TeO_2-Nb_2O_5-BaO-BaCl_2系统玻璃结构及银纳米晶引入研究

碲酸盐氧卤玻璃具有低声子能以及较好的稳定性和析晶性能等优秀的综合品质,是一类很有前途的光学玻璃材料。采用熔融法制备了不同组成的TeO2-Nb2O5-BaO-BaCl2系统玻璃,研究了网络结构变化和组成对该系统玻璃的成玻璃性能和析晶性能的影响,同时探讨了向玻璃基体内引入银纳米晶体的可能性。结果表明,BaCl2的引入使得玻璃网络结构中键合及基团种类增多,碲氧链间的连接加强,网络结构更加紧密,并且成玻璃区域有所扩展。TeO2-Nb2O5-BaO-BaCl2系统玻璃基体在保持自身结构稳定性的同时,更有利于AgCl纳米晶体析出,是一种适合金属纳米晶掺杂的优良光学玻璃基体材料。     

TeO2-AlF3(Al2O3)-LaF3-ZnF2玻璃的热稳定性和网络结构研究

制备了TeO2-AlF3 (Al2O3 )-LaF3-ZnF2体系氟氧化物玻璃.通过DSC和红外吸收光谱分析研究了Al2O3替代AlF3对氟氧化物碲酸盐玻璃热稳定性和网络结构的影响.结果表明:Al2O3替代AlF3使氟碲酸盐玻璃的玻璃转变温度和热稳定性明显提高,玻璃中形成的[AlO6]八面体使玻璃网络结构更加紧密.     

AgCl纳米晶掺杂铌碲酸盐系统非线性光学玻璃材料研究

铌碲酸盐非线性光学玻璃具有优良的三阶非线性光学效应,引入适量纳米晶体后,有望进一步提高玻璃的三阶非线性光学性能.本文采用在辅助电场诱导下的热处理方法在TeO2-Nb2O5-BaO-AgCl系统玻璃中析出AgCl纳米晶体,并研究了AgCl含量、热处理工艺及电场施加工艺对纳米晶析出和三阶非线性光学性能的影响.结果发现,在铌碲酸盐系统玻璃中引入0.1%～0.35%(质量分数)的AgCl,经热处理后可在玻璃中获得AgCl纳米晶体,而辅助电场提供的较小推动力可诱导更多的纳米晶体均匀析出,并且可以将其尺寸控制在20nm以下.采用辅助电场与热处理工艺相匹配的控制技术可以明显提高材料的三阶非线性光学性能.     

掺铒TeO2-Nb2O5-ZnO系统玻璃的上转换发光性能

稀土离子掺杂碲酸盐系统玻璃是一类应用前景良好的上转换发光材料.研究了含铒TeO2-Nb2O5-ZnO系统玻璃在980nm抽运下的上转换光谱,结果发现存在3个上转换荧光谱带,分别对应于2H11/2→4I15/2、4S3/2→4I15/2和4F9/2→4I15/2,而且Er3 含量的增加可明显提高材料在530、550和660nm附近的发光性能.少量的ZnO引入既可以大幅提升材料的上转换发光强度,又能保持铌碲酸盐玻璃良好的化学稳定性.材料的发光机制主要是激发态吸收(ESA)和能量转移(ET),最大声子能量的降低是上转换发光增强的主要原因.     

1.55μm光纤放大器用掺Er3+碲酸盐玻璃光谱性能研究

制备了TeO2-BaO(Li2O,Na2O)-La2O3掺铒碲酸盐玻璃系统,测量玻璃的密度、折射率和DSC曲线,以及玻璃的吸收光谱和荧光光谱.由测得的密度和折射率等参数,应用Judd-Ofelt理论和McCumber理论,计算出碲酸盐玻璃的各光学性能参数与受激发射截面.且从测得热稳定性能较好的TBLE3荧光发射谱图中得到该碲酸盐玻璃荧光半高宽(FWHM)为～60nm,σepeak×FHWM值高达～600,明显大于掺铒硅酸盐玻璃和磷酸盐玻璃,表明该种碲酸盐玻璃是光纤发大器用的理想基质材料.     

TeO2-Nb2O5-BaCl2-AlF3玻璃系统结构及光学性能研究

用传统熔融法制备了一种新型的氧卤碲酸盐玻璃:(80-x)TeO2-10Nb2O5-10BaCl2-xAlF3(x=10、20和30),用密度比重天平、玻璃热膨胀仪、棱镜耦合仪、显微拉曼光谱仪和红外-可见-紫外分光光度计研究了组分变化对物理性能、结构及光学性质的影响。研究结果表明,随着玻璃中AlF3含量增加,玻璃的密度和折射率减小;在Tg温度前,玻璃的平均线膨胀系数α减小;玻璃的热稳定性增强;玻璃结构中的双三角锥体[TeO4]和变形的双三角锥体[TeO3+1]以及三角棱锥体[TeO3]相对含量都相应减少;玻璃在紫外吸收边出现了蓝移现象,玻璃的直接和间接光学帯隙都增大。     

Pr3+掺杂铋碲酸盐玻璃的热膨胀与可见荧光发射

制备了Pr3 掺杂的高折射率7.5Li2O-7.5K2O-5BaO-5Bi2O3-75TeO2重金属铋碲酸盐玻璃.测定了玻璃的热膨胀曲线,计算了样品的热膨胀系数α,转变温度Tg和软化温度Tf.紫外灯下观察,Pr3 掺杂的玻璃样品发出橙红光.室温下记录了玻璃样品的吸收、激发和荧光发射光谱.光谱分析表明:紫外灯、蓝色激光二极管、蓝色发光二极管,以及氩离子激光器是Pr3 掺杂铋碲酸盐玻璃的有效激发光源.     

TeO2-ZnCl2-BaO-NaF玻璃系统的结构及中红外透过特性的研究

制备了一种新型的氧卤碲酸盐玻璃：（80-x）TeO2—15ZnCl2-xBaO-5NaF（x=30、20、10、0mol％），对玻璃的机械强度、热稳定性、拉曼光谱、紫外吸收光谱、红外透过光谱等特性进行了研究．通过拉曼光谱分析研究了玻璃组分含量的变化对玻璃结构和红外透过性能的影响．结果表明，随着BaO含量的增加，玻璃在红外波段透过率显著增加，并且红外透过截止波长向长波方向移动，本文对这一实验结果进行了机理性的研究探讨．同时，通过在熔制过程中通入高纯O2，以及引入适量的卤化物有效地除去玻璃中的[OH]基团，使玻璃的红外透过性能得到进一步的提高．这种新型的氧卤碲酸盐玻璃在中红外区域有较高的透过（≥80％），中红外波段透过截止波长达6．5μm，是一种红外透过性能优良的光学玻璃材料．     

TeO2对氟铝酸盐玻璃性质和结构的影响

以10MgF2—20CaF2—10SrF2—10BaF2—15YF3—35AlF3氟铝酸盐玻璃为基玻璃引入不同含量的TeO2得到了新的氟碲铝酸盐玻璃．用差热分析方法研究了TeO2对氟铝酸盐玻璃性能的影响，通过拉曼光谱和红外吸收谱来研究玻璃的结构变化．差热分析表明TeO2的增加使玻璃开始析晶温度瓦升高，融化温度％降低，成玻璃能力增加．玻璃结构分析表明氟碲铝酸盐玻璃的结构中存在[FnAl-O—AlFn]、[TeO3]、[TeO2F]和[TeOF2]等多面体，这些多面体由F^-和O^2-离子连接．这种新的氟碲铝酸盐玻璃有着良好的成玻璃能力，在0．75～5．00μm范围内玻璃具有很高的透过率，是一种具有应用前景的新的红外光学玻璃材料．     

Li2O含量对碲系玻璃温度及析晶性能的影响

通过DTA研究了TeO2-PbO-B2O3-Bi2O3-Li2O系统玻璃中TeO2、PbO物质的量比变化对玻璃转变温度(Tg)的影响,重点研究了n(TeO2)∶n(PbO)=2∶1条件下Li2O含量对玻璃转变温度的影响,并采用IR和XRD对玻璃的结构和析晶性进行了分析。结果表明:随着Li2O含量(2.7%~6.6%,摩尔分数)的增加,Tg呈N型变化趋势,当Li2O为2.7%(摩尔分数)时,Tg为最低值(300℃)。碲系统玻璃中形成了[TeO4]三角双锥体结构,它与[BO4]、[BiO6]等多面体共同构成了玻璃的三维网络结构,该玻璃经热处理后易形成Bi2TeO5晶体而会影响Tg。     

Devitrification of TeO2-doped Fluoroaluminate Glass

Crystallization behavior of the glass system AlF3-MgF2-CaF2-SrF2-BaF2-YFa-TeO2 （AMCSBY-TeO2） was studied by the nonisothermal method using differential thermal analysis. The activation energy E and Avrami exponent g were determined by nonisothermal method. It is found that the value of E varies with increasing TeO2 and reaches a minimum at 10 mol fraction TeO2, while g decreases from 3.65 to 1.78 with the addition of TeO2. X-ray diffraction shows that Ba2TeaOs, MgTe205, and SrTeOa phase formed when the glasses were reheated. The addition of TeO2 changes the crystallization mechanism and improves the stability of the fluoroaluminate glass.     

Thermal analysis of glasses in TeO2-BaF2-LaF3 systems

Divalent metal fluorides MF2 （M=Sr, Mg, Ca） in oxyfluoride tellurite glasses TeO2-BaF2-LaF3 were synthesized. The densities, refractive indices and characteristic temperatures of synthesized glasses were measured. The influence of divalent metal fluorides-MF2（M=Sr, Mg, Ca） on the thermal stability of oxyfluoride tellurite glasses TeO2-BaF2-LaF3 were studied. Results show that the replacement of BaF2 by SrF2 and MgF2 can enhance the thermal stability against crystallization of the glass. A glass system with good thermal stability was produced, which could be a potential candidate for the host materials of the fiber devices.     

1.3 μm Emission from Nd3+-doped Tellurite Glass Fiber

1 wt pct Nd2O3-doped tellurite bulk glass and fiber with the same composition of 75TeO2-15ZnO-5Na2O-5Li2O (molfraction, %) were fabricated. Judd-Ofelt analysis was carried out for the bulk. The emission from the 4F3/2→4I13/2 transition in fiber is at 1.33 μm wavelength with a spectral bandwidth of 55 nm, which is similar to that in bulk. In the case of the fiber, the lifetime of 4F3/2 level is 164μs, and the quantum efficiency is ～100%. The figure-of-merit for gain (σoT0) for Nd3 -doped tellurite glass is about 2.8×10-24 cm2.s, which is quite comparable with that in Nd3 -doped fluoroaluminate glasses, and is an order of magnitude larger than pr3 -doped fluoride glasses.     

掺Er3+碲酸盐玻璃光谱性质和热稳定性的提高研究

用高温熔融法制备了摩尔组分百分比为70TeO2-20(ZnO、WO3,AlO1.5)-9NaO0.5-1ErO1.5的碲酸盐玻璃样品.测量了玻璃样品的吸收光谱和荧光光谱,用差热分析方法(DTA)测试了玻璃的热稳定性.结合Judd-Ofelt理论和McCumber理论分别计算得到了三种玻璃样品的强度参数Ω1(t=2,4,...     

Raman Spectrum and Thermal Stability of a Newly Developed TeO2-BaO-BaF2-La2O3-LaF3 Glass

In this work, a new TeO2-BaO-BaF2-La2O3-LaF3 oxyfluorotellurite glass system is investigated. Differential thermal analysis (DTA) and structural analysis by Raman scattering spectra are reported on the glasses. The DTA results indicated that an increase of fluoride content in the glasses decreases the glass transition temperature (Tg) and increases the crystallization onset temperature (Tx). As a result the 70TeO2·20BaF2·10LaF3 glass showed a large Hruby's parameter, possessing excellent thermal stability. Changes in glass network structure with fluoride content are discussed based on the Raman scattering spectra of glasses. The glass network structures in the 70TeO2·(20-x)BaO·xBaF2·(10-y)La2O3·y1 aF3 glasses are basically composed of both Te(O, F)4 and Te(O, F)3 units, but the Te(O, F)4/Te(O, F)3 ratio in the glass becomes higher with increasing fluoride content. This may be considered one of the reasons why the 70TeO2·20BaF2·10LaF3 glass exhibits excellent thermal stability.     

掺铒碲酸盐玻璃的热力学稳定性和光谱性质的研究

分析了掺Er³⁺碲酸盐玻璃的热力学稳定性能,研究了掺Er3+碲酸盐玻璃的吸收和荧光光谱性质;应用Judd-Ofelt理论计算了碲酸盐玻璃中Er3+离子的强度参数Ω(Ω₂=4.79×10^-20cm², Ω₄=1.52×10^-20cm²,Ω₆=0.66×10^-20_cm2),计算了离子的自发跃迁几率,荧光分支比;应用McCumber理论计算了Er3+的受激发射截面(σ_e=10.40×10^-21cm²)、Er³⁺离子⁴I_13/2→⁴I_15/2 发射谱的荧光半高宽(FWHM=65.5nm)及各能级的荧光寿命(⁴I_13/2能级为τ_rad=3.99ms);比较了不同基质玻璃中Er3+离子的光谱特性,结果表明掺铒碲酸盐玻璃更适合于掺Er³⁺光纤放大器实现宽带和高增益放大.     

Intense red upconversion emission of Yb/Tm/Ho triply-doped tellurite glasses

By conventional melting and quenching methods, 3Yb2O3-0.2Tm2O3-xHo2O3 (wt%, x=0.2~1.2) was doped into an easily fiberized tellurite glass with composition of 78TeO2-10ZnO-12Na2O (mol%) to form YTH-TZN78 glasses. Under 976 nm excitation, the direct sensitizing effect of Yb ions (Yb→Ho) and indirect sensitizing and self-depopulating effects of Tm ions (Yb→Tm→Ho) were found to present intense red upconversion emission at 657 nm (Red, Ho:5F5→5I8) and were responsible for the absence of the usually observed 484 nm emission (Blue, Tm:1G4→3H36). Regardless of the dopant concentration of Ho ions, the intensity of the red emission at 657 nm (Red, Ho:5F5→5I8) is about three times stronger than that of the green one at 543 nm (Green, Ho:5S2→5I8). For this certain red emission at 657 nm, 0.4 wt% Ho2O3-doped YTH-TZN78 glass was found to present the highest emission intensity and is therefore determined as a promising active tellurite glass for red fiber laser development.     

离子交换法制备波导放大器的磷酸盐铒玻璃研究

研究了不同Al₂O₃、Na₂O、La₂O₃、Y₂O₃及AlF3含量的磷酸盐铒玻璃的物理化学性质和光谱性质,通过恒温水浴失重测试的方法探讨了玻璃组分Al₂O₃、Na₂O、La₂O₃、Y₂O₃及AlF₃对磷酸盐玻璃化学稳定性的影响.结果表明,Al₂O₃含量增加,玻璃化学稳定性提高,添加少量的AlF₃会降低玻璃的化学稳定性,与La₂O₃相比Y₂O₃对提高玻璃的热稳定性有益.通过对比不同组分玻璃样品的热性质、机械性质以及析晶、光谱性质的结果,初步得出了一个比较适于离子交换过程的磷酸盐铒玻璃成分.