Single crystals of the filled Ti2N-type η-phase Ti3Zn3O x (x = 1.07 and 1.23) prepared using a Bi flux

Abstract

Single crystals of the filled Ti2Ni-type Ti3Zn3O x η-phase (cubic, space group Fd\overline{3}m) having {111} facets were obtained by heating Ti, Zn and ZnO with a Bi flux. The lattice parameter of a single crystal prepared at 800°C was 11.4990 (2) Å, which is close to that of Ti3Zn3O∼0.5 (a = 11.502 Å), as reported by Rogl & Nowotny [Monatsh. Chem. (1977), 108, 1167–1180]. The occupancies of the O1 (16c) and O2 (8a) sites were 1 and 0.071 (12), respectively, and the composition of the crystal was determined to be Ti3Zn3O1.04. A single crystal from the sample prepared at 650°C had the same structure type, with a lattice parameter of 11.5286 (2) Å. However, O atoms were situated at a new 32e site in addition to the original 16c and 8a sites, and the Zn-atom positions were split in accordance with the new O-atom site. The chemical formula Ti3Zn3O1.27 determined by X-ray diffraction occupancy refinement agreed with the chemical composition obtained for the cross section of the single crystal determined with an electron probe microanalyzer.