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The influence of the conditions of the anodic formation and the thickness of Ag(I) oxide nanofilm on its semiconductor properties

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Abstract

The anodic formation of Ag(I) oxide nanofilms on polycrystalline silver and Ag–Au alloys as well as on low-index single crystals of silver in 0.1 М KOH was examined. By the methods of photocurrent i ph and photopotential E ph measurements, the n-type conductivity of Ag2O film was established. Since the film (6–120 nm) is thinner than the space charge region, the dependence of photocurrent and photopotential appears on the film thickness L: i ph ~L and E ph ~L 2. The transition from polycrystalline silver to single crystals as well as the addition of a small amount of gold (X Au ≤ 4 at.%) into the silver lattice decreases the degree of deviation from the stoichiometric composition Ag2O. The parameters of Ag2O film (optical absorption coefficient α, donor defects concentration N D, space charge region W, and Debye’s length of screening L D) depend on the index of a crystal face of silver, volume concentration of gold X Au in the alloy, and film-formation potential E. At Е = 0.52 V, the sequences of variation of these parameters correlate with the reticular density sequence. The growth of the potential disturbs these sequences. The band gap in Ag2O formed on Agpoly, Aghkl, and Ag–Au is 2.32, 2.23, and 2.19 eV. Flat band potential in Ag(I) oxide, formed on Agpoly in 0.5 M KOH is 0.37 V. The appearance of the clear dependence between the state of the oxide/metal interface and the structure-sensitive parameters of semiconductor Ag(I) oxide phase allows considering the anodic formation of Ag2O on Ag as a result of the primary direct electrochemical reaction, not of the precipitation from the near-electrode layer.

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Notes

  1. The evidence of enrichment of the surface of Ag–Au alloy with gold during the dealloying are presented, for example, in [22, 23].

  2. The numerical analysis shows that in thin films with a low level of light absorption (αL D < < 1), PP and PC values are negligibly small.

  3. In a special set of experiments, the dependence of the capacity of Agpoly/0.5 M KOH boundary on the potential was obtained. The extrapolation in the coordinates of Mott–Schottky gives the value of flat band potential for Ag2O E fb = 0.37 V in accordance with [42], where E fb = 0.33 V

  4. The problem of i ph decay in Ag(I) oxide on Aghkl after the film thickness achieves 50 nm needs further investigation in detail.

  5. Note that the accuracy of determination of band gap in Ag2O oxide ± 0.1 eV is low enough to draw conclusions on the influence of the crystal face and alloy composition on E bg.

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Acknowledgements

We are grateful to Professor Leonid Kazanskiy (The Institute of Physical Chemistry and Electrochemistry of Russian Academy of Science) for the assistance in the XPS investigations.

This work is supported by Russian Foundation of Basic Research (project 09-03-00554-a).

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Authors and Affiliations

  1. Department of Physical Chemistry, Voronezh State University, Universitetskaya pl. 1, Voronezh, 394006, Russia

    Alexander Vvedenskii, Svetlana Grushevskaya, Dmitrii Kudryashov & Sergei Ganzha

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  1. Alexander Vvedenskii
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  2. Svetlana Grushevskaya
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  3. Dmitrii Kudryashov
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  4. Sergei Ganzha
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Correspondence to Alexander Vvedenskii.

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Vvedenskii, A., Grushevskaya, S., Kudryashov, D. et al. The influence of the conditions of the anodic formation and the thickness of Ag(I) oxide nanofilm on its semiconductor properties. J Solid State Electrochem 14, 1401–1413 (2010). https://doi.org/10.1007/s10008-009-0952-9

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  • DOI: https://doi.org/10.1007/s10008-009-0952-9

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