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     

Research on upconversion luminescence in new Er3+/Yb3+codoped oxyfluoride borosilicate glass ceramics

The upconversion luminescence of Er3+/Yb3+ ions is researched in a novel transparent oxyfluoride borosil icate glass and glass ceramics under 980-nm excitation.Fluoride nanocrystals Ba2 YF7 are successfully precipitated in glass matrix,which is affirmed by the X-ray diffraction results.Compared with the parent glasses.significant enhancement of upconversion luminescence is observed in the Er3+/Yb3+ codoped transparent glass-ceramics.which may be due to the variation of coordination environment around Er3+ and Yb3+ ions after crvstallization.The possible upconversion mechanism is also discussed.     

以Eu-苯甲酸-1,10-菲咯啉为掺杂剂的SiO2,SiO2-B2O3和SiO2-B2O3-Na2O体系材料的结构及Eu3+的发光性质

用溶胶-凝胶法制备以Eu-苯甲酸-1,10-菲咯啉为掺杂剂的SiO2,SiO2-B2O3和SiO2-B2O3-Na2O为基质的发光材料.材料经1000℃退火处理后,结构十分稳定.通过激发光谱和发射光谱、红外光谱、TEM、XRD研究了基质结构对Eu3 发光性能的影响.结果显示:在589和614 nm处显示Eu3 的特征发射带,对应于Eu3 的5D0→7Fj(j=1,2)跃迁;与直接掺入EuCl3的玻璃材料相比,以Eu-苯甲酸-1,10-菲咯啉为掺杂剂的玻璃材料,虽然Eu的掺杂量较小,但Eu的发光强度较大.与以SiO2为基质的玻璃材料相比,以SiO2-B2O3为基质的玻璃材料Eu3 的发光减弱,其红外光谱显示形成Si-O-B键,说明该结构对Eu3 的发光有猝灭作用,以SiO2-B2O3-Na2O为基质的玻璃材料Eu3 的发光明显增强,其红外光谱显示不存在SiOB键的振动吸收,可能是Na取代B的位置,形成Si-O-Na键,此结构对Eu3 的发光有一定的增强作用.     

Upconversion luminescence in Er-doped germanate-oxyfluoride and tellurium-germanate-oxyfluoride transparent glass-ceramics

Upconversion luminescence has been studied for Er³⁺ in a germanate-oxyfluoride and a tellurium-germanate-oxyfluoride transparent glass-ceramic using 800 nm excitation. Significantly increased upconversion luminescence was observed from transparent glass-ceramics compared with that from their corresponding as-prepared glasses. In addition to a strong green emission centered at 545 nm from ⁴S_3/2 state and a weaker red emission centered at 662 nm from ⁴F_9/2 state generally seen from Er³⁺-doped glasses, a violet emission centered at 410 nm from ²H_9/2 state and a near-ultra-violet emission centered at 379 nm from ⁴G_11/2 state were also observed from transparent glass-ceramics. The upconversion luminescence of Er³⁺ ions in transparent glass-ceramics revealed sharp Stark-splitting peaks generally seen in a crystal host. The increased upconversion efficiency is attributed to the decreased effective phonon energy and the increased energy transfer between excited ions when Er³⁺ ions were incorporated into the precipitated β-PbF₂ nanocrystals.     

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.     

Upconversion fluorescence spectroscopy of Er~(3+)-doped lead oxyfluorosilicate glass

Upconversion fluorescence emission of Er3+-doped oxyfluorosilicate glass excited at 975 nm is experimentally investigated. The results reveal that the intense green and red emission, and weak blue emission centered at 525, 543, 655, and 410 nm, respectively. A two-photon upconversion process is assigned to the green and red emission while a three-photon process is responsible for blue upconversion. The possible upconversion mechanisms are discussed based on excited state absorption and energy transfer between excited Er3+ ions. The intense upconversion fluorescence of Er3+-doped lead oxyfluorosilicate glass may be a potentially useful material for developing upconversion optical devices.     

Blue Cooperative Luminescence In Yb3+-Doped Barium Gallogermanate Glass Excited At 976 nm

The Yb³⁺-doped barium gallogermanate glass has been prepared via the conventional melt method. The absorption spectra, the near infrared emission spectra, the upconversion emission spectra and the differential scanning calorimetry have been measured. Bright blue upconversion emission centered at 476 nm has been observed under the 976 nm laser diode excitation at room temperature. The blue upconversion emission mechanism has been discussed on the blue emission intensity and the measured lifetime. The slope of the log-log plot of the blue emission intensity versus the pump power is equal to 1.98, and the blue luminescence decay time is half of the near infrared fluorescence decay time, confirming that the blue emission comes from Yb³⁺-Yb³⁺ pairs cooperative upconversion mechanism. The result of differential scanning calorimetry suggests that this type of glass is suitable as a potential candidate for fiber drawing.     

Er3+掺杂重金属氧氟硅酸盐玻璃的上转换发光研究

研究了Er3+掺杂重金属氧氟硅酸盐玻璃的吸收光谱、上转换光谱和拉曼光谱，分析了重金属氧氟硅酸盐玻璃中Er3+的上转换发光机理. 结果表明：通过975nm的激光二极管激发，在室温下同时观察到蓝光(411nmj)、绿光(525和543nm)和红光(655nm)，分别是由于Er3+离子2H9/2→4I15/2, 2H11/2→4I15/2, 4S3/2→4I15/2, 和4F9/2→4I15/2跃迁. 随Er2O3浓度的增加，蓝光、绿光和红光的发光强度都增强，上转换发光机理主要涉及能量转移和激发态吸收，强烈的绿 关键词： Er3+离子 重金属氧氟硅酸盐玻璃 上转换光谱 发光机理     

Upconversion Luminescence of Er3+ Ions in Transparent Germanate Glass Ceramics Containing CaF2 Nanocrystals

The visible upconversion and near-infrared luminescence of Er3＋ ions in germanate glass ceramics containing GaF2 nanocrystals are investigated. The nanocrystals are characterized by x-ray diffraction （XRD） and transmission electron microscopy, showing their mean sizes less than 20hm. High transmittance of the glass ceramics is displayed by absorption spectra. The upconversion luminescence intensity in the glass ceramics increases significantly with increasing temperature. Both the shifts of the XRD peaks and the Stark-split shown in the luminescence spectra indicate the entrance of the Er3＋ ions into the CaF2 nanocrystals, which is confirmed by a Judd-Ofelt analysis. Possible mechanisms of the upconversion luminescence are analyzed.     

White light generation of glass ceramics containing Ba_2LaF_7：Eu~（2＋）,Tb~（3＋） and Sm~（3＋） nanocrystals

The Eu 2＋ /Tb 3＋ /Sm 3＋ co-doped oxyfluoride glass ceramics containing Ba2LaF7 nanocrystals are prepared in the reducing atmosphere.The X-ray difiraction results show that Eu 2＋ ,Tb 3＋ and Sm 3＋ ions are enriched into the precipitated Ba2LaF7 nanophase after the annealing process.It deduces efficient energy transfers from Eu 2＋ to Tb 3＋ and Sm 3＋ and intenses warm white luminescence of the glass ceramics. Comparing with the glass,the luminescence quantum yield of the glass ceramics is also enlarged by about 3 times.This demonstrates the potential white light-emitting diode application of the glass ceramics produced in this letter.     

Strong upconversion luminescence in Er~(3+)/Yb~(3+)-doped halide modified tellurite glass

Upconversion luminescence of Er3+/Yb3+-doped halide tellurite glass is investigated experimentally upon 976-nm excitation. Three intense emissions centered at 525, 545 and 655 nm owing to the transitions 2H11/2→4I15/2,4S3/2→4I15/2 and 4F9/2→4I15/2, respectively, are observed when pumping power is as low as 20 mW. The upconversion mechanisms and power dependent intensities are discussed. The high-populated 4I11/2 level is supposed to serve as the intermediate state responsible for the upconversion processes.     

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.     

Blue Upconversion Luminescence from Yb3+-doped Oxyfluoride Vitroceramics Excited by 960nm Laser

This paper investigates the upconversion luminescence of Yb3+-doped oxyfluoride vitroceramics excited by 960 nm diode laser. A new upconversion cooperative radiation luminescence is found, which is rather strong and positioned at 479.5 nm. It comes from a coupled state of two Yb3+ ion cluster. It is of significance due to the effective method to obtain compact blue light.     

氟化锆基质材料中单掺Yb3+的上转换特性

在众多的稀土掺杂氧化物、氟化物或氟氧化物基质材料的能量上转换研究当中,Yb^3 单独掺杂的能量上转换研究在国内报道的很少。这是因为,研究者们普遍都认为Yb^3 只是一种良好的敏化剂,主要起能量转移作用。采用固相合成法,稀土Yb单独掺杂ZrF4基质材料,在1200℃烧结合成了粉末样品。样品用功率为几mW的半导体红外激光980nm激发,肉眼就可看到上转换的明亮的红光。在实验室用功率为几十mW的半导体红外激光980nm激发,用光谱仪测量到红、绿、蓝及紫4个波段的上转换荧光光谱,其波峰在412,478,558,671nm波长处,实验反复验证,认为上转换来自Yb^3 的准能级向Yb^3 基态^2F7／2的跃迁。     

温度对稀土离子掺杂ZBLAN玻璃上转换发光的影响

研究了Er3+,Pr3+和Yb3+共掺杂ZBLAN玻璃在960nm激光泵浦下的上转换发光的温度特性.温度变化范围为室温到300℃.结果表明Pr3+离子的发光强度随温度的增加,先增加;达到极大后,随温度的增加下降.Er3+发光强度随温度增加单调下降.     

三价铕激活的(Y,La)2O2S二元体系的发光

为了寻找新的荧光粉基质料材,本文研究了在阴极射线、紫外线和X射线激发下,三价铕激活的(Y,La)2O2S二元体系的发光亮度、发射光谱和发光颜色等发光特性随组成变化的规律,并研究了三价铕离子浓度对(Y0.9La0.1)2O2S体系发光性能的影响。     

Sensitized thulium ultraviolet upconversion luminescence in Tm3+/Yb3+/Nd3+ triply doped nanoglass ceramics

Intense four- and five-photon ultraviolet upconversion processes through sensitization of Tm3+ ions in transparent SiO2-Al2O3-NaF-YF3 glass ceramics triply doped with Tm3+/Yb3+/Nd3+ under 796 nm excitation were investigated. Judd-Ofelt analyses evidenced the incorporation of rare-earth ions into the precipitated beta-YF3 nanocrystals. In contrast with the triply doped one, no ultraviolet upconversion luminescence was observed in the Tm3+/Nd3+ codoped glass ceramic, indicating that Yb3+ acts as bridging ions to enhance the energy transfer efficiency between Nd3+ and Tm3+. Based on the pumping power dependence of luminescence, upconversion mechanisms were proposed.     

Eu3+在硼酸盐玻璃中的发光以及Bi3+对Eu3+的敏化作用

本文研究了单掺和双掺(Eu3+,Bi3+,Fu3++Bi3+)约二十余种不同成份的硼酸盐玻璃,探讨了玻璃成份对Eu3+发光性质的影响和Bi3+对Eu3+的敏化作用.     

Enhanced Green Emission from Er<Subscript>2</Subscript>WO<Subscript>6</Subscript> Nanocrystals Embedded Composite Tellurite Glasses

A series of tungsten-tellurite glasses activated with different concentrations (0–1.5 mol %) of Er³⁺ has been synthesized. The structural properties of the best luminescent sample and the optical properties of its Er³⁺ ions, are studied both immediate after its preparation as well as after its ageing. On ageing the glass suffers structural reorganization and generates Er₂WO₆—nanocrystals in the matrix, which greatly enhances the normal and upconversion green luminescence efficiency of Er³⁺. The nanocrystal aided enhancement of normal and upconversion luminescence of Er³⁺ of the glass has been attributed to the crystal field effects of the new environment of Er³⁺ in the nanocrystals. A phenomenon of preferential enhancement of red upconversion luminescence at the cost of green upconversion luminescence of Er³⁺ at its higher concentrations in the glass has been observed and the related photo-physics is proposed. The material shows the prospect of being used as NIR solar concentrator.     

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