Evolution from Lead‐Based to Lead‐Free Piezoelectrics: Engineering of Lattices, Domains, Boundaries, and Defects Leading to Giant Response

Piezoelectric materials are known to mankind for more than a century, with numerous advancements made in both scientific understandings and practical applications. In the last two decades, in particular, the research on piezoelectrics has largely been driven by the constantly changing technological demand, and the drive toward a sustainable society. Hence, environmental‐friendly “lead‐free piezoelectrics” have emerged in the anticipation of replacing lead‐based counterparts with at least comparable performance. However, there are still obstacles to be overcome for realizing this objective, while the efforts in this direction already seem to culminate. Therefore, novel structural strategies need to be designed to address these issues and for further breakthrough in this field. Here, various strategies to enhance piezoelectric properties in lead‐free systems with fundamental and historical context, and from atomic to macroscopic scale, are explored. The main challenges currently faced in the transition from lead‐based to lead‐free piezoelectrics are identified and key milestones for future research in this field are suggested. These include: i) decoding the fundamental mechanisms; ii) large temperature‐stable piezoresponse; and iii) fabrication‐friendly and tailorable composition. Strategic insights and general guidelines for the synergistic design of new piezoelectric materials for obtaining a large piezoelectric response are also provided. The synergetic combination of conventional and emergent strategies to enhance piezoelectricity, with a deeper understanding of structure–property relationship using advanced state‐of‐the‐art techniques, can lead to a breakthrough in giant piezoelectricity with the desired characteristics.