Design for Highly Piezoelectric and Visible/Near‐Infrared Photoresponsive Perovskite Oxides

Abstract

Defect-engineered perovskite oxides that exhibit ferroelectric and photovoltaic properties are promising multifunctional materials. Though introducing gap states by transition metal doping on the perovskite B-site can obtain low bandgap (i.e., 1.1-3.8 eV), the electrically leaky perovskite oxides generally lose piezoelectricity mainly due to oxygen vacancies. Therefore, the development of highly piezoelectric ferroelectric semiconductor remains challenging. Here, inspired by point-defect-mediated large piezoelectricity in ferroelectrics especially at the morphotropic phase boundary (MPB) region, an efficient strategy is proposed by judiciously introducing the gap states at the MPB where defect-induced local polar heterogeneities are thermodynamically coupled with the host polarization to simultaneously achieve high piezoelectricity and low bandgap. A concrete example, Ni²⁺ -mediated (1-x)Na_0.5 Bi_0.5 TiO₃ -xBa(Ti_0.5 Ni_0.5 )O_3-δ (x = 0.02-0.08) composition is presented, which can show excellent piezoelectricity and unprecedented visible/near-infrared light absorption with a lowest ever bandgap ≈0.9 eV at room temperature. In particular, the MPB composition x = 0.05 shows the best ferroelectricity/piezoelectricity (d₃₃ = 151 pC N^-1 , Pr = 31.2 μC cm^-2 ) and a largely enhanced photocurrent density approximately two orders of magnitude higher compared with classic ferroelectric (Pb,La)(Zr,Ti)O₃ . This research provides a new paradigm for designing highly piezoelectric and visible/near-infrared photoresponsive perovskite oxides for solar energy conversion, near-infrared detection, and other multifunctional applications.