Bismuth-doped zinc aluminosilicate glasses and glass-ceramics with ultra-broadband infrared luminescence

Broadband infrared luminescence covering the optical telecommunication wavelength region of 0, E and S bands was observed from bismuth-doped zinc aluminosilicate glasses and glass-ceramics. The spectroscopic properties of the glasses and glass-ceramics depend on the thermal-treatment history. With the appearance of gahnite (ZnAl2O4) crystalline phase, the fluorescent peak moves to longer wavelength, but the fluorescent intensity decreases. The similar to 1300 nm fluorescence with a FWHM larger than 250 nm and a lifetime longer than 600 mu s possesses these optical materials with potential applications in laser devices and broadband amplifiers. The broad infrared luminescence from the bismuth-doped zinc aluminosilicate glasses and glass-ceramics might be from BiO or bismuth clusters rather than from Bi5+ and Bi3+. (c) 2005 Elsevier B.V. All rights reserved.

稀土离子掺杂的多组分玻璃光纤

abstract {Rare earth ions doped multi-component glass fibers have important application in broad band fiber amplifier and up-conversion fiber lasers. In this paper, the mechanism and the progress of study on rare earth ions doped multi-component glass fibers in broad band fiber amplifier and up-conversion fiber lasers are introduced and reviewed. The questions and the applications of rare earth ions doped multi-component glass fibers in the future are also prospected. Based on the present research progress, it is suggested to further study the tellurite and bismuth glasses, which are used as fiber materials in broad band fiber amplifier. To up-conversion fiber laser, it is still need to further investigate novel glasses, which has low phonon energy and good physical and chemical properties.}

Structural Integration of Tellurium Oxide into Mixed-Network-Former Glasses: Connectivity Distribution in the System NaPO3–TeO2

FSodium phosphate tellurite glasses in the system (NaPO3)(x)(TeO2)(1-x) were prepared and structurally characterized by thermal analysis, vibrational spectroscopy, X-ray photoelectron spectroscopy (XPS) and a variety of complementary solid-state nuclear magnetic resonance (NMR) techniques. Unlike the situation in other mixed-network-former glasses, the interaction between the two network formers tellurium oxide and phosphorus oxide produces no new structural units, and no sharing of the network modifier Na2O takes place. The glass structure can be regarded as a network of interlinked metaphosphate-type P(2) tetrahedral and TeO4/2 antiprismotic units. The combined interpretation of the O 1s XPS data and the P-31 solid-state NMR spectra presents clear quantitative evidence for a nonstatistical connectivity distribution. Rather the formation of homootomic P-O-P and Te-O-Te linkages is favored over mixed P-O-Te connectivities. As a consequence of this chemical segregation effect, the spatial sodium distribution is not random, as also indicated by a detailed analysis of P-31/No-23 rotational echo double-resonance (REDOR) experiments. ACHTUNGTRENUNG(TeO2)1 x were prepared and structurally characterized by thermal analysis,vibrat ional spectroscopy,X-ray photoelectron spectroscopy (XPS) and a variety of complementary solid-state nuclear magnetic resonance (NMR) techniques. Unlike the situation in other mixed-network-former glasses,the interaction between the two network formers tellurium oxide and phosphorus oxide produces no new structural units,and no sharing of the network modifier Na2O takes place. The glass structure can be regarded as a network of interlinked metaphosphate-type P(2) tetrahedral and TeO4/2 antiprismatic units. The combined interpretation of the O 1s XPS data and the 31P solid-state NMR spectra presents clear quantitative evidence for a nonstatistical connectivity distribution. Rather,the formation of homoatomic P O P and Te O Te linkages is favored over mixed P O Te connectivities. As a consequence of this chemical segregation effect,the spatial sodium distribution is not random,as also indicated by a detailed analysis of 31P/23Na rotational echo double-resonance (REDOR) experiments.

Structural investigation on TeO2-BiCl3 glassy system

Glass systems of composition xBiCl(3)-(1-x)TeO2 (x=0.2, 0.4, 0.5 and 0.6, respectively) have been investigated by means of DSC, infrared absorption spectroscopy and Raman spectroscopy in order to obtain information about the transformation of structure, thermal and optical properties in the formation of the glass network. The results confirm that the addition of BiCl3 network former increases the glass forming ability and the optical transmission range. And also from Raman results a structural evolution was observed where the number of structural units described as [TeO3] trigonal pyramids, [TeO3+1] polyhedra and ionic behavior bonds (NBO) increases at the expense of the [TeO4] trigonal bipyramids. Bi3+ ions exist in network structure as [BiO6] or [BiCl6] octahedral coordination. As upconversion luminescence glass host, this glassy system is desired for optical properties but the thermal stability will still be improved. (c) 2005 Elsevier B.V. All rights reserved.

Energy transfer and infrared-to-visible upconversion luminescence of Er3+/Yb3+-codoped halide modified tellurite glasses

We report on the energy transfer and frequency upconversion spectroscopic properties of Er3+-doped and Er3+/Yb3+-codoped TeO2-ZnO-Na2O-PbCl2 halide modified tellurite glasses upon excitation with 808 and 978 nm laser diode. Three intense emissions centered at around 529, 546 and 657 nm, alongwith a very weak blue emission at 4 10 nm have clearly been observed for the Er3+/Yb3+-codoped halide modified tellurite glasses upon excitation at 978 nm and the involved mechanisms are explained. The quadratic dependence of fluorescence on excitation laser power confirms the fact that the two-photon contribute to the infrared to green-red upconversion emissions. And the blue upconversion at 410 nm involved a sequential three-photon absorption process. (c) 2005 Elsevier Ltd. All rights reserved.

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.

Frequency up-conversion properties of Er3(+)-doped TeO2-ZnO-PbCl2 oxyhalide tellurite glasses

This paper reports on the successful preparation and a detailed study on the up-conversion properties of Er3+ -doped TeO2-ZnO-PbCl2 oxylialide tellurite glasses. Three intense emissions centered at around 527, 549 and 666 nm have been clearly observed under 977 nm excitation and the involved mechanisms have been explained. The green emissions centered at 527 and 549 nin are due to the H-2(11/2 ->) I-4(15/2) and S-4(3/2) -> I-4(15/2) transitions, and the red up-conversion emission centered at 666 nm is associated with the F-4(9/2) -> I-4(15/2) transitions of Er3+ ions, respectively. The quadratic dependence of fluorescence on excitation laser power confirm that two-photons contribute to up-conversion of the green-red emissions. (c) 2005 Elsevier B.V. All rights reserved.

Gain characteristics of Er3+-doped phosphate glass fibres

An erbium-doped phosphate glass fibre has been drawn by the rod-in-tube technique in our laboratory. The gain for the Er3+-doped phosphate glass fibre with different pump powers and with different input signal wavelengths is investigated. The 2.2-cm-long fibre, pumped by a single-mode 980-nm fibre-pigtailed laser diode, can provide a net gain per unit length greater than 1.8dB/cm. The pump threshold is about 50 mW at the wavelength of 1534 nm, and below 70 mW at 1550 nm. The gain linewidth of the Er3+-doped phosphate glass fibre is greater than 34 nm and can cover the C band in optical communication networks.

Special effects of YbF3 on the structural changes for fluorophosphate glass

From Raman and IR spectra, obvious differences of the glass structure were observed in non-Yb3+-doped and Yb3+ -doped fluorophosphate glasses. Results showed that Yb3+ ions can induce, in a better glass, polymerization and network uniformity. Compared with the monophosphate-mastered Yb3+-free glass, Yb3+-doped glass has a pyrophosphate environment. The main building blocks in Yb3+ -doped samples are metaphosphate groups, pyrophosphate groups (P-2(O,F)(7),PO3F), Al[F-6]+Al[O,F](6) and F3Al-O-AlF3 while those of the Yb3+ -free glasses are monophosphate groups P(O,F)(4), little pyrophosphate groups, Al[F-4]+Al[F-6]+Al[O,F](4)+Al[O,F](6) and F3Al-O-AlF3. The DSC analysis also showed a slight increase in crystallization stability. (c) 2005 Elsevier B.V. All rights reserved.

Broadband amplification and upconversion luminescence properties of Er3+/Yb3+ co-doped fluorophosphate glass

Broadband and upconversion properties were studied in Er3+/Yb3+ co-doped fluorophosphate glasses. Large Omega(6) and S-ed/(S-ed + S-md) values and the flat gain profile over 1530-1585 nm indicate the good broadband properties of the glass system. And a premise of using Omega(6) as a parameter to estimate the broadband properties of the glasses is proposed for the first time to our knowledge. Results showed that fluorescence intensity, upconversion luminescence intensity, the intensity ratio of red/green light (656 nm/545 nm) are closely related to the Yb3+:Er3+ ratio and Er3+ concentration, and the corresponding calculated lifetime of F-4(9/2) and S-4(3/2) states for red and green upconversion samples proves this conclusion. The upconversion mechanism is also discussed. (c) 2005 Elsevier Ltd. All rights reserved.

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.

Effects of PbF2 on the spectroscopic, lasing and structural properties of Yb3+-doped fluorophosphate glass

Effect of PbF2 on Yb3+ -doped fluorophosphate glasses is studied. Results indicate that proper amount of PbF2 has absolute advantages in improving the crystallization stability of fluorophosphate glasses. T, value performs a decreasing and increasing tendency with 25 mol% PbF2 as the turning-point. And the spectroscopic properties such as absorption and emission cross section, effective fluorescence linewidth are apparently enhanced with PbF2 over 25 mol%. Lasing parameters beta, I-sat and I-min increase slightly with the addition of PbF2. Raman analysis proves that over 20 mol% PbF2, destroys the phosphate vibration groups greatly. (c) 2005 Elsevier Ltd. All rights reserved.

Effect of PbCl2 addition on structure, OH- content, and upconversion luminescence in Yb3+/Er3+-codoped germanate glasses

Yb3+/ Er3+-codoped oxychloride germanate glasses have been synthesized by a conventional melting and quenching method. Structural properties were obtained based on Raman-spectra investigation, indicating that PbCl2 plays an important role in the formation of the glass network and has an important influence on the phonon density and the maximum phonon energy. The Judd - Ofelt intensity parameters and quantum efficiencies were calculated based on the Judd - Ofelt theory and lifetime measurements. The enhanced upconversion luminescence intensity of Er3+ with increasing PbCl2 content could not be explained only by the maximum phonon-energy change of the host glasses. For the first time, the effect of PbCl2 addition on phonon density, OH- content, and upconversion luminescence in oxychloride glasses has been discussed and evaluated. The results show that the effect of phonon density and OH- content on upconversion luminescence in oxychloride glasses is much stronger than that of the decrease of the maximum phonon energy. The possible upconversion luminescence mechanisms have also been estimated and are discussed.