Quantum description of the optical response of charged monolayer–thick metallic patch nanoantennas

Herrera, Mario Zapata; Kazansky, A. K.; Aizpurua, Javier; Borisov, Andrei G.

doi:10.1103/physrevb.95.245413

Cited by 10 publications

(6 citation statements)

References 99 publications

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“…At Φ ATA = 0.4 V, a Schottky barrier forms at the metal−semiconductor interface because of the flat band potential of TiO 2 (Φ fb = −0.6 V vs Ag/AgCl at pH = 7). 67 Under light illumination, excited electrons are generated and injected into the conduction band of TiO 2 . All results show that electron−hole generation is promoted dramatically by the strong photon localization under the modal strong coupling.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Finally, we propose the energy diagram of this ATA system as in Figure e. At Φ ATA = 0.4 V, a Schottky barrier forms at the metal–semiconductor interface because of the flat band potential of TiO 2 (Φ fb = −0.6 V vs Ag/AgCl at pH = 7) . Under light illumination, excited electrons are generated and injected into the conduction band of TiO 2 .…”

Section: Resultsmentioning

confidence: 99%

“…The k ox can be efficiently enhanced by the characteristic lifetime of the photon field under the formation of modal strong coupling. More quantitative analysis for the change in the Fermi level depending on k ox could be carried out by the combination of in situ optical measurements because LSP properties reflect the charge density of metal nanostructures as well as the charge localization at the interfaces. , Although there is still room for investigating its effect on charge separation efficiency, the modal strong coupling has now been revealed as the origin of the photocurrent at the ATA electrodes with higher OER efficiency.…”

Section: Resultsmentioning

confidence: 99%

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In Situ Monitoring of Electronic Structure in a Modal Strong Coupling Electrode under Enhanced Plasmonic Water Oxidation

2021

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Modal strong coupling between a localized surface plasmon resonance and Fabry–Pérot cavity accelerates plasmon-induced oxygen evolution reactions (OERs). In this study, graphene-based electrochemical Raman measurements were performed to clarify the absolute potential of the Fermi level of plasmonic nanoparticles to induce an efficient OER under modal strong coupling condition. The measurements revealed a correlation between OER performance and the Fermi level potential. The electrode with higher activity showed a more positive Fermi level than that with lower OER activity. We also observed characteristic electronic excitation of the plasmonic field under modal strong coupling. The investigations yielded significant information such as the characteristic electronic structures and controlled electronic excitation of the plasmonic field for effective OER. This sets important requirements for further developing plasmonic water oxidation devices.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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In Situ Monitoring of Electronic Structure in a Modal Strong Coupling Electrode under Enhanced Plasmonic Water Oxidation

2021

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“…In all of these methods, the local field properties are usually determined by the smooth boundaries of a nanoscale morphology of the nanostructure (tip or tip‐substrate cavity) with a more or less sophisticated description of the roughness. Even in quantum descriptions of the optical response of metallic cavities, a jellium model [37‐41] of the electron gas, which relies on a smooth description of the electronic density at the metal‐vacuum interface, is often considered as a valid approach to obtain the optical polarization of metallic nanoresonators within the use of the time‐dependent density functional theory (TDDFT). Beyond these continuous approaches, atomistic models that refer the optical response of matter to its atomic constituents provide a roadmap to reveal the role of subnanometric features in metallic cavities and tips that introduce significant differences in the local field distributions around the nanoresonators (tips and/or gaps) and thus on its action onto the molecules deposited nearby [42‐45] …”

Section: Introductionmentioning

confidence: 99%

Theoretical treatment of single‐molecule scanning Raman picoscopy in strongly inhomogeneous near fields

Zhang

Dong

Aizpurua

2020

J Raman Spectroscopy

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Tip‐enhanced Raman spectroscopy (TERS) of a single molecule is commonly described by considering the change in the polarizability of the molecule with respect to a normal coordinate induced by homogeneous illumination. However, the local fields induced by nanoscale and atomic‐scale features at the surface of metallic clusters and nanogaps show strong inhomogeneities in their spatial distribution, which induces breaking of Raman selection rules. In this context, the spatial extension of the molecular electronic states subjected to strongly varying local fields challenges the validity of the point–dipole approximation as an adequate description of TERS in such configurations. Here, we introduce a general treatment to simulate single‐molecule TERS spectra and their energy‐filtered vibrational fingerprints maps, in which the polarization properties of the single molecule and that of the optical enhancing nanoresonator can be calculated separately and then conveniently combined to obtain the total Raman cross section of the molecule under the strongly inhomogeneous field. We apply the general method to study tip‐enhanced scanning Raman picoscopy of a 4,4′‐bipyridine and biphenyl molecules in the proximity of a silver icosahedral cluster with a few atoms at the tip apex mimicking an enhancing picocavity. The polarization of the molecules is calculated within density functional theory (DFT), and the optical response of the tip is calculated within a classical atomistic discrete–dipole approximation. The Raman spectra are found to be extremely sensitive to the spatial distribution of the local fields and to the orientation of the molecule. Our calculations show that the spatial mapping of molecular vibrational fingerprints, as probed by a tip with atomic protrusions, is capable to reveal intramolecular features of a single molecule in real space and thus establish a robust basis for scanning Raman picoscopy.

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“…In recent years, the isolation of graphene [13] and the discovery of the extraordinary plasmonic properties this material has when doped with carriers [14][15][16][17][18][19] has inspired significant interest in stud ying the plasmons supported by metallic nanostructures with thicknesses ranging from several nanometers down to mono layers. [20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] These nanostructures support very strong fields that lead to increased light-matter interaction [14,24,[35][36][37][38][39] and produce a higher degree of confinement than regular 3D structures, enabling, for instance, the enhancement of higherorder multipolar transitions. [40][41][42] Furthermore, the reduced dimensionality of these nano structures makes it easier to modify their optical response by altering their distribu tion of free carriers, as has been both theo retically proposed [21,43] and experimentally demonstrated.…”

mentioning

confidence: 99%

Comparative Analysis of the Near‐ and Far‐Field Optical Response of Thin Plasmonic Nanostructures

Zundel

Gieri

Sanders

et al. 2022

Advanced Optical Materials

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Nanostructures made of metallic materials support collective oscillations of their conduction electrons, commonly known as surface plasmons. These modes, whose characteristics are determined by the material and morphology of the nanostructure, couple strongly to light and confine it into subwavelength volumes. Of particular interest are metallic nanostructures for which the size along one dimension approaches the nanometer or even the subnanometer scale, since such morphologies can lead to stronger light–matter interactions and higher degrees of confinement than regular three‐dimensional nanostructures. Here, the plasmonic response of metallic nanodisks of varying thicknesses and aspect ratios is investigated under far‐ and near‐field excitation conditions. It is found that, for far‐field excitation, the strength of the plasmonic response of the nanodisk increases with its thickness, as expected from the increase in the number of conduction electrons in the system. However, for near‐field excitation, the plasmonic response becomes stronger as the thickness of the nanodisk is reduced. This behavior is attributed to the higher efficiency with which a near‐field source couples to the plasmons supported by thinner nanodisks. The results of this work advance the understanding of the plasmonic response of thin metallic nanostructures, thus increasing their potential for the development of novel applications.

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Quantum description of the optical response of charged monolayer–thick metallic patch nanoantennas

Cited by 10 publications

References 99 publications

In Situ Monitoring of Electronic Structure in a Modal Strong Coupling Electrode under Enhanced Plasmonic Water Oxidation

In Situ Monitoring of Electronic Structure in a Modal Strong Coupling Electrode under Enhanced Plasmonic Water Oxidation

Theoretical treatment of single‐molecule scanning Raman picoscopy in strongly inhomogeneous near fields

Comparative Analysis of the Near‐ and Far‐Field Optical Response of Thin Plasmonic Nanostructures

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