具有丰富尖刺特征抬起型金纳米结构图形阵列衬底去耦合效应及SERS应用研究

In this project, we plan to combine the "top-down" technique on the basis of micro/nano fabrication and the "bottom-up"protocol on the basis of crystal growth in solution on the surface of substrate to construct the SERS substrate which characterizes as the large-area gold patterned array with abundant tipped microstructures, and to solve the issue in which the sensitivity and repeatability can not be achieved simultanously by one technique. Firstly, based on the nanoparticle-mediated aggregation growth，some approaches to selectly construct Au nanostructures on patterned substrate with abundant tipped feature will be in-depth investigated, and the control principle of sizes and morphologies during the anisotropic growth of gold nanostructure on fabricated pattern substrate will be revealed. Secondly, by means of the electromagnetic field calculation, the measurement of localized surface plasmon resonance and SERS performance, and the application of obtained SERS substrate in the prompt trace-detection of food safety, the influences of Au microstructures, the interaction between different tips, the composition and geometrical structure of substrate on the plasmonic feature of Au nanostructure will be understood, and the mechanism of reduced substrate effect by elevating Au multiple tipped structure and resulted huge electromagnetic enhancement will be revealed. This proposal is expected to obtain an ideal SERS substrate, displaying a super sensitivity, signal repeatability, processing reproducibility and reliability, hence has important academic value and application prospect.

本项目拟将自上而下的微纳图形加工技术与自下而上的衬底表面液相纳米晶生长相结合，构筑具有丰富尖刺特征的抬起型金纳米结构大面积图形阵列SERS 基底来解决SERS基底灵敏度及一致性二者无法兼顾的问题。首先，通过以纳米粒子为基本单元的聚集生长途径，探索在预制大面积图形衬底表面选择性构筑具有丰富尖刺特征的金纳米结构的方法，揭示衬底表面纳米晶各向异性生长习性及尖刺结构微观形貌调控基本规律。然后，通过电磁场理论计算并结合对所制备SERS基底的等离激元共振特性、拉曼光谱测试及其在食品安全检测中应用研究，理解金尖刺结构的微观形貌、尖刺间相互作用、衬底材质及抬起几何结构等因素对等离激元金尖刺结构与光相互作用的基本规律，揭示具有丰富尖刺特征抬起型金纳米结构的衬底去耦合效应及产生巨大电磁场增强的作用机制。期望获得高灵敏度、高信号重复性、高重现性及高可靠性的SERS基底。因此，本研究具有重要的学术价值和应用前景。

本项目针对表面等离激元增强拉曼光谱领域检测灵敏度和信号重复性不能兼顾的问题，采用自上而下的微纳图形加工技术与自下而上的衬底表面液相纳米晶生长相结合的途径，系统研究具有丰富尖刺特征的抬起型金纳米结构大面积图形阵列SERS基底的制备新方法，揭示了图形阵列衬底表面各向异性纳米晶生长的调控机理及光与物质相互作用的基本规律和物理本质，深入探讨了抬起型SERS基底在增强光谱技术及生物医学等领域应用的一系列重要科学问题。.本项目基于前期所提出抬起型阵列衬底和海胆状金介观超结构新型SERS基底（代表性工作发表在Nano Letters，2010, 10, 5006上）相结合的设计思路，深入研究了具有图形阵列衬底表面等离激元共振Au纳米结构的SERS特性，实现对CV分子检测限可达到10(-10)M水平，大面积阵列的信号重现性标准偏差<6%。通过对衬底表面Au纳米结构晶体生长中形核与长大过程和溶胶Au纳米颗粒自组装的深入研究，发展了多种阵列结构SERS基底的衬底材料、周期性结构、形态控制新方法，实现了抬起型阵列衬底表面贵金属纳米结构拓扑形貌的精细调控，获得了FTO导电玻璃表面多级花状Au纳米结构、硅基三维阵列结构SERS基底、柔性阵列结构SERS基底等一系列具有丰富尖刺特征的抬起型金纳米结构大面积图形阵列SERS基底，并研究了这些结构在等离子体纳米光学、生物、催化、能源存储等领域的应用。.本项目相关成果在Nature Communications，Advanced Functional Materials, Small, Analytical Chemistry, ACS Sensors等期刊发表SCI论文17篇，授权国家发明专利2项，17篇论文SCI引用超过160次。做国际国内学术会议邀请报告6次，担任Scientific Reports等国际、国内学术期刊编委，产生了广泛的学术影响。研究成果得到了包括美国麻省理工的Robert Langer教授、中科院院士江雷教授在Advanced materials、Advanced Science、Nature Communications等权威期刊的引用和高度评价。