Facilely Modified Nickel‐Based Hole Transporting Layers for Organic Solar Cells with 19.12% Efficiency and Enhanced Stability

Abstract Hole transporting layers (HTLs), strategically positioned between electrode and light absorber, play a pivotal role in shaping charge extraction and transport in organic solar cells (OSCs). However, the commonly used poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) HTL, with its hygroscopic and acidic nature, undermines the operational durability of OSC devices. Herein, an environmentally friendly approach is developed utilizing nickel acetate tetrahydrate (NiAc·4H₂O) and [2‐(9H‐carbazol‐9‐yl)ethyl] phosphonic acid (2PACz) as the NiAc·4H₂O/2PACz HTL, aiming at overcoming the limitations posed by the conventional PEDOT:PSS one. Encouragingly, a remarkable power conversion efficiency (PCE) of 19.12% is obtained for the OSCs employing NiAc·4H₂O/2PACz as the HTL, surpassing that of devices with the PEDOT:PSS HTL (17.59%), which is ranked among the highest ones of OSCs. This improvement is attributed to the appropriate work function, enhanced hole mobility, facilitated exciton dissociation efficiency, and lower recombination loss of NiAc·4H₂O/2PACz‐based devices. Furthermore, the NiAc·4H₂O/2PACz‐based OSCs exhibit superior operational stability compared to their PEDOT:PSS‐based counterparts. Of significant note, the NiAc·4H₂O/2PACz HTL demonstrates a broad generality, boosting the PCE of the PM6:PY‐IT and PM6:Y6‐based OSCs from 16.47% and 16.79% (with PEDOT:PSS‐based analogs as HTLs) to 17.36% and 17.57%, respectively. These findings underscore the substantial potential of the NiAc·4H₂O/2PACz HTL in advancing OSCs, offering improved performance and stability, thereby opening avenue for highly efficient and reliable solar energy harvesting technologies.