Multidirection Piezoelectricity in Mono- and Multilayered Hexagonal α‑In₂Se₃

Piezoelectric materials have been widely used for sensors, actuators, electronics, and energy conversion. Two-dimensional (2D) ultrathin semiconductors, such as monolayer h-BN and MoS₂ with their atom-level geometry, are currently emerging as new and attractive members of the piezoelectric family. However, their piezoelectric polarization is commonly limited to the in-plane direction of odd-number ultrathin layers, largely restricting their application in integrated nanoelectromechanical systems. Recently, theoretical calculations have predicted the existence of out-of-plane and in-plane piezoelectricity in monolayer α-In₂Se₃. Here, we experimentally report the coexistence of out-of-plane and in-plane piezoelectricity in monolayer to bulk α-In₂Se₃, attributed to their noncentrosymmetry originating from the hexagonal stacking. Specifically, the corresponding <i>d</i>₃₃ piezoelectric coefficient of α-In₂Se₃ increases from 0.34 pm/V (monolayer) to 5.6 pm/V (bulk) without any odd–even effect. In addition, we also demonstrate a type of α-In₂Se₃-based flexible piezoelectric nanogenerator as an energy-harvesting cell and electronic skin. The out-of-plane and in-plane piezoelectricity in α-In₂Se₃ flakes offers an opportunity to enable both directional and nondirectional piezoelectric devices to be applicable for self-powered systems and adaptive and strain-tunable electronics/optoelectronics