Doping-undoping mechanism

Figure 1 Doping/Undoping Mechanism for Poly(3-methylthiophene)...

The necessary porosity for thicker layers was introduced by appropriate current densities [321-323], by co-deposition of composites with carbon black [28, 324] (cf. Fig. 27), by electrodeposition into carbon felt [28], and by fabrication of pellets from chemically synthesized PPy powders with added carbon black [325]. Practical capacities of 90-100 Ah/kg could be achieved in this way even for thicker layers. Self-discharge of PPy was low, as mentioned. However, in lithium cells with solid polymer electrolytes (PEO), high values were reported also [326]. This was attributed to reduction products at the negative electrode to yield a shuttle transport to the positive electrode. The kinetics of the doping/undoping process based on Eq. (59) is normally fast, but complications due to the combined insertion/release of both ions [327-330] or the presence of a large and a small anion [331] may arise. Techniques such as QMB/CV(Quartz Micro Balance/Cyclic Voltammetry) [331] or resistometry [332] have been employed to elucidate the various mechanisms. 

FIG. 23. Transmission spectra for different materials in the (A) UV/Vis and (B) IR regions of the electromagnetic spectrum. The electrodes in (A) are (1) a thin film of ITO on quartz, (2) a thin film of boron-doped nanocrystalline diamond on quartz, (3) a thin film of mechanically polished and boron-doped diamond on an optically pure, white diamond substrate, and (4) a free-standing, boron-doped, and mechanically polished diamond disc. The electrodes in (B) are (5) an optically pure and mechanically polished white diamond disc, (6) an undoped and polished (both sides) Si substrate, and (7 and 8) moderately and heavily boron-doped microcrystalline diamond thin films deposited on the undoped Si. (Reprinted with permission from Interface 2003, 12, 33. Copyright (2003) The Electrochemical Society, Inc.) (From Ref. 158.)... 

As already mentioned, in addition to the estimation of the current efficiency of polymerization, EQCM is a convenient tool for measuring the doping level of CPs. It also gives information on the mechanism of the doping-undoping process. 

The effect of doping on mechanical properties has been reported by a number of workers. Yoshino et al. observed that undoped PTh had a higher... 

Chemical erosion can be suppressed by doping with substitutional elements such as boron. This is demonstrated in Fig. 14 [47] which shows data for undoped pyrolitic graphite and several grades of boron doped graphite. The mechanism responsible for this suppression may include the reduced chemical activity of the boronized material, as demonstrated by the increased oxidation resistance of B doped carbons [48] or the suppressed diffusion caused by the interstitial trapping at boron sites. 

Polyacetylene in the doped state is sensitive to air and moisture. Other polymers (e.g., those of pyrrole, thiophene, and benzene) are stable in air and/or toward humidity in their doped and undoped states. Generally, when stored in the doped state, the polymers lose doping level by mechanisms not fully understood in most cases the loss is reversible. 

Spray pyrolysis of ethanolic solutions of Fe(acetylacetone)3 or FeCls between 370°C and 450°C onto a glass substrate are reported for the fabrication of a-Fe20s thin-film photoanodes [75]. Upon illumination by a 150 W Xe lamp samples consistently demonstrate photocurrents of 0.9 mAcm , IPCE values up to 15%, and robust mechanical stability with no signs of photocorrosion for the undoped samples. With simultaneous multiple doping of 1% A1 and 5% Ti, an IPCE of 25% can be reached at 400 nm. Zn doping is known to induce p-type character in Ee20s thin film electrodes [76]. 

In the context of this chapter, we focus on the undoped or lightly doped 7i-conjugated systems that are commonly referred to as organic semiconductors. Conducting polymers, such as PEDOT PSS, plexcore, polyaniline, polypyrrole, and others are not addressed here as their charge transfer mechanisms are rather different and would warrant an article in its own right. 

Heavily doped (>1018/cm3) n-type Si and poly-Si etch faster in Cl- and F-containing plasmas than do their boron-doped or undoped counterparts (103a, 105, 111, 112). Because ion bombardment is apparently not required in these cases, isotropic etch profiles (undercutting) in n + poly-Si etching often occur. Although the exact mechanisms behind these observations are not completely understood, enhanced chemisorption (103b, 111) and space charge effects on reactant diffusion (112) have been proposed. 

---