Manganese doping for enhanced magnetic brightening and circular polarization control of dark excitons in paramagnetic layered hybrid metal-halide perovskites

Materials combining semiconductor functionalities with spin control are desired for the advancement of quantum technologies. Here, we study the magneto-optical properties of novel paramagnetic Ruddlesden-Popper hybrid perovskites Mn:(PEA) 2 PbI 4 (PEA = phenethylammonium) and report magnetically brightened excitonic luminescence with strong circular polarization from the interaction with isolated Mn 2+ ions. Using a combination of superconducting quantum interference device (SQUID) magnetometry, magneto-absorption and transient optical spectroscopy, we find that a dark exciton population is brightened by state mixing with the bright excitons in the presence of a magnetic field. Unexpectedly, the circular polarization of the dark exciton luminescence follows the Brillouin-shaped magnetization with a saturation polarization of 13% at 4 K and 6 T. From high-field transient magneto-luminescence we attribute our observations to spin-dependent exciton dynamics at early times after excitation, with first indications for a Mn-mediated spin-flip process. Our findings demonstrate manganese doping as a powerful approach to control excitonic spin physics in Ruddlesden-Popper perovskites, which will stimulate research on this highly tuneable material platform with promise for tailored interactions between magnetic moments and excitonic states. Combining magnetic and semiconducting properties in a single material offers great technological potential, all the more so if these are coupled with good optical properties. Here, Neumann et al. present a Manganese doped Ruddlesden-Popper perovskite with this trifecta of attributes.