5(6)羧基荧光素敏化TiO2纳米粒子的光致电子转移的荧光特性研究

通过水解TiCl₄制备了锐钛矿结构TiO₂纳米粒子, 并用时间分辨荧光光谱研究了5(6)CFL(5(6)-Carboxyfluorescein, 简称5(6)CFL)染料敏化TiO₂纳米粒子体系的光致电子转移动力学. 5(6)CFL染料敏化TiO₂纳米粒子能形成电荷转移复合物, 这归因于染料分子的激发电子态波函数Ψ(D^*)与电荷分离态波函数Ψ(D⁺ +e^-)之间的耦合作用. 当激发5(6)CFL染料敏化TiO₂纳米粒子体系时, 电子以两种不同方式注入TiO₂纳米粒子导带: 第一, 通过5(6)CFL染料分子的激发态注入; 第二, 从电荷转移复合物(5(6)CFL/TiO₂)直接注入. 时间分辨荧光光谱表明, 在水溶液中纯5(6)CFL染料的荧光以寿命为τ₁=41 ps (74.4%) 和τ₂=3.22 ns (25.6%) 的双e指数衰减, 而5(6)CFL染料敏化TiO₂纳米粒子体系的荧光分别以时间常数为τ₁=44 ps (90.4%), τ₂=478 ps (8.6%) 和τ₃=2.41 ns (1.0%) 的三e指数衰减. 本文的研究工作能够为染料敏化太阳能电池的光致电子转移机理提供有价值的参考.     

OH-对磷酸盐铒玻璃光谱性质的影响

本文系统研究了Yb³⁺、Er³⁺共掺磷酸盐铒玻璃中OH^-含量与铒玻璃荧光寿命和光谱性质的关系.结果表明OH^-基团的存在使得Er³⁺离子的荧光强度显著降低,荧光寿命大大缩短.比较了三种不同Al₂O₃含量(5mol%,8mol%和13mol%)的铒玻璃在2.9μm波长处的红外吸收系数与铒离子荧光寿命的关系,发现玻璃中OH^-在2.9μm的吸收系数和Er³⁺的⁴Ⅰ_13/2能级离子衰减速率成线性关系,不同Al₂O₃含量的玻璃具有不同Er³⁺和OH^-基团的相互作用参量和不同的荧光寿命值及量子效率.并从玻璃结构上解释了Al₂O₃含量对除水机制和光谱性质的影响.经过充分除水后的铒玻璃荧光寿命可达到9.1ms.     

射频电子枪中LaB6阴极的研究

 一种用于射频电子枪中的LaB₆热阴极已经研制成功。分别研究了(100)、 (110)、(111) 晶向LaB₆单晶的热发射特性。选用(100)晶向的LaB₆单晶材料作为发射体并用铼做基底材料。试验表明,在1823K工作条件下,其热发射电流密度达到 30A/cm²;在真空条件为5×10^-5Pa下,寿命已达10000小时以上。在室温下反复多次暴露大气后,其发射性能保持不变。     

环戊酮光电离解离的实验和理论研究

本文介绍了真空紫外光电离质谱结合理论计算研究环戊酮单分子的光电离解离过程. 在9.0∽15.5 eV能量范围内,测量了环戊酮离子及其碎片离子的光电离效率曲线. 通过光电离效率曲线,将环戊酮分子的电离能确定为9.23±0.03 eV,并确认碎片离子为：C₅H₇O⁺,C₄H₅O⁺,C₄H₈⁺,C₃H₃O⁺,C₄H₆⁺,C₂H₄O⁺,C₃H₆⁺,C₃H₅⁺,C₃H₄⁺,C₃H₃⁺,C₂H₅⁺, C₂H₄⁺. 利用量子化学计算方法,在ωB97X-D/6-31+G(d,p)理论水平基础上,提出了C₅H₈O⁺的解离机制. 通过对环戊酮解离路径的分析,发现开环和氢迁移过程为环戊酮离子解离的主要路径.     

DIRECT UPCONVERSION SENSITIZATION LUMINESCENCE OF Ho(0.1)Yb(5):OXYFLUORIDE VITROCERAMICS

This paper studies the upconversion luminescence phenomenon of the Ho,Yb co-doped oxyfluoride vitroceramics. There is one group of strong upconversion luminescence lines positioned at 536.5nm, 18639cm^-1; 540.5nm, 18501cm^-1; 544.0nm, 18399cm^-1, which is easily identified as the transitions of ⁵S₂→⁵I₈. There are other splendid upconversion luminescence lines, which are ⁵S₂→⁵I₇,⁵F₅→⁵I₈,⁵G₆→⁵I₈, (⁵G³G)₅ →⁵I₈,(³F³H⁵G)₄→⁵I₇,⁵G₄→⁵I₈ and (⁵G³H)₅→⁵I₈. It is also found that an interesting kind of upconversion cooperative radiation fluorescence comes from a kind of coupling state of clusters consisting of two Yb³⁺ ions.     

SPECTROSCOPIC INVESTIGATION ON THE PROPERTIES OF VISIBLE AND NEAR INFRARED EMISSIONS IN Tm3+, Ho3+ Co-DOPED YVO4 CRYSTALS

With the help of absorption and fluorescence spectra, the spectroscopic properties of Tm³⁺, Ho³⁺:YVO₄ crystals have been investigated under different dopant concentrations. The absorption results show that the maximum absorption in the spectral range of currently available powerful laser diodes (LD) is at 796 nm, corresponding to the transition ³H₆→³H₄ of Tm³⁺ in the crystals. Upon the excitation with a LD at 808 nm, we have detected ten fluorescence bands in the spectral range spanning from visible to infrared. In visible region 4 upconversion bands have been observed centered at 475, 547, 660, and 701 nm. Discussions of the energy transfer processes suggest that cross relaxations and excited absorptions with the involvement of Tm^{3+ 3}F₄, ³H₅ and Ho^{3+ 7}I₅ states are responsible for the four upconversion emissions. Comprising the relative integrated intersities of 2 μm (Ho³⁺: ⁵I₇→⁵I₈) and 1.8 μm (Tm³⁺: ³F_4→³H₆) bands we have observed an efficient energy transfer from Tm³⁺ (³F₄) to Ho³⁺ (⁵I₇). Examination of the ratios of the intensity of 2 μm band to that of 1.8 μm band as a function of the ratios of Tm³⁺ concentration (c_Tm) to Ho³⁺ concentration (c_Ho) indicates that small concentration ratios (c_Tm/c_Ho) lead to high efficient energy transfers of Tm³⁺(³F₄)→Ho³⁺(⁵I₇).     

Pr3+离子单掺LiLuF4单晶的坩埚下降法生长及光谱性能研究

本文应用坩埚下降法技术在全密封铂金坩埚条件下生长了不同Pr³⁺离子掺杂浓度的高质量LiLuF₄单晶. 测定了单晶体从420 nm至500 nm的激发光谱. 在446 nm光激发下,观察到单晶体480 nm(³P₀→³H₄)蓝色发射带、522 nm(³P₁→³H₅)绿色发射及605 nm(¹D₂→³H₄)的红色发射,其对应的平均寿命分别为38.5、37.3和36.8 μs. 其荧光寿命明显大于Pr³⁺掺杂的氧化物单晶. 同时研究了激发波长和掺杂浓度对发射强度以及色度坐标的影响. 获得最佳的Pr³⁺浓度为∽0.5 mol%,并分析了环境温度从298 K 到443 K变化对荧光强度的影响. 结果表明随着温度的增加,荧光强度逐步变弱,其中³P₀→³H₄(480 nm)能级跃迁受温度影响最大,其次是³P₁→³H₅和¹D₂→³H₄.     

钨酸钇钠晶体中Tm3+的光谱特性

测量了Tm³⁺:NaY(WO4)₂晶体的吸收光谱、发射光谱和激发光谱，利用J_O理论计算了钨酸钇钠晶体的强度参数：Ω₂=7.21304×10^-20cm²，Ω4=0.504766×10^-20cm²，Ω6=0.977784 ×10^-20cm²，以及Tm³⁺光学参数包括各能级的荧光寿命和荧光分支     

Er3+/Yb3+共掺碲钨酸盐玻璃的光谱性质和热稳定性的研究

制备了Er³⁺和Yb³⁺共掺的碲钨酸盐玻璃样品65TeO₂-25 WO₃-10R_mO_n(R_mO_n=PbO,BaO),(65+x)TeO₂-(25-x)WO ₃-10La₂O₃ (x=0,5,10), (60+x)TeO₂-(30 -x)WO₃-10Bi₂O₃ (x=0,5,10).测试了玻璃样品的吸收光谱、荧光光谱、能级寿命及热稳定性能.结果表明除含Bi ₂O₃的碲钨酸盐玻璃外，其余玻璃样品均没出现析晶开始温度(T_x)，说明碲钨酸盐 是一种适合于光纤拉制的玻璃基质材料.应用Judd-Ofelt理论计算了强度参数Ω_t(t=2, 4,6)，研究表明Ω₂在碲钨酸盐玻璃中主要受到Er-O键的共价性的影响，而Er^{3 +} 离子周围配位场的非对称性影响可以忽略.测得了Er³⁺在15 μm发射谱的荧光 半高宽 (FWHM=71—77nm)和Er³⁺的⁴I_13/2能级寿命 (τ^m=3—34 ms).应用McCumber理论计算了Er³⁺在15 μm处的受激发射截面(σ^peak=068—103×10^-20 cm²).比较了Er³⁺在不同玻璃基质里 的15 μm荧光带宽和发射截面，研究结果表明碲钨酸盐玻璃是一种制备宽带光纤放大器的理想基质材料.     

锶原子互组跃迁谱的实验研究

观测了热原子束中锶原子(5s²)¹S₀—(5s5p)³P₁ 互组跃迁的荧光谱和饱和荧光谱, 实验测定了不同的参量下 ⁸⁸Sr(5s²)¹S₀—(5s5p)³P₁ 互组跃迁荧光谱. 研究结果表明: 不同的实验参数(温度、激光光强、激光扫描频率)对谱线有较大的影响, (5s5p)³P₁态的长寿命特点导致谱线强度随激光扫描频率呈倒数关系变化; 由于Doppler增宽, 渡越增宽等因素的影响, 谱线线宽远大于其自然线宽且随激光扫描频率呈正比关系变化.     

Radiative lifetime measurements of odd-parity high-excited levels of Sn I by time-resolved laser spectroscopy

Natural radiative lifetimes of five higher-lying odd-parity levels 5p7s ³P₁^o, 5p5d ¹P₁^o, 5p6d ³F₂^o, ³D₁^o and ³F₃^o in neutral tin are measured by the time-resolved laser-induced fluorescence (TR-LIF) technique and the atomic beam method. All these lifetimes are not longer than 100 ns and they are found to be shorter than the lifetimes of even-parity levels in the same energy region. The results reported in this paper provide important transition parameters for highly-excited atomic Sn, which may be useful for theoretically calculating excited heavy atoms.     

Synthesis and Fluorescence Properties of Lanthanide (III) Perchlorate Complexes with Bis(benzoylmethyl) Sulfoxide

A ligand with two carbonyl groups and one sulfinyl group has been synthesized by a new method and its several lanthanide (III) complexes were synthesized and characterized by element analysis, molar conductivity, coordination titration analysis, IR, TG-DSC, ¹H NMR and UV spectra. The results indicated that the composition of these complexes is REL₅(ClO₄)₃·3H₂O (RE = La(III), Pr(III), Eu(III), Tb(III), Yb(III), L = C₆H₅COCH₂SOCH₂COC₆H₅). The fluorescent spectra illustrate that both the Tb (III) and Eu (III) complexes display characteristic metal-centered fluorescence in solid state, indicating the ligand favors energy transfer to the excitation state energy level of them. However, the Tb (III) complex displays more effective luminescence than the Eu (III) complex, which is attributed to especial effectively in transferring energy from the average triplet energy level of the ligands (T) onto the excited state (⁵D₄) of Tb (III) than that (⁵D₀) of Eu (III), showing a good antenna effect for Tb(III) luminescence. The phosphorescence spectra and the relationship between fluorescence lifetimes and fluorescence intensities were also discussed.     

Radiative lifetimes,branching ratios and absolute transition probabilities of atomic uranium by delayed photoionization measurements

Radiative lifetimes of ten even-parity energy levels of atomic uranium in the 15,500–19,000 cm^?1 region and branching ratios of six transitions originating either from ground level (⁵L ₆ ^o ) or from lowest metastable level (⁵K ₅ ^o ) at 620.32 cm^?1 are measured employing three-step delayed photoionization technique. The lifetimes of five energy levels and branching ratios of five transitions are measured for the first time. By combining the experimentally measured values of radiative lifetimes and branching ratios, we have determined the absolute transition probabilities of six transitions of uranium and compared with those previously reported in the literature.     

Experimental transition probabilities and improved level energies in Yb III

Radiative lifetimes of nine out of the twelve 4f¹³6p levels in Yb III have been measured, seven of these for the first time. A Penning discharge lamp is introduced as a continuous plasma source, in which the lifetimes are determined with the time-resolved laser-induced fluorescence technique by pumping from metastable 5d and 6s levels. Spectra of the same source are recorded with a Fourier-transform spectrometer, which are used to derive branching fractions of the 6p and 7s levels. Combined with the lifetimes, the branching fractions are used to determine 81 experimental transition probabilities. Wavelengths of 142 Yb III transitions are measured and the uncertainties of corresponding Ritz wavenumbers are improved by an order of magnitude from the prior values. The energy of the 5d (5/2,5/2)^○ ₀ level has been shifted 144.20 cm^-1 to the higher value 45421.045 cm^-1. Much emphasis is put on data treatment and error analysis. Electronic supplementary material Supplementary Online Material     

The Studies of Enhanced Fluorescence in the Two Novel Ternary Rare-Earth Complex Systems

Two novel ternary rare-earth complexes SmL₅·L^’·(ClO₄)₂·7H₂O and EuL₅·L^’·(ClO₄)₂·6H₂O (the first ligand L = C₆H₅COCH₂SOCH₂COC₆H₅, the second ligand L^’ = C₆H₄OHCOO⁻) were synthesized and characterized by element analysis, molar conductivity, coordination titration analysis, IR, TG-DSC, ¹HNMR and UV spectra. The detailed luminescence studies on the rare-earth complexes showed that the ternary rare-earth complexes presented stronger fluorescence intensities, longer lifetimes, and higher fluorescence quantum efficiencies than the binary rare-earth materials. After the introduction of the second ligand salicylic acid group, the relative emission intensities and fluorescence lifetimes of the ternary complexes LnL₅·L^’·(ClO₄)₂·nH₂O (Ln = Sm, Eu; n = 7, 6) enhanced more obviously than the binary complexes LnL₅·(ClO₄)₃·2H₂O. This indicated that the presence of both organic ligand bis(benzoylmethyl) sulfoxide and the second ligand salicylic acid could sensitize fluorescence intensities of rare-earth ions, and the introduction of salicylic acid group was a benefit for the fluorescence properties of the ternary rare-earth complexes. The fluorescence spectra, fluorescence lifetime and phosphorescence spectra were also discussed.     

Radiative lifetimes of some excited CoI states

The lifetimes of atomic CoI states have been determined using the delayed coincidence technique. A tunable dye laser pumped by a nitrogen laser was employed for the excitation of cobalt atoms in an atomic beam. The lifetimes were derived from the time dependent fluorescence intensity of the observed lines after the excitation. For the measurement of the lifetimes of thee ⁴ F _9/2,f ⁴ F ^9/2 andf ⁴ F _7/2 levels a two step excitation was applied. In case of overlapping measurement we find our results to be in good agreement with those reported by Becker [1].     

Nonradiative decay from 5d states of rare earths in crystals

Nonradiative decay from 4f^n?1 5d states was investigated for trivalent rare earths in Y₃Al₅O₁₂. The rates of both 5d→4f and 5d→5d transitions were determined from measurements of the lifetimes and intensities of 5d fluorescence from Ce³⁺ and Pr³⁺. Because of the stronger ion-lattice coupling, nonradiative decay rates for transitions involving 5d states are much faster than those between 4f states. Decay rates are dependent upon the temperature and the energy gap to the next-lower level. The temperature dependences of the 5d fluorescence lifetimes from 77 to 700°K are reported.     

Radiative lifetimes of superradiant populated Ba Rydberg levels

Radiative lifetimes of 6s7f¹F₃, as8f¹F₃, and 6s9d¹D₂ Ba Rydberg levels were measured in an atomic beam by time resolved recording of the exponential decay of the fluorescence. The excitation was performed by use of two pulsed dye lasers and a superradiant emission or a superradiant cascade controlled by a cavity.     

Energy transfer in europium doped yttrium vanadate crystals

The absorption, fluorescence and excitation spectra and fluorescence lifetimes were obtained at temperatures from 8 K to room temperature, for single crystals of yttrium vanadate doped with several concentrations of europium. A model is proposed to explain the luminescence properties of YVO₄ crystals based on transitions within the VO^3-₄ ion. The host sensitized energy transfer in YVO₄: Eu³⁺ is explained by amodel based on thermally activated exciton migration. The model predicts the observed temperature and concentration dependences for the fluorescence intensities and lifetimes. The diffusion coefficient, diffusion length, exciton hopping time and trapping rate are determined and compared with similar data obtained on other systems.     

Enhanced luminescence of rare-earthTb (III) by Tm (III) in bis(benzoylmethyl) sulfoxide complexes and intra-molecular energy transfer

Rare-earth complexes [(Tb_xTm_y)L₅(ClO₄)₂](ClO₄)·3H₂O(x:y=1.000:0.000, 0.999:0.001, 0.995:0.005, 0.990:0.010, 0.950:0.050, 0.900:0.100, 0.800:0.200, 0.700:0.300; L=C₆H₅COCH₂SOCH₂COC₆H₅) were synthesized and characterized with elemental analysis, infrared spectra (IR) and ¹H NMR. The photophysical properties of these complexes were studied in detail with ultraviolet absorption spectra, fluorescent spectra and lifetimes. The fluorescence spectra and decay curves of complexes indicated that the fluorescence emission intensity was enhanced and the fluorescence lifetime was prolonged by Tm (III), which may be due to the intra-molecular energy transfer between inert rare-earth ions and active rare-earth ions. The complexes showed the best properties when the mole ratio of Tb (III) to Tm (III) is 0.995:0.005. The intensity of fluorescence can be increased to 208%. Additionally, the energy-transfer mechanisms between the ligand and the central Tb (III) ions were discussed.