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Abstract The interfacial modification effect of the molybdenum trioxide (MoO 3 ) buffer layer inserted between Al and black phosphorus (BP) was investigated with photoemission spectroscopy. The results show that MoO 3 buffer layer can effectively prevent the destruction of the outermost BP lattice by Al thermal deposition and change the interface electronic structure between Al and BP. At the MoO 3 /BP interface, there is an interface dipole pointing from MoO 3 to BP. During the metal deposition process, an interfacial chemical reaction between Al and MoO 3 was found. These observations would provide insight for fabricating high-performance BP-based devices.more » « less