Bimolecular Generation of Excitonic Luminescence from Dark Photoexcitations in Ruddlesden–Popper Hybrid Metal-Halide Perovskites

The nature of photoexcitations in Ruddlesden-Popper (RP) hybrid metal halide perovskites is still under debate. While the high exciton binding energy in the hundreds of millielectronvolts indicates excitons as the primary photoexcitations, recent reports found evidence for dark, Coulombically screened populations, which form via strong coupling of excitons and the atomic lattice. Here, we use time-resolved mid-infrared spectroscopy to gain insights into the nature and recombination of such dark excited states in (BA)2(MA)n-1PbnI3n+1 (n = 1,2,3) via their intraband electronic absorption. In stark contrast to results in the bulk perovskites, all samples exhibit a broad, unstructured mid-IR photoinduced absorbance with no infrared activated modes, independent of excitonic confinement. Further, the recombination dynamics are dominated by a bimolecular process. In combination with steady-state photoluminescence experiments, we conclude that screened, dark photoexcitations act as a population reservoir in the RP hybrid perovskites, from which nongeminate formation of bright excitons precedes generation of photoluminescence.