Separation of Neighboring Terraces on a Flattened Si(111) Surface by Selective Etching along Step Edges Using Total Wet Chemical Processing.

We propose a bottom-up technique using total wet chemical treatments to separate neighboring terraces on Si(111). First, Ag cations were reduced at the step edges of a vicinal Si(111) surface composed of biatomic steps and flat terraces, resulting in self-assembled Ag rows consisting of nanodots and nanowires. By immersing this sample into a mixed solution of HF and H2O2, almost continuous nanotrenches with depths and widths of nanometer scales were fabricated along the edges. The potential electrochemical processes in the solution/Ag/Si system that lead to the formation of nanotrenches are discussed. Additionally, we present how we plan to use our approach to create atomic-thickness Si ribbons.

Comparative analysis of oxidation methods of reaction-sintered silicon carbide for optimization of oxidation-assisted polishing.

Combination of the oxidation of reaction-sintered silicon carbide (RS-SiC) and the polishing of the oxide is an effective way of machining RS-SiC. In this study, anodic oxidation, thermal oxidation, and plasma oxidation were respectively conducted to obtain oxides on RS-SiC surfaces. By performing scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM-EDX) analysis and scanning white light interferometry (SWLI) measurement, the oxidation behavior of these oxidation methods was compared. Through ceria slurry polishing, the polishing properties of the oxides were evaluated. Analysis of the oxygen element on polished surfaces by SEM-EDX was conducted to evaluate the remaining oxide. By analyzing the three oxidation methods with corresponding polishing process on the basis of schematic diagrams, suitable application conditions for these methods were clarified. Anodic oxidation with simultaneous polishing is suitable for the rapid figuring of RS-SiC with a high material removal rate; polishing of a thermally oxidized surface is suitable for machining RS-SiC mirrors with complex shapes; combination of plasma oxidation and polishing is suitable for the fine finishing of RS-SiC with excellent surface roughness. These oxidation methods are expected to improve the machining of RS-SiC substrates and promote the application of RS-SiC products in the fields of optics, molds, and ceramics.

Ultrasmooth reaction-sintered silicon carbide surface resulting from combination of thermal oxidation and ceria slurry polishing.

An ultrasmooth reaction-sintered silicon carbide surface with an rms roughness of 0.424 nm is obtained after thermal oxidation for 30 min followed by ceria slurry polishing for 30 min. By SEM-EDX analysis, we investigated the thermal oxidation behavior of RS-SiC, in which the main components are Si and SiC. As the oxidation rate is higher in the area with defects, there are no scratches or cracks on the surface after oxidation. However, a bumpy structure is formed after oxidation because the oxidation rates of Si and SiC differ. Through a theoretical analysis of thermal oxidation using the Deal-Grove model and the removal of the oxide layer by ceria slurry polishing in accordance with the Preston equation, a model for obtaining an ultrasmooth surface is proposed and the optimal processing conditions are presented.

Direct adhesion between Cu foil and polytetrafluoroethylene without increasing surface roughness for high-frequency printed wiring boards.

Polytetrafluoroethylene (PTFE) serves as a suitable dielectric substrate for high-frequency printed wiring boards (PWBs) owing to its excellent properties at high frequency. However, to the best of our knowledge, no study has investigated the strong adhesion between PTFE and Cu foil with low surface roughness. Therefore, in this study, pure-PTFE comprising a weak boundary layer (WBL) on the surface and glass-cloth-containing PTFE (GC-PTFE), which did not contain a WBL, were subjected to heat-assisted plasma (HAP) treatment. Thereafter, we investigated the surface chemical bonding state, surface morphology, and adhesion properties of the as-prepared PTFE toward Cu foil with low surface roughness. As observed, oxygen-containing functional groups were generated on the HAP-treated PTFE, and the WBL in the as-received pure-PTFE was eliminated via HAP treatment. Moreover, the surface roughness of the HAP-treated PTFE did not increase compared to that of as-received PTFE. After performing thermal compression under atmospheric conditions, the adhesion strength of both HAP-treated pure-PTFE and GC-PTFE was ∼0.9 N mm-1. In addition, the adhesion strength of Cu/pure-PTFE and Cu/GC-PTFE increased after thermal compression under a reduced pressure, and the adhesion strength of 1 N mm-1 was obtained. Although the Cu foil was not roughened, Cu/PTFE realized strong adhesive strength. The developed method is advantageous because maintaining a low interface roughness is crucial for applying PTFE to manufacture high-frequency PWBs.

Surface modification and adhesive-free adhesion of polytetrafluoroethylene (PTFE) and silicone gel containing oleophilic SiO2 powder by plasma treatment.

Polytetrafluoroethylene (PTFE) has high-frequency characteristics and low transmission loss, and is expected to be used as a substrate material of printed wiring board for high-frequency applications. Meanwhile, silicone gel has superior properties such as attaching/detaching, weather resistance, and human safety. If the PTFE and silicone gel can be strongly adhered to, they can be applied to internet of things (IoT) devices that can be attached and detached freely. However, adhesion between PTFE, which has poor adhesion, and silicone gel, which has low mechanical strength, is difficult and has not been reported. In this study, PTFE was modified with heat-assisted plasma treatment, and silicone gel was treated with oleophilic SiO2 powder to improve elastic modulus and modified with plasma jet treatment, and then bonded without adhesive. The adhesion strength of PTFE/silicone gel assembly was 1.13 N mm-1 when treated moderately, but only 0.01 N mm-1 when untreated and treated excessively. To investigate the factors causing the difference in the adhesion strength, the surface of silicone gel was evaluated by water contact angle measurement, Fourier transform infrared spectroscopy, and confocal laser scanning microscopy. When treated moderately, hydrophilic functional groups and cross-linking were most frequently increased. Furthermore, when treated excessively, surface degradation was observed, which was expected to lower the adhesion strength. The adhesive-free bonding between PTFE and silicone gel can open a new path for developing IoT devices that can be freely attached and detached.

Shape correction of optical surfaces using plasma chemical vaporization machining with a hemispherical tip electrode.

We propose a plasma chemical vaporization machining device with a hemispherical tip electrode for optical fabrication. Radio-frequency plasma is generated close to the electrode under atmospheric conditions, and a workpiece is scanned relative to the stationary electrode under three-axis motion control to remove target areas on a workpiece surface. Experimental results demonstrate that surface removal progresses although process gas is not forcibly supplied to the plasma. The correction of shape errors on conventionally polished spheres is performed. As a result, highly accurate smooth surfaces with the desired rms shape accuracy of 3 nm are successfully obtained, which confirms that the device is effective for the fabrication of optics.

Flexible selection of the functional-group ratio on a polytetrafluoroethylene (PTFE) surface using a single-gas plasma treatment.

During plasma treatment of polymers, etching occurs and functional groups are introduced on their surface. We assumed that controlling the etching rate would enable plasma treatment using a single gas to control the ratio of functional groups generated on a polymer's surface, although previous studies have indicated that several different types of functional groups are formed when the gaseous species are varied. In this study, we selected the base pressure (BP) as a parameter for controlling the etching rate and subjected polytetrafluoroethylene (PTFE) to plasma treatments using only He gas at various BPs. The chemical composition of the surface of the plasma-treated PTFE samples was evaluated by X-ray photoelectron spectroscopy (XPS), and the ratios of fluorine (CF3, CF2, C-F), oxygen (O-C[double bond, length as m-dash]O, C[double bond, length as m-dash]O, C-O), and carbon (C-C, C[double bond, length as m-dash]C) groups were quantified from the C 1s-XPS spectra. The fluorine-group ratio decreased and the oxygen- and carbon-group ratios increased with decreasing BP. The results demonstrated that plasma treatment using a single gas enabled flexible selection of the ratio of functional groups generated on PTFE via control of the BP.

Adhesive-Free Adhesion between Plasma-Treated Glass-Cloth-Containing Polytetrafluoroethylene (GC-PTFE) and Stainless Steel: Comparison between GC-PTFE and Pure PTFE.

In this study, the effect of plasma treatment on glass-cloth-containing polytetrafluoroethylene (GC-PTFE) was investigated. Previous plasma studies investigated pure PTFE (which does not contain glass cloth) but not GC-PTFE. The effect of Ar + H2O plasma treatment on GC-PTFE was investigated. The Ar + H2O plasma-treated GC-PTFE sheets were thermally compressed to stainless steel (SUS304) foils without using adhesive, and the GC-PTFE/SUS304 adhesion strengths were measured using a 90° peel test. The adhesion strength increased with the increase in the plasma treatment time (0.8 and 1.0 N/mm at 20 s and 300 s, respectively). Thus, strong adhesion between GC-PTFE/SUS304 was achieved without adhesive. This improvement in the adhesion properties of GC-PTFE can be attributed to the generation of oxygen-containing functional groups and the decrease in the surface roughness of the samples. Thereafter, the adhesion properties of GC-PTFE and pure PTFE were compared. Because, unlike pure PTFE, GC-PTFE has no weak boundary layer, GC-PTFE exhibited better adhesion properties than pure PTFE under short plasma treatment times.

Improvement in thickness uniformity of thick SOI by numerically controlled local wet etching.

Silicon-on-insulator (SOI) wafers are promising semiconductor materials for high-speed LSIs, low-power-consumption electric devices and micro electro mechanical systems (MEMS). The thickness distribution of an SOI causes the variation of threshold voltage in electronic devices manufactured on the SOI wafer. The thickness distribution of a thin SOI, which is manufactured by applying a smart cut technique, is comparatively uniform. On the other hand, a thick SOI has a large thickness distribution because a bonded wafer is thinned by conventional grinding and polishing. For a thick SOI wafer with a thickness of 1 microm, it is required that the tolerance of thickness variation is less than 50 nm. However, improving the thickness uniformity of a thick SOI layer to a tolerance of +/- 5% is difficult by conventional machining because of the fundamental limitations of these techniques. We have developed numerically controlled local wet etching (NC-LWE) technique as a novel deterministic subaperture figuring and finishing technique, which utilizes a localized chemical reaction between the etchant and the surface of the workpiece. We demonstrated an improvement in the thickness distribution of a thick SOI by NC-LWE using an HF/HNO3 mixture, and thickness variation improved from 480 nm to 200 nm within a diameter of 170 mm.

Finishing of AT-cut quartz crystal wafer with nanometric thickness uniformity by pulse-modulated atmospheric pressure plasma etching.

Quartz resonator is a very important device to generate a clock frequency for information and telecommunication system. Improvement of the productivity of the quartz resonator is always required because a huge amount of the resonator is demanded for installing to various electronic devices. Resonance frequency of the quartz resonator is decided by the thickness of the quartz crystal wafer. Therefore, it is necessary to uniform the thickness distribution of the wafer with nanometric level. We have proposed the improvement technique of the thickness distribution of the quartz crystal wafer by numerically controlled correction using atmospheric pressure plasma which is non-contact and chemical removal technique. Heating effects of the quartz wafer in the removal rate and the correction accuracy were investigated. The heating of the substrate and compensate of the scanning speed of the worktable according to the variation of the surface temperature enabled an increase of 50% in the etching rate and 10-nanometric-level accuracy in the correction of the thickness distribution of the quartz wafer, respectively.

Fabrication of discrete polystyrene nanoparticle arrays with controllable their structural parameters.

We have demonstrated the fabrication of two-dimensionally periodic non-close packed arrays of spherical polystyrene nanoparticles with controllable their structural parameters including diameter and interpartcile distance. The principle of this procedure relies on stepwise integration of spin-coat-assisted colloidal self-assembly of the single layer of close-packed polystyrene nanoparticle on a substrate, and subsequent etching of the particle under atmospheric pressure helium plasma. The plasma process converted the close-packed nanoparticle array into non-close-packed arrangement remaining with unchanged their original spherical shape and periodicity. Owing to the etching process underwent isotropically, the structural parameters could be controlled with nanometric accuracy by the treatment time. The etching rate strongly depended on the working pressure conditions, and the etching rate under 250 Torr was ca. 3 times faster than that of the 760 Torr. The effects of the working pressure indicated the neutral helium radicals and photons diffused from the plasma might be primarily responsible for the etching.

Simple and versatile route to high yield face-to-face dimeric assembly of Ag nanocubes and their surface plasmonic properties.

We have demonstrated the higher yield dimerization of single-crystalline Ag nanocubes through preciously controlled face-selective functionalization. With the achievement of the higher yield dimerization, we could thus observe some interesting optical properties of the dimer. Both experimental and theoretical studies revealed that the 50-nm-diameter Ag nanocubes dimers with a ca. 3.3 nm gap at their junction exhibited two plasmon peaks centered at 446 nm and 600 nm, which contributed to transverse and longitudinal plasmon resonances, respectively. Elctromagnetic calculations based on the FDTD method clearly showed that a greater enhancement of the local field occurred, with an average amplitude of the electric field of 22, at the fractal space between the aggregated Ag nanocubes when the dimer was illuminated under longitudinally polarized light.

Effects of He and Ar Heat-Assisted Plasma Treatments on the Adhesion Properties of Polytetrafluoroethylene (PTFE).

Heat-assisted plasma (HAP) treatment using He gas is known to improve the adhesive-bonding and adhesive-free adhesion properties of polytetrafluoroethylene (PTFE). In this study, we investigated the effects of He and Ar gaseous species on the HAP-treated PTFE surface. Epoxy (EP) adhesive-coated stainless steel (SUS304) and isobutylene-isoprene rubber (IIR) were used as adherents for the evaluation of the adhesive-bonding and adhesive-free adhesion properties of PTFE. In the case of adhesive bonding, the PTFE/EP-adhesive/SUS304 adhesion strength of the Ar-HAP-treated PTFE was the same as that of the He-HAP-treated PTFE. In the case of adhesive-free adhesion, the PTFE/IIR adhesion strength of the Ar-HAP-treated PTFE was seven times lower than that of the He-HAP-treated PTFE. The relation among gaseous species used in HAP treatment, adhesion properties, peroxy radical density ratio, surface chemical composition, surface modification depth, surface morphology, surface hardness, and the effect of irradiation with vacuum ultraviolet (VUV) and UV photons were investigated. The different adhesive-free adhesion properties obtained by the two treatments resulted from the changes in surface chemical composition, especially the ratios of oxygen-containing functional groups and C-C crosslinks.

Removal characteristics of plasma chemical vaporization machining with a pipe electrode for optical fabrication.

Plasma chemical vaporization machining (CVM) is a high-precision chemical shaping method using rf plasma generated in the proximity of an electrode in an atmospheric environment. The purpose of the present study is to clarify the removal characteristics of plasma CVM using a pipe electrode. Polished fused silica plates were processed by plasma CVM, polishing, and precision grinding under various conditions. The removal rate of plasma CVM was about 4 to 1100 times faster than that of polishing, and the maximum removal rate was almost equal to that of precision grinding. The roughness of the resultant surfaces was almost the same as that of the polished surfaces.

Damage-free highly efficient plasma-assisted polishing of a 20-mm square large mosaic single crystal diamond substrate.

Plasma-assisted polishing (PAP) as a damage-free and highly efficient polishing technique has been widely applied to difficult-to-machine wide-gap semiconductor materials such as 4H-SiC (0001) and GaN (0001). In this study, a 20-mm square large mosaic single crystal diamond (SCD) substrate synthesized by microwave plasma chemical vapor deposition (CVD) was polished by PAP. Argon-based plasma containing oxygen was used in PAP to modify the surface of quartz glass polishing plate, and a high material removal rate (MRR) of 13.3 µm/h was obtained. The flatness of SCD polished by PAP measured by an interferometer was 0.5 µm. The surface roughness measured by both scanning white light interferometer (SWLI) (84-µm square) and atomic force microscope (AFM) (5-µm square) was less than 0.5 nm Sq. The micro-Raman spectroscopy measurement results of mosaic SCD substrate processed by PAP showed that residual stress and non-diamond components on the surface after PAP processing were below the detection limit.

Strong Biomimetic Immobilization of Pt-Particle Catalyst on ABS Substrate Using Polydopamine and Its Application for Contact-Lens Cleaning with H2O2.

Polydopamine (PDA)-a known adhesive coating material-was used herein to strongly immobilize a Pt-particle catalyst on an acrylonitrile-butadiene-styrene copolymer (ABS) substrate. Previous studies have shown that the poor adhesion between Pt particles and ABS surfaces is a considerable problem, leading to low catalytic durability for H2O2 decomposition during contact-lens cleaning. First, the ABS substrate was coated with PDA, and the PDA film was evaluated by X-ray photoelectron spectroscopy. Second, Pt particles were immobilized on the PDA-coated ABS substrate (ABS-PDA) using the electron-beam irradiation reduction method. The Pt particles immobilized on ABS-PDA (Pt/ABS-PDA) were observed using a scanning electron microscope. The Pt-loading weight was measured by inductively coupled plasma atomic emission spectroscopy. Third, the catalytic activity of the Pt/ABS-PDA was evaluated as the residual H2O2 concentration after immersing it in a 35,000-ppm H2O2 solution (the target value was less than 100 ppm). The catalytic durability was evaluated as the residual H2O2 concentration after repeated use. The PDA coating drastically improved both the catalytic activity and durability because of the high Pt-loading weight and strong adhesion among Pt particles, PDA, and the ABS substrate. Plasma treatment prior to PDA coating further improved the catalytic durability.

Figuring of plano-elliptical neutron focusing mirror by local wet etching.

Local wet etching technique was proposed to fabricate high-performance aspherical mirrors. In this process, only the limited area facing to the small nozzle is removed by etching on objective surface. The desired objective shape is deterministically fabricated by performing the numerically controlled scanning of the nozzle head. Using the technique, a plano-elliptical mirror to focus the neutron beam was successfully fabricated with the figure accuracy of less than 0.5 microm and the focusing gain of 6. The strong and thin focused neutron beam is expected to be a useful tool for the analyses of various material properties.

Influence of air contamination during heat-assisted plasma treatment on adhesion properties of polytetrafluoroethylene (PTFE).

Plasma surface treatment is typically not effective on fluoropolymers containing polytetrafluoroethylene (PTFE). It is reported that heat-assisted plasma (HAP) treatment at high temperatures (above 200 °C) under atmospheric pressure helium (He) plasma improves the adhesion properties of PTFE. In this study, we investigated the influence of the air concentration during HAP treatment on the adhesion properties of PTFE. Air concentration was controlled via ambient air inflow amount, in other words, base pressure. The PTFE samples HAP-treated in different air concentrations were thermally compressed with an unvulcanized isobutylene-isoprene rubber (IIR). Then, the PTFE/IIR adhesion strength was measured via T-peel test. We show that, when PTFE was HAP-treated in 0.01% air, its PTFE/IIR adhesion strength was over 2 N mm-1; the IIR underwent cohesion failure. However, the PTFE/IIR adhesion strength drastically decreased in the presence of air contamination. The relationships between air concentration during HAP treatment, adhesion properties of PTFE, surface chemical composition, surface morphology, and surface hardness were investigated and discussed.

Surface Modification and Microstructuring of 4H-SiC(0001) by Anodic Oxidation with Sodium Chloride Aqueous Solution.

Anodic oxidation is a promising surface modification technique for the manufacture of SiC wafers owing to its high oxidation rate. It is also possible to fabricate porous SiC by anodic oxidation and etching owing to the material properties of SiC. In this study, the anodic oxidation of a 4H-SiC(0001) surface was investigated by performing repeated anodic oxidation and hydrofluoric acid etching on a 4H-SiC(0001) surface, during which the formation of porous SiC was observed and studied. Anodic oxidation is very effective for removing the surface damage formed by mechanical polishing, and the surface after removing the surface damage can be oxidized uniformly and has a higher oxidation rate than a surface newly finished by chemical mechanical polishing (CMP). We proposed a model based on the electrochemical impedance method to explain the difference in the oxidation between an as-CMP-finished surface and an oxidized/etched surface. Porous SiC was obtained in this study, which was due to the anisotropy of the SiC crystal. The structure of the porous SiC was significantly dependent on the etch pits generated at the beginning of anodic oxidation and can be controlled via anodic oxidation parameters. Anodic oxidation and hydrofluoric acid etching cannot remove porous SiC owing to the anisotropic oxidation of the SiC surface and the difficulty of anodizing SiC fibers. This study shows that anodic oxidation is a promising technique for the modification of SiC surfaces and the fabrication of porous SiC.

Improved Catalytic Durability of Pt-Particle/ABS for H2O2 Decomposition in Contact Lens Cleaning.

In a previous study, Pt nanoparticles were supported on a substrate of acrylonitrile⁻butadiene⁻styrene copolymer (ABS) to give the ABS surface catalytic activity for H2O2 decomposition during contact lens cleaning. Although the Pt-particle/ABS catalysts exhibited considerably high specific catalytic activity for H2O2 decomposition, the catalytic activity decreased with increasing numbers of repeated usage, which meant the durability of the catalytic activity was low. Therefore, to improve the catalytic durability in this study, we proposed two types of pretreatments, as well as a combination of these treatments before supporting Pt nanoparticles on the ABS substrate. In the first method, the ABS substrate was etched, and in the second method, the surface charge of the ABS substrate was controlled. A combination of etching and surface charge control was also applied as a third method. The effects of these pretreatments on the surface morphology, surface chemical composition, deposition behavior of Pt particles, and Pt loading weight were investigated by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), cross-sectional SEM, and inductively coupled plasma atomic emission spectroscopy (ICP-AES), respectively. Both etching and controlling the surface charge effectively improved the catalytic durability for H2O2 decomposition. In addition, the combination treatment was the most effective.