2012-08-012024-05-17https://scholars.lib.ntu.edu.tw/handle/123456789/681960摘要：將共軛高分子導入具有特殊的環境應答功能(例如：酸鹼值、溫度和光)之柔軟鏈段而形成的硬桿－柔軟嵌段高分子，被視為極具有開發新一代光電元件之潛力。這主要是藉由環境的改變，帶動了硬桿的共軛高分子產生結構形態與光電物理性質的衍變，因而能提供感測元件使用上於分子結構設計、尺寸及排列上的控制。目前大部分的實驗文獻都集中在含有一個共軛基團A以及一個柔軟成分B的二嵌段或三嵌段共聚合高分子系統，鮮少有三成分組成的A硬桿—B柔軟—C柔軟三嵌段共聚合物。從先前的研究經驗得知，ABC三嵌段線性共聚合物已經比AB二嵌段共聚合物系統隱含著更豐富的自組裝結構形態，而星狀的分子結構要比線性在溶液狀態下呈現了更多有趣且前所未見的形態。因此，我們提出此計畫，運用量子力學計算與分子動力學模擬方法探討線性及雜臂星狀二種分子結構的硬桿嵌段(PF或P3HT)─柔軟嵌段(PNIPAAm(溫度應答)或PDMAEMA(pH及溫度應答) ─柔軟嵌段(PNMA或PEO)三嵌段共聚合高分子在環境應答下其自組裝微結構形態與光電性質的關聯性。即使單就A硬桿—B柔軟—C柔軟三嵌段線性及星狀共聚合物在溶液態下的自組裝結構形態而言，已屬前瞻的尖端基礎研究，因為就我們所知，目前理論模擬計算方面尚無相關的研究文獻，實驗方面也僅有線性分子結構的相關合成及形態研究，尚無ABC三嵌段的星狀高分子合成出來。藉由一系列從量子到原子及介關尺度的研究，我們希望可以了解智慧型材料的分子設計、分子鏈構形和堆疊形態以及光電性質的關聯性，同時也可望能引發光電研發學者的腦力激盪，以提升並推廣其應用價值。<br> Abstract: Lately, the research and development on the conjugated polymers continue to emerge due to their great potentials for a wide range of optoelectronic and electronic applications, such as organic light emitting diodes (OLEDs), organic field-effect transistors (OFETs), and solar cell devices. By introducing one stimuli-responsive (pH, temperature, and light) coiled-like polymer into the conjugated rod-like polymer, the formed rod-coil block copolymers have been proposed as a potential material used in the newly optoelectronic devices. This is mainly attributed to the fact that various self-assembling morphologies as well as the corresponding optoelectronic properties can be induced by varying the environment. Most of the research has mainly focused on the rod-coil diblock and triblock copolymers with only one conjugated and one coiled component. There have been very few studies on the rod-based copolymers with three different components. In fact, copolymers with three different components exhibit a much richer variety of morphologies than those with two components. Moreover, star architecture of coiled ABC triblock copolymers can form quite unique and more diverse morphologies than the linear architecture. To our knowledge, there have been a few experimental studies on the linear but not on the star architecture of A-rod/B-coil/C-coil copolymers. Herein, we propose a theoretical study to explore the molecular conformation, self-assembling behavior, and optoelectronic properties of PF(P3HT)-PNIPAAM (PDMAEMA)-PNMA(PEO) triblock copolymers with two different linear and star architectures. In particular, molecular dynamics simulation and quantum mechanics methods are utilized. This research will be the first theoretical study to address the correlation between the self-assembling morphology types and optoelectronic properties in the conjugated-based stimuli-responsive block copolymers with three components. Through this series of quantum to atomistic to mesoscale simulation studies, we should provide remarkable insights to bridge the correlation between two important categories of self-assembling structures and optoelectronic properties.智慧型應答共軛─柔軟三嵌段共聚合物自組裝微結構形態光電物理特性分子動力學模擬量子力學模擬聚(3-己烷基&#22139吩)聚芴高分子smart responsive rod-coil triblock copolymersself-assembling morphologiesphotoelectrical propertiesmolecular dynamics simulationsquantum mechanicspoly(3-hexyl-thiophenes)polyfluorides