Engineering of the Electron Transport Layer/Perovskite Interface in Solar Cells Designed on TiO₂ Rutile Nanorods

Abstract The engineering of the electron transport layer (ETL)/light absorber interface is explored in perovskite solar cells. Single‐crystalline TiO₂ nanorod (NR) arrays are used as ETL and methylammonium lead iodide (MAPI) as light absorber. A dual ETL surface modification is investigated, namely by a TiCl₄ treatment combined with a subsequent PC₆₁BM monolayer deposition, and the effects on the device photovoltaic performance were evaluated with respect to single modifications. Under optimized conditions, for the combined treatment synergistic effects are observed that lead to remarkable enhancements in cell efficiency, from 14.2% to 19.5%, and to suppression of hysteresis. The devices show J_SC, V_OC, and fill factor as high as 23.2 mA cm⁻², 1.1 V, and 77%, respectively. These results are ascribed to a more efficient charge transfer across the ETL/perovskite interface, which originates from the passivation of defects and trap states at the ETL surface. To the best of our knowledge, this is the highest cell performance ever reported for TiO₂ NR‐based solar cells fabricated with conventional MAPI light absorber. Perspective wise, this ETL surface functionalization approach combined with more recently developed and better performing light absorbers, such as mixed cation/anion hybrid perovskite materials, is expected to provide further performance enhancements.