Effect of Edge Reconstruction on the Growth Mechanism of Black Phosphorene

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