一种可重复利用的Ag基SERS基底设计与加工
Design and Fabrication of a Reusable Ag-Based SERS Substrate
DOI: 10.12677/ms.2025.157157, PDF,   
作者: 刘仁星*, 林 雪:伊犁师范大学电子工程学院,新疆 伊宁
关键词: SERS基底痕量检测微纳米结构SERS Substrate Trace Detection Micro- and Nanostructures
摘要: 本研究针对现有表面增强拉曼散射(SERS)基底存在的一次性使用、环境要求严格、加工工艺复杂等问题,开发了一种基于扫描探针光刻(SPL)技术的可重复使用、灵敏度较高的Ag SERS基底。通过金刚石针尖的刻划结合所设计的加工轨迹,系统研究了法向载荷、间距、周期等参数对银表面微纳结构形成的影响,筛选出最佳SERS基底制备条件。结果表明,该方法可适用于金、银、铜等软金属,且在相同加工参数下,银基底的拉曼检测限显著优于金或铜基底。通过表面清洁和氧化层去除工艺,实现了Ag SERS基底的重复利用。本研究为低成本、高性能SERS基底的制备提供了新的参考。
Abstract: This study develops a novel reusable and highly sensitive Ag SERS substrate based on scanning probe lithography (SPL) technology to address the problems of existing surface-enhanced Raman scattering (SERS) substrates, including single-use nature, stringent environmental requirements, and complex fabrication protocols. Through the inscription of diamond tip-mediated mechanical machining combined with the designed processing trajectory, the impacts of parameters such as normal load, spacing, and period on the formation of micro- and nanostructures on Ag surfaces were systematically investigated to identify optimal preparation conditions for SERS substrate. The results show that the method can be applied to soft metals such as Au, Ag, Cu, etc., and the Raman detection limit of the Ag substrate is significantly better than that of the Au or Cu substrate under the same processing parameters. The reuse of the Ag SERS substrate was achieved via surface cleaning and oxide layer removal. This study provides a new reference for fabricating low-cost and high-performance SERS substrates.
文章引用:刘仁星, 林雪. 一种可重复利用的Ag基SERS基底设计与加工[J]. 材料科学, 2025, 15(7): 1477-1486. https://doi.org/10.12677/ms.2025.157157

参考文献

[1] Langer, J., Jimenez de Aberasturi, D., Aizpurua, J., Alvarez-Puebla, R.A., Auguié, B., Baumberg, J.J., et al. (2019) Present and Future of Surface-Enhanced Raman Scattering. ACS Nano, 14, 28-117. [Google Scholar] [CrossRef] [PubMed]
[2] Von Raben, K.U., Dorain, P.B., Chen, T.T. and Chang, R.K. (1983) and Formation on Oxygenated Ag Surfaces Exposed to Nitrogen Oxide Gases: A Sers Study. Chemical Physics Letters, 95, 269-273. [Google Scholar] [CrossRef
[3] Cialla-May, D., Zheng, X., Weber, K. and Popp, J. (2017) Recent Progress in Surface-Enhanced Raman Spectroscopy for Biological and Biomedical Applications: From Cells to Clinics. Chemical Society Reviews, 46, 3945-3961. [Google Scholar] [CrossRef] [PubMed]
[4] Song, C.Y., Yang, Y.J., Yang, B.Y., Sun, Y.Z., Zhao, Y.P. and Wang, L.H. (2016) An Ultrasensitive SERS Sensor for Simultaneous Detection of Multiple Cancer-Related miRNAs. Nanoscale, 8, 17365-17373. [Google Scholar] [CrossRef] [PubMed]
[5] Yang, Y., Zhu, J., Zhao, J., Weng, G., Li, J. and Zhao, J. (2019) Growth of Spherical Gold Satellites on the Surface of Au@Ag@SiO2 Core-Shell Nanostructures Used for an Ultrasensitive SERS Immunoassay of Alpha-Fetoprotein. ACS Applied Materials & Interfaces, 11, 3617-3626. [Google Scholar] [CrossRef] [PubMed]
[6] Du, J., Cui, J. and Jing, C. (2014) Rapid in Situ Identification of Arsenic Species Using a Portable Fe3O4@Ag SERS Sensor. Chemical Communications, 50, 347-349. [Google Scholar] [CrossRef] [PubMed]
[7] Hatab, N.A., Eres, G., Hatzinger, P.B. and Gu, B. (2010) Detection and Analysis of Cyclotrimethylenetrinitramine (RDX) in Environmental Samples by Surface‐Enhanced Raman Spectroscopy. Journal of Raman Spectroscopy, 41, 1131-1136. [Google Scholar] [CrossRef
[8] Pu, H., Xiao, W. and Sun, D. (2017) Sers-microfluidic Systems: A Potential Platform for Rapid Analysis of Food Contaminants. Trends in Food Science & Technology, 70, 114-126. [Google Scholar] [CrossRef
[9] Raja, S.S., Cheng, C., Sang, Y., Chen, C., Zhang, X., Dubey, A., et al. (2020) Epitaxial Aluminum Surface-Enhanced Raman Spectroscopy Substrates for Large-Scale 2D Material Characterization. ACS Nano, 14, 8838-8845. [Google Scholar] [CrossRef] [PubMed]
[10] Wang, Y., Lu, N., Wang, W., Liu, L., Feng, L., Zeng, Z., et al. (2013) Highly Effective and Reproducible Surface-Enhanced Raman Scattering Substrates Based on Ag Pyramidal Arrays. Nano Research, 6, 159-166. [Google Scholar] [CrossRef
[11] Kanipe, K.N., Chidester, P.P.F., Stucky, G.D. and Moskovits, M. (2016) Large Format Surface-Enhanced Raman Spectroscopy Substrate Optimized for Enhancement and Uniformity. ACS Nano, 10, 7566-7571. [Google Scholar] [CrossRef] [PubMed]
[12] Tao, Q., Li, S., Zhang, Q.Y., Kang, D.W., Yang, J.S., Qiu, W.W., et al. (2014) Controlled Growth of ZnO Nanorods on Textured Silicon Wafer and the Application for Highly Effective and Recyclable SERS Substrate by Decorating Ag Nanoparticles. Materials Research Bulletin, 54, 6-12. [Google Scholar] [CrossRef
[13] Xu, Y., Zhang, D., Lin, J., Wu, X., Xu, X., Akakuru, O.U., et al. (2022) Ultrahigh SERS Activity of the TiO2@Ag Nanostructure Leveraged for Accurately Detecting CTCs in Peripheral Blood. Biomaterials Science, 10, 1812-1820. [Google Scholar] [CrossRef] [PubMed]
[14] Wang, J., Hassan, M.M., Ahmad, W., Jiao, T., Xu, Y., Li, H., et al. (2019) A Highly Structured Hollow ZnO@Ag Nanosphere SERS Substrate for Sensing Traces of Nitrate and Nitrite Species in Pickled Food. Sensors and Actuators B: Chemical, 285, 302-309. [Google Scholar] [CrossRef
[15] Wu, H., Luo, Y., Hou, C., Huo, D., Zhou, Y., Zou, S., et al. (2019) Flexible Bipyramid-AuNPs Based SERS Tape Sensing Strategy for Detecting Methyl Parathion on Vegetable and Fruit Surface. Sensors and Actuators B: Chemical, 285, 123-128. [Google Scholar] [CrossRef
[16] Jin, B., He, J., Li, J. and Zhang, Y. (2018) Lotus Seedpod Inspired SERS Substrates: A Novel Platform Consisting of 3D Sub‐10 Nm Annular Hot Spots for Ultrasensitive SERS Detection. Advanced Optical Materials, 6, Article ID: 1800056. [Google Scholar] [CrossRef
[17] Lin, D., Wu, Z., Li, S., Zhao, W., Ma, C., Wang, J., et al. (2017) Large-Area Au-Nanoparticle-Functionalized Si Nanorod Arrays for Spatially Uniform Surface-Enhanced Raman Spectroscopy. ACS Nano, 11, 1478-1487. [Google Scholar] [CrossRef] [PubMed]
[18] Ou, F.S., Hu, M., Naumov, I., Kim, A., Wu, W., Bratkovsky, A.M., et al. (2011) Hot-Spot Engineering in Polygonal Nanofinger Assemblies for Surface Enhanced Raman Spectroscopy. Nano Letters, 11, 2538-2542. [Google Scholar] [CrossRef] [PubMed]
[19] Botta, R., Eiamchai, P., Horprathum, M., Limwichean, S., Chananonnawathorn, C., Patthanasettakul, V., et al. (2020) 3D Structured Laser Engraves Decorated with Gold Nanoparticle SERS Chips for Paraquat Herbicide Detection in Environments. Sensors and Actuators B: Chemical, 304, Article ID: 127327. [Google Scholar] [CrossRef
[20] Chirumamilla, M., Toma, A., Gopalakrishnan, A., Das, G., Zaccaria, R.P., Krahne, R., et al. (2014) 3D Nanostar Dimers with a Sub‐10‐nm Gap for Single‐/Few-Molecule Surface‐Enhanced Raman Scattering. Advanced Materials, 26, 2353-2358. [Google Scholar] [CrossRef] [PubMed]
[21] Dong, S., Zhang, X., Li, Q., Liu, C., Ye, T., Liu, J., et al. (2020) Springtail‐Inspired Superamphiphobic Ordered Nanohoodoo Arrays with Quasi‐Doubly Reentrant Structures. Small, 16, Article ID: 2000779. [Google Scholar] [CrossRef] [PubMed]
[22] Mu, C., Zhang, J. and Xu, D. (2009) Au Nanoparticle Arrays with Tunable Particle Gaps by Template-Assisted Electroless Deposition for High Performance Surface-Enhanced Raman Scattering. Nanotechnology, 21, Article ID: 015604. [Google Scholar] [CrossRef] [PubMed]
[23] Cho, W.J., Kim, Y. and Kim, J.K. (2011) Ultrahigh-Density Array of Silver Nanoclusters for SERS Substrate with High Sensitivity and Excellent Reproducibility. ACS Nano, 6, 249-255. [Google Scholar] [CrossRef] [PubMed]
[24] Ryu Cho, Y.K., Rawlings, C.D., Wolf, H., Spieser, M., Bisig, S., Reidt, S., et al. (2017) Sub-10 Nanometer Feature Size in Silicon Using Thermal Scanning Probe Lithography. ACS Nano, 11, 11890-11897. [Google Scholar] [CrossRef] [PubMed]
[25] Chen, S., Kim, S., Chen, W., Yuan, J., Bashir, R., Lou, J., et al. (2019) Monolayer MoS2 Nanoribbon Transistors Fabricated by Scanning Probe Lithography. Nano Letters, 19, 2092-2098. [Google Scholar] [CrossRef] [PubMed]
[26] Wu, L., Zhou, H., He, W., et al. (2022) Fabrication of Large-Area and Highly Uniform Interlaced Silicon Grating Arrays for High-Performance SERS Substrates. Surfaces and Interfaces, 32, Article ID: 102156.
[27] Zhang, J., Jia, T., Yan, Y., Wang, L., Miao, P., Han, Y., et al. (2019) Label-Free Highly Sensitive Probe Detection with Novel Hierarchical SERS Substrates Fabricated by Nanoindentation and Chemical Reaction Methods. Beilstein Journal of Nanotechnology, 10, 2483-2496. [Google Scholar] [CrossRef] [PubMed]
[28] Pineau, A., Benzerga, A.A. and Pardoen, T. (2016) Failure of Metals I: Brittle and Ductile Fracture. Acta Materialia, 107, 424-483. [Google Scholar] [CrossRef
[29] Zhang, J., Yan, Y., Hu, Z. and Zhao, X. (2016) Fabrication of Copper Substrates for Surface-Enhanced Raman Scattering Using the Microscratching Method. Proceedings of the Institution of Mechanical Engineers, Part B: Journal of Engineering Manufacture, 232, 1310-1315. [Google Scholar] [CrossRef
[30] 孔德鹏. AFM加工SERS基底与微流控系统集成研究[D]: [硕士学位论文]. 哈尔滨: 哈尔滨工业大学, 2021.
[31] Pelleg, J. (2013) Mechanical Properties of Materials. Springer. [Google Scholar] [CrossRef
[32] Gill, H.S., Thota, S., Li, L., Ren, H., Mosurkal, R. and Kumar, J. (2015) Reusable SERS Active Substrates for Ultrasensitive Molecular Detection. Sensors and Actuators B: Chemical, 220, 794-798. [Google Scholar] [CrossRef
[33] Markin, A.V., Markina, N.E., Popp, J. and Cialla-May, D. (2018) Copper Nanostructures for Chemical Analysis Using Surface-Enhanced Raman Spectroscopy. TrAC Trends in Analytical Chemistry, 108, 247-259. [Google Scholar] [CrossRef