高分子樹脂改質應用於負型光阻之製備及性質探討; Preparation and Characterization of Modified Binders Applied in Negative-type Photoresists

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題名:	高分子樹脂改質應用於負型光阻之製備及性質探討;Preparation and Characterization of Modified Binders Applied in Negative-type Photoresists
作者:	黃新義;Hsin-Yi Huang
貢獻者:	化學工程與材料工程研究所
關鍵詞:	彈性回復力;間隔物;光阻劑;高分子樹脂;binder;photoresist;photo spacer;elastic recovery
日期:	2010-06-19
上傳時間:	2010-12-08 13:34:59 (UTC+8)
出版者:	國立中央大學
摘要:	本論文主要利用自由基聚合法製備一系列的高分子樹脂(polymer binder)，探討高分子樹脂的各項物理特性，包括分子量、酸價、玻璃轉化溫度(Tg)、熱重損失溫度(Td)與化學結構等，再將高分子樹脂與交聯劑加入負型光阻中，經過微影製程後，形成柱狀體的間隔物(photo spacer)，探討對於間隔物機械性質與圖形外觀的影響。本論文包含三部份，第一部份主要為在固定使用高分子樹脂中，探討交聯劑或單體添加的效果。當添加7 wt.%聚二季戊四醇五丙烯酸酯(dipentaerythritol hexa-acrylate, DPHA) 的交聯劑於光阻配方中，間隔物擁有優異的機械特性(彈性回復力=80.7%)。在混合型系統中，最適化的配方比例為交聯劑(DPHA)固定10 wt.%之外，另外再添加2 wt.%的甲基丙烯酸正丁酯(n-butyl methacrylate, BuMA)或甲基丙烯酸苯甲酯(benzyl methacrylate, BzMA)或壓克力二氧化矽單體(acrylic-silica monomer, Pro-1264)於負型光阻中，可增加間隔物的機械性質。第二部份主要採用自由基聚合四成份高分子樹脂，單體包括甲基丙烯酸(methacrylic acid, MAA)、苯乙烯(styrene)、甲基丙烯酸異冰片酯(isobornyl methacrylate, IBMA)、苯基馬來醯亞胺(n-phenylmelaimide, PMI)，其中IBMA與PMI為具有環狀剛性結構的單體，結果顯示高分子樹脂的Tg與起始劑濃度、MAA單體比例等無明顯關聯，與剛性結構的單體(IBMA與PMI)比例組成有顯著的影響，PMI比例越高，高分子樹脂的Tg越高。高分子樹脂的Td與起始劑濃度、鏈轉移劑濃度、MAA單體比例等無明顯的關聯。另外，實驗發現當PMI比例提高時，熱重分析儀(thermal gravimetric analyzer)的圖形朝向較高溫度的區域移動。本實驗的高分子樹脂具備IBMA與PMI等剛性的結構，再加上含有多官能基的交聯劑(DPHA)，經過黃光微影製程後，曝光區產生高強度的互穿網結構，讓間隔物呈現出優異的機械特性(彈性回復力=81.1%)。第三部份將高分子樹脂與丙基異氰酸酯單體(isocyanurate)進行縮合反應，獲得具備光與熱交聯性質的新型高分子樹脂。結果顯示此新型高分子樹脂的Tg與丙基異氰酸酯單體的比例無明顯關聯，主要還是與本身高分子樹脂結構中的剛性鏈段(IBMA與PMI)有關聯。具備光交聯性質的新型高分子樹脂，經過微影製程後，高分子樹脂本身以及與交聯劑形成互穿網結構，能夠提升間隔物的彈性回復力約3-8%，並使間隔物呈現較為陡直的圓柱狀圖形。 A series of monomers were polymerized by free-radical polymerization and used as polymer binders in negative-type photoresists. Cylindrical patterns were found to be formed when the photoresists were applied on a glass substrate using a lithographic process. The characteristics (molecular weight, acid value, glass transition temperature, and thermal decomposition temperature) of the polymer binders and the mechanical properties and profile of the pattern formed in a photo spacer are discussed here. The study was divided into three parts. In the first part, the mechanical properties (elastic recovery = 80.7%) of the patterns obtained by adding 7 wt.% of dipentaerythritol hexa-acrylate (DPHA) to the photo spacers were investigated. In the binary system, the superior mechanical properties of patterns and the optimum compositions were obtained by using 2 wt.% of acrylic monomers (n-butyl methacrylate or benzyl methacrylate or Pro-1264) in the photoresists with a fixed DPHA content of 10 wt.%. In the second part, a series of cyclic monomers were polymerized by free-radical polymerization. For this, four-component polymer binders consisting of methacrylic acid (MAA), styrene, isobornyl methacrylate (IBMA), and phenylmelaimide (PMI) were used. The glass transition temperature (Tg) of the polymer binders was found to increase with the PMI content because of the rigid characteristics of the molecular structure of PMI. However, Tg of the polymer binders was largely independent of the initiator and MAA concentration for the range of values tested in this study. The thermal gravimetric analyzer curve of the binders shifted toward higher temperatures when the PMI content was increased. The patterns exhibited excellent mechanical properties, presumably due to the rigid characteristics of the molecular structures of PMI and IBMA. In the third part, diallyl monoglycidyl isocyanurate (DA-MGIC) was reacted with the obtained polymer binders to synthesize a novel polymer binder with photo- and thermal-curing properties. Tg of the polymer binders was found to be independent of the DA-MGIC concentration for the range of values tested in this study. The results showed that the patterns exhibited excellent mechanical properties and the taper angle of the patterns became steep because of to the photo-curing, thermal-curing, and interpenetration network characteristics of the novel polymer binder in the photo spacer.
顯示於類別:	[化學工程與材料工程研究所] 博碩士論文

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