臺灣博碩士論文加值系統

摘要

本研究中以甲基丙烯酸-2-�A基乙酯 (HEMA)、丙烯酸-2-�A基乙酯(HEA) 與甲基丙烯酸甲酯 (MMA)、二融環[2,2,1]庚烯-[2] (NB)、(-)-甲基丙烯酸菠酯 ((-)-BMA)，以及甲基丙烯酸 (MAA)等單體合成在側鏈上具有醇基的壓克力系高分子共聚合物，並針對側鏈醇基在光酸催化下與1,4-環己二酮脫水形成ketal基團而造成高分子交聯(Crosslinking)，與其應用在光酸催化負型光阻做一探討。我們使用HEMA及聚乙烯醇(PVA)的均聚合物與1,4-環己二酮配成光阻劑，在紅外線光譜中其醇基吸收隨曝後烤時間加長而減少，足以證明此一脫水架橋反應之進行。此外，HEA, HEMA在2比1的共聚合比之下，可以合成出一水可溶性的負型光阻系統，感度為90 mJ/cm2，但其物性與解析度不佳。因此導入MMA, NB, (-)-BMA等疏水性單體，依不同比例進行共聚，合成出鹼水可溶的負型光阻系統，感度為180 mJ/cm2且解析度可達2μm。文中並探討高分子親疏水性與對比值的關係，及1,4-環己二酮最適化的添加量。

另外，以ketal基團為保護基合成全環共聚物正型光阻，利用順2-丁烯-1,4-二醇與環己酮脫水環化，合成一環烯單體(DM)，與甲基丙烯酸、苯乙烯(SM)、甲基丙烯酸甲酯(MMA)、馬來酸酐(MA)、N-苯基馬來醯亞胺(NPM)等單體進行共聚合反應，發現DM只能與馬來酸酐、N-苯基馬來醯亞胺共聚而得到共聚合物，且由元素分析鑑定共聚合物組成後發現，在不同進料比之下其共聚物組成變化不大，因此推測此共聚合物具有一定程度的交替性(Alternation)。在熱性質分析中發現在未達到玻璃轉移溫度之前即有保護基裂解的熱重損失；在抗蝕刻性的實驗中，poly(DM-co-MA)的抗蝕刻速率相對於PMMA約為其0.71倍，相較之下有所改善，但仍不及含有苯環結構的聚合物，如聚苯乙烯。以polymer 9為二成分光阻做微影性質測試，其感度為150 mJ/cm2，對比值為2.6，其解析度可以達到0.5μm。

Abstract
A series of acrylic copolymers having pendant hydroxyl groups have been synthesized based on 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), methyl methacrylate (MMA), 2-norborene (NB), (-)-bornyl methacrylate ((-)-BMA), and methacrylic acid (MAA). Photodehydration crosslinking of poly(vinyl alcohol) and poly(HEMA) with 1,4-cyclohexanedione in the presence of photo acid generator was studied by FTIR spectroscopy. The sensitivities of the negative tone photoresists comprising various molar ratios of HEMA, MMA, (-)-BMA, NB, and MAA were estimated. The optimal sensitivity of 180mJ/cm2 and resolution of 2μm were achieved. The effects of adding amount of 1,4-cyclohexanedioneon the characteristics of photoresist were also investigated.

To investigate the application of copolymers having pendent ketal groups on positive tone photoresist, copolymerizations of 7,12-dioxaspiro- [5,6]dodec-9-ene monomer (DM), maleic anhydride (MA), N-phenyl maleimide (NPM) and various commercial monomers were carried out. It was found that DM can only copolymerized with MA and NPM. The compositions of the copolymers such synthesized were not so different even with various feed molar ratios. The results suggest that the copolymers may have certain amounts of alternating segment. From thermal analyses, it was found that the deprotecting temperature of ketal groups of the copolymers was lower than Tg. The etching resistance of copolymers were also estimated. As compare with PMMA, the etching rate of poly(DM-co-MA) is about 0.71. The value is better than acrylic polymers, but worse than polymers having aromatic rings, for example, polystyrene. Polymer 9 with photoacid generator was used as a positive tone photoresist. The sensitivity of 150mJ/cm2, contrast of 2.6, and resolution of 0.5μm were achieved.

目錄

中文摘要--------------------------------------------------------------------I
英文摘要--------------------------------------------------------------------II
目錄------------------------------------------------------------------------III
表目錄----------------------------------------------------------------------VII
圖目錄----------------------------------------------------------------------VIII
符號表----------------------------------------------------------------------XII

第一章 緒論
1-1前言---------------------------------------------------------------------1
1-2微影技術發展-------------------------------------------------------------1
1-3光阻的應用與其發展趨勢---------------------------------------------------2
1-4研究動機-----------------------------------------------------------------2

第二章 原理與文獻回顧
2-1 Ketal基團簡介-----------------------------------------------------------5
2-2微影製程-----------------------------------------------------------------6
2-2-1表面清洗---------------------------------------------------------------7
2-2-2塗底-------------------------------------------------------------------7
2-2-3上阻劑-----------------------------------------------------------------9
2-2-4預烤-------------------------------------------------------------------10
2-2-5曝光-------------------------------------------------------------------10
2-2-5-1接觸印法-------------------------------------------------------------10
2-2-5-2近距印法-------------------------------------------------------------10
2-2-5-3投射印法-------------------------------------------------------------11
2-2-6曝後烤-----------------------------------------------------------------14
2-2-7顯影-------------------------------------------------------------------15
2-2-8硬烤-------------------------------------------------------------------15
2-3光阻劑-------------------------------------------------------------------15
2-3-1光化學反應型-----------------------------------------------------------15
2-3-2化學增幅型-------------------------------------------------------------17
2-3-3 193奈米(ArF)光阻------------------------------------------------------20
2-4光酸---------------------------------------------------------------------22
2-5光阻特性-----------------------------------------------------------------22
2-5-1感度---------------------------------------------------------------22
2-5-2對比-------------------------------------------------------------------23
2-5-3解析度-----------------------------------------------------------------23
2-5-4熱穩定性---------------------------------------------------------------24
2-5-5接著性-----------------------------------------------------------------24
2-6微影製程之問題與解決-----------------------------------------------------26
2-6-1駐波現象---------------------------------------------------------------26
2-6-2單層光阻---------------------------------------------------------------27
2-6-3照後延遲---------------------------------------------------------------28
2-6-3-1暗室效應-------------------------------------------------------------28
2-6-3-2質子酸損失與擴散-----------------------------------------------------28
2-6-3-3質子酸遭鹼性污染物中和-----------------------------------------------28

第三章 實驗
3-1藥品---------------------------------------------------------------------30
3-2儀器---------------------------------------------------------------------31
3-3實驗步驟-----------------------------------------------------------------33
3-3-1藥品純化---------------------------------------------------------------33
3-3-2 ketal基架橋負型光阻系統合成---------------------------------------33
3-3-3主鏈全環正型光阻系統合成-----------------------------------------------36
3-3-4產物性質測試與分析-----------------------------------------------------40
3-3-5微影製程---------------------------------------------------------------43

第四章 Ketal基架橋負型光阻系統
4-1共聚物的合成-------------------------------------------------------------46
4-1-1含HEMA, HEA水溶性共聚物系----------------------------------------------46
4-1-2含HEMA、疏水基單體及MAA三成分共聚物系----------------------------------47
4-1-3疏水單元對Tg 的影響----------------------------------------------------47
4-2預烤與曝後烤條件之決定---------------------------------------------------48
4-2-1預烤時間與溫度的決定---------------------------------------------------48
4-2-2曝後烤時間與溫度的決定-------------------------------------------------49
4-3光酸催化產生ketal基團架橋機構探討----------------------------------------49
4-3-1紅外光光譜官能基鑑定---------------------------------------------------49
4-3-2模型分子1,1,4,4-tetraethoxyl cyclohexane (簡稱TC)
之合成及鑑定----------------------------------------------------------------51
4-4 1,4-環己二酮添加量的影響------------------------------------------------51
4-5 UV光之吸收光譜----------------------------------------------------------51
4-6熱性質分析---------------------------------------------------------------52
4-7共聚物黏度值測試---------------------------------------------------------52
4-8共聚物微影顯像特性探討---------------------------------------------------53
4-9耐蝕刻性質探討-----------------------------------------------------------54

第五章 主鏈全環共聚物正型光阻系統
5-1單體的合成及分析---------------------------------------------------------64
5-1-1 7,12-dioxaspiro-[5,6]dodec-9-ene monomer (簡稱DM)
之分析--------------------------------------------------------------64
5-1-2 Maleic anhydride derived monomer (簡稱MADM)之
分析------------------------------------------------------------------------64
5-2聚合物的合成及分析-------------------------------------------------------65
5-2-1聚合物的合成-----------------------------------------------------------65
5-2-2聚合物的分析-----------------------------------------------------------65
5-3酸催化去保護基之探討-----------------------------------------------------67
5-4 UV光之吸收特性----------------------------------------------------------68
5-5耐電漿蝕刻性質測試-------------------------------------------------------68
5-6微影性質探討-------------------------------------------------------------69
5-6-1高分子黏度與旋轉塗佈轉速-----------------------------------------------69
5-6-2特性曲線---------------------------------------------------------------69

第六章 結論-----------------------------------------------------------------79
參考文獻--------------------------------------------------------------------81

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