Synthesis, crystal structure and properties of a quaternary oxide with a new structure type, BiGaTi₄O₁₁

A new quaternary oxide, BiGaTi₄O₁₁ (bismuth gallium tetratitanium undecaoxide), was prepared by heating a mixture of the binary oxides at 1373 K in air. BiGaTi₄O₁₁ melts at 1487 K and prismatic single crystals were obtained from a sample melted at 1523 K and solidified by furnace cooling. The structure of BiGaTi₄O₁₁ was analyzed using single-crystal X-ray diffraction to be of a new type that crystallized in the space group Cmcm. A Bi³⁺ site is coordinated by nine O^2- anions, and three oxygen-coordinated octahedral sites are statistically occupied by Ga³⁺ and Ti⁴⁺ cations. A relative dielectric constant of 46 with a temperature coefficient of 57 ppm K^-1 in the temperature range 297-448 K was measured for a polycrystalline ceramic sample at 150 Hz-1 MHz with a dielectric loss tan δ of less than 0.01. Electrical resistivities measured at 1073 K by alternating-current impedance spectroscopic and direct-current methods were 1.16 × 10^-4 and 1.14 × 10^-4 S cm^-1, respectively, which indicates that electrons and/or holes were conduction carriers at high temperature. The optical band gap estimated by the results of diffuse reflectance analysis was 2.9-3.0 eV, while the band gap obtained from the activation energy for electrical conduction was 3.5 eV.