Origin of Oxidation Variations in Ambient-Stable β-InSe

Understanding and controlling the oxidation of layered materials remain critical issues in the final stages of their practical application in devices. Layered materials achieve a band gap by removing inversion symmetry. However, the oxidation process becomes complex, and the oxidation of these materials is not yet fully understood. As a representative example, InSe has attracted considerable attention due to its high charge mobility and Si-like band gap. However, conflicting observations such as oxidation by Se and In have been reported, including contrasting assessments of the oxidation susceptibility. In this study, we report in situ spectroscopy results detailing the origins of various oxidation pathways. We observed that at low defect densities the reduced reaction barrier of InSe due to Se vacancies leads to oxygen adsorption, while as defects increase, the lower electronegativity of In rises as a new pathway for oxidation. At low defect density, the bulk layer was more energetically favored for oxygen adsorption, allowing oxygen to diffuse to a depth sufficient to form pseudoheterojunctions and making the surface layer seemingly resistant to oxidation. Our results provide an answer to why the resulting diversity of optical responses is expected to increase as well as strategies to achieve gas stability.