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博碩士論文 etd-1011116-153954 詳細資訊
Title page for etd-1011116-153954
論文名稱
Title
可撓曲式電極與光萃取結構應用於有機電激發光二極體之研究
The Study of Flexible Electrode and Light Extraction Structure in Application of Organic Light-Emitting Devices
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
184
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2016-11-09
繳交日期
Date of Submission
2016-11-11
關鍵字
Keywords
透明導電薄膜、可撓式 OLED、導電高分子、內部光萃取結構、準光子晶體結構、蛾眼仿生抗反射結構
Conductive polymer, Flexible OLED, Transparent conductive film, Moth eye anti-reflection structure, Photonic quasi crystals, Internal light extraction structure
統計
Statistics
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中文摘要
本論文研究主要分為兩個區塊,第一個部分是透明可撓曲式電極,透過對導電高分子PEDOT:PSS進行不同的處理方式,達到提高薄膜電極的導電度,探討PEDOT:PSS導電度提升的機制,並應用此電極進行OLED元件的製作;第二個部分是利用奈米壓印技術製作次微米結構於基板上,利用不同的次微米結構當作內部光萃取結構結合OLED元件,分析該結構對於OLED元件出光效率的影響。
近年來透明可撓曲式電極研究中,導電高分子PEDOT:PSS薄膜透過浸泡酸性溶劑、有機溶劑摻雜或是非直子極性溶劑的浸漬處理等方式,達到導電度提升的效果。這三種不同架構下的處理方式分別都能使導電度提升二到四個數量級。而導電率大幅提升的原因在於PEDOT及PSS混合溶液比例的數量變化及分子間的排列情況,利用量測分析證實PEDOT:PSS導電率提升機制,得到穩定且高導電性的PEDOT:PSS薄膜,並應用於ITO-free有機元件具有極大的優勢。
在此部分研究中使用酸性溶劑對PEDOT:PSS薄膜進行浸泡處理,使薄膜導電度由未處理0.3 S/cm提升至1242 S/cm;而極性非質子溶劑DMSO經摻雜及浸漬處理兩種不同的方式分別對PEDOT:PSS溶液及薄膜進行摻雜及浸漬處理,成功的將導電度提升至718及1255 S/cm,有效的提升PEDOT:PSS薄膜導電性,最高達四個數量級,製程方式簡單、穩定、耗時短且窗口廣。後續對處理後的PEDOT:PSS薄膜進行UV-Vis、功函數、表面粗糙度等方面量測比較不同導電度之影響,並利用XPS及UV-vis光譜探討PEDOT:PSS薄膜導電度提升的機制,並使用反應式離子蝕刻機對PEDOT:PSS薄膜進行圖形化乾蝕刻處理,同以高導電性PEDOT:PSS薄膜作為陽極,製作有機發光元件並探討PEDOT:PSS薄膜特性對元件效率的影響,最後成功製成磷光藍光OLED,酸性溶劑浸泡處理之PEDOT:PSS陽極元件在亮度為1000 cd/m2時電流效率為13.4 cd/A,功率效率為6.8 lm/W,EQE為6.7%;DMSO摻雜及浸漬處理之PEDOT:PSS導電陽極元件在亮度為1000 cd/m2時電流效率為20.8 cd/A與15.4 cd/A,功率效率6.7 lm/W及6.3 lm/W,EQE為9.7%與7.7%;最後將DMSO摻雜處理之PEDOT:PSS薄膜陽極成長於PET基板上,並製作可撓式磷光藍光OLED元件,其亮度為1000 cd/m2時電流效率為15.7 cd/A,功率效率3.8 lm/W,EQE為7.9%。
而另一部分的研究主要是應用工研院機械所提供的次微米結構的準光子晶體 (Photonic Quasi Crystals, PQC) 與蛾眼仿生抗反射結構 (Moth Eye Anti-Reflection Structure, AR) 結構基板,將其應用於製作具內部光萃取結構之OLED元件,藉由陽極製程上的優化以及元件結構之設計,使得此種光萃取結構能夠有效降低元件內部的光損耗,提升有機發光二極體元件的光萃取效率及發光效率,達成高發光效率且輕薄的可撓式發光元件。
本研究分為五個階段:
1. 分別對PQC及AR結構基板進行穿透度、表面型態之量測與探討。
2. 使用光固化高折射率材料作為填平層:將光固化材料旋轉塗佈於PQC及AR結構基板上,再以室溫濺鍍製程成長銦錫氧化物薄膜 (ITO),接著量測並觀察其穿透率、表面粗糙度以及片電阻值之變化。
3. 對於OLED標準元件的製作上,進行藍光及綠光OLED元件發光效率的最佳化,然後分別應用在填平後的PQC及AR結構基板上製作出具有內部光萃取結構之藍光及綠光OLED元件,接著進行元件的光電特性量測,探討光萃取結構對於發綠光及藍光OLED元件的電性、亮度和發光效率之影響。
4. 將AR結構壓印在PET基板上,進行穿透度、表面型態之量測與探討。
5. 進行藍光以及白光OLED元件應用在PET AR結構基板上製作出具有內部光萃取結構之藍光與白光可撓OLED元件,接著進行元件的光電特性量測,探討光萃取結構對於發藍光及白光可撓OLED元件的電性、亮度和發光效率之影響。
最後本實驗成功的在具填平層之PQC及AR結構基板上分別製作具有內部光萃取結構之藍光和綠光OLED元件,其外部量子效率在亮度為1000cd/m2時的增進比例分別為 45.9%和19.8%,並成功製作出具有內部光萃取PET AR結構基板之藍光和白光可撓OLED元件,其中以白光可撓OLED元件的取光效率最為顯著,其外部量子效率在亮度為1000 cd/m2時的增進比例為27.8%。另外我們也提出各種改善元件光萃取效率之辦法,以達到更高的光耦合輸出。
Abstract
In order to obtain an anode with flexibility and high conductivity, lots of groups try to enhance the conductivity of PEDOT:PSS with adding polar solvents─such as glycol, ethanol and using post-treatment by immersing acid, dopant solvents and dipping process. These results show that, by varying the arrangement and ratio between PEDOT and PSS, those three different ways are all can enhance the conductivity more than four orders. In recent years has been measured and confirmed.
In this research, we use the polar aprotic solvents to treat the PEDOT:PSS solution and film by doping and dipping treatment. Through optimization of the parameters, we can effectively enhance the conductivity of PEDOT:PSS from 0.3 to 718 S/cm and 1255 S/cm by an easy, stable, fast and height adaptation method. Four orders of conductivity can be enhanced. The films with different treatment were investigated and compared with each other in the difference of optical conductivity, transmittance, work function, surface roughness, surface morphology, and stability. The films also use XPS and UV-vis absorption to analyze the conductivity enhancement mechanism. When the doping and dipping treatment PEDOT:PSS as anode of device at the luminance of 1000 cd/m2, the performance of current efficiency are 20.8 cd/A and 15.4 cd/A, power efficiency are 6.7 lm/W and 6.3 lm/W and EQE are 9.7% and 7.7%.
In this other side of study, we fabricated organic light-emitting diodes (OLEDs) with internal light extraction structure by using the plastic substrate with photonic quasi crystals (PQC) and moth eye anti-reflection structure (AR) provided by Industrial Technology Research Institute (ITRI) of Taiwan. Anodes fabrication and design of OLED device structure are optimized so that the optical losses inside the OLEDs with internal light extraction structure are minimized and light extraction efficiency of the OLEDs are enhanced. The study was divided into five stages:
1. The transmittance and morphology of PQC and AR nanostructure were measured and studied.
2. High refractive index material spin coated onto PQC and AR substrates as filled layer, then sputter-deposited of Indium Tin Oxide (ITO). The transmittance, morphology and sheet resistance of PQC and AR nanosubstrates covered by filled layer and ITO were measured and studied. And then, design and fabrication of ITO anodes were performed.
3. The optimized standard blue and green OLED device structures were chosen to fabricate green and blue OLEDs with internal light extraction structure. The opto-electrical properties of the devices were measured and studied.
4. The transmittance and morphology of AR on PET substrate were measured and studied.
5. The optimized standard blue and white OLED device structures were chosen to fabricate blue and white flexible OLEDs with internal light extraction structure. The opto-electrical properties of the devices were measured and studied.
Finally, we successfully fabricated blue OLEDs with PQC structure and green OLEDs with AR structure respectively. The blue and green OLEDs with internal light extraction structure have outstanding light extraction efficiency, which increase the external quantum efficiency (EQE) by 45.9% and 19.8% compared to standard OLEDs at 1000cd/m2 respectively, and we fabricated blue and white FOLEDs with internal light extraction AR nanostructure with ITO anode. Significantly, the white flexible OLEDs with internal light extraction structure have outstanding light extraction efficiency, which increase the external quantum efficiency (EQE) by 27.8% compared to white OLEDs on PET substrates at 1000 cd/m2. We also proposed various methods to improve light extraction efficiency of OLEDs.
目次 Table of Contents
致 謝 i
中文摘要 ii
Abstract iv
目 錄 vi
圖 目 錄 x
表 目 錄 xviii
第一章 緒論 1
1-1 前言 1
1-2 有機發光二極體的發展與歷史沿革 2
1-3 OLED 元件的基本結構 3
1-4 OLED 元件基本發光原理 4
1-4-1 有機及無機電激發光機制概略比較 6
1-4-2 OLED發光機制簡述 8
1-4-3 OLED之能量轉移機制 9
1-5 OLED 元件材料之介紹 14
1-5-1 高分子發光材料 14
1-5-2 小分子發光材料介紹 15
1-6 OLED 掺雜技術 17
1-7 濃度淬息效應 19
1-8 三重態自我毀滅現象 20
1-9 OLED 發光效率之定義和測量方法 20
1-10 OLED的色彩學原理 22
1-10-1 色彩學原理 22
1-10-2 CIE1931 色座標 23
1-11 參考文獻 26
第二章 實驗方法與步驟 30
2-1 實驗材料 30
2-2 實驗設備 30
2-2-1 製程設備 30
2-2-2 量測設備 35
2-3 實驗步驟 43
2-3-1 ITO基板蝕刻 43
2-3-2 ITO 基板清潔 44
2-3-3 小分子有機與金屬薄膜製程 44
2-3-4 元件封裝製程 45
2-3-5 薄膜電阻量測法 45
第三章 可撓式透明電極 47
3-1 前言與研究動機 47
3-2 透明導電薄膜簡介 47
3-2-1 金屬氧化物類 49
3-2-2 奈米金屬類 50
3-2-3 新型碳材料類 51
3-2-4 導電高分子類 51
3-3 導電高分子PEDOT:PSS 54
3-3-1 PEDOT:PSS發展 55
3-3-2 PEDOT:PSS導電機制 57
3-3-3 表面形態的改變 58
3-3-4 共振結構改變 59
3-3-5 分子構形排列 61
3-3-6 溶劑作用力的屏蔽效應 62
3-3-7 PEDOT:PSS電極應用 64
3-4 實驗架構 65
3-5 室溫濺鍍 ITO 製作及光電特性 66
3-6 PEDOT: PSS薄膜以酸性溶液浸泡處理 70
3-6-1 酸性溶液浸泡PEDOT:PSS薄膜製備及圖樣化 70
3-6-2 UV-vis穿透光譜分析 71
3-6-3 導電度量測與機制探討 72
3-6-4 PESA量測HOMO值 77
3-6-5 薄膜導電度穩定度探討 77
3-6-6 甲酸浸泡處理之PEDOT:PSS陽極應用於OLED元件光電特性分析 78
3-7 PEDOT: PSS薄膜以醇類與極性溶劑摻雜及浸漬處理 82
3-7-1 醇類與極性溶劑摻雜及浸漬處理PEDOT:PSS薄膜製備及圖樣化 82
3-7-2 UV-vis穿透光譜分析 83
3-7-3 導電度量測與機制探討 84
3-7-4 PESA量測HOMO值 91
3-7-5 薄膜導電度穩定度探討 91
3-7-6 DMSO摻雜及浸漬處理之PEDOT:PSS陽極應用於OLED元件光電特性分析 92
3-8 DMSO摻雜處理之PEDOT:PSS陽極應用於可撓式OLED元件光電特性分析 97
3-9 參考文獻 99
第四章 OLED結合內部光萃取結構 109
4-1 前言與研究動機 109
4-2 光子晶體簡介 112
4-2-1 光子晶體發展 114
4-2-2 光子晶體結構及特性 116
4-2-3 光子晶體理論基礎 118
4-2-4 光子晶體製程技術現況 121
4-2-5 光子晶體與OLED發光效率 125
4-3 實驗架構 127
4-4 PQC及AR結構基板光學特性與表面分析 128
4-5 光固化高折射率填平材料塗佈於光萃取結構基板上之量測 133
4-6 具填平層之PQC內部光萃取結構基板整合藍光磷光OLED元件製作與光電特性量測 136
4-7 具填平層之AR內部光萃取結構基板整合綠光磷光OLED元件製作與光電特性量測 139
4-8 可撓式PET AR結構基板光學特性與表面分析 142
4-9 可撓式PET AR結構基板整合藍光磷光OLED元件製作與光電特性量測 146
4-10 可撓式PET AR結構基板整合白光磷光OLED元件製作與光電特性量測 149
4-11 參考文獻 152
第五章 總結與展望 159
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