First-Principles Molecular Dynamics Insight into the Atomic Level Degradation Pathway of Phosphorene

[Image: see text] Despite its remarkable properties, phosphorene is not promising for device application due to its instability or gradual degradation under ambient conditions. The issue still persists, and no technological solution is available to address this degradation due to a lack of clarity about degradation dynamics at the atomic level. Here, we discuss atomic level degradation dynamics of phosphorene under ambient conditions while investigating the involvement of degrading agents like oxygen and water using density functional theory and first-principles molecular dynamics computations. The study reveals that the oxygen molecule dissociates spontaneously over pristine phosphorene in an ambient environment, resulting in an exothermic reaction, which is boosted further by increasing the partial pressure and temperature. The surface reaction is mainly due to the lone pair electrons of phosphorous atoms, making the degradation directional and spontaneous under oxygen atoms. We also found that while the pristine phosphorene is hydrophobic, it becomes hydrophilic after surface oxidation. Furthermore, water molecules play a vital role in the degradation process by changing the reaction dynamics path of the phosphorene–oxygen interaction and reducing the activation energy and reaction energy due to its catalyzing action. In addition, our study reveals the role of phosphorous vacancies in the degradation, which we found to act as an epicenter for the observed oxidation. The oxygen attacks directly over the vacant site and reacts faster compared to its pristine counterpart. As a result, phosphorene edges resembling extended vacancy are prominent reaction sites that oxidize anisotropically due to different bond angle strains. Our study clears the ambiguities in the kinetics of phosphorene degradation, which will help engineer passivation techniques to make phosphorene devices stable in the ambient environment.