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题名	Er~(3+)单掺和Er~(3+)/Yb~(3+)共掺蹄钨酸盐玻璃光谱性能研究
作者	李家成
学位类别	博士
答辩日期	2004
授予单位	中国科学院上海光学精密机械研究所
导师	胡和方
关键词	铒离子 铒单掺 铒／臆共掺 玻璃 磅钨酸盐玻璃 光谱性能
其他题名	Spectroscopic Properties of Erbium-doped and Erbium/Ytterbium-codoped Tungsten-tellurite Glasses
中文摘要	本研究的主要目的在于探索一种适用于光通信1.5μm波段的宽带掺铒光纤放大器和宽带掺铒光波导放大器基质材料。通过对Er~(3+)在玻璃中光谱性质的研究，为其在宽带掺饵光放大器基质材料上的潜在应用提供基础。论文首先在引言中概括了研究Er~(3+)单掺和Er~(3+)/Yb~(3+)共掺磅钨酸盐玻璃光谱性能的意义，接着在文献综述中介绍了磅酸盐玻璃、稀土离子掺杂的磅酸盐玻璃和掺铒磅酸盐玻璃光纤放大器的研究进展。在论文的第二章，介绍了本文的研究方法，详细介绍了实验的样品制备、性能测试及光谱参数的理论计算，包括Judd-Offelt理论和McCumber理论。在论文的第三章，研究了Er~(3+)单掺和Er~(3+)／Yb~(3+)共掺TeO_2-WO_3-La_2O_3玻璃的光谱性能。得到Er~(3+)在摩尔组成为75TeO_2-15WO_3-10La_2O_3的基质玻璃中具有较好的1.5μm波段发射带宽特性。同时发现Yb~(3+)共掺使Er~(3+) ~4I_(13/2)→~4I_(15/2)荧光发射半高宽（FWHM）增加，且在较高Er~(3+)浓度下Yb~(3+)共掺对FwHM的增加效果更明显，当Er~(3+)浓度在3.66×10~(20)/cm~3左右时，共掺Yb~(3+)使FWHM从单掺样品的65nm增加到共掺的79nm。在论文的第四章，首次研究了Er~(3+)单掺和Er~(3+)／Yb~(3+)共掺TeO_2-WO_3-ZnO（TWZ）玻璃系统的光谱性能，发现一些新现象并提出了一些新观点。研究得到Er~(3+)在摩尔组成为75TeO_2-20WO_3-5ZnO的基质中具有较好的1.5μm波段发射带宽特性，发现Er~(3+)在TWZ玻璃中1.5μm波段荧光浓度碎灭小。得到合适的Yb~(3+)共掺浓度约为Er~(3+)浓度的2倍，同时发现随Yb~(3+)浓度的增加，Er~(3+)1.5μm波段发射的FWHM从77nm增加到83nm。采用水分子伸缩振动吸收的观点对TWZ玻璃在2600～3600cm~(-1)波段的吸收进行了很好的解释；我们同时提出将样品在2600～3600cm~(-1)波段的吸收归因于（Te）-O-H、（W）-O-H两种自由羟基和（M）-OH…O强氢键轻基共同吸收的观点。计算得到Er~(3+)／Yb~(3+)共掺TWZ样品中Er~(3+)与OH基或水分子间相互作用常数k_(OH)约为（17.8±1）×10~(-20)cm~4·s~(-1)。研究发现不同厚度的Er~(3+)／Yb~(3+)共掺TWZ样品1.5μm波段的荧光有效线宽⊿λ_(eff)与荧光次峰值强度和主峰值强度的比值I_s/I_p存在很好的线性关系，线性拟合的结果验证了采用从发射截面曲线计算得出的发射带宽更能准确反映Er~(3+)l.5μm波段发射带宽的观点；首次提出采用Er~(3+)1.5μm波段荧光谱的次峰值强度和主峰值强度的比值外与从McCumber理论计算得到次峰值发射截面和主峰值发射截面的比值（σ_(es)／σ_(ep)）的差值或比值来判断基质中Er~(3+)荧光捕获效应强弱的方法。在论文第五章，对Er~(3+)单掺和Er~(3+)／Yb~(3+)共掺TeO_2-WO_3-ZnO玻璃光谱进行了改性研究。引入ZnF_2取代ZnO，得到在ZnF_2含量为8mol％时，Er~(3+)1.5μm波段发射的FWHM最大，为83nm；ZnF_2取代ZnO也使1.5μm波段的荧光强度和荧光寿命增加。根据拉曼散射光谱的结果我们同时提出该玻璃中引入的F~-阴离子主要与Zn~(2+)和Er~(3+)连接形成Zn-F键和Er-F键的观点。另外，在Twz玻璃中Ce~(3+)比B_2O_3具有更好的降低Er~(3+)上转换发光和增加~4I_(13/2)能级粒子数的综合作用，适量的Ce~(3+)的引入可同时增强Er~(3+)1.5μm波段荧光强度和减轻上转换发光，但少量高声子能量B_2O_3的引入却同时碎灭了Er~(3+)上转换荧光发射和1.5μm波段荧光发射。在论文的第六章，研究了Er~(3+)掺杂TeW_2-WO_3-ZnO-Na_2O（TWZN）四元玻璃的光谱性能。通过比较Er~(3+)在TWZN、TWZ、TeO_2-WO_3-Na_2O和TeO_2-ZnO-Na_2O玻璃中1.5μm波段的FWHM说明，Er~(3+)在四元TWZN玻璃中的1.5μm波段的FWHM比在三元TWZ玻璃中的FWHM更小，Er~(3+)在TWZ玻璃中具有最好的1.5μm波段发射带宽特性。拉曼光谱的分析说明，保持磅钨酸盐玻璃基质中[TeO_4]相对于[TeO_(3+1)][TeO_3]较高的含量和［WO_6］、［WO_4］相对高的含量有利于提高Er~(3+)在磅钨酸盐玻璃中1.5μm波段的发射带宽。最后是本论文的结论部分，总结了全文的实验研究结果，同时指出本研究存在的不足和需进一步研究之处。
英文摘要	The objective of this work is to develop a new kind of glass, which may be used as host material for broadband erbium-doped fiber amplifiers and erbium-doped optical waveguide amplifiers. Based on the investigation of the spectroscopic properties of erbium-doped and erbium/ytterbium-codoped tungsten-tellurite glasses, the potential application for the glasses used as host material for broadband optical amplifiers can be evaluated. The purpose and significance of this thesis are summarized in the introduction. Following the review of the development of the tellurite glasses and the rare-earth doped tellurite glasses, the latest development of erbium-doped tellurite glass fiber amplifiers is introduced in Chapter One. In the Second Chapter, the experiment methods are introduced, including the sample preparation procedures, physical and spectroscopic properties measurements, and the spectroscopic parameters calculation using Judd-Offelt theory and McCumber theory. In Chapter Three, the spectroscopic properties of the Er~(3+)-doped and Er~(3+)/Yb~(3+)-codoped TeO_2-WO_3-La_2O_3 glasses were investigated. The optimum molar composition of the matrix is 75TeO_2-15WO_3-10La_2O_3. In this glass, Er~(3+) ion had a larger emission bandwidth at 1.5-μm band. Results also showed that Yb~(3+)-codoping could enlarge the full width at half maximum (FWHM) of Er~(3+) at 1.5-μm band, especially at relatively high Er~(3+) doping level. When the Er~(3+) concentration is around 3.66*10~(20)/cm~3, Yb~(3+)-codoping enlarges the FWHM of Er~(3+) at 1.5-μm band from 65 nm to 79 nm. In Chapter Four, the spectroscopic properties of the Er~(3+)-doped and Er~(3+)/Yb~(3+)-codoped TeO_2-WO_3-ZnO (TWZ) glasses were investigated. Some new results have been found, and some new ideas were presented. The optimum molar composition of the host is 75TeO_2-20WO_3-5ZnO. In this glass, Er~(3+) ions had a larger emission bandwidth at 1.5-μm band. The effect of concentration quenching to 1.5-μm-fluorescence in this Er~(3+)-doped glass was found to be small. The optimum. Yb~(3+) concentration is almost double the Er~(3+) concentration. With the increase of the Yb~(3+) concentration, the FWHM of Er~(3+) at 1.5-μm band increased from 77 nm to 83 nm. The infrared absorption of TWZ glasses in 2600～3600cm~(-1) band was well explained based on the absorption of the water molecular stretching vibration. We presented that the absorption of TWZ glasses in 2600～3600cm~(-1) band could be also attributed to the absorption of the combination of the 'free' hydroxyls, (Te)-O-H and (W)-O-H, and the hydroxyl of the strong hydrogen band, (M)-O-H…O, which could also explain the absorption of samples in 2600～3600cm~(-1) band. The calculated interaction constant between Er~(3+) ions and hydroxyl or water molecular, k_(OH), was about (17.8±1) ·10~(-20)cm~4*s~(-1). The results of the radiation trapping of Er~(3+) at 1.5-μm band in Er~(3+)/Yb~(3+) codoped TWZ samples with different thickness showed that there existed a good linear relationship between the fluorescence effective line width, ⊿λ_(eff) and the ratio of the second peak intensity, I_s, to the strongest peak intensity, I_p, in the emission spectra. The linear fitting results approved the previous idea that the emission bandwidth obtained through the calculated emission cross-section curve could measure the emission bandwidth of Er~(3+) at 1.5-um band better. For the first time, we presented that the ratio of the I_2/I_p to theσ_(es)/σ_(ep) or the difference between the I_s/I_p and theσ_(es)/σ_(ep) can be used as a measurement of radiation trapping of Er~(3+) at 1.5-μm band. Here theσ_(es) and the σ_(ep) are the emission cross sections at wavelength of the second peak and the strongest peak respectively calculated by McCumber theory. In Chapter Five, the modified study on the spectroscopic properties of the Er~(3+)-doped and Er~(3+)/Yb~(3+)-codoped TWZ glasses were performed. Firstly, the substitution of ZnO by ZnF_2 can increased the intensity and lifetime of Er~(3+) emission at 1.5-μm band. The proper substitution proportion of ZnO by ZnF_2 could enlarge the FWHM of Er~(3+) emission at 1.5-μm band. The maximum FWHM was 83 nm with the ZnF_2 content of 8mol%. Secondly, the addition of Ce~(3+) with a proper concentration could both decrease the upconversion emission intensity and enhance the 1.5-μm band emission of Er~(3+) in Er~(3+)/Yb~(3+)-codoped TWZ samples. Finally, the introduction of B_2O_3 quenched not only the upconversion emission but also the emission of Er~(3+) at the 1.5-μm band in single doped TWZ samples. In Chapter Six, the spectroscopic properties of the Er~(3+)-doped TeO_2-WO_3-ZnO-Na_2O (TWZN) glasses were investigated. The comparison of the 1.5-μm band emission properties of Er~(3+) in TWZN, TWZ, TeO_2-WO_3-Na_2O and TeO_2-ZnO-Na_2O glasses showed that Er~(3+) ions had a smaller FWHM at the 1.5-μm band in TWZN glasses than that in TWZ glass and the Er~(3+)-doped TWZ glass had the largest FWHM at 1.5-μm band. Based on the analysis of the Raman scattering spectra, we assumed that a relatively high proportion of [TeO_4] to [TeO_(3+1)] and [TeO_3] and a relatively high content of [WO_6] and [WO_4] in glass structure was beneficial to enlarge the emission bandwidth of Er~(3+) at 1.5-μm band. Finally, all results of present work are outlined, and it is suggested that something should be done in the next stage.
语种	中文
内容类型	学位论文
源URL	[http://ir.siom.ac.cn/handle/181231/15389]
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	李家成. Er~(3+)单掺和Er~(3+)/Yb~(3+)共掺蹄钨酸盐玻璃光谱性能研究[D]. 中国科学院上海光学精密机械研究所. 2004.

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