Phase Coexistence and Metal-Insulator Transition in Few-Layer Phosphorene: A Computational Study

Abstract

Based on ab initio density functional calculations, we propose $\ensuremath{\gamma}\text{\ensuremath{-}}\mathrm{P}$ and $\ensuremath{\delta}\text{\ensuremath{-}}\mathrm{P}$ as two additional stable structural phases of layered phosphorus besides the layered $\ensuremath{\alpha}\text{\ensuremath{-}}\mathrm{P}$ (black) and $\ensuremath{\beta}\text{\ensuremath{-}}\mathrm{P}$ (blue) phosphorus allotropes. Monolayers of some of these allotropes have a wide band gap, whereas others, including $\ensuremath{\gamma}\text{\ensuremath{-}}\mathrm{P}$, show a metal-insulator transition caused by in-layer strain or changing the number of layers. An unforeseen benefit is the possibility to connect different structural phases at no energy cost. This becomes particularly valuable in assembling heterostructures with well-defined metallic and semiconducting regions in one contiguous layer.