Structure and Properties of Ir-Containing Oxides with Large Spin–Orbit Coupling: Ba2In2–xIrxO5+δ

In this work, the solid solution series Ba2In2–xIrxO5+δ (x = 0–1.4, 2) was synthesized, and its structural, magnetic, and charge-transport properties were measured. With increasing Ir content, three transitions in the room-temperature structure were observed: orthorhombic to tetragonal to cubic to a monoclinic distortion of a hexagonal BaTiO3 structure. Neutron diffraction shows Ba2In1.6­Ir0.4O5.4 to be cubic and Ba2InIrO6 to be monoclinic, the latter contrary to previously published X-ray diffraction refinements. Magnetization measurements show Curie–Weiss behavior for x = 0.2–0.6, which arises from nearly 50:50 ratio of Ir­(V) and Ir­(VI). To our knowledge, this is the first time Ir­(VI) has been stabilized with standard solid-state methods under ambient conditions. The electrical resistivity measurements show all the compounds studied are semiconducting and that resistivity decreases with increasing Ir content, suggesting the proximity to a metal–insulator transition. A sign reversal in the high-temperature Seebeck coefficient is observed indicating both electron and hole charge transport.