Surfactant-templated silica thin films are potentially important materials for applications such as chemical sensing. However, a serious limitation for their use in aqueous environments is their poor hydrolytic stability. One convenient method of increasing the resistance of mesoporous silica to water degradation is addition of alumina, either doped into the pore walls during material synthesis or grafted onto the pore surface of preformed mesophases. Here, we compare these two routes to Al-modified mesoporous silica with respect to their effectiveness in decreasing the solubility of thin mesoporous silicate films. Direct synthesis of templated silica films prepared with Al/Si = 1:50 was found to limit film degradation, as measured by changes in film thickness, to less than 15% at near-neutral pH over a 1 week period. In addition to suppressing film dissolution, addition of Al can also cause structural changes in silica films templated with the nonionic surfactant Brij 56 (C 16H 33(OCH 2CH 2) n∼10OH), including mesophase transformation, a decrease in accessible porosity, and an increase in structural disorder. The solubility behavior of films is also sensitive to their particular mesophase, with 3D phases (cubic, disordered) possessing less internal but more thickness stability than 2D phases (hexagonal), as determined with ellipsometric measurements. Finally, grafting of Al species onto the surface of surfactant-templated silica films also significantly increases aqueous stability, although to a lesser extent than the direct synthesis route.
Inorganic mesoporous thin-films are important for applications such as membranes, sensors, low-dielectric-constant insulators (so-called low κ dielectrics), and fluidic devices. Over the past five years, several research groups have demonstrated the efficacy of using evaporation accompanying conventional coating operations such as spin- and dip-coating as an efficient means of driving the self-assembly of homogeneous solutions into highly ordered, oriented, mesostructured films. Understanding such evaporation-induced self-assembly (EISA) processes is of interest for both fundamental and technological reasons. Here, we use spatially resolved 2D grazing incidence X-ray scattering in combination with optical interferometry during steady-state dipcoating of surfactant-templated silica thin-films to structurally and compositionally characterize the EISA process. We report the evolution of a hexagonal (p6 mm) thin-film mesophase from a homogeneous precursor solution and its further structural development during drying and calcination. Monte Carlo simulations of water/ethanol/surfactant bulk phase behavior are used to investigate the role of ethanol in the self-assembly process, and we propose a mechanism to explain the observed dilation in unit cell dimensions during solvent evaporation.
Using a micro-Contact Printing ({mu}-CP) technique, substrates are prepared with patterns of hydrophilic, hydroxyl-terminated SAMS and hydrophobic methyl-terminated SAMS. Beginning with a homogeneous solution of silica, surfactant, ethanol, water, and functional silane, preferential ethanol evaporation during dip-coating, causes water enrichment and selective de-wetting of the hydrophobic SAMS. Correspondingly, film deposition occurs exclusively on the patterned hydrophilic SAMS. In addition, by co-condensation of tetrafunctional silanes (Si(OR){sub 4}) with tri-functional organosilanes ((RO){sub 3}Si(CH{sub 2}){sub 3}NH{sub 2}), the authors have selectively derived the silica framework with functional amine NH{sub 2} groups. A pH sensitive, micro-fluidic system was formed by further conjugation reactions with pH sensitive dye molecules.