Evolution of Ferroelectricity in Sr_0.6Ba_0.4Nb₂O₆–BaTiO₃ Solid Solution with a Strong Electrocaloric Effect

In conventional knowledge, ferroelectric solid solutions were formed between members belonging to the same crystal structure family. Since both tungsten bronze and perovskite structures are constructed by connecting the corner-sharing oxygen octahedra, it offers a possibility for formatting an unusual solid solution between these two families. Herein, (1 - <i>x</i>)Sr_0.6Ba_0.4Nb₂O₆-<i>x</i>BaTiO₃, (1 - <i>x</i>)SBN-<i>x</i>BT, solid solutions were synthesized and the solution mechanism was resolved from a structure viewpoint. With increasing BT content, the solid solution persists of tetragonal tungsten bronze structure, but the lattice parameter <i>a</i> (= <i>b</i>) decreases whereas <i>c</i> increases, resulting in the significant reduction of grains anisotropy. The ferroelectric-relaxor phase transition temperature shows a monotonic increase as <i>x</i> increases. However, the ferroelectricity evolution is not monotonous as a function of BT content because of the competitive effects of Ba and Ti on the property. As a result, the <i>x</i> = 0.10 ceramic shows the strongest ferroelectricity and a remarkable electrocaloric effect of 1.4 K near room temperature. This work challenges the traditional view of solid solution formation and provides an alternative way to modulate the structure and properties of ferroelectrics.