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

Abstract 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.