LAUSR

Nonradiative losses caused by defects are the main obstacles to further advancing the efficiency and stability of perovskite solar cells (PSCs). There is focused research to boost the device performance by reducing the number of defects and deactivating defects; however, little attention is paid to the defect‐capture capacity. Here, upon systematically examining the defect‐capture capacity, highly polarized fluorinated species are designed to modulate the dielectric properties of the perovskite material to minimize its defect‐capture radius. On the one hand, fluorinated polar species strengthen the defect dielectric‐screening effect via enhancing the dielectric constant of the perovskite film, thus reducing the defect‐capture radius. On the other, the fluorinated iodized salt replenishes the I‐vacancy defects at the surface, hence lowering the defect density. Consequently, the power‐conversion efficiency of an all‐inorganic CsPbI3 PSC is increased to as high as 20.5% with an open‐circuit voltage of 1.2 V and a fill factor of 82.87%, all of which are among the highest in their respective categories. Furthermore, the fluorinated species modification also produces a hydrophobic umbrella yielding significantly improved humidity tolerance, and hence long‐term stability. The present strategy provides a general approach to effectually regulate the defect‐capture radius, thus enhancing the optoelectronic performance.