Crystal and magnetic structures of high pressure perovskite-type oxyfluorides,PbFeO2F and 0.5PbFeO2F-O-SPbTiO3 [Pb(Fe0.5Ti0.5)O2.5F0.5]

The perovskites PbFeO2F and 0.5PbFeO2F-0.5PbTiO 3 were synthesized at high temperatures (1000 °C) and high pressures (4-6 GPa). The crystal and magnetic structures were determined using powder neutron diffraction. Quenched PbFeO2F has the cubic perovskite-type, Pm3m, structure in which the Pb ion shifts from ideal A-site along the <110> directions, which is in good accordance with a previous report. The magnetic structure is anti ferromagnetic G-type with propagation vector * = (1/2 1/2 1/2) and an Fe³⁺ ordered moment of 3.83 μB at 283K. The Néel temperature is 655(5) K. Annealed PbFeO2F has a tetragonal perovskite-type structure at room temperature and transforms reversibly from tetragonal to cubic at approximately 470 K. A superlattice with dimensions a × a × 5c is observed both in electron and x-ray diffraction. The solid solution 0.5PbFeO2F-0. 5PbTiO3 belongs to the non-centrosymmetric space group P4mm. The magnetic structure is G-type anti ferromagnetic and shows a weak ferromagnetic moment at 4 K. Consequently, 0.5PbFeO2F-0.5PbTiO3 is simultaneously ferroelectric and a weak ferromagnet at low temperature. The Nèel temperature is 450 K but the temperature dependence of the ordered Fe moment is anomalous. © 2007 Materials Research Society.