白光LED用硅酸盐基稀土荧光粉的制备及发光性能研究
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摘要
采用高温固相反应法(SSR)和Pechini-溶胶凝胶法两种工艺制备了稀土离子掺杂的正硅酸盐荧光粉。利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、荧光分光光度计对样品进行了分析,研究了碱金属离子掺杂、稀土离子掺杂、合成工艺对荧光粉物相组成、微观结构、发光性能的影响。研究结果表明:(1)Pechini-溶胶凝胶法与高温固相反应法相比,制得的荧光粉物相更加纯净;粉体颗粒粒径更加均一,且呈球形形态,有利于涂覆。(2)Ba~(2+)掺杂的Sr_2SiO_4:Eu~(2+)中Eu~(2+)离子分布于两个不同的基体晶格位置,使发射光谱分别产生了绿光和黄光波段的发射;改变Ba~(2+)、Eu~(2+)离子掺杂浓度可以对荧光粉进行有效的光谱剪裁。碱金属离子Ba~(2+)的掺杂使Ba_xSr_(2-x-y)SiO_4:Euy2+荧光粉的α′-Sr_2SiO_4物相结构得到了稳定。碱土金属离子Ca~(2+)、Ba~(2+)掺杂的Li_2SrSiO_4:Eu~(2+)荧光粉具有宽带的激发和发射光谱,在色度图上分别位于蓝光区和黄光区。(3)阐述了稀土离子Eu~(2+)、Ce3+共掺杂的Li_2SrSiO_4荧光粉中其存在的能量传递现象,同时通过理论公式的计算和证明确定了能量传递的机制;稀土离子Eu~(2+)、Ce3+共掺杂的Li_2SrSiO_4荧光粉中存在电子偶极-偶极相互作用的Ce→Eu能量迁移现象;Li_2SrSiO_4:Ce, Eu在蓝光和黄光区域有两个发射峰,分别位于400 nm和570 nm处。当Ce3+离子浓度为0.005,Eu~(2+)离子浓度n≥0.75时,产生浓度猝灭现象。
Rare-earth doped silicates phosphors were prepared by high temperature solid state reaction (SSR) and Pechini-sol-gel route, respectively. Using X-ray Diffractometer (XRD), Scanning Electron Microscope (SEM) and fluorescent spectrophotometer, the influences of different doping ions including alkaline-earth metal ions and rare-earth ions, and preparing methods on phase compositions, microstructures and optical properties of silicates phosphors were studied. Experimental result show: (ⅰ) Comparing with SSR, Pechini-sol-gel route synthesized pure single phase phosphors with uniform phosphor particles and beneficial spherical shape. (ⅱ) Ba~(2+)-doped Sr_2SiO_4:Eu~(2+) phosphors (Ba_xSr_(2-x-y)SiO_4:Euy2+) show two intense emission bands at green and yellow regions of spectrum, originated from Eu~(2+) ions accommodated at two different sites in the host crystal, whose peaks depend on the concentrations of Ba~(2+) and Eu~(2+) ions. Additional, Ba~(2+)-doping favored the stabilization ofα′-Sr_2SiO_4 phase. Intense and broad excitation spectra and emission spectra were obtained by doping Ca~(2+) or Ba~(2+) ions in Li_2SrSiO_4:Eu~(2+) phosphor, which show blue emitting and yellow emitting in chromaticity diagram, respectively. (ⅲ) The energy transfer from Ce3+ to Eu~(2+) (Ce→Eu) was demonstrated to be the type of electric dipole-dipole interaction in the Eu~(2+) and Ce3+ codoped Li_2SrSiO_4 phosphor. There were broad blue and yellow emissions peaked at 400 nm and 570 nm, respectively. It was observed that Li_2SrSiO_4:0.5%Ce3+,0.75%Eu~(2+) displayed the highest emission intensity, and higher concentration of Eu~(2+) resulted in concentration quenching.
Rare-earth doped silicates phosphors were prepared by high temperature solid state reaction (SSR) and Pechini-sol-gel route, respectively. Using X-ray Diffractometer (XRD), Scanning Electron Microscope (SEM) and fluorescent spectrophotometer, the influences of different doping ions including alkaline-earth metal ions and rare-earth ions, and preparing methods on phase compositions, microstructures and optical properties of silicates phosphors were studied. Experimental result show: (ⅰ) Comparing with SSR, Pechini-sol-gel route synthesized pure single phase phosphors with uniform phosphor particles and beneficial spherical shape. (ⅱ) Ba~(2+)-doped Sr_2SiO_4:Eu~(2+) phosphors (Ba_xSr_(2-x-y)SiO_4:Euy2+) show two intense emission bands at green and yellow regions of spectrum, originated from Eu~(2+) ions accommodated at two different sites in the host crystal, whose peaks depend on the concentrations of Ba~(2+) and Eu~(2+) ions. Additional, Ba~(2+)-doping favored the stabilization ofα′-Sr_2SiO_4 phase. Intense and broad excitation spectra and emission spectra were obtained by doping Ca~(2+) or Ba~(2+) ions in Li_2SrSiO_4:Eu~(2+) phosphor, which show blue emitting and yellow emitting in chromaticity diagram, respectively. (ⅲ) The energy transfer from Ce3+ to Eu~(2+) (Ce→Eu) was demonstrated to be the type of electric dipole-dipole interaction in the Eu~(2+) and Ce3+ codoped Li_2SrSiO_4 phosphor. There were broad blue and yellow emissions peaked at 400 nm and 570 nm, respectively. It was observed that Li_2SrSiO_4:0.5%Ce3+,0.75%Eu~(2+) displayed the highest emission intensity, and higher concentration of Eu~(2+) resulted in concentration quenching.
引文
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