Local Structural Heterogeneity and Electromechanical Responses of Ferroelectrics: Learning from Relaxor Ferroelectrics

Owing to growing environmental concerns, the development of lead-free piezoelectrics with comparable performance to the benchmark Pb(Zr,Ti)O3 (PZT) becomes of great urgency. However, a further enhancement of lead-free piezoelectrics based on existing strategies has reached a bottleneck. Here we achieve a slush polar state with multiphase coexistence in lead-free potassium-sodium niobate (KNN) piezoceramics, which shows a novel relaxor behavior, i.e., frequency dispersion at the transition between different ferroelectric phases. It is very different from the conventional relaxor behavior which occurs at the paraelectric-ferroelectric phase transition. We obtain an ultrahigh piezoelectric coefficient (d33) of 650 ± 20 pC/N, the largest value of nontextured KNN-based ceramics, outperforming that of the commercialized PZT-5H. Atomic-resolution polarization mapping by Z-contrast imaging from different orientations reveals the entire material to comprise polar nanoregions with multiphase coexistence, which is again very different from conventional ferroelectric relaxors which have polar domains within a nonpolar matrix. Theoretical simulations validate the significantly decreased energy barrier and polarization anisotropy, which is facilitated by the high-density domain boundaries with easy polarization rotation bridging the multiphase-coexisting nanodomains. This work demonstrates a new strategy for designing lead-free piezoelectrics with further enhanced performance, which should also be applicable to other functional materials requiring a slush (flexible) state with respect to external stimulus.

Ultrahigh Performance in Lead-Free Piezoceramics Utilizing a Relaxor Slush Polar State with Multiphase Coexistence.

Based on the Ti-vacancy defect compensation model, (Ba1−xLnx)Zr0.2Ti0.8−x∕4O3 (Ln=La,Sm,Eu,Dy,Y) ceramics have been fabricated via the conventional solid-state reaction method. The microstructures, dielectric properties, and ferroelectric relaxor behavior of (Ba1−xLnx)Zr0.2Ti0.8−x∕4O3 ceramics have been investigated. The results indicate that rare-earth ions with various ionic radii enter the unit cell to substitute for A-site Ba2+ ions and inhibit the grain growth. The typical ferroelectric relaxor behavior is induced due to the rare-earth ions substitution. The diffuseness of the phase transition and the degree of ferroelectric relaxor behavior are enhanced, the TC is remarkably shifted to lower temperature, and the tunability is suppressed with the increase of x value and substituted ionic radius for (Ba1−xLnx)Zr0.2Ti0.8−x∕4O3 (x=0.005–0.04, Ln=La,Sm,Eu,Dy,Y) ceramics. Tunable ferroelectric materials with moderate dielectric constant and low dielectric loss can be obtained by manipulating the doping am...

Dielectric properties and relaxor behavior of rare-earth (La, Sm, Eu, Dy, Y) substituted barium zirconium titanate ceramics

(Ba0.90Ca0.10)(Zr0.25Ti0.75)O3 (BCZT) relaxor ferroelectric ceramics with grain sizes of 0.85, 2.5, 15, and 30μm were prepared from powders synthesized using a sol-gel process. The effects of grain size and dc field on the dielectric properties and tunabilities of BCZT ceramics were investigated. As the grain size decreased, the maximum dielectric constant decreased and the transition temperature increased. The BCZT ceramics with various grain sizes showed a typical relaxor ferroelectric behavior. The dielectric relaxation rate follows the Vogel–Fulcher relation. The dielectric constant is greatly suppressed and the low loss is obtained under a dc electric field. At room temperature (300K) and 20kV∕cm, the tunabilities and figures of merit are 42% and 62, 51% and 98, 56% and 193, and 51% and 182, respectively, for the BCZT ceramics with grain sizes of 0.85, 2.5, 15, and 30μm.

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X.G. Tang

Papers

Diffuse phase transition and dielectric tunability of Ba(ZryTi1−y)O3 relaxor ferroelectric ceramics