| Summary: | All-inorganic CsPbI<sub>3−x</sub>Br<sub>x</sub> perovskite solar cells (PSCs) are becoming increasingly mature due to their excellent optoelectronic properties. However, because of the poor environmental stability of the perovskite material, the device is susceptibly decomposed when exposed to moisture, high temperature, and high illumination. Therefore, a critical task is to address the problem of poor long-term stability in the environment, which serves as a significant obstacle impeding the commercialization of perovskite solar cells. This article introduces the incorporation of PEO into all-inorganic CsPbI<sub>3−x</sub>Br<sub>x</sub> perovskites with an advantageous thermal stability. PEO acts as a passivating agent near the grain boundary, and its high viscosity characteristics effectively improve the film-forming properties, leading to a substantial reduction in defects and to improving the surface uniformity. In addition, the grain boundaries that serve as water and oxygen penetration channels are filled, resulting in a substantial improvement in device stability. With 7.5 mg/mL PEO doping into CsPbI<sub>3−x</sub>Br<sub>x</sub>, the unencapsulated device maintained its original power conversion efficiency of 98% after being placed in a dark environment of 40% humidity and 25 °C for 10 days. Using PEO effectively enhanced the performance of the devices, with the highest PCE reaching 10.95%, significantly improving environmental stability.
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