Phosphorus Chains and Pentamers: The Precursors of Blue Phosphorene on the Ag(111) Substrate

Phosphorus (P) has many isomers of very similar stabilities that makes the controllable synthesis of each isomer difficult. Although numerous experiments have been devoted to the synthesis of blue phosphorene (BLP), there is still limited success. Here, we present a systematic theoretical study of the phosphorus isomers on the Ag(111) surface. We found that one-dimensional armchair chains have high stability at a low P concentration, and five-membered rings of phosphorus or phosphorus pentamers are the most stable structures at medium P concentration. We also identified a few patterns of phosphorus pentamers on the Ag(111) surface, one of which agrees well with experimental observation. Finding that BLP is highly stable at high P coverage, we predict the transformation from phosphorus chains through pentamers to BLP on the Ag(111) surface. Our theoretical study provides a guideline for the experimental synthesis of BLP on the Ag(111) surface.