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研究生: 黃升廷
Sheng-Ting Huang
論文名稱: 新型含氟聚醯亞胺與氧化物複合薄膜之合成及低介電與有機發光二極體軟性基板性質之探討
Synthesis and Characterization of Fluorinated Polyimides / Oxide Composite Films: Dielectric Properties and Applications as the Flexible Substrates for Organic Light Emitting Diodes
指導教授: 陳志堅
Jyh-Chien Chen
口試委員: 游進陽
Chin-Yang Yu
王英靖
none
學位類別: 碩士
Master
系所名稱: 工程學院 - 材料科學與工程系
Department of Materials Science and Engineering
論文出版年: 2014
畢業學年度: 102
語文別: 中文
論文頁數: 76
中文關鍵詞: 聚醯亞胺複合材料介電常數軟性基板折射率
外文關鍵詞: polyimide, composite material, dielectric constant, flexible substrate, refractive index
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  • 本研究由4,4’-oxydianiline(4,4’-ODA)經氧化、溴化、鈴木偶合反應與還原成功合成一新型二胺2,2’-bis[3,5-bis(trifluoromethyl)phenyl]-4,4’-oxydianiline(5),再與4,4'-(hexafluoroisopropylidene)diphthalic anhydride(6FDA)經一步法合成新型聚醯亞胺(PI-12F)。而此新型聚醯亞胺展現出低介電常數與高光學穿透度。PI-12F可於室溫下溶於一般有機溶劑,甚至是丙酮,玻璃轉移溫度(Tg)為245 ℃,熱裂解溫度(T5%)為505 ℃、紫外光-可見光光譜截止波長(λcut-off)為361 nm、穿透度80%時的紫外光-可見光光譜波長(λ80%)為410 nm、介電常數為2.6。為了提升PI-12F的性質,將其進一步與二氧化矽、二氧化矽中空球、二氧化鈦進行混摻,分別製備成複合薄膜PI-12F/S、PI-12F/HS、PI-12F/T系列。三種複合薄膜的玻璃轉移溫度(Tg)介於241~250℃,熱裂解溫度(T5%)介於446~504 ℃。藉由本研究的實驗可以推測,二氧化矽中空球的介電常數約在2.7~3.3之間。若高分子基材之介電常數低於2.7,則混摻二氧化矽中空球後介電常數會上升。若高分子基材之介電常數高於3.3,混摻二氧化矽中空球後介電常數則會下降。PI-12F/S與PI-12F/T系列的UV-vis截止波長介於377~406 nm,UV-vis λ80%介於432~484 nm,折射率則介於1.52~1.61。將PI-12F、PI-12F/S系列與PI-12F/T系列做為軟性基板製備為有機發光二極體(organic light emitting diode, OLED),其中以PI-12F/40T做為基板的OLED表現優異,其發光效率高達12.6 Cd/A,比以玻璃做為基板的OLED發光效率(Cd/A)增加了28%,故以PI-12F/40T做為軟性基板能成功製備成具有高發光效率的OLED。


    A novel diamine, 2,2’-bis[3,5-bis(trifluoromethyl)phenyl]-4,4’-oxydianiline (5) was synthesized by oxidation, bromination, Suzuki coupling reaction, and reduction from 4,4’-ODA. A novel polyimide(PI-12F) was prepared based on this novel diamine and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride(6FDA) by one-step method. The novel polyimide exhibited low dielectric constant and high optical transparency. PI-12F could dissolve in common organic solvents, even acetone at room temperature. The glass transition temperature (Tg) was 245℃.The 5% weight-loss temperature was 505℃.The UV-vis cut-off wavelength was 361 nm. The UV-vis λ80% was 410nm. The dielectric constant was 2.6. In order to enhance the properties of the PI-12F, PI-12F was further blended with silica, hollow silica sphere and titania to prepare the hybrid films (PI-12F/S, PI-12F/HS, PI-12F/T series). The glass transition temperature (Tg) of these three series of hybrid films were in the range of 241~250℃. The 5% weight-loss temperature were in the range of 446~504℃. We could presume the dielectric constant of hollow silica sphere was in the range of 2.7~3.3. If the dielectric constant of the polymer matrix was below 2.7, then the hollow silica sphere would increase the dielectric constant of the polymer. If the dielectric constant of the polymer matrix was above 3.3, then the hollow silica sphere would decrease the dielectric constant of the polymer. The UV-vis cut-off wavelength of PI-12F/S and PI-12F/T series were in the range of 377~406 nm. The UV-vis λ80% were in the range of 432~484nm. The refractive index were in the range of 1.52~1.61. Flexible OLEDs were fabricated with PI-12F, PI-12F/S and PI-12F/T series as substrates. The efficiency of OLED with PI-12F/40T as substrate was 12.6 Cd/A. Compared with the OLED with glass substrate, the efficiency of OLED with PI-12F/40T increased 28%. Therefore, PI-12F/40T would be a potential flexible substrate for flexible OLED.

    摘要 I Abstract II 誌謝 III 目錄 IV Figure索引 VI Scheme 索引 VIII Table索引 IX 1、 緒論 1 1.1前言 1 1.2聚醯亞胺的背景 2 1.3導入三氟甲基的聚醯亞胺 4 1.4聚醯亞胺複合材料 7 1.4.1溶膠─凝膠(sol-gel)法介紹 7 1.4.2 Sol-gel法在聚醯亞胺複合材料的應用 8 1.4.3 介面相容性 9 1.4.4 聚醯亞胺混摻無機物可改善的性質 12 1.5聚醯亞胺於低介電的應用 15 1.6有機發光二極體基板的應用 17 1.7研究動機 20 2、實驗部分 21 2.1實驗藥品 21 2.2實驗儀器 23 2.3單體合成 24 3、結果與討論 29 3.1單體的合成 29 3.2高分子的合成 36 3.3高分子複合材料製備 37 3.4 PI-12F的性質表徵 41 3.4.1 PI-12F的分子量與溶解度 41 3.4.2 PI-12F的結構表徵 43 3.4.3 PI-12F的光學性質 45 3.4.4 PI-12F的熱性質 47 3.5 聚醯亞胺低介電應用 49 3.5.1 PI-12F、PI-12F/30S、PI-12F/30HS的紅外光光譜表徵 49 3.5.2 PI-12F/30S、二氧化矽中空球、PI-12F/30HS表面形貌 50 3.5.3 PI-12F、PI-12F /30S、PI-12F /30HS的熱性質 53 3.5.4 PI-12F、PI-12F/30S、PI-12F/30HS的介電性質 55 3.6有機發光二極體元件之軟性基板應用 57 3.6.1 PI-12F、PI-12F/S系列與PI-12F/T系列的紅外光光譜表徵 57 3.6.2 PI-12F/30S與PI-12F/40T的表面形貌 59 3.6.3 PI-12F、PI-12F/S系列與PI-12F/T系列的熱性質 60 3.6.4 PI-12F、PI-12F/S系列與PI-12F/T系列的光學性質 63 3.6.5 以PI-12F、PI-12F/S、PI-12F/T系列製成的有機發光二極體之元件性質 67 4、結論 73 5、參考文獻 74

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