Thickness control and defects in oriented mesoporous silica films

By using a surfactant-based synthesis strategy, we have earlier demonstrated that the polymerization and growth of silicate micellar assemblies at the air-water interface, under quiescent and dilute acidic aqueous conditions, yields free-standing submicron thickness hexagonal mesoporous silica films in which the channels are oriented parallel to the film surface. TEM imaging studies of these thin films showed that microscopic defects pervade the channel structure with topologies resembling those found in lyotropic liquid crystals. This suggested that the mesoporous silica film evolved from silicification of a surface lyotropic silicate mesophase. Herein it is demonstrated that film growth, defect structure, extent of polymerization, and mesoporosity sensitively depend on the choice of synthesis acidity, temperature and mixing, and in the case of supported films, on the choice of substrate. In particular, a ten-fold increase in the thickness of the film can be obtained by simply lowering the acidity and moving to ambient temperature conditions whilst an alteration in mixing conditions can change the film from a discrete to a continuous morphology. Combined PXRD, TEM and nitrogen adsorption studies show that the silica films are hexagonal, oriented and mesoporous. Furthermore, the observation of a focal conic fan-type texture in the free-standing films shows that defect controlled director fields, that exist in a precursor hexagonal lyotropic silicate mesophase, are preserved in the channel structure of the mesoporous silica phase. Proof-of-existence of liquid crystalline texture in such free-standing mesoporous silica films, provides direct evidence that film growth evolves from the cooperative assembly and organization of silicate micellar species at the air-water interface.