Dy~(3+)-Tb~(3+)掺杂氟氧碲酸盐玻璃的光谱性能研究

实验采用高温熔融法制备了一系列Dy3+离子、Tb3+离子单掺或共掺氟氧碲酸盐玻璃样品.测试了不同摩尔含量的Dy3+离子和Tb3+离子的氟氧碲酸盐玻璃样品的密度,分析了紫外-可见透射光谱、激发光谱、发射光谱、发光衰减曲线,研究了不同摩尔含量的Dy3+离子和Tb3+离子的氟氧碲酸盐玻璃样品光谱性能及Dy3+离子到Tb3+离子能量传递机理.结果表明:Dy3+离子、Tb3+离子单掺或共掺氟氧碲酸盐玻璃样品的密度均大于5g·cm-3,最大可达6.09g·cm-3;Dy3+离子可以敏化Tb3+离子,促进其发光,但当Dy3+离子超过一定浓度后,会发生离子间浓度猝灭效应,Tb3+离子的发光反而降低.试验测得,Dy3+离子的最佳掺杂浓度为1.0mol%,此时,Tb3+离子掺杂浓度为6.0mol%,Tb3+离子发光效果最强.依据Dexter能量传输理论,并对Dy3+离子和Tb3+离子的能级图及能级间的跃迁进行分析,可知Dy3+离子和Tb3+离子间的能量传递方式为非辐射共振传递.     

氟化物对Er3+/Yb3+共掺的碲酸盐玻璃上转换和红外发光性能的影响

Er³⁺/Yb³⁺ 共掺的碲酸盐玻璃由于其良好的上转换发光性能而得到广泛的研究。本文将氟化物引入碲酸盐玻璃中,通过熔融法制备了量比为70TeO₂-（30-x）ZnO-xZnF₂-0.15Er₂O₃-1.5Yb₂O₃（x=0,5,10,15,20）的碲酸盐氧氟玻璃样品,并测试其热稳定性、拉曼光谱以及受激发射光谱。实验结果表明,随着氟化物含量的提高,Er³⁺离子的410,555,670 nm上转换发光和2~3 μm波段中红外发光得到增强,并且红光提高强度比绿光和蓝光更明显。在分析了氟离子引入后对上转换与近中红外波段发光的内在影响机制发现：碲酸盐玻璃系统中的氟化物一方面促进能量传递过程中Er³⁺离子的双光子吸收,促进粒子跃迁至相应的高能级;另一方面,引入氟化物后的碲酸盐玻璃的最大能量声子态密度下降也是降低无辐射跃迁概率、提高上转换和中红外发射强度的重要原因。     

卤化铅调整Tm3+/Yb3+共掺碲酸盐玻璃上转换发光研究

研究了卤化铅调整Tm³⁺/Yb³⁺共掺碲酸盐玻璃的热稳定性能、Raman 光谱和上转 换发光光谱，分析了Tm³⁺/Yb³⁺共掺氧卤碲酸盐玻璃的上转换发光 机理.结果发 现：混合卤化铅调整Tm³⁺/Yb³⁺共掺碲酸盐玻璃具有好的热稳定性 能、低的声 子能量、强的上转换蓝光.这表明混合卤化铅调整Tm³⁺/Yb³⁺共掺碲 酸盐玻璃是一种上转换蓝光激光器的潜在基质材料. 关键词： 氧卤碲酸盐玻璃 上转换光谱 发光机理 上转换蓝光激光器     

Eu~(3+)掺杂碲酸盐闪烁玻璃的研究

用高温熔融法制备了Eu3+掺杂的碲酸盐闪烁玻璃。测试了Eu3+不同掺杂浓度玻璃样品的密度、差热特性、吸收、发射、激发光谱及X射线激发下的闪烁光谱。研究了不同Eu3+掺杂浓度对玻璃样品的密度、光谱性能的影响规律及掺杂离子的浓度猝灭效应。研究结果表明:Eu3+掺杂碲酸盐具有较大的密度和较强的闪烁发光,随着Eu3+浓度增加,由于Eu3+间的间距减小,共振能量转移几率增大,致使发光强度增强;但当掺杂到7mol%的高浓度时,会发生浓度猝灭效应。     

Tb3+掺杂高密度锗酸盐闪烁玻璃的发光性质

采用高温熔融法制备了Tb³⁺掺杂高密度锗酸盐玻璃。分别测试了该玻璃的透过光谱、密度、荧光光谱、荧光寿命及X射线激发发光光谱,揭示了该玻璃的物理化学性质和发光性质。透过光谱表明该玻璃具有良好的可见光透过率。高含量的Lu₂O₃和Gd₂O₃使得玻璃的密度高达6.4 g/cm³。该玻璃在377 nm光和X射线激发下发出强的绿光。544 nm发光的荧光寿命为1.325~1.836 ms。研究结果表明,Tb³⁺掺杂高密度锗酸盐玻璃是一种可用于慢速事件X射线探测器的候选闪烁材料。     

应用于白光显示的Tm3+/Ho3+/Yb3+共掺碲酸盐玻璃上转换发光特性研究

用高温熔融法制备了Tm³⁺/Ho³⁺/Yb³⁺共掺碲酸盐玻璃(TeO₂-ZnO-La₂O₃)样品,测试了玻璃样品的吸收光谱和上转换发光光谱,分析了上转换发光机理.结果发现:在975 nm波长激光二极管(LD)激励下,制备的碲酸盐玻璃样品可以观察到强烈的红光(662 nm)、绿光(546 nm)和蓝光(480 nm)三基色上转换发光,红光对应于Tm³⁺离子 关键词： 碲酸盐玻璃 上转换发光 白光 3+/Ho³⁺/Yb³⁺共掺')" href="#">Tm³⁺/Ho³⁺/Yb³⁺共掺     

掺铒氟(卤)磷碲酸盐玻璃的上转换发光性能研究

研究了掺铒氟(卤)磷碲酸盐玻璃的吸收光谱和上转换荧光光谱，探讨了Er³⁺在 氟(卤)磷碲酸盐玻璃中的上转换发光机理.在975nm激光二极管抽运下产生强烈的上转换红光 及绿光，且红光的发光强度要远远大于绿光.以PbCl₂取代PbF₂后， 红光的发光强度下降，而绿光却没有明显变化；以ZnCl₂取代ZnF₂ 达5mol%时，红光和绿光的发光强度均明显增大. 关键词： 氟(卤)磷碲酸盐玻璃 上转换发光 3+离子')" href="#">Er³⁺离子     

Er3+/Nd3+/Tm3+共掺碲酸盐玻璃近红外发射和能量传递机理

为满足通信网络飞速发展对密集波分复用系统(DWDM)传输容量需求的不断增加,对DWDM系统核心器件掺铒光纤放大器(EDFA)性能的要求也越来越高。碲酸盐玻璃因其具有稀土离子溶解度高,声子能量低和高折射率等优点已成为替代传统掺铒石英光纤的理想材料。掺稀土碲酸盐玻璃可以作为宽带光纤放大器的理想增益介质来实现信号有效放大,因此提高掺铒碲酸盐玻璃光谱性能并拓展其放大带宽对DWDM系统扩容具有重要意义。通过Er³⁺、 Nd³⁺和Tm³⁺共同掺杂提高碲酸盐玻璃的放大带宽以获得超宽带发光。Er³⁺、 Nd³⁺和Tm³⁺分别通过跃迁产生1.55、 1.34和1.85μm波段的发光,且三个近红外发射波段基本相邻。采用三种离子共掺的方式,通过离子间发生能量传递(ET)来实现碲酸盐玻璃在连续光谱中的发光。在TeO₂-WO₃-ZnO-Na₂O-Er₂O₃碲酸盐玻璃中,先进...     

Tb/Eu 共掺锌硼磷酸盐白光发光玻璃的制备及其发光性能

采用熔体冷却法,通过控制玻璃基质组成及稀土离子添加量,制备了Tb、Eu单掺和Tb/Eu共掺的锌硼磷酸盐低熔点发光玻璃。测试了样品的红外光谱、吸收光谱、激发与发射光谱和荧光寿命,并计算CIE色坐标,研究了材料的微观结构及发光性能。结果表明：样品中部分Eu³⁺被还原为Eu²⁺,在380 nm波长激发下,Tb/Eu共掺发光玻璃同时出现Eu³⁺红光、Tb³⁺绿光和Eu²⁺蓝光的特征发射。增加基体中B₂O₃含量能强化玻璃网络结构,并改变Eu²⁺/Eu³⁺比例。发射光谱和荧光寿命测试表明,共掺的发光玻璃中存在Eu²⁺→Eu³⁺,Eu²⁺→Tb³⁺和Tb³⁺→Eu³⁺的能量传递。改变Tb、Eu的掺杂浓度能够有效改变发光玻璃的发光强度和颜色,最终得到色坐标为（0.318 7,0.286 1）、色温6 480 K的发光玻璃。     

一种新型掺铒碲酸盐玻璃的光谱性质研究

研究了一种新型掺Er³⁺碲酸盐玻璃的光谱性质；应用Judd-Ofelt理论计算了碲 酸盐玻璃中Er³⁺离子的强度参数Ω(Ω₂=479×10^-20 cm²,Ω₄= 152×10^-20cm²,Ω₆=066×10^-20cm2)，计算了离子的自发跃迁概 率，荧光分支比；应用McCumber理论计算了Er³⁺的受激发射截面(σ_{e=1040×1 0^-21cm²)，Er³⁺离子⁴I13/ 2→⁴I15/2发射谱的 荧光半高宽(FWHM=655nm)及各能级的荧光寿命(⁴I13/2 能级为τrad =399ms)；比较了不同基质玻璃以及不同类型碲酸盐玻璃中Er³⁺离子的光谱 特性， 结果表明该掺铒碲酸盐玻璃具有更好的光谱性能，更适合于掺Er³⁺光纤放大 器实现宽带和高增益放大. 关键词： 碲酸盐玻璃 光谱性质 Judd-Ofelt理论}     

Ce3+ 掺杂高密度氧化物玻璃的闪烁性能研究

用高温熔融法制备了以SiO₂-B₂O₃-Al₂O₃-Gd₂O₃为基质系统Ce³⁺掺杂的玻璃样品, 测试样品的密度、紫外——可见透射光谱、紫外激发光谱和主要的闪烁性能, 并且把一部分闪烁性能和PbWO晶体及BGO晶体做比较. 着重研究了不同Ce³⁺掺杂浓度与Gd³⁺ 离子的含量对玻璃样品闪烁性能的影响规律. 结果表明: 玻璃样品具有较大的密度; 样品的X射线激发发射光谱发射峰位置都在390 nm左右, 当Ce³⁺ 离子的掺杂浓度为1.0 mol%(摩尔分数)、Gd₂O₃含量为15 mol%时, 玻璃样品的发光峰强度达到BGO晶体发光强度的90%; 同样验证了Ce³⁺ 离子具有浓度猝灭效应; Gd³⁺可以敏化Ce³⁺离子发光, 但是Gd³⁺离子到达一定浓度时, 反而会产生猝灭效应, 降低了Ce³⁺ 离子的发光. Ce³⁺ 离子掺杂SiO₂-B₂O₃-Al₂O₃-Gd₂O₃系统的闪烁玻璃有望替代闪烁晶体广泛应用于高能物理中.     

Recombination luminescence of CaSO4:Tb3+ and CaSO4:Gd3+phosphors

A comparative study of the excitation of luminescence by VUV radiation as well as of thermally and photostimulated luminescence has been carried out for CaSO₄:Tb³⁺ and CaSO₄:Gd³⁺ phosphors, where Na⁺ or F⁻ ions are used for charge compensation. The distinction in hole processes for the phosphors with Na⁺ or F⁻ compensators is determined by the differing thermal stability of the holes localized at/near Tb³⁺Na⁺ and Gd³⁺Na⁺ (up to 100–160 K) or at/near Tb³⁺F⁻ V _Ca and Gd³⁺F⁻ V _Ca centers involving also a cation vacancy (up to 400–550 K). Tunnel luminescence in the pairs of localized electrons and holes nearby Tb³⁺ or Gd³⁺ has been detected. The mechanisms of electron-hole, hole-electron and tunnel recombination luminescence as well as a subsequent released energy transfer to RE³⁺ ions are considered.     

Energy transfer and photoextinction from Ln to Tb and Eu in aqueous chloride solutions

Energy transfer and photoextinction from Ln³⁺ to Tb³⁺ and Eu³⁺ in aqueous chloride solutions were studied by absorption, emission and excitation spectra. The energy gaps below the luminescent terms of Gd³⁺, Tb³⁺ and Eu³⁺ are spanned by 10, 5 and 4 quanta, respectively, of the highest energy vibration in aqueous solution, and luminescence is observed in each case. This is not so for other Ln³⁺ where nonradiative deactivation dominates over luminescence. It was verified that only Gd³⁺ could transfer energy to Tb³⁺ and Eu³⁺ ions in aqueous or acid solutions. The ions Pr³⁺, Nd³⁺, Sm³⁺, Dy³⁺, Ho³⁺ and Er³⁺ exhibited strong competitive absorption at certain wavelengths, resulting in the photoextinction of Tb³⁺ and Eu³⁺ emission.     

Intramolecular Energy Transfer and Co-luminescence Effect in Rare Earth Ions (La, Y, Gd and Tb) Doped with Eu3+ β-diketone Complexes

In this paper, Eu³⁺ β-diketone Complexes with the two ligands 1-(2-naphthoyl)-3, 3, 3-trifluoroacetonate (TFNB) and 2’2-bipyridine (bpy) have been synthesized. Furthermore, we reported a systematical study of the co-fluorescence effect of Eu(TFNB)₃bpy doped with inert rare earth ions (La³⁺, Gd³⁺ and Y³⁺) and luminescence ion Tb³⁺. The co-luminescence effect can be found by studying the luminescence spectra of the doped complexes, which means that the existence of the other rare earth ions (La³⁺, Y³⁺, Gd³⁺ and Tb³⁺) can enhance the luminescence intensity of the central Eu³⁺, which may be due to the intramolecular energy transfer between rare earth ions and Eu³⁺. The efficient intramolecular energy transfer in all the complexes mainly occurs between the ligand TFNB and the central Eu³⁺. Full characterization and detail studies of luminescence properties of all these synthesized materials were investigated in relation to co-fluorescence effect between the central Eu³⁺ and other inert ions. Further investigation into the luminescence properties of all the complexes show that the characteristic luminescence of the corresponding Eu³⁺ through the intramolecular energy transfers from the ligand to the central Eu³⁺. Meantime, the differences in luminescence intensity of the ⁵D₀→⁷F₂ transition, in the ⁵D₀ lifetimes and in the ⁵D₀ luminescence quantum efficiency among all the synthesized materials confirm that the doped complex Eu_0.5Tb_0.5(TFNB)₃bpy exhibits higher ⁵D₀ luminescence quantum efficiency and longer lifetime than the pure Eu(TFNB)₃bpy complex and other materials.     

VUV-UV excited luminescent properties of LnCa4O(BO3)3:RE (Ln=Y, La, Gd; Re=Eu, Tb, Dy, Ce)

Calcium lanthanide oxyborate doped with rare-earth ions LnCa₄O(BO₃)₃:RE³⁺ (LnCOB:RE, Ln=Y, La, Gd, RE=Eu, Tb, Dy, Ce) was synthesized by the method of solid-state reaction at high temperature. Their fluorescent spectra were measured from vacuum ultraviolet (VUV) to visible region at room temperature. Their excitation spectra all have a broadband center at about 188 nm, which is ascribed to host absorption. Using Dorenbos’ and Jφrgensen's work [P. Dorenbos, J. Lumin. 91 (2000) 91, R. Resfeld, C.K. Jφrgensen, Lasers and Excite States of Rare Earth [M], Springer, Berlin, 1977, p. 45], the position of the lowest 5d levels E(Ln,A) and charge transfer band E_ct were calculated and compared with their excitation spectra.Eu³⁺ and Tb³⁺ ions doped into LnCOB show efficient luminescence under VUV and UV irradiation. In this system, Ce³⁺ ions do not show efficient luminescence and quench the luminescence of Tb³⁺ ions when Tb³⁺ and Ce³⁺ ions are co-doped into LnCOB. GdCOB doped with Dy³⁺ shows yellowish white light under irradiation of 254 nm light for the reason that Gd³⁺ ions transfer the energy from itself to Dy³⁺. Because of the existence of Gd³⁺, the samples of GdCOB:RE³⁺ show higher excitation efficiency than LaCOB:RE³⁺ and YCOB:RE³⁺, around 188 nm, which indicates that the Gd³⁺ ions have an effect on the host absorption and can transfer the excitation energy to the luminescent center such as Tb³⁺, Dy³⁺ and Eu³⁺.     

Post annealing immersion: A new technique for studying rare earth ions in porous materials

A novel technique is introduced for studying how rare earth ions are incorporated into the matrix of porous materials. Tb³⁺-doped silica sol-gel is annealed to form porous glass and immersed in an aqueous Gd(NO₃)₃ solution. Re-heating removes the liquid and deposits Gd³⁺ ions on the internal pore surfaces. Spectroscopic investigation of Gd³⁺→Tb³⁺ energy transfer yields information about the location of Tb³⁺ dopant ions relative to pore surfaces. Results from post-annealing immersion experiments indicate that most Tb³⁺ dopant ions are close to pore surfaces when sol-gel glass is annealed to 700 °C. The observed energy transfer decreases with higher annealing temperatures, indicating that Tb³⁺ dopants in densified regions are isolated from Gd³⁺ ions deposited on pore surfaces. Al³⁺ co-doping affects both the overall sample density and the degree of Gd³⁺→Tb³⁺ interaction in post-annealing immersion samples.     

The effect of codopants on spectral-kinetic characteristics of luminescence of scintillation glasses doped with terbium ions

The effect of Ce³⁺ and Pr³⁺ ions on spectral-kinetic characteristics of luminescence of lithium–phosphate–borate glasses is studied. It is shown that terbium ion luminescence caused by transitions from ⁵D₃ and ⁵D₄ multiplets to the ground 7FJ term is detected in samples containing Tb³⁺/Ce³⁺ and Tb³⁺/Pr³⁺. It has been found that an increase in the concentration of cerium ions from 0.2 to 1 wt % leads to an increase in the intensity of main luminescence bands of terbium ions. In Tb³⁺/Pr³⁺ glasses, a decrease in the relative light yield is observed with an increase in the concentration of Pr³⁺ ions. Processes of energy transfer between Tb³⁺/Ce³⁺ and Tb³⁺/Pr³⁺ ions are discussed.     

Preparation and characterization of Tb and Tb(sal)3·nH2O doped PC:PMMA blend

Tb doped polycarbonate:poly(methyl methacrylate) (Tb-PC:PMMA) blend was prepared with varying proportions of PC and PMMA. Thermal and spectroscopic properties of the doped polymer have been investigated employing Fourier Transform Infrared (FTIR) absorption and differential scanning calorimetric (DSC) techniques. PC:PMMA blend (with 10 wt% PC and 90 wt% PMMA) shows better miscibility. Optical properties of the dopant Tb³⁺ ions have been investigated using UV-vis absorption and fluorescence excited by 355 nm radiation. It is seen that luminescence intensity of Tb³⁺ ion depends on PC:PMMA ratio and on Tb³⁺ ion concentration. Concentration quenching is seen for TbCl₃·6H₂O concentration larger than 4 wt%. Addition of salicylic acid to the polymer blend increases the luminescence from Tb³⁺ ions. Luminescence decay curve analysis affirms the non-radiative energy transfer from salicylic acid to Tb³⁺ ions, which is identified as the reason behind this enhancement.     

Single-bubble sonoluminescence of aqueous solutions of lanthanide chlorides and models of the sonochemistry of nonvolatile metal salts

The single-bubble sonoluminescence of d-f (Ce³⁺, Pr³⁺) and f-f (Tb³⁺) ions is detected in aqueous solutions of LnCl₃. It has been shown that the luminescence of these ions is sonophotoluminescence, i.e., the reemission of the absorbed short-wavelength part of the radiation spectrum of a blackbody, which appears in a bubble levitating in the field of a standing ultrasonic wave, in the bulk of the solution. In view of the revealed inefficiency of reemission in GdCl₃, the single-bubble sonoluminescence of Gd³⁺ has not been observed. The results indicate the low probability of the penetration of nonvolatile metal ions into the bubble in the hot shell model, which would be valid in single-bubble sonolysis and thereby confirm the validity of the injected droplet model, which explains the penetration to the bubble, electronic excitation, and luminescence of f-f ions Gd³⁺ and Tb³⁺ in multibubble sonolysis with an intensity much higher than the yield of their sonophotoluminescence.     

The effect of Gd3+ on the Eu3+ luminescence in RbGd3F10: Eu3+ compounds

Eu³⁺ luminescence is studied in the two polymorphic forms of RbGd₃F₁₀: Eu³⁺. In the phases where Gd³⁺ is partly replacedby Y³⁺ in order to obtain an independent variation of Eu³⁺ concentration, the quenching of Gd³⁺ luminescence by Eu³⁺ ions takes place very quickly with increasing Eu³⁺ concentration. So the transfer between Gd³⁺ and Eu³⁺ is very efficient. Besides, an important self quenching occurs as well between Gd³⁺ ions as between Eu³⁺ ions, showing strong interactions.