Tongjit Kidchob

Sol-gel reactions of 3-glycidoxypropyltrimethoxysilane in a highly basic aqueous solution

The reactions of 3-glycidoxypropyltrimethoxysilane in a highly basic aqueous solution have been studied by multinuclear magnetic resonance and light scattering techniques. The study has shown that in this peculiar chemical environment the alkoxy groups of 3-glycidoxypropyltrimethoxysilane undergo a fast hydrolysis and condensation which favor the formation of open hybrid silica cages. The silica condensation reaches 90% at a short aging time but does not go to completion even after 9 days. The highly basic conditions also slow down the opening of the epoxies which fully react only after several days of aging. The epoxy opening generates different chemical species and several reaction pathways have been observed; in particular, the formation of polyethylene oxide chains, diols, termination of the organic chain by methyl ether groups and formation of dioxane species. These reactions are slow and proceed gradually with aging; light scattering analysis has shown that clusters of dimensions lower than 20 nm are formed after two days of reactions, but their further growth is hindered by the highly basic conditions which limit full silica condensation and formation of organic chains.

Evaporation of Ethanol and Ethanol-Water Mixtures Studied by Time-Resolved Infrared Spectroscopy

The knowledge of the physics and the chemistry behind the evaporation of solvents is very important for the development of several technologies, especially in the fabrication of thin films from liquid phase and the organization of nanostructures by evaporation-induced self-assembly. Ethanol, in particular, is one of the most common solvents in sol-gel and evaporation-induced self-assembly processing of thin films, and a detailed understanding of its role during these processes is of fundamental importance. Rapid scan time-resolved infrared spectroscopy has been applied to study in situ the evaporation of ethanol and ethanol-water droplets on a ZnSe substrate. Whereas the evaporation rate of ethanol remains constant during the process, water is adsorbed by the ethanol droplet from the external environment and evaporates in three stages that are characterized by different evaporation rates. The adsorption and evaporation process of water in an ethanol droplet has been observed to follow a complex behavior: due to this reason, it has been analyzed by two-dimensional infrared correlation. Three different components in the water bending band have been resolved.

Thermal-induced phase transitions in self-assembled mesostructured films studied by small-angle X-ray scattering

Two examples of phase transition in self-assembled mesostructured hybrid thin films are reported. The materials have been synthesized using tetraethoxysilane as the silica source hydrolyzed with or without the addition of methyltriethoxysilane. The combined use of transmission electron microscopy, small-angle X-ray scattering and computer simulation has been introduced to achieve a clear identification of the organized phases. A structural study of the self-assembled mesophases as a function of thermal treatment has allowed the overall phase transition to be followed. The initial symmetries of mesophases in as-deposited films have been linked to those observed in samples after thermal treatment. The monodimensional shrinkage of silica films during calcination has induced a phase transition from face-centered orthorhombic to body-centered cubic. In hybrid films, instead, the phase transition has not involved a change in the unit cell but a contraction of the cell parameter normal to the substrate.

Densification of sol–gel silica thin films induced by hard X-rays generated by synchrotron radiation

In this article the effects induced by exposure of sol-gel thin films to hard X-rays have been studied. Thin films of silica and hybrid organic-inorganic silica have been prepared via dip-coating and the materials were exposed immediately after preparation to an intense source of light of several keV generated by a synchrotron source. The samples were exposed to increasing doses and the effects of the radiation have been evaluated by Fourier transform infrared spectroscopy, spectroscopic ellipsometry and atomic force microscopy. The X-ray beam induces a significant densification on the silica films without producing any degradation such as cracks, flaws or delamination at the interface. The densification is accompanied by a decrease in thickness and an increase in refractive index both in the pure silica and in the hybrid films. The effect on the hybrid material is to induce densification through reaction of silanol groups but also removal of the organic groups, which are covalently bonded to silicon via Si-C bonds. At the highest exposure dose the removal of the organic groups is complete and the film becomes pure silica. Hard X-rays can be used as an efficient and direct writing tool to pattern coating layers of different types of compositions.

Patterning block copolymer thin films by deep X-ray lithography

Developing fast, cheap and reliable micro and nanofabrication technologies for block copolymer thin films is a key issue for exploiting the wide potential applications of this class of materials. We have used a synchrotron source of high energy photons (hard X-rays) for developing a lithographic tool that allows direct writing of block-copolymer thin films. We have exposed films prepared by a tri-block copolymer, Pluronic F127, to increasing doses of radiation to evaluate the effect of high energy X-rays on the samples. The as-deposited films show a crystalline structure due to the crystallization of polyethylene oxide chains in Pluronic F127; the exposure to low doses causes a phase change from crystalline to amorphous, as is shown by infrared spectroscopy. Another effect of the exposure to X-rays of the block copolymer films is the surface roughness reduction which has been observed by atomic force microscopy, At higher doses the X-rays erase the film from the substrate allowing the formation of patterned polymeric structures. Deep X-ray lithography has proved to be a very effective tool to pattern block copolymer films by a direct, top-down method.

Kinetics of polycondensation reactions during self-assembly of mesostructured films studied by in situ infrared spectroscopy

In situ synchrotron FTIR experiments have been performed during evaporation-induced self-assembly (EISA) of mesoporous films and the role of silica polycondensation in obtaining highly organized mesostructures has been illuminated.

Liquid-Phase Preparation and Characterization of Zinc Oxide Nanoparticles

Zinc oxide (ZnO) nanoparticles have been prepared by a wet chemical method, from zinc acetate and LiOH ethanol-based solutions. The resulted nanoparticles were dispersed in a solvent. The effect of solvent (ethanol or butanol) and surfactant (polyethylene glycol-PEG 200) on the average size and size distribution of the nanoparticles was investigated by light scattering measurements. Smaller size was observed for ZnO nanoparticles dispersed in butanol and PEG 200. The statistical parameters of the Gaussian size distribution curves were calculated. ZnO nanoparticles have been prepared to be used as seeds on a substrate for the growth of ZnO nanowires. The morphology, surface roughness, crystalline structure, and orientation of the nanoparticles deposed on silicon substrate were characterized by atomic force microscopy and x-ray diffraction, respectively.