Excitation mechanisms and effects of dopant concentration in Gd2O2S : Tb3+ phosphor

Gadolinium oxysulfide powders doped with different Tb3+ concentrations were prepared from sulfur vaporization on rare earths' basic carbonate precursors. Single-phase Gd2O2S samples were obtained, with Tb3+ doping up to 9 at%. The study of the excitation mechanisms revealed that the Tb3+ emission might occur after the direct Tb3+ excitation either by energy transfer from Gd3+ or from the phosphor host. The characteristic terbium emission lines were observed, resulting from the radiative decay from D-5(3) or D-5(4), to F-7(j) levels. The cross-relaxation phenomenon was observed and its effects on the materials emission color were discussed based on the CIE diagram. By using time-resolved spectroscopy, D-5(3) -> F-7(J) and D-5(4) -> F-7(J) transitions were separated. (c) 2007 Elsevier B.V. All rights reserved.

Upconversion luminescence in Er3+ doped and Er3+/Yb3+ codoped zirconia and hafnia nanocrystals excited at 980 nm

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Time dependence and energy-transfer mechanisms in Tm3+Ho3+ and Tm3+-Ho3+ co-doped alkali niobium tellurite glasses sensitized by Yb3+

Glass samples with the composition (mol%) 80TeO(2)-10Nb(2)O(5)-5K(2)O-5Li(2)O, stable against crystallization, were prepared containing Yb3+, Tm3+ and Ho3+. The energy transfer and energy back transfer mechanisms in samples containing 5% Yb3+-5% Tm3+ and 5% Yb3+-5% Tm3+-0.5% Ho3+ were estimated by measuring the absorption and fluorescence spectra together with the time dependence of the Yb3+ F-2(5/2) excited state. A good fit for the luminescence time evolution was obtained with the Yokota-Tanimoto's diffusion-limited model. The up-conversion fluorescence was also studied in 5% Yb-5% Tm. 5% Yb-0.5% Ho and 5% Yb-5% Tm-0.5% Ho tellurite glasses under laser excitation at 975 nm. Strong emission was observed from (1)G(4) and F-3(2) Tm3+ energy levels in all samples. The S-5(2) Ho3+ emission was observed only in Yb3+Ho3+ samples being completely quenched in Yb3+/Tm3+/Tm3+ samples. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Structure and luminescence of Eu3+-doped class I siloxane-poly(ethylene glycol) hybrids

Transparent, flexible, and luminescent EU3+-doped siloxane-poly(ethylene glycol) (PEG) nanocomposites have been obtained by the sol-gel process. The inorganic (siloxane) and organic PEG phases are usually linked by weak bonds (hydrogen bonds or van der Waals forces), and small-angle X-ray scattering (SAXS) measurements suggest that the structure of these materials consists of fractal siloxane aggregates embedded in the PEG matrix. For low Eu3+ contents, n = 300 and n = 80, the aggregates are small and isolated and their fractal dimensions are 2.1 and 1.7, respectively. These values are close to those expected for gelation mechanisms consisting of reaction-limited cluster-cluster aggregation (RLCCA) and diffusion-limited cluster-cluster aggregation (DLCCA). For high Eu3+ content, SAYS results are consistent with a two-level structure: a primary level of siloxane aggregates and a second level, much larger, formed by the coalescence of the primary ones. The observed increase in the glass transition temperature for increasing Eu3+ content is consistent with the structural model derived from SAXS measurements. Extended X-ray absorption fine structure (EXAFS) and luminescence spectroscopy measurements indicate that under the experimental conditions utilized here Eu3+ ions do not strongly interact with the polymeric phase.

Upconversion luminescence and thermal effects in terbium-ytterbium codoped fluorogermanate glass-ceramic

Cooperative energy transfer upconversion luminescence is investigated in Tb(3+)/Yb(3+)-codoped PbGeO(3)-PbF(2)-CdF(2) glass-ceramic and its precursor glass under resonant and off resonance infrared excitation. Bright UV-visible emission signals around 384, 415, 438 nm, and 473-490, 545, 587, and 623 nm are identified as due to the (5)D(3)((5)G(6))->(7)F(1) (J=6,5,4) and (5)D(4)->(7)F(1) (J=6,5,4,3) transitions, respectively, and readily observed. The results indicate that cooperative energy transfer between ytterbium and terbium. ions followed by excited state absorption are the dominant upconversion excitation mechanisms involved. Comparison of the upconversion process in a glass-ceramic sample and its glassy precursor revealed that the former present much higher upconversion efficiency. The dependence of the upconversion emission upon pump power, temperature, and doping content is also examined.

Upconversion luminescence in Ho3+/Yb3+- and Tb3+/Yb3+-codoped fluorogermanate glass and glass ceramic

Energy-transfer excited upconversion luminescence in Ho3+/Yb3+- and Tb3+/Yb3+ -codoped PbGeO3-PbF2-CdF2 glass and glass-ceramic under infrared excitation is investigated. In Ho3+/Yb3+-codoped samples, green (545 nm), red (652 nm), and near-infrared (754 nm) upconversion emission corresponding to the S-5(2) (F-5(4)) -> I-5(8), F-5(5) -> I-5(8), and S-5(2)(F-5(4)) -> I-5(7) transitions, respectively, was observed. Blue (490 nm) emission assigned to the F-5(2,3) -> I-5(8) transition was also detected. In the Tb3+/Yb3+-codoped system, bright UV-visible emission around 384, 415, 438, 473-490, 545, 587, and 623 nm, identified as due to the D-5(3)((5)G(6)) -> F-7(J)(J = 6, 5, 4) and D-5(4) -> F-7(J)(J = 6, 5, 4, 3) transitions, was measured. The comparison of the upconversion process in glass ceramic and its glassy precursor revealed that the former samples present much higher upconversion efficiencies. The dependence of the upconversion emission upon pump power, and doping contents was also examined. The results indicated that successive energy-transfer between ytterbium and holmium ions and cooperative energy-transfer between ytterbium and terbium ions followed by excited-state absorption are the dominant upconversion excitation mechanisms herein involved. The viability of using the samples for three-dimensional solid-state color displays is also discussed. (c) 2007 Elsevier B.V. All rights reserved.

Effect of the ytterbium concentration on the upconversion luminescence of Yb3+/Er3+ co-doped PbO-GeO2-Ga2O3 glasses

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Spectroscopic properties and upconversion mechanisms in Er3+-doped fluoroindate glasses

Fluorindate glasses containing 1,2,3,4 ErF3 mol % were prepared in a dry box under argon atmosphere. Absorption, Stokes luminescence (under visible and infrared excitation), the dependence of 4S3/2, 4I11/2, and 4I13/2 lifetimes with Er concentration, and upconversion under Ti-saphire laser excitation at λ=790 nm were measured, mostly at T=77 and 300 K. The upconversion results in a strong green emission and weaker blue and red emissions whose intensity obeys a power-law behavior I∼Pn, where P is the infrared excitation power and n=1.6, 2.1, and 2.9 for the red, green, and blue emissions, respectively. The red emission exponent n=1.5 can be explained by a cross relaxation process. The green and blue emissions are due to excited state absorption (ESA) and energy transfer (ET) processes that predict a factor n=2 and n=3 for the green and blue emissions, respectively. From transient measurements we concluded that for lightly doped samples the green upconverted emission is originated due to both processes ESA and ET. However, for heavily doped samples ET is the dominant process.

Efficient UV-visible upconversion luminescence and thermal effects in terbium-ytterbium codoped fluorogermanate vitroceramic

Cooperative energy-transfer upconversion luminescence in Tb 3+/Yb 3+-codoped PbGeO 3-PbF 2-CdF 2 vitroceramic and its precursor glass under resonant and off-resonance infrared excitation, is investigated. Bright UV-visible emission signals around 384, 415, 438 nm, and 473-490, 545, 587, and 623 nm, identified as due to the 5D 3( 5G 6 → 7F J(J=6,5,4) and 5D 4 → 7F J(J=6,5,4,3) transitions, respectively, were readily observed. The results indicate that cooperative energy-transfer between ytterbium and terbium ions followed by excited-state absorption are the dominant upconversion excitation mechanisms herein involved. The comparison of the upconversion process in a vitroceramic sample and its glassy precursor revealed that the former present much higher upconversion efficiency. The dependence of the upconversion emission upon pump power, temperature, and doping content is also examined.