Molecularly Functionalized SnO₂Films by Carboxylic Acids for High-Performance Perovskite Solar Cells

Metal oxides are commonly employed as electron transport layers (ETLs) for n-i-p perovskite solar cells (PSCs), but the presence of surface traps and their mismatched energy alignment with perovskites limits the corresponding device performance. Therefore, the interfacial modification of ETLs by functional molecules becomes an important strategy for tailoring the interfacial properties and facilitating an efficient charge extraction and transport in PSCs. However, an in-depth understanding of the influences of their molecular structures on the surface chemistry and electronic properties of ETLs is rarely discussed. Herein, three carboxylic acid-based molecules with different chemical structures were employed to modify the SnO₂ ETL and their effects on the performance of PSCs were systematically investigated. We found that the alkyl-chain length and carboxyl number in molecular structures can dramatically alter their binding strength to SnO₂, providing a good strategy to fine-tune their film quality, electron mobility, and energy offset at the cathode interface. Benefiting from the optimal coordination ability of citric acid (CA) to SnO₂, the corresponding PSCs show better charge transport properties and suppressed nonradiative recombination, leading to a champion efficiency of 23.1% with much improved environmental stability, highlighting the potential of rational design of molecular modifiers for high-performance ETLs applied in PSCs.