Er3+/Yb3+共掺氟硅酸盐玻璃陶瓷的制备及其量子剪裁发光行为

本文报道了一类组成为50SiO2-10Al2O3-20ZnF2-20SrF2-3YbF3-0.05ErF3(mol%)的氟氧化物玻璃陶瓷的制备及其量子剪裁发光行为。XRD和TEM分析结果显示,玻璃陶瓷中均匀分布有尺度10~40nm的SrF2析晶相。光谱研究表明,玻璃陶瓷在Er3+激发峰波长377nm激发下存在Er3+向Yb3+的有效能量传递,可实现包括量子剪裁效应在内的波长变换功能。随着热处理温度的升高,玻璃陶瓷的近红外977nm发光逐渐增强,荧光寿命显著增长。     

Er3+/Tm3+/Yb3+共掺氟氧化物玻璃的上转换白光性质

采用高温固相法制备了Er3+/Yb3+、Tm3+/Yb3+和Er3+/Tm3+/Yb3+共掺杂的氟氧化物玻璃SiO2-Al2O3-Na2O-ZnF2,研究了980nm近红外激光激发下的上转换发光性质。研究表明,Er3+/Yb3+共掺样品呈现了上转换绿光和红光发射,Tm3+/Yb3+共掺样品呈现了强的上转换蓝光发射和弱的红光发射,Er3+/Tm3+/Yb3+三掺样品呈现了上转换白光发射。对上转换发光强度和激光功率的研究表明上转换绿光和红光发射是两光子吸收过程,上转换蓝光发射是三光子吸收过程。     

Er~(3+)/Yb~(3+)共掺SrF_2纳米晶的溶剂热合成及发光性能研究

采用溶剂热方法制备得到了Er3+和Yb3+共掺杂的SrF2纳米晶,并对其上转换发光性能进行了研究.X-射线衍射结果表明所制备的产物为纯的SrF2.随着溶剂热温度的升高,该纳米晶衍射峰的强度逐渐增强,且与SrF2的标准衍射峰相比,所有衍射峰均向高角度偏移.TEM的结果表明,溶剂热处理后,SrF2颗粒的分散性得到明显改善,且晶粒大小随着溶剂热温度的升高而增大.在980nm激光泵浦下Er3+和Yb3+共掺杂SrF2纳米晶仅能观察到弱的上转换发光,而在500℃和600℃热处理2h后,其上转换发光强度明显增强.上转换发光强度与泵浦功率的关系表明绿光和红光均为双光子吸收过程.     

Yb3+/Er3+共掺杂BaY2F8纳米颗粒的水热合成与上转换发光

采用水热方法合成了Yb3+/Er3+共掺杂BaY2F8纳米颗粒,并对其进行了不同温度的热处理,热处理温度为200℃-800℃。研究了热处理温度对纳米粒子的晶相、粒径和上转换发光强度的影响。结果发现随着热处理温度的升高,纳米粒子的粒径和上转换发光强度明显增加。讨论了BaY2F8:Yb3+,Er3+纳米粒子的上转换发光机理。     

铒单掺和铒/镱共掺氟氧玻璃的上转换发光性质研究

研究了室温下掺不同摩尔分数Er3+单掺和Er3+/Yb3+双掺的20GaF3-15InF3-17CdF2-15ZnF2-10SnF2-3P2O5-(20-x-y)PbF2-xErF3-yYbF3(x=0.1~0.4,y=1~4)氟氧玻璃的上转换发光性质。755nm激发下,在Er3+单掺系列玻璃中观察到紫色(410nm)、蓝色(465nm)和绿色(522nm、544nm)上转化发光,随着掺杂Er3+浓度的增大,各荧光强度增幅有变缓的趋势。980nm激发下,由于Yb3+的敏化作用,在Er3+/Yb3+双掺系列玻璃中观察到绿色(548nm、527nm)和红色(661nm)上转换发光,固定Er3+浓度,随着Yb3+浓度的增大,各荧光强度先增大后减小,当Yb3+、Er3+掺杂浓度比为15时发光强度最大。该氟氧玻璃具有比氟化物玻璃更好的抗析晶稳定性,掺稀土离子后在不同波长激发下可观察到明亮的红、绿色上转换荧光,是一种有潜质用于红、绿色上转换发光的材料。     

热解法制备KY3F10∶Yb3+、Tm3+纳米晶荧光标记材料

采用热分解法制备了yb3+和Tm3+共掺杂的KY3F10∶Yb3+、Tm3+纳米晶,用X射线衍射(XRD)、透射电镜(TEM)和上转换光谱对样品进行了表征.研究了Tm3+浓度对样品的上转换发光性能的影响.结果表明制备的样品为类球形立方相KY3F10∶yb3+、Tm3+纳米晶,粒子尺寸分布均匀,平均粒径约为13nm左右....     

NaYF4:Er3+和NaYF4:Yb3+/Er3+上转换荧光纳米晶的制备与表征

以EDTA为螯合剂,采用络合共沉淀法合成了NaYF4:Er3+和NaYF4:Yb3+/Er3+纳米晶.分别采用XRD、SEM、荧光分光光度计对合成的样品进行了结构、形貌和上转换荧光分析.XRD结果表明,制备的NaYF4:Er3+和NaYF4:Yb3+/Er3+均为纯立方相;SEM结果显示,制备的NaYF4:Er3+和NaYF4: Yb3+/Er3+晶粒粒径都在100nm左右,与NaYF4:Er3+相比,NaYF4:Yb3+/Er3+晶粒尺寸分布更均匀,分散性更好,符合作为荧光标记材料的要求;上转换荧光分析表明,在980nm激光器激发下,NaYF4:Yb3+/Er3+的发光强度比NaYF4:Er3+提高了1个数量级.     

Yb~(3+)/Tm~(3+)共掺杂BST铁电厚膜的制备及其上转换发光

利用丝网印刷工艺制备出稀土Yb3+/Tm3+共掺杂的Ba0.8Sr0.2TiO3铁电陶瓷厚膜,利用XRD、SEM、EDS、Raman和荧光光谱仪研究了稀土掺杂对厚膜微结构和发光性能的影响。实验发现,在低掺杂量时Yb3+、Tm3+离子在BST晶格中首先替代B位离子,高掺杂量时则同时占据A位和B位离子。掺杂后的厚膜仍表现为典型的铁电四方相结构。在800nm近红外激光激发下,共掺杂的BST厚膜中的Tm3+离子通过Yb3+离子的敏化作用在468与533nm处实现了间接上转换蓝色与绿色荧光输出,分别对应于Tm3+离子的1 G4→3 H6跃迁和1 D2→3F4跃迁。468nm蓝色荧光强度随着Yb3+、Tm3+离子比的增加先增强后减弱,在Yb3+、Tm3+离子共掺比为2∶1达到最大,并对上转换发光的机理进行了分析。     

YAG:Yb~(3+),Tm~(3+)纳米晶粉体的制备及其蓝色上转换发光

以稀土氧化物、硝酸铝为原料,采用溶胶-凝胶法合成了Yb3+、Tm3+共掺的钇铝石榴石(Y3Al5O12,YAG)纳米晶粉体。采用X射线衍射(XRD)确定了1200℃煅烧后的晶体粉为纯YAG结构,无杂质相,晶体尺寸约为90nm;该粉体在波长为980nm的半导体激光器激发下发射出中心波长为487nm的蓝色上转换荧光,对应于Tm3+离子的1G4→3H6的跃迁。发光强度和激发功率关系的研究揭示了其为双光子过程,Tm3+的激发态吸收及Tm3+、Yb3+间的交叉驰豫型能量传递和是该上转换发光的主要机制。     

Sr2YF7∶Yb,Tm纳米晶的水热制备及上转换发光性能研究

采用温和水热法制备了七氟钇锶(Sr_2YF_7):镱(Yb),铥(Tm)纳米晶(Sr2YF7∶Yb,Tm纳米晶),并对其微结构、形貌、粒径、发光性能进行了表征。结果显示,制备的Sr_2YF_7:Yb,Tm纳米晶为四方晶相结构,其形貌为类球型,平均粒径34nm;在980nm红外光激发下,其发射峰分别位于463nm、480nm、650nm处,I_蓝/I_红≈43,无紫外及红外发射峰出现,获得了上转换单色蓝光。依据发光强度与激发功率的关系,确定样品的蓝光与红光发射均为三光子过程,并分析了其上转换发光机制。     

Improved infrared emissions of Er(3+)-Tm3+ co-doped Al2O3 thin films: the role of cross relaxation among rare earth ions

We report the infrared emissions of Er(3+)-Tm3+ co-doped amorphous Al2O3 thin films pumped at 791 nm by a Ti:sapphire laser. The as-deposited films were annealed to improve the photoluminescence performance. Three cross relaxation channels among Er(3+)-Tm3+ and Tm(3+)-Tm3+ ions incorporated in the films were investigated as annealing temperature increases especially from 800 to 850 degrees C. In order to understand the Stark effect and cross relaxations, the photoluminescence spectra were deconvoluted by Gaussian fittings. Our results indicate that the luminescence intensity of 1.62 microm in comparison to 1.5 microm can be enhanced by the cross relaxation process [Er3+ (4I13/2) + Tm3+ (3H6) --> Er3+ (4I15/2) + Tm3+ (3F4)], and the longer-wavelength side of Er3+ emission can be improved by the CR process [Er3+ (4I15/2) + Tm3+ (3H4) --> Er3+ (4I3/2) + Tm3+ (3F4) at expense of the Tm3+ 1.47 microm emission which is also maybe quenched by the CR effect between themselves. These results suggest one possible approach to achieve broadband infrared emissions at the wavelength region of 1.45-1.65 microm from the Er(3+)-Tm3+ co-doped systems.     

Synthesis of colloidal upconverting NaYF4: Er3+/Yb3+ and Tm3+/Yb3+ monodisperse nanocrystals

The synthesis, characterization, and spectroscopy of upconverting lanthanide-doped NaYF4 nanocrystals (NCs) is presented. The monodisperse cubic NaYF4 NCs were synthesized via a thermal decomposition reaction of trifluoroacetate precusors in a mixture of technical grade chemicals, octadecene and the coordinating ligand oleic acid. In this straightforward method, the dissolved precursors are added slowly to the reaction solution through a stainless-steel canula resulting in highly luminescent nanocrystals with an almost monodisperse particle size distribution. The NCs were characterized through the use of transmission electron microscopy, selected area electron diffraction, 1H NMR, powder X-ray diffraction, and high-resolution luminescence spectroscopy. The NaYF4 NCs are capable of being of dispersed in nonpolar organic solvents thus forming colloidally stable solutions. The colloids of the Er3+, Yb3+ and Tm3+, Yb3+ doped NCs exhibit green/red and blue upconversion luminescence, respectively, under 980 nm laser diode excitation with low power densities.     

纤维状中空结构NaYF4:Yb3+, Er3+上转换材料的 合成及防伪应用

采用水溶性聚合物聚乙烯亚胺(PEI)调介下的水热法,一步合成了具有纤维状中空结构的六方相NaYF4:Yb3+,Er3+上转换荧光材料,并将其作为荧光填料,通过流延成膜法制备了具有上转换荧光性能的壳聚糖/聚乙烯醇(CS/PVA)荧光复合薄膜.探究了PEI配体含量和反应体系pH值对合成的上转换材料的形貌、晶型和荧光性能的影响,以及壳聚糖/聚乙烯醇荧光复合薄膜中荧光填料的最佳掺杂量.研究结果表明,在PEI含量为0.3 g且反应体系pH=5的条件下,合成的产物为具有纤维状中空结构的六方相NaYF4:Yb3+,Er3+.荧光光谱表明,合成的NaYF4:Yb3+,Er3+上转换材料在980 nm激光激发下具有优异的荧光性能.当荧光填料的掺杂质量分数为3.0％时,制备的NaYF4:Yb3+,Er3+/(CS/PVA)荧光复合薄膜具有最佳的透明度和上转换荧光特性.     

Controllable multicolor upconversion luminescence of lanthanide doped NaGdF4 nanocrystals through single laser excitation at 980 nm

Room temperature multicolor Upconversion (UC) luminescence in Yb3+, Tm3+, Er3+ ions doped NaGdF4 nanocrystals have been successfully synthesized by a hydrothermal method. As-prepared nanocrystals are highly crystalline and well-dispersed in cyclohexane to form stable and clear colloidal solutions, which demonstrates strong emission properties with a single laser excitation at 980 nm. The multicolor light consists of blue, green, and red UC radiations that correspond to transitions 1G4 --> 3H6 of Tm3+, 2H(11/2)/4S(3/2) --> 4I(15/2), and 4F(9/2) --> 4I(15/2) of Er3+ ions, respectively. The UC mechanisms were proposed based on spectral, kinetic, and pump power dependence analyses.     

Sensitized upconversion emissions of Tb3+ by Tm3+ in YF3 and NaYF4 nanocrystals

Yb3+-Tm3+-Tb3+-codoped YF3 and NaYF4 nanocrystals (NCs) were synthesized using a simple hydrothermal method. Under 980 nm excitation, violet and ultraviolet upconversion (UC) emissions of 5D3 --> 7FJ (J = 6, 5, 4) and 5D4 --> 7FJ (J = 6, 5, 4, 3) of Tb3+ ions were observed with the fluoride NCs. In the Yb-Tm-Tb codoped NCs, energy transfer (ET) processes from Tm3+ to Tb3+ were proposed to be the main mechanisms for the UC emissions of Tb3+ ions. They are more efficient than the phonon assisted cooperative sensitization of the Yb3+ couple proposed previously for similar material system. The analysis of power dependence indicated that populating the 5D4 level of the Tb3+ ions was a four photon UC process, which demonstrated the existence of the two step ET process of Yb3+ --> Tm3+ --> Tb3+. It was also found that UC luminescence properties of Tb3+ ions were sensitive to crystal structures.     

Er3+ -doped anatase TiO2 nanocrystals: crystal-field levels, excited-state dynamics, upconversion, and defect luminescence

A comprehensive survey of electronic structure and optical properties of rare-earth ions embedded in semiconductor nanocrystals (NCs) is of vital importance for their potential applications in areas as diverse as luminescent bioprobes, lighting, and displays. Er3+ -doped anatase TiO2 NCs, synthesized via a facile sol-gel solvothermal method, exhibit intense and well-resolved intra-4f emissions of Er3+ . Crystal-field (CF) spectra of Er3+ in TiO2 NCs are systematically studied by means of high-resolution emission and excitation spectra at 10-300 K. The CF analysis of Er3+ assuming a site symmetry of C(2v) yields a small root-mean-square deviation of 25.1 cm(-1) and reveals the relatively large CF strength (549 cm(-1) ) of Er3+, thus verifying the rationality of the C(2v) symmetry assignment of Er3+ in anatase TiO2 NCs. Based on a simplified thermalization model for the temperature-dependent photoluminescence (PL) dynamics from (4) S(3/2) , the intrinsic radiative luminescence lifetimes of (4) S(3/2) and (2) H(11/2) are experimentally determined to be 3.70 and 1.73 μs, respectively. Green and red upconversion (UC) luminescence of Er3+ can be achieved upon laser excitation at 974.5 nm. The UC intensity of Er3+ in Yb/Er-codoped NCs is found to be about five times higher than that of Er-singly-doped counterparts as a result of efficient Yb3+ sensitization and energy transfer upconversion (ETU) evidenced by its distinct UC luminescence dynamics. Furthermore, the origin of defect luminescence is revealed based on the temperature-dependent PL spectra upon excitation above the TiO2 bandgap at 325 nm.     

OH- 对 Tm3+/Yb3+ 共掺碲酸盐玻璃上转换发光的影响

研究了Tm3 /Yb3 共掺碲酸盐玻璃的Raman光谱、红外光谱和上转换发光光谱,分析了OH-对Tm3 上转换发光的影响。结果表明,氧氯碲酸盐玻璃的声子能量高于氧氟碲酸盐玻璃的声子能量,但是Tm3 /Yb3 共掺氧氟碲酸盐玻璃的上转换发光强度高于Tm3 /Yb3 共掺氧氯碲酸盐玻璃。分析认为这主要是由于OH-的影响,在氧氟碲酸盐玻璃中OH-的浓度较低,导致Tm3 的荧光寿命高,从而提高Tm3 的上转换发光。在一定程度上,OH-对Tm3 上转换发光的影响大于声子能量对Tm3 上转换发光的影响。研究结果有助于进一步提高Tm3 的发光效率。     

Upconversion luminescence of Er3+ in transparent SiO2—PbF2—ErF3 glass ceramics

Oxyfluoride glasses with the composition 50SiO2 · 50PbF2 · xErF3 (x=4 and 5) by molar ratio were developed. Transparent glass ceramics were obtained by heat-treating the 50SiO2 · 50PbF2 · xErF3 glasses at the first crystallization temperatures. X-ray diffraction analysis of the transparent glass ceramics revealed that fluorite type -PbF2:Er3+ solid solution regions of about 13.0 nm in diameter are precipitated in the glass matrix. The formation of this -PbF2:Er3+ solid solution was also supported by Eu3+ fluorescence spectra which were measured on specimens in which Eu substituted for Er. Under 800 nm laser excitation, the Er3+ upconversion luminescence of 50SiO2 · 50PbF2 · xErF3 glasses was barely detectable, but the 50SiO2 · 50PbF2 · xErF3 glass ceramics gave Er3+ upconversion luminescence at a very high efficiency. The reason for the highly efficient Er3+ upconversion luminescence in the 50SiO2 · 50PbF2 · xErF3 glass ceramics can be explained in terms of the very small multiphonon relaxation rates that are anticipated from consideration of the Eu3+ emission spectra.     

White up-conversion luminescent property in Re3+:Gd3Ga5O12 nanocrystals

Rare-earth ions doped Gd3Ga5O12 nanocrystals have been prepared by a propellant combustion synthesis method and their up-conversion properties were systematically investigated in this paper. XRD, SEM, TEM, and up-conversion emission spectra were used to characterize the synthesized nanocrystals. Energy transfer from Yb3+ to Er3+ and Tm3+ can occur simultaneously in the as-synthesized Gd3Ga5O12 nanocrystals. The up-conversion mechanisms and relevant energy transfer processes are discussed. A white light generation was observed when the Yb3+, Er3+ and Tm3+ were directly incorporated in the Gd3Ga5O12 lattice. And its calculated color coordinates is (0.35, 0.41) under the excitation at 974.5 nm. The bright white luminescent nanocrystals may have potential application in the field of lighting, displays and photonics.