Quantification of Surface Reactivity and Step-Selective Etching Chemistry on Single-Crystal BiOI(001)

To bridge the gap between the cleanliness of a freshly cleaved surface of 2D BiOI and that available from a purely chemical-etching means, we subjected single-crystal BiOI to a series of surface treatments and quantified the resulting chemical states and electronic properties. Vapor transport syntheses included both physical vapor transport from single-source BiOI, as well as chemical vapor transport from Bi₂O₃ + BiI₃ and from Bi + I₂ + Bi₂O₃. Surface treatments included tape cleaving, rinsing in water, sonication in acetone, an aqueous HF etch, and a sequential HF etch with subsequent sonication in acetone. X-ray diffraction, XRD, and X-ray photoelectron spectroscopy, XPS, probed the resulting bulk crystalline species and interfacial chemical states, respectively. In comparison with overlayer models of idealized oxide-terminated or iodide-terminated BiOI, angle-resolved XPS elucidated surface terminations as a function of each treatment. Ultraviolet photoelectron spectroscopy, UPS, established work-function, and Fermi-level energies for each treatment. Data reveal that HF etching yields interfacial BiI₃ at BiOI steps that is subsequently removed with acetone sonication. UPS establishes n-type behavior for the vapor-transport-synthesized BiOI, and surface work function and Fermi level shifts for each chemical treatment under study. We discuss the implications for processing BiOI nanofilms for energy-conversion applications.