Piezoelectricity in Multilayer Black Phosphorus for Piezotronics and Nanogenerators

Recently, piezoelectric characteristics have been a research focus for 2D materials because of their broad potential applications. Black phosphorus (BP) is a monoelemental 2D material predicted to be piezoelectric because of its highly directional properties and non-centrosymmetric lattice structure. However, piezoelectricity is hardly reported in monoelemental materials owing to their lack of ionic polarization, but piezoelectric generation is consistent with the non-centrosymmetric structure of BP. Theoretical calculations of phosphorene have explained the origin of piezoelectric polarization among P atoms. However, the disappearance of piezoelectricity in multilayer 2D material generally arises from the opposite orientations of adjacent atomic layers, whereas this effect is limited in BP lattices due to their spring-shaped space structure. Here, the existence of in-plane piezoelectricity is experimentally reported for multilayer BP along the armchair direction. Current-voltage measurements demonstrate a piezotronic effect in this orientation, and cyclic compression and release of BP flakes show an intrinsic current output as large as 4 pA under a compressive strain of -0.72%. The discovery of piezoelectricity in multilayer BP can lead to further understanding of this mechanism in monoelemental materials.