Fabrication of Perpendicularly Aligned Nanocylinder Array Structures and Nano-Metallized Materials Using Block Copolymer Films

该项目的目标是开发一种纳米结构材料的制造工艺，其尺寸范围为十纳米级（~ 10^0 nm），这是先进的光刻技术无法达到的。嵌段共聚物纳米结构是通过精心设计的功能单体的可控聚合和产生的嵌段共聚物的自组装来构建的，从而通过两个自下而上的过程，即功能单体的设计和嵌段共聚物的自组装，形成十纳米组装体。为了使该项目达到目标，采用嵌段共聚物作为纳米模板，可以使各种材料具有与嵌段共聚物完全相同的特定形状和尺寸的纳米结构。嵌段共聚物体系的优点之一是可显著扩展加工区域，可用于大面积加工。在本项目期间，先后制备了由亲水性聚氧乙烯嵌段（PEO）和疏水性聚甲基丙烯酸酯组成的独特嵌段共聚物，并在膜中再现了高度有序的六方圆柱形相结构。各种各样的材料如金属、金属氧化物、陶瓷、半导体和聚合物被用来掺入PEO域。所制备的杂化薄膜具有与嵌段共聚物完全相同的六方圆柱阵列结构。此外，还成功地提取了纳米结构在电、电子、磁和光学性质方面的特定功能。杂化薄膜通过功能化的PEO柱体表现出各向异性的电化学导电性，这在生物过滤器、有机太阳能电池、人工离子通道和各向异性导电纳米线等新器件的制造中具有重要意义。

A goal of this project was to develop a fabrication process of nano-structured materials with a size ranging to deca-nano meter level (〜10^0 nm), where can not be reached with advanced lithographic techniques. Block copolymer nanostructures are built up with controlled polymerization of well-designed functional monomers and self-assembling of the resulting block copolymers, leading to deca-nano assemblies with two step bottom-up process, i.e., design of functional monomers and self-assembling of block copolymers. In order to elevate this project to the goal, the block copolymers were employed to be utilized as nanotemplates, which can make various kinds of materials nanostructured with specific shapes and sizes exactly same as those of block copolymers. One of advantages of block copolymer systems is to significantly expand processing areas, which can be applied for large area fabrications. During the term of this project, unique block copolymers consisting of hydrophilic polyethylene oxide block (PEO) and hydrophobic polymethacrylate with liquid crsytallin side chains were successively produced and the highly ordered hexagonal cylindrical phase structures were reproductively fabricated in the films. The various kinds of materials such as metals, metal oxides, ceramics, semiconductors, and polymers were utilized to incorporate into the PEO domains. The resulting hybrid thin film exhibited the hexagonal cylinder array structures which had exactly same nano-futures with the block copolymers on the substrates. Furthermore, nanostructure-specific functions in electric, electronic, magnetic, and optical properties were successfully extracted. The hybrid thin film especially showed anisotropic electrochemical conductivity through the functionalized PEO cylinders, which could be essential on new device fabrications such as biofilter, organic solar cell, artificial ion-channel, and anisotropically conducting nanowire.