A new family of relaxor dielectrics with the tetragonal tungsten bronze structure (nominal composition Ba 6 M 3+ Nb 9 O 30 , M 3+ = Ga, Sc or In) were studied using dielectric spectroscopy to probe the dynamic dipole response and correlate this with the crystal structure as determined from powder neutron diffraction. Independent analyses of real and imaginary parts of the complex dielectric function were used to determine characteristic temperature parameters, T VF , and T UDR , respectively. In each composition both these temperatures correlated with the temperature of maximum crystallographic strain, T c/a determined from diffraction data. The overall behaviour is consistent with dipole freezing and the data indicate that the dipole stability increases with increasing M 3+ cation size as a result of increased tetragonality of the unit cell. Crystallographic data suggests that these materials are uniaxial relaxors with the dipole moment predominantly restricted to the B1 cation site in the structure. Possible origins of the relaxor behaviour are discussed.

We discuss the strategy for development of novel functional materials with the tetragonal tungsten bronze structure. From the starting composition Ba 6 GaNb 9 O 30 , 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.

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