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Tunable SERS Enhancement via Sub-nanometer Gap Metasurfaces

Cite this: ACS Appl. Mater. Interfaces 2022, 14, 13, 15541–15548
Publication Date (Web):March 28, 2022
https://doi.org/10.1021/acsami.2c01335
Copyright © 2022 American Chemical Society

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    Abstract

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    Raman sensing is a powerful technique for detecting chemical signatures, especially when combined with optical enhancement techniques such as using substrates containing plasmonic nanostructures. In this work, we successfully demonstrated surface-enhanced Raman spectroscopy (SERS) of two analytes adsorbed onto gold nanosphere metasurfaces with tunable subnanometer gap widths. These metasurfaces, which push the bounds of previously studied SERS nanostructure feature sizes, were fabricated with precise control of the intersphere gap width to within 1 nm for gaps close to and below 1 nm. Analyte Raman spectra were measured for samples for a range of gap widths, and the surface-affected signal enhancement was found to increase with decreasing gap width, as expected and corroborated via electromagnetic field modeling. Interestingly, an enhancement quenching effect was observed below gaps of around 1 nm. We believe this to be one of the few studies of gap-width-dependent SERS for the subnanometer range, and the results suggest the potential of such methods as a probe of subnanometer scale effects at the interface between plasmonic nanostructures. With further study, we believe that tunable sub-nanometer gap metasurfaces could be a useful tool for the study of nonlocal and quantum enhancement-quenching effects. This could aid the development of optimized Raman-based sensors for a variety of applications.

    Cited By

    This article is cited by 5 publications.

    1. Longjie Liang, Xiaoyu Zhao, Jiahong Wen, Jia Liu, Fengyi Zhang, Xiaojie Guo, Kun Zhang, Aofang Wang, Renxian Gao, Yaxin Wang, Yongjun Zhang. Flexible SERS Substrate with a Ag–SiO2 Cosputtered Film for the Rapid and Convenient Detection of Thiram. Langmuir 2022, 38 (45) , 13753-13762. https://doi.org/10.1021/acs.langmuir.2c01853
    2. Qinyu Li, Antoine Le Duigou, Jianglong Guo, Vijay Kumar Thakur, Jonathan Rossiter, Liwu Liu, Jinsong Leng, Fabrizio Scarpa. Biobased and Programmable Electroadhesive Metasurfaces. ACS Applied Materials & Interfaces 2022, 14 (41) , 47198-47208. https://doi.org/10.1021/acsami.2c10392
    3. Jinqiao Lu, De Zhang, Qiang Chen, Ziyang Shang, Jie Huang, Pei Liang. Nanoparticles/Parabolic Nanobowl Hybrid Structure as a Surface-Enhanced Raman Scattering Substrate: Insights Using the FDTD Method. The Journal of Physical Chemistry C 2022, 126 (33) , 14211-14218. https://doi.org/10.1021/acs.jpcc.2c04250
    4. Yan-Hua Yuan, Hai-Xin Gu, Qi-Yuan Xie, Jun Zhang. In-situ SERS detection of aromatic amine pollutants in fire-fighting wastewater using low-cost flexible substrates. Microchemical Journal 2022, 183 , 108139. https://doi.org/10.1016/j.microc.2022.108139
    5. Grégory Barbillon. Latest Advances in Metasurfaces for SERS and SEIRA Sensors as Well as Photocatalysis. International Journal of Molecular Sciences 2022, 23 (18) , 10592. https://doi.org/10.3390/ijms231810592

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