A-site size effect in a family of unfilled ferroelectric tetragonal tungsten bronzes: Ba4R0.67Nb10O30 (R = La, Nd, Sm, Gd, Dy and Y)Electronic supplementary information (ESI) available. See DOI: 10.1039/c4dt00126e

The effect of A-cation size on the structural and electrical properties in a family of ferroelectric tetragonal tungsten bronzes (TTBs) Ba 4 R 0.67 1.33 Nb 10 O 30 (R = La, Nd, Sm, Gd, Dy and Y; = vacancy) was investigated. In each case, the crystal structure, as determined from lab-based ambient powder X-ray diffraction (PXRD), is metrically tetragonal and can be refined in the P 4 bm space group. XRD data show an increased splitting of hk 0 00 l reflections with decreasing R cation size indicating an increasing tetragonal distortion (measured by tetragonality c / a ). Dielectric data and ferroelectric measurements indicate that the ferroelectric Curie temperature, T C , increases with decreasing R size and so a direct correlation between T C and tetragonality/ionic radius of R is demonstrated. Rietveld refinements show that the large A2-site is fully occupied by Ba 2+ and, in addition to the R cation size, the presence of vacancies at the A1-site (perovskite-like site) is also shown to strongly affect the stability of ferroelectricity in this structure type. The structure of a family of ferroelectric unfilled tetragonal tungsten bronze oxides can be approximated to be metrically tetragonal allowing a simple correlation of tetragonality with Curie temperature.