Towards large-area and defects-free growth of phosphorene on Nickel

Low-dimensional materials synthesis based on phosphorus atoms is under intense study, and it is still one of the big challenges. Phosphorene, a monolayer of black phosphorus, is one of the most promising candidates for transistor and photonics devices at atomistic thickness. However, the lack of large-scale and defects-free growth significantly obstructs its device development. Here, we demonstrate the large-scale and defect-free phosphorene synthesis on Nickel (Ni) substrate. In addition, the effect of substrate orientation on the controllable synthesis of possible allotropes has also been described. We have shown that blue phosphorene can be grown on Ni (111) and Ni (100). While {\gamma}-Phosphorene, named Navy Phosphorene hereafter, can be grown on Ni (110). Furthermore, we found that the synthesis goes through phosphorus pentamers (P5) to phosphorene; P5 is a vital precursor for phosphorene synthesis. Moreover, we confirm the high accuracy of the P-Ni, and P-P potentials and show that the molecular dynamics (M.D.) approach is a powerful tool to simulate the 2D materials synthesis in the vapor phase. This work provides a solid reference to understand and control the synthesis of large-area single-crystalline monolayer phosphorene.