MF2(M=Mg,Ca,Zn,Sr,Ba)对掺Yb3+磷酸盐玻璃性质的影响

熔制了60P2O5.6Al2O3@(33-x)BaO.xBaF2.1Yb2O3(x=0,3,6,9)和60P2O5.6Al2O3.27BaO@6MF2.1Yb2O3(M=Mg、Ca、Sr、Zn、Ba)(分子分数)玻璃,测试了其折射率、密度、转变温度、析晶温度、熔点温度、红外光谱和紫外吸收光谱,讨论了二价氟化物MF2(M=Mg、Ca、Sr、Zn、Ba)对磷酸盐玻璃热稳定性及内部结构的影响,测试了Yb3+离子的吸收光谱、荧光光谱、荧光寿命,计算了光谱参数,讨论了MF2对Yb3+磷酸盐玻璃光谱性质的影响.结果表明二价金属氟化物是作为网络外体进入到磷酸盐玻璃结构中,并没有改变磷酸盐玻璃内部的[PO4]链状结构,二价金属氟化物还有助于提高Yb3+离子的受激发射截面,和自发辐射几率,荧光半高宽.     

几种重金属氧化物和GeO2的加入对掺Yb3+氟磷玻璃的光谱和激光性能的影响

实验对比研究了Ga₂O₅、TeO₂、GeO₂、WO₃、Nb₂O₅和Bi₂O₅金属氧化物的掺入对氟磷激光玻璃的光谱和激光性能的影响。结果表明, TeO₂、GeO₂和Ga₂O₅的加入增大了Yb³⁺的吸收和发射截面; 其中, 掺有TeO₂的氟磷玻璃的Yb³⁺吸收和发射截面最大, 分别达到了1.95 pm²和0.85 pm²。Ga₂O₅、Nb₂O₅和GeO₂的加入对玻璃激光性能的提高具有极大的帮助; 其中, 在掺有Ga₂O₅的氟磷玻璃中激光参数SFL值最大, 为1.237。同时发现, 在TeO₂和GeO₂掺杂氟磷玻璃中也存在严重的Yb³⁺荧光俘获现象, 大大减弱了其激光性能。     

Gd2O3下转换发光材料的制备及光学性能研究

通过溶胶-凝胶法制备了Er³⁺/Yb³⁺双掺杂的Gd₂O₃下转换发光材料,按照掺杂摩尔百分比n(Gd³⁺)∶n(Er³⁺)∶n(Yb³⁺)=100∶2:x（x=0,3,6,9）调整Yb³⁺的掺杂比例,通过XRD、SEM、荧光光谱和荧光衰减研究了Er³⁺/Yb³⁺双掺对Gd₂O₃发光材料晶体结构、微观形貌、发光性能和量子传递效率的影响。结果表明,Er³⁺/Yb³⁺的掺杂没有改变Gd₂O₃的晶体结构,但使样品的特征衍射峰出现了高角度偏移;所有样品的晶粒尺寸约为65～85 nm,均属于纳米材料;随着Yb³⁺掺杂量的增加,样品在可见光区域和近红外光区域的衍射峰强度均表现出先升高后降低的趋势,其中2Er:3Yb掺杂比例的Gd     

Ni2+掺杂尖晶石相透明微晶玻璃制备及光学性能

实验制备了Ni²⁺掺杂的ZnO-MgO-Al₂O₃-SiO₂(ZMAS)体系的透明微晶玻璃, 研究了微晶玻璃的超宽带发光现象。热分析结果表明样品的玻璃化转变温度(T_g)和析晶峰温度(T_c)分别为754℃和948℃。采用X射线粉末衍射分析了两种热处理制度对玻璃的晶体形核、晶体生长及物相变化的影响, 结果表明: 采用阶梯温度热处理制度可以得到Ni²⁺掺杂的尖晶石相透明微晶玻璃。紫外-可见吸收光谱和荧光光谱测试表明制备的Ni²⁺掺杂ZMAS微晶玻璃中Ni²⁺以四配位和六配位共同存在于尖晶石相中, 红外荧光中心位于1324 nm的样品荧光半高宽达490 nm。样品的超宽带荧光主要是由于微晶玻璃中六配位Ni²⁺在ZnAl₂O₄和MgAl₂O₄形成的尖晶石相固溶体晶体场中的³T_2g(³F)→³A_2g(³F) 能级跃迁。实验结果表明, 制备的微晶玻璃在超宽带光纤放大器等光子器件中具有潜在的应用前景。     

阳离子场强对BaO-SiO2-Ln2O3微晶玻璃结构及高温性能影响

SiO₂-BaO基微晶玻璃以其膨胀系数高、耐高性能优异而成为耐高密封领域研究的热点,但稀土氧化物对该类封接玻璃改性的影响研究尚不多见。本工作研究不同高阳离子场强(Cation field strength,CFS)的稀土氧化物取代传统碱土氧化物BaO对新型富稀土—SiO₂-BaO-Ln₂O₃(SBLn,Ln=La、Sm、Er、Yb)系列玻璃的网络结构、结晶行为、微观结构和高温性能的影响。随着稀土阳离子场强由2.82(La³⁺)增大到3.98(Yb³⁺),SBLn玻璃的玻璃转变温度(T_g)、析晶起始温度(T_x)、析晶峰值温度(T_p)均逐渐增加,说明高稀土阳离子场强有利于提高SBLn玻璃的热稳定性。四类富稀土SBLn玻璃的结晶相均由Ba Si O₃和Ba Si₂O₅相组成,随稀土阳离子场强增大,Ba Si O₃     

Yb3+,Tb3+共掺杂Sr2B2O5荧光粉的制备及其下转换发光性能的研究

采用高温固相法合成了Tb³⁺, Yb³⁺共掺杂的Sr₂B₂O₅荧光粉。通过X射线衍射(XRD)和荧光光谱(PL)对样品的物相结构和发光性质进行了表征。XRD结果表明, 合成样品为单斜结构的Sr₂B₂O₅相。分别使用543 nm和980 nm的监测波长, 得到的激发光谱均在354 nm、374 nm处有较强的激发峰, 其中374 nm处最强, 说明Sr₂B₂O₅荧光材料在近紫外光区对太阳光有很强的吸收; 在374 nm( Tb³⁺:⁷F₆→⁵D₃) 紫外光激发下, 观察到Tb³⁺: ⁵D₄→⁷F_J ( J = 6, 5, 4, 3) 可见光区发射光, 并检测到Yb³⁺: ²F_5/2→²F_7/2的近红外发射光。通过研究激发光谱和发射光谱与Yb³⁺掺杂浓度的关系, 发现在单斜晶体Sr₂B₂O₅中, Yb³⁺具有很高的猝灭浓度。     

Bi2O3助熔剂对CaO-B2O3-SiO2/Al2O3玻璃陶瓷复合材料性能的影响

以CaO-B₂O₃-SiO₂(CBS)玻璃粉体和Al₂O₃陶瓷粉体为原料,通过在CBS与Al₂O₃的质量比固定为50:50的玻璃-陶瓷复合材料中添加适量的Bi₂O₃作为烧结助熔剂,探讨了Bi₂O₃助熔剂对CBS/Al₂O₃复合材料的烧结性能、介电性能、抗弯强度和热膨胀系数的影响规律.研究表明:Bi₂O₃助熔剂能通过降低CBS玻璃的转变温度和黏度促进CBS/Al₂O₃复合材料的致密化进程,于880 ℃下烧结即能获得结构较致密、气孔较少的CBS/Al₂O₃复合材料.然而,过量添加Bi₂O₃将使玻璃的黏度过低,从而恶化CBS/Al₂O₃复合材料的烧结性能、介电性能及抗弯强度.当Bi₂O₃的添加量为CBS/Al₂O₃复合材料的1.5wt%时,于880 ℃下烧结即能获得最为致密的CBS/Al₂O₃复合材料,密度为2.82 g·cm^-3,这一材料具有良好的介电性能(介电常数为7.21,介电损耗为1.06×10^-3),抗弯强度为190.34 MPa,0~300 ℃的热膨胀系数为3.52×10^-6 K^-1.     

复合持续时间对P2O5-Al2O3异相复合玻璃结构和力学性能的影响

近年来,分相玻璃以其独特的结构以及优异的物理化学性质引起了广泛关注。本研究结合气动雾化加料和机械搅拌,采用熔融冷却法制备了纳米SiO₂-Na₂O高硅玻璃颗粒增强的P₂O₅-Al₂O₃玻璃。通过改变复合持续时间,研究了玻璃的结构与力学性能之间的关系。结果表明,异相复合玻璃的杨氏模量高于P₂O₅-Al₂O₃玻璃,并且随着复合持续时间由10s增大到8min,玻璃的杨氏模量呈现先升高后降低的趋势,在复合持续时间为6min时,杨氏模量达到最大值80.7GPa。相比于P₂O₅-Al₂O₃玻璃,杨氏模量提高了18%。引入SiO₂-Na₂O高硅玻璃颗粒不仅能够在基体玻璃中形成第二相,而且会改变P₂O₅-Al     

无容器制备Er3+/Yb3+共掺La2O3-TiO2-ZrO2玻璃及其上转换发光研究

利用无容器技术制备了(La_0.94-xEr_0.06Yb_x)(Ti_0.95Zr_0.05)_2.25O₆(x=0~0.24, 间隔0.04)球状透明玻璃, 其稀土离子掺杂浓度最大值达到30%。通过DTA分析发现, 玻璃具有很好的热稳定性, x=0时玻璃化转变温度T_g和析晶起始温度T_o分别为818℃和906℃, ΔT(ΔT= T_o-T_g)为88℃, 玻璃形成能力较低。随着Yb³⁺浓度提高, T_g、T_o和ΔT逐渐下降, 说明Yb³⁺降低了玻璃的热稳定性和形成能力。利用紫外可见分光光度计测定了样品的吸收/透过光谱, 玻璃在975 nm具有很强的吸收峰, 表明Yb³⁺可以有效提高玻璃对入射光的吸收强度; 在可见光范围内除特征吸收外具有近70%的透过率, 说明玻璃具有良好的透可见光性能, 有望获得高强上转换发光输出。上转换荧光光谱研究表明: 在980 nm激光泵浦下, 获得了中心位于535、554和672 nm处的绿、红发光带, x=0.16的发光最强, 672 nm处的红光强度是x=0的近130倍。上转换发光强度与泵浦功率关系的分析表明: 535、554 nm处的绿光和672 nm处的红光发光均是双光子发光过程。     

Ce3+掺杂Li2O-MgO-Al2O3-SiO2玻璃的结构与荧光猝灭现象

采用熔融淬冷法制备了不同浓度Ce³⁺离子掺杂的20Li₂O-5MgO-20Al₂O₃-55SiO₂玻璃闪烁材料。采用X射线衍射(XRD)、高分辨透射电镜(HRTEM)技术、密度检测等方法研究了玻璃的微观结构随Ce³⁺离子掺杂浓度的变化规律, 采用荧光分光技术检测了玻璃的紫外光致激发光谱(PLE)、发射光谱(PE)。研究结果表明: 在不对称的晶体场作用下, Ce³⁺离子5d能级被劈裂为5个组分; 随着玻璃基质内Ce³⁺离子掺杂浓度增大, 玻璃的非晶化程度加深; 5d能级的劈裂宽度随之增大, 由此导致激发带向低能量端展宽、发射光谱明显红移; Ce³⁺离子的荧光发射强度随Ce³⁺离子掺杂浓度先升高、后降低, 浓度猝灭过程成为其荧光发射效率降低的主要原因。     

Spectra and laser properties of Er, Yb:phosphate glasses

The effects of Al₂O₃, Yb₂O₃, Er₂O₃ and OH on spectral properties of P₂O₅·Na₂O·SrO·Al₂O₃·Yb₂O₃·Er₂O₃ erbium phosphate glass were studied. 5, 8, 13 mol% Al₂O₃, 4, 5, 6, 7 and 8 mol% Yb₂O₃ and 0.05, 0.2, 0.4 mol% Er₂O₃ were used. It was found Al₂O₃ improves fluorescent lifetime of Er³⁺ ions, but the integrated absorption cross-section of Er³⁺ ions decreases with the increase of Al₂O₃ concentration. Evaluating from energy transfer efficiency of Yb³⁺ to Er³⁺ and spectral parameters of Yb³⁺ and Er³⁺, lower Al₂O₃ content, 6 mol% Yb₂O₃ and 0.2–0.4 mol% Er₂O₃ are preferred for LD pumped microchip laser application. OH groups in glass greatly affect fluorescent intensity and lifetime of Er³⁺, Yb³⁺:phosphate glass. The OH absorption coefficient at 3000 cm⁻¹ should be <1 cm⁻¹ for laser applications. Pumped with a 2 W, 974 nm InGaAs laser diode, CW laser centered at 1530 nm with slope efficiency of 10.6% and maximum output of 43 mW was achieved in our 2 mm thick Er³⁺, Yb³⁺:phosphate glass at room temperature.     

Spectroscopic properties of Yb in heavy metal contained fluorophosphate glasses

A new series of 20Bi(PO₃)₃–10Sr(PO₃)₂–35BaF₂–35MgF₂ doped with Yb³⁺ is introduced for fiber and waveguide laser applications. The stimulated emission cross-section σ_emi, which was found to be 1.37 pm² at the lasing wavelength of 996 nm, is the highest one among fluorophosphate glasses. It has been found that an extremely high gain coefficient of G = 1.65 ms pm⁴ and high quantum efficiency of η = 93% for 1 wt.% Yb₂O₃ doped systems. The various concentration effects on laser performance properties including minimum pumping intensity I_min, the minimum fraction of excited ions β_min and the saturation pumping intensity I_sat are analyzed as a function of Yb₂O₃ concentration. Those results obtained in current system had advantage over some fluorophosphate glasses reported.     

Al3+/Yb3+/P5+掺杂对石英玻璃紫外透过和紫外激发荧光的影响

采用溶胶-凝胶法结合高温真空烧结工艺制备了不同浓度的Al³⁺/Yb³⁺/P⁵⁺掺杂石英玻璃。研究了P⁵⁺和Al³⁺的引入对Yb³⁺掺杂石英玻璃紫外透过和紫外激发荧光光谱, 以及Yb4d电子结合能的影响, 并初步探索了其机理。研究结果表明, Al³⁺/Yb³⁺/P⁵⁺掺杂石英玻璃在190~300 nm波段的吸收主要来源于O^2-→Yb³⁺的电荷迁移吸收, 其谱带位置和Yb4d电子结合能随Yb³⁺的第二配位元素(Al、Si、P)电负性增大向高能方向移动。真空烧结条件下, 引入Al³⁺会引发石英玻璃中Yb³⁺还原为Yb²⁺, 其典型的吸收峰位于330 nm处; 然而, 在Al³⁺/Yb³⁺共掺的基础上再引入P⁵⁺, 且P⁵⁺/Al³⁺摩尔比大于1时, 可以有效抑制Yb²⁺的形成。紫外光激发引起的近红外发光(976 nm)是电子从电荷迁移态弛豫到Yb³⁺激发态向基态跃迁的结果, 可见发光(525 nm)归因于Yb²⁺的5d→4f跃迁。本文研究结果对通过优化工艺和调整组分制备出高性能的Yb³⁺掺杂光纤具有一定的指导意义。     

Low-temperature ionic conductivity of the solid solution in the system ZrO2–Y2O3–Yb2O3

Compositional dependence of ionic conductivity in the system ZrO₂–Y₂O₃–Yb₂O₃ was investigated in the temperature range 573–873 K using the complex impedance technique. It was shown that the conductivity decreases with increasing concentration of Yb₂O₃ in the system ZrO₂–Y₂O₃–Yb₂O₃. Analyzing the experimental data according to the classic Arrhenius equation showed that such an experimental phenomenon can be attributed to the tighter association between Yb³⁺ and oxygen vacancy, compared with that between Y³⁺ and oxygen vacancy, which hinders the migration of oxygen vacancy in the materials.     

Optimization of spectroscopic properties of Yb-doped refractory sesquioxides: cubic Y2O3, Lu2O3 and monoclinic Gd2O3

Absorption and emission spectra are given for Yb³⁺-doped Y₂O₃, Lu₂O₃ and Gd₂O₃ at room temperature. Y₂O₃ and Lu₂O₃ as close cubic matrices, show Yb³⁺ similar spectra different of Yb³⁺ in Gd₂O₃ monoclinic structure. Here, we use a new method to study and optimize the main spectroscopic properties with only one concentration gradient sample. Finally, assignments of Yb³⁺ Stark levels and Raman vibrations in Y₂O₃, Lu₂O₃ and Gd₂O₃ single crystal are given.     

Optical band gap studies on xPb3O4–(1−x)P2O5 lead[(II, IV)] phosphate glasses

A series of glasses in the xPb₃O₄–(1−x)P₂O₅ (red lead phosphate) (RLP) system with ‘x' varying from 0.075 to 0.4 were prepared by the single-step melt quenching process from Pb₃O₄ and NH₄H₂PO₄. The optical absorption spectra of these glasses have been recorded in the ultraviolet region from 200 to 400 nm and the fundamental absorption edges have been identified. The optical band gap E_opt values have been determined for all the glasses using the known theories. The (E_opt) values vary from 4.90 to 3.21 eV the highest being 4.57 eV, corresponding to the most stable glass of x=0.225. The absorption edge is attributed to the indirect transitions and the origin of the Urbach energy ΔE is suggested to be thermal vibrations. These glasses promise as potential candidates for application in optical technology compared to simple xPbO–(1−x)P₂O₅ (lead phosphate) (LP) glasses.     

Molecular dynamic simulation of heterogeneity and chemical states of fluorine in amorphous alkaline earth silicate systems

Chemical states of fluorine in fluorosilicate glasses in the system MF₂-MO-SiO₂ (M = Ca, Sr and Ba; SiO₂ content < 60 mol%) have been investigated by molecular dynamic (MD) simulations with a perfect ionic two-body potential. Comparison of the results with those derived by X-ray photoelectron spectra of the actual glasses demonstrates that MD simulations reproduce well the bonding states of fluorine in the systems as well as the formation of M-F clusters. The MD generated structure of imaginary glasses, or glasses not obtained by the conventional melt-quench technique, with 70 mol% SiO₂ indicates that an acidic environment induces a greater amount of F---Si bonds. Their M-F pair correlation functions plotted against normalized M-F distances suggest that relative ion positions in the clusters are very similar.     

Structure, nucleation and Eu luminescence in alkaline earth rare earth borate glass

In La₂O₃-MO-B₂O₃ ternary system, various glasses/ glass ceramics with M=Ca, Sr and Ba have been prepared. In this ternary system, homogeneous nucleation occuring in the B₂O₃ melt appears to be the cause for the formation of nanocrystallites, hence glass ceramics. The nucleation process is very much dependent on the alkaline earth used viz., with smaller alkaline earths like Ca, boron prefers (BO₄)⁵⁻ tetrahedral coordination with oxygen, while in the case of bigger alkaline earths like Ba and Sr, (BO₃)³⁻ triangular coordination seems to be predominant. Eu³⁺ in this glass system yields intense ⁵D₀→⁷F_j emission. A cursory view on the dependence of the various Judd-Ofelt parameters (Ω_k) indicates that Ω₂ parameter is very much dependent on the immediate vicinity of the luminescent ion (Eu³⁺) while Ω₄ is not. Various results based on these are discussed.