稀土硫氧化物红色长余辉材料的制备及研究
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摘要
长余辉材料就是能够存储外界光辐照的能量,然后在某一温度(室温)缓慢地以可见光的形式释放这些存储能量的材料。现有的长余辉材料包括蓝色、绿色和红色发光材料几种。近几年来,关于长余辉材料的研究报告纷纷出现,研究的重点主要是稀土元素掺杂的长余辉材料,尤其是碱土铝酸盐体系。已知性能最好的绿色长余辉材料是SrAlO_4;Eu~(2+),Dy~(3+),蓝色长余辉材料是CaAlO_4;Eu~(2+),Nd~(3+),并且实现了商品化。而红色长余辉材料的研究进展缓慢。Y_2O_2S;Eu~(3+)最早是一种高效电视机红粉,并不具有余辉特性。2000年Yoshinori等报道Ti和Mg共激活的Y_2O_2S;Eu~(3+)磷光体具有高亮度红色长余辉。大大提高了该体系材料的实用性。
在本文的第一章,我们综述了长余辉发光材料的研究进展、红色长余辉材料的研究现状、稀土硫氧化物材料的常用制备方法以及长余辉发光材料的余辉模型等。文章的第二章是实验部分,主要介绍了实验的方法和依据、所用药品和仪器以及样品的表征等;在文章的第三、四章,我们以Y_2O_2S为基质,采用固相反应法制备了Y_2O_2S;Eu~(3+),Si~(4+),Zn~(2+)和Y_2O_2S;Eu~(3+),Si~(4+),M~(2+)(M=Mg,Ca,Sr,Ba)系列新型红色长余辉材料,并且研究了Eu~(3+)的含量、制备工艺(烧结温度、时间、气氛、助溶剂及掺杂离子)等对合成的Y_2O_2S;Eu~(3+),Si~(4+),Zn~(2+)和Y_2O_2S;Eu~(3+),Si~(4+),M~(2+)(M=Mg,Ca,Sr,Ba)长余辉材料的影响。利用XRD,荧光光谱,热释光谱等分析手段对产物结构和性能进行了分析。通过热释光谱分析了其缺陷组成并计算了陷阱能级深度。确定了高温固相法合成Y_2O_2S;Eu~(3+),Si~(4+),M~(2+)发光材料的最佳条件。分析了碱土金属离子掺杂对Y_2O_2S;Eu~(3+),Si~(4+),M~(2+)(M=Mg,Ca,Sr,Ba)系列新型红色长余辉材料发光性能的影响。
Long-lasting phosphor in which energy could be reserved under the(ultraviolet) UV lamp or infrared femtosecond laser and finally thermal release as luminescence. Recently,long lasting phosphor has been rapidly developed.The phosphors available include blue,green,and red etc.Much work has been done on them.The studies focused mainly on rare earth doped phosphors,particularly alkaline earth aluminate system.The best known green afterglow material is SrAlO_4;Eu~(2+),Dy~(3+),blue afterglow material is CaAlO_4;Eu~(2+),Nd~(3+),both have been commercialized.However, the progress in developing red afterglow material is slow.Y_2O_2S;Eu~(3+)was found as highly effective television powder without long lasting properties.In 2000 Yoshinori et al reported that Ti~(4+)and Mg~(2+)co-doped Y_2O_2S;Eu~(3+)phosphor has high luminance red afterglow.
In the first part of this paper,we reviewed the research advance and luminescent model of long-lasting phosphor,research status of red persistence phosphor and preparation methods of sulfide-oxide long-lasting phosphor; In the second part,the experiment method,raw material,main instrument and characterization methods et al were introduced; and in the third and the fourth parts,taking Y_2O_2S as matrix,we synthesized Y_2O_2S;Eu~(3+),Si~(4+),Zn~(2+)and Y_2O_2S;Eu~(3+),Si~(4+),M~(2+)(M=Mg、Ca、Sr、Ba) novel red long-lasting phosphors by solid state reaction.The effect of the content of Eu~(3+)and preparation technology et al were studied.XRD and photoluminescence(PL) spectra as well as the luminance decay were used to characterize these long lasting phosphors.According to the thermo-luminescence spectra,we analysised the kinds of trap and calculated the trap deep.Then the best synthesis conditions were decided. And the effect of the doping of alkaline-earth metal ions in the phosphors Y_2O_2S;Eu~(3+), Si~(4+),M~(2+)(M=Mg,Ca,Sr,Ba)was also analysised.
在本文的第一章,我们综述了长余辉发光材料的研究进展、红色长余辉材料的研究现状、稀土硫氧化物材料的常用制备方法以及长余辉发光材料的余辉模型等。文章的第二章是实验部分,主要介绍了实验的方法和依据、所用药品和仪器以及样品的表征等;在文章的第三、四章,我们以Y_2O_2S为基质,采用固相反应法制备了Y_2O_2S;Eu~(3+),Si~(4+),Zn~(2+)和Y_2O_2S;Eu~(3+),Si~(4+),M~(2+)(M=Mg,Ca,Sr,Ba)系列新型红色长余辉材料,并且研究了Eu~(3+)的含量、制备工艺(烧结温度、时间、气氛、助溶剂及掺杂离子)等对合成的Y_2O_2S;Eu~(3+),Si~(4+),Zn~(2+)和Y_2O_2S;Eu~(3+),Si~(4+),M~(2+)(M=Mg,Ca,Sr,Ba)长余辉材料的影响。利用XRD,荧光光谱,热释光谱等分析手段对产物结构和性能进行了分析。通过热释光谱分析了其缺陷组成并计算了陷阱能级深度。确定了高温固相法合成Y_2O_2S;Eu~(3+),Si~(4+),M~(2+)发光材料的最佳条件。分析了碱土金属离子掺杂对Y_2O_2S;Eu~(3+),Si~(4+),M~(2+)(M=Mg,Ca,Sr,Ba)系列新型红色长余辉材料发光性能的影响。
Long-lasting phosphor in which energy could be reserved under the(ultraviolet) UV lamp or infrared femtosecond laser and finally thermal release as luminescence. Recently,long lasting phosphor has been rapidly developed.The phosphors available include blue,green,and red etc.Much work has been done on them.The studies focused mainly on rare earth doped phosphors,particularly alkaline earth aluminate system.The best known green afterglow material is SrAlO_4;Eu~(2+),Dy~(3+),blue afterglow material is CaAlO_4;Eu~(2+),Nd~(3+),both have been commercialized.However, the progress in developing red afterglow material is slow.Y_2O_2S;Eu~(3+)was found as highly effective television powder without long lasting properties.In 2000 Yoshinori et al reported that Ti~(4+)and Mg~(2+)co-doped Y_2O_2S;Eu~(3+)phosphor has high luminance red afterglow.
In the first part of this paper,we reviewed the research advance and luminescent model of long-lasting phosphor,research status of red persistence phosphor and preparation methods of sulfide-oxide long-lasting phosphor; In the second part,the experiment method,raw material,main instrument and characterization methods et al were introduced; and in the third and the fourth parts,taking Y_2O_2S as matrix,we synthesized Y_2O_2S;Eu~(3+),Si~(4+),Zn~(2+)and Y_2O_2S;Eu~(3+),Si~(4+),M~(2+)(M=Mg、Ca、Sr、Ba) novel red long-lasting phosphors by solid state reaction.The effect of the content of Eu~(3+)and preparation technology et al were studied.XRD and photoluminescence(PL) spectra as well as the luminance decay were used to characterize these long lasting phosphors.According to the thermo-luminescence spectra,we analysised the kinds of trap and calculated the trap deep.Then the best synthesis conditions were decided. And the effect of the doping of alkaline-earth metal ions in the phosphors Y_2O_2S;Eu~(3+), Si~(4+),M~(2+)(M=Mg,Ca,Sr,Ba)was also analysised.
引文
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