The electronic properties of a substance are perturbed by interactions of elementary excitations. The optical properties of the interacting states have been extensively studied and revealed to be correlated with the eigenfunctions of the isolated systems. On the other hand, the spatial characteristics of the states have been little studied because of the diffraction limit of light. In this study, we examine plasmon and exciton interactions in silver nanoplate and organic J-aggregate hybrid structures using scanning near-field optical microscopy. We reveal that the light transmission is enhanced when the plasmon and exciton resonantly interact with each other. We visualize the spatial distribution of the interacting states and find that the interaction of the high-order plasmons with the exciton enables manipulation of the electronic states in a spatially resolved manner. This study demonstrates that the optical field can be spatially controlled via coupling of the elementary excitations.

Plasmonic optical fields have been applied for surface-enhanced spectroscopy, chemical sensing, and bioimaging. Spatial distributions of optical fields are critical for optimizing their functionalities. In plasmon-enhanced fluorescence, both incoming and outgoing fields excited by the plasmon should contribute to the enhancement of the fluorescence. Spatial characteristics of plasmons are critical not only for the fundamental understanding of the plasmon but also for their practical applications. Here, we investigate the spatial characteristics of the excitation and relaxation processes near the gold nanoplate using time-resolved near-field two-photon microscopy. We reveal from near-field optical microscopy that the incident field is locally enhanced by the plasmon resonance effect and the lightning rod effect. Near-field time-resolved fluorescence imaging demonstrates that the fluorescence decay is accelerated entirely over the surface of the plate regardless of the spatial distribution of the incident field. These results provide deep insight into plasmonic optical fields and are of great importance for designing plasmon-based substrates for surface-enhanced spectroscopy and photochemical reactions.

Near-field optical microscopy visualizes spatial characteristics of elementary excitations induced in metal nanostructures. However, the microscopy is not able to reveal the absorption and scattering characteristics of the object simultaneously. In this study, we demonstrate a method for revealing the absorption and scattering characteristics of silver nanoplate by using near-field transmission and reflection spectroscopy. Near-field transmission and reflection images show characteristic spatial features attributable to the excited plasmon modes. The near-field refection image near the resonance shows a reversed contrast depending on the observed wavelength. Near-field reflection spectra show unique positive and negative resonant features. We reveal that the optical characteristics and the wavelength dependency of the optical contrast originate from the scattering and absorption properties of the plasmons, with the aid of the electromagnetic simulations.

Assemblies of gold nanorods capped with poly-diarylethene (DE) were chemically prepared in a solution. Plasmon assisted optical responses of the poly(DE) have been studied. Fluorescence from the open-form of DE was mostly quenched near 550nm due to interband transition of gold, while fluorescence near 700nm was slightly enhanced by the longitudinal plasmon resonance. Cycloreversion reaction of the gold nanorodpoly(DE) has been also studied, and it has been found that the reaction rate is enhanced by the plasmon excitation and increases nearly two-fold in the assembly. The magnitude of the enhancement is qualitatively consistent with the spatially and orientationally averaged value of the simulated optical field enhancements in the vicinity of the nanorod.

A detailed characterization of plasmon modes is important not only for a deeper understanding of plasmons but also for their practical applications. In this study, we investigated the three-dimensional near-field characteristics of high-order plasmon modes excited in a gold hexagonal nanoplate. From the near-field spectroscopic images, we found that both in-plane and out-of-plane plasmon modes observed near 900 nm were spectrally and spatially overlapped. We performed three-dimensional near-field measurement to reveal the optical characteristics of the overlapped modes in detail. We found that the steric near-field distribution near the nanoplate strongly depended on the plasmon mode, and the out-of-plane mode confines electromagnetic fields more tightly than the in-plane mode. We also found that the in-plane mode was dominantly visualized as the probe tip-sample distance increased. These findings demonstrate that the three-dimensional near-field technique enables selective visualization of a single plasmon mode even if multiple modes are spatially and spectrally overlapped.

Precise understanding of the spatiotemporal characteristics of plasmons is essential for the development of applications of plasmonic nanoparticles. In this study, we investigated the spatiotemporal properties of high-order plasmon modes induced in a gold triangular nanoplate by static and dynamic near-field measurements. The near-field transmission measurements revealed that in-plane and out-of-plane polarized plasmon modes were simultaneously excited and these modes spectroscopically and spatially overlapped. The superposition of these modes was visualized in the near-field two-photon excitation image of the nanoplate. We performed time-resolved autocorrelation measurements on the nanoplate and found that the correlation width was broader than the excitation pulse due to the plasmon dephasing process. From the correlation width map of the nanoplate, we experimentally demonstrated that the out-of-plane plasmon mode exhibits a longer dephasing time than the in-plane plasmon mode. These findings indicate that the out of -plane mode is desirable for improving the performance of plasmons in various applications.

We investigated the spectral and spatial characteristics of plasmons induced in chemically synthesized triangular gold nano- and microplates by aperture-type scanning near field optical microscopy. Near-field transmission images taken at plasmon resonance wavelengths showed two-dimensional oscillating patterns inside the plates. These spatial features were well reproduced by the square moduli of calculated eigen functions confined in the two-dimensional triangular potential well. From the irreducible representations of the eigen functions, it was found that both the out-of-plane modes and in-plane modes were clearly visualized in the near-field images. We compared near-field transmission images of a triangular nanoplate to those of a truncated one with a similar dimension and revealed that the fine details of the geometrical shape of the apex on the plate strongly influence the experimentally observed eigen mode structures. We also performed near-field transmission measurements of micrometer-scale triangular plates and found that wavy patterns were observed along the edges of the plates. The wavy features can be interpreted as the superposition of eigen modes with similar eigen energy. These findings prove that near-field transmission imaging enables one to directly visualize plasmonic eigen modes confined in the particle and provide fruitful information not only for a deeper understanding of plasmons but also for the application of the design and active control of plasmonic optical fields.

We developed an aperture-type near-field reflection spectral imaging method to obtain optical properties of materials with a nanometer spatial resolution. We adopted a phase-stepping technique to extract genuine near-field signals of a sample from the observed intensity spectra dominated by the large background, in a multiplex manner. We performed near-field reflection spectral imaging of a single silver nanoplate to evaluate the developed system and also to examine near-field optical properties of the nanoplate. The near-field reflection spectrum of the nanoplate shows multiple resonant features that are not observable by conventional methods. The near-field reflection image taken at the resonance shows unique spatial features attributable to the plasmon mode resonantly excited. The developed system is applicable to transparent samples as well as opaque ones and enables spectral as well as spatial characteristics of the samples to be revealed.