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If the charge asc is fully accommodated by electronic states near the Fermi energy, no space charge is formed in the electrode phase, and any voltage applied to the electrode appears exclusively across the Helmholtz layer, i.e. the system behaves like a metal. Degeneracy can be introduced not only by heavy doping, but also by high density of surface states in a semiconductor electrode (pinning of the Fermi level by surface states) or by polarizing a semiconductor electrode to extreme potentials, when the bands are bent into the Fermi level region. Another possibility of the appearance of a quasimetallic behaviour of metal oxides occurs with thin oxide films on metals. If the film thickness is sufficiently small (less than ca. 3 nm), the electrons can tunnel through the oxide film, and the charge transfer actually proceeds between the level of solution species and the Fermi level of the supporting metal (Fig. 4.12). Although the band model explains well various electronic properties of metal oxides, there are also systems where it fails, presumably because of neglecting electronic correlations within the solid. Therefore, J. B. Goodenough presented alternative criteria derived from the crystal structure, symmetry of orbitals and type of chemical bonding between metal and oxygen. This 'semiempirical' model elucidates and predicts electrical properties of simple oxides and also of more complicated oxidic materials, such as bronzes, spinels, perowskites, etc. There is a number of essentially non-conducting metal oxides acting as passive layers on electrodes; the best known example is A12O3. Metals that

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311 form insulating oxide films by anodic bias (eg Al, V, Hf, Nb, Ta, Mo) are termed 'valve metals' (cf Section 583) Some insulating oxides become semiconducting by doping This can be achieved either by inserting certain heteroatoms into the crystal lattice of the oxide, or more simply by its partial sub-stoichiometric reduction or oxidation, accompanied with a corresponding removal or addition of some oxygen anions from/into the crystal lattice (Many metal oxides are, naturally, produced in these mixed-valence forms by common preparative techniques) For instance, an oxide with partly reduced metal cations behaves as a n-doped semiconductor; a typical example is TiO2 Titanium dioxide is available as rutile (also in the form of sufficiently large single crystals) or anatase (only in polycrystalline form) Third modification, brookite, has no significance for electrode preparation.

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Figure 3.28. Photoresponsive behavior of the hydrogen-bonded LCE lms of (a) 21a + 21c and (b) 21b + 21c. Source: Mamiya et al., 2008.

Pure rutile or anatase are practically insulators, with conductivities of the order of 10~13S/cm Doping to n-type semiconducting state is performed, for example, by partial reduction with gaseous hydrogen, or simply by heating at temperatures about 500 C This is accompanied by a more or less deep coloration of the originally white material, and by an increase of the electronic conductivity by orders of magnitude Semiconducting titanium dioxide is one of the most important electrode materials in photoelectrochemistry (see Section 592) Another example of a non-stoichiometric, n-semiconducting oxide is PbO2 This has been extensively studied as a positive electrode material for lead/acid batteries Lead dioxide occurs in two crystal modifications, orthorhombic ar-PbO2, and more stable tetragonal j3-PbO2; both polymorphs show high electronic conductivity of the order of 102 S/cm, and a typical mixed-valence Pb(II)/Pb(IV) composition with the O/Pb ratio in the range about 183-196.

prepared LCE lms with a densely cross-linked, twisted con guration of azobenzene moieties (Harris et al., 2005b). The lms showed a large amplitude bending and coiling motion upon exposure to UV light, which results from the 901 twisted con guration of the LC alignment (Fig. 3.31). Most lately, Ikeda and coworkers prepared a continuous ring of the LCE lm by connecting both ends of the lm (Yamada et al., 2008). The azobenzene mesogens were aligned along the circular direction of the ring. As shown in

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