Incorporation of Aliovalent Dopants into the Bismuth-Layered Perovskite-Like Structure of BaBi4Ti4O15

The solid solubility of the aliovalent dopants Fe³⁺ and Nb⁵⁺ in the BaBi₄Ti₄O₁₅ compound, a member of the family of Aurivillius bismuth-based layer-structure perovskites, has been studied using quantitative wavelength-dispersive spectroscopic microanalysis (SEM/EPMA) in combination with X-ray powder diffractometry (XRPD). The samples with nominal (starting) compositions corresponding to the chemical formulas BaBi₄Ti_{4–4 X} Fe_{4 X} O₁₅ and BaBi₄Ti_{4–4 X} Nb_{4 X} O₁₅ were prepared by hot forging a mixture of BaTiO₃ and Bi₄Ti₃O₁₂ with additions of Fe₂O₃ or Nb₂O₅ followed by a long annealing at 1100°C. The study showed that an excess charge introduced into the structure by the substitution of Ti⁴⁺ ions with aliovalent dopants was preferentially compensated by a change in the ratio of Ba²⁺ to Bi³⁺ ions in the host structure according to the general formulas of the solid solutions Ba_{1–4 X} Bi_{4+4 X} Ti_{4–4 X} Fe^'_{4 X} O₁₅ and Ba_{1+4 X} Bi_{4–4 X} Ti_{4–4 X} Nb^·_{4 X} O₁₅.