准一维反铁磁体CsMnCl3·2D2O中激子的能量转移

在2—300K温度范围,研究了纯的及掺Mg²⁺,Ni²⁺和Co²⁺的准一维反铁磁体CsMnCl₃·2D₂O(CMC)中Mn²⁺离子的⁴T₁激子的能量转移动力学过程,发现在2—10K范围,激子的荧光强度和寿命随温度很快下降,较高浓度的杂质离子将进一步加快荧光的减弱和寿命的缩短。这种现象被归结为与磁相互作用和自旋有序相关联的多声子无辐射跃迁及施主—受主之间的能量转移。在更高的温度,能量转移速率增高,但由于仍然存在的自旋短程有序和Jahn-Teller效应,施主之间的能量迁移受到一定限制,出现非指数衰减过程。各种不同的杂质离子在某种程度上显示出不同的陷落作用和弛豫特性。 关键词：     

红色荧光联苯四甲酸碱式稀土配合物的合成及发光性能

以3,3',4,4'-联苯四甲酸二酐(BPDA)为配体原料合成了两种碱式铕和铽配合物,通过元素分析、红外光谱和热重分析等测试技术表征了配合物的结构组成,用紫外光谱和荧光光谱研究了配合物的发光性能。结果表明:两种配合物的组成分别为Tb₅L₃(OH)₃·8H₂O和Eu₅L₃(OH)₃·10H₂O(L=BPDA),稀土铕(Ⅲ)和铽(Ⅲ)与羧酸根的配位方式主要以桥式配位为主,兼有少量螯合配位。这些配合物的热稳定性能良好。铽配合物和铕配合物均呈现红色荧光,铽配合物归属于⁵D₄→⁷F₃跃迁(613 nm)的荧光寿命为491.11 μs,归属于⁵D₄→⁷F₅ 跃迁(544 nm) 的荧光寿命为27.9 μs;铕配合物归属于⁵D₀→⁷F₂ 跃迁 (613 nm) 的荧光寿命为329.5 μs,荧光量子产率为13.05%。     

PrxLa1-xP5O14的发光理论和浓度效应

本文利用Judd-Ofelt理论求得PrP₅O₁₄晶体的振子强度参数Q₂,比较了计算和实验的振子强度,计算了³P₁,³P₀,¹D₂和¹G₄能级的电偶极和磁偶极辐射跃迁几率及¹D₂→¹G₄和³H₄→³F₄能级对间的多极矩耦合的无辐射迁移几率。讨论了¹D₂能级发射强度的浓度效应。并且,给出¹D₂能级发射强度的表达式和强度随着浓度和单位时间内激发光引起的³H₄到¹D₂跃迁的诱导跃迁几率的变化图。 关键词：     

均苯三甲酸铕及铕镧配合物的合成及荧光性质

以均苯三甲酸为配体,水热条件下合成了均苯三甲酸铕及铕镧系列发光配合物La_xEu_1-x(BTC)·nH₂O(x=0,0.1,0.3,0.5,0.7,0.9),通过元素分析及化学滴定法测定了配合物的组成。用红外光谱对其进行了表征,确定了该系列配合物的组成为La_xEu_1-x(BTC)·nH₂O。研究了系列配合物的荧光性质,荧光光谱表明:该类配合物均能发出强的铕离子的特征荧光,并且镧元素的掺入能增强铕配合物的发光强度,但发射峰的位置基本上没有变化;其中⁵D₀→⁷F₁和⁵D₀→⁷F₂的跃迁发射较强,且均劈裂为两个峰(587,593nm)和(611,618nm),这是由于铕离子所处的配位环境引起的。     

CCl4,CH2Cl2和CHCl3对磷脂酰胆碱紫外电子吸收光谱的影响

测量了ＣＣｌ₄，ＣＨ₂Ｃｌ₂和ＣＨＣｌ₃对生物膜中磷脂酰胆碱作用的紫外电子吸收光谱，实验结果表明，由于ＣＣｌ₄，ＣＨ₂Ｃｌ₂和ＣＨＣｌ₃分子结构的差异，三种溶剂的极性依次递增，磷脂酰胆碱π－π^*电子跃迁的吸收峰红移。磷脂酰胆碱在ＣＣｌ₄中光谱呈单吸收峰，在ＣＨ₂Ｃｌ₂和ＣＨＣｌ₃中光谱特征呈双蜂结构，存在聚集体的激子态跃迁，由此给出了脂质分子聚集状态的光谱依据。 关键词：     

YNbO4：Tm3+/Yb3+上转换发光特性研究

按照50Nb₂O₅-（46-x）Y₂O₃-4Yb₂O₃-xTm₂O₃（x=0.1,0.2,0.5,1,2）的配比方式,采用高温固相法制备出了掺杂Tm³⁺/Yb³⁺的YNbO₄晶体粉末。在980 nm红外光激发下,观测到波长为478,645,707 nm的上转换荧光,分别对应于Tm³⁺离子的¹G₄→³H₆、¹G₄→³F₄、³F₃→³H₆能级跃迁过程。利用上转换发射功率与980 nm激光器工作电流关系估算出跃迁过程吸收光子数目为2.72,2.69,2.01,从而确定出前两者为三光子吸收过程,最后一个对应于双光子吸收过程。运用Judd-Ofelt理论研究样品光谱特性,根据样品的吸收谱得到样品的谱线强度参数Ω_t（t=2,4,6）,进而得出理论振子强度及实验振子强度,二者均方根偏差δ_rms=1.299×10^-7。计算了Tm³⁺离子向下能级跃迁的跃迁几率、跃迁分支比等参数。最后得出结论：（1）³F₄能级寿命较长,适合作为上转换中间能级;（2）³H₅能级寿命较长,且³H₅→³H₆跃迁分支比（96.46%）接近100%,可用于产生1 216 nm激光。     

上转换纳米粒子CaF2:Er3+,Yb3+的合成及其温敏特性

采用水热合成法制备了CaF₂：Yb³⁺,Er³⁺上转换纳米粒子。在980 nm激发下,研究了来源于Er³⁺的²H_11/2/⁴S_3/2→⁴I_15/2跃迁的绿光发射和来源于⁴F_9/2→⁴I_15/2跃迁的红光发射。由于Er³⁺具有一对热耦合能级（²H_11/2/⁴S_3/2）,所合成的样品在293~573 K温度范围内有良好的温敏特性。利用荧光强度比（FIR）技术,测得样品在483 K时具有最大灵敏度0.002 85 K^-1。     

稀土掺杂的NaGdF4上转换发光材料的合成与发光特性研究

采用水热法制备了一系列不同掺杂浓度的NaGdF₄:Re(Re=Tm³⁺,Er³⁺,Yb³⁺)上转换发光粉。通过X射线衍射(XRD)、电子扫描电镜(SEM)和上转换发射光谱对样品进行了表征。XRD研究结果表明:合成的样品均为六方结构NaGdF₄。估算的平均晶粒尺寸为41~43 nm。在980 nm红外光激发下,Er³⁺和Yb³⁺共掺杂的NaGdF₄发光粉发出分别来自于Er³⁺离子²H_{11/ 2},⁴S_3/2→⁴I_15/2跃迁的绿光和⁴F_9/2→⁴I_15/2跃迁的红光发射,Tm³⁺和Yb³⁺共掺杂的NaGdF₄发光粉发出分别来自Tm³⁺离子的¹G₄→³H₆跃迁的蓝光、¹G₄→³F₄和³F_2,3→³H₆跃迁的红光和³H₄→³H₆跃迁的近红外光发射。Er³⁺,Tm³⁺和Yb³⁺共掺杂的NaGdF₄发光粉的发光强度及红、绿、蓝光发射的相对强度受Yb³⁺离子掺杂浓度的影响。对样品中可能的上转换发光机制进行了讨论。计算的色坐标显示:可通过改变掺杂离子浓度对上转换发光的颜色进行调控。     

Cu(Ⅱ)及Zn(Ⅱ)与直链醚席夫碱配合物的合成与表征

合成了两种直链醚席夫碱双水杨醛缩二甘醇二胺(SALDA)和双水杨醛缩四甘醇二胺(SALTTA)及其新配合物[Zn(SALDA)](NO₃)₂·4H₂O和[Cu₃(SALTTA)(NO₃)₄](NO₃)₂·3H₂O.并以IR谱、UV谱,特别是¹H和¹³C NMR谱等方法进行了表征,并详细地讨论了合成方法,IR谱表明SALTTA中醚氧并未全部配位.     

在BaYF5中Eu2+和Ho3+的荧光和能量传递

在脉冲N₂分子激光激发下,研究了在BaYF,中Eu²⁺和Ho³⁺的发射光谱,激发光谱和荧光寿命,以及Ho³⁺的超灵敏跃迁(⁵I₈→⁵G₆)。在Ho³⁺发射光谱中,⁵S₂→⁵I₈跃迁占主导地位。从Eu²⁺ 关键词：     

Nd3+螯合物的含氢有机溶液光谱性能研究

研究了Nd(TTA)₃螯合物溶于二甲基甲酰胺溶剂的光谱性质，溶液中所有氢未置换为氘.测量了这种溶液体系的吸收谱、荧光谱和荧光寿命.在898和1058 nm波长处观察到明显的Nd³⁺荧光特征峰.用Judd-Ofelt理论对吸收谱进行分析计算，得到了三个强度参数Ω_t(t=2,4,6)分别为Ω₂=4.9×10^-20 cm², Ω₄=5.1×10^-20 cm²和Ω₆=2.5×10^-20 cm².利用强度参数计算了⁴F_3/2能级与⁴I_9/2和⁴I_11/2之间的跃迁强度S_ed、自发辐射系数A_ed以及荧光分支比β等，估算了⁴F_3/2能级的辐射跃迁寿命τ_r＝682 μs.实测1058和898 nm波长处荧光寿命τ大约为460和505 μs，因此荧光量子效率分别高达0.67和0.74.荧光量子效率高表明Nd³⁺在这种溶液中无辐射跃迁比较弱；强度参数Ω₂比较大，表明Nd³⁺在溶液中具有不对称配位场环境，不对称的配位场环境可大大促进Nd³⁺吸收激发能量.光谱质量因子Ω₄/Ω₆>1，使得898 nm的辐射强于1058 nm的辐射. 关键词： Nd 有机溶液 光谱性能 Judd-Ofelt理论     

钕玻璃的光谱性质

本文分析了Nd³⁺在玻璃中的stark分裂情况,描写了确定荧光能级的实验方法,并给出了钕在四种硅酸盐玻璃中亚稳态和基态能级Stark分裂的实验结果。同时,对十三种不同成份的玻璃,通过光谱实验确定了Nd^{3+ 4}F_3/2态的辐射和无辐射跃迁速率,受激发射截面σ,辐射量子效率η,荧光分支比β和亚稳态寿命τ等激光常用参数。并对实验结果进行了讨论。 关键词：     

A study of non-thermalized luminescence spectra: the case of Cu2O

The emission spectra of a non-thermalized distribution of excitons in Cu₂O have been studied experimentally and theoretically. The emission spectra were found to exhibit interesting dependence on both the excitation frequencies and on the sample temperatures. These experimental results are explained quantitatively by a simple model calculation of the exciton distribution in Cu₂O under continuous excitation. Using this model the exciton non-radiative lifetime was deduced from the emission spectra. In addition, the present theory accounts for the lineshape of the resonant Raman peaks in Cu₂O more satisfactorily than the existing theory.     

Radiative and non-radiative decays from the excited state of Ti3+ ions in oxide crystals

The fluorescence spectra of Ti³⁺ in Y₃Al₅O₁₂ (YAG), Al₂O₃ (sapphire), YAlO₃ (YAP) observed at 10 K are composed of zero-phonon lines accompanied by the broad vibronic sidebands. The temperature dependence of the fluorescence lifetime and of the total intensity of the broadband measured in YAG and Al₂O₃ indicate that the radiative decay times from the excited states are nearly constant in the range 10–300 K. This demonstrates that the broadband radiative emissions in Ti³⁺:YAG and Ti³⁺:Al₂O₃ are due to magnetic dipole transitions or to electric dipole transitions induced by static odd-parity distortion, respectively. The decrease of the fluorescence lifetime with increasing temperature in Ti³⁺:YAG and Ti³⁺:Al₂O₃ is due to non-radiative decay from the excited state which occurs through phonon-assisted tunnelling between the excited and ground states. The radiative decay of Ti³⁺:YAP is enhanced with increasing temperature, indicating that radiative decay rate contains a term associated with odd-parity phonons. Nevertheless, a non-radiative decay rate of 3.6 × 10⁴ s^–1 observed in the temperature range 10–300 K is due to excited state absorption, which depopulates the excited state and quenches the fluorescence at the laser wavelength.     

Influence of borate content on the radiative properties of Nd ions in fluorophosphate glasses

Spectroscopic properties of Nd³⁺ in barium fluoroborophosphate glassy matrix have been analyzed by fitting the experimental data with the standard Judd-Ofelt theory. Various spectroscopic parameters viz. radiative transition probabilities, radiative decay time, fluorescence branching ratios, electric dipole line strengths, stimulated emission cross-sections and optical gain of the principal fluorescence transitions from the ⁴F_3/2 metastable level are obtained. Results show that addition of borate content to the fluorophosphate matrix will reduce the fluorescence spectral properties of Nd³⁺. However, the radiative properties of the present fluoroborophosphate glassy matrix are found to be well improved over that of pure borate and phosphate matrix and is attributed to the influence of fluorine content in the glassy matrix. The changes in the position and the Judd-Ofelt intensity parameters are correlated with the structural changes in the host glass matrix. The shift of the hypersensitive band shows that the covalency of the rare earth to oxygen bond increases with the increase of Na₂O content. This covalency effect and the formation of the BO₄ groups with the addition of Na₂O content are responsible for the increase in the radiative properties of the present system. Quantitative estimation of the non-radiative processes such as multiphonon relaxation and quenching by water content was carried out and the results show that both are below the critical level for optimum laser performance.     

Crystal growth, Judd-Ofelt analysis and fluorescence properties of Tm: CaNb2O6 crystal

Tm³⁺-doped CaNb₂O₆ single crystal was successfully grown by the Czochralski technique. Based on the Judd-Ofelt theory, three spectroscopic parameters Ω_t (t=2,4,6), radiative transition probabilities, radiative lifetimes, branching ratios and oscillator strengths were obtained according to the absorption spectra and the fluorescence spectra. Both the radiative lifetimes corresponding to the ³F₄→³H₆ transition for the bulk and the powder samples were recorded, and the final value of the radiative lifetime was obtained to be 2.25 ms, which indicates the existence of the luminescence re-absorption in the bulk sample. The corresponding quantum efficiency of the ³F₄ level was calculated to be 96%.     

Structural and luminescence properties of Dy3+ ion in strontium lithium bismuth borate glasses

Different concentrations of dysprosium doped strontium lithium bismuth borate (SLBiB) glasses were synthesized by the conventional melt quenching method and characterized through X-ray diffraction, Raman, absorption and visible luminescence spectroscopies. These Dy³⁺ doped glasses are studied for their utility for white light emitting diodes. X-ray diffraction studies revealed amorphous nature of the studied glass matrices. Coexistence of trigonal BO₃ and tetrahedral BO₄ units was evidenced by Raman spectroscopy. From the absorption spectra, Judd–Ofelt (J–O) intensity parameters, Ω_λ (λ=2, 4 and 6), have been calculated. The hypersensitivity of the transition, ⁶H_15/2→⁶F_11/2 of Dy³⁺ has been discussed based on the magnitude of Ω₂ parameter. Using J–O intensity parameters, several radiative properties such as spontaneous transition probabilities (A_R), radiative branching ratios (β_R) and radiative lifetimes (τ_R) have been determined. From the emission spectra, a strong blue emission that corresponds to the transition, ⁴F_9/2→⁶H_15/2, was observed and it also shows combination of blue, yellow and red emission bands for these glasses. In addition to that, white light emission region have been observed from these studies.     

Judd–Ofelt treatment on luminescence of europium complexes with β-diketone and bis(β-diketone)

Eu(DBM)₃2H₂O and Eu₂(DDBM)₃H₂O were synthesized by reactions between EuCl₃ and chelating regents of β-diketone (dibenzoylmethane, HDBM) and bis(β-diketone) (1,3-bis(3-phenyl-3-oxopropanoyl)benzene, H₂DDBM), respectively, and their luminescence properties were investigated by the fluorescence spectra and metastable state decay spectra. It was found that the relative intensity ratio of ⁵D₀→⁷F₂ to ⁵D₀→⁷F₁transition and the radiative lifetime shows a little change attributing to the different symmetry of europium ions, which Ω₂ of Eu complexes with β-diketone and bis(β-diketone) are 13.08 and 12.24, respectively. Moreover, it was also found that the metastable state lifetime of Eu₂(DDBM)₃H₂O is much longer than that of Eu(DBM)₃2H₂O, due to smaller water quenching and lower triplet level of ligands. The Commission Internacionale d’Éclairage (CIE) chromaticity coordinates calculated from emission spectrum are x=0.637 and y=0.343 for Eu₂(DDBM)₃H₂O, which presents high red color purity near 100%.     

YAG:Pr3+的真空紫外光谱分析及其4f5d能级的研究

用共沉淀法制备出不同掺杂浓度的钇铝石榴石(Y₃Al₅O_{12，YAG)：Pr³⁺粉末.在不同温度下用同步辐射的真空紫外光(VUV)作为激发光 源测量了其发射和激发光谱.对YAG：Pr³⁺被VUV激发后的发光过程进行了分析， 并估算了YAG：Pr³⁺的声子能量、黄昆因子S及Stokes位移.当用170nm光激发样 品时，可能存在自陷激子和通过自陷激子能量传递引发的³P0发射 ，这种跃迁途径不同于用240nm和289nm两个波长激发后的跃迁途径；对Pr³⁺在Y AG中的4f5d能级进行了研究，从而对其4f5d组态有了一个较清晰的认识. 关键词： 3+')" href="#">YAG：Pr³⁺ 同步辐射 4f5d能级 VUV}