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, 2002; Park and Advincula, 2002) and surface mass transport (Wang et al, 1998) (which is described in more detail in Section 13) It should be noted, however, that in general the quality of the patterning is lower (Wang et al, 2004), presumably because of the constraints to chain motion that the ionic cross-links engender There are many examples of performing the multilayering with a polyelectrolyte and a small molecule azobenzene ionic dye (Dragan et al, 2003) In contrast to conventional doped systems, the chromophores in these systems do not suffer from aggregation instabilities (Advincula et al, 2001), and the azo photomotions do couple to the matrix, as evidenced by birefringence (dos Santos Jr et al, 2003; Bian et al, 2000) and surface patterning (He et al, 2000a,b).

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Here, the electrons are denoted e~ and the holes h + . The stability of n-Si, n-Ge, n-CdS, and n-GaAs photoanodes against photocorrosion increases in the presence of a solution species that reacts rapidly enough with photogenerated holes to compete with the surface oxidation. An alternative way is to cover the semiconductor electrode with an electronically conducting polymer film, such as polyvinylferrocene, polypyrrole, polyaniline, Nafion/tetrathiafulvalene, etc. These films are capable of efficiently capturing photogenerated holes and transport them to the solution, where they undergo a useful redox reaction (photoelectrosynthesis). The removal of photogenerated holes suppresses not only the photocorrosion, but also electron-hole recombination within the illuminated semiconductor, which increases the quantum yield of the photoelectrochemical process. Protection of p-type semiconductors by the mentioned conductive films is also possible; it enhances, for example, the rate of H2 evolution at semiconductor photocathodes. Various other semiconductor materials, such as CdSe, MoSe, WSe, and InP were also used in electrochemistry, mainly as n-type photoanodes. Stability against photoanodic corrosion is, naturally, much higher with semiconducting oxides (TiO2, ZnO, SrTiO3, BaTiO3, WO3, etc.). For this reason, they are the most important n-type semiconductors for photoanodes. The semiconducting metal oxide electrodes are discussed in more detail below. Metal oxides. Noble metals are covered with a surface oxide film in a broad range of potentials. This is still more accentuated for common metals, and other materials of interest for electrode preparation, such as semiconductors and carbon. Since the electrochemical charge transfer reactions mostly occur at the surface oxide rather than at the pure surface, the study of electrical and electrochemical properties of oxides deserves special attention.

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310 The electronic conductivity of metal oxides varies from values typical for insulators up to those for semiconductors and metals. Simple classification of solid electronic conductors is possible in terms of the band model, i.e. according to the relative positions of the Fermi level and the conduction/valence bands (see Section 2.4.1). A transition behaviour between a semiconductor and a metal can also be observed with metal oxides. This occurs when the Fermi level of the semiconductor is shifted (usually by heavy doping) into the conduction or valence band. This system is called degenerate semiconductor. If there exists a sufficient density of electronic states above and below thus shifted Fermi energy, the degenerate semiconductor can behave in contact with an electrolyte as a quasimetal electrode (e.g., with the charge transfer coefficient a close to 0.5, cf. Section 5.2.8). The quasimetallic behaviour of a degenerate semiconductor electrode is also conditioned by a sufficient capacity of the electronic states near the Fermi energy. Assuming, for simplicity, the double layer at the semiconductor/electrolyte interface as a parallel plate capacitor, whose capacity is independent of the potential difference across the electric double layer, the charge asc corresponding to a potential difference A|0 applied across the Helmholtz layer of thickness d is (cf. Section 4.5.1) osc = As2<t> 80/d (5.5.27)

These effects can again be attributed to the fact that the ionic attachment points act as cross-links in a dry PEM sample The aggregation and photochemical behavior of the azo chromophore (absorbance spectrum, isomerization rate, etc) vary depending on the nature of the counterpolymer (Dante et al, 1999) (and of course, is affected by any ionic ring substituent) These may be viewed as undesirable matrix effects, or as a way to tune the chromophore response The multilayering technique does not offer the precision and reproducibility of conventional inorganic lm preparation techniques It is, however, simple, versatile, and offers the possibility of combining unique structures and functionalities (for instance, it has been used to create superhydrophobic surfaces [Zhai et al, 2004], to make azo photochromic hollow shells [Jung et al, 2002], and is amenable to patterning [Nyamjav and Ivanisevic, 2004]).

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