New Degree of Freedom in Determining Superior Piezoelectricity at the Lead-Free Morphotropic Phase Boundary: The Invisible Ferroelectric Crossover

The morphotropic phase boundary (MPB) in lead-free ferroelectrics, starting from a quadruple point (QP), often displays large piezoelectric responses due to the flattened free-energy profiles. In this work, we found that the QP composition rendering most flattened energy profiles could also exhibit abnormally low piezoelectric constants in Hf-doped BaTiO3. Such an anomaly in the strength of piezoelectricity can be ascribed to the progressive influence of additional strain heterogeneity induced by the substitution of Hf4+ for Ti4+ in BaTiO3, which was overlooked previously. An intermediate level of strain heterogeneity can form an invisible ferroelectric crossover consisting of both micro- and nanodomains, resulting in a large elastic softening and high piezoelectricity. With a further increase in the level of strain heterogeneity, the extinction of regular ferroelectric domain structures and pinned polar dynamics resulted in the feeble piezoelectric outputs near the QP composition. Impressively, a giant d33 of ∼610 pC/N has been accordingly obtained through employing a ferroelectric crossover at off-QP composition in Zr-doped BaTiO3, further underpinning the critical role of uncovered ferroelectric crossover on piezoelectricity along MPB. This work offers another degree of freedom in the design of high-performance eco-friendly piezoelectric ceramics.