| 题名 | 稀土掺杂碲酸盐及卤氧碲酸盐玻璃2-3μm发光性能研究 |
| 作者 | 马瑶瑶 |
| 学位类别 | 博士 |
| 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 | 胡丽丽 |
| 关键词 | 碲酸盐玻璃，卤氧碲酸盐玻璃，稀土离子掺杂，2-3μm，能量传递 |
| 其他题名 | Spectroscopic properties of 2-3 μm emissions in rare-earth doped tellurite and halo-tellurite glasses |
| 中文摘要 | 近年来，输出波长在2-3 μm的中红外激光因在军事、医疗、环保、光通信等领域非常广阔的应用前景引起了科研人员的广泛关注。常用的2-3 μm波段发光离子主要有Er3+（2.7 μm）、Ho3+（2.0 μm, 2.9 μm）、Tm3+（1.8 μm）和Dy3+（2.9 μm）离子等。目前国内外对于2-3 μm波段发光材料基质研究主要集中在晶体、石英玻璃、氟化物玻璃和重金属氧化物玻璃中。碲酸盐玻璃是一种重要的重金属氧化物玻璃，具有折射率高、化学稳定性好、红外透过范围宽、声子能量低等优点，有望成为中红外发光波段适宜的玻璃基质。本论文研究目的是探索适用于中红外2-3 μm波段发光的稀土离子掺杂碲酸盐玻璃，并通过引入卤化物的方式改善氧化物体系热学及发光性能，从而获得2-3 μm发光性能改善的卤碲酸盐玻璃。 本论文共包含六个部分。 论文第一章为文献综述部分，首先对激光的产生及光纤激光器、中红外波段的发光离子及基质材料进行了概述，继而讨论了碲酸盐玻璃的研究现状及存在问题，从而提出本文研究内容及思路。 论文第二章主要介绍了碲酸盐玻璃的制备方法、物理化学性质测试、结构成分测试及光谱理论计算和分析方法等。 论文第三章介绍了碲酸盐及卤氧碲酸盐玻璃的成玻范围及热稳定性。以碲锌和碲钨两种碲酸盐玻璃作为基础组分，研究不同组分玻璃热稳定性。结果表明随着ZnO含量的增加，该碲酸盐玻璃的玻璃化转变温度Tg没有明显变化，然而随着WO3含量增加，玻璃化转变温度Tg明显增加。在碲锌体系中，ZnO含量为30 mol%时，ΔT最大，玻璃的热稳定性最好。研究了不同网络修饰体的加入对玻璃热稳定性能影响。实验结果表明与二元体系相比，加入Nb5+及La3+的三元体系的热稳定性明显改善，ΔT均大于130 ℃。研究了卤化物的加入对碲酸盐玻璃热学及透过性能的影响。ΔT随ZnF2含量的增加而有一定的增大。OH-吸收系数αOH-随氟化物加入逐渐降低，含30 mol%氟化物的样品的αOH-降为0.19 cm-1。 论文第四章讨论了几种稀土离子掺杂碲酸盐及氧氟碲酸盐玻璃 ~3 μm发光特性，并对发光过程中涉及到的能量传递过程进行了分析。首先研究了Er3+离子在网络修饰体不同的碲酸盐玻璃中的2.7 μm发光性能。结果表明碲锌体系2.7 μm的发光强度普遍大于碲钨玻璃体系的发光强度。且在TeO2-WO3-La2O3样品中获得了最大的受激发射截面值，为2.03×10-20 cm2。研究了Dy3+离子单掺及Dy3+/Tm3+离子共掺碲酸盐玻璃2.9 μm发光特性。808 nm LD泵浦下，在Dy3+/Tm3+离子共掺碲酸盐玻璃中获得了明显增强的2.9 μm荧光。通过F?rster-Dexter理论计算了Tm3+离子敏化Dy3+离子的微观能量传递系数。从Tm3+离子到Dy3+离子较大的能量传递系数表明二者可以实现有效的能量传递。所以Dy3+/Tm3+离子共掺碲酸盐玻璃有望成为2.9 μm波段的发光材料。研究了Er3+/Nd3+、Er3+/Ho3+稀土离子共掺氧氟碲酸盐玻璃（TF）中Er3+离子2.7 μm发光特性。808 nm LD泵浦下，Er3+/Nd3+共掺的氧氟碲酸盐玻璃2.7 μm荧光明显增强，说明Nd3+离子可以作为Er3+：4I11/2→4I13/2跃迁的敏化离子。同时，在共掺样品中，计算得到Er3+：4I13/2能级向Nd3+：4I15/2能级间的能量转移效率为84%，从而使Er3+离子1.5 μm荧光强度明显减弱。此外通过实验发现该玻璃体系中加入5 mol%GeO2可改善玻璃的热稳定性和光谱性质，其受激发射截面最大值可达1.11×10-20 cm2。980 nm LD泵浦下，Er3+/Ho3+离子共掺氧氟碲酸盐玻璃中Er3+离子1.5 μm荧光强度明显减弱，这说明Er3+：4I13/2能级上的粒子可以通过能量转移过程传递到Ho3+离子。计算所得的Er3+：4I13/2能级向Ho3+：5I7能级的能量转移效率为67.33%。Er3+/Ho3+离子共掺氧氟碲酸盐玻璃的受激发射截面值为1.82×10-20 cm2。这说明Er3+/Ho3+离子共掺氧氟碲酸盐玻璃有望作为2.7 μm的发光材料。 论文第五章设计并制备了含不同量氟化物掺Tm3+碲酸盐玻璃，以及Ho3+/Er3+/Yb3+三掺氧氟碲酸盐玻璃。首先研究了氟化物的加入对掺Tm3+碲酸盐玻璃热稳定性及2 μm光谱性质的影响。DSC结果表明，随着氟化物的加入，碲酸盐玻璃的玻璃化转变温度Tg稍有减小，而ΔT有明显的增加。随着氟化物的加入，Tm3+离子的1.8 μm发光逐渐增强。同时，Tm3+：3F4能级的荧光寿命明显增加，从1.22 ms增加到4.89 ms。接着从两个方面讨论了荧光寿命明显增加的原因。一方面，氟化物的加入在熔融过程中通过物理及化学过程减少了玻璃体系中OH-的含量，含30 mol%氟化物的碲酸盐玻璃（TZF30样品）的OH-吸收系数降低了30%，为0.19 cm-1。这减少了由OH-引起的无辐射跃迁几率。另一方面，随着氟化物不断加入，与稀土离子耦合的声子的电声耦合系数减小，从0.0134降为0.0101，这降低了多声子弛豫几率。综合两方面的原因，得出在碲酸盐玻璃中加入氟化物可以有效的提高Tm3+:3F4能级的荧光寿命。研究了Ho3+/Er3+/Yb3+三掺氧氟碲酸盐玻璃2.05 μm发光特性。利用Yb3+离子和Er3+离子共同敏化Ho3+离子，通过980 nm LD泵浦，获得了较强的2.05 μm荧光。相较于Ho3+/Yb3+离子共掺玻璃，三掺样品的2.05 μm发光有一定的增强，并且与Er3+/Yb3+共掺玻璃样品相比，Ho3+/Er3+/Yb3+三掺氧氟碲酸盐玻璃的1.5 μm荧光明显减弱，这说明Er3+离子可将能量转移给Ho3+离子。由此，Ho3+/Er3+/Yb3+三掺氧氟碲酸盐玻璃有望成为2.05 μm发光材料。 最后是论文的结论部分，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 | Owing to the increased interests in mid-infrared laser fiber (2-5 μm) used in laser surgery, environmental monitoring, bio-engineering, and remote chemical sensing fields, considerable researches have been performed to searching for new materials to be used as hosts for mid-infrared laser hosts recently. Er3+(2.7 μm), Ho3+(2.9 μm), Tm3+(1.8 μm) and Dy3+(2.9 μm) ions are common rare earth ions used for the 2-3 μm emission. Previous efforts have mainly been paid to the glasses such as silicate, fluoride, heavy-metal-oxide (HMO) glasses. Among many alternatives, tellurite glasses emerge as good candidates for mid-infrared fiber laser materials because of their lowest phonon energy (~760 cm-1) among all the oxide glasses with large refractive index and a broad transmission window (0.4-6 μm). This dissertation aims to search novel tellurite glass hosts suitable for mid-infrared wavelength around 2-3 μm. By introducing halogen compound to modify the thermal and spectroscopic properties of the tellurite glasses, we could obtain halo-tellurite glasses with modified 2-3 μm emission properties. This dissertation includes the following six chapters. Chapter 1 is literature review. Firstly, the principle of laser generation, developments and applications of laser, rare earth ions generating 2-3 μm lasers and hosts materials have been introduced briefly. The characteristic and the research progresses on optical tellurite glasses used as mid-infrared lasers have been reviewed. Then, the purpose and research content of the dissertation were proposed. In Chapter 2, the preparation procedures of tellurite glasses, physical properties measurements, structure and components measurements and spectroscopic theory analysis were introduced. In Chapter 3, the glass formation region and the thermal stability of tellurite and halo-tellurite glasses are studied. Based on tellurite-zinc and tellurite-tungsten glass systems, component dependence of glass thermal stability has been discussed. The glass transition temperature does not show obvious changes with the addition of ZnO in zinc-modified tellurite glass nevertheless Tg values increase rapidly with WO3 content in tungsten-modified tellurite glass. Zinc-modified tellurite glass with 30 mol% ZnO had the maximum value of ΔT. Compared with binary glass system, the glass stability of the ternary system with addition of Nb5+ and La3+ has been improved with values of ΔT bigger than 130 ℃. In Chapter 4, a series of rare-earth doped tellurite and halo-tellurite glasses with 3 μm emissions have been prepared. Firstly, 2.7 μm emission spectra of different modifiers modified tellurite glasses have been investigated. The results showed that 2.7 μm emission intensity of tellurite-zinc glasses were higher than that of tellurite-tungsten glasses The maximum emission cross section of 2.7 μm is 2.03×10-20 cm2 in tellurite-tungsten-lanthanum glass. Then 2.9 μm emission spectra of Dy3+ doped and Dy3+/Tm3+ codoped tellurite glasses have been prepared and investigated. Under 808 nm LD, intense 2.9 μm emission has been obtained in Dy3+/Tm3+ codoped samples. Efficient energy transfer from Tm3+ to Dy3+ ion is demonstrated. This makes Dy3+/Tm3+ codoped tellurite glasses promising materials for 2.9 μm laser. Finally, optical properties and energy transfer processes of Er3+/Nd3+、Er3+/Ho3+ codoped fluoride tellurite glasses were studied. Intense 2.7 μm emission was obtained in Er3+/Nd3+ codoped glasses by an 808nm LD which indicated Nd3+ can be a sensitized ion for Er3+:4I11/2→4I13/2 transition. Meaning while, 1.5 μm emission intensity decreased dramatically in Er3+/Nd3+ codoped samples and the energy transfer efficiency from Er3+ to Nd3+ ions was calculated to be 84% which decreases the population of Er3+:4I13/2 efficiently. In addition, addition of 5 mol%GeO2 in the glass can improve the thermal stability, as well as the emission properties. The emission cross section of TFGe glass is calculated to be 1.11×10-20 cm2. 1.5 μm emission intensity decreased dramatically in Er3+/Ho3+ codoped samples under 980 nm LD and the energy transfer efficiency from Er3+:4I13/2 state to Ho3+:5I7 state was calculated to be 67.33%. The emission cross section of Er3+/Ho3+ codoped glass is calculated to be 1.82×10-20 cm2. This makes Er3+/Ho3+ codoped tellurite glasses promising materials for 2.7 μm laser. In Chapter 5, a series of rare-earth doped fluo-tellurite glasses with 2 μm emissions have been prepared. Firstly, effects of different content of fluoride on the 1.8 μm emission intensity and lifetimes were investigated. Glass transition temperature (Tg) decreases slightly with increase of fluoride. The glass stability ΔT shows a moderate increases with the increase of the ZnF2 content. The 1.8 μm emission intensity increased gradually. As the concentration of ZnF2 increases, the lifetimes of Tm3+ ions increase dramatically from 1.22 ms to 4.89 ms. Then two reasons of increased lifetimes were discussed. On the one hand, substitution of ZnO with ZnF2 in tellurite glasses shows an efficient dehydration effects and the transmittance becomes higher as the fluoride concentration increases by volatilization during melting process. The OH- induced absorption coefficient αOH- in sample with 30 mol% ZnF2 decreased 30%, which is 0.19 cm-1. As the αOH- decrease with the fluoride substitution, WOH- is expected to decrease which results in a reduced nonradiative transition rate. On the other hand, the electron-phonon coupling strength parameter ( g) calculated from PSB spectra change from 0.0134 to 0.0101 with increasing concentration of fluoride ions. The weaker intensity of the electron-phonon coupling strength leads to a decrease in the phonon assisted nonradiative rate (WMPR). Based on these analyses, it is clear that fluoride ions substitution in present tellurite glasses monitor the increased radiative lifetime of Tm3+:3F4 level by reducing the OH- content and multiphonon relaxation. 2.05 μm emission spectra of Ho3+/Er3+/Yb3+ triply doped fluotellurite glasses have been prepared and investigated. 2.05 μm emission in Ho3+/Er3+/Yb3+ triply doped fluotellurite glasses pumped by 980 nm LD can be greatly enhanced by adding Er3+ and Yb3+ ions simultaneously. By detecting the up conversion, 1.5 μm and 2.05 μm emission spectra, the energy transfer processes between three rare-earth ions were discussed. Compared with Ho3+/Yb3+ codoped samples, 2.05 μm emission of Ho3+/Er3+/Yb3+ triply doped glass were stronger, and also 1.5 μm emission of Ho3+/Er3+/Yb3+ triply doped glass decreased obviously. The results indicate that efficient energy transfer from Er3+ to Ho3+ can be realized under 980 nm LD excitation. Therefore, this Ho3+/Er3+/Yb3+ triply doped glass is a promising candidate for efficient 2.05 μm laser. In Chapter 6, all results of this dissertation have been concluded. The deficiencies of this work and works needed to be done were pointed. |
| 语种 | 中文 |
| 内容类型 | 学位论文 |
| 源URL | [http://ir.siom.ac.cn/handle/181231/15923]  |
| 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 | 马瑶瑶. 稀土掺杂碲酸盐及卤氧碲酸盐玻璃2-3μm发光性能研究[D]. 中国科学院上海光学精密机械研究所. 2015. |
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