锗硅酸盐玻璃的制备和发光性能研究
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摘要
当今世界,能源危机和环境问题已成为影响人类可持续发展的重大问题,人们迫切希望应用节能环保的新技术,而光学玻璃就是具有这种魅力的新技术之一。锗硅酸盐光学玻璃因具有较低的声子能量,良好的玻璃形成能力以及较高的稀土离子溶解度,在光学领域,尤其是在信息处理,大屏幕显示,军事探测及激光医疗领域有广阔的发展潜力,近年来已引起学者的广泛兴趣。
本文首先回顾了稀土离子掺杂锗硅酸盐光学玻璃的发展应用及研究现状,在此基础上,采用高温熔融-退火法制备了锗硅酸盐光学玻璃及锗硅酸盐氟氧化物微晶玻璃。通过拉曼光谱,吸收-透过光谱,荧光光谱,X射线衍射等手段研究了氧化锗和氧化硅的比例、二价碱土金属氧化物的含量及种类、Dy203掺杂浓度、热处理时间和热处理温度对锗硅酸盐玻璃和锗硅酸盐氟氧化物微晶玻璃结构和性能的影响。主要得到了以下结果：
采用高温熔融法制备了不同氧化锗和氧化硅比例的锗硅酸盐玻璃。研究结果表明,在锗硅酸盐玻璃中同时存在[SiO4],[GeO4]以及[SiO4]&[GeO4]昆合网络结构。含不同比例氧化锗和氧化硅的锗硅酸盐玻璃，其Dy3+离子的猝灭浓度和发光强度存在很大不同。当GeO2:SiO2为20 mol%:30mol%, Dy2O3的掺杂浓度为1.00 mo1%时,Dy3+离子的发光强度达到最大。二价碱土金属氧化物主要影响玻璃中[Ge04]网络结构,但玻璃基质中Dy3+离子的发光强度却随着MgO→CaO→BaO的顺序减弱,原因是碱土金属离子半径越小,越能改善玻璃三维网络结构,提高稀土离子的分散率和发光效率。
通过对锗硅酸盐氟氧化物玻璃进行热处理得到微晶玻璃。XRD结果表明,玻璃中生成了晶粒尺寸为纳米级的Ba3AlF9晶相。玻璃在可见—红外光区有较高的透明度(90%)。580℃下热处理4h后的微晶玻璃其发光强度最强。而对玻璃样品在620℃C热处理后,玻璃中同时析出Ba3AlF9晶相和BaAl2Si2O8杂相,玻璃样品出现浑浊。另外,考察了Dy203掺杂浓度对玻璃析晶行为及光学性能的影响,发现当Dy203掺杂浓度为1.00 mo1%时,玻璃发光强度达到最强,当Dy203掺杂浓度达到3.00 mo1%时,玻璃中没有Ba3AlF9晶相的析出。通过比较未经热处理玻璃样品和经580℃下热处理4h的微晶玻璃样品的发射光谱得知,热处理后微晶玻璃样品的光学性能得到很大的改善。
Nowadays, environment and energy crisis have become international issues. The development of new technology is needed for protecting environment. As one of the most favorite energy-saving materials, optical glass has been paid more and more attention by researchers. Germanosilicate optical glass has been widely used for luminescent materials due to its low phonon energy, good ability of glass formation and high rare earth ions solubility. Recent years, germanosilicate optical glass has been recognized as a promising material in the fields of information processing, LSD, military and laser medicine.
First, this thesis reviewed the development and application of rare earth ions doped germanosilicate optical glass. Second, the germanosilicate optical glasses and oxyfluoride germanosilicate glass ceramics were prepared by melting-annealing/ quenching/thermal treatment method. The effects of the ratio of SiO2 and GeO2, the kinds of alkaline earth metal oxides, the concentration of Dy2O3, the heat treatment temperature and the heat treatment time on the structure and properties of germanosilicate optical glasses and oxyfluoride germanosilicate glass ceramics were studied by Raman spectra, absorption-transmission spectra, photoluminescence spectra and X-ray diffraction and son on. The details were listed as following:
The germanosilicate optical glasses with different ratio of SiO2 and GeO2 were prepared by melting-annealing method. The [SiO4] tetrahedron, [GeO4] tetrahedron and [SiO4] & [GeO4] polyhedrons exited together in the germanosilicate glass matrix. The luminescence intensity and quenching concentration of Dy3+ions were different when changing the ratio of SiO2 and GeO2. When the ratio of GeO2 and SiO2 was 20 mol%:30 mol% and the concentration of Dy2O3 was 1.00 mol%, the germanosilicate optical glasses had the strongest luminescence intensity. The kinds and contents of alkaline earth metal oxides had no effects on the structure of glass matrix while they had some effects on the luminescence intensity of Dy2O3. The luminescence intensity of Dy2O3 became lower when alkaline earth metal oxides changed as following:MgO→CaO→BaO. The reason was that the smaller of the cation radius, the better of the glass matrix network was improved, leading to the better dispersibility of Dy3+ions.
The oxyfluoride germanosilicate glass ceramics were prepared by heat treatment method. The XRD results showed that the Ba3AlF9 microcrystal was formed after heat treatment. The crystal size was smaller than 10 nm. The glass ceramic had high visible-IR transmittance (90%) and had the strongest luminescence intensity after heat treated at 580℃for 4 h. When heat treated at 620℃, the samples became opaque due to coexist of the Ba3AlF9 phase and BaAl2Si2O8 phase. The effects of the concentration of Dy2O3 on the crystallization and luminescence property of samples were studied. The results showed that when the concentration of Dy2O3 is 1.00 mol%, the samples had the strongest luminescence intensity. When the concentration of Dy2O3 increased to 3.00 mol%, there was no Ba3AlF9 microcrystal formed in the samples. The sample heat treated at 580℃for 4 h has the better photoluminescence properties than that of without heat treatment because the Dy3+ions dispersed well with low phonon energy environment of Ba3AlF9 nanocrystallines in the oxyfluoride germanosilicate glass ceramics.
本文首先回顾了稀土离子掺杂锗硅酸盐光学玻璃的发展应用及研究现状,在此基础上,采用高温熔融-退火法制备了锗硅酸盐光学玻璃及锗硅酸盐氟氧化物微晶玻璃。通过拉曼光谱,吸收-透过光谱,荧光光谱,X射线衍射等手段研究了氧化锗和氧化硅的比例、二价碱土金属氧化物的含量及种类、Dy203掺杂浓度、热处理时间和热处理温度对锗硅酸盐玻璃和锗硅酸盐氟氧化物微晶玻璃结构和性能的影响。主要得到了以下结果：
采用高温熔融法制备了不同氧化锗和氧化硅比例的锗硅酸盐玻璃。研究结果表明,在锗硅酸盐玻璃中同时存在[SiO4],[GeO4]以及[SiO4]&[GeO4]昆合网络结构。含不同比例氧化锗和氧化硅的锗硅酸盐玻璃，其Dy3+离子的猝灭浓度和发光强度存在很大不同。当GeO2:SiO2为20 mol%:30mol%, Dy2O3的掺杂浓度为1.00 mo1%时,Dy3+离子的发光强度达到最大。二价碱土金属氧化物主要影响玻璃中[Ge04]网络结构,但玻璃基质中Dy3+离子的发光强度却随着MgO→CaO→BaO的顺序减弱,原因是碱土金属离子半径越小,越能改善玻璃三维网络结构,提高稀土离子的分散率和发光效率。
通过对锗硅酸盐氟氧化物玻璃进行热处理得到微晶玻璃。XRD结果表明,玻璃中生成了晶粒尺寸为纳米级的Ba3AlF9晶相。玻璃在可见—红外光区有较高的透明度(90%)。580℃下热处理4h后的微晶玻璃其发光强度最强。而对玻璃样品在620℃C热处理后,玻璃中同时析出Ba3AlF9晶相和BaAl2Si2O8杂相,玻璃样品出现浑浊。另外,考察了Dy203掺杂浓度对玻璃析晶行为及光学性能的影响,发现当Dy203掺杂浓度为1.00 mo1%时,玻璃发光强度达到最强,当Dy203掺杂浓度达到3.00 mo1%时,玻璃中没有Ba3AlF9晶相的析出。通过比较未经热处理玻璃样品和经580℃下热处理4h的微晶玻璃样品的发射光谱得知,热处理后微晶玻璃样品的光学性能得到很大的改善。
Nowadays, environment and energy crisis have become international issues. The development of new technology is needed for protecting environment. As one of the most favorite energy-saving materials, optical glass has been paid more and more attention by researchers. Germanosilicate optical glass has been widely used for luminescent materials due to its low phonon energy, good ability of glass formation and high rare earth ions solubility. Recent years, germanosilicate optical glass has been recognized as a promising material in the fields of information processing, LSD, military and laser medicine.
First, this thesis reviewed the development and application of rare earth ions doped germanosilicate optical glass. Second, the germanosilicate optical glasses and oxyfluoride germanosilicate glass ceramics were prepared by melting-annealing/ quenching/thermal treatment method. The effects of the ratio of SiO2 and GeO2, the kinds of alkaline earth metal oxides, the concentration of Dy2O3, the heat treatment temperature and the heat treatment time on the structure and properties of germanosilicate optical glasses and oxyfluoride germanosilicate glass ceramics were studied by Raman spectra, absorption-transmission spectra, photoluminescence spectra and X-ray diffraction and son on. The details were listed as following:
The germanosilicate optical glasses with different ratio of SiO2 and GeO2 were prepared by melting-annealing method. The [SiO4] tetrahedron, [GeO4] tetrahedron and [SiO4] & [GeO4] polyhedrons exited together in the germanosilicate glass matrix. The luminescence intensity and quenching concentration of Dy3+ions were different when changing the ratio of SiO2 and GeO2. When the ratio of GeO2 and SiO2 was 20 mol%:30 mol% and the concentration of Dy2O3 was 1.00 mol%, the germanosilicate optical glasses had the strongest luminescence intensity. The kinds and contents of alkaline earth metal oxides had no effects on the structure of glass matrix while they had some effects on the luminescence intensity of Dy2O3. The luminescence intensity of Dy2O3 became lower when alkaline earth metal oxides changed as following:MgO→CaO→BaO. The reason was that the smaller of the cation radius, the better of the glass matrix network was improved, leading to the better dispersibility of Dy3+ions.
The oxyfluoride germanosilicate glass ceramics were prepared by heat treatment method. The XRD results showed that the Ba3AlF9 microcrystal was formed after heat treatment. The crystal size was smaller than 10 nm. The glass ceramic had high visible-IR transmittance (90%) and had the strongest luminescence intensity after heat treated at 580℃for 4 h. When heat treated at 620℃, the samples became opaque due to coexist of the Ba3AlF9 phase and BaAl2Si2O8 phase. The effects of the concentration of Dy2O3 on the crystallization and luminescence property of samples were studied. The results showed that when the concentration of Dy2O3 is 1.00 mol%, the samples had the strongest luminescence intensity. When the concentration of Dy2O3 increased to 3.00 mol%, there was no Ba3AlF9 microcrystal formed in the samples. The sample heat treated at 580℃for 4 h has the better photoluminescence properties than that of without heat treatment because the Dy3+ions dispersed well with low phonon energy environment of Ba3AlF9 nanocrystallines in the oxyfluoride germanosilicate glass ceramics.
引文
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