2024年4月11日发(作者：)

基于PS球自组装技术的微纳结构制备及SERS应用

摘 要

微纳结构以其特殊的光、电、磁等性质在众多领域有着广泛的应用，而周期

性排列的微纳结构因具有良好的结构有序性和可控性在表面增强拉曼散射

(Surface-enhanced Raman Scattering, SERS)基底制备领域引起了广泛关注。但基于

光刻工艺的SERS基底制备需要昂贵的设备，成本高，从而限制了这类SERS基

底的应用。采用低成本、多样化的胶体球自组装技术可方便、精确的制备周期性

排列的微纳结构。本文采用聚苯乙烯(Polystyrene, PS)球自组装技术制备微纳结构

作为SERS基底，同时研究SERS基底在检测方面的应用。主要开展的工作和成

果如下：

（1）基于气液界面法搭建了一套实验装置可制备出大面积紧密排列的聚苯

乙烯（PS）球自组装单层膜并平稳的转移到衬底上。通过反应离子刻蚀法（RIE）

制备了非紧密排列的PS球自组装掩膜，实验发现，PS球直径随着刻蚀时间的增

加而线性减小，由此可精确控制PS球掩膜以及微纳结构的尺寸。

（2）利用刻蚀工艺对PS球进行表面粗糙化，并形成纳米金颗粒从而制备了

大面积基于PS球结构的SERS基底。此SERS基底灵敏度高、重复性好。采用

时域有限差分法证实纳米金颗粒可以提供更多的电磁热点，SERS基底的增强因

子达到10

8

，相对标准偏差为6.64%-13.84%。将SERS基底用于检测孔雀石绿分

子，检测限达到50ng/mL，特征峰在1175、1365和1617cm

-1

处的拉曼信号强度

与孔雀石绿分子浓度的对数存在一定的线性关系。

（3）基于PS球自组装技术制备了大规模、周期性排列的纳米硅柱（SiNRs）

阵列，然后在SiNRs阵列表面溅射形成纳米金颗粒制备而成SERS基底，实现了

高灵敏度和高重复性的分子检测。纳米金颗粒提供了更多的电磁热点，SERS基

底的增强因子达到10

10

，相对标准偏差为6.68%-11.68%。马拉硫磷的检测限达

到 1ng/mL，且特征峰在1284cm

-1

处的拉曼信号强度与马拉硫磷浓度的对数呈良

好的线性关系。本论文并使用便携式拉曼光谱仪对SERS基底进行测试，展现了

所制备的SERS基底在现场实时检测的初步应用前景。

关键词：表面增强拉曼散射，聚苯乙烯球，自组装，孔雀石绿，马拉硫磷

I

Fabrication of Micro-Nanostructures Based on

Self-assembly of Polystyrene Spheres and Their

Applications in SERS

Abstract

Micro-nanostructures have been widely used in many fields because of their

special optical, electronic and magnetic properties, and periodic micro-nanostructures

have attracted much attention in the field of Surface-Enhanced Raman Scattering

(SERS) because of their good ordered structure and high controllability. However, the

fabrication of SERS substrates with micro-nanostructures by photolithography

requires expensive equipment and the cost is high, which limits the applications of

this SERS substrates. The micro-nanostructures with periodic arrangement can be

easily and accurately prepared by using low-cost and diversified colloidal sphere

self-assembly technology. In this paper, polystyrene (PS) sphere self-assembly

technique was used to prepare micro-nanostructures as SERS substrates. At the same

time, the potential applications of SERS substrates in the field of detection was

investigated. Based on this article, the main work and results are as follows:

(1) Based on the air-water interface method, a set of experimental apparatus was

built to prepare a large-scale close-packed PS sphere self-assembled monolayer and

transfer it to the substrate stably. Non-close-packed PS sphere monolayer mask was

prepared by reactive ion etching (RIE). It was found that the diameter of PS spheres

decreased linearly with the increase of etching time. So the size of the PS sphere mask

and the micro-nanostructures can be accurately controlled.

(2) We used etching process to roughen the surface of PS spheres and form Au

nanoparticles to prepare a large-scale nanostructures SERS substrate. The fabricated

SERS substrate had high reproducibility and sensitivity. The results of

finite-difference time domain (FDTD) simulations proved that Au nanoparticles and

clusters can provide more hot-spot, which enhance the enhancement factor (EF) to

more than 10

8

with a relative standard deviation (RSD) as low as 6.64%-13.84%. The

II