Abstract
Despite the rapidly increasing efficiencies of perovskite solar cells, the optoelectronic properties of this material class are not completely understood. Especially when measured photoluminescence (PL) spectra consist of multiple peaks, their origin is still debated. In this work, we investigate in detail double peak PL spectra of halide perovskite thin films and single crystals with different material compositions. By different optical spectroscopic approaches and quantitative models, we demonstrate that the additional PL peak results from an extensive self-absorption effect, whose impact is intensified by strong internal reflections. This self-absorption accounts for the unusual temperature dependence of the additional PL peak and it implies that absorption until far into the perovskite's Urbach tail is important. The internal reflections entail that even for thin films self-absorption can have a significant contribution to the PL spectrum. Our results allow for a clear assignment of the PL peaks by differentiating between optical effects and electronic transitions, which is a necessary requirement for understanding the optoelectronic properties of halide perovskites.