Publication date: 22nd July 2026
Perovskite solar cells are making their way to the market despite intrinsic instability issues remain. Also, replacing lead by less toxic elements remains a major challenge, with tin likely being the only suitable alternative. While lead-based perovskites are affected by instability related to iodide oxidation, tine based materials are plagued by stability of Sn(IV) phases, which are related to the lower oxidation potential of tin compared to lead. A related phenomenon is the stability of tin vacancies, which introduce significant p-doping in tin-halide perovskites, while their lead-based counterpart are essentially intrinsic semiconductors. Defect activity clearly controls doping and could also contribute to the instability towards Sn(IV) phases. Controlling doping and defect activity thus represents a pathway towards obtaining stable perovskites with optimal optoelectronic properties. The different defect activity of tin- and lead-based materials is at the origin of their respective thermal and phot-induced degradation phenomena, including halide demixing and loss of I2 in lead-halide perovskites.
Here we present results of advanced modelling studies on the defect mediated degradation pathways of prototypical lead- and tin-based materials. We show that iodine chemistry dominates lead-based perovskites while Sn-vacancies are central in promoting both material p-doping and formation of Sn(IV) phases. Interestingly, while p-doping dominates in the bulk, Sn oxidation is only favoured at surfaces or grain boundaries. Thus achieving uniform thin films coupled with proper surface passivation strategies represent a pathway towards achieving more stable THP-based devices. We further unveil the key factors determining the stability of mixed-halide THPs against photoinduced halide segregation phenomena. Molecular and ionic strategies to mitigate p-doping in THPs are also presented.
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