Spin-driven ferroelectric polarization from strong 4d-4f cross-coupling in 6H-perovskite Ba3HoRu2O9

The occurrence of spin-driven polarization is rarely observed in 4d or 5d transition-metal oxides, compared to their 3d-transition-metal oxide counterparts, despite theoretical predictions of the good possibility of multiferroicity in higher d-orbital systems. Here we have studied a prototype 4d-4f compound, Ba3HoRu2O9, through time-of-flight neutron diffraction, ac susceptibility, and complex dielectric spectroscopy. We demonstrate that the non-colinear structure involving two different magnetic ions, Ru(4d) and Ho(4f), breaks the spatial inversion symmetry via inverse Dzyaloshinskii Moriya (D-M) interaction through strong 4d-4f magnetic correlation, which results in non-zero polarization. The stronger spin-orbit coupling of 4d-orbital might play a major role in creating D-M interaction of non-linear spins. We have systematically investigated the magnetoelectric domain dynamics in this system, which exhibits intriguing behavior with shorter coherence lengths. Further, we have investigated the effect of external pressure on the magnetic transition. The result reveals an enhancement of ordering temperature by the application of external pressure (1.6K per GPa). We speculate that external pressure might favor stabilizing the magnetoelectric phase. Our study shows a route to designing magnetoelectric multiferroic compounds containing larger d-orbital through strong 4d-4f cross-coupling.