One Site, Two Cations, Three Environments: s2 and s0 Electronic Configurations Generate Pb-Free Relaxor Behavior in a Perovskite Oxide

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Surta, T Wesley ORCID: 0000-0002-2882-6483, Whittle, Thomas A, Wright, Matthew A, Niu, Hongjun, Gamon, Jacinthe, Gibson, Quinn D, Daniels, Luke M ORCID: 0000-0002-7077-6125, Thomas, William J, Zanella, Marco ORCID: 0000-0002-6164-6169, Shepley, Philippa M et al (show 6 more authors) , Li, Yang, Goetzee-Barral, Anton, Bell, Andrew J, Alaria, Jonathan ORCID: 0000-0001-5868-0318, Claridge, John B ORCID: 0000-0003-4849-6714 and Rosseinsky, Matthew J ORCID: 0000-0002-1910-2483 (2021) One Site, Two Cations, Three Environments: s2 and s0 Electronic Configurations Generate Pb-Free Relaxor Behavior in a Perovskite Oxide Journal of the American Chemical Society, 143 (3). pp. 1386-1398. ISSN 0002-7863, 1520-5126

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Abstract

The piezoelectric devices widespread in society use noncentrosymmetric Pb-based oxides because of their outstanding functional properties. The highest figures of merit reported are for perovskites based on the parent Pb(Mg_1/3Nb_2/3)O₃ (PMN), which is a relaxor: a centrosymmetric material with local symmetry breaking that enables functional properties, which resemble those of a noncentrosymmetric material. We present the Pb-free relaxor (K_1/2Bi_1/2)(Mg_1/3Nb_2/3)O₃ (KBMN), where the thermal and (di)electric behavior emerges from the discrete structural roles of the s⁰ K⁺ and s² Bi³⁺ cations occupying the same A site in the perovskite structure, as revealed by diffraction methods. This opens a distinctive route to Pb-free piezoelectrics based on relaxor parents, which we demonstrate in a solid solution of KBMN with the Pb-free ferroelectric (K_1/2Bi_1/2)TiO₃, where the structure and function evolve together, revealing a morphotropic phase boundary, as seen in PMN-derived systems. The detailed multiple-length-scale understanding of the functional behavior of KBMN suggests that precise chemical manipulation of the more diverse local displacements in the Pb-free relaxor will enhance performance.

Item Type:	Article
Uncontrolled Keywords:	3403 Macromolecular and Materials Chemistry, 34 Chemical Sciences, 3406 Physical Chemistry, 40 Engineering, 4016 Materials Engineering
Depositing User:	Symplectic Admin
Date Deposited:	26 Jan 2021 08:18
Last Modified:	23 May 2026 05:35
DOI:	10.1021/jacs.0c10572
Open Access URL:	https://doi.org/10.1021/jacs.0c10572
Related Websites:	Author Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3114818
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