Title:

Atomic Scale Investigation of Oxidation at the Black Phosphorus Surface

The oxidation of bulk black phosphorus (BP) is investigated using scanning tunneling microscopy/spectroscopy (STM/S). Dosing O2 at a pressure of 10-5 mbar for 1 minute creates two new types of defects on the surface. We identify these defects as atomic oxygen and phosphorus multivacancies using STM/S simulations. In addition to the physical changes to the surface, the electronic structure is also drastically altered by the introduction of oxygen. The band gap of BP, which is normally 300 meV, is lifted due to dosing. This change to the electronic structure is reversible by removing defects from a localized region with the STM tip. These are the first experimental results showing the atomic-scale oxidation of BP, an important step toward understanding the degradation process.

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