Relaxation dynamics of excited states of Tm3+ ions in TeO2-ZnO-Na2O-Y2O3 glasses

Tellurite glasses with the composition of xTm_2O_3-(6-x)Y_2O_3-3Na_2O-25ZnO-66TeO_2(where 0≤x≤6)were obtained by the melt-quenching technique.Absorption(300 K),excitation(300 K) and fluorescence spectra(300 K) as well as fluorescence decay curves of Tm~(3+)-doped title glasses are presented and discussed in details.The Judd-Ofelt analysis based on the room temperature absorption spectrum was applied for determination of fundamental fluorescence properties such as radiative transition probabilities(A_T),branching ratios(β_R),radiative lifetimes(τ_R) of the emitting levels of the Tm~(3+) ion and stimulated emission cross-sections(σ_(em)).Fluorescence spectra were recorded and analysed in the visible and near-infrared spectral range.The emission and effective cross-section were calculated for the ~3F_4→~3H_6 transition,showing that the investigated glasses are promising laser host materials,operating at 1.8 μm.The observed concentration quenching and non-exponential decay curves from the ~1 G_4 and ~3H_4 states indicate nonradiative energy transfer between Tm~(3+) ions.The analysis of non-exponential fluorescence decay curves from the ~1 G_4 and ~3H_4 levels was carried out in framework of the InokutiHirayama and Yokota-Tanimoto models and energy transfer microparameters were determined.The self-quenching model was proposed for describing relaxation of the first excited state of the Tm~(3+) ion.     

Design and achieving of multicolor upconversion emission based on rare-earth doped tellurite glasses

yD3＋/Tm3＋ co-doped and yD3＋/Ho3＋/Tm3＋ tri-doped tellurite glasses were synthesized by fusing the mixture of TeO2, PbF2, AIF3, BaF2, Yb2O3, Tm203 and H0203 in a cortmdum crucible at 850 ℃ for 20 min. The synthesized glasses were characterized by upconversion emission spectra under the excitation of 980 nm laser, and the emission colors were investigated according to the CIE-1931 standards. The results indicated that yD3＋/Tm3＋ co-doped tellurite glass exhibited blue upconversion emission with favor- able color coordinates of （0.20, 0.07）. Yb3＋, HO3＋ and Tm3＋ tri-doped tellurite glasses presented white upconversion luminescence under a single 980 nm laser excitation. Moreover, a very wide range of emission colors could be tuned by altering Ho3＋ concentration. Combining the contribution of adjusting Ho3＋ concentration and pump power, near equal energy white light was obtained.     

Structural and electrical properties of La2-xSrxMo2O9-δ

Sr-doped La2Mo2O9 were prepared by solid state reaction and characterized by XRD,impedance spectroscopy and HebbWagner polarization method.XRD patterns of the samples indicated that the solubility limit of Sr2+ in La2-xSrxMo2O9-δ was in the range of 7 mol.% to 7.5 mol.%,i.e.,the maximum stoichiometric coefficient x in La2-xSrxMo2O9-δ was larger than 0.14 and less than 0.15.The cubic lattice parameter of La2-xSrxMo2O9-δ(0相似文献   

Optical,thermal and luminescence properties of La2O3–Ga2O3–ZrO2 glasses co-doped with Tm3+/Yb3+ prepared by containerless technique

Bulk La₂O₃–Ga₂O₃–ZrO₂ (LGZ) glass and Tm³⁺/Yb³⁺ co-doped LGZ glasses were synthesized successfully using containerless technique. Raman spectra result reveals that the matrix sample possesses the low maximum phonon energy of ～642 cm^?1. The glasses show good compatibility between large Abbe numbers (>31) and high refractive indices (n_d > 1.93). Moreover, transmittance measurements reflect that the glasses have high infrared transmittance of ～81.9%, small OH^– absorption coefficient and long mid-infrared cut-off wavelengths (～7.5 μm). The surface morphology of host glass was characterized by scanning electron microscopy (SEM) micrograph and energy dispersive spectroscopy (EDS) tests reflect that the doped compositions are distributed into the matrix glass homogeneously. The results of thermal analysis show that the glasses have good thermal properties (T_g > 769 °C). Excited by 980 nm laser, an intense 1810 nm fluorescence is obtained originating from the transition: ³F₄ → ³H₆ of Tm³⁺ ion, accompanied by upconversion emission. It can be observed that 1810 nm fluorescence has the highest intensity at 1 mol% Yb₂O₃ and owns broad full width at half-maximum (>245 nm), the luminescence intensity of ³F₄ → ³H₆ transition increases with rising temperature from 300 to 550 K. Furthermore, the value of energy transfer efficiency shows that Yb³⁺ can transfer energy to Tm³⁺ effectively. By fitting the attenuation curves, the lifetimes of 1810 and 474 nm emission can be acquired.     

Kinetics of fluorescence properties of Eu~(3+) ion in strontium-aluminiumbismuth-borate glasses

Eu3＋ doped strontium-aluminium-bismuth-borate glasses with the chemical composition（50–x）B2O3＋20Bi2O3＋7Al F3＋ 8Sr O＋15Sr F2＋x Eu2O3（where x=0.1 mol.%, 0.5 mol.%, 1.0 mol.% and 1.5 mol.%） were prepared by the conventional melt quenching technique.Structural properties of the prepared glasses were analysed through X-ray diffraction（XRD）, scanning electron microscopy（SEM）, energy dispersive spectroscopy（EDS） and Raman spectral techniques.Thermal stability of glass was analysed by differential thermal analysis（DTA） curve.Photoluminescence characteristics were studied using excitation, emission spectra and decay curves of Eu3＋ doped strontium-aluminium-bismuth-borate glasses.The Judd-Ofelt（J-O） intensity parameters, Ωλ（λ=2, 4 and 6） were obtained using emission spectra and was used to identify the nature of Eu3＋ ions with their surrounding ligands.Using J-O parameters the transition probabilities（A）, stimulated emission cross-sections σE p, branching ratios（βR） and radiative lifetimes（τmeas and τcal） were evaluated for the 5D0→7F J（J=0, 1, 2, 3 and 4） transition of Eu3＋ ions in the present glasses.The decay profiles were found to be non exponential for all the concentrations and the measured lifetimes（τmeas） were obtained from the decay profiles.The higher values of A, σE p, βR and quantum efficiency（η） for 5D0→7F2 emission transition at 617 nm confirmed the present glass was as active medium for red laser emission applications.     

Energy transfer and 2 μm emission in Tm~(3+)/Ho~(3+) co-doped(Y_(0.87)La_(0.1)Zr_(0.03))_2O_3 nanopowders

(Y_(0.87)La_(0.1)Zr_(0.03))_2O_3 nanopowders doped with various concentrations of Tm~(3+) and Ho~(3+) were prepared by the citrate method. The standard cubic Y_2O_3 phase can be matched in the Tm~(3+)/Ho~(3+) co-doped(Y_(0.87)La_(0.1)Zr_(0.03))_2 O_3 nanopowders. The nanopowders exhibit average particle sizes of 40,60, 80 and 100 nm after calcinated at 900,1000,1100 and 1200℃,respectively. The energy transfer from Tm~(3+) to Ho~(3+) and the optimum fluorescence emission around 2 μm were investigated. Results indicate that the emission bands at around 1.86 and 1.95 μm correspond to ~3 F_4→~3 H_6 transition of Tm~(3+) and ~5 I_7→~5 I_8 transition of Ho~(3+), respectively.Better spectral properties were achieved in Tm~(3+)/Ho~(3+) co-doped(Y_(0.87)La_(0.1)Zr_(0.03))_2O_3 nanopowders with the average size of 100 nm obtained at the conditions of the treatment of precursors calcinated at 1200 ℃ for 2 h doped with 1.5 mol% Tm~(3+) and 1 mol% Ho~(3+).     

2 μm mid-infrared optical spectra of Tm3+-doped germanium gallate glasses

Glasses with the composition of 65GeO212Ga2O3-10BaO-8Li2O-5La2O3(molar ratio) doped with 1.526 wt.%, 3.006 wt.%, 5.836 wt.%, 11.028 wt.%, and 15.678 wt.% Tm2O3, respectively, were fabricated by conventional melting method. According to the absorption spectra and the Judd-Ofelt theory, the J-O strength parameters (Ω2,Ω4, Ω6) were calculated, with which the radiative transition probabilities,branching ratios and radiative lifetimes were obtained. The infrared emission spectra (with 808 nm LD excitation) at～1.47 and～1.8 μm of various concentrations of Tm3+-doped glasses were studied. The emission intensity at～1.8 μm reached to the maximum when the Tm2O3-doping concentration was near to be～3.006 wt.% (1.0 mol.%), and then decreased as doping concentration increased further. The mechanism of the fluorescence intensity change was explained with the cross-relaxation effect and the concentration quenching effect of Tm3+. Meanwhile, according to McCumber theory, the absorption and emission cross-sections corresponding to the 3F4→3H6 transitions of Tm3+ at 1.8 μm was obtained. For Tm3+-doped germanate glasses, the maximum emission cross-section reached a value higher than that re-ported for fluorozircoaluminate glasses. It is expected to be a favorable candidate host for～2.0 μm mid-inflated laser because the glass shows favorable optical spectra.     

Synthesis and Characterization of Lithium Borate Glasses Containing La<Subscript>2</Subscript>O<Subscript>3</Subscript>

The glass series with general formula 15 Li₂O–(85 − x) B₂O₃–x La₂O₃ was prepared. Electrical and optical properties of these glasses were studied. It is observed that the conductivity of these glasses decreases while density, glass transition temperature and refractive index increases with the addition of La₂O₃. Ion concentration of La³⁺ in glasses, polaron radius, field strength, molar refractivity and molar electronic polarizability were calculated. The absorption coefficient and direct optical band gaps are evaluated using the absorption edge calculations. The different factors that play a role for controlling the refractive indices such as electronic polarizability, field strength of cations and rigidity of glass structure are discussed in accordance with the obtained index data.     

Wastewater treatment using Fe-doped perovskite manganites by photocatalytic degradation of methyl orange,crystal violet and indigo carmine dyes in tungsten bulb/sunlight

We documented(ⅰ) the decolorization of wastewater in visible light,which contains methyl orange,crystal violet and indigo carmine dyes,using La_0.7Sr_0.3Mn_1-xFe_xO₃(x=0.0,0.05,0.1 and 0.5) manganites and(ⅱ) efficient separation of photocatalysts from water using magnetic field.These ceramic photocatalysts were sintered at 1050℃ for 12 h.Ceramics were characterized by X-ray diffraction(XRD),soft X-ray absorption spectroscopy(SXAS),Fourier transf...     

Thermal and radiative characteristics of oxyfluoride glass singly doped with lanthanide ions

Rare earths-doped oxyfluoride glasses based on germanium oxide and lead fluoride were prepared from commercial raw materials. The glasses with general composition of 50GeO2-(50-x-y)PbO-yPbF2-xLnF3 (Ln=Pr3+-Yb3+), contained different concentrations of optically active dopants (x=0.2 mol.% and 2 mol.%) and PbF2 (y≤15 mol.%). The differential thermal analysis (DTA) was used to determine both thermal characteristic and thermal stability properties of the glasses in the function of the kind of dopant, its concentration, and a glass composition. Characteristic glass temperatures such as glass transition temperature (Tg), glass crystallization temperature (Tc) and temperature corresponding to the maximum of the crystallization rate (Tpc) were evaluated. On the basis of obtained results, the thermal stabilities of glasses under study were evaluated using various thermal stability criteria (Dietzel factor ?T, Saad-Poulain factors H' and S). It was found that the increase in rare earth fluoride contents influenced thermal characteristics when the characteristic temperatures of the individual glass was shifted towards higher values. The effect of the PbF2 content and the kind of rare earth impurity on the glass stability was observed. Absorption spectra of lanthanide-doped glasses were measured at room temperature and used to determine the phenomenological intensity parameters Ωt and next, to estimate radiative properties of lanthanide ions in this matrix. Radiative transition probabilities of luminescent states of Ln3+, branching ratios and radiative lifetimes were determined. The variation of the Ωt along the lanthanide series was presented and discussed.     

Mechanical properties,thermophysical properties and electronic structure of Yb3+ or Ce4+-doped La2Zr2O7-based TBCs

First-principles calculations based on density functional theory were performed to investigate the cohesive energies, elastic modulus, Debye temperatures, thermal conductivities and density of states of La_2−xYb_xZr₂O₇, La₂Zr_2−xCe_xO₇ and La_2−xYb_xZr_2−xCe_xO₇ (x = 0.00, 0.25, 0.50, 0.75, 1.00) ceramics. The results show that doping Yb³⁺ or Ce⁴⁺ into La₂Zr₂O₇ reduces its elastic modulus, thermal conductivity and Debye temperature. Compared with La_2−xYb_xZr₂O₇ (x ≠ 0.00), La₂Zr_2−xCe_xO₇ compounds have better ductility and lower Debye temperature. The Debye temperature values of La₂Zr_2−xCe_xO₇ (x ≠ 0.00) compounds are in the range of 485.0–511.5 K. Among all components, the fluorite-type La_2−xYb_xZr_2−xCe_xO₇ (x = 0.75, 1.00) compounds exhibit better mechanical and thermophysical properties, and their thermal conductivity values are only 1.213–1.246 W/(m∙K) (1073 K), which are 14.5%–16.7% lower than that of the pure La₂Zr₂O₇. Thus, our findings open an entirely new avenue for TBCs.     

Gain properties of germanate glasses singly doped with Tm^3＋ and Ho^3＋ ions

Two kinds of germanate glasses singly doped with the ion concentration of 2.0mol.%Tm3+ and 2.0mol.%Ho3+, respectively, were prepared. According to McCumber theory, the absorption and stimulated emission cross-sections corresponding to the 3H6←→3F4 transitions of Tm3+ (at 1.8 μm) and the 5I8←→5I7 transitions of Ho3+ (at 2.0 μm) were obtained, and respective gain cross-section spectra were also computed as a function of population inversion according to absorption and emission cross-sections and the ion concentrations. For Tm3+-doped germanate glasses, the maximum of the absorption, emission, and gain cross-sections reached a value higher than those reported for fluorozirconate, fluoride, and oxyfluoride glasses. For Ho3+-doped germanate glasses, the maximum of absorption, emission, and gain cross-sections reached a value higher than that reported for fluorozircoaluminate glasses. Hence, these Tm3+-doped and Ho3+-doped germanate glasses exhibited an advantage for application in mid-infrared lasers at about 1.8 and 2.0 μm wavelength.     

Spectroscopic and fluorescence properties of Sm~(3+)-doped zincfluorophosphate glasses

Optical absorption and fluorescence spectra of Sm3＋-doped zincfluorophosphate glasses with molar composition of 44P2O5＋17K20＋9Al2O3＋（30-χ）ZnF2＋χSm2O3 （χ=0.01 mol.%, 0.05 mol.%, 0.1 mol.%, 0.5 mol.%, 1.0 mol.%, 2.0 and 3.0 mol.%） referred as PKAZFSm were prepared by melt quenching technique and were characterized through Raman, absorption, emission and decay curve analysis. From the absorption spectra, Judd-Ofelt intensity parameters were determined and were used to predict radiative properties such as transition probabilities （AR, radiative lifetimes （τR）, branching ratios （βR）, effective bandwidths （△λeff） and stimulated emission cross-section （σ（λp）） for the excited 4G5/2 luminescent level. The decay curve for the 4G5/2 level was single exponential for lower concentration and became non-exponential for higher concentrations. The non-exponential nature of the decay curves of the 4G5/2 level increased with increase in Sm3＋ ions concentration accompanied by decrease in lifetime due to energy transfer processes among the Sm3＋ ions. The non-exponential decay curves was well fitted to the generalized Inokuti-Hirayama model for S=6, indicating that the energy transfer among optically active ions was of dipole-dipole interaction. The cross-relaxation mechanism responsible for the quenching of lifetimes and the effect of variation of concentration on the spectroscopic properties were also discussed.     

Glass forming regions and concentration-dependent luminescence properties of Tb~(3+)-activated tellurium-lutetium-tungsten glasses

The glass-forming regions of tellurium-gadolinium-tungsten ternary system prepared at 1000℃for 60 min were firstly determined.To improve density,the full replacement of lutetium for gadolinium to form Tb³⁺-activated tellurium-lutetium-tungsten glasses with the composition of 64 TeO₂-20 WO₃-(16-y)Lu₂O₃-yTb₂O₃were designed for scintillation application.The concentration-dependent optical properties of Tb³⁺-activated tellurium-lutetium-tungsten glasses were fully investigated by transmittance,excitation and emission spectra,together with the luminescence decay curves.The energy transfer mechanism was discussed according to Huang’s rule.The optimized 4 mol%Tb₂O₃activated tellurium-lutetium-tungsten glasses with the density of 6.49 g/cm³and the lifetime of 0.551 ms are developing to be suitable for the potential detection of slow events in the future work.     

Effect of doped strontium on catalytic properties of La1‒xSrxMnO3 for rhodamine B degradation

A series of La_1‒xSr_xMnO₃ samples were prepared by sol–gel method and used to degrade rhodamine B (RhB) in water. All samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N₂ adsorption–desorption, temperature-programmed reduction of H₂ (H₂-TPR) and temperature-programmed desorption of O₂ (O₂-TPD). The results show that the degradation of RhB is highly dependent on the initial pH value of solution. Sr doping enhances the degradation ability of LaMnO₃ for RhB in the time range of 0–40 min under a strong acidic environment, but all samples exhibit similar degradation rate from 40 to 60 min. In La_0.7Sr_0.3MnO₃–RhB reaction system, there are two different degradation pathways, including N-de-ethylation, chromophore cleavage, ring-opening and mineralization. La_1‒xSr_xMnO₃ (x ≤ 0.3) has the perovskite structure of La–Mn oxides, while La_0.6Sr_0.4MnO₃ exhibits a Sr_0.4MnLa_0.6O_2.98 perovskite phase. Sr doping leads to distortion of rhombohedral crystal structure and increases the relative content of Mn⁴⁺. The perovskite structure is stable in strong acidic environment during RhB degradation, but the relative content of Mn⁴⁺ and Mn³⁺ on the material surface changes. Sr doped LaMnO₃ achieves specific surface area of 58.8 m²/g and total pore volume of 0.152 cm³/g. Furthermore, Sr²⁺ doping improves redox properties of La–Mn oxides, and the presence of defects makes oxygen diffusion easier compared with the undoped samples.     

Raman spectroscopy of borosilicate and germanate-silicate glasses and melts

33 mol % Na₂O · 67 mol % SiO₂ + xB₂O₃ (GeO₂) glasses and melts with x = 0 and 20 mol % are studied by high-temperature Raman spectroscopy. The laws of formation of the anion structure of glasses and melts of borosilicate and germanate-silicate systems are shown to be different. The dominant anion groups in the systems are identified, and the structural changes occurring with increasing temperature and during a glass-melt transition are detected.     

Effects of calcium substitute in LaMnO3 perovskites for NO catalytic oxidation

La1-x Cax MnO3 (x=0-0.3) perovskite-type oxides were synthesized by citrate sol-gel method. The physical and chemical properties were characterized by X-ray diffraction (XRD), Brumauer-Emmett-Teller method (BET), X-ray photoelectron spectroscopy (XPS), NO+O2 -TPD (temperature-programmed desorption), activated oxygen evaluation and H2 -TPR (temperature-programmed reduction) technologies. The results showed that NO catalytic oxidation activity was significantly improved by Ca substitution, especially for lower temperature activity. The La0.9 Ca0.1 MnO 3 sample showed the maximum conversion of 82% at 300 oC. The monodentate nitrates played a crucial role for the formation of NO2 . The reducibility of Mn 4+ ions and reactivity of activated oxygen were favorable for the catalytic performances of NO oxidation.     

Electrical properties of iron doped apatite-type lanthanum silicates

The effect of Fe doping on the electrical properties of lanthanum silicates was investigated. The apatite-type lanthanum silicates La10Si6-xFexO27-x/2 (x=0.2, 0.4, 0.6, 0.8, 1.0) were synthesized via sol-gel process. The unit cell volume increased with Fe doping because the ionic radius of Fe3+ ion is larger than that of Si4+ ion. The conductivities of La10Si6-xFexO27-x/2first increased and then decreased with the in-creasing of Fe content. The increase of the conductivity might be attributed to the distortion of the cell lattice, which assisted the migration of the interstitial oxygen ions. The decrease of the conductivity might be caused by the lower concentration of interstitial oxygen ions. The op-timum Fe doping content in lanthanum silicates was 0.6. La10Si5.4Fe0.6O26.7 exhibited the highest ionic conductivity of 2.712×10-2 S/cm at 800 ℃. The dependence of conductivity on oxygen partial pressure p(O2) suggested that the conductivity of La10Si6-xFexO27-x/2 was mainly con-tributed by ionic conductivity.     

Effects of lanthanum on abscisic acid regulation of root growth in Arabidopsis

Rare earth elements(REEs) were reported to have adverse biology effects on plant growth and production. However, whether REEs are involved in plant hormone abscisic acid signal is not clear. Here we reported that REE lanthanum(La) interacted with abscisic acid(ABA) in the regulation of seed germination and root growth in model plant Arabidopsis. La3+at a concentration of 10 μmol/L alleviated ABA depression of seed germination and reversed ABA inhibition of root elongation growth in Arabidopsis. Previous studies showed that ABA could promote root hair development. In the present study, La3+inhibited root hair development promoted by ABA. Moreover, La3+inhibited H2 O2 generation induced by ABA in root cells. Therefore we inferred that La3+might interact with ABA upstream of H2 O2 generation.     

Luminescent ionic lattice occupation and wide tunable emission spectra of La2MgZrO6:Bi3+,Eu3+ double perovskite phosphors for white light LED

La₂Mg_1-x/2Zr_1-x/2O₆:xBi³⁺(x=0.01-0.035,abbreviated as LMZ:Bi³⁺) and La_2-yMg_0.99Zr_0.99O₆:0.02Bi³⁺,yEu³⁺(y=0.1-0.11,abbreviated as LMZ:Bi³⁺,Eu³⁺) double-perovskite phosphors were prepared through high-temperature solid-phase method.The emission spectrum of LMZ:xBi³⁺(x=0.01-0.035)phosphors excited at 353 nm is asymmetric in the range be...