Feasible Way to Achieve Multifunctional (K, Na)NbO₃-Based Ceramics: Controlling Long-Range Ferroelectric Ordering

It is challenging to achieve highly tunable multifunctional properties in one piezoelectric ceramic system through a simple method due to the complicated relationship between the microscopic structure and macroscopic property. Here, multifunctional potassium sodium niobate [(K, Na)NbO₃ (KNN)]-based lead-free piezoceramics with tunable piezoelectric and electrostrictive properties are achieved by controlling the long-range ferroelectric ordering (LRFO) through antimony (Sb) doping. At a low Sb doping, the slightly distorted NbO₆ octahedron and the softened B–O repulsion well maintain the LRFO and induce plenty of nanoscale domains coexisting with a few polar nanoregions (PNRs). Thereby, the diffused rhombohedral–orthorhombic–tetragonal (R–O–T) multiphase coexistence with distinct dielectric jumping is constructed near room temperature, by which the nearly 2-fold increase in the piezoelectric coefficient (d₃₃ ∼ 539 pC/N) and the temperature-insensitive strain (the unipolar strain varies less than 8% at 27–120 °C) are obtained. At a high Sb doping, the LRFO is significantly destroyed, leading to predominant PNRs. Thus, a typical relaxor is obtained at the ferroelectric–paraelectric phase transition near room temperature, in which a large electrostrictive coefficient (Q₃₃ = 0.035 m⁴/C²), independent of the electric field and temperature, is obtained and comparable to that of lead-based materials. Therefore, our results prove that controlling the LRFO is a feasible way to achieve high-performance multifunctional KNN-based ceramics and is beneficial to the future composition design for KNN-based ceramics.