上转换发光氧氟微晶玻璃及光纤的制备与研究
文献类型：学位论文
| 作者 | 段忠超 |
| 学位类别 | 博士 |
| 答辩日期 | 2008 |
| 授予单位 | 中国科学院上海光学精密机械研究所 |
| 导师 | 胡丽丽 |
| 关键词 | 稀土离子 上转换发光 氧氟微晶玻璃 微晶玻璃光纤 |
| 其他题名 | Preperation and Properties of Upconversion Oxyfluoride Glass Ceramics and Fiber |
| 中文摘要 | 蓝绿光激光在高密度数据存储、水底通讯和大屏幕显示等许多领域有着广泛的应用价值。常用蓝绿光上转换光纤激光器都是采用氟化物玻璃光纤作为增益介质，但其较差的化学稳定性和较低的机械强度给实际应用带了困难。目前开发高效率、高强度的上转换发光玻璃对实现高功率蓝绿光激光输出有重要的意义。 本论文首先研究了氧氟微晶玻璃的组成、制备工艺等与玻璃物化性能和上转换发光性能的关系。结果发现SiO2-PbF2玻璃系统中引入少量Al2O3和CdF2可以改善玻璃的网络结构，从而提高玻璃的稳定性和机械强度；把玻璃样品在其析晶开始温度附近进行热处理后玻璃中析出大量β-PbF2晶粒，并且其化学稳定性和机械性能得到了显著提高；我们还研究了微晶化工艺和稀土掺杂浓度对Tm3+离子上转换发光性能的影响，在微晶玻璃中蓝光和红光上转换强度出现了减弱、近红外上转换发光得到了增强，通过分析给出了其上转换发光机理和可能的原因。Er3+离子的上转换发光强度在微晶玻璃中显著提高，掺杂0.1 mol%Er3+和2 mol%Yb3+的样品在460℃保温热处理2个小时后上转换强度达到最大。结合理论计算结果研究了Er3+离子的1.5μm荧光光谱性能，结果表明尽管它有着优良的上转换发光性能但并不适合用于光通讯放大。980nm LD泵浦下，Er3+-Tm3+-Yb3+三掺氧氟微晶玻璃样品可以同时获得红绿蓝三基色光的上转换发光，并且可以通过改变稀土掺杂浓度调节它们的强度比，这对实现上转换彩色显示有着重要意义。我们还研究了Dy3+在玻璃和微晶玻璃中的发光特性，980nm LD泵浦下，玻璃样品有微弱的蓝光上转换发光但微晶化后消失，由于Dy3+中间能级的分布比较密集，使得其上转换发光效率非常低。但是Dy3+的1.3μm荧光发射有较好的宽带特性和品质因数，因此在光通讯领域有着潜在的应用价值。 其次，我们还研究了稀土掺杂氧氟微晶玻璃光纤的制备方法及其对机械性能和发光性能的影响。以40SiO2-10AlO1.5-50PbF2玻璃为基质，确定了其最佳制备工艺，并分别制备了Tm3+、Er3+掺杂的氧氟玻璃光纤和微晶玻璃光纤。980nm LD泵浦下在氧氟微晶玻璃光纤中实现了上转换发光，通过实验我们研究分析了其上转换发光机理，发现与块体样品中的机理相同。值得指出的是，与块体样品相比，在光纤中Er3+或Tm3+短波长上转换发光与长波长发光强度的比都出现了减小。 |
| 英文摘要 | Blue and green lasers have many applications in the fields such as high density data storage, underwater communication and large-scale screen display. In general, blue and green upconversion fiber lasers use fluoride fiber as gain media. However fluoride glasses have poor chemical and mechanic properties which hinder its practical applications. Therefore, it is important to study the active glass and fiber with high efficiency and hardness to realize high power laser output. Firstly, we study the relationship between the compositions, preparation techniques and properties of oxyfluoride glass ceramics. It is found that in SiO2 -PbF2 glass system, the glass network is enhanced with the introduction of few Al2O3 and CdF2 contents. And so the stability and mechanical strength are improved. Many β-PbF2 crystals are precipitated in the glass after heat treatment. As a result, its chemical stability and mechanical strength are improved greatly. The dependence of upconversion intensity of Tm3+ on heat treating techniques and rare earth concentration is also investigated. The blue and red upconversion intensity decrease in some degree, while the NIR upconversion emission is enhanced with fluoride crystals precipitated. The upconversion mechanism of Tm3+ and possible reason for this abnormal phenomenon is also presented. The upconversion intensity of Er3+ ions is enhanced strongly and gets a maximum after heat treated at 460℃ for two hours with 0.1 mol% Er3+ and 2 mol% Yb3+. Based on Judd-Ofelt theory, we also study the 1.5μm emission properties of Er3+ and find it is not suitable for 1.5μm optical amplifier. However it is a very good upconversion material. Under 980nm laser diode pumped, the three basic colors of red, green and blue are obtained simultaneously in Er3+-Tm3+-Yb3+ co-doped oxyfluoride glass ceramics As its proportion can be adjusted by changing the rare earth concentrations, it is very interesting for full-color display. In the end, we study the spectroscopic properties of Dy3+ in oxyfluoride glass and glass ceramics. A slight blue upconversion is observed in glass, and it vanishes after heat treatment. Because of its dense energy level distribution, the upconversion efficiency of Dy3+ is very lower compared with Tm3+. However its 1.3μm emission property is very good for optical amplify. And we can make a conclusion that Dy3+ doped oxyfluoride glass can be used as potential optoelectronic communication device. Secondly, we study the preparation method and its effect on the physical and optical properties of rare earth doped glass ceramics fiber. Base on the selected oxyfluoride glass system, an optimum melt technique is design, and then Tm3+ doped oxyfluoride glass fiber, Er3+ doped glass fiber and glass ceramics fiber are fabricated. Upon 980nm LD pumped, bright upconversion luminescences are observed in the glass ceramics fiber for the first time. The upconversion properties of both Tm3+ and Er3+ in fiber are measured and analyzed on various conditions. The result indicates that their upconversion mechanism is similar to that in bulk samples. It is interesting to point out that the ratio of upconversion intensity in higher frequency wave band to lower frequency wave band becomes smaller compared with that in bulk samples. |
| 语种 | 中文 |
| 源URL | [http://ir.siom.ac.cn/handle/181231/15216]  |
| 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 | 段忠超. 上转换发光氧氟微晶玻璃及光纤的制备与研究[D]. 中国科学院上海光学精密机械研究所. 2008. |
入库方式： OAI收割
来源：上海光学精密机械研究所
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