Tunnelling Processes at Highly Doped ZnO‐Electrodes in Aqueous Electrolytes Part II: Electron Exchange with the Valence Band

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Abstract
Highly doped ZnO‐electrodes show a blocking region of only about 3 V. Above this region anodic breakdown currents set in which rise steeply with increasing potentials. The currents are attributed to the generation of holes by field emission of valence electrons into the conduction band. The generation of holes is shown by surface reactions, like the oxidative lattice decomposition, or by the current multiplication in particular oxidation reactions of organic substances which are well known as being caused by holes. Another indication of hole generation is the light emission during anodic breakdown currents caused by recombination of holes with electrons.On the polar ZnO surfaces (〈0001〉 and 〈0001〉 surface) considerable differences are observed in the anodic currents and in the composition of reaction products.

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