Electronic Self-passivation of Single Vacancy in Black Phosphorus via a Controlled Ionization


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We report that mono-elemental black phosphorus presents a new electronic self-passivation scheme of single vacancy (SV). By means of low-temperature scanning tunneling microscopy and bond-resolved non-contact atomic force microscopy, we demonstrate that the local reconstruction and ionization of SV into negatively charged $mathrm{SV}^-$ 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 $mathrm{SV}^-$ 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 $mathrm{SV}^-$ can be attributed to its weak dipole-like perturbation, consistent with density-functional theory and numerical calculations. Therefore, self-passivated $mathrm{SV}^-$ is electronically benign and acts as a much weaker scattering center, which may hold the key to further enhance the charge mobility of BP and its analogs.

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