The performance of perovskite solar cells with inverted polarity (p-i-n) is still limited by recombination at their electron extraction interface, which also lowers the power conversion efficiency (PCE) of p-i-n perovskite-silicon tandem solar cells. A MgFx interlayer with thickness of ~1 nanometer at the perovskite/C60 interface favorably adjusts the surface energy of the perovskite layer through thermal evaporation, which facilitates efficient electron extraction and displaces C60 from the perovskite surface to mitigate nonradiative recombination. These effects enable a champion open-circuit voltage of 1.92 volts, an improved fill factor of 80.7%, and an independently certified stabilized PCE of 29.3% for a monolithic perovskite-silicon tandem solar cell ~1 square centimeter in area. The tandem retained ~95% of its initial performance after damp-heat testing (85°C at 85% relative humidity) for >1000 hours.
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