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 (ABX 3 ), 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 cm 2 ) 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.

A set of novel branched molecules bearing a different number of 3,6-bis(4,4′-dimethoxydiphenylamino)carbazole-based (Cz-OMeDPA) periphery arms linked together by aliphatic chains have been developed, and their performance has been tested in perovskite solar cells (PSCs). Electrical and photovoltaic properties have been evaluated with respect to the number of Cz-OMeDPA moieties and the nature of the linking aliphatic chain. The isolated compounds possess sufficient thermal stability and are amorphous having high glass-transition temperatures (>120 °C) minimizing the risk of direct layer crystallization. The highest hole-drift mobility of μ 0 = 3.1 × 10 –5 cm 2 V –1 s –1 is comparable to that of the reference standard spiro-OMeTAD (4.1 × 10 –5 cm 2 V –1 s –1 ) under identical conditions. Finally, PSCs employing two new HTMs ( 2Cz-OMeDPA and 3Cz-OMeDPA-OH ) bearing two and three substituted carbazole chromophores, linked by an aliphatic chain, show a performance of around 20%, which is on par with devices using spiro-OMeTAD and demonstrates slightly enhanced device stability.