结构自还原效应对铋掺碱土金属硅磷铝硼玻璃超宽带近红外发光的影响

本文报道了结构自还原对铋掺杂碱土金属硅磷铝硼玻璃超宽带近红外发光性质的影响. 以Eu作为对比, 在空气气氛中采用高温熔融法分别制备了Eu₂O₃和Bi₂O₃掺杂的35SiO₂-25AlPO₄-12.5Al₂O₃-12.5B₂O₃-15RO(R=Ca,Sr,Ba) 玻璃. 结果证实该玻璃中可发生Eu³⁺→Eu²⁺的高温自还原现象, 且随着碱土金属离子半径增大Eu²⁺ 的自还原性减弱; 同样条件下Bi位于1300 nm波段的近红外发光却随之增强, 而位于1100 nm波段近红外发光和源于Bi²⁺的红光则减弱. 根据结构自还原机理及碱土离子半径变化对玻璃近红外超宽带发光性质的影响, 讨论了Bi离子的近红外发光中心的归属. 上述研究表明玻璃结构自还原特性可以为Bi近红外发光机理研究以及高效Bi掺杂超宽带近红外发光玻璃的设计提供一种有效的思路和方法. 关键词： 玻璃 铋掺杂 近红外发光 自还原效应     

非晶态锂离子导体B2O3-0.7Li2O-0.7LiCl-xAl2O3-0.1V2O5的电学性质和电子自旋共振研究

对两种非晶态B₂O₃-0.7Li₂O-0.7LiCl-xAl₂O₃-0.1V₂O₅(x=0.05和0.15),用差热分析、电导率测量、X射线衍射和电子自旋共振进行研究,发现:1)V₂O₅不仅作非晶网络形成剂,而且改变了晶化过程;2)对B₂O₃-Li_{2关键词：}     

非晶态锂离子导体B2O3-0.7Li2O-0.7LiCl-xAl2O3

木文研究了Al₂O₃对B₂O₃-0.7Li₂O-0.7LiCl非晶态的形成和电学性能的影响,我们发现:加入适量的Al₂O₃后,无需借助液氮骤冷技术,直接将熔体倾倒在室温下的紫铜板上就很容易形成大块非晶锂离子导体B₂O₃-0.7Li₂O-0.7LiCl-xAl₂O₃。Al₂O₃的加入使B₂O₃-0.7Li₂O-0.7LiCl的电导率有所降低,但在高温下不太明显,电导激活能略微升高,实验发现:Al₂O₃含量x=0.03是较合适的剂量,较容易形成大块非晶态,对电导率的影响也不大。 关键词：     

Eu3+掺杂Bi2O3-PbO-B2O3-ZnO玻璃光谱性质

用高温融熔法制备了Eu³⁺掺杂浓度为1%的(60-x)Bi₂O₃xPbO30B₂O₃10ZnO(x=0,10,30,摩尔分数)玻璃.测定了玻璃的差热分析曲线、吸收光谱、声子边带谱、发射光谱与激发光谱.由发射光谱与稀土Eu³⁺离子光学跃迁矩阵元的特点,计算了Eu³⁺光学跃迁的J-O参数Ω₂与Ω₄.结果显示强度参数Ω₂随着PbO量的增加而略减少,表明材料的对称性略增加,Eu—O键强减弱,共价性降低.PbO组分的增加,使玻璃的结晶起始温度与软化温度差降低,导致玻璃的热温度性变差.随着PbO的增加,电-声子耦合减弱.     

B2O3含量对掺铒碲铌酸盐玻璃光谱性质及热稳定性影响

制备了一系列碲铌酸盐玻璃85TeO₂-(15-x)Nb₂O₅-xB₂O₃-1%Er₂O₃(TNBx=0, 3, 6, 9, 12, 15).根据Judd-Ofelt(J-O)和McCumber理论,讨论和分析了B₂O₃含量对掺铒碲铌酸盐玻璃热稳定性及光谱性质影响.研究发现,玻璃开始析晶温度和玻璃转变温度差值ΔT(T_x-T_g),J-O强度参数,FWHM和峰值受激发射截面的乘积在B₂O₃引入摩尔分数为9%时达到最大值.同时,Er³⁺:⁴I_13/2能级寿命也随着B₂O₃含量的增加而单调增加.结果表明,在掺铒碲铌玻璃中,适量的B₂O₃能较好地提高玻璃的热稳定性能和Er³⁺离子的光谱性质.     

Ce3+掺杂SiO2-Al2O3-Gd2O3玻璃的闪烁性能

通常, Ce离子掺杂的低密度玻璃有较高的发光效率, 而高密度的Ce离子掺杂玻璃其发光效率很低. 为了解释这一现象, 采用高温熔融法获得了SiO₂-Al₂O₃-Gd₂O₃三元系统的玻璃形成区, 并在还原气氛下制备了Ce³⁺掺杂SiO₂-Al₂O₃-Gd₂O₃以及SiO₂-Al₂O₃-Gd₂O₃-Ln₂O₃ (Ln=Y, La, Lu)闪烁玻璃, 研究了其光谱和闪烁性能. 测试结果显示: 随着Gd₂O₃含量增加, 玻璃紫外截止波长发生红移, 荧光强度降低, 衰减时间缩短; 加入Lu₂O₃, La₂O₃, Y₂O₃后, 紫外截止波长发生红移, 荧光强度降低, 衰减时间变短; 当Gd₂O₃超过10% mol时, X射线荧光积分光产额从相当于锗酸铋 晶体的61%降低到13%. 荧光强度降低、衰减时间缩短的原因是随着玻璃的紫外截止波长红移玻璃的能带宽度变窄, 使得Ce³⁺离子的d电子轨道开始接近玻璃的导带, Ce³⁺离子受辐射后跃迁到d电子轨道的电子会通过导带与玻璃中的空穴复合, 产生电荷迁移猝灭效应.     

B2O3-Na2O-CaO-SiO2玻璃结构的拉曼光谱研究

制备了B₂O₃-Na₂O-CaO-SiO₂四元系若干玻璃样品,通过实验拉曼光谱和量子化学从头计算相结合的方法,对其微观结构进行了定性定量研究。结果表明,随着B₂O₃的加入,硅酸盐转变为硼硅酸盐结构。当质量比CaO/SiO₂=1时,B主要以[BO₃]的形式参与网络形成,并在B₂O₃含量为6 Wt%时迹象明显。拉曼光谱精细结构解谱的结果表明,B的加入使结构复杂化,体系中Q₁相对含量减少,Q₃相对含量增加,整体由以Q₂为主变为以Q₂、Q₃为主。     

非晶锂离子导体B2O3-0.7Li2O-0.7LiCl-xAl2O3晶化初期的核磁共振研究

通过真空密封热处理、避免了样品晶化后吸水引起的误差,采用脉冲法在293K和77K测量了晶化过程初期三种非晶锂离子导体B₂O₃-0.7Li₂O-0.7LiCl-xAl₂O₃(x=0.15,0.10和0.05)的⁷Li核磁共振谱。发现在低温(77K)只有固相锂离子对应的自旋-自旋弛豫时间T₂=87μs,严格按高斯函数衰减。在室温下固相锂离子对应的T_2s=127μs,仍是高斯型;但液相锂离子对应的T₂却按洛仑兹函数衰减。这反映出锂离子导体的固-液二相性。三种非晶B₂O₃-0.7Li₂O-0.7LiCl-xAl₂O₃(x=0.15,0.10和0.05)分别在热处理温度401,388和381℃附近,其液相锂离子对应的T_2l都剧增,其吸收谱线宽都变窄。由此再次验证了非晶母体与微晶之间的两相界面效应的物理图象。 关键词：     

光学碱度对Tb3+掺杂Bi2O3-B2O3玻璃发光性能的影响

采用熔融法制备了Tb³⁺掺杂的Bi₂O₃-B₂O₃系统玻璃,使用激发、发射及拉曼光谱分析了光学碱度与玻璃结构及发光性能的关系,同时绘制了Tb³⁺、Bi³⁺和Bi²⁺的能级图。研究结果表明：Tb³⁺掺杂的Bi₂O₃-B₂O₃玻璃由[BO₃]、[BiO₃]、[BO₄]及[BiO₆]共同组成,且随着光学碱度由0.63增加到0.93,玻璃的结构逐渐疏松。高的光学碱度使部分Bi³⁺变为Bi²⁺,发出571 nm（²P_3/2（2）→²P_1/2）的光,Bi³⁺→Tb³⁺的能量降低。在光学碱度及Tb³⁺、Bi³⁺和Bi²⁺离子的共同作用下,随着光学碱度的提高,玻璃的发光颜色由黄绿色变为白色。     

Er3+/Yb3+共掺杂铋酸盐玻璃的上转换发光和能量传递

用高温熔融法制备了Er³⁺/Yb³⁺共掺杂的45Bi₂O₃-45GeO₂-10PbO玻璃,对玻璃样品进行了光谱测试,分析了上转换发光机制和Yb³⁺→Er³⁺的能量传递效率。通过Yb³⁺离子浓度对Er³⁺离子在铋酸盐玻璃中的上转换荧光强度影响的研究,得到Er³⁺质量分数为0.5%以及Yb³⁺质量分数为2.5%时上转换发光强度最大。研究结果表明,在970nm泵浦激发下,Er³⁺/Yb³⁺共掺杂B₄₅G₄₅P₁₀玻璃在532,545,673nm处产生较强的上转换绿光和红光,是一种较为理想的上转换发光基质材料。     

Bi离子掺杂GeO2-Al2O3-M(M=Na2O，BaO，Y2O3)玻璃的光学性质

用高温熔融法制备了Bi离子掺杂浓度为1mol%的GeO-B₂O₃-Na₂O (GBNB)，GeO₂-Al₂O₃-Na₂O(GANB)，GeO₂-Al₂O₃-BaO(GABB)和GeO₂-Al₂O₃-Y₂O₃(GAYB)玻璃.测定了样品玻璃的差热曲线、吸收、发射光谱及荧光衰减曲线.实验发现GBNB，GANB，GAYB，GABB的吸收边带逐步发生红移.由于这些吸收边带是由Bi³⁺的6s²电子到Bi⁵⁺ 6s⁰空轨道的跃迁引起.因此推断GBNB，GANB，GAYB，GABB玻璃中Bi⁵⁺离子的含量逐步增加.在GABB，GAYB，GANB三个样品中观察到发光中心约1220nm超宽带荧光发射.荧光强度从GABB，GAYB，GANB逐步减弱，荧光半高宽和荧光寿命逐步变小.这些超宽带的荧光归属为Bi⁵⁺离子的发光所致.从吸收与荧光光谱的变化，推断在GeO₂-Al₂O₃玻璃中引入BaO，Y₂O₃组分有利于Bi⁵⁺离子的形成.讨论了BaO，Y₂O₃化学组分对Bi离子在玻璃中的价态影响的内在机理. 关键词： 5+离子')" href="#">Bi⁵⁺离子 超宽带发光 吸收带 荧光寿命     

掺铋离子BaO-B2O3玻璃的制备及其近红外发光性能的研究

采用高温熔融法制备了掺Bi离子的BaO-B₂O₃玻璃, 测定了样品玻璃的近红外以及可见光区的激发、 发射谱、 荧光衰减曲线以及Raman光谱. 在808 nm波长光的激发下, 在掺Bi离子的BaO-B₂O₃玻璃中发现了近红外发光现象, 且存在多个发光峰, 讨论了玻璃网络结构对Bi离子发光的影响, 对其发光机理进行了初步的探讨.     

Effect of Bi2O3 content on physical and optical properties of 15Li2O-15K2O-xBi2O3-(65−x) B2O3: 5V2O5 glass system

Multi-component bismuth borate glasses doped with vanadium ions 15Li₂O-15K₂O-xBi₂O₃-(65−x) B₂O₃: 5V₂O_5, (x=3, 5, 7, 10, 12 and 15) have been prepared using conventional melt quench technique. Characterization of the prepared glasses has been done using X-ray diffraction, differential scanning calorimetry and density measurements. The effect of Bi₂O₃ content on the optical properties of the present glass system is studied from the optical absorption spectra recorded in the wavelength range 200-800 nm. The fundamental absorption edge has been identified from the optical absorption spectra. The values of optical band gap for indirect allowed transitions have been determined using available theories. The origin of the Urbach energy is associated with the phonon-assisted indirect transitions. The density and molar volume studies indicate that Bi₂O₃ in these glasses is acting partly as network modifier and partly as network former. The variations in the optical band gap energies, density and molar volume with Bi₂O₃ content have been discussed in terms of changes in the glass structure. Values of the theoretical optical basicity, average crosslink density and the average electronic polarizability are also reported.     

The structural properties of CdO-Bi2O3 borophosphate glass system containing Fe2O3 and its role in attenuating neutrons and gamma rays

A glass system with chemical formula xBi₂O₃-(30−x)CdO-10B₂O₃-20Fe₂O₃-40P₂O₅ (0≤x≤30) wt% is prepared to be used as radiation shield. The mass attenuation coefficient and half value layer of the glass system to gamma rays have been measured experimentally and compared with those determined from theoretical calculations using the mixture rule of WinXCom program. A database of effective mass removal cross-sections for fast neutrons is also introduced in this work. The obtained results of this study are correlated to the structural properties of these glasses obtained from their IR spectra and the influence of gamma and neutrons irradiation on these structural properties.     

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.     

Writing of two-dimensional crystal curved lines at the surface of Sm2O3-Bi2O3-B2O3 glass by samarium atom heat processing

Two-dimensional crystal curved lines consisting of the nonlinear optical Sm_xBi_1−xBO₃ phase are fabricated at the surface of 8Sm₂O₃·37Bi₂O₃·55B₂O₃ glass by continuous wave Nd:YAG laser (wavelength: 1064 nm) irradiation (samarium atom heat processing) with a power of ∼0.9 W and a laser scanning speed of 5 μm/s. The curved lines with bending angles of 0-90° or with sine-shapes are written by just changing the laser scanning direction. The polarized micro-Raman scattering spectra for the line after bending are the same as those for the line before bending, indicating that the crystal plane of Sm_xBi_1−xBO₃ crystals to the crystal growth direction might be maintained even after the change in the laser scanning direction. It is found from laser scanning microscope observations that the crystal lines at the surface are swelled out smoothly, giving a height of about 10 μm.     

PbO–Bi2O3–Ga2O3–BaO glasses doped by Er as novel materials for IR emission

Infra-red luminescence (at wavelengths about 1600 and 2500 nm) from Er³⁺ ions embedded in PbO–Bi₂O₃–Ga₂O₃–BaO glass hosts is reported for room and helium liquid temperatures. The substantial influence of energy transfer processes between the host and Er³⁺ ions is shown experimentally through the dependences of photoluminescence on light polarization and excitation wavelength. Only the application of the polarized pumping YAG–Nd laser beam (λ=1060 nm) stimulates substantial luminescence with quantum efficiency up to 24%. The role of phonon-relaxation subsystem in the observed luminescence is discussed.     

IR and Raman investigation on the structure of (100-x)B2O3-x[0.5 BaO-0.5 ZnO] glasses

Glasses with molar composition of (100-x)B₂O₃-x[0.5 BaO-0.5 ZnO], x=40, 50, 60, 70 were prepared from the melts of ZnO, BaCO₃ and H₃BO₃ mixture. The structure and thermal behavior were characterized by IR and Raman spectroscopy, DSC and Dilatometer. The investigation shows that the transition of the structural unit [BO₄] (B^IV) to [BO₃] (B^III) happens when BaO and ZnO content x increases in the borate glass, resulting in fewer B^III-O-B^IV bonds and more B^III-O-B^III bonds. At the same time, the diborate groups, which are found to be the predominant structural group of the glass with high B₂O₃ content, gradually changes into ring-type metaborate, pyro- and orthoborate groups. With increasing ZnO and BaO content x, the glass transition temperature (T_g) and the softening point (T_f) decreases, while linear expansion coefficient (α) increases, that comes from the weakening of the glass network.     

Comparative study of thermal stability and crystallization kinetics of 70B2O3-30Bi2O3 and 70B2O3-30PbO glasses

Glasses with compositions 70B₂O₃-30Bi₂O₃ and 70B₂O₃-30PbO have been prepared and studied by differential thermal analysis (DTA). The crystallization kinetics of the glasses were investigated under non-isothermal conditions. From the dependence of glass-transition temperature (T_g) on heating rate, the activation energy for the glass transition was derived. Similarly the activation energy of the crystallization process was determined. Thermal stability of these glasses were achieved in terms of the characteristic temperatures, such as glass-transition temperature, T_g, onset temperature of crystallization, T_in, temperature corresponding to the maximum crystallization rate, T_p, beside the kinetic parameters, K(T_g) and K(T_p). The results revealed that 70B₂O₃-30PbO is more stable than 70B₂O₃-30Bi₂O₃. The crystallization mechanism is characterized for both 70B₂O₃-30Bi₂O₃ and 70B₂O₃-30PbO glasses (kinetic exponent n=2.06 for 70B₂O₃-30Bi₂O₃, and n=3.03 for 70B₂O₃-30PbO). The phases at which the glass crystallizes after the thermal process were identified by X-ray diffraction.