2011-08-012024-05-14https://scholars.lib.ntu.edu.tw/handle/123456789/656186摘要：軟鏈-軟鏈嵌段共聚物因可相分離形成多樣的規整微結構且具有如微影蝕刻等應用價值，故已被大量研究。硬桿-軟鏈共軛嵌段共聚物的研究雖然漸漸被重視，然而目前研究發現此類共聚物的微結構較為散亂，最主要原因為硬桿之間有極強的作用力，在相分離過程中會先行聚集。若硬桿-軟鏈共軛嵌段共聚物的微結構與方向性能有效被調控，則其應用性將大增，如可提升太陽能電池與有機發光二極體的效率等。本計畫目的在於結合實驗與理論分析來探討硬桿-軟鏈共軛嵌段共聚物在塊狀與薄膜中的微結構並利用超分子概念以尋求有效控制其微結構的方法。利用小分子與軟鏈-軟鏈嵌段共聚物透過氫鍵或靜電力結合已被證明可調控其相分離結構與薄膜中的方向性，然此一概念目前尚未應用於硬桿-軟鏈嵌段共聚物中。我們將合成一系列硬桿-軟鏈共軛嵌段共聚物，其中的軟鏈段可與小分子以非共價鍵結合，我們希望能藉由改變小分子的數量與外在條件如溫度、溶劑等來調整微結構的型態與尺寸，甚至能控制微結構在薄膜中的方向性。在本計畫中實驗分析與理論計算將同時進行、相互驗證，以期能發展出可預測、可調控的硬桿-軟鏈共軛嵌段共聚物微結構。<br> Abstract: The formation of modulated phases with predefined morphologies represents an efficient route to engineer mesoscale positional order in functional soft materials composed of block copolymers (BCPs). While much of the work to date has focused on using conventional flexible-chain BCPs, self-assembly of conjugated rod-coil BCPs has the additional large potential to directly produce novel soft materials, including ultrathin films. The main idea of this project is to design highly organized functional nanostructures based on the self-assembly of BCP supramolecules formed by conjugated copolymers and small molecules that are non-covalently (reversibly) attached to one of the BCP blocks. Such systems can spontaneously separate at nanoscale dimensions into regular periodic arrays of microdomains similar to those in conventional linear BCPs. The small molecules, in turn, self-assemble within one of the microdomains and thus a library of hierarchical structure-within-structure morphologies can be formed by varying the stoichiometry between the small molecules and block copolymers or by re-distributing small molecules between the microdomains using an external stimulus, such as heat. A central topic of the planned research involves gaining improved control over the structure formation and over the morphology of supramolecular assemblies arising as a result of the (micro)segregation of copolymers in bulk, at or near solid substrates. In particular, one would like to construct polymer systems, which undergo reversible transformations and, thus, can be switched forward and backward between different types of assemblies with tunable dimensions or between different types of desired morphologies. Using a multidisciplinary approach, combining advanced synthetic strategies, experimental and theoretical approaches as well as massive computer simulation (both fully atomistic and coarse-grained), we are going to attack this problem, aiming at predicting the stable assemblies built up from the BCP-based supramolecules and their phase diagrams for bulk state and in thin-film geometries.