Synthesis, spectroscopic properties and thermal stability of metal(II) tetraazaporphyrin complexes with two strong wavelength absorption

Three kinds of metal(II) tetraazaporphyrin complexes with blue-violet and red light wavelength absorption were synthesized by refluxing tetraazaporphyrin ligand and different metal(II) ions, respectively. Their structures were confirmed by elemental analysis, LDI-TOF-MS, FT-IR and UV-Vis. The solubility of metal(II) tetraazaporphyrin complexes in organic solvents and absorption properties of their chloroform solution and films on K9 glass in the region 250-800 nm were measured. The influence on the difference of absorption maximum from metal(II) tetraazaporphyrin complexes to tetraazaporphyrin ligand by different metal(II) ions was studied. In addition, the thermal stability of the complexes was also evaluated. (c) 2006 Elsevier Ltd. All rights reserved.

Effect of network modifiers on spectroscopic properties of erbium-doped phosphate glasses

The integrated absorption cross section Sigma(abs), I peak emission cross section sigma(cmi), Judd-Ofeld intensity parameters Omega(iota) ( t = 2,4,6), and spontaneous emission probability A(R) of Er3+ ions were determined for Erbium doped alkali and alkaline earth phosphate glasses. It is found the compositional dependence of sigma(emi) 5 almost similar to that of Sigma(abs), which is determined by the sum, of Omega(1) (3 Omega(2) + 10 Omega(4) + 21 Omega(6)). In addition, the compositional dependence of Omega(1) was studied in these glass systems. As a result, compared with. Omega(4) and Omega(6) the Omega(2) has a stronger compositional dependence on the ionic radius and content of modifers. The covalency of Er-O bonds in phosphate glass is weaker than that in silicate glass, germanate glass, aluminate glass, and tellurate glass, since Omega(6) of phosphate glass is relatively large. A(R) is affected by the covalency of the Er3+ ion sites and corresponds to the Omega(6) value.

Effect of alkaline-earth metal composition on spectroscopic properties of Er3+ in fluorophosphate glasses

Optical spectroscopic properties of Er3+-doped alkaline-earth metal modified fluoropho sphate glasses have been investigated experimentally for developing broadband fiber and planar amplifiers. The results show a strong correlation between the alkaline-earth metal content and the spectroscopic parameters such as absorption and emission cross sections, full widths at half-maximum and Judd-Ofelt intensity parameters. It is found that strontium ions could have more influences on the Judd-Ofelt intensity parameters and the absorption and emission cross sections than other alkaline-earth metal ions such as Mg2+, Ca2+, Ba2+. The sample containing 23 mol% strontium fluoride exhibits the maximum emission cross section of 7.58 x 10(-21) cm(2), the broadest full width at half-maximum of 65 nm and the longer lifetime of 8.6 ms among the alkaline-earth metal modified fluorophosphates glasses studied. The Judd-Ofelt intensity parameter Omega(6)s, the emission cross sections and the full widths at half-maximum in the Er3+-doped fluorophosphate glasses studied are larger than in the silicate and phosphate glasses.

Thermal stability and spectroscopic properties of Er3+-doped niobium tellurite glasses for broadband amplifiers

Three Er3+-doped tellurite glasses with compositions of 70TeO(2)-30ZnO, 70TeO(2)-20ZnO-10Nb(2)O(5) and 70TeO(2)-20ZnO-5BaO-5Nb(2)O(5) have been investigated for developing fiber and planar broadband amplifiers and lasers. The optical spectroscopic properties and thermal stability of Er3+-doped tellurite glasses have been discussed. The results show that the incorporation of Nb2O5 increases the thermal stability of Er3+-doped tellurite glasses significantly, Er3+-doped niobium tellurite glasses 70TeO(2)-20ZnO-10Nb(2)O(5) and 70TeO(2)-20ZnO-5BaO-5Nb(2)O(5) exhibit the good thermal stability (DeltaT > 150degreesC), the large emission cross-section (>10 x 10(-21) cm(2)) and broad full width at half maximum (similar to65 nm), will be preferable for broadband Er3+-doped fiber amplifiers. (C) 2004 Elsevier B.V. All rights reserved.

Effect of lithium-potassium mixed alkali on spectroscopic properties of Er3+-doped aluminophosphate glasses

Er3+-doped lithium-potassium mixed alkali aluminophosphate glasses belonging to the oxide system xK(2)O-(15x)Li2O-4B(2)O(3)-11Al(2)O(3)-5BaO-65P(2)O(5) are obtained in a semi-continuous melting quenching process. Spectroscopic properties of Er3+-doped glass matrix have been analysed by fitting the experimental data with the standard Judd-Ofelt theory. It is observed that Judd-Ofelt intensity parameters-Omega(t)(t=2, 4 and 6) of Er3+ change when the second alkali is introduced into glass matrix. The variation of line strength S-ed[I-4(13/2),I-4(15/2)] follows the same trend as that of the Omega(6) parameter. The effect of mixed alkali on the spectroscopic properties of the aluminophosphate glasses, such as absorption cross-section, stimulated emission cross-section, spontaneous emission probability, branching ratio and the radiative lifetime, has also been investigated in this paper.

Spectroscopic properties and Judd-Ofelt theory analysis of Dy3+ doped oxyfluoride silicate glass

Dy3+ doped oxyfluoride silicate glass was prepared and its optical absorption, 1.3 mu m emission, and upconversion luminescence properties were studied. Furthermore, the Judd-Ofelt [Phys. Rev. 127, 750 (1962); J. Chem. Phys. 37, 511 (1962)] intensity parameters, oscillator strengths, spontaneous transition probability, fluorescence branching ratio and radiative lifetime were calculated by Judd-Ofelt theory, while stimulated emission cross section of H-6(9/2)+F-6(11/2)-> H-6(15/2) transition was calculated by McCumber theory [Phys. Rev. A. 134, 299 (1964)]. According to the obtained Judd-Ofelt intensity parameters Omega(2)=2.69x10(-20) cm(2), Omega(4)=1.64x10(-20) cm(2), and Omega(6)=1.64x10(-20) cm(2), the radiative lifetime was calculated to be 810 mu s for 1.3 mu m emission, whose full width at half maximum and sigma(e) were 115 nm and 2.21x10(-20)cm(2), respectively. In addition, near infrared to visible upconversion luminescence was observed and evaluated. The results suggest that Dy3+ doped oxyfluoride silicate glass can be used as potential host material for developing broadband optical amplifiers and laser applications.

Spectroscopic properties of Er3+/Yb3+ codoped fluorophosphate glasses

Er3+/Yb3+ cocloped fluorophosphate glasses were prepared and their thermal stabilities, Raman spectra, absorption spectra, and fluorescence spectra were measured. It is found that proper content of NaF or PbF2 is helpful for the increase of stability against crystallization. The variation of AI(PO3)3 or NaF content in the composition affects not the maximum phonon energy but the phonon density. The introduction of PbF2 decreases the phonon energy slightly. Intense green and red upconversion luminescence was observed for the fluorophosphate glass with low phosphate content. A glass matrix for upconversion luminescence requiring neither expensive raw material nor special atmospheric conditioned preparation is provided. Infrared luminescence around 1530 nm was researched. Fluorophosphate glasses with bandwidth properties and stimulated-emission cross sections better than tellurite, germanate and silicate glasses are obtained. Through the introduction of NaF, the bandwidth properties are decreased. Through the introduction of PbF2 the gain properties are increased. On the whole, it is difficult to obtain a material with the best gain properties and bandwidth properties simultaneously. There should be a compromise between them according to the demand. (C) 2006 Elsevier B.V. All rights reserved.

Spectroscopic properties of fluorophosphate glass with high Er(3+)supercript stop concentration

Fluorophosphate glass with 4 mol.% ErF3 content was prepared. The different scanning calorimetry was conducted. Raman spectrum, infrared transmission spectrum, absorption spectrum were measured. Fluorescence spectrum and lifetime of emission around 1.53 mu m were measured under 970 nm laser diode excitation. The metaphosphate content in the composition is limited, but the maximum phonon energy of glass amounts to 1290 cm- 1, and is comparatively high. The full width at half maximum is about 56 nm, and is wider than for most of the materials investigated. The measured lifetime of I-4(13/2) -> I-4(15/2) transition, contributed by the high phonon energy, inefficient interaction of Er3+ ions, and low water content, amounts to no less than 7.36 ms though the Er3+ concentration is high. This work might provide useful information for the development of compact optical devices.

Influence of heat treatment on spectroscopic properties of Er3+ in multicomponent ZrF4-ZnF2-AlF3-YF3-MF2 (M = Ca, Sr, Ba) based glass

Er3+ doped multicomponent fluoride based glass was prepared. These precursor fluoride glass samples were then heated using different schedules. Crystalline phase particles were successfully precipitated in the multicomponent fluoride glass samples after heat treatment. The influence of heat treatment on the spectroscopic properties of Er3+ in multicomponent fluoride based glass samples were discussed. Small changes of the Judd-Ofelt parameters Omega(i) (i = 2,4,6) were found in multicomponent fluoride glass samples before and after heat treatment compared to oxyfluoride telluride glass. Preparation conditions used to produce transparent multicomponent fluoride glass ceramics doped with rare-earth ions are discussed. (c) 2007 Elsevier B.V. All rights reserved.

Spectroscopic properties of neodymium doped high silica glass and aluminum codoping effects on the enhancement of fluorescence emission

Nd3+ -codoped and Al3+-Nd3+-codoped high silica glasses have been prepared by sintering nanoporous glasses impregnated with Nd3+ stop and Al3+ ions. The Judd-Ofelt intensity parameters Omega(2,4,6) of Nd3+-doped high silica glasses were obtained and used to analyze aluminum codoping effects. Fluorescence properties of Nd3+-doped high silica glasses strongly depend on the Al3+ concentration. While Nd3+ ion absorption and emission intensities of obviously increase when aluminum is added to Nd3+-doped high silica glasses, fluorescence lifetimes decrease and aluminum codoping has almost no influence on the radiative quantum efficiencies. This indicates that aluminum codoping is responsible for an anti-quenching effect through a local modification of rare-earth environments rather than through physical cluster dispersion.

Influences of radiation trapping on spectroscopic properties of Er3+-doped fluorophosphate glasses

Fluorophosphate glasses with different contents of ErF3 were prepared. Due to the radiation trapping of Er, concentration dependence of the fluorescence lifetime is subject to distortion, and the stimulated-emission cross section calculated by the Fuchtbauer-Ladenburg equation is underestimated. The influence of radiation trapping on the measured fluorescence lifetime and width are investigated quantitatively. By comparing the intensity ratio of the 1556-1532 nm peak in the fluorescence spectrum with that in the stimulated-emission cross-section spectrum obtained according to the McCumber theory, the distortion ratio of fluorescence spectrum due to radiation trapping is obtained. An empirical way to quantitatively evaluate the influences of radiation trapping on fluorescence lifetime and width is proposed. (c) 2007 Optical Society of America.

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.

Novel erbium-doped TeO2-based oxysulfide glasses: thermal and spectroscopic properties

Er3+-doped TeO2-based oxysulfide glasses have been prepared in argon atmosphere in carbon crucibles. The thermal analysis and spectroscopic properties of Er (3+) have been considered in terms of sulfide influence. As a function of composition, we have principally measured optical absorption, spontaneous emission and lifetime measurements. Judd-Ofelt theory was introduced to calculate bandwidth and emission cross-section. The results show the product FVMM x sigma(c) increase from 476.8 8 to 635.04 10(-21) cm(2) nm evidently with the addition of 10 mol% PbS into tellurite glass, which indicates a perfect effect on spectra property of Er3+ ions. (C) 2004 Elsevier B.V. All rights reserved.

Effect of chloride ions' introduction on structural, thermal stability, and spectroscopic properties in Yb3+Er3+-codoped germanate-bismuth-lead glasses

Yb3+Er3+-codoped chloride-modified germanate-bismuth-lead glasses have been synthesized by the conventional melting and quenching method. Structural and thermal stability properties have been obtained on the basis of the Raman spectra and differential thermal analysis, which indicate that the PbCl2 addition has an important influence on the phonon density of states, maximum phonon energy, and thermal stability of host glasses. The Judd-Ofelt intensity parameters and quantum efficiencies were calculated on the basis of the Judd-Ofelt theory and lifetime measurements. For the 1.53 mu m emission band, the full widths at the half-maximum increase and peak wavelengths are blueshifted with increasing PbCl2 content. Moreover, the effect of the PbCl2 addition on the phonon density of states, OH- content, and upconversion luminescence has been discussed and evaluated. Our results reveal that, with increasing PbCl2 content, the decrease of phonon density and OH- content contributes more to the enhanced upconversion emissions than that of maximum phonon energy. (c) 2005 Optical Society of America

Effect of F- ions on physical and spectroscopic properties of Yb3+-doped TeO2-based glasses

The effects of F- ions on physical and spectroscopic properties of the Yb3+ in tellurite glass system are investigated. The results show that the glass system takes on good thermal stability with the content of ZnF2 lower than 15 mol%, both the emission cross-section and the fluorescence lifetime of Yb3+ ions increase evidently which indicate that such oxyfluoride tellurite glass system is a promising laser host matrix for high power generation. FT-IR spectra were used to analyze the effect of F- ions on the structure of tellurite glasses and OH- groups in this glass system. Analysis demonstrates that addition of fluoride decreases the symmetry of the structure of tellurite glasses which increases the emission cross-section and removes the OH- groups, and which improves the measured fluorescence lifetime of Yb3+ ions. (c) 2004 Elsevier B.V. All rights reserved.