Electronic structure and thermodynamic stability of uranium-doped yttrium iron garnet.

The electronic and thermodynamic properties of yttrium iron garnet (Y3Fe5O12, YIG), as a possible uranium-bearing phase, have been investigated using first-principles and semi-empirical methods. The electronic structures of pure and U-doped YIG were calculated and compared in order to obtain a fundamental understanding of the incorporation mechanism and stability of U in a YIG matrix. Uranium at the A-site is in 4 +  oxidation state, acting as a single donor and introducing a localized defect state in the band gap. The ionic relaxations show U at the A-site is an off-center impurity. At the B-site, uranium is in 5 +  oxidation state giving rise to two localized defect states in the middle of the band gap. At thermodynamic equilibrium the incorporation of U is limited by (i) the relatively narrow stability domain of the host YIG and (ii) the precipitation of uranium oxides as secondary phases. Under Y-rich growth conditions, YIG is unstable with respect to competing phases such as the iron oxides, Y2O3 and YFeO3. Under O-rich conditions, the incorporation U is obstructed by the formation of uranium-oxide precipitates. Under Fe-rich growth conditions, the formation energies of UY (U at the A-site) and UFe (U at the B-site) become negative for 0 ≤ EF ≤ 0.62 eV and 0 ≤ EF ≤ 0.77 eV, respectively, indicating that U might be incorporated in p-type YIG.