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研究生： 周蓁宜
Chou, Chen-Yi
論文名稱： 含部份水解亞磷酯基之聚芴：合成、鑑定及應用於提昇高分子發光二極體的效率
Polyfluorene Functionalized with Partially Hydrolyzed Phosphonate Groups: Synthesis, Characterization and Application in Electron Injection Layer to Enhance Efficiency of PLEDs
指導教授： 陳雲
Chen, Yun
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2013
畢業學年度： 101
語文別： 中文
論文頁數： 71
中文關鍵詞： 聚芴 、磷酸酯基 、高分子發光二極體 、電子注入層 、光電元件
外文關鍵詞： Polyfluorene, Phosphonate group, PLEDs, Electron-injection layer (EIL), Optoelectronic devices
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    • 本研究合成側鏈含部分水解亞磷酸酯(以鉀為對離子)之聚芴(PF-EPK)，與含亞磷酸酯側鏈之聚芴(PF-EP)摻混作為高分子發光二體之電子注入層。PF-EPK的水解比例約為65~70%是透過核磁共振光譜及熱重分析圖對照 PF-EP推算出。因PF-EP 和 PF-EPK兩者具極相似的聚芴主鏈及側鏈結構，在電化學性質上的氧化電位約-5.5 eV，而還原電位則約為-2.3 eV。藉由簡易混摻將PF-EPK加入PF-EP中做為電子注入層，應用於高分子發光二極體(ITO/PEDOT:PSS/EML/(PF-EP+PF-EPK)/Al)。選用商業化之發黃光共軛高分子Superyellow (SY)作為發光層(EML)，再以PF-EPK混摻PF-EP的薄層塗佈於其上。由於PF-EP和PF-EPK可溶於甲醇及微量水，其塗佈不會造成發光層界面遭溶劑侵蝕的問題。摻混PF-EPK於PF-EP中有效提升元件的發光效能，摻雜2.5 %之PF-EPK時其發光效能最佳，最大亮度、最大電流效率及最大功率效率分別為12052 cd/m2、3.62 cd/A 及1.38 lm/W。元件效能的提昇歸功於陰極鋁的修飾降低了電子注入的能障，因而促進電子注入，以光伏打量測之開路電壓(Voc)證實以2.5%之PF-EPK添加擁有最大偏壓，證實電子注入能力的提昇。此外，添加不等量之PF-EPK於PF-EP中，其成膜型態保持幾乎相同的粗糙度，且其在空氣中的穩定度和相容性均優於一般無機鹽類的摻混。以上結果顯示，側鏈含部分水解亞磷酸酯之聚芴(PF-EPK)是具有相當潛力的電子注入材料。

    Polyfluorene containing functional phosphonate pendent groups (PF-EP) was synthesized, from which the pendent phosphonate groups was partially hydrolyzed (with potassium as counter ion) to prepare PF-EPK for application as electron-injection layer in polymer light-emitting diodes (PLEDs). The amount of hydrolysis was estimated to be about 65-70%, by comparing the 1H NMR and TGA of PF-EPK with those of PF-EP. Both PF-EP and PF-EPK demonstrate similar electrochemical properties due to their polyfluorene main chain and similar pendent groups, the HOMO and LUMO levels were around -5.5 eV and -2.3 eV, respectively. Multilayer PLEDs (ITO/PEDOT:PSS/EML/PF-EP+PF-EPK/Al) were fabricated using blends of PF-EPK and PF-EP as electron-injection layer (EIL), commercially available Superyellow (SY) as emission layer (EML). Since PF-EP and PF-EPK are soluble in methanol with a small amount of water, interface mixing between EML and EIL can be avoided during spin-coating of the EIL. Blending of PF-EPK into PF-EP leads to enhanced device performance. The best performance was obtained for the device with PF-EP doped with 2.5% PF-EPK as EIL. The maximum luminance, maximum current efficiency and maximum luminous power efficiency were 12052 cd/m2, 3.62 cd/A and 1.38 lm/W, respectively. The improved device performance has been attributed to enhanced electron injection ability through cathode modification by the EIL. The open circuit voltage (Voc), obtained by photovoltaic measurements, showed the maximum bias at 2.5% PF-EPK, confirming the enhancement in electron-injection ability. The surface morphology of EIL remains almost unchanged regardless of blend ratios of PF-EPK. In addition, the blends of PF-EF with PF-EFK are more compatible and more stable in the air than those with inorganic salts. These results show that PF-EPK is a promising electron-injection material for optoelectronic devices.

    目 錄 摘要 I Abstract II 致 謝 III 目 錄 IV 流程目錄 VI 表目錄 VI 圖目錄 VII 第一章 緒論 1 1-1.前言 1 1-2.理論基礎 2 1-2-1.共軛導電高分子 2 1-2-2.螢光理論 5 1-2-3.影響螢光強度的因素 6 1-2-4.能量轉移 8 1-2-5.分子間激發態(Interchain Exciton) 9 第二章 文獻回顧 11 2-1.元件發光原理及結構 11 2-1-1.發光原理 11 2-1-2.單層元件 12 2-1-3.多層元件 13 2-2.有機發光二極體的效率 15 2-2-1.影響PLED發光效率參數 15 2-2-2.增進載子平衡的方法 15 2-2-3.提升電子注入效率 16 2-3.水/醇類共軛高分子在光電元件上的應用 18 2-3-1.氨基和四級銨鹽官能基之WSCPs 19 2-3-2.二乙醇胺官能基之WSCPs 20 2-3-3.其他官能基之WSCPs作為電子注入層在PLEDs上應用 21 2-4.亞磷酯基之聚芴(PF-EP)在有機發光電元件上的應用 22 2-5.研究動機 24 第三章 實驗內容 25 3-1.實驗裝置與設備 25 3-2.鑑定儀器 27 3-3.物性及光電性質測量儀器 28 3-4.藥品及材料 33 3-5.合成步驟與結果 34 3-6.單體與高分子合成 35 3-7.元件製作 38 第四章 結果與討論 41 4-1.單體與高分子的合成與鑑定 42 4-1-1.核磁共振光譜(NMR) 42 4-1-2.元素分析儀(EA) 47 4-2.高分子熱性質分析 48 4-2-1.熱重分析 48 4-3.電化學性質分析 50 4-3-1.高分子電化學性質探討 50 4-4.高分子PF-EP + PF-EPK在發光二極體(PLED)的元件特性 53 4-5.元件表現探討 59 4-5-1.元件陰極改質 59 4-5-2.電子注入層的成膜性 61 第五章 結論 64 參考文獻 66 流程目錄 Scheme 3-1. Synthesis of PF-EP and PF-EPK. 34 表目錄 Table 1-1. 取代基對物質螢光波長及效率的影響 7 Table 2-1. 各種金屬的功函數 16 Table 4-1. The synthetic result of compounds 47 Table 4-2. The synthetic result of polymer 47 Table 4-3. Electrochemical potentials of polymers. 51 Table 4-4. Optoelectronic properties of the light-emitting diodes 58 Table 4-5. Photovoltaic properties of the light-emitting diodes. 60 Table 4-6. Surface morphology of different films spin-coated on top of SY 62

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