Er~(3+)∶Yb~(3+)∶Tm~(3+)共掺硼硅酸盐玻璃光致发光温度特性和能级劈裂

高温固相烧结法制备了Er^3＋：Yb^3＋：Tm^3＋共掺硼硅酸盐玻璃．在978nm半导体激光器抽运下,测量了样品在300～573K下光致发光谱强度随温度的变化,讨论了室温时上转换绿光和红光等波段的光谱劈裂．分析了Er^3＋：Yb^3＋和Tm^3＋之间的能量传递机制．研究结果表明,当温度升高时,Er^3＋：Yb^3＋：Tm^3＋共掺硼硅酸盐玻璃的481nm蓝光、517和534nm绿光、以及657nm红光等光致发光强度单调下降,在490K时几乎消失．但900nm左右的近红外光谱则随温度的升高而持续增强,而且其中心波长向短波方向移动．在室温时,光谱劈裂明显,高温时劈裂逐渐消失．     

Er~(3+)铋铅锶玻璃吸收光谱和上转换光谱

制备了新型掺Er3+铋铅锶玻璃,研究了玻璃的吸收光谱和上转换光谱性质,应用Judd-Ofelt理论计算了铋铅锶玻璃的3个强度参量Ωt(t=2,4,6),分别为Ω2=3·27×10-20cm2,Ω4=1.15×10-20cm2,Ω6=0.38×10-20cm2。计算了Er3+离子的振子强度、自发辐射跃迁几率、荧光分支比和辐射寿命等光谱参数。研究了上转换发光强度随泵浦激光功率的变化,上转换荧光525,546和657nm曲线的斜率分别为1·86,1·88和1·85,表明红、绿光发射均为双光子吸收过程。     

新型掺铒铋酸盐玻璃上转换发光研究

制备了新型掺Er3 铋铅锶玻璃,研究了玻璃的吸收光谱和上转换光谱性质,应用Judd-Ofelt理论计算了铋铅锶玻璃的3个强度参量Ωt(t=2,4,6),分别为Ω2=3.27×10-20 cm2,Ω4=1.15×10-20cm2,Ω6=0.38×10-20 cm2.计算了Er3 离子的振子强度、自发辐射跃迁几率、荧光分支比和辐射寿命等光谱参数.研究了上转换发光强度随泵浦激光功率的变化,上转换荧光525,546和657 nm曲线的斜率分别为1.86,1.88和1.85,表明红、绿光发射均为双光子吸收过程.     

稀土掺杂的(K, Sr)Cl·SiO2复合凝胶的荧光性能

采用sol gel法制备了单掺铕及共掺铕、铈的(K,Sr)Cl·SiO2复合凝胶,研究了复合凝胶的荧光性能。根据荧光测试结果,复合凝胶中,Eu3+在没有还原剂的作用下,可以与基质作用形成还原态的Eu2+,复合凝胶表现出相应的Eu2+荧光性能;研究认为,Ce3+,Eu3+共掺杂时,复合凝胶激发光谱与发射光谱峰位基本不变,但强度有所不同。330nm处的激发光谱明显增强,且发射光谱随Ce3+的掺杂量增加而增强。当Ce3+掺杂浓度为3.0%(原子分数)时,复合凝胶具有最大的荧光发射强度,表明Ce3+具有很好的敏化作用。在Ce3+,Eu3+共掺杂复合凝胶体系中,复合凝胶荧光强度增大的原因既可能是电子转移过程,也可能是Ce3+→Eu2+的能量传递过程所致。     

铈掺杂高密度硼硅酸盐玻璃光谱性质研究

实验制备了一种密度为5.2 g.cm-3的高密度铈离子掺杂硼硅酸盐闪烁玻璃,该玻璃具有较高的析晶稳定性。测试了该闪烁玻璃的激发和发射光谱,其峰值波长分别对应于325和385 nm,斯托克斯位移为60 nm。当氧化铈掺杂浓度小于1%(质量分数)时,325 nm激发下的发射光谱强度随浓度的增加而提高,而掺杂浓度的进一步提高,由于三价态铈离子的自吸收等吸收猝灭效应导致380 nm的发射强度出现严重降低。掺杂1%(质量分数)的玻璃样品经245Gy的伽马射线辐照后,其可见波段的透过率并未出现明显降低,说明该玻璃具有较好的耐辐照性能。     

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.     

Tm~(3+)/Er~(3+)/Ho~(3+)共掺SiO_2-Bi_2O_3-AlF_3-BaF_2玻璃发光性能

采用高温熔融法制备了Tm~(3+)/Er~(3+)/Ho~(3+)共掺的铋硅酸盐50SiO 2-40Bi_2O_3-5AlF_3-5BaF_2玻璃。研究了在808 nm激光器(Laser Diode)激发下Tm~(3+)/Er~(3+)/Ho~(3+)共掺的铋硅酸盐在2 060 nm处的发光性能,同时测试及分析了该铋硅酸盐玻璃的差热特性、吸收光谱及荧光光谱。根据吸收光谱以及Judd-Oflet理论,计算了Ho~(3+)的Judd-Oflet强度参数Ωt(t=2,4,6)以及Tm~(3+)/Er~(3+)/Ho~(3+)相应的吸收截面。铋硅酸盐玻璃中,Tm_2O_3、Er_2O_3和Ho_2O_3掺杂浓度分别为0.75%、1.0%和0.5%时,2 060 nm处Ho~(3+)∶5I7→5I8发射峰强度达到最大。对Tm~(3+)/Er~(3+)/Ho~(3+)3种离子的光谱性质和离子间可能存在的能量传递也做了分析。Ho~(3+)在1 953 nm处的最大吸收截面σabs为9.08×10-21 cm~2,在2 060 nm处的最大发射截面σem为1.168×10-20 cm~2,辐射寿命τmea为2.75 ms,具有良好的增益效应σemτ(3.212×10-20cm~2·ms)。     

用于1．54μm微片激光器的高Er^3＋／Yb^3＋共掺杂的氟铝酸盐玻璃

本文系统制备了980nm半导体崩浦的应用于1．54μm波段微片激光器的高Er^3 ／Yb^3 共掺杂的氟铝酸盐玻璃。通过玻璃的吸收光谱，发射光谱和上转换荧光光谱的测试，对其光学性质、浓度淬灭及其淬灭机制进行了分析和讨论。当玻璃中Er^3 离子掺杂浓度低于10mol％的情况下，浓度淬灭现象较弱，Er^3 ／Yb^3 共掺杂的氟铝酸盐玻璃在由于Er^3 离子^4 I13／2→4^I 15／2跃迁所引起的1．54μm波段的发射强度比Er^3 单掺杂的氟铝酸盐玻璃中的荧光强度要强。在Er^3 离子掺杂浓度高于10mol％的情况下，由于Er^3 与Yb^3 之间的反能量转移过程，Er^3 ／Yb^3 共掺杂的氟铝酸盐玻璃的1．54μm波段的荧光浓度淬灭效应比Er^3 离子单掺杂的情况下明显。在Er^3 离子掺杂浓度小于10mol％的情况下，实验中发现可获得1．54μm波段高发射效率的Er^3 与Yb^3 离子最佳摩尔浓度掺杂比例约为1：1。     

Eu3+掺杂Y2O3-Al2O3-SiO2玻璃的制备与荧光性能研究

采用高温熔融法制备了Eu³⁺掺杂Y₂O₃-Al₂O₃-SiO₂荧光玻璃,探讨了成分对该体系玻璃形成能力的影响,并对不同Eu³⁺掺杂浓度下的荧光性能进行了研究.结果表明,熔融温度为1500℃条件下,SiO₂含量对该体系的玻璃形成能力影响明显,Y/Al摩尔比为3/5时,SiO₂含量在52%-68%(摩尔分数)范围内时可以获得玻璃.掺杂Eu³⁺的Y₂O₃-Al₂O₃-SiO₂玻璃具有荧光性能,在395nm波长激发下,在588 nm和614 nm处出现明显的发射峰.随着Eu³⁺掺杂浓度的增加,该荧光玻璃的发射波长不变,但发射强度有所变化;当Eu³⁺掺杂浓度为1.5%(摩尔分数)时,特征发射峰强度最大.     

Tm3+/Yb3+掺杂亚碲酸盐玻璃蓝红光上转换的研究

研究了掺Tm^3 /Yb^3 亚碲酸盐玻璃室温下的上转换发光。用970nm波长的半导体激光器作为泵浦源，得到了高效率的480nm波长上转换的荧光，通过对不同掺杂浓度样品的发光比较，发现了这种玻璃上转换发光的浓度猝灭现象，找出了这种玻璃得到高效率上转换发光的适宜浓度，并对Tm^3 的浓度猝灭现象进行了分析，通过对上转换发光强度与泵浦强度关系曲线的拟合，看到这种上转换是三光子吸收过程，这与通过能级图分析得到的结果相同，另外，也对650nm波长的转换发光进行了研究。     

Phosphine-catalyzed annulations of azomethine imines: allene-dependent [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] pathways

In this paper we describe the phosphine-catalyzed [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] annulations of azomethine imines and allenoates. These processes mark the first use of azomethine imines in nucleophilic phosphine catalysis, producing dinitrogen-fused heterocycles, including tetrahydropyrazolo-pyrazolones, -pyridazinones, -diazepinones, and -diazocinones. Counting the two different reaction modes in the [3 + 3] cyclizations, there are five distinct reaction pathways-the choice of which depends on the structure and chemical properties of the allenoate. All reactions are operationally simple and proceed smoothly under mild reaction conditions, affording a broad range of 1,2-dinitrogen-containing heterocycles in moderate to excellent yields. A zwitterionic intermediate formed from a phosphine and two molecules of ethyl 2,3-butadienoate acted as a 1,5-dipole in the annulations of azomethine imines, leading to the [3 + 2 + 3] tetrahydropyrazolo-diazocinone products. The incorporation of two molecules of an allenoate into an eight-membered-ring product represents a new application of this versatile class of molecules in nucleophilic phosphine catalysis. The salient features of this protocol--the facile access to a diverse range of nitrogen-containing heterocycles and the simple preparation of azomethine imine substrates--suggest that it might find extensive applications in heterocycle synthesis.     

Bi3+-Er3+ and Bi3+-Yb3+ Codoped Cs2AgInCl6 Double Perovskite Near-Infrared Emitters

Bi³⁺ and lanthanide ions have been codoped in metal oxides as optical sensitizers and emitters. But such codoping is not known in typical semiconductors such as Si, GaAs, and CdSe. Metal halide perovskite with coordination number 6 provides an opportunity to codope Bi³⁺ and lanthanide ions. Codoping of Bi³⁺ and Ln³⁺ (Ln=Er and Yb) in Cs₂AgInCl₆ double perovskite is presented. Bi³⁺-Er³⁺ codoped Cs₂AgInCl₆ shows Er³⁺ f-electron emission at 1540 nm (suitable for low-loss optical communication). Bi³⁺ codoping decreases the excitation (absorption) energy, such that the samples can be excited with ca. 370 nm light. At that excitation, Bi³⁺-Er³⁺ codoped Cs₂AgInCl₆ shows ca. 45 times higher emission intensity compared to the Er³⁺ doped Cs₂AgInCl₆. Similar results are also observed in Bi³⁺-Yb³⁺ codoped sample emitting at 994 nm. A combination of temperature-dependent (5.7 K to 423 K) photoluminescence and calculations is used to understand the optical sensitization and emission processes.     

Strong visible up-conversion emission in Tb3+, Tm3+ and Tb3+-Tm3+ co-doped tellurite glasses sensitized by Yb3+

Up-conversion luminescence characteristics under 975 nm excitation have been investigated with Tb3+/Tm3+/Yb3+ triply doped tellurite glasses. Here, green (547 nm: (5)D(4)-->(7)F(4)) and red (660 nm: (5)D(4)-->(7)F(2)) up-conversion (UC) luminescence originating from Tb3+ is observed strongly, because of the quadratic dependences of emission intensities on the excitation power. Especially, the UC luminescence was intensified violently with the energy transfer from the Tm3+ ions involves in the Tb3+ excitation. To the Tb3+/Tm3+/Yb3+ triply doped glass system, a novel up-conversion mechanism is proposed as follows: the energy of (3)G(4) level (Tm3+) was transferred to (5)D(4) (Tb(3+)) and the 477-nm UC luminescence of Tm3+ was nearly quenched.     

Pseudorotational dynamics of H3+ and Li3+

The origin of the pseudoprecession phenomenon is investigated through a computational study of the time evolution of H₃⁺ and Li₃⁺ by electron nuclear dynamics theory. In particular, the pseudorotation of both molecules is shown to induce a spatial rotation, which in turn leads to Coriolis coupling of the two orthogonal nuclear shape deformation modes. This effect is rooted in an anisotropy of the molecular ground state potential energy surface that is caused by the interaction between the D_3h ground state and a twofold degenerate first excited state. Computations are performed for a variety of vibrational energies. In addition, the impact of the anharmonicity of the ground state potential surface on the shape deformation modes and the coupling between them is discussed. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001     

Spectroscopic properties of Er3+, Yb3 + and Er3 + /Yb3+ doped metaphosphate glasses

The absorption and emission spectroscopies of Er3+ doped and Er3+/Yb3+ codoped Ca(PO3)2, Sr(PO3)2 and Ba(PO3)2 glasses have been studied. From the Judd-Ofelt intensity parameters, the spontaneous emission probabilities of some relevant transitions and the radiative lifetimes of several excited states of Er3+ have been calculated. The decay curves of the Er3+ emission at 1.5 microm have been measured at different temperatures. The data have been fitted using a stretched exponential function and the obtained experimental lifetimes have been compared with the calculated radiative lifetimes. The difference between the experimental and calculated lifetimes is attributed to the presence of traces of OH groups in the host glasses. The absolute OH content in some glasses has been determined from the infrared spectra. The emission spectra at 1.5 microm of the Er3+ ion in the codoped glasses have been measured at different temperatures. The integrated emission intensities decrease significantly on passing from room temperature to 13 K, suggesting a temperature dependence of the rate of the energy transfer process between Yb3+ and Er3+.     

Energy transfer between Gd3+ and Sm3+ the effect of Gd3+ on quenching of Sm3+ and intensity parameters of Sm3+ in borate glasses

Intensity parameters of Sm³⁺ in borate glasses were obtained by fitting the oscillator strengths to the Judd-Ofelt formula and a study of energy transfer from gadolinium to samarium was performed. An increase of samarium fluorescence originating from the ${}^4\text{G}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$ level was observed in the presence of gadolinium, in the concentration range of 0.1–3 wt% samarium with gadolinium constant at 3 wt%. The intensity of samarium fluorescence on excitation at 273 nm increased by one order of magnitude in the presence of gadolinium. From the excitation spectrum of the double-doped glasses (Gd + Sm), it was deduced that energy absorbed by gadolinium is transferred from ${}^6\text{P}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}$ gadolinium levels to the ${}^4\text{P}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ and ${}^4\text{P}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$ samarium levels.The mechanism of this energy transfer was obtained by plotting the energy transfer probabilities as a function of samarium concentration. A linear dependence of $\text{η}{}_0\text{η}$ (η intensity of gadolinium in the presence of samarium) versus square of concentration of Sm + Gd is obtained. From this it is concluded that the transfer is of electric-multipolar type, mainly dipole-dipole. A small increase (about 10%) of fluorescence of samarium in the presence of gadolinium excited at levels where no energy transfer can take place is attributed to the fact that the quenching of samarium occurring by the cross relaxation $\text{(}{}^4\text{G}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{→}{}^6\text{F}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}\text{) (}{}^6\text{H}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{→}{}^6\text{F}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}\text{)}$ is suppressed by the presence of gadolinium as seen from concentration dependence of samarium doped glasses compared to double-doped glasses.     

Er3+-Tm3+-Yb3+ tri-doped CaMoO4 upconverting phosphors in optical devices applications

The structural and optical properties of the Er³⁺-Tm³⁺-Yb³⁺codoped CaMoO₄ phosphors prepared by chemical route have been explored. The crystalline structures of the prepared phosphors have been investigated with the help of X-ray diffraction analysis. The presence of different vibrational modes and absorption bands arising due to the transitions from the ground state to different excited states of rare earth ions have been identified using the Raman and UV-VIS-NIR absorption spectra of the developed phosphor, respectively. The concentration quenching effect on the luminescence property of the prepared materials has been explained in detail. The upconversion luminescence property of the Er³⁺-Tm³⁺-Yb³⁺codoped CaMoO₄ phosphor annealed at different temperatures under 980 nm and 808 nm excitations have been reported. The energy transfer Er³⁺ → Tm³⁺, Yb³⁺ → Er³⁺ and Tm³⁺ has been found to be responsible for efficient UC emission. The dipole-dipole interaction is observed to be responsible for the concentration quenching of the luminescence intensity. The effect of annealing temperature on the upconversion luminescence property has been explained in detail. The results suggest that the developed tri-doped phosphor may be suitable in making the efficient NIR to visible upconverter and lighting based optical devices.     

沉淀法制备Sm3+,Er3+与Nd3+一次共掺杂的BaTiO3基半导体陶瓷电容器

在共沉淀法的基础上,通过双施主不同浓度的Nd3+和Sm3+,Er3+(4.0%～5.0%)掺杂,研究了BaTiO3基表面型陶瓷电容器的电性能,结果表明,Sm3+和Er3+的掺杂可以提高居里温度,但使介电常数降低,其含量为25%时可获得绝缘电阻500 MΩ左右,C/S为0.5895μf·cm-2电性能参数.     

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。