Picometer‐Level In Situ Manipulation of Ferroelectric Polarization in Van der Waals layered InSe

Abstract Ferroelectric 2D van der Waals (vdW) layered materials are attracting increasing attention due to their potential applications in next‐generation nanoelectronics and in‐memory computing with polarization‐dependent functionalities. Despite the critical role of polarization in governing ferroelectricity behaviors, its origin and relation with local structures in 2D vdW layered materials have not been fully elucidated so far. Here, intralayer sliding of approximately six degrees within each quadruple‐layer of the prototype 2D vdW ferroelectrics InSe is directly observed and manipulated using sub‐angstrom resolution imaging and in situ biasing in an aberration‐corrected scanning transmission electron microscope. The in situ electric manipulation further indicates that the reversal of intralayer sliding can be achieved by altering the electric field direction. Density functional theory calculations reveal that the reversible picometer‐level intralayer sliding is responsible for switchable out‐of‐plane polarization. The observation and manipulation of intralayer sliding demonstrate the structural origin of ferroelectricity in InSe and establish a dynamic structural variation model for future investigations on more 2D ferroelectric materials.