碱土金属氟卤化物中的Eu3+的荧光光谱特征

本文系统研究了MFX体系中Eu³⁺荧光光谱特征,着重讨论了X^-,M²⁺及杂质缺陷(主要为O^2-)对Eu³⁺发光的影响.     

Solid phase extraction for analysis of biogenic carbonates by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS): an investigation of rare earth element signatures in otolith microchemistry

Uptake of trace elements into fish otoliths is governed by several factors such as life histories and environment in addition to stock and species differences. In an attempt to elucidate the elemental signatures of rare earth elements (REEs) in otoliths, a solid phase extraction (SPE) protocol was used in combination with electrothermal vaporization (ETV) as a sample introduction procedure for the determinations by inductively coupled plasma quadrupole mass spectrometry (ICP-MS). Effects of various parameters, such as carrier gas flow rate, atomization temperature and chemical modification, were examined for optimization of the conditions by ETV-ICP-MS. Atomization was achieved at 2800 °C. Lower temperatures (i.e. 2600 °C) resulted in severe memory problems due to incomplete atomization. Palladium was used as a chemical modifier. It was found that an increase in Pd concentration up to 0.5 μg in the injection volume (70 μl) led up to four-fold enhancement in the integrated signals. This phenomenon is attributed to the carrier effect of Pd rather than the stabilization since no significant losses were observed for high temperature drying around 700 °C even in the absence of Pd. Preconcentration was performed on-line at pH 5 by using a mini-column of Toyopearl AF-Chelate 650M chelating resin, which also eliminated the calcium matrix of otolith solutions. After preconcentration of 6.4 ml of solution, the concentrate was collected in 0.65 ml of 0.5% (v/v) HNO₃ in autosampler cups, and then analyzed by ETV-ICP-MS. The method was validated with the analysis of a fish otolith certified reference material (CRM) of emperor snapper, and then applied to samples. Results obtained from otoliths of fish captured in the same habitat indicated that otolith rare earth element concentrations are more dependent on environmental conditions of the habitat than on species differences.     

稀土配合物Eu(asprin)_3phen发光特性的研究

将稀土配合物Eu(asprin)_3phen掺杂到导电聚合物PVK中,制成结构分别为ITO/PVK:RE配合物/LiF/AI(1),ITO/PVK:RE配合物/PBD/LiF/AI(2)的电致发光(EL)器件。发现二者的电致发光谱存在着较大的差别:在器件(1)中,来自Eu~(3 )的位于594nm(~5D_0→~7F_1)和614nm(~5D_0→~7F_2)处的发光强度大致相当,而在器件(2)中,EL主要来自Eu~(3 )位于614nm的发光,594nm处的发光很弱,与薄膜状态下的光致发光谱(PL)一致。并针对此现象进行了初步讨论。     

Gd2O3:Eu纳米晶的制备及其光谱性质研究

以EDTA为络合剂，聚乙二醇为有机分散剂，用络合溶胶—凝胶法制备出Gd2O3:Eu纳米晶。用XRD，SEM，X—射线能量色散谱仪(EDS)，荧光分光光度计等分析手段对Gd2O3:Eu的纳米晶结构、形貌、组分的均匀性以及发光特性进行了研究。结果表明：EDTA—M凝胶仅在800℃焙烧即可得到颗粒细小、组分均匀、纯立方相的Gd2O3:Eu纳米晶，颗粒基本呈球形，粒径为30nm左右。对样品的激发光谱、发射光谱测定表明：Gd2O3:Eu纳米晶在269nm光激发下发红光，发射光谱谱峰在611nm，与体材料基本相同；激发光谱中电荷迁移带(CTB)明显红移，从体材料的255nm移至269nm，移动了约14nm；猝灭浓度从体材料的6％提高到8％。     

Magnetic behaviour of TbMnFe

Neutron diffraction and M?ssbauer measurements have been carried out on the cubic Laves phase intermetallic TbMnFe. The magnetic moment on the transition metal atom is found to be low, 0.2μ _B, at room temperature. This moment is temperature independent down to 10 K. Magnetic moment on the rare earth atom varies from 2.5μ _B at 296 K to 7.27μ _B at 10 K. M?ssbauer spectra recorded at 298 K and 78 K have magnetic character but there is a large distribution of hyperfine field values. Both these features arise due to magnetic frustration created in the sample due to the competing ferro and antiferromagnetic interactions between the transition metal atoms.     

Estimating tail probabilities of heavy tailed distributions with asymptotically zero relative error

Efficient estimation of tail probabilities involving heavy tailed random variables is amongst the most challenging problems in Monte-Carlo simulation. In the last few years, applied probabilists have achieved considerable success in developing efficient algorithms for some such simple but fundamental tail probabilities. Usually, unbiased importance sampling estimators of such tail probabilities are developed and it is proved that these estimators are asymptotically efficient or even possess the desirable bounded relative error property. In this paper, as an illustration, we consider a simple tail probability involving geometric sums of heavy tailed random variables. This is useful in estimating the probability of large delays in M/G/1 queues. In this setting we develop an unbiased estimator whose relative error decreases to zero asymptotically. The key idea is to decompose the probability of interest into a known dominant component and an unknown small component. Simulation then focuses on estimating the latter ‘residual’ probability. Here we show that the existing conditioning methods or importance sampling methods are not effective in estimating the residual probability while an appropriate combination of the two estimates it with bounded relative error. As a further illustration of the proposed ideas, we apply them to develop an estimator for the probability of large delays in stochastic activity networks that has an asymptotically zero relative error.      

重稀土高氯酸盐甲基苯甲酰甲基亚砜配合物的合成及Tb3+的发光

合成了重稀土高氯酸盐甲基苯甲酰甲基亚砜配合物RE(ClO4)3·L5·C2H5OH(RE=Gd,Tb,Dy,Tm,Yb;L=C6H5COCH2SOCH3).经元素分析、稀土络合滴定、摩尔电导及热重分析确定了配合物的组成,测定了配体及配合物的IR谱、1H NMR及铽配合物的磷光光谱、荧光激发和发射光谱,根据荧光发射光谱数据计算了铽配合物的各能级值.     

纳米晶ZrO2:Er3+-Yb3+的制备及其室温上转换发射

用化学共沉淀法制备了ZrO₂:Er³⁺-Yb³⁺纳米晶粉体，所制备的纳米晶粉体具有较强的室温上转换发射和红外发射.研究了样品的晶体结构和上转换发光性质随着Yb³⁺掺杂浓度和煅烧温度的变化关系.通过X射线衍射谱分析发现，经800℃煅烧2h后得到的ZrO₂:Er³⁺-Yb³⁺纳米晶是四方相和单斜相的混合结构，经950℃煅烧2h后得到的样品以单斜相为主，随着Y     

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)。     

稀土氟化物Y0.97Er0.03F3纳米材料的制备及上转换发光

通过燃烧法和控温热反应法制备了稀土氟化物纳米材料，利用XRD和TEM对样品进行了分析和表征。测量了发射波长为980nm激光二极管激发下所得纳米材料的上转换发光性质。