嵌段共聚物產生的奈米結構因其在各個領域上都有潛在應用而受到相當大的重視，像是半導體產業中的微影蝕刻製程，近年來所需的線寬已達到小於10奈米。為了達到如此小的長度，嵌段共聚物必須同時具備低分子量以及非常強的嵌段間排斥力，使分子設計上相當具挑戰性。本論文研究一種新興聚合物「離子液體高分子物複合體」的自組裝行為，該材料通過將離子液體藉由共價鍵與聚合物末端鍵結而成。由於高分子鏈與離子液體之間有非常強的極性-非極性排斥力，此兩成分即使在低聚物狀態下也會產生微相分離，產生特徵尺寸小於10奈米的有序層狀結構以及六角堆積圓柱結構。
我們研究了兩種材料，低聚(二甲基矽氧烷)-離子液體 (ODMS-IL)以及聚(環氧乙烷)-離子液體 (PEO-IL)。我們發現所形成的有序結構、結構特徵距離以及有序-無序相轉化溫度都與離子液體部分所使用的陽離子和陰離子有很大的關聯，這部份可以藉由嵌段共聚物在微相分離上的基本物理學來解釋。此外，我們發現離子液體與PEO綴合後會對PEO的結晶動力學以及結晶能力產生強烈的影響，我們可以通過綴合物在無序熔融態時的結構來解釋這樣的行為。一旦離子液體在熔融態形成離子簇(ionic cluster)，PEO分子鏈的流動性就會受到此離子簇的限制，進而影響其結晶行為。
目前的結果顯示，將離子液體綴合至聚合物結構中是一種有效生成特徵尺寸小於10奈米的有序結構的方法。此外，將其使用於製造薄膜有序結構，並應用在光蝕刻領域上，是一件非常令人感興趣的研究。

The nanostructures generated by block copolymers have received considerable attention for their potential applications in various fields including lithography which requires the line width to reach below 10 nm. To attain such a small lengthscale structure, the block copolymer has to possess both low molecular weight and very strong interblock repulsion, which is challenging in terms of the molecular design to suffice the later condition. This thesis investigates the self-assembly behavior of an emerging polymer material called “polymer-ionic liquid conjugate” formed by covalently coupling ionic liquid (IL) moiety with the polymer at the chain end. Due to very strong polar-nonpolar repulsion between the polymer and the IL, these two constituents undergo microphase separation even in the oligomeric regime, leading to ordered lamellae or hexagonally-packed cylinder structures with sub-10 nm in feature size. Two material systems have been studied here, namely, oligo(dimethyl siloxans) (ODMS)-IL and poly(ethylene oxide) (PEO)-IL conjugates. We revealed that the type of ordered structure formed, the characteristic interdomain distance, and the order-disorder temperature of the ODMS-IL conjugates depended strongly on the cationic and anionic groups of the IL moiety, which could be understood using the basic physics of the microphase transition of block copolymers. Moreover, we revealed that conjugating with the IL moiety exerted a strong effect on the crystallization kinetics and crystallizability of PEO. The observed effect could be rationalized by the structure of the conjugate in the disordered melt state, where the crystallization of PEO was strongly suppressed by the restriction in chain mobility once the IL moiety formed ionic clusters in the melt state. The present work demonstrates that incorporating IL into the polymer structure offers an effective route for generating tunable nanostructures with sub-10 nm feature size and further works relevant to the fabrication of the structure in the thin film for lithography application should be of interest.

Abstract...................I
摘要 ...................III
Table of Contents...................V
List of Figures...................VII
List of Tables...................XI
Chapter 1 Introduction...................1
1.1 Background of research...................1
1.2 Polymer systems exhibiting microphase separation...........3
1.2.1 Block copolymer...................3
1.2.2 Graft copolymer...................8
1.2.3 End-functionalized polymer...................11
1.3 Research motivation and objective...................17
Chapter 2 Structure and Phase Behavior of Oligo(dimethylsiloxane)-Ionic Liquids Conjugates...................19
2.1 Introduction...................19
2.2 Experimental Section...................22
2.2.1 Materials...................22
2.2.2 SAXS Measurement...................24
2.3 Results and Discussion...................25
2.3.1 Self-assembled structure and phase behavior of ODMS-IL conjugates...................25
2.3.2 Phase behavior of the blends ODMS-IL conjugate and ODMS...................38
2.4 Conclusions...................48
Chapter 3 Structure and Phase Transition of Crystalline Polymer-Ionic Liquid Conjugate...................51
3.1 Introduction...................51
3.2 Experimental Section...................54
3.2.1 Materials...................54
3.2.2 SAXS Measurement...................55
3.2.3 Differential Scanning Calorimetry (DSC) Measurement.........56
3.3 Results and Discussion...................58
3.4 Conclusions...................70
Chapter 4 Overall Summary...................72
Chapter 5 References...................75

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