Optical properties and energy-transfer frequency upconversion of Yb 3+-sensitized Ho3+- And Tb3+-doped lead-cadmium-germanate glass and glass ceramic

In this report we investigate the optical properties and energy-transfer upconversion luminescence of Ho3+- and Tb3+/Yb 3+-codoped PbGeO3-PbF2-CdF2 glass-ceramic under infrared excitation. In Ho3+/Yb 3+-codoped sample, green(545 nm), red(652 nm), and near-infrared(754 nm) upconversion luminescence corresponding to the 4S 2(5F4) → 5I8, 5F5 → 5I8, and 4S2(5F4) → 5I 7, respectively, was readly observed. Blue(490 nm) signals assigned to the 5F2,3 → 5I8 transition was also detected. In the Tb3+/Yb3+ system, bright UV-visible emission around 384, 415, 438, 473-490, 545, 587, and 623 nm, identified as due to the 5D3(5G6) → 7FJ(J=6,5,4) and 5D4→ 7FJ(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 indicate 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.

BaMoO4:Tb3+ phosphor properties: Synthesis, characterization and photophysical studies

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Modifications induced by acetylacetone in properties of sol-gel derived Y3Al5O12:Tb3+ - I: Structural and morphological organizations

Acetylacetone has been used as a chemical modifier for the synthesis of undoped and Tb3+-doped Y3Al5O12 powders. A systematic investigation concerning its influence on the structural and morphological properties of amorphous and crystallized samples has been carried out. These properties have been comparatively studied by means of X-ray diffraction, infrared spectroscopy, SEM, XAS and SAXS. 27Al NMR and EPR experiments have been performed to complete the study. The combined results have evidenced that acetylacetone promotes organic groups departure during calcination, entailing a better structural organization at lower temperatures compared with unmodified powders. Structuration has been proven to occur at short-scale range until a 600°C heating treatment before being extended by coalescence at higher temperatures. Finally, the presence of acac ligands on the alkoxides leads to a monomer-cluster aggregation process, and thus to a more open network. © 2010 The Royal Society of Chemistry.

Synthesis, characterisation, luminescence and defect centres in solution combustion synthesised CaZrO3:Tb3+ phosphor

Tb3+ doped CaZrO3 has been prepared by an easy solution combustion synthesis method. The combustion derived powder was investigated by X-ray diffraction, Fourier-transform infrared spectrometry and scanning electron microscopy techniques. A room temperature photoluminescence study showed that the phosphors can be efficiently excited by 251 nm light with a weak emission in the blue and orange region and a strong emission in green light region. CaZrO3:Tb3+ exhibits three thermoluminescence (TL) glow peaks at 126 degrees C, 200 degrees C and 480 degrees C. Electron Spin Resonance (ESR) studies were carried out to study the defect centres induced in the phosphor by gamma irradiation and also to identify the centres responsible for the TL peaks. The room temperature ESR spectrum of irradiated phosphor appears to be a superposition of two distinct centres. One of the centres (centre I) with principal g-value 2.0233 is identified as an O- ion. Centre II with an axial symmetric g-tensor with principal values g(parallel to) = 1.9986 and g(perpendicular to) = 2.0023 is assigned to an F+ centre (singly ionised oxygen vacancy). An additional defect centre is observed during thermal annealing experiments and this centre (assigned to F+ centre) seems to originate from an F centre (oxygen vacancy with two electrons). The F centre and also the F+ centre appear to correlate with the observed high temperature TL peak in CaZrO3:Tb3+ phosphor. (c) 2012 Elsevier B.V. All rights reserved.

Nanocomposites materials generated from a spray

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Enhanced luminescence of Tb3+/Eu3+ doped tellurium oxide glass containing silver nanostructures

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Persistent luminescence behavior of materials doped with Eu2+ and Tb3+

In this work, the persistent luminescence mechanisms of Tb3+ (in CdSiO3) and Eu2+ (in BaAl2O4) based on solid experimental data are compared. The photoluminescence spectroscopy shows the different nature of the inter- and intraconfigurational transitions for Eu2+ and Tb3+, respectively. The electron is the charge carrier in both mechanisms, implying the presence of electron acceptor defects. The preliminary structural analysis shows a free space in CdSiO3 able to accommodate interstitial oxide ions needed by charge compensation during the initial preparation. The subsequent annealing removes this oxide leaving behind an electron trap. Despite the low band gap energy for CdSiO3, determined with synchrotron radiation UV-VUV excitation spectroscopy of Tb3+, the persistent luminescence from Tb3+ is observed only with UV irradiation. The need of high excitation energy is due to the position of F-7(6) level deep below the bottom of the conduction band, as determined with the 4f(8)-> 4f(7)5d(1) and the ligand-to-metal charge-transfer transitions. Finally, the persistent luminescence mechanisms are constructed and, despite the differences, the mechanisms for Tb3+ and Eu2+ proved to be rather similar. This similarity confirms the solidity of the interpretation of experimental data for the Eu2+ doped persistent luminescence materials and encourages the use of similar models for other persistent luminescence materials. (C) 2012 Optical Society of America

Down-conversion process in Tb3+-Yb3+ co-doped Calibo glasses

The down-conversion process in Tb3+-Yb3+ co-doped Calibo glasses was studied. The emission, excitation and time-resolved measurements indicated the existence of an energy conversion through the excitation of Tb3+ ions to near-infrared emission by Yb3+ ions. The emission intensity dependence on excitation power confirms that the one-photon process is responsible for the Yb3+ emission. An enhanced Yb3+ emission was observed with Yb3+ doping and an optimal energy transfer efficiency of 32% was obtained before reaching near-infrared emission quenching. The mechanism of the non-resonant energy transfer from Tb3+ to Yb3+ is discussed in terms of the Tb3+-Yb3+ cross-relaxation and multiphonon decay processes. (C) 2012 Elsevier B.V. All rights reserved.

Enhanced luminescence of Tb(3+)/Eu(3+) doped tellurium oxide glass containing silver nanostructures

We report on energy transfer studies in terbium (Tb(3+))-europium (Eu(3+)) doped TeO(2)-ZnO-Na(2)O-PbO glass containing silver nanostructures. The samples excitation was made using ultraviolet radiation at 355 nm. Luminescence spectra were recorded from approximate to 480 to approximate to 700 nm. Enhanced Eu(3+) luminescence at approximate to 590 nm (transition (5)D(0)-(7)F(1)) and approximate to 614 nm (transition (5)D(0)-(7)F(2)) are observed. The large luminescence enhancement was obtained due to the simultaneous contribution of the Tb(3+)-Eu(3+) energy transfer and the contribution of the intensified local field on the Eu(3+) ions located near silver nanostructures.

Effects of gamma radiation on the photoluminescence properties of polycarbonate matrices doped with terbium complex

Luminescent films containing terbium complex [Tb(acac)(3)(H(2)O)(3)] (acac = acetylacetonate) doped into a polycarbonate (PC) matrix were prepared and irradiated at low-dose gamma radiation with ratio of 5 and 10 kGy. The PC polymer was doped with 5% (w/w) of the Tb(3+) complex. The thermal behavior was investigated by utilization of differential scanning calorimetry (DSC) and thermogravimetry analysis (TGA). Changes in thermal stability due to the addition of doping agent into the polycarbonate matrix. Based on the emission spectra of PC:5% Tb(acac)(3) film were observed the characteristic bands arising from the (5)D(4) -> (7)F(J) transitions of Tb(3+) ion (J = 0-6), indicating the ability to obtain the luminescent films. Doped samples irradiated at low dose of gamma irradiation showed a decrease in luminescence intensity with increasing of the dose. (C) 2009 Elsevier Ltd. All rights reserved.

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.

Thermally enhanced cooperative energy-transfer frequency upconversion in terbium and ytterbium doped tellurite glass

Infrared-to-visible frequency upconversion through cooperative energy-transfer and thermal effects in Tb3+/Yb3+-codoped tellurite glasses excited at 1.064 mum is investigated. Bright luminescence emission around 485, 550, 590, 625 and 65 nm, identified as due to the D-5(4) --> F-7(J) (J= 6, 5, 4, 3, and 2) transitions of the terbium ions, respectively, was recorded. The excitation of the D-5(4) emitting level of the Tb3+ ions is assigned to cooperative energy-transfer from pairs of ytterbium ions.. The effect of temperature on the upconversion process was examined and the results revealed a fourfold upconversion enhancement in the 300-500 K interval. The enhancement of the upconversion process is due to the temperature dependence of the Yb3+-sensitizer absorption cross-section under anti-Stokes excitation. A rate-equation. model using multiphonon-assisted absorption for the ytterbium excitation combined with the energy migration effect between Yb-Yb pair, and Tb3+ ground-state depopulation via multiphonon excitation of the F-7(J) excited states describes quite well the experimental results. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Low voltage electroluminescence of terbium- and thulium-doped zinc oxide films

Strong interest in developing technology for visual information. stimulates research for thin film electroluminescent devices. Here, for the first time, we report that thulium- and terbium-doped zinc-oxide films are suitable for electroluminescence applications. Two different devices were assembled as lTO/LiF/ZnO:RE/LiF/Al or ITO/SiO2/ZnO:RE/SiO2/Al, where ZnO:RE is a film of zinc oxide containing 10 at% of Tb3+ or Tm3+. Electroluminescence spectra show that besides a broad emission band with maximum around 650 nm assigned to ZnO, also emission lines from Tb3+ at 484 nm (D-5(4) -> F-7(6)), 543 nm (D-5(4) -> F-7(6)), and 589 nm (D-5(4) -> F-7(4)), or from Tm3+ at 478 nm ((1)G(4) -> H-3(6)), and 511 mn (D-1(2) -> H-3(5)) were detected. Intensity of emission as function of applied voltage and current-voltage characteristic are shown and discussed. (c) 2005 Elsevier B.V. All rights reserved.

Frequency upconversion in rare-earth doped fluoroindate glasses

We present recent results on frequency upconversion (UPC) obtained in fluoroindate glasses (FIG) doped with Ho3+, Tm3+ and Nd3+ ions and codoped with Pr3+/Nd3+ and Yb3+/Tb3+ ions. The results for the Ho3+-doped samples show strong evidence of energy transfer (ET) between Ho3+ ions resonantly excited at 640 nm. The origin of the blue-green upconverted fluorescence observed was identified and the dynamics of the signals revealed the pathways involved in the UPC process. In the case of Tm3+-doped FIG, the samples were resonantly excited at 650 nm and the main mechanism that contributes for the red-to-blue upconversion is excited-state absorption (ESA). The FIG samples codoped with Pr3+/Nd3+ were excited at 588 nm in resonance with transitions starting from the ground state of the Nd 3+ and the Pr3+ ions. It was observed that the presence of Nd3+ ions enhanced the Pr3+ emission at 480 nm by two orders of magnitude. Multiphonon (MP)-assisted upconversion is also discussed for Nd3+-doped FIG pumped at 866 nm. Emission at 750 nm with a peculiar linear dependence with the laser intensity was observed and explained. A rate-equation model that includes MP absorption via thermally coupled electronic excited states of Nd3+ was developed and describes well the experimental results. The role played by effective phonon modes is clearly demonstrated. MP-assisted UPC process was also studied in Yb3+/ Tb3+-codoped FIG samples excited at 1064 nm, which is off-resonance with electronic transitions starting from the ground state. It was determined that the mechanism leading to Tb3+ emission in the blue is due to ET from a pair of excited Yb3+ ions followed by ESA in the Tb 3+ ions. © 2002 Académie des sciences/Éditions scientifiques et médicales Elsevier SAS.

Effects in the population inversion of3H4 level in Tm, Tm-Tb and Tm-Eu doped germanate glasses for amplifiers applications

The population inversion of the Tm3+ in GLKZ glass involved in the 1470 nm emission (3H4 → 3F 4) as a function of Tb (or Eu) concentration was calculated by computational simulation for a CW laser pumping at 792 nm. These calculations were performed using the experimental Tm→Tb an Tm→Eu transfer rates and the spectroscopic parameters of the Tm (0.1 mol %) system. The result shows that 0.2 mol % (Tb3+) and 0.4 mol % of Eu3+ ions propitiate best population inversion of Tm3+ (0.1 mol %) maximizing the amplification coefficient of germanate (GLKZ) glass when operating as laser intensity amplification at 1470 nm. Besides the effective deactivation of the 3F4 level, the presence of Tb3+ or Eu 3+ ions introduce a depopulation of the 3H4 emitting level by means of a cross relaxation process with Tm3+ ions. In spite of this, the whole effect is verified to be benefic for using Tm-doped GLKZ glass codoped with Tb3+ or Eu3+ as a suitable material for confectioning optical amplifiers that operates in the S-band for telecommunication.