铋酸盐玻璃结构和非线性及光谱性质研究
文献类型：学位论文
| 作者 | 范慧艳 |
| 学位类别 | 博士 |
| 答辩日期 | 2010 |
| 授予单位 | 中国科学院上海光学精密机械研究所 |
| 导师 | 胡丽丽 |
| 关键词 | 玻璃结构 光谱性质 铋酸盐玻璃 三阶非线性 Z-扫描 |
| 其他题名 | The study on structure, spectroscopic and nonlinear optical properties of bismuthate glasses |
| 中文摘要 | 铋酸盐玻璃作为优良的红外发光基质材料和非线性材料具有很重要的研究价值。制备工艺对铋酸盐玻璃的性能影响较大，研究熔制坩埚、气氛和制备温度对铋酸盐玻璃性质的影响有利于改善其光学性能。另一方面，铋酸盐玻璃的组成和结构对玻璃性能影响较大，研究不同组成铋酸盐玻璃的结构对掌握其性质变化规律，寻找最佳玻璃成份有重要意义。由于铋酸盐玻璃具有较高的折射率和较低的声子能量，可以作为优良的非线性材料和发光基质材料，有必要深入研究其三阶非线性性质和稀土在铋酸盐玻璃中的光谱性质。 本论文分七部分，第一部分是文献综述；第二部分阐述了本论文的实验条件和研究的理论基础；第三部分探讨了制备工艺条件对铋酸盐玻璃性质的影响；第四部分研究了Ga3+、Bi3+及Ge4+离子对铋酸盐玻璃结构的影响；第五部分结合铋酸盐玻璃的结构，研究了铋酸盐玻璃的三阶非线性性能。第六部分研究了Er3+、Tm3+和Yb3+离子在铋酸盐玻璃中的发光情况；第七章是本论文的结论。 本文首先研究了铋酸盐玻璃的制备工艺，探索出合理的熔制温度(1000~1100℃)，并使用刚玉坩埚，在通氧条件下获得了光学性能较好的铋酸盐玻璃。使用红外吸收谱，拉曼(Raman) 光谱和X-射线光电子谱(XPS)研究了Ga3+离子对60Bi2O3-(40-x)B2O3-xGa2O3 (x=5, 10, 15, 20 mol%) 玻璃的结构影响。结果表明有Bi5+离子存在于玻璃中，并且随着Ga2O3 含量的增加，Bi5+离子含量逐渐减小；Ga2O3的增加促进玻璃网络中[BO3]三角体向[BO4]四面体转变。玻璃形成体主要为[BiO6]八面体、[BO3]三角体、[BO4]四面体和 [GaO4] 四面体。并且推测[BO3]三角体可能存在于[GaO4]四面体和 [BiO6]八面体之间，可抑制玻璃的析晶。研究了Bi3+离子对 xBi2O3-35B2O3-(65-x)Ga2O3 (x=45, 50, 55, 60 mol%)玻璃结构的影响，结果表明B2O3主要以[BO3]三角体存在于玻璃中，随着Bi2O3含量的增加，玻璃中非桥氧含量增加，进一步促进玻璃中[BO4]四面体向[BO3]三角体转变。XPS研究结果表明，在Bi2O3含量高的玻璃中可能含有Bi5+离子。GeO2作为一种玻璃形成体，研究了它对铋酸盐玻璃50Bi2O3-(50-x) B2O3-xGeO2 (x=0, 5, 10, 15 mol%)结构的影响。结果表明：随着GeO2含量的增加，玻璃的非桥氧含量逐渐减少，玻璃的抗析晶性能提高，[BiO6]八面体、 [BO3]三角体、[BO4]四面体和[GeO4] 四面体构成玻璃形成体，B2O3主要以[BO3]三角体存在于玻璃中。 基于铋酸盐玻璃的高非线性特征，研究了铋酸盐玻璃的光学带隙和三阶非线性特性。在Bi2O3-B2O3-Ga2O3和Bi2O3-B2O3-GeO2三元系统中均存在双光子吸收，随着Ga2O3和GeO2含量的增加，光学带隙逐渐增加(2.8~3.2eV)，线性折射率和非线性折射率也随之增加，在上述三元铋酸盐玻璃系统中，计算得到的三阶非线性极化系数χ(3)最高可达2.26 ×10 -11esu。 最后，讨论了Er3+、Tm3+和Yb3+离子在铋酸盐玻璃中的光谱性质。研究了Er3+高掺在Bi2O3-B2O3-Ga2O3玻璃中1.5μm的发光特性，结果表明，Er3+离子在铋酸盐玻璃中具有较宽的带宽(94nm)，可能实现C+L波段的光放大。根据Beer-Lambert 和McCumber 理论计算了Er3+的吸收截面(6.45×10-21 cm2)和发射截面(7.03×10-21 cm2)。在53.3BiO1.5-33.3GeO2-13.4NaO0.5 (cation%)玻璃中研究Tm3+在1.8μm的发光特性。根据Judd-Ofelt理论计算结果，Tm3+离子具有较高的自发跃迁几率、较大的吸收截面和发射截面。后两者分别达到4.5×10-21 cm2和6.7×10-21 cm2。当Tm2O3含量为0.9 mol%时，发光强度最大。研究了不同Yb2O3含量在55Bi2O3-25B2O3-10Ga2O3-10SiO2-xYb2O3 (x=0.5; 1.0; 1.5; 2.0; 2.5; 3.0, 3.5; 4.0 mol%, 依次记为BBGS-1~8)玻璃的发光特性和激光参数。结果表明随着Yb3+离子的增加，荧光寿命从1.22ms减小至0.57ms。玻璃具有较大的吸收截面(σa=1.46ⅹ10-20cm2)和发射截面(σe=2.02ⅹ10-20cm2)，玻璃中的OH-基对Yb3+发光有严重的猝灭作用。 |
| 英文摘要 | Bismuthate glasses are a very potential material as infrared luminescence matrix and nonlinear material. The melting condition is very important factor for the optical property. So it is necessary to study the affect of melting temperature, atmosphere and crucible on glass stabilization and optical properties of bismuthate glass. It is also valuable to study the affect of glass composition on structure and properties. The bismuthate glass is a kind of excellent nonlinear material and luminescence matrix due to the high refractive coefficient and low phonon energy, so it is important to study the third-order nonlinear and luminescent properties in bismuthate glass. There are seven parts in this thesis. The review is presented in chapter one. Chapter two is the description of experiment condition and basal theory. The affect of melting conditions on optical properties of bismuthate glass is discussed in chapter three. Chapter four investigate the affect of Ga3+、Bi3+ and Ge4+ ions on bismuthate glasses. The third-order nonlinearity combined with glass structure is studied in chapter five. Chapter six research the luminence property of Er3+, Tm3+ and Yb3+ ions in bismuthate glasses. The last part is the conclusion of the thesis. The process of glass preparation is investigated. Low temperature (1000~1100℃), corundum crucible and oxygen atmosphere are appropriate to prepare bismuthate glasses. The structure of bismithate glasses is probed by Infrared, Raman and X-ray photoelectron spectroscopy (XPS). We studied the affect of Ga3+ ion on structure of 60Bi2O3-(40-x)B2O3-xGa2O3 (x=5, 10, 15, 20 mol%) glass. XPS result indicates that both Bi5+ and Bi3+ exist in 5mol% Ga2O3 content, while the amount of Bi5+ decrease with the increase of Ga2O3 and the addition of Ga2O3 causes a progressive coordination number change of the boron atom from 3 to 4. The glasses are mainly composed of [BiO6], [BO3], [BO4] and [GaO4] polyhedra. The glasses are supposed to have a layer structure. [BO3] triangle and [BO4] tetrahedra may locate between the [GaO4] tetrahedral and [BiO6] octahedra to prevent crystallization and to compensate electric charge. We studied the effect of Bi3+ ion on the structure of xBi2O3-35B2O3-(65-x)Ga2O3 (x=45, 50, 55, 60 mol%) glass structure. The result shows that borate oxide exits mainly in [BO3] units in the glass. [BO4] units are converted into [BO3] with increasing Bi2O3 by producing more non-bridging oxygens. Raman and XPS investigation indicate that Bi5+ ions may be formed in the glass with 60mol% Bi2O3. We studied the structure of 50Bi2O3-(50-x) B2O3-xGeO2 (x=0, 5, 10, 15 mol%) glass. The XPS result indicates Ge4+ ions form steady [GeO4] tetrahedra units in the glass network and the number of non-bridging oxygens decreases with the addition of GeO2. Secondly, the optical energy gap and third nonlinear property are studied. Two photons absorption occurred in Bi2O3-B2O3-Ga2O3 and Bi2O3-B2O3-GeO2 glasses. The linear, nonlinear refractive index and optical energy gap (2.8~3.2eV) increase with Ga2O3 and GeO2 contents. The calculated highest third-order nonlinear coefficient χ(3) is about 2.26 ×10 -11esu. At last, the luminescence properties of Er3+，Tm3+，Yb3+ ions in bismuthate glasses were discussed. The broad and flat 4I13/2→4I15/2 emission (FWHM~94 nm) and the large absorption and stimulated emission cross-sections (6.45×10-21 cm2 and 7.03×10-21 cm2) of Er3+ ions around 1.5μm can be obtained. Er3＋-doped bismuthate glass is potential for broadband optical amplifier application at C and L bands. The absorption spectra of Tm3+-doped 53.3BiO1.5-33.3GeO2-13.4NaO0.5 (cation%) glasses with various Tm3+ concentrations were measured to obtain the radiative lifetimes by Judd-Ofelt theory. The absorption (4.5×10-21 cm2) and emission (6.7×10-21 cm2) cross sections were calculated by Beer-Lambert and McCumber theory. The results show that the Tm3+ (3F4→3H6) in these glasses has high spontaneous radiative transition probabilities and large stimulated emission cross-section. The emission spectra were measured under the excitation of a 808 nm laser dioe (LD) and the maximum emission intensity at 1.8 μm is obtained at 0.9 mol% Tm2O3 in the glasses. The luminescence properties of Yb3+-doped 55Bi2O3-25B2O3-10Ga2O3-10SiO2-xYb2O3 (x=0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 2.5, 4.0 mol%) glasses were discussed. The absorption cross-section (σabs) and emission cross-section (σem) are 1.46×10-20cm2 and 2.02×10-20cm2 respectively. The fluorescent lifetime (τf) changes from 1.22 to 0.57 ms with increasing Yb3+ concentration. The content of OH- group in the glass is an important factor on luminescence quenching. |
| 语种 | 中文 |
| 源URL | [http://ir.siom.ac.cn/handle/181231/15635]  |
| 专题 | 上海光学精密机械研究所_学位论文 |
| 推荐引用方式 GB/T 7714 | 范慧艳. 铋酸盐玻璃结构和非线性及光谱性质研究[D]. 中国科学院上海光学精密机械研究所. 2010. |
入库方式： OAI收割
来源：上海光学精密机械研究所
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