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By Michel Froment

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Extra info for Passivity of Metals and Semiconductors. Proceedings of the Fifth International Symposium on Passivity, Bombannes, France, May 30–June 3, 1983, Organized by the Société de Chimie Physique

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38 20 151 1 (repassivated 1 / 1 I / / / / / / / / / / V°1 // // S^^^ / / / / ^ S ' 'repassivated ^» Fig. 3: Schottky-Mott diagram of the data given in Fig. 2 ^- -** *" ^ ^ initial // s I /// / /7 / V/ ^1 initial^—1 A — impl. 5 potential e(SHE)/V plots of Fig. 3 show, that the flat band potential is very similar for all Ti0 2 films. Repassivated diodes have the same slope as the pure films, but impox have a smaller slope. Since the slope yields the product D-N, the increase of D may contribute as well as that of N.

In order to derive the logarithmic law, we need to establish the variation, within the oxide film, of the local concentration of reduction defects in a higher oxide on a metal. For simplicity, we may consider the reduction defects, +2 in an NL0 3 crystal, to be M ions in interstitial sites of a cation-excess solid. These defect ions may be formed by ionizing metal atoms and moving them to interstitial sites at various distances below the oxide/gas interface. Compare ref. 7, pp. 259-61. We let Δψ be the potential drop between the metal and the oxide/gas interface.

4. Space charge barrier at the interface between a thick, semiconducting film and a redox electrolyte: solid lines: equilibrium potential; broken lines: at an anodic overpotential At potentials above the flat band potential, a space charge barrier exists at the film/electrolyte interface; its height and thickness are determined by the applied potential and by the Debye-length L, of the film (see fig. 4 ) . The transferring electron either tunnels through this barrier or passes over it. The most important tunnelling mechanisms are again direct elastic tunnelling and resonance tunnelling; the corresponding tunnelling probabilities are calculated in the same way as for the thin film mechanism.

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