CN1297542A - 辐射敏感性树脂组合物 - Google Patents
辐射敏感性树脂组合物 Download PDFInfo
- Publication number
- CN1297542A CN1297542A CN00800449A CN00800449A CN1297542A CN 1297542 A CN1297542 A CN 1297542A CN 00800449 A CN00800449 A CN 00800449A CN 00800449 A CN00800449 A CN 00800449A CN 1297542 A CN1297542 A CN 1297542A
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- CN
- China
- Prior art keywords
- novolac resin
- radiation
- thin
- resin composition
- film distillation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 230000005855 radiation Effects 0.000 title claims abstract description 33
- 239000011342 resin composition Substances 0.000 title claims abstract description 33
- 229920003986 novolac Polymers 0.000 claims abstract description 73
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 29
- 238000004821 distillation Methods 0.000 claims abstract description 27
- 239000010409 thin film Substances 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 238000005227 gel permeation chromatography Methods 0.000 claims abstract description 16
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 16
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical group [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 46
- 239000003513 alkali Substances 0.000 claims description 18
- 238000005194 fractionation Methods 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 10
- 238000004090 dissolution Methods 0.000 claims description 6
- 229920002521 macromolecule Polymers 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 8
- 239000000539 dimer Substances 0.000 abstract description 7
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 7
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 238000004458 analytical method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- -1 quinone compound Chemical class 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
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- 238000000576 coating method Methods 0.000 description 13
- 238000005259 measurement Methods 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
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- 238000001259 photo etching Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
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- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001263 acyl chlorides Chemical class 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- 239000000463 material Substances 0.000 description 3
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- 229940105324 1,2-naphthoquinone Drugs 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
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- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- LPCJHUPMQKSPDC-UHFFFAOYSA-N 3,5-diethylphenol Chemical compound CCC1=CC(O)=CC(CC)=C1 LPCJHUPMQKSPDC-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 102100036848 C-C motif chemokine 20 Human genes 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 101000713099 Homo sapiens C-C motif chemokine 20 Proteins 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229930192627 Naphthoquinone Natural products 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 229940100630 metacresol Drugs 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002791 naphthoquinones Chemical class 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000036211 photosensitivity Effects 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
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- 150000003739 xylenols Chemical class 0.000 description 2
- OKJFKPFBSPZTAH-UHFFFAOYSA-N (2,4-dihydroxyphenyl)-(4-hydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O OKJFKPFBSPZTAH-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供了一种辐射敏感性树脂组合物,其具有优异的、光刻胶需要的性质,如敏感性、图案形状和耐热性,并具有这些性质优良的平衡组合。所述组合物包含碱溶性树脂和具有醌二叠氮化物基团的光敏剂,其中,碱溶性树脂包含通过薄膜蒸馏法处理选择性除去单体和二聚物的酚醛清漆树脂。薄膜蒸馏法处理优选这样进行以使在处理前与处理后的酚醛清漆树脂在凝胶渗透色谱中,在280nm下检测,得到的图案满足下述关系:B2/B1≥0.95,C2/(A2+B2+C2)≤0.060;其中,A1、B1和C1分别为未处理的酚醛清漆图案中高分子区域、中分子区域和单体/二聚物区域,而A2、B2和C2则分别为处理后的酚醛清漆图案中高分子区域、中分子区域和的单体/二聚物区域。
Description
发明领域
本发明涉及一种新的辐射敏感性树脂组合物，更具体地，本发明涉及一种包含碱溶性酚醛清漆树脂的辐射敏感性树脂组合物，这种组合物适用于生产半导体，制备在液晶显示板中的显示表面，适用于生产用于热位差等的电路衬底以及类似的用途。
发明背景
在生产半导体集成电路如LS1、制备液晶显示板中的显示表面、生产用于热位差等的电路衬底等用途的广泛领域中，光刻法一直被用来形成微型元件或进行精细加工。在光刻法中，采用正型或负型辐射敏感性树脂组合物形成光刻图。这些辐射敏感性树脂组合物中，含有碱溶性树脂和醌二叠氮化物化合物的光敏剂的那些组合物是最常规采用的正型辐射敏感性树脂组合物。作为此类组合物，在许多文献中描述了具有不同配方的包含碱溶性树脂和醌二叠氮化物化合物的光敏剂的组合物，所述文献例如为：日本已审专利公开第23570/1979号(美国专利第3,666,473号)和第30850/1981号(美国专利第4,115,128号)，日本未审专利申请第73045/1980、205933/1986和51459/1987号等。从同时考虑酚醛清漆树脂和光敏剂的观点出发，目前已深入研究了含酚醛清漆树脂及醌二叠氮化物化合物的那些组合物。并且，考虑到酚醛清漆树脂，通过改善常规已知树脂的物理性质以及开发新的树脂，获得了具有优异性能的辐射敏感性树脂。例如，日本未审专利申请第140235/1985号和第105243/1989号公开了赋予特定分子量分布于酚醛清漆树脂以提供具有优异性能的辐射敏感性树脂组合物的技术。
然而，许多常规的辐射敏感性树脂组合物仅存在一些问题，例如，在包含敏感性、分辨率、焦点深度、图案轮廓、涂层-剩余比、耐热性等在内的各种性质间平衡较差，需要进一步进行改进。特别是在生产平板显示器的方法中，很重要的主题就是减少单体和二聚物在碱溶性树脂组份中的含量并改善上述性质。也就是说，目前还存在的问题是，当在衬底上涂敷辐射敏感性树脂组合物后进行预烘烤时，在碱溶性树脂中的单体和二聚物在预烘烤过程中会与溶剂一起气化，并使预烘烤炉的内部变脏，导致在生产装置的步骤中有杂质污染。例如日本未审专利申请第86831/1982号、第230136/1985号和第230164/1991号描述了通过溶剂分馏对低分子树脂组份进行分馏的方法。但是，这种溶剂分馏技术也存在问题，由于在树脂中的中等分子组份也会象单体和二聚物组份一样分馏出去，导致敏感性下降。作为一项防止和敏感性降低的技术，可以考虑对于具有先前的平均分子量降低的碱溶性树脂进行溶剂分馏。虽然可获得足够的敏感性，但是，这种碱溶性树脂却具有较差的涂层残余比和较差的耐热性，因此，很难获得一种具有如上所述各项性能间平衡良好的辐射敏感性树脂组合物。此外，通过溶剂分馏法分馏出来的大多数碱溶性树脂的低分子组份不能用作辐射敏感性树脂组合物的原料，只能作为废物弃用。这种生产方法不仅造成辐射敏感性树脂组合物的生产成本增加，而且带来严重的环境问题。
另一方面，作为分馏化合物的方法，公知的一种方法是薄膜蒸馏法。这种薄膜蒸馏法是一种通过采用机械离心力、惯性力、分散装置等在加热转盘等上形成被蒸馏的物质的薄膜进行蒸馏，从而加速单体的蒸发。迄今为止，已有报导将这种薄膜蒸馏法用于生产用作环氧树脂原料的多羟基化合物的生产过程(日本未审专利申请87538/1998)，用于纯化二甲苯酚的过程(捷克斯洛伐克发明人证书239793)以及用于除去蜡中的低熔点物质的方法中，所述蜡用于对静电图像显影的调色剂(日本未审专利申请36218/1995)。但是，目前还不知道可以采用这种薄膜蒸馏技术用于在辐射敏感性树脂组合物中的粘合剂树脂。虽然上述日本未审专利申请230164/1991认为，酚醛清漆树脂的小分子组份可通过薄膜蒸馏法除去，但是，其仅说明作为溶剂分馏法的一种等价技术，并未公开处理条件等。也就是说，其仅显示了一种可能性，并未表明薄膜蒸馏法比溶剂分馏法更优越。
本发明的目的是提供一种无上述缺陷的辐射敏感性树脂组合物，其具有光刻胶所需的优异的敏感性、分辨率、图案轮廓、耐热性等，并且这些性质具有良好的平衡。
发明概述
经过深入研究，本发明的发明人发现，上述发明目的可以通过下述手段实现，即在包含碱溶性树脂和醌二叠氮化物化合物基团的光敏剂的辐射敏感性树脂的酚醛清漆树脂组合物中，采用通过薄膜蒸馏法处理部分和选择性地除去单体和二聚物，从而使单体和二聚物在树脂中的量降至碱溶性树脂所给出的范围内，从而在此发现的基础上完成了本发明。
也就是说，本发明涉及一种包含碱溶性树脂和具有醌二叠氮化物基团的光敏剂的辐射敏感性树脂组合物，其中，碱溶性树脂为一种通过薄膜蒸馏法处理的酚醛清漆树脂。
附图简述
图1为说明酚醛清漆树脂的高分子区域A、中分子区域B和单体-二聚物区域C的GPC图。
图2为原料酚醛清漆树脂A-1的GPC图和峰参数表。
图3为按照薄膜蒸馏法处理原料酚醛清漆树脂A-1获得的酚醛清漆树脂A-2的GPC图和峰参数表。
图4为按照溶剂分馏法处理原料酚醛清漆树脂A-1获得的酚醛清漆树脂A-3的GPC图和峰参数表。
发明详述
用于本发明的酚醛清漆树脂为酚醛清漆型酚树脂，其是由一种或多种酚与醛如***进行缩聚生产的酚醛清漆型酚树脂。这些树脂进行薄膜蒸馏法以将单体和二聚物的含量降至给定范围。在本发明中，通过薄膜蒸馏法处理的酚醛清漆树脂在凝胶渗透色谱(GPC)(在280nm下检测)中其峰面积具有下述比例：
C2/(A2+B2+C2)≤0.060； B2/B1≥0.95其中，A1为高分子区域，B1为中分子区域，C1为分级处理前的原料酚醛清漆树脂单体/二聚物区域，而A2、B2和C2则分别为分级处理后的酚醛清漆树脂A1、B1和C1的对应区域。也就是说，优选酚醛清漆树脂包含不超过6％的单体/二聚物，并且在处理前与处理后中分子区域在GPC中B1和B2的面积之比不低于0.95(即，经处理中分子区域剩余最多)。
为了根据用聚苯乙烯标准测量的重均分子量显示这些区域的边界分子值，在中间区域B与高分子区域A间的边界值约为12,000±10％(在给定GPC条件下测量)，而在含三聚物的中间区域B与单体/二聚物区域C间的边界值约为160±10％。其一个实例如图1所示，是用GPC检测仪在280nm下对酚醛清漆树脂进行检测获得的，其中，由A、B和C表示的区域分别对应于高分子区域、中分子区域和单体/二聚物区域。
此外，按照聚苯乙烯标准测量，处理过的酚醛清漆树脂的分子量优选为2,000～25,000。如果经薄膜蒸馏法处理的酚醛清漆树脂的重均分子量低于2,000，则会导致形成图案的涂层性质和涂层残余性质变差，而如果该值大于25,000，则会导致敏感性下降。
进而，用上述薄膜蒸馏法处理的酚醛清漆树脂在2.38wt％氢氧化四甲基胺中的溶解速度优选为100或更多。如果通过薄膜蒸馏法处理后酚醛清漆树脂的溶解速度低于100，则会导致敏感性下降，使得图案形成能力变差或碱性显影时间增加很多，因此是不切合实际的。加入低分子化合物以防止敏感性下降会导致耐热性变差。
另外，在本发明中，通过薄膜蒸馏法除去单体和二聚物，但不除去中分子区域，因此，不会造成敏感性下降的问题，这与日本未审专利申请230164/1991等所述的溶剂分馏法不同。在该日本未审专利申请230164/1991中，敏感性的下降是通过加入低分子化合物作溶解加速剂来避免的。但是，加入太多的试剂会引起耐热性变差，并且难以使敏感性与耐热性达到很好的平衡。
首先，用作本发明辐射敏感性树脂组合物原料的碱溶性酚醛清漆树脂可由任一种常规方法生产，例如，通过使至少一种酚与醛如***在草酸作催化剂下进行缩聚反应。
作为用来生产上述碱溶性酚醛清漆树脂的酚，可以采用：甲酚，如邻甲酚、对甲酚和间甲酚；二甲酚，如3,5-二甲酚、2,5-二甲酚、2,3-二甲酚和3,4-二甲酚；三甲基苯酚，如2,3,4-三甲基苯酚、2,3,5-三甲基苯酚、2,4,5-三甲基苯酚和3,4,5-三甲基苯酚；叔丁基苯酚，如2-叔丁基苯酚、3-叔丁基苯酚和4-叔丁基苯酚；甲氧基苯酚，如2-甲氧基苯酚、3-甲氧基苯酚、4-甲氧基苯酚、2,3-二甲氧基苯酚、2,5-二甲氧基苯酚和3,5-二甲氧基苯酚；乙基苯酚，如2-乙基苯酚、3-乙基苯酚、4-乙基苯酚、2,3-二乙基苯酚、3,5-二乙基苯酚，2,3,5-三乙基苯酚和3,4,5-三乙基苯酚；氯苯酚，如邻氯苯酚、间氯苯酚、对氯苯酚和2,3-二氯苯酚；间苯二酚，如间苯二酚、2-甲基间苯二酚、4-甲基间苯二酚和5-甲基间苯二酚；邻苯二酚如5-甲基邻苯二酚；焦棓酚，如5-甲基焦棓酚；双酚，如双酚A、B、C、D、E或F；羟甲基甲酚，如2,6-二羟甲基-对甲酚；萘酚，如α-萘酚、β-萘酚等。
作为醛，可以使用：水杨醛、多聚甲醛、乙醛、苯甲醛、羟基苯甲醛、氯乙醛等，它们可以单独使用或以两种或多种的混合物使用或与***混合使用。
在本发明中，上述酚醛清漆树脂在薄膜离心蒸馏装置中于下述条件下进行蒸馏，压力为5～10托，温度为260～280℃，并很好地控制保留时间以基本除去单体和二聚物组份。如前所述，迄今还未将薄膜蒸馏法用于各种聚合物体系以除去未反应的单体、低分子量物质、挥发性成份等，在本发明中采用的方法与已知方法原则上相同。
为实现本发明调节处理过的酚醛清漆树脂中单体/二聚物的含量至不超过6％且尽可能少地除去三聚物或更长分子的低聚物的目的，即保持在处理后与处理前中分子区域中GPC中峰面积比B2/B1为0.95或更大，最好对薄膜蒸馏条件进行优化。因为，如果单体/二聚物含量超过6％，则会导致不想要的涂层-残余比例和耐热性，如果B2/B1小于0.95，则会导致敏感性不足。
作为具有醌二叠氮化物基团的光敏剂，可采用任一种公知的常规用于醌二叠氮化物-酚醛清漆树脂体系的光刻胶中的此类光敏剂。在本发明中，优选那些通过萘醌二叠氮化物磺酰氯或苯醌二叠氮化物磺酰氯与具有一个或多个能够与酰氯进行缩合反应的官能团的低分子或高分子化合物反应获得的化合物。作为能够与酰氯进行缩合反应的基团，可采用羟基、氨基等，特别优选羟基。作为能够与酰氯进行缩合反应并具有羟基的化合物，例如可以是：对苯二酚；间苯二酚；羟基二苯酮，如2,4-二羟基二苯酮、2,3,4-三羟基二苯酮、2,4,6-二羟基二苯酮、2,4,4′-三羟基二苯酮、2,3,4,4′-四羟基二苯酮、2,2′,4,4′-四羟基二苯酮和2,2′,3,4,6′-五羟基二苯酮；羟基苯基烷烃，如双(2,4-二羟基苯基)甲烷、双(2,3,4-三羟基苯基)甲烷和双(2,4-二羟基苯基)丙烷；和羟基三苯基甲烷，如4,4′,3″,4″-四羟基-3,5,3′,5′-四甲基三苯基甲烷和4,4′,2″,3″,4″-五羟基-3,5,3′,5′-四甲基三苯基甲烷。这些光敏剂可以单独使用或以两种或多种组合使用。
具有醌二叠氮化物基团的光敏剂的用量通常为5～50重量份，优选10～40重量份，以100重量份碱溶性树脂计。
本发明的酚醛清漆树脂可为光敏性酚醛清漆树脂。这种光敏性酚醛清漆树脂可通过上述碱溶性酚醛清漆树脂与具有醌二叠氮化物基团的光敏剂进行反应从而取代所述酚醛清漆树脂的羟基而获得。
用于溶解本发明辐射敏感性酚醛清漆树脂的溶剂包括：乙二醇单烷基醚，如乙二醇单甲基醚和乙二醇单乙基醚；乙二醇单烷基醚乙酸酯，如乙二醇单甲基醚乙酸酯和乙二醇单乙基醚乙酸酯；丙二醇单烷基醚，如丙二醇单甲基醚和丙二醇单乙基醚；丙二醇单烷基醚乙酸酯，如丙二醇单甲基醚乙酸酯和丙二醇单乙基醚乙酸酯；乳酸酯，如乳酸甲酯和乳酸乙酯；芳烃，如甲苯和二甲苯；酮如甲乙酮、2-庚酮和环己酮；酰胺如N,N-二甲基乙酰胺和N-甲基吡咯烷酮；内酯如γ-丁内酯。这些溶剂可以单独使用或以两种或多种的混合物使用。
如果需要的话，在本发明的辐射敏感性树脂组合物中还可选择性掺入常规用作辐射敏感性树脂组合物添加剂的染料、粘合助剂、表面活性剂等。染料的实例包括：甲基紫、结晶紫、孔雀石绿等；粘合助剂的实例包括：烷基咪唑啉、丁酸、烷基酸(alkylacid)、多羟基苯乙烯、聚乙烯基甲基醚、叔丁基酚醛清漆、环氧硅烷、环氧聚合物、硅烷等；表面活性剂的实例包括：非离子表面活性剂，如聚乙二醇(如聚丙二醇)和其衍生物(如聚氧乙烯月桂基醚)等，含氟表面活性剂，如Fluorad(商品名；由Sumitomo3M Co.生产)、Megafac(商品名；由Dainippon Ink Co.生产)、Sulfuron(商品名；由Asahi Glass Co.生产)或有机硅氧烷表面活性剂如KP341(商品名；Shin-etsu Kagaku Kogyo K.K.生产)。
进而，本发明的辐射敏感性树脂组合物可与诸如TiN、SiN、SiON的无机抗反射涂料或诸如AZBARLi、AZBARLiⅡ[由克拉瑞特(日本)株式会社生产]的有机抗反射涂料混合使用。
本发明的辐射敏感性树脂组合物可通过旋涂法等涂敷至衬底如具有抗反射涂层的硅片上，将涂敷了辐射敏感性树脂组合物的衬底进行烘烤以形成辐射敏感性树脂涂层。在形成光刻图时，在其上涂敷了辐射敏感性树脂涂层的衬底再进行辐射照射，如采用紫外线、远紫外线、X-射线或电子束，并用碱性显影溶剂进行显影，形成具有高分辨率和优异图案轮廓的正型光刻图。
最佳实施方式
通过下述实施例进一步说明本发明，但是，所述实施例并非对本发明保护范围的限制。
合成实施例1：合成原料酚醛清漆树脂A-1
将58.69的间甲酚、42.89的对甲酚、15.89的2,5-二甲苯酚、6.1g的2,4-二甲苯酚、85.29的37％的***水溶液及0.9869的草酸加至1L的可分开的烧瓶中，所述烧瓶备有搅拌器、冷凝器和温度计，在搅拌下反应在95～100℃下进行5小时。此后，将温度升温至180℃并蒸1小时以蒸出水和未反应的单体，再将压力逐渐减至10mmHg并升高温度至195℃以尽可能多地除去水、未反应的单体、甲醛、草酸，然后，降低温度至大约室温以回收酚醛清漆树脂。在下述“测量酚醛清漆A-1树脂分子量的条件”下在280nm的检测波长处进行凝胶渗透色谱(GPC)，获得如图2所示的结果。从结果可以看出，酚醛清漆树脂A-1的重均分子量(Mw)为10,900，在分子量区域轮廓中面积比A1∶B1∶C1为0.267∶0.635∶0.098。
此外，在下述过程中，酚醛清漆树脂的分子量以与合成实施例1相同的方式通过GPC测量。
(测量酚醛清漆树脂分子量的条件)
采用GPC柱测量酚醛清漆树脂的分子量(一个KF-804柱，两个KF-802柱和一个KF-801柱，由Showa Denko Co.生产)，流速为1.0ml/min，柱温为40℃，THF(四氢呋喃)的流动相用于液相色谱。
合成实施例2：通过薄膜蒸馏法由酚醛清漆树脂A-1除去低分子物质获得酚醛清漆树脂A-2
将400g在合成实施例1制得的酚醛清漆树脂A-1溶解于600g的丙二醇单甲基醚乙酸酯(PGMEA)中，向该溶液中加入纯水，将混合物搅拌15分钟。在大约室温下放置30分钟后，取出PGMEA树脂溶液层，使其流过薄膜蒸馏装置(由Hitachi Ltd.生产)，薄膜蒸馏在260℃及15mmHg的减压下进行，连接滴下PGMEA树脂溶液以回收酚醛清漆树脂A-2。按照GPC测量酚醛清漆树脂A-2的分子量，结果如图3所示。测量结果表明，酚醛清漆树脂A-2的重均分子量(Mw)为14,800，分子量区域A2∶B2∶C2的峰面积比为0.304∶0.641∶0.055。
合成实施例3：通过溶剂分馏法由酚醛清漆树脂A-1除去低分子物质荻得酚醛清漆树脂A-3
将450g在合成实施例1制得的酚醛清漆树脂A-1溶解于1150g的PGMEA中，并倒入3升的烧杯中。在用搅拌器于500rpm下搅拌下，逐渐加入1071g的庚烷，将转速增至4000rpm，再搅拌30分钟。然后，在室温下放置12小时，将该溶液转移至分液漏斗中，分离出PGMEA树脂溶液层(下层)，通过蒸发器除去残余在PGMEA树脂溶液中的庚烷，获得酚醛清漆树脂A-3的PGMEA溶液。按照GPC测量酚醛清漆树脂A-3的分子量，结果如图4所示。测量结果表明，酚醛清漆树脂A-3的重均分子量(Mw)为18,500，分子量区域A2∶B2∶C2的峰面积比为0.372∶0.573∶0.055。由面积比，计算在合成实施例1至3中获得的树脂A-1、A-2和A-3的B2/B1和C2/(A2+B2+C2)值，结果示于表1。
以下述方式进行A-1、A-2和A-3的溶液速度的测量和计算。结果示于表1。
(酚醛清漆树脂A-1、A-2和A-3的溶液速度的测量和计算)
将合成实施例1中获得的20g的酚醛清漆树脂A-1、A-2和A-3分别溶解于80g的丙二醇单甲基醚乙酸酯中，然后用0.5μm的聚四氟乙烯过滤器进行过滤。将形成的每种树脂溶液用旋涂器(LARC ULTIMA-1000，由Lithotec Japan Co.制备)涂敷至用HMDS处理过的4英寸硅片上，在加热板上于100℃下烘烤90秒，形成1μm厚的树脂涂层。涂层的厚度通过膜厚度测量装置(Lambda Ace，由Dainippon Screen Co.制备)进行精确测量。此后，将所获得的硅片浸于碱性显影剂溶液[AZ300MIF显影剂(2.38wt％的氢氧化四甲基胺水溶液)，所述显影剂由克拉瑞特(日本)株式会社制备]中并保持在23℃下，测量在硅片上的树脂涂层完全溶解所需的时间。酚醛清漆树脂的溶解速度由所测量的溶解时间数据计算。
合成实施例4：合成光敏剂B-1
将1mol的2,3,4,4′-四羟基二苯酮用作一种酚，将1,2-萘醌二叠氮化物-5-磺酰氯溶解于3倍摩尔量的丙酮中制备10％的溶液。以1,2-萘醌二叠氮化物-5-磺酰氯计，向其中滴加1.1倍摩尔当量的三乙胺，滴加过程中保持反应溶液的温度为20～23℃，随后再搅拌30分钟。滤出沉淀出来的三乙胺盐酸盐，将反应溶液倒入10倍量的0.1N的盐酸水溶液中。过滤收集沉淀出来的固体，用超纯水洗涤，然后在真空下干燥，获得萘醌二叠氮化物磺酸酯B-1的光敏剂。
实施例1、比较例1和2
将在合成实施例中获得的酚醛清漆树脂A-1至A-3和光敏剂B-1以下表1所述的比例混合，向其中加入表面活性剂MegafacR-08(由Dainippon Ink Chemical Industry,Co.生产)，将形成的混合物分别溶解于PGMEA中。然后，将每一种溶液通过0.5μm的膜聚四氟乙烯过滤器过滤，获得实施例1和比较例1和2的辐射敏感性树脂组合物。
采用旋涂器将这些辐射敏感性树脂组合物的每一种涂敷至HMDS-处理过的4英寸硅片上，所述旋涂器为由Lithotech JapanCo.制备的LARC ULTIMA-1000，对涂层于加热板上在100℃下预烘烤90秒，形成1.5μm厚的光刻胶涂层。涂层的厚度采用膜厚测量装置进行测量，所述装置为由Dainippon Screen Co.制造的Lambda Ace。然后，将每一种光刻胶涂层采用曝光波长为436nm(DSW6400,NA=0.42，由GCA Co.制造)的g-线曝光装置以逐步改变曝光量进行曝光。曝光后，按照桨式法(paddlemethod)将硅片浸入碱性显影剂(AZ300MIF显影剂，2.38wt％氢氧化四甲基胺水溶液)[由克拉瑞特(日本)株式会社制造]中于23℃下显影60秒获得光刻图。然后再次测量涂层的厚度。
接下来，将所获得的每一种光刻图在电子显微镜(SEM)扫描下进行观察，以观察敏感性和耐热性。
此后，以下述方式评价敏感性、涂层残余比和耐热性。
(1)敏感性
必须分辨10-μm线-和-空间(L/S)的最小曝光能量取为Eth(临界能量)，采用设计尺寸的掩模形成10-μm线-和-空间(L/S)的曝光能量取为E0(最佳能量)。
(2)涂层-残余比
按照下式计算的值被取作涂层-残余比(％)。
涂层-残余比=[(在曝光前的厚度-在显影后在未曝光区中涂层的厚度)/涂层在曝光前的厚度]×100
(3)耐热性
将在其上具有10-μm L/S图案的硅片在加热板上改变温度加热120秒。将线图案的截面图在SEM下进行观察，在光刻图的顶部变圆的温度被取作表明耐热性的温度。
表1
| 酚醛清漆树脂 | 溶解速度(/s) | 光敏剂 | 敏感性(mJ/cm2) | 涂层-残余比(％) | 耐热性(℃) | GPC图中的面积比 | |||||
| 化合物 | 加入量(重量份) | 化合物 | 加入量(重量份) | Eth | Eo | B2/B1 | C2/(A2+B2+C2) | ||||
| 实施例1 | A-2 | 100 | 183 | B-1 | 22.5 | 40.9 | 51.6 | 99.1 | 130 | 1.01 | 0.055 |
| 比较例1 | A-1 | 100 | 415 | B-1 | 22.5 | 3.1 | 3.9 | 58.7 | 115 | - | 0.098 |
| 比较例2 | A-3 | 100 | 95 | B-1 | 22.5 | 59.2 | 70.2 | 98.9 | 130 | 0.90 | 0.055 |
从以上描述中可以看出，涂层-残余比的降低可通过采用薄膜蒸馏法选择性除去单体和二聚物以使单体和二聚物在酚醛清漆树脂中的量落在给定范围内而避免。进而，敏感性的减少也可避免，这是因为，与采用溶剂分馏法除去单体和二聚物的情形相比，中分子区域的组份损失减少，因此，辐射敏感性树脂组合物具有优良的平衡性能。
发明优点
如前所述，本发明的辐射敏感性树脂组合物具有优异的、光刻胶需要的性能平衡的性质，如敏感性、图案轮廓和耐热性。
工业实用性
本发明的辐射敏感性树脂组合物可在生产半导体如LS1，制备在LCD仪表板的显示表面，生产用于热位差等的电路衬底等中用作光刻胶材料。
Claims (4)
1．一种包含碱溶性树脂和具有醌二叠氮化物基团的光敏剂的辐射敏感性树脂组合物，其中，碱溶性树脂为一种通过薄膜蒸馏法处理的酚醛清漆树脂。
2．根据权利要求1的辐射敏感性树脂组合物，其中，所述用薄膜蒸馏法处理的酚醛清漆树脂显示出：在凝胶渗透色谱中，在280nm下检测，在其峰面积中具有下述比例：
B2/B1≥0.95；C2/(A2+B2+C2)≤0.060其中，A1为原料酚醛清漆树脂进行分级处理前的高分子区域，B1为原料酚醛清漆树脂进行分馏处理前的中分子区域，C1为原料酚醛清漆树脂进行分级处理前的单体/二聚物区域，而A2、B2和C2则分别为酚醛清漆树脂进行分馏处理后的对应区域。
3．根据权利要求1的辐射敏感性树脂组合物，其中，用薄膜蒸馏法处理过的酚醛清漆树脂的平均分子量为2,000～25,000，按照聚苯乙烯标准测量。
4．根据权利要求1的辐射敏感性树脂组合物，其中，用薄膜蒸馏法处理过的酚醛清漆树脂在2.38wt％氢氧化四甲基胺水溶液的溶解速度为100埃/秒或更大。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP96352/99 | 1999-04-02 | ||
| JP96352/1999 | 1999-04-02 | ||
| JP9635299A JP4068260B2 (ja) | 1999-04-02 | 1999-04-02 | 感放射線性樹脂組成物 |
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| CN1297542A true CN1297542A (zh) | 2001-05-30 |
| CN1226669C CN1226669C (zh) | 2005-11-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB008004498A Expired - Fee Related CN1226669C (zh) | 1999-04-02 | 2000-03-03 | 辐射敏感性树脂组合物 |
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| Country | Link |
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| US (1) | US6384103B1 (zh) |
| EP (1) | EP1085378A4 (zh) |
| JP (1) | JP4068260B2 (zh) |
| KR (1) | KR100705302B1 (zh) |
| CN (1) | CN1226669C (zh) |
| MY (1) | MY122637A (zh) |
| TW (1) | TWI250380B (zh) |
| WO (1) | WO2000060416A1 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE10084285T1 (de) * | 1999-12-27 | 2002-04-11 | Polyplastics Co | Flammwidrige Harzzusammensetzung |
| JP4554122B2 (ja) * | 2001-08-06 | 2010-09-29 | 東京応化工業株式会社 | 化学増幅型ポジ型液晶素子用レジスト組成物 |
| KR100512171B1 (ko) * | 2003-01-24 | 2005-09-02 | 삼성전자주식회사 | 하층 레지스트용 조성물 |
| JP3977307B2 (ja) * | 2003-09-18 | 2007-09-19 | 東京応化工業株式会社 | ポジ型フォトレジスト組成物及びレジストパターン形成方法 |
| JP4929733B2 (ja) * | 2005-01-28 | 2012-05-09 | 住友ベークライト株式会社 | ノボラック型フェノール樹脂の製造方法 |
| US20170082923A1 (en) * | 2014-06-12 | 2017-03-23 | Dic Corporation | Photosensitive composition for permanent films, resist material and coating film |
| JP6621233B2 (ja) * | 2014-07-25 | 2019-12-18 | 東京応化工業株式会社 | 有機ｅｌ表示素子における絶縁膜形成用の感光性樹脂組成物 |
| TWI678596B (zh) * | 2018-09-13 | 2019-12-01 | 新應材股份有限公司 | 正型光阻組成物及圖案化聚醯亞胺層之形成方法 |
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| JPS5116079B2 (zh) * | 1972-06-13 | 1976-05-21 | ||
| JPS5884814A (ja) * | 1981-11-17 | 1983-05-21 | Dainippon Ink & Chem Inc | ノボラツク型フエノ−ル系樹脂の製造法 |
| DE3751743T2 (de) * | 1986-03-28 | 1996-11-14 | Japan Synthetic Rubber Co Ltd | Positiv arbeitende photoempfindliche Kunststoffzusammensetzung |
| JP2590342B2 (ja) * | 1986-11-08 | 1997-03-12 | 住友化学工業株式会社 | ポジ型フォトレジスト用ノボラック樹脂及びそれを含有するポジ型フォトレジスト組成物 |
| US5753406A (en) * | 1988-10-18 | 1998-05-19 | Japan Synthetic Rubber Co., Ltd. | Radiation-sensitive resin composition |
| CA2023791A1 (en) * | 1989-08-24 | 1991-02-25 | Ayako Ida | Radiation-sensitive positive resist composition |
| US5132376A (en) * | 1989-09-08 | 1992-07-21 | Ocg Microelectronic Materials, Inc. | Process for selective removal of dimeric species from phenolic polymers |
| JPH03230164A (ja) * | 1990-02-05 | 1991-10-14 | Toray Ind Inc | ポジ型フォトレジスト組成物 |
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1999
- 1999-04-02 JP JP9635299A patent/JP4068260B2/ja not_active Expired - Fee Related
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2000
- 2000-03-03 WO PCT/JP2000/001259 patent/WO2000060416A1/ja not_active Application Discontinuation
- 2000-03-03 US US09/701,851 patent/US6384103B1/en not_active Expired - Fee Related
- 2000-03-03 KR KR1020007013598A patent/KR100705302B1/ko not_active IP Right Cessation
- 2000-03-03 EP EP00906656A patent/EP1085378A4/en not_active Withdrawn
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| Publication number | Publication date |
|---|---|
| US6384103B1 (en) | 2002-05-07 |
| KR20010043974A (ko) | 2001-05-25 |
| WO2000060416A1 (fr) | 2000-10-12 |
| CN1226669C (zh) | 2005-11-09 |
| JP4068260B2 (ja) | 2008-03-26 |
| KR100705302B1 (ko) | 2007-04-11 |
| JP2000292919A (ja) | 2000-10-20 |
| EP1085378A1 (en) | 2001-03-21 |
| EP1085378A4 (en) | 2003-01-02 |
| MY122637A (en) | 2006-04-29 |
| TWI250380B (en) | 2006-03-01 |
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