Metal halide perovskites with remarkable optoelectronic properties have become a competitive candidate for supporting the efficiency progression of photovoltaics. As the latest reported power conversion efficiency of research cells is comparable to that of commercialized silicon cells1–3, the industrialization of perovskite solar cells is on the horizon4,5. However, most high-efficiency inverted perovskite solar cells based on self-assembled molecules (SAMs) face challenges owing to the aggregation and hydrophobicity of the SAMs. Here we report a ‘SAM-in-matrix’ strategy to distribute partial SAMs into a stable matrix of tris(pentafluorophenyl)borane, which breaks the original molecular-stacking-induced aggregation. Two-dimensional lattice Monte Carlo simulations and experimental results reveal that this strategy forms efficient charge transport channels. SAM-in-matrix hole-transport-layer-based devices show universally higher efficiencies for various SAMs, with compact surface coverage, good conductivity and substantially fewer buried nanovoids. Moreover, this strategy shows prominent application potential for scalable production. A SAM-in-matrix hole transport layer on fluorine-doped tin oxide/NiOx substrate facilitates the formation of large-area perovskite films with good crystalline quality and enhanced conductivity of NiOx. A 1 m × 2 m large-area perovskite solar module is thus achieved with a certified efficiency of 20.05%.
