Multifunctional Graphdiyne Enables Efficient Perovskite Solar Cells via Anti-Solvent Additive Engineering

• The use of novel nanographdiyne (o-TB-GDY) via anti-solvent additive engineering significantly enhances the nucleation and growth of perovskite crystals, leading to improved film quality, reduced film defects and suppressed non-radiative recombination. • o-TB-GDY primarily remains on the surface of the perovskite films after crystallization, where it strongly interacts with the under-coordinated Pb defects for effective passivation. • The optimized perovskite solar cells achieve a champion power conversion efficiency of 25.62% (certified as 25.01%) with good stability. • The PSCs exhibit largely enhanced stability, maintaining 92.6% of their initial PCEs after 500 h continuous 1-sun illumination at ~23 °C in a nitrogen-filled glove box.