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. The piezotronic effect in multilayer black phosphorus is observed successfully in experiment. The analysis of the non‐centrosymmetric lattice, the anisotropy of the Raman spectrum, the piezotronic effect, and piezoelectric signals are proposed to prove the piezoelectricity. This research opens the door for studying the mechanism of piezoelectricity in monoelemental materials and expands the scope of the application of black phosphorus such as strain‐tunable electronics/optoelectronics.