Synthesis of highly crystalline black phosphorus thin films on GaN
Dan Han, Qingming Liu, Qiang Zhang, Jianlong Ji, Shengbo Sang, Bingshe Xu
Abstract
Black phosphorus (BP) has recently garnered significant attention due to its specific physical properties. At present, high-quality few-layer and thin-film BP is obtained principally by mechanical exfoliation, restricting its device applications in the future. Here, a facile, direct synthesis of highly crystalline thin-film BP on GaN(001) substrates is achieved by conversion of red phosphorus to BP under atmospheric pressure. The synthesized ≈100-500 nm thick BP thin films with a length ranging from 4 to 15 μm can maintain long-term stability with no sign of oxidation after 5 months of exposure to ambient conditions, as indicated by energy dispersive spectroscopy (EDS). Cross-sectional spherical aberration correction transmission electron microscopy (STEM) analysis of the entire thin-film BP sample did not show any aggregation nucleation through the selected sample. The interface of the BP/GaN heterostructure is atomically sharp, which is very critical for high-performance device fabrication using a direct step in the future. And it is worth noting that there are fluctuations of a few atoms on the surface of GaN. Moreover, using first-principles approaches, here we establish a novel kinetic pathway for fabricating thin-film BP via epitaxial growth. The step of fluctuations with a few atoms on the GaN surface are first preferentially covered by P adatoms, then P adatoms cover the remaining part. Once formed, such a structure of thin-film BP is stable, as tested using EDS and STEM. Combining the results of the experiment and simulation, it can be revealed that the P adatom on undulatory GaN is sufficiently mobile and the undulating surface of GaN plays a major role in forming high-quality thin-films of BP. The preferentially covered nearby step growth mechanism discovered here may enable the mass production of high-quality thin-film BP, and could also be instrumental in achieving the epitaxial growth of thin-film BP on GaN and other 2D materials.