團聯式共聚物(BCP)的自組裝是少數能提供實際控制整體奈米結構的方法之ㄧ，自組裝之BCP在奈米科技有許多可能的應用，例如：光學能帶材料(photonic band gap materials)、奈米蝕刻模板(nanolithographic templates)等。過去BCP的研究大多數集中在具柔軟高分子鏈段的軟段-軟段團聯式共聚物(coid-coil diblock copolymer)；近年來，結合堅硬與柔軟的高分子鏈段所組成的硬段-軟段團聯式共聚物(rod-coil diblock copolymer)引起相當的注意，由於兩種不同構型的高分子結合，可呈現許多複雜的結構和階層性自組裝行為。
本研究主要探討以共軛高分子為主體的硬段-軟段團聯式共聚物，我們利用SAXS、WAXS以及TEM對共軛高分子聚3-己基噻吩 (poly(3-hexylthiophene), P3HT)以及P3HT-b-PMMA硬段-軟段團聯式共聚物的自組裝行為做探討，結果顯示該共聚物呈現階層性自組裝結構：包括由P3HT鏈段與PMMA鏈段微相分離(microphase seperation)所產生P3HT microdomain大尺度之結構(約20 nm)；與P3HT鏈段在其microdomain中所形成之較小尺度(約5nm)之結構，此小尺度結構為P3HT鏈段較不規則之自我聚集堆疊，是由於PMMA鏈段阻礙P3HT鏈段進行規則之層狀堆疊，而誘導出此結構之生成，由變溫SAXS實驗解析出此結構之有序-無序狀態轉變 (order-disorder transition)約在50 ~ 80℃。

Block copolymer (BCP) self-assembly is an essential part of nanotechnology, and it offers one of the few practical strategies for making ensembles of nanostructures. Self-assembled BCPs have found applications in a number of fields of nanotechnology such as photonic band gap materials, nanostructured networks, nanolithographic templates, etc. Most of the research in this field has been focused on coil-coil BCPs with flexible polymer chains. During the past two decades, rod-coil BCPs, where one of the constituting blocks has a rigid conformation and the other is flexible, have attracted great attention. Due to the combination of two extreme polymer chain conformations (rigid and flexible), complex phase structures and morphologies have been observed.
In this study, the self-assembled structure of a conjugated rod-coil P3HT47-b-PMMA220 diblock copolymer was investigated using SAXS, WAXS and TEM. The results showed that this copolymer self-organized to from hierarchical structure with two different length scales. The larger-length-scale structure was formed due to microphase separation between P3HT and PMMA block resulting in P3HT microdomain of ca. 20 nm in diameter embedded in PMMA matrix. The P3HT microdomain further consisted of a smaller-length-scale structure due to the formation of ca. 5 nm in diameter nano-ribbons. The regular layered structure due to the microphase separation between to backbone and side chain of P3HT, in this case, was hindered due to covalent linking with PMMA chains. Furthermore, from temperature-dependent SAXS experiment, an order-disorder transition (ODT) of the nano-ribbon structure in the copolymer was revealed between 50 ~ 80℃.

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