共軛高分子聚3-己基噻吩Poly(3-hexylthiophene) (P3HT) 由於具有良好的帶電載子移動性以及自組裝形成高規則度的結構，因此在太陽能電池或薄膜電晶體等都有相當廣泛的應用。然而P3HT的型態受到分子量、regioregularity (RR)值及製膜時所使用的溶劑相當大的影響。此外，共軛高分子在溶液態的自組裝過程相當緩慢，若我們將溶液靜置一段時間，即進行老化(aging)過程，會導致共軛高分子在不同尺度下的結構改變。
本研究主要探討P3HT單一鏈段在使用不同溶劑製備時的型態(conformation)和螢光性質，利用單分子光譜(single molecule spectroscopy，SMS)的技術來觀察單分子鏈尺度下的高分子表現。本研究使用之兩P3HT其RR值分別為92.5%及93%，雖然其具有相似之分子量和RR值，但在實驗中觀察到的型態和螢光性質的表現上卻有明顯不同，而此”分子內(intra-chain)”的差異在塊材(bulk)或高濃度溶液中會更加被放大。實驗結果顯示此兩種P3HT相較於使用四氫呋喃(THF)之樣品，在使用二甲苯(xylene)製備時會有較短的螢光週期，我們推測在此單分子鏈尺度下的型態和螢光性質差異是由於分子鏈段內其head-to-tail(HT)和head-to-head (HH)序列分布的不同所造成。
本研究的另一目的在於了解老化過程對P3HT單分子鏈段其形態及螢光性質的影響，而使用的為RR值97%之P3HT。實驗結果顯示老化過程會引發分子內的重新排列，而非分子鏈間的聚集(aggregation)，進而增加分子鏈段的排列性。此部分實驗也可得知老化過程不僅在高濃度狀態下能引發分子間的聚集，在稀薄濃度時也會導致分子內的重新排列。

Table of Contents
Table of Contents I
List of Figures III
List of Tables IX
Chapter 1 Introduction 1
1-1 Introduction of luminescent conjugated polymers and their applications 1
1-2 Introduction and application of poly(3-hexylthiophent) (P3HT) 2
1-2-1 Introduction of P3HT 2
1-2-2 Application in organic field effect transistors (OFETs) 4
1-2-3 Application in polymer solar cells 5
1-3 Factors affecting P3HT chain conformation 6
1-3-1 Effects of molecular weight 6
1-3-2 Effects of poly(3-hexylthiophene) regioregularity 10
1-3-3 Effects of solvent quality 14
1-3-4 Influences of aging and gelation processes 21
1-4 Single molecule spectroscopy technique 27
Chapter 2 Research motivation and objective 31
Chapter 3 Experimental Section 32
3-1 Material 32
3-2 Ensemble UV-vis absorption and Photoluminescence measurements 32
3-3 Mobility measurement 32
3-4 Single molecule spectroscopy (SMS) 33
Chapter 4 Results and discussion 36
4-1 Behavior of P3HT in different solvents 36
4-1-1 Basic characterizations of P3HT samples 36
4-1-2 Aging-induced gelation of the xylene solutions studied by ensemble absorption spectra and optical microscope 40
4-1-3 Conformation of isolated P3HT chains 43
4-1-4 Fluorescence properties of the isolated P3HT chains 50
4-1-5 Correlation between conjugation length and fluorescence lifetime 59
4-2 Conformational structure and fluorescence properties of P3HT after aging treatment 66
4-2-1 Bulk properties of aged P3HT-3/xylene solution 66
4-2-2 Effect of solution aging on the conformational structure of isolated P3HT chains 71
4-2-3 Fluorescence properties of the isolated P3HT chains after aging treatment 75
4-2-4 Correlation between conjugation length and fluorescence lifetime of P3HT-3 after aging treatment of the solution 83
Chapter 5 Conclusion 86
Chapter 6 References 87

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