核壳纳米结构壳中Yb离子对稀土上转换发光温度特性的影响

采用油酸盐法分别制备出均匀的上转换发光裸核纳米粒子及其包覆具有不同Yb³⁺浓度掺杂的NaYF₄:Yb³⁺,Er³⁺核壳纳米结构的上转换纳米粒子。在不同温度下(90~450 K),研究分析了在壳中掺杂不同浓度Yb³⁺的NaYF₄:Yb³⁺,Er³⁺@NaYF₄:x%Yb³⁺核壳纳米体系的上转换发光特性。结果表明:在NaYF₄:Yb³⁺,Er³⁺上转换体系中,惰性壳中的525 nm(²H_11/2 →⁴I_15/2)发射峰呈现出与活性壳中不一样的趋势。壳层中掺杂的Yb³⁺通过声子对纳米粒子内部发光与表面及外界之间的相互作用起到了重要的"桥"连作用。     

Gd1-xEuxAl3(BO3)4纳米晶的合成及其发光性能

以高温固相反应法合成了Gd_1-xEu_xAl₃(BO₃)₄:Eu³⁺纳米荧光粉。使用XRD分析确定了样品的物相,并根据谢乐公式计算出其微晶的纳米粒度。采用了“粉末悬浮法”以甘油为分散介质,在RF540荧光光度计上测试了纳米晶荧光粉的激发光谱和发射光谱。GdAl₃(BO₃)₄基质本身发光,GdAl₃(BO₃)₄:Eu纳米荧光粉表现了Eu³⁺的特征发射光谱,其中最强峰为⁵D₀→⁷F₂发射,表明晶体结构中没有对称中心格位。实验表明在GdAl₃(BO₃)₄:Eu纳米晶荧光粉中,存在Gd³⁺对Eu³⁺发光的基质敏化作用。     

K离子掺杂增强NaErF4体系上转换发光

制备了一系列Na_1-xK_xErF₄@NaLuF₄的核壳纳米结构,核中K⁺掺杂摩尔分数变化范围为0%~8%。XRD分析结果揭示这些具有不同K掺杂浓度的纳米粒子均为β-相纳米结构。研究结果表明：随着K⁺浓度的增加,纳米结构中Er³⁺~650 nm处的红带发光强度呈现先增强后减弱的规律,当K⁺摩尔分数为4%时,Na_0.96K_0.04ErF₄@NaLuF₄纳米晶的发光强度达到最大,为未掺杂K⁺的NaErF₄@NaLuF₄纳米晶发光强度的3.7倍。其发光增强的原因在于K⁺的掺杂降低了Er³⁺微环境晶场宇称对称性,提高了Er³⁺离子⁴F_9/2→⁴I_5/2能级辐射跃迁几率,进而增强了Er³⁺的650 nm红带的上转换发光强度。     

Yb3+,Tm3+离子掺杂浓度对NaYF4：Yb3+,Tm3+发光光谱的影响

利用高温热溶剂法合成了不同Yb³⁺和Tm³⁺掺杂浓度的NaYF₄：Yb³⁺,Tm³⁺上转换发光纳米粒子。利用扫描电子显微镜、X射线衍射分析、荧光光谱对样品进行形貌和发光性质的表征。结果表明,不同Yb³⁺和Tm³⁺离子掺杂浓度对纳米粒子的上转换发光性质有很大影响。随着Tm³⁺离子浓度的提高,Tm³⁺离子之间的浓度猝灭和交叉弛豫效应对发光强度的影响愈来愈显著,导致纳米粒子的发光猝灭;同样,随着Yb³⁺浓度的提高,纳米粒子的发光强度也是先增大后减小,这是因为Yb³⁺离子浓度掺杂过高导致发光猝灭。     

铕掺杂纳米氧化锌发光材料的制备及其性能研究

采用均匀沉淀法,制备了平均粒径在20nm左右掺杂铕的纳米氧化锌粉体,通过XRD、粒度分析仪、FL、IR测试方法分别对其物相结构及组成、粒径分布和光致发光性能进行了分析.结果表明:所制样品仍然为六方晶系纤锌矿结构,Eu3+全部进入到ZnO晶格中;且Eu3+掺入量为5％时发光效果较好;所制样品颗粒粒度较小,粒径分布均匀.     

2017年10期电子期刊

为了增强β-NaGdF₄：Yb³⁺,Tm³⁺纳米晶的上转换发光,克服外延增长钝化壳增大尺寸的不足,利用阳离子交换法制备核壳纳米结构,研究了样品在980 nm激发下的上转换发光性质。首先,利用高温热分解法制备了直径为10 nm的β-NaGdF₄：Yb³⁺,Tm³⁺纳米晶;然后,将制备的纳米晶与Gd³⁺在油酸-十八烯混合溶液中在300℃进行交换反应。实验结果表明,随着表面Yb³⁺和Tm³⁺被Gd³⁺取代,钝化壳的形成抑制了内部Yb³⁺的表面去激发过程,增强了内部Yb³⁺（²F₅）→ Tm³⁺（³H₅,³F_2,3）的能量传递,上转换发光逐渐增强。交换30 min后,Tm³⁺的³H₄ →³H₆近红外发光增强达到最大,为对照样品的6.5倍,而尺寸基本保持不变。在生物成像方面,上转换纳米晶的尺寸必须与生物分子相匹配,同时发光强度要高,阳离子交换法既能增强近红外发光,又能保持原来小的尺寸,在生物成像领域具有很好的应用前景。     

Dy3+掺杂NaYF4纳米粒子的制备及其上转换发光性质

制备了Dy³⁺掺杂 NaYF₄上转换发光纳米晶体,通过X射线衍射(XRD)、扫描电子显微镜(SEM)、荧光(FL)光谱、红外光谱仪(FT-IR)对合成样品的结构、形貌和发光性能进行表征。探讨了稀土离子掺杂浓度和焙烧温度对NaYF₄∶Dy³⁺纳米晶的结构、形貌和发光的影响。在776 nm红外光下激发样品,出现479,574 nm上转换发射峰,实现了蓝、绿上转换发光。绿光来自于Dy³⁺的⁴F_9/2→⁶H_13/2跃迁,蓝光是由Dy³⁺的⁴F_9/2→ ⁶H_15/2跃迁产生的。     

Y2O3:Eu纳米晶中能量传递相互作用的研究

通过浓度猝灭曲线确定了引起Y₂O₃纳米晶中Eu³⁺发光浓度猝灭的是交换相互作用.测量了两种颗粒尺寸下Eu³⁺的⁵D₀—⁷F₂跃迁发光衰减曲线随掺杂浓度的变化,利用交换相互作用的理论衰减曲线对实验衰减曲线进行拟合.计算Eu³⁺离子的交换相互作用能量传递的效率,分析了Y₂O_{3关键词： 能量传递 2}O₃Eu纳米晶')" href="#">Y₂O₃Eu纳米晶 发光衰减     

纳米ZnO和ZnO∶Eu3+的表面效应及发光特性

纳米ZnO,ZnO:Eu3+及其添加覆盖层样品的光谱性质表明,表面有机物覆盖层具有改善发射光谱,增强基质与Eu3+间能量传递的良好效果.通过比较不同温度(60,800℃)处理的ZnO:Eu3+发光强度,发现了小尺度(纳米)颗粒的特殊发光行为 关键词： ZnO 表面覆盖层 Eu掺杂     

红色长余辉材料Mg2SiO4：Dy3+,Mn2+的制备及发光特性

用高温固相法制备了长余辉发光材料Mg₂SiO₄:Dy³⁺,Mn²⁺,对这种材料的红色长余辉性质进行了研究.对以不同掺杂浓度单掺杂Mn²⁺、单掺杂Dy³⁺以及双掺杂Dy³⁺,Mn²⁺的Mg₂SiO₄体系,通过在紫外激发下的发射光谱及其激发光谱的研究,确认了在双掺杂体系中,峰值为660nm的发光带对应着Mn²⁺的⁴T₁(⁴G)→⁶A₁(⁶S)跃迁,Mn²⁺为主要发光中心.Mn²⁺的660nm发射的激发谱分布很宽,样品在近紫外和可见光区都有良好的吸收,长波边可达600nm,是这种材料的一个显著优点.还研究了双掺杂体系中Dy³⁺对Mn²⁺的660nm发光带的敏化作用.另外,通过对单掺杂、双掺杂体系热释光曲线的比较,揭示了双掺杂体系中Dy³⁺的陷阱作用.     

Photoluminescence properties of Y0.75-xGdxAl0.10BO3:Eu3+0.10, 0.05R3+ (R= Sc, Bi) (0.00≤x≤0.45)

Y$_{0.75 - x}$Gd_xAl_0.10BO$₃:Eu$^{3+}_0.10, 0.05R³⁺ ($R$=Sc, Bi) ($0.00 ≤ x ≤ 0.45$) powder samples are prepared by solid-state reaction and their luminescence properties are investigated. With the replacement of Y³⁺$ ions by Sc³⁺$ (or Bi³⁺)$ and Gd³⁺$ ions in (Y,Al)BO$₃:Eu, the intensities of emission at 254 and 147~nm are remarkably improved, because Sc³⁺$ ions can absorb UV light and transfer the energy to Eu³⁺$ ions efficiently. Moreover, Gd³⁺$ and Bi$^{3 + }$ ions act as an intermediate ``bridge' between the sensitizer and the activator (Eu³⁺)$ in energy transfer to produce light in the (Y, Gd)BO$₃:Bi³⁺$, Eu³⁺$ system more effectively. After doping an appropriate concentration of Gd³⁺$ into Y$_{0.50}$Gd$_{0.25}$Al_0.10BO$₃:Eu³⁺_{0.01}$, Bi$^{3+}_{0.05}$, the emission intensity reaches its maximum, which is nearly 110{\%} compared with the red commercial phosphor (Y,Gd)BO$₃:Eu and better chromaticity coordinates (0.650, 0.350) are obtained.     

Optical properties of (ZnO)0.5(P2O5)0.5 glasses doped with Gd2O3:Eu nanoparticles and Eu2O3

Binary (ZnO)_0.5(P₂O₅)_0.5 glasses doped with Eu₂O₃ and nanoparticles of Gd₂O₃:Eu were prepared by conventional melt-quench method and their luminescence properties were compared. Undoped (ZnO)_0.5(P₂O₅)_0.5 glass is characterized by a luminescent defect centre (similar to L-centre present in Na₂O-SiO₂ glasses) with emission around 324 nm and having an excited state lifetime of 18 ns. Such defect centres can transfer the energy to Eu³⁺ ions leading to improved Eu³⁺ luminescence from such glasses. Based on the decay curves corresponding to the ⁵D₀ level of Eu³⁺ ions in both Gd₂O₃:Eu nanoparticles incorporated as well as Eu₂O₃ incorporated glasses, a significant clustering of Eu³⁺ ions taking place with the latter sample is confirmed. From the lifetime studies of the excited state of L-centre emission from (ZnO)_0.5(P₂O₅)_0.5 glass doped with Gd₂O₃:Eu nanoparticles, it is established that there exists weak energy transfer from L-centres to Eu³⁺ ions. Poor energy transfer from the defect centres to Eu³⁺ ions in Gd₂O₃:Eu nanoparticles doped (ZnO)_0.5(P₂O₅)_0.5 glass has been attributed to effective shielding of Eu³⁺ ions from the luminescence centre by Gd-O-P type of linkages, leading to an increased distance between luminescent centre and Eu³⁺ ions.     

The influence of Pr co-doping on the luminescent properties of Lu2O3:5 mol% Eu films

Uniform and crack free polycrystalline lutetium oxide (Lu₂O₃:(Eu,Pr)) films were fabricated by Pechini sol-gel method combined with the spin-coating technique. X-ray diffraction (XRD) and atomic force microscope (AFM) characterizations indicated that the obtained film was composed of polycrystalline cubic Lu₂O₃ phase with an average grain size around 30 nm. The photoluminescence(PL) spectra and decay performances of the Lu₂O₃:5 mol% Eu films co-doped by 0-0.5 mol% Pr³⁺ with different concentrations were characterized. It was found that the afterglow was reduced obviously due to the introduction of 0-0.5 mol% Pr³⁺ in the Lu₂O₃:5 mol% Eu films coupled by decrease in the emission intensity at 612 nm. The mechanism of afterglow diminishing was discussed based on the thermoluminescence measurements.     

Charge states of the activator and size effects in BaF2: Eu nanophosphors

ABSTRACT

According to the spectra of stationary X-ray excited luminescence (XEL) of BaF₂: Eu nanophosphors at 80 and 294 K, it was revealed that the thermal annealing of fine-grained nanoparticles (d?=?35?nm) in the range of 400–1000°C, which is accompanied by an increase of their sizes in the range of 58–120?nm, does not result in effective changes of the charge state of Eu^{3 +} → Eu^{2 +} activator, in contrast to CaF₂: Eu nanoparticles. The maximum light output of X-ray excited luminescence of BaF₂: Eu nanophosphors in the 590?nm emission band of Eu³⁺ ion was observed at an annealing temperature of 600°C with the average size of nanoparticles 67?nm. The subsequent growth of annealing temperatures, especially in the range of 800–1000°C, causes decrease in the light output of X-ray excited luminescence due to the increase of defect concentration in the lattice as a result of sharp increase of nanoparticle sizes and their agglomeration. In BaF₂: Eu nanoparticles of 58?nm size, according to the thermostimulated luminescence (TSL) spectrum, transformation of Eu³⁺ → Eu²⁺ under the influence of long-time X-ray irradiation was revealed for the peak of 151?K. Thus, X-ray excited luminescence spectra of BaF₂: Eu nanophosphors are formed predominantly due to the emission of Eu³⁺ ions, while emission of Eu²⁺ ions is observed in the TSL spectra.     

Preparation and luminescence properties of Tb doped ZrO2 and BaZrO3 phosphors

ZrO₂:Tb³⁺ and BaZrO₃:Tb³⁺ powders are prepared by combustion synthesis method and the samples were further heated to 500, 700 and 1000 °C to improve the crystallinity of the materials. The structure and morphology of materials have been examined by X-ray diffraction, Raman spectra and scanning electron microscopy. It is remarkable that all the samples of ZrO₂:Tb³⁺ and BaZrO₃:Tb³⁺ have similar morphology. These images exhibited homogeneous aggregates of varying shapes and sizes, which are composed of a large number of small cuboids and broken cuboids. The cuboids and broken cuboids size of all the samples are less than 0.5 μm. Photoluminescence for both materials increases with increase of temperature and found maximum for the samples heated to 1000 °C with 5 mole% doping of Tb³⁺ ions. Luminescence is almost double for the zirconia compared to that of barium-zirconate.     

Synthesis and luminescence properties of nanocrystalline Gd2O3:Eu by combustion process

The nanocrystalline Gd₂O₃:Eu³⁺ powders with cubic phase were prepared by a combustion method in the presence of urea and glycol. The effects of the annealing temperature on the crystallization and luminescence properties were studied. The results of XRD show pure phase can be obtained, the average crystallite size could be calculated as 7, 8, 15, and 23 nm for the precursor and samples annealed at 600, 700 and 800 °C, respectively, which coincided with the results from TEM images. The emission intensity, host absorption and charge transfer band intensity increased with increasing the temperature. The slightly broad emission peak at 610 nm for smaller particles can be observed. The ratio of host absorption to O²⁻-Eu³⁺ charge transfer band of smaller nanoparticles is much stronger compared with that for larger nanoparticles, furthermore, the luminescence lifetimes of nanoparticles increased with increasing particles size. The effects of doping concentration of Eu³⁺ on luminescence lifetimes and intensities were also discussed. The samples exhibited a higher quenching concentration of Eu³⁺, and luminescence lifetimes of nanoparticles are related to annealing temperature of samples and the doping concentration of Eu³⁺ ions.     

Preparation and luminescence properties of SrTiO3:Pr,Al phosphor from the glycolate method

Spherical SrTiO₃:Pr³⁺,Al³⁺ phosphor with high crystallinity and uniform particle size distribution was formed from the glycolate precursor. The glycolate precursor was obtained by heating the mixed solution of metallic nitrates and titanium oxychloride in ethylene glycol up to 200 °C. The thermal decomposition of the glycolate precursor proceeded through three major stages, i.e., (i) evolution of glycols (∼200 °C), (ii) decomposition of glycolate precursor, and (iii) decomposition of strontium carbonate and crystallization of SrTiO₃:Pr³⁺,Al³⁺ phosphor.SrTiO₃:Pr³⁺,Al³⁺ phosphor exhibited a strong red emission, peaking at about 617 nm. SrTiO₃:Pr³⁺,Al³⁺ phosphor obtained from the glycolate complex has higher luminescent properties than the conventional solid state reaction and the Pechini method in terms of photoluminescence (PL) and cathodoluminescence (CL). High crystallinity, low residual carbon content and small grain size with uniform shape would enhance the luminescence intensity of phosphor by the glycolate method due to high surface area per unit volume and low organic content compared with the Pechini method. Also, Al³⁺ ion is more effective than Ga³⁺ ion to enhance PL intensity of SrTiO₃:Pr³⁺,Al³⁺ phosphor because of smaller Al³⁺ ion radius. Therefore, the glycolate method has been demonstrated to be a convenient and unique process for the production of muticomponent oxide with smaller grain size and higher crystallinity compared with the conventional mixed oxide reaction and the polymer precursor method.     

The charge states’ conversion of the activator ions in CaF2:Eu nanophosphors

According to stationary X-ray-excited luminescence spectra and thermally stimulated luminescence spectra of CaF₂:Eu nanophosphors, it was found that Eu³⁺?→?Eu²⁺ conversion can occur during thermal annealing of fine-grained (d?=?25?nm) nanoparticles in the 200–800°C range, which is accompanied by an increase in their size within 40–189?nm. An important role of the exciton mechanism of Eu²⁺ luminescence excitation was revealed according to the temperature dependence of X-ray-excited luminescence spectra of CaF₂:Eu nanoparticles of 114?nm size. The maximum of the X-ray-excited luminescence light output of CaF₂:Eu nanophosphors in the Eu²⁺ ions’ emission band was traced out at 400–500°C annealing temperature and at the size of nanoparticles of 114–180?nm. The subsequent growth of the annealing temperatures, particularly in the 800–1000°C range, causes the reduction of X-ray-excited luminescence light output because of the increment of lattice defects’ concentration due to a sharp increase in the size of nanoparticles and their agglomeration.     

纳米Y_2O_3：Eu~（3＋）荧光强度降低的J-O理论分析

用均相沉淀法制备了纳米Y2O3：Eu3＋样品。归纳了纳米Y2O3：Eu3＋荧光强度降低的原因及提高途径。应用Judd-Ofelt理论从Y2O3：Eu3＋的发射光谱编程计算了纳米与微米Y2O3：Eu3＋的跃迁强度参数之比Ω′2/Ω2,比值均小于1,这表明纳米Y2O3：Eu3＋颗粒的5D0→7F2电偶跃迁几率比微米材料小,5D0→7F2跃迁几率小则612nm的荧光强度低。因此纳米YO：Eu3＋颗粒的荧光强度较微米材料低。     

Luminescence studies on ZnO-P2O5 glasses doped with Gd2O3:Eu nanoparticles and Eu2O3

Zinc phosphate glasses doped with Gd₂O₃:Eu nanoparticles and Eu₂O₃ were prepared by conventional melt-quench method and characterized for their luminescence properties. Binary ZnO-P₂O₅ glass is characterized by an intrinsic defect centre emission around 324 nm. Strong energy transfer from these defect centres to Eu³⁺ ions has been observed when Eu₂O₃ is incorporated in ZnO-P₂O₅ glasses. Lack of energy transfer from these defect centres to Eu³⁺ in Gd₂O₃:Eu nanoparticles doped ZnO-P₂O₅ glass has been attributed to effective shielding of Eu³⁺ ions from the luminescence centre by Gd-O-P type of linkages, leading to an increased distance between the luminescent centre and Eu³⁺ ions. Both doped and undoped glasses have the same glass transition temperature, suggesting that the phosphate network is not significantly affected by the Gd₂O₃:Eu nanoparticles or Eu₂O₃ incorporation.