Surface Energy Engineering of Buried Interface for Highly Stable Perovskite Solar Cells with Efficiency Over 25

The abundant oxygen‐related defects (e.g., O vacancies, O–H) in the TiO2 electron transport layer results in high surface energy, which is detrimental to effective carrier extraction and seriously impairs the photovoltaic performance and stability of perovskite solar cells. Here, novel surface energy engineering (SEE) is developed by applying a surfactant of heptadecafluorooctanesulfonate tetraethylammonium (HFSTA) on the surface of the TiO2. Theoretical calculations show that the HFSTA‐TiO2 is less prone to form O vacancies, leading to lower surface energy, thus improving the carrier‐extraction efficiency. The experimental results show that superior perovskite film is obtained due to the reduced heterogeneous nucleation sites and improved crystallization process on the modified TiO2. Furthermore, the flexible long alkyl chains in HFSTA considerably relieve the compressive stresses at the buried interface. By combining the passivation of TiO2, crystallization process modulation, and stress relief, a champion PCE up to 25.03% is achieved. The device without encapsulation sustains 92.2% of its initial PCE after more than 2500 h storage under air ambient with relative humidity of 25–30%. The SEE of a buried interface paves a new way toward high‐efficiency, stable perovskite solar cells. The abundant oxygen‐related defects seriously impair the photovoltaic performance and stability of perovskite solar cells. Here, a novel surface energy engineering (SEE) is developed by applying a surfactant HFSTA on the surface of the TiO2 substrate. By combining the passivation of TiO2, crystallization process modulation and stress relief, PCE of 25.03% is achieved on champion device along with improved stability.