A first principle study on the role of Li intercalation in the structural transition from a few-layer black to blue phosphorene*

A systematic study on the role of Li intercalation played in the structure transition from a few-layer black to blue phosphorene has been carried out from first principle calculations based on the density functional theory. It is found that, depending on Li concentration and configuration intercalated on black phosphorene surface, the structure of the black phosphorous is either maintained its A17 symmetry, transferred to blue phosphorene with A7 symmetry, or distorted to form zigzag chains. Specifically, it was found that within a certain Li configurations intercalated on black phosphorene, Li atoms could play as ‘catalysts’ to drive the specific P atoms moving along specific directions, resulting bond breaking and forming, and subsequently, transforming a few-layer black to a few-layer blue phosphorene. This study opened a new pathway that, at a certain high rate Li intercalation, a feasible transition pathway from black to blue phosphorene. The role of the Li intercalation induced phase transition will be further studied and discussed, which will guide us to identify the specific conditions for such structural transformation.