Absorption and emission spectra of Ce{sup 3+} in elpasolite lattices Page: 3 of 38
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For the lanthanide series the Ce3+ ion has been extensively studied and measured
levels have been reported for both the ground 4f1 configuration and the excited 5d1
configuration. Figure 1 shows schematically the energy levels and nomenclature used for
the 4f1 and 5d1 configurations of the Ce3+ ion diluted in choro-elpasolite hosts. The 6 K
4f-5d absorption and magnetic circular dichroism (MCD) spectra of Ce3+ diluted in
Cs2NaYCl6 were reported by Schwartz and Schatz. 9 They located the 5d 2T2g F8 and F7
levels at 28196 cm-land 29435 cm-1 respectively. No further electronic absorption
transitions were detected up to 50000 cm-1. The 5d 2Eg F8 level was thus assumed to be
>20000 cm-1 above the 2T2g baricenter. The EPR spectrum of the Ce3+ ion in Cs2NaYCl6
has also been measured. 10 The 5d-4f luminescence from the 2T2g state was recently
reported under low resolution at 80 K, with about a 30 s lifetime ." The decay curves
for X-ray- and vacuum ultraviolet- excited emission of Ce3+/Cs2LiYCl6 and
Ce3+/Cs2LiLaCl6 have recently been reported.1 Ionova et al. have cited the lowest 7 -
f charge transfer band in CeCl63- near 60000 cm- .
van't Spijker et al,15 reported the excitation spectra of the 425 nm (23530 cm-1)
emission of Ce3+ in Cs2NaLaCl6, Cs2NaCeCl6 and Cs2NaLuCl6. In each case, bands were
observed near 210 nm and attributed to f - 2Eg d transitions of Ce3+. The wavelengths of
these bands have been listed by Dorenbos,16 with the addition of 210, 217 nm (47620,
46083 cm 1) for Ce3+/Cs2NaYCl6. The doublet structure (separation of the peak maxima ~
1540 cm 1) corresponded to absorption from both the 2F512 and 2F7w2 f-electron states to the
d-electron 2Eg state at room temperature. Hence it is well-substantiated that the 2Eg state is
near 47000 cm-1 in these cubic elpasolite hosts. This state also has been observed at
42200 cm-1 in the 300 K photoacoustic spectrum of Ce3+/BaF2.
Rodnyi et al. 1 observed bands in the 300 K excitation spectrum of the 3.3 eV
luminescence of Ce3+ in Cs2LiLaCl6 at 35730, 37908, 41134 and 45247 cm 1, which were
assigned to f - d transitions of Ce3+. The 19 eV-excited emission spectrum of Cs2LiLaCl6
doped with 1% Ce3+ gave a broad band at 26616 cm 1, assigned to d - f emission of Ce3,
in addition to a broader feature (33069 cm-1) assigned to core-valence luminescence. No
emission was evident from the 2Eg state of Ce3.
In a more recent study of Ce3+ - doped Cs2LiYX6, 18 even the neat Cs2LiYCl6 showed
extensive bands between 48000-100000 cm-1 in the excitation spectra of the 'host'3
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Tanner, Peter A.; Mak, Chris S.K.; Edelstein, Norman M.; Murdoch, Keith M.; Liu, Guokiu; Huang, Jin et al. Absorption and emission spectra of Ce{sup 3+} in elpasolite lattices, article, June 12, 2003; Berkeley, California. (https://digital.library.unt.edu/ark:/67531/metadc736930/m1/3/: accessed April 23, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; crediting UNT Libraries Government Documents Department.