Two-terminal monolithic perovskite/silicon tandem solar cells demonstrate huge advantages in power conversion efficiency compared with their respective single-junction counterparts1,2. However, suppressing interfacial recombination at the wide-bandgap perovskite/electron transport layer interface, without compromising its superior charge transport performance, remains a substantial challenge for perovskite/silicon tandem cells3,4. By exploiting the nanoscale discretely distributed lithium fluoride ultrathin layer followed by an additional deposition of diammonium diiodide molecule, we have devised a bilayer-intertwined passivation strategy that combines efficient electron extraction with further suppression of non-radiative recombination. We constructed perovskite/silicon tandem devices on a double-textured Czochralski-based silicon heterojunction cell, which featured a mildly textured front surface and a heavily textured rear surface, leading to simultaneously enhanced photocurrent and uncompromised rear passivation. The resulting perovskite/silicon tandem achieved an independently certified stabilized power conversion efficiency of 33.89%, accompanied by an impressive fill factor of 83.0% and an open-circuit voltage of nearly 1.97 V. To the best of our knowledge, this represents the first reported certified efficiency of a two-junction tandem solar cell exceeding the single-junction Shockley–Queisser limit of 33.7%.
