Electronic Self-Passivation of Single Vacancy in Black Phosphorus via Ionization

We report that monoelemental black phosphorus presents a new electronic self-passivation scheme of single vacancy (SV). By means of low-temperature scanning tunneling microscopy and noncontact atomic force microscopy, we demonstrate that the local reconstruction and ionization of SV into negatively charged ${\mathrm{SV}}^{\ensuremath{-}}$ leads to the passivation of dangling bonds and, thus, the quenching of in-gap states, which can be achieved by mild thermal annealing or STM tip manipulation. SV exhibits a strong and symmetric Friedel oscillation (FO) pattern, while ${\mathrm{SV}}^{\ensuremath{-}}$ shows an asymmetric FO pattern with local perturbation amplitude reduced by one order of magnitude and a faster decay rate. The enhanced passivation by forming ${\mathrm{SV}}^{\ensuremath{-}}$ can be attributed to its weak dipolelike perturbation, consistent with density-functional theory numerical calculations. Therefore, self-passivated ${\mathrm{SV}}^{\ensuremath{-}}$ is electrically benign and acts as a much weaker scattering center, which may hold the key to further enhance the charge mobility of black phosphorus and its analogs.