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研究生:呂淮安
研究生(外文):Huai-AnLu
論文名稱:以水/醇可溶性之含氮冠醚基芴衍生物為電子注入層製備高效率高分子發光二極體
論文名稱(外文):Fabrication of Highly Efficient PLEDs Using Water/Alcohol-Soluble Fluorene Derivative Containing Azacrown Ether Groups as Electron Injection Layer
指導教授:陳雲陳雲引用關係
指導教授(外文):Yun Chen
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學工程學系碩博士班
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2012
畢業學年度:100
語文別:中文
論文頁數:115
中文關鍵詞:高分子發光二極體電子注入層冠醚
外文關鍵詞:PLEDcrown etherwet processeselectron-injection layer
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高分子發光二極體(Polymer Light-Emitting Diode, PLED)是藉由從陽極與陰極注入電洞及電子,並在發光層中再結合,進而發出不同的光色,因此電荷注入及傳輸速率的平衡是影響發光效率最重要的因素。然而在大部分的有機共軛材料中,電洞通常比電子容易注入且有較好的傳輸能力,因此增進電子的注入與傳輸能力是提升PLED元件效率最有效的方法之一。許多研究利用低功函數金屬來提升電子的注入能力,然而低功函數金屬在大氣中的穩定性差,又必須以真空蒸鍍的方法來製備,成本高且不易控制其蒸鍍條件,因此可用濕式製程成膜的有機電子注入材料近年來蓬勃發展。
本研究合成含有三個含氮冠醚基團的芴衍生物FTC[51],並以FTC及含鹼金屬弱酸鹽類(M+)的FTC作為電子注入層,取代傳統的低功函數金屬,並以濕式製程(Spin-Coating)製備高效率高分子發光二極體。由於電子注入層的效果顯著,元件陰極只需以水、氧穩定的高功函數鋁金屬(Al)作為電極,即可達到高效率高分子發光二極體的目的。本研究選用的發光層有PF-Green-B與HY-PPV兩種,由能階上已可看出FTC具有電子注入與電洞阻隔的效果。其中以[FTC+碳酸鉀(K2CO3)]為電子注入層的元件有最好的效率表現。若以PF-Green-B為發光層,最大電流效率由無電子注入層的0.72 cd/A提升至21.58cd/A,約有30倍的提升;最大功率效率則由0.27 lm/W提升至12.42 lm/W,整整46倍的提升。若以HY-PPV為發光層,最大電流效率由無電子注入層的0.07 cd/A提升至6.93 cd/A,整整99倍的提升;最大功率效率則由0.03 lm/W提升至5.27 lm/W,約有177倍的提升。整體元件的效率、亮度均有顯著的提升,起始操作電壓亦有明顯的下降,達到高效率高分子發光二極體的目的。效率提升的原因推測為電子注入能力的提升與電洞阻隔的效果,本研究並以原子力顯微鏡、Hole-only元件、Electron-only元件、光伏打量測來證明各種使元件效率提升的假設。
To improve emission efficiency of polymer light-emitting diodes (PLEDs), we employed a water/alcohol-soluble fluorene derivative (FTC) having three terminal azacrown ether groups as electron-injection layer (EIL) to fabricate multi-layer PLEDs by spin-coating process. The results show that FTC or FTC plus M2CO3 (M: Na, K, Cs) are effective electron-injection layer for PLEDS with stable aluminum as cathode.
The structure of FTC was satisfactorily characterized by 1H NMR, COSY, NOESY, 13C NMR, FT-IR and elemental analysis. Its electrochemical properties were investigated by cyclic voltammetry (CV); the HOMO and LUMO levels were estimated to be -5.88 eV and -2.88 eV, respectively. Multi-layer PLEDs [ITO/PEDOT:PSS/EML/EIL/Al] were fabricated by wet process using two commercialized emitting materials (PF-Green-B or HY-PPV) as emission layer (EML) and FTC (or FTC in the presence of metal cations) as electron-injection layer (EIL). The insertion of the EIL enhances the device performance significantly. Particularly, the device using FTC plus K2CO3 as the electron-injection layer revealed the highest performance. For the devices based on PF-Green-B, the maximum luminance, maximum current efficiency and maximum luminous power efficiency were 17461 cd/m2, 21.58 cd/A, and 12.42 lm/W, respectively, which were superior to those without electron injection layer (1217 cd/m2, 0.72 cd/A, 0.27 lm/W). For the devices based on HY-PPV, the maximum luminance, maximum current efficiency and maximum luminous power efficiency were 10986 cd/m2, 6.93 cd/A, and 5.27 lm/W, respectively, which were also much higher than those without electron-injection layer. In addition, the turn-on voltages were also significantly reduced (from 5.7 V to 3.7 V, from 5.5 V to 2.5 V).
Electron-only and hole-only devices were fabricated to study the influence of the extra electron-injection layer. Insertion of EIL, whether it was neat FTC or FTC in the presence of M2CO3 (M: Na, K, Cs), results in great increase in electron current density and simultaneous reduction in hole current density. This will effectively raise the recombination ratio of electrons and holes because most conjugated emitting polymers (PF-Green-B or HY-PPV) are hole-transporting materials. Increased recombination ratio leads to enhanced emission efficiency. Moreover, they can be deposited by wet processes due to the solubility of FTC in mixture solvents of alcohol and water. Current results show that FTC and FTC plus M2CO3 are promising electron-injection materials for optoelectronic devices using aluminum as cathode.
第一章 緒論 1
1-1. 前言 1
1-2. 理論基礎 5
1-2-1. 共軛導電高分子 5
1-2-2. 螢光理論 8
1-2-3. 影響螢光強度的因素 10
1-2-4. 能量轉移 11
1-2-5. 分子間激發態(Interchain Exciton) 13
第二章 文獻回顧 15
2-1 元件發光原理及結構 15
2-1-1. 發光原理 15
2-1-2. 單層元件 16
2-1-3. 多層元件 18
2-2 有機電激發光材料 19
2-2-1. 有機電激發光材料的分類 19
2-2-2. 共軛高分子發光材料 20
2-2-3. 電洞注入材料(Hole Injection Material, HIM) 21
2-2-4. 電洞傳輸材料(Hole Transporting Material, HTM) 22
2-2-5. 電子傳輸材料(Electron Transporting Material, ETM) 24
2-3 有機發光二極體的效率 26
2-3-1. 影響PLED發光效率的參數 26
2-3-2. 增進載子平衡的方法 27
2-3-3. 提升電子注入效率 27
2-4 研究動機 29
第三章 實驗內容 31
3-1. 實驗裝置與設備 31
3-2. 鑑定儀器 32
3-3. 物性及光電特性測量儀器 33
3-4. 實驗藥品及材料 40
3-5. FTC的合成步驟 42
3-6. 元件設計及製作 44
第四章 結果與討論 50
4-1. FTC的鑑定 51
4-1-1. FTC的核磁共振光譜(1H NMR) 51
4-1-2. FTC的二維核磁共振光譜(COSY) 51
4-1-3. FTC的二維核磁共振光譜(NOESY) 53
4-1-4. FTC的13C NMR光譜圖 53
4-1-5. FTC的紅外光譜(FT-IR) 53
4-1-6. 元素分析(EA) 57
4-2. 熱性質分析 58
4-2-1. 微差掃描熱卡計(DSC) 58
4-2-2. 熱重量分析(TGA) 59
4-3. 電化學性質分析 61
4-4. 光學性質分析 64
4-4-1. UV/Vis吸收光譜和PL螢光光譜 64
4-5. 高分子發光二極體(PLED)元件特性 67
4-5-1. PF-Green-B與Carbonate元件性質 71
4-5-2. PF-Green-B與Acetate元件性質 75
4-5-3. HY-PPV與Carbonate元件性質 79
4-5-4. HY-PPV與Acetate元件性質 83
4-6. 元件效率提升的探討 87
4-6-1. 有機材料的成膜性質 88
4-6-2. Hole-only 元件 92
4-6-3. Electron-only 元件 96
4-6-4. 元件陰極的改質 100
4-6-5. FTC與鹼金屬的弱酸鹽 104
第五章 結論 109
參考文獻 112

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