Chemical Vapor Transport Growth of Bulk Black Phosphorus Single Crystal
Phosphorene, which is designated as monolayer or a few-layer of orthorhombic black phosphorus (BP), has emerged as a new promising member of the two-dimensional material family. A plethora of exciting applications of phosphorene have been reported based on its intriguing properties. Unfortunately, due to the lack of reliable method for direct synthesis of highly crystalline phosphorene, bulk BP single crystal has been the sole precursor to attain high-quality phosphorene. Chemical vapor transport (CVT) reaction method has been deemed the most successful method for the growth of bulk BP single crystal. Herein, recent progress in controlled growth of bulk BP single crystal by CVT reaction is briefly reviewed. The emphasis is focused on reaction system, nucleation and growth mechanism of CVT synthesis of bulk BP crystal as well as the recent development on growth of doped and substituted BP single crystal by CVT reaction method. The challenges and perspectives ahead of CVT growth of BP crystal are also pointed out.