CN102929102B - 一种深紫外化学增幅型正性光致抗蚀剂 - Google Patents
一种深紫外化学增幅型正性光致抗蚀剂 Download PDFInfo
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Abstract
本发明公开了一种深紫外化学增幅型正性光致抗蚀剂。本发明的深紫外化学增幅型正性光致抗蚀剂包括环戊烯海松酸、二乙烯基醚、光产酸剂和有机溶剂。本发明的深紫外化学增幅型正性光致抗蚀剂具有良好的感度和良好的透明性。
Description
技术领域
本发明涉及感光材料领域,尤其涉及一种深紫外化学增幅型正性光致抗蚀剂。
背景技术
“化学增幅”的概念是80年代初IBM公司的伊藤(Ito)等人最先提出的。作为一种新型光致抗蚀剂,化学增幅抗蚀剂与原有光致抗蚀剂不同。原有光致抗蚀剂在曝光时每吸收一个光子最多发生一次交联或分解反应,效率较低,而化学增幅抗蚀剂一般由光产酸剂(PAG,Photoacid Generator)和酸敏成膜树脂组成,在曝光时光产酸剂分解出强酸,催化酸敏树脂的分解或交联,由于催化剂在反应中可以循环使用,因此效率很高。248nm光致抗蚀剂是最早应用“化学增幅”概念的抗蚀剂,一般采用聚对羟基苯乙烯的衍生物作为成膜树脂,芳基碘鎓盐或硫鎓盐为光致产酸剂。通常要求成膜树脂在248nm处要具有较高的透明性,聚对羟基苯乙烯及其衍生物本身在248nm处透明性较好,但是如果聚合物中含有杂质,树脂的透明性大大降低,因此,这种光致抗蚀剂对聚对羟基苯乙烯纯度的要求较高,制作工艺复杂。
发明内容
本发明的目的是提供一种具有良好的感度的深紫外化学增幅型正性光致抗蚀剂。
本发明的深紫外化学增幅型正性光致抗蚀剂,包括环戊烯海松酸、二乙烯基醚,光产酸剂和有机溶剂,所述环戊烯海松酸的结构式如下
其中,所述二乙烯基醚为乙二醇二乙烯基醚、丙二醇二乙烯基醚、丁二醇二乙烯基醚、二乙二醇二乙烯基醚、1,3-二乙烯氧基乙氧基苯、1-甲基-1,2-二乙烯氧基乙烷或1,7-二乙烯氧基乙氧基萘。
所述光产酸剂优选地选自三苯基硫鎓三氟甲磺酸盐、S-(2-萘甲酰)甲基四氢噻吩鎓三氟甲磺酸盐、三(4-甲基苯基)硫鎓三氟甲磺酸盐、七氟丙烷磺酸盐、(4-甲基苯基)二苯基三氟甲磺酸盐、(对-叔-丁基苯基)二苯基硫鎓三氟甲磺酸盐和三(对-叔-丁基苯基)硫鎓三氟甲磺酸盐中的至少一种。
所述有机溶剂优选地选自丙酮、甲基乙基酮、环己酮、乙二醇乙醚、乙二醇一乙酸酯、二甘醇、丙二醇、丙二醇一乙酸酯、乳酸甲酯、丙二醇甲醚醋酸酯和乙二醇甲醚醋酸酯中的至少一种。
其中,所述环戊烯海松酸和所述二乙烯基醚的摩尔比为5:4~1:2,优选地1:1~2:3。
其中,所述光产酸剂的质量为所述环戊烯海松酸与所述二乙烯基醚质量总和的0.5%~5%,优选地1.0%~3.0%。
其中,所述光产酸剂、环戊烯海松酸、二乙烯基醚的质量总和为所述有机溶剂质量为的10%~35%,更优选地10~30%。
其中,所述环戊烯海松酸按照如下方法制备:
将脂松香加热至210~250℃,氮气气氛下滴加环戊烯酸,滴加完毕后,在210~250℃的条件下继续反应,反应完成后得到环戊烯海松酸粗产物,将所述粗产物用四氯化碳、三氯甲烷、丙酮、环己酮或乙醚洗涤,得到环戊烯海松酸。
本发明的另一个目的是提供一种环戊烯海松酸。
本发明的环戊烯海松酸其结构式如下
所述环戊烯海松酸的软化点为130~132℃,酸值为295mg KOH/g。
本发明将松香酸和环状烯烃酸通过狄尔斯-阿尔德反应(Diels-Alder,D-A)反应制得具有大的脂环结构的二酸,即环戊烯海松酸,该二酸不含苯环结构,在深紫外区具有良好的透明性,使其具有良好的感度。
本发明的环戊烯海松酸可以与二乙烯基醚和光产酸剂组成深紫外化学增幅型正性光致抗蚀剂,该抗蚀剂具有良好的感度。
具体实施方式
环戊烯海松酸的合成
将脂松香加入带搅拌及冷凝装置的四口瓶中加热至210~250℃,同时导入氮气,缓慢滴加环戊烯酸,滴加时间控制在2~5小时,滴加完毕后,体系在210~250℃的条件下继续反应3~5h,降温出料得到环戊烯海松酸粗产物,将产物用四氯化碳、三氯甲烷、丙酮、环己酮或乙醚洗涤一次,得到环戊烯海松酸。
松香酸 环戊烯酸 环戊烯海松酸
合成例1:
将50g脂松香加入带搅拌及冷凝装置的四口瓶中加热至230℃,同时导入氮气,缓慢滴加环戊烯酸17g,滴加时间控制在2小时,滴加完毕后,体系在230℃的条件下继续反应3h,降温出料得到环戊烯海松酸粗产物,将产物用四氯化碳洗涤一次。对洗涤并干燥后的产物进行分析。结果:软化点130~132℃,酸值295mg KOH/g。用高效液相色谱法(High Performance Liquid Chromatography,HPLC)测得目标产物含量约为75%。
合成例2:
将50g脂松香加入带搅拌及冷凝装置的四口瓶中加热至210℃,同时导入氮气,缓慢滴加环戊烯酸17g,滴加时间控制在5小时,滴加完毕后,体系在210℃的条件下继续反应4h,降温出料得到环戊烯海松酸粗产物,将产物用三氯甲烷洗涤一次。对洗涤并干燥后的产物进行分析。结果:软化点130~132℃,酸值295mg KOH/g。用HPLC测得目标产物含量约为75%。
合成例3:
将50g脂松香加入带搅拌及冷凝装置的四口瓶中加热至250℃,同时导入氮气,缓慢滴加环戊烯酸17g,滴加时间控制在3小时,滴加完毕后,体系在250℃的条件下继续反应5h,降温出料得到环戊烯海松酸粗产物,将产物用丙酮洗涤一次。对洗涤并干燥后的产物进行分析。结果:软化点130~132℃,酸值295mg KOH/g。用HPLC测得目标产物含量约为75%。
环戊烯海松酸在固体膜层中可以与二乙烯基醚在加热条件下(80℃以上)发生反应,产物在稀碱水中难溶。这样形成的产物在光产酸剂产生的强酸催化下,在温度高于100℃时,可以迅速分解,从而变成稀碱水易溶。因此,用此二酸、二乙烯基醚和产酸剂可组成一种正性的光致抗蚀剂。
可供选择的二乙烯基醚:乙二醇二乙烯基醚、丙二醇二乙烯基醚、丁二醇二乙烯基醚、二乙二醇二乙烯基醚、1,3-二乙烯氧基乙氧基苯、1-甲基-1,2-二乙烯氧基乙烷、1,7-二乙烯氧基乙氧基萘等。
可供选择的光产酸剂:产酸剂可以使用在传统化学放大光刻胶作为酸生成剂而典型使用的任何物质、优选的产酸剂有三苯基硫鎓三氟甲磺酸盐、S-(2-萘甲酰)甲基四氢噻吩鎓三氟甲磺酸盐、三(4-甲基苯基)硫鎓三氟甲磺酸盐,七氟丙烷磺酸盐、(4-甲基苯基)二苯基三氟甲磺酸盐、(对-叔-丁基苯基)二苯基硫鎓三氟甲磺酸盐、三(对-叔-丁基苯基)硫鎓三氟甲磺酸盐等,以上产酸剂可以单一使用也可以两种或多种混合使用。
有机溶剂:有机溶剂可以是能够溶解光致抗蚀剂中组分以产生均匀溶液的任何溶剂,优选的溶剂有丙酮、甲基乙基酮、环己酮、乙二醇乙醚、乙二醇一乙酸酯、二甘醇、丙二醇、丙二醇一乙酸酯、乳酸甲酯、丙二醇甲醚醋酸酯、乙二醇甲醚醋酸酯等,以上溶剂可以单一使用也可以两种或多种混合使用。
实施例1-10正性光致抗蚀剂
按照下表制备正性光致抗蚀剂。
为了用本发明所述的正性光致抗蚀剂形成光致抗蚀剂图案,所实施的常规的光刻蚀步骤如下:
首先,使用匀胶机将光致抗蚀剂涂敷在诸如硅晶片的基质上以形成光致抗蚀剂层,60℃前烘90s;
然后将光致抗蚀剂暴露在预定图案的掩膜板下面,曝光后100℃下后烘2min;
最后对曝光后的光致抗蚀剂涂层进行显影,显影液选用0.38wt%的四甲基氢氧化铵,显影液温度为25℃,显影时间为60s。
上表中所述环戊烯海松酸和二乙烯基醚的用量是用质量来表示,两者的质量比关系是由两者的摩尔比推算出来的。
由上表可以看出本发明的正性光致抗蚀剂的感度在18~42mJ/cm-2之间,具有良好的感度,因此,可以得出所述正性光致抗蚀剂在深紫外区具有良好的透明性。
以上说明对本发明而言只是说明性的,而非限制性的,本领域普通技术人员理解,在不脱离所附权利要求所限定的精神和范围的情况下,可做出许多修改、变化或等效,但都将落入本发明的保护范围内。
Claims (11)
2.根据权利要求1所述的正性光致抗蚀剂,其特征在于,所述二乙烯基醚为乙二醇二乙烯基醚、丙二醇二乙烯基醚、丁二醇二乙烯基醚、二乙二醇二乙烯基醚、1,3-二乙烯氧基乙氧基苯、1-甲基-1,2-二乙烯氧基乙烷或1,7-二乙烯氧基乙氧基萘。
3.根据权利要求1所述的正性光致抗蚀剂,其特征在于,所述光产酸剂选自三苯基硫鎓三氟甲磺酸盐、S-(2-萘甲酰)甲基四氢噻吩鎓三氟甲磺酸盐、三(4-甲基苯基)硫鎓三氟甲磺酸盐、七氟丙烷磺酸盐、(4-甲基苯基)二苯基三氟甲磺酸盐、(对-叔丁基苯基)二苯基硫鎓三氟甲磺酸盐和三(对-叔丁基苯基)硫鎓三氟甲磺酸盐中的至少一种。
4.根据权利要求1所述的正性光致抗蚀剂,其特征在于,所述有机溶剂选自丙酮、甲基乙基酮、环己酮、乙二醇乙醚、乙二醇单乙酸酯、二甘醇、丙二醇、丙二醇单乙酸酯、乳酸甲酯、丙二醇甲醚醋酸酯和乙二醇甲醚醋酸酯中的至少一种。
5.根据权利要求4所述的正性光致抗蚀剂,其特征在于,所述环戊烯海松酸和所述二乙烯基醚的摩尔比范围为1:1~2:3。
6.根据权利要求1-4中任一所述的正性光致抗蚀剂,其特征在于,所述光产酸剂的质量为所述环戊烯海松酸与所述二乙烯基醚质量总和的0.5%~5%。
7.根据权利要求6所述的正性光致抗蚀剂,其特征在于,所述光产酸剂的质量为所述环戊烯海松酸与所述二乙烯基醚质量总和的1.0%~3.0%。
8.根据权利要求1-4中任一所述的正性光致抗蚀剂,其特征在于,所述光产酸剂、环戊烯海松酸和二乙烯基醚的质量总和为所述有机溶剂质量的10%~35%。
9.根据权利要求8所述的正性光致抗蚀剂,其特征在于,所述光产酸剂、环戊烯海松酸和二乙烯基醚的质量总和为所述有机溶剂质量的10~30%。
10.根据权利要求1所述的正性光致抗蚀剂,其特征在于,所述环戊烯海松酸按照如下方法制备:
将脂松香加热至210~250℃,氮气气氛下滴加环戊烯酸,滴加完毕后,在210~250℃的条件下继续反应,反应完成后得到环戊烯海松酸粗产物,将所述粗产物用四氯化碳、三氯甲烷、丙酮、环己酮或乙醚洗涤,得到环戊烯海松酸。
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