Two-dimensional (2D) layered materials with a non-centrosymmetric structure exhibit great potential for nano-scale electromechanical systems and electronic devices. Piezoelectric and ferroelectric 2D materials draw growing interest for applications in energy harvesting, electronics, and optoelectronics. This article first reviews the preparation of these functional 2D layered materials, including exfoliation methods and vapor phase deposition growth, followed by a general introduction to various piezo/ferro-electric characterization methods. Typical 2D piezoelectric and ferroelectric materials and their electronic properties, together with their potential applications, are also introduced. Finally, future research directions for 2D piezoelectric and ferroelectric materials are discussed.

Piezoelectric materials have been widely used for sensors, actuators, electronics, and energy conversion. Two-dimensional (2D) ultrathin semiconductors, such as monolayer h-BN and MoS 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-InSe. Here, we experimentally report the coexistence of out-of-plane and in-plane piezoelectricity in monolayer to bulk α-InSe, attributed to their noncentrosymmetry originating from the hexagonal stacking. Specifically, the corresponding d piezoelectric coefficient of α-InSe 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-InSe-based flexible piezoelectric nanogenerator as an energy-harvesting cell and electronic skin. The out-of-plane and in-plane piezoelectricity in α-InSe 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.

2D ferroelectric material has emerged as an attractive building block for highdensity data storage nanodevices. Although monolayer van der Waals ferroelectrics have been theoretically predicted, a key experimental breakthrough for such calculations is still not realized. Here, hexagonally stacking α-In 2 Se 3 nanoflake, a rarely studied van der Waals polymorph, is reported to exhibit out-of-plane (OOP) and in-plane (IP) ferroelectricity at room temperature. Ferroelectric multidomain states in a hexagonal α-In 2 Se 3 nanoflake with uniform thickness can survive to 6 nm. Most strikingly, the electric-field-induced polarization switching and hysteresis loop are, respectively, observed down to the bilayer and monolayer (≈1.2 nm) thicknesses, which designates it as the thinnest layered ferroelectric and verifies the corresponding theoretical calculation. In addition, two types of ferroelectric nanodevices employing the OOP and IP polarizations in 2H α-In 2 Se 3 are developed, which are applicable for nonvolatile memories and heterostructure-based nanoelectronics/ optoelectronics.