Atomic Visualization and Switching of Ferroelectric Order in β‐In₂Se₃ Films at the Single Layer Limit

Abstract 2D ferroelectrics have received wide interest due to the remarkable quantum states of emerging physics at reduced dimensionality, associated with their exotic properties in high‐performance and nonvolatile functional devices. Here, by combing molecular beam epitaxy synthesis and scanning tunneling microscopy characterization, two metastable phases of layered In₂Se₃ films: β′‐ and β*‐In₂Se₃ are reported, which develop different types of in‐plane spontaneous polarizations, thus resulting in different striped morphologies. The anti‐ferroelectric order in β′‐In₂Se₃ and ferroelectric order of β*‐In₂Se₃ are identified, respectively, down to the 2D limit by comprehensive investigations of structural and spectroscopic signatures, including the lattice distortion, the spatial profile of images, the formation of domain structure, and the electronic band‐bending by polarization charges at edges. The ferroelectric switching between those two phases are further controlled via applying an electric field generated from the scanning tunneling microscopy tip in a reversible manner. The intriguing tunability between the (anti‐)ferroelectric orders in the 2D limit provides a promising platform for studying the interplay between electronic structure and ferroelectricity in van der Waals materials, and promotes potential development of miniaturized transistors and memory devices based on electric polarizations.