Investigation of the Structure and Luminescence Mechanism of Tm3+-Doped LiYF4: New Theoretical Perspectives

The absorption and emission transitions of Tm3+-doped LiYF4 have been extensively investigated due to the excellent properties and enormous applications of these materials as laser materials. However, the challenging issues regarding the local structure and luminescence mechanism have not been conclusively established to date. To address these challenges, the CALYPSO structure search method is employed, and the results first reveal the ground-state structure of Tm3+-doped LiYF4, which crystallizes in the space group P4 (No. 81) of the tetragonal system. The Y3+ ions are replaced by Tm3+ ions, forming a local configuration of [TmF8]5–. Furthermore, the complete Stark energy levels of Tm3+-doped LiYF4 are predicted by using our newly developed WEPMD method, which provides preliminary preparation for further spectral exploration. Judd–Ofelt analysis is performed to evaluate the electric dipole transition intensities. Two prominent transitions, 3H5 → 3H6 (1223 nm) and 3H4 → 3H6 (801 nm), are predicted to be ...