Surface Energy of Black Phosphorus Alloys with Arsenic

Abstract Black phosphorus belongs to the most intensively studied two‐dimensional materials with many unusual properties. It is capable of forming solid solutions with arsenic, which allows continual tuning of its properties. The vapour phase transport method was used for effective synthesis of black phosphorus and its alloys with arsenic of defined composition using SnI₄/Sn mineralising agent. The incorporation of arsenic up to over 50 at.% was confirmed by X‐ray photoelectron spectroscopy. Structural changes were observed by X‐ray diffraction and Raman spectroscopy. Density functional theory calculations were used to calculate the change of lattice parameters due to alloying, to model Raman activity of the bP−As alloy and to estimate the surface energy of the alloy. The surface properties of black phosphorus and its alloys with arsenic were measured by inverse gas chromatography. Although the differences of surface energy between black phosphorus and its alloys were relatively low, the surface energy profiles were unusually flat, indicating a sparsity of high‐energy sites on the surface of the alloys.