Our laboratory has reported that periodic micro swelling structures on silicone rubber surfaces are photochemically formed, and the surface has superhydrophobicity. At the conference, the formation of capsule structures on the top of periodic micro swelling structures on silicone rubber surface by 193 nm ArF excimer laser irradiation will be reported. The microcapsule structure is formed by irradiating the silicone rubber with silica microspheres aligned in a single layer with the 193 nm ArF excimer laser. The formation method and the nature of the microcapsule structure will be discussed.
Our laboratory has reported that periodic micro swelling structures on silicone rubber surfaces are photochemically formed, and the surface has superhydrophobicity. At the conference, the formation of cup-shaped structures on the top of periodic micro swelling structures on silicone rubber surface by 193 nm ArF excimer laser irradiation will be reported. The micro-cup structure is formed by irradiating the silicone rubber with silica microspheres aligned in a single layer with the 193 nm ArF excimer laser. The formation method and the nature of the micro-cup structure will be discussed.
In recent years, polycarbonate (=PC) is gathering attention as a light and strong material for smart windows. In the presentation, a patterning method of Al deposited film on silicone hard-coated polycarbonate by 157 nm F2 laser irradiation will be reported. A photomask placed on Al thin film and irradiated by F2 laser and the non-irradiated area was removed by KOH aq. The mechanism of the patterning will be discussed based on XPS, AFM, and ATR-FTIR measurement.
Light-weighting of vehicle is now strongly required for reducing gasoline consumption and CO2 emission. In this study, F2 laser was irradiated to the surface of hard silicone resin, coated by dip coating method onto the film of acrylic resin on a polycarbonate substrate. The surface part of the silicone resin was photo-chemically modified into SiO2. One of two types of aperture mask, 3×3 mm2 and 50×50 μm2, was set on the sample surface. The single pulse fluence was varied from 4 to 14 mJ/cm2, pulse repetition frequency was set to 10 Hz, and irradiation time was changed from 30 to 120 s. N2 gas was induced around the surface of the sample. After modification, SiO2 modified layer was etched by HF 1% diluted solution, and the etched depth was measured by a stylus-type surface profilometer. As a result of experiments, stress in the SiO2 modified layer increased by increasing of F2 laser irradiation time. In case of using aperture mask of 3×3 mm2, cracks were generated only on the irradiated area for longer irradiation time than 60 s. It is considered that the tensile stress in the modified layer exceeded the tensile fracture strength of 48 MPa of typical SiO2. When a mesh mask of 50×50 μm2 aperture was used, no crack generated even for a long irradiation of 200 s. We found, the tensile stress in SiO2 modified film can be reduced remarkably with using smaller aperture size of mesh mask, and it is very effective to prevent cracking.
A 157 nm F2 laser was used for the surface and interface modifications of Al thin films on silica glass substrate for
fabricating a pattern of Al thin films. The F2-laser irradiated surface swelled remarkably by inducing the strong oxidation
reaction of Al thin films to form Al2O3 protective layer. High adhesion strength of 663 kgf/cm2 between Al and silica
glass was also obtained for the F2-laser-irradiated sample, compared with the cases in the ArF-laser irradiated, fourth
harmonic of Nd:YAG-laser irradiated and nonirradiated samples of 326, 19 and 16 kgf/cm2, respectively. Thus, the F2-
laser irradiated sample showed high abrasion resistance for embossing a fine pattern of Al thin films on silica glass.
Mechanism of the F2-laser-induced surface and interface modifications was discussed, comparing with the cases in the
ArF laser and fourth harmonic of Nd:YAG laser.
Silicone-coated polycarbonate (PC) through an acrylic primer was photochemically modified into silica (SiO2) by 157
nm F2 laser. The photomodified surface showed high scratch resistance comparable to the case in a bulk silica.
Corresponding to the conversion of silicone into silica on PC, the photomodified surface was found to be shrunk,
measured by a surface profilometer. For instance, the coated silicone on PC reduced the thickness of approximately 15 %
when the F2 laser modified silicone into silica 0.59 μin thickness. An excess irradiation of F2 laser for the
photochemical modification induced the degradation of acrylic primer underneath silicone.
F2-laser writing of silica (SiO2) optical waveguides has been successfully demonstrated on the surface of silicone [(SiO(CH3)2)n] rubber by the photochemical modification of silicone into silica. The 2-mm-thick silicone rubber was exposed to the 157-nm F2-laser beam through a thin (~0.2 mm) air layer. A proximity Cr-on-CaF2 photomask with 8- to 16-micron-wide slits controlled the exposure size to define the width of the silica waveguide. Optimum laser conditions to generate crack-free waveguides with good transparency were found by varying the laser fluence, pulse repetition rate and total exposure. The optimized waveguides were found to guide both red (~635-nm) and infrared (~1550-nm) wavelengths with light end-fired from standard single-mode fiber.
The ablation of silicone rubber (polydimethysiloxane, [SiO(CH3)2]n) by 157-nm F2 laser irradiation has been studied. The ablation threshold fluence (Fth) was approximately 140 mJ/cm2. The irradiated surface swelled and was modified to SiO2 for laser fluences below Fth. No carbon contamination was observed in the SiO2. Above Fth, the surface of etched silicone rubber was structurally well defined and precisely patterned. The chemical composition of the etched surface demonstrated little change. When the silicone rubber was irradiated at laser fluences of nearly Fth, conical structures were formed on the surface. It is supposed that residual carbon photodissociated by laser irradiation initiated cone formation by locally shifting Fth to a higher value. In situ mass spectrometric analysis of gaseous products evolved during F2 laser irradiation of silicone rubber showed that CH3 and CH4 components dominated for laser fluences below Fth, and CO component dominated for laser fluences above Fth. The high photon energy (7.9 eV) of an F2 laser could photodissociate preferentially weak bonds (Si-C) of silicone for lower laser fluence and almost all bonds (Si-C, C-H, Si-O) of silicone for higher laser fluence.
Photocatalytic titanium dioxide (TiO2) thin films with large specific surface area were deposited on Si wafers by pulsed laser deposition with sintered TiO2 targets in oxygen gas atmosphere. Angular distributions of the number of droplets and the film thickness were examined. The surface roughness and the film thickness depended on the oxygen gas pressure. Photocatalytic effect of the films deposited at various substrate temperatures was evaluated by photobleaching of methylene-blue-aqueous solution. The TiO2 film deposited at the substrate temperature of 250°C was anatase-type crystal and this film indicated the highest photocatalytic effect.
We deposited SiO2 films with different refractive indices by pulsed laser deposition with silicone targets. The deposition rate could control the refractive index of the films. The refractive index of the film deposited at 0.05 nm/pulse is greater than that of the film at 0.1 nm/pulse. The origin of the refractive index changes was to be film porosity changes, which was observed by surface profile meter. The deposited films were free of impurities such as OH and carbon. Thus, a 0.4- μm-thick SiO2 cladding film deposited at 0.1 nm/pulse was firstly formed on the whole surface of Si wafer, and then a 1- μm-thick SiO2 core film at 0.05 nm/pulse was fabricated in a line on the sample. Again, the sample was coated with a 0.1- μm-thick film at 0.1 nm/pulse. The sample functioned as an optical waveguide for a 633-nm line of He-Ne laser.
Silicon dioxide (SiO2) thin films were deposited at room temperature by 193-nm ArF excimer laser ablation of silicone in oxygen atmosphere. Only the side chains of the target were photo-dissociated during ablation to deposit Si-O bonds on a substrate in high laser fluence at about 10 J/cm2. Oxygen gas worked to oxidize the Si-O bonds ejected from the target to from SiO2 thin films at the gas pressure of 4.4 X 10-2 Torr, in addition to reducing the isolated carbon mixed into the films. We also found that the deposited rate could control refractive index of the films. The refractive index of the film deposited at 0.05 nm/pulse is greater than that of the film at 0.1 nm/pulse. Thus, a 0.2-micrometers thick SiO2 cladding film deposited at 0.1 nm/pulse was firstly formed on the whole surface of a 100- micrometers -thick polyester film, and then a 0.6 micrometers -thick SiO2 core film at 0.05 nm/pulse was fabricated in a line on the sample. The sample functioned as a waveguide device for a 633-nm line of He-Ne laser.
We used 395-nm and 790-nm femtosecond laser pulses to deposit aluminum-doped zinc oxide films by pulsed laser deposition. Electrical resistivity of the films was lowered (5.6 x 104(Omega) cm) at 200 degree(s)C for the 395-nm laser pulses, while maintaining the optical transparency. In addition, the deposition rate increased six times. Optical emission was measured to compare the plumes generated by 395-nm and 790-nm laser pulses. We found that the emission from ions was suppressed relative to neutral atoms. Also the kinetic energy of ejected species was nearly doubled for the 395-nm laser pulses.
Polymethyl methacrylate (PMMA) surface was photochemically modified in open air by using an ArF excimer laser and an ammonia-water solution. Photo-excited C-H bonds of the surface were effectively dehydrogenated with hydrogen atoms which were photodissociated from the ammonia-water solution. The dangling bonds of the dehydrogenated carbon atoms were combined with the NH2 and OH radicals which were also photodissociated. Thus, the sample surface showed hydrophilic property only on the photomodified parts. Based on the photomodification technique, a commercial hard-contact lens was also photomodified for tear affinity.
A tough adhesivity of teflon and stainless steel using an epoxy resin-based bonding agent was performed. The chemical stability of teflon is attributed to the C-F bond composed. Thus, it is considered to pull out the fluorine atoms selectively from the area irradiated with an ArF excimer laser light and to substitute a functional group displaying excellent affinity with bonding agents to create a powerful adhesivity. The defluorination of the surface was performed with boron atoms which were photodissociated from orthoboric acid water solution. The hydroxyl groups, which have a good affinity with epoxy bonding agent, were substituted only at area exposed to the laser light. The modified teflon surface with the epoxy bonding agent, and shearing tensile strength were performed. The strength was 110 Kgf/cm2.
A powerful adhesion of fluororesin (Teflon) featuring its excellent corrosion resistance and stainless steel was performed by using an epoxy resin-based bonding agent. Adhesion strength was 500 times more than that of untreated teflon, which has virtually no affinity with chemicals and solids. The teflon surface was irradiated by an ArF excimer laser light with energy higher than the carbon-fluorine bond, in a tetrahydroborate (BNaH4) and methyl alcohol (CH3OH) mixed solution ambient. The defluorination of the surface was performed with the boron atoms which were photodissociated from BNaH4. The fluorine atoms of the surface was replaced with the CH3 and OH radicals, also photo dissociated from CH3OH. The methyl(-CH3) and hydroxyl(-OH) groups, which have a good affinity with epoxy bonding agent, were substituted only for the area exposed to the laser light. The modified teflon surface was adhered to a stainless steel with the epoxy bonding agent, and shearing tensile strength test was performed. The strength was 100 Kgf/cm2, whereas untreated teflon's strength is 0.2 Kgf/cm2 or less. Thus the adhesion was improved considerably.
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