GeO2-Bi2O3-MOx(MOx=WO3, BaO)玻璃近红外超宽带发光的研究

用高温熔融法制备了(99.5-χ) GeO₂-χBaO-0.5Bi₂O₃(χ=3, 6, 9mol%)与(99.5-φ)GeO₂-φWO₃-0.5Bi₂O₃(φ=3，6，9mol%)玻璃，测定了样品的发射光谱(800nmLD激发)、吸收光谱、荧光衰减和差热曲线.实验结果表明，在GeO₂-WO₃-Bi₂O₃系统玻璃中，随着WO₃含量的增加，在1260nm处的发光强度增强，荧光半高宽(FWHM)增宽，荧光寿命增长，而且玻璃的吸收边带发生明显的红移；在GeO₂-BaO-Bi₂O₃系统玻璃中，随着BaO含量的增加，玻璃在1290nm处发光强度增强，FWHM增宽，荧光寿命增长，吸收边带也有明显的红移.从吸收边带发生红移的情况，结合发射光谱和荧光衰减曲线特性，我们推断玻璃样品在近红外的宽带发光可能由Bi⁵⁺离子所引起.从荧光特性估算了玻璃的σ_p×τ和σ_p×Δλ值，这些玻璃均具有较小的σ_p×τ和较大的σ_p×Δλ特性，说明GeO₂-Bi₂O₃-MO_x(MO_x=WO₃, BaO) 系统玻璃是研制成近红外(O到S波段)超宽带光纤放大器的良好材料.     

抗癌药物铂络合物构效关系的物理方法研究

本文用X射线衍射、傅里叶变换红外光谱、差热分析等物理方法研究了抗癌药物铂络合物特性、结构以及构效关系。研究结果表明:cis-[Pt(NH₃)₂Cl₂]属简单斜方晶系,晶格常数a=0.9221nm,b=0.8771nm,c=0.6890nm.草酸二氨合铂的结构为斜方晶系,其晶格常数为:a₁=1.0721nm,a₂=0.6402nm,a₃=1.8570nm,并用傅里叶变换红外光谱、差热分析、元素分析等方法对它们理化特性进行了研究.     

Tm3+/Yb3+共掺碲酸盐玻璃的近红外发光及能量传递机理

采用高温熔融法制备了组分为TeO₂-ZnO-Na₂O的Tm³⁺离子单掺和Tm³⁺/Yb³⁺共掺碲酸盐玻璃,应用Judd-Ofelt理论计算分析了玻璃样品的强度参量Ω_t(t=2, 4, 6),自发辐射跃迁几率A,荧光分支比β和荧光辐射寿命τ_rad等光谱参量,测量得到了不同Yb³⁺离子掺杂浓度下玻璃样品的Tm³⁺离子上转换发光谱.结果显示,在980 nm泵浦光激励下玻璃样品发射出强烈的近红外上转换荧光.对Tm³⁺离子上转换发光分析表明,强烈的Tm³⁺离子近红外上转换发光主要来自于Yb³⁺/Yb³⁺离子间的共振能量传递以及基于单声子和双声子辅助的Yb³⁺/Tm³⁺离子间的非共振能量传递过程,并进一步计算得到了声子贡献比和能量传递系数.最后,计算分析了Tm³⁺:³F₄→³H₆能级间跃迁的1.8 μm波段吸收截面、受激发射截面和增益系数.研究表明,Yb³⁺/Tm³⁺共掺TeO₂-ZnO-Na₂O玻璃可以作为近红外波段固体激光器的潜在增益基质.     

Wn(n=3—27)原子团簇结构的第一性原理计算

使用密度泛函理论下的第一性原理方法，对W_n原子团簇(n=3—27)的结构特性进行了理论计算. 得到了W_n团簇(n=3—7)的最低能量结构和(n=8—27)的局域能量极小的典型结构. 使用凝胶模型，提出的电子组态1s²1p⁶1d¹⁰2s²1f¹⁴2p⁶3s     

基质发光材料Na5Eu(MoO4)4和NaEu(MoO4)2的制备和发光

本文研究了化学计量的基质发光材料Na5Eu(MoO4)4和NaEu(MoO4)2.它们都属于四方晶系,空间群为I41/α .NaEu(Mo04)2属于白钨矿(scheelite)结构,一个晶胞中有2个分子式NaEu(MoO4)2(z=2);而Na5Eu(Mo4O)4属于类自钨矿(scheelite-like)结构,一个晶胞中有4个分子式Na5Eu(MoO4)4(z=4).X射线衍射确定的晶胞常数,对Na5Eu(MoO4)4,α=1.1439nm和c=1.1486nm(密度d计算=4.01g/cm3,z=4);对NaEu(MoO4)2,α=0.5236nm和c=1.1439nm(密度d计算=5.24g/cm3,z=2).由差热法和X射线衍射法确定了Na2MoO4-Eu2(MoO4)3的相图.Na5Eu(MoO4)4分解为NaEu(MoO4)2的温度是700℃.本文确定了制备纯 Na5Eu(MoO4)和NaEu(MoO4)2的方法,并研究了上述两种材料的激发光谱和发光光谱.确定了用X射线粉末衍射谱和发光光谱鉴别Na5Eu(MoO4)4和NaEu(MoO4)2的方法.在365nm紫外光激发下,Na5Eu(MoO4)4的发光比Na5Eu(WO4)4的强得多,在室温下,Na5Eu(MoO4)4,NaEu(MoO4)2和Na5Eu(WO4)4的相对发光积分亮度比为3.8:3.2:1.0.     

激光诱导荧光光谱识别动脉粥样硬化斑块的研究

采用氩离子激光为激发光源,分别研究了离体正常动脉壁、动脉粥样硬化斑块和血液等的激光诱导荧光光谱.结果表明,正常动脉壁样品组的荧光光谱强度最大值明显高于动脉粥样硬化斑块样品组;斑块的荧光光谱在516 nm处存在一个小波谷,而正常动脉组织的荧光光谱则无此波谷;斑块组织在598 nm处与578 nm处的荧光强度比值R(I₅₉₈ nm/I₅₇₈ nm)远低于正常动脉壁的比值;血红蛋白含量是引起粥样斑块与正常动脉壁的R(I₅₉₈ nm/I₅₇₈ nm)值不同的主要原因.     

Gd2O3:Eu3+纳米晶的燃烧合成及光致发光性质

采用柠檬酸作燃烧剂用燃烧合成法制备了Gd₂O₃:Eu³⁺纳米晶.用X射线衍射仪(XRD)、高分辨透射电子显微镜(HRTEM)和荧光分光光度计等对Gd₂O₃:Eu³⁺纳米晶的结构、形貌和发光性能进行了分析.结果表明：不同柠檬酸与稀土离子配比(C/M)制备的样品经800℃ 退火1 h后，均得到了纯立方相的Gd₂O₃:Eu³⁺纳米晶，晶粒尺寸约为30 nm，尺寸分布较窄，其中以C/M=1.0时制备的纳米晶结晶性最好，发光强度最大.Gd₂O₃:Eu³⁺纳米晶主发射峰位置均在612 nm处 (⁵D₀→⁷F₂跃迁)，激发光谱中电荷迁移态发生红移，观察到Gd³⁺向Eu³⁺的有效能量传递.对柠檬酸与稀土离子配比(C/M)对结晶度、发光性质等的影响也进行了分析和讨论.     

Eu2+在xMF2-yYF3体系中光谱性质及其变化规律

合成了Eu2+激活的碱土稀土复合氟化物体系xMF2-yYF3(x=1,2,3;y=0,1,2,3,4,5;M=Ca,Sr,Ba),系统地研究了Eu2+在该体系中的光谱性质及其变化规律,讨论了影响Eu2+光谱的因素。     

Optical parameters of Nd3＋：Er3＋：yb3＋ co-doped borosilicate glasses and their energy transfers at high temperature

This paper reports that a series of Nd³⁺:Er³⁺:Yb³⁺ co-doped borosilicate glasses have been prepared and their absorption spectra measured. The J--O intensity parameters Ω_k (k=2, 4, 6), spontaneous radiative lifetime τ_rad, spontaneous transition probability A, fluorescence branching ratio β and oscillator strength f_ed of the Nd³⁺ ions at room temperature are calculated based on Judd--Ofelt (J--O) theory. The temperature dependence of the up-conversion photoluminescence characteristics in a Nd³⁺:Er³⁺:Yb³⁺ co-doped sample is studied under a 978 nm semiconductor laser excitation, and the energy transfer mechanisms among Yb³⁺, Er³⁺ and Nd³⁺ ions are analysed. The results show that the J--O intensity parameters Ω₂ increase when the Nd³⁺ concentration of the Nd³⁺:Er³⁺:Yb³⁺ co-doped borosilicate glasses increases. The possibility of spontaneous transition is small and lifetimes are long at levels of ⁴F_5/2 and ⁴F_3/2. The intensity of Nd³⁺ emissions at 595, 691, 753, 813 and 887 nm are markedly enhanced when the sample temperature exceeds 400 K. The reasons being the cooperation of the secondary sensitization from Er³⁺ to Nd³⁺ and the contribution of a multi-phonon.     

高分辨的一氧化二氮光解离实验研究

利用"时间切片"离子速度成像技术研究了N₂O分子在134.20、135.20和136.43 nm波长下的真空紫外光解动力学. 实验中通过采集解离产物O(¹S_J=0)的离子影像来研究O(¹S_J=0)+N₂(X¹∑_g⁺)这一解离通道. 从各个波长下的实验影像可获得产物N₂(X¹∑_g⁺)的振动态分辨的结构,进而得到产物的总平动能谱和产物N₂的振动态布居. 实验结果表明在实验的光解波长下,产物N₂(X¹∑_g⁺)主要布居在v=2和v=3. 此外,还得到了产物N₂的振动态分辨的各向异性参数β,从中发现产物N₂的β值在三个解离波长下均表现出相似的特征,即随着振动量子数的增大,β值从趋近于2逐渐减小至1.4. 这一现象表明低振动态产物是通过一个以平行跃迁解离为主的解离过程产生的,而高振动态的产物来自于一个更加弯曲的中间构型的解离. 此推论与在平动能谱中所见到的最强转动态布居随着振动量子数的增大而出现的位移是相一致的.     

红色LiMBO3 : Re3+(Re=Eu,Sm) 发光材料的特性

采用固相法制备了红色LiM(M=Ca, Sr, Ba)BO₃ : Re³⁺(Re=Eu, Sm)发光材料,研究了材料的发光性能。研究发现LiM(M=Ca, Sr, Ba)BO₃ : Eu³⁺材料呈现多峰发射,最强发射分别位于610,615,613 nm处,分别监测这三个最强峰,所得激发光谱峰值位于369,400,470 nm。LiM(M=Ca, Sr, Ba)BO₃ : Sm³⁺材料也呈多峰发射,分别对应Sm³⁺的⁴G_5/2→⁶H_5/2、⁴G_5/2→⁶H_7/2和⁴G_5/2→⁶H_9/2跃迁发射;分别监测602,599,597 nm三个最强发射峰,所得激发光谱峰值位于374,405 nm。研究了激活剂浓度对材料发射强度的影响,结果随激活剂浓度的增大,发射强度先增强后减弱,即,存在浓度猝灭效应。实验表明,加入电荷补偿剂Li⁺、Na⁺或K⁺均可提高LiM(M=Ca, Sr, Ba)BO₃ : Re³⁺(Re=Eu, Sm)材料的发射强度。     

Sol-gel synthesis, structural and optical properties of rare earth ions (Sm or Dy) activated Ca3Ga2Si3O12 powder phosphors

Structural, morphological and optical properties of rare earth ions (RE³⁺=Sm³⁺ or Dy³⁺) activated Ca₃Ga₂Si₃O₁₂ (CaGaSi) phosphors synthesized by the sol-gel method are reported. XRD results confirmed the cubic phase structure of RE³⁺:CaGaSi phosphors. From the SEM images of RE³⁺:CaGaSi phosphors, it is observed that the particles are agglomerated. Photoluminescence spectra of Sm³⁺:CaGaSi phosphors have shown bright orange red emission at 598 nm (⁴G_5/2→⁶H_7/2) with an excitation wavelength of λ_exci=401 nm. In the case of Dy³⁺:CaGaSi phosphors bright yellow emission has been observed at 574 nm (⁴F_9/2→ ⁶H_13/2) with λ_exci=451 nm. From the PL spectral results, the rare earth ion concentration of CaGaSi phosphors is optimized.     

The kinetic limitation of anti-stokes luminescence of Er3+ and Yb3+ doped infrared upconversion materials

Infrared-to-visible wave-length conversion in the Yb³⁺−Er³⁺ doped phosphors system has been described by a simple three level model based on two ions mechanism. The excitation in the range of 900–1000 nm of an IR-photon is first absorbed by Yb³⁺ ion as a sensitizer attributed to the resonant energy transition in Er³⁺ ion from ⁴ I _3/2 → ⁴ S _15/2 and ¹ F _9/2 → ⁴ I _15/2, respectively for green and red emission. The essential energy transfer processes in this system i.e. upconversion from ⁴ I _11/2 and ¹ I _13/2, cross-relaxation from ⁴ S _3/2 and ¹ F _9/2 are taken into account. The limitations of the rate-equation approach are examined with a focus on the underlying dynamics of this rare-earth system.     

Synthesis and up-conversion luminescence properties of Ho3+, Yb3+ co-doped BaLa2ZnO5

Up-conversion phosphors BaLa₂ZnO₅ co-doped with Ho³⁺/Yb³⁺ were synthesized by high temperature solid-state reaction method. The phase composition of the phosphors was characterized by X-ray diffraction (XRD). The structure of BaLa₂ZnO₅: 0.75% Ho/15% Yb phosphor was refined by the Rietveld method and results showed the decreased unit cell parameters and cell volume after doping Ho³⁺ and Yb³⁺, indicating Ho³⁺ and Yb³⁺ have successfully replaced La³⁺. Under the excitation of 980 nm diode laser, the strong green and weak red up-conversion emissions centered at 548 nm, 664 nm and 758 nm were observed, which originating from ⁵S₂, ⁵F₂→⁵I₈, ⁵F₄→⁵I₈ and ⁵S₂, ⁵F₂→⁵I₇ transitions of Ho³⁺ ions, respectively. The optimum doping concentrations of Ho³⁺ and Yb³⁺ were determined to be 0.75% and 15%, and the corresponding Commission International de L'Eclairage (CIE) coordinates are calculated to be x=0.298 and y=0.692. The related UC mechanism of Ho³⁺/Yb³⁺ co-doped BaLa₂ZnO₅ depending on pump power was studied in detail. The results indicate that BaLa₂ZnO₅: Ho³⁺/Yb³⁺ can be an effective candidate for up-conversion yellowish-green light emitter.     

Mechanoluminescence Study of Europium Doped CaZrO<Subscript>3</Subscript> Phosphor

Behaviour displayed by mechanoluminescence (ML) in CaZrO₃:Eu³⁺ doped phosphors with variable concentration of europium ions are described. When the ML is excited impulsively by the impact of a load on the phosphors the ML intensity increases with time, attains a maximum value and then it decreases. In the ML intensity versus time curve, the peak increases and shifts towards shorter time values with increasing impact velocities. Sample was synthesized by combustion synthesis method with variable concentration of Eu³⁺ ions (0.1, 0.2, 0.5, 1, 1.5 mol%) and characterized by X-ray diffraction technique. The total ML intensity I_T is defined as the area below the ML intensity versus time curve. Initially I_T increases with impact velocity V₀ of the load and then it attains a saturation value for higher values of impact velocities which follow the relation I_T = I_T ⁰ exp.(?V_c/V₀) where I_T ⁰ and V_c are constants. Total ML intensity increases linearly with the mass of the phosphors for higher impact velocities. The ML intensity I_m, corresponding to the peak of ML intensity versus time curve increases linearly with the impact velocities. The time t_m, is found to be linearly related to 1000/V₀. The mechanoluminescence induced by impulsive excitation in europium doped CaZrO₃ phosphors plays a significance role in the understanding of biological sensors and display device application.     

硼酸对亚微米级Ca3Sc2Si3O12:Ce绿色荧光粉的制备及发光性能的影响

采用凝胶-燃烧法合成了Ca₃Sc₂Si₃O₁₂ ∶Ce绿色LED用荧光粉,用X射线粉末衍射(XRD)、扫描电镜(SEM)、荧光光谱仪等对合成产物进行了分析和表征.结果表明:通过添加H₃BO₃做助熔剂,制得的荧光粉晶相纯正,颗粒形貌均呈现为较规则的类球形,而且所得荧光粉的粒径均小于1 μm.发射光谱呈现为一宽带,发射主峰位于505 nm,该宽峰对应于Ce³⁺关键词： 白光LED 荧光粉 3Sc₂Si₃O₁₂ ∶Ce')" href="#">Ca₃Sc₂Si₃O₁₂ ∶Ce 发光     

Synthesis and photoluminescence properties of the high-brightness Eu3+-doped Sr3Bi(PO4)3 phosphors

A series of orange reddish emitting phosphors Eu³⁺-doped Sr₃Bi(PO₄)₃ have been successfully synthesized by conventional solid-state reaction, and its photoluminescence (PL) properties have been investigated. The excitation spectra reveal strong excitation bands at 392 nm, which match well with the popular emissions from near-UV light-emitting diode chips. The emission spectra of Sr₃Bi(PO₄)₃:Eu³⁺ phosphors invariably exhibit five peaks assigned to the ⁵D₀→⁷F_J (J=0, 1, 2, 3, 4) transitions of Eu³⁺ and have dominating emission peak at 612 nm under 392 nm excitation. The luminescence intensity was enhanced with increasing Eu³⁺ content and the emission reached the maximum intensity at x=0.05 in Sr₃Bi(PO₄)₃:xEu³⁺. The energy transfer behavior in the phosphors was discussed. The Commission Internationale de lEclairage (CIE) chromaticity coordinates, the quantum efficiencies, and the decay curves of the entitled phosphors excited under 392 nm are also investigated. The experimental results indicate that the Eu³⁺-doped Sr₃Bi(PO₄)₃ phosphors are promising orange reddish-emitting phosphors pumped by near-UV light.     

共沉淀法制备Y2SiO5∶Er3+ ,Yb3+ ,Tm3+及其上转换发光性能研究

采用化学共沉淀法制备了系列Y_1.98-2xYb_2x Er_0.02SiO₅(0.00≤x≤0.15)以及Y_1.736Yb_0.24Er_0.02Tm_0.004SiO₅上转换发光材料,比较了室温下Y_1.98-2xYb_2x Er_0.02 SiO₅ (x=0.00,0.08)样品在400—1600 nm范围内的吸收光谱,测量了所有样品在976 nm OPO激光器激发下的上转换发射光谱,以及Er³⁺离子⁴S_3/2(⁴F_9/2)→⁴I_15/2,Tm³⁺离子¹G₄→³H₆荧光衰减曲线和不同激发功率下的上转换蓝光发射强度,从而分析讨论了Er³⁺,Tm³⁺在Y₂SiO₅中的上转换发光机理.研究结果表明:在1250 ℃相对较低的温度下合成了X2型单斜晶系Y₂SiO₅ ∶Ln³⁺(Ln³⁺=Er³⁺,Yb³⁺,Tm³⁺),Yb³⁺的敏化显著增强了样品在976 nm附近的吸收能力,并大幅度加宽了该处的吸收带.分析上转换发射光谱发现:上转换绿光和红光强度都随着Yb³⁺浓度的增加先增强后减弱,但红光的猝灭浓度较高,归因于Er³⁺→Yb³⁺反向能量传递ETU4和Yb³⁺→Er³⁺正向能量传递ETU3过程的发生;上转换蓝光发射是三光子吸收过程,是通过Yb³⁺,Tm³⁺之间三次声子辅助的能量转移方式实现的. 关键词： 上转换 共沉淀 2SiO₅∶Er³⁺')" href="#">Y₂SiO₅∶Er³⁺ 3+')" href="#">Yb³⁺ 3+')" href="#">Tm³⁺     

Synthesis and optical properties of Ce-doped Y3Mg2AlSi2O12 phosphors

Y_3−xMg₂AlSi₂O₁₂:Ce_x³⁺ (x=0.015, 0.03 and 0.06) phosphors possessing garnet crystal structure were synthesized by the sol–gel combustion technique. The samples were characterized by application of powder X-ray diffraction (XRD), photoluminescence (PL) spectroscopy, thermal quenching (TQ) and scanning electron microscopy (SEM). Moreover, luminous efficacies (LE), color points and quantum efficiencies (QE) were calculated. Optical properties were studied as a function of Ce³⁺ concentration and annealing temperature. XRD analysis revealed that sintering of polycrystalline Y₃Mg₂AlSi₂O₁₂:Ce³⁺ powders at 1550 °C results in nearly single-phase garnet materials. Phosphors showed broad emission band in the range of 500–750 nm and had the maximum intensity at 600 nm, which results in strongly red-shifted phosphors compared with conventional YAG:Ce phosphors emitting at 560 nm. However, strong concentration quenching has also been observed, probably due to increased Stokes shift.     

Optical Analysis of Er3+:Boro-Fluoro-Phosphate Glasses

This paper deals with the preparation and optical analysis of Er³⁺ (0.2 mol%) boro-fluoro-phosphate glasses in the following glass compositions:

• Series A: 69.8 B₂O₃–10 P₂O₅–10(ZnO/CdO/TeO₂)–10 AlF₃

• Series B: 69.8 B₂O₃–10 P₂O₅–10(ZnO/CdO/TeO₂)–10 LiF

Measured Vis-NIR absorption spectra of Er³⁺:boro-fluoro-phosphate glasses have revealed nine absorption bands at 377 nm, 405 nm, 450 nm, 486 nm, 519 nm, 543 nm, 649 nm, 973 nm and 1529 nm, which correspond with the transitions of ⁴I_15/2 → ⁴G_11/2, (²G_9/2,⁴H_9/2), ⁴F_5/2, ⁴F_7/2, ²H_11/2, ⁴S_3/2, ⁴F_9/2, ⁴I_11/2, and ⁴I_13/2, respectively. With an excitation at λ _exci = 375 nm, a bright green emission (⁴S_3/2 → ⁴I_15/2) at 547 nm has been observed from these erbium glasses. Judd–Ofelt characteristic intensity Ω_λ (λ = 2, 4, 6) parameters are obtained from the absorption spectra, and these results were used to compute the radiative properties of Er³⁺:boro-fluoro-phosphate glasses. The NIR emission (⁴I_13/2 → ⁴I_15/2) at 1547 nm from these glasses was measured with an Ar⁺ laser (514.5 nm) as an excitation source.