Broadband near-infrared emission in Er3+-Tm3+ codoped chalcohalide glasses

The near-IR emission spectra of Er3+-Tm3+ codoped 70GeS2-20In2S3-10CsI chalcohalide glasses were studied with an 808 nm laser as an excitation source. A broad emission extending from 1.35 to 1.7 microm with a FWHM of approximately 160 nm was recorded in a 0.1 mol.% Er2S3, 0.5 mol.% Tm2S3 codoped chalcohalide glass. The fluorescence decay curves of glasses were measured by monitoring the emissions of Tm3+ at 1460 nm and Er3+ at 1540 nm, and the lifetimes were obtained from the first-order exponential fit. The luminescence mechanism and the possible energy-transfer processes are discussed with respect to the energy-level diagram of Er3+ and Tm3+ ions.     

Ce~(3+)和Tb~(3+)掺杂钆-钡-硅酸盐闪烁玻璃的发光性能

采用高温熔融法制备Ce~(3+)或Tb~(3+)单掺和Ce~(3+)/Tb~(3+)共掺钆-钡-硅酸盐闪烁玻璃。通过透射光谱、光致激发和发射光谱、X射线激发发射光谱及荧光衰减曲线等手段对其发光性能进行研究。实验结果表明:在紫外光的激发下,Tb~(3+)掺杂闪烁玻璃发出明亮的绿光(544 nm),而Ce~(3+)掺杂闪烁玻璃发出蓝紫光。对于Ce~(3+)/Tb~(3+)共掺闪烁玻璃,在紫外光和X射线激发下均观察到Ce~(3+)离子敏化Tb~(3+)离子发光的现象,这是由于存在Ce~(3+)→Tb~(3+)的能量转移。Ce~(3+)/Tb~(3+)共掺闪烁玻璃的最佳Ce2O3掺杂摩尔分数为0.2%,此时Ce~(3+)离子向Tb~(3+)离子的能量传递效率为45.7%。在X射线激发下,Ce_2O_3摩尔分数为0.2%的Ce~(3+)/Tb~(3+)共掺闪烁玻璃在544 nm处的发光强度是Bi_4Ge_3O_(12)(BGO)闪烁晶体在500 nm处发光强度的4.2倍,积分闪烁效率达到BGO晶体的55.6%,这有利于在高分辨率医学成像中降低辐射剂量。     

Influences of Doping and Annealing on the Structural and Photoluminescence Properties of Y2O3 Nanophosphors

This paper reports the structural and optical properties of rare earth doped and codoped yttrium oxide nanophosphors. Dysprosium (Dy³⁺) and Terbium (Tb³⁺) doped and codoped yttrium oxide (Y₂O₃) phosphors were prepared by combustion synthesis method and subsequently annealed to high temperature to eliminate the hydroxyl group (?OH) and to get more crystallinity. The formation of compounds was confirmed by the X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR). The diffuse reflectance spectra (DRS) of doped and codoped Y₂O₃ powder phosphors were measured and it is observed that the absorption edge of the doped samples is shifted towards blue region with respect to undoped sample. The bandgap of the prepared samples were evaluated with the help of Kubelka-Munk function using Diffuse Reflectance Spectra (DRS) and an increase in bandgap was observed with the decrease in crystallite size. A strong characteristics emission from Tb³⁺ and Dy³⁺ ions was identified and the influence of doping concentration and annealing temperature on photoluminescence properties was systematically studied. Transfer of energy was observed in dysprosium–terbium codoped Y₂O₃ nanophosphor at room temperature from Dy³⁺ ions toTb³⁺ ions.     

掺铒重金属氧氟硅铋酸盐玻璃的光谱性质

研究了重金属氧氟硅铋酸盐玻璃 (50-x)SiO2 xBi2O3 50PbF2(x=0, 3, 5, 8, 10, 13, 15 mol%)中Er3+离子的吸收光谱、荧光光谱、荧光半高宽、荧光 寿命和热稳定性能.应用Judd Ofelt理论计算了玻璃的强度参数Ωt(t=2,4,6)，应用 McCumber计算了能级4I13/2→4I15/2跃迁的受激发射截面. 结果发现荧光半高宽与Ω6有较大联系，Ω6越大，荧光半高宽越宽.对Er3+ 关键词： 重金属氧氟硅铋酸盐玻璃 光谱性质 Er3+离子 Judd Ofelt参数     

Second-harmonic generation in thermally poled chalcohalide glass

Second-harmonic generation in 60GeS(2)-20Ga(2)S(3)-20KBr chalcohalide glass was investigated by the thermal poling method. A large second-order nonlinear susceptibility, as high as 7.0 pm/V, was obtained in a poled sample by Maker fringe analysis. We believe this to be the first time that a clear second-harmonic wave was observed in chalcohalide glasses containing large amount of alkali ions (6.25 at. %). Such observation is of great potential use in all optical waveguide devices.     

Fluorescence characteristics of Dy ions in calcium fluoroborate glasses

Calcium fluoroborate (CFB) glasses doped with different concentrations of trivalent dysprosium ions were prepared and investigated by the FTIR, optical absorption, photoluminescence and decay analysis. Free-ion Hamiltonian model and Judd-Ofelt theory have been used to analyze the energy level scheme and the spectral intensities of Dy³⁺ ions in CFB glasses. From the emission spectra it is observed that the samples emit intense light yellowish color which is nearer to white light. Chromaticity color coordinates have been calculated and the dominant emission wavelength has also been indicated. Decay curves of ⁴F_9/2 level for the samples with different concentrations have been analyzed using the Inokuti-Hirayama model and the energy transfer and non-radiative decay rates have been determined.     

The effect of Ce3+ ions on the spectral and decay characteristics of luminescence phosphate-borate glasses doped with rare-earth ions

The luminescent characteristics of Li₂O-B₂O₃-P₂O₅-CaF₂ (LBPC) glasses doped with Gd³⁺ and Tb³⁺ ions and codoped with Ce³⁺ are studied by pulsed optical spectrometry under electron beam excitation. It is found that in glass with Ce³⁺ and Gd³⁺ ions a decrease in the decay time of gadolinium luminescence in the 312-nm band (⁶ P _J → ⁸ S _7/2) was observed. It is shown that in the glass LBPC: Tb, Ce, an increase in the emission intensity in the main radiative transitions in terbium ion was observed. In the kinetics of luminescence band 545 nm of LBPC: Tb, Ce glasses, is present stage of buildup, the character of which changes with the doped of Ce³⁺ ions. The mechanism of energy transfer in LBP glasses doped with rare elements is discussed.     

Optical spectroscopy of Cr3+ and Cr3+-Tm3+ in alkaline silicate glasses

Conclusions Alkaline silicate glasses seem to be good candidates as host materials for codoping with Cr³⁺ and Tm³⁺. Cr³⁺ ions occupy mainly low-field sites in them, and their broadband emission overlaps Tm³⁺ excitation. As a consequence very high efficiency for the energy transfer Cr³⁺→Tm³⁺ is achieved with moderate concentrations of these ions. Moreover, the average lifetime of the Cr³⁺ ions in codoped glasses is long enough to allow significant energy storage by flashlamp pumping. Published in Zhurnal Prikladnoi Spektroskopii, Vol. 62, No. 5, pp. 115–120, September–October, 1995.     

Erratum to Formation and control of Au and Ag nanoparticles inside borate glasses using femtosecond laser and heat treatment

We report the spectroscopic properties of femtosecond laser-irradiated sodium-alumino-borate glass doped with silver and gold ions. We precipitated gold and silver nanoparticles by laser irradiation and annealing at 400°C for 30 min. The irradiation and annealing treatment produced different absorption and emission characteristics in Au³⁺ doped and Au³⁺, Ag⁺ codoped glasses, and the possible mechanisms of the observed results are discussed. The size of the nanoparticles was estimated by TEM and absorption band analysis.     

熔制温度对铋离子掺杂钡铝硅酸盐玻璃发光性能的影响

研究了熔制温度对铋离子掺杂钡铝硅酸盐玻璃发光性能的影响.当用紫外光和808nm的激光二极管激发时,分别在425nm和1330nm附近观察到可见和宽带红外发光.可见荧光的发射强度随着熔制温度的升高逐渐下降,而红外发光强度随着熔制温度的升高先是增强然后减弱.对光致发光的机理进行了探讨.     

Energy transfer and mid-infrared luminescence properties of Tm3+ /Dy3+ codoped chalcohalide glasses

A series of chalcohalide glasses based on the composition 0.9 (Ge25 Ga5 S70)-0.1CsI doped with the different Tm3+ / Dy3+ ions ratio were synthesized by melt-quenching technique. The absorption spectra, and mid-infrared fluorescence of different glass samples under 800 nm laser excitation were measured. The results prove that, Tm3+ is an efficient sensitizer, which can enhance the Dy3+ : 2.9 microm fluorescence intensity significantly. A decrease in the intensity of 1.8 microm fluorescence and lifetimes of the Tm3+ : (3)F4 level occurred with increasing the concentration of Dy3+ ions from 0 to 1 Wt% where Tm3+ concentration was fixed to 0.5 Wt%. Also a wide spectral overlap between Tm+ : 1.8 microm emission and the absorption of Dy3+ : 6 H(15/2) --> (6)H(11/2) showed that the effective energy transfer between the two rare-earth ions was mainly attributed to the resonance energy from Tm3+: (3)F4 to Dy(3)+ : (6)H(11/2) level.     

Spectroscopic study of optical centers formed in Bi-, Pb-, Sb-, Sn-, Te-, and In-doped germanate glasses

We have shown that the broadband near-IR (NIR) fluorescence recently discovered in Bi-doped glasses is not specific due solely to Bi ions. Glasses doped with different 6p (Bi, Pb) and 5p (Sn, Sb) ions exhibit very similar behavior characterized by four major spectral peaks observed in two-dimensional excitation-emission plots and the lifetime of metastable level of about 400 mus. Our results challenge the existing models of optical centers in Bi-doped glasses. Point defect optical centers caused by the presence of 6p (Bi, Pb) and 5p (Sn, Sb) ions are proposed for the explanation of NIR emission in these laser materials.     

Yb3+/Er3+共掺锗碲酸盐玻璃上转换发光增强机理的研究

玻璃的最大声子能量决定稀土离子的上转换发光强度，但本研究发现：Yb^3 ／Er^3 共掺锗碲酸盐玻璃在980nm LD抽运下，上转换荧光强度随着Bi2O3对PbO的取代和碱金属离子半径的增大而明显增强．而Raman光谱显示基质玻璃的最大声子能量并不随Bi2O3对PbO的取代和碱金属离子半径的增大而变化，但玻璃的最大声子密度随着Bi2O3对PbO取代和碱金属离子半径的增大而降低．从玻璃无辐射跃迁概率的角度，通过分析表明，最大声子密度的降低是玻璃上转换发光强度增强的主要原因．     

结构自还原效应对铋掺碱土金属硅磷铝硼玻璃超宽带近红外发光的影响

本文报道了结构自还原对铋掺杂碱土金属硅磷铝硼玻璃超宽带近红外发光性质的影响. 以Eu作为对比, 在空气气氛中采用高温熔融法分别制备了Eu₂O₃和Bi₂O₃掺杂的35SiO₂-25AlPO₄-12.5Al₂O₃-12.5B₂O₃-15RO(R=Ca,Sr,Ba) 玻璃. 结果证实该玻璃中可发生Eu³⁺→Eu²⁺的高温自还原现象, 且随着碱土金属离子半径增大Eu²⁺ 的自还原性减弱; 同样条件下Bi位于1300 nm波段的近红外发光却随之增强, 而位于1100 nm波段近红外发光和源于Bi²⁺的红光则减弱. 根据结构自还原机理及碱土离子半径变化对玻璃近红外超宽带发光性质的影响, 讨论了Bi离子的近红外发光中心的归属. 上述研究表明玻璃结构自还原特性可以为Bi近红外发光机理研究以及高效Bi掺杂超宽带近红外发光玻璃的设计提供一种有效的思路和方法. 关键词： 玻璃 铋掺杂 近红外发光 自还原效应     

Efficient near-infrared emission from neodymium by broadband sensitization of bismuth in zeolites

Nd-Bi codoped zeolites were prepared by an ion-exchange process, and the optical properties were investigated by photoluminescence (PL) and PL excitation spectra, and decay time measurements. The results show that the NIR emission of Nd(3+) ions is significantly enhanced by the introduction of bismuth in codoped samples, and the lifetime reaches 246?μs. It is also observed that NIR-active Bi acts as a sensitizer of Nd(3+) ions. The energy transfer efficiency is also estimated. The peculiar optical properties make Nd-Bi codoped zeolites promising for potential application in biological probes.     

Effect of Yb on red to blue conversion fluorescence of Tm in fluorozirconate glass

The mechanisms governing the upconversion fluorescence from the ¹G₄ level of Tm³⁺ ions have been investigated in fluorozirconate glass doped with Tm³⁺ only and codoped with Tm³⁺ and Yb³⁺ ions, under 649 (³H₄→¹G₄) and 684 nm (³H₆→³F₃) excitation wavelengths. The emission intensity depends on the excitation power quadratically in both samples, showing the two-photon absorption nature of the processes. An enhancement of the ¹G₄→³H₆ emission was observed in the codoped sample under 684 nm excitation. The upconversion emission in the single doped sample is mainly due to the E.S.A. process upon both excitations. The dominant mechanism was found to be the energy transfer processes between Tm³⁺ and Yb³⁺ ions in the codoped sample when the excitation was tuned at 684 nm. The upconverted emission intensity shows a different temperature dependence under the two excitations in the codoped sample. However, for the 649 nm excitation the dependence is the same in both samples. This confirms the dominance of the E.S.A. process under 649 nm excitation in both, singly and doubly doped samples.     

Er3+单掺和Er3+/Yb3+双掺铋硼酸盐玻璃的研究

用高温熔融法制备了Er^3 单掺和Er^3 /Yb^3 双掺铋硼酸盐玻璃样品，测量了上述玻璃样品的吸收光谱，荧光光谱，荧光寿命以及红外透过率。对高浓度掺杂Er^3 的铋硼酸盐玻璃中的浓度猝灭现象作出了解释。分析了Er^3 ／Yb^3 双掺铋硼酸盐玻璃样品中Yb^3 离子对Er^3 离子的敏化过程。研究发现Er^3 ／Yb^3 双掺铋硼酸盐玻璃在1．5～1．6μm波段有宽达81nm的荧光半峰全宽。实验还发现在熔制过程中通入氧气对其荧光寿命和红外透过率都有明显的提高。由于该玻璃材料表现出较好的物化性能。因此该材料可望成为宽带光纤放大器的适宜的基质材料。     

Effect of some doping elements on the ionic conduction of mixed alkali-alumino-borosilicate glasses

Summary Some borosilicate glasses containing an equimolar ratio of different alkali types (K⁺ and Na⁺ ions) doped with 0.1 mole% R (R=Mn, Tb, Y, or Gd) were prepared. The results of d.c. electrical conductivity show that the absolute values of resistivities and the corresponding activation energies for the doped glasses are lower than those for glasses without doped ions. This behaviour is explained on the basis of the formation of elastic dipoles in such glasses and of the change of their fields owing to the existence of the doping ions. By thermal treatment of these glasses, it is found that the activation energies for the doped glasses are different from those obtained for glassess prepared without doping ions. This peculiarity is explained on the basis of the phase separation process in such glasses.     

Superbroadband 1310 nm emission from bismuth and tantalum codoped germanium oxide glasses

Near-infrared broadband emission from bismuth-tantalum-codoped germanium oxide glasses was observed at room temperature when the glasses were pumped by an 808 nm laser diode. The emission band covered the O, E, S, C, and L bands (1260-1625 nm), with a maximum peak at approximately 1310 nm, a FWHM broader than 400 nm, and a lifetime longer than 200 micros. The observed broadband luminescence was attributed to bismuth clusters in the glasses. Bismuth-tantalum-codoped germanium oxide glass might be promising as amplification media for broadly tunable lasers and wideband amplifiers in optical communications.     

Er~(3+)/Ce~(3+)共掺TeO_2-Bi_2O_3-TiO_2玻璃的热稳定性和光谱特性研究

用高温熔融法制备了Er3+/Ce3+共掺新型碲酸盐玻璃(TeO2-Bi2O3-TiO2).采用差热分析方法研究了玻璃的热稳定性,测试并分析了不同Ce3+离子掺杂浓度下Er3+离子的吸收光谱、上转换光谱和荧光光谱特性.研究结果表明,制备的碲酸盐玻璃具有很好的热稳定性,玻璃析晶温度Tx与玻璃转变温度Tg之差(ΔT=Tx-Tg)达到了185℃,高于其它文献的报道;同时,Ce3+离子共掺引入的能量转移(Ce3+∶2F5/2+Er3+∶4I11/2→Ce3+∶2F7/2+Er3+∶4I13/2)有效地抑制了Er3+离子上转换发光并显著增强了1.53μm波段荧光强度,而发射截面随着Ce3+离子掺杂浓度相应增大.优异的热稳定性以及光谱性能揭示Er3+/Ce3+共掺碲酸盐玻璃是一种潜在的制备宽带掺铒光纤放大器的理想增益介质.