Temperature-Independent, Large Dielectric Constant Induced by Vacancy and Partial Anion Order in the Oxyfluoride Pyrochlore Pb2Ti2O6−δF2δ

In mixed-anion systems, partial anion order can be the key to realizing enhanced dielectric properties. A novel A2B2X6X′0.5-type oxyfluoride pyrochlore, Pb2Ti2O5.4F1.2, was prepared through the conventional solid-state reaction. Characterization of the oxyfluoride pyrochlore by synchrotron X-ray diffraction and electron diffraction revealed the existence of partial O2–/F– order at the X site, in which F– is involved in fac-type Ti­(O/F)6 coordination, associated with the O2–/vacancy order at the X′ site. Although Pb2Ti2O5.4F1.2 adopts a centrosymmetric structure, the refined occupancy factors suggested the existence of local polarization. Partial O2–/F– anion order stabilized the large displacement of Ti4+, leading to a high dielectric constant (as high as 800) with a low-temperature coefficient. These results suggest that mixing heteroanions in pyrochlores provides a basis for exploring novel dielectric materials.