横田 幸恵

We designed and fabricated gold curvilinear nanorod periodical arrays using microfabrication techniques. The gold curvilinear nanorods had two distinct resonant peaks in the near-infrared region between 1630 nm and 3000 nm. Similar peak was observed in gold straight nanorods at specific lengths. At lengths identical to the arc length of the curvilinear nanorod, the peak was in the relative range of 3000 nm, which corresponds to the longitudinal plasmon mode (L-mode). At lengths identical to half of the arc length of the curvilinear nanorod, the peak was close to 1630 nm. Plasmon resonant peaks were tunable in the infrared region by changing the arc length of the curve, the line width, and distance between the curvilinear nanorods. In particular, when two curvilinear nanorods were closely packed in a range of less than 100 nm, the peak wavelength of curvilinear nanorod was shifted due to the plasmonic coupling of each mode.

Size, shape, and density-controlled metal nanostructure, Au nanodot lattices fabricated by electron beam lithography, were embedded in thin organic solar cell consisting of PC71BM: PCPDTBT. The effects of their size and density on device performance were examined. Even though dipole resonances of Au nanodots were consistent with the absorption range of the active materials, there were no improvements in device performance under any sizes and densities. In addition, under high volume density of Au nanodots to PEDOT: PSS layer, the device performance was deteriorated. These results indicated that not only size and density but also other factors which determine light scattering characteristics greatly affect the device performance of solar cells. (C) 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

We have designed a series of hydroxy(aryl)-(3)-iodane-[18]crown-6 complexes, prepared from the corresponding iodosylbenzene derivatives and superacids in the presence of [18]crown-6, and have investigated their reactivities in aqueous media. These activated iodosylbenzene monomers are all non-hygroscopic shelf-storable reagents, but they maintain high oxidizing ability in water. The complexes are effective for the oxidation of phenols, sulfides, olefins, silyl enol ethers, and alkyl(trifluoro)borates under mild conditions. Furthermore, hydroxy-(3)-iodane-[18]crown-6 complexes serve as efficient progenitors for the synthesis of diaryl-, vinyl-, and alkynyl-(3)-iodanes in water. Other less polar organic solvents, such as methanol, acetonitrile, and dichloromethane, are also usable in some cases.

Gold-bowtie nanostructures are fabricated by electron beam lithography and lift-off techniques. Their optical properties are investigated by both experimental studies and numerical simulations. The influence of sharpness and gap of nano-bowtie on optical properties such as extinction cross section, local electric field intensity, and surface resonance wavelength is explored. The experimental extinction spectra agree well with the simulation results. This investigation may help us to design plasmonic sub-wavelength gold-bowtie nanostructure with desired spectral properties. © 2013 Elsevier B.V.

We performed a quantitative analysis of plasmon-assisted two-photon photochromic reactions on light-harvesting gold nanodimer structures. Our strategy for the quantitative analysis of two-photon-induced photochemical reactions on gold nanostructures is using not only a confined photochemical reaction chamber but also a solution system. The strong intensification of near-field light at the nanogap positions on gold nanodimer pairs promoted two-photon absorption by a closed-form diarylethene derivative, resulting in highly efficient photochromic conversion to the open-form structure.

Ag/Au bimetallic nanoparticles possess the combinatory advantages of Au and Ag nanoparticles and can also be utilized to tune the properties of localized surface plasmon resonance. Ag/Au bilayer nanorods were prepared by electron beam lithography, and their spectral properties were investigated. Compared with Ag monolayer nanorods, Ag/Au bilayer nanorods show broader localized surface plasmon resonance bands, and the longitudinal mode and transverse mode localized surface plasmon bands show blueshift and redshift, respectively. The maximum near-field intensity of the longitudinal mode of the Ag/Au nanorod is less than half that of the Ag/Au nanorod without gold layer. Shape-induced modification of Ag/Au bilayer nanorods on their spectral properties was also discussed. (C) 2011 Optical Society of America

Metallic bowtie nanostructures as plasmonic nanoantennas can create highly enhanced local fields when resonating with the incident light. With Au bowtie nanostructures fabricated by lithography method, we experimentally observed that the photoluminescence (PL) spatial profile from a single Au bowtie nanoantenna was strongly dependent on the excitation light polarization. While varying the incident light polarization, the spatial distribution of the PL intensity in the nanogap of an Au bowtie changed as predicted by the simulation results on the electromagnetic field enhancement distribution. The polarization feature of the PL intensity relative to the polarization direction of incident excitation light was also discussed. The study may find application in the design of polarization sensitive plasmonic sensors. (C) 2011 Elsevier B.V. All rights reserved.

Plasmonic spectral properties of silver nanoblocks fabricated by electron beam lithography are investigated. The extinction spectra of silver nanoblocks showed a red shift, broadening, and damping with the passage of storage time. In contrast, silver nanoblocks with titanium coating on the top did not show apparent spectral change even after storage for two months. Morphological change of the silver nanoblocks was characterized by scanning electron microscope. The present work clearly demonstrates that coating titanium on the top of the silver nanostructures is an effective way to prevent them from chemical corrosion and stabilize their plasmonic spectral properties.

Photochemically induced protein crystallization byprotein's multiphoton excitation based on enhanced field of localized surface plasmon resonance (LSPR) of gold nanostructures was investigated. As strong photons-molecules coupling fields, gold nanostructures composed of nanoblocks and gold nanocolloid were used. With gold nanostructures, we could observe enzyme activity decrease by light irradiation that protein does not absorb. Surface observation of gold nanostructure by DFM (non-contact dynamic force microscope) shows that proteins were aggregated at around the nanoblock due to photochemical reaction by enhanced field. Crystallization probability depends on the excitation photon fluence, which indicates 3 photons absorption process occurred. (C) 2011 Elsevier B.V. All rights reserved.

The instability of silver nanoblocks under atmospheric conditions is investigated. The localized surface plasmon resonance band of the silver nanoblocks shows a red shift, broadening, and damping with increasing storage time under atmospheric conditions. The change in spectral properties of silver nanoblocks is considered to be due to sulfidation of silver and structural breakage of silver nanoblock based on scanning electron microscope observation and numerical simulation. The effect of aspect ratio of silver nanoblocks on the change in spectral properties of the nanoengineered silver blocks is also discussed. (C) 2011 Optical Society of America

We perform direct local-field imaging of a plasmon-resonant gold nanoparticle pair separated by a gap of several nanometers using a scattering-type near-field optical microscope with a sharp silicon tip of atomic force microscope. The sharp tip allows the access for the nanogap and the high spatial resolution. Our results provide experimental evidence that the nanogap structure produces an optical spot with the size of a single nanometer (< 10 nm). This is not only of fundamental importance in the field of nanophotonics, but also provide significant information for the development of plasmonic devices with the nanogap structures. (C) 2011 Optical Society of America

Well defined gold nanostructures of various sizes are fabricated on glass substrates using high-resolution electron-beam lithography/lift-off techniques and detailed surface-enhanced Raman scattering (SERS) properties of crystal violet molecules are studied in order to elucidate electromagnetic (EM) field enhancement effects on the fabricated structures. SERS measurements are performed with high reproducibility using in situ Raman microspectroscopy in aqueous solution. An analysis based on EM theory is performed using field-enhancement factors obtained from finite-difference time-domain (FDTD) simulations and the analysis reproduces experimental results very well. It is noteworthy, furthermore, that the proposed analytic method of EM effects on SERS allows the estimate of the ideal local temperature of gold nanostructures by canceling out the difference in EM field factors at Stokes and anti-Stokes Raman scattering wavelengths. Thus, these experimental results demonstrate that quantitative analysis based on EM theory can be obtained using highly controlled gold nanostructures for SERS measurements with high reproducibility, a result that is promising for the construction of a SERS analysis chip. Although no SERS chip reported so far has been usable for quantitative analysis, this study opens the door for construction of a quantitative SERS chip.

We have demonstrated the essential nanogap effects on surface-enhanced Raman scattering (SERS) signals obtained from two diagonally aligned gold nanoparticles with several nanometre separations, which were precisely fabricated on a glass substrate. This is the first proof of principle for extracting the light localization effects on SERS due to the formation of nanogaps from experimentally observed SERS signals.

The polarization dependence of excitation light for fluorescence enhancement of near-infrared dyes immobilized in hydrophobic DNA thin film on glass substrates with regularly arranged Au nanoblocks was investigated. The enhancement factor for S-polarized excitation was about 1.2 to 1.5 times as large as that for P-polarized excitation. P-polarized light contributed to the excitation of plasmon band both of horizontal and vertical direction of Au nanoblocks. The vertical direction corresponds to the short axis for height direction which has the absorption in visible region did not contribute the excitation of IR780. When the absorption band of Au array and the fluorescence band of IR780 were overlapped, the fluorescence enhancement did not depend on the polarization of excitation light. It is suggested that the fluorescence quenching originates from the energy transfer from the excited state of IR780 to Au nanoblocks or the increased deactivation of excited dye molecules induced by resonance with Au nanoblocks.

Fluorescence intensity of near Infrared dyes immobilized in hydrophobic DNA thin film spin-coated on glass substrates with regularly arranged gold (Au) nanoblocks was about 2 5 times larger than that without Au nanoblocks, strongly suggesting the fluorescence intensity was enhanced by increased electric field intensity of excitation light due to local plasmon resonance of Au nanoblocks

Nanoparticles of noble metals exhibit localized surface plasmons (LSPs) associated with the enhancement of an electromagnetic field due to its localization in nanometric domains at the surface of nanoparticles. We demonstrate the plasmonic photoelectric conversion from visible to near-infrared wavelength without deteriorating photoelectric conversion by using electrodes in which gold nanorods are elaborately arrayed on the surface of a TiO2 single crystal.

Nanopatterns of a TiO2-organic hybrid material have been fabricated with the use of a localized surface plasmon (LSP). The TiO2-organic hybrid material was prepared by the sol-gel method and was coated on a glass substrate with gold nanoblocks. After the hybrid films were irradiated with a femtosecond laser, the unreacted parts were removed, leaving the TiO2-organic hybrid materials around the nanoblocks. In the nanopatterns of the TiO2-organic hybrid materials, the pi - pi* transition absorption band of the chelate compound formed between Ti-alkoxide and beta-diketone was excited by the two-photon absorption induced by the LSP of gold nanoblocks, and the chelate compound was decomposed and dissolved in alcohol. It was confirmed that the hybrid material changed to anatase upon sintering above 450 degrees C.

Photoinduced shape changes of metal nanostructures in halide solutions were investigated using gold and silver nanoblocks (NBs) patterned on a glass substrate, instead of nanoparticles dispersed in solution. It was found that size reduction of the NBs by halide etching was enhanced by photoirradiation. Furthermore, it was revealed that the halide etching efficiency corresponded to the intensity of the electric field induced by localized surface plasmon resonance (LSPR) of the NBs. The enhancement of halide etching by LSPR was explained on the basis of electron transfer reactions from metal NBs. Throughout this study, it was demonstrated that metal NBs fabricated on a substrate constitute a powerful system to investigate photoinduced shape changes of nanostructures, because of their defined shape, position, and configuration. (C) 2010 Elsevier B.V. All rights reserved.

Nanoparticles of noble metals exhibit localized surface plasmons (LSP) associated with enhancement of the electromagnetic field due to its localization in nanometric domains at the surface of nanoparticles. Especially, nanogapmetallic structures show strong enhancement of the electromagnetic field at the nanogap position. This can be achieved up to 10(5) times larger than the incident light field. We have explored the possibility to use the localized field for nanogap-assisted surface plasmon nanolithography. For the purpose, monidisperse arrays consisting of pairs of rectangular gold nanoblocks separated by nanogaps were fabricated on glass substrates using electron beam lithography and lift-off techniques. Nanoblock structures were used as photomasks for contact exposure of thinfilms of positive photoresist on glass substrates. Thus, ordered clusters of nanoparticles separated by nanogaps can provide a stable and versatile platform for further development of optical subwavelength nanolithography. To the best of our knowledge, this is the first proof-of-principle demonstration of such a technique.

Interdigitated array electrodes with surface-enhanced Raman scattering (SERS) functionality for in situ qualitative and quantitative analysis of electroactive species are demonstrated. Gold nanostructured interdigitated array electrodes (NIDAEs) were fabricated by electron beam lithography, and used for an electrochemical SERS study of K(3)[Fe(CN(6))] in aqueous KClO(4) solution in single and generation-collection modes. The generation-collection mode experiment showed amplification of the SERS band intensity for adsorbed ferricyanide ions at the negative end of the applied potential, while in single mode it was reduced to near zero. This new finding reveals that NIDAEs offer a new opportunity for analytical science by improving analytical sensitivity and detection ability of electroactive species. The electric fields accumulating at nanogaps are promising for manipulating linear and nonlinear optical phenomena. In addition, miniaturized NIDAEs are of great importance for developing lab-on-a-chip devices, and are useful for measurements within small space/volume domains, requiring only small amounts and/or concentrations of analytes.

This work describes fabrication of three-dimensionally nano-textured silicon surface structures metalized by thin gold films,and their application for optical sensing and detection of solute molecules utilizing surface-enhanced Raman scattering (SERS) effect. Two types of sensitive surfaces were prepared by different techniques. The first of them was a checkerboard pattern of 3D nanoblocks defined in compact areas on the surface of a silicon wafer using highly accurate electron-beam lithography (EBL) technique, and fabricated by dry reactive-ion etching (RIE) technique with subsequent metalization of the surface by gold sputtering. The second type of sensitive surface consisted of a square array of nano-apertures. defined on a large area of the silicon surface by a less accurate but simpler ultraviolet holographic lithography, and subsequently fabricated in a sequence of dry and wet etching as well as gold sputtering steps. The fabricated structures were found to exhibit significant near-field enhancement, as evidenced by strong SERS signal from the sensors immersed in aqueous pyridine solutions with concentrations as low as 10(-9) M due to the presence of well-defined 3D periodic texture of the structure. (C) 2008 Elsevier BY. All rights reserved.

Photopolymerization of commercial photoresist SU-8 assisted by plasmonic near-field enhancement in nanogaps separating gold nanoblocks was investigated. Photopolymerization rates enhanced by orders of magnitude were found in gold nanoblock structures with nanogaps narrower than 10 nm. The mechanisms responsible for local and nonlocal nonlinear photopolymerization of SU-8 are discussed.

We investigate functional capabilities of large arrays of gold and silver nanorods as elements of plasmonic devices. The samples were fabricated by electron beam lithography and lift-off techniques on glass substrates. The areas patterned by the nanorods or other nanoparticles can be large, with dimensions of up to about one centimeter. Structural and optical characterization has allowed confirmation of a high homogeneity of the fabricated ensembles of nanorods, and a high sensitivity of their longitudinal extinction bands to the variations of the nanorod length and the refractive index of the environment. Applications of nanorods as refractive-index sensors is discussed.

We demonstrate the possibility to achieve optical triggering of photochemical reactions via two-photon absorption using incoherent light sources. This is accomplished by the use of arrays of gold nanoparticles, specially tailored with high precision to obtain high near-field intensity enhancement.

Highly homogeneous arrays of Ag, Au and Cu nanorods were fabricated on glass substrates using electron-beam lithography and lift-off techniques. Optical properties of the fabricated structures related to localized surface plasmons (LSP), and their dependencies on the nanorod size were studied experimentally by optical extinction spectroscopy. Spectral tuning of LSP resonant scattering bands in a wide spectral range, from visible to near-infrared wavelengths, can be accomplished by tailoring of the nanorod dimensions, aspect ratios, and heights. The observed results qualitatively agree with Gans theory and numerical modeling by finite-difference time-domain technique.