Dynamic self-assembly of small molecules enables the spontaneous fabrication of hole conductors at perovskite/electrode interfaces for over 22% stable inverted perovskite solar cells

]carbazol-7-yl)butyl)phosphonic acid (BCB-C4PA), for the DSA process, to optimize both self-assembly ability and interfacial energy alignment. Benefitting from this unconventional DSA approach and BCB-C4PA, a champion PCE of 22.2% is achieved along with remarkable long-term environmental stability for over 2750 h, which is among the highest reported efficiencies for SAM-based PSCs. This investigation provides a creative, unique and effective molecular approach for preparing reliable charge transport layers, opening up new avenues for the further development of efficient interfacial contacts for PSCs.