Effect of Edge Reconstruction on the Growth Mechanism\nof Black Phosphorene

Based\non our previous studies, the reconstruction of interlayer\nedges of black phosphorene (BP) is identified as a key factor impeding\nthe growth of large-size BP films through the CVD method. In this\nstudy, we systematically explore the complex growth mechanisms of\nBP, specifically focusing on how edge reconstruction influences the\ngrowth of BP. The results reveal that BP with reconstructed edges\nis highly stable. Growth necessitates initially opening a unit at\nthe reconstructed edge, requiring a higher energy barrier than that\nof pristine BP without reconstructed edges. Despite this challenge,\novercoming it facilitates subsequent phosphorus atom additions, thereby\npromoting favorable growth conditions for reconstructed-edge BP. Overall,\nour research highlights the interplay between edge reconstruction\nand BP growth dynamics, offering insights for the rational design\nand synthesis of large-area, high-quality monolayer BP, thus advancing\nits potential in electronic and optoelectronic applications.