Nanoscale Chemical Imaging Using Tip‐Enhanced Raman Spectroscopy: A Critical Review

Schmid, Thomas; Opilik, Lothar; Blum, Carolin; Zenobi, Renato

doi:10.1002/anie.201203849

Cited by 297 publications

(230 citation statements)

References 132 publications

(137 reference statements)

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“…Au, Ag), is positioned close to the surface under investigation, thus creating a single, localised hotspot [115][116][117][118]. The location of the hotspot can be controlled laterally using piezo-driven positioners, effectively combining the concept of borrowed SERS with scanning probe microscopy.…”

Section: Ec-tersmentioning

confidence: 99%

Advances in surface-enhanced vibrational spectroscopy at electrochemical interfaces

Wain

O’Connell

2017

Advances in Physics: X

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Electrochemical interfaces are ubiquitous, and characterisation tools that allow us to interrogate them on the molecular scale underpin a wide range of technologies. Because of their dynamic nature, in situ or operando measurement is often necessary, and the coupling of electrochemical techniques with spectroscopic methods is a powerful solution to this challenge. Vibrational spectroscopy in particular can provide important insights into the chemical nature of species adsorbed at electrode surfaces. When combined with electrochemistry, the influence of a potential perturbation to the interface can be studied, helping to build a complete picture of molecular processes in complex electrochemical systems. Here, we review the latest advances in vibrational spectroscopy at electrochemical interfaces, with a focus on surfaceenhanced approaches including surface-enhanced Raman scattering, shell-isolated nanoparticle-enhanced Raman spectroscopy, tip-enhanced Raman spectroscopy and surface-enhanced infrared absorption spectroscopy.

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Section: Ec-tersmentioning

confidence: 99%

Advances in surface-enhanced vibrational spectroscopy at electrochemical interfaces

Wain

O’Connell

2017

Advances in Physics: X

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“…The reflectance of the samples has been recorded in quasinormal incidence (6 • ) using a Varian Cary 5000 UV-visible spectrometer. An example of reflectance spectra recorded on sample B is shown in Fig.…”

Section: B Optical Measurements: Original Setup and Proceduresmentioning

confidence: 99%

“…At thermal equilibrium, one can extract a temperature-independent line shape, using Eqs. (4), (6), and (10):…”

Section: B Spectral Response For Electronic Scatteringmentioning

confidence: 99%

“…The impressive enhancement, up to 10 8 , of the vibrational fingerprint of molecules located at specific sites ("hot spots") on the surface of metallic particles is responsible of a further huge development of Raman spectrometry [2]. The possibilities of acquiring vibrational information down to a single molecule [3,4] and controlling a single hot spot with high spatial resolution using tip-enhanced Raman spectroscopy (TERS) [5][6][7][8] have led to new insights on local mechanisms at the origin of SERS. From the beginning, these mechanisms have been commonly referred to as electromagnetic (EM) [9] when due to local electromagnetic inductive effects, or chemical (CM) [10] when due to resonant charge transfer effects, the first one giving the largest contribution to the enhancement factor [11].…”

Section: Introductionmentioning

confidence: 99%

“…This background also appears in TERS measurements and its origin is here also subject to various interpretations, such as far-field contribution, luminescence from the tip itself, or molecular fluorescence [6,23,24]. The possible role of luminescence processes, mainly with gold-(or copper-) based nanostructures, cannot be discarded because of the presence of real electronic (interband) transitions in the visible range [25].…”

Section: Introductionmentioning

confidence: 99%

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Plasmon-resonant Raman spectroscopy in metallic nanoparticles: Surface-enhanced scattering by electronic excitations

et al. 2015

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Since the discovery of surface-enhanced Raman scattering (SERS) 40 years ago, the origin of the "background" that is systematically observed in SERS spectra has remained questionable. To deeply analyze this phenomenon, plasmon-resonant Raman scattering was recorded under specific experimental conditions on a panel of composite multilayer samples containing noble metal (Ag and Au) nanoparticles. Stokes, anti-Stokes, and wide, including very low, frequency ranges have been explored. The effects of temperature, size (in the nm range), embedding medium (SiO 2 , Si 3 N 4 , or TiO 2 ) or ligands have been successively analyzed. Both lattice (Lamb modes and bulk phonons) and electron (plasmon mode and electron-hole excitations) dynamics have been investigated. This work confirms that in Ag-based nanoplasmonics composite layers, only Raman scattering by single-particle electronic excitations accounts for the background. This latter appears as an intrinsic phenomenon independently of the presence of molecules on the metallic surface. Its spectral shape is well described by revisiting a model developed in the 1990s for analyzing electron scattering in dirty metals, and used later in superconductors. The g s factor, that determines the effective mean-free path of free carriers, is evaluated, g expt s = 0.33 ± 0.04, in good agreement with a recent evaluation based on time-dependent local density approximation g theor s = 0.32. Confinement and interface roughness effects at the nanometer range thus appear crucial to understand and control SERS enhancement and more generally plasmon-enhanced processes on metallic surfaces.

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Raman Spectroscopy in Analysis of Biomolecules

Niaura

2014

Encyclopedia of Analytical Chemistry

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Raman spectroscopy (RS) is a vibrational spectroscopy technique based on the phenomenon of inelastic light scattering from matter (the Raman effect). It is a versatile tool for probing of biological events at the molecular level and for identification of biomolecules. The characteristic mark of modern RS is the variety of techniques used to explore the Raman effect. In this article the advantages and limitations of different methodologies including conventional Raman, resonance Raman (RR), ultraviolet resonance Raman (UVRR), surface‐enhanced Raman (SER), surface‐enhanced resonance Raman (SERR), Fourier transform Raman (FT‐Raman), micro‐Raman, time‐resolved Raman, and coherent anti‐Stokes Raman scattering (CARS) spectroscopies that can be used for analysis of structure and function of biomolecules are discussed. RR and UVRR spectroscopies are particularly important in biological applications since chromophoric groups (active centers in proteins, aromatic amino acid residues, and nucleotides), which in many cases are responsible for the function of biomolecules, can be probed selectively, by tuning the excitation wavelength to the electronic absorption transition of the chromophore. Surface‐enhanced techniques (SER and SERR) are the most sensitive, allowing RS of single biomolecules. The interpretation of the Raman spectra of biomolecules requires identification of spectra‐structure correlations. Numerous marker bands for conformation, hydrogen bonding, protonation, and hydrophobic interaction of the main constituents of biopolymers are provided and discussed.

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Nanoscale Chemical Imaging Using Tip‐Enhanced Raman Spectroscopy: A Critical Review

Cited by 297 publications

References 132 publications

Advances in surface-enhanced vibrational spectroscopy at electrochemical interfaces

Advances in surface-enhanced vibrational spectroscopy at electrochemical interfaces

Plasmon-resonant Raman spectroscopy in metallic nanoparticles: Surface-enhanced scattering by electronic excitations

Raman Spectroscopy in Analysis of Biomolecules

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