Strong Piezoelectricity and Improved Rectifier Properties in Mono‐ and Multilayered CuInP₂S₆

Abstract Most atomically thin piezoelectrics suffer from weak piezoelectric response or current rectification along the thickness direction, which largely hinders their applications in a vertical crossbar architecture. Therefore, exploring new types of ultrathin materials with strong longitudinal piezoelectric coefficient and rectification is highly desired. In this study, the monolayer of van der Waals CuInP2S6 (CIPS) is successfully exfoliated and its strong piezoelectricity in the out‐of‐plane direction with an effective coefficient d33eff of ≈5.12 pm V⁻¹, which is one or two orders of magnitude higher than that of most existing monolayer materials with intrinsic d33, is confirmed. A prototype vertical device is further constructed and the current rectification is achieved through the flexoelectricity induced by the scanning tip force. The switching between low and high rectification states can be readily controlled by tuning the mechanical loads. These findings manifest that CIPS possesses promising application in vertical nanoscale piezoelectric devices and provides a novel strategy for achieving a good current rectification in ultrathin piezoelectrics.