Monoclinic zirconium dioxide (m-ZrO2) is a wide-band-gap functional oxide with many applications. Understanding the role of intrinsic defects and dopants is important for improving the properties of m-ZrO2 relevant to its applications. In this work, we characterize the electronic states and energy levels of oxygen vacancies (VO’s) and n-type Nb, Ta, Rb, H, and F dopants in the bulk and at the majority (1̅11) surface of m-ZrO2, using accurate dielectric-dependent hybrid functional calculations. Our results show that VO’s generally behave as deep donors with the excess electrons localized at the vacant O sites in the form of F centers, in agreement with previous studies. In contrast, surface VO’s at two-fold coordinated oxygen sites show a rather shallow (1+/0) transition level. Shallow levels are also obtained for adsorbed hydrogen (Hads) and fluorine substituting an oxygen atom (FO) either in the bulk or at the surface, whereas Nb and Ta form deep levels.
All Science Journal Classification (ASJC) codes
- Electronic, Optical and Magnetic Materials
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films