Guanidinium Passivation for Air‐Stable Rubidium‐Incorporated Cs(1 − x)RbxPbI2Br Inorganic Perovskite Solar Cells

Inorganic CsPbI 2 Br perovskite has gained growing attention due to its potential for improving device performance and stability. However, the notorious phase transition from the photoactive to photoinctive phase in ambient atmosphere hinders its further development. Herein, air‐stable rubidium (Rb)‐incorporated Cs ( 1 − x ) Rb x PbI 2 Br perovskite with guanidinium bromide (GABr) post‐treatment is demonstrated. The incorporation of smaller monovalent Rb cation contributes to a contraction of the perovskite crystal, leading to an improvement in structure stability. In addition, GABr modification induces a 2D/3D heterostructure perovskite with high crystallinity, appropriate surface morphology, favorable electronic properties, and significantly reduced trap‐state density. Consequently, the fabricated perovskite solar cells deliver a power conversion efficiency (PCE) of 15.6%, which is much higher than the 12.9% reported for reference CsPbI 2 Br‐based devices. Meanwhile, the significantly enhanced long‐term (88% of initial PCE after 60 days), thermal (76% of initial PCE after 30 days) as well as light soaking (90% of initial PCE after 300 min) stability in ambient atmosphere is demonstrated.