One Site, Two Cations, Three Environments: s(2) and s(0) Electronic Configurations Generate Pb-Free Relaxor Behavior in a Perovskite Oxide

[Image: see text] 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(1/3)Nb(2/3))O(3) (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(1/2)Bi(1/2))(Mg(1/3)Nb(2/3))O(3) (KBMN), where the thermal and (di)electric behavior emerges from the discrete structural roles of the s(0) K(+) and s(2) Bi(3+) 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(1/2)Bi(1/2))TiO(3), 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.