
Luminescence spectra of lanthanides in the vacuum ultraviolet spectral region have revealed interesting features for ${4f}^{n}\ensuremath{\leftrightarrow}{4f}^{n\ensuremath{-}1}5d$ $(f\ensuremath{-}d)$ transitions. For ${\mathrm{Tb}}^{3+},$ ${\mathrm{Dy}}^{3+},$ ${\mathrm{Ho}}^{3+},$ ${\mathrm{Er}}^{3+},$ and ${\mathrm{Tm}}^{3+}$ in ${\mathrm{LiYF}}_{4},$ weak $f\ensuremath{-}d$ bands are present in the excitation spectra at lower energy than the usually observed strong $f\ensuremath{-}d$ bands. The weakness of the bands is explained by the spin-forbidden character of transitions from the ${4f}^{n}$ ground state to these ${4f}^{n\ensuremath{-}1}5d$ states. For ${\mathrm{Er}}^{3+}$ and ${\mathrm{Tm}}^{3+},$ upon excitation in the higher energetic ${4f}^{n\ensuremath{-}1}5d$ states two kinds of $f\ensuremath{-}d$ emission are observed: fast spin-allowed emission with a decay time in the order of ns, and slow spin-forbidden emission with a decay time in the order of \ensuremath{\mu}s. These two types of $f\ensuremath{-}d$ emission are also found for ${\mathrm{Er}}^{3+}$ and ${\mathrm{Tm}}^{3+}$ in other fluoride hosts.
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