Multifunctional Resonance Bridge‐Mediated Dynamic Modulation of Perovskite Films For Enhanced Intrinsic Stability of Photovoltaics

Abstract The improving intrinsic stability, determining the life span of devices, is a challenging task in the industrialization of inverted perovskite solar cells. The most important prerequisite for boosting intrinsic stability is high‐quality perovskite films deposition. Here, a molecule, N‐(2‐pyridyl)pivalamide (NPP) is utilized, as a multifunctional resonance bridge between poly(triarylamine) (PTAA) and perovskite film to regulate the perovskite film quality and promote hole extraction for enhancing the device intrinsic stability. The pyridine groups in NPP couple with the phenyl groups in PTAA through π−π stacking to improve hole extraction capacities and minimize interfacial charge recombination, and the resonance linkages (NCO) in NPP dynamically modulate the perovskite buried defects through strong PbO bonds based on the fast self‐adaptive tautomerization between resonance forms (NCO and N⁺CO⁻). Because of the combined effect of the reduction defect density and improved energy level in the perovskite buried interfaces as well as the optimized crystal orientation in perovskite film enabled by the NPP substrate, the devices based on NPP‐grown perovskite films show an efficiency approaching 20% with negligible hysteresis. More impressively, the unencapsulated device displays start‐of‐the‐art intrinsic photostability, operating under continuous 1‐sun illumination for 2373 h at 65 °C without loss of PCE.