Synergistic Diammonium‐Imidazole Interface Reconstruction toward Efficient and Stable Inverted Perovskite Photovoltaics

ABSTRACT Buried interfacial imperfections between perovskite and hole‐transport layer (HTL) represent a primary origin of non‐radiative recombination and operational instability in inverted perovskite solar cells (PSCs). Incomplete self‐assembled monolayers (SAM) coverage and inferior interfacial contact produce energetic disorder, hindering charge extraction to result in substantial photovoltage loss. Here, we introduce a bifunctional post‐assembly interfacial reconstruction strategy employing 1‐(2‐hydroxyethyl) imidazole (2Hyimi) and 1,3‐diaminopropane dihydroiodide (PDADI) to simultaneously improve both energy‐level alignment for charge extraction and the wetting/nucleation environment at the HTL/perovskite interface during film formation. The amino groups in PDADI and the imidazole groups in 2Hyimi synergistically coordinate with residual and undercoordinated Pb 2+ ions, effectively passivating buried interfacial traps, enhancing hole extraction and suppressing non‐radiative recombination. Concurrently, the hydroxyl‐terminated 2Hyimi improves surface wettability, promoting uniform crystallization and preferred orientation in large‐area perovskite films. As a result, inverted PSCs achieve an efficiency of 26.46%, and perovskite solar modules with an active area of 51.50 cm 2 reach 23.33%. Under ISOS‐L‐2 conditions, the target devices retain 92.29% of the initial efficiency after 1000 h at continuous maximum‐power‐point tracking, demonstrating excellent operational stability. This work establishes cooperative dual‐molecular interfacial engineering as a scalable route to simultaneously enhance efficiency and stability in inverted perovskite photovoltaics.