Multiferroic properties in Fe-site engineered PbFe1/2Nb1/2O3 with distinct antisymmetric spin interaction

Multiferroic Fe-site engineered lead iron niobate [Pb(Fe1/2Nb1/2)O3, PFN] was prepared by partially substituting Fe with Ni, Co, and Cr, which comprise distinct Bohr magnetons, to investigate the effect of the variation in spin configurations on magnetic and multiferroic properties. All the studied compositions exhibited a single-phase perovskite structure, wherein the lattice constant decreased with increasing substitutions. The inherent ferroelectric order was preserved when Ni or Co ions were introduced, while the introduction of Cr made the samples too lossy, which prevented the verification of the possible ferroelectricity. Substitution of Fe with different transition metals in PFN, which is originally paramagnetic at room temperature, resulted in oriented spin configurations that led to distinct magnetic orders: soft ferromagnetic, hard ferromagnetic, and antiferromagnetic orders for Ni, Co, and Cr, respectively. This distinction mainly stems from the interspin distance and the spin moment, both of which are important factors during the spin exchange interaction. The interspin distance of pristine and Cr-substituted PFN is too long and short, respectively, to induce ferromagnetic properties. Moreover, at room temperature, magnetic-field-dependent magnetoelectric coupling was observed only for the Ni- and Co-substituted PFN owing to their asymmetric spin configuration. This research could lead to a general method for modulating the magnetic properties of multiferroic perovskite oxides.