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.

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.

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.

Investigation of the effect of fluoride ions introduction on structural, OH- content and up-conversion luminescence properties in Er3+-doped heavy metal oxide glasses

Effect of fluoride ions introduction on structural, OH- content and up-conversion luminescence properties in Er3+-doped heavy metal oxide glasses have been investigated. Structure was investigated, indicating that fluoride has an important influence on the phonon density, maximum phonon energy of host glasses. With increasing fluoride content, the up-conversion luminescence intensity and quantum efficiencies increase notably, which could not be explained only by the maximum phonon energy change of host glasses. Our results show that, with the introduction of PbF2, the decrease of phonon density and OH- content contributes more to the enhanced up-conversion emissions than that of maximum phonon energy. (c) 2005 Elsevier B.V. All rights reserved.

Intense blue up-conversion luminescence in Tm3+/Yb3+ codoped oxyfluoride glass-ceramics containing beta-PbF2 nanocrystals

Up-conversion luminescence properties of a Tm3+/Yb3+ codoped oxyfluoride glass-ceramics under 980nm excitation are investigated. Intense blue emission centered at 476nm, corresponding to (1)G(4) -> H-3(6) transitions of Tm3+ was simultaneously observed in the transparent oxyfluoride glass ceramics at room temperature. The intensity of the blue up-conversion luminescence in a 1 mol% YbF3-containing glass-ceramic was found to be about 40 times stronger than that in the precursor oxyfluoride glass. The reason for the intense TM3+ up- conversion luminescence in the oxyfluoride glass-ceramics is discussed. The dependence of up-conversion intensities on excitation power and possible up-conversion mechanism are also evaluated. (c) 2005 Elsevier B.V. All rights reserved.

Mechanisms and concentrations dependence of up-conversion luminescence in Tm3+/Yb3+ codoped oxyfluoride glass-ceramics

The up-conversion properties of Tm3+/Yb3+ codoped oxyfluoride glass-ceramics under 980 nm excitation were investigated. Intense blue up-conversion luminescence due to the Tm3+: (1)G(4) -> H-3(6) transition was observed in the glass-ceramics. The intensity of the blue up-conversion luminescence in a 1 mol% YbF3-containing glass-ceramic was found to be about 40 times stronger than that in the precursor oxyfluoride glass. The up-conversion mechanism is proposed. The reason for the intense Tm3+ up-conversion luminescence in the oxyfluoride glass-ceramics and the concentrations dependence of upconversion luminescence are also discussed. (c) 2005 Elsevier B.V. All rights reserved.

Structural and up-conversion luminescence properties in Tm (3+)/Yb3+-codoped heavy metal oxide-halide glasses

Tm3+/Yb3+-codoped heavy metal oxide-halide glasses have been synthesized by conventional melting and quenching method. Structural properties were obtained based on the Raman spectra, indicating that halide ion has an important influence on the phonon density and maximum phonon energy of host glasses. Intense blue and weak red emissions centered at 477 and 650 nm, corresponding to the transitions (1)G(4) -> H-3(6) and (1)G(4) -> H-3(4), respectively, were observed at room temperature. The possible up-conversion mechanisms are discussed and estimated. With increasing halide content, the up-conversion luminescence intensity and blue luminescence lifetimes of Tm3+ ion increase notably. Our results show that with the substitution of halide ion for oxygen ion, the decrease of phonon density and maximum phonon energy of host glasses both contribute to the enhanced up-conversion emissions. (c) 2005 Elsevier B.V. All rights reserved.

Transparent Ni2+-doped MgO-Al2O3-SiO2 glass ceramics with broadband infrared luminescence

We report on transparent Ni2+-doped MgO-Al2O3-SiO2 glass ceramics with broadband infrared luminescence. Ni2+-doped MgO-Al2O3-SiO2 glass is Prepared by using the conventional method. After heat treatment at high temperature, MgAl2O4 crystallites are precipitated, and their average size is about 4.3nm. No luminescence is detected in the as-prepared glass sample, while broadband infrared luminescence centred at around 1315nm with full width at half maximum (FWHM) of about 300nm is observed from the glass ceramics. The observed infrared emission could be attributed to the T-3(2g)(F-3) -> (3)A(2g)(F-3) transition of octahedral Ni2+ ions in the MgAl2O4 crystallites of the transparent glass ceramics. The product of the fluorescence lifetime and the stimulated emission cross section is about 1.6 X 10(-24) s cm(2).

Comparative investigation of up-conversion luminescence in Tm3+-doped oxide-chloride germanate and tellurite glasses

Tm3+-doped oxide-chloride germanate and tellurite glasses have been synthesized by conventional melting method. Intense up-conversion luminescence emissions were simultaneously observed at room temperature in these glasses. The possible up-conversion mechanisms are discussed and estimated. However, in these Tm3+-doped glasses, tellurite glass showed weaker up-conversion emissions than germanate glass, which is inconsistent with the prediction from the difference of maximum phonon energy between tellurite and germanate glasses. In this paper, Raman spectroscopy was employed to investigate the origin of the difference in up-conversion luminescence in the two glasses. Our results confirm that, besides the maximum phonon energy, the phonon density of host glasses is also an important factor in determining the up-conversion efficiency. (c) 2005 Elsevier Ltd. All rights reserved.

Up-conversion luminescence analysis in ytterbium-sensitized erbium-doped oxide-halide tellurite and germanate-niobic-lead glasses

Ytterbium-sensitized erbium-doped oxide-halide tellurite and germanate-niobic-lead glasses have been synthesized by conventional melting method. 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 in these glasses. The quadratic dependence of the 525, 546 and 657 nm emissions on excitation power indicates that a two-photon absorption process occurs. Tellurite glass showed a weaker up-conversion emission than germanate-niobic-lead glass, which is inconsistent with the prediction from the difference of maximum phonon energy between tellurite and germanate-mobic-lead glasses. In this paper, Raman spectroscopy was employed to investigate the origin of the difference in up-conversion luminescence in the two glasses. Compared with phonon side-band spectroscopy, Raman spectroscopy extracts more information including both phonon energy and phonon density. Our results reveal that the phonon density and the maximum phonon energy of host glasses are both important factors in determining the up-conversion efficiency. (c) 2005 Elsevier B.V. All rights reserved.

Effect of bismuth oxide introduction on spectroscopic properties of Er3+/Yb3+ co-doped aluminophosphate glasses

The absorption spectra, emission spectra and infrared spectra of Er3+/Yb3+ co-doped xBi(2)O(3)-(65 - x)P2O5-4Yb(2)O(3)-11Al(2)O(3)-5BaO-15Na(2)O were measured and investigated. Spontaneous emission probability, radiative lifetime and branching ratios of Er3+ were calculated according to the Judd-Ofelt theory. The role of substitution of Bi2O3 for P2O5 on luminescence of Er3+/Yb3+ co-doped aluminophosphate glasses has been investigated. The calculated radiative lifetimes (tau(rad)) for I-4(13/2) and I-4(11/2) were decreasing with Bi2O3 content increases, whereas the measured total lifetime (tau(meas)) for I-4(13/2) showed linearly increasing trends. The effect of Bi2O3 introduction on OH- groups was also discussed according to the IR transmittance spectra of glasses. It was found that FWHM of glasses were not affected with the substitution of Bi2O3 for P2O5. The emission spectra intensity increased with Bi2O3 content due to the decreases of phonon energy and OH- content in glasses. (C) 2007 Elsevier B.V. All rights reserved.

Energy transfer between Cr3+ and Ni2+ in transparent silicate glass ceramics containing Cr3+/Ni2+ co-doped ZnAl2O4 nanocrystals

The emission intensity of Ni2+ at 1200 nm in transparent ZnO-Al2O3-SiO2 glass ceramics containing ZnAl2O4 nanocrystals is improved approximately 8 times by Cr3+ codoping with 532 nm excitation. This enhanced emission could be attributed to an efficient energy transfer from Cr3+ to Ni2+, which is confirmed by time-resolved emission spectra. The energy transfer efficiency is estimated to be 57% and the energy transfer mechanism is also discussed. (C) 2008 Optical Society of America.

Enhanced broadband near-infrared luminescence from transparent Yb 3+/Ni2+ codoped silicate glass ceramics

The near-infrared emission intensity of Ni2+ in Yb3+/Ni2+ codoped transparent MgO-Al2O3-Ga2O3-SiO2-TiO2 glass ceramics could be enhanced up to 4.4 times via energy transfer from Yb3+ to Ni2+ in nanocrystals. The best Yb2O3 concentration was about 1.00 mol%. For the Yb3+/Ni2+ codoped glass ceramic with 1.00 mol% Yb2O3, a broadband near-infrared emission centered at 1265 nm with full width at half maximum of about 300 nm and lifetime of about 220 mu s was observed. The energy transfer mechanism was also discussed. (C) 2008 Optical Society of America.

Enhanced broadband near-infrared luminescence in transparent silicate glass ceramics containing Yb3+ ions and Ni2+-doped Li Ga5 O8 nanocrystals

Spectral properties of Yb3+/Ni2+ codoped transparent silicate glass ceramics containing LiGa5O8 nanocrystals were investigated. The near-infrared emission intensity of Ni2+ was largely increased with Yb3+ codoping due to Yb3+-> Ni2+ energy transfer. The qualitative calculation of the energy transfer constant Cs-a and rate Ps-a showed that the Yb3+-> Ni2+ energy transfer was much greater than in the opposite direction. Yb3+/Ni2+ codoped glass ceramics with 0.75 mol % Yb2O3 exhibited a near-infrared emission with full width at half maximum of 290 nm and fluorescent lifetime of 920 mu s. The glass ceramics are promising for broadband optical amplification.

Enhanced luminescence from transparent Ni2+-doped MgO-Al2O3-SiO2 glass ceramics by Ga2O3 addition

Transparent Ni2+-doped MgO-Al2O3-SiO2 glass ceramics without and with Ga2O3 were synthetized. The precipitation of spinel nanocrystals, which was identified as solid solutions in the glass ceramics, could be favored by Ga2O3 addition and their sizes were about 7.6 nm in diameter. The luminescent intensity of the Ni2+-doped glass ceramics was largely enhanced by Ga2O3 addition which could mainly be caused by increasing of Ni2+ in the octahedral sites and the reduction of the mean frequency of phonon density of states in the spinel nanocrystals of solid solutions. The full width at half maximum (FWHM) of emissions for the glass ceramics with different Ga2O3 content was all more than 200 nm. The emission lifetime increased with the Ga2O3 content and the longest lifetime is about 250 mu s. The Ni2+-doped transparent glass ceramics with Ga2O3 addition have potential application as broadband optical amplifier and laser materials. (C) 2007 Elsevier Ltd. All rights reserved.