Foldable Hole‐Transporting Materials for Merging Electronic States between Defective and Perfect Perovskite Sites

Defective and perfect sites naturally exist within electronic semiconductors, and considerable efforts to reduce defects to improve the performance of electronic devices, especially in hybrid organic-inorganic perovskites (ABX₃ ), are undertaken. Herein, foldable hole-transporting materials (HTMs) are developed, and they extend the wavefunctions of A-site cations of perovskite, which, as hybridized electronic states, link the trap states (defective site) and valence band edge (perfect site) between the naturally defective and perfect sites of the perovskite surface, finally converting the discrete trap states of the perovskite as the continuous valence band to reduce trap recombination. Tailoring the foldability of the HTMs tunes the wavefunctions between defective and perfect surface sites, allowing the power conversion efficiency of a small cell to reach 23.22% and that of a mini-module (6.5 × 7 cm, active area = 30.24 cm² ) to reach as high as 21.71% with a fill factor of 81%, the highest value reported for non-spiro-OMeTAD-based perovskite solar modules.