Pressure-induced charge orders and their postulated coupling to magnetism in hexagonal multiferroic LuFe2O4

Hexagonal LuFe2O4 is a promising charge order (CO) driven multiferroic material with high charge and spin-ordering temperatures. The coexisting charge and spin orders on Fe3+/Fe2+ sites result in magnetoelectric behaviors, but the coupling mechanism between the charge and spin orders remains elusive. Here, by tuning external pressure, we reveal three charge-ordered phases with suggested correlation to magnetic orders in LuFe2O4: (i) a centrosymmetric incommensurate three-dimensional CO with ferrimagnetism, (ii) a non-centrosymmetric incommensurate quasi-two-dimensional CO with ferrimagnetism, and (iii) a centrosymmetric commensurate CO with antiferromagnetism. Experimental in situ single-crystal X-ray diffraction and X-ray magnetic circular dichroism measurements combined with density functional theory calculations suggest that the charge density redistribution caused by pressure-induced compression in the frustrated double-layer [Fe2O4] cluster is responsible for the correlated spin-charge phase transitions. The pressure-enhanced effective Coulomb interactions among Fe-Fe bonds drive the frustrated (1/3, 1/3) CO to a less frustrated (1/4, 1/4) CO, which induces the ferrimagnetic to antiferromagnetic transition. Our results not only elucidate the coupling mechanism among charge, spin, and lattice degrees of freedom in LuFe2O4, but also provide a new way to tune the spin-charge orders in a highly controlled manner.

Automated summary

Hexagonal LuFe2O4 exhibits various charge-ordered phases with different magnetic orders under external pressure. The redistribution of charge density induced by pressure in the frustrated double-layer [Fe2O4] cluster is responsible for the correlated spin-charge phase transitions. Enhanced Coulomb interactions among Fe-Fe bonds drive the frustrated charge order into a less frustrated charge order, leading to the transition from ferrimagnetism to antiferromagnetism. This study not only elucidates the coupling mechanism among charge, spin, and lattice degrees of freedom in LuFe2O4, but also provides a new approach for tuning spin-charge orders.