Doping mechanisms and electrical properties of bismuth tantalate fluorites

Abstract

Phase-pure bismuth tantalate fluorites were successfully prepared via conventional solid-state method at 900 °C in 24–48 h. The subsolidus solution was proposed with the general formula of Bi_3+x Ta_1−x O_7−x (0 ≤ x ≤ 0.184), wherein the formation mechanism involved a one-to-one replacement of Ta⁵⁺ cation by Bi³⁺ cation within ~4.6 mol% difference. These samples crystallised in a cubic symmetry, space group Fm-3 m with lattice constants, a = b = c in the range 5.4477(± 0.0037)–5.4580(± 0.0039) Å. A slight increment in the unit cell was discernible with increasing Bi₂O₃ content, and this may attribute to the incorporation of relatively larger Bi³⁺ cation in the host structure. The linear correlation between lattice parameter and composition variable showed that the Vegard’s law was obeyed. Both TGA and DTA analyses showed Bi_3+x Ta_1−x O_7−x samples to be thermally stable as neither phase transition nor weight loss was observed within ~28–1000 °C. The AC impedance study of Bi₃TaO₇ samples was performed over the frequency range 5–13 MHz. At intermediate temperatures, ~350–850 °C, Bi_3+x Ta_1−x O_7−x solid solution was a modest oxide ion conductor with conductivity, ~10⁻⁶–10⁻³ S cm⁻¹; the activation energy was in the range 0.98–1.08 eV.