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研究生:吳哲睿
研究生(外文):Jhe-Ruei Wu
論文名稱:以聚苯胺/銀奈米複合材料與苯胺寡聚物為有機發光二極體之電洞注入層的探討
論文名稱(外文):A study on organic light-emitting diodes with polyaniline/silver nanocomposite and oligomer of aniline as a hole injection layer
指導教授:邱寬城
指導教授(外文):Kuan-Cheng Chiu
學位類別:碩士
校院名稱:中原大學
系所名稱:物理研究所
學門:自然科學學門
學類:物理學類
論文種類:學術論文
論文出版年:2010
畢業學年度:98
語文別:中文
論文頁數:56
中文關鍵詞:有機發光二極體表面改質苯胺寡聚物聚苯胺電洞注入層
外文關鍵詞:Surface modificationOLEDOligomerPANIHIL
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本研究在有機發光二極體 (Organic light-emitting diode, OLED) 元件中,使用溶於NMP溶劑中的聚苯胺 (Polyaniline, PANI) 摻雜不同濃度之硝酸銀與苯胺寡聚物 (Oligomer of aniline) 共四種溶液旋轉塗佈於陽極上作為電洞注入層 (Hole injection layer, HIL)。由電流對電壓與光強度對電壓的量測結果可以得知PANI摻雜硝酸6% 與苯胺寡聚物兩種溶液旋轉塗佈於陽極上作為HIL,會使得元件整體效能有較大的提升,所以本研究利用下述量測方式來分析導致效能提升或降低(相較於沒有HIL之傳統結構元件)的機制為何。
藉由掃描式電子顯微鏡 (SEM) 之俯視圖來分析各種HIL之表面形貌是否有助於電荷傳遞,並由側視圖可以得到HIL之膜厚。
藉由原子力顯微鏡 (AFM) 來分析各種HIL之表面粗糙度來判斷哪種HIL 與電洞傳輸層 (Hole transport layer, HTL) 間有較好的接合面,同時好的接合面也意味著電洞由HIL注入到HTL有較好的注入效率,並使得元件整體效能提升。
藉由X光粉晶繞射儀 (XRD) 來觀測PANI摻雜硝酸銀的粉末溶於NMP並利用旋轉塗佈於陽極上成膜後,薄膜中是否仍有奈米銀顆粒存在,以探討奈米銀顆粒對於電荷傳導機制的影響,進而影響到元件整體的效能。
藉由光穿透頻譜來觀測經過HIL表面改質後之陽極透光率;因為透光率會直接影響到元件的光強度,從而影響到元件的發光效率。


In this study, there are four solutions fabricated by polyaniline (PANI) doped with different concentration of silver nitrate and aniline of oligomer which are respective dissolved in the solvent of NMP. These solutions are spin-coat on the anode of organic light-emitting diode (OLED) as a hole injection layer (HIL). Through the results of measuring the current density versus voltage and the EL intensity versus voltage, it shows a significant increase of OLED device’s performance when the solutions of PANI doped with silver nitrate 6% and aniline of oligomer are spin-coated as a HIL. There are some measurements to analyze the mechanism of the OLED device’s performance is increasing or decreasing which are below this paragraph.
Through scanning electron microscope (SEM) to analyzes the morphology of top view of the different HIL whether contribute to charge transport. And the thickness could be taken by the side view of the different HIL.
Through atomic force microscopy (AFM) to analyzes the surface roughness of different HIL. Then we can discern which one of the HILs provided with the better contact of the interface between the HIL and hole transport layer (HTL). And the better contact of the interface implies that there is a hole injection from HIL to HTL has higher injection efficiency.
Through X-ray diffraction to observe the powder of PANI doped with different concentration of silver nitrate dissolved in the solvent of NMP which spin-coating on the anode. To discuss whether the thin film on anode possess of nano-silver granule, then we may discuss the nano-silver granule whether play an important role in the charge transport mechanism.
Through optical transmission to observe the transmissivity of the anode after surface modification. Because of the transmissivity will affect the light-emitting intensity immediately.


中文摘要……………………………………………………………….………… I
英文摘要…………………………………………………………………………. II
誌謝…………………………………………………………………..................... III
目錄……….…………….….…….………………...………….…….…………… IV
圖目錄…………………………………………………………………………......VI
表目錄…………………………………………………………………………..... VIII
第一章 簡介………….……………………………………………….................. 1
1.1 前言…………………....……………………………………..…………… 1
1.2 有機電致螢光概述…....……………………………………..…………… 2
1.3 有機發光二極體原理....……………………………………..…………… 4
1.4 OLED元件電流限制....……………………………………..…………… 8
1.5 ITO陽極表面改質……………………………………………………….. 11
第二章 實驗原理與方法….…………………………………………………….. 12
2.1 物理汽相沉積法概述...………………………………..…………………. 12
2.2 旋轉塗佈法概述………………………………………..………………… 12
2.3 聚苯胺/銀粉末製備……………………………………………………… 13
2.4 聚苯胺/銀粉末條件參數的定義……………………………………….... 13
2.5 實驗裝置與樣品製備…………………………………………………..… 14
2.6 J-V與EL-V量測…………………………………………………………. 20
2.7 光穿透頻譜量測……………………………………………………….…. 22
第三章 結果與討論………………………………………..….………………… 24
3.1 電流密度對電壓與光度對電壓作圖之分析…………………………….. 24
3.2 電洞注入層之表面形貌分析…………………………………………...... 32
3.3 XRD之結果分析…………………...……………..……………………... 40
3.4 光穿透頻譜分析......…………………………………………………..…. 42
第四章 結論與未來展望……………………………………………………..… 44
參考文獻…………………………….……………………………….….……....... 46





圖目錄
圖 1.1 2006-2016 OLED 面板出貨金額預測(單位:百萬美元)。................. 3
圖1.2 (a) Anthracene分子結構圖,(b) 芳香雙胺化物 (Aromatic diamine) 結構
圖,(c) Alq3 之結構圖,(d) 柯達公司所發明之雙層異質結構的有機薄膜
元件示意圖。.............................................................................................. 5
圖1.3.1 OLED雙層結構發光原理示意圖。....................................................... 6
圖1.3.2 OLED發光機制的兩種類型。............................................................... 7
圖1.4 (a) Richardson-Schottky熱注入理論模型,(b) Fowler-Nordheim穿隧理論
模型。......................................................................................................... 10
圖2.5.1 (a) 蒸鍍腔體內部構造示意圖,(b) 放置ITO玻璃基板之基座示意圖。
(1) 基座放置凹槽;(2) MASK旋轉盤;(3) 基板端大擋板;(4) 粉末端
小擋板;(5) 坩鍋;(6) 加熱絲。......................................................... 17
圖2.5.2 本實驗之元件架構圖。......................................................................... 18
圖2.5.3 (a) Alq3分子結構圖,(b) NPB分子結構圖,(c) Oligomer分子結構圖。
………………………………………………………………………… 19
圖2.6 J-V與EL-V量測系統架構圖。............................................................... 21
圖2.7 光穿透量測系統架構圖。…………………………………………….... 23
圖3.1.1 Conventional元件之 (a) J-V 與 (b) EL-V Semi-log作圖。…….... 25
圖3.1.2 Ag (0%) 元件之 (a) J-V 與 (b) EL-V Semi-log作圖。………….. 26
圖3.1.3 Ag (6%) 元件之 (a) J-V 與 (b) EL-V Semi-log作圖。…………. 27
圖3.1.4 Ag (12%) 元件之 (a) J-V 與 (b) EL-V Semi-log作圖。……....... 28
圖3.1.5 Oligomer元件之 (a) J-V 與 (b) EL-V Semi-log作圖。…………. 29
圖3.1.6 五種元件數據合併之 (a) J-V 與 (b) EL-V 作圖。………………... 30
圖3.1.7 五種元件數據合併之 (a) J-V 與 (b) EL-V Semi-log作圖。……. 31
圖3.2.1 五種不同樣品之SEM俯視圖分別為:(a) 無塗佈之ITO,(b) Ag (0%),
(c) Ag (6%),(d) Ag (12%),(e) Oligomer樣品1,(f) Oligomer樣品2。
(附註:(a) 之比例尺為50 nm,(b)-(e) 之比例尺為200 nm,(f) 之比
例尺為500 nm。)………………………………………………….. 35
圖3.2.2 五種不同樣品之AFM圖分別為:(a) ITO,(b) Ag (0%),(c) Ag (6%),
(d) Ag (12%),(e) Oligomer。…………………………………......... 36
圖3.2.3 Ag (0%)、Ag (6%) 及Ag (12%) 之SEM側視圖:(a) Ag (0%) 樣品1,
(b) Ag (0%) 樣品2,(c) Ag (6%) 樣品1,(d) Ag (6%) 樣品2,(e) Ag
(12%) 樣品1,(f) Ag (12%) 樣品2。……………………………… 37
圖3.2.4 (a) SEM側視圖出現異常白色光團 (比例尺500 nm),(b) SEM側視圖
出現異常白色光團 (比例尺 1 μm),(c) Oligomer之SEM側視圖。
……………………………………………………………………….. 39
圖3.3 PANI摻雜硝酸銀6% 與12% 之較高轉速與較低轉速的XRD頻譜圖。
………………………………………………………………………….. 41
圖3.4 光穿透頻譜(波長範圍500-570 nm)。……………………………… 43


表目錄
表一 SEM俯視圖之區塊與團簇的表面覆蓋率。……................................... 38
表二 由AFM所得之表面粗糙度。……………………………………….… 38
表三 由SEM所得之兩個樣品的ITO與HIL平均薄膜厚度。…………… 38

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