臺灣博碩士論文加值系統

本研究希望藉由小角度X光散射於奈米尺度下的解析特性，觀察不相容的共軛半導體高分子P3HT與絕緣高分子PMMA是否於甲苯溶液中形成各自的液相，以及可能的液相分佈情形。並進一步探討，添加的奈米碳管是否會於溶液中選擇性的分佈於特定液相中。
從不同濃度下分別討論P3HT與PMMA溶解於甲苯溶液內的情形。PMMA分子於溶液中的鏈團形狀不受溶液濃度而改變，然而橢盤狀鏈團的平均迴轉半徑(Rg)會隨濃度提升而下降。而當P3HT溶於甲苯溶劑時，由於P3HT與甲苯溶劑親和性較差，鏈團於溶劑中的形狀會隨濃度而變化。隨著溶液濃度的提高，P3HT扁盤狀鏈團逐漸趨向橢圓柱狀並進一步轉變為較長的柱狀鏈團，鏈團的尺寸亦隨濃度變化有不同的大小。
接著以純P3HT與PMMA液相之散射強度為依據，理論計算含有不同體積分率的P3HT與PMMA液相之混摻溶液的散射強度。與實驗獲得之混摻溶液的散射曲線相比後發現，理論計算曲線與實驗曲線於全q值區間Power law散射曲線的斜率變化皆相同。表示混摻溶液內分子鏈團的形狀與大小皆不受混摻比例的影響。可推論，P3HT與PMMA形成各自的液相分佈於溶液中，分子鏈團並不互相影響。
另一方面，兩相溶液中PMMA成份體積分率的減少，會使得散射曲線計算之K值逐漸下降。在兩相散射密度不變的前提下，意味著兩相界面面積會隨PMMA體積分率而改變。進一步藉由薄膜形態的觀察，確認隨著PMMA體積分率下降，PMMA的團狀區域尺寸減小，造成界面面積減小，和小角度散射觀察結果相符。
在P3HT/PMMA混摻溶液加入奈米碳管的系統內，添加的奈米碳管會選擇性的分佈於共軛高分子的液相之中，此點可由散射起始強度數值與P3HT液相體積分率的關係得知。然而，共軛高分子液相的體積分率，將影響懸浮於溶液中奈米碳管的含量，進而導致整體液相的散射強度隨著P3HT液相體積的增加而增加。

關鍵詞： 小角度X光散射,聚甲基丙烯酸甲酯,聚已基噻吩,相分離

SUMMARY

The liquid phase separation behavior in solution system of poly(3-hexylthiophene-2,5-diyl)(P3HT) and poly(methyl methacrylate)(PMMA) have been explored. The solvent affinity was a critical factor for the conformation change of dissolved polymer molecule, which provides the essential condition to elucidate the occurrence of phase separation in solution. By fitting the calculation of sorted polymer solution with the binary solution system, the liquid phases are stable staying in the blend system and the electron density of phases do not be influenced by the blend ratio. The trend of surface area change by Porod analysis is same with the observation in the thin film. Upon obtained results, polymer liquid phases are independent in blend system and do not affect each other. Furthermore, the suspended CNTs contents were related with the volume ratio of P3HT component in the solution and do not change the liquid phase distribution in the solution, which is a strength evidence to confirm the occurrence of phase separation in solution. In summary, the liquid phase of two polymer components in blend system have not been unveiled by SAXS analysis before. The SAXS analysis in solution experiment is a helpful method for similar binary system of liquid state.

Key words: P3HT, PMMA, SAXS, liquid phase separation

一、緒論1
1.1 前言與研究動機1
二、 文獻回顧2
2.1 小角散射的基本原理2
2.1.1 X-ray散射定理2
2.1.2 散射物體與散射強度間的關係4
2.1.3 稀薄懸浮粒子系統8
2.1.4 非粒子兩相系統與多相系統15
2.2 小角度X光散射之應用19
2.2.1 高分子於有機溶劑中之構象19
2.2.2 奈米碳管的分散性與形貌變化22
2.2.3 PCBM混摻聚賽吩高分子的聚集行為25
2.2.4 計算PCBM聚集結構的介面面積27
三、 實驗材料及方法30
3.1 實驗材料30
3.2 實驗分析儀器32
3.3 實驗步驟34
四、 結果與討論35
4.1 有機溶液中高分子鏈段的行為35
4.1.1 濃度效應對PMMA分子鏈團形狀與大小的影響35
4.1.1 濃度效應對P3HT分子鏈團形狀與大小的影響38
4.1.2 奈米碳管對P3HT與PMMA分子鏈團形狀大小的影響41
4.2 P3HT與PMMA高分子液相混摻效應44
4.2.1 混摻比例對溶液散射強度的影響44
4.2.2 不同液相對混摻溶液散射強度的貢獻47
4.2.3 兩液相界面面積與混摻比例的關係53
4.3 奈米碳管於兩液相系統內選擇性分佈57
4.3.1 奈米碳管數量對溶液散射曲線的影響57
4.3.2 奈米碳管對P3HT成份液相電子密度的影響59
五、 結論65
六、 參考文獻列表67

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