纳米金属敏化稀土/共轭高分子的高效光电复合材料研究

This proposal suggests to sensitize (1) the luminescence property of organic lanthanide complexes (OLC) and their related polymer-based compostes and (2) photoelectrical conversion of conjugate polymers by surface plasmon resornance (SPR) effect of nano metals. Firstly, we will investigate the luminescence enhancement of a composite nanostructure, in which nanoAg is as the central core, SiO2 as spacer shell, as well as the luminescence organic lanthanide complexes (OLC) as the outest sheath of the composite nanoparticle. The energy generated from surface plasmonic resornance (SPR) effect of nanometal particle from incident light transfers to OLC via the spaer layer of SiO2 and the emisssion intensity of OLC will be enhanced. Adjusting the structural factors, such as the size of nanometal particles, thickness of SiO2 spacer, the content of OLC at the surfce of SiO2, and the OLC components, the maximum emission intensity of OLC will be gained through the optimization. Because different lanthanide ions (Ln3+) can emit different light at different wavelength, we can get seerial composite nanoparticles emitting different wavelength lights from visible to infrared. This is very easy with the composite nanoparticles just by changing different lanthanide ions in OLC emission dots and also we can get compounding color via using two or more kinds of lanthanide ions. Additionally,covlently or physically modifying the surface of the composite nanoparticles, we can impart the additional surface functions including nucleation effect on host polymers, such as iPP, PE, PET and so on, to form clearer optical materials. Secondly, the purpose of this proposal is to sensitize the conjugate polymers to obtain the high photoelectrical conversion efficiency by using this highly efficient SPR nanostructure of metal@SiO2 through the embedment of this metal@SiO2 into conjugate polmymer film. In this specially designed metal@SiO2-in-film (MIF) structure, the SPR energy transfers directly to conjugate polymer matrix in its vicinity, and thus the induced light absorption of the composite film makes the high photoelectrical conversiton. Our data gained from the experiments have confirmed this enhanced photo absorption and the increase of convesion efficiency.

本项目研究纳米金属的表面等离子体（SPR）效应增强有机稀土发光或敏化共轭高分子光电转换，分别获得高效发光或光电转换的高分子基复合材料。经对无机包覆纳米金属的核壳结构的结构参数调控，实现两个最佳敏化：（1）核壳纳米金属SPR效应敏化其表面键合的有机稀土络合物（OLC）高效发光，并经对纳米结构外表面修饰，获得核壳纳米金属与基体高分子易于相容的界面结构和对基体高分子形态结构诱变（成核添加效应）的规律；（2）核壳纳米金属敏化其近域的共轭高分子光电转换性最佳，获得光电活性高分子π电子激发和空穴-电子分离的高效性。本项目以考察纳米材料结构与复合材料性能为主要关注。创新点在于通过纳米金属复合结构的设计和调控，将SPR效应用于提高固体发光和光电转换复合材料的性能，其中发光材料具有光谱敏锐性和多色谱性，光电转换具有高效性。从而，为高效柔性发光和光电材料面向柔性光致发光和柔性太阳能电池等领域提供依据。

本项目针对稀土杂化高分子存在的关键科学和技术问题，对“纳米金属敏化稀土/共轭高分子的高效光电复合材料研究”进行了为期4年的工作，完成了项目计划任务书规定的四项研究内容和相应的研究目标，取得了如下成果：. 成果之一：构筑“核-隔层-蒙皮”三层结构的纳米结构，大幅提高了稀土离子的发光强度，获得了最佳结构因素和机理，获取纳米银几何尺寸在20→70nm之间、SiO2隔离层在3→40nm之间变化的结构可控性。. 成果之二：发明了模拟蛋白聚糖生物发光材料。通过与美国专家的合作，我们发现了生物高分子与稀土络合物制备的杂化发光纳米胶束的新方法，获得了具有水溶性的发光胶束。. 成果之三：调整优化纳米结构，“核-隔层-蒙皮”三层纳米结构的表面修饰改善了与基体高分子的界面相容性。. 成果之四：金属敏化共轭高分子并应用于聚合物太阳能电池。纳米金属plasmon效应将补偿吸收的光能量转移给OLC发光点，用于聚合物太阳能电池，使聚合物太阳能电池的光电转换效率提高了15-17%。. 成果之五：纳米荧光纤维的研究，采用了两种技术路线：一是有机稀土固体胶束作为发光组分，二是纳米金属planmon复合纳米结构作为发光组分。. 发表论文26篇（计划任务规定８篇），其中SCI论文18篇（计划任务书要求8篇）；申请发明专利4项（计划任务书要求申请４项），已授权３项，PCT申请1项；培养博士生3名、硕士生12名，博士后2名。. 合作专家美国的L. A. Belfiore教授获得山东省的齐鲁友谊奖一项。. 项目实施期间，凝练了一支由11位外国专家组成的合作团队（其中9位非华裔），并获国家外国专家局的国家高的学校学科创新引智计划（111计划）。. 总之，本项目产生的结果，可以解决稀土离子掺杂高分子，获得柔性发光功能材料方面的大部分科学和技术问题，为我国开发高分子基稀土功能材料，提供了有利的科学和技术证据。