Rational Supramolecular Design of Multifunctional Fluorinated Porphyrins for Efficient and Stable Indoor Carbon-Based...

Precise molecular design is essential for controlling interfacial defects in carbon-based perovskite solar cells (C-PSCs), where recombination losses from the perovskite/hole-transporting layer (HTL) interface and grain boundaries (GBs) limit device performance. Herein, zinc pentafluorophenyl porphyrin (ZnPF) derivatives are developed as supramolecular passivators through p-selective nucleophilic aromatic substitution and incorporated into perovskite films via a green anisole-based antisolvent strategy. Systematic variation of the aromatic substituents provided insight into the relationship between molecular structure, supramolecular packing, and defect passivation. In particular, the p-phenoxy substituent in ZnPF-2 balanced steric effects and promoted ordered molecular packing, leading to more effective interfacial passivation. This multifunctional passivation improved perovskite crystallinity and charge-carrier transport while suppressing non-radiative recombination and interfacial leakage currents. Consequently, ZnPF-2-modified devices achieved a remarkable power conversion efficiency (PCE) of 34.29% under 1000 lx illumination, while also showing consistent gains under AM 1.5G conditions and in a compositionally distinct perovskite system, supporting the transferability of the strategy. Moreover, the hydrophobic ZnPF modification improved long-term durability, with devices preserving over 90% of their initial efficiency after 1600 h under ambient storage. This work establishes supramolecular fluorinated porphyrins as effective passivators, demonstrating how rational molecular design can contribute to sustainable indoor photovoltaic applications.