Defect-induced modification of electronic and optical properties of CeO2 unveiled by many-body Green’s function theory

Abstract

We explore the impact of point defects, including oxygen vacancies (Ov), cerium interstitials (Ce-int), and hydroxyl groups (Hy), on the electronic and optical properties of bulk CeO2 using many-body Green’s function theory (GW method and Bethe–Salpeter equation). Although these three defects all produce occupied electronic levels near the conduction band minimum, they impose quite different effects. Ov and Ce-int induce strong peaks in the low-energy region of the imaginary part of the microscopic dielectric function, indicating stronger electronic screening compared to the pristine CeO2. This causes pronounced narrowing of the bandgap, e.g., by 0.8 eV in G0W0 and 1.6 eV in the eigenvalue self-consistent GW for Ov. Comparatively, Hy affects little electronic screening and bandgap at different levels of GW calculations. For the lowest several 4f orbitals, the exchange part of the self-energy (|Σx| > 9 eV) in GW is much stronger than the correlation part (|Σc| < 5 eV) for Ov and Ce-int, while |Σc| is much stronger than |Σx| instead for the pristine CeO2 and Hy. Quasiparticle weights in Ov and Ce-int decrease by a large quantity compared to the pristine CeO2. Consideration of Ov and Ce-int might to some extent relieve the discrepancy between the GW bandgap of the pristine CeO2 and the experimental gap. Ov and Ce-int could reduce the excitonic binding energy several times and result in optical absorption, which corresponds to the experiments.