Interface materials offer a means to achieve electrical control of ferrimagnetism at room temperature as was recently demonstrated in (LuFeO₃)_m/(LuFe₂O₄)₁ superlattices. A challenge to understanding the inner workings of these complex magnetoelectric multiferroics is the multitude of distinct Fe centres and their associated environments. This is because macroscopic techniques characterize average responses rather than the role of individual iron centres. Here, we combine optical absorption, magnetic circular dichroism and first-principles calculations to uncover the origin of high-temperature magnetism in these superlattices and the charge-ordering pattern in the m = 3 member. In a significant conceptual advance, interface spectra establish how Lu-layer distortion selectively enhances the Fe²⁺ →  Fe³⁺ charge-transfer contribution in the spin-up channel, strengthens the exchange interactions and increases the Curie temperature. Comparison of predicted and measured spectra also identifies a non-polar charge ordering arrangement in the LuFe₂O₄ layer. This site-specific spectroscopic approach opens the door to understanding engineered materials with multiple metal centres and strong entanglement.

Results of switching behavior of the improper ferroelectric LuFeO₃ are presented. Using a model set of films prepared under controlled chemical and growth-rate conditions, it is shown that defects can reduce the quasi-static switching voltage by up to 40% in qualitative agreement with first-principles calculations. Switching studies show that the coercive field has a stronger frequency dispersion for the improper ferroelectrics compared to a proper ferroelectric such as PbTiO₃ . It is concluded that the primary structural order parameter controls the switching dynamics of such improper ferroelectrics.