Jean-Marc Berquier

Substrates do influence the ordering of mesoporous thin films

Two kinds of ordered structures, a cylindrical hexagonal and a compact hexagonal arrangement of micelles, were synthesized using either CTAB or a Pluronic block copolymer as templating agents. The ordering of thin films deposited on glass, dielectrics (Si3N4, SiTiOx) and a metal with a native oxide (Ti) were compared. We observed that the ordered texture of the films was greatly influenced by the substrate. In order to differentiate the effects of surface roughness and surface forces, glass substrates were systematically modified by grafting ethylene oxide/propylene oxide (EO/PO) statistical copolymers. Varying the EO content allowed fine tuning of the hydrophilicity of the surface. In this case, the same phase and quality of ordering as on bare glass is observed but with a systematic higher contraction of the ordered structure. This is ascribed to the similar chemical nature between the grafted substrate and the templating molecules, which fasten the formation of the ordered structure.

Ag nanoparticles synthesised in template-structured mesoporous silica films on a glass substrate

Ag nanoparticles have been synthesised within a mesoporous template-structured silica film by a chemical route which includes ion-exchange with Ag(NH3)2+ followed by reduction.

Synthesis of Transparent Mesoporous and Mesostructured Thin Silica Films

A novel method for obtaining crack-free transparent periodic mesoporous thin films is described. Such films are prepared by a simple sol-gel process using surfactants as templates, with a pre-treatment of the glass substrate. The silicate precursor (tetraethoxysilane) is pre-hydrolyzed under acidic conditions before dissolving directly cetyltrimethylammonium bromide (CTAB). The solution is then spin-coated on pre-treated glass substrate. After the film has been deposited, it is calcined in air. X-ray Diffraction (XRD) has been used to characterize the film before and after thermal treatment. The film consists of a nanocomposite material with a periodic structure. Before calcination the XRD pattern has a sharp peak at d = 3.8 nms which is broadened and shifted by about 3.0 nm after calcination. Infrared transmission spectra have been performed on the films. Analysis of the free OH group stretching vibration indicates the removal of the surfactant after calcination in addition to an enhancement of the specific surface area.

Infrared Evidence for Hoffman Reaction During Calcination of Surfactant-Templated Silica Films and Analysis of the Resulting Surface Sites

Fourier Transform Infrared transmission spectroscopy is used to characterize surfactant-templated silica films on glass. The calcination process is followed in situ and evidence for the removal of the surfactant along the Hoffman reaction is given. Once calcined, the surface of the pores of the mesoporous films is proven by deuteration experiment to be hydroxylated. Bands are attributed to isolated and hydrogen-bonded silanols. Silylation reaction with hexamethyldisilazane only occurs with isolated silanol groups.

Poly(methylmethacrylate) adsorption onto flat substrates of glass and silica: Influence of water traces in solvent

The adsorbed amount of PMMA on flat glass and silica is measured by infrared external reflection. The effect on PMMA adsorption of water traces in solvent is emphasized: the adsorbed amount increases with the water concentration. Flat glass and silica are compared: on contrary of what is expected, adsorbed amount on glass is higher than on silica. This result is interpreted as due to the difference of behaviour between glass and silica with respect to water adsorption.