Role of the local structure and the energy trap centers in the quenching of luminescence of the Tb3+ ions in fluoroborate glasses: a high pressure study.

The concentration and pressure dependent luminescence properties of the Tb(3+) ions in a lithium fluoroborate glasses have been studied by analyzing the deexcitation processes of the (5)D(4) level at ambient conditions as well as a function of pressure up to 35 GPa at room temperature. The luminescence spectra of Tb(3+) ions have been measured as a function of pressure and observed a continuous redshift as well as a progressive increase in the magnitude of the crystal-field splittings for the (5)D(4)-->(7)F(3,4,5) transitions. Monitoring the (5)D(4)-->(7)F(5) transition, the luminescence decay curves have been measured and analyzed in order to understand the dynamics of the deexcitation of the Tb(3+) ions in these glasses. At ambient conditions a nonexponential behavior has been found for doping concentrations as low as 0.1 mol % of Tb(4)O(7), although no cross-relaxation channels exist to explain this behavior. The modelization of the energy transfer processes surprisingly shows that the nonexponential character of the decay curves of the (5)D(4) level with concentration or with pressure has to be ascribed to energy transfer to traps without migration of energy between Tb(3+) ions. For all the experimental situations the nonexponential character of the decay curves is well described by the generalized Yokota-Tanimoto model with a dipole-dipole interaction between the Tb(3+) ions and the nearby luminescence quenching traps. The luminescence properties observed with releasing pressure are slightly different to those obtained while increasing pressure suggesting a local structural hysteresis in the lithium fluoroborate glass matrix giving rise to the generation of a new distribution of environments for the Tb(3+) ions.

Luminescence properties of Sm(3+)-doped P(2)O(5)-PbO-Nb(2)O(5) glass under high pressure.

Samarium doped lead phosphate glass modified with niobium having a composition (in mol%) of 55P(2)O(5)+39.5PbO+5Nb(2)O(5)+0.5Sm(2)O(3) has been prepared by the conventional melt quenching technique. The emission spectra and the decay curves for the (4)G(5/2) level of Sm(3+) ions have been measured as a function of pressure up to 23.6 GPa at room temperature. A discontinuity in the observed shifts and crystal-field splittings as a function of pressure around 9-10 GPa suggests that a phase transition is taking place in the glass matrix. The [Formula: see text], (6)H(7/2) and (6)H(9/2) transitions are shifted towards the lower energy side with magnitudes of -7.1, -7.6 and -5.5 cm(-1) GPa(-1) up to 8.9 GPa (phase 1) and -5.6, -4.9 and -4.4 cm(-1) GPa(-1) beyond 10.3 GPa (phase 2), respectively. A much stronger increase in the splitting of the [Formula: see text] and [Formula: see text] Stark levels with pressure is observed in phase 1 than in phase 2. The lifetime of the (4)G(5/2) level decreases from 2.29 ms (0 GPa) to 0.64 ms (23.6 GPa) with pressure. The decay curves of the (4)G(5/2) level exhibit non-exponential behavior for all the pressures and were fitted by the generalized Yokota-Tanimoto model to probe the nature of the energy transfer process. The best fits with S = 6 indicate that the energy transfer between donor and acceptor is of dipole-dipole type. The crystal-field splitting experienced by the Sm(3+) ions in the title glass are found to be larger than those found in borate, K-Ba-Al phosphate and tellurite glasses.

Photoluminescence from the (5)D(0) level of Eu(3+) ions in a phosphate glass under pressure.

The pressure dependence of the luminescence from [Formula: see text] transitions of Eu(3+) ions in 58.5P(2)O(5)-9Al(2)O(3)-14.5BaO-17K(2)O-1Eu(2)O(3) glass has been investigated up to 38.3 GPa at room temperature. The relative luminescence intensity ratio of [Formula: see text] to [Formula: see text] transitions of the Eu(3+) ions is found to decrease with increasing pressure, indicating a lowering of the asymmetry around the Eu(3+) ions with pressure. The [Formula: see text] transitions exhibit pressure-induced red shifts of different magnitude, which suggests a decrease in Slater parameters (F(k)) and in the spin-orbit coupling parameters (ζ) for the Eu(3+) ions. Stark components of the (7)F(1) level have been used to evaluate the crystal-field (CF) parameters B(20) and B(22), which are in turn used to estimate the CF strength experienced by the Eu(3+) ions in the glass. The observed increase in the CF strength parameter is found to have an almost cubic dependence on pressure. Luminescence decay curves for the [Formula: see text] transition are found to be single exponential over the entire pressure range studied. The lifetime did not change under pressure up to 5 GPa, although a significant change in the CF strength is noticed in this pressure range. The reduction of lifetime observed at pressures above 5 GPa could be partially due to an increase of pressure-induced defect centres. Such a process can then explain the hysteresis observed in the variation of lifetime and crystal-field strength on the release of pressure.