Iodonium Initiators: Paving the Air‐free Oxidation of Spiro‐OMeTAD for Efficient and Stable Perovskite Solar Cells

Abstract To date, perovskite solar cells (pero‐SCs) with doped 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxyphenylamine)‐9,9′‐spirobifluorene (Spiro‐OMeTAD) hole transporting layers (HTLs) have shown the highest recorded power conversion efficiencies (PCEs). However, their commercialization is still impeded by poor device stability owing to the hygroscopic lithium bis(trifluoromethanesulfonyl)imide and volatile 4‐tert‐butylpyridine dopants as well as time‐consuming oxidation in air. In this study, we explored a series of single‐component iodonium initiators with strong oxidability and different electron delocalization properties to precisely manipulate the oxidation states of Spiro‐OMeTAD without air assistance, and the oxidation mechanism was clearly understood. Iodine (III) in the diphenyliodonium cation (IP + ) can accept a single electron from Spiro‐OMeTAD and forms Spiro‐OMeTAD⋅ + owing to its strong oxidability. Moreover, because of the coordination of the strongly delocalized TFSI − with Spiro‐OMeTAD⋅ + in a stable radical complex, the resulting hole mobility was 30 times higher than that of pristine Spiro‐OMeTAD. In addition, the IP‐TFSI initiator facilitated the growth of a homogeneous and pinhole‐free Spiro‐OMeTAD film. The pero‐SCs based on this oxidizing HTL showed excellent efficiencies of 25.16 % (certified: 24.85 % for 0.062‐cm 2 ) and 20.71 % for a 15.03‐cm 2 module as well as remarkable overall stability.