Mie-Resonant Nanophotonic-Enhancement of Asymmetry in Sodium Chlorate Chiral Crystallization.

Studies on chiral spectroscopy have recently demonstrated strong enhancement of chiral light-matter interaction in the chiral near-field of Mie resonance in high-refractive-index dielectric nanostructures by studies on chiral spectroscopy. This situation has motivated researchers to demonstrate effective chiral photosynthesis under a chiral near-field beyond circularly polarized light (CPL) as a chiral source. However, the effectivity of the chiral near-field of Mie resonance for chiral photosynthesis has not been clearly demonstrated. One major challenge is the experimental difficulty in evaluating enantiomeric excess of a trace amount of chiral products synthesized in the near-field. Here, by adopting sodium chlorate chiral crystallization as a phenomenon that includes both synthesis and the amplification of chiral products, we show that crystallization on a Mie-resonant silicon metasurface excited by CPL yields a statistically significant large crystal enantiomeric excess of ∼18%, which cannot be achieved merely by CPL. This result provides implications for efficient chiral photosynthesis in a chiral near-field.

Chiral Spinodal-like Ordering of Homoimmiscible Water at Interface between Water and Chiral Ice III.

Diversity in structures of water endowed by a hydrogen-bonding network plays crucial roles in wide varieties of phenomena in nature. Chiral ordering of water molecules is an intriguing phenomenon from the viewpoint of bimolecular functions. However, experimental reports on chiral ordering have been limited to the water molecules interacting with biomolecules on the molecular scale. It remains unclear whether pure liquid water forms long-range chiral ordering without any interaction with biomolecules. Here, we show that chiral anisotropy can be observed in the macro/mesoscopic network pattern of an unknown water layer formed via spinodal phase separation-like dynamics at the interface between water and ice III with a chiral crystal structure. We named this unknown water homoimmiscible water. Our observations infer that the unknown water is a chiral liquid crystal. This possibility opens new avenues for a wide variety of research fields such as liquid polymorphism, biology, earth and planetary science, and so forth from the perspective of chirality.

Formation of two-dimensional diamond-like colloidal crystals using layer-by-layer electrostatic self-assembly.

We report here that a two-dimensional (2D) diamond-like structure of micron-sized colloidal particles can be obtained by layer-by-layer self-assembly. Positively and negatively charged silica particles, 1 µm in diameter, were used in the experiments. On a positively charged, flat glass substrate, the first layer of negatively charged particles was prepared to form a non-close-packed 2D crystal. Then the second and third layers were fabricated using electrostatic adsorption. The positions of adsorbed particles were controllable by tuning the zeta-potential of the particles and the salt concentration of the medium. The FDTD calculations show that the 2D diamond structures of particles with higher refractive index (titania) have an absorption band in the wavelength range corresponding to the photonic band gap of the 3D bulk crystal. We expect these findings to be useful for the fabrication of novel photonic materials.

Anisotropy in spinodal-like dynamics of unknown water at ice V-water interface.

Experimentally demonstrating the existence of waters with local structures unlike that of common water is critical for understanding both the origin of the mysterious properties of water and liquid polymorphism in single component liquids. At the interfaces between water and ices Ih, III, and VI grown/melted under pressure, we previously discovered low- and high-density unknown waters, that are immiscible with the surrounding water. Here, we show, by in-situ optical microscopy, that an unknown water appears at the ice V-water interface via spinodal-like dynamics. The dewetting dynamics of the unknown water indicate that its characteristic velocity is ~ 90 m/s. The time evolution of the characteristic length of the spinodal-like undulation suggests that the dynamics may be described by a common model for spinodal decomposition of an immiscible liquid mixture. Spinodal-like dewetting dynamics of the unknown water transiently showed anisotropy, implying the property of a liquid crystal.

Heteroepitaxial Growth of Colloidal Crystals: Dependence of the Growth Mode on the Interparticle Interactions and Lattice Spacing.

Epitaxial growth is one of the most important techniques for the control of crystal growth, especially for growing thin-film semiconductor crystals. Similarly, colloidal epitaxy, a template-assisted self-assembly method, is a powerful technique for controlling the structure of colloidal crystals. In this study, heteroepitaxial growth, which differs from homoepitaxial growth of conventional colloidal epitaxy, using foreign colloidal crystals as a substrate, was used to grow single-component colloidal crystal films. The Frank-van der Merwe (FM), Stranski-Krastanov (SK), and Volmer-Weber (VW) modes were observed, and the mode varied with the lattice-misfit ratio and interparticle interactions between the substrate and epitaxial phase. The transition of the growth mode (from SK to VW) and the coexistence of different growth modes (FM and VW) were observed, and their processes were revealed by in situ observation. Colloidal heteroepitaxy was confirmed to be useful for controlling structure, which will enable exploration of novel colloidal self-assembly structures.

Low- and High-Density Unknown Waters at Ice-Water Interfaces.

Experimental confirmation of liquid polymorphs of water, high-density liquid (HDL) and low-density liquid (LDL), is desired for understanding not only the liquid state of matter but also the origin of the mysterious properties of water. However, this remains challenging because the liquid-liquid critical point of water lies in experimentally inaccessible supercooling conditions known as "no man's land". Here, we show by in situ optical microscopy that droplets and layers of low- and high-density unknown waters (LDUW and HDUW) appear macroscopically depending upon ice polymorphs at non-equilibrium interfaces between water and ices under experimentally accessible (de)pressurization conditions. These unknown waters were found to have characteristic velocities (about 20 and 100 m/s for LDUW and HDUW, respectively) different from water (about 40 m/s) and quasi-liquid layers (QLLs) (about 2 and 0.2 m/s for droplet and layer forms of QLLs, respectively). Our discoveries provide insight on liquid polymorphism of water.

Feasibility of control of particle assembly by dielectrophoresis in liquid-cell transmission electron microscopy.

Liquid-cell transmission electron microscopy (LC-TEM) is a useful technique for observing phenomena in liquid samples with spatial and temporal resolutions similar to those of conventional transmission electron microscopy (TEM). This method is therefore expected to permit the visualization of phenomena previously inaccessible to conventional optical microscopy. However, dynamic processes such as nucleation are difficult to observe by this method because of difficulties in controlling the condition of the sample liquid in the observation area. To approach this problem, we focused on dielectrophoresis, in which electrodes are used to assemble particles, and we investigated the phenomena that occurred when an alternating-current signal was applied to an electrode in an existing liquid cell by using a phase-contrast optical microscope (PCM) and TEM. In PCM, we observed that colloidal particles in a solution were attracted to the electrodes to form assemblies, that the particles aligned along the electric field to form pearl chains and that the pearl chains accumulated to form colloidal crystals. However, these phenomena were not observed in the TEM study because of differences in the design of the relevant holders. The results of our study imply that the particle assembly by using dielectrophoretic forces in LC-TEM should be possible, but further studies, including electric device development, will be required to realize this in practice.

Heteroepitaxial fabrication of binary colloidal crystals by a balance of interparticle interaction and lattice spacing.

HYPOTHESIS: The colloidal epitaxy utilizing a patterned substrate is used to fabricate colloidal crystals of the same structure and lattice spacing with the substrate, which is an effective technique for creating desired nanoscale architectures. However, this technique has been mainly limited to a single-component system. The colloidal epitaxy is versatile if multicomponent colloidal crystals can be produced, which is inspired by our previous study regarding binary colloidal crystals (b-CCs) fabricated at the edge of single-component crystals. EXPERIMENTS: We have examined various particle size combinations of binary colloidal mixture and substrates for heteroepitaxial growth of b-CCs. Colloidal crystallization was achieved through depletion attraction induced by added polymers. FINDINGS: We demonstrated heteroepitaxial growth of b-CCs on the foreign colloidal crystals as the substrate. Under depletion attraction, deviation from equilibrium interparticle distance because of lattice mismatch between the substrate and epitaxial layers induces strain energy among the particles, yielding the b-CCs to attain minimum strain energy. Various types of b-CCs are created by adjusting the particle size ratio and polymer concentration. The heteroepitaxial growth technique enables the fabrication of complex multicomponent colloidal crystals that greatly facilitate versatile applications of the colloidal crystals.

High-Density Liquid Water at a Water-Ice Interface.

Because ice surfaces catalyze various key chemical reactions impacting nature and human life, the structure and dynamics of interfacial layers between water vapor and ice have been extensively debated with attention to the quasi-liquid layer. Other interfaces between liquid water and ice remain relatively underexplored, despite their importance and abundance on the Earth and icy extraterrestrial bodies. By in situ optical microscopy, we found that a high-density liquid layer, distinguishable from bulk water, formed at the interface between water and high-pressure ice III or VI, when they were grown or melted in a sapphire anvil cell. The liquid layer showed a bicontinuous pattern, indicating that immiscible waters with distinct structures were separated on the interfaces in a similar manner to liquid-liquid phase separation through spinodal decomposition. Our observations not only provide a novel opportunity to explore ice surfaces but also give insight into the two kinds of structured water.

Plasmonic Manipulation-Controlled Chiral Crystallization of Sodium Chlorate.

Plasmonic manipulation using well-designed triangular trimeric gold nanostructures achieves a giant (greater than 50%) crystal enantiomeric excess (CEE) of sodium chlorate (NaClO3). Stronger asymmetric interactions between molecule and light are pursued to reach high enantiomeric excess. The well-designed gold nanostructures immersed in a saturated NaClO3 D2O solution were irradiated with linear, left-hand, and right-hand circular polarizations of a 1064 nm continuous-wave laser. Within seconds of the start of the irradiation, an achiral metastable crystal was formed at the laser focus, and further irradiation induced a subsequent polymorphic transition to the chiral crystal. The crystal chirality is sensitive to the handedness of circular polarization, allowing for efficient enantioselectivity. The mechanisms to achieve this giant CEE are proposed based on the results of electromagnetic field analysis generated near the nanostructure by the finite element method.

Effects of Solution Flow on the Growth of Colloidal Crystals.

For the versatile potential applications of colloidal crystals, precisely controlling their growth is required to achieve properties such as high crystallinity and large-area crystals. Because colloidal crystallization is a self-assembly process of dispersed particles in a solution, solution flow directly and markedly changes the behavior of particles. Thus, the effects of solution flow on the growth of colloidal crystals were investigated in the present study. We found three different effects of solution flow on the growth of colloidal crystals: enlarging the first layer, facilitating the growth of superlattice structures, and forming a new circular packing structure. Specifically, in the single-component system, because the flow speed is lower closer to the bottom of the cell, the second and further layers dissolve owing to the large flow speed, whereas the first layer remains undissolved at the appropriate flow speed. The dissolved particles (particles that are detached from the crystals and returned back into the aqueous medium) are transported near the first layer, where they facilitate the growth of the first layer. In a binary system, when colloidal crystals with different particles are neighboring each other, the flow dissolves the surface of each crystal, which forms a dense, melt-like phase between crystals, from which a superlattice structure such as AB2 grows. The flow often moves the second layer more than the first layer because the flow speed varies with the distance from the bottom. This causes the second layer to slide above the first layer of the neighboring crystals composed of different particle sizes, which transform from the initial face-centered cubic structure of the first layer into a circular pattern with strain. These findings contribute to establishing a sophisticated control method for growing colloidal crystals.

Generation of high-quality terahertz OAM mode based on soft-aperture difference frequency generation.

We demonstrate the generation of high-quality tunable terahertz (THz) vortices in an eigenmode by employing soft-aperture difference frequency generation of vortex and Gaussian modes. The generated THz vortex output exhibits a high-quality orbital angular momentum (OAM) mode with a topological charge of ℓTHz = ±1 in a frequency range of 2-6 THz. The maximum average power of the THz vortex output obtained was ∼3.3 µW at 4 THz.

Highly intense monocycle terahertz vortex generation by utilizing a Tsurupica spiral phase plate.

Optical vortex, possessing an annular intensity profile and an orbital angular momentum (characterized by an integer termed a topological charge) associated with a helical wavefront, has attracted great attention for diverse applications due to its unique properties. In particular for terahertz (THz) frequency range, several approaches for THz vortex generation, including molded phase plates consisting of metal slit antennas, achromatic polarization elements and binary-diffractive optical elements, have been recently proposed, however, they are typically designed for a specific frequency. Here, we demonstrate highly intense broadband monocycle vortex generation near 0.6 THz by utilizing a polymeric Tsurupica spiral phase plate in combination with tilted-pulse-front optical rectification in a prism-cut LiNbO3 crystal. A maximum peak power of 2.3 MW was obtained for THz vortex output with an expected topological charge of 1.15. Furthermore, we applied the highly intense THz vortex beam for studying unique nonlinear behaviors in bilayer graphene towards the development of nonlinear super-resolution THz microscopy and imaging system.

In situ live observation of nucleation and dissolution of sodium chlorate nanoparticles by transmission electron microscopy.

The formation of crystals from solution requires the initial self-assembly of units of matter into stable periodic structures reaching a critical size. The early stages of this process , called nucleation, are very difficult to visualize. Here we describe a novel method that allows real time observation of the dynamics of nucleation and dissolution of sodium chlorate clusters in an ionic liquid solution using in situ transmission electron microscopy. Using ionic liquids as solvent circumvents the problem of evaporation and charging, while the nucleation frequency was reduced by using saturated solutions. We observe simultaneous formation and dissolution of prenucleation clusters, suggesting that high-density fluctuations leading to solid cluster formation exist even under equilibrium conditions. In situ electron diffraction patterns reveal the simultaneous formation of crystalline nuclei of two polymorphic structures, the stable cubic phase and the metastable monoclinic phase, during the earliest stages of nucleation. These results demonstrate that molecules in solution can form clusters of different polymorphic phases independently of their respective solubility.