Uniform Stepped Interfacial Energy Level Structure Boosts Efficiency and Stability of CsPbI2Br Solar Cells

All‐inorganic CsPbI2Br perovskite has attracted great attention as an absorber for perovskite solar cells (PSCs) due to its excellent thermal and light resistance. However, its device performance is restricted by the large energy level offset between CsPbI2Br and the most commonly used hole‐transporting layer (HTL). Herein, multicarbazolyl‐substituted benzonitrile (4t‐5CzBn) is inserted into the interface between CsPbI2Br and HTL to form a uniform stepped (0.24 eV) interfacial energy level structure, which reduces the energy loss and boosts the hole extraction of CsPbI2Br PSCs. The incorporation of 4t‐5CzBn induces the increase in open‐circuit voltage and fill factor from 1.256 V and 74.5% to 1.335 V and 82.3%, respectively. The optimized device achieves a power conversion efficiency of 17.34%, which is among the highest reported values of CsPbI2Br PSCs. Besides the energy level tuning effect, the tert‐butyl groups in 4t‐5CzBn improve the moisture‐resistance of CsPbI2Br PSCs. The unencapsulated device maintains over 75% of its initial efficiency after 700 h storage in air. These results demonstrate that the rational tuned energy level step benefits the performance improvement of CsPbI2Br PSCs. Multicarbazolyl‐substituted benzonitrile is used as an interface manipulation layer between CsPbI2Br and hole‐transport layer, yielding the enhanced power conversion efficiency of 17.34% and stability of perovskite solar cells.