Junya Ishioka

Chiral Charge-Density Waves

We discovered the chirality of charge-density waves (CDW) in 1T-TiSe₂ by using STM and time-domain optical polarimetry. We found that the CDW intensity becomes Ia₁∶Ia₂∶Ia₃ = 1∶0.7 ± 0.1∶0.5 ± 0.1, where Ia(i) (i=1,2,3) is the amplitude of the tunneling current contributed by the CDWs. There were two states, in which the three intensity peaks of the CDW decrease clockwise and anticlockwise. The chirality in CDW results in the threefold symmetry breaking. Macroscopically, twofold symmetry was indeed observed in optical measurement. We propose the new generalized CDW chirality H(CDW) ≡ q₁·(q₂×q₃), where q(i) are the CDW q vectors, which is independent of the symmetry of components. The nonzero H(CDW)-the triple-q vectors do not exist in an identical plane in the reciprocal space-should induce a real-space chirality in CDW system.

Tuning Optoelectrical Properties of ZnO Nanorods with Excitonic Defects via Submerged Illumination

When applied in optoelectronic devices, a ZnO semiconductor dominantly absorbs or emits ultraviolet light because of its direct electron transition through a wide energy bandgap. On the contrary, crystal defects and nanostructure morphology are the chief key factors for indirect, interband transitions of ZnO optoelectronic devices in the visible light range. By ultraviolet illumination in ultrapure water, we demonstrate here a conceptually unique approach to tune the shape of ZnO nanorods from tapered to capped-end via apical surface morphology control. We show that oxygen vacancy point defects activated by excitonic effects near the tip-edge of a nanorod serve as an optoelectrical hotspot for the light-driven formation and tunability of the optoelectrical properties. A double increase of electron energy absorption on near band edge energy of ZnO was observed near the tip-edge of the tapered nanorod. The optoelectrical hotspot explanation rivals that of conventional electrostatics, impurity control, and alkaline pH control-associated mechanisms. Thus, it highlights a new perspective to understanding light-driven nanorod formation in pure neutral water.

A pathway of nanocrystallite fabrication by photo-assisted growth in pure water

We report a new production pathway for a variety of metal oxide nanocrystallites via submerged illumination in water: submerged photosynthesis of crystallites (SPSC). Similar to the growth of green plants by photosynthesis, nanocrystallites shaped as nanoflowers and nanorods are hereby shown to grow at the protruded surfaces via illumination in pure, neutral water. The process is photocatalytic, accompanied with hydroxyl radical generation via water splitting; hydrogen gas is generated in some cases, which indicates potential for application in green technologies. Together with the aid of ab initio calculation, it turns out that the nanobumped surface, as well as aqueous ambience and illumination are essential for the SPSC method. Therefore, SPSC is a surfactant-free, low-temperature technique for metal oxide nanocrystallites fabrication.

Superconducting gap and pseudogap structure in LaFeAsO1-xF x probed by STM/STS

We report the electron tunneling study on LaFeAsO 1- x F x ( x =0.07) using low temperature UHV-STM/STS. Tunneling spectra below T c clearly shows the gap structure. We found three anomalies as kinks in the tunneling differential conductance curve: 1) Superconducting gap structure Δ SC =6 meV. 2) Small pseudogap Δ PGS =20 meV. 3) Large pseudogap Δ PGL =100–150 meV. Corresponding value of 2Δ SC / k B T c =5.8 suggests strong coupling superconductivity. Tunneling spectra at T =80 K show dip structure. The kink around V =150 mV still exist.

In situ direct observation of photocorrosion in ZnO crystals in ionic liquid using a laser-equipped high-voltage electron microscope

ZnO photocatalysts in water react with environmental water molecules and corrode under illumination. ZnO nanorods in water can also grow because of water splitting induced by UV irradiation. To investigate their morphological behavior caused by crystal growth and corrosion, here we developed a new laser-equipped high-voltage electron microscope and observed crystal ZnO nanorods immersed in ionic liquid. Exposing the specimen holder to a laser with a wavelength of 325 nm, we observed the photocorrosion in situ at the atomic scale for the first time. This experiment revealed that Zn and O atoms near the interface between the ZnO nanorods and the ionic liquid tended to dissolve into the liquid. The polarity and facet of the nanorods were strongly related to photocorrosion and crystal growth.

Anisotropic surroundings effects on photo absorption of partially embedded Au nanospheroids in silica glass substrate

The influence of a directly adjacent or an anisotropic surrounding medium alters the plasmonic properties of a nanoparticle because it provides a mechanism for symmetry breaking of the scattering. Given the success of ion irradiation induced embedment of rigid metallic nanospheroids into amorphous substrate, it is possible to examine the effect of the silica glass substrate on the plasmonic properties of these embedded nanospheroids. In this work presented here, discrete dipole approximation (DDA) calculations for the Au nanospheroids’ optical properties were performed based on 3–dimensional (3D) configuration extracted from planar SEM micrographs and cross–sectional TEM micrographs of the Au nanospheroids partially embedded in the silica glass, and the well–matched simulations with respect to the experimental measurements could demonstrate the dielectric constant at the near surface of silica glass decreased after Ar–ion irradiation.

Plasmonic surface nanostructuring of Au-dots@SiO2 via laser-irradiation induced dewetting

The in situ observation of Au dot formation and the self-assembly dynamics of Au nanoparticles (NPs) was successfully demonstrated via dewetting of Au thin films on SiO2 glass substrates under nano-second pulsed laser irradiation using a multi-quantum beam high-voltage electron microscope. Moreover, using electron energy-loss spectroscopy (EELS) performed in a scanning transmission electron microscope (STEM), the plasmonic properties of the formed Au/SiO2 nanostructure were analyzed to demonstrate its validity in advanced optical devices. The uniformly distributed Au NPs evolved into a dot alignment through movement and coalescence processes was demonstrated in this in situ observation. We carried out the plasmon-loss images of the plan view and the cross-section of the Au/SiO2 nanostructures were obtained at the plasmon-loss peak energy for investigate the three-dimensional distribution of surface plasmon. Furthermore, discrete-dipole approximation (DDA) calculations were used to simulate the plasmonic properties, such as the surface plasmon resonance and the surface plasmon field distribution, of isolated single Au/SiO2 nanostructures. This STEM-EELS-acquired surface plasmon map of the cross-sectional sample is in excellent agreement with the DDA calculations. This results demonstrated the influence of the contact condition between Au NP and SiO2 glass on the plasmonic properties, and may improve the technology for developing advanced optical devices.

Effects of ion and nanosecond-pulsed laser co-irradiation on the surface nanostructure of Au thin films on SiO2 glass substrates

Ion irradiation and short-pulsed laser irradiation can be used to form nanostructures on the surfaces of substrates. This work investigates the synergistic effects of ion and nanosecond-pulsed laser co-irradiation on surface nanostructuring of Au thin films deposited under vacuum on SiO2 glass substrates. Gold nanoparticles are randomly formed on the surface of the substrate after nanosecond-pulsed laser irradiation under vacuum at a wavelength of 532 nm with a repetition rate of 10 Hz and laser energy density of 0.124 kJ/m2. Gold nanoparticles are also randomly formed on the substrate after 100-keV Ar+ ion irradiation at doses of up to 3.8 × 1015 ions/cm2, and nearly all of these nanoparticles are fully embedded in the substrate. With increasing ion irradiation dose (number of incident laser pulses), the mean diameter of the Au nanoparticles decreases (increases). However, Au nanoparticles are only formed in a periodic surface arrangement after co-irradiation with 6000 laser pulses and 3.8 × 1015 ions/cm...