Room‐Temperature Ferroelectricity in Hexagonally Layered α‐In2Se3 Nanoflakes down to the Monolayer Limit

Abstract 2D ferroelectric material has emerged as an attractive building block for high‐density data storage nanodevices. Although monolayer van der Waals ferroelectrics have been theoretically predicted, a key experimental breakthrough for such calculations is still not realized. Here, hexagonally stacking α‐In2Se3 nanoflake, a rarely studied van der Waals polymorph, is reported to exhibit out‐of‐plane (OOP) and in‐plane (IP) ferroelectricity at room temperature. Ferroelectric multidomain states in a hexagonal α‐In2Se3 nanoflake with uniform thickness can survive to 6 nm. Most strikingly, the electric‐field‐induced polarization switching and hysteresis loop are, respectively, observed down to the bilayer and monolayer (≈1.2 nm) thicknesses, which designates it as the thinnest layered ferroelectric and verifies the corresponding theoretical calculation. In addition, two types of ferroelectric nanodevices employing the OOP and IP polarizations in 2H α‐In2Se3 are developed, which are applicable for nonvolatile memories and heterostructure‐based nanoelectronics/optoelectronics.