Contrast Mechanisms of Solution-Dispersed Graphene Compounds in Twilight Fluorescence Microscopy.

Twilight fluorescence microscopy is a newly developed technique that is capable of imaging a single-layer graphene compound dispersed in a liquid. A graphene solution mixed with a highly concentrated dye is placed on a glass plate and is irradiated by the excitation beam with an incident angle that has a finite width around the total internal reflection angle. Both the evanescence field and the faint refracted beam decay exponentially as they travel from the glass surface. The dye fluorescence excited by both beams is used as illumination. A simplified theory for dark contrast of graphene compounds is developed based on absorption and Förster resonance energy transfer (FRET), assuming that (1) FRET has a sharp cutoff distance, (2) FRET is independent of the number of layers, and (3) Dexter electron transfer is negligible. The contrast of a reduced graphene oxide multilayer, whose layer heights have been determined by atomic force microscopy, shows good agreement with the simplified theory under various dye concentrations. The FRET cutoff distance is found to be much shorter than one expected for graphene and similar to the distance between two small molecules. This short cutoff distance is the main reason for the assumption to be valid.

Minimizing Unintentional Strain and Doping of Single-Layer Graphene on SiO2 in Aqueous Environments by Acid Treatments.

The effects of treating SiO2/Si with either acidic or alkaline solutions on single-layer graphene were investigated using Raman microscopy. It is well-known that in air graphene on SiO2 is unintentionally strained and hole-doped to different degrees, varying widely by sample. It is also known that various amine compounds act as electron donors to graphitic materials. In this study, a SiO2/Si substrate was simply dipped in either a concentrated HCl solution or pH 9.0 NaOH solution and then rinsed, prior to transferring graphene on it. The G and 2D peaks were followed at a fixed position on a single-layer graphene flake in water and various concentrations of pH 7.4 tris(hydroxymethyl)aminomethane (Tris) buffer. The results demonstrate that these treatments reduce the sample variation, improve the stability against Tris, and even bring some graphene samples close to a freestanding state. The Raman analysis reveals that the main effect of dipping is to relieve strain. The undoping effect on some samples is explained by the HCl solution becoming trapped between the graphene and SiO2 surface.

Wetting reversal at gelation transition freezes thermodynamically unstable states.

The contact angle of a drop of gelling solution on a flat, solid surface was monitored as the hot solution was allowed to cool. When a solvent with a high cohesive energy and a wettable solid surface was used, a wetting solution turned into a dewetting solid at the gelation transition. The density profiles in gel as probed by confocal Raman microscopy reveal that the adsorption of both gelator and solvent shifts at the transition and the solvent is severely depleted from the interfacial region. Thus, the wetting reversal is accompanied by the interfacial desolvation. As a result of the adsorption shift during the gelation process in progress, a locally concentrated region of the gelator is frozen in space far away from the surface. This is a thermodynamically unstable state but can be realized reproducibly. The profile analysis also shows that the effect of the surface extends out to a few hundred micrometers, 2 orders of magnitude larger than the bulk correlation length.

Synchronized oscillations of carbon nanotubes dispersed in solution.

Although synchronized oscillations are found in a variety of systems and living organisms in nature, there has been no report on technologically important materials. We have observed by a fluorescence microscope that a large number of carbon nanotubes (CNTs) dispersed in an aqueous mixture of the surfactant and dye execute synchronized oscillations spontaneously. The movement was quantified to give a power spectrum, revealing a single, sharp synchronization peak at 20 Hz. It was found not to be affected nor created by external vibrations. The surfactant concentration dependence demonstrates that the Kuramoto model is applicable to describe the CNT synchronization. It is always associated with the power-law noise, indicating the presence of complex heterogeneous networks. These results suggest a highly cooperative form of the sparse CNT network connected with variable linkages.

Gel network amplifies Nano-Scale adsorption at Solid/Liquid interface to Sub-Millimeter-Scale.

HYPOTHESIS: We have proposed a spreading-flow model of the solvent movement in a gel, which states that the solvent flows along the gel network segment much easier than in any other direction. An excess amount of the solvent component adsorbed on a flat solid surface in a gel will be transferred over the macroscopic gel network by the spreading-flow. Then, by measuring the concentration distribution of each solvent near the solid surface at the sub-millimeter scale, it should be possible to evaluate adsorption occurring on the nanometer scale. EXPERIMENTS: Confocal Raman microscopy was employed to map the concentration distributions of mixed solvents of p-xylene, mesitylene, and octanenitrile gelled by 12-hydroxystearic acid near the atomically flat mica surface. The measured concentration profiles were analyzed by the spreading-flow theory to construct adsorption isotherms. FINDINGS: Nearly all isotherms follow power laws with similar exponents, which is consistent with the van der Waals multilayer adsorption with weak adsorbate-adsorbent interactions. The present study demonstrates the concept of gel network amplification and its usefulness for probing nano-phenomena using macro-technology.

Strain-induced creation and switching of anion vacancy layers in perovskite oxynitrides.

Perovskite oxides can host various anion-vacancy orders, which greatly change their properties, but the order pattern is still difficult to manipulate. Separately, lattice strain between thin film oxides and a substrate induces improved functions and novel states of matter, while little attention has been paid to changes in chemical composition. Here we combine these two aspects to achieve strain-induced creation and switching of anion-vacancy patterns in perovskite films. Epitaxial SrVO3 films are topochemically converted to anion-deficient oxynitrides by ammonia treatment, where the direction or periodicity of defect planes is altered depending on the substrate employed, unlike the known change in crystal orientation. First-principles calculations verified its biaxial strain effect. Like oxide heterostructures, the oxynitride has a superlattice of insulating and metallic blocks. Given the abundance of perovskite families, this study provides new opportunities to design superlattices by chemically modifying simple perovskite oxides with tunable anion-vacancy patterns through epitaxial lattice strain.

Peculiar Solvent Flow along the Gel Network after Gelation at Interfaces.

Spatial distributions of solvents in a gel interfacing a solid surface are mapped using confocal Raman microscopy. A binary mixture of completely miscible liquids, p-xylene and octanenitrile, is gelled while in contact with various solid surfaces. Despite its miscibility, p-xylene is found to distribute in excess near the completely wet surfaces soon after the gelation while the gelator distributes uniformly. The concentration excess decreases linearly over the distance from the surface and extends over 200 µm. The excess profile is only kinetically stable and relaxes to a completely mixed state over 104 s. All results can be explained by hydrodynamic theory based on a solvent flow along the network segment, whose property is similar to the spreading of a liquid droplet on a completely wet surface. The strength of the flow is determined by a balance between the spreading p-xylene flux from the adsorbed layer and the outward p-xylene diffusion into the surrounding medium.

Direct Observations of Graphene Dispersed in Solution by Twilight Fluorescence Microscopy.

Graphene and graphene oxide (GO) in solution were directly observed by a newly developed twilight fluorescence (TwiF) microscopy. A nanocarbon dispersion was mixed with a highly concentrated fluorescent dye solution and placed in a cell with a viewing glass at the bottom. TwiF microscopy images the nanocarbon material floating within a few hundred µm of the glass surface by utilizing two optical processes to provide a faintly illuminating backlight and visualizes GO as either a dark image by absorption and energy transfer processes or a bright image by alternation of fluorophore chemistry and autofluorescence. Individual graphene and GO sheets ranging from submicron to submillimeter widths were clearly imaged at different wavelengths, which were selectable based on the dye used. Graphene could be differentiated from GO coexisting in the same solution. Partial transparency revealed layering and network structures. Motions in tumbling flow were recognized in real time. An effect of changing the solvent and the process of adhesion on the glass surface were followed in situ.

Spontaneous Rotation of Nonlinear Pattern Formed by Aqueous Colloidal Suspension between ITO Electrodes during Electrolysis Perpendicular to Gravity.

A colloidal fluid is found to rotate spontaneously during electrolysis when gravity acts perpendicular to the direction of an applied electric field. An aqueous dispersion containing charged colloidal particles is placed inside an O-ring sandwiched between two parallel ITO electrodes. A clip is used to hold the assembly together to prevent the liquid from leaking out. The assembly is positioned such that the electrodes stand vertically, i.e., the electric field during electrolysis points perpendicular to gravity. When a direct-current voltage is applied to initiate the electrolysis of water, a nonlinear colloidal pattern is formed by electroconvective flow. Moreover, the entire fluid rotates spontaneously about the O-ring center with a constant angular velocity. The rotational dynamics are governed by how strong and where the assembly is clipped relative to the gravitational direction. A new phenomenological relationship between the angular velocity, compression vector, and gravity is derived. Coupling of an electrochemical reduction reaction of the ITO film with electroconvection during electrolysis is proposed as a mechanism for the rotational motion.

Rod-like architecture and helicity of the poly(C)/schizophyllan complex observed by AFM and SEM.

Microscopic studies of the complex between poly(C) and schizophyllan (SPG), employing both AFM and SEM, revealed that the complex takes the same rod-like architecture on the mica surface as those of the renatured SPG and the original triple helix of SPG, indicating that the complex also has a helical structure. The SEM observations showed the helical pattern on the rod surface, only when the sample was metal shadowed. The pitch evaluated from the image is comparable with that obtained from crystallographic data. The ability to visualize the helical structure can be explained from the hypothesis that the platinum grains may assemble on the sample using the molecular surface of the SPG (or complex) as the template.

Length scales necessary for proper averaging to characterize polymerization in nanosystems: topochemical polymerization of diacetylene nanocrystals dispersed in a polystyrene matrix as probed by confocal Raman microscopy.

The scales necessary to make appropriate spatial averaging on solid-state polymerization were investigated by confocal Raman microscopy with a mapping resolution of 2 µm. Nanocrystals of an aliphatic diacetylene with an average size of 0.14 µm, each separated by 0.3 µm on average, were dispersed in a polystyrene matrix and were polymerized by UV irradiation. The distribution of nanocrystals was inhomogeneous over approximately 20 µm scale. A large crystal of the same monomer shows that photoinitiation is already averaged at the microscope resolution, while the color transition from the blue to the red form requires a scale greater than 5 µm. For the nanocrystals at low conversion, UV-vis absorption spectroscopy measured over a centimeter scale indicates linear polymerization kinetics and a higher polymer yield at a higher temperature. By contrast, the Raman microscopy reveals that, whereas the 20 µm region of high monomer concentrations yields more polymers at -24 °C, the region of low monomer concentrations gives more polymers at 20 °C. We propose thermal initiation, which is not efficient in the large crystals, as an additional initiation process for the apparent discrepancy, implying that the initiation process is not averaged below 20 µm scale for the dispersed nanocrystals.

Nonlinear pattern formation by electroconvection of carbon nanotube dispersions.

Applications of dc electric field across parallel plate electrodes filled with an aqueous dispersion of carbon nanotubes produce slowly changing, geometrically regular patterns over the anode surface. The pattern is made visible by nonuniform concentration distributions of black-colored carbon nanotubes. Temporal developments of the pattern can be categorized to the cell pattern appearing soon after the application of the field and the butterfly pattern that follows the cell pattern. An existence of a threshold voltage and the electrode separation dependence on the cell polygon size indicate that the cell pattern is formed by electroconvection induced by electrolysis of water. In contrast, the butterfly pattern does not show the same dependencies and is a characteristic of the nanotube dispersion. Furthermore, it depends on the direction of the electric field relative to gravity, suggesting that it involves a new lateral force that has never been reported.

Nanotube foam prepared by gelatin gel as a template.

It has been known that simply mixing single-walled carbon nanotubes (SWCNTs) in an aqueous solution of gelatin disperses SWCNTs well for a period of months. Gels made from the gelatin-SWCNT mixture are also stable and have a clear, black color. Scanning electron microscopy shows that gelatin molecules self-organize into a foamlike structure. All SWCNTs are embedded in the gelatin film that makes up the foam walls. Those SWCNTs belonging to one face of the foam cell cannot approach other faces to make van der Waals contact. Thus, the foam structure is associated with stabilization of the SWCNT dispersion. The gelatin can be removed thermally while maintaining the foam structure to give a sponge made of nanotube foams. This highly porous solid is electrically conducting and mechanically stable and can be used as a structural frame for composite materials.

van der Waals layer-by-layer construction of a carbon nanotube 2D network.

The acid-treated single-walled carbon nanotubes (SWCNTs) dispersed in water are only kinetically stable with electrostatic double layer repulsions just balancing against van der Waals (VDW) attractions. Introducing any external factor to disturb this balance causes immediate coagulation of SWCNTs. Here, an amine-covered flat substrate was immersed in the dispersion to initiate adsorption of SWCNTs onto the substrate surface. By repeating an adsorption-rinse-dry cycle, it was possible to deposit SWCNT bundles in a layer-by-layer fashion and to develop a 2D network consisting only of SWCNTs that are held by VDW interaction. We show that (1) adsorbed solution-grown aggregates are not relevant for the network connectivity, (2) 2D percolation takes place at very low surface coverage, (3) the electrical resistivity follows a power law against the layering cycles, (4) not only the adsorbed amount but also the added amount per layering cycle increases linearly with the SWCNT concentration, and (5) after the adsorption is initiated by amines, VDW attraction takes over for subsequent adsorption, with the consequence that the newly adsorbed SWCNTs are used to thicken each arm of the network rather than to cover more free surfaces.