摘要： All-perovskite tandem cells have been considered a potential candidate for bringing the power conversion efficiency (PCE) beyond the Shockley– Queisser limit of single-junction device while retaining the advantages of earth-abundant materials and solution processability. However, a challenging issue with regard to realizing such solution-processed devices is the fulfillment of complex and coupled requirements of the interconnecting layer (ICL), including solvent resistance to protect underlying perovskite film, high electrical properties for carrier transport and recombination, and high optical transmission. In this work, a new thermionic emission–based ICL with enhanced solvent resistance features is demonstrated. Fundamentally, the thermionic emission plays a critical role in the electron transport process in the ICL, which is confirmed through both experimental and theoretical studies. Besides achieving high optical transmission and electrical properties, the new ICL chemically protects the underlying perovskite film by introducing a fluoride silane– incorporated polyethylenimine ethoxylated hybrid system that also passivates the surface defects to reduce electrical loss. The monolithic all-perovskite tandem cells demonstrate highest PCE of 17.9% (from current density–voltage scan) and the highest steady-state efficiency is 16.1% for a typical device. Consequently, this work contributes to not only understanding the fundamental mechanism of ICLs but also promotes robust and low-cost photovoltaics.