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Chemical Bath Deposition of ZnO Nanowires Using Copper Nitrate as an Additive for Compensating Doping
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    Chemical Bath Deposition of ZnO Nanowires Using Copper Nitrate as an Additive for Compensating Doping
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    • Clément Lausecker
      Clément Lausecker
      Université Grenoble Alpes, CNRS, Grenoble INP, LMGP, 38000 Grenoble, France
      Université Grenoble Alpes, CNRS, CEA/LETI-Minatec, Grenoble INP, LTM, 38054 Grenoble, France
      Université Grenoble Alpes, CEA, LETI, 38054 Grenoble, France
    • Bassem Salem*
      Bassem Salem
      Université Grenoble Alpes, CNRS, CEA/LETI-Minatec, Grenoble INP, LTM, 38054 Grenoble, France
      *Email: [email protected]
      More by Bassem Salem
    • Xavier Baillin
      Xavier Baillin
      Université Grenoble Alpes, CEA, LETI, 38054 Grenoble, France
    • Odette Chaix-Pluchery
      Odette Chaix-Pluchery
      Université Grenoble Alpes, CNRS, Grenoble INP, LMGP, 38000 Grenoble, France
    • Hervé Roussel
      Hervé Roussel
      Université Grenoble Alpes, CNRS, Grenoble INP, LMGP, 38000 Grenoble, France
    • Sébastien Labau
      Sébastien Labau
      Université Grenoble Alpes, CNRS, CEA/LETI-Minatec, Grenoble INP, LTM, 38054 Grenoble, France
    • Bernard Pelissier
      Bernard Pelissier
      Université Grenoble Alpes, CNRS, CEA/LETI-Minatec, Grenoble INP, LTM, 38054 Grenoble, France
    • Estelle Appert
      Estelle Appert
      Université Grenoble Alpes, CNRS, Grenoble INP, LMGP, 38000 Grenoble, France
    • Vincent Consonni*
      Vincent Consonni
      Université Grenoble Alpes, CNRS, Grenoble INP, LMGP, 38000 Grenoble, France
      *Email: [email protected]
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2021, 60, 3, 1612–1623
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    https://doi.org/10.1021/acs.inorgchem.0c03086
    Published January 14, 2021
    Copyright © 2021 American Chemical Society

    Abstract

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    The controlled incorporation of dopants like copper into ZnO nanowires (NWs) grown by chemical bath deposition (CBD) is still challenging despite its critical importance for the development of piezoelectric devices. In this context, the effects of the addition of copper nitrate during the CBD of ZnO NWs grown on Au seed layers are investigated in detail, where zinc nitrate and hexamethylenetetramine are used as standard chemical precursors and ammonia as an additive to tune the pH. By combining thermodynamic simulations with chemical and structural analyses, we show that copper oxide nanocrystals simultaneously form with ZnO NWs during the CBD process in the low-pH region associated with large supersaturation of Cu species. The Cu(II) and Zn(II) speciation diagrams reveal that both species show very similar behaviors, as they predominantly form either X2+ ions (with X = Cu or Zn) or X(NH3)42+ ion complexes, depending on the pH value. Owing to their similar ionic structures, Cu2+ and Cu(NH3)42+ ions preferentially formed in the low- and high-pH regions, respectively, are able to compete with the corresponding Zn2+ and Zn(NH3)42+ ions to adsorb on the c-plane top facets of ZnO NWs despite repulsive electrostatic interactions, yielding the significant incorporation of Cu. At the highest pH value, additional attractive electrostatic interactions between the Cu(NH3)42+ ion complexes and negatively charged c-plane top facets further enhance the incorporation of Cu into ZnO NWs. The present findings provide a deep insight into the physicochemical processes at work during the CBD of ZnO NWs following the addition of copper nitrate, as well as a detailed analysis of the incorporation mechanisms of Cu into ZnO NWs, which are considered beyond the only electrostatic forces usually driving the incorporation of dopants such as Al and Ga.

    Copyright © 2021 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c03086.

    • Thermodynamic constants used in Visual MINTEQ, in situ pH measurements during CBD, and temperature-dependent Raman spectra of ZnO NWs grown at a pH0 of 7.1 and with a Cu(NO3)2/Zn(NO3)2 ratio of 5% (PDF)

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    Cited By

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    This article is cited by 25 publications.

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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2021, 60, 3, 1612–1623
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.0c03086
    Published January 14, 2021
    Copyright © 2021 American Chemical Society

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