Effect of electronic doping and traps on carrier dynamics in tin halide perovskites

Tin halide perovskites have recently emerged as promising materials for low band gap solar cells. Much effort has been invested on controlling the limiting factors responsible for poor device efficiencies, namely self-p-doping and tin oxidation. Both phenomena are related to the presence of defects; however, full understanding of their implications in the optoelectronic properties of the material is still missing. We provide a comprehensive picture of the competing radiative and non-radiative recombination processes in tin-based perovskite thin films to establish the interplay between doping and trapping by combining photoluminescence measurements with trapped-carrier dynamic simulations and first-principles calculations. We show that pristine Sn perovskites, i.e. sample processed with commercially available SnI₂ used as received, exhibit extremely high radiative efficiency due to electronic doping which boosts the radiative band-to-band recombination. Contrarily, thin films where Sn⁴⁺ species are intentionally introduced show drastically reduced radiative lifetime and efficiency due to a dominance of Auger recombination at all excitation densities when the material is highly doped. The introduction of SnF₂ reduces the doping and passivates Sn⁴⁺ trap states but conversely introduces additional non-radiative decay channels in the bulk that fundamentally limit the radiative efficiency. Overall, we provide a qualitative model that takes into account different types of traps present in tin-perovskite thin films and show how doping and defects can affect the optoelectronic properties.