Insights Into to the KX (X = Cl, Br, I) Adsorption‐Assisted Stabilization of CsPbI2Br Surface

Abstract Despite the excellent optoelectronic properties, organic‐inorganic hybrid perovskite solar cells (PSCs) still present significant challenges in terms of ambient stability. CsPbI 2 Br, a member of all‐inorganic perovskites, may respond to this challenge because of its inherent high stability against light, moisture, and heat, and therefore has gained tremendous attraction recently. However, the practical application of CsPbI 2 Br is still impeded by the notorious phenomenon of photoinduced halide segregation. Herein, by applying first‐principles calculations, the stability, electronic structure, defect properties, and ion‐diffusion properties of the stoichiometric CsPbI 2 Br (110) surface and that with the adsorption of KX (X = Cl, Br, I) are systematically investigated. It is found that the adsorbed KX can serve as an external substitute of the halogen vacancies on the surface, therefore inhibiting halogen segregation and improving the stability of the CsPbI 2 Br surface. The KX can also eliminate deep‐level defect states caused by antisites, thereby contributing to the promoted optoelectronic properties of CsPbI 2 Br. The mechanistic understanding of surface passivation in this work can lay the foundation for the future design of CsPbI 2 Br PSCs with optimized optoelectronic performance.