Optical characterization, 1.5 μm emission and IR-to-visible energy upconversion in Er-doped fluorotellurite glasses

The optical properties of Er³⁺ ions in a novel glass based on TeO₂-PbF₂-AlF₃ oxyfluoride tellurites have been investigated using steady-state and time-resolved spectroscopies as a function of the rare-earth doping concentration. Basic optical characterizations have been performed measuring and calculating the absorption and emission spectra and the cross-sections, the Judd-Ofelt intensity parameters, the radiative probabilities and the fluorescence decays and lifetimes. Special attention has been devoted to the broad ⁴I_13/2→⁴I_15/2 emission transition at around 1.53 μm since, with a wide broadening of around 70 nm and a relative long lifetime of around 3 ms compared to others glass hosts, it shows potential applications in the design of erbium-doped fiber amplifiers. The absorption, the stimulated emission and the gain cross-sections of this transition have been obtained and compared with that obtained in different hosts. Finally, infrared-to-visible upconversion processes exciting at around 800 nm have been analyzed and different mechanisms involved in the energy conversion have been proposed.     

1.4 μm emission properties and local environments of Tm ions in tellurite glass modified with MoO3

The 1.4 μm emission properties of Tm³⁺ ions embedded in tellurite glass containing MoO₃ have been investigated in an effort to develop non-crystalline materials for ultra broadband optical amplifier. Spectral lineshape and bandwidth of the 1.4 μm emission exhibited a negligible dependence on amount of MoO₃, while the measured lifetime of the Tm³⁺:³H₄ state decreased with increase in MoO₃ content. Multiphonon relaxation turned out to become stronger with increase in MoO₃ amount, which coincided with the further broadened Raman scattering bandwidth of the MoO₃-containing tellurite glass. The spectroscopic properties of Tm³⁺ ions doped in our modified tellurite glasses are discussed in connection with the local structural parameters obtained from Tm L₃-edge EXAFS analysis.     

Thermal and optical properties of Tm: Li6Gd(BO3)3 crystal: A potential candidate for 1.83 μm lasers

Single crystal of Tm³⁺: Li₆Gd (BO₃)₃ was grown by the Czochralski method. The heat capacity was measured from 308 to 673 K. The absorption spectra of the crystal in three mutually perpendicular arbitrary directions were measured at room temperature. Based on the Judd-Ofelt theory and the spectra measured in three mutually perpendicular directions, the intensity parameters Ω_t (t=2, 4, 6), the line strengths, the oscillator strengths, the radiative rates, radiative lifetimes and fluorescent branching ratios were calculated. We calculated the emission cross-section by the reciprocity method and also obtained the gain cross-section.     

1.54 μm emission mechanism of Er-doped zinc oxide thin films

Zinc oxide (ZnO) and Er-doped zinc oxide (ZnO:Er) thin films were formed by pulsed laser deposition, and characterized by photoluminescence (PL) and X-ray diffraction (XRD) in order to clarify the 1.54 μm emission mechanism in the ZnO:Er films. Er ions were excited indirectly by the 325 nm line of a He-Cd laser, and the comparison of the ultraviolet to infrared PL data of ZnO and ZnO:Er films showed that the 1.54 μm emission of Er³⁺ in ZnO:Er film appears at the expense of the band edge emission and the defect emission of ZnO. The crystallinity of the films was varied with the substrate temperature and post-annealing, and it was found that the intensity of the 1.54 μm emission is strongly related with the crystallinity of the films. There are three processes leading to the 1.54 μm emission; absorption of excitation energy by the ZnO host, energy transfer from ZnO to Er ions, and radiative relaxation inside Er ions, and it is suggested that the crystallinity plays an important role in the first two processes.     

First high-resolution analysis of the 4ν1+ν3 band of nitrogen dioxide near 1.5 μm

The high-resolution absorption spectrum of the 4ν₁+ν₃ band of the ¹⁴N¹⁶O₂ molecule was recorded by CW-Cavity Ring Down Spectroscopy between 6575 and 6700 cm⁻¹. The assignments involve energy levels of the (4,0,1) vibrational state with rotational quantum numbers up to K_a=8 and N=48. A large majority of the spin-rotation energy levels were reproduced within their experimental uncertainty using a theoretical model which takes explicitly into account the Coriolis interactions between the spin-rotational levels of the (4,0,1) vibrational state and those of the (4,2,0) and of (0,9,0) dark states, the anharmonic interactions between the (4,2,0) and (0,9,0) states together with the electron spin-rotation resonances within the (4,0,1), (4,2,0) and (0,9,0) states. Precise vibrational energies, rotational, spin-rotational, and coupling constants were determined for the {(4,2,0), (0,9,0), (4,0,1)} triad of interacting states. Using these parameters and the value of the transition dipole-moment operator determined from a fit of a selection of experimental line intensities, the synthetic spectrum of the 4ν₁+ν₃ band was generated and is provided as Supplementary Material.     

Spectral broadening and luminescence quenching of 1.53 μm emission in Er-doped zinc tellurite glass

The emission spectra and the lifetime of the lasing transition ⁴I_13/2→⁴I_15/2 in Er³⁺-doped TeO₂-ZnO binary glass have been studied. The investigation includes Raman scattering spectroscopy as well as optical absorption, luminescence, and lifetime measurements techniques. The influence of erbium concentration on the line-shape of this electron transition has been analyzed. It was observed that the increasing of Er³⁺ ion concentration, in the 0.2-4 mol% range, results in a structural changes and a significant spectral broadening of the 1.53 μm emission band. Reabsorption has been evoked to explain the broadening of the ⁴I_13/2→⁴I_15/2 emission line. In the paper, is also reported the effect of the erbium content on the emission intensity of the ⁴I_13/2→⁴I_15/2 transition as well as on the lifetime of the ⁴I_13/2 level. Based on the electrical-dipole interaction theory, the luminescence concentration quenching mechanism by hydroxyl groups is analyzed. The data suggest that <10% of hydroxyl groups are coupled to erbium ions in the zinc tellurite glass network.     

Growth, polarized spectral properties, and 1.5–1.6 μm laser operation of Er:Yb:Sr3Gd2(BO3)4 crystal

An Er:Yb:Sr₃Gd₂(BO₃)₄ crystal was grown by the Czochralski method. The polarized spectral properties of the crystal were investigated, including the polarized absorption and fluorescence spectra and fluorescence decay. The fluorescence quantum efficiency of the upper laser level ⁴I_13/2 of Er³⁺ ions and the efficiency of the energy transfer from Yb³⁺ to Er³⁺ ions were calculated. End-pumped by a diode laser at 970 nm in a hemispherical cavity, a 1.6 W quasi-cw laser at 1.5–1.6 μm with a slope efficiency of 18% and an absorbed pump threshold of 5.9 W was achieved in a 1.8-mm-thick Z-cut Er:Yb:Sr₃Gd₂(BO₃)₄ crystal. This crystal has a flat and broad gain curve at 1.5–1.6 μm and so is also a potential gain medium for tunable and short pulse lasers.     

Experimental low energy values of CH4 transitions near 1.33 μm by absorption spectroscopy at 81 K

The high resolution absorption spectrum of methane has been recorded at liquid nitrogen temperature by direct absorption spectroscopy between 1.36 and 1.30 μm (7351-7655 cm⁻¹) using a cryogenic cell and a series of distributed feed back (DFB) diode lasers. The investigated spectral range corresponds to the high energy part of the icosad dominated by the ν₂+2ν₃ band near 7510 cm⁻¹. The positions and strengths at 81 K of 3473 transitions were obtained from the spectrum analysis. The minimum value of the measured line intensities (at 81 K) is on the order of 10⁻²⁶ cm/molecule, i.e. significantly lower than the intensity cut off of the HITRAN database in the region (4×10⁻²⁵ cm/molecule at 296 K). From the variation of the line strength between 81 and 296 K, the low energy values of 1273 transitions could be determined. They represent 69% and 81% of the absorbance in the region at 296 and 81 K, respectively. The obtained results are discussed in relation with the few rovibrational assignments previously reported in the region.     

6.2 W laser-diode end-pumped continuous-wave Nd:YALO3 laser at 1.34 μm

We report a compact and efficient LD end-pumped linearly polarized Nd:YAP laser operating at 1.34 μm. The laser system with different crystal lengths, output couplers and cavity types were compared. Based on optimizing of the pump system and laser cavity, 6.2 W laser radiation at 1341.4 nm with c-axis polarized was achieved, corresponding to an optical conversion efficiency of about 24.8% with respect to the incident pump power. The laser threshold was only about 1.3 W and the optical slope efficiency was up to 27.2%.     

Temperature dependence of the absorption spectrum of CH4 by high resolution spectroscopy at 81 K: (I) The region of the 2ν3 band at 1.66 μm

In a recent contribution, (Gao B, Kassi S, Campargue A. Empirical low energy values for methane transitions in the 5852-6181 cm⁻¹ region by absorption spectroscopy at 81 K. J Mol Spectrosc 2009;253:55-63.), the low energy values of methane transitions between 1.71 and 1.62 μm were derived from the variation of the line intensities between 296 and 81 K. The line intensities at 81 K were retrieved from the high resolution absorption spectrum of methane recorded at liquid nitrogen temperature by direct absorption spectroscopy using a cryogenic cell and a series of distributed feed back (DFB) diode lasers. For the line intensities at 296 K, the values provided by the HITRAN database were used. As a consequence of the relatively high intensity cut off (4×10⁻²⁴ cm/molecule) of the HITRAN line list in the considered region, the lower energy values were derived for only 845 of the 2187 transitions measured at 81 K. In the present work, our line list was extended by the retrieval of many weak line intensities leading to a set of 3251 transitions. The minimum value of the measured line intensities (at 81 K) is on the order of 10⁻²⁶ cm/molecule. In relation with the project “Greenhouse Gases Observing Satellite” (GOSAT), a much more complete line list for CH₄ at 296 K has become available (intensity cut off of 4×10⁻²⁶ cm/molecule). By applying the two temperature method to our line intensities at 81 K and GOSAT intensities at 296 K, the lower energy values of 2297 transitions could be derived. These transitions represent 99.1% and 90.8% of the total absorbance in the region, at 81 and 296 K respectively. This line list provided as Supplementary Material allows then accounting for the temperature dependence of CH₄ absorption below 300 K. The investigated spectral range is dominated by the 2ν₃ band near 6005 cm⁻¹ which is of particular interest for atmospheric retrievals. The factor 2 narrowing of the Doppler linewidth from room temperature down to 81 K has allowed the resolution of a number of 2ν₃ multiplets and improving the line intensity retrievals. A detailed comparison with GOSAT and HITRAN line lists has revealed a number of possible improvements.     

Structural and photoluminescence properties of SnO2:Ga films deposited on α-Al2O3 (0 0 0 1) by MOCVD

Gallium-doped tin oxide (SnO₂:Ga) films have been prepared on α-Al₂O₃ (0 0 0 1) substrates at 500 °C by the pulse mode metalorganic chemical vapor deposition (MOCVD) method. The relative amount of Ga (Ga/(Ga+Sn) atomic ratio) varied from 3% to 15%. Post-deposition annealing of the films was carried out at different temperatures for 1.5 h in ambient atmosphere . The structural, electrical, optical and photoluminescence (PL) properties of the films have been investigated as a function of annealing temperature. All the films have the rutile structure of pure SnO₂ with a strong (2 0 0) preferred orientation. A single ultraviolet (UV) PL peak near 337.83 nm was observed at room temperature for the 3% Ga-doped as-grown film and near 336 nm for the 15%-doped film, which can be ascribed to electron transition from the oxygen vacancy and interstitial Ga³⁺ donor levels to the acceptor level formed by the substitution of Ga³⁺ for the Sn site. After annealing, the luminescence spectra have changed a little bit, which is being discussed in detail.     

The 2ν3 band of CH4 revisited with line mixing: Consequences for spectroscopy and atmospheric retrievals at 1.67 μm

This paper presents a study of absorption in N₂-broadened P and R manifolds of the 2ν₃ band of CH₄ near 6000 cm⁻¹ using high resolution laboratory and atmospheric spectra. This region is of prime importance for the retrieval of methane abundances in the Earth's atmosphere using ground-based or space-borne spectrometers. Recent laboratory investigations have been devoted to the methane spectroscopic parameters in this band, motivated by their previous poor knowledge and their increasing use by remote sensing experiments. In the absence of a better model, previous studies have used Voigt line shapes and thus purposely neglected line mixing (LM). In this paper, we first present direct comparisons between measured laboratory spectra and the results of a model which accounts for LM without adjusting any of the spectroscopic parameters. A good agreement is obtained and the results show that LM does have a significant influence on the shapes of P and R manifolds. Hence, most previously observed discrepancies were not due to improper broadening and shifting coefficients but to the neglect of this effect. This also confirms that widths and shifts derived in recent 2ν₃ band studies neglecting LM are “effective” and lack physical meaning, as suggested in a previous work [17] (Frankenberg et al., 2008). In a second step, the conclusions from the laboratory data are tested using ground-based atmospheric solar absorption spectra. The fit residuals obtained confirm the quality of the proposed model and evidence the impact of line mixing on CH₄ atmospheric spectra. The present results also confirm that laboratory and atmospheric spectra can alternatively be accurately modeled neglecting LM and using ad hoc broadening and shifting parameters. Conclusions of this exercise can be drawn from two perspectives. From the point of view of spectroscopy and understanding of processes, accurate line parameters will not be deduced from fits of laboratory measurements unless line-mixing effects are included in the spectral-shape model. In the meantime, and from the point of view of atmospheric retrievals, neglecting LM with suitable effective line parameters is convenient and accurate (within current retrieval uncertainties). Note that this is only true if this approach is not used for total pressures significantly above 1 atm (e.g. Jupiter).     

Rovibrational spectroscopy of the Fermi-interacting ν4 = 1 and ν3 = ν6 = 1 levels of DCF3

The high-resolution infrared spectrum of deuterated fluoroform (DCF₃) was studied in the 700 and 1200 cm⁻¹ regions, with the aim of assigning and analyzing the ν₄ CF₃ asymmetric stretching vibration. The Fermi-type anharmonic coupling between the ν₄ = 1 and ν₃ = ν₆ = 1 rovibrational levels, already mentioned in an early work of Ruoff et al. [Spectrochimica Acta Part A 31A (1975) 1099-1100], was studied here for the first time under high resolution. Assignments in the ν₃ + ν₆/ν₄ band system were confirmed and extended by the identification of the ν₃ + ν₆ − ν₆ and ν₄-ν₆ bands in the 700 cm⁻¹ region, the latter being enhanced near the Fermi crossings of the studied levels. Data from both the hot and difference bands were included in the analysis. The close separation of the studied vibrational levels of about 14.8 cm⁻¹ produces a large variety of resonance crossings which involve levels with . Besides the Fermi () and Coriolis () resonances, they were accounted for by inclusion of additional higher-order ( and ) interaction terms between the vibrational states. The least-squares fit of more that 16,000 vibration-rotation transitions provides a quantitative reproduction of data in all bands.     

NaK bound-free and bound-bound 4 Σ → aΣ emission

The relative transition dipole moment function M(R) for the 4 ³Σ⁺ → a³Σ⁺ electronic transition in the sodium-potassium molecule (NaK) has been determined by fitting experimental bound-free and bound-bound emission spectra. The fit is performed using a modified version of the BCONT computer program, which was originally developed by Le Roy. Spectra previously measured in this laboratory from low-lying ro-vibrational levels of the 4 ³Σ⁺ state and new spectra from high-lying levels are included in the fit. A slight adjustment to the inner, repulsive wall of the 4 ³Σ⁺ potential leads to an improved form for that curve. The fitted M(R), when appropriately scaled, agrees very well with recent ab initio calculations of Magnier et al.     

Li2K(IO3)3与Li2NH4(IO3)3的晶体结构

本文用X射线粉末法测定了Li₂K(IO₃)₃与Li₂NH₄(IO₃)₃的晶体结构和原子参数。发现Li₃K(IO₃)₃,Li₂NH₄(IO₃)₃与Li₂Rb(IO₃)₃同晶型,属单斜晶系,空间群为P2₁/α,每个单胞含有四个化合式量。室温的点阵常数分别为α=11.198?,b=11.046?,c=8.254?,β=111.53°,及α=11.327?,b=11.078?,c=8.341?,β=111.87°。讨论了二元化合物的形成与离子半径的关系。 关键词：     

High sensitivity CW-cavity ring down spectroscopy of N2O near 1.5 μm (III)

We present the third part of the investigation of the high sensitivity absorption spectrum of nitrous oxide by CW-Cavity Ring Down Spectroscopy near 1.5 μm. In the two first contributions (A. Liu, et al., J. Mol. Spectrosc. 244 (2007) 33-47 and A. Liu, et al., J. Mol. Spectrosc. 244 (2007) 48-62) devoted to the 5905-6833 cm⁻¹ region, more than 9000 line positions of five isotopologues (¹⁴N₂¹⁶O, ¹⁵N¹⁴N¹⁶O, ¹⁴N¹⁵N¹⁶O, ¹⁴N₂¹⁷O and ¹⁴N₂¹⁸O), were rovibrationally assigned to a total of 115 bands, most of them being newly detected. The achieved sensitivity (α_min∼3 × 10⁻¹⁰ cm⁻¹) allowed for the detection of lines with intensity weaker than 2 × 10⁻²⁹ cm/molecule. In this contribution, the investigated region was extended up to 7066 cm⁻¹. The analysis based on the predictions of the effective Hamiltonian model has allowed assigning about 1500 transitions to 17, 1, 2 and 1 bands of the ¹⁴N₂¹⁶O, ¹⁴N¹⁵N¹⁶O, ¹⁵N¹⁴N¹⁶O and ¹⁴N₂¹⁸O isotopologues, respectively. Eleven of these 21 bands are newly reported, while the observations of the transitions are extended to higher J values for most of the others. The band by band analysis has allowed reproducing the measured line positions within the experimental uncertainty (about 1 × 10⁻³ cm⁻¹) and determining the corresponding spectroscopic parameters. A detailed analysis of the rovibrational perturbations affecting three bands of ¹⁴N₂¹⁶O is presented.     

Transport properties and in-situ Raman spectroscopy study of BaCe0.9Y0.1O3 − δ as a function of water partial pressures

The total conductivity of BaCe_0.9Y_0.1O_3 − δ material was measured under air, in a large p(H₂O) range up to 0.30 bar. The defect concentrations (OH_O^·, V_O^· · and h^·) and electrical conductivities were calculated on the basis of chemical constants (diffusion coefficients and equilibrium constants reported in the past literature) and compared to the experimental data. Protonic transport number as high as 0.8 was found at 700 °C, under air containing 0.30 bar of water, which allows a possible extension of the protonic temperature range of this material using water rich atmosphere. In-situ Raman spectroscopy under wet and dry air was performed from room temperature up to 700 °C in two wavenumber ranges. At low wavenumber, characteristic of lattice vibrations, this study clearly shows that no significant changes occur upon water insertion while at high wavenumbers, characteristic of OH vibrations, two contributions to the OH vibrations were found. This is discussed in terms of proton environment and transient hydrogen bonds. Moreover, this in situ study confirms that, at moderate p(H₂O), water insertion becomes significant at temperature below 650 °C.     

High-temperature magnetic properties of noninteracting randomly oriented single-domain Fe3 − δO4 nanoparticles

Magnetic measurements have been performed on 40-nm sphere-like Fe_3 − δO₄ (δ=0.043) nanoparticles using a Quantum Design vibrating sample magnetometer. Coating Fe_3 − δO₄ nanoparticles with SiO₂ effectively eliminates magnetic interparticle interactions so that the coercive field HC in the high-temperature range between 300 K and the Curie temperature (855 K) can be well fitted by an expression for noninteracting randomly oriented single-domain particles. From the fitting parameters, the effective anisotropy constant K is found to be (1.38±0.11)×¹⁰⁵ erg/cm³, which is very close to the bulk magnetocrystalline anisotropy constant of 1.35×¹⁰⁵ erg/cm³. Moreover, the inferred mean particle diameter from the fitting parameters is in quantitative agreement with that determined from transmission electron microscope. Such a quantitative agreement between data and theory suggests that the ensemble of our SiO₂-coated sphere-like Fe_3 − δO₄ nanoparticles represents a good system of noninteracting randomly-oriented single-domain particles.     

Infrared absorption cross sections for propane (C3H8) in the 3 μm region

Infrared absorption cross sections for propane have been measured in the 3 μm spectral region from spectra recorded using a high-resolution FTIR spectrometer (Bruker IFS 125 HR). The spectra of mixtures of propane with dry synthetic air were recorded at 0.015 cm⁻¹ resolution (calculated as 0.9/MOPD using the Bruker definition of resolution), at a number of temperatures and pressures appropriate for atmospheric conditions. Intensities were calibrated using two propane spectra (recorded at 278 and 293 K) taken from the Pacific Northwest National Laboratory (PNNL) IR database.     

水热法制备的Li4-3xEux(MoO4)2微晶及其发光性能

采用水热法制备了Li_4-3xEu_{x(MoO4)2系列红色荧光粉.通过X射线衍射(XRD)、扫描电镜(SEM )和荧光分析(FL)对产物的微结构、形貌和发光性能进行表征分析.XRD分析表明,制备的Li4-3xEux(MoO4)2微晶均为白钨矿四方结构.SEM结果显示:随着x的增大,Li4-3xEux(MoO4)2微晶的晶粒尺寸相应减小,在0.2~0.5 μm之间变化.荧光分析结果表明:源于Eu³⁺的⁵D0→⁷F2和⁵D0→⁷F1电荷转移的592 nm和614 nm的特征发射峰显现明显,后者的发射强度远远大于前者.随着x的增大,样品中Eu³⁺的两个特征发射峰的强度先增大后减小,在x=1.0时达到最大.}