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Grain boundary passivation studied by in situ scanning tunneling microscopy on microcrystalline copper

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Abstract

Electrochemical scanning tunneling microscopy (ECSTM) was applied to analyze in situ the passivation of grain boundaries on microcrystalline copper in 0.1 M NaOH aqueous solution. Two types of boundaries, assigned to coherent twin and random grain boundaries, were studied in three different states of the copper surface: metallic after cathodic reduction of the air-formed native oxide film, passive after anodic polarization at 0.7 V vs. SHE to form the duplex Cu(I)/Cu(II) oxide film, and metallic after cathodic reduction of the passive film. The depth measured at several sites along the grain boundaries was extracted from statistical line profile analysis and discussed using an original model allowing differentiating metal consumption by dissolution or by passive film formation at grains and grain boundaries. The results highlight different local passivation properties between randomly oriented grains and grain boundaries and also between the two different types of grain boundaries. Both at coherent twin and random grain boundaries, it is found that more copper irreversibly dissolves during passivation and less copper is consumed to grow the passive film, suggesting a more hydroxylated/hydrated composition less dense in copper than on grains. At random grain boundaries, irreversible dissolution is found to be enhanced and the passive film to be thicker.

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Authors and Affiliations

  1. Chimie ParisTech - CNRS, Institut de Recherche de Chimie Paris, PSL Research University, 11 rue Pierre et Marie Curie, 75005, Paris, France

    Hu Chen, Vincent Maurice, Lorena H. Klein & Philippe Marcus

  2. Department of Materials Science and Engineering, Ghent University (UGent), Technologiepark 903, Zwijnaarde, 9052, Ghent, Belgium

    Linsey Lapeire & Kim Verbeken

  3. Research Group Electrochemical and Surface Engineering (SURF), Vrije Universiteit Brussel, Pleinlaan 2, 1050, Brussels, Belgium

    Herman Terryn

Authors
  1. Hu Chen
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  2. Vincent Maurice
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  3. Lorena H. Klein
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  4. Linsey Lapeire
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  5. Kim Verbeken
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  6. Herman Terryn
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  7. Philippe Marcus
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Correspondence to Vincent Maurice or Philippe Marcus.

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Chen, H., Maurice, V., Klein, L.H. et al. Grain boundary passivation studied by in situ scanning tunneling microscopy on microcrystalline copper. J Solid State Electrochem 19, 3501–3509 (2015). https://doi.org/10.1007/s10008-015-2787-x

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  • DOI: https://doi.org/10.1007/s10008-015-2787-x

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