Structural Evolution and Enhanced Piezoelectric Activity in Novel Lead-Free BaTiO₃-Ca(Sn_1/2Zr_1/2)O₃ Solid Solutions

In this study, a series of solid solutions of (1−x)BaTiO₃-xCa(Sn_1/2Zr_1/2)O₃ (abbreviated as (1−x)BT-xCSZ, x = 0.00–0.15) ceramics have been prepared by the conventional solid-state reaction method to search for high performance lead-free piezoelectric materials. The structural evolution, microstructure, and piezoelectric properties are investigated. X-ray diffraction (XRD) results indicate that the phase symmetry strongly depends on the CSZ content. A tetragonal phase is well-maintained in the compositions of 0 ≤ x ≤ 0.03, and coexistence of tetragonal and cubic phases is obtained in the range of x = 0.06–0.09, beyond which a pure cubic phase becomes stable. More importantly, a significantly enhanced piezoelectric coefficient of d₃₃ = 388 ± 9 pC/N is attained in the composition of x = 0.06 in the MPB region, where a tetragonal ferroelectric phase and an ergodic relaxor phase with average cubic symmetry coexist. Based on the analysis of crystal structure and dielectric properties, a temperature-composition phase diagram consisting of four phase regions is established. This study indicates that the lead-free BT-CSZ binary system has great potential for use in electromechanical transducer applications.