Resonance‐Mediated Dynamic Modulation of Perovskite Crystallization for Efficient and Stable Solar Cells

Abstract Manipulating perovskite crystallization to prepare high‐quality perovskite films is the key to achieving highly efficient and stable perovskite solar cells (PSCs). Here, a dynamic strategy is proposed to modulate perovskite crystallization using a resonance hole‐transporting material (HTM) capable of fast self‐adaptive tautomerization between multiple electronic states with neutral and charged resonance forms for mediating perovskite crystal growth and defect passivation in situ. This approach, based on resonance variation with self‐adaptive molecular interactions between the HTM and the perovskite, produces high‐quality perovskite films with smooth surface, oriented crystallization, and low charge recombination, leading to high‐performance inverted PSCs with power conversion efficiencies approaching 22% for small‐area devices (0.09 cm 2 ) and up to 19.5% for large‐area devices (1.02 cm 2 ). Also, remarkably high stability of the PSCs is observed, retaining over 90%, 88%, or 83% of the initial efficiencies in air with relative humidity of 40–50%, under continuous one‐sun illumination, or at 75 °C annealing for 1000 h without encapsulation.