An Acceptor–Donor–Acceptor Molecule Tailored Versatile Buffer Enabling Efficient and Stable Perovskite Solar Cells

Abstract Interface in perovskite solar cells (PSCs) is of vital importance because it dominates deep‐level defects and non‐radiative recombination, thus impacting both efficiency and stability further. Herein, a symmetrical acceptor–donor–acceptor (A–D–A) conjugated molecule with the core architecture of terthieno[3,2‐b hiophene and 2‐(3‐oxo‐2,3‐dihydro‐1 H‐inden‐1‐ylidene)malononitrile, named 6TIC, as a versatile buffer layer, is adopted to enhance photovoltaic performance and stability simultaneously. It is found that the conjugated molecule filling at grain boundaries and surface can not only chemically anchor with perovskite components to substantially eliminate interfacial defects and suppress detestable non‐radiative recombination, but also effectively improve the energy level alignment and facilitate charge transfer efficiency at the interface, resulting in an excellent power conversion efficiency of 24.81% with an admirable fill factor of 84.5%. Furthermore, benefiting from the unexceptionable surface protection effect of the hydrophobic buffer layer, greatly improved operational stability is delivered, with retaining 90% of initial efficiency for 960 h aging in a relative humidity of 60 ± 5% air and 1450 h aging under continuous 85 °C heating stress. This strategy may provide a new avenue for advancing high‐efficiency and stable PSCs.