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题名	掺稀土氟磷酸盐玻璃中红外发光特性的研究
作者	田颖
学位类别	博士
答辩日期	2012
授予单位	中国科学院上海光学精密机械研究所
导师	张军杰
关键词	氟磷酸盐玻璃、 2 μm 、3 μm 、氟化物玻璃、中红外发光特性
其他题名	Spectroscopic properties of mid-infrared emissions in rare-earth ions doped fluorophosphate glass
中文摘要	近年来，输出波长在2-3μm的中红外固体激光器，因在军事、医疗、光通信、环境监测等领域广阔的应用前景引起了广泛的关注。目前，国内外对2 μm发光的稀土离子掺杂激光材料的研究非常多，其基质主要有晶体、石英玻璃、硅酸盐玻璃、氟化物玻璃、重金属氧化物玻璃等。对3μm发光的稀土离子掺杂激光材料的研究主要是晶体、氟化物玻璃和硫系玻璃。国外对于氟磷酸盐玻璃的研究已经表明氟磷酸盐玻璃在平面波导放大器、超短脉冲、短波长及近红外激光源等方面具有优良的应用前景，但关于2-3 μm发光的氟磷酸盐玻璃的研究极少。 氟磷酸盐玻璃综合了氟化物玻璃和磷酸盐玻璃的优点，适量磷酸盐的加入提高了玻璃的化学稳定性、热稳定性，同时还保留了氟化物玻璃良好的光谱性能，并且氟磷酸盐玻璃成份可调性大、稀土离子掺杂浓度高、成本相对低廉、非线性折射率低、自聚焦效应小，可以用于高能激光系统中，是一种比较理想的有望获得2-3μm激光输出的材料。 本论文主要包括七章：前两章分别是文献综述和实验方法及理论基础，第三、四、五、六章是本论文的核心部分，第七章是结论。 论文首先在文献综述中简要介绍了激光及激光器的应用及发展。综述了2-3μm稀土离子掺杂玻璃材料的研究进展。概述了氟磷酸盐玻璃的特点及研究进展，进而提出本论文的研究内容和研究思路。 论文的第二章，介绍了实验方法、氟磷酸盐、氟化物玻璃样品的制备、性能测试及光谱参数的理论计算等。 论文的第三章通过改变碱土金属化合物的相对含量和种类，制备了一系列的氟磷玻璃，研究了玻璃的各项热学性能。最终获得Tg为490°C、ΔT为124°C、抗析晶性能好的多元氟磷酸盐玻璃系统 20Al(PO3)3 - 17BaF2 - 13MgF2 - 10CaF2-20SrF2-20NaF组分。还对氟磷酸盐玻璃进行了新的探索，引入了卤化物，制备了Er3+掺杂的氟卤磷酸盐玻璃。通过Raman光谱、吸收光谱、1.55μm发光的荧光光谱、寿命衰减曲线及Judd-Ofelt强度参数、发射截面、有效线宽等参数的计算，表明Er3+掺杂的氟卤磷酸盐玻璃具有较好的带宽特性和增益性能，有望成为Er3+光纤放大器的增益材料。 论文的第四章设计并制备了多系列2μm发光的稀土氟磷酸盐玻璃。通过研究一系列不同浓度掺Tm3+的氟磷玻璃，发现本论文设计的氟磷酸盐玻璃可以高掺Tm3+离子，当稀土离子浓度达到10mol%时，仍没有出现较强的荧光淬灭现象。研究了Tm3+/Yb3+和Ho3+/Yb3+双掺的氟磷玻璃，利用Yb3+离子敏化Tm3+或Ho3+离子，在980nm LD泵浦下，分别获得了中心波长在1.8μm和2.05μm的荧光。结果表明，Tm3+/Yb3+和Ho3+/Yb3+双掺的氟磷玻璃热学性能优良，可从中获得有效的1.8μm和2μm的荧光。系统研究了一系列Ho3+/Tm3+双掺的氟磷玻璃，探讨了不同浓度比下Tm3+和Ho3+离子之间的能量转移机理。其中制备的1 mol% Ho3+/4 mol% Tm3+共掺的氟磷酸盐玻璃，发射截面σem达到6.15×10-21 cm2，并且具有高的自发跃迁几率(76.54 s-1)，有望在Ho3+/Tm3+双掺的氟磷玻璃中获得2μm的激光。研究了Ho3+/Tm3+/Yb3+三掺的氟磷玻璃，通过普通商用980nmLD泵浦，获得了2μm荧光。Yb3+离子在氟磷酸盐玻璃中可以有效地敏化Tm3+离子和Ho3+离子，其能量传递效率可达70.56%。研究了Ho3+/Yb3+/Ce3+三掺的氟磷酸盐玻璃，利用Ce3+离子引起能量转移5I6(Ho3+)+2F5/2(Ce3+)→5I7(Ho3+)+2F7/2(Ce3+)，加速Ho3+:5I7能级上的粒子数积累，进而得到有效的2μm 发光。通过Förster-Dexter理论计算了Ce3+离子引入前后，Yb3+离子敏化Ho3+离子的微观能量传递系数，实验结果表明Ce3+离子引入后，Yb3+到Ho3+能量传递系数增大到9.52×10-40 cm6/s，可以实现有效的传递。 论文的第五章设计并制备了多系列 3 μm发光的稀土氟磷酸盐玻璃。研究了Er3+/Pr3+共掺的氟磷酸盐玻璃，利用Pr3+离子的3F3,4能级来削减Er3+:4I13/2能级上的能量，获得2.7 μm的荧光，其发射截面为6.57×10−21 cm2，高于已报道的氟化物玻璃。研究了Er3+/Nd3+共掺的氟磷酸盐玻璃，分别利用800 nm LD和980 nm LD激发样品，分析了产生不同发光中心的能量转移机理，并计算了能量转移微观系数和效率。在980 nm LD泵浦下，Er3+/Nd3+共掺的氟磷玻璃可以获得更强的2.7 µm的发光。Er3+:4I13/2能级到Nd3+:4I15/2能级的能量转移效率为83.91%，说明Nd3+离子有效地削弱了2.7 μm发光的下能级，有利于实现上下能级粒子数反转。研究了Er3+/Tm3+/Ho3+三掺的氟磷玻璃，红外透过性能好。在980nmLD泵浦条件下，得到了较强的2.7 µm的发光，发射截面为6.02×10−21 cm2，和宽带2 µm的发光，有效线宽高达196nm。通过荧光衰减曲线计算了Er3+: 4I13/2能级到Ho3+:5I7和Tm3+:3F4能级的能量转移效率高达87.08%，这说明Tm3+和Ho3+离子共掺可以有效的削弱2.7 µm发光的下能级，有利于2.7 µm发光，也有利于Tm3+的1.8µm发光和Ho3+的2µm发光。Er3+/Tm3+/Ho3+三掺的氟磷玻璃△T高达 222 °C，抗析晶性能好，有望成为红外波段激光器增益介质的备选材料。研究了Dy3+/Tm3+双掺的氟磷玻璃，红外透过性能良好，玻璃中OH-基含量仅为26.4 ppm。在808nmLD泵浦条件下，获得了较强的2.9µm的发光。通过荧光光谱和荧光衰减曲线等验证了Tm3+:3F4能级可以将能量传递给Dy3+: 6H11/2能级，能量转移效率为52.73%，此过程对2.9µm发光有重要意义。 论文的第六章设计并制备了多系列3 μm发光的稀土氟化物(ZBLAY)玻璃。研究了Er3+单掺的ZBLAY玻璃，在980nmLD泵浦条件下，获得2.7µm发光，发射截面高达9.16×10−21 cm2。研究了Er3+/Tm3+共掺的ZBLAY玻璃，红外透过率高，OH-吸收系数仅为0.252 cm-1。在800nmLD和980nmLD泵浦条件下，观察到了2.7µm的发光及一些其他波段的荧光，分析了稀土离子之间能量转移机理。Er3+:4I13/2能级到Tm3+:3F4能级的能量转移效率为58.22%，说明Tm3+离子有效地削弱了2.7μm发光的下能级，有利于实现上下能级粒子数反转。研究了Er3+/Tm3+/Pr3+三掺的ZBLAY玻璃。在980nmLD泵浦下，获得了2.7μm的发光，1.5 μm 处的宽带发光以及1.8μm，2.3μm的发光，探讨了Er3+、Tm3+、Pr3+三种离子间的能量转移机理。Er3+/Tm3+/Pr3+共掺为获得2.7 μm激光提供了一种新的稀土离子掺杂方式的选择。研究了Dy3+掺杂的ZBLAY玻璃，在808nmLD泵浦下，获得了中心波长在2.84 μm，荧光半高宽达到213nm的宽带发光。2.84μm发光的发射截面σe为1.17×10−20 cm2，2.84μm发光的理论量子效率为52.48%。Dy3+掺杂ZBLAY玻璃是一种有望获得高效2.8 μm激光的材料。研究了Ho3+/Tm3+共掺的ZBLAY玻璃2μm发光特性。利用Yokota-Tanimoto和Förster-Dexter理论计算了在ZBLAY玻璃中，Tm3+离子敏化Ho3+离子的微观能量传递系数。在800nmLD泵浦下，获得了量子效率高达80.35%的2μm发光，并且增益性能指标达到83.16pm2•ms，为2μm光纤激光领域提供了新的激光工作物质的选择。 最后是本论文的结论部分，总结了全文的实验结果，同时指出本研究存在的不足和需要进一步研究之处。
英文摘要	Recently, 2-3 μm solid-sate lasers have drawn considerable attention due to their wide applications, such as military, surgery, communication and remote sensing. Up to now, there are many reports about rare earth ions doped materials for 2 μm emissions and lasers, such as crystal, silica glass, fluoride glass, heavy-metal-oxide (HMO) glass. Reports about rare earth ions doped materials for 3 μm emissions and lasers are mainly focused on crystal, fluoride glass and chalcogenide glass. It has been proved in many researches that fluorophosphate glasses can be used as planar waveguide amplifiers, ultrashort pulse laser, and near-infrared laser source. However, there are few spectroscopic investigations of the 2-3 μm emissions in rare earth ions doped fluorophosphate(FP) glasses. FP glasses combine the advantages of fluoride and phosphate glasses. They possess good thermal stability and moisture resistance, high solubility for rare-earth ions, tailorable properties by varying the fluoride to phosphate ratio, and relatively low cost. Besides, FP glasses are excellent materials to be employed in high power laser systems due to their low nonlinear refractive index, which will minimize associated phenomena such as self-focusing and self-phase modulation in high-power laser. Thus, FP glasses can be selected as 2-3μm laser materials. This dissertation includes the following seven chapters. The first two chapters are literature review, experimental methods and theoretical basis. The III, IV, V and VI chapters are the core part of the dissertation. Chapter VII is the conclusion. In Chapter I, the developments and applications of laser have been briefly introduced firstly. The research progresses on 2-3μm laser and emissions in rare-earth ions doped glasses have been reviewed. And the characteristics and development of fluorophosphate glasses have been presented. Then, the purpose and research content of the dissertation were proposed. In Chapter II, the experimental methods were introduced, including the preparation procedures of fluorophosphate and fluoride glasses, physical and spectroscopic properties measurements, and theory analysis. In Chapter III, a series of fluorophosphate glasses have been prepared by changing the relative concentrations of the type and content of alkaline earth metal compounds. The composition of 20Al(PO3)3-17BaF2-13MgF2-10CaF2-20SrF2-20NaF has been selected as main system due to its good thermal stability(Tg:490°C，ΔT:124°C). Effects of chloride ion introduction on structural and 1.55 μm emission properties in Er3+-doped fluorophosphates glasses have been investigated by the Raman spectra, absorption and emission spectra, and fluorescence decay measurements. The Judd-Ofelt intensity parameters, emission cross section and effective emission bandwidth of 1.55 μm emission in prepared samples have been measured and calculated. Desirable spectroscopic characteristics of Er3+-doped chloride fluorophosphate glass indicate that it is a promising material for 1.5 μm lasers. In Chapter IV, a series of rare-earth doped fluorophosphate glasses with 2 μm emissions have been prepared. FP glasses with high thulium doping concentration up to 10 mol % Tm3+ have been investigated. Intensive 1.8μm fluorescence was demonstrated with lower concentration quenching. Tm3+/Yb3+ and Ho3+/Yb3+ codoped FP glasses have been prepared by conventional melt-quenching method. Upon excitation of a conventional 980 nm laser diode, 1.8μm and 2.05μm emission is obtained from Tm3+/Yb3+ and Ho3+/Yb3+-codoped FP glasses, respectively. The thermal stability of the glasses and the energy transfer between rare-earth ions were analyzed. Hence, this Tm3+/Yb3+ and Ho3+/Yb3+-codoped FP glasses possessing good thermal stability and spectroscopic properties are good candidates for efficient 2.0 μm lasers. A series of Ho3+/Tm3+ codoped FP glasses have been prepared by changing the concentration of Tm3+ ions with fixed Ho3+ concentration. The energy transfer between Ho3+ and Tm3+ in different samples was analyzed. It was found that the emission cross section and spontaneous radiative probability can reach as high as 6.15×10-21 cm2 and 76.54 s-1, respectively, in 1 mol% Ho3+/4 mol% Tm3+ codoped sample. 2μm emission has been obtained in Ho3+/Tm3+/Yb3+ triply doped FP glass pumped by 980nmLD. It was also found that the 2.05μm emission of Ho3+ can be greatly enhanced by adding Tm3+ and Yb3+ simultaneously. Additionally, the microparameters of the energy transfer processes were quantitatively analyzed. The energy transfer efficiency from Yb3+ to acceptors can reach as high as 70.56%. This Ho3+/Tm3+/Yb3+ triply FP glass possessing high energy transfer coefficient and excellent thermal stability is a promising candidate for efficient 2 μm laser. Effect of Ce3+ ions introduction on 2 μm emission properties and energy transfer mechanism in Yb3+/Ho3+ doped FP glass has been investigated. Ho3+:5I7 level can be fast populated by energy transfer process 2F5/2 (Ce3+) + 5I6(Ho3+) → 2F7/2 (Ce3+) + 5I7(Ho3+) with phonon-assisted energy transfer, which is beneficial to 2.0 μm emission. In addition, the energy transfer coefficient from Yb3+ to Ho3+ is 9.52×10-40 cm6/s in Yb3+/Ho3+/Ce3+ triply doped sample and three times larger than that in undoped Ce3+ sample. These results suggest that this Yb3+/Ho3+/Ce3+ FP glass with excellent thermal stability and efficient energy transfer from Yb3+ to Ho3+ is a good candidate for 2 μm laser. In Chapter V, a series of rare-earth doped FP glasses with 3 μm emissions have been prepared. Er3+/Pr3+ codoped FP glasses have been prepared. The Er3+:4I13/2 level can be effectively quenched by the Pr3+:3F3,4 level, which is beneficial to 2.7 μm emission. The emission cross section of 2.7 μm emission in FP glass can reach as high as 6.57×10−21 cm2. The fluorescence properties of 2.7μm emission as well as near infrared emissions in Er3+/Nd3+ doped FP glasses have been investigated under 800 and 980 nm excitation. The fluorescence dynamics and energy transfer processes between Er3+ and Nd3+ ions in different pumping schemes was reported. Three Judd-Ofelt intensity parameters, energy transfer microparameters and efficiency have been determined using Judd-Ofelt and Förster-Dexter theory. The calculated energy transfer efficiency of the Er3+:4I13/2 level to the Nd3+:4I15/2 level was as high as 83.91%. The results indicated that Nd3+ could be an efficient sensitizer for Er3+ to obtain mid-infrared emission and the more suiable pumping scheme of 2.7 μm laser applications for Er3+/Nd3+ doped FP glass was 980nm excitation. The fluorescence characteristics and energy transfer upon excitation of a conventional 980 nm laser diode in Er3+/Tm3+/Ho3+ doped FP glass have been investigated. Based on the lifetime decay curves, the energy transfer efficiency of the Er3+: 4I13/2 level to the Ho3+:5I7 and Tm3+:3F4 levels can reach 87.08%, which is beneficial to 2.7 μm emission. The emission cross section of 2.7 μm emission was calculated to be 6.02×10−21 cm2. And the effective bandwidth of 2.0 μm emission due to Tm3+ and Ho3+ ions can reach as high as 196 nm. These results indicated the advantageous spectroscopic characteristics of Er3+/Tm3+/Ho3+ triply doped FP glass together with the outstanding thermal properties (△T, 222 °C) may become an attractive host for the mid-infrared solid state lasers. FP glass codoped with Dy3+ and Tm3+ ions has been synthesized with low OH content (26.4 ppm). Photoluminescence around 2.9 μm was successfully obtained in present glass excited by a conventional 808 nm laser diode. Based on the absorption, fluorescence spectra and lifetime measurements, the energy transfer efficiency from the Tm3+:3F4 level to the Dy3+: 6H11/2 level was calculate to be 52.73%, which plays an important role in getting 2.9 μm emission. In Chapter VI, a series of rare-earth doped ZrF4-BaF2-LaF3-AlF3-YF3 (ZBLAY) glasses with 2-3 μm emissions have been prepared. 2.7 µm emission with large emission cross section (9.16×10−21 cm2) has been obtained in Er3+ doped ZBLAY glass. Er3+/Tm3+ codoped ZBLAY glass has been prepared with low OH- absorption coefficient (0.252 cm-1). The fluorescence dynamics and energy transfer processes between Er3+ and Tm3+ ions in different pumping schemes was investigated. The calculated energy transfer efficiency of the Er3+:4I13/2 level to the Tm3+:3F4 level was as high as 58.22%. 2.7μm, 1.5 μm, 1.8μm, and 2.3μm emissions have been observed in Er3+/Tm3+/Pr3+ triply doped ZBLAY glass when pumped by 980nmLD. The emission characteristics and energy transfer between Er3+, Tm3+ and Pr3+ ions were investigated. The Er3+:4I13/2 level can be effectively quenched by the Tm3+:3F4 and Pr3+:3F3,4 levels, which is beneficial to 2.7 μm emission. Er3+/Tm3+/Pr3+ triply doping way is an effective alternative to get 2.7μm emission. 2.84 μm emission with a large bandwidth of 213 nm has been obtained in Dy3+ doped ZBLAY glass. The prepared Dy3+ doped ZBLAY glass possessing high quantum efficiency (52.48 s-1) in theory along with large calculated emission cross section (1.17×10-20 cm2 ) has potential applications in 2.8 μm laser. Intense 2.0 μm emission has been obtained in Ho3+/Tm3+ codoped ZBLAY glass. The energy transfer microscopic parameter has been calculated with the Yokota-Tanimoto and Förster-Dexter models. High quantum efficiency(80.35%) and large gain parameter (83.16pm2•ms) of 2 μm emission indicated this Ho3+/Tm3+ codoped ZBLAY glass should be a promising material for 2.0 μm laser. Finally, all results of present work have been concluded in Chapter VII. And it has mentioned that something should be improved and done in future.
语种	中文
内容类型	学位论文
源URL	[http://ir.siom.ac.cn/handle/181231/15715]
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	田颖. 掺稀土氟磷酸盐玻璃中红外发光特性的研究[D]. 中国科学院上海光学精密机械研究所. 2012.

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