Although the emission of lanthanide (Ln) ions doped cubic sesquioxides has been subject of extensive studies, there are fundamental issues still to be elucidated. Specifically, compared to the well-understood emission of Ln at C2 sites, the emission at the inversion S6 (C3i) sites, representing ¼ of the total sites, has been identified only for Pr, Nd, Eu, Sm and Yb. Here, we present a first report and improved identification of the emission, excitation and decay properties of Tb, Dy and Pr at S6 sites in Y2O3 by use of time-gated luminescence spectroscopy. The green emission of Tb at S6 sites is characterized by an intensity ratio relative to the cyan band at 490 nm of 10 compared to 2 measured for Tb at C2 sites. Dy at S6 sites displays a relatively intense, near-infrared emission at 765 nm which is red-shifted by ca. 200 nm relative to yellow peaked emission of Dy at C2 sites. The emission lifetimes of 9.4 and 4.8 ms, associated with Tb and Dy at S6 sites, exceed by a factor of 5 and 10 those of C2 counterparts. It is also found that Dy may be regarded as a sensitive probe for the inversion symmetry, comparable with the more recognized Eu. The participation of Ln at S6 sites to the up-conversion emission is revealed for the first time in Sm doped Y2O3 and Eu /Tb, Yb co-doped Y2O3 and explained in terms of successive ground state and excited state absorptions and cooperative energy transfer, respectively.
Read full abstract