. 13(b)] with the anion on the organic side, some of the lateral anions act as counter-ions during electrochemical oxidation. The cation of the salt is expelled from, or included in, the material during oxidation or reduction, respectively. These are self-compensating or self-doping (chemical or physical terminology, respectively) materials.76... 

Figure 13. (a) Substituted polypyrrole, (b) self-doped polypyrrole, (c) heteroaromatic polymer showing the monomer unit, (d) composite polypyrrole-polyelectrolyte, and (e) hybrid material. (Polyaniline macroion photo supplied by Gomez-Romero and M. Lira.)... 

Self-doped polymers, 334 Semicircles, Albery and Mount interpretation of, 584 Semiconductor electrodes with polymer layers, 499 diffusion length in, 492 Semiconductors, lifetime for carriers and, 495... 

Following the discovery of the unique electronic properties of polypyrrole, numerous polymers of pyrrole have been crafted. A copolymer of pyrrole and pyrrole-3-carboxylic acid is used in a glucose biosensor, and a copolymer of pyrrole and A-methylpyrrole operates as a redox switching device. Self-doping, low-band gap, and photorefractive pyrrole polymers have been synthesized, and some examples are illustrated [1,5]. 

A. Fukase and J. Kido, Organic electroluminescent devices having self-doped cathode interface layer, Jpn. J. Appl. Phys., 41 L334-L336 (2002). 

Polyphthalamides (PPA), 10 216-217 ASTM standards for, 19 793 Poly(p-phenylene) (PPP), 22 207t 23 717 conducting, 7 523, 527 molecular structure of, 22 211 optical band gap, 7 529t room temperature conductivity, 7 532 water-soluble, electroactive, self-doped sulfonatoalkoxy-substituted, 23 720 Poly(p-phenylene benzobisoxazole) (PBO), 19 714... 

Water-soluble derivatives of polythiophene have been made allowing counterions bound to the polymer backbone to self-dope with the protons (e.g., lithium and sodium ions) injecting electrons into the pi-system. Thus, combinations of sodium salts and proton salts (e.g., prepared from poly-3-(2-ethanesulfonate)thiophene) have been prepared that are both water-soluble and conducting. 

Jung JW, Lee JU, Jo WH (2009) High-efficiency polymer solar cells with water-soluble and self-doped conducting polyaniline graft copolymer as hole transport layer. J Phys Chem C 114 633... 

The electron transport mechanism in mesoporous Ti02 film is modeled mainly by using diffusion theory, except in the report by Augustinski et al.,45) who proposed the explanation that the initial film charging by dye-sensitization, in terms of the self-doping, causes an insulator-metal (Mott) transition in a donor band of Ti02, accompanied by a sharp rise in conductivity of the nanoparticles. 

The range of soluble polythiophenes has been growing rapidly to include side chains up to docosane 267), ether and amide links in the side chains 268), and water-soluble polymers with sulfonated side chains (Table 1) which are claimed to be self-doping in that the sulphonate may act as the counterion to the delocalized chain cation 269,270). In principle, these polymers can be p-doped and undoped by the transport of a proton or a small cation rather than a large anion, and so may respond more rapidly. By treatment of an aqueous solution with NOPF6, a doped solution can be made, which slowly degrades. 

These quarternized polymers can be viewed as self-doped but exhibit relatively low intrinsic conductivities. The polymers can be oxidatively doped with iodine, or reductively doped with TTF, to give highly conducting polyacetylenes with conductivities of 10"4 and 10 1 S/cm, respectively. One additional attractive feature of this system is that, unlike PA, these quarternized PAs are very stable in air. 

M. S. Freund and B. A. D. Deore, Ed. Self-Doped Conducting Polymers , John Wiley Sons, New Jersey, 2007. 

Title Method of Making Novel Water-Soluble and Self-doped Polyaniline Graft Copolymers... 

Polyaniline has been grafted onto the poly(styrenesulfonic acid-co-aminostyrene) backbone using aniline, ammonium persulfate, and hydrochloric acid. The graft copolymer is water soluble and self-doping and can be used in electrical and marine anticorrosive applications. 

Preparation of Self-doped Polyaniline Graft Copolymer... 

The synthesis of self-doped conducting polyaniline was achieved by sulfonation of the aromatic units with fuming sulfuric acid. The sulfonated polyaniline has a conductivity of 0.1 S/cm, which is independent of pH [191]. 

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