近年來，空間侷限環境對聚合物的相轉變行為已經成為廣泛關注的話題。本研究主要探討聚(3-己基噻吩)(P3HT)在陽極氧化鋁模板(AAO)奈米侷限環境下的結晶方向性。P3HT是一種半導體結晶的聚合物也是有機共軛高分子，其良好的結晶性與光電性質，加上本身的自組裝特性，能夠形成規則的奈米結構，目前廣泛運用於共軛高分子太陽能電池(CPSC)及有機場效電晶體(OFETS)等光學元件中。P3HT的光電特性深受其結晶度與巨觀結晶排列規則度影響，因此，控制這兩個參數對材料的光物理性質極為重要。
在本研究中，藉由國家同步輻射中心的光束線17A-廣角度X光散射(WAXS)來分析P3HT滲透入AAO奈米孔洞後的散射圖譜，利用特徵散射峰和型態分析上的資訊，探討晶體之結晶方向性受結晶溫度的影響，藉由掃描式電子顯微鏡(SEM)觀測P3HT在AAO模板中的晶體結構。由SEM的結果可以發現，利用不同配置樣品的方法與不同結晶條件，P3HT晶體在AAO奈米孔洞中皆為奈米柱的型態而不是奈米管。由WAXS的結果發現，P3HT之結晶方向性在不同結晶條件下，P3HT晶體大多傾向垂直方向結晶(edge-on orientation type)。然而，也可以在一定的結晶條件下促使小部分的P3HT晶體呈現水平方向(face-on orientation type)結晶。由DSC圖譜可以觀察到，相較於P3HT薄膜，在侷限環境下，P3HT的熔點與結晶溫度皆會有明顯的下降；且在較大的侷限環境，會使P3HT的熔點與結晶溫度下降的幅度有顯著的提升。

The effect of spatial confinement on the structure and phase transition behavior of polymer has been a subject of extensive interest. This study is centered on resolving the preferred orientation of poly(3-hexylthiophene) (P3HT) crystallites formed within the 2D nanoconfined space of Anodic Aluminum Oxide Template (AAO) nanochannels. P3HT is a crystalline semiconduting polymer which has attracted significant attention due to its potential in the application as the active material for bulk heterojunction solar cell and organic field-effect transistors (OFETS). The opto-electronic properties of P3HT are expected to strongly depend on its degree of crystallinity and the gobal arrangement of the crystallites; therefore, controlling these two morphological paraemeters is important for tailoring the photophysical properties of the material. In this work, we incorporated P3HT into AAO nanochannels with the diameter of 20 and 100 nm and examined the crystal orientation within the channels as a function of the post treatment condition Tc by means of 2D wide angle X-ray diffraction patterns collected at BL01C2 and BL17A1 at the National Synchrotron Radiation Research Center (NSRRC). The P3HT crystallites predominantly adopted the edge-on orientation with the crystalline backbone aligning perpendicularly to the long axis of the cylindrical pores since this type of orientation was kinetically favored for the long range crystal growth along the channel axis. However, using AAO nanochannels with smaller diameter and an annealing or recrystallization treatment at 160˚C induced the formation of a small fraction of the face-on orientation. It was also found that the as-cast P3HT in the confined space with smaller pore size exhibited higher degree of crystallinity and better orientation. The samples prepared from the xylene solution generally possessed better orientation and higher crystallinity than those prepared from the THF solution. However, we found that melt recrystallization removed the nucleus in the samples, which hindered the crystal growth, resulting in a decrease in the degree of crystallinity.

Table of Contents
Abstract II
摘要 IV
致謝 V
Table of Contents VI
List of Figures VIII
List of Tables XI
Chapter 1 Introduction 1
1.1 Spatially confined polymer system 1
1.2 Anodic Aluminum Oxide Template (AAO) 8
1.3 Poly(3-alkylthiophene) (P3HT) 14
1.4 Motivation and Objectives of the Study 25
Chapter 2 Experimental Section 27
2.1 Materials 27
2.2 Experimental design 28
2.3 Sample Preparation 29
2.4 Characterization 29
2.4.1 Wide Angle X-ray Scattering (WAXS) Measurements 29
2.4.2 Field Emission Scanning Microscope (SEM) 30
Chapter 3 Results and Discussion 31
3.1 Effect of casting solvent 31
3.1.1 Morphology of P3HT in AAO nanochannels 31
3.1.2 Crystallinity of P3HT in AAO nanochannels 32
3.1.3 Crystal orientation of P3HT in AAO nanochannels 36
3.2 Effect of pore size of AAO nanochannels 40
3.2.1 Geometric morphology of P3HT in AAO nanochannels with different pore sizes 40
3.2.2 Crystallinity of P3HT in AAO nanochannels different pore diameters 40
3.2.3 Crystal orientation of P3HT in AAO nanochannels with different pore diameters 41
3.3 Effect of melt recrystallization 42
3.3.1 Crystallinity of P3HT in AAO nanochannels after melt recrystallization 42
3.3.2 Crystal orientation of P3HT in AAO nanochannels after melt recrystallization 43
3.4 Discussion 45
Chapter 4 References 50

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