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研究生： 蔡妙欣
Tsay, Miau-Shing
論文名稱： 負型感光性聚醯亞胺之製備及光阻特性探討
Preparation and photoresist characteristic of negative photosensitive polyimide
指導教授： 王春山
Wang, Chun-Shan
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2002
畢業學年度： 90
語文別： 中文
論文頁數： 117
中文關鍵詞： 聚醯亞胺 、含矽雙胺 、感光性
外文關鍵詞： diaminopolysiloxane, photosensitive, polyimide
相關次數： 點閱：68  下載：9 
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    • 本論文主要探討兩種同時具有羥基之不同結構雙胺合成PI1及 PI2系列之聚醯亞胺，比較這兩組PI所配製的光阻性質差異。利用兩種具有羥基的雙胺(4,4’-diamino-4”-hydroxytriphenylmethane
    (DHTM)、4,4’-diamino-4”-hydroxytriphenylamine(DHTA))及含矽雙胺(diaminopolysiloxane(DAPS))依不同比例與3,3’,4,4’-benzo- phenone tetracarboxylic dianhydride(BTDA)合成兩組聚醯亞胺(PI1 & PI2)。將所合成的聚醯亞胺做FTIR、UV、TGA、DSC、I.V.、及溶解度測試，並與光酸發生劑(tripheylsulfonium hexafluoro- antimonate salts(TSFA))和交聯劑(2,6-dimethylol-4-methyl- phenol(DMMP))配製成負型感光性聚醯亞胺。
    於PI1(DHTM/DAPS = 70/30)及PI1(DHTM/DAPS = 60/40)系統中，添加15% TSFA 和21% DMMP，經90℃軟烤20 min，130℃曝後烤10 min，再於60℃下2.5% tetramethylammonium hydroxide(TMAH)水溶液分別顯影30 min及35 min之微影製程下，可得感度470 mJ/cm2 及560 mJ/cm2。對於PI2(DHTA/DAPS = 70/30)及PI2(DHTA/DAPS= 60/40)系統中，以相同的微影製程下，改變顯影時間為40 min及50 min，可得感度607 mJ/cm2 及720 mJ/cm2。結果顯示，PI1系列之光阻感度比PI2系列的高出130 ~ 160 mJ/cm2左右。

    In this study, two series of polyimides (PI1&PI2) were synthesized. One was produced by the reaction of two kinds of diamine compounds consisting of diaminopolysiloxane and 4,4’- diamino-4”-hydroxytriphenylmethane(DHTM) in various ratio wi- th 3,3’,4,4’-benzophenone tetracarboxylic dianhydride(BDTA). The other was produced by the reaction of two kinds of diamine compounds consisting of diaminopolysiloxane and 4,4’-diamino -4”-hydroxytriphenylamine(DHTA) in various ratio with 3,3’,4, 4’-benzophenone tetracarboxylic dianhydride (BDTA). FTIR, UV, I.V., DSC, TGA and solubility test had been done to all ratio of polyimides. The photosensitive photoresist compositions were comprised by the above synthesized polyimide, a photo crosslinking agent(2,6-Dimethylol-4-methylphenol, DMMP) and a photo acid generator(triphenylsulfonium hexafluoroanti- monate salts, TSFA) to form the negative type polyimide photo- resist which can be developed with an aqueous alkali solution.
    Comparison of the photosensitive characteristics of above photoresists, it was found that the negative photoresist comprised of PI1(DHTM/DAPS = 70/30 or DHTM/DAPS = 60/40), 15% TSFA and 21% DMMP showed a sensitivity of 470 mJ/cm2(or 560 mJ/cm2) when the resist film was prebaked at 90℃ for 20 min, post exposure baked at 130℃ for 10 min and developed in 2.5% aqueous tetramethylammonium hydroxide(TMAH) at 60℃ for 30 min (or 35min).
    While the other photoresist which comprised of PI2(DHTA/ DAPS = 70/30 or DHTA/DAPS = 60/40), 15% TSFA and 21% DMMP exhibited a sensitivity of 607 mJ/cm2(or 720 mJ/cm2)when the resist film was prebaked at 90℃ for 20 min, post exposure baked at 130℃ for 10 min and developed in 2.5% aqueous tetramethyl- ammonium hydroxide(TMAH) at 60℃ for 40 min(or 50 min).By cont- rast,the sensitivity of PI1 is higher than PI2 for about 130 to 160 mJ/cm2.

    中文摘要Ⅰ 英文摘要Ⅱ 誌謝Ⅳ 目錄Ⅴ 表目錄Ⅸ 圖目錄Ⅹ 第一章 緒論1 1-1 前言1 1-2 研究動機3 第二章 原理與文獻回顧4 2-1 文獻回顧4 2-2 聚醯亞胺合成之環化法反應機構理論11 2-3 化學增幅及其反應機構13 2-3-1 化學增幅13 2-3-2 化學增幅反應機構16 2-4 感光性聚醯亞胺光阻簡介19 2-5 光阻特性20 2-6 光學微影製程概述24 2-7 光酸、光鹼生成劑36 2-8 離子性光酸生成劑分類及其反應機構37 第三章 實驗40 3-1 藥品與儀器40 3-1-1 藥品40 3-1-2 儀器42 3-2 溶劑與二酸酐之純化44 3-2-1 二酸酐之純化44 3-2-2 溶劑之純化44 3-3 單體的合成44 3-3-1 DHTM之合成44 3-3-2 DHTA之合成47 3-4 聚醯亞胺之合成49 3-4-1 PI1之合成49 3-4-2 PI2之合成51 3-5 結構與物性分析52 3-5-1 紅外線光譜分析52 3-5-2 核磁共振光譜分析52 3-5-3 本性黏度測定52 3-5-4 溶解度測試53 3-5-5 熱重分析儀測試53 3-5-6 微差掃瞄熱分析儀測試53 3-5-7 紫外線吸收光譜儀53 3-6 微影製程54 第四章 結果與討論56 4-1 合成單體之分析56 4-1-1 DHTM單體之分析56 4-1-2 DBTA單體之分析57 4-1-3 DHTA單體之分析58 4-2 聚醯亞胺之合成與性質分析59 4-2-1 FTIR測試 4-2-2 本性黏度測試59 4-2-3 TGA測試59 4-2-4 DSC測試60 4-2-5 溶解度測試61 4-3 感光性聚醯亞胺之分析62 4-3-1 交聯反應62 4-3-2 UV吸收光譜62 4-3-3 UV light之特性吸收64 4-3-4 軟烤條件之選擇64 4-3-5 曝後烤之條件選擇65 4-3-6 顯影條件之選擇65 4-3-7 光阻之特性曲線66 4-3-8 交聯劑量之選擇66 4-3-9 顯影結果66 第五章 結論67 參考文獻105 自述10 表目錄 Table 4-1 DHTM之元素分析68 Table 4-2 DBTA之元素分析68 Table 4-3 DHTA之元素分析68 Table 4-4 PI1之本性黏度69 Table 4-5 PI2之本性黏度69 Table 4-6 PI1之熱烈解溫度及熱重殘餘量70 Table 4-7 PI2之熱烈解溫度及熱重殘餘量71 Table 4-8 PI1之玻璃轉移溫度72 Table 4-9 PI2之玻璃轉移溫度72 Table 4-10 PI1之溶解度73 Table 4-11 PI2之溶解度74 圖目錄 Fig.3-1 反應系統裝置圖46 Fig.4-1 DHTM之IR圖譜75 Fig.4-2 DHTM之H1-NMR圖譜76 Fig.4-3 DHTM之Mass圖譜77 Fig.4-4 DBTA之IR圖譜78 Fig.4-5 DBTA之H1-NMR圖譜79 Fig.4-6 DBTA之Mass圖譜80 Fig.4-7 DHTA之IR圖譜81 Fig.4-8 DHTA之H1-NMR圖譜82 Fig.4-9 DHTA之Mass圖譜83 Fig.4-10 PI1及PI2之IR圖譜84 Fig.4-11 PI1之TGA(N2)曲線圖85 Fig.4-12 PI2之TGA(N2)曲線圖86 Fig.4-13 PI1之DSC曲線圖87 Fig.4-14 PI2之DSC曲線圖88 Fig.4-15 UV吸收光譜圖89 Fig.4-16 UV吸收光譜圖90 Fig.4-17 PI1光阻之UV吸收光譜圖91 Fig.4-18 PI2光阻之UV吸收光譜圖92 Fig.4-19 軟烤條件之選擇93 Fig.4-20 PI1(DHTM/DPSX=70/30)光阻曝後烤條件之選擇94 Fig.4-21 PI1(DHTM/DPSX=60/40)光阻曝後烤條件之選擇95 Fig.4-22 PI2(DHTA/DPSX=70/30)光阻曝後烤條件之選擇96 Fig.4-23 PI2(DHTA/DPSX=60/40)光阻曝後烤條件之選97 Fig.4-24 PI1光阻顯影條件之選擇98 Fig.4-25 PI2光阻顯影之條件選擇99 Fig.4-26 PI1光阻之特性曲線100 Fig.4-27 PI2光阻之特性曲線101 Fig.4-28 PI1光阻交聯劑量之選擇102 Fig.4-29 PI2光阻交聯劑量之選擇103 Fig.4-30 PI1及PI2光阻之SEM圖104

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