EFFECT OF LOCALIZED ELECTRONIC STATES ON SIMPLE ELECTRON TRANSFER REACTIONS AT FILM-COVERED ELECTRODES

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Abstract
Various mechanisms for electron transport across thin insulator or semiconductor films in metal-film-metal and metal-film-electrolyte systems are discussed. For thin layers (i. e. ≤ 50 Å) the transport mechanism may thus be direct and resonance elastic tunnelling, and inelastic tunnelling, whereas electron transfer across thicker layers proceeds by band conduction or phonon-assisted hopping via localized electronic states. Experimental data for electron transfer across thin polyacrylonitrile films on stainless steel or platinum substrates in both solid-state junctions and electrochemical systems involving simple redox reactions are presented. Comparison with predicted relationships between current density, overvoltage, and film properties shows that the electron transfer mechanism in these systems is likely to be inelastic tunnelling and/or phonon-assisted hopping

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