Plasmon-enhanced spectroscopy of absorption and spontaneous emissions explained using cavity quantum optics

Itoh, Tamitake; Yamamoto, Yuko S.; Ozaki, Yukihiro

doi:10.1039/c7cs00155j

Cited by 119 publications

(161 citation statements)

References 47 publications

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“…2m) intensities, which were measured at the same point, and is comparable to the huge enhancement factor reported in gap-mode SERS. 30 The enhancement is mainly due to the plasmonic nano-cavity and was not influenced by external factors such as the bias voltage introduced by the STM feedback system (see Supplementary Fig. 7).…”

Section: Subnanometre Resolution Stm-ters In Ambientmentioning

confidence: 96%

Visualization of subnanometric phonon modes in a plasmonic nano-cavity via ambient tip-enhanced Raman spectroscopy

et al. 2019

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Phonons provide information on the physicochemical properties of a crystalline lattice from the material's vibrational spectrum. Optical phonons, in particular, can be probed at both micrometre and nanometre scales using light-based techniques, such as, micro-Raman and tip-enhanced Raman spectroscopy (TERS), respectively. Selection rules, however, govern the accessibility of the phonons and, hence, the information that can be extracted about the sample. Herein, we simultaneously observe both allowed and forbidden optical phonon modes of defect-free areas in monolayer graphene to study nanometre scale strain variations and plasmonic activation of the Raman peaks, respectively, using our home-built TERS system in ambient. Through TERS imaging, strain variations and nanometre-sized domains down to 5 nm were visualised with a spatial resolution of 0.7 nm. Moreover, such subnanometric confinement was found to activate not only the D and D' forbidden phonon modes but also their D + D' combination mode. With our TERS in ambient system, the full phonon characterisation of defect-free graphene and other 2D nanomaterials is now possible, which will be useful for subnanometre strain analysis and exploring the inherent properties of defect-free materials.

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Section: Subnanometre Resolution Stm-ters In Ambientmentioning

confidence: 96%

Visualization of subnanometric phonon modes in a plasmonic nano-cavity via ambient tip-enhanced Raman spectroscopy

et al. 2019

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“…Indeed, the DR1 concentration imposes a penetration depth of the pump light in the film samples of 10 owing to the plasmonic resonance of the Au-NPs which occurs at 532 nm. SEA finds its origin in Fermi's golden rule 71 ; and much like surface enhanced fluorescence, and Raman and hyper-Raman scattering, SEA is a plasmonically enhanced effect, wherein the absorption cross section of a dressed chromophore, σ ω ( ) SEA ex , is expressed as a product of the chromophore's intrinsic absorption cross-section ( )…”

Section: Scientific Reports |mentioning

confidence: 99%

Surface Enhanced Visible Absorption of Dye Molecules in the Near-Field of Gold Nanoparticles

Elhani

Ishitobi

Inouye

et al. 2020

Sci Rep

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Surface enhanced absorption is a plasmonic effect parenting to surface enhanced fluorescence and Raman scattering, and it was clearly reported to occur in the infrared region of the spectrum of light. In this paper, we unambiguously show that it also occurs in the visible region of the spectrum by using a dye; i.e. an azo-dye, which exhibits a good light absorption in that region, and gold nanoparticles, which act as plasmonic nanoantennas that capture and re-radiate light, when the azo-dyes and the nanoparticles are incorporated in the bulk of solid films of polymer. In such a configuration, it is possible to use a dye concentration much larger than that of the nanoparticles and absorption path lengths much larger than those of the molecularly thin layers used in surface enhanced effects studies. In addition, the dye undergoes shape and orientation change; i.e. isomerization and reorientation, upon polarized light absorption; and the observation of surface enhanced visible absorption is done by two separate experiments; i.e. UV-visible absorption spectroscopy and photo-induced birefringence, since the signals detected from both experiments are directly proportional to the extinction coefficient of the dye. Both the dye's absorption and photoorientation are enhanced by the presence of the nanoparticles.electrical current when integrated in photovoltaic cells 27 . Gold NPs (Au-NPs) have been used for enhancing photovoltaic properties of dye-sensitized solar cells 28,29 and perovskite solar cells 30 , as well as in photocatalysis and environmental remediation [13][14][15]31,32 , and plasmonic photothermal therapy of cancer 33 as well as applications in imaging, sensing, biology and medicine 20 . Thin films containing photoresponsive units act as transducers that can convert incident light into molecular motion, resulting in numerous applications such as holography and data storage, as well as photomechanics and mass motion and micro-nano machines [34][35][36][37][38][39] , and so on 40,41 . For optically thin films, increasing the absorption results in improved transduction. In this paper, we report on the plasmonic enhancement of absorption and photo-orientation of azo-dye molecules in the presence of Au-NPs embedded in solid polymer films. The azo-dyes absorb visible light efficiently and undergo molecular shape change; i.e. trans ↔cis photoisomerization, and reorientation upon light absorption; i.e. photoorientation 42,43 .Azo-dye containing materials have been studied extensively in the past decades owing to interest in both fundamental and applications aspects [44][45][46][47][48][49] , and recent reviews provide a comprehensive view about the progress of research in this field 40,41 , and few studies reported the use of metal and semi-conductor NPs to enhance optical storage in azo-polymers 50,51 . The study reported in this paper is along the series of the studies, carried out by our group, which combine photo-reactivity in layered dielectric organic materials and plasmonic materials, including metals and ...

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“…In the cavity quantum electrodynamics (cavity QED) model, the EM coupling hybridizes plasmon resonance with molecular exciton resonance, and the hybridized resonance changes the energies by half of 2 g , where g is the EM coupling rate, from the original resonance energies under the rigorous resonant condition shown in Fig. 1(a) [13,14]. The changes in resonance energies appear as spectral splitting by 2 g , as shown in Fig.…”

Section: Introductionmentioning

confidence: 99%

Absorption cross-section spectroscopy of a single strong-coupling system between plasmon and molecular exciton resonance using a single silver nanoparticle dimer generating surface-enhanced resonant Raman scattering

2019

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This study investigated spectral changes in the absorption cross-sections of single strong coupling systems composed of single silver nanoparticle dimers and a few dye molecules during the quenching of surface-enhanced resonant Raman scattering 2 (SERRS). The absorption cross-section was obtained by subtracting the scattering cross-section from an extinction cross-section. The spectral changes in these cross-sections were evaluated using a classical hybridization model composed of a plasmon and a molecular exciton including a molecular multi-level property. The changes in the scattering and extinction cross-sections exhibit blue-shifts in their peak energy and increased peak intensities, respectively, during SERRS quenching. These properties are effectively reproduced in the model by decreasing the coupling energy. In particular, the peaks in the scattering and extinction cross-sections appear as peaks or dips in the absorption cross-sections depending on the degree of scattering loss, which reflects the dimer sizes. These results are useful for optimizing photophysical and photochemical effects mediated by the electronic excited states of strong coupling systems.

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Plasmon-enhanced spectroscopy of absorption and spontaneous emissions explained using cavity quantum optics

Cited by 119 publications

References 47 publications

Visualization of subnanometric phonon modes in a plasmonic nano-cavity via ambient tip-enhanced Raman spectroscopy

Visualization of subnanometric phonon modes in a plasmonic nano-cavity via ambient tip-enhanced Raman spectroscopy

Surface Enhanced Visible Absorption of Dye Molecules in the Near-Field of Gold Nanoparticles

Absorption cross-section spectroscopy of a single strong-coupling system between plasmon and molecular exciton resonance using a single silver nanoparticle dimer generating surface-enhanced resonant Raman scattering

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