A-site size effect in a family of unfilled ferroelectric tetragonal tungsten bronzes: Ba4R0.67Nb10O30 (R = La, Nd, Sm, Gd, Dy and Y)

Abstract

The effect of A-cation size on the structural and electrical properties in a family of ferroelectric tetragonal tungsten bronzes (TTBs) Ba₄R_0.67□_1.33Nb₁₀O₃₀ (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 P4bm space group. XRD data show an increased splitting of hk0 00l 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 Ba²⁺ 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.