Bifunctional 4,5-Diiodoimidazole Interfacial Engineering Enables Simultaneous Defect Passivation and Crystallization Control for High-Efficiency Inverted Perovskite Solar Cells.

Despite the rapid efficiency advancement of perovskite solar cells (PSCs), non-radiative recombination at the buried interface between self-assembled monolayers (SAMs) and perovskite remains a critical bottleneck, primarily due to interfacial defects and energy level mismatch. In this study, we demonstrate a bifunctional interlayer engineering strategy by introducing 4,5-diiodoimidazole (4,5-Di-I) at the Me-4PACz/perovskite interface. This approach uniquely addresses two fundamental limitations of SAM-based interfaces: the insufficient defect passivation capability of conventional Me-4PACz due to steric hindrance effects and the poor perovskite wettability on hydrophobic SAM surfaces that exacerbates interfacial voids. The imidazole derivatives not only form strong Pb-N coordination bonds with undercoordinated Pb²⁺ but also modulate the surface energy of Me-4PACz, enabling the growth of pinhole-free perovskite films with preferential crystal orientation. The champion device with 4,5-Di-I modification achieves a power conversion efficiency (PCE) of 24.10%, with a V_OC enhancement from 1.12 V to 1.14 V, while maintaining 91% of initial PCE after 1300 h in N₂ atmosphere (25 °C), demonstrating superior stability under ISOS-L-2 protocols. This work establishes a universal strategy for interfacial multifunctionality design, proving that simultaneous defect suppression and crystallization control can break the long-standing trade-off between efficiency and stability in solution-processed photovoltaics.