臺灣博碩士論文加值系統

本研究立足於超臨界沉積技術之下，利用超臨界二氧化碳當溶劑沉積有機發光薄膜Alq3於ITO基板上，以加熱基板作為析出驅動力，承接實驗室學長所得之較佳鍍膜參數，並且嘗試再次修正以及改善這些參數，以期能製作出適用於機發光二極體元件之Alq3薄膜。之後對製作出之薄膜進行一系列的量測及探討，並且由獲得的數據對其做一評估。
在批次系統中，鍍膜槽的體積會影響到薄膜析出的驅動力，因此我們嘗試增加鍍膜槽體積來提升薄膜的厚度，省去了二次成長所耗的時間，且利用atomic force microscopy(AFM)所得之薄膜粗糙度小於2.7nm，厚度也達到60nm的水準。熱處理同樣也會影響Alq3的表面形貌，適當的熱處理(5min)可以進一步提升薄膜粗糙度為2.1nm。而量測部分使用four-point probe(四點探針)、X-ray photoelectron spectroscopy (XPS)等儀器來測量元件的性質。鍍膜完成後通入N2並且抽真空後再做回火所得之薄膜，其在XPS圖譜上出現了與真空蒸鍍相同之化學組成及原子百分比，而功函數方面利用循環伏安法所測得之HOMO以及LUMO值也有接近真空蒸鍍的水準。

關鍵字：超臨界二氧化碳、有機發光二極體、超臨界沉積技術

Abstract
Our research based on the supercritical deposition technique, using supercritical carbon dioxide as solvent to deposit Alq3 (tris-(8-hydroxy-quinoline) aluminum) light emitting thin film on the ITO (indium tin oxide) substrate. In order to apply this technique in organic light emitting diode devices, we apply heating substrate as driving force, and follow the better deposition parameters our obstetrician finding out, and try to fix or improve some parameters. Finally a series of measuring and studying will be proceed to the thin film we fabricated, then we utilize the data to comment this technique.
The volume of depositing cell will affect the driving force of the film forming in batch system, so we try to increase the film thickness by increasing the volume of depositing cell which can eliminate the time cost by secondary deposition. The film fabricate by this method has a thickness of 60nm, and average roughness is also less than 2.7nm. Heat treatment can also affect the film morphology of Alq3, proper treatment time (about 5 min) can improve the roughness to 2.1nm. We use four-point probe, X-ray photoelectron spectroscopy (XPS) to measure the properties of our multi-layer device. The multi-layer organic light emitting device is composed of glass substrate/ITO/PEDOT(60nm)/Alq3 (60nm)/Al(100nm). After the deposition process, the thin film will be annealed at a surrounding which is vacuumed after few times of nitrogen vented. The XPS peak of the heat treated thin film has the same chemical composition and atomic percentage with the thin film fabricated by vacuum deposition method, and the work function measured by cyclic-voltammetry method is also closed to the vacuum deposion process, both the LUMO and HOMO.
Key words：supercritical carbon dioxide、organic light emitting device、 supercritical deposition technique

目錄
摘要………………………………………………………………………I
Abstract.…………………………………………………………………I
目錄……….………………………………………………………………IV
圖目錄……………………………………………………………………IX
表目錄…………………………………………………………………XIII
第一章 緒論………………………………………………………………1
1.1研究背景與動機……………………………………………………1
1.2研究內容……………………………………………………………2
第二章 文獻回顧…………………………………………………………3
2.1有機發光二極體……………………………………………………3
2.1.1有機發光二極體發展歷史……………………………………3
2.1.2有機發光二極體之基本構造及原理…………………………5
2.1.3發光效率………………………………………………………12
2.1.4元件的劣化原因………………………………………………14
2.1.5選擇有機發光材料……………………………………………17
2.1.6現有製程………………………………………………………18
2.1.7OLED元件現況…………………………………………………20
2.2超臨界流體原理及應用……………………………………………22
2.2.1超臨界流體……………………………………………………22
2.2.2超臨界流體種類以及sc-CO2…………………………………24
2.2.3超臨界流體的應用……………………………………………26
2.3超臨界流體之成膜技術……………………………………………28
2.3.1各種方式成膜技術……………………………………………28
2.3.2超臨界流體沈積技術…………………………………………30
第三章 實驗設計與步驟…………………………………………………32
3.1實驗流程……………………………………………………………32
3.2高壓反應器設計……………………………………………………35
3.2.1增壓系統………………………………………………………36
3.2.2鍍膜槽設計……………………………………………………38
3.2.3保護蓋設計……………………………………………………39
3.2.4解壓系統………………………………………………………40
3.3玻璃清洗……………………………………………………………41
3.4旋轉塗佈PEDOT以及批次沉積Alq3薄膜……………………………43
3.4.1旋轉塗佈PEDOT…………………………………………………43
3.4.2批次沉積Alq3薄膜……………………………………………45
3.5表面形貌確認以及功函數的計算…………………………………48
3.5.1表面形貌確認…………………………………………………48
3.5.2功函數的計算…………………………………………………48
3.5.3循環伏安計量法(Cyclic Voltammetry, CV)介紹…………48
3.6多層膜OLED元件製作………………………………………………50
3.7元件電性量測………………………………………………………52
3.8檢測儀器介紹………………………………………………………53
3.8.1表面分析………………………………………………………53
3.8.2光電檢測………………………………………………………57
3.9實驗儀器及規格……………………………………………………58
3.10實驗藥品……………………………………………………………60
第四章 結果與討論………………………………………………………61
4.1批次操作下提升鍍膜槽體積對Alq3薄膜的影響…………………61
4.2批次操作下熱處理對Alq3薄膜的影響……………………………64
4.2.1批次操作下改變熱處理溫度對Alq3薄膜的影響……………64
4.2.2批次操作下熱處理對不同鍍膜槽體積之薄膜的影響………68
4.3薄膜形貌觀察………………………………………………………70
4.3.1原子力顯微鏡掃描薄膜表面…………………………………70
4.3.2 X射線光電子能譜儀測量……………………………………72
4.3.3利用循環伏安法測量功函數…………………………………80
4.4電性量測……………………………………………………………83
4.4.1 Alq3薄膜電阻測量……………………………………………83
4.4.2 I-V curve量測………………………………………………85
第五章 結果與討論………………………………………………………87
5.1總結…………………………………………………………………87
5.2、未來展望…………………………………………………………88
參考資料……………………………………………………………………89








圖目錄
圖2.1、柯達公司首創採用異質接面雙層結構示意圖…………………4
圖2.2、OLED元件發光原理示意圖………………………………………5
圖2.3、有機發光體基本結構Type 1……………………………………6
圖2.4、有機發光體基本結構Type 2……………………………………7
圖2.5、有機發光體基本結構Type 3……………………………………8
圖2.6、有機發光體基本結構Type 4……………………………………9
圖2.7、傳統封裝OLED元件結構圖………………………………………10
圖2.8、元件壽命測試圖…………………………………………………16
圖2.9、水氣對OLED元件破壞機制圖……………………………………16
圖2.10、Alq3化學結構式…………………………………………………17
圖2.11、vacuum thermal evaporation裝置示意圖……………………19
圖2.12、OVPD裝置示意圖…………………………………………………19
圖2.13、一般物質三相圖…………………………………………………23
圖2.14、結合物理及化學沈積於OLED材料沈積裝置圖…………………31
圖3.1、實驗操作流程設計圖……………………………………………34
圖3.2、增壓系統示意圖…………………………………………………37
圖3.3、反應器示意圖……………………………………………………38
圖3.4、保護蓋示意圖……………………………………………………39
圖3.5、解壓裝置示意圖…………………………………………………40
圖3.6、玻璃清洗示意圖…………………………………………………42
圖3.7、旋轉塗佈機裝置圖………………………………………………44
圖3.8、批次反應器裝置圖………………………………………………46
圖3.9、多層膜材料能階圖………………………………………………50
圖3.10、多層膜製作流程圖………………………………………………51
圖3.11、電性量測裝置圖…………………………………………………52
圖3.12、循環伏安儀裝置示意圖…………………………………………53
圖3.13、探針測量高低差示意圖…………………………………………54
圖3.14、XPS工作原理示意圖……………………………………………55
圖3.15、四點探針工作原理示意圖………………………………………56
圖3.16、常見二極體I-V Curve …………………………………………57
圖4.1、批次操作下不同體積對膜厚之影響……………………………63
圖4.2、批次操作下沉積時間對粗糙度之影響…………………………63
圖4.3、批次操作下熱處理對膜厚之影響………………………………66
圖4.4、批次操作下熱處理對粗糙度之影響……………………………66
圖4.5、批次操作下熱處理5min之表面…………………………………67
圖4.6、批次操作下熱處理30min之表面………………………………67
圖4.7、批次操作下熱處理對粗糙度之影響……………………………69
圖4.8、批次操作下熱處理對粗糙度之影響……………………………69
圖4.9、真空蒸鍍之Alq3薄膜表面形貌及粗糙度………………………71
圖4.10、超臨界沉積之Alq3薄膜表面形貌及粗糙度……………………71
圖4.11、超臨界沉積Alq3之XPS全域圖…………………………………74
圖4.12、真空蒸鍍Alq3之XPS全域圖……………………………………74
圖4.13、超臨界沉積Alq3之C 1s圖………………………………………76
圖4.14、真空蒸鍍Alq3之C 1s圖…………………………………………76
圖4.15、超臨界沉積Alq3之O 1s圖………………………………………77
圖4.16、真空蒸鍍Alq3之O 1s圖…………………………………………77
圖4.17、超臨界沉積Alq3之N 1s圖………………………………………78
圖4.18、真空蒸鍍Alq3之N 1s圖…………………………………………78
圖4.19、超臨界沉積Alq3之Al 2p圖……………………………………79
圖4.20、真空蒸鍍Alq3之Al 2p圖………………………………………79
圖4.21、超臨界沉積Alq3之CV圖…………………………………………82
圖4.22、真空蒸鍍Alq3之CV圖……………………………………………82
圖4.23、OLED元件之I-V curve…………………………………………86
圖4.24、OLED元件之電流密度對電壓曲線關係圖………………………86

表目錄
表2.1、液體、氣體及超臨界流體的物理性質比較……………………23
表2.2、常見之超臨界流體臨界物理參數………………………………24
表2.3、超臨界二氧化碳製作薄膜方法及貢獻…………………………29
表3.1、電漿清洗之條件…………………………………………………42
表4.1、不同回火條件下之Alq3薄膜的原子百分………………………73
表4.2、超臨界沉積以及真空蒸鍍所得之Alq3薄膜的原子百分比……75
表4.3、電導及電導率計算表……………………………………………84

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