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Atomic structure of single-crystalline black phosphorus was studied by highresolution synchrotron-based photoelectron diffraction (XPD). The results showthat the topmost phosphorene layer in the black phosphorus is slightlydisplaced compared to the bulk structure and presents a small contraction inthe direction perpendicular to the surface. Furthermore, the XPD results showthe presence of a small buckling among the surface atoms, in agreement withpreviously reported scanning tunneling microscopy results. The contraction ofthe surface layer added to the presence of the buckling indicates an uniformityin the size of the sp3 bonds between P atoms at the surface.

Surface Structure Determination of Black Phosphorus Using Photoelectron Diffraction