CN110133963A - 感光性聚酰亚胺组成物及其所制成的光阻膜 - Google Patents

感光性聚酰亚胺组成物及其所制成的光阻膜 Download PDF

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CN110133963A
CN110133963A CN201810383164.5A CN201810383164A CN110133963A CN 110133963 A CN110133963 A CN 110133963A CN 201810383164 A CN201810383164 A CN 201810383164A CN 110133963 A CN110133963 A CN 110133963A
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photosensitive polyimide
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杨子瑾
钟明哲
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New Materials Co ltd
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Abstract

一种感光性聚酰亚胺组成物，其包括具有以式(1)所示的结构单元及以式(2)所示的结构单元的聚酰亚胺树脂、醌迭氮磺酸盐、热硬化剂、以及热酸产生剂。式(1)及(2)中，n为10‑600的整数，Ar1为四价有机基团，Ar2为二至四价有机基团；Ar3为二价芳基，R1为一OH基或COOH基。本发明也提供一种以前述感光性聚酰亚胺组成物制成的光阻膜。

Description

感光性聚酰亚胺组成物及其所制成的光阻膜
技术领域
本发明涉及一种感光性树脂组成物，尤其涉及一种可用来制作半导体装置中的绝缘层或保护层的感光性聚酰亚胺(Photosensitive polyimide，PSPI)组成物。
背景技术
感光性聚酰亚胺树脂具有耐热性、机械物性优异，而且尺寸稳定性也优异，常用于在耐热性涂层材料领域、印刷电路基板的层间绝缘材料、半导体的绝缘材料等电绝缘材料。然而，传统的聚酰亚胺树脂不具耐化学性，所以在作为半导体制程中的絶缘层时，常会因后续制程的酸/碱环境而受损。
发明内容
本发明改善前述聚酰亚胺树脂的缺点，提供了一种感光性树脂组成物，使其在硬烤之后不但具有耐热性，也具良好的耐化学性。
本发明提供一种正型感光性树脂组成物，其包括具有以式(1)所示的结构单元及以式(2)所示的结构单元的聚酰亚胺树脂、醌迭氮磺酸盐、热硬化剂、以及热酸产生剂。
式(1)及(2)中，n为10-600的整数，Ar1为四价有机基团，Ar2为二至四价有机基团；Ar3为二价芳基，R1为一OH基或COOH基。
在本发明的一实施例中，相对于聚酰亚胺树脂100重量份，醌迭氮磺酸盐为10-30重量份。
在本发明的一实施例中，相对于聚酰亚胺树脂100重量份，热硬化剂为10-50重量份。
在本发明的一实施例中，热硬化剂可包括环氧系化合物及三聚氰胺系化合物。环氧系化合物与三聚氰胺系化合物的重量比例可为3:1-4:3。
在本发明的一实施例中，热酸产生剂为锍鎓盐。
在本发明的一实施例中，相对于聚酰亚胺树脂100重量份，热酸产生剂为1-5重量份。
在本发明的一实施例中，锍鎓盐为选自由氯化物、溴化物、对甲苯磺酸盐、三氟甲烷磺酸盐、四氟硼酸盐、四(五氟苯基)硼酸盐、四(五氟苯基)镓酸盐、六氟磷酸盐、六氟砷酸盐、及六氟锑酸盐所组成族群中的至少一种。
本发明也提供一种以前述感光性聚酰亚胺组成物制成的光阻膜。
前述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，而可依照说明书的内容予以实施，并且为了让本发明的前述和其他目的、特征和优点能够更明显易懂，以下特举较佳实施例，详细说明如下。
具体实施方式
本发明所提供的感光性聚酰亚胺组成物为一种正型感光性树脂组成物，主要包含聚酰亚胺树脂、作为感光剂的醌迭氮磺酸盐、热硬化剂、以及热酸产生剂。如此成分的组成物在硬烤之后不但具有耐热性，也具良好的耐化学性，更能满足特殊规格需求的绝缘层的制造要求。
本发明所使用的聚酰亚胺树脂，较佳为具有以式(1)所示的结构单元及以式(2)所示的结构单元。
式(1)及(2)中，n为10-600的整数，前述聚酰亚胺树脂分子量范围在5000-50000之间，Ar1为四价有机基团，Ar2为二至四价有机基团；Ar3为二价芳基，R1为一OH基或COOH基。
Ar1为
Ar2为
其中m为1-20的整数，及X1为
-O-，-S-，-C(CF3)2-.-C(Ch3)2-
-Ch2-，-SO2-，-NHCＯ－，
其中m为1-20的整数，Z为H或甲基。
Ar3为
例如，本发明的聚酰亚胺树脂较佳为以下式(3)的化学式，式(3)中，n为10-600的整数。
本发明所使用的感光剂可为醌迭氮磺酸盐，例如重氮萘醌。相对于聚酰亚胺树脂100重量份，醌迭氮磺酸盐为10-30重量份。
热硬化剂的调配量相对于聚酰亚胺树脂100重量份为10-50重量份，特别是以20-30重量份为佳。热硬化剂可包括环氧系化合物及三聚氰胺(Melamine)系化合物。环氧系化合物与三聚氰胺系化合物的重量比例可为3:1-4:3。
前述三聚氰胺系化合物可为但不限于三聚氰胺、六羟甲基三聚氰胺六甲基醚、六羟甲基三聚氰胺六丁基醚、四甲氧基甲基苯并胍胺、四丁氧基甲基苯并胍胺等的其中之一或二种以上的组合。较佳为三聚氰胺。
前述环氧系化合物可为但不限于酚醛清漆型环氧树脂、双酚A二缩水甘油醚、双酚F二缩水甘油醚、三酚基丙烷三缩水甘油醚等的三苯基甲烷型环氧树脂、3,4-环氧基环己基甲基-3,4-环氧基环己烷羧酸酯等的环状脂肪族环氧树脂、二缩水甘油基酞酸酯、二缩水甘油基六氢酞酸酯、二甲基缩水甘油基酞酸酯等的缩水甘油基酯系树脂、四缩水甘油基二氨基二苯基甲烷、三缩水甘油基对氨基苯酚、二缩水甘油基苯胺、二缩水甘油基甲苯胺、四缩水甘油基双氨基甲基环己烷等的缩水甘油基胺系树脂等的其中一种或其组合。较佳为三缩水甘油基对氨基苯酚、及双酚A二缩水甘油醚。
本发明的感光性聚酰亚胺组成物的重要特点之一为添加了热酸产生剂。热酸产生剂可选用锍鎓盐。在调配量方面，相对于聚酰亚胺树脂为100重量份，热酸产生剂可约占1-5重量份。在一实施例中，热锍鎓塩可选自但不限定于氯化物、溴化物、对甲苯磺酸盐、三氟甲烷磺酸盐、四氟硼酸盐、四(五氟苯基)硼酸盐、四(五氟苯基)镓酸盐、六氟磷酸盐、六氟砷酸盐、及六氟锑酸盐中的至少一种。较佳为六氟磷酸盐、四(五氟苯基)硼酸盐。
前述组成物的各成分可溶于有机溶剂中。所选用的有机溶剂可为但不限定于γ-丁内酯(GBL,gamma-Butyrolactone)，其重量约占本发明的正型感光性聚酰亚胺组合物的总重的55％-85％。有机溶剂也可使用目前常为业界使用的N-甲基吡咯烷酮、二甲基乙酰胺、甲基甲酰胺等溶解能力强的极性溶剂有机溶剂，但只溶解于N-甲基吡咯烷酮等含氮系极性溶剂等的酰亚胺树脂存在由吸湿性导致的白化等问题，保存稳定性不充分。因此，使用前述树脂得到的涂膜(薄膜)会产生无法得到酰亚胺树脂本来所具有的强韧的涂膜、优异的电特性等的问题。因此可溶于γ-丁内酯等溶解能力较弱的有机溶剂的酰亚胺树脂是更优选的。
本发明的感光性聚酰亚胺组成物，如上所述，可以溶液的型态存在，以经预烤、曝光、显影、后烤等程序而得的光阻膜，膜厚的范围约可在1μm～10μm之间。预烤温度约为100℃-120℃，后烤温度约为200℃-250℃。本发明的感光性聚酰亚胺组成物溶液的配制，为先配制适量的聚酰亚胺溶液，加入所需的感光剂、热硬化剂及热酸产生剂等成分，并加入溶剂以将感光性聚酰亚胺组成物溶液稀释至所需浓度，以备后续的使用。需注意者，本文所提到的光阻膜，乃泛称半导体装置中的绝缘层或保护层等结构，特别是可用于碱性水溶性显影，并可广泛运用于半导体及显示器产业、芯片封装，显示器绝缘层及IC芯片保护层。
聚酰亚胺树脂的配制例
使用配备有一机械搅拌器与氮气进口的1000毫升的三颈圆底烧瓶，加入18.3公克(50毫摩尔)的六氟-2,2-二(3氨基-4-羟苯基)(Hexofluoro-2,2-bis(3-amino-4-hydroxyphenyl))、12.3公克(30毫摩尔)的2,2-二(4-(4-氨基苯氧基)苯基)丙烷(2,2-bis(4-(4-aminophenoxyl)phenyl)propane)、2.02公克(10毫摩尔)的4,4’-氧二苯胺(4,4’-Oxydianiline)、20.5公克(50毫摩尔)的TMEG及15.5公克(50毫摩尔)的双(3,4-二羧苯基)醚二酐(bis(3,4-dicarboxyphenyl)ether dianhydride)，并加入400克的N-甲基-2-吡咯烷酮(N-methyl-2-pyrrolidone)溶剂。将前述溶液于0℃搅拌4小时后，再加入2.18克(20毫摩尔)的封止剂3-氨基苯醇(3-aminophenol)，并于室温下再搅拌4小时，再加入80克的二甲苯后升温至180℃搅拌3小时。冷却后可得到黏稠聚酰亚胺树脂。
取前述聚酰亚胺树脂100重量份以表1的配方比例制作实施例1-实施例3、及比较例1-比较例4的感光性聚酰亚胺组成物。为了验证本发明的感光性聚酰亚胺组成物所制成的光阻膜的耐化学性、及绝缘性，将各种不同成分的组合物以表2的制程条件制成光阻膜，以进行耐化实验、及绝缘性测试。其中TMAH2.38wt％为作为显影剂的四甲基氢氧化铵的浓度。
表1
耐化测试程序
将前述制程制备的光阻膜先测量膜厚，得到(T0)，将后烤后的光阻膜浸于25℃，75％浓硝酸中1分钟，然后浸于25℃丙酮20分钟，再浸于25℃，75％浓硝酸1分钟，测量膜厚(TA)，观察残膜率(TA/T0)，残膜率是指耐化测试结束后所残留的膜厚与后烤后的膜厚的比值。各种不同成分组成物所制成的光阻膜的耐化测试结果列于表3，其中的SIB3是代表四(五氟苯基)硼酸盐。绝缘性测试
使用4339B高电阻计(安捷伦制造)量测前述制程制备的光阻膜的表面电阻值(Ω)，以Rs表示、及体积电阻值(Ω)，以Rv表示，结果如下表3所表示。
表2
膜厚 预烤 曝光 显影 后烤
2.5μm 100℃/2分钟 150mJ 30秒(TMAH 2.38wt％) 200℃/1小时
表3
残膜率 Rs Rv
实施例1 96.3％ 6.37E+16 3.25E+17
实施例2 96.0％ 5.98E+16 2.74E+17
实施例3 97.6％ 6.51E+16 3.83E+17
比较例1 70.3％ 4.73E+16 1.55E+17
比较例2 63.5％ 3.91E+16 1.47E+17
比较例3 51.9％ 3.51E+16 2.06E+17
比较例4 75.2％ 4.82E+16 1.89E+17
以上的测试证明了本发明的感光性聚酰亚胺组合物所制成的光阻膜具有优异的耐化学性，其中热硬化剂及热酸产生剂的适当选用及调配，更有助于提升光阻膜的耐化学性。
综上所述，本发明提供一种正型感光性聚酰亚胺组合物，可用于碱性水溶性显影，并可广泛运用于半导体及显示器产业、芯片封装，显示器绝缘层及IC芯片保护层。其具有高感度，良好的分辨率，低的硬烤温度，高膜厚保持率，高耐溶剂性，也具有优异的热安定性及良好的机械、电气及化学性质，相较于聚酰亚胺有更高的产品良率且可简化制程，降低成本。
以上所述，仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限制，虽然本发明已以较佳实施例揭露如上，然而并非用以限定本发明,任何熟悉本专业的技术人员,在不脱离本发明技术方案范围内，当可利用前述揭示的方法及技术内容作出些许的更动或修饰为等同变化的等效实施例，但凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明技术方案的范围内。

Claims (12)

1.一种感光性聚酰亚胺组成物，其特征在于，包括具有以式(1)所示的结构单元及以式(2)所示的结构单元的聚酰亚胺树脂、醌迭氮磺酸盐、热硬化剂、以及热酸产生剂；
式(1)及(2)中，n为10-600的整数，Ar1为四价有机基团，Ar2为二至四价有机基团；Ar3为二价芳基，R1为一OH基或COOH基。
2.如权利要求1所述的感光性聚酰亚胺组成物，其特征在于，相对于所述聚酰亚胺树脂100重量份，所述醌迭氮磺酸盐为10-30重量份。
3.如权利要求1所述的感光性聚酰亚胺组成物，其特征在于，相对于所述聚酰亚胺树脂100重量份，所述热硬化剂为10-50重量份。
4.如权利要求3所述的感光性聚酰亚胺组成物，其特征在于，所述热硬化剂包括环氧系化合物及三聚氰胺系化合物。
5.如权利要求4所述的感光性聚酰亚胺组成物，其特征在于，所述环氧系化合物与所述三聚氰胺系化合物的重量比例为3:1-4:3。
6.如权利要求5所述的感光性聚酰亚胺组成物，其特征在于，所述热酸产生剂为锍鎓盐。
7.如权利要求6所述的感光性聚酰亚胺组成物，其特征在于，相对于所述聚酰亚胺树脂100重量份，所述热酸产生剂为1-5重量份。
8.如权利要求6所述的感光性聚酰亚胺组成物，其特征在于，所述锍鎓盐为选自由氯化物、溴化物、对甲苯磺酸盐、三氟甲烷磺酸盐、四氟硼酸盐、四(五氟苯基)硼酸盐、四(五氟苯基)镓酸盐、六氟磷酸盐、六氟砷酸盐、及六氟锑酸盐所组成族群中的至少一种。
9.如权利要求1所述的感光性聚酰亚胺组成物，其特征在于，所述聚酰亚胺树脂为式(3)所示的结构；
式(3)中，n为10-600的整数。
10.一种光阻膜的制造方法，其特征在于，包括：
将如权利要求1至9中的任一项所述的感光性聚酰亚胺组成物涂布于基板；
对所述感光性聚酰亚胺组成物进行曝光；以及
进行显影。
11.如权利要求10所述的光阻膜的制造方法，其特征在于，于对所述感光性聚酰亚胺组成物进行曝光之前，还包括以100℃-120℃进行预烤。
12.如权利要求10所述的光阻膜的制造方法，其特征在于，于进行显影之后，还包括以200℃-250℃进行后烤。
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