Defect engineering electrical properties of lead‐free potassium sodium niobate‐based ceramics

Defect engineering plays an important role in property modification for piezoelectric materials. In this work, we pay much attention to the effect of Nb nonstoichiometry on structure and properties of typical 0.95(K0.45Na0.55)Nb1+xO3–0.05Bi0.5Na0.5HfO3 ceramics. Large piezoelectric constant (d33 ~ 425 pC/N and d33∗ ~482 pm/V) together with high Curie temperature (TC ~ 315°C) have been achieved in the ceramics with excess Nb content (x = 0.01). However, the ceramics with deficient Nb element have seriously suppressed cryogenic εr‐T curves and deteriorated electrical properties. Multi‐scale characterizations including phase structure, microstructure, defect structure and domain structure have been adopted to explain the corresponding phenomenon. Defect complex VNb″″′-VO·· caused by deficient Nb induces clamped domain wall motion, leading to blocked polarization vector and poor electrical properties. On the contrary, the enhanced properties for the ceramics with excess Nb are attributed to easier domain switching due to the suppressed vacancies. We believe that defect engineering, for example nonstoichiometry, cannot only modulate electrical properties but also help us to understand some fundamental and critical problems about KNN‐based ceramics.