Yukihiro Tominari

Vibration Modes at Terahertz and Infrared Frequencies of Ionic Liquids Consisting of an Imidazolium Cation and a Halogen Anion

The terahertz and infrared frequency vibration modes of room-temperature ionic liquids with imidazolium cations and halogen anions were extensively investigated. There is an intermolecular vibrational mode between the imidazolium ring of an imidazolium cation, a halogen atomic anion with a large absorption coefficient and a broad bandwidth in the low THz frequency region (13–130 cm−1), the intramolecular vibrational modes of the alkyl-chain part of an imidazolium cation with a relatively small absorption coefficient in the mid THz frequency region (130–500 cm−1), the intramolecular skeletal vibrational modes of an imidazolium ring affected by the interaction between the imidazolium ring, and a halogen anion with a relatively large absorption coefficient in a high THz frequency region (500–670 cm−1). Interesting spectroscopic features on the interaction between imidazolium cations and halogen anions was also obtained from spectroscopic studies at IR frequencies (550–3300 cm−1). As far as the frequency of the intermolecular vibrational mode is concerned, we found the significance of the reduced mass in determining the intermolecular vibration frequency.

Terahertz and Infrared Spectroscopy of Room-Temperature Imidazolium-Based Ionic Liquids

The terahertz- and infrared-frequency vibrational modes of various room-temperature imidazolium-based ionic liquids with molecular anions were examined extensively. We found that the molar-concentration-normalized absorption coefficient spectra in the low-wavenumber range for imidazolium cations with different alkyl-chain lengths were nearly identical for the same anion. Regarding the overall view of a wide range of imidazolium-based ionic liquids, we found that the reduced mass of the combination of an imidazolium-ring cation and the anion and the force constant play significant roles in determining the central frequency of the broad absorption band. In addition to these findings, we also discuss the correlation between the (+)C-H stretching vibrational modes in the 3000-3300 cm(-1) range of the infrared spectra and the intermolecular vibrational band in the low-wavenumber range. Finally, we describe some interesting characteristics of the intermolecular vibrational band observed in a wide range of imidazolium-based ionic liquids.

Bacteriorhodopsin-based bipolar photosensor for biomimetic sensing

Bacteriorhodopsin (bR) is a promising biomaterial for several applications. Optical excitation of bR at an electrode-electrolyte interface generates differential photocurrents while an incident light is turned on and off. This unique functional response is similar to that seen in retinal neurons. The bR-based bipolar photosensor consists of the bR dip-coated thin films patterned on two ITO plates and the electrolyte solution. This bipolar photocell will function as a biomimetic photoreceptor cell. The bipolar structure, due to the photocurrent being generated in alignment with the cathodic direction, makes the excitatory and inhibitory regions possible. This scheme shows our bipolar cell can act as a basic unit of edge detection and forms the artificial visual receptive field.

Duality picture of Superconductor-insulator transitions on Superconducting nanowire

In this study, we investigated the electrical transport properties of niobium titanium nitride (NbTiN) nanowire with four-terminal geometries to clarify the superconducting phase slip phenomena and superconducting-insulator transitions (SIT) for one-dimensional superconductors. We fabricated various nanowires with different widths and lengths from epitaxial NbTiN films using the electron beam lithography method. The temperature dependence of resistance R(T) below the superconducting transition temperature Tc was analyzed using thermal activation phase slip (TAPS) and quantum phase slip (QPS) theories. Although the accuracy of experimental data at low temperatures can deviate when using the TAPS model, the QPS model thoroughly represents the R(T) characteristic with resistive tail at low temperatures. From the analyses of data on Tc, we found that NbTiN nanowires exhibit SIT because of the change in the ratio of kinetic inductance energy and QPS amplitude energy with respect to the flux-charge duality theory.

Infrared Spectroscopy of Ionic Liquids Consisting of Imidazolium Cations with Different Alkyl Chain Lengths and Various Halogen or Molecular Anions with and without a Small Amount of Water

Infrared spectroscopy was performed on ionic liquids (ILs) that had imidazolium cations with different alkyl chain lengths and various halogen or molecular anions with and without a small amount of water. The molar concentration normalized absorbance due to +C-H vibrational modes in the range of 3000 to 3200 cm-1 was nearly identical for ILs that had imidazolium cations with different alkyl chain lengths and the same anions. A close correlation was found between the red-shifted +C-H vibrational modes, the chemical shift of +C(2)-H proton, and the energy stabilization of the hydrogen-bonding interaction. The vibrational modes of the water molecules interacting with anions in the range between 3300 and 3800 cm-1 was examined. The correlation between the vibrational frequencies of water, the frequencies of +C-H vibrational modes, and the center frequency of intermolecular vibrational modes due to ion pairs was discussed.

Terahertz time domain and far-infrared spectroscopies of side-chain electro-optic polymers

We investigated the dielectric properties of side-chain electro-optic polymers in a broad THz frequency region (90 GHz to 7 THz). For this investigation, we used terahertz time domain spectroscopy and the absorption coefficient in a broader frequency region of up to 20 THz that was obtained by far-infrared spectroscopy. The polymers studied were a new methacrylate polymer with a high-hyperpolarizability chromophore as the sidechain, a side-chain copolymer Disperse Red 1 polymethylmethacrylate, and pure polymethylmethacrylate. The dielectric properties in the low THz frequency region (~0.1 THz) provide us with important information about the intrinsic refractive index for ultrahigh-speed electro-optic modulation (~100 GHz), as well as versatile information such as the absorption coefficient and dielectric loss. The THz and far-infrared spectroscopic data in the wide frequency region provide us with the fundamental data for applications of side-chain electro-optic polymers within THz generation and detection.

Optical Properties of Low-Loss Ag Films and Nanostructures on Transparent Substrates

We demonstrate the fabrication of a low-loss single-crystalline Ag nanostructure deposited on transparent substrates. Our approach is based on an epitaxial growth technique in which a NaCl(001) substrate is used. The NaCl substrate is dissolved in water to allow the Ag film to be transferred onto the desired substrates. Focused ion beam milling is subsequently employed to pattern a nanoarray structure consisting of 200 nanorods. The epitaxial Ag films with nanoarray structures grown in the study exhibited very flat and smooth surfaces having excellent crystallinity and local misorientation of less than 1°. Further, spectroscopic ellipsometry measurements indicated that the imaginary part of the dielectric constant of the single-crystalline film was smaller than that of a conventional polycrystalline film. Moreover, we used the three-dimensional finite-difference time-domain method to analyze the plasmonic properties of the nanoarray structure by considering the actual processed structure. Characteristically, when the SiO2 substrate was etched by ion beam milling to a depth of 30 nm, the spectrum showed a spectral shape 20% sharper than that of the substrate with no etching (depth: 0 nm). The plasmonic performance of the single-crystalline Ag nanostructure was largely determined by its structural precision and the dielectric properties of the metal.