Creation of Single Vacancies in hBN with Electron Irradiation

Abstract Understanding electron irradiation effects is vital not only for reliable transmission electron microscopy characterization, but increasingly also for the controlled manipulation of 2D materials. The displacement cross sections of monolayer hexagonal boron nitride (hBN) are measured using aberration‐corrected scanning transmission electron microscopy in near ultra‐high vacuum at primary beam energies between 50 and 90 keV. Damage rates below 80 keV are up to three orders of magnitude lower than previously measured at edges under poorer residual vacuum conditions, where chemical etching appears to dominate. Notably, it is possible to create single vacancies in hBN using electron irradiation, with boron almost twice as likely as nitrogen to be ejected below 80 keV. Moreover, any damage at such low energies cannot be explained by elastic knock‐on, even when accounting for the vibrations of the atoms. A theoretical description is developed to account for the lowering of the displacement threshold due to valence ionization resulting from inelastic scattering of probe electrons, modeled using charge‐constrained density functional theory molecular dynamics. Although significant reductions are found depending on the constrained charge, quantitative predictions for realistic ionization states are currently not possible. Nonetheless, there is potential for defect‐engineering of hBN at the level of single vacancies using electron irradiation.