Spatial Heterogeneity of Biexcitons in Two-Dimensional Ruddlesden–Popper Lead Iodide Perovskites

Quantum confinement in two-dimensional (2D) Ruddlesden–Popper (RP) perovskites leads to the formation of stable quasi-particles, including excitons and biexcitons, the latter of which may enable lasing in these materials. Due to their hybrid organic–inorganic structures and the solution phase synthesis, microcrystals of 2D RP perovskites can be quite heterogeneous, with variations in excitonic and biexcitonic properties between crystals from the same synthesis and even within individual crystals. Here, we employ one- and two-quantum two-dimensional white-light microscopy to systematically study the spatial variations of excitons and biexcitons in microcrystals of a series of 2D RP perovskites BA2MA n–1Pb n I3n+1 (n = 2–4, BA= butylammonium, MA = methylammonium). We find that the average biexciton binding energy of around 60 meV is essentially independent of the perovskite layer thickness (n). We also resolve spatial variations of the exciton and biexciton energies on micron length scales within individual crystals. By comparing the one-quantum and two-quantum spectra at each pixel, we conclude that biexcitons are more sensitive to their environments than excitons. These results shed new light on the ways disorder can modify the energetic landscape of excitons and biexcitons in RP perovskites and how biexcitons can be used as a sensitive probe of the microscopic environment of a semiconductor.