Van der Waals layered CuInP 2 S 6 (CIPS) is an ideal candidate for developing two-dimensional microelectronic heterostructures because of its room temperature ferroelectricity, although field-driven polarization reversal of CIPS is intimately coupled with ionic migration, often causing erratic and damaging switching that is highly undesirable for device applications. In this work, we develop an alternative switching mechanism for CIPS using flexoelectric effect, abandoning external electric fields altogether, and the method is motivated by strong correlation between polarization and topography variation of CIPS. Phase-field simulation identifies a critical radius of curvature around 5 μm for strain gradient to be effective, which is realized by engineered topographic surfaces using silver nanowires and optic grating upon which CIPS is transferred to. We also demonstrate mechanical modulation of CIPS on demand via strain gradient underneath a scanning probe, making it possible to engineer multiple polarization states of CIPS for device applications.

CuInP2S6 with robust room-temperature ferroelectricity has recently attracted much attention due to the spatial instability of its Cu cations and the van der Waals (vdW) layered structure. Herein, we report a significant enhancement of its remanent polarization by more than 50% from 4.06 to 6.36 µC cm− 2 under a small pressure between 0.26 to 1.40 GPa. Comprehensive analysis suggests that even though the hydrostatic pressure suppresses the crystal distortion, it initially forces Cu cations to largely occupy the interlayer site, causing the spontaneous polarization to increase. Under intermediate pressure, the condensation of Cu cations to the ground state and the polarization increase due cell volume reduction compensate each other, resulting in a constant polarization. Under high pressure, the migration of Cu cations to the center of the S octahedron dominates. These findings improve our understanding of this fascinating vdW ferroelectric material, and suggest new ways to improve its properties.