A Pressure-Induced Inverse Order-Disorder Transition in Double Perovskites

Angew Chem Int Ed Engl. 2020 May 18;59(21):8240-8246. doi: 10.1002/anie.202001922. Epub 2020 Apr 6.

Abstract

Given the consensus that pressure improves cation ordering in most of known materials, a discovery of pressure-induced disordering could require recognition of an order-disorder transition in solid-state physics/chemistry and geophysics. Double perovskites Y2 CoIrO6 and Y2 CoRuO6 polymorphs synthesized at 0, 6, and 15 GPa show B-site ordering, partial ordering, and disordering, respectively, accompanied by lattice compression and crystal structure alteration from monoclinic to orthorhombic symmetry. Correspondingly, the long-range ferrimagnetic ordering in the B-site ordered samples are gradually overwhelmed by B-site disorder. Theoretical calculations suggest that unusual unit-cell compressions under external pressures unexpectedly stabilize the disordered phases of Y2 CoIrO6 and Y2 CoRuO6 .

Keywords: double perovskites; lattice compression; magnetic frustration; pressure-induced B-site disorder; statistical model.