Upconversion luminescence of TM3+/Yb3+ codoped oxyfluoride glasses

Novel oxyfluoride glasses are developed with the composition of 30SiO(2)-15Al(2)O(3)-28PbF(2)-22CdF(2)-0.1TmF(3)-xYbF(3) -(4.9-x) AlF3(x = 0, 0.5, 1.0, 1.5, 2.0) in mol fraction. Furthermore, the upconversion luminescence characteristics under a 970nm excitation are investigated. Intense blue, red and bear infrared luminescences peaked at 453nm, 476nm, 647nm and 789nm, which correspond to the transitions of Tm3+: D-1(2) -> F-3(4), (1)G(4) -> H-3(6), (1)G(4) -> F-3(4), and H-3(4) -> H-3(6), respectively, are observed. Due to the sensitization of Yb3+ ions, all the upconversion luminescence intensities are enhanced considerably with Yb3+ concentration increasing. The upconversion mechanisms are discussed based on the energy matching rule and quadratic dependence on excitation power. The results indicate that the dominant mechanism is the excited state absorption for those upconversion emissions.

Local order around rare earth ions during the devitrification of oxyfluoride glasses

Erbium L-3-edge extended x-ray absorption fine structure (EXAFS) measurements were performed on rare earth doped fluorosilicate and fluoroborate glasses and glass ceramics. The well known nucleating effects of erbium ions for the crystallization of cubic lead fluoride (based on x-ray diffraction measurements) and the fact that the rare earth ions are present in the crystalline phase (as indicated by Er3+ emission spectra) seem in contradiction with the present EXAFS analysis, which indicates a lack of medium range structural ordering around the Er3+ ions and suggests that the lead fluoride crystallization does not occur in the nearest neighbor distance of the rare earth ion. Molecular dynamics simulations of the devitrification process of a lead fluoride glass doped with Er3+ ions were performed, and results indicate that Er3+ ions lower the devitrification temperature of PbF2, in good agreement with the experimental results. The genuine role of Er3+ ions in the devitrification process of PbF2 has been investigated. Although Er3+ ions could indeed act as seeds for crystallization, as experiments suggest, molecular dynamics simulation results corroborate the experimental EXAFS observation that the devitrification does not occur at its nearest neighbor distance. (c) 2008 American Institute of Physics.

Lead-cadmium oxyfluoride glasses and glass-ceramics

Glasses and glass-ceramics have been obtained in oxyfluoride systems involving lead and cadmium fluorides and one of the well-known glass former oxides SiO2, B2O3 and TeO2. Vitreous domains were established and a wide range of compositions including high heavy metal contents lead to stable glasses. Amorphous structures have been studied by short-range order spectroscopy techniques (Raman scattering and x-ray absorption) and molecular basic structures have been identified. Besides the usual oxides, the role of glass former could also be proposed for cadmium ions. Special attention has been paid for crystallization process. Cubic lead fluoride, cubic lead tellurite, tetragonal tellurium oxide and a solid solution of the type Pb1-xCdxF2 are obtained as crystallization products depending on the composition and temperature of heat treatments. Pb1-xCdxF2 solid solutions are well known superionic materials and obtaining this solid solution as a crystal phase could be very interesting for applications concerning ionic electrical conduction properties. The addition of rare earth ions led to the control of the crystallization process. In the presence of the nucleating ion only the cubic form beta-PbF2 was identified. Rare earth ions are present in the crystal phase and crystal-like spectroscopic properties were observed suggesting interesting applications for these perfectly transparent glass ceramics in photonics.

Study of fluorine losses in oxyfluoride glasses

Glasses in PbGeO3-PbF-CdF2 and GeO2-PbO-PbF2-CdF2 systems were studied and the fluorine losses during synthesis were investigated. Samples were characterized by differential scanning calorimetry (DSC), X-ray diffraction, Fourier transform infrared spectroscopy (FTIR) and Raman scattering spectroscopy. The use of stoichiometric germanate glass, PbGeO3, instead of introducing individual oxides (GeO2 + PbO) lead to decreasing fluorine losses, as detected by a fluorine ion selective electrode. The main structural features obtained from vibrational spectroscopy could be described by a metagermanate basic structure permeating fluorine rich regions. (c) 2005 Elsevier B.V. All rights reserved.

Structural and spectroscopic study of oxyfluoride glasses and glass-ceramics using europium ion as a structural probe

Transparent oxyfluoride glasses and beta-PbF(2) nanocrystals containing glass-ceramics were prepared with varying Eu(3+) content (0.3, 0.4, 0.5 and 0.6%). The effect of Eu(3+) content on the preparation of glass-ceramics was investigated. From differential scanning calorimetry, the T(x)-T(g)(T(x)-temperature of the onset of crystallization; T(g)-glass transition temperature) parameter for glasses has shown slight variation, and an exothermic peak near T(g) called the ceramization temperature (T(c)) has been observed. Heat treatments were performed at this temperature to obtain transparent glass-ceramics containing beta-PbF(2) nanocrystals, identified by x-ray diffraction. Heat treatments for different periods of time were performed and were observed to be very important in the control of the crystal size and of the crystallization rate. Based upon the absorption spectra, the scattering level due to the presence of beta-PbF(2) nanocrystals in the glass-ceramics was observed to be similar to that for the mother glasses. Detailed analysis of emission spectra and decay time measurements led to the identification of Eu(3+) ions as the beta-PbF(2) crystalline phase. Excitation spectra at 70 K show the interaction of Eu(3+) ions with the fluorogermanate network.

Femtosecond laser writing of buried waveguides in erbium III-Doped oxyfluoride glasses and nano-glass-ceramics

Femtosecond-pulsed laser writing of waveguides, a few mm long, is demonstrated; waveguides were written orthogonally to the writing beam inside the bulk of ErIII-doped oxyfluoride glasses at a depth of 160 mum. The writing beam was 795 nm wavelength, 54 fs pulse duration and 11 MHz repetition rate. Tracks were written at pulse energies of 13.1 nJ to 26.1 nJ and sample translational velocity of 10 mmmiddot.s-1 to 28 mmmiddots-1. The influence of translational velocity and pulse energy on the cross-sectional shape and integrity of the written tracks is reported. Tracks tend to be narrower as the pulse energy is lowered or translational velocity decreased. Above 22.9 nJ, pulse energy, tracks tend to crack. The estimated refractive index profile of one track has a maximum increase of refractive index of 0.003 at the centre. These glasses normally form nano-glass-ceramics on heat treatment just above the glass transformation temperature (Tg). Here, a post-fs-writing heat-treatment just above Tg causes nano-ceramming of the glass sample and removes a light-guiding peripheral region of the fs-written tracks suggesting that this region may have been fs-modified by stress alone. Waveguiding at 651 nm and 973 nm wavelengths, and upconversion, are demonstrated in optimally written tracks.

Femtosecond laser writing of buried waveguides in erbium III-Doped oxyfluoride glasses and nano-glass-ceramics

Femtosecond-pulsed laser writing of waveguides, a few mm long, is demonstrated; waveguides were written orthogonally to the writing beam inside the bulk of ErIII-doped oxyfluoride glasses at a depth of 160 mum. The writing beam was 795 nm wavelength, 54 fs pulse duration and 11 MHz repetition rate. Tracks were written at pulse energies of 13.1 nJ to 26.1 nJ and sample translational velocity of 10 mmmiddot.s-1 to 28 mmmiddots-1. The influence of translational velocity and pulse energy on the cross-sectional shape and integrity of the written tracks is reported. Tracks tend to be narrower as the pulse energy is lowered or translational velocity decreased. Above 22.9 nJ, pulse energy, tracks tend to crack. The estimated refractive index profile of one track has a maximum increase of refractive index of 0.003 at the centre. These glasses normally form nano-glass-ceramics on heat treatment just above the glass transformation temperature (Tg). Here, a post-fs-writing heat-treatment just above Tg causes nano-ceramming of the glass sample and removes a light-guiding peripheral region of the fs-written tracks suggesting that this region may have been fs-modified by stress alone. Waveguiding at 651 nm and 973 nm wavelengths, and upconversion, are demonstrated in optimally written tracks.

Electron spin resonance studies of d5 ions (Fe3+ and Mn2+) in lead oxide-lead halide glasses

Electron spin resonance (ESR) of d5 ions (Fe3+ and Mn2+) has been investigated in PbO---PbF2 and PbO---PbCl2 glasses in wide ranges of composition. ESR spectra of d5 ions in these glasses exhibit significant differences which we have attributed to at least three important causes: (i) The ionic potentials of Fe3+ and Mn2+ are different. Hence Fe3+ ions tend to acquire their own environment while Mn2+ ions take up substitutional (Pb2+ ion) positions. (ii) The sizes and nephelauxetic behaviours of O2- and F- ions are similar. Thus even when there is a mixed anionic coordination, the environment of Mn2+ ions is highly symmetrical in oxyfluoride glasses. The Mn2+ spectra in oxychloride glasses are considerably different. (iii) Increase in halide ion concentration increases the ionicity of lead-ligand bonding and favours a more symmetrical environment around dopant ions in halide-rich glasses. The features in ESR spectra have been interpreted in the light of known behaviour of d5 ions in glasses and also in the context of known structural features of PbO---PbX2 glasses. Dopant ions appear to cluster at high concentrations although isolated low-symmetry sites are still observed. Effects of crystallization and annealing upon ESR spectra have also been investigated.

Conductivity and F-19 NMR in PbGeO3-PbF2-CdF2 glasses and glass-ceramics

The temperature dependence of the electrical conductivity and the F-19 nuclear magnetic resonance (NMR) of PbGeO3-PbF2CdF, glasses and glass ceramics are investigated. The measured conductivity values of the glasses are above 10(-5) Skin at 500 K, and increase with increasing lead fluoride content. Activation energies extracted from the conductivity data are in the range 0.59-0.73 eV. Results are consistent with the hypothesis that in these oxyfluoride glasses lead fluoride rich clusters are dispersed in a metagermanate based matrix providing increasing mobility pathways for conducting ions. The conductivity of a sample of the glass ceramic of composition (mol%) 60PbGeO(3-)20PbF(2)-20CdF(2) was found to be smaller than that in the corresponding glass, suggesting that there are poor ionic conducting regions in the interface between the nanometer sized crystals. The temperature dependence of the F-19 relaxation times, measured in the range 100-800 K, exhibit the qualitative features associated with high fluorine mobility in both, glass and glass ceramics materials. We suggest that de-convolution of the spin-lattice relaxation rates observed in the glass ceramics shows that the observed high temperature rate maximum is associated with the diffusional motions of the fluorine ions in beta-PbF2 crystals. (c) 2005 Elsevier B.V. All rights reserved.

Lead-cadmium fluorogermanate glasses and transparent glassceramics. Spectroscopy and structure

In Lead-cadmium fluorogermanate glasses (PbF2-CdF 2-PbGeO3) the addition of metal fluorides to the base PbGeO3 glass leads to a decrease of the glass transition temperature (Tg) and to an enhancement of the ionic conductivity properties. Based on different spectroscopic techniques (19F NMR, Ge K-edge X-ryas absorption and Raman scattering) an heterogeneous glass structure is proposed at the molecular scale, which can be described by fluoride rich regions permeating the metagermanate chains. The temperature dependence of the 19F NMR lineshapes and relaxation times exhibits the qualitative and quantitative features associated with the high fluoride mobility in these systems. Eu 3+ emission and vibronic spectra are used to follow the crystallization process leading to transparent glass ceramics.

970nm抽运下Tm^3／Yb^3＋共掺氧氟玻璃的频率上转换发光

稀土离子掺杂的氧氟玻璃是一种新型上转换发光材料。制备了Tm^3／Yb^3＋单掺、共掺的摩尔分数为n（SiO2）-0．30，n（PbF2）-0．50，n=（Al2O3）=0．15，n（AlF3）=（0．049-x），n（TmF3）=y，n（YbF3）=x（x=0，0．001，0．010，0．015，0．020，y=0，0．001）系统氧氟玻璃，研究了其上转换发光特性、分析了其上转换发光机理。研究发现，在970nm抽运光源激发下，Tm^3＋单掺时没有可见光上转换发射；而加入Yb^3＋后产生了强的蓝光（452n

新型氧氟化物玻璃的化学稳定性

对新型含碲氧氟化物玻璃在中性、碱性、酸性条件下的化学稳定性进行了研究。实验表明：水的侵蚀使玻璃表面形成碱性沉淀物．阻碍了侵蚀反应进一步发生，使在抗水实验中，质量损失并不随碲含量的增加而增加。对碱侵蚀后的样品用盐酸漂洗的实验显示，随氧化碲含量增加，玻璃化学稳定性变差；经碱腐蚀后，玻璃表面雾化，可见透过率明显减低。碱中浸泡后未用酸漂洗的样品在3100nm附近出现明显的水吸收峰；盐酸处理后，羟基吸收峰消失，但整体的中红外透过率下降。玻璃在酸性条件下侵蚀相同时间的质量损失是碱中的7倍．但由于是均匀腐蚀，侵蚀前后玻

透红外大尺寸氧氟化物玻璃研究

锗酸盐和氟铝酸盐透红外玻璃材料作为窗口或头罩材料具有广泛的应用前景。结合锗酸盐玻璃含有少量水的问题，在成分中引入氟化物，实验表明：随氟化物含量增加．玻璃中羟基含量逐渐降低。同时通过对熔制温度的调整，获得了不合羟基的红外玻璃。针对氟铝酸盐玻璃在冷却过程中易析晶的问题，在氟化物组分中加入少量重金属氧化物TeO2，得到析晶性能好的氧氟铝酸盐玻璃。同时给出了两类红外材料的一些物理、化学性质。

Host dependent frequency upconversion of Yb3+/Tm3+-codoped oxyfluoride tellurite glasses

The upconversion luminescence properties of Yb3+/Tm3+-codoped oxyfluoride tellurite glasses under 980 nm excitation are investigated experimentally. The intense blue and relatively weak red emissions centered at 475 and 649 nm corresponding to the transitions (1)G(4) -> H-3(6) and (1)G(4) -> H-3(4) of Tm3+, respectively, are simultaneously observed at room temperature. The effect of PbF2 on upconversion intensity is observed and discussed, and possible upconversion mechanisms are evaluated. The intense blue upconversion luminescence of Yb3+/Tm3+-codoped oxyfluoride tellurite glasses may be a potentially useful material for developing blue upconversion optical devices. (c) 2005 Elsevier B.V. All rights reserved.

Host dependent thermal stability and frequency upconversion of Er3+-doped heavy metal oxyfluoride germanate glasses

The upconversion properties of Er3+-doped heavy metal oxyfluoride germanate glasses under 975 nm excitation have been investigated. The intense green (551 and 529 nm) and relatively weak red (657 nm) emissions corresponding to the transitions S-4(3/2) -> I-4(15/2), H-2(11/2) -> I-4(15/2) and F-4(9/2) -> I-4(15/2), respectively, were simultaneously observed at room temperature. The content of PbF2 has an important influence on the upconversion luminescence emission. With increasing content of PbF2, the intensities of green (529 nm) and red (657 nm) emissions increase slightly, while the green emission (551 nm) increases markedly. These results suggest that PbF2 has an influence on the green (551 nm) emission more than on the green (529 nm) and red (657 nm) emissions.