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  • Letter
  • Open Access

Ab initio vacancy formation energies and kinetics at metal surfaces under high electric field

Shyam Katnagallu1,*, Christoph Freysoldt1,†, Baptiste Gault1,2, and Jörg Neugebauer1

  • 1Max Planck Institut fϋr Eisenforschung GmbH, Max-Planck- Str. 1, 40237, Düsseldorf, Germany
  • 2Royal School of Mines, Imperial College, Prince Consort Road, SW7 2BP, London, United Kingdom

  • *s.katnagallu@mpie.de
  • †c.freysoldt@mpie.de
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Phys. Rev. B 107, L041406 – Published 20 January, 2023

DOI: https://doi.org/10.1103/PhysRevB.107.L041406

Abstract

Recording field ion microscope images under field-evaporating conditions and subsequently reconstructing the underlying atomic configuration, called three-dimensional field ion microscopy (3D-FIM), is one of the few techniques capable of resolving crystalline defects at an atomic scale. However, the quantification of the observed vacancies and their origins are still a matter of debate. It was suggested that high electrostatic fields (1–5 V/Å) used in 3D-FIM could introduce artifact vacancies. To investigate such effects, we used density functional theory simulations. Stepped nickel and platinum surfaces with kinks were modeled in the repeated-slab approach with a (971) surface orientation. An electrostatic field of up to 4 V/Å was introduced on one side of the slab using the generalized dipole correction. Contrary to what was proposed, we show that the formation of vacancies on the electrified metal surface is more difficult compared to a field-free case. We also find that the electrostatic field can introduce kinetic barriers to a potential “vacancy annihilation” mechanism. We rationalize these findings by comparing to insights from field evaporation models.

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Phys. Rev. B 107, L041406– Published 20 January, 2023
  • Received 14 September 2022
  • Revised 7 December 2022
  • Accepted 9 January 2023
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Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI. Open access publication funded by the Max Planck Society.

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