光谱学方法研究Tm3+离子的上转换发光影响因素

应用激光光谱学的研究手段和方法,探讨了红色激光抽运Tm3+离子掺杂纳米体系中上转换荧光辐射性质的影响因素.通过变化基质和改变样品的环境温度,研究了声子能量大小对Tm3+离子掺杂纳米体系中上转换效率的影响.结果显示:合适声子能量可以有效提高Tm3+离子蓝色上转换效率.此外,依据声子能量与温度之间的联系,改变样品环境温度可调节低声子基质材料中Tm3+离子激发态能级的布居速率,改变上转换效率.     

光谱学方法研究Tm~(3+)离子的上转换发光影响因素

应用激光光谱学的研究手段和方法,探讨了红色激光抽运Tm3+离子掺杂纳米体系中上转换荧光辐射性质的影响因素.通过变化基质和改变样品的环境温度,研究了声子能量大小对Tm3+离子掺杂纳米体系中上转换效率的影响.结果显示:合适声子能量可以有效提高Tm3+离子蓝色上转换效率.此外,依据声子能量与温度之间的联系,改变样品环境温度可调节低声子基质材料中Tm3+离子激发态能级的布居速率,改变上转换效率.     

Tm~(3+)掺杂Ge-Ga-Se玻璃中红外发光特性与多声子弛豫分析

用熔融急冷法制备了系列不同Tm3+掺杂浓度的Ge30Ga5Se65玻璃样品,测试了样品折射率、拉曼光谱、吸收光谱以及800nm激光泵浦下的近红外及中红外波段荧光光谱和荧光寿命。用Judd-Ofelt理论计算了Tm3+在Ge30Ga5Se65玻璃中的强度参数Ωi(i=2,4,6)、自发辐射跃迁概率A、荧光分支比β和辐射寿命τrad等光谱参数。讨论了800nm激光泵浦下掺杂1Wt%Tm3+样品在近红外1.23,1.48和1.8μm处的发光特性及各量子效率,研究了800nm激光泵浦下的样品中红外荧光特性与掺杂浓度之间的关系,计算了常温下该基质玻璃中Tm3+:3H5→3F4跃迁对于3.8μm处的多声子弛豫速率Wmp和Ge30Ga5Se65玻璃基质中多声子弛豫常数W(0)和电子-声子结合常数α值。结果表明Ge30Ga5Se65硒基玻璃较低的声子能量可以大大降低稀土离子能级间跃迁的多声子弛豫概率,从而提高中红外荧光发光效率,因此硒基玻璃作为稀土离子的掺杂基质材料对实现中红外荧光输出是非常有利的。     

提高能量上转换效率的实验探讨

通过以TeO₂,GeO₂,ZnF₂,SiO₂,PbF₂等为主体的氟氧化物玻璃陶瓷基质材料的研究提出了提高上转换效率的某些条件.选择低声子能量的基质,且基质的M系数接近稀土离子的M系数的氟氧化物基质材料是高效上转材料的基础,选择激发光光子能量与稀土离子、敏化稀土离子能级匹配是高效上转换材料的必要条件.为设计研究稀土掺杂能量上转换材料提供了有理论和应用价值的结果. 关键词： 能量上转换 氟氧化物玻璃陶瓷 稀土掺杂     

稀土掺杂材料的上转换发光

稀土掺杂材料的上转换发光是实现光波频率转换的重要途径,也是稀土掺杂发光材料研究的重要内容。本文从介绍与上转换相关的基本概念出发,阐述了稀土离子上转换发光的发展历史;对稀土离子掺杂材料的能量传递、激发态吸收、合作敏化、合作发光、双光子吸收激发及光子吸收雪崩等上转换发光机制进行了概述,并对各机制进行了比较;对不同稀土离子掺杂体系中上转换发光的机制进行了总结;对以往研究的稀土掺杂上转换发光材料的基质,包括粉体材料、晶体材料、非晶材料进行了概括;最后对影响稀土离子上转换发光效率的因素进行了分析,提出了在上转换发光材料的设计中应重点考虑基质对泵浦光及上转换发射光的吸收、基质材料的声子能量、稀土离子的掺杂方案及泵浦途径等因素。     

Dy3+掺杂Ge-Ga-S-CsI玻璃中红外发光特性研究

用熔融淬冷法制备了系列掺杂浓度的Dy³⁺:Ge-Ga-S-CsI硫卤玻璃样品,测试了样品拉曼光谱、折射率、吸收光谱、近红外及中红外荧光谱.应用Judd-Ofelt理论计算了Dy³⁺离子的强度参数 (Ω_i, i=2,4,6)、自发辐射跃迁概率(A)、荧光分支比(β)、以及辐射寿命(τ_rad)等光谱参数.研究了810 nm激光抽运下样品中红 关键词： 硫系玻璃 中红外发光 3+掺杂')" href="#">Dy³⁺掺杂 多声子弛豫     

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     

Ho~(3+)/Yb~(3+)共掺杂玻璃陶瓷50SiO_2-50PbF_2的上转换及中红外发光特性

玻璃陶瓷又称为纳米微晶玻璃,是玻璃基质中包含约10nm的纳米微晶。在稀土掺杂的玻璃陶瓷中,稀土主要掺杂在氟化物纳米晶中。这种材料在发光应用中具有氟化物和氧化物的优点,是上转换发光和中红外发光效率高的基质材料。研究Ho3+/Yb3+共掺杂的玻璃陶瓷(50SiO2-50PbF2-1.0YbF3-0.5HoF3)的上转换和中红外发光性质。玻璃陶瓷吸收光谱的半高宽比玻璃前驱物更窄,而且长波吸收峰的Stark劈裂更加明显,表明稀土离子掺杂在晶体中。通过吸收光谱计算了J-O参数,Ω2值(0.17×10-20 cm2)比氟化物玻璃ZBLA(2.28×10-20 cm2)的低很多。在980nm激光激发下,Ho3+/Yb3+共掺杂的玻璃陶瓷有很强的绿光上转换荧光和蓝光、红光上转换荧光。与玻璃相比,绿光和蓝光光强增强明显,而红光基本不变。玻璃陶瓷中的Ho离子掺杂在声子能量低的PbF2晶体中,低的声子能量使发光能级的无辐射弛豫率降低,从而增加了绿光和蓝光的上转换效率。低的无辐射弛豫率同时也降低了红光上转换中间能级(5 I7)的粒子数布居,因此红光上转换没有增强。在980nm激光激发下Ho3+/Yb3+共掺杂的玻璃陶瓷有很强的2.9μm中红外荧光,而在玻璃前驱物中观察不到中红外荧光。     

高浓度敏化剂掺杂的NaYF4∶Yb3+,Er3+纳米材料的合成及发光性能研究

为了探究泵浦功率对不同浓度敏化剂离子掺杂的上转换材料发光特性的影响,采用溶剂热法,成功制备了不同浓度敏化剂Yb3+掺杂的NaYF₄∶Yb3+, Er3+上转换纳米颗粒。首先对这种纳米晶体的结构和形貌进行了详细的分析,使用X射线粉末衍射仪和透射电子显微镜测试了制备的纳米晶体的结构和形貌。表征结果证明了制备的纳米颗粒均为结晶性良好、形状规则的六方相纳米晶体,随着Yb3+掺杂浓度的提高,纳米晶体的粒径有所增加。在此基础上,通过控制泵浦功率对不同浓度敏化剂Yb3+掺杂的NaYF₄∶Yb3+, Er3+上转换纳米颗粒在980 nm激发光下的光致发光特性做了详细的研究。对于不同浓度敏化剂掺杂的样品,随着泵浦功率的提高,上转换发光的强度增强,这可以归因于高泵浦功率促进材料对激发光的吸收。上转换发光的红绿比也得到了提高, 值得注意的是, 在不同浓度敏化剂Yb3+掺杂的样品中,发光的红绿比改变的程度和可调谐的范围有所不同。为了深入的了解上转换发光机制,对不同浓度样品中可能发生的电子能量传递机制进行了讨论并提出假设,认为上转换发光过程中,不同浓度样品中红绿比变化程度的不同是发光离子组合之间的平均距离和包括多声子弛豫、交叉弛豫和反向能量传递的非弛豫过程的综合作用。在低浓度敏化剂掺杂的样品中,由于掺杂浓度导致Yb3+和Er3+之间的平均距离较大,反向能量传递过程比较微弱。在非弛豫过程中,发生在同一发光中心Er3+上的多声子弛豫和相邻发光中心Er3+之间的交叉弛豫为主要过程。随着泵浦功率的提高,高能级的布居速率增加减弱了非辐射弛豫对发光的影响,材料的红绿比只有微弱的提高,绿光是上转换发光中的主要成分。随着掺杂浓度的提高,敏化剂离子Yb3+和激活剂离子Er3+之间的平均间距减小,反向能量传递过程得到增强,成为非辐射弛豫过程中的主要部分。由于泵浦功率增强而提高的高能级对上转换发光的贡献,通过相邻敏化剂和激活剂离子之间的反向能量传递过程得到迅速的衰减,使红光成为上转换发光中的主要成分。在980 nm的近红外光激发下,在不同浓度Yb3+掺杂的样品中存在不同侧重的非辐射弛豫过程, 由于多声子弛豫、交叉弛豫和反向能量传递共同作用,红绿比随着泵浦功率提高而增加。这种发光特性不但使得我们得到红光性能更好的上转换荧光材料,而且可以通过测定材料的红绿比来判定材料的掺杂浓度。经过进一步的设计和修饰,这种纳米材料很有潜力作为一种多功能光动力治疗纳米平台在生物检测领域中得到应用。不同浓度样品中可能发生的电子能量转移过程的提出,有利于对上转换发光机理的了解和稀土发光离子组合的设计和优化。     

碱金属离子对稀土掺杂氟化物上转换荧光的影响

提高稀土掺杂材料的上转换荧光效率具有重大的应用价值。本文通过水热法合成了不同种类的碱金属离子掺杂氟化物上转换荧光材料,通过对比样品上转换荧光特性研究其中碱金属离子的作用。发现锂离子能够明显改善稀土掺杂NaYF_4的上转换荧光强度,并在稀土掺杂LiYF_4中实现了比常用的NaYF_4中强近7倍的上转换荧光发射。此外,在具有较高上转换效率的LiYF_4基质中通过浓度优化,合成了具有高效白光上转换发射的荧光粉,其CIE坐标值为(0.32,0.36)。本项工作将对高效稀土掺杂上转换材料及照明器件的构建提供一定的参考。     

Spectroscopic properties of Nd—doped phosphate glass with a high emission cross section

Neodymium doped phosphate glasses have been prepared by the semi-continuous melting technique. Their absorption and emission spectra have been recorded at room temperature. The Judd－Ofelt theory has been applied to evaluate the stimulated emission cross sections of ⁴F_3/2→⁴I_11/2 transition for Nd³⁺. The higher stimulated emission cross section, 4.0×10^-20cm², is obtained. The fluorescence decays of the ⁴F_3/2→⁴I_11/2 transition of Nd³⁺ are measured for the samples doped (0.7－10) wt% of Nd₂O₃ at room temperature. The concentration quenching of Nd-doped phosphate glass is mainly attributed to cross-relaxation and energy migration. The site-dependent properties of fluorescence spectra and the fluorescence lifetime of the Nd³⁺-doped phosphate glass (with 2.2wt%Nd₂O₃) are studied using laser-induced fluorescence line narrowing techniques, and the site-to-site variations of optical properties are observed at low temperature.     

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.     

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.     

One color,pulsed excited-state upconversion in YAG:Tm3+

One color red laser pumping of YAG:Tm³⁺ crystals results in a strong upconverted near ultraviolet and blue fluorescence from the excited¹ D ₂ and¹ G ₄ multiplets. It is found that under pulsed-pumping conditions the quasi-resonant excited-state absorption from the³ H ₄ multiplet is the responsible process. Analysis of the upconverted emission confirmed previous results on³ H ₄ level assignments as well as on inhomogeneous line broadening in the YAG structure.     

OH-对磷酸盐铒玻璃光谱性质的影响

本文系统研究了Yb³⁺、Er³⁺共掺磷酸盐铒玻璃中OH^-含量与铒玻璃荧光寿命和光谱性质的关系.结果表明OH^-基团的存在使得Er³⁺离子的荧光强度显著降低,荧光寿命大大缩短.比较了三种不同Al₂O₃含量(5mol%,8mol%和13mol%)的铒玻璃在2.9μm波长处的红外吸收系数与铒离子荧光寿命的关系,发现玻璃中OH^-在2.9μm的吸收系数和Er³⁺的⁴Ⅰ_13/2能级离子衰减速率成线性关系,不同Al₂O₃含量的玻璃具有不同Er³⁺和OH^-基团的相互作用参量和不同的荧光寿命值及量子效率.并从玻璃结构上解释了Al₂O₃含量对除水机制和光谱性质的影响.经过充分除水后的铒玻璃荧光寿命可达到9.1ms.     

Short-wavelength luminescence in Ho-doped KGd(WO4)2 crystals

Emissions from the high-lying excited states, energy transfer and upconversion processes are investigated in Ho³⁺-activated KGd(WO₄)₂ crystal. The spectral assignment based on time-resolved emission spectra allowed to identify various near ultra-violet (UV), blue and green emissions starting from the excited ³H₅, ⁵G₄, ⁵G₅, ⁵F₃ and ⁵S₂ levels. The temporal behavior of these transitions after pulsed excitation was analyzed as a function of temperature and holmium ions concentration. The shortening and nonexponentiality of the decays, observed with increasing activator concentrations, indicated cross-relaxation (CR) among the Ho³⁺ ions. Cross-relaxation rates were experimentally determined as a function of activator concentration and used to evaluate the values of the nearest-neighbor trapping rates X₀₁ and to model the decays. It was observed that KGW, despite higher than in YAG maximum phonon energy of about 900 cm⁻¹, is more efficient short-wavelength emitter than YAG. Examples of the excited-state absorption (ESA) and energy transfer (ET) mechanisms responsible for the upconverted, short-wavelength emissions were identified by analyzing fluorescence dynamics and possible energy resonances.     

Up-conversion emission in triply-doped Ho/Yb/Tm KGd(WO4)2 single crystals

Detailed spectroscopic studies of the triply doped KGd(WO₄)₂:Ho³⁺/Yb³⁺/Tm³⁺ single crystals (which exhibit multicolor up-conversion fluorescence) are reported for the first time. The absorption spectra of crystals were measured at 10 and 300 K; the room temperature luminescence spectra were excited at 980 nm wavelength. The dependence of the intensity of luminescence on the excitation power for three different concentration of Ho³⁺, Yb³⁺ and Tm³⁺ ions was investigated. Efficient green and red up-converted luminescence of Ho³⁺ ions and weak blue up-conversion luminescence of Tm³⁺ ions were observed in spectra. The red emission of Ho³⁺ ions is more intensive than their green emission. Dependence of the up-conversion luminescence intensity on the excitation power and impurities concentration was also studied; the number of phonon needed for efficient up-conversion was determined for each case. All possible energy transfer processes between different pairs of the impurity ions' energy levels are also discussed.     

Spectroscopic properties in Er Er3+/Yb3+Co-doped fluorophosphate glass

Using the technique of high-temperature melting, a new Er³⁺/Yb³⁺ co-doped fluorophosphate glass was prepared. The absorption and fluorescence spectra were investigated in depth. The effect of Er³⁺ and Yb³⁺ concentration on the spectroscopic properties of the glass sample was also discussed. According to the Judd-Ofelt theory, the oscillator strength was computed. The lifetime of ⁴I_13/2 level (τ_m) of Er³⁺ ions was 8.23 ms, and the full width at half maximum of the dominating emission peak was 68 nm at 1.53 τ_m. The large stimulated emission cross section of the Er³⁺ was calculated by the McCumber theory. The spectroscopic properties of Er³⁺ ion were compared with those in different glasses. The full width at half maximum and σ_e are larger than those of other glass hosts, indicating this studied glass may be a potentially useful candidate for high-gain erbium-doped fiber amplifier.     

Near infrared to red and yellow to blue upconversion emissions from Pr: ZrF4-BaF2-LaF3-YF3-AlF3-NaF glasses

This paper describes the development and a detailed analysis carried out on the luminescence characteristics of Pr³⁺ doped ZrF₄-BaF₂-LaF₃-YF₃-AlF₃-NaF glasses. In the present work our objectives are to elucidate the possible mechanisms that are responsible for NIR to red upconversion process and yellow to blue upconversion emission in terms of energy level schemes from the praseodymium containing fibre optical glass composition. We have studied their different physical and optical properties. Besides our investigation on the upconversion emission of these glasses, normal fluorescence studies have also been undertaken in explaining the mechanisms in demonstrating bright red and blue emissions upon excitations at visible and UV wavelengths. Besides these measurements works, a bright blue colour emission was observed under an UV source and upconverted prominent red emissions were observed with a laser diode (LD of ). Similarly under a yellow light source, a blue colour emission was observed from these praseodymium glasses studied.     

Er3+/Yb3+掺杂氟硅铅酸盐微晶玻璃的上转换发光

制备了微晶体尺寸大约在10—12 nm范围内的Er³⁺,Yb³⁺共掺杂透明氟硅铅酸盐微晶玻璃.相同功率激发下,纳米微晶玻璃中Er³⁺离子的²H_11/2,⁴S_3/2→⁴I_15/2的绿色上转换荧光和⁴F_9/2→关键词： 3+')" href="#">Er³⁺ 3+')" href="#">Yb³⁺ 能量传递 纳米微晶玻璃