New transparent Er3+-doped oxyfluoride tellurite glass ceramic with improved near infrared and up-conversion fluorescence properties

Transparent glass ceramics have been obtained by nucleation and growth of Y2Te6O15 or Er2Te5O13 cubic phase in a new Er3+-doped oxyfluoride tellurite glass. Effect of beat treatment on absorption spectra, luminescence and up-conversion properties in the oxyfluoride tellurite glass has been investigated. With heat treatment the ultraviolet absorption edge red shifted evidently for the oxyfluoride telluride glass. The near infrared emission that corresponds to Er3+:I-4(13/2)-> I-4(15/2) can be significantly enhanced after heat treatment. Under 980 nm LD pumping, red and green up-conversion intensity of Er3+ in the glass ceramic can be observed much stronger than that in the base glass. (C) 2006 Elsevier B.V. All rights reserved.

Stability against crystallization and spectroscopic properties of Tm3+ doped fluorophosphate glasses

Fluorophosphate glasses with various content of Al(PO3)(3) were prepared. With the increment of Al(PO3)(3) content, density decreases while refractive index increases, and transition temperature, crystallization peak temperature and melt temperature increase which were suggested by differential scanning calorimetry. These glasses exhibit the best stability against crystallization with 7-9 mol'Yo Al(PO3)(3) content. Normalized Raman spectra were used to analyze structure and phonon state. The increment of Al(PO3)(3) content does not affect phonon energy but results in the augment of phonon density. Absorption spectra were measured. H-3(6) -> F-3(4) transition exhibits absorption at L band of the third communication window. Compared with the energy of Tm3+ excited states in other glass system, F-3(4) energy of Tm3+ in these glasses is considerable higher and H-3(4) energy is considerable lower, and it can be predicted that emission band of H-3(4) -> F-3(4) transition is close to the amplified band of gain-shift Tm3+ doped fiber amplifier. Analyses of Judd-Ofelt theory suggest when Al(PO3)(3) content is no more than 7 mol%, Judd-Ofelt parameters Omega(t) and the lifetime of H-3(4) energy level of TM3+ vary little with the increment of Al(PO3)(3) content, and when Al(PO3)(3) content is more than 7 mol%, Omega(2) and Omega(6) increase and radiative lifetime of H-3(4) energy level of Tm3+ drops sharply with the increment of Al(PO3)(3) content. (c) 2006 Elsevier B.V. All rights reserved.

Effect of bismuth oxide on the thermal stability and Judd-Ofelt parameters of Er 3(+)/Yb3(+) co-doped aluminophosphate glasses

The Er3+/Yb3+ co-doped glasses with compositions of xBi(2)O(3)-(65-x)P2O5-4Yb(2)O(3)-11Al(2)O(3)-5BaO-15Na(2)O (where x = 0, 2.5, 5, 7.5 and 10 mol%) were prepared using the normal melt quench technique. The optical absorption spectra of the glasses were recorded in the wavelength range 300-1700 nm. The effect of Bi2O3 content on the thermal stability and absorption spectra of glasses was investigated. In addition, the Judd-Ofelt parameters and oscillator strengths were calculated by employing Judd-Ofelt theory. It was observed that the positions of the fundamental absorption edge and cut-off wavelength shifted towards red as the content of Bi2O3 increased. However, there were no red shifts found both in the peak wavelength and in the center of mass wavelength of all absorption bands with Bi2O3 content increasing. The results of Judd-Ofelt theory analysis showed that Judd-Ofelt parameters Omega(t), (t = 2, 4, 6) changed sharply when Bi2O3 concentration exceeded 5 mol%. The variation trends of experimental oscillator strength were similar with those of Judd-Ofelt parameters as function of Bi2O3 concentrations. Moreover, differential scanning calorimetry experiments showed that the increases of Bi2O3 content weakened the network structure and then lowered the thermal stability of the glasses. The spontaneous emission probability A(rad), branching ratio beta and the radiative lifetime tau(rad) were also calculated and analyzed. The stimulated emission cross-section of Er3+ was calculated according to the McCumber theory. It was found that the stimulated emission cross-section of Er3+ was monotonically increases with Bi2O3 content increasing. (C) 2006 Elsevier B.V. All rights reserved.

TeO2-Nb2O5-YF3玻璃系统的形成区及性质研究

制备了一种新型的氧卤碲酸盐玻璃：TeO2-Nb2O5-YF3,给出并研究了TeO2-Nb2O5-YF3三元系统的玻璃形成范围。测试了玻璃的密度、折射率、差热(DTA)、拉曼光谱、红外透射光谱以及紫外吸收光谱,通过光谱分析研究了组分含量的变化对玻璃结构及红外透射特性的影响。实验结果表明,TeO2-Nb2O5-YF3玻璃系统具有优良的成玻璃性能和热稳定性等特性,而且在2.8～3.3 μm区域内无明显的[OH]基团吸收,在中红外3～5 μm区域具有优良透射性能,因此在中红外透射方面具有潜在应用价值。

TeO2-ZnCl2-BaO-NaF玻璃系统的结构及中红外透过特性的研究

制备了一种新型的氧卤碲酸盐玻璃：（80-x）TeO2—15ZnCl2-xBaO-5NaF（x=30、20、10、0mol％），对玻璃的机械强度、热稳定性、拉曼光谱、紫外吸收光谱、红外透过光谱等特性进行了研究．通过拉曼光谱分析研究了玻璃组分含量的变化对玻璃结构和红外透过性能的影响．结果表明，随着BaO含量的增加，玻璃在红外波段透过率显著增加，并且红外透过截止波长向长波方向移动，本文对这一实验结果进行了机理性的研究探讨．同时，通过在熔制过程中通入高纯O2，以及引入适量的卤化物有效地除去玻璃中的[OH]基团，使

X 射线转换屏用Tb3+激活磷酸盐发光玻璃

Phosphate glasses 60P2O5-15CS2O- 15Al2O3-10BaO were made by high temperature melt-annealing method. The absorption spectra, excitation spectra and emission spectra of Gd³⁺-Tb³⁺ and Ce3+-Gd³⁺-Tb³⁺ co-doped phosphate glass 60P2O5-15CS2O- 15Al2O3-10BaO were studied. The experimental results indicate that, the doping of Ce3+ and Gd³⁺ in Tb³⁺ phosphate glass has a good effect on the 545 nm emission of Tb³⁺ at UV excitation. The Ce3+-Gd³⁺-Tb³⁺ co-doped phosphate glass have a good x-ray luminescence at the radiation of x-ray with energy in 50-120 kev, and a high space resolution. The Ce3+-Gd³⁺-Tb³⁺ co-doped phosphate luminescence glass is a promising material for using in the digital radiography system in medical devices.

不同玻璃组分对掺铒碲酸盐玻璃 光谱性质的影响

Series of tellurite glasses were prepared by traditional melting method, the glass composition were changed and the different effects of glass modifier oxides(alkali metals and alkaline earth metal oxides) and glass intermediate (Y2O3, GeO2, Nb2O5, WO3) on the optical and spectroscopic properties of Er³⁺ doped tellurite glass were researched and compared. The infrared transmitting spectra, absorption spectra and fluorescence spectra were tested, the results showed that Nb2O5 and WO3 in the glass act as part of the body's role in the formation of the network, caused the reduction of transmitting range in infrared wavelength, which decrease the transmitting properties of tellurite glass. The introduction of high valence cationic ions, WO3 especially, can increase the FWHM of Er³⁺ for the increased polarization effect. With the decreasing of cationic field of glass modifier ions, the ion filed of the environment around Er³⁺ increased, subsequently, the role of ligand field polarization effect reduced, which makes the luminescence lifetime increase, and on the contrary the FWHM decrease monotonously.

Optical transitions and upconversion luminescence of Er3+/Yb3+-codoped halide modified tellurite glasses

Er3+-doped halide modified tellurite glasses were synthesized by conventional melting and quenching method. The Judd-Ofelt analysis was performed on the absorption spectra and the transition probabilities, excited state lifetimes, and the branching ratios were calculated and discussed. The intense infrared and visible fluorescence spectra under 980 nm excitation were obtained. Strong upconversion signal was observed at pumping power as low as 30 mW in the glasses with halide ions. The upconversion mechanisms and power dependent intensities were discussed, which showed two-photon process are involved for the green and red emissions. The decay times of the emitting states and the corresponding quantum efficiency were determined and explained. (C) 2004 American Institute of Physics.

Thermal analyses, spectral characterization and structural interpretation of Yb3+ doped TeO2-ZnO-ZnCl2 glasses

Bulk-lasses have been prepared in the TeO2-ZnO-ZnCl2 systems. Their characteristic temperatures were determined and analyzed. Raman and FT-IR spectra were used to analyze the effect of ZnCl2 on the structure and spectral properties of tellurite glasses and OH- groups in this glass system. The spectroscopic properties including absorption spectra, emission cross-sections and fluorescence lifetimes of Yb3+ in TeO2-ZnO-ZnCl2 were measured and calculated. It is demonstrated that the progressive replacement less than 20 mol% of TeO2 by ZnCl2 improves the thermal stability, removes the OH- groups, turns TeO4 bipyramidal arrangement into TeO3 (and/or TeO3+1) trigonal pyramids structures and results in the decrease of the symmetry of the structure, which increases the emission cross-sections and lifetimes. But when the content of ZnCl2 up to 30 mol%, the glass system becomes more hygroscopic and introduces more OH- groups, which decrease the emission cross-sections and shorten the lifetimes. The results show that the glass system with (TeO2)-Te-69-(ZnO)-Zn-10-20ZnCl(2)-1Yb(2)O(3) is a desirable component for active laser media for high power generation. (c) 2005 Elsevier B.V. All rights reserved.

Host dependent frequency upconversion of Er3+-doped oxyfluoride germanate glass

Er3+-doped oxyfluoride germanate glasses have been synthesized by the conventional melting and quenching method. The Judd-Ofelt intensity parameters were calculated based on the Judd-Ofelt theory and absorption spectra measurements. With the substitution of PbF2 for PbO, the Omega(2) parameter decreases, while the Omega(6) parameter increases. These change trends indicate that fluoride anions come to coordinate erbium cations and the covalency of the Er-O bond decreases. Structural and thermal stability properties were obtained by Raman spectra and differential thermal analysis, indicating that PbF2 plays an important role in the formation of glass network and has an important influence on the maximum phonon energy and thermal stability of host glasses. Intense green and red emissions centered at 525, 546, and 657 nm, corresponding to the transitions H-2(11/2) -> I-4(15/2), S-4(3/2) -> I-4(15/2), and F-4(9/2) -> I-4(15/2), respectively, were simultaneously observed at room temperature. With increasing PbF2 content, the intensity of red (657nm) emissions increases significantly, while that of the green (525 and 546nm) emission increases slightly. The results indicate that PbF, has more influence on the red (657nm) emission than the green (525 and 546nm) emissions in oxyfluoride germanate glasses. The possible upconversion luminescence mechanisms have also been estimated and discussed. (c) 2005 Elsevier B.V. All rights reserved.

Fluorescence lifetime increasing with F- ions into ytterbium-doped germanium-lead-tellurite glasses

The effects of F- ions in a germanium-lead-tellurite glass system oil the spectral and potential laser properties of the Yb3+ are investigated. The absorption spectra, lifetimes, the emission cross-sections and the minimum pump intensities of the glass system with and without F- ions have been measured and calculated. The results show that the fluorescence lifetime and the minimum pump intensity of Yb3+ ions increase evidently, which indicates that germanium lead-oxyfluoride tellurite glass is a promising laser host matrix for high power generation. FT-IR spectra were used to analyse the effect of F- ions on OH- groups in this glass system. Analysis demonstrates that addition of fluoride removes the OH- groups and results in improvement of fluorescence lifetime of Yb3+.

The spectroscopic properties of Er3(+)-doped TeO2-Nb2O5 glasses with high mechanical strength performance

(100 - x)TeO2 - xNb(2)O(5) (x=5-20) mobic tellurite glasses doped with 0.5 mol.% Er2O3 were synthesized, and their thermal, mechanical, and spectroscopic properties were measured and compared to the properties of the typical 75TeO(2)-20ZnO-5Na(2)O (TZN) tellurite glass. The refractive index (n(d)), density (p), and glass transition temperature (T-g) of bulk glasses increase with the Nb2O5 content. The Vickers microhardness (H-v) of bulk glass in niobic tellurite glasses also increases with the Nb2O5 content. The values (2.5-3.2 GPa) of H, in the niobic tellurite glasses are 47-88% larger than that (1.7 GPa) in TZN glass. The effect of Nb2O5 content on absorption spectra, the Judd-Ofelt parameters Omega(t) (t = 2, 4, 6), fluorescence spectra and the lifetimes of Er3+ :I-13/2 level were also investigated, and the stimulated emission crosssection was calculated from McCumber theory. With increasing Nb2O5 content in the glass composition, the Omega(t) (t = 2, 4, 6) parameters, fluorescence full width at half maximum (FWHM) Of I-13/2 of Er3+ increase, while the I-4(13/2) lifetimes of Er3+ decreases. Compared with TZN glass, the gain bandwidth properties of Er3+-doped TeO2-Nb2O5 glass is much larger than in tellurite glass based TeO2-ZnO-Na2O system, bismush-based glass, germanate, and silicate glasses, which indicates that TeO2-Nb2O5 glasses are better choice as a practical available host material for broadband Er3+-doped amplifier. (c) 2005 Elsevier B.V. All rights reserved.

The effect of OH- groups on the spectroscopic properties of erbium-doped tellurite glasses

A series of five different concentration erbium-doped tellurite glasses with various hydroxl groups were prepared. Infrared spectra of glasses were measured. In order to estimate the exact content of OH- groups in samples, various absorption coefficients of the OH- vibration band were analyzed under the different oxygen bubbling times. The absorption spectra of the glasses were measured, and the Judd-Ofelt intensity parameters Omega(i) of samples with the different erbium ions concentration and OH- contents were calculated on the basis of the Judd-Ofelt theory. The peak stimulated emission cross-section of (I13/2 ->I15/2)-I-4-I-4 transition of the samples was finally calculated by using the McCumber theory. The fluorescence spectra of Er3+:I-4(13/2)->I-4(15/2) transition and the lifetime of Er3+:I-4(13/2) level of the samples were measured. The effects of OH- groups on the spectroscopic properties of Er3+ doped samples with the different concentrations were discussed. The results showed that the OH- groups had great influences on the Er3+ lifetime and the fluorescence peak intensity. The OH- group is a main influence factor of fluorescence quenching when the doping concentration of Er2O3 is smaller than 1.0 mol%, but higher after this concentration, the energy transfer of Er3+ ions turns into the main function of the fluorescence quenching. And basically, there is no influence on the other spectroscopic properties (FWHM, absorption spectra, peak stimulated emission cross section, etc.).

荧光俘获效应对掺铒氧化物玻璃光谱性质的影响

测试了不同掺杂浓度和样品厚度下掺铒磷酸盐和碲酸盐玻璃的吸收光谱、荧光光谱和荧光寿命，计算了Er^3＋离子在1．53μm处的吸收截面（σa）、发射截面（σe）、自发辐射跃迁概率（Arad）、辐射跃迁寿命（τrad）、以及辐射跃迁量子效率（η）等光谱参数．讨论了荧光俘获效应对掺铒磷酸盐和碲酸盐玻璃光谱性质及光谱参数的影响．结果表明即使在铒离子低掺杂浓度（0．1mol％Er2O3）下，荧光俘获效应也普遍存在于掺铒玻璃材料中，使得荧光寿命（τt）和荧光半高宽（FWHM）随样品的厚度和铒离子掺杂浓度增加而增大，导致

Spectroscopic properties and thermal stability of Er3+/Yb3+-codoped fluorophosphate glasses

A comprehensive study on the thermal stability and spectroscopic properties of Er3+/Yb3+-codoped Al(PO3)(3)-based fluorophosphate glasses is reported of the 1.5μ m fibre amplifiers in this paper. From optical absorption spectra, the Judd-Ofelt parameters of Er3+ in the glasses and several important optical properties, such as the radiative transition probability, the branching ratio and the spontaneous emission probability, have been calculated by using Judd-Ofelt theory. The fluorophosphate glass exhibits broadband near-infrared emission at 1.53μ m with a full width at half-maximum over 63nm, and a large calculated stimulated-emission cross-section of 6.85 x 10(-21)cm(2).