Defect-Polaron and Enormous Light-Induced Fermi-Level Shift at Halide Perovskite Surface

Halide perovskites intrinsically contain a large amount of point defects. The interaction of these defects with photocarriers, photons, and lattice distortion remains a complex and unresolved issue. We found that for halide perovskite films with excess halide vacancies, the Fermi level can be shifted by as much as 0.7 eV upon light illumination. These defects can trap photocarriers for hours after the light illumination is turned off. The enormous light-induced Fermi level shift and the prolonged electron trapping are explained by the capturing of photocarriers by halide vacancies at the surface of the perovskite film. The formation of this defect–photocarrier complex can result in lattice deformation and an energy shift in the defect state. The whole process is akin to polaron formation at a defect site. Our data also suggest that these trapped carriers increase the electrical polarizability of the lattice, presumably by enhancing the defect migration rate.