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

作者：Munoz Garcia Ana Belen; Barandiaran Zoila; Seijo Luis^*

来源：Journal of Materials Chemistry, 2012, 22(37): 19888-19897.

DOI：10.1039/c2jm34479c

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 4f(1), 5d(1), and 6s(1) 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 -%26gt; 5d transitions. This result rules out the involvement of antisite defects in the recently reported excitation of the lowest 5d -%26gt; 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 5d(1) 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.

• 出版日期2012