Three-component photopolymers based on thermal crosslinking and acidolytic de-crosslinking of vinyl ether groups. 2. effects of acid components on photopolymer characteristics

The three-component photopolymers consisting of poly(p-hydroxystyrene) (PHS) or poly(styrene-co-acrylic acid) (PSA) as the binder polymer, 2,2-bis(4-(2-(vinyloxy)ethoxy)phenyl)propane (BPA-DEVE) or 1,1,1-tris(4-(2-(vinyloxy)ethoxy)phenyl)ethane (THPETEVE) as the crosslinking agent, and a photoacid generator were investigated with regard to their lithographic characteristics and thermal crosslinking reactivity because of the acidity of the acid component. The thermal crosslinking rate can be represented as the pseudo first-order reaction. The PSA copolymer with an acrylic acid unit has the higher crosslinking rate and sensitivity, and the lower activation energy. Under low baking temperatures at which crosslinking does not take place, dual-mode resist behavior is observed.     

Study of radical generated from coumarin dye-sensitized photo-initiator systems in high-speed photopolymer coating layers using laser flash photolysis

Radical generation from photoinitiation systems containing carbonylbiscoumarin dye with a radical-generating reagent, 3,3′-carbonylbis[7-(diethylamino)-2H-1-benzopyran-2-one] (KCD-DA), with 2,2′-bis(2-chloro-phenyl)-4,4′5,5′-tetraphenyl-1, 1′-bi-1H-imidazole (BI) in a poly(methyl methacrylate) film has been investigated by laser flash photolysis using a total reflection cell. Imidazolyl radical (Im·) was predominantly generated from carbonylbiscoumarin triplet-sensi-­tized decomposition of BI, the quantum yield, Φ^o_Im· of Im· at an infinite concentration of BI was measured, Φ^o_Im· = 1.3. The high quantum yield, Φ^o_Im·, implies an efficient KCD-DA triplet-sensitized photoinitiation system containing BI. Copyright © 1998 John Wiley & Sons, Ltd.     

Photochemistry of naphthalimide photoacid generators

The photophysical properties of a series of 1,8-naphthalimide photoacid generators were studied by steady state fluorescence and phosphorescence spectroscopy. Emission and excitation anisotropies, triplet quantum yields in polar and nonpolar solvent and photoacid generation were evaluated. The singlet excited state exhibits a low polarity and is strongly deactivated by an efficient intersystem crossing process. In protic solvent, a homolytic singlet cleavage of the N-O bond occurs and leads to the acid production. The existence of a triplet state close to the singlet state was clearly evidenced. The presence of close singlet excited states is supported by fluorescence anisotropy and picosecond laser spectroscopy experiments. Results of DFT calculations well confirm the experimental contentions and yield important information about the cleavage process involved in such compounds.     

Growth of Tb3Ga5O12 fiber and bulk crystals using micro-pulling-down apparatus

A micro-pulling-down process, using Ir crucibles and RF heating, has been used to grow single-crystal fiber and bulk crystals of Tb₃Ga₅O₁₂ garnet (TGG). Single crystals ranging up to 450 mm in length have been produced. The crystals were 1–4 mm in diameter and were seeded-grown in the direction close to 1 1 1. The maximal crystal diameter achieved was 10 mm. Dependence of behavior of the solid–liquid interface on the growth parameters (temperature and pulling-rate) is discussed in detail.     

A novel UV-sensitive photopolymerization system with microgel matrix

A series of crosslinked microgels with quaternary ammonium ions on the surface was prepared by quaternization with N,N-dimethylbenzylamine in the presence of microgel particles prepared by emulsion copolymerization of styrene (St), chloromethylstyrene (CMS) and divinylbenzene (DVB). Microgels with diameters in the range of 15–100 nm were successfully dispersed in organic solvents such as 2-methoxyethanol and 2-ethoxyethanol without an emulsifier. A photosensitive layer was formed by coating a photosensitive solution on a grained aluminum plate. The solution was comprised of the microgels, the multifunctional monomer and standard ultraviolet (UV) photoinitiators, such as 2,4-diethyl thioxanthone (DETX)/ethyl p-di-ethylaminobenzoate (EPA). This gave a heterogeneous photosensitive layer which produced good polymer patterns after exposure to UV light followed by development in tap water. A typical polymer layer, consisting of the microgels (poly(styrene-co-N,N-dimethylbenzylvinyl-benzylammonium chloride-co-divinylbenzene)), DETX/EPA, and the multifunctional acrylate monomers, exhibited photosensitivity of 0.06 mJ/cm² for UV light. This sensitivity is much higher than the homogeneous photopolymerization system with an analogous composition.     

Scintillation properties of Yb-doped garnet crystals

Luminescence properties of heavily Yb-doped Lu₃Al₅O₁₂ (Yb:LuAG) and Lu₃Ga₅O₁₂ (Yb:LGG) single crystals grown by micro-pulling-down method were characterized. Charge transfer luminescence of Yb³⁺ was observed in both crystals. Photoluminescence spectra, temperature dependence of emission intensity and decay kinetics of these crystals were studied. Mean decay time of about 24 ns at 90 K (Yb5%:LuAG) and 21 ns at 110 K (Yb5%:LuGG) were observed. Strong thermal quenching at room temperature was measured for both Yb:LuAG and Yb:LGG.     

Growth of KLN fiber crystals and its application for blue-violet light geration

Potassium lithium niobate (KLN) fiber crystals have been grown by μ-pulling down method. The KLN fibers doubled around 806 nm radiation for type I noncritical phase matching at room temperature. We observed ～0.6 mW output power from single-pass second harmonic generation at an input power of 700 mW.     

Photoreactive fluorinated polyimide protected by tetrahydropyranyl (THP) group based on chemical amplification: Acid generation in polyimide film and lithographic properties

The photochemistry of photoacid generator (PAG), diphenyliodonium 9,10-dimethoxyanthracene-2-sulfonate (DIAS) and diphenyliodonium 8-anilinonaphthalene-1-sulfonate (DIANS) was investigated in both alkalinesoluble polyimide (6FDA-AHHFP) and novolak films. The quantum yields of photodissociation of DIAS and DIANS in both 6FDA-AHHFP and novolak films. The quantum yields of photodissociation of DIAS and DIANS in both 6FDA-AHHFP and novolak films were determined as 0.11, 0.21, 0.12 and 0.26, respectively. On the other hand, the quantum yields for acid generation from DIAS and DIANS in both of these films were 0.07, 0.18, 0.09 and 0.22, respectively, in the presence of an acid indicator. These results indicate that the values of the quantum yields of photodissociation and photoacid formation for DIAS and DIANS in 6FDA-AHHFP film are lower than those in novolak film. In order to elucidate the lowering of the quantum yields in 6FDA-AHHFP film, fluorescence quenchings of sodium 9,10-dimethoxy-anthracene-2-sulfonate and ammonium 8-anilinonaphthalene-1-sulfonate by a model compound of polyimide was carried out in acetonitrile. The fluorescences of these two salts were efficiently quenched by the model compound with the diffusion-controlled rate constant in acetonitrile, suggesting that a strong electron-accepting capability of the imide carbonyl group may hinder the electron transfer process within PAG molecules in 6FDA-AHHFP film. Although a polyimide (6F-THP) protected by tetrahydropyranyl group is insoluble in aqueous base, 6F-THP film containing PAG became soluble in a 2:1 mixture of 2.0 wt% tetramethylammonium hydroxide (TMAH) and methanol by exposure to 365 nm light and successive post-exposure baking (PEB) at 120°C for 10 min. The sensitivity and contrast of 6F-THP with DIANS after the PEB conditions mentioned above were 110 mJ/cm² and 3.7, respectively. A high-resolution pattern with a good profile was transferred into the 3 μm thickness of the 6F-THP film.     

Chemical oscillation with periodic adsorption and desorption of surfactant ions at a water/nitrobenzene interface.

Chemical oscillations with periodic adsorption and desorption of surfactant ions, alkyl sulfate ions, at a water/nitrobenzene interface have been investigated. The interfacial tension was measured with a quasi elastic laser scattering (QELS) method and the interfacial electrical potential was obtained. We found that this oscillation consists of a series of abrupt adsorptions of ions, followed by a gradual desorption. In addition, we observed that each abrupt adsorption was always accompanied by a small waving motion of the liquid interface. From the analysis of the video images of the liquid interface or bulk phase, we could conclude that each abrupt adsorption is caused by nonlinear amplification of mass transfer of ions from the bulk phase to the liquid interface by a Marangoni convection, which was generated due to local adsorption of the surfactant ions at the liquid interface that resulted in the heterogeneity of the interfacial tension. In the present paper, we describe the mechanism of the chemical oscillation in terms of the hydrodynamic effect on the ion adsorption processes, and we also show the interfacial chemical reaction with ion exchange during the ion desorption process.     

Hydrodynamically induced chemical oscillation at a water/nitrobenzene interface

By measuring a time course of interfacial tension and interfacial electrical potential, we successfully observed oscillatory phenomena that were based on alternatively appearing adsorption and desorption processes of anionic surfactant molecules (sodium dodecyl sulfate (SDS)) at the water/nitrobenzene interface. These oscillation patterns were drastically modified by slightly changing the rate of SDS aqueous solution injection into the water phase. When 10 mM of SDS aqueous solution was injected at a low rate, for example, at less than 1 microl/min, abrupt adsorption was repeatedly followed by slow desorption of DS- ions; in other words, the sequence of the oscillation and relaxation processes was repeated. However, when it was injected at a higher rate, no remarkable periodic phenomenon occurred after the first oscillation. In addition, the rapid adsorption process was observed to be accompanied by a flip motion of the liquid/liquid interface and a flow along the interface. This is caused by a Marangoni convection that is brought about by the generation of heterogeneity of interfacial tension. Furthermore, by estimating the flow speed, it was determined that the faster flow tends to quench the periodic oscillation patterns.