Electronic and vibrational surface-enhanced Raman scattering: from atomically defined Au(111) and (100) to roughened Au

Inagaki, Motoharu; Isogai, Taichi; Motobayashi, Kenta; Lin, Kai-Qiang; Ren, Bin; Ikeda, Katsuyoshi

doi:10.1039/d0sc02976a

Cited by 31 publications

(54 citation statements)

References 74 publications

(125 reference statements)

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“… 35 A shortcoming of commonly used SERS substrates such as roughened metal surfaces or colloidal aggregates is that they give rise to spectra of limited reproducibility regarding intensity and appearance. 36 These limitations originate from the heterogeneity of the plasmonic resonances present on the substrate as well as the stochastic placement of individual sample molecules with respect to local electromagnetic hotspots. On the other hand, TERS probes like the one used in this study can be fabricated with a high degree of reproducibility and a precisely tuned plasmonic resonance behavior (see Methods ).…”

Section: Results and Discussionmentioning

confidence: 99%

Tip-Enhanced Stokes–Anti-Stokes Scattering from Carbyne

et al. 2022

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Carbyne, a linear chain of carbon atoms, is the truly one-dimensional allotrope of carbon and the strongest known Raman scatterer. Here, we use tip-enhanced Raman scattering (TERS) to further enhance the Raman response of a single carbyne chain confined inside a double-walled carbon nanotube. We observe an increase of the anti-Stokes scattering by a factor of 3290 and a 22-fold enhancement of the anti-Stokes/Stokes ratio relative to far-field measurements. The power dependence of the anti-Stokes/Stokes ratio under TERS conditions is indicative of coherent Stokes–anti-Stokes scattering mediated by an excited phonon. The role of resonance effects and laser-induced heating are discussed and potential opportunities are outlined.

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Section: Results and Discussionmentioning

confidence: 99%

Tip-Enhanced Stokes–Anti-Stokes Scattering from Carbyne

et al. 2022

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“…For comparison of scattering responses in the anti‐Stokes and Stokes branches, ultranarrow band notch filters (reflecting volume Bragg grating, OptiGrate Corp) was used to remove the Rayleigh scattering under excitation of 1.96 eV (NEO‐30MS1, NEOARK). [ 8,17 ]…”

Section: Methodsmentioning

confidence: 99%

“…Recently, several studies showed that the origin of the SERS background on Au surface can be well explained by ERS rather than PL. [ 6–8 ] For other metals, however, the origin of the background generation is still under discussion. Such controversy about the mechanism is partly due to a lack of information about ERS in metals; the cross section of ERS in noble metals is generally very small.…”

Section: Introductionmentioning

confidence: 99%

Surface‐Enhanced Electronic Raman Scattering at Various Metal Surfaces

Kamimura

Kondo

Motobayashi

et al. 2022

Physica Status Solidi (b)

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Surface‐enhanced Raman scattering (SERS) has been extensively used to obtain vibrational information at metal/dielectric interfaces because of its extremely high chemical sensitivity and surface selectivity. Since the discovery of this effect in 1970s, however, the origin of the spectral background has remained questionable. Because the “background” signals dominate in the low‐frequency region, it is necessary to deeply understand this phenomenon for analyzing SERS spectra properly in the wide spectral range. Herein, scattering spectra for various metal surfaces are measured with and without excitation of plasmonic resonances in the wide frequency ranges covering both Stokes and anti‐Stokes branches, including very low‐frequency region. The comparison of the spectra between smooth surfaces and plasmonic rough surfaces of Au, Ag, and Pt and the theoretical evaluation of local fields at the metal/air interfaces indicate that electronic Raman scattering accounts for the background continuum in SERS spectra. This is also confirmed by the comparison of the spectra with and without ultrathin Ag films on a same Au surface. An analytical method of SERS spectra is demonstrated in which both contributions of electronic Raman scattering and vibrational Raman scattering are considered.

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“…Next, determination of the in situ SERS Stokes ( I s ) and anti-Stokes ( I as ) intensities was further carried out to quantify the laser-induced temperature rise at the junction of the metal particles ( i.e., hot spots) 14 on self-assembled GNP arrays of 100.9 nm (GNP1) and 42.7 nm (GNP2), respectively. On each array, the laser with 10, 25, 50, and 100% of full power generated four spectral lines, respectively (Fig.…”

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confidence: 99%