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研究生：	王鼎衡 Wang, Ting-Heng
論文名稱：	高發光效率與低效率滾降的黃色與暖白色有機發光二極體之開發: 元件優化、界面Exciplex能量轉移機制探討及元件效率滾降模型建立 Development of High-Efficiency and Low-Efficiency Roll-off Yellow and Warm White Organic Light-Emitting Diodes(OLEDs): Component Optimization, Investigation of Interface Exciplex Energy Transfer Mechanism, and Establishment of OLED Efficiency Roll-off Model
指導教授：	朱聖緣 Chu, Sheng-Yuan
學位類別：	碩士 Master
系所名稱：	電機資訊學院 - 電機工程學系 Department of Electrical Engineering
論文出版年：	2023
畢業學年度：	111
語文別：	中文
論文頁數：	119
中文關鍵詞：	OLED 、磷光材料、載子復合機制、滾降機制、Exciplex
外文關鍵詞：	OLED, phosphorescent material, carrier recombination mechanism, roll-off mechanism, exciplex
相關次數：	點閱：86 下載：0
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在眾多OLED結構設計中，Exciplex系統因其在元件中的良好性能而變得越來越重要，因為只要利用兩種具有匹配的分子軌道能級的供體分子和受體分子相互作用即可形成Exciplex中性分子，其優勢為降低單重態與三重態之間的能隙以獲得容易的RISC(具有TADF效應)、擁有雙極傳輸特性、降低激子淬滅以及高效的能量傳輸通道。但是，基於Exciplex的OLED往往會在較高電流密度下出現效率滾降，進而限制元件整體效率與亮度性能。同時，Exciplex存在複雜的製造工藝(材料選擇、混合比例以及再現性)。因此，基於Exciplex的OLED仍然存在許多問題。所以本研究的元件將設計圍繞Exciplex系統展開，以達到改善效率滾降、降低製成複雜性與提升再現性的目的。
本論文包含兩大部分，第一部分針對界面Exciplex輔助單主體的黃色磷光OLED進行設計簡化與優化。首先，選擇TCTA與TPBI作為界面形成Exciplex的組合，並將客體磷光材料(PO-01)摻雜至TPBI，使界面Exciplex輔助TPBI主體誘導複合區的有效激子定位。同時，主體的PL與客體的吸收重疊面積大以及適當的能級對齊。因此，此EML設計有助於提高主客體能量轉移效率。接著，通過單載子元件分析，改善元件中載子平衡與控制載子在適當的位置進行復合。再者，通過調整客體摻雜濃度，提升元件效率與降低效率滾降，以此實現77.8 cd/A的CEmax與27.4 %的EQEmax與分別為3.3%與4.4%的低滾降效率。然後，藉由理想因子分析元件主要的載子復合機制，並與其他主體結構進行比較，以此證明本研究之EML的優勢。最後，利用光電與材料量測儀器找出影響元件效率的原因。
第二部分是基於第一部分的結構加入藍色磷光材料(FIrpic)至TCTA，然後調整藍色與黃色客體摻雜濃度比例以及調整EML之主體與客體之相對位置，後續藉由改變傳輸層厚度與調變藍色磷光摻雜濃度，獲得32.6%的高EQEmax。同時，實現良好的暖白光發射穩定性，並且具有17.2%的溫和滾降效率。最後，利用TTA與SPA模型分析元件效率滾降機制，並測試元件再現性與利用和第一部分類似的光電與材料量測儀器找出影響元件效率的原因。

In this work, we demonstrated the strategic design of forming exciplex at the interface using TPBI and TCTA, which simplifies the structure of yellow OLEDs and achieves high device efficiency. By utilizing the interface exciplex and TPBI as the host, and doping PO-01 (10 wt%) in TPBI, optimal energy transfer and exciton utilization were achieved, resulting in the highest device efficiency: current efficiency (CE) of 77.8 cd/A, power efficiency (PE) of 47.9 lm/W, and external quantum efficiency (EQE) of 27.4%. Subsequently, by doping FIrpic into TCTA with proper structural adjustments, high-efficiency warm white OLEDs with an external quantum efficiency exceeding 30% were achieved, and we fully discuss the efficiency roll off mechanism.

摘要 I
致謝 XVI
目錄 XVII
表目錄 XXI
圖目錄 XXII
第一章 緒論	1
1 前言 1
2 激基複合物(Exciplex)之理論介紹與文獻回顧 2
3 研究動機與研究方向 6
4 有機發光二極體基於激基複合物效應文獻整理 8
第二章 理論介紹和機制探討 11
1 基礎理論 11
1.1 能帶理論 11
1.2 有機材料的特性 13
1.3 受激發光理論 15
1.4 分子間的能量轉移機制 18
2 電激發光元件結構與理論 20
2.1 元件電流的限制 22
2.2 元件的結構 26
3 有機發光二極體之各層材料介紹 27
3.1 電洞注入及傳輸材料 27
3.2 電子注入及傳輸材料	28
3.3 主體材料 29
3.4 陽極材料與陰極材料 29
3.5 黃色客體發光材料 30
3.6 藍色客體發光材料 30
4 有機發光二極體的效率提升與改進 31
4.1 影響有機發光二極體的關鍵參數 32
4.2 增進載子的平衡方法 33
4.3 增進出光率的方法 34
第三章 實驗步驟與方法 36
1 元件製程與量測流程 36
2 真空熱蒸鍍系統設備 37
3 實驗材料 38
4 ITO基板前置處理步驟 40
5 真空熱蒸鍍機製程步驟 41
6 實驗量測與分析儀器 42
6.1 單體沉積速率測定 42
6.2 電致發光光譜與電性量測 42
6.3 穿透/吸收光譜儀 42
6.4 時間解析光激螢光(Time-Resolved Photoluminescence) 43
6.5 微拉曼及微光激發光譜儀 43
6.6 接觸角量測儀 44
6.7 紫外光電子能譜儀-UPS分析 45
6.8 原子力顯微鏡 46
6.9 變電壓阻抗分析儀 46
7 效率滾降與激子複合機制之理論模型 47
7.1 三重態-三重態湮滅(Triplet-Triplet Annihilation ; TTA ) 47
7.2 單重態-極化子湮滅(Singlet-polariton Annihilation ; SPA) 47
7.3 理想因子 48
第四章 結果與討論 49
1 基於界面Exciplex的黃色磷光OLED實現高效率與低滾降效率 50
1.1 改善元件載子傳輸之單載子元件比較 50
1.2 改善元件載子平衡之結構 52
1.3 改善元件載子傳輸平衡之V-J-L與效率表現 53
1.4 調整EML客體摻雜濃度之元件結構 58
1.5 調整EML客體摻雜濃度之元件V-J-L與效率表現 59
1.6 探討不同主體結構對激子複合的影響-基於理想因子 62
1.7 探討黃色OLED元件結構的能量轉移機制與確定Exciplex的形成 66
1.8 主體與客體的光致發光與吸收光譜 68
1.9 調整EML客體摻雜濃度之穿透光譜 69
1.10 確定主客體能量轉移之電致發光光譜 70
1.11 調整EML黃色客體摻雜濃度之能隙變化 71
1.12 調整EML黃色客體摻雜濃度之UPS能譜分析 72
1.13 調整EML黃色客體摻雜濃度之接觸角測量和表面能分析 75
1.14 調整EML黃色客體摻雜濃度之表面粗糙度(AFM)分析 76
1.15 調整EML黃色客體摻雜濃度之時間解析光激螢光分析 78
1.16 調整EML黃色客體摻雜濃度的元件之電容頻譜分析 79
2 基於界面Exciplex之WOLED實現高效率與低滾降效率 81
2.1 確定初步之EML的藍色與黃色發光客體摻雜濃度比例 81
2.2 調整EML之主體與客體之相對位置的三種結構 83
2.3 調整EML三種結構的V-J-L與效率表現 84
2.4 探討WOLED的三種結構之能量轉移機制 87
2.5 調整EML的藍色發光客體摻雜濃度之元件結構 89
2.6 調整EML的藍色發光客體摻雜濃度之元件結構V-J-L與效率表現 90
2.7 改善元件載子傳輸之單載子元件比較 92
2.8 改善元件載子平衡之結構 94
2.9 改善元件載子傳輸平衡之V-J-L與效率表現 95
2.10 探討WOLED元件結構在不同亮度下的穩定性 100
2.11 調整EML藍色客體摻雜濃度之能隙變化 101
2.12 調整EML藍色客體摻雜濃度之UPS能譜分析 102
2.13 調整EML藍色客體摻雜濃度以及輔助主體中黃色客體摻雜濃度之時間解析光激螢光分析 105
2.14 調整EML客體摻雜濃度之穿透光譜 106
2.15 探討WOLED元件結構在最佳化參數的穩定性 106
2.16 探討WOLED元件結構在最佳化參數的滾降效率模型擬合 107
第五章 結論與未來展望 109
1 結論 109
2 未來展望 109
參考文獻 111
                                    

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