Photoacoustic Spectroscopy Study on the Luminescence Properties of SM3+ Complexes

The luminescence properties, energy transfer processes and energy levels of solid state Sm³⁺complexes with salicylic acid (SAL) and dibenzoylmethide (DBM) are studied by using photoacoustic (PA) spectroscopy at room temperature. The different energy transfer paths and the efficiency of intramolecular energy transfer between the ligands and the central ion are discussed according to Dexter's theory.     

Photoacoustic Spectra of Sm3+, Eu3+, Dy3+ Complexes

The complexes crystals of Sm(Ac)3.4H₂O, Eu(Ac)3.4H₂O and a new complex Dy2(Ac)(NO3)4.12H₂O were synthesized and their PA spectra were determined firstly. All their PA spectra absorptions are interpreted. The fluorescence properties of Sm³⁺, Eu³⁺, Dy³⁺ and the relaxation process models were studied by their PA spectra.     

Ce3+离子敏化Eu3+∶Cr3+∶Sm3+∶YAG外延层的荧光现象

对Ce3+ ∶Eu3+ ∶Cr3+ ∶Sm3+ ∶YAG处延层中的荧光敏化现象进行了报道和分析 ,在较高浓度的Ce3+ 离子掺杂时 ,外延层在蓝色、绿色波段出现了新的荧光谱线 ,可解释为在Ce3+ 离子敏化作用下 ,Eu3+ 离子产生了由高位激发态能级5Di(i=1,2 ,3)直接到基态能级7Fj(j =0 ,1,2 ,3)的辐射跃迁过程 ,并且这种Ce3+ ∶Eu3+ ∶Cr3+ ∶Sm3+ ∶YAG外延层还是一种新颖的白色单晶荧光材料。     

GdBO3：Pr3+，Yb3+中Pr3+到Yb3+的能量传递及发光性质

采用高温固相法制备了一系列单掺或双掺Pr3+和Yb3+的GdBO3材料,分别测试分析了材料的物相结构和发光性质。在446 nm蓝光( Pr3+：3 H4→3 P2)激发下,检测到Yb3+的近红外特征发射,表明样品中存在Pr3+到Yb3+的能量传递。 Pr3+的掺杂浓度一定时,样品的发光会随着Yb3+掺杂浓度的改变而发生变化。通过对比不同掺杂情况下Pr3+：3 P0能级的衰减曲线,发现随着Yb3+的掺杂浓度的增加,该能级的荧光寿命不断缩短;同时利用不同条件下的衰减特性计算得出不同 Yb3+掺杂浓度样品的能量传递效率。用 Inokuti-Hirayama模型分析表明Pr3+-Yb3+能量传递类型为偶极子-偶极子相互作用。     

Ce^3＋离子敏化Eu^3＋：Cr^3＋：Sm^3＋：YAG外延层的荧光现象

对Ce^3 :Eu^3 :Cr^3 :Sm^3 :YAG外延层中的荧光敏经现象进行了报道和分析，在较高浓度的Ce^3 离子掺杂时，外处层在蓝色、绿色波段出现了新的荧光谱线，可解释为在Ce^3 离子每化作用下，Eu^3 离子产生了由高位激发态能级^5Di(i=1,2,3）直接到基态能级^7Fj(j=0,1,2,3）的辐射跃迁过程，并且这种Ce^3 :Eu^3 :Cr^3 :Sm^3 :YAG外延层还是一种新颖的白色单晶荧光材料。     

Highly Chemoselective Thiocarbonyl Oxidation upon Reaction of 4-Methyl-3-phenyl-2-thiazolidinethione with Singlet Oxygen

4-Methyl-3-phenyl-2-thiazolidinethione was reacted with both photochemically and chemically generated singlet oxygen. Despite reaction conditions which were selected to favor oxidation of the sulfide group, both reactions afforded a single product arising solely from thiocarbonyl oxidation.     

A Study on Photoacoustic Phase Spectra of Rare Earth Complexes with Oxine

Photoacoustic phase is the time delay that occurs from light to acoustic signal. the phase includes two components: one is the time delay that occurs during the process in which light absorbed by a sample converts into heat; the other is the time delay caused from heat to acoustic signal. a modified formula of PA phase is presented based on the R-G theory considering the phase caused by non-radiative relaxation processes. the phase is associated with absorption coefficient (β), thermal diffusion length of sample (μ_s), the longest lifetime of all excited states (r), and the ratio of rapid to slow heat component (R). When the photoacoustic signal is saturated the phase is associated with only T and R. the effect of different rare earth ions on the PA phase spectra of the ligand (oxine) in the rare earth complexes are reported and are well explained by using the phase formula of PA saturation.     

稀土配合物分子内能量传递和弛豫过程的光声和荧光光谱研究

将光声光谱和荧光光谱两种互补的手段结合起来 ,从无辐射跃迁和辐射跃迁两个角度讨论了固态稀土配合物的激发 弛豫过程。测定了稀土配合物 (Tb(AA) 3·2H2 O、Tb(AA) 3bpy和Tb(AA) 3phen)固体粉末的光声光谱和荧光光谱。与荧光光谱相结合 ,光声光谱反映了不同配合物发光效率的变化 ,Tb(AA) 3phen、Tb(AA) 3·2H2 O和Tb(AA) 3bpy的发光效率依次增强。研究了配合物的分子内能量传递和弛豫过程 ,配体最低三重态能级与稀土离子共振能级之间的能级差是否匹配是配体敏化中心离子发光的关键因素     

FLUORESCENCE MECHANISMS OF Tm3+- AND Yb3+/Tm3+ DOPED AlF3-BASED FLUORIDE GLASS

A complete set of spectroscopic parameters, including Judd-Ofelt parameters, radiative transition probabilities, radiative lifetime, branching ratios and integrated absorption cross section, have been calculated for Tm³⁺- doped fluoroaluminate (AYF) glass, based on the measured absorption spectra. The mechanism of Tm³⁺→Tm³⁺ and Yb³⁺\Leftrightarrow Tm³⁺ energy transfers and fluorescence properties have been investigated in both Tm³⁺ single-doped and Yb³⁺/Tm³⁺ double-doped AYF glasses. The cross-relaxation process, ³F₄+³H₆→2³H₄, is proved, which makes the optimum Tm³⁺ concentration of 1.77μm fluorescence (³H₄→³H₆) much higher than 1.45μm fluorescence (³F₄→³3H₄) in Tm³⁺:AYF glasses. In Yb³⁺/Tm³⁺:AYF glasses, a stronger concentration quenching is found for the 476nm emission than that for the 797nm emission, and is discussed under the 970nm-excitation.     

Spectroscopy Study on Cobalt EDTA Complexes

The photoacoustic spectra of Co(H2EDTA)·3H20, Ca[Co(EDTA)H20]·4H20, Sr[Co(HEDTA)H20]2·4H20, Ba[Co(HEDTA)H20]2·4H20 complexes crystal are determined in the region of 300–800nm. In these spectra, the separations of absorption bands observed at 510nm and 650nm, the peak widths of 510nm band are variable in this series complexes. It is explained by the electron mutual effect, strength of ligand field and the symmetry of coordination group. The structure characters of these series complexes are also discussed.     

LaOBr:Tb3+，Dy3+的发光特性及高压研究

 采用高温常压方法合成了稀土发光材料LaOBr:Tb³⁺，Dy³⁺，采用高温高压方法对材料进行了处理，研究了高温高压处理前后样品发光特性的变化，并进行了发光衰减测量。结果表明，Dy³⁺的掺杂可以将Tb³⁺的⁵D₃能级的激发能有效地驰豫到⁵D₄能级，从而使⁵D₄~⁷F_J（J＝0, 1,…,6）的发射，尤其是⁵D₄~⁷F₅的发射明显增强，使得样品的发光亮度大大提高。Dy³⁺，Tb³⁺间存在交叉驰豫共振能量传递。高压处理过程引入的杂质、材料氧化及压致晶场变化都对材料的发光特性产生影响。     

Ce3+和Yb3+共掺杂的Y3Al5O12 可见及量子剪裁近红外发光性质

室温下观察了YAG：Ce和YAG：Ce,Yb材料在可见以及近红外区域的发光特性,并通过对Ce³⁺的5d能级辐射跃迁寿命以及Yb³⁺的²F_5/2能级布居时间和辐射跃迁寿命的比较研究,提出了光诱导的电荷转移态以及电荷转移辐射跃迁的能量传递机制,同时借助于能级图描述了从Ce³⁺到Yb³⁺的量子剪裁近红外发光过程。     

稀土氧化物粉末样品的光声光谱研究

利用光声光谱方法对几种常见的稀土氧化物粉末样品在紫外-可见、近红外, 以及中红外波段的光声光谱进行了测量与分析。根据光声光谱图和稀土离子的能级图, 对稀土离子的激发态电子的辐射和无辐射跃迁进行了探讨。与传统的透射谱和吸收谱相比较, 光声光谱具有分辨率高、快速、无损检测等优点, 特别适合于研究不透明、高反射和高散射粉末样品的光学性质。     

Pr3+、Tb3+共掺的NaGdF4和GdB3O6的VUV荧光性质

分别制备了单掺和双掺Pr³⁺和Tb³⁺的NaGdF₄和GdB₃O₆等材料,研究了其真空紫外荧光性质。发现在VUV光的激发下,Gd³⁺离子在Pr³⁺和Tb³⁺的能量传递过程中起着重要的作用。Gd³⁺离子不存在时,Pr³⁺和Tb³⁺之间没有明显的能量传递过程。当体系中加入Gd³⁺离子后,Pr³⁺将大部分能量传递给中间体Gd³⁺,Gd³⁺再将能量传递给Tb³⁺,实现了将Pr³⁺的近紫外光转化为Tb³⁺的绿色光的转换过程。     

稀土配合物的光声位相研究

对光声位相理论进行了研究,依此理论解释了稀土二苯甲酰甲烷配合物的光声位相谱。利用计算位相的方法得到在配体吸收处不同铽配合物的位相偏移,对位相差与不同铽配合物的分子内弛豫过程作了研究。     

Cr3+/Tm3+/Ho3+共掺氟磷酸盐玻璃的制备及性能表征

制备了不同 Al(PO₃)₃含量的掺铥系列氟磷酸盐玻璃,研究了其结构、热稳定性和光谱性质. 研究了不同摩尔百分数 Al(PO₃)₃掺杂下 Cr³⁺/Tm³⁺/Ho³⁺共掺氟磷酸盐玻璃在 2.0μm 处的发光特性. 并且用Judd-Ofelt理论计算了强度参量,并由此计算了激发能级的自发辐射跃迁速率、辐射寿命、荧光分支比等光谱参量. 结果表明,随着 Tm³⁺浓度增加,2.0μm 处发光的强度逐渐增强. 证明了Tm³⁺(³F₄) →Ho³⁺(⁵I₇)能量转移是非常有效的,并与掺杂浓度有关. 关键词： 氟磷酸盐玻璃 能量传递 荧光光谱 吸收光谱     

Er,Yb共掺杂氟氧混合物玻璃的紫色上转换发光研究

制备了Er^3 ：Yb^3 共掺杂氟氧混合物玻璃,利用R-500型分光光度计,在He-Ne激光器632．8m波长激光激发下,观测到了Er^3 离子的绿色与紫色上转换荧光,并就其上转换机制进行了讨论。     

二苯基亚砜、苯甲酸与轻稀土高氯酸四元配合物的合成表征及光致发光

合成并表征了高氯酸稀土与二苯基亚砜、苯甲酸的四种四元配合物。经元素分析、稀土络合滴定、摩尔电导率及差热-热重分析,表明四元配合物组成为[REL5L′(ClO4)] (ClO4) (RE= La,Pr,Nd,Eu;L=C6H5SOC6H5,L′=C6H5COO-)。在红外光谱中,第一配体二苯基亚砜的νS O的特征吸收峰出现在1 037cm-1处,而各稀土配合物的νS O向低波数移动到984 ～989 cm-1,红移50 cm-1左右,表明稀土离子与亚砜基团的氧原子之间发生配位作用。第二配体苯甲酸钠的反对称伸缩振动吸收峰νas(COO -)出现在1 550 cm-1,对称伸缩振动吸收峰νs(COO -)出现在1 416 cm-1处,羧基伸缩振动吸收频率差Δn[νas(COO -)-νs(COO -)]值为134cm-1;在所有配合物的红外光谱图中νas(COO -)向高波数方向发生了位移,而νs(COO -)向低波数方向发生了位移,并且Δn值均大于钠盐的Δn值,由此可以认为配合物中羧基是通过单齿方式与稀土离子配位。测定了配合物在丙酮溶液中的摩尔电导率,根据配合物在常见有机溶剂中的摩尔电导率与正负离子的关系结合配合物的红外光谱中高氯酸根离子的四条特征吸收带,表明配合物为1:1型电解质,两个ClO4-无机抗衡阴离子,其中一个在外界,一个进入内界与稀土离子配位。配合物的荧光发射光谱表明,四元配合物的荧光强度比二苯基亚砜高氯酸稀土二元配合物的荧光强度提高469%。磷光光谱表明苯甲酸三重态能级的下限和二苯亚砜三重态能级的上限重叠,导致三重态能级范围扩大,由此可见第二配体的加入提高了配体的三重态能级与Eu3 离子5D0能级的匹配程度。同时在配合物的荧光发射光谱中还可以看到铕离子的电偶极跃迁强度大于磁偶极跃迁,表明稀土离子不处于晶体场的对称中心。在四元配合物中,由于第二配体的加入,往往会降低配合物的对称性,从而增强稀土离子的荧光强度。本文合成的稀土配合物具有良好的荧光性能,而且在室温下稳定,溶解性好,分解温度较高。     

Photoacoustic spectroscopy study on the co-fluorescence effect of Eu-La-Hba solid complexes

The photoacoustic (PA) spectra of Eu³⁺-La³⁺-Hba complexes are reported (Hba: benzoic acid). It is found that the PA intensity of the ligand bears a relation to the energy transfer processes. For Eu³⁺-La³⁺-Hba coprecipitates, with increasing the concentration of La³⁺, the PA intensity in the region of the ligand absorption decreases firstly, then increases. It is indicated that the addition of the second rare earth ion La³⁺-changes the relaxation processes of the complexes. The changes of fluorescence spectra turn out to be complementary to the PA spectra. The intramolecular energy transfer and intermolecular energy transfer processes in the coprecipitates are discussed.