Robust Imidazole‐Linked Covalent Organic Framework Enabling Crystallization Regulation and Bulk Defect Passivation for Highly Efficient and Stable Perovskite Solar Cells

The low crystallinity of the perovskite layers and many defects at grain boundaries within the bulk phase and at interfaces are considered huge barriers to the attainment of high performance and stability in perovskite solar cells (PSCs). Herein, a robust photoelectric imidazole‐linked porphyrin‐based covalent organic framework (PyPor‐COF) is introduced to precisely control the perovskite crystallization process and effectively passivate defects at grain boundaries through a sequential deposition method. The 1D porous channels, abundant active sites, and high crystallization orientation of PyPor‐COF offer advantages for regulating the crystallization of PbI2 and eliminating defects. Moreover, the intrinsic electronic characteristics of PyPor‐COF endow a more closely matched energy level arrangement within the perovskite layer, which promotes charge transport and thereby suppresses the recombination of photogenerated carriers. The champion PSCs containing PyPor‐COF achieved power conversion efficiencies of 24.10% (0.09 cm2) and 20.81% (1.0 cm2), respectively. The unpackaged optimized device is able to maintain its initial efficiency of 80.39% even after being exposed to air for 2000 h. The device also exhibits excellent heating stability and light stability. This work gives a new impetus to the development of highly efficient and stable PSCs via employing COFs. 1D porous channels and high crystalline orientation of imidazole‐linked porphyrin‐based covalent organic framework (PyPor‐COF) facilitate the crystallization and defect elimination of the perovskite film. The recombination of photogenerated carriers is thus reduced and the perovskite solar cells exhibit excellent efficiency and high stability.