臺灣博碩士論文加值系統

本研究是利用超臨界流體沈積技術來形成有機發光二極體(OLED)薄膜。主要藉由基板加熱作為超臨界二氧化碳(SCCO2)飽和溶液下異質成核的驅動力，使成長機制由島狀成長形成連續的薄膜。在半流動式操作下，雖然基板溫度升高會增加析出量卻不利於吸附量，而於55℃時有較佳覆輔v與島疏密度。萃取槽壓力從23.8 MPa至30.6 MPa的改變可增進12.5%的覆輔v，可減少連續成膜所需最少循環次數。另外，添加乙醇共溶劑雖可增快沈積速率，但其成膜的臨界膜厚卻大於50 nm Alq3需求膜厚，經添加0.8 ml發現可達此要求。最後在30.6 MPa、35℃萃取槽、55℃基板溫度與0.8ml乙醇條件下，製作OLED元件並測試電流-電壓特徵曲線，其起始電壓為3.6 V，在電壓10 V下有6.23 mA/cm2的電流密度且無漏電流的現象，符合OLED元件要求。證明超臨界流體沈積技術來製作OLED薄膜是可行的。

This study is to investigate the technique of supercritical fluid deposition to form thin film of organic light emitting diode (OLED). Using the elevating substrate temperature as a driving force of heterogeneous nucleation in supercritical carbon dioxide (SCCO2) saturation solution, the growing mechanism changed from island mode to a continuous layer. In the operation of semi-flow type, the higher substrate temperature might be able to enhance nucleation of OLED, but reducing the amount of adsorption on the substrate. It has a better coverage rate and island density on the substrate at 55℃. When the pressure of extraction chamber increases from 23.8MPa to 30.6MPa, the coverage rate could be improved 12.5% and the minimum cycling number to form a continuous layer can be decrease. Moreover, although adding ethanol as co-solvent could increase the deposition rate, the critical thickness of the thin-film was beyond the required Alq3 thickness of 50nm. It was found that 0.8 ml of ethanol could meet the demand. By using the conditions of 30.6MPa and 35℃extraction chamber, 55℃substrate temperature and 0.8ml ethanol, a OLED device was manufactured to perform the measurement of I-V characteristics. With no electric leakage, the initial voltage was 3.6V and the current density was 6.23mA/cm2 at 10V, which matched the requirement of OLED device. Hence, the technique of supercritical fluid deposition has shown a promise for fabricating OLED thin film.

中文摘要......................................I
英文摘.......................................II
目錄........................................III
圖目錄.......................................VI
表目錄........................................X
符號說明.....................................XI
第一章 緒論...................................1
第二章 文獻回顧...............................3
2.1 有機發光二極體...........................3
2.1.1 簡介有機發光二極體....................3
2.1.2 有機發光二極體元件的構造..............4
2.1.3 有機發光二極體的限制..................6
2.1.4 元件劣化原因..........................8
2.1.5 有機發光材料的選用...................10
2.1.6 現有製程.............................11
2.2 超臨界二氧化碳之成膜技術................13
2.2.1 二氧化碳的簡介.......................13
2.2.2 超臨界的基本性質.....................14
2.2.3 各類型的成膜技術.....................16
2.2.4 超臨界二氧化碳流體沈積技術...........18
2.3 成膜原理與操作變數......................21
2.3.1 簡介各種析出的形貌...................21
2.3.2 成膜原理.............................25
2.3.3 參數影響.............................30
第三章 實驗設計與步驟........................35
3.1 實驗流程................................35
3.2 超臨界二氧化碳操作系統..................37
3.3 超臨界二氧化碳之溶解度的測定............42
3.4 可沈積多層膜的驗證......................45
3.5 超臨界下析出的實驗......................48
3.6 半流動式操作實驗........................52
3.7 有機發光二極體的試做....................54
3.8 量測儀器的簡介..........................57
3.9 薄膜品質的判定..........................61
3.10 研究相關藥品與設備......................62
第四章 結果與討論............................64
4.1 溫度對溶解度的影響......................64
4.2 超臨界下可堆疊多層膜的實際驗證..........66
4.3 析出的驅動力對表面形貌的影響............68
4.4 Alq3沈積於ITO玻璃之螢光激發光譜.........72
4.5 流動式操作下萃取管溫度對表面形貌的影響..74
4.6 流動式操作下流速對析出的影響............77
4.7 流動式操作下薄膜的成長機制..............79
4.8 半流動式操作下循環操作次數對析出的影響..84
4.9 半流動式操作下基板溫度對析出的影響......87
4.10 半流動式下共溶劑添加量的影響............90
4.11 半流動式含共溶劑下基板溫度之影響........93
4.12 薄膜性質量測............................95
第五章 總結與未來展望.......................102
5.1 總結...................................102
5.2 未來展望...............................104
參考文獻....................................105

圖目錄

圖2.1 傳統有機發光二極體之結構示意圖...........5
圖2.2 薄膜式封裝之結構示意圖...........5
圖2.3 Alq3的化學結構圖...........10
圖2.4 真空熱蒸鍍機示意圖...........12
圖2.5 OVPD裝置示意圖...........12
圖2.6 一般物質的壓力對溫度之三相圖...........15
圖2.7 常見超臨界下化學流體沈積法之操作裝置圖...........19
圖2.8 靜態式之過飽和析出薄膜裝置圖...........20
圖2.9 分子或原子在流體中析出的形貌之示意圖...........21
圖2.10 三種薄膜成長機制之示意圖...........24
圖2.11 固體溶質析出時ΔG的變化關係圖...........26
圖2.12 Mier Theory示意圖...........28
圖2.13 二氧化碳對於特定物質的溶解特性...........31
圖2.14 沈積速度與基板溫度所影響的薄膜型態示意圖...........32
圖3.1 實驗操作的流程圖...........36
圖3.2 增壓系統示意圖...........38
圖3.3 萃取系統示意圖...........39
圖3.4 鍍膜系統示意圖...........40
圖3.5 排放系統示意圖...........41
圖3.6 溶解度檢測裝置圖...........43
圖3.7 可操作冷或熱的基板裝置圖...........46
圖3.8 利用溫差與壓降之鍍膜槽示意圖...........49
圖3.9 半流動式鍍膜槽示意圖...........53
圖3.10 有機發光二極體製作的流程圖...........55
圖3.11 二極體之電流-電壓特徵曲線...........60
圖4.1 30.6 MPa下不同萃取溫度：35 ℃、50 ℃、65 ℃、80 ℃，以RESOLV法所轉換之UV-VIS吸收光譜...........65
圖4.2 (a)、(c)、(e)、(g) 為Alq3氯仿飽和溶液旋轉塗佈以2400 r.p.m. 20秒之薄膜，分別將其置於30.6 MPa以不同的萃取溫度與基板溫度 (b)50℃、35℃(d)50℃、65℃(f)35℃、20℃(h)35℃、50℃後之形貌...........67
圖4.3 萃取壓力30.6 MPa、萃取溫度0 ℃、基板溫度35 ℃、流速1 ml/s下含0.5mm狹縫所析出之形貌...........69
圖4.4 將圖4.3放大倍率之形貌與示意圖...........69
圖4.5 萃取壓力30.6 MPa、萃取溫度0℃、基板溫度35℃、流速1 ml/s下不含狹縫所析出之形貌...........71
圖4.6 將圖4.5放大倍率之形貌與示意圖...........71
圖4.7 ITO玻璃基板、Alq3粉末與利用超臨界流體沈積Alq3於ITO基板之螢光激發光譜...........73
圖4.8 在相同流動式的操作條件下，改變不同萃取溫度與基板溫度：(a)0℃、40℃(b)20℃、60℃(c)40℃、80℃之形貌...........75
圖4.9 流動式下萃取管溫度與核島疏密度的關係圖...........76
圖4.10 在流動式相同操作條件下，以不同流速(a)0.02 ml/s(b) 2ml/s(c)4 ml/s之形貌...........78
圖4.11 在相同的流動式操作條件下，以不同二氧化碳使用量(a)20 ml(b)40 ml(c)60 ml所析出之形貌...........80
圖4.12 半流動式相同的操作條件下，改變不同萃取壓力(a)10.2 MPa(b)17.4 MPa(c)23.8 MPa(d)30.6 MPa之形貌...........82
圖4.13 半流動式下萃取壓力對核島的疏密度之關係圖...........83
圖4.14 半流動式下萃取壓力對覆輔v之關係圖...........83
圖4.15 半流動式相同的操作條件下，改變不同的循環次數(a)1次(b)3次(c)5次(d)7次(e)9次之形貌...........85
圖4.16 半流動式下覆輔v與循環次數關係圖...........86
圖4.17 半流動式相同的操作條件下，改變不同的基板溫度(a)55℃(b)60℃(c)65℃(d)70℃(e)75℃之形貌...........88
圖4.18 半流動式下基板溫度對疏密度之關係圖...........89
圖4.19 半流動式下基板溫度對覆輔v之關係圖...........89
圖4.20 半流動式相同的操作條件下，改變不同乙醇的添加量(a)0.2 ml(b)0.5 ml(c)1.0 ml(d)2.0 ml(e)4.0 ml之形貌...........91
圖4.21 半流動式下乙醇添加量對疏密度之關係圖...........92
圖4.22 半流動式下乙醇的添加量對覆輔v之關係圖...........92
圖4.23 半流動式下，添加乙醇時，改變不同基板溫度(a)55℃(b)60℃(c)65℃(b)70℃之形貌...........94
圖4.24 半流動式下，添加乙醇時基板溫度對疏密度之關係圖...........95
圖4.25 半流動式下，添加乙醇時基板溫度對覆輔v之關係圖...........95
圖4.26 不同形貌下A、B、C、D、E之電流-電壓曲線關係...........100
圖4.27 半流動式下操作下，不同共溶劑含量(1.0 ml、0.9 ml、0.8 ml)之電流-電壓曲線關係圖...........101

表目錄

表2.1 氣體、液體與超臨界流體性質比較表.................13
表2.2 超臨界二氧化碳各種方式之成膜研究.................15
表2.3 均質成核與異質成核之比較表.......................20
表4.1 成膜參數對應表...................................96
表4.2 薄膜性質量測對應表...............................97

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