P-doped

Dopant species can be codeposited with the Si02 by introducing small amounts of the dopants in hydride or haUde form. P-doped Si02, called P-glass, functions as an insulator between polysiUcon gates and the top metallisation layer of ICs. It is also used as a final passivation layer over devices, and as agettering source (17). 

The stoichiometry of the redox reactions of conducting polymers (n and m in reactions 1 and 2) is quite variable. Under the most widely used conditions, polypyrroles and polythiophenes can be reversibly oxidized to a level of one hole per ca. 3 monomer units (i.e., a degree of oxidation, n, of ca. 0.3).7 However, this limit is dictated by the stability of the oxidized film under the conditions employed (Section V). With particularly dry and unreactive solvents, degrees of oxidation of 0.5 can be reversibly attained,37 and for poly-(4,4 -dimethoxybithiophene), a value of n = 1 has been reported.38 Although much fewer data are available for n-doping, it appears to involve similar stoichiometries [i.e., m in Eq. (2) is typically ca. 0.3].34,39"41 Polyanilines can in principle be reversibly p-doped to one... 

In most cases, oligomers are initially generated in solution,61-64 but most rapidly precipitate onto the electrode surface and/or couple with adsorbed chains, and become oxidized 62,63,65 As a result, an oxidized (p-doped) polymer film is deposited on the electrode surface with, in most cases, high faradaic efficiency. Since ca. 0.3 electrons are required to dope the film to the polymerization potential, the overall polymerization + deposition process consumes ca. 2.3 electrons per monomer unit. 

Figure 4 compares cyclic voltammograms for a redox polymer (poly-[Fe(5-amino-1,10-phenanthroline)3]3+/2+)91 and p-doping and undoping of a conducting polymer (polypyrrole).92 The voltammogram for the redox... 

Figure 4. (A) Cyclic voltammograms over a range of scan rates for a redox polymer (poly-[Fe 5-amino-1,10-phenanthrotme)3]3+/>)91 and (B) p-doping and undoping of a conducting polymer (polypyrrole) (B). [(A) Reprinted from X. Ren and P. O. Pickup, Strong dependence of the election hopping rate in poly-tris(5-amino-1,10-phenan-throline)iron(HI/II) on the nature of the counter-anion J. Electroanal. Chem. 365, 289-292,1994, with kind permission from Elsevier Sciences S.A.]...

Hie electrochemical characteristics of overoxidation vary widely among polymers, solvents, and nucleophiles.129 Its rate depends on the degree of oxidation of the polymer (and therefore on the potential applied), and the concentration127 and reactivity of the nucleophile. Polypyrroles usually become overoxidized at lower potentials than polythiophenes because of their lower formal potentials for p-doping. In acetonitrile, the reactivity of the halides follows their nucleophilicity in aprotic solvents,... 

The electronic conductivity of a conducting polymer can vary by more than 10 orders of magnitude with changing potential. For lightly p-doped materials, the conductivity generally increases exponentially with increasing potential (see Fig. 11). Slopes of 60-130 mV decade-1 are... 

The intrinsic ion-exchange properties of p-doped polymers have been used to bind electrocatalytic anions such as porphyrins238 and phthalocy-anines.239 Cation-substituted polymers have been used to bind anions such as [Fe(CN)6]3-/4-,235 oxometallates,240 and porphyrins241 and anion-substituted polymers have been used to bind a variety of cationic species such as [Co(2,2/-bipyridine)3]3+/2+)58 [Ru(NH3)6]3+/ 2+,183 and porphyrins.242... 

Reaction of an alkyl (usually trimethyl) of Group-IIIb element (Al, Ga, In) with a hydride of a Group-Vb element (P, As, Sb) at 600-800°C and 1 atm. [4i][42] p. doping obtained from addition of diethyl zinc or bis(cyclopentadienyl) magnesium. 

The molar ratio of the III compound to the V compound is typically l/lO.t ] To obtain the desired semiconductor properties, dopants are added such as zinc (from diethyl zinc) or magnesium (from bis(cyclopentadienyl) magnesium) for p doping, and silicon (from silane) or selenium (from hydrogen selenide) for n doping. 

Tittes K, Plieth W (2007) Electrochemical deposition of ternary and binary systems from an alkaline electrolyte—a demanding way for manufacturing p-doped bismuth and antimony teUurides for the use in thermoelectric elements. J Solid State Electrochem 11 155-164... 

The oxidation and/or reduction reactions yield polymeric systems having an extended Jt-electron system along the chain. Doping to the conducting state, in the instance of polyacetylene by exposnre to iodine vapor (p-doping, oxidizing). 

Instabilities of doped conductive polymers are largely an environmental problem Some polymers when p-doped to the limit have oxidation potentials high enough to attack the most inert solvents. Most will attack water even at much lower doping levels. 

FIGURE 26.6 (a) p-doped conductive polymer in battery cell configuration (b) -doped... 

Figure 1.2 Modulus of the field enhancement factor versus the aspect ratio a = b and wavelengths X for SPM tips of different materials (a) gold, (b) platinum, (c) silver, (d) p-doped silicon, (e) tungsten. Reprinted with permission from J. Jersch, Applied Physics A, 66, 29 (1998). Copyright 1998, Springer-Verlag.

Table 5.3 Examples of electronically conducting polymers, y is the level of electrochemical doping and k is the maximum electrical conductivity. Except for poly acetylene and polyparaphenylene, only p-doping is considered... 

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