【作者】 万垂铭；

【导师】 孟建新；

【作者基本信息】 暨南大学 ， 分析化学， 2010， 硕士

【摘要】 稀土Nd3+掺杂的近红外发光具有穿透深度大、线宽窄、背景小等特点,在生物分析标记物等方面有重要的应用前景。其应用的重要瓶颈是其近红外发光强度比较弱。通过敏化离子与Nd3+之间的能量传递是提高其近红外发光强度的重要方式。Eu2+具有4f→5d电偶极允许跃迁,可以高效地吸收激发光能量,并可能传递能量给Nd3+离子并敏化其发光。本文致力于研究Eu2+敏化的新型高效Nd3+掺杂近红外发光材料并探讨Eu2+对Nd3+近红外发光能量传递的机理。具体实验内容有：用高温固相法制备了Ca2BO3Cl：Eu2+,Nd3+近红外发光材料,结果表明,Eu2+的掺入可提高Nd3+的近红外发光强度,Eu2+,Nd3+的掺杂量分别为0.03、0.05时,近红外发光最强。证明了Eu2+通过无辐射能量传递方式向Nd3+有效地传递了能量,对Nd3+近红外有很好的敏化作用。用高温固相法制备了Ca3SiO4Cl2：Eu2+,Nd3+、Ca8Mg(SiO4)4Cl2：Eu2+,Nd3+发光材料,发现其中Eu2+对Nd3+的近红外发光存在敏化作用。研究了Eu2+、Nd3+的掺杂浓度对近红外发光性能的影响及相对强度变化的规律。考察了煅烧温度、煅烧时间对近红外发光性能的影响。在Ca8Mg(SiO4)4Cl2:Eu2+,Nd3+体系中,样品的近红外发光强度随着Eu2+的掺杂浓度的增大先增强后减弱,Eu2+的掺杂量为0.08时,近红外发光最强；Nd3+的掺杂浓度为0.10时,近红外发光最强。样品在煅烧温度为1100℃下煅烧3h,近红外发光最强。分析了Eu2+与Nd3+之间能量传递的机理：Eu2+具有4f→5d跃迁轨道,可以有效地吸收能量,并将能量转移到的Nd3+的能级上,发生能量传递,增强Nd3+的近红外发光。用高温固相法制备了Sr4Si3O8Cl4：0.08Eu2+,0.08Nd3+发光材料,发现了该体系中Eu2+对Nd3+的近红外发光存在敏化作用,近红外发光强度提高了10倍左右,Eu2+向Nd3+的能量传递效率为19.7%。研究了Ca,Mg掺杂的Sr4Si3O8Cl4：0.08Eu2+,0.08Nd3+系列发光材料,随着Ca含量的增加,样品的近红外发光呈现逐渐增强的趋势。样品的近红外发光强度随着Mg含量的增加呈现逐渐减弱的趋势。用固相法制备了LiSrPO4：Eu2+、LiCaPO4：Eu2+、KCaPO4：Eu2+、NaCaPO4：Eu2+系列的高效蓝色、绿色荧光粉,优化了各荧光粉的制备条件。其中,研究表明LiSrPO4：Eu2+随着掺杂量的变化出现不同的发光中心；LiCaPO4：Eu2+是一种新型高效蓝色荧光粉；掺杂少量的Y3+可提高KCaPO4：Eu2+荧光粉的发光强度。进一步研究了LiSrPO4：Eu2+,Nd3+、LiCaPO4：Eu2+,Nd3+、KCaPO4：Eu2+,Nd3+、NaCaPO4：Eu2+,Nd3+近红外发光材料,考察了不同Eu2+发射波长对Nd3+近红外发光的敏化效果；系统地研究了煅烧温度、煅烧时间、掺杂量等各因素对NaCaP04：Eu2+,Nd3+体系近红外发光材料的影响,分析探讨了ABP04体系中Eu2+-Nd3+之间的能量传递机理。更多还原

【Abstract】 There is highly considerable attention on near-infrared(NIR) luminescence of Nd3+,due to its many advantages such as strong penetrability,narrow linewidth and free of background for biological analysis. However, the NIR luminescence intensity of Nd3+ doped in inorganic materials is still weak, which is difficiult for its application. It is an important way to enhance the luminescence intensity through the energy transfer between sensitizer and Nd3+. Eu2+ is an important sensitizer and activator with allowed 4f-5d electric dipole transition for luminescence, which is highly efficient absorb and emission and transfer the energy to other ionic. The passage contributes to prepare novel NIR luminescence materials doped Nd3+ and discusses the energy transfer mechanism between Eu2+ and Nd3+. The experiments as follows:Near-infrared luminescence material Ca2BO3Cl:Eu2+,Nd3+ was synthesized by high temperature solid state method. All results show that near-infrared luminescence of Nd3+ could be greatly enhanced codope Eu2+. There is the greatest NIR luminescence when the concentration of Eu2+ and Nd3+ is 0.03、0.05, respectively. The nonradiation energy transfer from Eu2+to Nd3+ has been confirmed.NIR luminescence phosphors Ca3SiO4Cl2:Eu2+,Nd3+、Ca8Mg(SiO4)4Cl2:Eu2+, Nd3+ were prepared by high temperature solid state method. It was found that Eu2+ has efficiently sensitized the NIR luminescence of Nd3+. The concentration of Eu2+ and Nd3+ effect on luminescence intensity was investigated and relationships between sintered temperature, sintered time and luminescence intensity were also studied. Such as Ca8Mg(SiO4)4Cl2:Eu2+,Nd3+, NIR luminescence intensity firstly increased with Eu2+ concentration, then reduced, the optimal concentration is 0.10. The phosphors sintered at 1100℃for 3 h give the strongest NIR luminescence intensity. The energy from Eu2+ efficiently excited transfer to the lever of Nd3+, the emission intensity of Nd3+ is greatly enhanced.Phosphors Sr4Si3O8Cl4:0.08Eu2+,0.08Nd3+ were synthesized by high temperature solid state method. The NIR luminescence of Nd3+ could be efficiently sensitized by Eu2+, the emission intensity of Nd3+ enhanced 10 times, the energy transfer efficiency between Eu2+ and Nd3+ is 19.7%. Series phosphors codoped Ca2+ and Mg2+ in Sr4Si3O8Cl4:0.08Eu2+,0.08Nd3+ have been studied. NIR luminescence intensity increased with the Ca2+ concentration and reduced with the Mg2+ concentration. Series efficient green or blue phosphors LiSrPO4:Eu2+、LiCaPO4:Eu2+、KCaPO4:Eu2+>、NaCaPO4:Eu2+ have been prepared by solid state method, the prepared conditions were optimization. Results show that there are two different emission centers in LiSrPO4:Eu2+ host with increased Eu2+ concentration. LiCaPO4:Eu2+ is a novel efficient blue-emitting phosphor. The emission intensity from KCaPO4:Eu2+ was enhanced by doping Y3+. Furthermore, NIR luminescence phosphors LiSrPO4:Eu2+,Nd3+、LiCaPO4:Eu2+,Nd3+、KCaPO4:Eu2+,Nd3+、NaCaPO4:Eu2+,Nd3+ have been studied. The effect of emission wavelength from Eu2+ on NIR luminescence of Nd3+ was investigated. The effects of sintered temperature, sintered time and concentration on NIR luminescence were also investigated. The energy transfer mechanism between Eu2+ and Nd3+ was discussed.更多还原