Giant intrinsic piezoelectricity in 2D hybrid organic-inorganic perovskites [C 6 H 11 NH 3 ] 2 MX 4 (M = Ge, Sn, Pb; X = Cl, Br, I).

2D-piezoelectric materials are attractive for micro-electromechanical systems (MEMS), medical implants and wearable devices because of their numerous exceptional properties. 2D-hybrid organic-inorganic perovskites (HOIPs) have attracted extensive research interest due to their merits of structural diversity, good mechanical flexibility, and ease of fabrication. The electronic energy band, charge density and the elastic properties of 2D-HOIP-[C6 H11 NH3 ]2 MX4 (M = Ge, Sn, Pb; X = Cl, Br, I) were investigated using first-principles calculations. The excellent piezoelectricity of 2D-HOIP-[C6 H11 NH3 ]2 MX4 has been analyzed in detail. More importantly, 2D-[C6 H11 NH3 ]2 MX4 have giant intrinsic positive and negative out-of-plane piezoelectric coefficients under the effect of van der Waals interaction. The d 31 and d 32 of [C6 H11 NH3 ]2 SnBr4 are 82.720 pm V-1 and -36.139 pm V-1 , respectively, which are among the largest piezoelectric coefficients among all kinds of atomic-thick 2D materials reported. The high flexibility together with the giant out-of-plane piezoelectricity would endow these 2D-HOIP-[C6 H11 NH3 ]2 MX4 with potential applications in ultrathin piezoelectric cantilever and diaphragm devices.