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Tip-Enhanced Raman Spectroscopy

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Raman Spectroscopy

Part of the book series: Springer Series in Optical Sciences ((SSOS,volume 248))

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Abstract

Tip-enhanced Raman spectroscopy (TERS) is a cutting-edge analytical technique that combines the power of Raman spectroscopy with apertureless near-field optical microscopy (s-SNOM). It uses a metallic tip that resonates with the local mode of the surface plasmon to enhance Raman signals by several orders of magnitude. This leads to the detection of weak vibrational modes that are not observable by conventional Raman spectroscopy. TERS has found numerous applications in various fields. In chemistry, TERS has been used to study catalytic reactions and investigate the properties of single molecules. In nanotechnology, TERS enables imaging of the structural and chemical properties of nanomaterials. TERS also has potential applications in medical diagnostics and therapeutics, as it allows the detection and analysis of biomolecules in high sensitivity and non-destructive manner. In biomedicine, TERS is used to investigate biomolecules, such as proteins, DNA, and lipids, at single-molecule level. In this Chapter, the history, basic principle, common experiment setup, application, and outlook of TERS technology are discussed.

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Notes

  1. 1.

    It is interesting to mention in here that the Raman effect was also discovered in 1928 [1]. It was not, however, until 70 years later that Raman and sSNOM techniques were finally combined as TERS.

  2. 2.

    The following discussion applies for both aperture and scattering SNOM.

  3. 3.

    Also known as plane wave spectrum.

  4. 4.

    \({\varvec{E}}({\varvec{r}})\) Is also known as “total field”. The concept of “total field” is very important in the numerical simulation of electromagnetic (EM) field.

  5. 5.

    Thus, “wavelength” is not a good physical quantity to define light as it depends on the refractive index of medium. However, due to historical and customary reasons, “wavelength” is still the most common concept for the definition of light.

  6. 6.

    Also known as optical transfer function (OTF).

  7. 7.

    Imaginary part of refractive index is zero.

  8. 8.

    Or a sub wavelength aperture, which is actually Synge’s idea [13]. See Fig. 11.2i(a).

  9. 9.

    The Structured Illumination Microscopy (SIM) also relies on the same working principle.

  10. 10.

    Also known as the Transverse Electric (TE) mode.

  11. 11.

    Also known as the Transverse Magnetic (TM) mode.

  12. 12.

    Also known as p-polarized.

  13. 13.

    If the readers are interested in the numerical simulation of EM field, the online course (https://empossible.net/) and latest publication “Electromagnetic and Photonic Simulation for the Beginner: Finite-Difference Frequency-Domain in MATLAB” by Raymond C. Rumpf are strongly recommended.

  14. 14.

    It is worth to stress in here that the laser energy is further confined by the TERS probe (see Fig. 11.8 and associated discussion).

  15. 15.

    More specifically, \({{\varvec{E}}}_{{\varvec{z}}}\) component is highest with p-polarized illumination with NA ~ 1. For more detail, please see the Sect. 11.2 Evanescent fields from Principles of Nano-Optics [21].

  16. 16.

    It should be “total field” (near-field plus far-field, see Fig. 11.3i(a)) more precisely. However, due to historical reason, it is commonly just referred to as “near-field”.

  17. 17.

    Background suppression can also be achieved via evanescent field excitation, for more detail see Fig. 11.10.

  18. 18.

    The beam profile (\({\left|{{\varvec{E}}}_{0}\right|}^{2}\)) of NA = 1.4 focused 532 nm wavelength light at glass/air interface is shown in Fig. 11.8.

  19. 19.

    More precisely, the NA > 1 component of the focused light mainly contributes the excitation, see Sect. 11.3.1 and Fig. 11.10.

  20. 20.

    See Fig. 11.10iii(a) and associated discussion.

  21. 21.

    Due to the uniform properties and good stability, low-dimensional materials (especially graphene, SWCNT, TMDs) are ideal samples for evaluating the TERS enhancement factor (\({\left|{\varvec{E}}/{{\varvec{E}}}_{0}\right|}^{4}\)) [40, 58, 87].

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Acknowledgements

WW thanks for financial support through the DFG, CRC-TRR 234 “CataLight” Project C4. VD appreciates financial support via the DFG Collaborative Research Center SFB 1375 (NOA) Project CO2.

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Authors and Affiliations

  1. Leibniz Institute of Photonic Technology (IPHT), 07745, Jena, Germany

    Wei Wang & Volker Deckert

  2. Institute of Physical Chemistry, Friedrich Schiller University Jena, 07743, Jena, Germany

    Wei Wang & Volker Deckert

  3. Abbe Center of Photonics, Friedrich Schiller University Jena, 07745, Jena, Germany

    Volker Deckert

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  1. School of Nano Sciences, Central University of Gujarat, Gandhinagar, Gujarat, India

    Dheeraj Kumar Singh

  2. School of Materials Science and Technology, Indian Institute of Technology (BHU), Varanasi, India

    Ashish Kumar Mishra

  3. School of Science, Constructor University, Bremen, Bremen, Germany

    Arnulf Materny

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Wang, W., Deckert, V. (2024). Tip-Enhanced Raman Spectroscopy. In: Singh, D.K., Kumar Mishra, A., Materny, A. (eds) Raman Spectroscopy. Springer Series in Optical Sciences, vol 248. Springer, Singapore. https://doi.org/10.1007/978-981-97-1703-3_11

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