We discuss the strategy for development of novel functional materials with the tetragonal tungsten bronze structure. From the starting composition Ba6GaNb9O30, the effect of A- and B-site substitutions on the dielectric properties is used to develop an understanding of the origin and stability of the dipolar response in these compounds. Both tetragonal strain induced by large B-site cations and local strain variations created by isovalent A-site substitutions enhance dipole stability but result in a dilute, weakly correlated dipolar response and canonical relaxor behaviour. Decreasing cation size at the perovskite A2-site increases the dipolar displacements in the surrounding octahedra, but insufficiently to result in dipole ordering. Mechanisms introducing small A-site lanthanide cations and incorporation of A-site vacancies to induce ferroelectricity and magnetism are presented.
Keywords: dielectric properties; ferroelectric; multiferroic; relaxor; structure–property relationships.