以旋塗與奈米壓印製作發光層之有機發光二極體

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研究生：	彭祥灝 Peng, Shiang-Hau
論文名稱：	以旋塗與奈米壓印製作發光層之有機發光二極體 Organic Light-Emitting Diodes with Spin-Coated and Nano-Imprinted Emissive Layers
指導教授：	周卓煇 Jou, Jwo-Huei
口試委員:	岑尚仁陳建志薛景中蔡永誠
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：	2013
畢業學年度：	101
語文別：	中文
論文頁數：	109
中文關鍵詞：	有機發光二極體、旋塗、奈米壓印
外文關鍵詞：	Organic Light-Emitting Diode, Spin-Coat, Nano-Imprint
相關次數：	點閱：4 下載：0
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有機發光二極體因可應用於顯示及照明，逐漸受到矚目；為早日應用，製造成本將是首要考量；因此，許多研究紛紛投入研製溼式製程；市場研究機構Nanomarkets預估，2013年溼式製程材料產值為5,000萬美元，2019年將大幅成長至80,000萬美元，再次顯示發展溼式製程的重要；據此，本研究使用兩種不同的溼式製程，製備有機發光二極體的發光層。
第一部分，我們利用旋塗製程，製備藍光及綠光有機發光二極體；其中，新穎綠磷光材料bis[5-methyl-8-trifluoromethyl-5H-benzo(c)(1,5) naphthyridin-6-one]iridium(picolinate) (3-CF3BNO)，具有短激態生命期(0.39 μs)及相對高量子產率(72%)，與適當的主體搭配，當亮度在100及1,000 cd/m2時，效率分別為52及61 lm/W、外部量子效率為18%及23%，為目前綠光元件在濕式製程中的能量效率世界記錄。
第二部分，為克服小分子型材料不易轉印，我們研發一小分子及高分子型混合式主體方法，成功將發光層轉印至元件上，製備藍、綠、紅及白光有機發光二極體，所得的元件最大亮度分別為29,000、29,000、4,000及18,000 cd/m2；能成功轉印可歸因於混合式主體可提供高分子型主體好的成膜特性，亦具備小分子型主體好的電致發光特性。

Organic light-emitting diodes (OLEDs) are attracting increasing interest owing to their promising applications in flat panel displays and solid-state lighting. To make it applicable soon, manufacturing cost is the top priority to be considered. Therefore, this can explain why numerous researches have been paid much effort on design and fabrication of solution process. Nanomarkets estimates that the output value of solution-processable materials is 50 million US dollars in 2013, and will markedly increase to 800 million in 2019, again indicating that the importance of development of solution process. In this report, two different solution processes are employed to fabricate the emissive layers in OLED devices.
In the first part, blue and green OLEDs are fabricated via solution process by using a novel phosphorescent material, bis[5-methyl-8-trifluoromethyl-5H-benzo(c) (1,5) naphthyridin-6-one] iridium(picolinate) (3-CF3BNO), which has a short excited-state lifetime (0.39 μs) and a relatively high quantum yield (72 %). Coupled with an appropriate host material, the resultant green OLED shows an efficacy of 52 and 61 lm/W and external quantum efficiency of 18 and 23 % at 100 and 1,000 cd/m2, the highest among all reported solution-processed green OLEDs.
In the second part, to overcome the disadvantage of molecular material that is not easy to be used in contact-printing, a method of blending with molecular and polymer host is designed and fabricated to contact-print the emissive layer onto the OLED devices successfully. By using this method, the maximum luminance of fabricated blue, green, red, and white OLEDs is 29,000, 29,000, 4,000, and 18,000 cd/m2, respectively. That contact-printing can be achieved successfully may be attributed to the blended host, which is composed of a polymer host with a good film integrity and a molecular host with a fine electroluminescence character.

摘要    II
Abstract    IV
誌謝    VI
圖目錄    XI
表目錄    XIV
壹、緒論    1
貳、文獻回顧    3
2-1、有機發光二極體的歷史發展    3
2-2、發光原理    14
2-3、有機發光二極體材料之發展    23
2-3-1、陽極材料    23
2-3-2、電洞傳輸材料    24
2-3-3、電子傳輸材料    25
2-3-4、發光材料    26
2-3-5、電子注入材料    27
2-3-6、陰極材料    28
2-4、高效率OLED元件之發展    29
2-4-1、光色定義    29
2-4-2、高效率OLED元件    31
2-4-3、磷光發光材料開發    32
2-4-5、元件結構設計    32
2-4-6、不同製程之高效率綠磷光元件    33
2-5、OLED元件之製造方法    36
2-5-1、蒸鍍製程    36
2-5-2、濕式製程    37
2-5-2-1、旋轉塗佈法    38
2-5-2-2、噴墨印刷法    38
2-5-2-3、刮刀塗佈法    39
2-5-2-4、狹縫式塗佈法    40
2-5-2-5、凹板印刷塗佈法    41
2-5-2-6、奈米壓印製程    42
參、實驗方法    47
3-1-1、材料    47
3-1-2、綠光染料3-CF3BNO之合成    50
3-1-3、量子產率(quantum yield)之量測    52
3-1-4、激態生命期(excited-state lifetime)之量測    52
3-1-5、光致發光光譜(Photoluminescent spectrum, PL spectrum)之量測    53
3-1-6、紫外光吸收光譜(ultraviolet visible absorption, UV-VIS absorption)之量測    54
3-1-7、熱重分析(Thermogravimetry Analysis, TGA)之量測    54
3-2、元件設計及製備    55
3-2-1、元件之製作流程及電路設計    55
3-2-2、基材清洗    56
3-2-3、主體與發光染料溶液之配製 (小分子旋塗法)    57
3-2-4、旋轉塗佈    58
3-2-5、蒸鍍源之製備(溶劑預混法)    58
3-2-6、印模製備    59
3-2-7、壓印裝置    60
3-2-8、蒸鍍裝置    62
3-2-9、有機層的製備    63
3-2-10、負電極的製備    63
3-2-11、蒸鍍速率之測定與校正    63
3-3、元件電流、電壓、亮度與演色性特性量測    65
3-3-1、發光效率之計算    66
3-3-2、電致發光光譜(Electroluminescent spectrum, EL spectrum)之量測    66
肆、結果與討論    67
4-1、以旋轉塗佈法製備發光層    67
4-1-1、新穎綠磷光材料之物理性質    67
4-1-2、不同綠光磷光染料對元件光電特性之影響    69
4-1-3、不同主體對綠光元件光電特性之影響    72
4-2、以壓印製程製備有機發光二極體之發光層    82
4-2-1、新穎綠磷光材料之物理性質    82
4-2-2、氧氣電漿處理對印模表面潤濕性之影響    83
4-2-3、上墨方式對薄膜均勻性之影響    84
4-2-4、轉印參數對轉印效果之影響    85
4-2-5、熱處理對轉印效果之影響    86
4-2-6、接觸印刷製備紅、綠、藍及白光發光層    88
伍、結論    95
陸、參考文獻    98
附錄、個人著作目錄    106
(A) 期刊論文    106
(B) 研討會論文    109
(C) 專利    109

                                

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