Multiple Hydrogen-Bonding-Mediated Co-Assembled Monolayers for Efficient and Stable Wide-Bandgap Perovskite Solar Cells

Inverted wide-bandgap perovskite solar cells (PSCs) are essential for tandem photovoltaics, yet their performance and stability are often limited by poor buried interfacial quality and severe nonradiative recombination. Herein, we report a multiple hydrogen-bonding-mediated coassembled monolayer (Co-SAM) strategy by incorporating 5-hydroxyisophthalic acid (HISPA) into Me-4PACz to regulate the buried NiO x /perovskite interface. Driven by electrostatic complementarity, HISPA can establish multiple hydrogen-bonding and π–π interactions with Me-4PACz, effectively suppressing its solution self-aggregation and enabling the formation of a uniform and dense Co-SAM on NiO x . Meanwhile, HISPA modulates the surface chemical state of NiO x by passivating surface defects, which optimizes hole extraction and mitigates interface-induced perovskite decomposition. At the perovskite interface, HISPA can interact with Pb 2+, I –, and FA + through coordination and hydrogen bonding, suppressing detrimental intermediate phases, mitigating lattice mismatch, and inhibiting ion migration and halide segregation. Consequently, the inverted 1.68 eV PSCs based on Co-SAM achieve a champion efficiency of 23.02% (0.042 cm 2 ) and retain 22.17% at a scalable area of 1.05 cm 2, accompanied by great thermal, environmental, and photostability. Furthermore, an efficiency of 30.61% is realized in 4-terminal perovskite/silicon tandem solar cells, demonstrating the practical potential of this strategy.