In Situ Surface Fluorination of TiO 2 Nanocrystals Reinforces Interface Binding of Perovskite Layer for Highly Efficient Solar Cells with Dramatically Enhanced Ultraviolet‐Light Stability

Low‐temperature solution‐processed TiO 2 nanocrystals (LT‐TiO 2 ) have been extensively applied as electron transport layer (ETL) of perovskite solar cells (PSCs). However, the low electron mobility, high density of electronic trap states, and considerable photocatalytic activity of TiO 2 result in undesirable charge recombination at the ETL/perovskite interface and notorious instability of PSCs under ultraviolet (UV) light. Herein, LT‐TiO 2 nanocrystals are in situ fluorinated via a simple nonhydrolytic method, affording formation of Ti─F bonds, and consequently increase electron mobility, decrease density of electronic trap states, and inhibit photocatalytic activity. Upon applying fluorinated TiO 2 nanocrystals (F‐TiO 2 ) as ETL, regular‐structure planar heterojunction PSC (PHJ‐PSC) achieves a champion power conversion efficiency (PCE) of 22.68%, which is among the highest PCEs for PHJ‐PSCs based on LT‐TiO 2 ETLs. Flexible PHJ‐PSC devices based on F‐TiO 2 ETL exhibit the best PCE of 18.26%, which is the highest value for TiO 2 ‐based flexible devices. The bonded F atoms on the surface of TiO 2 promote the formation of Pb─F bonds and hydrogen bonds between F − and FA/MA organic cations, reinforcing interface binding of perovskite layer with TiO 2 ETL. This contributes to effective passivation of the surface trap states of perovskite film, resulting in enhancements of device efficiency and stability especially under UV light.