| 题名 | 稀土铒离子掺杂铝镓酸盐中红外光谱性质研究 |
| 作者 | 张威 |
| 学位类别 | 硕士 |
| 答辩日期 | 2015 |
| 授予单位 | 中国科学院上海光学精密机械研究所 |
| 导师 | 张丽艳 |
| 关键词 | 铝镓酸盐玻璃 3μm 声子能量 稀土离子掺杂 |
| 其他题名 | Mid-infrared Spectroscopic Properties of Erbium infrared Spectroscopic Properties of Erbium infrared Spectroscopic Properties of Erbium infrared Spectroscopic Properties of Erbium infrared Spectroscopic Properties of Erbiuminfrared Spectroscopic Properties of Erbium infrared Spectroscopic Properties of Erbium infrared Spectroscopic Properties of Erbiuminfrared Spectroscopic Properties of Erbiuminfrared Spectroscopic Properties of Erbium infrared Spectroscopic Properties of Erbium infrared Spectroscopic Properties of Erbium infrared Spectroscopic Properties of Erbium-doped doped Gallioalumi |
| 中文摘要 | 3~5μm中红外激光是重要的大气传输窗口之一，在中红外雷达、激光对抗等军事领域和空气污染、环境监测、激光手术等民用领域都有着很大的应用潜力。其中Er3+离子作为主要的3μm波段发光离子，目前仅在ZBLAN光纤中实现激光输出。然而氟化物玻璃体系存在化学稳定性差、机械强度低、激光损伤阈值低、热稳定性差并且制备困难等缺点，限制了氟化物玻璃材料在实际中的应用。氧化物玻璃具有良好的化学和热学稳定性，以及较高的机械强度等特点，国内外对氧化物玻璃作为中红外发光的基质材料进行了大量研究。然而目前所用的氧化物玻璃,如锗酸盐玻璃其抗冲击性能好，但声子能量高（~900cm-1），碲酸盐玻璃声子能量稍低但热学性质较差，均不适合作为3μm发光的理想基质。 本论文一共分为六章： 在论文第一章，首先在文献综述中介绍了稀土离子种类和稀土离子的跃迁机理，然后概述了3μm稀土离子掺杂玻璃基质材料的基本特点以及研究进展，最后提出了本课题主要的研究内容和思路。 在论文第二章，主要介绍了本文的研究方法，详细介绍了实验的样品制备和加工、性能测试以及光谱参数的理论计算，包括Judd-Ofelt理论和McCumber理论。 在论文第三章，通过实验筛选获得了成玻性能良好的铝镓酸盐玻璃，与ZBLAN相比，该玻璃具有较高的玻璃化转变温度（646℃），良好的热学稳定性（Tx-Tg=160℃），较低的热膨胀系数（8.7×10-6/K），并且其最大主声子能量（663cm-1）低于其他氧化物玻璃体系，此外其红外截止边5.2μm，能有效的提高了中红外2.7μm发光强度。 在论文第四章，制备了一系列不同Er3+离子掺杂浓度的铝镓酸盐激光玻璃，并获得了2.7μm的荧光输出。随着Er2O3掺杂量逐渐增加，铝镓酸盐玻璃的2.7μm荧光逐渐增强，并在Er2O3掺杂量到达7mol%时荧光强度达到最大值。此后随着Er2O3继续的增加，其荧光强度降低。Er: 4I11/2→4I13/2能级跃迁受激发射截面高达14.9×10 -21 cm2。Er3+：4I11/2→4I13/2能级的自发辐射跃迁几率为27.91s-1，辐射寿命τrad为6.8ms，并且具有较高的荧光分支比18.98%。通过吸收和受激发射截面计算了玻璃中Er3+离子的增益参数。当P>0.6，开始在铝镓酸盐玻璃中获得正增益的特性。 在论文第五章，以第四章为基础，分析了Er3+/Yb3+共掺和Er3+/Tm3+共掺的铝镓酸盐玻璃的3μm光谱性质。通过一系列实验，确定了最佳Yb3+离子掺杂浓度。当掺杂0.5 mol% Yb 2O3 和7 mol% Er2O3时，Er 3+离子4I11/2能级向4I13/2能级跃迁产生的荧光最强，在2708nm处的受激发射截面为8.28×10-21cm2，其Er3+： 2.7μm发光宽度的Δλeff值为69.2 nm。根据Dexter-F?rster理论计算了Yb3+→Er3+的能量传递微观系数 8.14×10-40cm6/s，并且研究了高浓度Er3+掺杂情况下，Er3+与Yb3+离子之间能量传递机理。此外制备了Er3+/Tm3+共掺的铝镓酸盐玻璃，通过差热分析，Er3+/Tm3+共掺玻璃样品的转变温度和析晶起始温度分别为695℃和832℃。Er3+/Tm3+共掺样品Er3+：4I11/2→4I13/2跃迁辐射几率和荧光分支比分别为22.88 s-1和23.8%，并计算得到了在2708μm处的发射截面为8.3×10-21cm-2，研究了在980nm LD泵浦条件下，Er3+与Tm3+离子之间的能量传递机理，Er3+：4I13/2能级寿命从单掺样品的683.2μs降低到Er3+/Tm3+共掺样品的309.3μs，通过测试荧光衰减曲线计算了能量转移效率，Er3+：4I13/2能级到Tm3+：3F4能级的能量转移效率为54.7%。 最后是论文的结论部分，总结了全文的实验结果，指出了本论文的创新点和不足之处。 |
| 英文摘要 | Mid-infrared laser around 3~5 μm is one of the important atmospheric transmission window, which have many applications in the area of military and civilian field, such as infrared radar, laser countermeasure, environmental minitoring and laser surgery. Er3+ ions doped laser glass has been paid great attention because of their 4I11/2→4I13/2 transition at 2.7 μm. To date, fiber laser at 2.7 μm have been achieved solely in Er3+-doped ZBLAN glass fiber. However, ZBLAN fibers have drawbacks of low thermal and chemical stabilities, comples synthesizing route, fragility, hygroscopocity, and high cost set limits on the demonstration of high power 2.7 μm lasers. Oxide glass, such as germanate, tellurite, bismuthate glasses attract more interest owing to their more stable chemical and thermal properities. Unfortunately, one of the disadvantages of these glasses is the higher maximum phonon energy, such as germanate (~900 cm-1), tellurite (~750 cm-1) have low phonon energy but have poor thermal properities. Therefore, we should find more suitable glass for mid-infrared laser. This dissertation include six chapters: Firstly, the glasses and transitions of rare earth ions have been introduced. And then, the developments and applications of mid-infrared laser have been briefly introduced. Last, the purpose and research content of the dissertation were proposed. In the section of literature summarization, the experiment methods are introduced, including the sample preparation proceduces, physical and spectroscopic properties measurements, and the spectroscopic parameters calculation using Judd-Ofelt and McCumber theroy. In chapter Ⅲ, we developed a novel kind of gallioaluminate glasses with alkaline and lakaline-earth metals involved. Compared with ZBLAN, gallioaluminate glasses have a high Tg (646°C) value, excellent anti-crystallization stability (ΔT=160°C) , lower coefficient of thermal expansion (8.7×10-6/K) and lower main phonon energy (663 cm–1), besides the cut-off edge in infrared region is as long as 5.3 μm. These results suggest that this kind of gallioaluminate glass has potential application in 2.7μm lasers. In chapter Ⅳ, a series of Er3+-doped gallioaluminate glasses were synthesized by conventional melting and quenching technique, and achieve broadband emission around 2.7 μm. The maximum value of the 2.7 μm emission intensity can be seen at the concentration of 7.0 mol% Er2O3. The emission cross of Er3+:4I11/2→4I13/2 is 14.9×10-21cm2. The higher radiative transition probability (27.91s-1) , branching ratio (18.98%) and the lifetime (6.8 ms) of Er3+:4I11/2→4I13/2 transition. We can obtain the positive gain when P > 0.6, gain cross section followed by increased with the increase of P values. Based on the result of chapter Ⅳ, the emission intensity of 2.7 μm achieves largest when the concentration of 7.0 mol% Er2O3. In chapterⅤ, the 3 μm emission spectroscopic properties of the Er3+/Yb3+ and Er3+/Tm3+-codoped gallioaluminate glasses were investigated. The intensity of 2.7 μm emission becomes largest at the content of Er3+/Yb3+ as 7 mol% and 0.5 mol%. The emission cross section of 2.7μm is 8.28×10-21cm2, and the full width at half maximum (Δλeff) is 69.2 nm. According to theory of Dexter-F?rster, the energy migration coefficient from Yb3+ to Er3+ is 8.14×10-40cm6/s. The spectroscopic properties and energy transfer process of Er3+/Yb3+ in the high Er2O3 doped gallioaluminate glass. Besides, Er3+/Tm3+-codoped gallioaluminate glasses were synthesized, and according to DSC, glass transition temperature and crystallization onset temperature is 695℃and 832℃, respectively. The higher radiative transition probability (22.88s-1) and branching ratio (23.8%) of Er3+:4I11/2→4I13/2 transition, and the emission cross section is 8.3 ×10-21cm-2. We also researched the energy transfer process of Er3+/Tm3+ under the pumped of 980 nm. After codoped with Tm3+, lifetime of Er3+:4I13/2 in Er3+ singly doped gallioaluminate glass from 683.2 μs to 309.3 μs. And energy transfer efficiency from Er3+ to Tm3+ reaches 54.7%. 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/181231/16923]  |
| 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 | 张威. 稀土铒离子掺杂铝镓酸盐中红外光谱性质研究[D]. 中国科学院上海光学精密机械研究所. 2015. |
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