Various polysilane-acrylic block copolymers have been prepared by photopolymerization of vinyl monomers using poly(methylphenylsilane) (PMPS) as a macromolecular photo-radical initiator. The block copolymers have been applied to positive resists for electron beam (EB) lithography. PMPS-methyl α-chloroacrylate copolymer (P(MPS-co-MClA)) was found to have a good sensitivity to the EB irradiation, high heat resistance, and dry etching resistance.

抄録全体を表示

We have investigated the laser ablation of UV transparent materials of PTFE, FEP, quartz and sapphire with a femtosecond-pulsed UV laser at the wavelength of 268nm. Upon laser irradiation, a fine etching without debris was obtained on the surfaces of PTFE and quartz. The laser-ablated surfaces were analyzed by optical microscopy. The ablation mechanism is discussed in terms of multi-photon absorption and thermal diffusion induced by a ultra-short pulse of the laser.

抄録全体を表示

The surface of sedimentary aerosol particles of polyacrolein (polyAC) was chemically modified by 1, 3, 5, 7-tetramethylcyclotetrasiloxane (TTS) vapor under light irradiation with a low pressure mercury lamp and with N₂ laser. FT-IR spectra measured with the surface-modified polyAC particles strongly suggested that Si-O bond of electronically excited TTS molecule was cleaved and the resulting active end groups produced silacyclobutane structure at one end or SiO-C bond at the other end on the surface of polyAC particles. Prolonged light irradiation with a low pressure mercury lamp produced poly(methylsiloxane) as the major product. From a gaseous mixture of TIS and AC, composite aerosol particles were produced under irradiation with a medium pressure mercury lamp through a UV31 and a UVD33S filters. Aerosol particle formation process of the gaseous mixture was monitored by measuring monitor (He-Ne laser) light intensity scattered by the aerosol particles which were produced under light irradiation. With increasing partial pressure of TTS, induction period to detect scattered light became longer and the scattered light intensity became weaker. These results strongly suggested that electronically excitedAC molecules were consumed by the chemical reaction with TTS to induce polymerization reaction of TTS.

抄録全体を表示

Calix[4]resorcinarene bearing azobenzene moieties (CADR) was prepared by etherification of calix[4]resorcinarene (C4RA) with Disperse Red-1 derivatives (_DR-1s). The photofunctional properties were evaluated by measuring second harmonic generation (SHG), electro-optic (E-O) coefficient and surface relief grating (SRG). The second harmonic coefficient (d₃₃) of CADR and the electro-optic coefficient (γ₃₃) at the wavelength of 1064nm were 97.06×10^-9 [esu] and 18.43 [pm/V] without corona poling treatment. The diffraction image by SRG was successfully recorded and the hologram of 1μm width was also obtained.

抄録全体を表示

Steady-state photocurrent in poly(N-vinylcarbazole)(PVCz)(26, 48wt%)/poly(methyl methacrylate)(PMMA) blends is for the first time measured. The PVCz(26, 48wt%)/PMMA blends showed almost the same carrier-generation efficiencies at electric fields higher than 1×10^-5V•cm^-1. The results are explained by high miscibility of the PVCz(26, 48wt%)/PMMA blends, suggesting the existence of PVCz chains in continuous PMMA-rich phase in the phase-separated structure. The miscibility is evaluated by means of excimer fluorescence of PVCz in these blends, fluorescence microscopy, and differential scanning calorimetry. Phase diagram of PVCz/PMMA/benzene ternary system is determined by cloud-point measurements.

抄録全体を表示

The sensitivities to γ rays were investigated for photo acid generators: N-sulfonyloxy phthalimide 2, N-sulfonyloxy succinimide 3, N-sulfonyloxy 1, 8-naphthalimide 4, N-tosyloxy 5-norbomene-2, 3-dicarboximide 5, triphenylsulfonium trifluoromethane-sulfonate 6, diphenyliodonium chloride 7 and chloroform 8. The acid generation efficiency was monitored by the use of acid sensitive dye, fluoran dye 1a. The efficiency for γ irradiation decreased in the order 7>2>6>5>3>4. In the case of 8, decomposition of 1a was accompanied. 7 and 8 were of no practical use because volatile hydrogen chloride was generated. The others (2-6) generate methanesulfonic acid, p-toluenesulfonic acid or trifluoromethanesulfonic acid which are not so volatile acid as hydrogen chloride. N-sulfonyloxy imide compounds (2-5) have an advantage for practical use as dosimeter because these reagents dissolve in either polar or nonpolar solvent.

抄録全体を表示

The charge resonance (CR) interactions in α-substituted-(4-nitrostyryl)pyridinium derivatives have been investigated. The CR bands of dimer radical cation in α-substituted bichromophoric compounds were observed with a peak around 1010nm upon irradiation at 405nm in acetonitrile (ACN) at room temperature. These bands were weak because of their restricted geometrical conformation as compared with γ-substituted one. The CR band of dimer radical cation in α-substituted monochromophoric compound was observed at 993nm in 1, 2-dimethoxyethane. No CR band for this compound in ACN as a polar solvent strongly suggested that radical is difficult to be generated because of increased distance between the tetraphenylborate anion as a donor to the styrylpyridinium chromophore as an acceptor.

抄録全体を表示

Photoreactions and aggregation of spiropyran with a long alkyl chain (SP98) were studied by surface reflection spectroscopy at the air-water interface. SP98 in mixtures with arachidic acid formed stable monolayers on pure water or on a subphase containing Cd²⁺. Colored photomerocyanine (PMC98) was formed at the air-water interface by UV-irradiation. The reflection peak of PMC98 shifted from 545nm to 618nm with increasing surface pressure on a subphase containing Cd²⁺. The latter corresponded to the peak of aggregates observed in non-polar solutions. PMC98 formed J-like aggregates at surface pressures above 10-20mN m^-1 on the subphase containing Cd²⁺, but hardly formed them on pure water. The back reaction from PMC98 to SP98 upon visible irradiation depended on the surface pressure and the subphase. About 36% of aggregated PMC98 remained even after 90min at 30mN m^-1, while at 10 and 1.5mN m^-1 PMC98 converted completely to SP98 within 20 and 10min, respectively.

抄録全体を表示

5, 8-Diphenyl-5, 8-dihydroanthra[1, 9-bc:4, 10-b′c′]diquinoline (ADQ, 3) and its endoperoxide (ADQepo, 4) were photochromic compounds with high heat stability. By heating above 100°C, colorless ADQepo (4) was slowly converted to green ADQ (3) in toluene. Reaction of ADQepo with some protic acid gave ADQ (3) at room temperature. The mechanism of this reaction was proposed based on the measurement of electronic spectrum.

抄録全体を表示

Leuco methylene blue color formers, 3, 7-bis(dimethylamino)-10-(o-nitrobenzyloxycarbonyl) phenothiazine (4) and 3, 7-bis(dimethylamino)-10-(tert-butoxycarbonyl)phenothiazine (5) were synthesized in order to obtain novel functional materials. These compounds, (4) and (5), showed good coloring reaction in acetonitrile by UV irradiation. The dimethylsulfoxide (DMSO) solution of 4 showed little change by heating at 70°C in the presence of p-toluenesulfonic acid. On the other hand, the DMSO solution of 5 showed the blue coloration under the same condition. The acetonitrile solutions of 4 or 5 did not change to blue by γ irradiation.

抄録全体を表示

The sensitization mechanisms for photoinitiations comprising a 1, 7, 13-trimethyl-2, 5, 9, 12-tetrahydro-2, 5;9, 12-diethano-isoindolomethene difluoroborate (BBP) and a 2, 8-diethyl-1, 3, 5, 7, 9-pentamethylbipyrromethene difluoroborate (EBP), and a radical generating reagent; 3, 3′, 4, 4′-tetrakis(t-butyldioxycarbonyl)benzophenone (BTTB) in a poly(methyl methacrylate) (PMMA) film have been investigated by laser flash photolysis using a total reflection cell. Effect in sensitization mechanisms with incorporating bicyclo group into bipyrromethene dye was discussed.

抄録全体を表示

A new method of photochemical generation of sulfonic acid is described. N-sulfonyl-arylsulfonamide which is synthesized easily from arylsulfonamide and sulfony chloride produce sulfonic acids on photoexcitation. Quantum yields of their decomposition are between 0.2 to 0.5, depending on their substituents. A typical example is N-(4-methoxyphenysulfony)-N-methyl-4-methoxyphenysulfonamide which shows quantum yield of 0.5. It is almost the same value as commonly used photo-sulfonic acid generating compounds. Photodecompositon products were characterized by HLPC and Mass spectroscopy, and photodecompositon mechanism is proposed.

抄録全体を表示

A simple amorphous molecule, tri(3, 5-di-tert-butoxycarbonyloxybenzyl) 1, 3, 5-benzenetetracarboxylate (4) was prepared from 1, 3, 5-benzenetricarbonyl trichloride (3) and 3, 5-di(tert-butoxycarbonyloxy)benzyl alcohol (2). Compound 4 can form an uniformm transparent film by spin-casting on silicone wafer and the film has a good transparency above 300nm wavelength. The chemically amplified photoresist system based on 4 containing 5wt% of diphenyliodonium 9, 10-dimethoxyanthracene-2-sulfonate (DIAS) showed a sensitivity of 19mJ/cm² and a contrast of 17 with 365nm light.

抄録全体を表示

The laser photopolymers and the laser imaging systems equipped with various laser diodes such as 410nm-Violet laser, 532nm-frequency-doubled laser and high-power-infrared laser are presented. The photopolymer's performances such as sensitivity, resolution and safety-light character dependent on the wavelength and power of laser light are discussed from the image-formation mechanisms.

抄録全体を表示

Fabrication of organic electro luminescence device using wet process is required in the view point of the process simplification and the reduction of the production cost. In this study, several ruthenium complex monomers were synthesized. Their energy band gaps were measured by using photo-acoustic spectroscopy and the luminescence spectra were measured by photoluminescence spectroscopy. It was found that the peak wavelength can be control from 630nm to 720nm by adding the functional group to the ruthenium complex monomer. It was also found that by adding polyethylene oxide and LiCF₃SO₄ and sodium hydroxide into the ruthenium complex, the light intensity of the organic light emitting device was increased from 1500cd/m² to 2000cd/m² and the response delay which is the characteristic of the electro chemical luminescence is drastically improved.

抄録全体を表示

We have now prepared five boryl anthracene derivatives and evaluated them as an undoping type of emitting material for organic light emitting diodes (OLEDs). The derivatives had high glass transition temperatures because of a three dimensional molecular conformation of a dimesitylboryl anthracene. The OLEDs with the boryl anthracene derivatives showed high performance. For example, the efficiencies of green devices were over 15lmW^-1 and the efficiency of a blue device reached 6.1lmW^-1. The steric geometry of the boryl anthracene derivatives functions as an inhibitor of a intermolecular interaction. The longevity of an orange device had no problem for a practical use.

抄録全体を表示

Several kinds of multi color polymer EL devices were fabricated by means of the photo-bleaching method. Poly(N-vinylcarbazole)(PVK) was dispersed with photo-bleaching dopants having green or yellow fluorescent colors. In order to tune the emission Dolor and pattern the device, the PVK emitter layer was exposed to specific lights after formed by spin coating so that a specific dye is photo-bleached and becomes non-emissive. Green and blue (G-B), two color and yellow, green and blue (Y-G-B), three color devices were fabricated successfully.

抄録全体を表示

Various structures of organic light-emitting devices (OLEDs) including electrophosphorescence were measured for their capacitances. The zero bias capacitances were in inverse proportion to the total thickness of organic layers. Positive bias voltage only affected the capacitances. It is suggested that Joule heating of organic layers caused the dependences of the capacitances on voltage. The maximal capacitances were scattered from 7 to 34nF/cm², and in inverse proportion not only to the total thickness, but also to the single layer thickness of Alq. The similarity of these proportionality factors suggested that the dielectric constants of the hole transports and Alq were not so different, and the contribution of Alq layer was dominant for the maximal capacitance. The capacitances of OLEDs were roughly estimated from total thickness without respect to the difference of dielectric constants of whole layers.

抄録全体を表示

We have developed an organic light emitting device fabricated on polymer film substrate (F-OLED). This device has thin film multi-layered structure; substrate/gas barrier film/transparent anode/organic emitting layers/metal cathode/passivation film, and also has a lot of attractive features, approx.0.2mm thickness, approx. 1gr weight (including driving IC), slightly bendable and so on. It utilizes silicone oxynitride (SiON) on the substrate side as gas barrier film and silicone nitride (SiNx) as passivation film on the device side, so it makes possible to keep a good luminance after 500 hours storage test under 60deg.C.95%RH.

抄録全体を表示