Yb~(3 )对Tm~(3 )间接敏化与基质晶格关系

Yb3 敏化Tm3 有两种方式 ,一种是直接敏化上转换 ,另一种是间接敏化上转换。前种直接采用 980nm激光激发 ,而后者可用 80 7nm激光激发 ,无疑后者有利于提高上转换发光的量子效率。由于基质晶格的晶体场强度不同 ,对称性有高有低 ,造成的稀土离子的能级分裂不同 ,通过分析双掺BaY2 F8,Cs3Yb2 Cl9等材料的光谱资料并结合生长的双掺Yb3 ,Tm3 ∶ZnWO4 单晶光谱的实际测试与分析 ,提出了Yb3 和Tm3 间的间接敏化共振能量传输的新观点 ,并具体分析了能形成这一上转换机制的条件。与间接敏化非共振能量传输不同 ,一是Yb3 的2 F5/2 →2 F7/2 的跃迁应与Tm3 3H4 →1 G4 能级间隔尽可能接近 ;二是Yb3 激发态能级2 F5/2 与Tm3 的3H4 能级尽可能接近。这要求基质材料的晶体场场强要弱 ,对称性要低。间接敏化共振能量传输极有可能引起光子雪崩上转换 ,这将为探索实用上转换激光晶体提供有益经验。     

976nm激发下Tm^3＋／Yb^3＋共掺TiBa玻璃微球上转换发光的形貌共振

制备了Tm^3 /Yb^3 共掺高折射率TiBa玻璃微球,玻璃基材主要成分为：TiO2,BaCO3和SiO2,稀土（％,摩尔分数）掺杂0.5Tm2O3和3Yb2O3。用976nm激光激发测量了它们的上转换蓝光发射。利用光学微腔理论讨论了玻璃微球荧光光谱中的形貌共振,并用Mie理论公式对共振峰间隔进行了计算,实验结果与计算结果相符。     

GdF3∶Er^3＋,Yb^3＋的合成和上转换发光特性

采用水热法制备了Er^3＋离子浓度为3%,Yb^3＋离子浓度分别为10%,20%的GdF3∶Er^3＋,Yb^3＋。XRD结果表明：合成的样品均为正交结构的GdF3,Gd0.87Yb0.10Er0.03F3和Gd0.77Yb0.20Er0.03F3样品的晶粒尺寸分别为28和26nm。研究了980nm红外光激发的上转换发射光谱。结果表明：红光和绿光发射分别来自于Er^3＋离子的2H11/2,4S3/2→4I15/2和4F9/2→4I15/2跃迁。样品的绿光发射强度较红光发射强。但绿光和红光发射的相对强度比例与Yb^3＋离子浓度有关。对Gd0.87Yb0.10Er0.03F3和Gd0.77Yb0.20Er0.03F3样品中可能的上转换发光机制进行了讨论。     

用脉冲激光溅射法制备的Yb^3＋和Er^3＋共掺杂氟化物薄膜的上转换发光

脉冲激光溅射法（PLD），作为一种制备高质量薄膜的方法，被广泛地用于制备超导、铁电等薄膜。用PLD法制备的Yb^3 和Er^3 共掺杂氟化物薄膜的上转换发光性质。在978nm LD激发下，薄膜发出强烈的橙色光，用日立－F4500光谱仪测量了其上转换发光光谱，观测到了Er^3 很强的^2H9/2→^4I15/2(408nm),^2H11/2→^4I15/2(520nm),^4S3/2→^4I15/2(550nm)和^4F9/2→^4I15/2(650nm)跃迁发射峰。给出了上转换发光强度随激发强度的关系，分析了其上转换发光机制及紫色上转换发光增强的原因。     

两种基质中Er^3＋的上转换发光特性

合成了一种新型共掺杂Er^3 和Yb^3 的氟氧化物（ZnF2-SiO2基质）材料,研究了Er^3 在这种基质材料中的吸收和在980nm激发下的上转换发光,并对比了同等激发条件下Er^3 离子在ZBLAN玻璃和这种氟氧化物中的上转换发光特性。实验发现两种基质中Er^3 离子吸收峰位置基本相同,但吸收强度明显不同。氟氧化物中Er^3 离子的上转换发光强度要低于ZBLAN基质中Er^3 离子的上转换发光强度,不同的是Er^3 离子在氟氧化物基质中红光发射强度要强于绿光强度。分析了两种基质中Er^3 的上转换发光机制,氟氧化物基质中Er^3 离子红绿光发射均为双光子过程,ZBLAN基质中Er^3 离子绿光发射为双光子过程,而红光发射为双光子和三光子混合过程。     

水热合成稀土氟化物材料YLiF4∶Yb,Tm的上转换发光特性

利用水热法合成了掺杂Tm3 和Yb3 的YLiF4材料, 并研究了Tm3 和Yb3 在材料中的光吸收, 以及980 nm红外光激发下不同Tm3 浓度掺杂下的上转换发光特性. 实验发现, 在980 nm激光激发下, 材料可发出可见光. 上转换发光光谱中包括蓝光和红光. 与蓝光相比, 红光强度要弱1～2个数量级. 上转换发光强度和浓度关系研究显示, 当Tm3 浓度为0.3% (摩尔分数)时上转换发光达到最强, 大于0.3% (摩尔分数)后发光开始减弱. 通过分析输出光强与泵浦功率的双对数曲线, 发现Tm3 的蓝光发射和红光发射均属于双光子过程.     

Excitation Energy-Transfer Processes in the Sensitization Luminescence of Europium in a Highly Luminescent Complex

The excitation energy transfer (EET) pathways in the sensitization luminescence of Eu^III and the excitation energy migration between the different ligands in [Eu(fod)₃dpbt] [where fod=6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione and dpbt=2-(N,N-diethylanilin-4-yl)-4,6-bis(3,5-dimethylpyrazol-1-yl)-1,3,5-triazine], exhibiting well-separated fluorescence excitation and phosphorescence bands of the different ligands, were investigated by using time-resolved luminescence spectroscopy for the first time. The data clearly revealed that upon the excitation of dpbt, the sensitization luminescence of Eu^III in [Eu(fod)₃dpbt] was dominated by the singlet EET pathway, whereas the triplet EET pathway involving T₁(dpbt) was inefficient. The energy migration from T₁(dpbt) to T₁(fod) in [Eu(fod)₃dpbt] was not observed. Moreover, upon the excitation of fod, a singlet EET pathway for the sensitization of Eu^III luminescence, including the energy migration from S₁(fod) to S₁(dpbt) was revealed, in addition to the triplet EET pathway involving T₁(fod). Under the excitation of dpbt at 410 nm, [Eu(fod)₃dpbt] exhibited an absolute quantum yield for Eu^III luminescence of 0.59 at 298 K. This work provides a solid and elegant example for the concept that singlet EET pathway could dominate the sensitization luminescence of Eu^III in some complexes.     

Tm3+/Yb3+共掺氧氯碲酸盐玻璃上转换发光研究

制备了Tm^3＋/Yb^3＋共掺氧氯碲酸盐玻璃, 研究了玻璃的热稳定性能、 Raman光谱和上转换发光光谱, 分析了上转换发光机制. 结果表明： 通过980 nm的激光二极管激发, 在室温下同时观察到强烈的蓝光（476 nm）和微弱的红光（649 nm）, 分别是Tm^3＋离子的1G4→3H6和1G4→3H4跃迁. 随氯化铅含量增加, 基质玻璃的热稳定性能增强, 基质玻璃的声子能量降低, 上转换蓝光和红光的强度增加. 表明Tm^3＋/Yb^3＋共掺氧氯碲酸盐玻璃是一种上转换蓝光激光器的潜在基质材料.     

在硅磷酸镧中Ce^3＋离子对Tb^3＋离子的敏化

实验表明在La2O3·0.01SiO2·0.95P2O5基质中Ce^3 对Tb^3 有强的敏化作用。254nm紫外光激发下温度对Tb^3 激活的Ce^3 、Tb^3 共激活试样的发射强度的Ce^3 、Tb^3 共激活的试样Tb^3 的^5D4→^7F6:5:4跃迁的发射强度随湿度的变化。计算了Ce^3 到Tb^3 的能量传递效率。初步探讨了Ce对Tb的能量传递机理。     

Investigation on Luminescence Properties of a Long Afterglow Phosphor Ca2SnO4:Tm3+

A series of new long afterglow phosphors Ca₂SnO₄:x Tm³⁺ were synthesized by using traditional solid‐state reactions. XRD measurements and Rietveld refinement revealed that the incorporation of the Tm³⁺ dopants generated no second phase other than the original one of Ca₂SnO₄, which indicated that the dopants completely merged into the host. The corresponding optical properties were further systematically studied by photoluminescence, phosphorescence, and thermoluminescence (TL) spectroscopy. The results show that the Tm³⁺‐related defects account for the bright bluish green afterglow emission from the characteristic f–f transitions of Tm³⁺ ions. The bluish green long‐lasting phosphorescence could be observed for 5 h by the naked eye in a dark environment after the end of UV irradiation. Two TL peaks at 325 and 349 K from the TL curves were adopted to calculate the depth of the traps, which were 0.45 and 0.78 eV, respectively. The mechanism of the long afterglow emission was also explored.     

Tb~(3+)在YAG中的发光及Tb~(3+)与Tm~(3 +)间的能量传递

采用溶胶 -凝胶方法合成了系列化合物 (Y1 -x- yTbxTmy) 3Al5O1 2 ,研究了Tb3+在该化合物中的发光及其浓度对发光性质的影响 ,以及Tb3+与Tm3+间的能量传递现象。     

Unprecedented Sensitization of Visible and Near‐Infrared Lanthanide Luminescence by Using a Tetrathiafulvalene‐Based Chromophore

Ligand L was synthesized and then coordinated to [Ln(hfac)₃] ? 2 H₂O (Ln^III=Tb, Dy, Er; hfac^?=1,1,1,5,5,5‐hexafluoroacetylacetonate anion) and [Ln(tta)₃]?2 H₂O (Ln^III=Eu, Gd, Tb, Dy, Er, Yb; tta^?=2‐thenoyltrifluoroacetonate) to give two families of dinuclear complexes [Ln₂(hfac)₆( L )] ? C₆H₁₄ and [Ln₂(tta)₆( L )] ? 2 CH₂Cl₂. Irradiation of the ligand at 37 040 cm^?1 and 29 410 cm^?1 leads to tetrathiafulvalene‐centered and 2,6‐di(pyrazol‐1‐yl)‐4‐pyridine‐centered fluorescence, respectively. The ligand acts as an organic chromophore for the sensitization of the infrared Er^III (6535 cm^?1) and Yb^III (10 200 cm^?1) luminescence. The energies of the singlet and triplet states of L are high enough to guarantee an efficient sensitization of the visible Eu^III luminescence (17 300–14 100 cm^?1). The Eu^III luminescence decay can be nicely fitted by a monoexponential function that allows a lifetime estimation of (0.49±0.01) ms. Finally, the magnetic and luminescence properties of [Yb₂(hfac)₆( L )] ? C₆H₁₄ were correlated, which allowed the determination of the crystal field splitting of the ²F_7/2 multiplet state with M_J=±1/2 as ground states.     

NaY(WO4)2:Eu3+/Tb3+/Tm3+白色荧光粉的制备与发光性能

采用溶剂热法合成了一种单一相白色荧光粉NaY(WO4)2:Eu3+,Tb3+,Tm3+.通过X射线衍射(XRD)、扫描电镜(SEM)、X射线能谱(EDS)及荧光光谱(PL)对制备的系列样品的物相、形貌和荧光性质进行了表征.结果表明:在荧光粉NaY(WO4)2:x％Eu3+,4％Tb3+,1％Tm3+(x=5,10,15,20)中,随着Eu3+掺入量的增加,发光从绿光区进入白光区.同时观察到Tb3+到Eu3+的有效能量传递.