飞秒激光直写加工SERS基底及其应用

尹智东,倪才鼎,吴思竹,等. 飞秒激光直写加工SERS基底及其应用[J]. 光电工程,2023,50(3): 220322. doi: 10.12086/oee.2023.220322
引用本文: 尹智东,倪才鼎,吴思竹,等. 飞秒激光直写加工SERS基底及其应用[J]. 光电工程,2023,50(3): 220322. doi: 10.12086/oee.2023.220322
Yin Z D, Ni C D, Wu S Z, et al. Femtosecond laser direct writing processing of SERS substrates and applications[J]. Opto-Electron Eng, 2023, 50(3): 220322. doi: 10.12086/oee.2023.220322
Citation: Yin Z D, Ni C D, Wu S Z, et al. Femtosecond laser direct writing processing of SERS substrates and applications[J]. Opto-Electron Eng, 2023, 50(3): 220322. doi: 10.12086/oee.2023.220322

飞秒激光直写加工SERS基底及其应用

  • 基金项目:
    国家自然科学基金资助项目(52175396);中央高校基本科研经费(JZ2022HGPA0312)。
详细信息
    作者简介:
    *通讯作者: 劳召欣,laozx@hfut.edu.cn
  • 中图分类号: TN249

Femtosecond laser direct writing processing of SERS substrates and applications

  • Fund Project: National Natural Science Foundation of China (52175396), and the Central Universities Fundamental Research Funds (JZ2022HGPA0312)
More Information
  • 表面增强拉曼光谱(Surface-enhanced Raman spectroscopy,SERS)是一种高灵敏度、高分辨率的分子识别技术,在多个领域具有非常重要的应用价值。飞秒激光直写作为一种新兴的低成本、高分辨率、高灵活性的微纳加工方法,在制备SERS基底领域得到了广泛的应用。本文重点概述了四种飞秒激光直写制备SERS基底的加工方法,主要包括飞秒激光双光子还原、飞秒激光切割金属、飞秒激光切割-溅射、飞秒激光3D打印。文章简单介绍了各方法制备SERS基底的性能与应用场景,阐述了飞秒激光直写加工在制备SERS基底中的优势,旨在为今后相关研究提供参考。

  • Overview: Surface-Enhanced Raman spectroscopy (SERS) is a highly sensitive and high-resolution molecular recognition technique with important applications in many fields. As an emerging low-cost, high-resolution, and high-flexibility micro-nano processing method, femtosecond laser direct writing has been widely used in the field of preparing SERS substrates. Compared with traditional processing methods for preparing SERS substrates, femtosecond laser direct writing processing has certain advantages in terms of flexibility, three-dimensional molding, processing material range, processing accuracy, and other aspects. In this review, we classify the processing methods of femtosecond laser preparation of SERS substrates into four categories, including femtosecond laser two-photon metal reduction, femtosecond laser cutting metal, femtosecond laser cutting-sputtering, and femtosecond laser 3D printing. Femtosecond laser two-photon metal reduction uses the two-photon reduction effect to reduce metal cations in metal solutions to metals, such as silver ions in silver nitrate solutions to silver nanoparticles. This method is suitable for the one-step preparation of SERS substrates in closed microchannels. Femtosecond laser cutting metal directly prepares the SERS substrate structure on a metal substrate. This method takes advantage of the high peak power of the femtosecond laser to ablate the surface of the metal sample to obtain a patterned surface structure. At the same time, femtosecond laser ablation produces particle fragments, which are usually redeposited on the patterned surface, resulting in SERS "hot spots". Femtosecond laser direct cutting of metal can prepare SERS substrates in one step, which has the advantages of high processing efficiency and simple processing and is more conducive to the application of large-scale production of practical SERS detection. Femtosecond laser cutting-sputtering is to process any structure on non-metallic substrates such as polymers and then sputtering/evaporating metal nanoparticles on the surface of the structure. This method can prepare transparent and flexible SERS substrates, which are rich in application scenarios. Femtosecond laser 3D printing is to use the three-dimensional processing ability of femtosecond lasers to obtain rich "hot spots" by designing the structure of SERS substrates, and then using template-guided self-assembly technology with different driving forces to deposit/evaporate metal nanoparticles at designated locations. In this paper, we first introduce the current methods for preparing SERS and then conduct a comprehensive review of the processing methods of four femtosecond lasers to prepare SERS substrates. Finally, the advantages and disadvantages of the four femtosecond laser preparation methods for SERS substrate are briefly summarized, and the development prospects of this technology are prospected, aiming to provide it for future related research.

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  • 图 1  四种飞秒激光制备SERS基底加工方法[7, 30-32]

    Figure 1.  Four methods of femtosecond laser preparation SERS substrate [7, 30-32]. Figure reproduced with permission from: ref. [7] © Wiley; ref. [30-31] © Elsevier; ref. [32] © The Royal Society of Chemistry

    图 2  SERS原理。 (a) 波纹金属表面上分子的非弹性光散射[33]; (b) 贵金属表面发生等离子体共振现象[36]

    Figure 2.  SERS principle. (a) Inelastic light scattering of molecules on corrugated metal surfaces[33]; (b) localized surface plasmon resonances (LSPRs) on the surface of precious metals[36]. Figure reproduced with permission from: (a) ref. [33] © American Chemical Society; (b) ref. [36] © The Royal Society of Chemistry

    图 3  自上而下微加工和微粒自组装方法制备SERS微结构。 (a) RIE[45]; (b, c) EBL[46-47]; (d~f) 纳米颗粒自组装[48-50]. 比例尺:(e) 20 nm;(f) 200 nm

    Figure 3.  Preparation of SERS microstructures by top-down micromachining and particle self-assembly. (a) RIE[45]; (b, c) EBL[46-47]; (d-f) Nanoparticle self-assembly[48-50]; Scale bar: (e) 20 nm; (f) 200 nm. Figure reproduced with permission from: (a) ref. [45] © American Chemical Society; (b) ref. [46], (e) ref. [49] and (f) ref. [50] © under a Creative Commons Attribution-NonCommercial-No- Derivatives 4.0 International License; (c) ref. [47] © American Chemical Society; (d) ref. [48] © The American Association for the Advancement of Science

    图 4  微柱自组装方法制备SERS微结构。 (a) 金纳米微柱自组装[55]; (b) 聚合物-银微柱自组装[56];(c) 聚合物-银微柱自组装[57]; (d) 银微柱自组装[58];(e)聚合物-金微柱自组装[59]

    Figure 4.  Preparation of SERS microstructure by microcolumn self-assembly methods. (a) Self-assembly of gold nanopillars[55]; (b) Self-assembly of polymer-silver micropillars[56]; (c) Self-assembly of polymer-silver micropillars[57]; (d) Self-assembly of silver micropillars[58]; (e) Self-assembly of polymer-gold micropillars[59]. Figure reproduced with permission from: (a) ref. [55] and (e) ref. [59] © American Chemical Society; (b) ref. [56], (c) ref. [57] and (d) ref. [58] © Wiley

    图 5  飞秒双光子金属还原制备SERS基底。(a) 双光子还原原理[70]; (b) 双光子还原银微线[71];(c~e) 微通道SERS基底[72-74]; 比例尺:(b) 10 µm; (e) 1 µm

    Figure 5.  Femtosecond two-photon reduction to prepare SERS substrates. (a) Two-photon reduction principle[70]; (b)Two-photon reduced silver microwire[71]; Scale bar: (b) 10 μm; (e) 1 μm. Figure reproduced with permission from: (a) ref. [70], (b) ref. [71], (c) ref. [74] and (e) ref. [71] © Wiley; (d) ref. [72] © The Royal Society of Chemistry

    图 6  飞秒激光切割金属制备SERS基底。(a) 飞秒激光直接烧蚀金属表面形成纳米结构机理[80]; (b) Ag周期性表面[91]; (c) 铜表面直接制备超亲水-超疏水图案化基底结构[30];(d) S-Ag-Ar基底[92]; (e) 钛合金SERS基底[93]

    Figure 6.  Femtosecond laser cutting metal to prepare SERS substrate. (a) Femtosecond laser directly ablated metal surface forming nanostructure principle [80]; (b) Ag periodic surface[91]; (c) Superhydrophilic - superhydrophobic patterned substrate structures were prepared directly on copper surface [30]; (d) S-Ag-Ar substrate[92]; (e) Titanium alloy SERS substrate[93]. Figure reproduced with permission from: (a) ref. [80] © Elsevier; (b) ref. [91], (c) ref. [30] and (d) ref. [92] © Elsevier; (e) ref. [93] © under a Creative Commons Attribution-NonCommercial-No- Derivatives 4.0 International License

    图 7  飞秒激光切割-溅射制备SERS基底。(a) 大面积SERS基底[105]; (b) 柔性透明SERS基底[31]; (c) 玻璃SERS基底[106]; (d) 疏水-超疏水SERS基底[107]; (e) 超疏水-亲水SERS基底[108]

    Figure 7.  Femtosecond laser cutting-sputtering to prepare a SERS substrate. (a) Large area SERS substrate[105]; (b) Flexible transparent SERS substrate[31]; (c) Glass SERS substrate[106]; (d) Hydrophobic-superhydrophobic SERS substrate[107]; (e) Superhydrophobic-hydrophilic SERS substrate[108] . Figure reproduced with permission from: (a) ref. [108], (b) ref. [31] and (c) ref. [106] © Elsevier; (d) ref. [107] © BioMed Central Ltd unless otherwise stated; (e) ref. [108] © American Chemical Society

    图 8  双光子直写结合金属蒸镀。(a, b) 光纤端面三维SERS结构[121-122]

    Figure 8.  Two-photon direct writing combined metal evaporation. (a, b) 3D SERS structure of fiber surface [121-122]. Figure reproduced with permission from: (a) ref. [121] © under a Creative Commons Attribution-NonCommercial-No-Derivatives 4.0 International License; (b) ref. [122] © Wiley

    图 9  飞秒激光加工毛细力自组装制备SERS基底。(a) 毛细力自组装[126];(b) 基于毛细力自组装微通道的三维SERS结构[7]

    Figure 9.  Femtosecond laser processing capillary self-assembly to prepare SERS substrate. (a) Capillary force self-assembly[126]; (b) Three-dimensional SERS structure based on capillary force self-assembly microchannels[7]. Figure reproduced with permission from: (a) ref. [126] © American Chemical Society; (b) ref. [7] © Wiley

    表 1  四种飞秒激光加工SERS基底各方法对比

    Table 1.  Comparison of four methods for processing SERS substrates by femtosecond laser

    基底类型及维度微纳结构分析物检测浓度下限/mol增强因子特殊基底参考文献
    双光子还原金属—-三维银微花阵列4-AP10−101×108封闭微通道[71]
    银钯纳米颗粒R6G10−92.6×108封闭微通道[73]
    银纳米颗粒CV10−13/封闭微通道[74]
    粗糙银纳米结构R6G10−91×107光纤端面[78]
    飞秒激光切割金属—二维
    金纳米颗粒R6G10−92.4×108金板[94]
    铜微粒和粒子团R6G10−142.09×1014铜板[30]
    银微粒和粒子团R6G10−85.3×1014银板[92]
    钛合金纳米颗粒R6G10−117.85×105钛合金[97]
    飞秒激光切割-溅射—二维金铂纳米颗粒R6G10−68.46×107[105]
    银纳米颗粒R6G10−125.6×107柔性FEP膜[31]
    银纳米颗粒R6G/2×105玻璃[106]
    金纳米颗粒R6G10−6/PTFE[117]
    银纳米颗粒R6G10−175.19×1013铜箔[109]
    飞秒激光3D打印—三维金纳米颗粒水晶紫10−6/光纤端面[121]
    金纳米颗粒R6G10−73×103光纤端面[122]
    金纳米颗粒R6G10−68×107开放微通道[7]
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收稿日期:  2022-11-30
修回日期:  2023-02-03
录用日期:  2023-02-06
网络出版日期:  2023-03-16
刊出日期:  2023-03-25

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