Eu(BA)_3Phen掺杂聚丙烯腈纳米纤维的荧光特性研究

通过苯甲酸和1,10-菲啰啉为配体合成Eu(BA)3Phen三元配合物,并利用静电纺丝技术制备了以聚丙烯腈聚合物为载体的荧光纳米纤维.采用扫描电子显微镜、荧光和绝对光谱测试分别对其微观形貌和荧光特性进行研究.测试与分析结果表明,Eu(BA)3Phen配合物掺杂聚丙烯腈纤维直径约为200nm,直径均匀且取向随机.在中波紫外辐射下,纳米纤维呈现出明亮的红色荧光.随着Eu(BA)3Phen配合物掺杂量的增加,配体到稀土离子之间能量传递更有效,使得纳米纤维的发光强度显著增强.在电功率为115.61mW的308nm中波紫外发光二极管激发下,1wt%、2wt%和4wt%Eu(BA)3Phen掺杂聚丙烯腈纳米荧光纤维总的发射光子数分别为25.71×10~(11)、61.50×10~(11)和106.12×10~(11) cps,其中Eu3+的5D0’7F2跃迁发射的光子数分别高达15.98×10~(11)、41.21×10~(11)和70.76×10~(11) cps.纤维中Eu3+在5D0’7F2发射的最大受激发射截面为4.12×10-21 cm~2,呈现出纳米荧光纤维较强的光辐射能力.光谱参数的绝对化表征表明Eu(BA)3Phen掺杂聚丙烯腈纳米纤维光子转换的高效性,展示了其作为紫外-可见光转换层在柔性太阳能电池增感领域广阔的应用前景.     

白光LED用红色荧光粉CaSnO3:Eu3+的制备及光学性质

采用水热法制备了CaSnO3:Eu3+红色荧光粉,利用X射线粉末衍射、场发射扫描电镜和荧光光谱对CaSnO3:Eu3+粉末进行了表征.实验结果表明,这种新型的荧光粉可以被紫外光280 nm、近紫外光395 nm和蓝光465nm有效地激发,发射主峰位于614nm.光谱分析结果表明,Eu3+离子在晶体结构中占据了非反演对称中心的位置.395,465 nm的吸收与目前广泛应用的紫外和蓝光LED芯片的输出波长匹配.因此,这种荧光粉是一种可能应用在白光LED上的红色荧光材料.     

白光LED用荧光粉Ba_(1.97)Ca_(1-x)(B_3O_6)_2∶Eu_(0.03)~(2+),Mn_x~(2+)的制备及其发光特性

采用高温固相反应法制备了Ba1.97Ca1-x(B3O6)2∶Eu2+,Mnx2+(x=0,0.03,0.06,0.15)荧光粉,研究了其相组成与荧光特性。结果表明,样品具有单相Ba2Ca(B3O6)2晶体结构。Eu2+同时占据Ba2+格位和Ca2+格位。在317 nm波长的紫外光激发下,Eu2+辐射出峰值在450 nm附近的宽谱蓝光。通过能量传递作用,Mn2+辐射峰值为600 nm左右的宽谱红光。蓝光和红光叠加形成色坐标为(x=0.371,y=0.282)的近白光发射。样品的激发光谱分布在250~400 nm的波长范围,有望在紫外激发的白光LED中获得应用。     

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。     

Eu3+在层状钙钛矿M2TiO4（M=Ca,Sr,Ba）红色荧光粉中的发光特性

采用高温固相法制备了Eu3+掺杂的层状钙钛矿M2TiO4∶Eu3+(M=Ca,Sr,Ba)红色荧光粉,借助X射线衍射、紫外可见漫反射光谱和荧光光谱研究了不同煅烧温度下粉体的晶相组成及其光致发光性能。结果表明:在煅烧温度1 000℃保温2h时即可得到纯相Sr2TiO4和Ba2TiO4粉体,但即使进一步的升高温度并延长保温时间均无法得到Ca2TiO4粉体。Ba2TiO4∶Eu3+粉体在395nm激发下发射594nm(5 D0→7 F1)和615nm(5 D0→7 F2)橙红光。Sr2TiO4∶Eu3+粉体区别于通常Eu3+的特征发射,在近紫外和蓝光激发下主要发射578nm(5 D0→7 F0)和626nm(5 D0→7 F2)的强烈橙/红光,具有更好的红光色纯度和发光强度,其中363nm电荷迁移激发下具有最高的发光效率,是一种适用于近紫外和蓝光LED芯片的红光材料。     

白光LED用红色荧光粉KLa（MoO4）2:Eu3+的制备及发光性能

采用水热法制备红色荧光粉KLa(MoO4)2:Eu3+,通过X射线粉末衍射(XRD)、场发射扫描电镜(FE-SEM)和荧光光谱(PL)对样品进行了表征。实验结果表明:pH值是合成样品KLa(MoO4)2:Eu3+的关键因素,当溶液pH值接近7时,荧光粉的纯度较高,分散性良好、粒度均匀、呈规则球形。这种荧光材料可以被紫外光279 nm、近紫外光395 nm和蓝光465 nm有效激发,发射主峰位于617 nm,是一种可应用于白光LED转换用的新型红色荧光粉。     

LED用绿色荧光粉BaAl2-xSixO4-xNx∶Eu的合成及发光性能研究

采用高温固相法,在1 300~1 400℃的还原气氛条件下,合成了BaAl2-xSixO4-xNx∶Eu2+绿色荧光材料。该荧光材料是在BaAl2O4∶Eu荧光粉的基础上,通过(SiN)+替代(AlO)+来获得的。随着N元素的引入,BaAl2O4∶Eu荧光粉的激发和发射光谱均发生红移。此时,BaAl2-xSixO4-xNx∶Eu2+荧光材料可以被390~440nm范围内的近紫外-蓝光有效激发,发射出500~526 nm的绿光。因此,BaAl2-xSixO4-xNx∶Eu2+荧光粉是一种可用于白光LED的绿色荧光材料。     

发光二极管用红色荧光粉SrMoO4:Eu3+的制备和发射性质

采用化学共沉淀法制备了适合于紫外、近紫外、蓝光发光二极管(LED)激发的红色荧光粉SrMoO4:Eu3+.研究了样品的晶体结构和发光性质.结果表明:化学共沉淀法合成的SrMoO4:Eu3+荧光粉为四方纯相,其激发光谱包括一个宽带峰和一系列尖峰,峰值位于280nm(宽带峰中心),395nm,465nm,可以被紫外LED和蓝光LED有效激发.在395nm的激发下,测得发射光谱的强发射峰位于613nm,对应Eu3+离子的5D0→7F2跃迁.Eu3+离子掺杂浓度的改变对基质的晶格常数、Eu3+离子在晶体中对称性及发光性能有较大影响.通过对比不同掺杂浓度Eu3+离子的发射谱,发现在SrMoO4基质中Eu3+离子掺杂存在浓度猝灭现象,其最佳掺杂浓度为15%.     

Sr_(1-y)Eu_ySi_2O_(2-z)N_(2+2z/3)的发光性质及其在白光LED上的应用

采用高温固相法合成出系列黄绿色Sr1-yEuySi2O2-zN2+2z/3荧光材料,进行了光学性质表征并探索了其在LED上的应用。在Eu2+掺杂浓度为0～0.200范围内,所合成的化合物为系列色坐标可调的黄绿光-黄光连续固溶体,在250～500nm具有高的激发效率,激发和发射光谱位置及其发射强度随Eu2+浓度改变产生规律性变化;利用光谱理论系统研究了Eu2+的最低5d吸收能级、5d轨道重心移动、晶体场分裂和Stokes位移对激发和发射光谱位置、半峰全宽和荧光寿命的影响及其相互关系。该类荧光材料在77～425K具有良好的温度特性,425K时的发射强度为77K的58%左右。首次将它们和近紫外LED(～400nm)、蓝光LED(～460nm)封装成高亮度黄绿光和黄光LED以及白光LED,发光效率高达19lm/W,这些封装的LED的发光性能也随着Eu2+浓度,以及粉胶比例变化而呈规律性变化。     

CdxZn1-xO：Eu^3＋荧光粉的制备及其发光性质

采用高温固相法在1100℃下合成了Eu3 掺杂的CdxZn1-xO发光材料。采用X射线衍射对所合成样品的结构进行了表征。分析了不同浓度Cd2 的掺杂对于样品发光及激发峰位置的影响。通过对荧光光谱的测试,表明Cd2 的引入使得体系的禁带宽度变窄,并且通过Cd2 掺杂浓度的变化,可以对样品的激发光谱峰值在380～410nm进行调制,样品的发光以520nm处的宽带发射为主,并没有明显的Eu3 的特征发射,表明基质与Eu3 之间的能量传递并不有效。在加入Li 作为电荷补偿剂之后,出现了来自Eu3 的特征发射,相应的发射光谱的发射主峰位于609nm。样品380～410nm的激发峰范围覆盖了紫外LED芯片的输出波长。因此,这种荧光粉是一种可能应用在白光LED上的红色荧光粉材料。     

Fabrication and amplified spontaneous emission of Eu(DBM) <Subscript>3</Subscript>Phen doped step-index polymer optical fiber

A step-index polymer optical fiber (SI POF) with a core of poly(methyl methacrylate) (PMMA) containing Eu(DBM)₃Phen has been fabricated by a preform technique. Fluorescence analysis showed that there is not obvious change in the local environment around Eu³⁺with the increase of Eu(DBM)₃Phen doping concentration. Amplified spontaneous emission (ASE) phenomenon of the doped SI POF by end-pumping with an Ar⁺-laser of 457.9 nm at ambient temperature was observed. The threshold of the pump power for the onset of ASE is found to be 120 mW for the doped SI POF with a length of 50 cm, the length is also found to be the optimal length for maximum ASE power under the input power of 200 mW. The maximum quantum conversion efficiency of the fiber is about 40%.     

第二配体对Sm(DBM)3掺杂的PMMA样品发光的影响

分别使用phen（1,10-邻菲咯啉）、TOPO（三正辛基氧化磷）、TPPO（三苯基氧化磷）作为第二配体与Sm（DBM）3（DBM：二苯甲酰甲烷）相互作用,合成了相应的配合物,然后分别将其掺入MMA中,进行聚合得到了固体样品。测量了不同第二配体样品及无第二配体样品的激发和发射光谱,对谱峰做了指认。发射谱中主要发射峰均为Sm^3＋的特征发射,有机配体的发光带很弱,说明从有机配体到稀土发光中心的能量传递非常有效。监测Sm^3＋离子644nm发射峰（^4G5/2→^6H9/2）测量了样品的激发光谱。结果显示,第二配体的加入改变了有机配体的能级结构,激发边出现明显的移动,同时紫外区的激发效率发生了变化,对发光产生了显著的影响。还测量了上述样品中Sm^3＋的^4G5/2能级的发光衰减曲线,拟合出该能级的跃迁寿命,针对不同第二配体的情况进行了比较分析。实验结果表明,第二配体的共轭性和化学键匹配对发光强度影响很大,在我们的结果中,第二配体为TPPO时发光效率最高。     

Synthesis, photoluminescence and bioconjugation of rare-earth (Eu) complexes-embedded silica nanoparticles

Eu(DBM)₃Phen-embedded silica nanoparticles were synthesized in water-in-oil (W/O) microemulsion containing aqueous phase of Eu(DBM)₃Phen, surfactant Triton X-100, cosurfactant octanol and oil-phase cyclohexane. The size and morphology of the nanoparticles were characterized by transmission electron microscopy (TEM). The low-temperature time-resolved emission spectra indicate that the Eu complex in the silica nanoparticles have longer lifetime than that of the pure complex. Under 355 nm continuous excitation, the nanoparticles show high resistance to photobleaching. The free amino groups were attached to silica surfaces by copolymerization of 3-aminopropyl(triethoxy)silane. Preliminary results demonstrated that the silica-coated Eu complex nanoparticles can be a probe in the detection of biomolecular interactions.     

Clustering study in Eu(DBM)3Phen-doped polymer optical fibers by optical properties and near-field scanning microscopy

The clusters of Eu3+ ion in Eu(DBM)3Phen-doped polymethyl methacrylate (PMMA) have been studied by three means. The relative fluorescence intensity ratio of the 5D0 → 7F2 to 5D0 → 7F1 transitions with different concentrations of Eu3+ in Eu(DBM)3Phen-doped PMMA and metastable-state (5D0) lifetime dependence on Eu3+ concentration are analyzed. The analysis indicates that there are no clustering effects in Eu3+ ions of Eu(DBM)3Phen-doped PMMA when the Eu3+ doping concentration is up to 1.0 wt.-%. At the same time, the clustering effect has not been observed by the scanning near-field optical microscopy (SNOM) in Eu(DBM)3Phen-doped PMMA with 1.0 wt.-% of Eu3+ ions. The analysis reveals that a high concentration of Eu3+ can be incorporated into polymer optical fiber (POF) without clustering effect.OCIS codes: 180.5810, 300.6280, 250.5460, 160.5690.     

铕铽共掺稀土聚合物的光谱分析及发光性能研究

合成了一种新型的稀土配合物Eu_0.5Tb_0.5(TTA)₃Phen,并采用原位乳液聚合法进一步制备了Eu_0.5Tb_0.5(TTA)₃Phen/PMMA稀土聚合物。利用红外光谱仪(IR)、电子探针X射线能谱仪等对其结构进行了表征,利用扫描隧道电子显微镜(SEM)、荧光光谱仪(FS)等研究了其微观形貌,并探讨了其发光性能。结果表明,聚合物中PMMA与稀土部分Eu_0.5Tb_0.5(TTA)₃Phen通过键合的方式结合, 仍保持Eu0.5Tb_0.5(TTA)₃Phen原有的发光特性;在365 nm紫外光的激发下,产生发光峰在611.8 nm附近、谱线带宽为10.4 nm的红光发射,发光亮度高,色纯度高;Eu_0.5Tb_0.5(TTA)₃Phen/PMMA具有良好的发光性能,其发光强度与MMA加入的含量有关。     

Eu3+配合物掺杂聚合物的制备与光谱性能研究

以噻吩甲酰三氟丙酮(2-thenoyltrifluoroacetone , TTFA), 六氟乙酰丙酮(hexafluoro- acetylacetone, HFA)和甲基联苯甲酰(dibenzoylmethide, DBM) 分别为配体合成了Eu3+的三种β-二酮类配合物Eu(TTFA)3、Eu(HFA)3和 Eu(DBM)3,以及掺杂这三种配合物的聚合物（聚甲基丙烯酸甲酯,PMMA）,并用分光光度计对它们的荧光光谱特性进行了分析研究.结果表明,三种配合物中Eu(TTFA)3荧光强度最强,并分析了其原因,发现能级匹配、配体取代基、配体结构对称性等均对配合物发光效率有重要的影响.通过比对,证明了TTFA是Eu3+发红色荧光的优良配体.进一步研究还发现,Eu(TTFA)3掺杂PMMA中稀土离子的荧光强度和荧光寿命均随掺杂浓度（质量分数为0.08～0.5）的增加而增大.     

Analysis on fluorescence of dual excitable Eu(TTA)3DPBT in toluene solution and PMMA

Photoluminescence of Eu(TTA)₃DPBT (TTA=thenoyltrifluoro-acetonate DPBT=2-(N,N-diethylanilin-4-yl)-4,6-bis(3,5-dimethylpyrazol-1-yl)-1,3,5-triazine) in toluene and PMMA thin film are measured with excitation at 350 and 404 nm, respectively, and analyzed using Judd-Ofelt theory. Under excitation at 350 nm, it is found that Eu(TTA)₃DPBT in toluene has a larger Ω₂ value (14.33×10⁻²⁰ cm²) than that (12.70×10⁻²⁰ cm²) of Eu(TTA)₃Phen (Phen=1,10-phenanthroline) in the same solvent, and has a smaller Ω₂ value (12.70×10⁻²⁰ cm²) in PMMA than that (Ω₂=14.09×10⁻²⁰ cm²) of Eu(TTA)₃Phen in PMMA. At the same time, it can be seen that under excitation at 350 nm Ω₂ value of Eu(TTA)₃DPBT in toluene is larger than that in PMMA. Excited by 404 nm, Ω₂ of Eu(TTA)₃DPBT obtained in toluene and in PMMA are the same as that excited at 350 nm. The transition probability (A), emission cross-section (σ) and the fluorescence branching ratio (β) are also evaluated. The lifetime of ⁵D₀ metastable state is measured on 350 and 404 nm excitation, respectively. For the former situation, it is 455 μs in toluene and 640 μs in PMMA, for the latter it is 460 μs in toluene and 664 μs in PMMA. By comparing absorptions with excitations, it can be found that DPBT is more efficient than TTA as an energy donor. Phosphorescence spectra are also measured to estimate the lowest triplet level and analyze the energy transfer for DPBT and TTA, from which it is found that the energy transfer from TTA to DPBT occurs in the luminescent process.     

沉积法自组装三维有序的Eu(DBM)3Phen/SiO2胶体球

采用修饰的St ber法合成了300 nm的Eu(DBM)3Phen/SiO2胶体杂化球,并通过沉积法将这种胶体杂化球组装成厚度为5 mm,面积为12 cm2的三维有序结构。通过扫描电子显微镜观察发现这些胶体球在垂直于烧杯底面的所有层面中都显示了立方密堆积的结构。元素分析进一步证实了荧光分子被包埋在SiO2胶体球中。在355 nm的激发下,这种三维有序结构具有铕离子的特征发射。     

Ordered luminescent nanohybrid thin films of Eu(BA)3Phen nanoparticle in polystyrene matrix from diblock copolymer self-assembly

A simple route for fabricating highly ordered luminescent thin films based on hybrid material of diblock copolymer and europium complex, assisted with self-organization of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymer upon solvent annealing, is presented. PS-b-PEO self-organized into hexagonal patterns and europium complex of Eu(BA)₃Phen was selectively embedded in PS blocks after solvent annealing in benzene or benzene/water vapor. During benzene annealing, the orientation of the PEO cylindrical domains strongly depended on the Eu(BA)₃Phen concentration. In contrast, when the hybrid thin films were annealed in mixture of benzene and water vapor, high degree of orientation of the PEO cylindrical domains is more easily obtained, which is independent of Eu(BA)₃Phen concentration. Furthermore, preferential interaction of PEO domains with water induces a generation of nanopores in the hybrid thin film. Atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were used to characterize the long-range lateral order and phase composition of the hybrid thin films. The ordered nanohybrid thin films kept the fluorescence property of Eu(BA)₃Phen and showed a strong red emission under the 254 nm light's irradiation. The fluorescence property was confirmed by photoluminescence (PL) spectra.     

掺Eu3+硅基材料的发光性质

通过溶胶－凝胶技术制备了掺Eu^3 的硅基材料并测试了其三维荧光光谱、激光谱和发射光谱，结果显示，最佳激发波波长为350nm,最强荧光波长为620nm；在350nm光激发下的发射光谱显示Eu^3 的特征发射光谱，产生4条谱带，分别是577nm(^5D0-^7F0)，588nm(^5D0-^7F1),596nm(^5D0-^7F1)和610nm(^5D0-^7F2)。