Defect complexes in Ti-doped sapphire: A first principles study

TL;DR

This study uses first-principles calculations to analyze defect formation and concentrations in Ti-doped sapphire, revealing that complex defects can be as prevalent as isolated ones and affect the material's electronic structure.

Contribution

It provides a detailed first-principles analysis of defect complexes in Ti-doped sapphire, including formation energies, concentrations, and electronic effects, which was not previously comprehensively studied.

Findings

Complex defect concentrations can surpass isolated defect concentrations.

Ti-deficient conditions favor Ti4+ defects and increase isolated defect fractions.

Complex defects introduce new electronic levels within the band gap.

Abstract

First-principles calculations have been performed to study the formation of defect complexes in Ti doped alpha-Al2O3 crystals. The formation energies of isolated Ti3+ and Ti4+ defects, pairs, triples and quadruples of Ti ions and Al vacancies are computed under different equilibrium conditions of Al-Ti-O related phases. Taking into account charge neutrality of the whole system we determine the equilibrium concentrations of simple and complex defects as well as the total equilibrium concentration of Ti in an alpha-Al2O3 crystal. It is shown that the equilibrium concentration of complex defects can be on the same order of or even larger than the concentrations of isolated substitutional Ti3+ and Ti4+ defects. It is found that in Ti-deficient conditions the relative fraction of isolated defects increases and the balance is shifted towards Ti4+ defects. A universal relation between equilibrium concentrations of isolated and complex defects is obtained. The band structure of the system with complex defects is calculated and extra levels inside the band gap caused by such defects are found.