Eu3+掺杂的PMMA-络合物体系的发光特性

研究了聚甲基丙烯酸甲脂PMMA-Eu(DBM)3(phen)和PMMA-辛酸铕体系的发光特性。已有的结果表明，聚甲基丙烯酸甲脂PMMA—Eu(DBM)3(phen)体系具有较高的色纯度，Eu^3 的主发射峰几乎只有613nm(Eu^3 的^5D0→^7F2)被观测到，其发射强度比PMMA-辛酸盐体系的高一个量级，是潜在的高效稀土红光材料。     

铕(Ⅲ)-呋喃甲酸配合物的光谱表征

以硝酸铕 ,呋喃甲酸和邻菲咯啉 (phen)合成了配合物 [Eu(FA) 3·2H2 O]·NO3(4 ,4’ Hbpy) ,[Eu(FA) 3·phen]H2 O和Eu(FA) 2 ·NO3·phen。用元素分析、红外吸收光谱、紫外吸收光谱和溶液荧光光谱对配合物进行了组成确定和表征。溶液荧光光谱表明 ,配合物 [Eu(FA) 3·2H2 O]·NO3(4 ,4’ Hbpy)的发光强度比混配配合物Eu(FA) 2 ·NO3·phen和 [Eu(FA) 3·phen]H2 O的发光强度小很多 ,而且发光寿命较短 ,三元配合物 [Eu(FA) 3·phen]H2 O的发光强度比四元配合物Eu(FA) 2 ·NO3·phen的发光强度略大     

基于邻菲咯啉的反应型三元铕配合物的合成与荧光性质

以二苯甲酰甲烷(HDBM)为第一配体,5-丙烯酰胺基-1,10-菲咯啉(Aphen)为活性第二配体,制备了新的反应型三元铕配合物Eu(DBM)₃Aphen。通过元素分析、红外光谱和热分析对配合物进行了组成确定,采用紫外光谱、荧光光谱、荧光寿命和荧光量子产量研究了配合物的光物理性能。结果表明,在紫外光激发下,配合物Eu(DBM)₃Aphen能发射Eu3+的特征荧光,其荧光发射强度、单色性、荧光寿命和荧光量子产率等均显著高于文献报道的丙烯酸配合物Eu(DBM)₂AA的相应数值,表明配合物Eu(DBM)₃Aphen不仅可作为潜在的红色发光材料,还可作为反应型的配合物,为制备具有优异发光性能的稀土聚合物提供了一条新的途径。     

利用微腔调节铕配合物实现多色电致发光

制备了以TCTA和CBP为空穴传输层、Eu(DBM)3Bath为发光层、TPBI为电子传输层的有机多层薄膜微腔电致发光器件。通过光学微腔来改变Eu(DBM)3Bath不同能级之间的跃迁速率,从而实现了Eu3+的5D0→7 F0(580 nm)、5 D0→7 F2(612 nm)以及5 D0→7 F3(652 nm)的多色电致发光。其中,发光主峰在5 D0→7 F2(612 nm)的微腔OLED最大电流效率超过20 cd/A,最大亮度超过1 300 cd/m2。     

一种新型共掺杂稀土配合物的发光特性

制备了一类以苯甲酰水杨酸 (BenzoylSalicylicAcid ,BSA)为第一配体 ,邻菲罗啉 (phenanthroline ,phen)为第二配体的共掺杂稀土铕镧配合物La0 6Eu0 4(BSA) 3 phen。用其作为发光层材料制作了电致发光器件 :ITO/PVK :La0 6Eu0 4(BSA) 3 phen/Alq/Al。讨论并证明了稀土La3 与Eu3 之间存在F rster能量传递。同时将该器件与器件ITO/PVK :Eu(BSA) 3 phen/Alq/Al和ITO/PVK :Tb0 6Eu0 4(BSA) 3 phen/Alq/Al的发光进行了比较。表明该器件具有单色性好 ,整流性好的特性 ,同时得到了最大亮度为 10 2尼特的红光     

在高氯酸铕-二苯亚砜-邻菲罗啉三元配合物中Pr3+对Eu3+发光的影响

合成了一系列异核配合物[(Eu1-xPrx)(DPSO)(phen)3(ClO4)2]ClO4*nH2O(x=0.000～0.200, DPSO为二苯亚砜, phen为邻菲罗啉, n=1, 2, 3, 4, 5, 6). 对配合物进行了组成分析, 摩尔电导, IR光谱及荧光激发和发射光谱的测定. 荧光光谱测定结果表明 本身不发光的Pr3+对Eu3+的发光产生较大影响, 当Pr3+的掺入量为0.001 mol时, 可使Eu3+的发光强度提高到200%以上,随着Pr3+浓度的增大,对Eu3+的发光先敏化后猝灭.Eu3+在配合物中所处的格位对称性低,无对称中心.     

新型稀土铕,铽β-二酮配合物的合成与荧光性质

采用克莱森缩合反应合成了一种新型的β-二酮化合物1-(4-氨基苯)-4,4,4-三氟丁烷-1,3-二酮(p-NBFA)。以其为第一配体,邻菲咯啉(phen)为第二配体,合成出新型Eu(Ⅲ),Tb(Ⅲ)三元配合物。通过元素分析确定了配合物的组成为Eu(p-NBFA)3phen和Tb(p-NBFA)3phen。红外光谱的分析表明p-NBFA中的氧原子以及phen中的氮原子与稀土离子进行了配位。紫外光谱表明第一配体p-NBFA为能量传递的主体,第二配体phen起协同作用。通过荧光光谱研究了配合物的发光性质,结果显示在Tb(p-NBFA)3phen中,除Tb3+的特征发射外,还可以观察到470nm的发射,进一步的研究表明,此处发射为配体p-NBFA的发射,这是由于配体的能级与Tb3+的发射能级较近,产生了逆传能过程。而在Eu(p-NBFA)3phen的发射谱中,均表现出稀土离子的特征发射,且发光强度较大,说明配体的能级与Eu3+的发射能级比较匹配。     

银颗粒对Lu2O3:Eu薄膜光学性质影响

采用溶胶凝胶和提拉法制备了含有银颗粒的Lu2O3:Eu薄膜,利用X射线衍射,吸收光谱,光致发光光谱(PL)及荧光衰减光谱对其进行了表征,结果表明:所得材料在800℃下结晶完好,在发射光谱中观察到了银颗粒导致的Eu3 的发光增强效应,讨论了银颗粒对LU2O3:Eu薄膜发光性质的影响.     

静电纺丝技术制备Eu(BPA)3 phen/聚丙烯腈纤维及其性能

为了增强稀土络合物的物理化学性能和成型加工性能,以扩大稀土发光材料在防伪、荧光标识与OLED等领域中的应用,本文将实验合成的铕的络合物溶于聚丙烯腈,通过静电纺丝技术制备了一种新型的Eu(BPA)_3phen/PAN紫外荧光复合纳米纤维。采用扫描电子显微镜(SEM)、X射线能量色散谱仪(EDS)、傅立叶红外光谱仪(FT-IR)、热重差热分析仪(TG-DSC)与荧光光谱仪(FL)对发光纳米纤维的性能进行分析。实验结果表明,复合纤维的直径分布在200～400 nm,且随机取向。热重分析表明,Eu(BPA)_3phen/PAN复合纤维的初始分解温度约为310℃,热稳定性较好。此外,研究了掺杂不同浓度Eu(BPA)_3phen对纤维发光性能的影响,发现纤维的荧光发射强度随着Eu(BPA)_3phen含量的增加呈现先增后减的变化趋势,当Eu(BPA)_3phen的含量为2.5%时,荧光强度最高。这种新型的的Eu(BPA)_3phen/PAN荧光复合纤维在防伪和OLED等方面具有潜在应用价值。     

聚偏二氟乙烯/(Y0.97Eu0.03)2O3稀土氧化物纳米复合材料制备、形貌及发光性能

借助超声技术采用一种简便易行的共沉淀方法制备出聚偏二氟乙烯(PVDF) /钇铕稀土氧化物((Y0.97Eu0.03)2O3)纳米粒子发光纳米复合材料。复合材料的断面形貌和(Y0.97Eu0.03)2O3纳米粒子在PVDF基体中的分散状态通过扫描电子显微镜(SEM)进行了研究,其发光性质通过荧光光谱进行表征。SEM结果表明:当(Y0.97Eu0.03)2O3纳米粒子添加量在1% ～5%时,(Y0.97Eu0.03)2O3纳米粒子在PVDF基体中形成尺寸在50 nm～2μm的团聚体,其尺寸随(Y0.97Eu0.03)2O3添加量增加而增大;当(Y0.97Eu0.03)2O3添加量小于1%时, (Y0.97Eu0.03)2O3纳米粒子在PVDF基体中实现了较好分散。发光光谱结果表明制备的纳米复合材料具有明显的红光发射特征,对应于(Y0.97Eu0.03)2O3纳米粒子的本征发射。制备的高分子发光纳米复合材料将来有望在光学材料中获得应用。     

Synthesis and luminescence properties of mesophase silica thin films doped with in-situ formed europium complex

Mesophase silica thin film doped with in-situ formed ternary Eu complex was synthesized by adding ligands (DBM=dibenzoylmethane, phen=1,10-phenanthroline), Eu ions (EuCl₃·6H₂O), and Pluronic P123 triblock copolymer into hydrolyzed tetramethoxy-silane (TMOS). The structure of this inorganic/organic film was characterized as a 2d-hexagonal structure by X-ray diffraction (XRD) and TEM analysis. The excitation spectra (λ_em=612 nm) and emission spectra (λ_ex=325 nm) indicated that the ternary complex, Eu-DBM-phen, was formed in-situ during the formation of the film. The mesophase silica thin film doped with the in-situ formed Eu complex showed a higher quantum efficiency compared to a pure Eu(DBM)₃phen complex and a mesophase silica thin film doped with in-situ formed binary Eu-phen complex.     

Electrical conductivity and luminescence of metal-organic nanocomposites

We presented the results of experimental study of electrical and luminescence properties of planar nanocomposites based on gold island films and layers of efficient organic luminophores — aluminum (III) 8-hydroxyquinolinate (Alq₃) and europium β-diketonates [Eu(DBM)₃ bath, Eu(DBM)₃ phen, and Eu(DBM)₃]. The mechanisms of electroluminescence of such hybrid systems are discussed and the processes of luminescence excitation in the organic component of nanocomposites are considered in detail. It is shown that the spectral characteristics of europium β-diketonates are controlled by the Eu³⁺ ion fluorescence. The proposed mechanisms of nanocomposite electroluminescence are confirmed by the results of measurements of cathodoluminescence spectra of organic luminophores.     

Optical transition properties of Eu in Eu(DBM)3phen mono-dispersed microspheres for microcavity laser application

Mono-dispersed microspheres of ternary complex Eu(DBM)₃phen (DBM=dibenzoylmethide; phen=1,10-phenanthroline) were prepared through a facile process. The obtained sample was characterized by means of X-ray powder diffraction (XRD) and scanning electron microscope (SEM). And the luminescence properties of the Eu(DBM)₃phen were investigated by the fluorescence spectra and the fluorescence decay. According to Judd-Ofelt theory, the optical transition intensity parameters Ω_λ (λ=2, 4 and 6) were obtained to be 20.99×10⁻²⁰, 0.98×10⁻²⁰ and 1.79×10⁻²⁰ cm², respectively. The radiative transition properties of ⁵D₀ level, including transition rates, branch ratios and radiative transition lifetime were calculated. As a potential material for microsphere lasers, the optical gain performance for ⁵D₀→⁷F₂ transition was also evaluated.     

Synthesis and luminescence of Eu(III) complexes with macrocyclic azacrown ethers and 1,10-phenanthroline

Complexes of Eu(III) with mixed macrocyclic azacrown ethers and 1,10-phenanthroline (phen) were synthesized and their luminescence properties measured. The specific azacrown ethers used were 1,4,8,11-tetraazacyclotetradecane-1,4,8,11-tetraacetate (TETA) and 1,4,8,12-tetraazacyclopentadecane ([15]aneN₄). The phen-coordinated complexes excited by UV light produced a very bright red emission via an intra-molecular energy transfer from phen to Eu(III). For [Eu(TETA)·(phen)·(H₂O)]⁻ and [Eu([15]aneN₄)·(phen)₂]³⁺, the quantum yields of sensitized luminescence were 8.4% and 7.8%, respectively, and were much greater than those from non-sensitized luminescence of 1.2% and 4.4%, respectively. The decay times of the corresponding phen-coordinated complexes, as measured at room temperature, were 1.6 and 0.6 ms, respectively, and were much longer than those of the phen-uncoordinated complexes of 0.3 and 0.2 ms, respectively.     

Energy transfer from Eu(III) complexes to dyes in their mixed nanostructures. II

The effects of the concentration of a number of dyes in an aqueous solution and of the method of formation of mixed nanostructures of dyes and Eu(MBTA)₃phen (MBTA is p-methoxybenzoyltrifluoroacetone; phen is 1,10-phenanthroline) complexes that form these structures on the luminescence decay kinetics of Eu(III) ions are studied. It is shown that, in the concentration range 5–50 nM of Nile blue, the concentration dependences of the luminescence decay and of the decrease in τ _lum of Eu(III) nearly coincide and are nearly linear. The dependence of the ratio of I _lum of Eu(III) to the intensity of the sensitized delayed fluorescence of Nile blue on the delay time of the probe pulse is analyzed; it is found that the majority of dye molecules incorporated in nanostructures of Eu(MBTA)₃phen complexes emit sensitized delayed fluorescence with times 1–50 μs. Analysis of the effect of the structure of nanostructures on the quenching of I _lum of Eu(III) by the dye at different concentrations of Eu(III) shows that nanostructures of Eu(MBTA)₃phen and Eu(NTA)₃phen (NTA is 2-naphthoyltrifluoroacetone) complexes appear in the aqueous solution at a concentration of Eu(III) of 0.1 μM (the MBTA or NTA concentration is 50 μM, and the concentration of phen is 17 μM) and exist in the solution at the Eu(III) concentrations up to ～5 μM. This confirms the conclusion on the occurrence range of nanostructures of Ln complexes previously made based on the analysis of columinescence in these structures.     

Columinescence of dye molecules in nanostructures of metal ion complexes

The mechanism of columinescence (fluorescence sensitization) of dyes incorporated in nanostructures of metal complexes is studied. It is shown for the first time that the columinescence of dyes is due to the transfer of excitation energy from ligands and metal ions of complexes that form nanostructures. It is proven that the dye columinescence of rhodamine 6G (R6G) molecules incorporated into nanostructures of Al(DBM)₃phen, Al(DBM) _n (OH)_{6 ? 2n} , and Eu(DBM)₃phen (DBM is dibenzoylmethane) nanostructures is completely determined by the singlet excitation energy migration from ligands to R6G molecules. It is shown that, at small concentrations of R6G, the R6G columinescence intensity is lower in nanostructures of metal complexes with a high probability of S-T conversion and that this difference disappears at large concentrations of R6G. In the case of Nile blue (whose S ₁ level lies below the ⁵ D ₀ level of Eu(III)) incorporated in nanostructures of Eu(DBM)₃phen complexes, as well as in nanostructures of Al(DBM)₃phen and Gd(DBM)₃phen complexes with admixture of Eu complexes, we observed the S-S energy transfer from DBM to NB in addition to the delayed sensitized fluorescence of NB previously observed in nanostructures of Eu complexes, which was caused by the energy transfer from the ⁵ D ₀ level of Eu(III) to NB. At dye concentrations below 100 nM, the efficiency of NB sensitization due to the migration of singlet excitation energy from DBM is lower than in the case of the energy transfer from Eu(III) ions, while, at large concentrations of the dye, the S-S energy transfer successfully competes with the sensitization of NB by Eu(III) ions. The use of dye columinescence makes it possible to easily determine dye concentrations of 2–100 nM in solutions with standard spectrofluorimeters.     

Deactivation pathways of the electronic excitation of ions of lanthanide complexes in polymers with functional groups

Complexes Eu(TTA)₃phen and Eu(MBTA)₃phen, as well as complexes Tb(MBTA)₃phen and Tb(TTA)₃phen, which do not luminesce in solutions, are shown to luminesce in polymer films (TTA is thenoyltrifluoroacetone, MBTA is n-methoxybenzoyltrifluoroacetone, and phen is o-phenanthroline). Luminescence of complexes of Eu and Tb in films of a polymer, poly(methylene-bis-anthranilamide) 1,6-hexamethylenedicarboxylic acid (PAA-5), having a high concentration of functional anthranilate groups, is studied. From the behavior of the luminescence intensity (I _lum), the luminescence decay time, and the luminescence spectra of complexes of these lanthanides in polymer films, the following regular features were revealed. (i) During the film preparation at 90°C, Ln complexes are attached to PAA-5 via anthranilate groups. (ii) Irradiation of these films in the range of the absorption band of ligands (TTA or MBTA) leads to deactivation of the electronic excitation of ions according to the diketone detachment mechanism and to further binding of complexes to polymers. In this case, I _lum(Eu(III)) decreases because the introduction of anthranilate groups of the polymer into the first coordination sphere of Eu(III) complexes enhances the nonradiative deactivation of these ions, whereas I _lum(Tb(III)) increases since the introduction of these groups suppresses the nonradiative deactivation of Tb complexes through triplet states of ligands (TTA and MBTA). (iii) Upon storage of films in the dark (20°C), complexes detach themselves from the polymer and return to their initial structure. In PAA-5 films into which Eu and Tb complexes were simultaneously introduced, the color of the emission from the irradiation spot changes from red to green.     

Metal plasmon enhanced europium complex luminescence

The plasmon enhanced luminescence of a rare-earth complex Tris(6, 6, 7, 7, 8, 8, 8-heptafluoro-2, 2-dimethyl-3, 5-octanedionato) europium (Eu(fod)₃) was investigated. A polyvinyl alcohol (PVA) thin film was successfully adopted as a spacer to separate the Eu complex from the silver island film (SIF), and five-fold enhancement of the radiative decay rate of the Eu complex on SIF was demonstrated based on the luminescence intensity and lifetime measurement. Investigation of the distance dependent luminescence indicates that 7 nm is an optimal distance for SIF enhanced Eu luminescence. Plasmon enhanced rare-earth luminescence based on an organic film spacer would find potential applications in plasmon enhanced organic light emitting diode (OLED) devices.