偶氮系光敏感化合物合成及甲基丙烯酸酯系感光性高分子正、負型光阻製備與研究

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姓名

鄭宗興(Tzong-Shing Cheng) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

偶氮系光敏感化合物合成及甲基丙烯酸酯系感光性高分子正、負型光阻製備與研究
(The Study and Preparation of Synthetic Diazo-series Photosensitive Compounds and Positive/Negative Photo resist of Methacrylic Ester Series Photosensitive Polymers)

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摘要(中)

本論文研究重點主要為研究Methacrylic Acid（MAA）及2-Hydroethyl Methacrylate（2-HEMA）與偶氮類光敏感化合物1,2-Naphthoquinone-2-diazido-5-sulfonyl Chloride（5-NDSC）之合成製備光阻材料添加之單體PAC(A)及PAC(B)，以及利用Tricyclo [5,2,1,02,6]decane-dimethanol（TDMol）與5-NDSC進行酯化反應以獲得雙偶氮類光敏感化合物PAC(C)，及利用1-Chloroadamantane（1-ClAd）分別與MAA、2-HEMA來製備Adamantyl methacrylate （AdMA）與Adamantyl hydroethyl methacrylate（AdHEMA），並利用合成共振光譜儀（NMR）及紅外線光譜儀（IR）研究其結構正確性，同時利用MAA及2-HEMA分別與Benzyl methacrylate （BzMA）、3,3,5-Trimethylcyclohexyl Methacrylate （THCHMA）、AdMA及AdHEMA來製備四種不同成分及比例下之光阻基材（THM, AHM, BHM and AHHM: Binder (1) to (4)），並進一步於對上述製備之前驅物與光阻基材中探討在不同成分及比例下所製備之正型光阻材料及熱性質。結果顯示此系列之光阻基材中熱裂解溫度皆達300℃以上且Tg點亦高達150℃（BHM, THM）（第二章及第三章），並利用田口工程技術延伸應用製備正型光阻材料最佳化配方調製以獲得及了解最佳化熱性質能力（第四章）。於第五章中則利用TDMol與Methyl Acrylate（MA）先行合成雙官能團架橋單體Dimethyl-acryl-tricyclo[5,2,1,02,6]decane-dimethyl ester （TA），並利用NMR判定其結構，再進行與dipentaerythrithol hexaacrylate（DHPA）及BHM共混下添加光啟始劑1-(4-methylthiophenyl-2- (N-morpholino) propan-1-one（PI-777）及光增感劑2-isopropylthioxanthone（ITX）以製備負型光阻材料（NPR），並探討其共混下之熱性質現象及厚膜光阻可行性，藉由near UV微影製程及電子顯微鏡（SEM）證明其縱深比達八倍以上。進一步於第六章中探討利用所製備負型光阻材料（NPR）添加導電粉體並利用濕式研磨及分散技術以獲得導電性負型光阻材料（CNPR），藉由四點探針電導儀以確立其導電性，其阻抗值介於5 ~ 10 ohm之間。
此研究成果中成功製備出Acrylic series之正型與負型光阻材料，並且光阻基材可同時應用於正型與負型之間，並且此基材利用紫外線光譜儀（UV）測試結果顯示在300 nm波長以下逐一衰減，顯現光阻基材應用於KrF （248 nm）與ArF（193 nm）之可行性。

摘要(英)

This thesis investigated in synthesized of photo active compound ((PAC (A), PAC (B) and PAC (C)) by using methacrylic acid (MAA), 2-Hydroethyl Methacrylate (2-HEMA) and Tricyclo [5,2,1,02,6]decane- dimethanol (TDMol) with an 1,2-Naphthoquinone-2-diazido-5-sulfonyl Chloride (5-NDSC) and prepared of photo resist binder (1) to binder (4) by free radical polymerization using MAA and 2-HEMA within Adamantyl methacrylate (AdMA), Adamantyl hydroethyl methacrylate (AdHEMA), 3,3,5-Trimethylcyclohexyl Methacrylate (THCHMA) and Benzyl methacrylate (BzMA).which analyzed thermal property and film performance discussion in chapter 2 to 4. It is found that the thermal reliability of positive photo resist within this acrylic series is excellent by I-line (365 nm wavelength) lithography process and scanning electronic microscopy (SEM). In the chapter 4, the major discussion about Taguchi method and formulation of positive photo resist, measured the thermo-decomposition temperature by TGA, It is found that the optimal formulation of positive photo resist on the lithography process is definitely verified after having SEM surface analysis on the result. The chapter 5 discussions about negative photo resist (NPR). It is applied to ultra thick photo resist (e.g. Micro electronic mechanical system,MEMS), and synthesized of difunctional monomer of Dimethyl-acryl-tricyclo [5,2,1,02,6]decane-dimethyl ester (TA) by esterification using Methyl Acrylate (MA) and Tricyclo [5,2,1,02,6]decane dimethanol (TDMol). The other hand, prepared of formula for ultra thick negative photo resist. A few designed formulas at difference ratios are conducted by co-mixing 1-(4-methylthiophenyl-2- (N-morpholino) propan-1-one (PI-777) of the photo initiator, 2-isopropylthioxanthone (ITX) of the photo sensitizer, TA and dipentaerythrithol hexaacrylate (DHPA) of multifunctional monomer. additionally, the prepared of conductive negative photo resist (CNPR), dispersion technology by wetting mill process. measured of Surface examination was obtained by 4-point probe, its electric conductivity is 5 to 10 ohm in 2 mil diameter of array conductive photo resist to discuss in chapter 6.
It is Succeed in prepared of positive and negative photo resist in this study within acrylic series binder, measured the ultraviolet absorption by UV apparatus, It is found decrease below in UV absorption curve which start on 300 nm wavelength. This materials applied to KrF (248 nm) and ArF (193 nm) to thinkable.

關鍵字(中)

★ 厚膜光阻
★ 正型光阻
★ 負型光阻
★ 感光性高分子
★ 導電光阻

關鍵字(英)

★ photosensitive polymer
★ ultra thick photo resist
★ conductive photo resist
★ positive photo resist
★ negative photo resist

論文目次

摘要 …………………………………………………………………………… I
Abstract ……………………………………………………………………… III
誌謝 ……………………………………………………………………………… V
圖目錄 …………………………………………………………………………… X
表目錄 .......................................................... XV
第一章緒論 ……………………………………………………………………… 1
1-1. 感光性高分子材料介紹 ………………………………………… 2
1-2. 研究發展歷史及技術沿革 …………………………………… 11
1-3. 研究動機 ……………………………………………………… 33
1-4. 研究目的 ………………………………………………………… 34
1-5. 參考文獻 ………………………………………………………… 39
第二章單偶氮類光敏感單體製備與丙烯酸甲酯系光阻基材製備及正型光阻性質探討 ……………………………………………………………………… 41
摘要 ……………………………………………………………………… 42
2-1. 前言 ……………………………………………………………… 43
2-2. 實驗藥品 ………………………………………………………… 49
2-3. 實驗儀器 ………………………………………………………… 50
2-4. 實驗方法 ………………………………………………………… 51
2-5. 結果與討論 ……………………………………………………… 58
2-6. 結論 ……………………………………………………………… 133
2-7. 參考文獻 ………………………………………………………… 135
第三章雙偶氮類光敏感化合物製備與芳香族、脂肪族丙烯酸甲酯系光阻基材製備及正型光阻性質探討 ……………………………………………… 137
摘要 …………………………………………………………………… 138
3-1. 前言 ……………………………………………………………… 139
3-2. 實驗藥品 ………………………………………………………… 142
3-3. 實驗儀器 ………………………………………………………… 143
3-4. 實驗方法 ………………………………………………………… 144
3-5. 結果與討論 …………………………………………………… 147
3-6. 結論 ……………………………………………………………… 160
3-7. 參考文獻 ………………………………………………………… 161
第四章利用田口工程製備正型感光性高分子及熱性質探討 …………… 163
摘要 ………………………………………………………………… 164
4-1. 前言 …………………………………………………………… 165
4-2. 實驗藥品 ………………………………………………………… 168
4-3. 實驗儀器 ……………………………………………………… 169
4-4. 實驗方法 ……………………………………………………… 170
4-5. 結果與討論 …………………………………………………… 182
4-6. 結論 ……………………………………………………………… 204
4-7. 參考文獻 ……………………………………………………… 205
第五章脂肪族光單體合成、添加與芳香族丙烯酸甲酯系光阻基材混合製備負型厚膜光阻之性質探討 ………………………………………………… 206
摘要 …………………………………………………………………… 207
5-1. 前言 ……………………………………………………………… 208
5-2. 實驗藥品 ……………………………………………………… 211
5-3. 實驗儀器 ………………………………………………………… 212
5-4. 實驗方法 ……………………………………………………… 213
5-5. 結果與討論 ……………………………………………………… 216
5-6. 結論 ……………………………………………………………… 220
5-7. 參考文獻 ………………………………………………………… 221
第六章導電性負型光阻材料製備及其應用研究 …………………………… 222
摘要 …………………………………………………………………… 223
6-1. 前言 ……………………………………………………………… 224
6-2. 實驗藥品 ………………………………………………………… 225
6-3. 實驗儀器 ……………………………………………………… 226
6-4. 實驗方法 ……………………………………………………… 227
6-5. 結果與討論 ……………………………………………………… 229
6-6. 結論 ……………………………………………………………… 230
6-7. 參考文獻 ………………………………………………………… 231
第七章總結論 ………………………………………………………………… 232
作者簡介與著作 ………………………………………………………………… 235

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指導教授

林孝宗(Hsiao-Tsung Lin)

審核日期

2004-10-22

推文