Frontier Research Center, Canon Inc., 3-30-2 Shimomaruko, Ohta-ku, Tokyo 146-8501, Japan.
J Am Chem Soc. 2010 Jul 14;132(27):9414-9. doi: 10.1021/ja102537s.
Tetrahedral amorphous carbon (ta-C) films with nanoscale structural anisotropy, which are obliquely deposited on a substrate by a filtered cathodic vacuum arc deposition (FAD) technique, allow anisotropic growth of mesostructured silica films thereon. The ta-C films have a uniformly tilted nanoscale columnar structure, which is caused by the self-shadowing effect during the oblique deposition, and consequently, the surface of the film can be morphologically anisotropic when the deposition angle is large enough. When silica films with a two-dimensional hexagonal mesostructure are grown under hydrothermal conditions on these ta-C films, the cylindrical mesochannels are aligned perpendicularly to the deposition direction of ta-C. The distribution of the in-plane alignment direction of the mesochannels can be controlled by the deposition angle of ta-C; it becomes narrower with the increase of the deposition angle and the consequent increase of the surface roughness. The observed alignment of the mesochannels is caused by the anisotropic accommodation of the surfactant molecules on the structurally anisotropic surface of the ta-C films, which is consistent with the fact that the ta-C films prepared at small deposition angles with smoother surface morphology have little alignment controllability. The ta-C film can be removed with the surfactant by calcination, allowing the formation of an aligned mesoporous silica film directly on a substrate. In contrast to this, obliquely evaporated SiO(2) films with a distinct tilted columnar structure and an anisotropic surface morphology provide neither continuous film formation nor controlled alignment of mesochannels even after providing hydrophobicity by a silylation process. This suggests the specificity, in particular, intrinsic strong hydrophobicity, of the ta-C films for the aligned mesostructured silica film formation.
具有纳米级结构各向异性的四面体非晶碳(ta-C)薄膜通过过滤阴极真空弧沉积(FAD)技术倾斜沉积在基底上,允许其上的介孔二氧化硅薄膜各向异性生长。ta-C 薄膜具有均匀倾斜的纳米级柱状结构,这是由于倾斜沉积过程中的自遮蔽效应引起的,因此当沉积角度足够大时,薄膜的表面可以具有形态各向异性。当在这些 ta-C 薄膜上通过水热条件生长具有二维六方介孔结构的二氧化硅薄膜时,圆柱状介孔通道垂直于 ta-C 的沉积方向排列。介孔通道的面内排列方向的分布可以通过 ta-C 的沉积角度来控制;随着沉积角度的增加和表面粗糙度的增加,它变得更窄。观察到的介孔通道的排列是由表面活性剂分子在 ta-C 薄膜的各向异性表面上的各向异性容纳引起的,这与在具有更平滑表面形貌的小沉积角度下制备的 ta-C 薄膜几乎没有排列可控性的事实一致。可以通过煅烧用表面活性剂去除 ta-C 薄膜,从而允许在基底上直接形成排列整齐的介孔二氧化硅薄膜。与此相反,具有明显倾斜柱状结构和各向异性表面形貌的倾斜蒸发 SiO2 薄膜即使通过硅烷化处理提供疏水性也不能提供连续的薄膜形成或介孔通道的受控排列。这表明 ta-C 薄膜具有特定的、特别是内在的强疏水性,对于排列整齐的介孔结构二氧化硅薄膜的形成具有特异性。