铝酸盐钕玻璃结构和宽带发光特性的研究
文献类型：学位论文
| 作者 | 康帅 |
| 文献子类 | 博士 |
| 导师 | 胡丽丽 |
| 关键词 | 铝酸盐玻璃 Aluminate glass 钕离子 Nd3+ ions 宽带光谱 broadband emission 结构 structure |
| 其他题名 | Broadband luminescence and structure property of Nd3+ ions doped Aluminate glass |
| 英文摘要 | 自从激光出现以来，超高功率激光就是激光科学的主要方向之一。近年来，超高功率激光因为在前沿物理科学研究和 “ 快点火”方向的巨大作用而越发受到科研人员的重视和关注。激光增益介质作为高功率激光装置及激光技术的核心和基石，具有重要的科研意义。本论文方向为研制适用于混合型钕玻璃高功率激光系统的宽带发光钕玻璃。论文内容主要分析了钕离子掺杂铝酸盐玻璃的物理性质、结构性质和光谱性质；同时对铝酸盐玻璃中钕离子发光光谱展宽机理进行了研究和探讨。最后，本课题初步探索出多种新型宽带铝酸盐钕玻璃配方，丰富了已有钕玻璃的数据库。 本论文主要包括 6 章：第一章是文献综述部分，第二章是本文实验方法及稀土光谱学的理论基础；第三到五章是本论文的核心部分；第六章是结论。 第一章简要的介绍了激光和高功率激光的发展与应用；简述了各种高功率激光增益介质的优缺点；分析得出混合型钕玻璃体系对宽带钕玻璃的需求；同时讨论了稀土离子电子组态和稀土发光特性；最后提出了宽带钕玻璃研发工作的必要性和紧迫性。基于此目的，第一章结尾部分提出本论文在开发新型钕玻璃和研究荧光展宽机理等方向的思路。 论文的第二章，介绍了试验方法和各种测试表征手段，同时概述了稀土光谱参数和相关理论计算。铝酸盐玻璃热稳定性较差，以往文献中通过引入少量 SiO2 增强玻璃的抗析晶能力。本论文第三章主要讨论了在传统低硅铝酸盐组分中， SiO2 含量从 0mol%变化至 12m ol%对铝酸盐玻璃物理热学性质、结构和 Nd3+离子光谱性质的影响。随着 SiO2 增加，玻璃的密度和折射率下降；玻璃化转变温度 Tg 和析晶起始温度 Tx 上升。Raman 光谱表明，高场强的 Si4+离子夺取并积聚非桥氧，形成[SiO4]四面体的 Q0结构；同时导致 Al-O 网络中非桥氧数量逐渐减小。吸收光谱峰型变化证实 Nd-O 键共价性下降。 与此同时， Nd3+离子荧光峰半高宽从 39.7nm 缩窄至 36.3nm ，有效线宽从 48.2nm 缩窄至 44.7nm ； 计算得到 Nd3+离子受激发射截面 σe 从 1.84×10-20cm2增大至 2.04×10-20cm2。 本章最后对大尺寸低硅铝酸盐玻璃制备工艺进行了探索。 实验第四章讨论了铝酸盐玻璃中引入其它玻璃形成体氧化物（B2O3、 GeO2、Ga2O3） ，对玻璃物理热学性质、结构和 Nd3+离子光谱性质的影响。其中，高场强 B3+离子掺杂铝酸盐玻璃后，玻璃结构和光谱性质与 Si 掺杂所引起变化类似。 Raman 光谱证实 B3+夺取并积聚 Al-O 网络中的非桥氧，形成高解聚态硼氧三角体[BO 3]的 Q0结构。B2O3 含量增加导致玻璃化转变温度 Tg显著降低，热稳定性参数△T 逐渐增大。吸收光谱峰型变化证明 Nd-O 键共价性程度下降；荧光光谱中，Nd3+离子荧光峰半高宽从从 40.1nm 减小至 34.3nm ，有效线宽从 50nm 缩窄至 41.6nm。Fuchtbauer- Ladenburg 公式计算得到 Nd3+离子受激发射截面 σe 从 1.6× 10-20cm2 增大至 2.04× 10-20cm2 。因为 Ge4+离子场强稍弱，其夺取非桥氧的能力弱于 B3+、Si4+离子。所以GeO2 在玻璃中形成[GeO 4]的 Q2结构。随着 GeO2 含量上升，玻璃特征温度 Tg和 Tx 显著降低；同时 Nd-O 键共价性下降。Nd3+离子荧光峰半高宽从 40.5nm减小至 36nm ，有效线宽从 49.60 缩窄至 44.6nm 。Fuchtbauer- Ladenburg 公式计算得到 Nd3+离子受激发射截面 σe 从 1.6× 10-20cm2 增大至 1.85× 10-20cm2。与 B3+、Si4+、Ge4+不同，Ga3+离子场强较弱，无法夺取铝氧网络中的非桥氧。随着 Ga2O3 取代 Al 2O3，玻璃的特征温度 Tg 和 T x 显著下降，热稳定参数 ΔT 和 H’先增大后减小，说明出现混合形成体效应。 Raman 光谱显示玻璃逐渐由铝酸盐结构转变为镓酸盐结构。在不同组成的铝镓酸盐玻璃中，Nd3+离子发射带宽变化不 明显， 其中荧光峰 FWMH 约为 39nm， 有效线宽 约为 37nm。Fuchtbauer- Ladenburg 公式计算得到 Nd3+离子受激发射截面 σe 从铝酸盐玻璃中 1.79×10-20cm2 逐渐增大至镓酸盐玻璃中 2.06×10-20cm2。第四章最后部分探索了大尺寸铝镓酸盐钕玻璃的熔制工艺，得出多个热稳定性好的宽带铝酸盐钕玻璃组分配方。 第五章讨论了铝酸盐玻璃中网络修饰体含量变化和 Nd3+离子浓度变化对其光谱性质的影响。发现随着玻璃中 CaO/Al 2O3 比例的提高，玻璃的特征温度 Tg 从 839°C 下降至 767°C，同时玻璃的热稳定参数 ΔT 和 H’先增大后减小，在 CaO/Al2O3=2 时达到极大值；研究确定了热稳定性最佳的铝酸盐玻璃组分中碱铝比。Raman 光谱表明玻璃中 CaO 含量升高导致玻璃中 NBOs 数量增多，引起玻璃网络解聚程度增大。光谱分析说明随着 CaO 含量提高， Nd-O 键共价性程度逐渐升高； Nd3+离子荧光峰半高宽从38.6nm 展宽至 41.2nm ，Δλeff 从 47.5nm 展宽至 50.2nm。计算得到 Nd3+离子受激发射截面 σe 从 2.11×10-20cm2 降低至 1.35×10-20cm2。 实验制备了不同 Nd2O3 掺杂浓度的低锗铝酸盐钕玻璃，研究其光谱性质变化。随 Nd2O3 浓度上升， 钕离子荧光峰出现浓度展宽现象， 荧光半高宽从 33.8nm增加至 41.6nm ；荧光强度先上升后下降，Nd2O3 为0.5mol%时达到最大值，随后出现浓度淬灭现象。同时，Nd2O3 浓度上升引起荧光寿命下降，当Nd2O3 >0.5mol%时，出现浓度淬灭，荧光寿命下降速度加快。实验制备了不同 Nd2O3 掺杂浓度的铝镓酸盐钕玻璃，并研究其光谱性质变化。随 Nd2O3 浓度上升，荧光峰出现浓度展宽现象，荧光半高宽从 34.1nm 展宽至39.6nm；荧光强度先上升后下降，在 Nd2O3=0.5mol%时达到最大值；荧光寿命逐渐下降，在 Nd2O3>0.5mol%后，出现浓度淬灭。 最后一章是本论文的结论部分，总结了全文的主要研究结果。; In recent years, high-power-laser has drawn considerable attention because of its important role in the forefront scientific research and laser inertial confinement fusion engineering. “Mixed glass” is a technical solution to get ultra fast and high power laser. As the basement of lasers science, the development of new laser material is very important. The motivation of this study is to develop the new type of broadband emission Nd3+ doped laser glasses, which have potential application in the “mixed-glass” high-power-laser system. In this paper, the physical, structural and spectroscopy properties of Nd3+ doped aluminate glass have been investigated and analyzed; the broadening mechanism of Nd emission spectrum has also been researched. As a result, several Nd:Aluminate glasses with broadband emission and good thermal stability have been developed. This dissertation includes the following six chapters. The first chapter is the literature review. Chapter two is the experimental methods and theoretical basis about rare-earth ions luminescence. The 3-5th chapters are the core contents of the dissertation. The last chapter is the conclusion. The first chapter introduced the development and application of laser and high power laser; the gain medium in high power laser was briefly discussed; meanwhile, the electronic configuration and luminescent property of rare earth ions were summarized. Finally, the purpose and research content of the dissertation were put forward. In chapter II, the experimental and test methods are introduced; including the preparation procedures of glasses, physical and spectroscopic properties measurements. The analysis method of the experimental data is reviewed as well. Due to the poor thermal stability of aluminate glass, SiO2 was usually introduced to improve the resistance to crystallization of glass. In chapter III, the effect of SiO2 on the physical, thermal, structure and the Nd3+ ions spectroscopic properties of low silica aluminate glass were investigated. The density and refractive index of aluminate glass were found to decrease with the increase of SiO2 content; while the glass characteristic temperature Tg and Tx increase. Raman spectra showed that the non-bridging-oxygens (NBOs) in the glass network [AlO4] were captured and accumulated by Si4+ ions due to their high field strength. The decreasing covalency degree of Nd-O bond was confirmed by the change in the absorption spectra; meanwhile, the fluorescence spectra showed that the FWMH of fluorescence peak of Nd3+ ioins narrowed from 39.7 nm to 36.27 nm, the effective bandwidth also decreased from 48.2 nm to 44.7 nm. The value of σem is inversely proportional to the emission bandwidth, which was found to increase from 1.84 × 10-20 to 2.04 × 10-20 cm2. The preparation of large size aluminate glass was presented in chapter 3. In the fourth chapter, the effects of glass formers (B2O3, GeO2, Ga2O3) on the physical, thermal, structure properties of the aluminate glass and the spectroscopic properties of neodymium ions were discussed. The effect of B3+ ions on the structural and spectra properties of Nd3+ doped aluminate glass was similar to those of Si4+ ions. The glass characteristic temperature Tg and Tx were found to decrease with the increase of B2O3. Raman spectra showed that the NBOs in [AlO4] were captured and accumulated by the Q0 speice of [BO3] triangle, due to the higher field strength of B3+ ions. The decreasing covalency degree of Nd-O bond was confirmed by the change in the absorption spectra; meanwhile, the fluorescence spectra showed that the FWMH of fluorescence peak narrowed from 40.1 nm to 34.3 nm and the effective bandwidth decreased from 50 nm to 41.6nm; the value of σem was found to increase from 1.6 × 10-20 to 2.04 × 10-20cm2. In low GeO2 containing aluminate glass, due to the electric field of Ge4+ ion is lower than that of Si4+ and B3+ ions, Ge4+ ion could only form the Q2 speice of [GeO4] tetrahedron by capturing NBOs in Al-O network. The increase of GeO2 leads to the decrease in the covalency degree of Nd-O bond. The fluorescence spectra showed that the FWMH of fluorescence peak of Nd3+ ioins narrowed from 40.6 nm to 36 nm and the effective bandwidth decreased from 49.5 nm to 44.6nm, with the increasing GeO2 content; the value of σem was found to increase from 1.6×10-20 cm2 to 1.85×10-20 cm2. Ga3+ ion has a weak electric field, it can not capture NBOs from Al-O network. With Ga2O3 replacing Al2O3 gradually, the characteristic temperature Tg and Tx decreased significantly; due to the mixed glass former effect, the thermal stability parameters △T and H’ had maximum value at Ga2O3 =20mol% composition. The Raman spectra showed that the glass structure was changed from the aluminate to galliunate glass gradually. The FWMH of emission bandwidth was around 39nm in the different aluminogalliunate glasses; while the effective bandwidth was around 47nm; the emission cross section σem increased from 1.79×10-20 cm2 to 2.06×10-20 cm2. At the end of this chapter, the melting process of large size Aluminum glass was explored. The several glass compositions of Nd: Aluminate glasses with good thermal stability and broadband emission of Nd3+ ion were obtained. In the fifth chapter, the influence of the network modifier and neodymium concentration on the spectroscopic properties of Nd:Aluminate glass was discussd. With the increase of CaO/Al2O3 ratio, the glass transition temperature Tg decreased from 839 °C to 767 °C. The thermal stability parameters △T and H’ had maximum value at CaO/Al2O3 ratio of 2, which corresponds to the most stable glass composition. The Raman spectra showed the NBOs and the depolymerization degree increased with the increase of CaO content. The spectral analysis showed the covalency degree of Nd-O increased gradually with the increase of CaO; the fluorescence FWHM increased from 38.6nm to 41.2nm, and the effective bandwidth also increased from 47.5nm to 50.2nm; while the stimulated emission cross section σem reduced from 2.11×10-20cm2 to 1.35×10-20cm2. The spectroscopic properties of Nd3+ ions were studied in the low GeO2 containing aluminate glass with different Nd2O3 contents. With the increase of Nd2O3 concentration, the FWMH of fluorescence peak increased from 33.8nm to 41.6nm. Due to the concentration quenching of Nd3+ ions, the fluorescence intensity reached the maximum value at Nd2O3 of 0.5mol%; the fluorescence lifetime decreased obviously when Nd2O3> 0.5mol% due to concentration quenching. The gallioaluminate glasses with different Nd2O3 contents were prepared and studied. With the increase of Nd2O3 concentration, the FWMH of fluorescence peak increased from 34.1nm to 39.6nm. The changes in the fluorescence intensity and fluorescence lifetime verified the concentration quenching occoured in Nd2O3> 0.5mol% samples. Finally, the main results of this dissertation have been concluded in chapter six. In recent years, high-power-laser has drawn considerable attention because of its important role in the forefront scientific research and laser inertial confinement fusion engineering. “Mixed glass” is a technical solution to get ultra fast and high power laser. As the basement of lasers science, the development of new laser material is very important. The motivation of this study is to develop the new type of broadband emission Nd3+ doped laser glasses, which have potential application in the “mixed-glass” high-power-laser system. In this paper, the physical, structural and spectroscopy properties of Nd3+ doped aluminate glass have been investigated and analyzed; the broadening mechanism of Nd emission spectrum has also been researched. As a result, several Nd:Aluminate glasses with broadband emission and good thermal stability have been developed. This dissertation includes the following six chapters. The first chapter is the literature review. Chapter two is the experimental methods and theoretical basis about rare-earth ions luminescence. The 3-5th chapters are the core contents of the dissertation. The last chapter is the conclusion. The first chapter introduced the development and application of laser and high power laser; the gain medium in high power laser was briefly discussed; meanwhile, the electronic configuration and luminescent property of rare earth ions were summarized. Finally, the purpose and research content of the dissertation were put forward. In chapter II, the experimental and test methods are introduced; including the preparation procedures of glasses, physical and spectroscopic properties measurements. The analysis method of the experimental data is reviewed as well. Due to the poor thermal stability of aluminate glass, SiO2 was usually introduced to improve the resistance to crystallization of glass. In chapter III, the effect of SiO2 on the physical, thermal, structure and the Nd3+ ions spectroscopic properties of low silica aluminate glass were investigated. The density and refractive index of aluminate glass were found to decrease with the increase of SiO2 content; while the glass characteristic temperature Tg and Tx increase. Raman spectra showed that the non-bridging-oxygens (NBOs) in the glass network [AlO4] were captured and accumulated by Si4+ ions due to their high field strength. The decreasing covalency degree of Nd-O bond was confirmed by the change in the absorption spectra; meanwhile, the fluorescence spectra showed that the FWMH of fluorescence peak of Nd3+ ioins narrowed from 39.7 nm to 36.27 nm, the effective bandwidth also decreased from 48.2 nm to 44.7 nm. The value of σem is inversely proportional to the emission bandwidth, which was found to increase from 1.84 × 10-20 to 2.04 × 10-20 cm2. The preparation of large size aluminate glass was presented in chapter 3. In the fourth chapter, the effects of glass formers (B2O3, GeO2, Ga2O3) on the physical, thermal, structure properties of the aluminate glass and the spectroscopic properties of neodymium ions were discussed. The effect of B3+ ions on the structural and spectra properties of Nd3+ doped aluminate glass was similar to those of Si4+ ions. The glass characteristic temperature Tg and Tx were found to decrease with the increase of B2O3. Raman spectra showed that the NBOs in [AlO4] were captured and accumulated by the Q0 speice of [BO3] triangle, due to the higher field strength of B3+ ions. The decreasing covalency degree of Nd-O bond was confirmed by the change in the absorption spectra; meanwhile, the fluorescence spectra showed that the FWMH of fluorescence peak narrowed from 40.1 nm to 34.3 nm and the effective bandwidth decreased from 50 nm to 41.6nm; the value of σem was found to increase from 1.6 × 10-20 to 2.04 × 10-20cm2. In low GeO2 containing aluminate glass, due to the electric field of Ge4+ ion is lower than that of Si4+ and B3+ ions, Ge4+ ion could only form the Q2 speice of [GeO4] tetrahedron by capturing NBOs in Al-O network. The increase of GeO2 leads to the decrease in the covalency degree of Nd-O bond. The fluorescence spectra showed that the FWMH of fluorescence peak of Nd3+ ioins narrowed from 40.6 nm to 36 nm and the effective bandwidth decreased from 49.5 nm to 44.6nm, with the increasing GeO2 content; the value of σem was found to increase from 1.6×10-20 cm2 to 1.85×10-20 cm2. Ga3+ ion has a weak electric field, it can not capture NBOs from Al-O network. With Ga2O3 replacing Al2O3 gradually, the characteristic temperature Tg and Tx decreased significantly; due to the mixed glass former effect, the thermal stability parameters △T and H’ had maximum value at Ga2O3 =20mol% composition. The Raman spectra showed that the glass structure was changed from the aluminate to galliunate glass gradually. The FWMH of emission bandwidth was around 39nm in the different aluminogalliunate glasses; while the effective bandwidth was around 47nm; the emission cross section σem increased from 1.79×10-20 cm2 to 2.06×10-20 cm2. At the end of this chapter, the melting process of large size Aluminum glass was explored. The several glass compositions of Nd: Aluminate glasses with good thermal stability and broadband emission of Nd3+ ion were obtained. In the fifth chapter, the influence of the network modifier and neodymium concentration on the spectroscopic properties of Nd:Aluminate glass was discussd. With the increase of CaO/Al2O3 ratio, the glass transition temperature Tg decreased from 839 °C to 767 °C. The thermal stability parameters △T and H’ had maximum value at CaO/Al2O3 ratio of 2, which corresponds to the most stable glass composition. The Raman spectra showed the NBOs and the depolymerization degree increased with the increase of CaO content. The spectral analysis showed the covalency degree of Nd-O increased gradually with the increase of CaO; the fluorescence FWHM increased from 38.6nm to 41.2nm, and the effective bandwidth also increased from 47.5nm to 50.2nm; while the stimulated emission cross section σem reduced from 2.11×10-20cm2 to 1.35×10-20cm2. The spectroscopic properties of Nd3+ ions were studied in the low GeO2 containing aluminate glass with different Nd2O3 contents. With the increase of Nd2O3 concentration, the FWMH of fluorescence peak increased from 33.8nm to 41.6nm. Due to the concentration quenching of Nd3+ ions, the fluorescence intensity reached the maximum value at Nd2O3 of 0.5mol%; the fluorescence lifetime decreased obviously when Nd2O3> 0.5mol% due to concentration quenching. The gallioaluminate glasses with different Nd2O3 contents were prepared and studied. With the increase of Nd2O3 concentration, the FWMH of fluorescence peak increased from 34.1nm to 39.6nm. The changes in the fluorescence intensity and fluorescence lifetime verified the concentration quenching occoured in Nd2O3> 0.5mol% samples. Finally, the main results of this dissertation have been concluded in chapter six. |
| 学科主题 | 材料学 |
| 源URL | [http://ir.siom.ac.cn/handle/181231/31010]  |
| 专题 | 中国科学院上海光学精密机械研究所 |
| 作者单位 | 中国科学院上海光学精密机械研究所 |
| 推荐引用方式 GB/T 7714 | 康帅. 铝酸盐钕玻璃结构和宽带发光特性的研究[D]. |
入库方式： OAI收割
来源：上海光学精密机械研究所
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