我們使用時間解析螢光技術，研究兩個以矽烷基 (SiMe2) 作為間隙物且具有立體規則性 (regioregular) 之電子傳遞共聚物單體DA與雙聚體ADDA分子，其中給體D與受體A分別為aniline以及trans-stilbene之發色團。由於單一矽烷基與π-系統沒有電子共軛，可以視為絕緣間隙物，共聚物的光物理性質會類似於其相對應的單體，而烷基則可以增加共聚物在有機溶劑中的溶解度。以266 nm波長飛秒雷射光源激發，共聚物單體與雙聚體之螢光訊號在最初有一個迅速的1-5 ps的衰減成分和接近系統響應函數的快速上升訊號~ 0.4 ps (τ_v^A)，接著以四個自然指數衰減，其時間常數分別為數十個至一百個皮秒 (〖 τ〗_B, 〖 τ〗_C)，數個奈秒 (〖 τ〗_o^A, τ_Re^CT)。τ_v^A指認為分子的振動能態鬆弛與溶劑能量穩定化(solvation)的過程。而〖 τ〗_B 則指認為光異構化與電荷轉移途徑的生命期，〖 τ〗_o^A則指認為trans-stilbene色團 S1激發態的螢光生命期，其中〖 τ〗_B與溶劑的黏度和極性呈現出線性關係，證實在trans-stilbene S1激發態構型緩解為主要的緩解途徑之一。〖 τ〗_C, τ_Re^CT則與溶劑極性呈現出反向線性關係，吾人指認〖 τ〗_C, τ_Re^CT分別為電荷分離態激發態的生成與重合生命期。皮秒時間解析螢光指出 DA與ADDA中電荷傳遞與異構化的速率分別為 (130 ps)-1以及 (126 ps)-1，並分別以(4.3 ns)-1以及 (4.2 ns)-1的速率進行電子重合，與文獻中的結果相符。電子傳遞主要是透過鍵與鍵電子耦合作用力，而 DA與 ADDA中電子傳遞速率的無差異，則暗示兩種共聚物內部的給體–受體之間具有相似的偶合作用力。本實驗結果顯示以矽烷基為間隙物的共聚物小分子，由於合成相當簡易與有效的電子傳遞，在光引誘電子傳遞材料之應用方面具有很好的發展潛力。

摘要 I
ABSTRACT III
謝誌 V
第一章 緒論 1
1.1 飛秒雷射光譜簡介 1
1.2 電子轉移理論 2
1.3 實驗目的 11
第二章 文獻回顧 12
2.1 給體受體分子簡介與論文回顧 13
2.1.1 亞甲矽烷基的光化學反應 14
2.1.2 苯乙烯的光化學反應 16
2.1.3 苯胺的光化學反應 19
2.2 給體―橋梁―受體之光致電子轉移系統 22
第三章 實驗系統與儀器架設 25
3.1 穩態(steady-state)紫外-可見光吸收光譜儀與螢光分光光譜儀 25
3.2 時間解析系統 26
3.2.1 雷射光源 26
3.2.2 二倍頻及三倍頻光源 29
3.2.3 時間相關單光子計數系統(Time Correlated Single Photon Counting) 30
3.2.3.1 原理 30
3.2.3.2 實驗架設 34
3.2.4 螢光上轉換 (Fluorescence Up-Conversion) 系統 35
3.2.4.1 原理 35
3.2.4.2 相位匹配 (Phase Matching) 36
3.2.4.3 實驗架設 42
3.2.5 實驗條件 44
3.3 樣品 45
第四章 實驗結果與數據分析 47
4.1 前言 47
4.2 實驗結果與數據分析 48
4.2.1 穩態光譜 48
4.2.2 DA共聚單體與ADDA雙聚體激發態生命期的量測 57
第五章 光致電子轉移機制探討 92
5.1 穩態光譜之解析 92
5.2 生命期之指認 107
第六章 結論與未來展望 126
參考文獻 128

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