Unveiling Photoluminescence Signatures of Magneto-Optical Coupling in Layered Hybrid Manganese Chloride Perovskites

Abstract

Understanding the interplay between magnetic ordering and light emission is crucial for developing magneto-optical technologies. However, this phenomenon is poorly understood since observations of this coupling vary significantly across materials. In this context, hybrid organic-inorganic metal halide perovskites (HOIPs) that incorporate Mn2+ ions are a chemically and structurally tunable platform for exploring this phenomenon, since they exhibit magnetic ordering and photoluminescence (PL) emission. Here, we study two antiferromagnetic Mn-based HOIPs with different organic cations that result in distinct lattice stiffness, Mn2+-Mn2+ distance and octahedral distortion. Temperature-dependent PL excitation spectroscopy reveals changes in crystal field splitting energy and Racah parameters well above the N\'eel temperature (TN), indicating the emergence of Mn2+-Mn2+ magnetic interactions prior to reach long-range magnetic ordering. These variations align with the observed changes in temperature-PL evolution. The compound with a more rigid lattice shows stronger changes closer to TN, suggesting combined effects of magnetic polarons and spin-canting. In contrast, magnetic polaron-induced magnetic modifications prevail in the HOIP with a softer lattice. These results reveal the complexity of the magneto-optical coupling in Mn-based HOIPs and provide new insights into this field extensible to other 2D materials that exhibit this phenomenon with potential for advanced magneto-optical applications.