| 题名 | 稀土掺杂重金属氧卤玻璃光谱性质研究 |
| 作者 | 徐时清 |
| 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 | 姜中宏 |
| 关键词 | 重金属氧卤玻璃 稀土离子 光谱性质 上转换发光 光放大器 |
| 其他题名 | Spectroscopic properties of rare-earth doped heavy metal oxyhalide glasses |
| 中文摘要 | 本研究主要目的在于探索适用于宽带掺Er3+光纤放大器和蓝绿光波段激光器用基质玻璃材料。通过对掺Er3+重金属氧氟玻璃的光谱性质和析晶稳定性研究以及稀土离子掺杂重金属氧卤玻璃的上转换发光研究，为其在宽带掺Er3＋光纤放大器和蓝绿光波段激光器中的潜在应用提供基础。论文第一章首先综述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，然后提出本文的研究内容和研究思路。论文第二章介绍了实验方法和光谱参数计算的基础理论，主要包括玻璃样品的制备和各种性质的测试以及光谱理论计算。论文第三章研究了掺Er3+重金属氧氟硅酸盐玻璃和锗酸盐玻璃的光谱性质和物化性质。结果发现重金属氟化物（PbF2）的加入能提高掺Er3+硅酸盐玻璃的带宽特性和增益性能；随PbF2含量增加，掺Er3＋重金属氧氟硅酸盐玻璃的荧光半高宽（FWHM）和荧光寿命增加，吸收截面和受激发射截面略有下降，其中Er3+掺杂SPF50玻璃的带宽特性接近磅酸盐和秘酸盐玻璃，大于硅酸盐、锗酸盐和磷酸盐玻璃，其增益性能大于蹄酸盐、秘酸盐、硅酸盐、锗酸盐和磷酸盐玻璃。在掺Er3+重金属氧氟硅酸盐玻璃的研究基础上，研究了Bi2O3对掺Er3+重金属氧氟硅酸盐玻璃光谱性质的影响，发现随BiZO3含量增加，玻璃样品的FWHM和受激发射截面在Bi2O3=5mol％时出现最大值，而荧光寿命略有下降。最后分析了PbF2含量对掺Er3+锗酸盐玻璃光谱性质的影响，发现随PbF2含量增加，吸收截面和受激发射截面略有下降，而FWHM、荧光寿命、有效吸收线宽和有效发射线宽以及带宽特性和增益性能都增加。论文第四章研究了掺Er3＋重金属氧氟玻璃的上转换发光。通过研究1．3＋单掺和Yb3＋／Er3＋共掺重金属氧氟硅酸盐玻璃的上转换发光，首次在含硅酸盐基质玻璃中发现上转换蓝光，但是与上转换绿光和红光发光强度相比，上转换蓝光的强度比较微弱。随Er2O3和Yb2O3浓度增加，Er3＋离子上转换蓝光、绿光和红光均增强，其中YbZo3浓度对Er3“离子上转换发光影响较大，与Er3+单掺SPFEY0玻璃相比，Yb3＋／Er3＋共掺SPFEYS玻璃上转换蓝光（4osnm）、绿光（52，和545nm）和红光（667nm）的发光强度分别增加104.8、156.9、64.6和21.4倍；上转换机理分析表明，Er3＋离子上转换发光强度增加，主要是由于能量转移增大；上转换绿光和红光都是双光子吸收过程，而上转换蓝光是一个三光子吸收过程。通过研究掺Er3＋重金属氧氟锗酸盐和蹄酸盐玻璃的上转换发光，发现PbFZ的加入，降低了锗酸盐和磅酸盐玻璃的声子能量，因此随PbF2含量增加，掺Er3＋重金属氧氟锗酸盐和蹄酸盐玻璃的上转换发光都明显增加。研究了oH基吸收对掺Er3+磅酸盐玻璃上转换发光的影响，结果表明，OH基吸收对Er3+离子上转换发光具有较大影响，与不除水的Er3＋掺杂TZL玻璃相比，除水后的Er3+掺杂TZL玻璃的上转换绿光（531和545nm）和红光（656nm）发光强度分别提高了1.85、1.7和5.6倍。红外透过光谱研究发现，随PbFZ含量增加，重金属氧氟锗酸盐和磅酸盐玻璃的OH基吸收明显减小，因此掺Er3＋重金属氧氟锗酸盐和蹄酸盐玻璃上转换发光增强，一方面是受到基质玻璃声子能量降低的影响，另一方面是由于基质玻璃中OH基吸收减少的结果。论文第五章研究了Yb3+/Tm3+共掺重金属氧卤磅酸盐玻璃的上转换发光。在磅酸盐玻璃中加入卤化物，发现降低了基质玻璃的声子能量，其中PbBr2影响趋势最大，PbF：最小；降低了基质玻璃的OH基吸收，其中PbF2除水能力最强，而PbBrZ最弱。随PbF2、PbCl2和PbBrZ含量增加，Tm3＋离子的上转换蓝光、红光和近红外光均增加。研究了oH基吸收对Yb3勺Tm3十共掺磅酸盐玻璃上转换发光的影响，发现OH基吸收对Yb3＋／Tm3＋共掺磅酸盐玻璃上转换发光具有较大影响，与不除水的Yb3＋／Tm3十共掺蹄酸盐玻璃相比，除水后Tm3＋离子的上转换蓝光、红光和近红外光分别提高了2.9、2.2和2.8倍。研究发现Yb3＋／Tm3＋共掺TPF40玻璃的上转换发光强于Yb3＋／Tm3＋共掺TPC40玻璃，分析表明主要是由于oH基吸收的影响，因为TPF40玻璃声子能量低于TPC40玻璃，而TPF4O玻璃的OH基吸收系数大大低于TPc40玻璃。因此随PbF2、PbCl2和PbBr2含量增加，Tm3+离子的上转换发光增加，一方面是由于基质玻璃声子能量降低的结果，另一方面还受到OH基吸收的影响。研究了混合卤化铅效应调整Yba＋／Tm3＋共掺磅酸盐玻璃的上转换发光和析晶稳定性，发现Yb3勺Tm3＋共掺TPcFB玻璃具有最强的上转换发光和最好的析晶稳定性。为了提高Yb3＋／Tm3＋共掺TPCFB玻璃的发光性能，研究了Tm2O3和Yb2O3浓度对Yb3+／Tm3＋共掺TPCFB玻璃上转换发光的影响，发现随Tm2O3和Yb2O3浓度增加，都出现浓度碎灭效应。上转换机理分析表明，Tm3”离子的上转换蓝光和红光都是三光子吸收过程，而近红外光是一个双光子吸。收过程。、最后是本论文的结论部分，概括了全文创新性的实验研究结果。 |
| 英文摘要 | The goal of this dissertation is to search for glass hosts suitable for broadband Er3+-doped fiber amplifiers (EDFA), blue and green lasers. This research on spectral properties and crystallization stability of Er3+-doped heavy metal oxyfluoride silicate glasses and upconversion luminescence of rare earth-doped heavy metal oxyhalide glasses lay a foundation for the potential use of broadband EDFA and blue and green lasers. In chapter 1, firstly the recent developments of rare earth doped fiber amplifiers, upconversion luminescence of rare earth ions and the theory foundation of rare earth ions-doped laser glasses were overviewed, and then the studied content and idea of this dissertation were presented. In chapter 2, the experiment method and the basic theory of the spectrum parameters calculating were introduced, and the content mainly involved in the glass samples preparation, some properties testing and the spectrum theory calculating. In chapter 3, the spectral, physical and chemical properties of Er3+-doped heavy metal oxyfluoride silicate and germanate glasses were studied. The results showed that the heavy metal fluoride (PbF2) could increase the bandwidth properties and gain performance of Er +-doped silicate glasses. With increasing PbF2 content, the fluorescence full width at half maximum (FWHM) and fluminescence lifetimes of Er +-doped heavy metal oxyfluoride silicate glasses were improved, and the absorption and stimulated emission cross-sections of Er3+-doped heavy metal oxyfluoride silicate glasses were lowered slightly. Especially, the bandwidth property of Er3+-doped SPF50 glass was closed to those of tellurite and bismuth glasses and better than those of silicate, germanate and phosphate glasses, and the gain performance of Er3+-doped SPF50 glass was better than those of tellurite, bismuth silicate, germanate and phosphate glasses. On the basis of investigation on Er3+-doped heavy metal oxyfluoride silicate glasses, the effect of Bi2C>3 on spectroscopic properties of Er3+-doped heavy metal oxyfluoride silicate glasses was studied. With increasing Bi2C>3 content, the results showed that FWHM and stimulated emission cross-section of the glass samples reached its maximum at Bi2O3%=5 mol.% and fiuminescence liftimes were lowered slightly. Finally, the effect of PbFa content on spectroscopic properties of Er3+-doped germanate glasses was analyzed. It is found that the absorption and stimulated emission cross-sections of Er3+-doped germanate glasses were lowered slightly, but FWHM, fluorescence lifetimes, effective absorption and emission linewidth, bandwidth properties and gain performance of Er3+-doped germanate glasses were improved with increasing PbF2 content. In chapter 4, upconversion luminescence of Er3+-doped heavy metal oxyfluoride glasses were investigated. Upconverson blue emission in silicate host glass was found for the first time by investigation on Er3+-doped heavy metal oxyfluoride silicate glasses, but the upconverson blue emission intensity was very weak compared with upconverson green and red emissions. With increasing E^Ch and Yb2C>3 content, upconverson blue, green and red emissions were improved, and the effect of Yb2C>3 content was bigger than that of Er2C>3 content. Compared with Er3+-doped SPFEYO glass, and upconverson blue (408 nm), green (529 and 545 nm) and red (667) emissions of Yb3+/Er3+-codoped SPFEY5 increased by a factor about 104.8, 156.9, 64.6, and 21.4, respectively. The upconversion mechanism analysis showed that the increasing of upconverson emission intensities of Er3+ was mainly due to energy transfer augmented. The upconversion processes involved a sequential two-photon absorption for the green and red emissions, while a sequential three-photon absorption for the blue emission. By investigation on upconversion emission of Er3+-doped heavy metal oxyfluoride germanate and tellurite glasses, it is found that the phonon energies of germanate and tellurite glasses were lowered due to PbF2 addition, and so upconversion emission of Er3+-doped heavy metal oxyfluoride germanate and tellurite glasses were improved obviously with increasing Pbp2 content. The effect of OH group absorption on Er3+-doped tellurite glasses was studied, and the results showed that OH group absorption had important effect on upconversion emission of Er3+. Compared with Er3+-doped TZL glass with no remove water, upconversion green (531 and 545 nm) red emission intensities of Er3+-doped TZL glass with remove water increased by a factor about 1.85, 1.7 and 5.6, respectively. The infrared spectra showed that OH group absorption in heavy metal oxyfluoride germanate and tellurite glasses were lowered obviously with increasing PbF2 content. So upconversion luminescence of Er3+-doped heavy metal oxyfluoride germanate and tellurite glasses were improved, one was due to the lower phonon energies of host glasses, and another was due to the decreasing of OH group absorption in host glasses. In chapter 5, upconversion luminescence of Yb +/Tm3+-codoped heavy metal oxyhalide tellurite glasses were investigated. The phonon energies of host glasses were lowered due to adding halide into tellurite glasses, the influence tendency of PbBr2 was the biggest, and PbF2 was the smallest. OH group absorption of host glasses were lowered due to adding halide into tellurite glasses, the remove water ability of PbF2 was the strongest, and PbBr2 was the weakest. With increasing PbF2, PbCl2 and PbBr2 content, upconversion blue, red and near infrared light emission intensities were all improved. The effect of OH group absorption on Yb3+/Tm3+-codoped tellurite glasses was studied, and the results showed that OH group absoiption had important effect on upconversion emission of Tm3+. Compared with Yb3+/Tm3+-codoped tellurite glass with no remove water, upconversion blue, red and near infrared light emission intensities of Yb3+/Tm3+-codoped tellurite glass with remove water increased by a factor about 2.9, 2.2 and 2.8, respectively. The study found that upconversion emission intensity of Yb3+/Tm3+-codoped TPF40 glass was more than that of Yb3+/Tm3+-codoped TPC40 glass, and the analysis considers it to the influence of OH group absorption because the phonon energy of TPF40 glass was lower than that of TPC40 glass and OH group absorption coefficient of TPF40 glass was lower than that of TPC40 glass. So upconversion luminescence of Tm3+ was improved with increasing PbF2, PbCl2 and PbBr2 content, one was due to the lower of phonon energies, and another was due to the decreasing of OH group absorption. Upconversion luminescence and crystallization stability of mixed halide lead modified Yb3+/Tm3+-codoped tellurite glasses were studied, and the results showed that Yb3+/Tm3+-codoped TPCFB glass possessed the strongest upconversion emission and the best crystallization stability. In order to increase luminescence properties, the effect of Tm2O3 and Yb2O3 content on upconversion luminescence of Yb +/Tm +-codoped TPCFB glass was investigated, and the results showed that it exsited concentration quenching with increasing Tni2O3 and Yb2O3 content. The upconversion mechanism analysis showed that the upconversion processes involved a sequential two-photon absorption for near infrared light emission, while a sequential three-photon absorption for the blue and red emissions. Finally, it is conclusion of this dissertation, which generalizes the innovative results of experiments in this dissertation. |
| 语种 | 中文 |
| 内容类型 | 学位论文 |
| 源URL | [http://ir.siom.ac.cn/handle/181231/15408]  |
| 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 | 徐时清. 稀土掺杂重金属氧卤玻璃光谱性质研究[D]. 中国科学院上海光学精密机械研究所. 2004. |
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