固相燃烧法合成稀土钼酸盐发光材料及发光性质研究
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摘要
稀土钼酸盐发光材料由于具有良好的光热稳定性和化学稳定性，是一种很好的发光基质材料，但关于稀土钼酸盐发光材料的研究却少有报道。传统的稀土钼酸盐合成方法是高温固相法，但该方法得到的产物粒度大，而研磨又会引入杂质且破坏晶型，降低发光亮度。为此，本论文探索了新的合成方法，即固相燃烧法，成功制备了稀土钼酸盐系列发光材料并对发光性质进行了研究。主要内容和结果如下：
采用固相燃烧法，成功制备稀土钼酸盐上转换荧光粉。通过XRD、SEM、荧光分光光度计等分析测试仪器对合成物质的物相组成、微结构以及发光性能进行了测试分析。结果表明：制备的稀土钼酸盐粉体平均颗粒尺寸约1μm，且无需球磨便为分布均匀的类球形颗粒。同时该方法克服了传统固相法反应温度高、时间长、能耗高等缺点，是一种实现简单、快速、节能、高效、优质地合成稀土发光材料的好方法。
在Yb~(3+)／Er~(3+)共掺杂稀土钼酸盐荧光粉系列中，分别研究了Er~(3+)在钼酸钇、钼酸钆和钼酸镧基质中的发光情况以及不同基质对上转换发光的影响。详细研究了在不同稀土钼酸盐基质中，Er~(3+)掺杂浓度对上转换发光强度的影响，结果表明，当Er~(3+)浓度为3mol％时，绿光上转换发射强度均最高。最后对Yb~(3+)／Er~(3+)离子上转换发光机理进行了详细的讨论。
在Yb~(3+)／Ho~(3+)共掺杂稀土钼酸盐荧光粉系列中，对Ho~(3+)在钼酸钇、钼酸钆和钼酸镧基质中的发光情况以及不同基质对上转换发光的影响进行了研究。详细研究了在不同稀土钼酸盐基质中Ho~(3+)掺杂浓度对上转换发光强度的影响，结果表明，当Ho~(3+)浓度为2mol％时，红光上转换发射强度均最高。最后对Yb~(3+)／Ho~(3+)离子上转换发光机理也进行了详细的讨论。
Owing to the good stability in light, heat and chemical characteristics, the rare earth-doped molybdate is a good kind of luminescent material, but there are few reports on it. Solid state method is a traditional method to synthesize the rare earth-doped molybdate, by which the obtained particle size is very large, moreover, grinding will bring impurity and destroy crystal leading to decreased luminescent intensity. Therefore, this paper explores a new synthesis method, namely, the solid state combustion method, to synthesize the rare earth-doped molybdate successfully. The main contents and results are as following:
The rare earth doped molybdate up-conversion phosphor is synthesized by the solid state combustion method. The phase, micro-structure and luminescent properties of samples are characterized by X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM) and spectroscopic analysis. The results show that the average size of the rare earth-doped molybdate particle is about 1μm. The particles, which have narrow particle size distribution, are quasi-spherical without ball-milling. At the same time, solid state combustion method overcomes the disadvantages of the traditional solid method such as the high temperature, long reaction-time and high energy-cost. It is a simplification, speediness, economy, high efficiency and high quality method to synthesize luminescent materials.
As to the luminescent powders of molybdate doped with Yb~(3+) and Er~(3+) ions, the luminescence properties of Er~(3+) in yttrium molybdenum oxide, gadolinium molybdenum oxide and lanthanum molybdenum oxide and the effect of different host materials on the up-conversion luminescence are studied. In addition, the influence of doping concentration of Er~(3+) ions on the luminescent properties is studied detailedly. The
采用固相燃烧法，成功制备稀土钼酸盐上转换荧光粉。通过XRD、SEM、荧光分光光度计等分析测试仪器对合成物质的物相组成、微结构以及发光性能进行了测试分析。结果表明：制备的稀土钼酸盐粉体平均颗粒尺寸约1μm，且无需球磨便为分布均匀的类球形颗粒。同时该方法克服了传统固相法反应温度高、时间长、能耗高等缺点，是一种实现简单、快速、节能、高效、优质地合成稀土发光材料的好方法。
在Yb~(3+)／Er~(3+)共掺杂稀土钼酸盐荧光粉系列中，分别研究了Er~(3+)在钼酸钇、钼酸钆和钼酸镧基质中的发光情况以及不同基质对上转换发光的影响。详细研究了在不同稀土钼酸盐基质中，Er~(3+)掺杂浓度对上转换发光强度的影响，结果表明，当Er~(3+)浓度为3mol％时，绿光上转换发射强度均最高。最后对Yb~(3+)／Er~(3+)离子上转换发光机理进行了详细的讨论。
在Yb~(3+)／Ho~(3+)共掺杂稀土钼酸盐荧光粉系列中，对Ho~(3+)在钼酸钇、钼酸钆和钼酸镧基质中的发光情况以及不同基质对上转换发光的影响进行了研究。详细研究了在不同稀土钼酸盐基质中Ho~(3+)掺杂浓度对上转换发光强度的影响，结果表明，当Ho~(3+)浓度为2mol％时，红光上转换发射强度均最高。最后对Yb~(3+)／Ho~(3+)离子上转换发光机理也进行了详细的讨论。
Owing to the good stability in light, heat and chemical characteristics, the rare earth-doped molybdate is a good kind of luminescent material, but there are few reports on it. Solid state method is a traditional method to synthesize the rare earth-doped molybdate, by which the obtained particle size is very large, moreover, grinding will bring impurity and destroy crystal leading to decreased luminescent intensity. Therefore, this paper explores a new synthesis method, namely, the solid state combustion method, to synthesize the rare earth-doped molybdate successfully. The main contents and results are as following:
The rare earth doped molybdate up-conversion phosphor is synthesized by the solid state combustion method. The phase, micro-structure and luminescent properties of samples are characterized by X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM) and spectroscopic analysis. The results show that the average size of the rare earth-doped molybdate particle is about 1μm. The particles, which have narrow particle size distribution, are quasi-spherical without ball-milling. At the same time, solid state combustion method overcomes the disadvantages of the traditional solid method such as the high temperature, long reaction-time and high energy-cost. It is a simplification, speediness, economy, high efficiency and high quality method to synthesize luminescent materials.
As to the luminescent powders of molybdate doped with Yb~(3+) and Er~(3+) ions, the luminescence properties of Er~(3+) in yttrium molybdenum oxide, gadolinium molybdenum oxide and lanthanum molybdenum oxide and the effect of different host materials on the up-conversion luminescence are studied. In addition, the influence of doping concentration of Er~(3+) ions on the luminescent properties is studied detailedly. The
引文
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[2] 徐叙珞，苏勉曾．发光学与发光材料．北京：化学工业出版社，2004．
[3] 肖志国．发光材料及其制品．北京：化学工业出版社，2002．
[4] Guokui Liu, B Jacquier. Spectroscopic properties of rare earth in optical materials．北京：清华大学出版社，2005．
[5] M Saad, M Poulain. Fluoride glass synthesis by sol-gel process. J. Non-Cryst. Solids, 1995,184:352-355.
[6] P A Tick, N F Borrelli, L K Cornelius et al. Transparent glass ceramics for 1300nm amplifier applications. J. Appl. Phys., 1995,78(11):6367-6374.
[7] M Dejneka, B Samson. Rare-earth-doped fibers for telecommunications applications. Mater. Res. Soc. Bull., 1999,24(9):39-45.
[8] E Downing, L Hesselink, J Ralston, et al. A three-color, solid-state, three-dimensional display. Science, 1996,273:1185-1189.
[9] M J Dejneka. Transparent Oxyfluoride Glass Ceramics. Mater. Res. Soc. Bull., 1999,23(11):57.
[10] F Auzel. Upconversion and Anti-Stokes Processes with f and d Ions in Solids. Chem. Rev., 2004,104:139-173.
[11] Yi G S, Sun B Q, Yang F Z, et al. Synthesis and characterization of high-efficiency nanocrystal up-conversion phosphors: Ytterbium and Erbium codoped lanthanum molybdate. Chem Mater., 2002,14:2910-2914.
[12] 夏艳琴．Bi2O3与NaYF4体系的上转换研究：(硕士学位论文)．湘潭：湘潭大学，2006．
[13] 李建宇．稀土发光材料及其应用．北京：化学工艺出版社，2003．
[14] 中科院长春物理研究所固体发光编写组．固体发光．1976．
[15] 田莹．纳米氧化物和硫氧化物的合成、表征及发光性质的研究：(硕士学位论文)．大连：大连海事大学，2006．
[16] L A Riseberg, H W Moos. Multiphonon orbit-lattice relaxation of excited stated states of rare-earth ions in crystals. Phys. Rev.,1968,174:429-438.
[17] Auzel F. Computeur quantique par transfert d'energie de Yb~(3+) a Tm~(3+) dans un tungstate mixte et dans un verre gemanate. J Comt Rend., 1966,263B:819-821.
[18] Patil K C, Aruna S T, Mimani T. Combustion synthesis: an update. Curr Opin Solid St M., 2002,6:507-512.
[19] Merzhanov A G. History and Recent Developments in SHS. Ceramics International., 1995,21(5):371-379.
[20] 殷声．燃烧合成．北京：冶金工业出版社，1999．
[21] 郑仕远，李荣缇，罗永明．自蔓延燃烧发光材料合成技术．山东陶瓷，1999，22(4)：4-11．
[22] 殷声，赖和怡．自蔓延高温合成技术和材料．北京：冶金工业出版社，1995．
[23] Xiao S G, Yang X L, Liu Z W et al. Up-conversion in Er~(3+):Y_2O_3 nanocrystals pumped at 808nm. J Appl Phys., 2004,96:1360-1364.
[24] Wittke J P, Ladany I, Yocom P N. Y_2O_3:Yb, Er New red emitting infared exicted phosphor. J Appl Phys., 1972,43(2):595-900.
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