Ternary doping of Na⁺, Bi³⁺ and La³⁺ to improve piezoelectric constant and electrical resistivity simultaneously in calcium bismuth niobate ceramics

High Curie-temperature layer-structured calcium bismuth niobate (CaBi₂Nb₂O₉) piezoelectric ceramics are promising for important application in high-temperature vibration sensors. However, such application is currently limited due to not only poor high-temperature piezoelectric constant (d₃₃), which is attributable to spontaneous polarization along a-b plane and high coercive fields, but also inferior high-temperature electrical resistivity, which results from volatilization of Bi₂O₃ during the sintering process that increases defect concentration of oxygen vacancies. Herein, we report a Na⁺, Bi³⁺ and La³⁺ ternary-doping-strategy to obtain Ca_0.8(Na_0.5La_0.3Bi_0.2)_0.2Bi₂Nb₂O₉ ceramics, which exhibited higher piezoelectric constant and larger electrical resistivity as accompanied by a better thermal stability at high-temperatures. The piezoelectric constant was enhanced from 8.8 pC/N in pristine CaBi₂Nb₂O₉ to 13.4 pC/N in Ca_0.8(Na_0.5La_0.3Bi_0.2)_0.2Bi₂Nb₂O₉ ceramics, which is ascribed to the presence of pseudo-tetragonal structural distortion after La³⁺ doping. In addition, the electrical resistivity at 600 °C was increased by more than one-order of magnitude from 3.7 × 10⁴ Ω cm in pristine CaBi₂Nb₂O₉ to 1.4 × 10⁶ Ω cm in Ca_0.8(Na_0.5La_0.3Bi_0.2)_0.2Bi₂Nb₂O₉ ceramics. Such significant improvement in electrical resistivity results from the reduction in oxygen vacancies due to ternary doping of Na⁺, Bi³⁺ and La³⁺ and stronger binding interaction between La³⁺ dopants and O²⁻ in (Bi₂O₂)²⁺ layers in Ca_0.8(Na_0.5La_0.3Bi_0.2)_0.2Bi₂Nb₂O₉ ceramics. This work demonstrates an important way of employing chemical doping to improve piezoelectric constant and electrical resistivity simultaneously at high-temperatures to tune structural distortion in bismuth-layered structural CaBi₂Nb₂O₉ ceramics.