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Metal and magnetic overlayers alter the surface of the topological insulator(TI) bismuth selenide (Bi$_2$Se$_3$) through proximity effects but also bychanging the composition and chemical structure of the Bi$_2$Se$_3$sub-surface. The interface between Bi$_2$Se$_3$ and Mn metal or manganeseselenide was explored using x-ray photoelectron spectroscopy (XPS) revealingchemical and electronic changes at the interface. Depositing Mn metal onBi$_2$Se$_3$ without an external source of Se shows unexpected bonding withinthe Mn layer due to Mn-Se bonding as Se diffuses out of the Bi$_2$Se$_3$ layerinto the growing Mn film. The Se out-diffusion is further evidenced by changesin Bi core levels within the Bi$_2$Se$_3$ layers indicating primarily Bi-Bibonding over Bi-Se bonding. No out-diffusion of Se occurred when excess Se issupplied with Mn, indicating the importance of supplying enough chalcogen atomswith deposited metals. However, Bi$_2$Se$_3$ core level photoelectronsexhibited a rigid chemical shift toward higher binding energy after depositinga monolayer of MnSe$_{2-x}$, indicating a dipole within the overlayer.Stoichiometry calculations indicated that the monolayer forms MnSepreferentially over the transition metal dichalcogenide (TMD) phase MnSe$_2$,providing a consistent picture of the dipole formation in which a plane of Seanions sits above Mn cations. This study shows that chemical diffusion anddipole formation are important for Mn-Bi$_2$Se$_3$ andMnSe$_{2-x}$-Bi$_2$Se$_3$ and should be considered carefully for TMD/TIinterfaces more generally.

Chemical Migration and Dipole Formation at van der Waals Interfaces between Magnetic Transition Metal Chalcogenides and Topological Insulators