Phase Instability in van der Waals In2 Se3 Determined by Surface Coordination.

van der Waals In2 Se3 has attracted significant attention for its room-temperature 2D ferroelectricity/antiferroelectricity down to monolayer thickness. However, instability and potential degradation pathway in 2D In2 Se3 have not yet been adequately addressed. Using a combination of experimental and theoretical approaches, we here unravel the phase instability in both α- and β'-In2 Se3 originating from the relatively unstable octahedral coordination. Together with the broken bonds at the edge steps, it leads to moisture-facilitated oxidation of In2 Se3 in air to form amorphous In2 Se3-3x O3x layers and Se hemisphere particles. Both O2 and H2 O are required for such surface oxidation, which can be further promoted by light illumination. In addition, the self-passivation effect from the In2 Se3-3x O3x layer can effectively limit such oxidation to only a few nanometer thickness. The achieved insight paves way for better understanding and optimizing 2D In2 Se3 performance for device applications.