Cascade Reaction in Organic Hole Transport Layer Enables Efficient Perovskite Solar Cells

The doped organic hole transport layer (HTL) is crucial for achieving high-efficiency perovskite solar cells (PSCs). However, the traditional doping strategy undergoes a time-consuming and environment-dependent oxidation process, which hinders the technology upgrades and commercialization of PSCs. Here, we reported a new strategy by introducing a cascade reaction in traditional doped Spiro-OMeTAD, which can simultaneously achieve rapid oxidation and overcome the erosion of perovskite by 4-tert-butylpyridine (tBP) in organic HTL. The ideal dopant iodobenzene diacetate was utilized as the initiator that can react with Spiro to generate Spiro⋅⁺ radicals quickly and efficiently without the participation of ambient air, with the byproduct of iodobenzene (DB). Then, the DB can coordinate with tBP through a halogen bond to form a tBP-DB complex, minimizing the sustained erosion from tBP to perovskite. Based on the above cascade reaction, the resulting Spiro-based PSCs have a champion PCE of 25.76 % (certificated of 25.38 %). This new oxidation process of HTL is less environment-dependent and produces PSCs with higher reproducibility. Moreover, the PTAA-based PSCs obtain a PCE of 23.76 %, demonstrating the excellent applicability of this doping strategy on organic HTL.