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研究生： 林睿真
Lin, Jui-Chen
論文名稱： 微奈米壓印用含酸含矽阻劑材料的合成及應用
Acidic and Silated Resists materials for Micro/Nano imprint Lithography
指導教授： 許聯崇
Hsu, Lien-chung
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學及工程學系
Department of Materials Science and Engineering
論文出版年： 2006
畢業學年度： 94
語文別： 中文
論文頁數： 124
中文關鍵詞： 壓印 、微奈米
外文關鍵詞： micro/nano, imptint
相關次數： 點閱：42  下載：0 
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    • 本論文係開發適用於熱壓印型奈米壓印之阻劑層材料，為因應不同的需求分別作兩大系列阻劑之合成。酸性壓克力阻劑部份經由Methyl methacrylate（MMA）、normal-Butylacrylate（n-BA）、Methacrylic acid（MAA）三種單體經由自由基聚合（free radical
    polymerization）而得，另外，矽化酸性壓克力阻劑則是依據酸性壓克力阻劑的單體組成配方再添加不同含量之含矽單體(3-Methacryloyloxypropyl)tris (trimethylsiloxy) silane 聚合所得。
    酸性高分子阻劑部份，經由熱重量分析以及微差掃描分析顯示，實驗所得阻劑能夠適用於熱壓型微奈米壓印製程，且玻璃轉換溫度（Tg）低於傳統的熱壓型阻劑PMMA，即能適用在較低壓印溫度。此外，藉由添加酸性單體MAA，使得阻劑能夠溶解於鹼性的TMAH(aq)中，能夠有效的縮減壓印製程中的去阻劑（Stripping）時間，提高產量，同時不需使用昂貴的反應性離子蝕刻儀或是有機溶劑去除阻劑，最後將阻劑應用在壓印製程上，成功製造出PLED軟性顯示器。
    矽化酸性高分子阻劑部份，為了提高阻劑抵抗氧電漿蝕刻的能力，在酸性壓克力阻劑中添加了含矽之壓克力單體，合成出一系列矽化酸性阻劑，同樣通過熱安定性測試且經由微差掃描分析結果得到玻璃轉換溫度約在50℃上下。其中蝕刻速率結果，可證明添加含
    矽單體對於抗蝕刻能力的提升。最後使用此阻劑，成功的轉印出奈米級的圖案，且線寬之收縮率在掃描式電子顯微鏡觀察可達3%以下，顯示此系列阻劑應用在微奈米壓印上之潛力。

    Two different series of resists for hot embossing nanoimprinting were
    developed. One is the acidic resists which were prepared by the free r a d i c a l p o l y m e r i z a t i o n o f m e t h y l m e t h a c r y l a t e ( M M A ) ,normal-butylacrylate(n-BA), and methacrylic acid(MAA) in PGMEA.
    The other series of the resists containing silane moiety, acylic monomer (3-methacryloyloxypropyl)tris (trimethylsiloxy) silane, to promote the oxygen plasma resistance.
    In the part of the acidic resists, the glass transition temperatures and the thermal stabilities were examined by DSC and TGA, and the
    results demonstrated that the novel resists would be suitable for the
    application of hot-embossing nanoimprint lithography. Moreover, the addition of MAA made it possible for the resists to dissolve in base
    solution, TMAH, and it would be helpful to reduce the time in the resist stripping step. Finally, the resist were applied in the imprinting to fabricate PLED( polymer light emitting diode) device on a flexible substrate.
    The second series of resists also passed the thermal stability tests, and their Tgs were around 50℃. The results of the etching rate tests proved the improvement of etching resistance by adding the silane monomer. At last, the resist was used in the nanoimprint lithography, and it can completely transfer the nano-scale patterns of the silicon mold to the substrate. From the observation of SEM, the shrinkage of the pattern was less than 3%, so they demonstrated that this series ofresists has potential to be used in nanoimprint lithography.

    中文摘要..................................................................... I 英文摘要.................................................................... II 誌謝......................................................................... V 目錄........................................................................ VI 表目錄...................................................................... IX 圖目錄....................................................................... X 第一章序論................................................................... 1 1-1 前言..................................................................... 1 1-2 研究動機與目的........................................................... 5 第二章文獻回顧以及原理介紹................................................... 7 2-1 壓印技術................................................................. 7 2-1-1 熱壓型奈米壓印技術..................................................... 7 2-1-2 紫外光硬化奈米壓印微影技術............................................ 13 2-1-3 軟微影技術............................................................ 16 2-1-4 混合型壓印技術........................................................ 18 2-1-5 雷射輔助直接轉印技術.................................................. 22 2-2 蝕刻障礙層材料.......................................................... 25 2-2-1 熱塑型高分子阻劑...................................................... 25 2-2-2 感光型高分子.......................................................... 26 2-2-3 熱固型高分子.......................................................... 29 2-3 阻抗層高分子材料之設計原理.............................................. 31 2-3-1 含酸壓克力系列阻抗層高分子材料合成.................................... 31 2-3-2 矽化酸性壓克力系列阻抗層高分子材料合成................................ 33 第三章實驗過程與方法........................................................ 34 3-1 實驗用藥品與儀器........................................................ 34 3-1-1 藥品.................................................................. 34 3-1-2 實驗儀器.............................................................. 35 3-2 高分子阻劑合成.......................................................... 37 3-2-1 酸性阻劑之合成........................................................ 37 3-2-2 矽化酸性阻劑之合成.................................................... 38 3-2-3 高分子阻劑純化........................................................ 39 3-3 結構鑑定與分析.......................................................... 42 3-3-1 黏度測定.............................................................. 42 3-3-2 核磁共振光譜(1H-NMR,13C-NMR)分析...................................... 42 3-3-3 元素分析儀............................................................ 43 3-3-4 凝膠滲透層析儀分析.................................................... 43 3-3-5 熱重損失分析.......................................................... 44 3-3-6 微差掃描熱分析........................................................ 45 3-3-7 溶解速率測試.......................................................... 46 3-3-8 蝕刻速率測試.......................................................... 46 3-3-9 旋轉塗布膜厚測試...................................................... 47 3-4 微奈米壓印微影製程及有機發光元件製作.................................... 48 3-4-1 模具的清洗及前處理.................................................... 48 3-4-2 旋轉塗布.............................................................. 49 3-4-3 軟烤.................................................................. 51 3-4-4 壓印.................................................................. 52 3-4-5 蝕刻去除殘餘層........................................................ 56 3-4-6 圖案的觀察............................................................ 59 3-4-7 蝕刻氧化銦錫層........................................................ 60 3-4-8 剝除阻劑.............................................................. 61 3-4-9 PLED元件製造.......................................................... 61 第四章實驗結果與討論........................................................ 65 4-1 阻劑之合成.............................................................. 65 4-1-1 含酸阻劑之合成........................................................ 65 4-1-2 矽化含酸阻劑之合成.................................................... 67 4-2阻劑之結構與性質鑑定..................................................... 68 4-2-1 黏度測定.............................................................. 68 4-2-2 核磁共振光譜分析...................................................... 69 4-2-3 元素分析結果.......................................................... 70 4-2-4 分子量測定............................................................ 71 4-2-5 熱重損失分析.......................................................... 72 4-2-6 微差掃描熱分析........................................................ 75 4-2-7 溶解速率測試.......................................................... 76 4-2-8 蝕刻速率測試.......................................................... 77 4-2-9 旋轉塗布膜厚測試...................................................... 78 4-3 阻劑在微奈壓印上之應用.................................................. 79 4-3-1 酸性壓克力阻劑應用在PLED發光元件之製作................................ 79 4-3-2 矽化酸性壓克力阻劑在奈米壓印之應用.................................... 80 第五章結論................................................................. 116 參考文獻................................................................... 118

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