Extremely Monodispersed Micrometer-Scale Spherical Particle Synthesis of Ag Inside a Microdroplet Vaporizing in Plasma.

Spherical Ag particles have received considerable attention because of their unique properties as well as their applications in various fields. In the present study, the synthesis of micrometer-scale spherical Ag particles with an extremely narrow size distribution is demonstrated using a simple capacitively coupled atmospheric-pressure plasma reactor with an inkjet head. Droplets of a Ag nitrate aqueous solution are ejected from the inkjet head to synthesize Ag particles. The gaseous temperature in the reactor is adjusted such that Ag can be melted with a negligibly small vapor pressure. These particles exhibit a spherical shape with a smooth surface. The mean diameter of the particles is 0.91 ± 0.013 µm with a small coefficient of variation of 1.5%, the smallest value ever reported for Ag particles of less than 1 µm. The grain sizes of the particles are larger than 100 nm, as expected from the broadening of the X-ray diffraction peaks. The excellent monodispersity of the particles synthesized by this method may expand the applications with micrometer-scale spheres such as ball spacer, microsized ball bearing, and inks for printed electronics.

Maze-solving in a plasma system based on functional analogies to reinforcement-learning model.

Maze-solving is a classical mathematical task, and is recently analogously achieved using various eccentric media and devices, such as living tissues, chemotaxis, and memristors. Plasma generated in a labyrinth of narrow channels can also play a role as a route finder to the exit. In this study, we experimentally observe the function of maze-route findings in a plasma system based on a mixed discharge scheme of direct-current (DC) volume mode and alternative-current (AC) surface dielectric-barrier discharge, and computationally generalize this function in a reinforcement-learning model. In our plasma system, we install two electrodes at the entry and the exit in a square lattice configuration of narrow channels whose cross section is 1×1 mm2 with the total length around ten centimeters. Visible emissions in low-pressure Ar gas are observed after plasma ignition, and the plasma starting from a given entry location reaches the exit as the discharge voltage increases, whose route converging level is quantified by Shannon entropy. A similar short-path route is reproduced in a reinforcement-learning model in which electric potentials through the discharge voltage is replaced by rewards with positive and negative sign or polarity. The model is not rigorous numerical representation of plasma simulation, but it shares common points with the experiments along with a rough sketch of underlying processes (charges in experiments and rewards in modelling). This finding indicates that a plasma-channel network works in an analog computing function similar to a reinforcement-learning algorithm slightly modified in this study.

Surface-Specific Modification of Graphitic Carbon Nitride by Plasma for Enhanced Durability and Selectivity of Photocatalytic CO2 Reduction with a Supramolecular Photocatalyst.

Photocatalytic CO2 reduction is in high demand for sustainable energy management. Hybrid photocatalysts combining semiconductors with supramolecular photocatalysts represent a powerful strategy for constructing visible-light-driven CO2 reduction systems with strong oxidation power. Here, we demonstrate the novel effects of plasma surface modification of graphitic carbon nitride (C3N4), which is an organic semiconductor, to achieve better affinity and electron transfer at the interface of a hybrid photocatalyst consisting of C3N4 and a Ru(II)-Ru(II) binuclear complex (RuRu'). This plasma treatment enabled the "surface-specific" introduction of oxygen functional groups via the formation of a carbon layer, which worked as active sites for adsorbing metal-complex molecules with methyl phosphonic-acid anchoring groups onto the plasma-modified surface of C3N4. Upon photocatalytic CO2 reduction with the hybrid under visible-light irradiation, the plasma-surface-modified C3N4 with RuRu' enhanced the durability of HCOOH production by three times compared to that achieved when using a nonmodified system. The high selectivity of HCOOH production against byproduct evolution (H2 and CO) was improved, and the turnover number of HCOOH production based on the RuRu' used reached 50 000, which is the highest among the metal-complex/semiconductor hybrid systems reported thus far. The improved activity is mainly attributed to the promotion of electron transfer from C3N4 to RuRu' under light irradiation via the accumulation of electrons trapped in deep defect sites on the plasma-modified surface of C3N4.

Cross-Linking-Filler Composite Materials of Functionalized Hexagonal Boron Nitride and Polyrotaxane Elastomer.

This study demonstrates cross-linking-filler composites in which covalent bonds between the fillers and polymer chains act as the main cross-linking points for the development of flexible and thermally conductive materials. Cross-linking-filler composites are fabricated using functionalized hexagonal boron nitride (hBN) fillers and polyrotaxane, called slide-ring polymers. The hBN particles modified with a carbon layer were produced by plasma processing in hydroquinone aqueous solution and functionalized with isocyanate groups. As the functionalized hBN provides cross-linking points for polyrotaxane, the cross-linking-filler composites can reduce cross-linking agents among polyrotaxane and exhibit considerable flexibility. Young's moduli of the cross-linking-filler composites are much lower than those of previously reported polyrotaxane composites while retaining their toughness. These values are relatively close to those of unfilled polyrotaxane elastomers, despite containing hBN fillers with a content of 50 wt %. Thus, the cross-linking-filler composites exhibit a combination of flexibility and thermal conductivity, which few hBN/elastomer composites have achieved.

Carbon Layer Formation on Hexagonal Boron Nitride by Plasma Processing in Hydroquinone Aqueous Solution.

Although hexagonal boron nitride (hBN) is a thermally conductive and electrically insulating filler in composite materials, surface modification remains difficult, which limits its dispersibility and functionalization. In this study, carbon layer formation on hBN particles by plasma processing in hydroquinone aqueous solution was investigated as a surface modification technique. Carbon components with features of polymeric hydrogenated amorphous carbon were found to be uniformly distributed on the hydroquinone-aided plasma-modified hBN (HQpBN) particles. Electron spin resonance measurements revealed abundant unpaired electrons in HQpBN, indicating that defects were formed on hBN by plasma processing and that the carbon layer contained dangling bonds. The defects on hBN could help in the attachment of the carbon layer, whereas the dangling bonds could act as reactive sites for further functionalization. The carbon layer on HQpBN was successfully functionalized with isocyanate groups, thus confirming the ability of this carbon layer to facilitate surface modification. These results demonstrate that the carbon layer formed on hBN can provide a designable interface in organic/inorganic composite materials.

Electric-Field-Induced Coherent Anti-Stokes Raman Scattering of Hydrogen Molecules in Visible Region for Sensitive Field Measurement.

Nonintrusive optical measuring of electric fields in space is crucial for various sciences and technologies. In this study, a simple and highly sensitive optical electric field measurement is demonstrated in high-pressure hydrogen by performing electric-field-induced coherent anti-Stokes Raman scattering (E-CARS) in the visible region. The minimum detectable electric field is 0.5 V/mm at atmospheric pressure. This method does not require excited or atomic species and shows a considerably higher sensitivity than those demonstrated by the commonly applied E-CARS method in the infrared region and electric-field-induced second-harmonic generation. This method can be applied to various Raman-active molecules.

Soft X-ray emission spectroscopy for the electronic state of water molecules influenced by plasma-treated multi-walled carbon nanotubes.

In this study, soft X-ray emission spectroscopy of an aqueous colloidal dispersion of multi-walled carbon nanotubes modified via the plasma process in an aqueous solution was performed for investigating the electronic state of water molecules on the colloidal particles. In the aqueous dispersion, reconstruction of the hydrogen-bonded network was implied by the O 1s spectral changes in the 1b1' and 1b1'' peaks. Furthermore, the O 1s spectral intensity around the 3a1 state was enhanced to an unusually broad energy range in comparison with previous studies. This unusual spectral change might be attributed to the hybridization of the electronic states of oxygen-containing functional groups on the surface of the plasma-modified multi-walled carbon nanotubes and that of the surrounding water molecules. Our observation indicates not only reconstruction of the hydrogen-bonded network in the aqueous dispersion but also a significant interaction of the electronic states between the water molecules and the plasma-modified multi-walled carbon nanotubes.

Synthesis of a metal-organic framework by plasma in liquid to increase reduced metal ions and enhance water stability.

Synthesis of a metal-organic framework by plasma in liquid was demonstrated with HKUST-1 as an example. HKUST-1 synthesized by this method contains a higher amount of monovalent copper ions than that synthesized by other conventional methods. The enhanced water stability was also confirmed.

Dynamics of solvated electrons during femtosecond laser-induced plasma generation in water.

We studied the dynamics of solvated electrons in the early stage of plasma generation in water induced with an intense femtosecond laser pulse. According to the decay kinetics of solvated electrons, a fast recombination process of solvated electrons (geminate recombination) occurred with a more prolonged lifetime (500 ps to 1 ns) than that observed in previous pulse photolysis studies (10-100 ps). This unusually longer lifetime is attributed to additional production of solvated electrons due to abundant free electrons generated with the laser-induced plasma, implying significant influence of free electrons on the dynamics of solvated electrons.

Slide-Ring Material/Highly Dispersed Graphene Oxide Composite with Mechanical Strength and Tunable Electrical Conduction as a Stretchable-Base Substrate.

The development of stretchable elastomer composites with considerable mechanical strength and electrical conductivity is desired for future applications in communication tools, healthcare, and robotics. Herein, we have developed a novel stretchable elastomer composite by employing a slide-ring (SR) material as a matrix for restoration and graphene oxide (GO) as a precursor for a conductive filler. Highly dispersed GO in an organic solvent, prepared via a new method developed by the authors, allowed the uniform dispersion of GO into the matrix by simply mixing the solvent and SR. The resultant SR/GO composite exhibited considerably high mechanical toughness and cyclic durability. These properties were approximately maintained after pulse laser irradiation to add electrical conductivity on the composite by photoreducing of the dispersed GO, and its electrical conductivity was higher than that of the SR/graphene, carbon nanotubes, or graphite composites. The potential of the SR/GO composite as a stretchable base substrate for wearable devices was demonstrated by producing a prototype humidity sensor, a human motion monitoring sensor, and an electrical heater based on the composite with conductive circuits drawn using pulse laser patterning.

Plasma-Ice Interface as Thermodynamically Size-Tunable Reaction Field: Development of Plasma-Assisted Freeze Templating.

Interfaces or interfacial layers, such as gas-liquid interfaces, are critical for many physical and chemical reactions and are utilized for designing a wide range of materials. In this study, we propose a plasma-assisted freeze templating (PFT) method for materials processing. It uses a new type of interfacial reaction field, i.e., plasma-ice interface. In PFT, a micro- or nanoscale liquid layer formed on the ice body of a frozen aqueous solution is used as a reaction field in which the solutes are highly enriched and the chemical reactions are initiated by reactive species from the plasma. We demonstrated the synthesis of a self-standing gold nanoparticle (AuNP) film of porous structure by PFT in which a helium cryoplasma jet was irradiated onto a frozen solution of auric ions. This PFT method accomplished a surfactant-free and area-selective synthesis of a AuNP film and was unique in comparison with the conventional chemical synthesis of nanostructured gold materials. Furthermore, simple control of the AuNP film was demonstrated by tuning the thickness of the thin liquid layer. This was done by changing the temperature or concentration of the aqueous solution. PFT was demonstrated as a thermodynamically size-tunable scheme for material design; it exploits the plasma-ice interface and is expected to become a novel technique for a wide range of micro- and nanoengineering applications.

ZnO nanorods prepared via ablation of Zn with millisecond laser in liquid media.

ZnO nanomaterials with controlled size, shape and surface chemistry are required for applications in diverse areas, such as optoelectronics, photocatalysis, biomedicine and so on. Here, we report on ZnO nanostructures with rod-like and spherical shapes prepared via laser ablation in liquid using a laser with millisecond-long pulses. By changing laser parameters (such as pulse width and peak power), the size or aspect ratio of such nanostructures could be tuned. The surface chemistry and defects of the products were also strongly affected by applied laser conditions. The preparation of different structures is explained by the intense heating of liquid media caused by millisecond-long pulses and secondary irradiation of already-formed nanostructures.

Rapid breakdown mechanisms of open air nanosecond dielectric barrier discharges.

The discharge initiation mechanism of nanosecond dielectric barrier discharges in open air has been clarified with time-dependent measurement of the discharge electric field by electric-field-induced coherent Raman scattering and optical emission. Our experimental observations have revealed that, in the prebreakdown phase of a nanosecond dielectric barrier discharge, the externally applied fast-rising electric field is strongly enhanced near the cathode due to large accumulation of space charge, which then strongly enhances ionization near the cathode. Once a sufficiently large number of ionizations take place, the location of peak ionization forms a front and propagates toward the cathode with strong optical emission, which establishes the discharge. This process is essentially different from the well-known Townsend mechanism for slower discharges.

Structure of laboratory ball lightning.

Trajectories of self-sustained laboratory ball lightning, generated by arc discharges with silicon, are investigated for understanding the possibility of buoyant flight. Extremely low apparent densities are found, nearly approaching that of standard air. The freely buoyant balls are observed to survive for about 0.1 s, with significantly buoyant balls surviving for several seconds. These ball lightning objects are found to have a density and size that can easily allow them to be carried by a gentle breeze of a few meters per second. The results are interpreted by a model that is an extension of that first proposed by Abrahamson and Dinniss [J. Abrahamson and J. Dinniss, Nature (London) 403, 519 (2000)]. The buoyant behavior of ball lightning seen in our experiments is believed to arise as a result of the formation of a nanoparticle oxide network growing from a molten silicon core.

Ion energy distribution and gas heating in the cathode fall of a direct-current microdischarge.

This paper reports on measurements of the ion energy distribution (IED) at the cathode of an argon dc microdischarge using energy-resolved molecular beam mass spectrometry. The measurements are conducted at a fixed pressure-electrode separation product (pd) of 1 cm Torr with a maximum discharge pressure of 20 Torr. The measured IED is compared to the theory of Davis and Vanderslice [W. D. Davis and T. A. Vanderslice, Phys. Rev. 131, 219 (1963)]. A higher pressure in a case of almost constant normalized current densities by pressure (Jp(-2) = 0.080+/-0.006 mA/cm(-2) Torr(-2)) yields a lower ratio of the ion mean free path to the sheath thickness. The results in almost constant Jp(-2) case then indicate that a scaling law of Jp(-2) is no longer applicable for IED of microdischarge. Expected background gaseous temperatures from IEDs with the collisional Child law have reasonable increasing with increased current density (J) in both cases of almost constant Jp(-2) and a constant pressure of 10 Torr. Supported by temperature measurement by laser absorption spectroscopy, it is demonstrated that the expanded theory might be applicable also to microdischarges (Ar approximately 20 Torr) with temperature adjusting.