磁热法高效量子点的合成及其与聚合物界面组装调控研究

For large-scale fabrication of fluorescent quantum dots in situ by magneto-caloric method, the design, construction, assembly of materials at molecular level and the exploration of structure-effect relationship are carried out, so as to realize the integration of the fluorescent material structure and function. Utilizing the high frequency induction heating source (new magneto-calorific device technology) possessing obvious energy saving, non-contact, high speed and high efficiency, we explore the new method for efficient quantum dots and the approach of large-scale fabrication and green quantum dots powder. The quantum effect and the rule of luminescent property are revealed at magneto-calorific technology. Initially, the block copolymers with controllable molecular structures, unique properties and more carboxyl coordination sites will be designed and synthesized via the combination of catalytic chain transfer polymerization (CCTP). With the aid of liquid-liquid interface self-assemble technology, the design of the functional groups and forces between quantum dots and polymer are studied. The mechanism of quantum dots synthesis, coordination principle, the energy transfer, internal structure characteristics and the regulative mechanism of quantum yield are further researched. The polymer are introduced in the assembly system and the law of molecular modification and dispersion stability are also explored, to achieve quantum dots more controllable function, good stability and good film-forming plasticity. We also try to apply the green and red fluorescence narrow distribution quantum dots in the mainstream LED display and quantum dots sensitized solar cell, which provides effective practice for industrial application.

本项目以大规模磁热原位反应制备荧光量子点入手，从分子水平上设计、构筑和组装荧光材料，探索其构效关系，从而实现对荧光材料结构和功能一体化之目标。以利用节能、非接触、速度快、高效率高频感应加热源（新型磁热技术）为手段探索制备高效量子点新方法及其量产化、绿色化粉体量子点途径；揭示磁热下量子点量子效应及荧光性质调控规律。采用催化链转移（CCTP）聚合制备结构、分子量以及性能可控的含有多羧基配位点的嵌段共聚物，同时借助液-液相界面自组装法研究量子点与聚合物的界面组装的官能团与作用力的设计，探索其合成机理、配位原理、能量传递以及内在结构特征、量子产率调控机理，在组装体系中引入聚合物配体，探索对量子点进一步分子修饰和分散稳定等规律，实现其多功能化、稳定性好、成膜可塑性佳之特点，尝试适应于以绿光与红光荧光窄分布的主流LED。

本项目以实现磁热原位反应量产化制备荧光量子点新方法为目标，同时在分子水平上对量子点聚合物复合荧光材料进行设计、构筑和组装，并探索其在显示、照明等领域的应用。本项目工作主要包括以下三个方面：1）开发了新型磁热原位反应制备新方法，实现量子点的快速、规模化制备。利用磁热法实现了以多种前驱体来快速规模化制备碳量子点，可以在一小时内得到多达80g碳量子点粉末（产量比传统方法提高近160倍）。发现了不同阳离子对碳量子点荧光的调控作用，成功制备了蓝、绿、黄三种颜色的的碳量子点。开发出磁热微流控技术实现了半导体量子点的连续化制备，可同时制备CdSe和CdSe@ZnS量子点，量子产率可达70%，发射波长在515-630nm范围内可调。这些成果为量子点的规模化制备和产业化提供了新途径和新思路。2）利用油-水界面微流控组装技术，通过聚合物微球与量子点表面基团的配位作用和静电作用，进行精确组装调控，实现了聚合物微球与量子点材料的复合杂化，形成了具有多维结构杂化材料，如半导体量子点、碳量子点与聚合物微球的杂化微珠，具有良好机械强度的碳量子点与聚己内酯杂化纳米纤维膜，聚合物与碳量子点复合材料构筑的蜂窝状膜等，研究了量子点在复合过程中的荧光淬灭与增强规律，解决了量子点在与聚合物复合过程中的荧光淬灭问题。3）研究了量子点及其聚合物杂化功能化材料在广色域显示、LED照明器件、敏化太阳能电池、防伪、指纹提取、伤口敷料及前端聚合方面的潜在应用，为荧光量子点材料工业化应用提供了科学依据与理论指导。发表SCI收录论文11篇；参加本领域国内外学术会议4次；培养研究生7人。