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Metal halide perovskites have shown exceptionally slow hot-carrier cooling, which has been attributed to various physical mechanisms without reaching a consensus. Here, experiment and theory are combined to unveil the carrier cooling process in formamidinium (FA) and caesium (Cs) tin triiodide thin films. Through impulsive vibrational spectroscopy and molecular dynamics, much shorter phonon dephasing times of the hybrid perovskite, which accounts for the larger blueshift in the photoluminescence seen at high excitation density for FASnI 3 compared to CsSnI 3 is reported. Density functional theory investigations reveal that the largest contribution to the blueshift is accounted by a giant, dynamic band-filling effect in Sn-based perovskites, which in turn can explain the cooling disparity with the Pb-based counterparts. Several years after the first experimental observations, here a deeper understanding of the cooling mechanism of these materials is provided. Design principles for hot-carrier materials, which may be useful for future implementations of hot-carrier solar cells are further provided., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

The migration of mobile ions through the metal halide perovskite layer is still one of the main reasons for the poor stability of perovskite solar cells, LEDs, and photodetectors. To characterize mobile ions in the perovskite layer, time- and frequency-based electrical measurements are promising techniques. However, the presence of transport layers complicates their interpretation, limiting the information about mobile ions that can be extracted, and it is not clear how different features in frequency- and time-domain measurements relate to mobile ions. Here, we characterize a transport-layer-free device with capacitance frequency, capacitance transient, and current transient measurements in the dark, under illumination, and at different temperatures. We extract characteristic ionic signatures from the measurements, which we reproduce with drift-diffusion simulations for each technique. This allows us to explain the origins of the different ionic signatures, advancing our understanding of how electronic characterization techniques can be used to study the properties of mobile ions., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Slow hot-carrier cooling may potentially allow overcoming the maximum achievable power conversion efficiency of single-junction solar cells. For formamidinium tin triiodide, an exceptional slow cooling time of a few nanoseconds was reported. However, a systematic study of the cation influence, as is present for lead compounds, is lacking. Here, we report the first comparative study on formamidinium, methylammonium, and cesium tin triiodide thin films. By investigating their photoluminescence, we observe a considerable shift of the emission peak to high energy with the increase of the excited-state population, which is more prominent in the case of the two hybrid organic-inorganic perovskites (∼45 meV vs ∼15 meV at 9 × 10 17  cm -3 carrier density). The hot-carrier photoluminescence of the three tin compositions decays with a 0.6-2.8 ns time constant with slower cooling observed for the two hybrids, further indicating their importance., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)