高效率雙波段螢光白光有機發光二極體之研製

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研究生：	王仲培 Chung-Pei Wang
論文名稱：	高效率雙波段螢光白光有機發光二極體之研製 Fabrication Study of High-efficiency Two-wavelength Fluorescent White Organic Light-emitting Diodes
指導教授：	周卓煇 Jwo-Huei Jou
口試委員:
學位類別：	博士 Doctor
系所名稱：	工學院 - 材料科學工程學系 Materials Science and Engineering
論文出版年：	2006
畢業學年度：	95
語文別：	中文
中文關鍵詞：	雙波段螢光白光、有機發光二極體、主體材料、電洞傳輸材料、電子傳輸材料、透明導電陽極
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本研究利用真空蒸鍍，製備一系列具單一發光層之雙波段螢光白光有機發光二極體（White organic light-emitting diodes，WOLEDs），所製備之WOLEDs，可分為兩部份探討。.
第一部份：高效率雙波段螢光白光有機發光二極體，分別利用三種不同主體材料：di(4-fluoro-phenyl)amino-di(styryl)biphenyl (DSB)、9,10-di-(2-na-phthyl)-anthracene (ADN)與1-tert-butyl-9,10- bis(2-nap-htyl)-anthracene (BANE)，並選用紅光染料4-(dicyano- me-thylene)-2-meth-yl-6-(julolidin-4-yl-vinyl)-4H-pyran (DCM2)，所搭配的電洞傳輸材料為N,N’-bis-(1- naphthy)-N,N’di- phenyl-1,1’- biphenyl4-4’-diamine (NPB)，電子傳輸材料為1,3,5- tris(N-phenyl- benzimidazol-2-yl)benzene (TPBi)；利用溶劑預溶混合主、客體發光材料，再將乾燥所得之混合物作為蒸鍍源，所得WOLEDs元件結構依序為透明導電陽極ITO（1250 Å）/電洞傳輸層NPB（450 Å）/發光層（250 Å）/電子傳輸層TPBi（400 Å）/電子注入層LiF（8 Å）/陰極Al（1500 Å）；當以DSB為主體材料，DCM2摻雜濃度為0.15 wt%時，所得的雙波段泛白光元件中，在亮度為100 cd/m2時，發光效率最大可達14.8 lm/W或15.6 cd/A，其CIE色座標為(0.424, 0.441)，元件最大發光亮度可達24,600 cd/m2；獲此高效率的原因可歸因為：一、高效率藍綠光DSB主體材料之選擇，二、具有高Förster能量轉移效率之主、客體發光系統，可使電子-電洞產生之激態能量，有效轉移給客發光分子；三、能階適當之元件設計，使電洞、電子容易注入發光層，進而被侷限於單一發光層中，增加發光效率。
第二部份：可撓式高效率白光有機發光二極體，選用PES做為可撓式OLEDs基材，這是因為PET之表面粗糙度大於PES，而表面粗糙度是影響元件表現的重要因素，再利用磁控濺鍍法於PES上製備透明導電陽極ITO，並於ITO與PES之間鍍製不同厚度之SiO2薄膜，以降低表面粗糙度，其SiO2薄膜最佳厚度為150 Å，ITO電阻率為3.9 × 10-4 Ω-cm，Rms為14 ± 1 Å。元件結構為PES/SiO2（150Å）/ITO （500Å）/NPB（500 Å）/發光層（350 Å）/TPBi （400 Å）/LiF （8 Å）/Al （1500 Å），ITO鍍製溫度為200℃，可在廣義白光範圍得到最大亮度為9,000□cd/m2，最大發光效率為13.2 lm/W，在元件亮度為100 cd/m2時，其CIE色座標為（0.391, 0.438）。獲此高效率的原因可歸因為：一、最適化之SiO2薄膜厚度（150 Å）以降低PES表面粗糙度，二、高溫鍍製（200℃）ITO薄膜，具有最佳之導電性質。

目錄
獻…..……………………………………………………………………Ⅰ
摘要.………….…………………………………………………………Ⅱ
致謝.……..…………..…………………………………….……………Ⅲ
目錄…..…………………………………………………………………VI
表目錄.……………….…………………………………………………..Ⅹ
圖目錄.……….…………………………………………………………..ⅩI
壹、    緒論..……………………………………………………………..…1
貳、    文獻回顧..………………………………………………………......4
2-1、有機發光二極體的歷史發展…………………….. .…….…...4
2-2、發光原理……………………………………………………...10
2-3、有機發光材料之演進…………….…………………………..15
2-4、可撓式基材之發展…………………….…..............................21
2-5、可撓式有機發光二極體…………………….…......................24
2-6、白光有機發光二極體之發展………………………….….....26
2-6-1、單層發光白光元件…………………………………......27
2-6-2、積層發光白光元件…………………………………......32
參、    實驗方法..…………………………………………………………38
3-1、材料……..…..…………………………………….………….38
3-2、透明導電陽極及SiO2薄膜之製備………….………………39
3-3、可撓式基材粗糙度與電性量測………….……………….....40
3-3-1、原子力顯微鏡………….…………………………………..40
3-3-2、霍爾效應量測儀………….………………………………..40
3-4、蒸鍍裝置……………...……………………………..……….41
3-5、蒸鍍速率之測定與校正.….………………………………....41
3-6、蒸鍍源之製備..………………………………………………43
3-7、基材清洗…….....…………….……………………………....43
3-8、元件之電路設計…………….….…………………………....44
3-9、元件電流、電壓與亮度特性量測.………………………....44
3-10、發光效率之計算…….……………………………………....45
3-11、電致發光光譜（electroluminescent spectra）量測….…....46
3-12、光激發光光譜（photoluminescent spectra）量測….……..46
3-13、紫外光吸收光譜（ultraviolet visible, UV-vis）量測….….46
肆、    結果與討論……………………………………………………47
4-1 藍光有機發光二極體…….….……………………………….47
4-1-1主體材料之特性分析……………………………………47
4-1-2、藍光有機發光二極體之製備…………………………...48
4-1-3、元件電壓對電流密度之影響…………………………...49
4-2、雙波段白光有機發光二極體………………………………...49
4-2-1、元件結構及鍍膜參數………………………………….49
4-2-2、主體材料對元件發光效率之影響……………………...50
4-2-3、元件電壓對電流密度之影響…………………………..51
4-2-4、元件之能階……………………………………………...51
4-2-5、Förster能量轉移……………………………………......52
4-2-6、高效率白光OLEDs………………………………….....53
4-2-7、高效率白光OLEDs之電致發光光譜………………….54
4-3、高效率可撓式白光OLEDs…………………………………..55
4-3-1、可撓式基材對OLEDs之影響……………….…………55
4-3-2、可撓式基材粗糙度對透明導電陽極之影響…………...55
4-3-3、SiO2薄膜厚度對可撓式白光有機發光二極體之影響……………………………………………………………….56
4-3-4、ITO鍍製溫度對電性之影響……………………………57
4-3-5、元件結構及鍍膜參數…………………………………...58
4-3-6、元件之亮度-電壓-電流密度關係……………………....59
4-3-7、元件發光效率……………….…………………………60
4-3-8、元件之CIE色座標……………………………………...60
4-3-9、元件之電致發光光譜………………….…….…………61
伍、結論…………………………………………………….…………..62
陸、參考資料……………………………………………………………64
柒、表與圖……………………………………………………………...72

                                

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