Epitaxial nucleation and lateral growth of high-crystalline black phosphorus films on silicon

Black phosphorus (BP) is a promising two-dimensional layered semiconductor material for next-generation electronics and optoelectronics, with a thickness-dependent tunable direct bandgap and high carrier mobility. Though great research advantages have been achieved on BP, lateral synthesis of high quality BP films still remains a great challenge. Here, we report the direct growth of large-scale crystalline BP films on insulating silicon substrates by a gas-phase growth strategy with an epitaxial nucleation design and a further lateral growth control. The optimized lateral size of the achieved BP films can reach up to millimeters, with the ability to modulate thickness from a few to hundreds of nanometers. The as-grown BP films exhibit excellent electrical properties, with a field-effect and Hall mobility of over 1200 cm²V^-1s^-1 and 1400 cm²V^-1s^-1 at room temperature, respectively, comparable to those exfoliated from BP bulk crystals. Our work opens the door for broad applications with BP in scalable electronic and optoelectronic devices.