CN111763147A - 由甲基六氢化萘二酮合成的可降解型光刻胶树脂单体及其合成方法 - Google Patents
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- -1 methylhexahydronaphthalene dione Chemical compound 0.000 title claims abstract description 13
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- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
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Abstract
Description
技术领域
本发明涉及光刻胶树脂领域,特别涉及树脂单体及其合成方法。
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。
树脂是由多种树脂单体聚合而成的聚合物,其中酸敏树脂单体是实现曝光前后树脂在显影液中溶解差异的重要组成部分,常见的酸敏树脂单体只有一个酸敏基团,树脂单体为线性聚合物,耐刻蚀性能较弱,并且,曝光后在显影液中的溶解差仅仅靠酸敏树脂单体决定,从而造成分辨率出现不足的现象发生。
发明内容
本发明要解决的技术问题是克服现有技术的缺陷,提供一种由甲基六氢化萘二酮合成的可降解型光刻胶树脂单体及其合成方法。
为了解决上述技术问题,本发明提供了如下的技术方案:
本发明提供一种新的树脂单体,其结构式如下所示:
优选的,所述树脂单体的具体结构包括:
此外,本发明还提供一种树脂单体的合成方法,该树脂单体的合成方法的反应路线为:
该树脂单体的具体合成步骤为:
第一步格氏反应,在惰性气体保护下,(4as,8ar)-4a-甲基六氢化萘-2,7(1H,3H)-二酮(Ⅰ)与烷基格氏试剂或者环烷基格氏试剂反应,反应结束后加水淬灭,后处理纯化得到中间体(Ⅱ);
第二步酯化反应,在碱性条件下,中间体(Ⅱ)与丙烯酰氯或者甲基丙烯酰氯反应,后处理纯化后得到树脂单体(Ⅲ)。
作为本发明的一种优选技术方案,所述格氏反应的温度为0-30摄氏度;所述格氏反应的溶剂为无水乙醚。
作为本发明的一种优选技术方案,所述酯化反应的反应温度0-70摄氏度,酯化反应的溶剂选自四氢呋喃、甲苯或者氯仿。
与现有技术相比,本发明的有益效果如下:
本发明提供了一种新的光刻胶树脂单体,该树脂单体含有两个不饱和碳碳双键,在与其它树脂单体(包括仅含一个聚合基团的酸敏树脂单体)聚合过程中能够产生交联,形成三维网状结构的聚合树脂,产生交联的聚合树脂具有更好的耐刻蚀性能,曝光时,光酸产生剂产生酸,在曝光区,主链上的(甲基)丙烯酸酯在酸性条件下断裂,聚合物树脂主链断裂产生分子量更小的产物,增加了曝光后树脂在显影液中的溶解性,由于曝光前后的聚合物树脂在显影液中溶解速度差增大,有利于改善显影后图形的边缘粗糙度,大大提高了光刻图案的分辨率,并且,该树脂单体含有桥环结构,增加了未曝光区域的耐刻蚀性能,对于分辨率的提高也有显著的贡献。
具体实施方式
以下结合实施例对本发明的优选实施例进行说明,应当理解,此处所描述的优选实施例仅用于说明和解释本发明,并不用于限定本发明。
实施例1
第一步:a、制备甲基格氏试剂:将镁屑(2.7g,111mmol)加入到无水乙醚(15mL)中,然后加入一粒碘片,再将甲基溴(10.6g,112mmol)溶解在乙醚(25mL)中配制成溶液,氮气保护下,先向上述反应液中加入甲基溴的乙醚溶液(6mL),几分钟后,反应液微沸,碘的颜色消失,搅拌下,继续滴加剩余的甲基溴的乙醚溶液,补加乙醚(20mL),升温保持微沸,回流半小时;b、合成中间体1-2:氮气保护下,将制备好的甲基格氏试剂用冰水冷却,搅拌下滴加(4as,8ar)-4a-甲基六氢化萘-2,7(1H,3H)-二酮(10.0g,55mmol)的乙醚(20mL)溶液,控制滴加速度,保持反应液微沸,滴加结束后,在25摄氏度下继续搅拌半小时,反应液中有白色固体析出,将反应液用冰水冷却,慢慢滴加20%稀硫酸(20mL),滴加结束后,分离醚层,水相用乙酸乙酯(100mL×3)萃取三次,合并有机相,有机相浓缩后的粗品经柱层析纯化得到中间体1-2(9.2g,43mmol,78.1%);
第二步:将中间体1-2(9.2g,43mmol)溶解在四氢呋喃(120mL)中,加入三乙胺(17.6g,174mmol),用冰水冷却到0摄氏度,在氮气保护下,向其中慢慢滴加丙烯酰氯(7.9g,87mmol)的四氢呋喃(50mL)溶液,反应液升至25摄氏度继续反应5小时,反应液真空下浓缩除去溶剂,加入乙酸乙酯(50mL),加入饱和碳酸氢钠水溶液(20mL),分离有机相,水相用乙酸乙酯(80mL×3)萃取三次,合并有机相,有机相用饱和食盐水洗涤,无水硫酸钠干燥后旋干得到粗品,粗品用甲基叔丁基醚打浆得到化合物1-3(10.6g,33mmol,76.3%)。
实施例2
第一步:操作步骤以及原料投料量与实施例1的第一步反应相同,反应得到化合物2-2(9.5g,45mmol,80.6%);
第二步:操作步骤与实施例1的第二步反应相同,其中反应物以及投料量:中间体1-2(9.2g,43mmol)替换为中间体2-2(9.5g,45mmol),丙烯酰氯(7.9g,87mmol)替换为甲基丙烯酰氯(9.4g,90mmol),三乙胺(17.6g,174mmol)替换为三乙胺(18.1g,178mmol),得到化合物2-3(12.3g,35mmol,78.9%)。
实施例3
第一步:操作步骤与实施例1的第一步相同,其中甲基溴(10.6g,112mmol)更改为乙基溴(12.1g,111mmol),得到化合物3-2(10.5g,44mmol,78.7%);
第二步:操作步骤与实施例1的第二步反应相同,其中反应物以及投料量:中间体1-2(9.2g,43mmol)替换为中间体3-2(10.5g,44mmol),三乙胺(17.6g,174mmol)替换为三乙胺(17.7g,175mmol),得到化合物3-3(11.8g,34mmol,77.5%)。
实施例4
第一步:操作步骤与实施例3的第一步相同,得到化合物4-2(10.3g,43mmol,77.2%);
第二步:操作步骤与实施例1的第二步反应相同,其中反应物以及投料量:中间体1-2(9.2g,43mmol)替换为中间体4-2(10.3g,43mmol),丙烯酰氯(7.9g,87mmol)替换为甲基丙烯酰氯(9.0g,86mmol),三乙胺(17.6g,174mmol)替换为三乙胺(17.4g,171mmol),得到化合物4-3(12.7g,34mmol,78.7%)。
实施例5
第一步:操作步骤与实施例1的第一步相同,其中,甲基溴(10.6g,112mmol)替换为环己基溴(18.1g,111mmol),得到化合物5-2(12.2g,35mmol,63.1%);
第二步:操作步骤与实施例1的第二步反应相同,其中反应物以及投料量:中间体1-2(9.2g,43mmol)替换为中间体5-2(12.2g,35mmol),丙烯酰氯(7.9g,87mmol)替换为丙烯酰氯(6.4g,71mmol),三乙胺(17.6g,174mmol)替换为三乙胺(14.2g,140mmol),得到化合物5-3(10.5g,23mmol,65.7%)。
实施例6
第一步:操作步骤与实施例5的第一步相同,得到化合物6-2(12.5g,36mmol,64.6%);
第二步:操作步骤与实施例1的第二步反应相同,其中反应物以及投料量:中间体1-2(9.2g,43mmol)替换为中间体6-2(12.5g,36mmol),丙烯酰氯(7.9g,87mmol)替换为甲基丙烯酰氯(7.5g,72mmol),三乙胺(17.6g,174mmol)替换为三乙胺(14.6g,144mmol),得到化合物6-3(10.8g,22mmol,62.1%)。
与现有技术相比,本发明的有益效果如下:
本发明提供了一种新的光刻胶树脂单体,该树脂单体含有两个不饱和碳碳双键,在与其它树脂单体聚合过程中能够产生交联,形成三维网状结构的聚合树脂,产生交联的聚合树脂具有更好的耐刻蚀性能,曝光时,光酸产生剂产生酸,在曝光区,主链上的(甲基)丙烯酸酯在酸性条件下断裂,聚合物树脂主链断裂产生分子量更小的产物,增加了曝光后树脂在显影液中的溶解性,由于曝光前后的聚合物树脂在显影液中溶解速度差增大,有利于改善显影后图形的边缘粗糙度,大大提高了光刻图案的分辨率,并且,该树脂单体含有桥环结构,增加了未曝光区域的耐刻蚀性能,对于分辨率的提高也有显著的意义。
最后应说明的是:以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (8)
4.根据权利要求3所述的由甲基六氢化萘二酮合成的可降解型光刻胶树脂单体的合成方法,其特征在于,所述格氏反应的温度为0-30摄氏度。
5.根据权利要求3所述的由甲基六氢化萘二酮合成的可降解型光刻胶树脂单体的合成方法,其特征在于,所述格氏反应的溶剂为无水乙醚。
6.根据权利要求3所述的由甲基六氢化萘二酮合成的可降解型光刻胶树脂单体的合成方法,其特征在于,所述酯化反应的反应温度为0-70摄氏度。
7.根据权利要求3所述的由甲基六氢化萘二酮合成的可降解型光刻胶树脂单体的合成方法,其特征在于,所述酯化反应的溶剂选自四氢呋喃、甲苯或者氯仿。
8.根据权利要求3所述的由甲基六氢化萘二酮合成的可降解型光刻胶树脂单体的合成方法,其特征在于,为保证酯化反应的碱性条件,需要向体系中添加三乙胺或者吡啶。
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