• • PCEs exceeding 27% in PSCs rival crystalline silicon, but industrial viability demands interfacial stability and large-area manufacturability.
• • SAMs offer tunable energy levels and reduced defects but suffer from aggregation and hydrophobicity, leading to nonuniform nucleation and pinholes in large-area coatings.
• • Co-SAMs have been explored but remain effective only for small or mini-modules, leaving scalability unresolved.
• • The 'SAM-in-matrix' strategy using BCF disrupts π–π stacking, yielding an amorphous, uniform, and highly wettable HTL, addressing key scale-up bottlenecks.