稀土无机发光材料:电子结构、光学性能和生物应用

目前,稀土无机发光材料在激光、光通讯、平板显示、荧光生物标记和纳米光电子器件等领域具有广泛的应用前景.稀土离子(从Ce到Yb)是一类性能优异的结构和光谱探针,其在不同介质材料中的光学性能主要取决于其局域态的电子结构和激发态动力学.对稀土发光材料开展深入的光学和光电子学基础研究有助于发现新颖的光学性能或开辟新的应用领域.依托研制的低温高分辨激光光谱和上转换量子产率等仪器,本课题组致力于稀土无机发光材料电子结构与性能研究,近年来在发光材料的控制合成、电子结构、光学性能及生物应用等方面取得了系列重要结果.这些研究有望加快实现稀土无机发光材料在生物应用的突破,实现稀土资源的高值利用.     

稀土掺杂光学超晶格的自变频激光模型与应用

通过结合准相位匹配理论和空间分布自混频（或自倍频）激光模型提出了稀土掺杂光学超晶格材料自变频激光理论模型，该模型计入了弱聚焦的高斯光束空间分布，泵浦耦合以及非理想周期结构的影响，并应用该理论模型对Nd^3 离子掺杂非理想周期极化铌酸锂（Nd^3 :APLN)晶体同步自变频多波长激光进行了模拟计算，计算结果，尤其是阈值、可见激光总输出功率和同步可见激光谱线相对强度分布等与实验结果符合得很好，从而表明该模型的有效性。     

纺锤形铁黄α—FeOOH微晶合成动力学研究

本文对纺锤形α－ＦｅＯＯＨ微晶合成动力学过程进行了研究，利用复相反应经验动力学方程，考察了初始浓度，反应温度和空气流量对Ｆｅ（ＯＨ）２－ＦｅＣＯ３悬浮液氧化速率的影响，确定了α－ＦｅＯＯＨ成核－生长速率方程，证实了晶粒生长阶段存在溶解－氧化的动态平衡，根据活化能大小，推断相界面氧化反应为该相反应的控制步骤，还对α－ＦｅＯＯＨ成核生长微观机理作了初步探讨。     

无机纳米发光材料研究展望:如何走出自己的舒适区?

无机纳米发光材料由于其独特的发光性质,具有广泛的应用前景。本文结合作者的科研经历,展望了无机纳米发光材料未来的发展机遇和挑战,聚焦该领域前沿“痛点”和“冷门”,探讨研究工作如何面向国家重大需求。倡议科学家应走出自己的研究舒适区,树立自己的标签性工作,共同推进无机纳米发光材料研究的可持续发展。     

UPCONVERSION FLUORESCENCE DYNAMICS OF Tm3+ IONS IN LiYF4 CRYSTAL

According to Judd-Ofelt parameter calculation and energy transfer theory, the cross-relaxation process of the Tm³⁺ ions is investigated. A four-level system of coupled rate equations is established to study the fluorescence dynamics of Tm³⁺ in LiYF₄ crystal. Attentions are focused on the upconversion luminescence ¹G₄→³H₆ (483.0 nm) in Tm³⁺:LiYF₄. The relationship between the avalanche properties (critical pump rate, fluorescence intensity and buildup time) originated by resonant excited state absorption and the doped Tm³⁺ concentration is discussed, and some useful conclusions are drawn.     

4f~25g~1组态对Nd~(3 )∶YVO_4晶体光谱的影响

从ＪｕｄｄＯｆｅｌｔ理论和群链方案出发，在考虑了ＹＶＯ４晶体中Ｎｄ３＋的４ｆ２５ｇ１组态或７阶奇晶场的影响下，理论上导出了晶场作用下电偶极跃迁矩阵元公式，据此计算Ｎｄ３＋∶ＹＶＯ４有关光谱跃迁相对强度和偏振性质．与只考虑４ｆ２５ｄ１组态的影响相比，４Ｆ３／２→４Ｉ１１／２跃迁谱线相对强度的ＲＭＳ值由００８降为００５，计算结果与实验更加一致     

光子雪崩上转换的四能级模型

提出了四能级耦合系统的光子雪崩上转换模型,首先从理论上分析了光子雪崩产生的条件,给出了雪崩阈值以及在低于或高于阈值条件下荧光强度随时间变化关系;再将该模型结合数值分析应用于Ｔｍ＾３＋：ＬｉＹＦ４晶体这一列,理论分析结果与实验基本一致。因此应用此模型及其理论结果将有助于探索新型光子雪崩上转换材料。     

GROUP-CHAIN SCHEME ANALYSIS OF THE ENERGY LEVELS AND MAGNETIC PROPERTIES OF Nd3+ IN LiYF4 CRYSTAL

Based on the analysis of group-chain scheme, the crystal-field-level fitting of Nd³⁺: LiYF₄ has been carried out, in which the Nd³⁺ inos occupy positions with site symmetry S₄. The RMS deviation of energy-level fitting is 12.8cm^-1. Using the obtained wave functions, g-factors of the fround state are calculated,which are g_∥=2.067 and g_⊥=2.631, in good agreement with the experimental values(g_∥=1.978 and g_⊥=2.554). The method proposed turns out to be effective in the study of spectral properties of localized centres in laser crystals.     

Structure and luminescence of Ca2Si5N8：Eu^2＋ phosphor for warm white light-emitting diodes

We have synthesized Ca 2 Si 5 N 8:Eu 2+ phosphor through a solid-state reaction and investigated its structural and luminescent properties.Our Rietveld refinement of the crystal structure of Ca 1.9 Eu 0.1 Si 5 N 8 reveals that Eu atoms substituting for Ca atoms occupy two crystallographic positions.Between 10 K and 300 K,Ca 2 Si 5 N 8:Eu 2+ phosphor shows a broad red emission band centred at ～1.97 eV-2.01 eV.The gravity centre of the excitation band is located at 3.0 eV-3.31 eV.The centroid shift of the 5d levels of Eu 2+ is determined to be ～1.17 eV,and the red-shift of the lowest absorption band to be ～ 0.54 eV due to the crystal field splitting.We have analysed the temperature dependence of PL by using a configuration coordinate model.The Huang-Rhys parameter S=6.0,the phonon energy ν=52 meV,and the Stokes shift S=0.57 eV are obtained.The emission intensity maximum occurring at ～200 K can be explained by a trapping effect.Both photoluminescence (PL) emission intensity and decay time decrease with temperature increasing beyond 200 K due to the non-radiative process.     

稀土掺杂无机纳米晶及其时间分辨荧光生物检测应用

时间分辨荧光生物标记作为一种灵敏的非放射性标记技术,在科研及医疗机构已获得广泛应用.传统的时间分辨荧光标记以稀土螯合物作为分子探针,存在着光化学稳定性差、长期生物毒性以及价格昂贵等缺点.稀土掺杂无机纳米晶因其优异的光化学与光物理性能,是目前普遍看好且有望成为替代稀土螯合物的新一代时间分辨纳米荧光探针.利用稀土纳米探针的...