Ti doping-induced magnetic and morphological transformations in Sr- and Ca-substituted BiFeO3

Abstract

The investigation focuses on the crystal structure, microstructure, local ferroelectric and magnetic properties of the Bi0.9Sr0.1Fe1−xTixO3−δ (x = 0.05, 0.1, 0.15; δ = (0.1 − x)/2) multiferroics prepared by a solid-state reaction method. All the samples have been found to be isostructural with the pure BiFeO3 (the material crystallizes in a polar rhombohedral structure belonging to the space group R3c). It has been shown that the pattern of changes in the lattice parameters of the Bi0.9Sr0.1Fe1−xTixO3−δ samples can be interpreted as consistent with the doping-driven elimination of anion vacancies at x ⩽ 0.1 and the formation of cation vacancies at x > 0.1. The readjustment of the defect structure associated with the mechanism of charge compensation in the aliovalent-substituted BiFeO3 is accompanied by correlated changes in the morphology, ferroelectric/ferroelastic domain structure and magnetic properties of the materials. In particular, it has been found that the deviation from the ideal (δ = 0) cation–anion stoichiometry in the Bi0.9Sr0.1Fe1−xTixO3−δ system leads to a significant decrease in the average size of crystal grain and ferroelectric domains and gives rise to an antiferromagnetic-weak ferromagnetic transformation. Results of this study have been compared with those obtained for equally substituted samples of the Bi0.9Ca0.1Fe1−xTixO3−δ series (Khomchenko and Paixão 2015 J. Phys.: Condens. Matter 27 436002) to demonstrate how the variation in the chemical pressure introduced by the partial replacement of Bi3+ with bigger (Sr2+) and smaller (Ca2+) ions can affect the multiferroic behavior of Ti-doped bismuth ferrites.