Electronic and structural properties
of cubic Lu2O3 with either single oxygen vacancy,
oxygen vacancy–vacancy
pair, or a Frenkel pair (an oxygen vacancy and an interstitial oxygen)
were analyzed using ab initio density functional
theory calculations. A plane-wave ultrasoft pseudopotential approach
with local density approximation functional was used to optimize the
geometries. A full-potential linearized augmented plane-wave method
with meta-generalized gradient approximation was applied to the optimized
geometries to calculate the electronic properties of the systems.
Defect-related bands were observed between the valence band and the
conduction band. Different charge states of the defects were considered.
Both oxygen vacancy and oxygen vacancy–vacancy pairs behave
as moderately deep electron traps (trap depth 1.3–2.7 eV).
Trapped electron localization at the vacancy site(s) was confirmed
using electron density and electron localization function plots. The
bands originating from oxygen vacancy–vacancy pairs in Lu2O3 exhibit some dependence on the distance between
the two entities. The resulting energy differences (considered from
an optical absorption point of view) cover ultraviolet, visible, and
infrared ranges. Thus, it is plausible that oxygen vacancy–vacancy
pairs are responsible for the coloration that is sometimes observed
in Lu2O3 powders and crystals. On the contrary,
the Frenkel pair exhibits no systematic dependence of the defect-related
bands on the distance between its oxygen vacancy and interstitial
oxygen, while the resulting defect-related bands look similar to those
corresponding to the isolated defects. Frenkel pairs are thus considered
a probable mechanism of oxygen vacancy formation and stabilization
of Lu2O3. Additionally, a brief review of the
relevant experimental data is provided in the introduction.