• • The AOCzPA SAM with hydrogen-bond networks achieves a PCE of 21.56% in 1.77 eV wide-bandgap PSCs, with V_OC of 1.35 V and FF of 85.76%, demonstrating minimal voltage losses and suppressed non-radiative recombination, critical for high-efficiency tandem top cells.
• • The hydrogen-bond network narrows the energy offset to 0.42 eV, aligning HOMO levels for barrier-free hole extraction, which reduces interfacial charge transfer losses and enhances fill factor, directly impacting module-level power output.
• • The design suppresses detrimental self-aggregation via twisted carbazole dimer conformation, preventing π–π stacking and creating an amorphous, homogeneous molecular distribution, which improves interfacial adhesion and long-term operational stability under thermal stress.
• • The amide groups form cooperative hydrogen bonds with TCO surfaces (C=O···HO–In/Sn and N–H···O–In/Sn), strengthening anchoring and mechanical robustness, essential for scalable fabrication and durability in tandem devices.