稀土掺杂重金属氧化物玻璃及光纤的光谱性质研究
文献类型：学位论文
| 作者 | 王训四 |
| 学位类别 | 博士 |
| 答辩日期 | 2007 |
| 授予单位 | 中国科学院上海光学精密机械研究所 |
| 导师 | 刘立人 |
| 关键词 | 重金属氧化物玻璃 光谱性质 上转换荧光 宽带放大 光纤制备 |
| 其他题名 | Investigation in optical properties of rare-earth ions doped heavy metal oxide glass and fiber |
| 中文摘要 | 随着计算机网络及其数据传输业务的飞速发展，人们对提高波分复用系统传输容量的需求日益增长，传统的石英基质EDFA由于其本身带宽的限制而不能满足这种需求。虽然有许多物理特性改良或结构设计的方法用来增加石英基质EDFA的传输带宽，但不能从根本上解决石英基质本身带来的限制，因此寻找合适的Er3+ 掺杂基质材料，实现光信号的宽带高增益放大，对于光学通信系统传输容量的扩展，具有非常重要的意义。另外，鉴于蓝绿光等短波长激光器在光学通信、数据存储、激光打印、水下传输以及生物医学等方面广泛的应用，如何获得廉价、高效、小型化的蓝绿光激光器也是光电子器件和光电子材料领域的热点和难点。在获得蓝绿光输出的诸多方法中，利用稀土离子的上转换方法具有许多明显的优势，它有利于廉价、紧凑小型激光器系统的发展。本论文结合当前对光通讯材料发展的需求，研究了适用于获得宽带放大的碲酸盐和铋酸盐玻璃基质中的Er3+ ，Tm3+ 发光性能，总结出发光性能参数随玻璃成分变化的规律，同时也研究了适合于获得蓝绿光激光输出的碲酸盐玻璃材料中的Er3+ ，Tb3+ 的发光特性并获得发光效率和稳定性能俱佳的上转换发光材料。最后对重金属氧化物玻璃光纤的拉制工艺进行了大量的研究，提出了采用半圆夹芯法制作单模标准光纤，同时改进了旋转＋浇铸＋抽真空拉丝的管棒法拉丝工艺，获得了尺寸和通光性能俱佳的碲酸盐玻璃光纤。具体内容如下： 论文首先综述了稀土掺杂光纤放大器和稀土离子上转换发光的研究进展以及稀土离子掺杂激光玻璃的理论基础，接着综述了当前各种光纤制作技术及其优缺点，最后给出本文的研究内容和研究思路。 在论文的第二章，介绍了重金属氧化物玻璃的制备、测试实验方法和相关的光谱参数计算等基础理论，主要包括各种玻璃的制备，玻璃样品的各种测试以及Judd-Ofelt、FL、McCumber等光谱参数计算理论。 论文第三章分析了Er3+ 离子在碲酸盐和铋酸盐玻璃中的光谱性质，分析GeO2含量的增加对掺铒TeO2-GeO2-Nb2O5-Li2O玻璃基质的热稳定性和光谱性能的影响，即在玻璃基质物理性质改善的情况下分析Er3+ 在该碲酸盐玻璃中的荧光发射特性，得出了GeO2含量为10 mol.%时，该玻璃具有最佳成光纤性能且保证了最佳的Er3+ 荧光性能。然后研究Ce3+ 引入后对Er3+ 掺杂的铋－硼－硅酸盐中所带来的光谱性质的影响，分析玻璃基质声子能量的改变对声子辅助能量转移(PAT)率的影响，从而通过适当配比提升Er3+ 离子1.5m波段的荧光发射特性。研究发现，当B2O3引入后引起的玻璃基质声子能量达到1200cm-1的时候，Er3+ 能级4I11/2上粒子的无辐射跃迁速率从~ 313 s-1剧增到~515s-1，从而能获得较大的1.5m荧光发射效率。 在研究Er3+ 掺杂的碲酸盐荧光特性基础上，论文第四章研究了引入Tm3+ 离子共掺后的超宽带荧光特性，即在Tm3+ /Er3+ /Ce3+ 共掺的铋－硅酸盐中研究其物理和光谱性质，在采用800nmLD激光对该玻璃样品进行泵浦后，能获得了FWHM为117nm 的超宽带荧光发射。该荧光具备寿命长、带宽宽、谱线平坦的综合优势，当Tm3+ /Er3+ /Ce3+ 掺杂比例为1:1:3能获得最佳的荧光发射特性。最后在能量转移和无辐射驰豫相关匹配理论的基础上分析了该玻璃中的超宽带发光机理。 论文第五章中，进一步分析了Er3+ ，Tm3+ 离子碲酸盐玻璃中的上转换光谱特性。通过在TeO2-ZnO-Na2O玻璃基质中引入Bi2O3成份，从而研究Er3+ /Yb3+ 在980nmLD激光泵浦下的上转换发光特性。实验结果表明低声子能量的Bi2O3的引入，引起Er3+ 离子4F9/2能级跃迁的淬灭，改善了绿光的发射性能。最后讨论了TeO2-ZnO-Na2O组份碲酸盐玻璃中Tm3+ /Yb3+ /Tb3+ 单掺或多掺情况下所获得的新的上转换发光现象，详细的讨论了在Yb3+ 敏化后Tb3+ 在合作上转换过程中产生的上转换发光现象，尤其是Tm3+ 的引入，明显促进了Tb3+ 的上转换发光。 论文第六章在研究玻璃成纤性质基础上改进碲酸盐玻璃光纤制作工艺，提出或改良了三种有效的光纤制作方法。从制作光纤最简易的方法――机械组合式的半圆合成法，到采用真空设备和高速旋转装置的套管拉丝方法，都实现了单模尺寸光纤的制作。尤其是在套管法＋抽真空缩棒的拉丝方法中，实现了较好的芯层和包层界面熔合和光纤芯层和包层外形同心度。 在对玻璃样品进行比较分析的基础上，第七章阐述了利用所研制的玻璃光纤进行光谱性能分析，对Er3+ 离子在TeO2-GeO2-Nb2O5-Li2O玻璃光纤中发射的1.5m波段荧光光谱性质进行研究。在研究该Er3+ /Yb3+ 共掺光纤ASE、上转换荧光光谱与泵浦功率、光纤长度的相互关系中，借助能级方程和光波导条件对ASE光分布进行模拟分析，并用实验数据进行验证。在特定泵浦条件下获得最大ASE强度时的最佳光纤长度，得出了在574mW光泵浦强度时光纤最佳长度为56.5cm。 最后是本论文的结论部分，概括了全文创新性的研究结果。 |
| 英文摘要 | With the rapid development of computer networks and other data-ransmittiong services, the demand for the increase of transmission capacity of wavelength- division-multiplexing (WDM) system is urgent. The conventional silica based Er3+ -doped fiber amplifier (EDFA) can’t meet this requirement because of its intrinsic bandwidth limit. Though many physical and structural methods have been used to flatten the gain spectrum and broaden the amplification bandwidth of silica based EDFA, it is important to find another glass matrix for Er3+ doping to obtain an intrinsically broader gain bandwidth than that of silica based EDFA, which is beneficial to the enlargement of transimission capacity. Besides, owing to its potential applications in the fields of color display, optical data storage, biomedical diagnostics and undersea transimmion of blue and green lasers, how to obtain cheap, efficient and compact visible lasers are now becoming hot topics and challenges in the fields of optoelectronic materials and components. Among the several methods of obtaining blue and green light output, many advantages are expected by using the upconversion emission of rare earth ions. Based on the requirements of the development of optoelectronic materials, the luminescent properties of Er3+ and Tm3+ doped tellurite and bismuth-based glasses suitable for broadband and high gain of amplification were studied and the optical parameters changes with the glass composition were discussed. Besides, the upconversion properties of Er3+, Tm3+ and Tb3+ -doped tellurite glasses, which has potential applications in the fields of up-conversion laser materials. In the last, it was also investigated in the techniques of fiber fabrication to non-silicate glasses in detail; three kinds of new methods for fiber fabrication were developed as they all exhibit the validity to fiber fabrication. The dissertation is divided into eight chapters in all. In chapter 1, the progress and significance for studying rare earth doped wide band fiber amplifiers and high power fiber lasers are introduced, and some related techniques for fiber fabrication are reviewed. Then, the contents of this dissertation and the methods of research are proposed on the basis of foregoing studies. Chapter 2 describes some useful theories for spectral analysis to rare earth doped glasses, such as the Judd-Ofelt and Fuchtbauer-Ladenburg theories. The methods of the glass fabrication and characterization are also reviewed in this chapter. Chapter 3 deals with the influence of doping GeO2 on TeO2-GeO2-Nb2O5-Li2O glasses and B2O3 on bismuth based glasses. It is found that the optimum content of GeO2 is 10mol.% and the glass performance is significantly improved. Then, a kind of bismuth based glasses co-doped with Er3+ and Ce3+ were fabricated, whose characteristics were affected by adding B2O3 because of the changes of the phonon energy. The phonon energy was used to improve the rate of phonon assisted energy transfer (PAT), as it was originated from the Ce3+ in the glasses. With optimum concentrations of B2O3 and phonon energy of 1200cm-1, the transition rate of Er3+:4I11/2→4I13/2 was increased quickly from ~313s-1 to ~515s-1, and the 1.5m fluorescence emission of Er3+ was improved obviously. In chapter 4, the supper wide band fluorescence of Tm3+ /Er3+ in bismuth-silicate glasses co-doped with Ce3+ was investigated, the fluorescence exhibits the long lifetime and wide plain emission spectrum when the concentration proportion of Tm3+ /Er3+ /Ce3+ is 1:1:3. The experimental results were also discussed in detail based on the related theories. Chapter 5 investigates the influence of doping Bi2O3 on TeO2-ZnO-Na2O-Bi2O3 glasses. With increasing Bi2O3 contents, the Er3+:4F9/2 level was nearly been quenched, as the rate of relaxation changed. Then, a special but strong up-conversion fluorescence of Tb3+ appears when Tm3+ /Yb3+ /Tb3+ was co-doped in the tellurite glasses, since there exists new ways of energy transfer from Yb3+ and Tm3+ to Tb3+ , such as the cooperation energy transfer. Three methods for optical fiber fabrication are presented in chapter 6. The composing method with semi-column cladding is a convenient way to make the standard mono-mode fiber. The casting way assures the well performance of interface between core and cladding of fibers. And then, after improved with vacuuming and collapsing process, the method of rod in tube can make a fiber with well interface and shape. In chapter 7, two kinds of mono-mode fiber with Er3+ single doped and Er3+ /Yb3+ co-doped TeO2-GeO2-Nb2O5-Li2O glass hosts were fabricated, some important results were investigated, such as the fiber ASE intensity and up-conversion fluorescence varying with the pumping laser power and fiber length. The rate equation and fiber wave-guide theories were used to analyze the relation between the ASE intensity and the fiber length under the certain pumping power. The optimum fiber length of 56.5cm under excitation power of 574mW was obtained to the specified fiber. Chapter 8 presents the general conclusions for this dissertation. |
| 语种 | 中文 |
| 源URL | [http://ir.siom.ac.cn/handle/181231/15434]  |
| 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 | 王训四. 稀土掺杂重金属氧化物玻璃及光纤的光谱性质研究[D]. 中国科学院上海光学精密机械研究所. 2007. |
入库方式： OAI收割
来源：上海光学精密机械研究所
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