H. Ebendorffheidepriem et al., EFFECT OF GLASS COMPOSITION ON JUDD-OFELT PARAMETERS AND RADIATIVE DECAY-RATES OF ER3-GLASSES( FLUORIDE PHOSPHATE AND PHOSPHATE), Journal of non-crystalline solids, 240(1-3), 1998, pp. 66-78
For fluoride phosphate and phosphate glasses, Judd-Ofelt Ohm(t) parame
ters, spontaneous emission probabilities, radiative lifetimes and bran
ching ratios of several Er3+ transitions were determined from the abso
rption spectra by the Judd-Ofelt treatment. The compositional changes
of Ohm(2) and Ohm(6) are attributed to changes in the bonding between
Er3+ and surrounding ligand groups. The phosphate groups play a specia
l role. They show electron donation from the 2p orbitals of the oxygen
ions, as well pi-electron donation from the resonating P-O pi-bond. L
arger electron donation from the ligand anions leads to larger Ohm(2),
but smaller Ohm(6). By contrast, larger pi-electron donation from the
phosphate groups increases Ohm(6). The changes of Ohm(2) with increas
ing phosphate content and with variation of modifier ions are ascribed
to changes in the content and polarizability of the oxygen ions, lead
ing to changes in the electron donation from the ligands at the rare e
arth (RE) sites. In the case of Pb2+, changes in the degree of asymmet
ry at the RE sites could also be important. The smaller Ohm(6) paramet
er of phosphate glasses compared with fluoride phosphate grasses is ca
used by larger sigma-electron donation due to larger oxygen content an
d by smaller pi-electron donation due to smaller delocalization of the
pi-bonds. The changes of Ohm(6) with phosphate content, in the case o
f fluoride phosphate glasses and with variation of modifier ions, are
dominated by changes in the pi-electron donation. (C) 1998 Elsevier Sc
ience B.V. All rights reserved.