團聯式共聚高分子自組裝行為及複合金奈米材 料之結合與應用

Abstract

近幾年來，團聯式共聚高分子(Block copolymer )的相分離與自組裝研究引起了學術界與工業界廣泛的注意。主要是因為團聯式共聚高分子可以組裝為奈米等級的規則結構，因此可望用於太陽能電池、藥物傳遞、與資料存取…等應用，由於團聯式共聚高分子的相互作用力與體積比率的不同，可能相分離為，如：球型(sphere)、圓柱型(cylinder)、或是層狀(lamella)的自組裝結構。過去關於團聯式共聚高分子的研究，主要都是在塊材方面的研究，因此這幾年開始有相關的研究在團聯式共聚高分子在受限環境中會形成的特殊的自組裝行為。這些特殊的自組裝只有在受限的環境才可以被觀察到。 本工作主要的目的為研究雙親性團聯式共聚高分子於圓柱型奈米孔洞內，會具有的特殊相分離與自組裝現象。我們主要使用的方法是以陽極氧化鋁模板(AAO)為主的模板法，這些模板具有可控制大小的奈米級圓柱形孔洞，我們以不同的方法將這些高分子導入圓形孔洞後，便將陽極氧化鋁選擇性移除，之後便可以掃描式電子顯微鏡與穿透式電子顯微鏡來觀察，雙親性團聯式共聚高分子的相分離現象。此外我們也利用P4VP可與金屬前驅物形成錯合物的現象，將如金的材料導入團聯式共聚高分子中，可因此製備特殊形態的金奈米結構。 以及為了提升金奈米材料與團聯式共聚高分子的應用性，在本研究中進一步探討金奈米材料，在合成以及後續的分離方法，由團聯式共聚高分子有良好的自組裝特性，因此在複合共聚高分子及金奈米材料時，對於金奈米材料的合成品質及純度要求提高，因而開發快速簡便的多層液相分離系統。 本論文不僅提供新穎的雙親性團聯式共聚高分子奈米材料的製備方式，同時在後續沿伸應用上，搭配金奈米柱材料在合成以及分離時，所需要整合的製備技術。

In recent years, the phase separation and self-assembly behavior of block copolymers have attracted wide attention. Because block copolymers can self-assemble into nano-scale ordered structures, they can be applied in applications such as organic solar cells, drug devilry, and data storage. They can phase separate into morphologies such as lamella, cylinder, and sphere. In the past, most researches of block copolymers focus on the bulk behavior. Recently, there have been more studies on the self-assembly behavior of block copolymers in confined geometries. Special phase-separated morphologies, which have not been observed in the bulk state, have been observed in confined geometries. Despite this, the phase-separated morphologies of block copolymers in confined geometries are still not fully understood. The main goal of this work is to study the phase separation and self-assembly of block copolymers confined in the cylindrical nanopores of anodic aluminum oxide (AAO) templates. We use polystyrene-block-poly-4-vinylproediene (PS-b-P4VP) as the materials, which form cylindrical morphology on flat substrates. After the PS-b-P4VP chains are introduced into the nanopores using a special solvent-annealing-induced nanowetting in templates (SAINT) method, the AAO templates can be selectively removed. Because of the confined environment of the cylindrical nanopores, one-dimensional block copolymer nanorods or nanotubes can be prepared. We find that the morphologies of the block copolymer nanostructures depend on the types of the annealing solvents. For example, when toluene is used as the annealing solvent, block copolymer nanotubes can be fabricated. In addition, we also develop a hyper process to effectively separate gold nanostructures with different sizes and shpes. The purified gold nanostructure can establish a well-fined relationship between gold nanostructures and block copolymers and to explore the usage of hybrid materials in technological applications. In the future, we will study the confinement effect further by using AAO templates with different pores diameters. The block copolymer nanostructures will also be applied to applications such as local surface plasmon resonance.