Stratified Oxygen Vacancies Enhance the Performance of Mesoporous TiO₂ Electron Transport Layer in Printable Perovskite Solar Cells

Abstract The low electrical conductivity and the high surface defect density of the TiO 2 electron transport layer (ETL) limit the power conversion efficiency (PCE) of corresponding perovskite solar cells (PSCs). Here, the conductivity and defect modulation of the mesoporous TiO 2 (mp‐TiO 2 ) ETL via oxygen vacancy (OV) management by the reduction and oxidation treatment are reported. Reduction treatment via reducing agent introduces abundant OVs into the TiO 2 nanocrystalline particles on the surface and at the subsurface. The following oxidation treatment via hydrogen peroxide removes the surface OVs while remains the subsurface OVs, resulting in stratified OVs. The stratified OVs improve the conductivity of TiO 2 ETL by increasing carrier donors and decrease nonradiative centers by reducing surface defects. Such synergy ensures the capability of mp‐TiO 2 as the well‐performed ETL with improved energy level alignment, suppressed interface recombination, enhanced carrier extraction, and transport. As a result, printable hole‐conductor‐free carbon‐based mesoscopic PSCs based on the modulated mp‐TiO 2 ETL demonstrate a highest reported PCE of 18.96%.