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Morphology, semiconductor properties, and chemical stability of AG(I) oxide anodically formed on silver and silver alloys

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Abstract

Silver(I) oxide was anodically formed in a deaerated 0.1 M KOH aqueous solution on Ag and Ag–Zn alloys (from 5 to 30 at.% of zinc) subjected to anodic selective dissolution in a deaerated 0.01 M HNO3 + 0.09 М KNO3 aqueous solution. Under these conditions, a layer is formed on the surface of the alloy enriched with silver and structural defects whose concentration is significantly higher than the equilibrium one. Scanning electron microscopy, impedancemetry, and photopotential measurements were used. It was determined that irrespective of the concentration of the non-equilibrium defects in the surface layer of the alloy, the n-type silver(I) oxide was formed with prevailing donor defects, spheroid morphology, and a relatively low chemical stability in an aqueous alkaline solution. The higher the concentration of zinc in the alloy and structural defects in its surface layer, the lower the diameter of silver(I) oxide crystallites. An increase in the flat band potential of silver(I) oxide from 0.428 to 0.454 V following an increase in the concentration of superequilibrium defects in the alloy’s surface layer from 17.1⋅10−4 to 65.3⋅10−4 at.% is only observed for the alloy with the concentration of zinc of 5 at.%. The concentration of donor defects in the silver(I) oxide generally increases following an increase in the concentration of zinc in the alloy. The dependence of concentration of donor defects in the silver(I) oxide on the concentration of superequilibrium defects in the alloys surface layer is non-monotonic. The rate constant of chemical dissolution of the silver(I) oxide decreases following both an increase in the concentration of zinc in the alloy and an increase in the concentration of defects in its surface layer.

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Notes

  1. The experiments were performed at the VSU Centre for Collective Use of Scientific Equipment.

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Acknowledgements

The study was supported by the Ministry of Science and Higher Education of the Russian Federation under Agreement N 075-15-2021-1351 in part of functional materials properties analysis.

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Authors and Affiliations

  1. Voronezh State University, 1 Universitetskaya pl, Voronezh, 394018, Russian Federation

    M. Y. Bocharnikova, S. N. Grushevskaya, O. A. Kozaderov & A. V. Vvedensky

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  1. M. Y. Bocharnikova
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  2. S. N. Grushevskaya
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  3. O. A. Kozaderov
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  4. A. V. Vvedensky
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Correspondence to S. N. Grushevskaya.

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Bocharnikova, M.Y., Grushevskaya, S.N., Kozaderov, O.A. et al. Morphology, semiconductor properties, and chemical stability of AG(I) oxide anodically formed on silver and silver alloys. J Solid State Electrochem 28, 243–253 (2024). https://doi.org/10.1007/s10008-023-05654-z

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