Degradation of phosphorene in air: understanding at atomic level

Phosphorene is a promising two-dimensional (2D) material with a direct band gap, high carrier mobility, and anisotropic electronic properties. Phosphorene-based electronic devices, however, are found to degrade upon exposure to air. In this paper, we provide an atomic level understanding of the stability of phosphorene in terms of its interaction with O₂ and H₂O. The results based on density functional theory together with first principles molecular dynamics calculations show that O₂ could the spontaneously dissociate on phosphorene at room temperature. H₂O will not strongly interact with pristine phosphorene, however, an exothermic reaction could occur if phosphorene is first oxidized. The pathway of oxidation first, followed by exothermic reaction with water is the most likely route for the chemical degradation of phosphorene-based devices in air. (paper)