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Tip-enhanced Raman scattering

Nature Reviews Methods Primers volume 4, Article number: 47 (2024) Cite this article

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Abstract

Tip-enhanced Raman scattering (TERS) is one of the few methods to access the molecular composition and structure of surfaces with extreme lateral and depth resolution, down to the nanometre scale and beyond. This Primer examines the underlying physical principles driving signal enhancement and lateral resolution of TERS, laying the foundation for both theoretical understanding and practical applications. Addressing critical factors such as reproducibility, averaging and general limitations, we delve into the nuances of TERS experiments. Various TERS modifications are introduced, highlighting diverse optical geometries and tip feedback schemes tailored to the specific experimental needs. State-of-the-art TERS studies are showcased to illustrate its versatility, encompassing structural analysis of biomolecules, nanoscale investigation of chemical reactivity and exploration of the intrinsic physical properties of 2D materials. These TERS applications serve as a comprehensive overview of current advancements in the field, encapsulating the breadth of TERS experiments.

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Fig. 1: Simulation of plasmon-enhanced Raman signals, combining electromagnetic and chemical enhancement.
Fig. 2: TERS setup configurations.
Fig. 3: Different processes and parameters determining the TERS peak pattern and deviations from bulk Raman spectra.
Fig. 4: Synergistic TERS for correlating the chemical composition and nanomechanical properties of core crosslinked block copolymer core–corona micelles.
Fig. 5: Application of TERS spectroscopy to biological samples.
Fig. 6: Application of TERS technology in nanoscale chemical reactivity.
Fig. 7: TERS imaging of reconstructed low-angle twisted bilayer graphene and lateral graphene homojunctions.

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Acknowledgements

V.D. and C.H. acknowledge funding from the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) — CRC 1278 PolyTarget, project number 316213987 (project B04) and SFB 1375 (39881677, project C2). S.G. gratefully acknowledges funding from the European Research Council (ERC) under the European’s Horizon 2020 research and innovation programme — QUEM-CHEM (grant number 772676), ‘Time- and space-resolved ultrafast dynamics in molecular plasmonic hybrid systems’ and by the DFG (German Research Foundation) — SFB 1375 (39881677, project A4). A.J. acknowledges support from FAPEMIG (APQ-01860-2229868, RED0008123) and CNPq (307619/2023-0, APQ-04852-23, 421469/2023-4), Brazil. J.A. acknowledges support from grant PID2022-139579NB-I00 of the Spanish Ministry of Science and Innovation and grant number IT 1526-22 from the Department of Education of the Basque Government. C.H. and Z.Z. acknowledge support from the National Natural Science Foundation of China (numbers U22A6005 and 12304426) and the Natural Science Foundation of Shaanxi Province (numbers 2024JC-JCQN-07 and 22JSZ010).

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Authors and Affiliations

  1. Institute of Physical Chemistry and Abbe Center of Photonics, Friedrich-Schiller University, Jena, Germany

    Christiane Höppener, Stefanie Gräfe, Stephan Kupfer & Volker Deckert

  2. Leibniz Institute of Photonic Technology, Jena, Germany

    Christiane Höppener & Volker Deckert

  3. Donostia International Physics Center DIPC, Donostia-San Sebastián, Spain

    Javier Aizpurua

  4. Ikerbasque, the Basque Foundation for Science, Bilbao, Spain

    Javier Aizpurua

  5. Department of Electricity and Electronics, EHU/UPV, Donostia-San Sebastián, Spain

    Javier Aizpurua

  6. School of Physics and Information Technology, Shaanxi Normal University, Xi’an, China

    Huan Chen & Zhenglong Zhang

  7. Fraunhofer Institute for Applied Optics and Precision Engineering, Jena, Germany

    Stefanie Gräfe

  8. Departamento de Física, Universidade Federal de Minas Gerais, Minas Gerais, Brazil

    Ado Jorio

Authors
  1. Christiane Höppener
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  2. Javier Aizpurua
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  3. Huan Chen
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  4. Stefanie Gräfe
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  5. Ado Jorio
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  6. Stephan Kupfer
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  7. Zhenglong Zhang
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  8. Volker Deckert
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Contributions

Introduction (C.H., S.G., S.K., J.A. and V.D.); Experimentation (C.H., H.C., Z.Z. and V.D.); Results (C.H. and V.D.); Applications (C.H., A.J., H.C., Z.Z. and V.D.); Reproducibility and data deposition (C.H. and V.D.); Limitations and optimizations (C.H. and V.D.); Outlook (C.H., J.A., H.C., S.G., A.J., S.K., Z.Z. and V.D.); overview of the Primer (C.H., J.A., H.C., S.G., A.J., S.K., Z.Z. and V.D.).

Corresponding author

Correspondence to Volker Deckert.

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Glossary

Adaptive optics

A technical approach to improve the quality of an optical system by reducing the wavefront distortions (increasing the phase matching) imposed by diffractive optical elements, light scattering in thick samples and the variation in the index of refraction along the light path by using deformable mirrors or liquid crystal spatial light modulators.

Boundary element methods

Methods to solve Maxwell’s equation, which relies on the discretization of the surface elements of a configuration, wherein the boundary conditions are applied to each finite element of the elements of the interface.

Chemical effects

Stem from close-range and site-specific interactions between the surface-immobilized sample and the metallic nanoparticle and comprises non-resonant and resonant contributions and charge-transfer phenomena between the sample and the plasmonic nanoparticle.

Coherence length

The distance an electromagnetic wave can travel in a material and keeps its coherence, or maintain its phase.

Electromagnetic effect

Responsible for the locally confined and enhanced electric field and field gradients near the plasmonic particle.

Finite-difference time-domain methods

Grid-based differential numerical methods that allow to solve Maxwell’s equations in an iterative scheme.

Finite element methods

Numerical approaches that can solve partial differential equations by dividing the system into a certain number of smaller subsystems (finite elements).

Force–volume AFM spectroscopy

An advanced imaging atomic force microscopy (AFM) mode enabling a quantification of certain nanomechanical properties (adhesion, stiffness, Young’s modulus, dissipation and viscoelasticity) of a sample by recording entire extend-and-retract force–distance curves for each image pixel.

GPAW

A python implementation of the time-dependent density functional theory approach based on the projector augmented wave method.

Kohn anomaly

An anomaly in the phonon dispersion relation of graphene and metals, which arises from electron–phonon interaction, leading to a failure of the Born–Oppenheimer approximation.

Picocavity

Atomic-scale structure constituted by one or few metallic atoms protruding from the surface, which enables localization of light onto the atomic scale, often phrased as ‘atomic protrusion’.

Polarizability tensor

Describes the induced dipole moment along one direction as a function of the local electric field in any given direction; according to the general selection rules in Raman spectroscopy, a vibration is Raman active only if the polarizability changes along the displacement vector of the specific vibrational normal mode.

Rayleigh line

Corresponds to the peak in a spectrum that arises from elastic scattering of the incident light in a sample, that is, at a frequency or energy corresponding to the incident light.

Spatial field confinement

The ability of a plasmonic nanostructure to convert free propagating radiation into localized energy, that is, the obtained spatial extension of the formed secondary electromagnetic filed at the tip apex.

Strain solitons

Nonlinear quasi-stationary localized strain waves in solids that occur at boundaries of symmetry-broken stacking domains (in the case of graphene, AB and BA stacking domains).

Synergistic TERS

A terminology to summarize comparative approaches pairing tip-enhanced Raman scattering (TERS) as a pivotal method with a secondary, ideally complementary analytical technique.

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Höppener, C., Aizpurua, J., Chen, H. et al. Tip-enhanced Raman scattering. Nat Rev Methods Primers 4, 47 (2024). https://doi.org/10.1038/s43586-024-00323-5

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