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题名	新型中红外氟化物玻璃光谱性质及光纤研究
作者	薛天锋
文献子类	博士
导师	胡丽丽
关键词	氟化物玻璃 Fluoride glass 2.7μm 2.7 μm 中红外发光 Mid-infrared emission 玻璃光纤 Glass fiber
其他题名	Research on spectroscopic properties of novel mid-infrared fluoride glass and fiber
英文摘要	中红外激光及其器件在医疗、军事武装、远程遥控探测和环境质量监控等领域都有极为广泛的应用。氟化物玻璃由于在中红外波段的透光率高、声子能量低、稀土离子掺杂能力强，而成为极佳的中红外基质材料，是目前唯一获得中红外激光输出的玻璃基质材料。然而，氟化物玻璃差的耐潮解能力会导致其表面容易被水腐蚀。氟化物玻璃光纤中的微晶在很大程度上归因于光纤预制棒表面被水潮解浸湿，制备的氟化物玻璃光纤的韧性强度也同样受此性能影响而减弱。因此，有必要去研究、优化氟化物玻璃基质材料。本论文的主要目的是开发新型的中红外氟化物激光玻璃材料，并研究其中红外荧光特性。 本论文主要分为六个章节。第一章是文献综述，介绍了传统的氟化物玻璃和近年来新开发的新型氟化物玻璃，以及这些掺稀土氟化物玻璃在中红外波段的发光及激光性能的研究进展。 论文第二章主要讲述了实验方法和理论基础。包括玻璃和光纤的制备、测试方法，玻璃光谱性质的研究理论，例如Judd-Ofelt(J-O)理论、吸收和荧光光谱的研究方法以及稀土离子间的能量传递理论等。 论文第三章到第五章是主体部分。第三章介绍了一种用传统的高温熔制方法制备的新型氟镓酸盐玻璃。首先研究了其热稳定性、热膨胀性质以及物理化学等性能。该玻璃基质具有较低的最大声子能量、高的中红外透过率以及优良的物理化学性能。其次，制备了掺铒氟镓酸盐玻璃，通过测试吸收光谱、荧光光谱，在Judd-Ofelt理论基础上，研究了玻璃的中红外发光性能和受激辐射参数。所研究的掺铒氟镓酸盐玻璃对应的Er3+:4I11/2→4I13/2辐射跃迁在2.71 μm处具有大的荧光分支比β(21.71%) 和受激发射截面(1.04 × 10?20 cm2)。最后制备了Er3+/Pr3+、Er3+/Nd3+共掺的氟镓酸盐玻璃，分析了Pr3+、Nd3+对Er3+的敏化作用。基于Judd-Ofelt和Fuchbauer-Ladenburg理论，研究讨论了Pr3+/Er3+、Nd3+/Er3+共掺氟镓酸盐玻璃的中红外发光特性，并且与单掺铒的玻璃做了分析对比。研究表明，新型的掺稀土氟镓酸盐玻璃是中红外激光材料的潜在选择。 论文的第四章制备了GaF3修饰的一种新型的掺铒氟碲酸盐玻璃，通过差热分析和拉曼光谱表明该玻璃基质具有高的热稳定性和较低的声子能量。在980 nm半导体激光器(LD)激发下，对应Er3+:4I11/2→4I13/2的辐射跃迁，在2.71 μm附近观察到强的中红外发光现象。通过测试玻璃的吸收和荧光光谱，基于Judd-Ofelt理论，得到玻璃的受激辐射参数。该新型掺铒玻璃具有比其它碲酸盐玻璃更高的热稳定性(Tg = 360 °C)和位于2.71 μm波段较大的受激发射截面(1.62 × 10–20 cm2)。研究表明该新型氟碲酸盐玻璃有望成为新型中红外激光光纤材料。 第五章介绍了氟锆酸盐玻璃及光纤的研究，制备了PbF2改性的掺铒氟锆酸盐玻璃。在980 nm LD激发下，在2.71 μm附近观察到基于Er3+ 4I11/2→4I13/2跃迁的强的中红外荧光。测试了其物理化学性能、吸收光谱以及中红外荧光光谱，基于Judd-Ofelt理论，研究了该玻璃的受激辐射参数及其它光谱性质，并且与相同铒离子浓度的ZBLAN玻璃进行了对比。研究表明，相对于Er:ZBLAN玻璃，PbF2改性的掺铒氟锆酸盐玻璃具有更大的折射率、自发辐射几率(Arad, 29.76 s?1)和位于2.71 μm波段的更大的受激发射截面(1.25 × 10?20 cm2)。并且，相对于ZBLAN玻璃，该PbF2改性的氟锆酸盐玻璃具有更好的化学稳定性。因此如果拉制成光纤，有望获得耐潮解、韧性强度更高的氟化物光纤，研究结果表明该玻璃是一种具有潜在应用价值的中红外激光材料。 其次，利用甩管法和管棒法制备了阶跃型的氟化物光纤预制棒，纤芯和包层分别为ZBLAN-Pb和ZBLAN玻璃。分别研究了这两种玻璃的玻璃转变温度、开始析晶温度、热膨胀系数及折射率分布曲线，验证了这两种玻璃可以制备芯包结构的氟化物光纤预制棒。使用二次甩管法和管棒法相结合制作的光纤预制棒，在本实验室的光纤拉丝塔上拉制了单模氟化物光纤，拉制的光纤纤芯和包层的直径分别为20和120 μm。经过测试损耗，在2.2-4 μm波段的光纤损耗为2.5-32 dB/m。高的损耗归因于原料中的过渡金属离子、玻璃内部的羟基基团以及内部散射缺陷。如果采取高纯原料、配合合理的光纤拉制参数以及控制玻璃熔制和拉丝环境，光纤损耗有望进一步降低。 第六章是本论文的结论部分，总结分析了全文的实验结果和创新点，同时指出了本论文的不足之处以及下一步工作需要改进之处。; Mid-infrared(MIR) lasers have significant applications in many fields such as military, surgery, remote sensing, and environmental monitoring. Fluoride glasses are excellent MIR medium materials due to their good MIR transmission characteristics, low phonon energy, and high solubility for rare earth (RE). To date, fluoride system is the only host glass that has exhibited laser output in MIR region. However, fluoride glass has poor resistance to water corrosion, and the surface of the glass may be damaged by atmospheric humidity. The microcrystals produced by moisture corrosion on the preform surface were found to be largely responsible for the low fiber strength. Therefore, the poor chemical stability of fluoride glass has been an obstacle to fabricating high-strength fibers, and it is significant to develop or optimize new mid-infrared fluoride glasses. Therefore, the aim of this work is to develop new fluoride glasses for mid-infrared lasers. Meanwhile, the fluorescence characteristics in the MIR region should be investigated. This dissertation includes the following six chapters. Chapter I is the literature reviews, which mainly introduce the various fluoride glasses and research progress of fluoride glass in the MIR filed. Chapter II is the experimental methods and theoretical basis. It includes preparation of glasses and fibers, and research methods of some spectroscopic properties, such as Judd-Ofelt theory, methods of calculating absorption and emission cross sections, energy migration theory of RE ions, etc. Chapters from III to V are the core parts of the dissertation. In chapter III, a new kind of fluoride glass is developed which is called fluorogallate glass. The matrix glass material for MIR is studied and prepared using traditional high temperature melting method. Firstly, the DSC curves, thermal expansion coefficient, physical and chemical properties of the proposed glass are studied. The matrix glass processes low maximum phonon energy, high MIR transmittance, good thermal and chemical stability. Secondly, the spectroscopic properties of the Er3+-doped fluorogallate glass in MIR region are investigated. Based on Judd–Ofelt theory, intensity parameters and radiative properties are determined from the absorption and emission spectra. The proposed glass possesses a large fluorescence branching ratio β(21.71%) and a maximum stimulated emission cross-section σem of Er3+:4I11/2 → 4I13/2 transition at 2.71 μm(1.04 × 10?20 cm2). Thirdly, series Er3+/x co-doped fluorogallate glasses ware prepared, the effect of sensitization ions on Er3+ ions and the energy transfer processes between them have been investigated. These sensitized ions are Nd3+and Pr3+. Based on Judd-Ofelt (J-O) and Fuchbauer-Ladenburg theories, their luminescence properties are investigated in the MIR region and compared with Er3+ single-doped fluorogallate glass. The energy transfer mechanism between Er3+ and other sensitized ions is also investigated. The results suggest that the new fluorogallate glass might be considered as a promising material for MIR high-power fiber lasers. Chapter IV talks about the Er3+-doped fluorotellurite glasses modified by GaF3. High thermal stability and relatively low phonon energy are confirmed by differential thermal analysis and Raman spectroscopy, respectively. Upon 980 nm excitation, intense luminescence emission around 2.71 μm from the Er3+:4I11/2→4I13/2 transition is observed in the glass. Based on the Judd-Ofelt theory, intensity parameters and radiative properties are determined from the absorption and emission spectra. The proposed glass possesses high thermal stability (Tg of ~360 °C) and a large stimulated emission cross section, σem, at 2.71 μm (1.62 × 10–20 cm2). The results indicate that it can be potentially applied in high-power MIR fiber lasers. In chapter V, firstly, Er3+-doped fluoride glass modified by PbF2 is developed. Upon 980 nm laser-diode excitation, intense luminescence emission around 2.71 μm from the Er3+ 4I11/2→4I13/2 transition is observed. On the basis of the Judd–Ofelt theory, the intensity parameters and radiative properties are determined from the absorption and emission spectra. Compared with conventional Er3+-doped fluoride glass (Er:ZBLAN), the proposed glass possesses a large spontaneous emission probability (Arad, 29.76 s?1) and a high stimulated emission cross-section (σem) at 2.71 μm (1.25 × 10?20 cm2). In addition, fibers with high strength might be drawn from the glass preform owing to its good chemical stability; therefore, it may be useful for increasing the output power of MIR lasers. The results indicate that the present glass can be a good candidate for MIR fiber lasers. Secondly, a step-index fluoride glass fiber preform is prepared with rotational casting and rod-in-tube techniques. The core and cladding glass compositions are ZBLAN-Pb and ZBLAN glass, respectively. Their corresponding glass transition temperature (Tg), crystallization temperature (Tx), thermal expansion coefficient (α), and refractive index (n) are also studied in order to demonstrate the feasibility of optical fiber preform preparation.The fluoride glass fibre is successfully drawn and the diameter of the core and the cladding is 20 and 120 μm, respectively. The optical loss in these fibres was presently as high as 2.5-32 dB/m at 2.5-4 μm due to OH groups, metal impurities in the raw materials, and drawing induced scattering defects. Fibre losses are expected to improve with proper control of fibre drawing parameters, and with the use of high purity starting materials and controlled atmospheric melting and drawing. In chapter VI, all results of the present work have been summarized. And it is also mentioned that something should be improved in future.
学科主题	材料学
内容类型	学位论文
源URL	[http://ir.siom.ac.cn/handle/181231/31056]
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	薛天锋. 新型中红外氟化物玻璃光谱性质及光纤研究[D].

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