It has been experimentally observed that Ti doping of bulk ZrO2 induces a large red-shift of the optical absorption edge of the material from 5.3 to 4.0 eV [Livraghi et al., J. Phys. Chem. C, 2010, 114, 18553–18558]. In this work, density functional calculations based on the hybrid functional B3LYP show that Ti dopants in the substitutional position to Zr in the tetragonal lattice cause the formation of an empty Ti 3d band about 0.5 eV below the bottom of the conduction band. The optical transition level εopt(0/−1) from the topmost valence state to the lowest empty Ti impurity state is found at 4.9 eV in a direct band gap of 5.7 eV. The calculated shift is consistent with the experimental observation. The presence of Ti3+ species in Ti-doped ZrO2, probed by means of electron paramagnetic resonance (EPR), is rationalized as the result of electron transfers from intrinsic defect states, such as oxygen vacancies, to substitutional Ti4+ centers.
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