Plasmon dephasing time and optical field enhancement in a plasmonic nanobowl substrate studied by scanning near-field optical microscopy.

Plasmonic substrates have been extensively investigated due to their potential applications in fluorescence microscopy, chemical sensing, and photochemical reactions. The optical properties of the substrate depend on the spatial and temporal features of the plasmon excited. Hence, the ability to directly visualize plasmon dynamics is crucial. In this study, we investigated the spatial and temporal properties of plasmon excitation in a plasmonic nanobowl substrate consisting of a periodic hexagonal array of nanoscale bowl-like structures developed with self-assembly. Near-field transmission imaging revealed that multiple plasmon resonance bands are observed from visible to near-infrared spectral region, and the optical contrast of the image is dependent on the observed band. Near-field two-photon photoluminescence microscopy revealed that the probability of excitation inside each nanoscale bowl-like structure is greater than that in the surrounding area. Near-field time-resolved imaging revealed that the nanobowl substrate exhibited a substantially long plasmon dephasing time, exceeding 12 fs. Based on the spectral features of the near-field and far-field spectra, we found that optically dark plasmon mode is excited by the near-field illumination and only partly contributes to the long dephasing time observed. This fact indicates that the dephasing time is extended by some other mechanism in the periodic substrate. We revealed from this study that the enhanced optical fields induced in the nanobowl structure originate from the photosynergetic effect of the cavity mode and plasmon mode excited.

Nanoantenna effect dependent on the center structure of Bull's eye-type plasmonic chip.

A bright spot is observable in the center of Bull's eye plasmonic pattern with a fluorescence microscope due to the plasmonic nanoantenna effect. In this effect, a propagating wave of surface plasmon resonance concentrates in the center. This study focused on the relationship between the center structure of Bull's eye pattern and the nanoantenna effect in four fabricated Bull's eye-type plasmonic chips with centers of different sizes (full- or half-pitch diameter) and shapes (convex or concave). The fluorescence intensity of the fluorescent nanoparticles adsorbed to these plasmonic chips was measured with an upright-inverted microscope to evaluate the plasmonic chip enhancement factor composed of the product of the excitation and emission enhancement and individual factors. When the emission enhancement factor was investigated under nonresonance excitation conditions, by the disappearance of a bright spot, excitation enhancement was found to contribute to the plasmonic nanoantenna effect. The concave Bull's eye structure with a half-pitch diameter demonstrates the highest nanoantenna effect due to the formation of a larger constructive wave in the superposition of the diffraction wave of incident light under resonance conditions. In addition, the electromagnetic field intensity simulated by discrete dipole approximation agrees with the microscopy results. Overall, the results indicate that the plasmonic nanoantenna effect could be controlled depending on the resonance condition and center structure.

Observation of the plasmon mode transition from triangular to hexagonal nanoplates.

The geometrical shape of a metal nanostructure plays an essential role in determining the optical functionality of plasmonic cavity modes. Here, we investigate the geometrical modification effect on plasmonic cavity modes induced in two-dimensional gold nanoplates. We perform near-field transmission measurements on triangular and tip-truncated triangular nanoplates and reveal that the plasmonic cavity modes are qualitatively consistent with each other as long as the snipping size is not significant. To elucidate the tip-truncation effect on plasmonic cavity modes in detail, we carry out numerical simulations for nanoplates with various snipping sizes and find that tip truncation affects not only the optical selection rules but also the energy relation for the plasmonic cavity modes. These findings provide a foundation for the rational design of plasmonic cavities with desired optical functionality.

Spatial characteristics of optical fields near a gold nanorod revealed by three-dimensional scanning near-field optical microscopy.

We visualize plasmon mode patterns induced in a single gold nanorod by three-dimensional scanning near-field optical microscopy. From the near-field transmission imaging, we find that 3rd and 4th order plasmon modes are resonantly excited in the nanorod. We perform electromagnetic simulations based on the discrete dipole approximation method under focused Gaussian beam illumination and demonstrate that the observed near-field spectral and spatial features are well reproduced by the simulation. We also reveal from the three-dimensional near-field microscopy that the 4th order plasmon mode confines optical fields more tightly compared with the 3rd order mode. This result indicates that the even-order plasmon modes are promising for enhancing the light-matter interactions.

Near-field transmission and reflection spectroscopy for revealing absorption and scattering characteristics of single silver nanoplates.

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.

Gold Ultrathin Nanorods with Controlled Aspect Ratios and Surface Modifications: Formation Mechanism and Localized Surface Plasmon Resonance.

We synthesized gold ultrathin nanorods (AuUNRs) by slow reductions of gold(I) in the presence of oleylamine (OA) as a surfactant. Transmission electron microscopy revealed that the lengths of AuUNRs were tuned in the range of 5-20 nm while keeping the diameter constant (∼2 nm) by changing the relative concentration of OA and Au(I). It is proposed on the basis of time-resolved optical spectroscopy that AuUNRs are formed via the formation of small (<2 nm) Au spherical clusters followed by their one-dimensional attachment in OA micelles. The surfactant OA on AuUNRs was successfully replaced with glutathionate or dodecanethiolate by the ligand exchange approach. Optical extinction spectroscopy on a series of AuUNRs with different aspect ratios (ARs) revealed a single intense extinction band in the near-IR (NIR) region due to the longitudinal localized surface plasmon resonance (LSPR), the peak position of which is red-shifted with the AR. The NIR bands of AuUNRs with AR < 5 were blue-shifted upon the ligand exchange from OA to thiolates, in sharp contrast to the red shift observed in the conventional Au nanorods and nanospheres (diameter >10 nm). This behavior suggests that the NIR bands of thiolate-protected AuUNRs with AR < 5 are not plasmonic in nature, but are associated with a single-electron excitation between quantized states. The LSPR band was attenuated by thiolate passivation that can be explained by the direct decay of plasmons into an interfacial charge transfer state (chemical interface damping). The LSPR wavelengths of AuUNRs are remarkably longer than those of the conventional AuNRs with the same AR, demonstrating that the miniaturization of the diameter to below ∼2 nm significantly affects the optical response. The red shift of the LSPR band can be ascribed to the increase in the effective mass of electrons in AuUNRs.

Near-field spectroscopic properties of complementary gold nanostructures: applicability of Babinet's principle in the optical region.

We examine the far-field and near-field properties of complementary screens made of nanostructured gold thin films, a rectangular nanowire and a nanovoid, using an aperture-type scanning near-field optical microscope and electromagnetic field calculations, and discuss the applicability of Babinet's principle in the optical region. The far-field transmission spectra of the complementary screens are considerably different from each other. On the other hand, genuine near-field extinction spectra exhibit nearly complementary characteristics. The spatial features of the observed near-field images for the complementary screens show little correlation. We have found from the Fourier analysis of the simulated images that high spatial-frequency components of the electromagnetic fields show mutual spatial correlation. These results suggest that Babinet's principle is applicable to the high spatial-frequency components of electromagnetic fields for the complementary screens.

Observation of Plasmon Wave Packet Motions via Femtosecond Time-Resolved Near-Field Imaging Techniques.

The generation and dynamics of plasmon wave packets in single gold nanorods were observed at a spatiotemporal scale of 100 nm and 10 fs via time-resolved near-field optical microscopy. Following simultaneous excitation of two plasmon modes of a nanorod with an ultrashort near-field pulse, a decay and revival feature of the time-resolved signal was obtained, which reflected the reciprocating motion of the wave packet. The time-resolved near-field images were also indicative of the wave packet motion. At some period of time after the excitation, the spatial features of the two modes appeared alternately, showing motion of plasmonic wave crests along the rod. The wave packet propagation was clearly demonstrated from this observation with the aid of a simulation model. The present experimental scheme opens the door to coherent control of plasmon-induced optical fields in a nanometer spatial scale and femtosecond temporal scale.

Local optical responses of plasmon resonances visualised by near-field optical imaging.

The unique optical characteristics of noble metal nanostructures have their origin principally in surface plasmon resonances. To exploit and design the unique characteristics arising from plasmons, an investigation of optical field structures adjacent to the nanostructure is of fundamental importance. As the spatial scale of the optical field structures is essentially smaller than the radiation wavelength in resonance with the plasmon, optical imaging methods that achieve spatial resolution beyond the diffraction limit of light are necessary to visualise the fields. In this article, we review the studies of direct experimental visualisation of plasmon resonances using near-field optical microscopy. We briefly describe the method of near-field optical microscopy used to study noble metal nanoparticles and show with several typical single gold nanoparticles that the spatial features of plasmon resonances, in particular the standing wave functions of the plasmons, can be directly visualised by near-field imaging. We then describe our recent efforts to visualise ultrafast dynamics in metal nanostructures following plasmonic excitation, which are based on near-field ultrafast imaging measurements. Another notable aspect of metal nanostructures that has attracted attention recently is the chirality of plasmons. Here, we describe a method and examples of near-field optical imaging and analyses of chiral plasmons excited on metal nanostructures.

Optical control of plasmonic fields by phase-modulated pulse excitations.

We developed an advanced near-field optical method by combining an ultrafast near-field optical microscope with a prism-based pulse shaping system. We used this apparatus to visualize plasmonic optical fields and to measure the lifetime of plasmons excited on a rough gold film. We also studied the influence of the phase-modulation of the excitation pulse on the spatial distribution of the optical fields. We found that the spatial distribution of the optical fields can be controlled by a negatively chirped pulse.

Spatial distribution of enhanced optical fields in one-dimensional linear arrays of gold nanoparticles studied by scanning near-field optical microscopy.

We visualized the enhanced optical field distributions in one-dimensional linear array structures of gold nanospheres by using scanning near-field optical microscopy. The characteristic field distribution depends on the chain length of the one-dimensional structures. The distribution of optical field is reproduced qualitatively by model calculations based upon finite-difference time-domain (FDTD) method. From the analysis, we have found that the characteristic distribution of the enhanced field arises from interparticle interactions, which cause propagation of the plasmon excitation in the inner part of the linear array, and trapping of it by a localized mode at the edges.

Strong optical coupling between mutually orthogonal plasmon oscillations in a silver nanosphere-nanowire joined system.

A top-to-bottom joined system consisting of a silver nanowire and nanospheres was fabricated by embedding silver nanospheres on a glass or silicon substrate on which 3-aminothiophenol as an analyte molecule was adsorbed, and then placing silver nanowires on the substrate to make gap sites between a nanowire and nanospheres. In the far-field Raman measurements, the sphere under the wire exhibited more than 60 times higher Raman enhancement than isolated spheres. The surface enhanced Raman scattering (SERS) spectra obtained by the 647.1 nm excitation showed highly polarized feature, exhibiting ca. 4 times higher SERS intensity for the electric field parallel to the wire axis than that perpendicular to the wire axis while those by the 514.5 nm excitation showed non-polarized feature against the incident electric field direction. The polarized feature by the 647.1 nm excitation is explained in terms of optical coupling in a vertical direction to the substrate plane, between the silver nanosphere and the longitudinal surface plasmon mode of the nanowire. The longitudinal plasmon of the nanowire functions as an antenna of the incident radiation field in this type of coupled plasmon mode, to yield the confined field. Near-field two-photon excitation imaging measurements as well as numerical calculations of the localized electric field around the system support this idea and indicate that the coupling between the surface plasmon of silver nanospheres and the longitudinal mode of silver nanowires is site-selective.

Anomalous light transmission from plasmonic-capped nanoapertures.

We report an anomalous light transmission phenomenon for a nanoaperture on an opaque screen when the aperture is covered with an opaque cap. In conventional optics, light transmission must decrease when the aperture is capped. However, we found that light transmission is enhanced when the nanodisk is in close proximity to the aperture at a wavelength close to the plasmon resonance. This effect even occurs when the disk is larger than the aperture.

Photoluminescence from Carbon Dot-Gold Nanoparticle Composites Enhanced by Photonic and Plasmonic Double-Resonant Effects.

Carbon dots (CDs) exhibit chemical stability and low toxicity, so they are promising for biomedical and imaging applications. The quantum yield of the photoluminescence is typically 10-20%, which limits practical applications. We fabricate carbon dot-gold nanoparticle photonic crystals (CD-GNP PCs) and demonstrate enhanced photoluminescence intensity from the carbon dots using the photonic and plasmonic double-resonant effects. A severalfold enhancement was obtained compared to the neat CD. The method developed in this study provides a universal scheme to enhance light-emitting materials, which is promising for the development of ultrahigh molecular sensing and bioimaging techniques.

Space-Selective Fabrication of Light-Emitting Carbon Dots in Polymer Films Using Electron-Beam-Induced Chemical Reactions.

Nanocarbon-based materials have excellent properties, including high electrical conductivity as well as charity-dependent optical absorption and luminescence; therefore, the materials are promising in applications for nanoelectric devices, nanophotonics, and so on. Carbon dots (CDs) are one of the carbon materials recently fabricated. Optical properties of CDs have been reported to be similar to those of polycyclic aromatic hydrocarbons (PAHs). For this reason, the CDs are considered to be composed of PAH. Synthesis of CDs has previously been accomplished through hydrothermal synthesis and microwave irradiation. These methods require a long synthesis time, and the processes involve multiple steps. In this study, we developed a fabrication method of CDs in simple and spatially selective ways, by using radical reactions in an organic polymer film with focused electron-beam irradiation. We investigated various organic polymers as reaction materials and found that polystyrene has a higher efficiency for CD formation than other organic polymers investigated. Absorption, photoluminescence, and Raman scattering properties of the electron-beam-irradiated sample were in good agreement with those reported for the CDs. The technique developed in this study is promising for fabricating light-emitting CDs and photonic crystals in a simple and flexible manner.

Characterization of Overlapped Plasmon Modes in a Gold Hexagonal Plate Revealed by Three-Dimensional Near-Field Optical Microscopy.

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.

Static and Dynamic Near-Field Measurements of High-Order Plasmon Modes Induced in a Gold Triangular Nanoplate.

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.

Multiple Resonances Induced by Plasmonic Coupling between Gold Nanoparticle Trimers and Hexagonal Assembly of Gold-Coated Polystyrene Microspheres.

Optical properties of a gold nanoparticle trimer assembly coupled with gold-coated hexagonally close-packed polystyrene microspheres were investigated by linear and nonlinear spectroscopy. The observed reflection spectrum shows multiple peaks from the visible to near-infrared spectral regions. The spectroscopic properties were also examined by a finite-difference time-domain simulation. We found that the optical response of plasmons excited in the gold nanoparticle trimers was significantly modulated by strong coupling of the plasmons and the photonic mode induced in the gold-coated polystyrene assembly. Two-photon induced photoluminescence and Raman scattering from the sample were investigated, and both signals were significantly enhanced at the gold nanoparticle assembly. The simulations reveal that the electric fields can be enhanced site-selectively, not only at the interstitial sites in the nanoparticle assembly but also at the gaps between the particle and the gold film due to plasmonic interactions, by tuning the wavelength and are responsible for the strong optical responses.

Near-field two-photon-induced photoluminescence from single gold nanorods and imaging of plasmon modes.

We investigated the two-photon-induced photoluminescence properties of single gold nanorods by scanning near-field spectroscopy. The process was found to be initiated by a sequential one-photon absorption for creating a pair of an electron and a hole in the sp and d bands. Photoluminescence is then radiated when the electron near the Fermi surface recombines with the hole near the X and L symmetry points. The polarization characteristics of emitted photons from the X and L regions were found to be different. These characteristics can be understood by the crystalline structure and the band structure of the gold nanorod. We found characteristic spatial oscillatory features along the long axis of the nanorods in photoluminescence excitation images. The images were well reproduced by density-of-states maps of the nanorods calculated with Green's dyadic method and were attributed to the spatial characteristics of the wave functions of the plasmon modes inside the nanorods.

Morphological and spectroscopic properties of thin films of self-assembling amphiphilic porphyrins on a hydrophilic surface as revealed by scanning near-field optical microscopy.

We fabricated porphyrin thin films on mica surfaces from acidic aqueous solutions of the preorganized H-aggregates of amphiphilic porphyrins by the simple spin-coating method. The morphological and spectroscopic properties of the film were investigated by scanning near-field optical microscopy. The results obtained in this study demonstrate that the preorganized structure in solution can be transferred as a thin film with a thickness of the monolayer level without losing their substantial structure and photophysical properties.