Abstract

Single crystals of suboxide solid solutions Ti12-δGaxBi3-xO10 (x = 1.42-1.74; δ = 0.77-0.62) were prepared at 900 °C with a Bi flux. Crystal structure analysis by X-ray diffraction (XRD) revealed that the solid solutions are isostructural with Ti12-δSn3O10 (cubic, space group Fm3̅m). The cell parameter a decreases from 13.5616(3) to 13.5402(5) Å with increasing Ga content, x, while the total valence electron number of Ti12-δGaxBi3-xO10 is maintained at 117.1 by decreasing Ti defects, δ. Stella octangula is formed by sharing of the edges of four supertetrahedra composed of O-centered Ti tetrahedra and trigonal bipyramids (oxide part). Another superpolyhedron is formed by sharing of the pyramidal planes of Ga/Bi-centered, Ti-monocapped square antiprisms (intermetallic part). These two parts are incorporated in the structure. A polycrystalline bulk of a solid solution with x = 2.01 and δ = 0.67 [a = 13.53772(13) Å] was synthesized by reaction sintering at 950 °C from a mixture of Ti, TiO2, Bi2O3, and Ga2O3. The resistivities measured for the bulk were (2.2-2.4) × 10-5 Ω m in the temperature range from 10 to 300 K.

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