The electron-transport processes in structures with oxidized porous silicon (OPS) are investigated during adsorption and desorption of polar molecules from atmosphere when the air pressure varies. It is shown that the cause of the existence of the open-circuit voltage in Pd-OPS-p(+)-Si-Al structures in the initial state is the surface-charge change on the Pd-OPS interface due to the polar-molecule adsorption from atmospheric air. The desorption of atmospheric-air molecules leads to a change in the current-voltage characteristics of structures, growth of the metal-OPS barrier in samples with the Schottky barrier, and initiation of current instabilities. The nanocrystalline nature of OPS manifests itself in the charge-carrier localization in quantum dots (QDs) during desorption in samples with space-charge-limited currents.
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