Molecule‐Doped Nickel Oxide: Verified Charge Transfer and Planar Inverted Mixed Cation Perovskite Solar Cell

Abstract Both conductivity and mobility are essential to charge transfer by carrier transport layers (CTLs) in perovskite solar cells (PSCs). The defects derived from generally used ionic doping method lead to the degradation of carrier mobility and parasite recombinations. In this work, a novel molecular doping of NiO x hole transport layer (HTL) is realized successfully by 2,2′‐(perfluoronaphthalene‐2,6‐diylidene)dimalononitrile (F6TCNNQ). Determined by X‐ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy, the Fermi level ( E F ) of NiO x HTLs is increased from −4.63 to −5.07 eV and valence band maximum (VBM)‐ E F declines from 0.58 to 0.29 eV after F6TCNNQ doping. The energy level offset between the VBMs of NiO x and perovskites declines from 0.18 to 0.04 eV. Combining with first‐principle calculations, electrostatic force microscopy is applied for the first time to verify direct electron transfer from NiO x to F6TCNNQ. The average power conversion efficiency of CsFAMA mixed cation PSCs is boosted by ≈8% depending on F6TCNNQ‐doped NiO x HTLs. Strikingly, the champion cell conversion efficiency of CsFAMA mixed cations and MAPbI 3 ‐based devices gets to 20.86% and 19.75%, respectively. Different from passivation effect, the results offer an extremely promising molecular doping method for inorganic CTLs in PSCs. This methodology definitely paves a novel way to modulate the doping in hybrid electronics more than perovskite and organic solar cells.