Green Solvent Processable, Asymmetric Dopant‐Free Hole Transport Layer Material for Efficient and Stable n‐i‐p Perovskite Solar Cells and Modules

Abstract The use of dopant‐free hole transport layers (HTLs) is critical in stabilizing n‐i‐p perovskite solar cells (pero‐SCs). However, these HTL materials are often processed with toxic solvents, which is not ideal for industrial production. Upon substituting them with green solvents, a trade‐off emerges between maintaining the high crystallinity of the HTL materials and ensuring high solubility in the new solvents. In this paper, we designed a novel, linear, organic small molecule, BDT‐C8‐3O, by introducing an asymmetric polar oligo(ethylene glycol) side chain. This method not only overcomes the solubility limitations in green solvents but also enables stacking the conjugated main chains in two patterns, which further enhances crystallinity and hole mobility. As a result, the n ‐ i ‐ p pero‐SCs based on chlorobenzene‐ or green (natural compound) solvent 3‐methylcyclohexanone‐processed BDT‐C8‐3O HTL that without any dopant delivered world‐recorded power conversion efficiencies of 24.11 % (certified of 23.82 %) and 23.53 %, respectively. The devices also demonstrated remarkable operational and high‐temperature stabilities, maintaining over 84 % and 79.5 % of their initial efficiency for 2000 h, respectively. Encouragingly, dopant‐free BDT‐C8‐3O HTL exhibits significant advantages in large‐area fabrication, achieving state‐of‐the‐art PCEs exceeding 20 % for 5×5 cm 2 modules (active area: 15.64 cm 2 ), even when processed using green solvents.