Synthesis and Upconversion Luminescence of LaF_3:Yb^(3+),Er^(3+)/SiO_2 Core/Shell Microcrystals

LaF3：Yb^3＋ , Er^＋ microcrystals were synthesized by a hydrothermal method, and then, the LaF3： Yb^3＋ , Er^＋ microcrystals were coated with silica. Phase identification of LaF3： Yb^3＋ , Er^＋ and LaF3： Yb^3＋ , Er^＋/SiO2 was performed via XRD. The TEM image showed that the size of LaF3： Yb^3＋ , Er^＋ was 150 nm and LaF3： Yb^3＋ , Er^＋/SiO2 presented clearly a core/shell structure with 20 nm shell thickness. The upconversion spectra of LaF3： Yb^3＋ , Er^＋ and LaF3： Yb^3＋ , Er^＋/SiO2 in solid state and in ethanol were studied with a 980 nm diode laser as the excitation source. The upconversion spectra showed that the silica shell had little effect on the properties of fluorescence of the LaF3：Yb^3＋ , Er^＋ microcrystals. At the same time, the green luminescence photo of LaF3： Yb3＋, Er3＋/SiO2 in the PBS buffer was obtained, which indicated that the LaF3： Yb^3＋ , Er^＋/SiO2 could be used in biological applications.

Three-color upconversion luminescence of rare earth codoped oxyhalide tellurite glasses

The red, green, and blue upconversion properties of Er^3＋/Tm^3＋/Yb^3＋-codoped oxyhalide tellurite glasses were studied under 980 nm LD excitation. The intense red （657 nm）, green （530 and 545 nm）, and blue （476 nm） emissions were simultaneously observed at room temperature. The results showed that the mixed halide modified tellurite glass （TZFCB） had strong upconversion emissions. The effect of halide on upconversion intensity was observed and discussed, and possible upconversion mechanisms were evaluated. The intense red, green, and blue upconversion luminescence of Er^3＋/Tm^3＋/Yb^3＋-codoped oxyhalide tellurite glasses might be a potentially useful material for developing three-dimensional displays applications.

Investigation on Upconversion Luminescence of Tm^(3+)/Yb^(3+)-Codoped Oxychloride Tellurite Glasses

Tm^3 ＋/Yb^3 ＋-codoped oxychloride tellurite glasses were prepared. Thermal stability, Raman spectra and upconversion luminescence spectra were studied, and upconversion luminescence mechanisms were analyzed. The results show that the intense blue and relatively weak red emissions centered at 476 and 649 nm corresponding to the transitions ^1G4→^3H6 and ^1G4→^3H4 of Tm^3＋ , respectively, were simultaneously observed at room temperature under 980 nm LD excitation. With increasing while PbCl2 content, thermal stability of host glasses increases, phonon energy of host glasses decreases, and upconversion luminescence intensities increase, which indicate that Tm^3＋/ Yb^3＋-codoped oxychloride tellurite glasses can be used as potential host materials for upconversion blue lasers.

Laser-diode excited intense upconversion luminescence of Er^3＋ in bismuth-lead-germanate glasses

We have investigated infrared-to-visible upconversion luminescence of Er^3＋ in bismuth-lead-germanate glasses. The UV cutoff wavelength is shortened while its lifetime is increased almost linearly, with PbF2 substituting for PbO in the bismuth-lead germanate glasses. Three emissions centred at around 529, 545 and 657 nm are clearly observed, which are identified as originating from the ^2H11/2→^4 I15/2,^4S3/2→^4 I15/2 and ^4 F9/2 →^4 I15/2 transitions, respectively. It is noted that all the upconversion emission intensities increase with PbF2 concentration increasing. The ratio between the intensities of red and green emissions increases with the increasing of PbF2 content. Energy transfer processes and nonradiative phonon-assisted decays account for the populations of the ^2 H11/2,^4 S3/2 and ^4F 9/2 levels. The quadratic dependence of fluorescence on excitation laser power confirms a two-photon process to contribute to the upconversion emissions.

Influence of Coordinate Field Index on Upconversion Luminescence in Er ^(3+) Doped Tellurite Glasses

The upconversion luminescence in Er 3+ doped tellurite glasses (MKT: TeO_2-MgO-K_2O) were performed. Two green emission bands at 521 and 550 nm, corresponding to the 2H_ 11/2→4I_ 15/2 and 4S_ 3/2→4I_ 15/2 transitions, respectively, were observed. Coordinate field index, which was proposed by deducing from Pauling′s rules on the basis of Zachariasen′s random network theory, can be used to rationalize the remarkable variation in the intensity of upconversion luminescence.

Research on upconversion luminescence in new Er^(3+)/Yb^(3+) codoped oxyfluoride borosilicate glass ceramics

The upconversion luminescence of Er^3＋/Yb^3＋ ions is researched in a novel transparent oxyfluoride borosil- icate glass and glass ceramics under 980-nm excitation. Fluoride nanocrystals Ba2YF7 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 Er^3＋/Yb^3＋ codoped transparent glass-ceramics, which may be due to the variation of coordination environment around Er^3＋ and Yb^3＋ ions after crystallization. The possible upconversion mechanism is also discussed.

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.

Effect of glass network modifier R_2O(R=Li, Na and K) on upconversion luminescence in Er^(3+)/Yb^(3+) co-doped NaYF_4 oxyfluoride glass-ceramics

The effect of glass network modifier R2O （R=Li, Na, K） on upconversion luminescence in Er3＋/yb3＋ co-doped NaYF4 oxyfluoride glass-ceramics was investigated. NaYF4 nanocrystals with different sizes were studied under glass network modifier alkali mental oxide. The nanocrystals size in NaYF4 of Li2O modified samples was 11 nm, whereas in the Na20 and K2O modified sample, the crystal size was 25 and 43 nm, respectively. It was found that red, yellow and green upconversions were observed in SAL, SAN, SAK glass ceramics. The reported results would deepen the understanding of size effects on the lanthanide upcon- version in nanocrystals.

Large reversible upconversion luminescence modification and 3D optical information storage in femtosecond laser irradiation-subjected photochromic glass

Fast response,high luminescence contrast,three-dimensional(3D)storage,and nondestructive reading are key factors for the optical storage application of photochromic materials.Femtosecond(fs)laser direct writing technology with multiphoton nonlinear absorption is becoming a useful tool for microprocessing functional units in the 3D space of glass owing to its remarkable advantages,such as a fast processing speed and high processing accuracy.Herein,the photochromism of transparent glass codoped with rare-earth ions was investigated under 800-nm fs laser irradiation,affording a fast response.The photochromic glass achieves an upconversion luminescence(UCL)modification of 92%.The photochromic glass can be bleached back to its original color using heat treatment.The transmittance and UCL modification show excellent reproducibility under alternating stimulations between 800-nm fs laser irradiation and heat treatment.The data can be written in the interior of the transparent photochromic glass using 800-nm fs laser irradiation,facilitating 3D information storage.These results suggest that the 800-nm fs laser irradiation-subjected photochromic glass is an ideal optical data storage medium.

Upconversion luminescence of Tm^3＋/Yb^3＋ codoped oxyfluoride glasses

Novel oxyfluoride glasses are developed with the composition of 30SiO2-15Al2O3-28PbF2-22CdF2-0.1TmF3 - xYbF3 - （4.9 - x） AlF3（x=0, 0.5, 1.0, 1.5, 2.0） in tool fraction, Furthermore, the upconversion luminescence characteristics under a 970nm excitation are investigated. Intense blue, red and near infrared luminescences peaked at 453nm, 476nm, 647nm and 789nm, which correspond to the transitions of Tm^3＋： ^1D2 →^3F4, ^1G4 →^3H6, ^1G4 →^3F4, and ^3H4 →^3H6, respectively, are observed. Due to the sensitization of Yb^3＋ ions, all the upconversion luminescence intensities are enhanced considerably with Yb^3＋ concentration increasing. The upconversion mechanisms are discussed based on the energy matching rule and quadratic dependence on excitation power. The results indicate that the dominant mechanism is the excited state absorption for those upconversion emissions.

Upconversion Luminescence of Er^3＋ and Co-Doped Er^3＋/Yb^3＋ Novel Transparent Oxyfluoride Glasses and Glass Ceramics： Spectral and Structural Properties

Transparent oxyfluoride silicate precursor glasses and glass ceramics with the novel composition （1） SiO2-PbO-PbFE-Er2O3, （2） SiO2-GeOE-PbO-PbFE-Er2O3 （3） SiO2-Al2O3-Y2O3-Na2O-NaF-LiF-Er2O3-YbF3 doped with Er^3＋ and co-doped with Er^3＋/Yb^3＋ ions were synthesized. X-ray diffraction analysis （XRD） and Er3＋ absorption spectra revealed precipitation of PbF2 nanocrystals dispersed in the glassy matrix. Under 980 nm laser excitation, intense green, red and near IR bands of upconversion luminescence （UCL） were recorded both before and after heat treatment. In the glass ceramics the upconversion intensity increased significantly. To our knowledge, for the first time the composition of the glass ceramics characterized by the small-angle neutron scattering （SANS） showed the cluster organization of PbF2 nanocrystals.

基于单颗粒微米核壳晶体的微区上转换发射光谱构筑微纳光子学条形码

基于外延生长技术构建不同结构特性的核壳结构已成为调控稀土掺杂微纳晶体材料发光特性的有效技术手段之一.为此,本文基于多次外延生长并引入NaYF_(4)中间隔离层,构建了具有壳层独立发光特性NaYF_(4):50%Yb^(3+)/2%Tm^(3+)@NaYF_(4)@NaYF_(4):20%Yb^(3+)/2%Er^(3+)@NaYF_(4)@NaYbF_(4):2%Er^(3+)多层微米核壳晶体.在980 nm激光激发下,借助共聚焦显微光谱测试系统,通过改变单颗粒微米晶体的激发位置,研究了单颗粒核壳微米晶体不同微区内的发光和能量传递特性.实验结果表明:在相邻发光层之间引入NaYF_(4)惰性壳,不仅可实现单颗粒微米晶体区域内发光的调控,且可有效抑制了各壳层离子间的相互作用,实现了各壳层的多彩独立发射.同时,基于单颗粒核壳微米晶体不同区域内多彩发射特性,构建具有信息可调的微纳光子学条形码.由此可见,本文所构建具有区域化可调发射的微米核壳结构,可在不同的激发条件下实现其发光的多彩可调,其丰富光谱指纹信息为单颗粒微米材料在光学防伪领域中的应用提供了新的途径.

Tm^(3+)/Yb^(3+)掺杂亚碲酸盐玻璃蓝红光上转换的研究

研究了掺Tm3+ /Yb3+ 亚碲酸盐玻璃室温下的上转换发光。用 970nm波长的半导体激光器作为泵浦源 ,得到了高效率的 480nm波长上转换的荧光。通过对不同掺杂浓度样品的发光比较 ,发现了这种玻璃上转换发光的浓度猝灭现象 ,找出了这种玻璃得到高效率上转换发光的适宜浓度 ,并对Tm3+ 的浓度猝灭现象进行了分析。通过对上转换发光强度与泵浦强度关系曲线的拟合 ,看到这种上转换是三光子吸收过程 ,这与通过能级图分析得到的结果相同。另外 ,也对 65 0nm波长的上转换发光进行了研究。

掺铒氧氟碲酸盐玻璃的上转换发光研究

研究了掺铒氧氟碲酸盐玻璃的吸收光谱和上转换发光光谱,分析了Er3+离子在氧氟碲酸盐玻璃中的上转换发光机理.结果表明:通过975nm的激光二极管(LD)激发,在室温下同时观察到强烈的绿光(524和545nm)和红光(655nm),分别是由于Er3+离子2H(11/2)→4I(15/2),4S(3/2)→4I(15/2),和4F(9/2)→4I(15/2)跃迁.随PbF2含量增加,绿光的发光强度增加趋势较小,而红光的发光强度增加趋势大于绿光.上转换发光机理主要涉及能量转移和激发态吸收,强烈的绿光和红光激发都是由于双光子吸收过程.

Tm^(3+)/Yb^(3+)共掺氧氯碲酸盐玻璃上转换发光研究

制备了Tm3+/Yb3+共掺氧氯碲酸盐玻璃,研究了玻璃的热稳定性能、Raman光谱和上转换发光光谱,分析了上转换发光机制。结果表明:通过980 nm的激光二极管激发,在室温下同时观察到强烈的蓝光(476 nm)和微弱的红光(649 nm),分别是Tm3+离子的1G4→3H6和1G4→3H4跃迁。随氯化铅含量增加,基质玻璃的热稳定性能增强,基质玻璃的声子能量降低,上转换蓝光和红光的强度增加。表明Tm3+/Yb3+共掺氧氯碲酸盐玻璃是一种上转换蓝光激光器的潜在基质材料。

976nm激发下Tm^(3+)/Yb^(3+)共掺TiBa玻璃微球上转换发光的形貌共振

制备了Tm3+ /Yb3+ 共掺高折射率TiBa玻璃微球 ,玻璃基材主要成分为 :TiO2 ,BaCO3和SiO2 ,稀土 (% ,摩尔分数 )掺杂 0 5Tm2 O3和 3Yb2 O3。用 976nm激光激发测量了它们的上转换蓝光发射。利用光学微腔理论讨论了玻璃微球荧光光谱中的形貌共振 ,并用Mie理论公式对共振峰间隔进行了计算 ,实验结果与计算结果相符。

Ag纳米晶对Tm/Yb共掺碲酸盐玻璃上转换发光性能的影响

在稀土离子掺杂碲酸盐玻璃中引入Ag纳米晶,通过等离子共振(SPR)可使荧光发射得到增强,上转换发光效率得到明显提升。研究了Ag纳米晶对Tm3+/Yb3+共掺碲酸盐玻璃上转换发光的影响,分析了上转换发光机理。结果发现,经过(330℃,30 min)热处理后,玻璃中析出了Ag纳米颗粒,尺寸为5～8 nm。Ag纳米晶的引入可使玻璃上转换蓝、红光由三光子吸收转变为双光子吸收。由于局域场表面等离子体共振增强以及Ag与Tm3+之间的能量转移,使得含Ag纳米晶玻璃的荧光强度比不含Ag纳米晶的玻璃提高了约5倍。

Nd^(3+)/Yb^(3+)共掺La_2O_3-TiO_2-ZrO_2微晶玻璃的制备及上转换发光研究(英文)

利用气悬浮方法制备了Nd3+/Yb3+共掺La2O3-TiO2-ZrO2前驱体玻璃,通过热处理获得了微晶玻璃。通过DTA对前驱体玻璃的热稳定性进行了研究。利用光致发光谱,TEM和EDS对微晶玻璃进行了表征分析,并研究了热处理对上转换发光的影响。结果表明:玻璃转变温度和析晶起始温度分别为799℃和880℃.在980 nm激光激发下,样品发射出中心位于497,523,545,603和657 nm处的五条发光带。热处理后样品上转换发光强度提高,经过880℃保温50 min热处理的微晶玻璃显示了最强的上转换发光,在545 nm处的发光强度是前驱体玻璃的11倍,这是由于在微晶玻璃基质中存在致密柱状晶和Nd3+离子在晶体中富集造成的。

960nm激光泵浦下Er^(3+)和Yb^(3+)掺杂氟氧化物微晶玻璃上转换发光特性

对经特殊退火后的Ｅｒ３＋和Ｙｂ３＋离子共掺杂氟氧化物微晶玻璃的上转换发光特性进行了研究．研究结果表明，在９６０ｎｍ激光泵浦下，这种玻璃具有较高的上转换发光．通过我们的研究，弄清了在这种材料中Ｅｒ３＋的发光行为、上转换通道和Ｅｒ３＋和Ｙｂ３＋离子之间的能量传递过程．

Er^(3+)掺杂含Ba_2LaF_7纳米晶氧氟硼硅酸盐玻璃陶瓷发光性能的研究(英文)

制备了含有Ba2LaF7纳米晶的Er3+掺杂氧氟硼硅盐玻璃陶瓷,并对其光谱特性进行了研究.根据X射线粉末衍射结果可确认制备出Ba2LaF7纳米晶.根据吸收曲线计算了相应的Judd-Ofelt参数,Ω2随着热处理温度的升高而减小,证明Er3+离子进入到Ba2LaF7纳米晶中.由于Ba2LaF7纳米晶的低声子能量,在玻璃陶瓷中观察到强烈的红光和绿光上转换发光,其上转换发光机理可以归为双光子过程.