Clarification of fast metal sphere movement in glass.

In this study, metal spheres were implanted into glass by continuous-wave (CW) laser illumination, which manipulated the metal sphere inside the glass. The spheres moved at approximately 100 mm/s, which is 100 times faster compared to conventional movement. The movement mechanism was clarified by in situ, cross-sectional, and microscopic observations. With a high laser power density, the metal spheres moved fast with plasma emission, and their trajectory contained fine iron particles. The temperatures of the metal sphere with slow (<0.1 mm/s) and fast (>1 mm/s) speeds were 1,900 and 2,900 K, respectively.

The possibility of multi-layer nanofabrication via atomic force microscope-based pulse electrochemical nanopatterning.

Pulse electrochemical nanopatterning, a non-contact scanning probe lithography process using ultrashort voltage pulses, is based primarily on an electrochemical machining process using localized electrochemical oxidation between a sharp tool tip and the sample surface. In this study, nanoscale oxide patterns were formed on silicon Si (100) wafer surfaces via electrochemical surface nanopatterning, by supplying external pulsed currents through non-contact atomic force microscopy. Nanoscale oxide width and height were controlled by modulating the applied pulse duration. Additionally, protruding nanoscale oxides were removed completely by simple chemical etching, showing a depressed pattern on the sample substrate surface. Nanoscale two-dimensional oxides, prepared by a localized electrochemical reaction, can be defined easily by controlling physical and electrical variables, before proceeding further to a layer-by-layer nanofabrication process.

Moving force of metal particle migration induced by laser irradiation in borosilicate glass.

We optically manipulated a metal particle in borosilicate glass. The glass in the neighborhood of the laser-heated metal particle softened; hence, the metal particle was able to migrate in the glass. In this letter, the driving force of the metal particle toward the light source in the glass provided by laser illumination was investigated. The variation in the surface tension of the glass at the interface between the glass and the metal particle induced by the temperature gradient was calculated via a numerical temperature calculation. It was found that the temperature at the laser-illuminated surface of a stainless-steel particle with a radius of 40 µm was ~320 K higher than that on the nonilluminated side. The force applied to the metal particle from the surrounding glass was calculated to be ~100 µN, which was approximately equal to the viscous resistance force. In addition, the experimental and numerically calculated speeds of the moving particle, which was measured while varying the laser power, are discussed.

Synthesis of 2-azulenyl-1,1,4,4-tetracyano-3-ferrocenyl-1,3-butadienes by [2+2] cycloaddition of (ferrocenylethynyl)azulenes with tetracyanoethylene.

1-, 2-, and 6-(Ferrocenylethynyl)azulene derivatives 10-16 have been prepared by palladium-catalyzed alkynylation of ethynylferrocene with the corresponding haloazulenes under Sonogashira-Hagihara conditions. Compounds 10-16 reacted with tetracyanoethylene (TCNE) in a [2+2] cycloaddition-cycloreversion reaction to afford the corresponding 2-azulenyl-1,1,4,4,-tetracyano-3-ferrocenyl-1,3-butadiene chromophores 17-23 in excellent yields. The redox behavior of the novel azulene chromophores 17-23 was examined by using cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their multistep electrochemical reduction properties. Moreover, a significant color change was observed by visible spectroscopy under electrochemical reduction conditions.

Synthesis, properties, and redox behavior of tetracyanobutadiene and dicyanoquinodimethane chromophores bearing two azulenyl substituents.

Acetylene derivatives with an azulenyl group at both terminals have been prepared by palladium-catalyzed alkynylation under Sonogashira-Hagihara conditions. These alkynes reacted with tetracyanoethylene and 7,7,8,8-tetracyanoquinodimethane in a formal [2 + 2] cycloaddition-retroelectrocyclization reaction to afford the corresponding new tetracyanobutadienes (TCBDs) and dicyanoquinodimethanes (DCNQs), respectively, in excellent yields. Intramolecular CT absorption bands were found in the UV-vis spectra of the novel chromophores, and CV and DPV showed that they exhibited a reversible two-stage reduction wave, due to the electrochemical reduction of TCBD and DCNQ moieties. Color changes were also observed during the electrochemical reduction.

Synthesis of push-pull chromophores by the sequential [2 + 2] cycloaddition of 1-azulenylbutadiynes with tetracyanoethylene and tetrathiafulvalene.

Azulene-substituted butadiynes have been prepared by Cu-mediated cross- and homo-coupling reactions. The azulene-substituted butadiynes reacted with tetracyanoethylene in a formal [2 + 2] cycloaddition reaction to afford the corresponding 1,1,4,4-tetracyanobutadiene chromophores, in excellent yields. Further [2 + 2] cycloaddition with TTF and TCNE gave novel donor-acceptor chromophores and novel azulene-substituted 6,6-dicyanofulvene derivatives.

Synthesis of donor-acceptor chromophores by the [2 + 2] cycloaddition of arylethynyl-2H-cyclohepta[b]furan-2-ones with 7,7,8,8-tetracyanoquinodimethane.

Arylethynyl-2H-cyclohepta[b]furan-2-ones reacted with 7,7,8,8-tetracyanoquinodimethane (TCNQ) in a formal [2 + 2] cycloaddition reaction, followed by ring opening of the initially formed cyclobutene derivatives, to afford the corresponding dicyanoquinodimethane (DCNQ) chromophores in excellent yields. The intramolecular charge-transfer (ICT) interactions between the 2H-cyclohepta[b]furan-2-one ring and DCNQ acceptor moiety were investigated by UV/Vis spectroscopy and theoretical calculations. The redox behavior of the novel DCNQ derivatives was examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their multistep electrochemical reduction properties depended on the number of DCNQ units in the molecule. Moreover, a significant color change was observed by visible spectroscopy under electrochemical reduction conditions.

Synthesis of redox-active, intramolecular charge-transfer chromophores by the [2+2] cycloaddition of ethynylated 2H-cyclohepta[b]furan-2-ones with tetracyanoethylene.

Ethynylated 2H-cyclohepta[b]furan-2-ones 5-15 have been prepared by Pd-catalyzed alkynylation of 3-iodo-5-isopropyl-2H-cyclohepta[b]furan-2-one (2) with the corresponding ethynylarenes or the reaction of 2-iodothiophene with 3-ethynyl-5-isopropyl-2H-cyclohepta[b]furan-2-one (4) under Sonogashira-Hagihara conditions. Compounds 5-15 reacted with tetracyanoethylene in a formal [2+2] cycloaddition reaction, followed by ring opening of the initially formed [2+2] cycloadducts, cyclobutenes, to afford the corresponding 1,1,4,4-tetracyanobutadienyl (TCBD) chromophores 16-26 in excellent yields. The intramolecular charge-transfer interactions between the 2H-cyclohepta[b]furan-2-one ring and TCBD acceptor moiety were investigated by UV/Vis spectroscopy and theoretical calculations. The redox behavior of the novel TCBD derivatives 16-26 was examined by cyclic voltammetry and differential pulse voltammetry, which revealed multistep electrochemical reduction properties, depending on the number of TCBD units in the molecule. Moreover, a significant color change was observed by UV/Vis spectroscopy under electrochemical reduction conditions.

High-aspect-ratio structure fabrication on (110)-oriented silicon surfaces using tribo-nanolithography.

This study investigated methods of fabricating high-aspect-ratio structures on a silicon surface using a combination of tribo-nanolithography and wet chemical etching. Tribo-nanolithography forms an amorphous phase on a single-crystal silicon surface that has an etch resistance against potassium hydroxide so that a protruding structure can be fabricated by wet chemical etching. To fabricate high-aspect-ratio structures, (110)-oriented silicon was used, and the effect of machining parameters on the structure shape was investigated. The results showed that a structure with vertical side walls could be fabricated by machining along the (112) direction. The etch resistance against potassium hydroxide depended on the normal load and number of repetitions, and the width and the maximum height were functions of these conditions. The aspect ratio of the structure increased with the etch time as long as the amorphous phase was maintained. A sub-micrometer-scale high-aspect-ratio structure was fabricated based on these results, demonstrating the possibility of using this simple and effective method.

Micro/nano surface modification on brittle materials by tribo nanolithography using PCD tool.

In this study, brittle materials were mechanically modified under precise normal force control at the mN approximately microN level using PCD tools as a nano tool. The lab-made PCD attached micro cantilevers were customized for tribo nanolithography. The machined patterns were measured under an atomic force microscope (AFM) to obtain the machining characteristics of the samples for each set of conditions. Then the samples were etched using aqueous solution to verify the etch characteristics of the machined surface. Our results showed that either protruding or depressed patterns could be generated on the scratched surface by controlling normal load, scan pitch, and etching condition. The unique mask effect of brittle material after mechanical scratching under PCD tool can be controlled by the conventional mechanical machining conditions such as chip formation, plastic flow, and material removal. We used SEM, TEM, SIMS, and AFM to investigate the etch characteristics and structural change of brittle material under nano scale mechanical machining conditions.

Modeling the direct activation of dihydrogen by a P2C2 cyclic biradical: formation of a cyclic bis(P-H lambda(5)-phosphorane).

The synthesis of a remarkable cyclic bis(P-H lambda(5)-phosphorane) is reported. A stable phosphorus-heterocyclic biradical, 1,3-diphosphacyclobutane-2,4-diyl, sequentially accepts negatively and positively charged hydrogen atoms to afford 2,4-diphospha-1,3-cyclobutadiene with a diylidic structure containing two P-H bonds.

Highly charged ion beam applied to lithography technique.

In various fields of nanotechnology, the importance of nanoscale three-dimensional (3D) structures is increasing. In order to develop an efficient process to fabricate nanoscale 3D structures, we have applied highly charged ion (HCI) beams to the ion-beam lithography (IBL) technique. Ar-ion beams with various charge states (1+ to 9+) were applied to fabricate spin on glass (SOG) and Si by means of the IBL technique. The Ar ions were prepared by a facility built at Kochi University of Technology, which includes an electron cyclotron resonance ion source (NANOGAN, 10 GHz). IBL fabrication was performed as a function of not only the charge state but also the energy and the dose of Ar ions. The present results show that the application of an Ar(9+) beam reduces the etching time for SOG and enhances the etching depth compared with those observed with Ar ions in lower charged states. Considering the high-energy deposition of HCI at a surface, the former phenomena can be understood consistently. Also, the latter phenomena can be understood based on anomalously deep structural changes, which are remarkable for glasses. Furthermore, it has also been shown that the etching depth can be easily controlled with the kinetic energy of the Ar ions. These results show the possibilities of the IBL technique with HCI beams in the field of nanoscale 3D fabrication.

Experimental and theoretical study on the driving force and glass flow by laser-induced metal sphere migration in glass.

Light is able to remotely move matter. Among various driving forces, laser-induced metal sphere migration in glass has been reported. The temperature on the laser-illuminated side of the sphere was higher than that on the non-illuminated side. This temperature gradient caused non-uniformity in the interfacial tension between the glass and the melted metal as the tension decreased with increasing temperature. In the present study, we investigated laser-induced metal sphere migration in different glasses using thermal flow calculations, considering the temperature dependence of the material parameters. In addition, the velocity of the glass flow generated by the metal sphere migration was measured and compared with thermal flow calculations. The migration velocity of the stainless steel sphere increased with increasing laser power density; the maximum velocity was 104 µm/s in borosilicate glass and 47 µm/s in silica glass. The sphere was heated to more than 2000 K. The temperature gradient of the interfacial tension between the stainless steel sphere and the glass was calculated to be -2.29 × 10-5 N/m/K for borosilicate glass and -2.06 × 10-5 N/m/K for silica glass. Glass flowed in the region 15-30 µm from the surface of the sphere, and the 80-µm sphere migrated in a narrow softened channel.

High Stabilities of Di(1-azulenyl)(4-hydroxyphenyl)methyl Hexafluorophosphates and Polarized Properties of alpha,alpha-Di(1-azulenyl)-1,4-benzoquinone Methides.

Acid-catalyzed condensation of azulenes 8a-c with 4-hydroxy- and 3,5-di-tert-butyl-4-hydroxybenzaldehyde leads to substituted di(1-azulenyl)(4-hydroxy- and 3,5-di-tert-butyl-4-hydroxyphenyl)methanes 7a- f, which are easily converted into substituted di(1-azulenyl)(4-hydroxy- and 3,5-di-tert-butyl-4-hydroxyphenyl)methyl cations 5a-f by oxidation with DDQ. The spectroscopic data are consistent with the protonated cationic structures of 5a-f. The electrochemical reduction of 5a-f showed a reversible wave at -0.74 to -0.86 V (V vs Ag/Ag(+)) upon cyclic voltammetry (CV), although 5d and 5e showed an irreversible wave at -0.79 V. The relatively high reduction potentials of 5a-f, compared with those of di(1-azulenyl)phenylmethyl cations 2a-c, exhibit the stabilization by 4-hydroxy substituents on the phenyl groups. These salts (5a-f.PF(6)(-)) bearing 4-hydroxyl groups on the phenyl rings have been converted by treatment with bases to alpha,alpha-di(1-azulenyl)-1,4-benzoquinone methides 6a-f, which revert to 5a-f.PF(6)(-) upon reprotonation with HPF(6). These quinone methides (6a-f) are highly polarized by the extreme-electrodonating properties of 1-azulenyl groups. The highly polarized properties of 6a-f reflected to the high pK(a) values of their conjugate acids (5a-c, 6.5-7.1, and 5d-f, 3.4-3.8). The strong solvatochromic effects also provide strong evidence of a large contribution of dipolar forms (6') in the ground state. The relatively low oxidation potentials of 6a-f (+0.35 to +0.47 V vs Ag/Ag(+)) reflected facile formation of phenoxy radical cations, stabilized by two 1-azulenyl groups.

Diverse reactions of sterically-protected 1,3-diphosphacyclobutane-2,4-diyls with hydride.

Hydride-induced elimination of resonance stabilized substituents from a phosphorus center of 1,3-diphosphacyclobutane-2,4-diyls leads to the formation of versatile cyclic phosphaallyl anions that are useful for the construction of various electrophile-modified biradical species.

Three-dimensional fabrication on GaAs surfaces using electron-beam-induced carbon deposition followed by wet chemical etching.

We propose a method for fabricating three-dimensional structures on GaAs surfaces using electron beam (EB) irradiation followed by wet chemical etching. An etch-resistant hydrocarbon layer forms on the GaAs surface with the EB irradiation. Structures can be fabricated after etching using the hydrocarbon layer to block the etching. The height dependence on the irradiation and etching conditions was investigated as a means of controlling the height of the structures. A higher structure was fabricated at higher doses. The etching selectivity changed with the concentration of the etchant. A three-dimensional structure was fabricated based on these results, demonstrating the possible use of this method as a novel three-dimensional fabrication method for GaAs surfaces.

Synthesis, properties, and redox behavior of mono-, bis-, and tris[1,1,4,4,-tetracyano-2-(1-azulenyl)-3-butadienyl] chromophores binding with benzene and thiophene cores.

Mono-, bis-, tris-, and tetrakis(1-azulenylethynyl)benzene and mono- and bis(1-azulenylethynyl)thiophene derivatives 5-10 have been prepared by Pd-catalyzed alkynylation of ethynyl arenes with 1-iodoazulene derivative or the 1-ethynylazulene derivative with tetraiodobenzene and iodothiophenes under Sonogashira-Hagihara conditions. Compounds 5-10 reacted with tetracyanoethylene in a [2+2] cycloaddition reaction to afford the corresponding 1,1,4,4,-tetracyano-2-(5-isopropyl-3-methoxycarbonyl-1-azulenyl)-3-butadienyl chromophores 12-16 in excellent yields, except for the reaction of the tetrakis(1-azulenylethynyl)benzene derivative. 1,1,4,4,-Tetracyano-2,3-bis(1-azulenyl)butadiene (17) was also prepared by the similar reaction of bis(1-azulenyl)acetylene (11) with tetracyanoethylene (TCNE). The redox behavior of novel azulene derivatives 12-17 was examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed multistep electrochemical reduction properties. Moreover, a significant color change was observed by visible spectroscopy under electrochemical reduction conditions.

Synthesis and intramolecular pericyclization of 1-azulenyl thioketones.

Several azulene-substituted thioketones, 1-thiobenzoylazulene (1a) and di(1-azulenyl) thioketone (2a) and their derivatives (1b and 2b-d) with alkyl substituents on each azulene ring, were prepared and their intramolecular pericyclization reaction was examined. The thioketones with a 3-alkyl substituent on each azulene ring exhibited the presumed pericyclization reaction under thermal and acid-catalyzed conditions, although the cases of the 1-azulenyl thioketones without the 3-alkyl substituents afforded a complex mixture under similar conditions. The intramolecular reaction following the intramolecular hydrogen transfer afforded the products 13b, 14b, and 14c. The products 13b and 14b were converted into the corresponding cations 18(+) and 19(+), which have structural similarity with that of the phenalenyl cation. These cations exhibited the expected two-step reduction waves upon CV, although the ESR analysis revealed that the neutral radical state did not have the presumed high stability.

Synthesis, stabilities, and redox behavior of mono-, di-, and tetracations composed of di(1-azulenyl)methylium units connected to a benzene ring by phenyl- and 2-thienylacetylene spacers. A concept of a cyanine-cyanine hybrid as a stabilized electrochromic system.

This paper describes the preparation of two tetracations 4a(4+) and 4b(4+) composed of di(1-azulenyl)methylium units based on a new structural principle of a cyanine-cyanine hybrid for the design of electrochromic materials with two color changes. Di- and monocations 5a(2+), 5b(2+) and 6a+, 6b+ composed of di(1-azulenyl)methylium units were also prepared for the purpose of comparison. The pKR+ values of the tetracations are rather high despite their tetracationic structure, although the stability of these cations decreases with the increase of the number of the existing cation units. The cyclic voltammetry (CV) of these cations revealed the presumed multielectron redox properties. However, the tetracations did not exhibit the idealized electrochemical behavior, in which subsequent two-electron reduction was presumed as the cyanine-cyanine hybrid, probably due to the less effective electrochemical interaction among the positive charges. The scope of the creation of the novel polyelectrochromic materials taking the new structural principle is demonstrated by these examples.