Supramolecular Cavity Confinement Inducing Ordered C ₆₀ Assembly and Suppressed Interfacial Non‐Radiative Recombination for Efficient and Scalable Perovskite Solar Cells

ABSTRACT Charge‐carrier non‐radiative recombination at the perovskite/C 60 interface seriously limits the device efficiency and operational stability. Herein, we report a cavity‐confined and directionally assembled strategy by introducing 4‐tert‐butylcalix[6]arene (4tBu‐C[6]A) at the perovskite/C 60 interface, which facilitates uniform and compact C 60 deposition via size matching and host–guest interactions. The calixarene‐cavity enables strong π–π stacking with C 60 , which is further enhanced by the electron‐donating tert‐butyl groups, thus firmly immobilizing and improving the dispersion of C 60 . Moreover, the lower‐rim hydroxyl groups in 4tBu‐C[6]A interact with the under‐coordinated Pb 2+ and couple with the 1,3‐propyldiammonium diiodide interfacial molecules, strengthening the field‐effect interfacial passivation, accelerating electron transport, and enhancing the quasi‐Fermi level splitting. This supramolecular template strategy enables a minimal non‐radiative voltage loss of 68 mV. Consequently, the inverted perovskite devices achieve power conversion efficiencies of 26.68%, 25.13%, and 23.07% on active areas of 0.09, 1, and 12.96 cm 2 , respectively. Additionally, the target devices retain over 80% of their initial efficiencies after 1100 h of maximum power point tracking. This work provides a scalable interfacial engineering strategy for perovskite photovoltaics and highlights the potential of supramolecular chemistry in functional optoelectronic interfaces.