Probing nanoscale spatial distribution of plasmonically excited hot carriers

Huang, Su-Dan; Wang, Xiang; Zhao, Qing; Zhu, Jinfeng; Li, Chawei; He, Yuhan; Hu, Shu; Sartin, Matthew M.; Yan, Sen; Ren, Bin

doi:10.1038/s41467-020-18016-4

Cited by 75 publications

(93 citation statements)

References 54 publications

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“…28 ). Since each Ag nanoparticle was isolated by the SiO 2 insulating shell, the hot carriers must have been mainly excited on the Au(111) surface, in line with the previous studies 63 . Nevertheless, compared to the TERS system, such an Ag@SiO 2 /Au substrate configuration shows a lower efficiency for hot-carrier creation and thus a lower reactivity for 2D polymerization (Supplementary Fig.…”

Section: Resultssupporting

confidence: 84%

“…16 – 19 ), the strongest LSP coupling can be excited in the TERS nanogap under 633 nm laser illumination, where hot electron-hole pairs will be created by surface-collision assisted absorption (Landau damping) 62 . In other words, collective oscillations of electrons in the localized hotspots enable strong absorption of the incident photons, creating a steady-state probability of the electrons with energies between E F and E F + 1.96 eV, and leaving the holes with energies between E F and E F − 1.96 eV, respectively 63 . Hot carriers then quickly redistribute their excess energy by electron–electron scattering processes towards a Fermi–Dirac distribution 63 .…”

Section: Resultsmentioning

confidence: 99%

“…In other words, collective oscillations of electrons in the localized hotspots enable strong absorption of the incident photons, creating a steady-state probability of the electrons with energies between E F and E F + 1.96 eV, and leaving the holes with energies between E F and E F − 1.96 eV, respectively 63 . Hot carriers then quickly redistribute their excess energy by electron–electron scattering processes towards a Fermi–Dirac distribution 63 . A three-step model can be considered for the indirect hot-electron transfer, absorption of photons, followed by the creation of hot carriers, and finally, transfer of electrons from metals to unoccupied molecular orbitals 60 .…”

Section: Resultsmentioning

confidence: 99%

“…50 nm) of hot electrons on Au/Ag surfaces and the measured transport distance (ca. 20 nm) of similar hot carriers 61 , 63 , the spatial reach (ca. 3.125 × 3.125 nm 2 ) of the hot electrons is much smaller in the plasmon-induced [4+4]-cycloaddition system (Fig.…”

Section: Resultsmentioning

confidence: 99%

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In-situ nanospectroscopic imaging of plasmon-induced two-dimensional [4+4]-cycloaddition polymerization on Au(111)

et al. 2021

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Plasmon-induced chemical reactions (PICRs) have recently become promising approaches for highly efficient light-chemical energy conversion. However, an in-depth understanding of their mechanisms at the nanoscale still remains challenging. Here, we present an in-situ investigation by tip-enhanced Raman spectroscopy (TERS) imaging of the plasmon-induced [4+4]-cycloaddition polymerization within anthracene-based monomer monolayers physisorbed on Au(111), and complement the experimental results with density functional theory (DFT) calculations. This two-dimensional (2D) polymerization can be flexibly triggered and manipulated by the hot carriers, and be monitored simultaneously by TERS in real time and space. TERS imaging provides direct evidence for covalent bond formation with ca. 3.7 nm spatial resolution under ambient conditions. Combined with DFT calculations, the TERS results demonstrate that the lateral polymerization on Au(111) occurs by a hot electron tunneling mechanism, and crosslinks form via a self-stimulating growth mechanism. We show that TERS is promising to be plasmon-induced nanolithography for organic 2D materials.

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Section: Resultssupporting

confidence: 84%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 2 more Smart Citations

In-situ nanospectroscopic imaging of plasmon-induced two-dimensional [4+4]-cycloaddition polymerization on Au(111)

et al. 2021

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“…Ren's group used electrochemical TERS (EC-TERS) to monitor the decarboxylation reaction on gold nanoparticles driven by surface plasmon [103]. They have shown nanoscale spatial resolution reactive hot carrier distribution at the particle surface and tuned the Fermi level of the electrode by adjusting the applied bias during TERS mapping to turn on/off the decarboxylation.…”

Section: Nanoscale Analysis Of Plasmonic Processes In Electrochemicalmentioning

confidence: 99%

Nanoscale structural characterization of plasmon-driven reactions

Kurouski

2021

Nanophotonics

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Illumination of noble metal nanostructures by electromagnetic radiation induces coherent oscillations of conductive electrons on their surfaces. These coherent oscillations of electrons, also known as localized surface plasmon resonances (LSPR), are the underlying physical cause of the electromagnetic enhancement of Raman scattering from analytes located in a close proximity to the metal surface. This physical phenomenon is broadly known as surface-enhanced Raman scattering (SERS). LSPR can decay via direct interband, phonon-assisted intraband, and geometry-assisted transitions forming hot carriers, highly energetic species that are responsible for a large variety of chemical transformations. This review critically discusses the most recent progress in mechanistic elucidation of hot carrier-driven chemistry and catalytic processes at the nanoscale. The review provides a brief description of tip-enhanced Raman spectroscopy (TERS), modern analytical technique that possesses single-molecule sensitivity and angstrom spatial resolution, showing the advantage of this technique for spatiotemporal characterization of plasmon-driven reactions. The review also discusses experimental and theoretical findings that reported novel plasmon-driven reactivity which can be used to catalyze redox, coupling, elimination and scissoring reactions. Lastly, the review discusses the impact of the most recently reported findings on both plasmonic catalysis and TERS imaging.

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Electrochemistry and Optical Microscopy

Kanoufi

2021

Encyclopedia of Electrochemistry

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Electrochemistry exploits local current heterogeneities at various scales ranging from the micrometer to the nanometer. The last decade has witnessed unprecedented progress in the development of a wide range of electroanalytical techniques allowing to reveal and quantify such heterogeneity through multiscale and multifonctionnal operando probing of electrochemical processes. However most of these advanced electrochemical imaging techniques, employing scanning probes, suffer from either low imaging throughput or limited imaging size. In parallel, optical microscopies, which can image a wide field of view in a single snapshot, have made considerable progress in terms of sensitivity, resolution and implementation of detection modes. Optical microscopies are then mature enough to propose, with basic bench equipment, to probe in a non destructive way a wide range of optical (and therefore structural) properties of a material in situ, in real time: under operating conditions. They offer promising alternative strategies for quantitative high-resolution imaging of electrochemistry. The first sections recall the optical properties of materials and how they can be probed optically. They discuss fluorescence, Raman, surface plasmon resonance, scattering or refractive index. Then the different optical microscopes used to image electrochemical processes are examined along with some strategies to extract quantitative electrochemical information from optical images. Finally the last section reviews some examples of in situ imaging, at micro-to nanometer resolution, and quantification of electrochemical processes ranging from solution diffusion to the conversion of molecular interfaces or solids.]

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Probing nanoscale spatial distribution of plasmonically excited hot carriers

Cited by 75 publications

References 54 publications

In-situ nanospectroscopic imaging of plasmon-induced two-dimensional [4+4]-cycloaddition polymerization on Au(111)

In-situ nanospectroscopic imaging of plasmon-induced two-dimensional [4+4]-cycloaddition polymerization on Au(111)

Nanoscale structural characterization of plasmon-driven reactions

Electrochemistry and Optical Microscopy

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