Initial Growth Mechanism of Blue Phosphorene on Au(111) Surface

Blue phosphorene (blue P), a new two-dimensional allotrope of phosphorus, has attracted great attentions due to its high carrier mobility, suitable band gap and appreciable. Stability comparable to black phosphorene (black P). Motivated recent experimental success in synthesizing monolayer blue P on Au(111) surface, here we investigate the nucleation mechanism and growth behavior of P-N clusters on Au(111) substrate by ab initio calculations. During, the initial growth stage, P-N clusters transform from dispersed atoms to zigzag chain at N = 4, and further turn to ring-based one-dimensional chain at N = 11. This peculiar behavior is ascribed to the competition between the interaction among P atoms and the attraction on P atoms by Au substrate. On the basis of the interaction energies between black/blue phosphorene and Au(111) surface, we further propose that monolayer blue P can be synthesized on a chemical active metal substrate, while a relatively inert metal substrate would be beneficial to the growth of monolayer black P. Our theoretical findings offer experimentalists insightful guidance to fabricate monolayer blue P or black P by choosing appropriate substrate.