PMMA-YAG:Ce3+纳米有机复合荧光发光材料的可控制备与光增强研究

The phosphor powder is a key material of realizing white LED lighting, but so far，the fluorescent material technology to can be used integration with the LED device and to batch madding functional element failed to achieve a breakthrough.The project proposes, using nanometer YAG: Ce as luminescent particles, and with PMMA as matrix material, prepares nanometer composite organic light emitting material by using in situ synthesis process, and enhance light intensity and light extraction efficiency by using the surface plasma technology. Application principle of thermodynamics and kinetics of chemical reaction study the interactions rules between the nano luminescent particles and the organic matrix material, grasp the their reaction mechanism and the Interface structure characteristic, understand Internal relationship about the new type nanometer luminescent materials light effect, thermal stability with matrix material, achieve controlling synthesis of the nanometer organic composite luminescent materials.Constructing structure prototype of the luminescent element based on metal surface plasma light enhancement and light extraction, applying etching technology to prepare nano-scale surface metal structure, with light enhance and the light extraction efficiency as the objective function, the using lightwave electromagnetic theory analysis, reveals the law on the photon transmission, energy transfer and enhancement in novel luminescent material, and the realizing the high efficiency light enhancement and extraction. For batch manufacturing of the high efficient, stable the nanometer organic composite luminescent element provide scientific and technological basis.

荧光粉是实现LED白光照明的关键材料，但迄今为止可与器件集成并能批量制成功能元件的荧光材料技术未能取得突破。本课题以纳米级YAG:Ce为发光颗粒，以PMMA为基质材料，采用原位合成工艺制备纳米有机复合发光材料，并通过表面等离子技术高效增强发光强度与光取出效率。应用热力学及反应动力学原理研究纳米荧光发光颗粒与有机基质材料之间的相互作用规律，掌握纳米发光颗粒与基质之间的反应机理与结构特点，认识新型纳米有机复合发光材料光效、热稳定性与基质材料之间的内在联系，实现纳米有机复合发光材料的可控制备；构建基于金属表面等离子光增强与光取出的发光元件结构原型，应用刻蚀技术制备纳米尺度表面金属结构，以光增强与光取出效率为目标函数，应用光波电磁理论进行分析研究，揭示新型发光材料中光子的传输、能量的传递与增强规律，实现光的高效增强与取出；为真正实现高效稳定的纳米有机复合发光元件的可批量制造提供科学依据与技术基础。

研究具有微纳米尺度的高性能白光LED用荧光发光粉可控制备、解决发光效率低、性能不稳定的难题。其研究内容：研究多元稀土离子共掺技术对YAG、Y2O2S基质材料进行晶体结构和带隙调控，实现多色荧光发射，提升荧光粉的发光效率，改善荧光粉的稳定性；研究核壳结构YAG荧光粉和YAG有机-无机荧光发光薄膜，应用金属表面等离子与发光材料之间的光耦合原理，对发光材料发射光谱进行拓展，实现荧光发光增强；研究波长转换元件与光学透镜为一体的光学集成器件基本结构。发展新型基于单基质的三原色荧光粉的制备方法与光色调控技术。其研究成果：. （1）研究了多元共掺对YAG:Ce3+, Gd3+/La3+、YAG:Ce3+, Pr3+荧光粉晶体结构、发光性能及温度猝灭特性的影响。采用Gd和La作为主晶格的取代元素，增强了YAG:Ce为基质荧光粉的红光成分，提高了色温和显色指数。少量的Pr3+掺杂可诱导轻微的晶格参数增加。在340nm或460nm的激发下，分别在534nm和610nm处显示宽峰和窄峰。在610nm处出现的峰增加了荧光粉的红光发射，改善了YAG:Ce3+的显色性。对发光性能测试和荧光寿命的测试证明了荧光能量从Ce3+到Pr3+的转移。. （2）研制的钼酸盐荧光粉CaMoO4:Eu3+;Eu3+/Sm3+;Eu3+/Sm3+/Li+，与单掺Eu3+的钼酸钙红色荧光粉相比，由于Li+电荷补偿和Sm3+→Eu3+的能量转移，显示出更强的发光强度和优良的热稳定性。. （3）发展了一种新型的光色可调的NaCaPO4:Tb3+,Mn2+荧光粉。通过Mn2+/Tb3+单掺杂和双掺杂NaCaPO4基质材料实现荧光粉的光色可调。. （4）以Y2O2S为基质材料制备了三原色发光材料。在Y2O2S:Yb/Ho，Y2O2S:Yb/Eu和Y2O2S:Yb/Tm体系中，当质量比为5:2:12.25时为其色坐标为（0.3336,0.3341），成功地获得了输出白光的发光材料。. （5）制备了Ag-YAG:Ce3+-PMMA复合薄膜的荧光，揭示了表面等离子体荧光发光增强规律。相对荧光增强倍数约为1.3倍。荧光临界猝灭Ag掺入浓度与荧光粉掺入量有关。. （6）制备了覆盖二维周期性Ag纳米结构的Ag/ZnO薄膜。结果发现周期性Ag纳米结构表面等离激元能使ZnO薄膜的发射光谱得到显着增强。