Frontier Research Center, Canon Inc., Ohta-ku, Tokyo, Japan.
Phys Chem Chem Phys. 2012 Jan 28;14(4):1418-23. doi: 10.1039/c1cp23244d. Epub 2011 Dec 1.
Exceptionally strong Bragg diffraction from a mesoporous silica film is achieved by exposing the as-deposited film to vapor of chlorotrimethylsilane (Me(3)SiCl) before extracting the surfactant. The intensity of the X-ray diffraction peak increased 7 times after the surfactant removal and it approached 30% reflectivity. This large increase of diffraction intensity cannot be explained simply by the improved contrast of the electron density, and rearrangement of the pore wall during the Me(3)SiCl vapor treatment is suggested. It is shown by infrared spectroscopy that Me(3)SiCl with a high grafting reactivity effectively caps the silanol groups and prevents the following condensation, which causes the structural degradation. The substitution of the hydrogen atom of hydroxyl groups with trimethylsilyl groups should help the improvement of the structural regularity by reducing the hydrogen bonds in the pore wall. The achieved strong diffraction opens the gate for the application of these regular mesoporous films prepared by a self-assembly process to optical elements in the X-ray region.
通过在提取表面活性剂之前,让沉积的薄膜暴露于氯三甲基硅烷(Me(3)SiCl)蒸汽中,介孔二氧化硅薄膜实现了异常强的布拉格衍射。在去除表面活性剂后,X 射线衍射峰的强度增加了 7 倍,接近 30%的反射率。这种衍射强度的大幅增加不能仅仅用电子密度对比度的提高来解释,因此推测在 Me(3)SiCl 蒸汽处理过程中孔壁发生了重排。红外光谱表明,具有高接枝反应性的 Me(3)SiCl 有效地封端了硅醇基团,并阻止了随后的缩合反应,从而导致结构降解。用三甲基硅烷基取代羟基中的氢原子,通过减少孔壁中的氢键,有助于提高结构的规则性。所实现的强衍射为通过自组装工艺制备的这些规则介孔薄膜在 X 射线区域的光学元件中的应用开辟了道路。