Ge0.57Ti0.43O2: a new high-pressure material with rutile-type crystal structure

Abstract

Single crystals of a GeO2–TiO2 solid solution with the corresponding composition Ge0.57Ti0.43O2 (germanium titanium tetraoxide) were obtained by devitrification of germania-titania glass at high pressure and temperature. The new compound crystallizes in the rutile structure type (space group P42/mnm), where Ge and Ti share the same position M (site symmetry m.mm), with occupancy values of 0.57 (3) and 0.43 (3), respectively, and one O-atom position (m.2m). The M site is in a sixfold O-atom coordination and, as in the original TiO2 rutile structure, an elongation of the O—M—O bonds along the c-axis direction of the coordination polyhedron and deviation of the angles from 90° lead to a decrease in the coordination symmetry from octahedral to tetragonal. The Ge and Ti atoms are fully disordered in the structure, which indicates that the rutile structure is surprisingly pliant given the differing sizes of the two cations.