Synergistic Electron-Deficient Surface Engineering: A Key Factor in Dictating Electron Carrier Extraction for Perovskite Photovoltaics

作者：Chi Li, Paramaguru Ganesan, Yuheng Li, Shicheng Tang, Yao Wang, Chunming Liu, Lusheng Liang, Yaming Yu, Abd. Rashid bin Mohd Yusoff, Michaël Grätzel, Peng Gao · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c07357 · 被引用次数：25 · 研究领域：Perovskite Materials and Applications、ZnO doping and properties、Gas Sensing Nanomaterials and Sensors

Work function modulation of transparent conductive oxides via self-assembled monolayers (SAMs) facilitates efficient hole or electron extraction in optoelectronic devices. However, recent SAMs for perovskite solar cells (PSCs) diverge from traditional interfacial dipole orientation design principles, instead leveraging electron-rich and electron-deficient surface modifications. In light of these discrepancies, this study systematically analyses electron-deficient materials of varying strength, revealing the dominance of surface modifications over interfacial dipole orientation. Specifically, modulating the electron-withdrawing strength by replacing the carboxylic acid group (Bpy-COOH) with a cyanoacrylic acid moiety (Bpy-CAA) in dual-functional bipyridine-based electron-selective molecular layers (ESMLs) enhances adsorption, electron extraction, and passivation in n-i-p PSCs. Consequently, Bpy-CAA devices achieve 23.98% efficiency, surpassing Bpy–COOH–based devices (23.20%), and maintain an impressive 21.63% efficiency in 1 cm 2 cells, the highest reported for 1 cm 2 n-i-p PSCs utilizing organic ESMLs. A remarkable efficiency of 26.00% is achieved by integrating Bpy-CAA as an interfacial layer into SnO 2 /ESML/perovskite contacts while adapting this architecture into four-terminal perovskite/silicon tandem solar cells (4T-P/STSCs) yields an impressive efficiency of 30.83%, ranking among the highest reported efficiencies for 4T-P/STSCs. Overall, this work demonstrates that the...