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Tuning Oxide Properties by Oxygen Vacancy Control During Growth and Annealing
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Oxygen vacancy diffusion in bare ZnO nanowires.

Bei Deng1, Andreia Luisa da Rosa, Th Frauenheim

  • 1Department of Physics and Materials Science, City University of Hong Kong, Hong Kong SAR, China. aprqz@cityu.edu.hk.

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Summary

Oxygen vacancies (VO) are common defects in zinc oxide (ZnO) nanowires. Their migration is easier within nanowires than bulk material, favoring movement to the surface.

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Area of Science:

  • Materials Science
  • Solid State Physics
  • Surface Science

Background:

  • Oxygen vacancies (VO) are prevalent native defects in zinc oxide (ZnO).
  • These defects significantly influence ZnO's properties and applications in optoelectronics and photocatalysis.
  • Understanding VO behavior is crucial for tailoring ZnO nanodevices.

Purpose of the Study:

  • Investigate the migration behavior of oxygen vacancies (VO) in ultra-thin zinc oxide nanowires (NWs).
  • Determine the energetics and pathways of VO migration using computational methods.
  • Correlate theoretical findings with experimental observations in ZnO nanostructures.

Main Methods:

  • Employ density functional theory (DFT) calculations.
  • Analyze the formation energy (Ef) of oxygen vacancies at different sites (bulk, shallow, surface).
  • Calculate migration barriers for oxygen vacancies within ZnO nanowires.

Main Results:

  • Oxygen vacancies exhibit higher formation energy inside ZnO nanowires compared to surface sites.
  • Migration barriers for VO are lower in ZnO nanowires than in bulk ZnO.
  • Migration of VO from the bulk to the surface of the nanowire is energetically favorable.
  • Distinct geometric relaxations and structural reconstructions occur around VO.

Conclusions:

  • ZnO nanowires facilitate easier diffusion of oxygen vacancies compared to bulk ZnO.
  • A higher concentration of oxygen vacancies is expected at the surface of ZnO NWs.
  • These findings support experimental observations and guide the development of ZnO-based devices.