導電高分子為軟性電子材料，具備可撓、可塑形、薄膜化、與液相大面積製造的優勢，相對於矽，砷化鎵、氮化鎵、磷化銦等剛性、易碎、不可撓的無機半導體材料，軟性電子材料在穿戴裝置與物聯網應用中極具發展優勢。此外，有機半導體的主要成分為碳，相對大量使用砷、鎵、銦、硒等稀有元素的無機半導體，碳基半導體更環保、經濟、且具永續性．透過組合各種分子單元，可設計出符合應用需求的電子結構，成為未來新穎穿戴式電子元件的前瞻材料。
本研究使用噻吩(thiophene)單元為基礎之共軛高分子，其結構中的含硫雜環相對於純碳基苯環，有更強的電子耦合與分子間作用力，因而形成相對有序的分子堆疊與非侷域電子結構，可提升有機薄膜的導電性；反之，當高分子鏈隨機排列，形貌缺陷阻礙載子傳導，將很大程度地降低載子遷移率。因此透過有序化排列導電高分子可更強化其載子傳導，成為改善高分子電子元件效能的重要手段。為探討分子間作用力與電子耦合對形貌與電子結構的影響，本研究將比較3-己烷噻吩(P3HT)與其衍生材料 Poly(3,6-dialkylthieno[3,2-b]thiophene-co-bithiophene) (PATBT)在不同製程參數下的巨觀形貌與微觀分子堆疊。相較於P3HT，PATBT的結構設計旨在利用熔接的噻吩單元(fused thiophene) 增加分子平面性(planity)，使π軌域電子非局域化，藉此縮小高分子材料本身能隙寬度，提高其材料載子傳導能力；此外，高平面性的thieno[3,2-b]thiophene分子單元有很強的分子間作用力，可形成液晶相，因此有機會得到比P3HT更加有序的形貌。
本論文利用”三明治結構”(Sandwich structure)的成膜系統，藉由控制玻璃間隔片與高分子溶液所產生之毛細拉力，在有奈米溝槽的基板表面定向排列高分子鏈，比較不同製程參數，如成膜溫度、溶劑種類、與表面能對兩種高分子排列行為的影響，藉以調控高分子之排列能力。巨觀上，利用原子力顯微鏡觀察高分子薄膜之纖維形貌。微觀上，藉由極化拉曼光譜量測垂直與平行奈米溝槽排列的分子振盪，利用相互垂直的雷射極化激發分子振盪，因此兩正交極化光的拉曼訊號強度比值可代表共軛高分子排列之異向性程度，意即高分子鏈在微觀尺度的有序程度。以溶質－溶劑分子間作用力的理論模型為基礎，我們不只成功排列出P3HT與PATBT高分子纖維，更得到可對應巨觀形貌的微觀分子排列，建立可系統化調控分子排列的實驗方法學。

The semiconducting polymer materials draw researcher’s attention due to their device flexibility and solution process ability. Poly(3-hexylthiophene)(P3HT) and its derivatives are the most broadly applicable conjugated polymers such as organic thin-film transistors, organic photovoltaic devices, photodetectors, thermoelectric generators, etc. When considering device performance, charge mobility is an essential element; the higher mobility, the better performance. In organic thin films, random chain alignment impedes charge transport and results in low carrier mobility. Therefore controlling morphology is the key toward high performance organic electronics. This thesis utilizes a strategy called “sandwich casting” to produce unidirectional alignment in polymeric thin films. This method induce the anisotropic capillary force between glass spacers and polymer solution. Through this unique control in microscopic regime , the polymer chain can be uniaxially aligned along the nanogrooved substrate. Comparing different physical modulations such as process temperature and solvents, we developed a reliable methodology to control polymer morphology. Through the AFM images, the macroscopic morphology of polymers shows the fiber-like chain alignment. For microscopic investigation, the polarized Raman spectroscopy is applied. The intensity of Raman on the two polarized directions is quantitatively discussed and is correlated to the degree of anisotropy which indicates the level of uniaxially alignment in molecular level.

Key words : Conjugated polymer, Polythiophene, Ordered morphology, anisotropy

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