壳聚糖/LaF3:Eu3+纳米复合粒子的简易合成及发光特性

在水溶液中采用化学共沉淀法制备了壳聚糖/LaF3∶Eu3+纳米复合粒子.通过透射电子显微镜(TEM),X射线衍射(XRD),傅立叶变换近红外(FT-IR)光谱对样品进行了表征.结果表明:所得纳米复合粒子大小在 20 nm左右,粒径均匀,表面包覆的壳聚糖使其易溶于水,并具备了与生物蛋白偶联的多个基团.测量了该纳米复合粒子的激发光谱与发射光谱,详细说明了各发光峰对应能级的跃迁及其发光机理,分析了不同掺杂浓度对其相对发光强度的影响.结果表明:当 Eu3+离子掺杂摩尔分数为 10%时,样品的相对发光强度达到最大值.最后介绍了壳聚糖/LaF3∶Eu3+纳米复合粒子与荧光蛋白 FITC偶联的方法,以表明其在生物学中潜在的应用价值.     

纳米晶Gd2O3 ∶ Eu3+的制备与发光性质

利用共沉淀法制备了纳米晶Gd₂O₃ : Eu³⁺发光粉体。 在不同掺杂浓度、不同煅烧温度的系列样品中,均观测到Eu³⁺离子的特征发射。样品的晶相与发射性质的研究表明:所制备的样品经800~1 300 ℃热处理后,晶相为立方相,1 400 ℃时开始向单斜相转变。荧光强度与Eu³⁺离子掺杂浓度关系研究表明:在不同掺杂浓度中,Eu³⁺离子浓度为4%时其相对发射强度最强。在三个不同的煅烧温度中,经800 ℃煅烧的样品其发光效果最好。此外还观察到电荷转移激发态以及基质、Gd³⁺与Eu³⁺之间的能量传递。激发谱包含三部分,即电荷转移带、Eu³⁺的4f内壳层电子跃迁和Gd³⁺的激发谱。     

Ca9R(VO4)7 : Eu3+ 发光粉的发光特性

采用高温固相法制备了Eu³⁺离子激活的Ca₉R(VO₄)₇(R = Y, La, Gd)红色发光粉,并利用荧光光谱对发光粉的特性进行研究。激发光谱中,Ca₉Y(VO₄)₇ : Eu³⁺ , Ca₉La(VO₄)₇ : Eu³⁺和Ca₉Gd(VO₄)₇ : Eu³⁺都有两个宽的VO^3-₄激发带和Eu³⁺的特征激发峰。发射光谱中,在Ca₉Y(VO₄)₇ : Eu³⁺ 和Ca₉La(VO₄)₇ : Eu³⁺中的350~550 nm范围内出现VO^3-₄的发射带,而在Ca₉Gd(VO₄)₇ : Eu³⁺中却没有观察到VO^3-₄的发射。在这三种发光粉中,Ca₉Gd(VO₄)₇ : Eu³⁺的发光强度远远高于其它两种,这是由于Gd³⁺的存在有效地使能量通过Gd³⁺ →VO^3-₄ → Eu³⁺及Gd³⁺ → Eu³⁺的两种方式进行能量传递,从而提高了Eu³⁺发光效率。     

Eu掺杂SiO2纳米基质的发光特性

采用溶胶-凝胶(sol-gel)法制备了Eu掺杂的SiO₂干凝胶,分别用光致发光(PL)光谱、透射电镜(TEM)、扫描电镜(SEM)、红外吸收(IR)谱等分析手段对样品进行了表征,研究了SiO₂的基质中Eu³⁺、Eu²⁺的发光特性以及退火温度对发射光谱的影响,并对其发光机理进行了分析。结果表明,样品掺杂均匀,颗粒尺寸大约在50~80 nm,硼(B)离子进入SiO₂网格,成为了基质的一部分,改变了基质的网络结构。当采用258 nm激发样品时,随着退火温度的升高,红光发射强度先增强后减弱。对于经800 ℃退火处理的样品红光发射最强,出现了576 nm(⁵D₀ →⁷F₀),620 nm(⁵D₀ →⁷F₂),658 nm(⁵D₀ →⁷F₃)3条谱线,其中主峰位于 620 nm红光发射,对应于Eu³⁺离子的⁵D₀ →⁷F₂超灵敏跃迁,进一步说明B离子参与到基质中,形成了Si—O—B键,导致Eu³⁺离子所处配位环境的对称性降低,从而有利于Eu³⁺离子的特征发射;当采用271 nm激发样品时,随着退火温度的升高,蓝光发射强度先增强后减弱,经850 ℃退火的样品400~500 nm蓝光发射最强,归属于Eu²⁺的5d→4f的跃迁发射,证明在铝离子(Al³⁺)存在的情形下,在高温退火过程中Al³⁺部分取代Si⁴⁺形成AlO^-₄基团,掺杂Eu³⁺填补AlO^-₄基团附近的空位,增加了Eu³⁺周围的AlO^-₄四面体中氧原子的电子给予能力,使得Eu³⁺还原成Eu²⁺,从而得到了较强的蓝光发射。但是,当退火温度达到900 ℃时,由于稀土离子发生位置的迁移形成团簇红光和蓝光都明显地降低。     

纳米CaO ∶ Eu3+的制备及发光性质

利用共沉淀法制备了纳米CaO : Eu³⁺发光粉体。并对不同掺杂浓度和不同煅烧温度下所制备的CaO : Eu³⁺粉体进行室温发光性质的研究。在室温下观测到CaO : Eu³⁺样品具有较强的Eu³⁺离子特征发射。通过对不同煅烧温度下样品发射谱的对比,发现样品在591 nm和610 nm处的发射峰积分强度比随着煅烧温度的升高而降低,说明在不同的煅烧温度下,Eu³⁺占据了两种不同的格位。对样品强发射峰进行监测,可观测到样品中的O^2-和Eu³⁺离子之间形成的电荷迁移态。通过对比不同掺杂浓度下Eu³⁺离子发射光谱,发现将Eu³⁺掺杂到CaO基质中的适宜浓度为4%。     

长余辉材料SrAl2O4 ∶ Eu,Dy中Eu的 价态变化及对发光性能的影响

采用高温固相法,先在空气气氛下制备了SrAl₂O₄ ∶ Eu,Dy,后对其进行还原→氧化→还原处理。X射线衍射结果表明,经过还原→氧化→还原处理后样品的晶体结构没有改变。样品的发射光谱测试表明,在高温空气气氛下有少量的Eu³⁺还原成Eu²⁺。Eu³⁺和Eu²⁺有不同的发光特性,Eu³⁺产生的是线状特征光谱,发射峰值在592,616 nm。Eu²⁺产生的是带状光谱,带的中心位置在513 nm。经过还原处理的样品和经过氧化处理的样品相比,Eu²⁺的浓度得到显著提高,而Eu³⁺的浓度则急剧下降。对Eu²⁺的氧化、Eu³⁺的还原的机理进行了细致地讨论。另外,样品的热释光谱测试表明,经过氧化气氛处理和经过还原气氛处理过的样品的热释光峰值有很大的变化,但陷阱能级深度基本不变,在0.65 eV左右。这表明,对长余辉材料SrAl₂O₄ ∶ Eu,Dy进行还原→氧化→还原处理,Eu离子价态和发光强度会产生变化,并不影响其中Dy离子的陷阱能级。     

YVO4·xTiO2 : Eu3+荧光粉的发光性质

采用高温固相方法合成了YVO₄ ·xTiO₂ : Eu³⁺(x=0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9)粉末状发光材料,经X射线衍射分析结构发现材料为两相共存。一相为YVO₄,属四方锆英石结构;另一相为Y₂Ti₂O₇,属立方烧绿石结构。研究了YVO₄ ·xTiO₂ : Eu³⁺在UV及VUV激发下的光谱性质,讨论了Ti 的掺杂对材料发光性能的影响,发现适量的Ti的掺入可以提高材料 基质对UV及VUV的吸收。在UV及VUV激发下,YVO₄· xTiO₂ : Eu³⁺荧光粉的发射光谱主峰在616 nm和619 nm,证明Eu³⁺占据了晶格中非反演对称中心的位置。在YVO₄ ·xTiO₂ : Eu³⁺的激发光谱中,有一中心位于155 nm的吸收带,它属于基质的吸收带。     

SrB4 O7 : Eu磷光粉的制备及其发光性能

采用高温固相法合成了SrB₄O₇ : Eu荧光粉,并研究了不同原料、掺杂浓度、煅烧温度等因素对其发光性能的影响。发射光谱测试结果表明:SrB₄O₇ : Eu荧光粉的最佳Eu掺杂浓度为2%左右,进一步增大掺杂浓度会导致浓度猝灭。煅烧温度对基质组成影响较大,随着温度的升高,基质中BO₄四面体所占比例增大,有利于Eu³⁺离子的还原。以水合硼酸锶为原料制得样品的发光强度高于以SrCO₃和H₃BO₃为原料制得样品的发光强度。     

LiMBO3 : Dy3+材料的发光特性

采用固相法制备了LiM(M=Ca, Sr, Ba)BO₃ : Dy³⁺材料,并研究了材料的发光特性。LiM(M=Ca, Sr, Ba)BO₃ : Dy³⁺材料的发射光谱均呈多峰发射,对应于Ca,Sr,Ba,其主发射峰分别是Dy³⁺的⁴F_9/2→⁶H_15/2(484,486,486 nm),⁶H_13/2(577,578,578 nm)和⁶H_11/2(668,668,666 nm)跃迁。监测黄色发射峰时,所得激发光 谱峰值位置相同,主激发峰分别为331,368, 397,433,462,478 nm,对应Dy³⁺的⁶H_15/2→ ⁴D_7/2,⁶P_7/2,⁶M_21/2,⁴G_11/2,⁴I_15/2和⁶F_9/2跃迁。研究了敏化剂Ce³⁺及电荷补偿剂Li⁺、Na⁺和K⁺对LiM(M=Ca, Sr, Ba)BO₃ : Dy³⁺材料发光强度的影响。结果显示:加入敏化剂Ce³⁺提高了材料的发光强度,发光强度最大处对应的Ce³⁺浓度为3%;加入电荷补偿剂Li⁺、Na⁺和K⁺后,材料的发光强度也得到了明显提高,但发光强度最大处对应的Li⁺、Na⁺和K⁺浓度不同,依次为4%、4%和3%。     

高性能Sr2-xBaxSiO4 : Eu2+ 荧光材料的合成及发光

研究了Sr_2-xBa_xSiO₄ : Eu²⁺ 荧光材料作为白光LED发光体的可行性和应用特性。采用高温固相法制备了Sr_2-xBa_xSiO₄ : Eu²⁺ 材料系列样品,对样品的成分配比、阴离子掺杂、合成温度和时间进行了系统实验,利用XRD、SEM、光谱测试及封装测试等手段对样品的组成、结构、形貌特征及应用性能进行了表征。研究表明Sr_2-xBa_xSiO₄ : Eu²⁺ 荧光材料具有激发范围宽(300~500 nm)、发射范围宽(500~600 nm)的特点。通过控制碱土金属的比例可以精确控制材料的发射波长,在Ba掺杂范围0≤x<0.5内可以获得550~560 nm的发射,与YAG材料相比在光谱上增加了红色成分。通过引入恰当助熔成分进行阴离子掺杂,精确控制烧结工艺等手段极大提高了550~560 nm发射的发光强度和光转换效率。封装应用和测试证明,本研究优化制备的高性能Sr_2-xBa_xSiO₄ ∶ Eu²⁺ 荧光材料的光转换效率普遍可达到YAG材料的95％,在显色指数、色温和色纯度方面也优于或相当于YAG材料,并且具有较好的芯片适应性和较多的红色成分,是较为理想的应用于白光LED的荧光材料,特别适合于暖白光LED的制备。     

Preparation and luminescence of water soluble poly (N-vinyl-2-pyrrolidone)/LaF3:Eu nanocrystals

Lanthanide-doped luminescent nanocrystals have great potential as biological luminescent labels, but their use has been limited because of most of these nanocrystals are hydrophobic. In this work, water soluble LaF₃:Eu³⁺ down-conversion nanocrystals were prepared by encapsulated individual nanocrystals with polyvinylpyrrolidone (PVP). Their morphology, surface structure and luminescence properties were explored in detail. The results indicate that these nanocrystals can be readily dispersed in water, forming a stable and transparent colloidal solution. The colloidal solution displayed unique red luminescence with high emission intensity under ultraviolet excitation. These results suggest that these nanocrystals have great potential as luminescent labeling materials for biological applications.     

Facile synthesis, structural and optical characterization of LnF3:Re nanocrystals by ionic liquid-based hydrothermal process

A novel and easy synthesis of highly luminescent rare-earth ion-doped LnF₃ (LnF₃:Re) nanocrystals by ionic liquid-based hydrothermal process was reported. Ionic liquids [bmim]BF₄ (1-butyl, 2-methylimidazolium tetrafluoroborate) acts as co-solvent, template and reactant. X-ray diffraction and field emission scanning electron microscopy were used to characterize the structural properties of the products. The luminescent properties of LaF₃:Re nanocrystals were evaluated under ultraviolet (397 nm for Eu³⁺, 254 nm for Ce³⁺, Tb³⁺) and (or) near-infrared (980 nm for Er³⁺) excitation. Under 980 nm laser excitation, intense green upconversion emissions were observed for LaF₃:Er(1%) samples in the solid state and dispersion in water and ethanol. The quantum efficiency of LaF₃:Ce(15%),Tb(5%) nanocrystals was about 34%. Our reports provide a facile method for the preparation of LnF₃:Re nanocrystals with excellent photoluminescent properties.     

Water-Soluble Ln<Superscript>3+</Superscript>-Doped LaF<Subscript>3</Subscript> Nanoparticles: Retention of Strong Luminescence and Potential as Biolabels

The use of optically robust, luminescent lanthanide-based particles is becoming an area of interest for biolabel-related chemistry, due to their long lifetimes and range of non-overlapping absorption and emission lines from the visible to the near-infrared. We report the synthesis and optical properties of water-soluble, luminescent Ln³⁺-doped nanoparticles (NPs) coordinated with a hydrophilic (RO)PO₃²⁻ ligand that facilitates the stabilization of the NPs in aqueous conditions, and that regulates particle growth to the nanometer range. The use of lanthanide ions as dopants, in particular Eu³⁺ and Er³⁺ ions, yields optically robust particles with narrow emission lines in the visible (591 nm) and in the near-infrared (1530 nm), respectively. Luminescent lifetimes range from the microsecond to the millisecond for Er³⁺ and Eu³⁺ ions, respectively, and the NPs are not expected to be susceptible to photo-bleaching due to the fact that the emissions arise from intra-4f transitions of the lanthanide ions.     

Hydrothermal synthesis and optical characteristics of Eu in Zn2SnO4 nanocrystals

Zn₂SnO₄:Eu³⁺ nanocrystals were one-step synthesized by hydrothermal method for the first time. All the products were systematically characterized by powder X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), electron probe X-ray microanalyzer (EPMA), photoluminescence (PL) and photoluminescent excitation (PLE). The characteristic peak of Eu³⁺-doped in Zn₂SnO₄ nanocrystals was also detected. The luminescent properties of blank and Eu³⁺-doped Zn₂SnO₄ nanocrystals were reported.     

Photon down-shifting by energy transfer from Sm3+ to Eu3+ ions in sol-gel SiO2-LaF3 nano-glass-ceramics for photovoltaics

95SiO₂?C5LaF₃ sol-gel derived nano-glass-ceramics single doped with Eu³⁺ or Sm³⁺ and codoped with both of them were successfully obtained. XRD measurements confirm the precipitation of LaF₃ nanocrystals after the ceramming process, with mean size ranging from 10 to 20?nm which increases with the thermal treatment temperature. The incorporation of rare-earth ions into precipitated LaF₃ nanocrystals was confirmed from luminescence spectra. Intense yellow-red emissions were detected under UV and blue light excitation in single and codoped samples. The effect of codoping with Eu³⁺ and Sm³⁺ ions and the energy transfer mechanism between them have been analyzed in order to increase the yellow-red emissions.     

Ultra-small sized Y2O3:Eu3+ nanocrystals: One-step polyoxometalate-assisted synthesis and their photoluminescence properties

A novel hydrothermal approach for the preparation of europium(III)-doped yttrium oxide (Y₂O₃:Eu³⁺) nanocrystals was reported. The as-synthesized Y₂O₃:Eu³⁺ nanocrystals with diameter of about 5 nm are highly uniform and dispersed in water. The Y₂O₃:Eu³⁺ nanocrystals were characterized by high-resolution transmission electron microscopy and fluorescence spectroscopy. Due to their well dispersity in water, low toxicity, and good photoluminescence, the Y₂O₃:Eu³⁺ nanocrystals can potentially be used in high-definition displays and fluorescence probe in bioimaging.     

Preparation and characterization of upconversion luminescent LaF3:Yb,Er/LaF3 core/shell nanocrystals

LaF₃:Yb³⁺,Er³⁺/LaF₃ core/shell nanocrystals were successfully synthesized using solvothermal method. The crystal structure, morphology and photoluminescence properties of as-prepared nanocrystals were investigated in detail. XRD patterns show that the obtained LaF₃:Yb³⁺,Er³⁺ core and LaF₃:Yb³⁺,Er³⁺/LaF₃ core/shell nanocrystals exhibit hexagonal structure. The average particle size is about 9.3 nm and 11.4 nm for core and core/shell nanocrystals, respectively. Compared with LaF₃:Yb³⁺,Er³⁺ nanocrystals, both the upconversion emission intensity and the lifetime increase in LaF₃:Yb³⁺,Er³⁺/LaF₃ core/shell nanocrystals. The enhancement can be attributed to the LaF₃ shell which can eliminate the nonradiative centers on the surface of LaF₃:Yb³⁺,Er³⁺ nanocrystals.     

Non-collinear spin DFT for lanthanide ions in doped hexagonal NaYF4

Trivalent lanthanide ions (Ln³⁺) doped in hexagonal (β)-NaYF₄ nanocrystals (Na₂₄Y₂₃Ln₁F₉₆, Ln = La, Ce, Pr, Nd, Pm, Sm, Eu, Gd) were systematically studied by density functional theory (DFT) with a perturbative account for spin–orbit coupling. The simulated results, including the optimised molecular structures, electronic and magnetic properties, are compared to previous spin-polarised DFT studies in the same system. The spin–orbit coupling effects become significant with the increase in the number of unpaired 4f electrons in the doped lanthanide ions, particularly for the Sm³⁺-, Eu³⁺- and Gd³⁺-doped nanocrystals. Abnormal behaviour of Eu³⁺-doped nanocrystals was observed due to the Wybourne–Downer mechanism. A ‘sandwich-like’ 2p–4f–4d,5d electronic structure for Na₂₄Y₂₃Ln₁F₉₆ and the energies of the highest occupied 4f electrons from Ce³⁺ to Gd³⁺ are consistent with Dorenbos's relationship. The energy difference between the first and second Russell–Saunders terms (^2S+1L) of the lanthanide dopant is consistent with Carnall's experimental results and with earlier spin-polarised DFT calculations.     

Characterization of Er-doped fluoride glass ceramics waveguides containing LaF3 nanocrystals

Highly Er³⁺-doped fluoride glass ceramics planar waveguides containing LaF₃ nanocrystals have been fabricated by physical vapor deposition (PVD). The solubility of Er³⁺ in the segregated nanocrystals can reach 30 mol% which is much larger than the value found in LaF₃-oxide glass ceramics. A quantitative analysis of the photoluminescence of the 1.54 μm emission band of Er³⁺ ions has demonstrated that erbium ions are partitioned in both crystals and vitreous phase. The short lifetime (2.2 ms) measured for erbium incorporated in LaF₃ crystal lattice is a consequence of concentration quenching while the lifetime is close to 10 ms in the glassy phase. The emission bandwidth has been found to be greater than that of the precursor glass (71 nm at the half-height width). The high Er³⁺ concentration and spectral width could make this nanostructured fluoride material suitable for planar amplifier in the C telecommunication band.     

Hydrothermal synthesis of Sb doped and (Sb, Eu) co-doped YBO3 with nearly white light luminescence

Sb³⁺-doped, Eu³⁺-doped and (Sb³⁺, Eu³⁺) co-doped YBO₃ crystals have been synthesized using Y₂O₃, B₂O₃, SbCl₃ and Eu₂O₃ as raw materials through a hydrothermal method. Phase-pure YBO₃ crystal with hexagonal flake shape has been synthesized at 473 K for 3 days. The photoluminescent property of YBO₃ with different activators were investigated using luminescent spectrometer at room temperature. The color of the (Sb³⁺, Eu³⁺) co-doped YBO₃ crystal could be controlled from blue to red by changing the Sb³⁺/Eu³⁺ ratio in the initial reactants. The nearly white emission could be obtained through changing the Sb³⁺/Eu³⁺ ratio in reaction.