Origin of giant negative piezoelectricity in a layered van der Waals ferroelectric

Recent research on piezoelectricmaterials is predominantly devoted to enhancing the piezoelectric coefficient, but overlooks its sign, largely because almost all of them exhibit positive longitudinal piezoelectricity. The only experimentally known exception is ferroelectric polymerpoly(vinylidene fluoride) and its copolymers, which condense via weak van der Waals (vdW) interaction and show negative piezoelectricity. Here we report quantitative determination of giant intrinsic negative longitudinal piezoelectricityand electrostrictionin another class of vdW solids—two-dimensional (2D) layered ferroelectric CuInP 2 S 6 . With the help of single crystal x-ray crystallography and density-functional theory calculations, we unravel the atomistic origin of negative piezoelectricityin this system, which arises from the large displacive instability of Cu ions coupled with its reduced lattice dimensionality. Furthermore, the sizable piezoelectricresponse and negligible substrate clamping effect of the 2D vdW piezoelectricmaterials warrant their great potential in nanoscale, flexible electromechanical devices.