Efficient and Stable p–i–n Perovskite Solar Cells Enabled by In Situ Functional Group Conversion

Chemical additives play a critical role in the crystallization kinetics and film morphology of perovskite solar cells (pero-SCs), thus affecting the device performance and stability. Especially, carboxylic acids and their congeners with a −COOH group can effectively serve as ligands to fortify the structural integrity and mitigate the risk of lead efflux. However, direct addition of −COOH into the precursor solution could retard the crystallization kinetics of the perovskite during film formation due to the strong coordination. Here, we present a novel approach of in situ functional group conversion using Bis(2,5-dioxopyrrolidin-1-yl) 4,7,10,13-tetraoxahexadecanedioate (Bis-PEG4-NHS ester) as an additive in the antisolvent, which underwent a functional group transformation from −COOR to −COOH during the annealing process through a hydrolysis reaction of Bis-PEG4-NHS ester. The corresponding hydrolysates exhibit enhanced interactions with PbI2 and FAI, contributing to the structural integrity and the defect passivation. Our findings offer valuable insights into the chemical interactions within the crystal growth process, achieving the p–i–n pero-SC device with an efficiency of 25.79% (certified as 25.47%) and notable long-term stability.