Mixed Sn-Pb halide perovskites are promising absorber materials for solar cells due to the possibility of tuning the bandgap energy down to 1.2-1.3 eV. However, tin-containing perovskites are susceptible to oxidation affecting the optoelectronic properties. In this work, we investigated qualitatively and quantitatively metastable oxygen-induced doping in isolated ASn_xPb_1-xI₃ (where A is methylammonium or a mixture of formamidinium and cesium) perovskite thin films by means of microwave conductivity, structural and optical characterization techniques. We observe that longer oxygen exposure times lead to progressively higher dark conductivities, which slowly decay back to their original levels over days. Here oxygen acts as an electron acceptor, leading to tin oxidation from Sn²⁺ to Sn⁴⁺ and creation of free holes. The metastable oxygen-induced doping is enhanced by exposing the perovskite simultaneously to oxygen and light. Next, we show that doping not only leads to the reduction in the photoconductivity signal but also induces long-term effects even after loss of doping, which is thought to derive from consecutive oxidation reactions leading to the formation of defect states. On prolonged exposure to oxygen and light, optical and structural changes can be observed and related to the formation of SnO_x and loss of iodide near the surface. Our work highlights that even a short-term exposure to oxygen immediately impairs the charge carrier dynamics of the perovskite, while structural perovskite degradation is only noticeable upon long-term exposure and accumulation of oxidation products. Hence, for efficient solar cells, exposure of mixed Sn-Pb perovskites to oxygen during production and operation should be rigorously blocked.

Metal-halide perovskites deposited by wet-chemical deposition have demonstrated great potential for various electronic applications, including solar cells. A remaining question is how light-induced excess charges become distributed over such polycrystalline material. Here, we examine the local conductive properties of MAPbI₃ and CsFAPbI₃ by using scanning microwave microscopy (sMIM) in the dark and light. sMIM is an atomic force microscopy (AFM)-based technique measuring variations of the in-phase and out-of-phase signals due to changes in the tip-sample interaction, yielding MIM-Re and MIM-Im images, respectively. Combining this information leads to a picture for CsFAPbI₃ in which excess charges are distributed evenly over the grains, but due to local defect-rich areas, possibly related to different crystal facets, local perturbations in carrier concentration exist. For solar cells, this distribution in carrier concentration under illumination leads to variation in the local Fermi level splitting, which should be suppressed to reduce the voltage deficit.