CN113493382A - 一种碱溶性良好的光刻胶酸敏树脂单体及其合成方法和应用 - Google Patents
一种碱溶性良好的光刻胶酸敏树脂单体及其合成方法和应用 Download PDFInfo
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 42
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- 239000002253 acid Substances 0.000 title claims abstract description 25
- 239000003513 alkali Substances 0.000 title claims abstract description 20
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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Abstract
Description
技术领域
本发明涉及光刻胶树脂单体领域,尤其涉及光敏型树脂单体及其合成方法和应用。
背景技术
光刻技术是指利用光刻材料(特指光刻胶)在可见光、紫外线、电子束等作用下的化学敏感性,通过曝光、显影、刻蚀等工艺过程,将设计在掩膜版上的图形转移到衬底上的图形微细加工技术。
光刻材料(特指光刻胶),又称光致抗蚀剂,是光刻技术中涉及的最关键的功能性化学材料,主要成分是树脂、光酸产生剂、以及相应的添加剂和溶剂,这类材料具有光(包括可见光、紫外线、电子束等)化学敏感性,经光化学反应,本身在显影液中的溶解性发生变化。根据光化学反应机理不同,光刻胶分为正性光刻胶与负性光刻胶:曝光后,光刻胶在显影液中溶解性增加,得到与掩膜版相同图形的称为正性光刻胶;曝光后,光刻胶在显影液中溶解性降低甚至不溶,得到与掩膜版相反图形的称为负性光刻胶。
正性光刻胶的光刻显影剂为碱性,常用的为四甲基氢氧化铵(TMAH), 光刻胶曝光前后需要在显影剂中存在溶解速度差,这个差值的大小很大程度上影响光刻图形的分辨率和边缘粗糙度,这种溶解差取决于光敏树脂单体曝光前后的性质差异,一些含内酯结构的聚合单元也具有改良溶解差的作用。常见的光敏单体包括:环状叔丁基醇酯结构、半缩醛(酮)结构,叔丁醇酯结构。
发明内容
本发明提出了一种碱溶性良好的光刻胶酸敏树脂单体及其合成方法和应用。
为了实现上述目的,本发明采用了如下技术方案:
优选的,所述光刻胶酸敏树脂单体具体选自以下结构之一:
上述碱溶性良好的光刻胶酸敏树脂单体的合成方法,包括以下合成路线:
合成步骤为:
S1:初始原料为含碳碳双键的环酮Ⅰ,环酮Ⅰ与卤素单质在第一反应溶剂中进行加成反应生成两个卤素取代的中间体Ⅱ,所述第一反应溶剂选自二氯甲烷、氯仿、甲苯中的其中一种或多种;
S2:所述中间体Ⅱ在强碱作用下与醇类原料R3OH在第二反应溶剂中反应形成醚结构的中间体Ⅲ;所述第二反应溶剂选自N,N-二甲基甲酰胺、二甲基亚砜、四氢呋喃中的一种或者多种;
S3:所述中间体Ⅲ与R2MgX格式试剂在第三反应溶剂中发生格氏反应生成叔醇结构的中间体Ⅳ;所述第三反应溶剂选自无水***或无水四氢呋喃;
S4:所述中间体Ⅳ与(甲基)丙烯酸或者(甲基)丙烯酰氯在第四反应溶剂中发生酯化反应生成光刻胶酸敏树脂单体Ⅴ;所述第四反应溶剂为二氯甲烷、氯仿、甲苯中的其中一种或者多种。
优选的,S1中,所述环酮Ⅰ选自以下结构之一:
优选的,S2中,还包括如下技术特征中的至少一项:
a1)所述强碱选自氢化钠、氢氧化钠、氢氧化钾、叔丁醇钠或者叔丁醇钾;
a2)所述醇类原料R3OH选自甲醇、乙醇、正丙醇、异丙醇和叔丁醇。
优选的,S3中,所述R2Mg选自以下结构之一:
优选的,所述中间体Ⅲ的另一种合成路线为:
A1:初始原料为含碳碳双键双键的环酮Ⅰ,所述环酮Ⅰ与氧化剂发生氧化反应生成环氧结构的中间体Ⅵ;
A2:所述中间体Ⅵ在酸性条件下水解成二醇中间体Ⅶ;
A3:所述中间体Ⅶ与R3X在碱性条件下脱去HX生成中间体Ⅲ。
优选的,还包括如下技术特征中的至少一项:
A1中,所述氧化剂选自间氯过氧苯甲酸或者过氧化氢;
A2中,所述酸选自盐酸或者硫酸;
A3中,所述碱选自氢化钠、氢氧化钠、氢氧化钾、叔丁醇钠和叔丁醇钾中的一种。
上述碱溶性良好的光刻胶酸敏树脂单体用于制备光刻胶。
与现有技术相比,本发明实现的有益效果:本发明提供了一种碱溶性良好的光刻胶酸敏树脂单体,所述酸敏树脂单体含脂肪环,脂肪环上相邻的碳原子上连接有两个醚,环上连接丙烯酸酯或者甲基丙烯酸酯的碳原子为叔碳结构,本结构的树脂单体与其它树脂单体共聚形成聚合物时,聚合物应用于光刻胶,可增加光刻胶的耐刻蚀性能,改善与晶圆(一般为硅片)的粘附力,并且能够增加光刻胶在曝光前后的碱溶性差,有利于改善光刻胶的线边缘粗糙度,提高分辨率。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。
实施例1
将2-环戊烯-1-酮Ⅰ-a(20g,244mmol)溶解在二氯甲烷(300mL) 中,冰水浴冷却到0℃,在氮气保护下慢慢滴加液溴(42.8g,268mmol),反应液升到室温,搅拌反应2小时,反应液用饱和硫代硫酸钠(50mL) 淬灭,加水(100mL)稀释,分液,水相用二氯甲烷(100mL*3)萃取三次,合并有机相,合并后有机相用饱和食盐水(100mL)洗涤,无水硫酸钠干燥,有机相在真空下旋干得到中间体Ⅱ-a(57.2g, 236mmol,收率:97.1%)。
将氢化钠(23g,958mmol)加入到N,N-二甲基甲酰胺(200mL) 中,冷却到0℃,慢慢滴加甲醇(30g,936mmol),升到80℃搅拌半小时,冷却到0℃,慢慢滴加中间体Ⅱ-a(57.2g,236mmol)的N,N- 二甲基甲酰胺(200mL),滴加结束后升温到80℃继续搅拌5小时,将反应液冷却到室温,慢慢倒入冰水(200mL)中,用乙酸乙酯 (300mL*3)萃取三次,合并后的有机相用饱和食盐水(300mL)清洗,无水硫酸钠干燥,有机相在真空下旋干得到中间体Ⅲ-a(31.7g, 220mmol,93.0%)。
将镁(8g,329mmol)加入到无水***(100mL)中,加入一小粒碘,氮气保护下,慢慢滴加甲基溴(5g,53mmol)的***(20mL)溶液,升温保持溶液微沸,碘颜色消失,继续滴加甲基溴(26.3g, 277mmol)的***(100mL)溶液,回流半小时,冷却到0℃,向其中滴加Ⅲ-a(31.7g,220mmol)的***(200mL)溶液,升到室温下搅拌反应2小时,冰水冷却,加入20%稀硫酸淬灭反应,分液,水相用乙酸乙酯(200mL*3)萃取三次,有机相用饱和食盐水洗涤,无水硫酸钠干燥后,在真空下旋干得到中间体Ⅳ-a(29.6g,185mmol,收率: 84.0%)。
将中间体Ⅳ-a(29.6g,185mmol)加入到二氯甲烷(300mL)中,加入三乙胺(47g,464mmol),冷却到0℃,滴加丙烯酰氯(20.1g, 222mmol),升到室温搅拌4小时,加水(200mL)淬灭反应,水相用二氯甲烷(200mL*3)萃取三次,合并有机相用饱和食盐水(200mL) 洗涤,无水硫酸钠干燥,真空下旋干得到粗品,粗品用蒸馏的方式进行纯化后得到树脂单体Ⅴ-a(37.5g,175mmol,收率:94.7%)。提供了中间体Ⅲ-a的另一种合成方法:
将2-环戊烯-1-酮Ⅰ-a(20g,244mmol)加入到甲醇(200mL) 中,加入氢氧化钠(29.2g,730mmol),慢慢滴加30%的过氧化氢溶液(83g),在室温下搅拌1小时,过滤,滤液加入用硫代硫酸钠饱和溶液淬灭,真空浓缩除去大部分甲醇,补加水(150mL),水相用乙酸乙酯(200mL*3)萃取三次,合并有机相,饱和食盐水(150mL) 洗涤,无水硫酸钠干燥,真空下旋干得到中间体Ⅵ-a(21.5g,219mmol,收率:90%)。
将中间体Ⅵ-a(21.5g,219mmol)加入到20%稀硫酸水溶液(200mL) 中搅拌1小时,用碳酸钠调节pH到中性,真空下旋干,加入甲醇 (150mL)搅拌,过滤除去固体,有机相真空下旋干得到中间体Ⅶ-a (23.7g,204mmol,收率:93.1%)。
冰水浴冷却下将氢化钠(12.3g,513mmol)加入到无水N,N-二甲基甲酰胺(300mL)中,慢慢滴加中间体Ⅶ-a(23.7g,204mmol),升到室温搅拌半小时,冰水浴冷却到10℃以下,慢慢滴加碘甲烷 (63.7g,449mmol),滴加结束后升到室温继续搅拌3小时,冰水冷却到10℃以下,用10%的氢氧化钠水溶液淬灭反应,水相有乙酸乙酯 (200mL*3)萃取三次,合并有机相,有机相用饱和食盐水洗涤,无水硫酸钠干燥,真空下旋干得到中间体Ⅲ-a(27.6g,191mmol,收率: 93.8%)。
实施例2
将双环[2.2.1]庚-5-烯-2-酮Ⅰ-b(20g,185mmol)溶解在二氯甲烷(300mL)中,冰水浴冷却到0℃,在氮气保护下慢慢滴加溴(29.6g, 185mmol),反应液升到室温,搅拌反应2小时,反应液用饱和硫代硫酸钠(50mL)淬灭,加水(100mL)稀释,分液,水相用二氯甲烷(100mL*3)萃取三次,合并有机相,合并后有机相用饱和食盐水 (100mL)洗涤,无水硫酸钠干燥,有机相在真空下旋干得到中间体Ⅱ-b(47.3g,177mmol,收率:95.4%)。
将氢化钠(17g,708mmol)加入到N,N-二甲基甲酰胺(200mL) 中,冷却到0℃,慢慢滴加甲醇(22.7g,708mmol),升到80℃搅拌半小时,冷却到0℃,慢慢滴加中间体Ⅱ-b(47.3g,177mmol)的N,N- 二甲基甲酰胺(200mL),滴加结束后升温到80℃继续搅拌5小时,将反应液冷却到室温,慢慢倒入冰水(200mL)中,用乙酸乙酯 (300mL*3)萃取三次,合并后的有机相用饱和食盐水(300mL)清洗,无水硫酸钠干燥,有机相在真空下旋干得到中间体Ⅲ-b(27.5g, 162mmol,收率:91.5%)。
将镁(6g,247mmol)加入到无水***(100mL)中,加入一小粒碘,氮气保护下,慢慢滴加甲基溴(5g,53mmol)的***(20mL)溶液,升温保持溶液微沸,碘颜色消失,继续滴加甲基溴(18g,190mmol) 的***(100mL)溶液,回流半小时,冷却到0℃,向其中滴加中间体Ⅲ-b(27.5g,137mmol)的***(200mL)溶液,升到室温下搅拌反应2小时,冰水冷却,加入20%稀硫酸淬灭反应,分液,水相用乙酸乙酯(200mL*3)萃取三次,有机相用饱和食盐水洗涤,无水硫酸钠干燥后,在真空下旋干得到中间体Ⅳ-b(27.5g,137mmol,收率: 85.0%)。
将中间体Ⅳ-b(27.5g,137mmol)加入到二氯甲烷(300mL)中,加入三乙胺(35g,346mmol),冷却到0℃,滴加丙烯酰氯(15g, 166mmol),升到室温搅拌4小时,加水(200mL)淬灭反应,水相用二氯甲烷(200mL*3)萃取三次,合并有机相用饱和食盐水(200mL) 洗涤,无水硫酸钠干燥,真空下旋干得到粗品,粗品用蒸馏的方式进行纯化后得到树脂单体Ⅴ-b(32.6g,128mmol,收率:93.4%)。
实施例3
将4,4-二甲基-2-环己基-1-酮Ⅰ-c(20g,161mmol)溶解在二氯甲烷(300mL)中,冰水浴冷却到0℃,在氮气保护下慢慢滴加溴 (28.3g,177mmol),反应液升到室温,搅拌反应2小时,反应液用饱和硫代硫酸钠(50mL)淬灭,加水(100mL)稀释,分液,水相用二氯甲烷(100mL*3)萃取三次,合并有机相,合并后有机相用饱和食盐水(100mL)洗涤,无水硫酸钠干燥,有机相在真空下旋干得到中间体Ⅱ-c(44.2g,156mmol,收率:96.6%)。
将氢化钠(15g,625mmol)加入到N,N-二甲基甲酰胺(200mL) 中,冷却到0℃,慢慢滴加甲醇(20g,624mmol),升到80℃搅拌半小时,冷却到0℃,慢慢滴加中间体Ⅱ-c(44.2g,156mmol)的N,N- 二甲基甲酰胺(200mL),滴加结束后升温到80℃继续搅拌5小时,将反应液冷却到室温,慢慢倒入冰水(200mL)中,用乙酸乙酯 (300mL*3)萃取三次,合并后的有机相用饱和食盐水(300mL)清洗,无水硫酸钠干燥,有机相在真空下旋干得到中间体Ⅲ-c(27.4g, 147mmol,收率:94.5%)。
将镁(5.4g,222mmol)加入到无水***(100mL)中,加入一小粒碘,氮气保护下,慢慢滴加甲基溴(5g,53mmol)的***(20mL) 溶液,升温保持溶液微沸,碘颜色消失,继续滴加甲基溴(11.8g, 124mmol)的***(100mL)溶液,回流半小时,冷却到0℃,向其中滴加中间体Ⅲ-c(27.4g,147mmol)的***(200mL)溶液,升到室温下搅拌反应2小时,冰水冷却,加入20%稀硫酸淬灭反应,分液,水相用乙酸乙酯(200mL*3)萃取三次,有机相用饱和食盐水洗涤,无水硫酸钠干燥后,在真空下旋干得到中间体Ⅳ-c(28.2g,139mmol,收率:94.8%)。
将中间体Ⅳ-c(28.2g,139mmol)加入到二氯甲烷(300mL)中,加入三乙胺(42.3g,418mmol),冷却到0℃,滴加丙烯酰氯(14g, 155mmol),升到室温搅拌4小时,加水(200mL)淬灭反应,水相用二氯甲烷(200mL*3)萃取三次,合并有机相用饱和食盐水(200mL) 洗涤,无水硫酸钠干燥,真空下旋干得到粗品,粗品用蒸馏的方式进行纯化后得到树脂单体Ⅴ-c(34.5g,135mmol,收率:96.5%)。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (9)
3.根据权利要求1或2所述的一种碱溶性良好的光刻胶酸敏树脂单体的合成方法,其特征在于,包括以下合成路线:
合成步骤为:
S1:初始原料为含碳碳双键的环酮Ⅰ,所述环酮Ⅰ与卤素单质在第一反应溶剂中进行加成反应生成两个卤素取代的中间体Ⅱ,所述第一反应溶剂为二氯甲烷、氯仿、甲苯中的其中一种或多种;
S2:所述中间体Ⅱ在强碱作用下与醇类原料R3OH在第二反应溶剂中反应形成醚结构的中间体Ⅲ;所述第二反应溶剂为N,N-二甲基甲酰胺、二甲基亚砜、四氢呋喃中的一种或者多种;
S3:所述中间体Ⅲ与R2MgX格式试剂在第三反应溶剂中发生格氏反应生成叔醇结构的中间体Ⅳ;所述第三反应溶剂为无水***或无水四氢呋喃;
S4:所述中间体Ⅳ与(甲基)丙烯酸或者(甲基)丙烯酰氯在第四反应溶剂中发生酯化反应生成光刻胶酸敏树脂单体Ⅴ;所述第四反应溶剂为二氯甲烷、氯仿、甲苯中的其中一种或者多种。
5.根据权利要求3所述的一种碱溶性良好的光刻胶酸敏树脂单体,其特征在于,S2中,还包括如下技术特征中的至少一项:
a1)所述强碱选自氢化钠、氢氧化钠、氢氧化钾、叔丁醇钠或者叔丁醇钾;
a2)所述醇类原料R3OH选自甲醇、乙醇、正丙醇、异丙醇或叔丁醇。
8.根据权利要求7所述的一种碱溶性良好的光刻胶酸敏树脂单体的合成方法,其特征在于,还包括如下技术特征中的至少一项:
A1中,所述氧化剂为间氯过氧苯甲酸或者过氧化氢;
A2中,所述酸选自盐酸或者硫酸;
A3中,所述碱选自氢化钠、氢氧化钠、氢氧化钾、叔丁醇钠和叔丁醇钾中的一种。
9.根据权利要求1或2所述的一种碱溶性良好的光刻胶酸敏树脂单体用于制备光刻胶。
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Application publication date: 20211012 |
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