The solid solution of (x)Ba_0.7Ca_0.3TiO₃-(1-x)BaZr_0.2Ti_0.8O₃ is known to exhibit high piezoelectric constants. Discrepancies in the reported phase transitions and structure around room temperature, however, have complicated the understanding of the enhanced properties. Rietveld refinement of high-resolution X-ray diffraction is employed here to establish and refine the crystallographic structure at temperatures from −100 °C to 150 °C for x = 0.5. A combination of rhombohedral R3m and tetragonal P4mm is found to coexist at temperatures of 20 °C and −25 °C, bordered by single phase rhombohedral and tetragonal regions at lower (i.e., −100 °C) and higher (i.e., 70 °C) temperatures, respectively. The diffractograms also show signs of strain and domain wall scattering that are linked to the sample history.

Crystallographic texture engineering through templated grain growth (TGG) has gained prominence as a highly effective strategy for optimizing the electromechanical performance of lead-free piezoelectric ceramics, offering a pathway toward sustainable alternatives to lead-based systems like lead zirconate titanate (PZT). By achieving high degrees of texture, with Lotgering factors (LFs) often exceeding 90%, these systems have demonstrated piezoelectric properties that rival or even surpass their lead-based counterparts. Despite these advancements, the field lacks a comprehensive understanding of how specific template parameters influence the texture quality and functional properties across different material systems. This review provides an in-depth analysis of the influence of the template morphology, composition, and crystallographic orientation on the texturing of key lead-free systems, including BaTiO₃ (BT), (K_0.5Na_0.5)NbO₃ (KNN), and Bi_0.5Na_0.5TiO₃ (BNT). Furthermore, it explores how the template selection affects the induced crystallographic direction, and how this impacts the material’s phase structure and domain configurations, ultimately influencing the piezoelectric and dielectric properties. By consolidating the existing knowledge and identifying current challenges, this work highlights key strategies for optimizing the texture and electromechanical performance in lead-free ceramics, providing essential insights for future research aimed at advancing high-performance, environmentally friendly piezoelectric materials for applications such as sensors, actuators, and energy-harvesting devices.