【作者】 杨殿来；

【导师】 林海；

【作者基本信息】 大连轻工业学院 ， 材料学， 2006， 硕士

【摘要】 稀土掺杂的光学玻璃在荧光显示器、光学探测器、光学存储器、固体激光器、光学光纤、波导激光器和光学放大器等方面有着巨大的应用前景，一直是人们研究的热点和焦点。在氧化物玻璃中，碲酸盐玻璃的声子能量远小于硼酸盐玻璃、磷酸盐玻璃、硅酸盐玻璃和锗酸盐玻璃，稀土离子可以获得高效的荧光发射。在传统碲酸盐玻璃的基础上，添加氧化铋，不仅能进一步降低玻璃的声子能量，同时有助于提高玻璃的折射率，提高稀土离子的辐射弛豫速率，获得高效跃迁发射。基于这种考虑，我们合成设计了新型的铋碲酸盐玻璃，研究稀土离子在其中的光学与光谱特性，取得以下成果与进展：1．制备了Pr³⁺掺杂7.5Li₂O-7.5K₂O-5BaO-5Bi₂O₃-75TeO₂铋碲酸盐玻璃（LKBBT—Ⅰ）。紫外灯和蓝色发光二极管下观察，玻璃发出明亮的红光。488nm激发下记录了pr³⁺的可见荧光光谱有6个发射峰，位于530nm，616nm，647nm，684nm，708nm和732nm，分别对应pr³⁺的³P₀→³H₅，¹D₂→³H₄，³P₀→³F₂，¹D₂→³H₅，³P₀→³F₃和³P₀→³F₄跃迁。Pr³⁺的激发光谱（监测647nm发射）由3个激发峰组成，分别位于448nm，473nm和486nm。2．对Tm³⁺／Yb³⁺共掺杂LKBBT—Ⅰ玻璃的吸收、荧光和红外透过光谱展开了测试与分析，根据J-O理论，求得Tm³⁺的振子强度参数O_t（t=2，4，6）分别为3.90×10^-20，2.03×10^-20和9.03×10^-21cm²，并进一步计算出Tm³⁺在玻璃中各能级跃迁的振子强度、自发辐射跃迁几率、辐射寿命和荧光分支比等光谱参数。980nm半导体激光器激发下观察到强烈的蓝色和近红外上转换荧光，测量并讨论了蓝色、近红外上转换荧光强度与激光功率的关系，并判断出蓝光和近红光的发射分别为三光子和双光子过程。3．合成制备了具有高折射率Sm³⁺掺杂5Li₂O-5K₂O-5BaO-10Bi₂O₃-75TeO₂铋碲酸盐玻璃（LKBBT—Ⅱ）。对玻璃的吸收和荧光光谱进行了测试与分析，根据Judd-Ofelt理论对吸收光谱进行拟合，求得Sm³⁺的振子强度参数O_t（t=2，4，6）分别为4.73×10^-20，2.78×10^-20，1.77×10^-20cm²，并进一步计算出Sm³⁺在玻璃中各能级跃迁的振子强度、自发辐射跃迁几率、辐射寿命和荧光分支比等光谱参数。紫外光激发下，Sm³⁺掺杂铋碲酸盐玻璃发出明亮的橙红色光。4．Eu³⁺掺杂LKBBT—Ⅱ铋碲酸盐玻璃中除了观察到位于587，615，652和703nm，对应^D₀→⁷F_J（J=1，2，3，4）的常见跃迁发射，还获得了从更高能级⁵D_J（J=1，2，3）的向下跃迁发射。包括位于420nm，431nm，446nm，466nm，490nm，513nm，537nm和556nm的发射峰，分别对应于⁵D₃→⁷F₁，⁵D₃→⁷F₂，⁵D₃→⁷F₃，⁵D₃→⁷F₄，⁵D₂→⁷F₂，⁵D₂→⁷F₃，⁵D₁→⁷F₁和⁵D₁→⁷F₂的多通道跃迁发射。新型铋碲酸盐玻璃中，多种稀土离子pr³⁺、Sm³⁺、Eu³⁺等的掺杂产生一些重要的荧光性质。在这种新玻璃体系中掺入不同稀土离子后，获得了多种光学和发光玻璃。其中Tm³⁺／Yb³⁺共掺杂的玻璃及Sm³⁺和Eu³⁺掺杂的玻璃有可能成为性能良好的激光和发光玻璃。上述获得的新的现象和研究结果，为新型荧光显示器件及稀土掺杂新激光玻璃和光纤的发展提供了理论上的依据和新材料物质保证。更多还原

【Abstract】 Glasses doped with various rare-earth ions are important materials for fluorescent display devices, optical detectors, bulk lasers, optical fibers, waveguide lasers and optical amplifiers. Of the oxide glasses, tellurite glasses catch much attention in recent years because their maximum phonon energy is lower than those in silicate, borate, phosphate and germanate glasses. Rare-earth ions can be expected that the non-radiative loss to the lattice will be small and the fluorescence quantum efficiency will be high in tellurite glasses.In this work, alkali-barium-bismuth-tellurite （LKBBT） glasses were designed based upon traditional tellurite glasses. Optical and luminescence properties of rare-earth ions in bismuth tellurite glasses have been studied at room temperature. The results and progresses obtained are as follows.1. Pr³⁺—doped bismuth tellurite glass with molar composition 7.5Li₂O-7.5K₂O-5BaO-5Bi₂O₃-75TeO₂（LKBBT—Ⅰ） glass has been fabricated and characterized. The glass emits red lights under the excitation of long-wave UV and blue lights. The emission spectrum of Pr³⁺-doped bismuth tellurite glass under 488nm excitation consists of six intense emission bands peaking at 530nm, 616nm, 647nm, 684nm, 708nm and 732nm, owing to the ³P₀→³H₅, ¹D₂→³H₄, ³P₀→³F₂, ¹D₂→³H₅, ³P₀→³F₃ and ³P₀→³F₄ transitions, respectively. The excitation spectrum for 647nm emission of Pr³⁺ consists of three bands peaking at 448nm, 473nm and 486nm, respectively.2. Tm³⁺/Yb³⁺—codoped LKBBT—Ⅰglasses have been synthesized. The absorption spectra, fluorescence spectra and IR transmittance spectra of this glass were measured and analyzed. Based on J-O theory, and intensity parameters O_t（t=2, 4, 6） were obtained to be 3.90×10^-20, 2.03×10^-20, 9.03×10^-21cm², respectively. Then the radiative transition probabilities, radiative lifetimes and fluorescence branching ratio were calculated. Intense blue three-photon upconversion fluorescence and near-infrared two-photon upconversion fluorescence were investigated under the excitation of a 980nm diode laser at room temperature. 3. Sm³⁺—doped 5Li₂O-5K₂O-5BaO-10Bi₂O₃-75TeO₂ （LKBBT—Ⅱ） glasses with high refractive index have been synthesized. The absorption and fluorescence spectra of this glass were measured and analyzed. The absorption spectra was fitted by J-O theory, and intensity parameters O_t（t=2, 4, 6）were found to be 4.73×10^-20, 2.78×10^-20, 1.77×10^-20cm², respectively. Then the relative intensity of spectral lines of every energy level transition, radiative transition probabilities, radiative lifetimes and fluorescence branching ratio were calculated. In the Sm³⁺—doped bismuth tellurite glasses, Sm³⁺ emit intense reddish-orange lights under the excitation of long-wave UV and blue lights.4. Eu³⁺—doped LKBBT—Ⅱglass emit bright red lights under UV irradiation. The emission spectra of Eu³⁺ in LKBBT glasses under 395nm excitation exhibits the well-known emission bands centered around 587, 615, 652 and 703nm, and owing to the ⁵D₀→⁷F_J（J=1, 2, 3, 4） transitions, respectively. The most interesting feature obtained of emission spectrum is fluorescence from the higher ⁵D levels （⁵D₁, ⁵D₂ and ⁵D₃） have also been detected in the Eu³⁺ doped LKBBT glass. The 420nm, 431nm, 446nm, 466nm, 490nm, 513nm, 537nm and 556nm bands can be assigned to ⁵D₃→⁷F₁, ⁵D₃→⁷F₂, ⁵D₃→⁷F₃, ⁵D₃→⁷F₄, ⁵D₂→⁷F₂, ⁵D₂→⁷F₃, ⁵D₁→⁷F₁ and ⁵D₁→⁷F₂ transitions, respectively. This phenomena is rarely reported in other host material.These new phenomena and results of studies provide the theoretical basis and pledge of new material for new types of fluorescence display devices and development of rare—earth doped new laser glasses and fibres.更多还原