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作者(中文):董福慶
作者(外文):Tung, Fu-Ching
論文名稱(中文):面型預混蒸鍍製作有機元件
論文名稱(外文):OLED fabrication by using planar evaporation with premetered solvent-mixed organic compounds
指導教授(中文):周卓煇
指導教授(外文):Jou, Jwo-Huei
口試委員(中文):蔡永誠
賴識翔
溫世文
岑尚仁
口試委員(外文):Tsai, Yung-Cheng
Lai, Shih-Hsiang
Wen, Shih-Wen
Chen, Sun-Zen
學位類別:博士
校院名稱:國立清華大學
系所名稱:材料科學工程學系
學號:100031823
出版年(民國):106
畢業學年度:105
語文別:中文
論文頁數:220
中文關鍵詞:有機發光二極體面型蒸鍍源溶劑預混法低色溫類燭光有機發光二極體直接模擬蒙地卡羅法材料利用率面型閃蒸加熱器
外文關鍵詞:Organic Light Emitting Diodesplanar evaporation sourcepremetered solvent-mixed organic compoundslow color temperatureCandle Light-Style OLEDDirect Simulation Monte Carlo methodmaterial utilizationplanar flash evaporation heater
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OLED除了具有低耗電性、可撓性等優點外,可隨設計需求而調整的演色性與色溫以及平面式面光源等等的特性,使其展現與傳統光源截然不同的特色,在照明市場上將有其獨特的發展空間。OLED元件中材料佔元件成本1成,設備卻佔了4成,特將製程設備做一研究。而OLED元件在照明上為一平面式面光源,而其用在AMOLED顯示器上,更具有畫質優異,全彩化、廣視角、響應速度快、低耗能與輕薄等優異特性。只要未來技術成熟,元件成本降低與壽命增長,將會大幅侵入現有之顯示器與照明市場,預估可達5兆台幣之產值。
目前在OLED元件製程上,最關鍵之製程與設備技術在於有機奈米薄膜蒸鍍製程上,現今之點蒸鍍與線蒸鍍機台仍面臨材料利用率偏低與成本過高之瓶頸。且在傳統蒸鍍機台上,對於精準的比例控制多元材料摻雜共蒸鍍膜,幾乎是不容易達成的,要不就是良率偏低。為解決此問題,本研究利用創新概念之面型蒸鍍源技術,並以平行直接模擬蒙地卡羅法(DSMC)模擬分析設計,成功開發出面型蒸鍍驗證平台設備。面型蒸鍍源搭配溶劑預混塗佈專利技術,可容易進行多元材料摻雜共蒸且無摻雜數目之限制,進而提高元件結構設計與製作可行性之自由度,並以此新穎面型蒸鍍源設備技術成功驗證出,膜厚不均勻度<5 %,且材料利用率可達70%,並成功置換HTL層,製作出演色性指數>70之OLED元件。
本研究探討利用平行直接模擬蒙地卡羅法(DSMC)模擬分析設計面蒸鍍源真空腔體,求取設計上最佳參數。之後利用面型蒸鍍源搭配溶劑預混塗佈之方法探究其蒸鍍薄膜之性能,其中驗證蒸鍍至基板上之薄膜均勻性與材料利用率,以及製作元件來驗證面型蒸鍍源鍍膜之理論與功能及其設備可行性。
本研究成功的將二元材料之主體與藍色染料經過溶劑預混塗佈後以面型蒸鍍源製備出之薄膜層,其膜厚不均勻度為± 2.7 %;四元材料之預混面蒸之薄膜層,其膜厚不均勻度為± 2.8 %;五元材料之預混面蒸之薄膜層,其膜厚不均勻度為± 2.86 %。同時,材料利用率最高可達77.8 % ,此值比傳統點蒸鍍的3 % ~ 5 %的材料利用率,以及比線型蒸鍍源的20 % ~ 50 %要來得高,可大幅節省製作材料成本。本研究之面型蒸鍍源系統可製備出膜厚不均勻度小於5 %,材料利用率超過70 %的薄膜膜層。利用此新穎面型蒸鍍源蒸鍍電洞傳輸層,其他層則用傳統點蒸鍍源鍍膜,進而成功製備出OLED元件,其在亮度1,000 cd/m2與演色性70下,能量效率達至21.1 lm/W。另外,面型閃蒸加熱器模擬之鍍膜均勻性可達 ± 1.75 %。IR閃蒸面型蒸鍍源經實際製作,其溫度均勻性小於4 %,而膜厚不均勻性為 ± 5.81 %。而在不同的T/S間距下,其平均膜厚不均勻性為 ± 3.18 %。此新穎面型蒸鍍源蒸鍍系統可獲得大面積的薄膜均勻性與各種材料的高材料利用率。
環保與節能減碳意識抬頭,未來主流的照明光源應該要是無藍害且健康的,也要是節能環保的。白熾燈泡它具有低藍光輻射,因此至今它都是被認為最友善的光源,從對於人眼、褪黑激素產生、工藝品、生態環境與夜空光害來看,都是損害較小的。但是卻因為耗能而面臨淘汰的命運。所以本研究乃是以低色溫連續光譜元件結構來進行開發,DeviceⅠ在亮度100 nits (cd/m2)下,其色溫CT皆在2400 ~ 2500,皆屬於低色溫元件。DeviceⅡ在亮度100 nits (cd/m2)下,其色溫CT皆在2100 ~ 2300,也皆屬於低色溫元件,再由元件發光光譜來看,藍光495 nm ~ 450 nm相對強度弱很多,而小於450 nm的紫光與紫外光並不存在,故此種OLED元件可視為一對人眼友善的照明光源。
OLED lighting exhibits the characteristics of low power consumption, flexibility, planar lighting source, and can be adjusted with the design requirements of color rendering and color temperature, which are entirely distinct from the traditional lighting source. OLED will have substantial development in the general lighting market in the future. The cost of OLED materials is for 10%, and the of equipment is for 40% in OLED manufacturing. The equipment is worth to do research for improvement for reducing cost of OLED manufacturing.
OLED device is a planar lighting source. The AMOLED display exhibits the outstanding characteristics with excellent picture quality, full-color, wide viewing angle, fast response speed, low power consumption, and light and thin.
As long as the technology is mature in the future, the device cost will be reduced and the device lifetime will be increased. It would be substantially intrusive into the displays and lighting market, and it will be estimated value of NT $5 trillion.
The key issue of manufacturing OLED device is the nano-thin-film deposition of the organic materials in evaporation process. Nowadays, evaporation machine still faces the bottleneck of low material utilization and high costs.
Organic light-emitting diode fabrication is suffering from extremely high material wasting during deposition especially using a typical point or even line source. Moreover, the need of depositing a high number of emitters and host(s) with a precise composition control in a single layer makes traditional vapor codeposition systems nearly impossible, unless otherwise with a very low yield.
To improve, we have developed a novel thin-film deposition system with a planar source loadable with any premetered solventmixed organic compounds, plausibly with no component number limitation.We hence demonstrate experimentally, along with a Monte Carlo simulation, in the report the feasibility of using the technique to deposit on a large area-size substrate various organic materials with a relatively high material utilization rate coupling with high film uniformity. Specifically, nonuniformity of less than ± 5 % and material utilization rate of greater than 70 % have been obtained for the studied films.
This study investigated the use of parallel direct simulation Monte Carlo method (DSMC) and design of vacuum chamber with the planar source to obtain the optimal parameters. We use the novel thin-film deposition system with a planar source loadable with any premetered solventmixed organic compounds to verify film uniformity and material utilization of the coating to substrate, as well as to verify OLED devices performance manufacturing by the planar source.
Using such a planar source has at least three advantages, namely, a high material utilization rate, high film uniformity, and high degree of device design freedom. To the moment, we successfully achieved a layer with a host and a blue dye with a film nonuniformity of ± 2.7%. Specifically, the film was prepared using the solvent premixing deposition method. Moreover, by using the newly developed planar source, a 77.8%material utilization rate was obtained, which is much higher than the 3% to 5% rate observed when using the typical point source. The system has enabled the organic thin films to be deposited with less than 5% nonuniformity and a material utilization rate of over 70%. We successfully demonstrate the fabrication of anOLED device with the hole transporting layer deposited by the new systemwith the planar source and the other layers deposited by the conventional system. The power efficiency of the OLED device is 21.1 lm/W with a CRI of 70 at 1,000 cd/m2. The evaporation system equipped by the novel planar source can obtain large-area uniformity for thin-film evaporation and high material utilization rate of various organic materials.
In addition, the coating film thickness uniformity of the simulation with IR flash heater can be reached to ± 1.75%.
IR flash planar evaporation source after the actual manufacturing, its temperature uniformity is less than 4%, and film thickness uniformity is of ± 5.81 %. The average film thickness uniformity of different distance from target substrate to planar source (T/S) is about ± 3.18%.
A blue-hazard free, healthy light source will become the mainstream of future lighting, wherein higher energy saving is always a must. Although the use of incandescent bulbs is the friendliest electricity-driven lighting measure from the perspectives of the human eye, melatonin generation, artifacts, ecosystems, the environment, and night skies due to their intrinsically low blue emission, they are phasing out because of energy wasting. We hence devise an organic light-emitting diode which exhibits a low color temperature and a color mimicking that of a candlelight. The color temperatures of deviceⅠstructure are 2400 ~ 2500 at the luminance of 100 nits (cd/m2). The color temperatures of deviceⅡstructure are 2100 ~ 2300 at the luminance of 100 nits (cd/m2). In the spectrum, the blue light (450 nm ~ 495 nm) intensity of these devices are lower than other lights. These devices do not exhibit violet light (< 450 nm), proving the feasibility to fabricate a human-friendly light source with a low color temperature.
摘要 I
英文摘要 III
致謝 VI
目 錄 VII
表目錄 IX
圖目錄 X
壹、緒論 1
貳、文獻回顧 7
2.1有機發光二極體研究的歷史發展 7
2.2有機發光二極體的發光原理 44
2.2.1有機發光二極體的元件結構與各層機制 56
2.2.2摻雜型發光層:主發光體與客發光體間能量轉移機制 69
2.2.3高分子(polymer)有機發光材料 73
2.3光譜與光色 74
2.4色溫的影響 76
2.5白光與演色性 79
2.6 元件的效率 83
2.7 OLED元件壽命之影響因素 87
2.8 有機發光二極體的元件技術產業應用 90
2.8.1 OLED在顯示器技術發展: 91
2.8.2白光OLED照明應用技術發展 95
2.9 有機發光二極體的設備概況 101
2.9.1 OLED有機薄膜材料分類 101
2.9.2 OLED蒸鍍製程設備之發展 103
2.10 熱蒸鍍理論方法 111
2.10.1 OLED熱蒸鍍理論 111
2.10.2 膜厚分佈的理論分析 115
2.10.3 蒸發源間距與光學薄膜厚度的關係 119
參、實驗方法 123
3.1 新穎面蒸鍍設備 123
3.2面型蒸鍍實驗步驟 126
3.3 面型蒸鍍模擬分析 127
3.4.1 直接模擬蒙地卡羅法(DSMC method) 128
3.4.2 平行直接模擬蒙地卡羅法(Parallel DSMC Method) 129
3.4.3 單一材料蒸鍍源理論模擬分析參數設定 130
3.4面蒸鍍鍍膜測試方法與OLED元件製作方法 136
3.4.1 本研究所使用的材料: 136
3.4.2 噴塗蒸鍍源膜厚不均勻性測試實驗方法 140
3.4.3 材料利用率測試實驗方法 142
3.4.4 元件結構與元件製備方法 143
3.4.5 元件光電特性量測: 149
3.5面蒸鍍閃蒸模擬方法 150
肆、結果與討論 155
4.1 平行直接模擬蒙地卡羅法模擬結果 155
4.1.1面型蒸鍍平台之溫度模擬結果 155
4.1.2面型蒸鍍平台之氣體粒子數密度模擬結果 156
4.1.3面型蒸鍍平台之氣場流速模擬結果 157
4.1.4面型蒸鍍平台之基板與平面蒸鍍源溫度變化與粒子數密度模擬結果 159
4.1.5 面型蒸鍍平台之基板與平面蒸鍍源間距T/S之影響 160
4.1.6膜厚均勻性模擬分析 164
4.2 新穎面型蒸鍍鍍膜平台測試結果 166
4.2.1薄膜膜厚均勻性測試結果 166
4.2.2 材料利用率測試結果 175
4.2.3 元件製作特性量測結果 177
4.3面蒸鍍閃蒸模擬結果 185
伍、結論 194
5.1 新穎的面蒸鍍源系統結論 194
陸、參考文獻 198
柒、附錄 219
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