A Graded Redox Interfacial Modifier for High‐Performance Perovskite Solar Cells

Perovskite solar cells have emerged as a potential competitor to the silicon photovoltaic technology. The most representative perovskite cells employ SnO₂ and spiro-OMeTAD as the charge-transport materials. Despite their high efficiencies, perovskite cells with such a configuration show unsatisfactory lifespan, normally attributed to the instability of perovskites and spiro-OMeTAD. Limited attention was paid to the influence of SnO₂, an inorganic material, on device stability. Here we show that improving SnO₂ with a redox interfacial modifier, cobalt hexammine sulfamate, simultaneously enhances the power-conversion efficiency (PCE) and stability of the perovskite solar cells. Redox reactions between the bivalent cobalt complexes and oxygen lead to the formation of a graded distribution of trivalent and bivalent cobalt complexes across the surface and bulk regions of the SnO₂. The trivalent cobalt complex at the top surface of SnO₂ raises the concentration of (SO₃NH₂)^- which passivates uncoordinated Pb²⁺ and relieves tensile stress, facilitating the formation of perovskite with improved crystallinity. Our approach enables perovskite cells with PCEs of up to 24.91 %. The devices retained 93.8 % of their initial PCEs after 1000 hours of continuous operation under maximum power point tracking. These findings showcase the potential of cobalt complexes as redox interfacial modifiers for high-performance perovskite photovoltaics.