Eu0.5Tb0.5(TTA)3Bipy/PMMA的制备及发光性能

合成了一种新型的稀土配合物Eu0.5Tb0.5(TTA)3Bipy,并采用原位乳液聚合法制备了Eu0.5Tb0.5(TTA)3Bipy/PMMA稀土聚合物材料.利用红外光谱仪(IR)、电子探针X射线能谱仪等对稀土聚合物发光材料的结构进行表征,并利用扫描隧道电子显微镜(SEM)、荧光光谱仪(FS)等分别研究了该发光材料的微观形貌,探讨了其发光性能.结果表明,Eu0.5Tb0.5(TTA)3Bipy/PMMA仍保持Eu0.5Tb0.5(TTA)3Bipy原有的发光特性;在365nm紫外光的激发下,产生发光峰在612nm附近、谱线带宽为10.4nm的红光发射,发光亮度高,色纯度高,是性能优良的稀土聚合物发光材料.     

稀土离子掺杂硼酸钙发光材料的合成与光谱性质

以硼砂和氯化钙为原料,主要采用化学共沉淀法成功合成了稀土离子Eu3+、Tb3+掺杂的硼酸钙发光材料。通过X射线衍射、荧光光谱对样品物相和发光性能进行了表征。探究了不同的实验条件(即不同煅烧温度、稀土离子浓度)对其发光性能的影响,样品的激发光谱表明,在800℃时,CaB2O4∶Tb3+的发光能力最强;掺杂稀土Tb3+离子的发光材料在5%时发光性能最强。在221nm紫外光激发下,样品在612nm和543nm处有Eu3+和Tb3+离子明显的特征发射峰,而且掺杂Eu3+离子的发光材料的发光性能随着Eu3+浓度的增加而增强。     

铕掺杂聚甲基丙烯酸甲酯的光致发光性能

利用不饱和二元羧酸3-己烯二酸(H2L)、1,10-邻菲咯啉(Phen)与稀土铕的氯化物EuCl3反应,合成了具有发光性能的稀土铕三元配合物Eu2L3Phen.4H2O。将铕配合物与聚甲基丙烯酸甲酯(PMMA)掺杂后,研究了掺杂型高分子材料的光致发光性能。研究结果表明,Eu配合物能发出很强的铕离子特征荧光,当配合物Eu2L3Phen.4H2O与聚甲基丙烯酸甲酯掺杂后,高分子材料仍能发出配合物Eu2L3Phen.4H2O的特征荧光,高分子材料的发光强度随着配合物在聚甲基丙烯酸甲酯中掺杂量的增加而增加。     

2,2,2-胺三乙酰二苄胺及其稀土配合物的合成、表征与荧光性质

为研究三脚架型配体稀土配合物的组成、可能的配位状态及荧光性质,合成了三脚架型配体--2,2,2-胺三乙酰二苄胺(L)及其6个稀土配合物.通过红外光谱、核磁共振波谱、元素分析、差热-热重分析、摩尔电导率及荧光光谱等方法对L及其稀土配合物的组成及性质进行了表征.结果表明, L能够与稀土离子配位,生成n(RE)∶n(L)=1∶1的配合物;Tb(Ⅲ)配合物在紫外光激发下,在490nm、545nm、590nm、620nm附近出现强度不同的Tb3+特征荧光发射峰,分别归属于Tb3+的5D4→7F6、5D4 →7F5、5D4→7F4、5D4→7F3能级跃迁;而其Eu(Ⅲ)配合物的荧光发射微弱,其它配合物没有荧光发射.说明L的三重态能量与Tb3+最低激发态能级匹配较好,能起到较好的敏化作用,提高Tb3+的发光强度.     

电致发光稀土高分子的研究进展

稀土高分子材料不仅具有小分子稀土离子配合物优异的发光特性,而且具备高分子聚合物的易弯曲和加工等性能。本文介绍了稀土高分子材料的研究历程,并综述了Eu3+、Tb3+高分子电致发光材料的国内外研究现状。     

稀土铕有机配合物的研究进展及其应用

目的 介绍稀土铕有机配合物的原理、分类、应用及其最新研究进展,为高性能稀土铕配合物的研发提供一定的思路和依据。方法 通过查阅国内外学者近年来对稀土铕有机配合物的各种研究文献,对稀土铕有机配合物的主配体种类及应用进行整理总结。结果 稀土铕有机配合物的主配体有四大类,即β-二酮类、羧酸及羧酸盐类、有机高分子类与超分子大环类,该配合物主要应用于荧光材料、发光材料、磁性材料和生物等四大领域。结论 铕有机配合物的荧光性能良好,且高分子类配合物易加工成型;有机高分子类铕配合物可以结合Eu3+和高分子的优点,在提高其与聚合物材料相容性的前提下,有望成为一种新型的功能材料。     

稀土配合物Eu(TTA)3Phen掺杂的PMMA树脂的制备及其发光性能研究

用新的合成方法合成了稀土配合物Eu(TTA) 3Phen。研究了该配合物的IR、UV、TGA、元素分析和荧光光谱。该配合物具有良好的发光性能和热稳定性。采用加热方法将Eu(TTA) 3Phen掺入PMMA树脂中 ,制成发光塑料树脂 ,并测定其发光性能。结果表明 ,Eu(TTA) 3Phen掺入PMMA树脂后仍保持该稀土配合物原有的发光特性 ,制成的Eu(TTA) 3Phen -PMMA树脂复合材料具有良好的发光性能 ,其发光强度与Eu(TTA) 3Phen掺入的含量有关。     

铕配位丙烯酸与甲基丙烯酸甲酯的聚合及荧光研究

由三氯化铕、邻菲哆啉、噻吩基三氟-1,3-丁二酮及丙烯酸合成铕配位单体(ECM)后,再与甲基丙烯酸甲酯(MMA)聚合成侧链连有红色发光铕配住的聚合物(ECM与MMA的物质的量比1∶60/1∶30).聚合物荧光光谱包括350～500nm和602～630nm两个区域,最大发射波长613nm.Eu3+的发光来自ECM中各配位体的能量传递和聚合物链的Forster能量转移.该类聚合物具有优良的荧光性能、溶解性和分散性.     

稀土铕高分子荧光配合物的制备及性能研究

稀土配合物作为发光材料已广泛应用于众多领域,为了使材料获得更稳定更持久的发光性能,本文以N-乙烯基甲酰胺(NVF)和丙烯酰胺(AM)为共聚单体,水为溶剂,在高温、引发剂条件下经自由基溶液聚合制备出含有氨基、羧基等多种配位官能团的水溶性高分子聚合物两性聚乙烯胺(PVAm),并以此作为高分子配体,再辅以1,10-邻菲咯啉(phen)作为第二配体,用三价稀土离子铕(Eu)的盐溶液与之配位,制备出具有优良荧光效应的稀土配合物Eu(PVAm)_3phen荧光粉。对高分子配体PVAm进行IR、NMR等分析,找出配位官能团,并对稀土配合物的外观形貌进行荧光显微镜等观察分析,对配合物的结构进行XRD等表征,并分析其紫外光谱、荧光光谱、荧光余辉亮度。配合物在220～275 nm范围内对紫外光有较强的吸收,最大吸收峰在260 nm处。配合物在580、593、614、650 nm的4处有明显的荧光发射峰。     

稀土Eu配合物液晶聚合物性能研究

介绍了一类含Eu配合物的新型荧光液晶聚合物材料。通过把手性液晶单体M1(烯丙氧基苯甲酸胆甾醇酯,液晶区间达132.1℃)和具有荧光性能的金属稀土E+3配合物(C3)接枝到含氢硅氧烷上,制备得到含有稀土3价Eu配合物的侧链液晶聚合物。研究了Eu配体的共轭作用与荧光性能的关系。在紫外光激发下,该聚合物在室温下就显示较强的荧光,主波长为617 nm,Eu含量在4%~8%范围内荧光强度随Eu含量的增加而增强,Eu含量达到8%时,荧光最强,低于和高于8%,荧光强度下降。单体C3的荧光配合物的荧光强度仅为其荧光液晶聚合物在主波长荧光强度的30%,揭示了荧光液晶聚合物的优势。与不含Eu的聚合物相比,液晶织构类型不变,但熔点略有升高,而清亮点呈下降趋势。这类材料除具有配合物荧光性外,其液晶性的存在使加工性提高。该类新材料尚处于理论研究阶段,但为应用研究提供了基础,并揭示该类材料广阔的应用前景。     

光固化EA体系中Eu(TTA)(AA)2Phen配合物的原位法合成及荧光性能

利用“原住法”合成技术，在EA(双酚A环氧丙烯酸酯树脂)中，合成了稀土荧光配合物Eu(TTA)(AA)2Phen(TTA：噻吩甲酰基三氟丙酮；AA：丙烯酸；Phen：邻菲咯啉)，利用红外光谱、紫外一可见光谱和荧光光谱对体系进行了表征。红外光谱的研究表明，配合物在EA体系中的特征吸收峰被基质树脂所掩盖，主要表现为基质树脂的特征吸收；紫外一可见光谱的研究表明，该体系在350nm附近出现配体TTA的强特征吸收，在低于300nm时，吸收峰被基质树脂掩盖；荧光光谱的研究表明，配合物在EA体系中能发出强的铕离子的特征荧光．并且低于铕质量分数为0．4％的范围内，荧光强度与稀土离子含量接近线性关系。     

铕配合物的合成及其荧光防伪油墨的制备

选用苯甲酸(BA)、噻吩甲酰三氟丙酮(TTA)、邻菲咯啉(Phen)作为配体合成了Eu(BA)3Phen三元配合物、Eu(BA)(TTA)2Phen四元配合物,将其作为荧光剂,制备了稀土荧光防伪油墨。红外光谱的分析表明配体与铕离子发生了配位。测定了配合物和荧光防伪油墨的荧光性能,发射波长为614 nm,制备的稀土荧光防伪油墨在可见光下印迹无色,在紫外灯下呈现明显红色荧光。     

Synthesis and luminescence properties of ternary complexes of Sm x Tb1−x (TTA)3Phen nanoparticles and their surface modification

A series of Sm _x Tb_1?x (TTA)₃Phen (x = 1.0, 0.9, 0.7, 0.5, 0.3, 0.1, 0) complexes was synthesized by wet chemical method and characterized using Fourier transform infrared spectroscopy and fluorescence spectroscopy. The IR absorption spectra indicate that α-thenoyltrifluoroacetone was coordinated to the rare earth ions and that chemical bonds were formed between rare earth ions and the nitrogen atoms in 1,10-Phenanthroline (Phen). The fluorescence spectra of the complexes indicate that the emission intensity of Sm³⁺ was enhanced by the addition of substitutive Tb³⁺. These data show that not only the ligands (TTA and Phen) but also Tb³⁺ could absorb and transmit energy to Sm³⁺ in the complexes. Formation of dual-core complexes appears to be responsible for co-fluorescence, which can greatly promote the illuminant ability of Sm (TTA)₃Phen complex. After further encapsulation by SiO₂, the Sm _x Tb_1?x (TTA)₃Phen@SiO₂ core–shell structure was very stable to UV light.     

Preparation of Eu3+-Y3+ coactivating Na+ based red-emitting luminous materials for light-emitting diodes and investigation of its characteristics

By solid-state reaction and doping, a series of red-emitting phosphors Na(x)Y(0.92-x/3)(MoO(4))(y)(WO(4))(1-y)O(0.5) : zEu(3+) have been synthesized. Through optimization of the process conditions and photoluminescent analysis, one type of red emission is obtained that matches nicely with ultraviolet light-emitting diode (UV-LED) chips.     

Synthesis and photoluminescence of nano-sized (Gd,Y)PO4:Eu3+ by solution combustion method

We synthesized (Gd(1-x)Yx)(0.94)PO4:Eu(0.06) (0 < or = x < or = 1.0) phosphor powders of an ultra-fine size (approximately 23 nm), smooth surface, and spherical and regular morphologies by the solution combustion method. The crystallite sizes of the annealed (Gd(1-x)Yx)(0.94)PO4:Eu(0.06) phosphors with x = 0, 0.25, 0.5, 0.75, and 1.0 were 63.3, 62.3, 49.9, 45.1, and 43.3 nm, respectively. The photoluminescent characteristics of the phosphors were studied under vacuum ultraviolet excitation, depending on the Y3+ concentration. The intensity of the peaks corresponding to the red emission increased with increases in the Y3+ concentration. The Y(0.94)PO4:Eu(0.06) phosphor emitted the strongest intensity and the purest red color.     

Preparation, Characterization and Luminescent Properties of MCM-41 Type Materials Impregnated with Rare Earth Complex

Hybrid materials incorporating Eu-(TTA)(3). 2H(2)O (7hereafter designated as Eu-TTA, with TTA: thenoyltrifluoroacetone) in unmodified or modified MCM-41 by 3-aminopropyl-triethoxysilane (APTES) were prepared by impregnation method. The obtained materials were characterized using X-ray diffraction (XRD), IR and diffuse reflectance spectroscopy and luminescence spectra. All the hybrid samples exhibited the characteristic emission bands of EU3+ under UV light excitation at room temperature, and the excitation spectra showed significant blue-shifts compared to the pure rare-earth complex. Although the red emission intensity in the modified hybrid was almost the half of the red emission intensity in the pure Eu-TTA complex at room temperature, the hybrid showed a much higher thermal stability due to the shielding character of the MCM-41 host.     

Effect of compatibility between europium complexes and styrene monomer on preparation of europium-encapsulated microspheres by dispersion polymerization

Two europium organic complexes of Eu(DBM)₃Phen (DBM = dibenzoylmethane, Phen = 1,10-phenanthroline) and Eu(TTA)₃·2H₂O (TTA = 2-thenoyltrifluoroacetone) with different structures are successfully encapsulated into polystyrene (PSt) microspheres by in situ dispersion polymerization. These fluorescent microspheres are monodisperse and spherical in shape with the homogeneous distribution of europium complexes in the polymer matrix, as investigated by field emission scanning electron microscopy and confocal laser scanning microscopy. The europium content in the microspheres is measured by inductively coupled plasma atomic emission spectrometer. It is shown that the compatibility of the europium complex with the styrene monomer has a great impact upon the europium content in the PSt microspheres by dispersion polymerization. As the complex amount increases, the europium content in the microspheres containing Eu(DBM)₃Phen increases, while that in the microspheres containing Eu(TTA)₃·2H₂O first increases and then reaches a saturated value at a high addition amount. Fluorescence properties indicate that the PSt polymer is a valuable matrix for improving the emission intensity of Eu(DBM)₃Phen yet not an ideal matrix for Eu(TTA)₃·2H₂O, which is demonstrated by the measurement of fluorescence lifetime.     

Decoration of surface-carboxylated graphene oxide with luminescent Sm3+-complexes

A Sm³⁺ complex, tris-(2-thenoyltrifluoroacetone) mono-1,10-phenanthroline-Sm³⁺ [Sm(TTA)₃(Phen)], can be easily integrated in situ via covalent functionalization to surface-carboxylated graphene oxide (GO-COOH) from a ethanol solution. The Sm³⁺ containing material has been comprehensively characterized via Fourier transform infrared spectra, X-ray photoelectron spectroscopy, UV–Vis absorption spectra, luminescence spectra, transmission electron microscopy, powder X-ray diffraction, thermogravimetric analysis (TG and DTG). The integration of rare earth complexes (RE) onto GO-COOH, as well as the individual nature of the hybrids, is confirmed. The GO-COOH with high load capacity can integrate more RE than GO. The brilliant optical properties of the GO-COOH-RE complex hybrids make them promising candidates applying in many practical fields, such as biomedical applications.     

GeS_2-Ga_2S_3-AgCl玻璃的光学特性研究

采用熔融-淬冷法制备了摩尔组成为(100-x)(0.85GeS2-0.15Ga2S3)-xAgC l(x=0,5,10,15,20)硫卤玻璃,测试了样品的密度、转变温度、析晶温度、可见到中远红外透过光谱、吸收光谱以及折射率参数,根据Z-扫描测试原理用钛宝石飞秒激光器测试了样品的三阶非线性特性.利用经典的Tauc方程计算了样品光学带隙允许的直接跃迁、允许的间接跃迁及Urbach能量.讨论了玻璃的摩尔折射度、金属标准值、光学带隙、Urbach能量对玻璃样品折射率的影响.结果表明:该系统玻璃具有较宽光谱,从可见到中远红外透过区域(0.46~11.50)μm,可作为潜在的多光谱成像材料.随AgC l含量的增加,玻璃的折射率随着摩尔折射度增大而增大,金属标准值、光学带隙与Urbach能量有减小的趋势,而玻璃的三阶非线性性能得到明显提高.