In this study, we examined the luminescence response of Ti-doped Al2O3 crystals to high-energy vacuum ultraviolet (UV) excitation. In addition to the thoroughly studied emission band of Ti3+ in the near-infrared region and blue emission at 420nm, we detected a UV emission band at 290nm. The excitation spectra of all emission bands were measured over the 420eV spectral range. Our results indicate that intrinsic anion defects are involved in the process of the excitation of the 420nm emission assigned to the charge transfer transitions 2pO23dTi4+. Analysis of the spectral and decay characteristics of the UV emission enables us to suggest that this band is associated with radiative decay of excitons localized at Ti ions.

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