Rare Earth Photoluminescence in Bismuth-Germanate Crystals

In the present work, the photoluminescence (PL) spectra of bismuth germanate (BGO) doped with trivalent rare earth element (REE) ions with different doping concentrations (0.03 wt% Eu, 0.4 wt% Tm, and 1.1 wt% Nd) are reported in the temperature range from 10 to 300 K using different detectors, namely, photomultiplier tube (PMT), InGaAs (IGA), and Si. The luminescence in the NIR region was also measured at room temperature. Two broad emission bands attributed to undoped BGO were found at circa 1350 and 1800 nm, respectively. The broad-band emissions are replaced by narrow-band line emissions defined by the trivalent rare earth dopants. The emission spectra from rare earth ion–doped BGO extend from 500 to 2000 nm. Rare earth ions act as the dominant recombination centers and define the emission spectra. This is interpreted as resulting from direct charge transfer from intrinsic defect traps to rare earth recombination centers. The temperature-dependent luminescence of BGO doped with 0.4 wt% Tm is also presented.     

β-NaGd_(0.794)Yb_(0.200)Ho_(0.001)Tm_(0.005)F_4纳米颗粒的白色上转换发光

利用简单的水热合成法制备了β-NaGd0.794Yb0.200Ho0.001Tm0.005F4纳米颗粒。采用X射线粉末衍射(XRD)技术测定了样品的物相,结果显示样品为六角相。通过透射电子显微镜(TEM)和高分辨透射电子显微镜观察的结果样品为椭球和六角形状,颗粒的平均尺寸为23 nm。用980 nm半导体激光二极管为激发光源,测定了样品的室温上转换发射谱,结果表明:样品分别发射红、绿和蓝色光,其相对发射强度,从强到弱的顺序为蓝色、绿色和红色,与其对应辐射跃迁分别为Tm3+离子的1G4→3H6,Ho3+离子的5F4→5I8,5F5→5I8跃迁。样品发射的蓝、绿和红光组合而发出强的白色上转换发光,其色品坐标为(x=0.271 7,y=0.267 3)。     

Dual drug-loaded paclitaxel–thymoquinone nanoparticles for effective breast cancer therapy

The present study highlights the beneficial synergistic blend of anticancer drug paclitaxel (PTX) and thymoquinone (TQ) in MCF-7 breast cancer cells. We aimed to augment the therapeutic index of PTX using a polymeric nanoparticle system loaded with PTX and TQ. PLGA nanoparticles encapsulating the two drugs, individually or in combination, were prepared by single emulsion solvent evaporation method. The formulated nanoparticles were homogenous with an overall negative charge and their size ranging between 200 and 300 nm. Entrapment efficiency of PTX and TQ in the dual drug-loaded nanoparticles was found to be 82.4 ± 2.18 and 65.8 ± 0.45 %, respectively. The release kinetics of PTX and TQ from the nanoparticles exhibited a biphasic pattern characterised by an initial burst, followed by a gradual and continuous release. The anticancer activity of nanoparticles encapsulating both the drugs was higher as compared to the free drugs in MCF-7 breast cancer cells. The combination index for the dual drug-loaded NPs was found to be 0.688 which is indicative of synergistic interaction. Thus, here, we propose the synthesis and use of dual drug-loaded TQ and PTX NPs which exhibits enhanced anticancer activity and can additionally help to alleviate the toxic effects of PTX by lowering its effective dose.     

Additive colouring of CaF2:Yb crystals: determination of Yb2+ concentration in CaF2:Yb crystals and ceramics

When growing CaF₂ crystal doped with rare-earth ions, most of these ions are present in a trivalent state. However, due to contact with graphite crucible, a small proportion of a number of ions (Eu, Sm, Yb and Tm) are reduced to a bivalent state. A similar situation takes place during fabrication of CaF₂ ceramics doped with rare-earth metals. This fact is of particular importance for laser CaF₂:Yb crystals (ceramics), a promising material for short-pulse, high-power, high-energy diode-pumped solid state lasers since the presence of bivalent Yb ions can be a source of thermal losses. To date, there has been no technique to determine Yb²⁺ concentration in as-grown crystals. The proposed technique is based on a total reduction of Yb³⁺ ions via the heating of as-grown CaF₂ crystals with known concentration of Yb in the reducing atmosphere of metal vapour and determining the cross section of absorption bands of Yb²⁺ ions. The knowledge of these parameters allows estimation of the Yb²⁺ content in CaF₂:Yb crystals or ceramics by analysing their absorption spectra. Examples of using this technique are given. The technology of CdF₂ crystals reduction (an “additive colouring”) and features of colouring of crystals doped with rare-earth ions are considered.     

Tunable Upconversion Emissions from Lanthanide-doped Monodisperse β-NaYF4 Nanoparticles

We report upconversion multicolor tuning based on uniform β-NaYF₄:Yb/Tm/Er nanoparticles. The as-synthesized nanoparticles with an average diameter of 25 nm are well dispersed in a wide range of nonpolar solvents including hexane, cyclohexane, dichloromethane, and toluene. These nanoparticles show intense upconversion emissions and the color output can be precisely modulated by adjusting activator ratios of Tm³⁺ to Er³⁺. Dopant-concentration dependent emission properties of the triply doped particle system are also investigated. In addition, we demonstrate that these nanoparticles can be readily transferred to polar solvents such as ethanol and water by growing a thin silica layer (10 nm) around the particles, providing potential applications in biological labeling and imaging.     

Enhanced Up-Conversion Emission in Al<Superscript>3+</Superscript> Co-Doped ZnGa<Subscript>2</Subscript>O<Subscript>4</Subscript>:Yb<Superscript>3+</Superscript>,Tm<Superscript>3+</Superscript> Powder Phosphors

Yb³⁺-Tm³⁺ co-doped up-conversion powder phosphors using Zn(Al_xGa_1-x)₂O₄ (ZAGO) as the host materials were synthesized via solid-state reaction successfully. In addition, the morphology, structural characterization and up-conversion luminescent properties were all investigated by scanning electron microscope (SEM), x-ray diffraction (XRD) and fluorescence spectrophotometer (F-7000), respectively. Under the excitation of a 980 nm laser, all as-prepared powders can carry out blue emission at about 477 nm (corresponding to ¹G₄ → ³H₆ transition of Tm³⁺ ions), and red emission at about 691 nm (attributed to ³F₃ → ³H₆ transition of Tm³⁺ ions). Also, the influence of doping Al³⁺ ions were investigated. In brief, the doping of Al³⁺ ions has no effect on the position of emission peak. Howbeit the up-conversion efficiency and intensity of ZAGO:Yb,Tm phosphors are stronger than ZGO:Yb,Tm and ZAO:Yb,Tm phosphors, while the crystallinity is the opposite. More particularly, all as-prepared powder phosphors emit strong luminescence, which is observable by the naked eye, demonstrating the potential applications in luminous paint, luminescent dye, etc.     

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.     

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Data on classification of spectra and energy levels of atoms of rare earth elements with unfilled 4f-shells have been collected, systematized and analyzed. A brief account is given of methods for determining transition probabilities and lifetimes of the excited states of atoms and ions. Oscillator strengths for spectral lines of Nd(I), Sm(I), Eu(I), Gd(I), Dy(I), Tm(I) and Yb(I) have been measured using Rojdestvensky's hook method. Lifetimes of some of the excited states of Eu(I), Yb(I) and Yb(II) have been determined by using simultaneously the methods of delayed coincidence, hooks, and total absorption. Our results have been compared with those of other investigators. Atoms with unfilled 4f-shells show some regularities.     

Energy migration toward a dye in nanoparticles from complexes with short fluorescent state lifetimes

We have studied regular features of the fluorescence sensitization (cofluorescence) of coumarin 30 and rhodamine 6G introduced into nanoparticles from complexes Ln(PhBTA)₃phen, where PhBTA is p-phenylbenzoyltrifluoroacetone and Ln is a triply charged Pr, Nd, Sm, Eu, Er, or Yb ion, which absorbs in the fluorescence range of ligands of complexes and dyes. We show that both the cofluorescence intensities (I _cofl) of rhodamine 6G in nanoparticles from Sm and Eu complexes and the behavior of intensity I _cofl on the content of rhodamine 6G coincide with the corresponding data obtained for nanoparticles from La and Lu complexes doped with rhodamine 6G molecules. A considerable decrease in I _cofl of rhodamine 6G is observed only in nanoparticles from complexes Nd(PhBTA)₃phen. In nanoparticles from Pr, Nd, Sm, Eu, Er, and Yb complexes doped with coumarin 30, it has been observed that, depending on the choice of the central ion, I _cofl of coumarin 30 is 2 to 80 times lower compared to I _cofl of the dye in nanoparticles from La and Lu complexes. A separate analysis of the influence of these ions on the energy transfer from complexes to coumarin 30 and on the fluorescence intensity of coumarin 30 incorporated into nanoparticles from these ions showed that a decrease in I _cofl of coumarin 30 by a factor of 2?C20 occurs due to the reduction of ??_fl of ligands of complexes under the influence of the interaction with Pr, Nd, Sm, Eu, Er, and Yb ions. Since ??_fl of complexes La(PhBTA)3phen is ??2 ps, while that of complexes Gd(PhBTA)3phen is ??1 ps, then, in nanoparticles with a maximal decrease in I _cofl of coumarin 30, ??_fl of complexes is reduced to ??0.1 ps. It has been found that, in nanoparticles from complexes with this ??_fl, energy migration over complexes takes place. However, as distinct from nanoparticles from La, Lu, and Y complexes, the free path length of singlet excitons in nanoparticles from complexes of absorbing ions is smaller than the nanoparticle size.     

Tm3+/Yb3+共掺杂玻璃和玻璃陶瓷中蓝色 上转换发光中的能量传递过程

利用高温固相法制备了Tm³⁺/Yb³⁺共掺杂的氟氧化物玻璃和玻璃陶瓷材料,在980 nm的激光激发下,样品发射出明亮的蓝色上转换荧光。通过对玻璃和玻璃陶瓷样品的对比,发现Tm³⁺离子和Yb³⁺离子之间存在着Tm³⁺(³H₄)→Yb³⁺(²F_5/2)的反向能量传输通道,并且与晶场有较强的依赖关系。分析了在玻璃和玻璃陶瓷中蓝色上转换发光过程,随着敏化剂Yb³⁺浓度的增加,在玻璃中正向和反向能量传递的竞争作用使得Tm³⁺离子在Yb³⁺离子的最佳浓度时上转换发光最强;而在玻璃陶瓷中, Tm³⁺离子的上转换发光始终随着Yb³⁺离子的浓度增加而增强。     

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.     

798 nm半导体激光激发下Yb3+, Tm3+:ZBLAN玻璃的上转换发光

在用７９８ｎｍ半导体激光直接激发Ｔｍ＾３＋离子至＾３Ｆ４能级时,Ｔｍ＾３＋和Ｙｂ＾３＋共掺的锆系氟化物（Ｔｍ＾３＋,Ｙｂ＾３＋;ＺＢＬＡＮ）玻璃中观测到了较强的上转换蓝光。分析了发光机理：Ｔｍ＾３＋离子把能量传递给Ｙｂ＾２＋离子,被激发的Ｙｂ＾３＋离子又把能量传递给Ｔｍ＾３＋离子,从而把Ｔｍ＾３＋激发至发射蓝光的能级＾１Ｇ４和＾１Ｄ２。对这种泵浦机制的特点进行了讨论。     

NaYF4∶Eu3+, Tm3+, Yb3+材料中Stokes和反Stokes发光研究

合成了Eu3+,Tm3+和Yb3+掺杂的NaYF₄材料。360 nm光激发呈蓝色发光,峰值位于452 nm,对应Tm3+的1D₂→3F₄跃迁;395 nm光激发呈橙色发光,峰值位于591 nm,对应Eu3+的5D₀→7F₁跃迁;409 nm光激发呈红色发光,峰值位于613 nm,对应Eu3+的5D₀→7F₂跃迁;980 nm光激发呈蓝色和红色发光,发光峰位于474和646 nm。蓝光来源Tm3+的1G₄ →3H₆跃迁,红光来源Tm3+的1G₄→3F₄跃迁。在双对数曲线中,蓝光474 nm和红光646 nm的斜率分别为2.1和2.4,在980 nm光激发下,蓝光和红光发射都是双光子过程。还研究了材料的吸收光谱,并利用X射线衍射,扫描电镜测试了材料的物相结构和微观形貌。结果表明：NaYF₄∶Eu3+, Tm3+, Yb3+材料具有较规则的六方相结构,结晶良好。     

Energy transfer between lanthanide ions in nanostructures of their complexes. I

We study the regular features of the behavior of the intensity I _lum and the luminescence decay time τ _lum of complexes of Eu and Tb ions with several β-diketones and 1,10-phenanthroline in the case where these complexes from nanostructures with complexes of lanthanide ions that are electronic excitation acceptors of these Eu and Tb ions. The composition of mixed nanostructures formed in a solution is shown to depend on the method of their preparation, on the ability of complexes to form mixed rather than homogeneous nanostructures, and on the concentration of complexes in the solution. We reveal that complexes of Yb, Tm, and Dy ions simultaneously increase I _lum and τ _lum of Eu complexes due to energy transfer through ligands of complexes and decrease the value of these quantities for Eu complexes due to energy transfer from Eu(III) ions to ions of Yb, Tm, and Dy. For all interacting complexes, the changes in I _lum and τ _lum of complexes of Eu (Tb) in the presence of complexes, energy acceptors, are shown to be determined by competition between two processes: a decrease in these quantities due to energy transfer between ions and their increase caused by an increase in the probability of nonradiative transitions in Eu (Tb) ions due to an increase in the size of structures. We propose a method of separation of these two processes.     

Tm~(3+)/Er~(3+)/Yb~(3+)掺杂的镓锗酸盐玻璃光谱性能及能量传递

采用熔融淬冷法制备得到透明的Tm~(3+)/Er~(3+)/Yb~(3+)掺杂镓锗钠玻璃。对比研究了808 nm和980 nm激发下Tm_2O_3含量对样品可见-红外光学光谱特性的影响。结合稀土离子能级结构,分析了Tm~(3+)、Er~(3+)和Yb~(3+)离子之间的能量传递机制。结果表明:在808 nm和980 nm的激发下,Tm~(3+)/Er~(3+)/Yb~(3+)掺杂样品中均观察到了473,655,521,544 nm的蓝、红和绿光。在808 nm激发下,随着Tm~(3+)浓度的增加,Tm~(3+):1 800 nm和Er~(3+):1 530 nm发射强度的比率I1.8/I1.53逐渐增大。由于在Tm~(3+)和Er~(3+)间的能量传递有效地改变了红光和绿光的发射强度,473,521,655 nm的发光强度呈现先升高再降低的趋势,在Tm_2O_3掺杂摩尔分数为0.3%时达到最大值。而在980 nm激发下,由于Yb~(3+)对Er~(3+)和Tm~(3+)的能量传递起主要作用,使得其上转换红光(655 nm)、绿光(521 nm和544 nm)和蓝光(473 nm)的发光强度高于808 nm激发下的上转换发光。     

α-TeO2∶Tm3+,Ho3+,Yb3+纳米材料的红绿蓝色上转换发光（英文）

利用简单的水热合成法成功制备出α-TeO2∶Ho3+,Yb3+、α-TeO2∶Tm3+,Yb3+和α-TeO2∶Tm3+,Ho3+,Yb3+纳米材料,用980 nm的近红外光作为激发光源测定了样品的室温上转换发射光谱。结果表明:样品α-TeO2∶Ho3+,Yb3+分别发射绿光(545 nm)和红光(651 nm),分别对应于Ho3+离子的5S2→5I8和5F5→5I8能级跃迁。随着Yb3+的摩尔分数从5%增加到15%,样品在545 nm处的绿光强度明显变大,发光颜色由黄光向绿光转变。样品α-TeO2∶Tm3+,Yb3+在476 nm处发射出蓝光,对应于Tm3+离子的1G4→3H6能级跃迁,两个弱红光峰(651,675 nm)分别对应于Tm3+离子的1G4→3F4和3F2→3H6能级跃迁。随着Yb3+离子浓度的提高,蓝光与红光的相对强度也在显著提高。基于可调控性蓝光、绿光和红光的产生,α-TeO2∶Tm3+,Ho3+,Yb3+纳米材料能产生不同颜色的光,包括白光。     

强上转换发光的LiLu_(1-x)Yb_xF_4∶Tm@LiGdF_4核壳纳米晶的制备

利用高温热分解法制备了LiLuF_4∶Yb,Tm@LiGdF_4核壳纳米晶。在980nm激光激发下,与未包覆的样品相比,LiLuF_4∶Yb,Tm@LiGdF_4核壳纳米晶的发光增强了15倍左右,这主要是因为通过惰性壳层的包覆可以有效抑制表面猝灭效应。另外,随着核中Yb~(3+)离子的摩尔分数从20%增加到100%,上转换发光强度逐渐增大,最大增加了12.4倍左右。这主要是由于增加Yb~(3+)离子的浓度可以增加纳米粒子对激发光的吸收和提高Yb~(3+)到Tm~(3+)的能量传递速率。所制备的LiYbF_4∶2%Tm@LiGdF_4核壳纳米晶的发光效率高达4%。     

Influence of complexing ion on the fluorescence sensitization efficiency for oxazine dyes in nanoparticles of Sc,Eu, Sm,and Lu diketonates

The fluorescence sensitization regularities have been investigated for oxazine dyes (Nile blue, cresyl violet (oxazine-9), and oxazine-170) in nanoparticles of complexes of 2-naphthoyltrifluoroacetone with trivalent ions of rare-earth metals. The fluorescence sensitization efficiencies of dyes in nanoparticles from the Sc(III), Eu(III), Sm(III), and Lu(III) complexes are compared. It is shown that the fluorescence sensitization efficiencies of dyes in nanoparticles from the Sc(III), Eu(III), and Sm(III) complexes has similar values and greatly exceed that for nanoparticles from the Lu(III) complexes. The quantum yields of sensitized fluorescence are determined for dyes in nanoparticles from the Sc(III), Eu(III), and Sm(III) complexes. The nanoparticles doped with oxazine-170 from Eu(III) complexes are found to have the strongest fluorescence.     

A fluorescent probe for detecting thiamine using the luminescence intensity of nanoparticles

Determination of molecules and biomolecules using nanoparticles is promising in the development of analytical techniques. Modified Eu-doped Y₂O₃ nanoparticles (Y₂O₃:Eu NPs) by captopril have been used as a probe for thiamine (vitamin B₁) determination. According to the fluorescence enhancement of modified Eu-doped Y₂O₃ nanoparticles caused by thiamine, a simple and sensitive method were proposed for its detection. The increase in modified Y₂O₃:Eu NPs fluorescence signal as a function of thiamine concentration was found to be linear in the concentration range of 0–44 μM. The limit of detection (LOD) of thiamine by this method was 0.144 μM. All the measurements were performed in natural pH, at the room temperature under ambient conditions. Possible interaction mechanism was discussed.     

Synthesis,Characterization, and Antibacterial Activity of RE(III) Complexes with L-Isoleucine and 1,10-Phenanthroline

Six new ternary rare-earth (La, Eu, Sm, Nd, Y, Yb) complexes with L-isoleucine and 1,10-phenanthroline have been synthesized. Their compositions were characterized as RE(Ile)₃PhenCl₃ · 4H₂O (RE = La, Eu, Sm, Nd, Y, Yb; Ile = L-isoleucine; phen = 1,10-phenanthroline) by elemental analysis, EDTA titration, molar conductance measurement, UV spectra, FT-IR spectra, and TG-DTA. The average diameters of growth inhibition area and the minimal inhibitory concentration (MIC) of the complexes were studied by disc diffusion method and dilution method in nutrient broth. The results showed that the ternary rare-earth complexes strongly exhibited the antibacterial activity against Escherichia coli and Staphylococcus aureus and that their antibacterial effects were better than those of rare-earth chlorides, L-isoleucine, and 1,10-phenanthroline.