Cation ordering, ferrimagnetism and ferroelectric relaxor behavior in Pb(Fe

Ceramic samples of the multiferroic perovskite Pb(Fe1−xScx)2∕3W1∕3O3 with 0 ≤ x ≤ 0.4 have been synthesized using a conventional solid-state reaction method, and investigated experimentally and theoretically using first-principle calculations. Rietveld analyses of joint synchrotron X-ray and neutron diffraction patterns show the formation of a pure crystalline phase with cubic ( Fm3̅m Fm3̅m ) structure with partial ordering in the B-sites. The replacement of Fe by Sc leads to the increase of the cation order between the B′ and B′′ sites. As the non-magnetic Sc3+ ions replace the magnetic Fe3+ cations, the antiferromagnetic state of PbFe2∕3W1∕3O3 is turned into a ferrimagnetic state reflecting the different magnitude of the magnetic moments on the B′ and B′′ sites. The materials remain ferroelectric relaxors with increasing Sc content. Results from experiments on annealed and quenched samples show that the cooling rate after high temperature annealing controls the degree of cationic order in Pb(Fe1−xScx)2∕3W1∕3O3 and possibly also in the undoped PbFe2∕3W1∕3O3