Antisite defects in Ce-doped YAG (Y3Al5O12): first-principles study on structures and 4f–5d transitions

Abstract

The interactions between Ce³⁺ and antisite defects (AD) in YAG (Y₃Al₅O₁₂) are studied by means of first-principles calculations: periodic-boundary-conditions density-functional-theory for a 160 atom YAG unit cell with one Ce³⁺ and one or two ADs, and complete-active-space second-order perturbation theory for the 4f¹, 5d¹, and 6s¹ electronic manifolds of the (CeO₈Al₂O₄)¹⁵⁻ embedded cluster. Attractive interactions are found between Ce³⁺ and the ADs. The formation of one AD is more favorable in Ce:YAG than in YAG, but the formation of a second AD is less favorable, which means that the presence of Ce tends to lower the concentration of antisite defects in YAG. The interaction between Ce³⁺ and antisite defects blueshifts the two lowest Ce³⁺ 4f → 5d transitions. This result rules out the involvement of antisite defects in the recently reported excitation of the lowest 5d → 4f emission with photons below the zero-phonon line and leaves other distorted Cerium centers for consideration, like Ce³⁺ interacting with interstitial non-stoichiometric Yttrium or with vacancies. The reasons behind the blueshifts are analyzed in detail: they are dominated by a decrease in the effective ligand-field splitting of the 5d¹ manifold, almost entirely due to the structural changes of short- and long-range and with almost negligible electronic effects from the Y and Al site exchanges.