Films of mesoporous materials attract broad interest because of their wide applicability in the fields of optics and electronics. Although many of these films have a regular local porous structure, the structural regularity has not been used practically yet because of difficulties in its control on macroscopic scales. Here, we demonstrate the preparation of mesoporous silica films whose porous structure can be described as a single crystal, that is, a long-range order of cage-like pores is maintained over centimetre scales. These films have a three-dimensional hexagonal (space group P6(3)/mmc) porous structure, and the in-plane arrangement of the pores is strictly controlled by a polymeric substrate surface that has been treated by rubbing. This new class of single-crystalline films with mesoscopic periodic structure is a significant breakthrough in bottom-up nanotechnology, and could lead to novel devices, for example, optics in a soft X-ray region, and quantum electronics.

The feasibility of alignment control of low-molecular-weight guest species by controlling the orientation of mesochannels in a mesoporous silica host has been shown for the first time; spectroscopically anisotropic absorption behaviour of a cyanine dye was observed upon its incorporation into the mesochannels of a mesoporous silica film with uniaxially aligned porous structure, proving that the preferred alignment of the dye molecules was achieved on a macroscopic scale.

This article reports the structural variation of SBA-type mesostructured silica formed from a mixture of tetraethyl orthosilicate (TEOS), alkyltrimethylammonium bromides, and 1,3,5-trialkylbenzenes under acidic conditions. Swollen 2D hexagonal mesophases were formed from the silica source and hexadecyltrimethylammonium bromide (C16TAB) with varying amounts of trimethylbenzene (TMB) and triethylbenzene (TEB), whereas drastic structural changes were observed with triisopropylbenzene (TIPB). Characterization by X-ray diffraction and transmission electron microscopy observation revealed that the mesophase was changed from hexagonal p6mm to cubic Pm3n to cubic Fm3m with increasing amounts of TIPB. Thus, the addition of TIPB leads to the preferential formation of spherical micelles rather than the swelling of rodlike micelles. When tetradecyltrimethylammonium bomide (C14TAB) was used, similar structural changes were triggered by smaller amounts of TIPB; however, almost no structural change was observed when octadecyltrimethylammonium bromide (C18TAB) was used. These findings provide a better understanding of the roles of 1,3,5-trialkylbenzenes in the structural control of silica-alkyltrimethylammonium mesophases.

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The effects of organic additives on the structure of phenylene-bridged periodic mesoporous organosilica have been investigated. The mesostructure and pore size were controlled by adding organic additives, such as 1,3,5-triisopropylbenzene and benzyl alcohol under acidic or basic conditions.