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研究生：	宋雅嬴 Sung, Ya-Ying
論文名稱：	壓克力系高分子之合成及其在化學增幅正型光阻劑之應用研究 Synthesis of Acrylic Polymers and Their Applications on the Chemical Amplified Positive Tone Photoresist
指導教授：	劉瑞祥 Liu, Jui-Hsiang
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：	2005
畢業學年度：	93
語文別：	中文
論文頁數：	91
中文關鍵詞：	光酸發生劑、正型光阻劑、化學增幅型
外文關鍵詞：	Photoresist, PAG
相關次數：	點閱：42 下載：5
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　　在本研究中，以壓克力系的甲基丙烯酸甲酯(Methyl methacrylate, MMA)和側鏈含脂肪環之單體(-)-bornyl methacrylate ((-)-BMA)、α-methacryloxy-γ-butyrolactone (MABL)，以及具有酸不穩定基團之甲基丙烯酸三級丁酯(t-BMA)和tetrahydropyranyl methacrylate (THPMA)等單體依照不同莫耳比進行共聚合反應，並添加鏈轉移劑正-丁基硫醇(n-Butyl mercaptan)來降低分子量，合成出鹼水可溶的正型光阻系統。並藉由FT-IR、1H-NMR、UV、和EA進行單體及高分子結構之鑑定，而在熱性質與分子量之分析方面，則分別由TGA、DSC和GPC等儀器進行檢測。

　　本研究所合成之壓克力系高分子，經由紫外光光譜儀測試得知最大吸收波長約在230nm左右，故可應用於g-line (436nm)、i-line (365nm)和ArF (193nm)等光蝕刻微影技術。所合成之共聚物與光酸發生劑等配製成化學增幅正型光阻劑，藉由微影製程之測試，探討各光阻之特性曲線，結果顯示相同高分子因為保護基的不同，而有不同的感度，約為60~114 mJ/cm2，含有MABL單體的聚合物有較高之感度。在抗蝕刻試驗中，發現共聚物組成含有高碳氫比之bornyl環狀基團時，其蝕刻速率明顯下降，而聚合物中含有MABL單體時，對整體的耐乾式蝕刻特性亦有顯著的提升。最後以具有較佳感度與對比值之PR2光阻劑做顯像，其解像力可達1.5μm。

　A series of acrylic copolymers containing acid labile groups and alicyclic units have been synthesized based on tetrahydropyranyl
methacrylate (THPMA), tert-butyl methacrylate (t-BMA), (-)-bornyl methacrylate ((-)-BMA), α-methacryloxy-γ-butyrolactone (MABL) and methyl methacrylate (MMA). n-Butyl mercaptan was used as a chain transfer agent to control the molecular weight of polymers. The structures
of the synthesized copolymers were all confirmed using FT-IR, 1H-NMR, UV-Vis, and EA. Thermal properties and molecular weight were evaluated
using TGA/DSC and GPC, respectively.

　The λmax of the acrylic copolymers is around 230 nm. The copolymerscan be applied on the filed of g-line (436 nm), i-line (365 nm), and ArF (193 nm) photoresists. Thermal properties and solubility in various alkaline aqueous solutions of the photoresists were all evaluated. The photosensitive and exposed characteristics of the photoresists prepared in this investigation were all estimated. The optimal sensitivity of 60 mJ/cm2 and resolution of 1.5μm of the positive tone photoresist with PR2 was achieved. The stability and the reliability of the photoresist with copolymers
synthesized in this investigation were all confirmed. Dry etching resistance of the prepared copolymers were compared with those of polystyrene and PMMA, alicyclic aliphatic polymers prepared in this investigation were
found to obviously improve the plasma etching resistance.

摘要..................................................................I
Abstract..............................................................II
目錄..................................................................III
表目錄................................................................VI
圖目錄................................................................VII
Scheme................................................................XI
符號表................................................................XII

第一章、緒論
 1-1 前言.............................................................1
  1-2 微影發展技術....................................................2
  1-3 光阻的應用與其發展趨勢..........................................4 

第二章、原理與文獻回顧
  2-1 游離基連鎖聚合反應..............................................5
      2-1-1 熱分解起始劑..............................................5
      2-1-2 鏈轉移反應................................................6
  2-2 半導體製........................................................7
  2-3 微影製程........................................................8
      2-3-1 晶圓表面清潔..............................................8
      2-3-2 塗底(Priming).............................................9
      2-3-3 光阻塗佈(Resist coating)..................................10
      2-3-4 預烤(Prebaking)...........................................12
      2-3-5 曝光(Exposure)............................................12
      2-3-6 曝後烤(Post exposure baking, PEB).........................17
      2-3-7 顯影(Development).........................................17
      2-3-8 硬烤(Hard baking).........................................18
  2-4 化學增幅型光阻劑................................................18
      2-4-1 何謂光阻劑................................................18
      2-4-2 化學增幅型(Chemical amplification)........................19
      2-4-3 193奈米(ArF)光阻..........................................23
  2-5 光阻特性........................................................25
      2-5-1 感度(Sensitivity).........................................25
      2-5-2 對比(Contrast)............................................26
      2-5-3 解析度(Resolution)........................................26
      2-5-4 熱穩定性(Thermal stability)...............................27
      2-5-5 接著性(Adhesion)..........................................27
      2-5-6 抗蝕刻性(Reactive ion etching resistance).................27
  2-6 研究動機........................................................28

第三章、實驗
  3-1 藥品............................................................30
  3-2 儀器............................................................32
  3-3 合成與聚合反應方法..............................................33
      3-3-1 試藥前處理................................................33
      3-3-2 光阻材料之製備............................................33
      3-3-3 單體與共聚合物的分析鑑定..................................40
      3-3-4 微影製程..................................................41

第四章、結果與討論
  4-1 單體之合成及分析................................................44
  4-2 聚合物的合成....................................................45
      4-2-1 含THPMA、(-)-BMA和MMA之共聚物.............................45
      4-2-2 含THPMA、MABL和MMA之共聚物................................46
      4-2-3 含t-BMA、(-)-BMA和MMA之共聚物.............................48
      4-2-4 含t-BMA、MABL和MMA之共聚物................................49
  4-3 微影製程性質探討................................................50
      4-3-1 正型光阻用高分子之特性探討................................50
      4-3-2 UV光之特性吸收............................................51
      4-3-3 光阻劑之配製..............................................51
      4-3-4 光阻劑旋轉塗佈轉速之決定..................................52
      4-3-5 預烤參數之測定............................................53
      4-3-6 曝後烤條件之決定..........................................53
      4-3-7 顯影條件之決定............................................56
      4-3-8 光阻劑特性曲線分析........................................58
      4-3-9 光阻劑之顯像分析..........................................60
      4-4 耐蝕刻性質探討..............................................61
	
第五章 結論...........................................................86

參考文獻..............................................................87

                                    

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校外：2006-06-15公開

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