Circular dichroism of pseudo-two-dimensional metal nanostructures: Rotational symmetry and reciprocity.

Circular dichroism (CD) spectra for pseudo-two-dimensional chiral nanomaterials were systematically investigated and analyzed in relation to the rotational symmetry of the nanomaterials. Theoretically, an ideal two-dimensional chiral matter is CD inactive for light incident normal to the plane if it possesses threefold or higher rotational symmetry. If the matter has two- or onefold rotational symmetry, it should exhibit CD activity, and the CD signal measured from the back side of the matter is expected to be inverted from that measured from the front side. For pseudo-two-dimensional chiral gold nanostructures fabricated on glass substrates using electron beam lithography, matter with fourfold rotational symmetry is found to be CD active, even when special care is taken to ensure that the optical environments for the front and back sides of the sample are equivalent. In this case, the CD signal measured from the back side is found to be almost exactly the same as that measured from the front side. It is revealed that the observed chiro-optical behavior arises from three-dimensional chiral characteristics due to differences in the surface shape between the front and back sides of the structures. For matter that is two- or onefold rotationally symmetric, the CD signal measured from the back side is not coincident with that from the front side. For certain wavelength regions, the CD signals measured from the front side and back side are observed to be similar, while at other wavelengths, the inverted component of the CD signals is found to dominate. The observed CD spectral behavior for reciprocal optical measurement configurations is considered to be determined by a balance between the in-plane isotropic and anisotropic components of the chiral permittivity.

Directional Supramolecular Polymerization in a Dynamic Microsolution: A Linearly Moving Polymer's End Striking Monomers.

Although directional chain reactions are common in nature's self-assembly processes and in covalent polymerizations, it has been challenging to perform such processes in artificial one-dimensional self-assembling systems. In this paper, we describe a system, employing perylene bisimide (PBI) derivatives as monomers, for selectively activating one end of a supramolecular polymer during its growth and, thereby, realizing directional supramolecular polymerization. Upon introduction of a solution containing only a single PBI monomer into the microflow channel, nucleation was induced spontaneously. The dependency of the aggregation efficiency on the flow rate suggested that the shear force facilitated collisions among the monomers to overcome the activation energy required for nucleation. Next, by introducing a solution containing both monomer and polymer, we investigated how the shear force influenced the monomer-polymer interactions. In situ fluorescence spectra and linear dichroism revealed that growth of the polymers was accelerated only when they were oriented under the influence of shear stress. Upon linear motion of the oriented polymer, polymer growth at that single end became predominant relative to the nucleation of freely diffusing monomers. When applying this strategy to a two-monomer system, the second (less active) monomer reacted selectively at the forward-facing terminus of the first polymer, leading to the creation of a diblock copolymer through formation of a molecular heterojunction. This strategy-friction-induced activation of a single end of a polymer-should be applicable more generally to directional supramolecular block copolymerizations of various functional molecules, allowing molecular heterojunctions to be made at desired positions in a polymer.

Supramolecular Chirality Synchronization in Thin Films of Plasmonic Nanocomposites.

Mirror symmetry breaking in materials is a fascinating phenomenon that has practical implications for various optoelectronic technologies. Chiral plasmonic materials are particularly appealing due to their strong and specific interactions with light. In this work we broaden the portfolio of available strategies toward the preparation of chiral plasmonic assemblies, by applying the principles of chirality synchronization-a phenomenon known for small molecules, which results in the formation of chiral domains from transiently chiral molecules. We report the controlled cocrystallization of 23 nm gold nanoparticles and liquid crystal molecules yielding domains made of highly ordered, helical nanofibers, preferentially twisted to the right or to the left within each domain. We confirmed that such micrometer sized domains exhibit strong, far-field circular dichroism (CD) signals, even though the bulk material is racemic. We further highlight the potential of the proposed approach to realize chiral plasmonic thin films by using a mechanical chirality discrimination method. Toward this end, we developed a rapid CD imaging technique based on the use of polarized light optical microscopy (POM), which enabled probing the CD signal with micrometer-scale resolution, despite of linear dichroism and birefringence in the sample. The developed methodology allows us to extend intrinsically local effects of chiral synchronization to the macroscopic scale, thereby broadening the available tools for chirality manipulation in chiral plasmonic systems.

Synthesis of Chiral Labtb and Visualization of Its Enantiomeric Excess by Induced Circular Dichroism Imaging.

Crystalline particles of a microporous, robust, and chiral metal-organic framework (MOF) were synthesized and their enantiomer excess (ee) was visualized for each microparticle by CD imaging. Labtb, a thermally and chemically robust MOF, was employed in this study because it shows a chiral space group. Although Labtb has been obtained as a racemic conglomerate, enantioselective synthesis of Labtb was achieved via a chiral precursor complex consisting of lanthanum and homochiral phenylalanine. Methyl orange (MO) was introduced into the micropores of chiral Labtb, which showed a strong induced CD signal for the absorption band of MO chromophores. High ee of the chiral Labtb was revealed by microscopic CD observation at the particle-level. This result provides a facile way to obtain a robust MOF that has chiral nanospace.

Circular Dichroism Microscopy Free from Commingling Linear Dichroism via Discretely Modulated Circular Polarization.

In this work, we developed a circular dichroism (CD) imaging microscope with a device to suppress the commingling of linear birefringence (LB) and linear dichroism (LD) signals. CD signals are, in principle, free from the commingling influence of LD and LB if the sample is illuminated with pure circularly polarized light, with no linear polarization contribution. Based on this idea, we here propose a novel circular polarization modulation method to suppress the contribution of linear polarization, which enables high-sensitivity CD detection (10-4 level in optical density unit or mdeg level in ellipticity) for microscopic imaging at a nearly diffraction limited spatial resolution (sub-µm level). The highly sensitive, diffraction-limited local CD detection will make direct analyses of chiral structures and spatial mappings of optical activity feasible for µm- to sub-µm-sized materials and may yield a number of applications as a unique optical imaging method.

Optical Activity Governed by Local Chiral Structures in Two-Dimensional Curved Metallic Nanostructures.

Chiral nanostructures show macroscopic optical activity. Local optical activity and its handedness are not uniform in the nanostructure, and are spatially distributed depending on the shape of the nanostructure. In this study we fabricated curved chain nanostructures made of gold by connecting linearly two or more arc structures in a two-dimensional plane. Spatial features of local optical activity in the chain structures were evaluated with near-field circular dichroism (CD) imaging, and analyzed with the aid of classical electromagnetic simulation. The electromagnetic simulation predicted that local optical activity appears at inflection points where arc structures are connected. The handedness of the local optical activity was dependent on the handedness of the local chirality at the inflection point. Chiral chain structures have odd inflection points and the local optical activity distributed symmetrically with respect to structural centers. In contrast, achiral chain structures have even inflection points and showed antisymmetric distribution. In the near-field CD images of fabricated chain nanostructures, the symmetric and antisymmetric distributions of local CD were observed for chiral and achiral chain structures, respectively, consistent with the simulated results. The handedness of the local optical activity was found to be determined by the handedness of the inflection point, for the fabricated chain structures having two or more inflection points. The local optical activity was thus governed primarily by the local chirality of the inflection points for the gold chain structures. The total effect of all the inflection points in the chain structure is considered to be a predominant factor that determines the macroscopic optical activity. Chirality 28:540-544, 2016. © 2016 Wiley Periodicals, Inc.

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.

Stress inversion from initial tensile to compressive side during ultrathin oxide growth of the Si(100) surface.

We report the real-time observation of the stress change during sub-nanometer oxide growth on the Si(100) surface. Oxidation initially induced a rapid buildup of tensile stress up to -1.9 × 10(8) N m(-2) with an oxide thickness of 0.25 nm, followed by gradual compensation by a compressive stress. The compressive stress saturated at 5 × 10(7) N m(-2) for an oxide thickness of 1.2 nm. The analysis, assisted by theoretical study, indicates that the observed initial tensile stress is caused by oxygen bridge-bonding between the Si dimers. Atomistic model calculations considering mutually orthogonal orientations of the Si(100) surface structure reproduce the stress inversion from the tensile to the compressive side.

Circular dichroism nano-imaging of two-dimensional chiral metal nanostructures.

Here we report on a nanoscale circular dichroism (CD) imaging for a two-dimensional chiral pair of nanostructures to elucidate the relationship between nanoscale chirality and CD activity. The chiral pair exhibited local ellipticity as high as 42 degrees in the CD signal at the center, with signals of both handedness coexisting in one nanostructure.

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.

The growth process of first water layer and crystalline ice on the Rh(111) surface.

The adsorption states and growth process of the first layer and multilayer of water (D(2)O) on Rh(111) above 135 K were investigated using infrared reflection absorption spectroscopy (IRAS), temperature programed desorption, spot-profile-analysis low-energy electron diffraction, and scanning tunneling microscopy (STM). At the initial stage, water molecules form commensurate ( radical3x radical3)R30 degrees islands, whose size is limited for several hexagonal units; the average diameter is approximately 2.5 nm. This two-dimensional (2D) island includes D-down species, and free OD species exist at the island edge. With increasing coverage, the D-up species starts to appear in IRAS. At higher coverages, the 2D islands are connected in STM images. By the titration of Xe adsorption we estimated that the D-down domain occupies about 55% on Rh(111) at the saturation coverage. Further adsorption of water molecules forms three-dimensional ice crystallites on the first water layer; thus, the growth mode of crystalline water layers on Rh(111) is a Stranski-Krastanov type. We have found that an ice crystallite starts to grow on D-down domains and the D-down species do not reorient upon the formation of a crystalline ice.

Simultaneous scanning tunneling microscopy and stress measurements to elucidate the origins of surface forces.

We have developed a new combined measurement system to investigate the underlying origins of forces on solid state surfaces from the viewpoint of atomic surface morphology. This system consists of two main parts: the measurements of force based on displacements and detailed atomic resolution observations of the surface morphology. The former involves a large sample cantilever and a capacitive detection method that provide sufficient resolution to detect changes of a few meV/atom or pN/atom at surfaces. For the latter, a scanning tunneling microscope was incorporated to observe structural changes occurring on the surface of the cantilever sample. Although this combined observation is not trivial, it was accomplished by carefully designing sample dimensions while suppressing the self-oscillation of the cantilever. To demonstrate the performance of this system a preliminary study of the room temperature adsorption of Br(2) on the clean Si(111)-7x7 surface is presented.