本論文研究陽離子型環銥金屬錯合物[Ir(ppy)2bpy]+放光電子能態間之能量轉移，以自行架設之時間相關單一光子技術系統、奈秒時間解析螢光系統，測量[Ir(ppy)2bpy]+於氯仿、二氯甲烷、乙腈、二甲基甲醯胺等幾種常用溶劑及反微胞系統中之放光行為，並發展動力學機制與瞭解環境侷限效應。為了使研究成果與實際的元件應用更為貼近，我們使用界面活性劑磺基琥珀酸钠二辛酯(Dioctyl sodium sulfosuccinate, AOT)形成反微胞系統，創造介於液態與固態間的侷限環境， AOT適用的非極性溶劑環境相當廣泛，其反微胞內徑由極性溶劑與界面活性劑之分子數比值Ws決定(W_s "=" "[Polar solvent]" /"[AOT]" )，本研究中使用兩種反微胞尺寸，分別是Ws=2及Ws=4。在[Ir(ppy)2bpy]+的全光譜中，我們總共發現六個放光電子激發態的存在，其中五個衰減成分由生命期短至長排序為τ1~τ5，上昇成分則令為τr。在藍色譜帶有兩成分存在，生命期τ2約1.5ns的貢獻能態指認為配位基ppy內電荷轉移能態3ILCTppy，生命期τ5在1.4~2.9 μs的貢獻能態為配位基間電荷轉移能態3LLCT。在綠色譜帶亦有兩生命期較短的成分存在，分別是來自3MLCTppy，生命期τ3為幾個奈秒的放光；以及來自3MLCTppy/bpy混合能態，生命期τ1範圍在0.21~0.45 ns的快速衰減成分。快速上升成分與生命期幾百奈秒的下降成分則屬於橘色譜帶，上升成分生命期τr約0.19~0.45 ns，是由3MLCTppy/bpy至3MLCTbpy能態的激子轉移造成；而生命期τ4約幾百個奈秒的衰減成分則是3MLCTbpy能態的放光。藉由各成分生命期及貢獻比例隨溶劑極性變化的趨勢，我們修正之前吳等人(J. Phys. Chem. A 2010, 114 (38), 10339-44.)針對[Ir(ppy)2bpy]+的電子激態動力學模型，更貼切的描述[Ir(ppy)2bpy]+在不同極性環境下的能量轉移情形。

摘要 I
目錄 II
圖目錄 V
表目錄 XXIII
第一章 緒論 1
1.1 前言 1
1.2 有機電致發光材料沿革 1
1.3 過渡金屬錯合物發光原理 2
1.4 主客化學 4
1.5 文獻回顧 5
1.5.1 環銥金屬錯合物 5
1.5.2 環境侷限效應與反微胞系統 13
1.6 研究動機 18
第二章 實驗系統架設與樣品配製 19
2.1 紫外光-可見光吸收分光光度計與螢光分光光度計 19
2.2 奈秒(nanosecond)時間解析放光光譜技術 20
2.3 時間相關單一光子計數系統(Time-Correlated Single Photon Counting, TCSPC) 22
2.3.1 原理 22
2.3.2 鑑別器(Discriminator) 25
2.3.2.1 前緣式鑑別器 (Leading-edge discriminator，LED) 25
2.3.2.2 分數式鑑別器 (Constant-fraction discriminator，CFD) 26
2.3.3 偵測器(Detector) 26
2.3.4 前置放大器(Pre-amplifier) 28
2.3.5 時間振幅轉換器(Time-to-amplitude converter, TAC) 28
2.3.6 時間相關單光子計數系統架設 29
2.4 動態光散射儀 31
2.5 實驗設定條件 32
2.6 合成方法 34
2.7 實驗藥品濃度與配置方法 35
2.7.1 樣品配置方法 35
第三章 實驗結果 37
3.1 反微胞尺寸鑑定 37
3.2 理論計算結果 37
3.3 穩態吸收與放光光譜 39
3.3.1 一般溶劑系統 39
3.3.2 DMF/AOT反微胞系統 40
3.4 量子產率(Quantum yield) 41
3.5 奈秒時間解析光譜 42
3.5.1 一般溶劑系統 42
3.5.2 DMF/AOT反微胞系統 43
3.6 短時域放光衰減光譜 44
3.6.1 一般溶劑系統 44
3.6.2 DMF/AOT反微胞系統 46
第四章 動力學模式與討論 123
4.1 [Ir(ppy)2bpy]+之AOT反微胞溶液 123
4.2 動力學模型的推導修正 123
4.2.1 一般溶劑系統 123
4.2.2 DMF/AOT反微胞系統 126
第五章 結論及未來展望 135
參考文獻 137
附錄 TD-DFT理論計算 141

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