Effect of PbCl2 addition on structure, OH− content, and upconversion luminescence in Yb3+/Er3+-codoped germanate glasses

Yb³⁺/Er³⁺-codoped oxychloride germanate glasses have been synthesized by a conventional melting and quenching method. Structural properties were obtained based on Raman-spectra investigation, indicating that PbCl₂ plays an important role in the formation of the glass network and has an important influence on the phonon density and the maximum phonon energy. The Judd–Ofelt intensity parameters and quantum efficiencies were calculated based on the Judd–Ofelt theory and lifetime measurements. The enhanced upconversion luminescence intensity of Er³⁺ with increasing PbCl₂ content could not be explained only by the maximum phonon-energy change of the host glasses. For the first time, the effect of PbCl₂ addition on phonon density, OH^– content, and upconversion luminescence in oxychloride glasses has been discussed and evaluated. The results show that the effect of phonon density and OH^– content on upconversion luminescence in oxychloride glasses is much stronger than that of the decrease of the maximum phonon energy. The possible upconversion luminescence mechanisms have also been estimated and are discussed.     

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：Yb³⁺/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Bi₂O ₃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Bi ₂O₃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.     

Spectroscopic properties of Er/Yb codoped fluorophosphate glasses

Er³⁺/Yb³⁺ codoped 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 Al(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.     

Upconversion luminescence of Tm/Yb-codoped oxyhalide tellurite glasses

Thermal stability, Raman spectra and blue upconversion luminescence properties of Tm³⁺/Yb³⁺-codoped halide modified tellurite glasses have been studied. The results showed that the mixed halide modified tellurite glass (TFCB) has the best thermal stability, the lowest phonon energies and the strongest upconversion emissions. The effect of halide on upconversion intensity is observed and discussed and possible upconversion mechanisms are evaluated. The intense blue upconversion luminescence of Tm³⁺ in TFCB glass may be a potentially useful material for developing upconversion optical devices.     

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．     

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     

Er,Yb:YAG微晶玻璃发光特性的研究

高温熔制Er³⁺，Yb³⁺离子掺杂CaO-Y₂O₃-Al₂O₃-SiO₂系统玻璃，并进行微晶化处理，研究了微晶玻璃中Er³⁺离子的发光及上转换发光特性，分析了微晶玻璃上转换发光机理.结果表明：原始玻璃经热处理得到了Er,Yb:YAG微晶玻璃，微晶玻璃中Er³⁺离子在室温下⁴I_13/2→⁴I_15/2跃迁产生横盖1450—1650nm区间的超宽带荧光，荧光半高宽达180nm，这可能由于YAG微晶相中Er³⁺离子与玻璃相中残留Er³⁺离子的共同发光；Er³⁺与Yb³⁺离子局域基质声子能量的降低使微晶玻璃Er³⁺离子上转换发光强度与原始玻璃相比显著提高，绿光、红光上转换荧光强度比玻璃样品分别增强约7和3倍；微晶化后Er³⁺，Yb³⁺离子局域环境发生变化也导致微晶玻璃中Er³⁺离子绿光、红光上转换发光相对强度发生变化. 关键词： 铒 镱:钇铝石榴石 微晶玻璃 荧光光谱     

高能、超短脉冲、可调谐激光器用掺镱氟磷酸盐玻璃研究进展

Yb^3 与其它稀土离子相比有最简单的能级结构，这使它具有一些独特的性质，如避免激发态吸收，消除上转换和浓度猝灭等，因此它是高能输出激光器介质的理想掺杂离子。氟磷玻璃综合了氟化物玻璃和磷酸盐玻璃的优点，可降低磷酸盐的声子能量，改善其易吸湿性；提高氟化物玻璃的物理化学性能等，这使它成为稀土掺杂可调谐光纤激光器的很好的掺杂介质。众多研究表明，Yb^3 掺杂氟磷玻璃是一种很有前途的激光工作物质。本文总结了Yb^3 掺杂氟磷玻璃的特点，性质，结构及存在的问题。     

Comparative investigation of up-conversion luminescence in Tm-doped oxide-chloride germanate and tellurite glasses

Tm³⁺-doped oxide-chloride germanate and tellurite glasses have been synthesized by conventional melting method. Intense up-conversion luminescence emissions were simultaneously observed at room temperature in these glasses. The possible up-conversion mechanisms are discussed and estimated. However, in these Tm³⁺-doped glasses, tellurite glass showed weaker up-conversion emissions than germanate glass, which is inconsistent with the prediction from the difference of maximum phonon energy between tellurite and germanate glasses. In this paper, Raman spectroscopy was employed to investigate the origin of the difference in up-conversion luminescence in the two glasses. Our results confirm that, besides the maximum phonon energy, the phonon density of host glasses is also an important factor in determining the up-conversion efficiency.     

Erbium doped phospho-tellurite glasses for 1.5 μm optical amplifiers

Erbium doped phospho-tellurite glasses with the alkali ions sodium and lithium is made and their optical and physical properties are studied. Glasses with high glass transition temperature and phonon energy which are suitable for fabrication of integrated optical amplifiers and lasers is obtained. From the optical absorption spectra the Judd-Ofelt parameters (Ω_t) and their radiative lifetimes are calculated. Absorption and emission cross-section spectra of the glasses for the transitions between ⁴I_13/2 and ⁴I_15/2 levels are reported.     

Enhancement of upconversion luminescence due to the formation of nanocrystals in Er3+-doped tellurite glasses

Optically transparent Er3+-doped tellurite-based nanocrystallized glasses with the composition of 70TeO2·15Lie2O·0·15Nb2O5·0.5Er2O3(mol)have been perpared by a conventional melting quenching and the subsequent heat treatment porcesses.The sizes of grown nanocrystals in glass matrix appear to be35-50 nm from the X-ray diffraction (XRD) measurement. The microhardness measurement shows that the Vickers hardness values of the nanocrystallized tellurite glasses are larger (33%-62%) than those inthe base glass. The Raman spectra imply that the maximum phonon energy of the based glass decreases and shifts from 668 to 638 cm-1 after heat-treatment. Visible upconversion luminescence and infrared luminescence of the base glass and heat-treated glasses under 980-nm laser diode (LD) excitation are investigated. The 524-, 546- and 656-nm upconversion intensities by 980-nm pumping increase significantly.     

Tm3+/Yb3+共掺碲酸盐玻璃的近红外发光及能量传递机理

采用高温熔融法制备了组分为TeO2-ZnO-Na2O的Tm3+离子单掺和Tm3+/Yb3+共掺碲酸盐玻璃,应用Judd-Ofelt理论计算分析了玻璃样品的强度参量Ωt(t=2,4,6),自发辐射跃迁几率A,荧光分支比β和荧光辐射寿命τrad等光谱参量,测量得到了不同Yb3+离子掺杂浓度下玻璃样品的Tm3+离子上转换发光谱.结果显示,在980nm泵浦光激励下玻璃样品发射出强烈的近红外上转换荧光.对Tm3+离子上转换发光分析表明,强烈的Tm3+离子近红外上转换发光主要来自于Yb3+/Yb3+离子间的共振能量传递以及基于单声子和双声子辅助的Yb3+/Tm3+离子间的非共振能量传递过程,并进一步计算得到了声子贡献比和能量传递系数.最后,计算分析了Tm3+∶3 F4→3 H6能级间跃迁的1.8μm波段吸收截面、受激发射截面和增益系数.研究表明,Yb3+/Tm3+共掺TeO2-ZnO-Na2O玻璃可以作为近红外波段固体激光器的潜在增益基质.     

Comparative investigation of up-conversion luminescence in Tm/Yb-codoped germanate-niobic and germanium-bismuth glasses: effect of phonon density on up-conversion emission

Tm³⁺/Yb³⁺-codoped germanate-niobic (GN) and germanium-bismuth (GB) glasses have been synthesized by conventional melting and quenching method. Intense blue and weak red emissions centered at 477 and 650 nm, corresponding to the transitions ¹G₄→³H₆ and ¹G₄→³H₄, respectively, were observed at room temperature. The possible up-conversion mechanisms are discussed and estimated. GN glass showed a weaker up-conversion emission than GB glass, which is inconsistent with the prediction from the difference of maximum phonon energy between GN and GB glasses. In this paper, Raman spectroscopy was employed to investigate the origin of the difference in up-conversion luminescence in the two glasses. Compared with phonon side-band spectroscopy, Raman spectroscopy extracts more information including both phonon energy and phonon density. For the first time, our results reveal that, besides the maximum phonon energy, the phonon density of host glasses is also an important factor in determining the up-conversion efficiency.     

Investigation on nonradiative decay of I13/2→I15/2 transition of Er-doped oxide glasses

Nonradiative decay of ⁴I_13/2→⁴I_15/2 transition of Er³⁺ has been investigated in a series of oxide glasses. For Er³⁺-doped glass samples, the Judd-Ofelt analysis on absorption spectra was performed and the fluorescence lifetime was determined by extrapolating to zero Er³⁺ concentration limit. Infrared spectra were measured in order to investigate the influence of OH⁻ groups in different glasses. The effects of glass matrix on the decay rate were discussed from the viewpoint of phonon energy, variations of effective fields, and OH⁻ groups. Compared to other glasses, phosphate glass presents low quantum efficiency and large nonradiative decay rate due to its high phonon energy and hygroscopic behavior.     

Tm3+/Yb3+共掺碲酸盐玻璃的近红外发光及能量传递机理

采用高温熔融法制备了组分为TeO₂-ZnO-Na₂O的Tm³⁺离子单掺和Tm³⁺/Yb³⁺共掺碲酸盐玻璃,应用Judd-Ofelt理论计算分析了玻璃样品的强度参量Ω_t(t=2, 4, 6),自发辐射跃迁几率A,荧光分支比β和荧光辐射寿命τ_rad等光谱参量,测量得到了不同Yb³⁺离子掺杂浓度下玻璃样品的Tm³⁺离子上转换发光谱.结果显示,在980 nm泵浦光激励下玻璃样品发射出强烈的近红外上转换荧光.对Tm³⁺离子上转换发光分析表明,强烈的Tm³⁺离子近红外上转换发光主要来自于Yb³⁺/Yb³⁺离子间的共振能量传递以及基于单声子和双声子辅助的Yb³⁺/Tm³⁺离子间的非共振能量传递过程,并进一步计算得到了声子贡献比和能量传递系数.最后,计算分析了Tm³⁺:³F₄→³H₆能级间跃迁的1.8 μm波段吸收截面、受激发射截面和增益系数.研究表明,Yb³⁺/Tm³⁺共掺TeO₂-ZnO-Na₂O玻璃可以作为近红外波段固体激光器的潜在增益基质.     

混合形成体对掺铒碲酸盐玻璃的热力学稳定性和发光性能的影响

研究了混合形成体效应对掺铒碲酸盐玻璃热力学稳定性、1.53 μm发光特性和上转换发光强度的影响.通过拉曼光谱测试,分析了WO₃,Nb₂O₅,GeO₂等氧化物对Er³⁺离子配位场结构,以及对发光谱的非均匀展宽机理的作用.结果表明,通过掺杂适当声子能量的网络形成体氧化物,不但可获得热力学稳定性较好的玻璃,还可有效降低Er³⁺离子⁴I_11/2能级的寿命,在抑制Er³⁺离子在可见光波段的上转换发光的同时不致劣化其在1.53 μm的发光特性.本文制得的碲酸盐玻璃具有较大的受激发射截面((9.64—10.96)×10^-21cm²)和荧光半高宽(FWHM)(50—67 nm),热力学稳定性良好,是一种理想的掺Er³⁺宽带有源光纤用基质玻璃. 关键词： 掺铒碲酸盐玻璃 混合形成体 1.53 μm发光 声子能量     

Super broadband reddish emitting glass with Eu2+ doped for warm-white light-emitting diodes

We present our recent achievements of glasses able to produce ultra-broadband visible fluorescence. The luminescence system was Eu²⁺ doped low silica calcium aluminosilica (LSCAS) glass excited by blue light. The LSCAS glass has the superior properties of oxide glasses and the low phonon energy property of non-oxide glasses. The large Stokes-shift (12163 cm^?1) and smoothing broadband emission (from 450 nm to 800 nm) were explained by the strong electron–phonon interaction and a remarkable nephelauxetic effect. Besides, given the broad excitation band in blue range, the commercialized blue LED will be a good excitation source. Therefore, these glasses have large potential to be used as warm-white light phosphor material.     

调控声子提高Tm3+掺杂体系的频率上转换荧光

应用激光光谱学技术,探讨了Tm³⁺离子掺杂透明氟氧化物玻璃陶瓷体系中声子调控对红色激光抽运荧光辐射性质的影响. 研究了基质结构和样品环境温度与电声子相互作用的联系以及声子变化对于荧光辐射产生的影响. 发现改变基质材料的SiO₂含量能影响蓝色上转换荧光效率. 另外,依据温度与声子能量之间的联系,通过改变样品环境温度可明显调节低声子基质材料中掺杂离子激发态能级的布居速率,改变上转换效率. 关键词： 荧光辐射 声子 无辐射弛豫 荧光寿命     

Upconversion and color tunability in Tm/Ho/Yb doped low phonon energy bismuth tellurite glasses

Low phonon energy Tm³⁺/Ho³⁺/Yb³⁺ triply doped bismuth tellurite glasses exhibiting multicolor upconversion fluorescences have been fabricated and characterized. The multicolor fluorescence composed of three primary colors green, red and blue upconversion emissions from Ho³⁺ and Tm³⁺ has been investigated. By adjusting the excitation power, the fluorescence colors can be tuned from multicolor to white color, and the dependence of color tunability on pump power has been presented in the CIE 1931 chromaticity diagram. With the increase in pumping power, the color coordinates move along the down-left direction and hit the equal energy point. The upconversion and color tunability via changing the pump power of infrared excitation in Tm³⁺/Ho³⁺/Yb³⁺ triply doped bismuth tellurite glasses will lead to new breakthrough in the field of three-dimensional solid-state displays and white-light emitting devices.     

TmYb共掺氟氧化物玻璃的间接上转换敏化发光的研究

研究了Tm(0.1)Yb(10.9)氟氧化物玻璃在800nm半导体激光激发下的间接上转换敏化发光现象.通过Tm(0.1)Yb(3)：ZBLAN玻璃和Tm(0.1)Yb(10.9)氟氧化物玻璃中Tm³⁺离子上转换发光的比较研究,发现在间接上转换敏化的情况下,Tm(0.1)Yb(10.9)氟氧化物玻璃中Tm³⁺离子的上转换发光极大地增强,超过了Tm(0.1)Yb(3)：ZBLAN玻璃的水平.说明在此类上转换激发机制下,有着较高的稀土溶解度和较大的截止声子能量的材料可能有最佳的上转换效率,它将可能有比目前最好的ZBLAN材料高许多的上转换发光强度,这对于上转换研究迅速走向实际应用有重大的意义.目前尚未见到其他类似研究报道. 关键词：