PTAA‐Based Perovskite Photovoltaics Catching up: Ionic Liquid Engineering‐Assisted Crystallization Through Sequential Deposition

Abstract PTAA as a widely studied polymeric hole transporting material, has garnered significant attention due to its outstanding thermal and chemical stability. However, the performance of PTAA‐based p‐i‐n devices is shown to lag behind counterpart utilizing oxides or SAMs. In this study, the ionic liquid, 1‐ethyl‐3‐methylimidazolium formate (EMIMCOOH), is innovatively introduced into the lead iodide (PbI 2 ) precursor solution, resulting in a more pronounced mesoporous PbI 2 film with expended pore‐size and denser pores. This enhancement is attributed to the coordination bond between the ─C═O group in EMIMCOOH and Pb 2+ . This intensified mesoporous morphology not only facilities the reaction between PbI 2 and the organic layer, but also promotes the PbI 2 conversion into perovskite material. Importantly, the incorporation of EMIMCOOH slows down the perovskite conversion process, increasing perovskite domain size and suppressed Pb 0 trap density, resulting in a uniform perovskite layer with enhanced charge transport properties, as evidenced by the conducting atomic force microscope (c‐AFM) results. As a result, the incorporation of EMIMCOOH yields a power conversion efficiency (PCE) of 24.10% and a high fill factor exceeding 85%. Notably, the PCE of the EMIMCOOH‐modified device can still maintain 86% of the initial value after 1500 h at 25 °C in an N 2 atmosphere.