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研究生：	陳惠姿 Chen, Hui-Tzu
論文名稱：	正型鹼性水溶液顯影耐高溫感光性聚亞醯胺-聚苯噁唑共聚合物(PI-PBO)之研究 Novel Positive-working Aqueous Base Developable Photosensitive Poly(imide-benzoxazole) for Microelectronic Applications
指導教授：	許聯崇 Hsu, Lien-Chung Steve
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：	2004
畢業學年度：	92
語文別：	中文
論文頁數：	133
中文關鍵詞：	聚亞醯胺、感光性、正型、聚苯噁唑
外文關鍵詞：	photosensitive, polybenzoxazole, polyimide, positive-working
相關次數：	點閱：58 下載：4
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　　利用BisAPAF(2,2-Bis.1,3-amino- 4-hydroxyphenyl hexafluoropropane)、ODC(Oxydibenzoyl chloride)、TAC(Trimellitic anhydride chloride)、PMDA (Pyromellitic dianhydride)以及IC(Isophthaloyl chloride)等單體在無水極性溶劑NMP (N-methyl -2-pyrolidinone)中進行聚縮合反應，成功地合成出3 種不同結構之PI-PBO 『Poly(imide-benzoxazole)』前驅物PAA-PHA『Poly(amic acid-hydroxyamide)』。將其於350℃高溫環化後得到3組不同結構之新型的PI-PBO 共聚合物。
　　此3 種不同結構PAA-PHA 之固有黏度(inherent viscosity)為0.17~0.33 (dL/g)，其結構由FTIR 及1H-NMR 圖譜及元素分析中得到鑑定。此3 種聚合物皆為非晶質結構；並都具有高的玻璃轉移溫度(Tg)，及良好的熱安定性。此3 組不同結構之PI-PBO 前驅物PAA-PHA 於許多常用之溶劑中之溶解度甚佳；而其高溫環化後之PI-PBO 共聚合物則表現出良好之耐化學藥品性質。此3 組PI-PBO 共聚合物皆具有非常低之吸水性特別適合應用於要求低吸水性的電子產品方面。
　　將所合成出之3 組新的PAA-PHA 中加入DNQ 感光劑成功地製備出正型鹼性水溶液顯影的耐高溫感光材料。將此3 組感光配方，以0.6%TMAH水溶液為顯影液進行微影製程圖案轉移，其解析度皆可到達5μm左右，而光敏感度為209~256mJ/cm2 由光學顯微鏡(OM)及掃描式電子顯微鏡(SEM)觀察，其圖案也十分完整。

　　Three kinds of novel positive working aqueous base developable photosensitive poly(imide-benzoxazole) precursors based on poly(amic acid- hydroxyamide)s bearing phenolic hydroxyl groups and carboxylic acid groups, a diazonaphthoquinone (DNQ) photosensitive compound and a solvent have been developed. These three kinds of poly(amic acid- hydroxyamide)s were prepared from the polymerization of 2, 2'-bis-(3-amino-4- hydroxyphenyl)hexafluoropropane (BisAPAF), trimellitic anhydride chloride (TAC) ,4,4’-oxydibenzoyl chloride (ODC), Isophthaloyl chloride (IC) and Pyromellitic dianhydride (PMDA). Subsequently, thermal cyclization of the poly(amic acid-hydroxyamide) precursors at 350 ℃ produced the correspondingpoly(imide-benzoxazole)s. The inherent viscosity of the precursor polymers were 0.17~0.33 dL/g. The cyclized poly(imide- benzoxazole)s showed a highglass transition temperature and good thermal stability. The structures of the precursor polymers and the fully cyclized polymers were characterized by FTIR,1H-NMR and elemental analysis. The photosensitive precursor containing 25 % DNQ photoactive compound showed good sensitivity and contrast in a 3 µm film with a 0.6 wt % tetramethylammonium hydroxide (TMAH) developer. The patterns with resolution of 5 µm were obtained from these compositions.

總目錄
中文摘要....................................... I
英文摘要.......................................II
誌謝..........................................III
總目錄.........................................IV
表目錄........................................ IX
Scheme 目錄.....................................X
圖目錄........................................ XI
第一章緒論..................................... 1
1-1 前言....................................... 1
1-2 研究動機................................... 5
第二章文獻回顧與原理........................... 7
2-1 聚亞醯胺的發展與相關介......................7
2-2-1 加成型聚亞醯胺...........................10
2-1-2 縮合型聚亞醯胺...........................12
2-1-3 改質型聚亞醯胺...........................17
2-2 聚苯噁唑的發展與相關介紹...................17
2-3 感光性高分子的發展.........................21
2-3-1 開環的負型PSPI...........................23
2-3-2 閉環的負型PSPI...........................25
2-3-3 開環的正型PSPI...........................25
2-3-4 閉環的正型PSPI...........................27
2-4 感光性高分子的應用.........................28
2-5 微影成像技術及原理.........................30
2-5-1 表面清洗.................................31
2-5-2 塗底.....................................31
2-5-3 光阻旋塗.................................32
2-5-4 軟烤.....................................35
2-5-5 曝光法...................................35
2-5-6 光罩.....................................37
2-5-7 光源.....................................38
2-5-8 顯影.....................................38
2-5-9 硬烤.....................................38
2-5-10 蝕刻....................................39
2-5-11 光阻剝除................................39
2-6 光阻特性...................................39
2-6-1 感光度...................................39
2-6-2 對比度...................................42
2-6-3 解析度...................................42
2-6-4 熱穩定性.................................43
2-6-5 接著性...................................43
2-6-6 顯像性...................................43
第三章實驗步驟.................................44
3-1 實驗用藥品與儀器...........................44
3-1-1 藥品.....................................44
3-1-2 實驗儀器.................................45
3-2 二酸酐的純化...............................46
3-3 單體合成...................................46
3-3-1 純化.....................................46
3-3-2 ODC 單體之合成...........................47
3-4 實驗步驟...................................48
3-4-1 PI-PBO-1 前驅物PAA-PHA-1 之合成..........48
3-4-2 PI-PBO-2 前驅物PAA-PHA-2 之合成..........50
3-4-3 PI-PBO-3 前驅物PAA-PHA-3 之合成..........52
3-5 PI-PBO 薄膜的製備..........................54
3-5-1 PI-PBO-1 薄膜製備........................54
3-5-2 PI-PBO-2 薄膜製備........................55
3-5-3 PI-PBO-3 薄膜製備........................56
3-6 結構鑑定與分析.............................57
3-6-1 紅外線吸收光譜(FT-IR)分析................57
3-6-2 核磁共振光譜(1H-NMR)分析.................57
3-6-3 黏度測定.................................57
3-6-4 元素分...................................58
3-6-5 X 光繞射(XRD)分析........................58
3-6-6 熱重分析儀(TGA)分析......................58
3-6-7 熱機械分析(TMA)..........................59
3-6-8 溶解度測試...............................59
3-6-9 吸濕性測試...............................59
3-6-10 機械分析................................59
3-7 微影製程...................................60
3-7-1 矽晶片表面處理...........................60
3-7-2 前驅物感光配方的配製.....................60
3-7-3 紫外-可見光光譜(UV-Vis)分析..............61
3-7-4 旋轉塗佈(spin coating)...................61
3-7-5 軟烤(prebaking)..........................62
3-7-6 曝光(exposure)...........................62
3-7-7 顯影(development) .......................62
3-7-8 溶解速率的計算...........................62
3-7-9 前驅物環化熱處理.........................62
3-7-10 感光的PAA-PHA 配方加熱後熱重量的變化....63
3-7-11 特性曲線的製作..........................63
3-7-12 圖案的觀察..............................64
第四章結果與討論...............................65
4-1 聚合物的合成與分析.........................65
4-1-1 BisAPAF-60%ODC-40%TAC 系統...............67
4-1-2 BisAPAF-80%ODC-20%PMDA 系統..............68
4-1-3 BisAPAF-80%IC-20%PMDA 系統...............70
4-2 高分子材料熱分析...........................72
4-2-1 微差掃描熱分析(DSC)......................72
4-2-2 熱重分析(TGA) ...........................72
4-2-3 熱機械性質分析(TMA)......................74
4-3 高分子材料溶解度分析.......................75
4-4 高分子材料吸濕性分析.......................76
4-5 機械性質測試...............................77
4-6 感光性高分子的顯影特性分析.................78
4-6-1 UV-Visible 光譜分析......................80
4-6-2 膜厚大小與旋塗速率、固含量的關係.........81
4-6-3 軟烤溫度的選擇...........................82
4-6-4 DNQ(PIC-3)含量的影響.....................82
4-6-5 顯影液濃度的選擇.........................84
4-6-6 感光的PAA-PHA 配方加熱後的變化...........85
4-6-7 特性曲線的製作...........................86
4-6-8 OM 圖形觀察..............................87
4-6-9 SEM 圖形觀察.............................88
第五章結論....................................128
參考文獻......................................129
                                    

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校內：2006-06-23公開
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