新型硫系玻璃红外材料的制备及其性能研究
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摘要
硫系玻璃具有较低的声子能量、优异的红外透过率、良好的化学稳定性和热稳定性,被认为是具有广泛应用前景的红外传输材料和红外激光基质材料。然而目前的基础材料研究中依然有几个主要的问题制约着硫系玻璃研究与应用的进一步的展。首先,目前在稀土掺杂硫系玻璃的研究中存在的首要的问题就是稀土离子在硫系玻璃中的掺杂浓度不高,大大降低了激光工作介质在泵浦时的泵浦效率。其次,基质玻璃中的杂质离子对稀土掺杂离子发光寿命也有很大的影响。因此,要获得高量子效率,就必须尽可能地降低基质玻璃中-OH含量。同样作为红外传导光纤材料,优秀的可见/红外透过性能也是我们迫切需要的。再者,硫系玻璃的热学性能普遍较差,这也大大降低了玻璃的走向实用化。
针对目前硫系玻璃的基础研究中所存在的问题,本论文的工作主要集中在以下两个方面:
(一)制备了新型的可高浓度掺杂稀土离子的硫系基质玻璃,即Dy~(3+):GeGaS-CdS玻璃。测试性能包括可见,近红外吸收光谱、DTA、ICP、XRD、显微硬度、荧光光谱等,并分别进行讨论。测试结果表明,Dy~(3+)掺杂的GeGaCdS玻璃有望作为近红外波段内基于硫系玻璃的激光器、放大器和高亮度光源的潜在的候选材料。
(二)制备了新型的具有优秀红外透过性能的GeGaS-NaF硫系玻璃。对样品进行的性能测试包括红外透过光谱、可见/近红外吸收光谱、DSC、拉曼光谱等。本文创新性地将氟引入到硫系玻璃中。测试结果表明:随着氟的引入,玻璃的可见/红外透过性能明显改善,玻璃的热稳定性提高。氟取代了Ge周围的一个S的位置,形成了[≡Ga←F-Ge≡]结构单元。以上结果表明:GeGaS-NaF玻璃有望作为红外传导光纤的优秀的候选材料。
Chalcogenide glass possess many unique optical properties,such as wide IR transparency,high refractive index,low phonon energy,a high optical non-linear coefficient,good chemical durability and glass-forming ability and a wide variety of photo-induced phenomena.But there are some bottleneck problems which restricting further research and application of chalcogenide glass.Firstly of all,the rare-earth ions doping concentration is limited.Secondly,the impurities in chalcogenide host glass have a detrimental effect on the IR transparency,the refractive index,the solubility of RE ions and the fluorescence efficiency.In order to obtain high quantum efficiency,it is necessary to reduce the impurities,such as -OH, as much as possible.In the meantime,the visible/infrared transparency of chalcogenide glass is very important for infrared fibre material.Moreover,the poor thermal properties of chalcogenide glass also should be improved for practical use.
In view of the basic problems in chalcogenide glass research,this thesis focuses on two kinds of chalcogenide glass as following:
(A) We present a novel GeGaCdS chalcogenide glass doped with high Dy~(3+) concentration for the first time.Their thermodynamic performances,Vickers micro-hardness as well as optical properties were measured and are discussed in detail.Dy~(3+)-doped GaGaCdS glasses would be good potential candidates of chalcogenide glass for lasers,amplifiers,and high brightness sources in the nearand mid-IR region.
(B) We present a novel GeGaS-NaF chalcogenide glass with good infrared transparency.The results show that when fluorin is introduced into chalcogenide glass,the infrared transparency is markedly improved,the thermodynamic performance is modified.The Raman spectroscopy indicates that the introduced fluoride could replace the position of S around the Ge and form[=Ga←F-Ge=] structural units.These results show that GeGaS-NaF glass would be an excellent candidate for infrared fibre material.
针对目前硫系玻璃的基础研究中所存在的问题,本论文的工作主要集中在以下两个方面:
(一)制备了新型的可高浓度掺杂稀土离子的硫系基质玻璃,即Dy~(3+):GeGaS-CdS玻璃。测试性能包括可见,近红外吸收光谱、DTA、ICP、XRD、显微硬度、荧光光谱等,并分别进行讨论。测试结果表明,Dy~(3+)掺杂的GeGaCdS玻璃有望作为近红外波段内基于硫系玻璃的激光器、放大器和高亮度光源的潜在的候选材料。
(二)制备了新型的具有优秀红外透过性能的GeGaS-NaF硫系玻璃。对样品进行的性能测试包括红外透过光谱、可见/近红外吸收光谱、DSC、拉曼光谱等。本文创新性地将氟引入到硫系玻璃中。测试结果表明:随着氟的引入,玻璃的可见/红外透过性能明显改善,玻璃的热稳定性提高。氟取代了Ge周围的一个S的位置,形成了[≡Ga←F-Ge≡]结构单元。以上结果表明:GeGaS-NaF玻璃有望作为红外传导光纤的优秀的候选材料。
Chalcogenide glass possess many unique optical properties,such as wide IR transparency,high refractive index,low phonon energy,a high optical non-linear coefficient,good chemical durability and glass-forming ability and a wide variety of photo-induced phenomena.But there are some bottleneck problems which restricting further research and application of chalcogenide glass.Firstly of all,the rare-earth ions doping concentration is limited.Secondly,the impurities in chalcogenide host glass have a detrimental effect on the IR transparency,the refractive index,the solubility of RE ions and the fluorescence efficiency.In order to obtain high quantum efficiency,it is necessary to reduce the impurities,such as -OH, as much as possible.In the meantime,the visible/infrared transparency of chalcogenide glass is very important for infrared fibre material.Moreover,the poor thermal properties of chalcogenide glass also should be improved for practical use.
In view of the basic problems in chalcogenide glass research,this thesis focuses on two kinds of chalcogenide glass as following:
(A) We present a novel GeGaCdS chalcogenide glass doped with high Dy~(3+) concentration for the first time.Their thermodynamic performances,Vickers micro-hardness as well as optical properties were measured and are discussed in detail.Dy~(3+)-doped GaGaCdS glasses would be good potential candidates of chalcogenide glass for lasers,amplifiers,and high brightness sources in the nearand mid-IR region.
(B) We present a novel GeGaS-NaF chalcogenide glass with good infrared transparency.The results show that when fluorin is introduced into chalcogenide glass,the infrared transparency is markedly improved,the thermodynamic performance is modified.The Raman spectroscopy indicates that the introduced fluoride could replace the position of S around the Ge and form[=Ga←F-Ge=] structural units.These results show that GeGaS-NaF glass would be an excellent candidate for infrared fibre material.
引文
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