Identification and Manipulation of Defects in Black Phosphorus

J Phys Chem Lett. 2022 Jul 14;13(27):6276-6282. doi: 10.1021/acs.jpclett.2c01370. Epub 2022 Jul 1.

Abstract

We identify and manipulate commonly occurring defects in black phosphorus, combining scanning tunneling microscopy experiments with density functional theory calculations. A ubiquitous defect, imaged at negative bias as a bright dumbbell extending over several nanometers, is shown to arise from a substitutional Sn impurity in the second sublayer. Another frequently observed defect type is identified as arising from an interstitial Sn atom; this defect can be switched to a more stable configuration consisting of a Sn substitutional defect + P adatom, by application of an electrical pulse via the STM tip. DFT calculations show that this pulse-induced structural transition switches the system from a non-magnetic configuration to a magnetic one. We introduce States Projected Onto Individual Layers (SPOIL) quantities which provide information about atom-wise and orbital-wise contributions to bias-dependent features observed in STM images.