TW201811806A - 抗蝕劑剝離液組合物、顯示器基板及其製造方法 - Google Patents
抗蝕劑剝離液組合物、顯示器基板及其製造方法 Download PDFInfo
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- TW201811806A TW201811806A TW106114964A TW106114964A TW201811806A TW 201811806 A TW201811806 A TW 201811806A TW 106114964 A TW106114964 A TW 106114964A TW 106114964 A TW106114964 A TW 106114964A TW 201811806 A TW201811806 A TW 201811806A
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- Prior art keywords
- acid
- methyl
- ammonium
- liquid composition
- stripping liquid
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 239000000758 substrate Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000005260 corrosion Methods 0.000 title abstract description 23
- 230000007797 corrosion Effects 0.000 title abstract description 22
- 229910052750 molybdenum Inorganic materials 0.000 title description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title description 8
- 239000011733 molybdenum Substances 0.000 title description 8
- -1 aminoalkyl silane Chemical compound 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 11
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 29
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 10
- 239000012964 benzotriazole Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000002798 polar solvent Substances 0.000 claims description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- NSQYXCMVSMXQRN-UHFFFAOYSA-N 5-methyl-4,5,6,7-tetrahydro-2h-benzotriazole Chemical compound C1C(C)CCC2=NNN=C21 NSQYXCMVSMXQRN-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims description 4
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- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 3
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 3
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- XKGUZGHMWUIYDR-UHFFFAOYSA-N benzyl n-(3-fluoro-4-morpholin-4-ylphenyl)carbamate Chemical compound C=1C=C(N2CCOCC2)C(F)=CC=1NC(=O)OCC1=CC=CC=C1 XKGUZGHMWUIYDR-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 3
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 3
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003586 protic polar solvent Substances 0.000 claims description 3
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- NFJSYLMJBNUDNG-UHFFFAOYSA-N 1,3-dipropylimidazolidin-2-one Chemical compound CCCN1CCN(CCC)C1=O NFJSYLMJBNUDNG-UHFFFAOYSA-N 0.000 claims description 2
- KQIXMZWXFFHRAQ-UHFFFAOYSA-N 1-(2-hydroxybutylamino)butan-2-ol Chemical compound CCC(O)CNCC(O)CC KQIXMZWXFFHRAQ-UHFFFAOYSA-N 0.000 claims description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 2
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- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 claims description 2
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims description 2
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- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 2
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- WDGIOFVKXHIBHX-UHFFFAOYSA-N 4,6-dimethyl-4,5,6,7-tetrahydro-2H-benzotriazole Chemical compound CC1CC(CC=2NN=NC21)C WDGIOFVKXHIBHX-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 claims description 2
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- GYUILFHTAOHDDJ-UHFFFAOYSA-N 4-methyl-5-(2-methylphenyl)-2h-triazole Chemical compound N1N=NC(C=2C(=CC=CC=2)C)=C1C GYUILFHTAOHDDJ-UHFFFAOYSA-N 0.000 claims description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 239000001729 Ammonium fumarate Substances 0.000 claims description 2
- 239000004251 Ammonium lactate Substances 0.000 claims description 2
- 239000001715 Ammonium malate Substances 0.000 claims description 2
- HVHTXGMZXGWLFR-UHFFFAOYSA-N CC1CC2=C(NN=N2)CC1C Chemical compound CC1CC2=C(NN=N2)CC1C HVHTXGMZXGWLFR-UHFFFAOYSA-N 0.000 claims description 2
- LYQBBEFEQFFWLR-UHFFFAOYSA-N CC1CCCC=2NN=NC=21 Chemical compound CC1CCCC=2NN=NC=21 LYQBBEFEQFFWLR-UHFFFAOYSA-N 0.000 claims description 2
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- PVCJKHHOXFKFRP-UHFFFAOYSA-N N-acetylethanolamine Chemical compound CC(=O)NCCO PVCJKHHOXFKFRP-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 2
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- 229940043376 ammonium acetate Drugs 0.000 claims description 2
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- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- CKKXWJDFFQPBQL-SEPHDYHBSA-N azane;(e)-but-2-enedioic acid Chemical compound N.N.OC(=O)\C=C\C(O)=O CKKXWJDFFQPBQL-SEPHDYHBSA-N 0.000 claims description 2
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- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 claims description 2
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- NGPGDYLVALNKEG-UHFFFAOYSA-N azanium;azane;2,3,4-trihydroxy-4-oxobutanoate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)C(O)C([O-])=O NGPGDYLVALNKEG-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- CKKXWJDFFQPBQL-UAIGNFCESA-N diazanium;(z)-but-2-enedioate Chemical compound [NH4+].[NH4+].[O-]C(=O)\C=C/C([O-])=O CKKXWJDFFQPBQL-UAIGNFCESA-N 0.000 claims description 2
- OKUGAOMPLZNWRT-UHFFFAOYSA-N diazanium;pentanedioate Chemical compound [NH4+].[NH4+].[O-]C(=O)CCCC([O-])=O OKUGAOMPLZNWRT-UHFFFAOYSA-N 0.000 claims description 2
- FRRMMWJCHSFNSG-UHFFFAOYSA-N diazanium;propanedioate Chemical compound [NH4+].[NH4+].[O-]C(=O)CC([O-])=O FRRMMWJCHSFNSG-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
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- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
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Abstract
本發明提供抗蝕劑剝離液組合物、顯示器基板及其製造方法，所述抗蝕劑剝離液組合物的特徵在於，包含(a)具有下述化學式1的結構的胺基烷基矽烷系化合物、(b)烷醇胺、和(c)極性有機溶劑。下述化學式1中，R1
、R2
和R3
各自獨立地為碳原子數1~4的烷基，R4
為碳原子數1~5的伸烷基，及R5
和R6
各自獨立地為氫原子、碳原子數1~5的烷基、羥基或碳原子數1~4的烷氧基，在R5
為羥基或烷氧基的情況下，R6
為氫原子或烷基，在R6
為羥基或烷氧基的情況下，R5
為氫原子或烷基。 [化學式1]
Description
發明領域 本發明涉及應用防電偶及縫隙腐蝕能力優異的胺基烷基矽烷系化合物的抗蝕劑剝離液組合物，使用其製造的顯示器基板的製造方法及由其製造的顯示器基板。
發明背景 近年來，隨著顯示器基板的高解析度呈現要求增加，持續進行著使每單位面積的像素數增加的努力。根據這樣的趨勢，要求配線寬度的減小。為了應對於此，導入幹式蝕刻工序等工序條件也變得越來越苛刻。此外，由於平板顯示裝置的大型化，也要求配線中的信號速度加快，因此電阻率比鋁低的銅被用作配線材料。受此影響，對於作為抗蝕劑去除工序的剝離工序中所使用的剝離液的需求性能也變高。具體而言，對於針對金屬配線的腐蝕抑制力等，要求相當高水準的剝離特性。特別是，除了鋁以外，也要求對於銅的腐蝕抑制能力，為了確保價格競爭力，也要求基板的處理張數增加之類的經濟性。應對如上所述的業界的需求，公開了新技術。
比如，韓國註冊專利10-1557778中公開了包含烷醇胺、有機溶劑等的抗蝕劑剝離液組合物，但沒有改善針對包含鉬等金屬的下部金屬膜或金屬配線等的防腐蝕力。 現有技術文獻 專利文獻
專利文獻1：韓國註冊專利第10-1557778號
發明概要 所要解決的課題 本發明是用於解決如上問題的發明，其目的在於，提供對於包含鉬的下部金屬膜或金屬配線的防腐蝕力優異，且表現出高剝離力的抗蝕劑剝離液組合物，使用其製造的顯示器基板的製造方法及由其製造的顯示器基板。 解決課題的方法
為了達成上述目的，本發明提供一種抗蝕劑剝離液組合物，其特徵在於，包含：(a)具有下述化學式1的結構的胺基烷基矽烷系化合物、(b)烷醇胺、和(c)極性有機溶劑，但不包含氫氧化銨。
本發明提供一種顯示器基板的製造方法，其包括使用上述抗蝕劑剝離液組合物來清洗顯示器基板的工序。
此外，本發明提供由上述製造方法製造的顯示器基板。 發明效果
本發明的抗蝕劑剝離液組合物使用在去離子水及極性溶劑中溶解力優異的胺基烷基矽烷系化合物，因而不會使包含鋁、銅、鎢、鉬、鈦和鈮的下部金屬膜或金屬配線發生腐蝕，且具有表現高剝離力的效果。
具體實施方式 本發明涉及抗蝕劑剝離液組合物、使用其製造的顯示器基板的製造方法及由該方法製造的顯示器基板。
本發明的抗蝕劑剝離液組合物的特徵在於，包含(a)胺基烷基矽烷系化合物、(b)烷醇胺和(c)極性有機溶劑，且不包含氫氧化銨，特別是由於使用在去離子水及極性溶劑中溶解力優異的胺基烷基矽烷系化合物，因而不會使鋁、銅、鎢、鉬、鈦及包含它們的下部金屬膜或金屬配線發生腐蝕，具有表現高剝離力的效果。本發明的抗蝕劑剝離液組合物可以進一步包含(d)防腐蝕劑。
以下，按構成詳細說明本發明的內容。 (a) 胺基烷基矽烷系化合物
本發明中使用的(a)胺基烷基矽烷系化合物具有下述化學式1的結構。 [化學式1]
上述化學式1中， R1
、R2
和R3
各自獨立地為碳原子數1~4的烷基， R4
為碳原子數1~5的伸烷基， R5
和R6
各自獨立地為氫原子、碳原子數1~5的烷基、羥基或碳原子數1~4的烷氧基，在R5
為羥基或烷氧基的情況下，R6
為氫原子或烷基，在R6
為羥基或烷氧基的情況下，R5
為氫原子或烷基。 上述碳原子數1~4的烷基在具有3個以上碳原子的情況下，可以為直鏈或支鏈狀。 作為化學式1所表示的(a)胺基烷基矽烷系化合物的種類，優選可以舉出(2-胺基乙基)三乙氧基矽烷、(3-胺基丙基)三甲氧基矽烷、(3-胺基丙基)三乙氧基矽烷等，它們可以單獨或將兩種以上混合使用。
此外，本發明中，上述(a)胺基烷基矽烷系化合物中可以進一步添加(3-胺基丙基)矽烷三醇等化合物而使用。
本發明的(a)胺基烷基矽烷系化合物防止抗蝕劑剝離中可能發生的金屬的腐蝕的能力優異，尤其通過實驗確認到在包含鋁、鉬、以及銅和鉬的合金中所發生的電偶腐蝕及縫隙腐蝕的防腐蝕力優異。
相對於組合物總重量，上述化學式1所表示的(a)胺基烷基矽烷系化合物的含量優選為0.001重量% ~3.0重量%，更優選為0.005重量%~1.0重量%。如果低於0.001重量%，則在剝離或利用去離子水的沖洗工序中金屬配線可能發生腐蝕，在超過3.0重量%的情況下，無法獲得防腐蝕劑含量增加所帶來的腐蝕防止效果的提高，因而在經濟方面不佳。 (b) 烷醇胺
本發明的烷醇胺發揮如下作用：在幹式或濕式蝕刻、灰化(ashing)或離子注入工序(ion implant processing)等各種工序條件下，有效地滲透至被改性或被交聯的抗蝕劑(resist)的高分子基體中，破壞存在於分子內或分子間的結合。此外，在殘留於基板上的抗蝕劑內的結構上脆弱的部分形成空隙，使抗蝕劑改性為無定形的高分子凝膠(gel)塊狀態，從而能夠使附著於基板上部的抗蝕劑被容易地去除。
上述烷醇胺可以舉出單乙醇胺、二乙醇胺、三乙醇胺、單丙醇胺、2-胺基乙醇、2-(乙基胺基)乙醇、2-(甲基胺基)乙醇、N-甲基二乙醇胺、N,N-二甲基乙醇胺、N,N-二乙基胺基乙醇、2-(2-胺基乙基胺基)-1-乙醇、1-胺基-2-丙醇、2-胺基-1-丙醇、3-胺基-1-丙醇、4-胺基-1-丁醇、二丁醇胺、(甲氧基甲基)二乙醇胺、(羥基乙基氧基甲基)二乙基胺、甲基(甲氧基甲基)胺基乙醇、甲基(丁氧基甲基)胺基乙醇、2-(2-胺基乙氧基)乙醇、1-(2-羥基乙基)哌嗪、1-(2-羥基乙基)甲基哌嗪、N-(2-羥基乙基)嗎啉、N-(3-羥基丙基)嗎啉等，它們可以單獨或將兩種以上混合使用。但是，本發明可以不包含氫氧化銨。在包含氫氧化銨的情況下，可能會對Mo或Mo合金膜質產生侵蝕(Attack)，尤其優選不包含四甲基氫氧化銨。
相對於整體組合物總重量，本發明的(b)烷醇胺的含量優選為0.1~20.0 重量%，更優選為0.5~10.0重量%。如果低於0.1 重量%，則可能發生抗蝕劑去除力降低，如果超過20.0重量%，則無法獲得烷醇胺含量增加所來的抗蝕劑去除力提高的效果而不經濟，而且可能發生使針對金屬膜質的腐蝕水準提高的問題。 (c) 極性有機溶劑
本發明中使用的(c)極性有機溶劑可以舉出質子性極性溶劑和非質子性極性溶劑，它們可以單獨或將兩種以上混合使用。作為上述質子性極性溶劑的優選的例子，可以舉出乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單異丙基醚、乙二醇單丁基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單異丙基醚、二乙二醇單丁基醚、三乙二醇單甲基醚、三乙二醇單乙基醚、三乙二醇單異丙基醚、三乙二醇單丁基醚、聚乙二醇、聚丙二醇、聚乙二醇單甲基醚、聚乙二醇單丁基醚、丙二醇單甲基醚、二丙二醇單甲基醚、三丙二醇單甲基醚等伸烷基二醇單烷基醚、丙二醇單甲基醚乙酸酯和四氫糠醇等，它們可以單獨或將兩種以上混合使用。
作為上述非質子性極性溶劑的優選的例子，可以舉出Ｎ-甲基吡咯烷酮(NMP)、Ｎ-乙基吡咯烷酮等吡咯烷酮化合物；1,3-二甲基-2-咪唑烷酮、1,3-二丙基-2-咪唑烷酮等咪唑烷酮化合物；γ-丁內酯等內酯化合物；二甲基亞碸(DMSO)、環丁碸等亞碸化合物；磷酸三乙酯、磷酸三丁酯等磷酸酯化合物；碳酸二甲酯、碳酸亞乙酯等碳酸酯化合物；甲醯胺、N-甲基甲醯胺、N-乙基甲醯胺、N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、乙醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、N-(2-羥基乙基)乙醯胺、N,N-二甲基丙醯胺、3-甲氧基-N,N-二甲基丙醯胺、3-(2-乙基己基氧基)-N,N-二甲基丙醯胺、3-丁氧基-N,N-二甲基丙醯胺等醯胺化合物，它們可以單獨或將兩種以上混合使用。
上述(c)極性有機溶劑發揮使凝膠化的抗蝕劑高分子溶解的作用，此外在抗蝕劑剝離之後去離子水的沖洗過程中使利用水的剝離液的去除順利進行，從而使剝離液以及所溶解的抗蝕劑的再吸附/再附著最小化。為了適當的剝離力，優選上述(c)極性有機溶劑的沸點既不過高也不過低，且可以混合使用。上述極性有機溶劑可以根據剝離工序中所追加要求的性能而追加。
相對於整體組合物總重量，上述(c)極性有機溶劑的含量為75.0~99.8重量%是適當的。如果低於75.0重量%，則可能發生溶解力降低，在利用去離子水的沖洗工序中可能發生抗蝕劑的再吸附/再附著。此外，如果超過99.8重量%，則(b)烷醇胺的含量相對減少而剝離力可能降低。 (d) 防腐蝕劑
本發明的組合物可以進一步包含(d)防腐蝕劑，具體而言，本發明的防腐蝕劑可以舉出：甲酸、乙酸、丙酸之類的單羧酸；草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、馬來酸、富馬酸、戊烯二酸之類的二羧酸；偏苯三酸、丙三羧酸之類的三羧酸；羥基乙酸、乳酸、水楊酸、蘋果酸、酒石酸、檸檬酸、葡糖酸和羥基羧酸等有機酸類；琥珀酸醯胺酯、蘋果酸醯胺酯、馬來酸醯胺酯、富馬酸醯胺酯、草酸醯胺酯、丙二酸醯胺酯、戊二酸醯胺酯、乙酸醯胺酯、乳酸醯胺酯、檸檬酸醯胺酯、酒石酸醯胺酯、葡糖酸醯胺酯、甲酸醯胺酯和尿酸醯胺酯等有機酸醯胺酯類；苯并三唑、甲苯基三唑、甲基甲苯基三唑、2,2'-[[[苯并三唑]甲基]亞胺基]雙乙醇、2,2'-[[[甲基-1氫-苯并三唑-1-基]甲基]亞胺基]雙甲醇、2,2'-[[[乙基-1氫-苯并三唑-1-基]甲基]亞胺基]雙乙醇、2,2'-[[[甲基-1氫-苯并三唑-1-基]甲基]亞胺基]雙乙醇、2,2'-[[[甲基-1氫-苯并三唑-1-基]甲基]亞胺基]雙羧酸、2,2'-[[[甲基-1氫-苯并三唑-1-基]甲基]亞胺基]雙甲胺和2,2'-[[[胺-1氫-苯并三唑-1-基]甲基]亞胺基]雙乙醇、4-甲基-1-氫-苯并三唑、6-甲基-4,5,6,7-四氫-1H-苯并[1,2,3]三唑、4-甲基-4,5,6,7-四氫-1H-苯并[1,2,3]三唑、5-甲基-4,5,6,7-四氫-1H-苯并[1,2,3]三唑、5,6-二甲基-4,5,6,7-四氫-1H-苯并[1,2,3]三唑、4,6-二甲基-4,5,6,7-四氫-1H-苯并[1,2,3]三唑和5-甲基-1-氫-苯并三唑之類的唑系化合物；2,6-二甲基苯酚、2,4,6-三甲基苯酚、2,6-二乙基苯酚、2,6-二乙基-4-甲基苯酚、2,6-二丙基苯酚、2,6-二丙基-4-甲基苯酚、2,6-二叔丁基苯酚、2,4,6-三叔丁基苯酚和2,6-二-叔丁基-4-甲基苯酚之類的對稱型酚系化合物；等，但不限定於此。它們可以單獨或將兩種以上混合使用。
相對於組合物總重量，本發明的(d)防腐蝕劑的含量可以為0.001~1.0重量%。在防腐蝕劑的含量低於0.001重量%的情況下，存在銅表面發生微腐蝕的問題，在含量超過1.0重量%的情況下，無法獲得含量增加所帶來的防腐蝕效果而不經濟。
本發明的抗蝕劑剝離液組合物可以在半導體或電子產品、尤其顯示器用抗蝕劑的去除工序中有效地使用。
即，本發明包含顯示器基板的製造方法及由上述製造方法製造的顯示器基板，該顯示器基板的製造方法包括利用本發明的抗蝕劑剝離液組合物來清洗顯示器基板的工序。
以下，通過實施例更詳細說明本發明。然而，下述實施例僅用於更具體地說明本發明，本發明的範圍不受下述實施例的限定。下述實施例可以在本發明的範圍內被本領域的技術人員合理地修改、變更。 ＜實施例及比較例＞ 抗蝕劑剝離液組合物的製造
將下述表1中記載的成分以相應的混合比進行混合而製造實施例及比較例的抗蝕劑剝離液組合物。 [表1]
註) APTES：(3-胺基丙基)三乙氧基矽烷 APSTO：(3-胺基丙基)矽烷三醇 AEE：2-(2-胺基乙氧基)-1-乙醇 MAE：2-(甲基胺基)乙醇 MDEA：N-甲基二乙醇胺 IME：咪唑烷乙醇 NMF：N-甲基甲醯胺 NEF：N-乙基甲醯胺 NMP：N-甲基吡咯烷酮 MDG：二乙二醇單甲基醚 EDG：二乙二醇單乙基醚 BDG：二乙二醇單丁基醚 MTG：三乙二醇單甲基醚 TTA：甲苯基三唑 MTBT：6-甲基-4,5,6,7-四氫-1H-苯并[1,2,3]三唑 TMAH(25)：四甲基氫氧化銨溶液(H2
O中25 wt.%) ＜實驗例1＞ 剝離液的光致抗蝕劑剝離力評價
為了確認抗蝕劑剝離液組合物的剝離效果，在玻璃基板上塗布1.7μm的正型光致抗蝕劑(DWG-520：本公司PR)後，在170℃在加熱板(Hot plate)上實施10分鐘後烘(Hard bake)而準備基板。將抗蝕劑剝離液組合物以50℃恒定維持溫度後，將上述基板以30秒的間隔浸漬而評價剝離力。之後，為了去除殘留在基板上的剝離液，利用去離子水(DIW；Deilonized water)實施1分鐘清洗，為了去除清洗後殘留在基板上的DIW，利用氮氣將基板完全乾燥。用肉眼確認完成評價的基板，測定抗蝕劑被完全去除的時間，並將該結果示於下述表2中。可以認為時間越短，剝離效果越優異。 ＜實驗例2＞ 剝離液金屬配線防腐蝕力評價
為了進行抗蝕劑剝離液組合物對於金屬配線的腐蝕防止能力評價，根據通常的方法，使用薄膜濺射法在玻璃基板上形成Mo/Al、Cu/X層(X：Ti、Mo、MoTi、MoW、MoNb)。之後，形成光致抗蝕劑圖案，通過濕式蝕刻方式分別準備將金屬膜蝕刻的基板。使用簡易剝離噴灑(Strip Spray)評價設備，使剝離液組合物以60℃恒定維持溫度，對於上述基板以2kgf/cm2
壓力進行2分鐘噴灑剝離，然後使用簡易DIW清洗噴灑設備將上述完成剝離的基板在常溫下以2kgf/cm2
壓力實施3分鐘噴灑清洗。關於完成清洗的基板，使用N2
實施乾燥，將上述剝離工序中實現DIW 清洗和乾燥的工序反覆實施3次，利用電子顯微鏡(SEM，Hitachi S-4700)評價該基板。將該結果示於下述表2中，根據各金屬腐蝕程度，在未觀察到腐蝕時表示為◎，在觀察到少許腐蝕但應用於膜質應用時沒有問題時表示為○，在觀察到腐蝕且應用於膜質時很可能出現問題時表示為△，在觀察到嚴重腐蝕且無法應用於膜質時表示為×。
[表2]
參照上述實驗結果可以確認到，由於本發明的抗蝕劑剝離液組合物使用在去離子水及極性溶劑中溶解力優異的胺基烷基矽烷系化合物， 因而不會使鋁、銅、鎢、鉬、鈦及包含它們的金屬配線發生腐蝕，且具有高剝離力效果。此外，可以確認到，在包含氫氧化銨、即四甲基氫氧化銨的比較例7和8的情況下，侵蝕(attack)Mo或Mo合金膜質而發生了嚴重的腐蝕。
Claims (13)
- 一種抗蝕劑剝離液組合物，其特徵在於，包含： (a)具有下述化學式1的結構的胺基烷基矽烷系化合物、 (b)烷醇胺、和 (c)極性有機溶劑， 且不包含氫氧化銨， 化學式1所述化學式1中， R1 、R2 和R3 各自獨立地為碳原子數1~4的烷基， R4 為碳原子數1~5的伸烷基，及 R5 和R6 各自獨立地為氫原子、碳原子數1~5的烷基、羥基或碳原子數1~4的烷氧基，在R5 為羥基或烷氧基的情況下，R6 為氫原子或烷基，在R6 為羥基或烷氧基的情況下，R5 為氫原子或烷基。
- 如請求項1所述的抗蝕劑剝離液組合物，其特徵在於，進一步包含(d)防腐蝕劑。
- 如請求項2所述的抗蝕劑剝離液組合物，其特徵在於，所述(d)防腐蝕劑為Cu防腐蝕劑。
- 如請求項1所述的抗蝕劑剝離液組合物，其特徵在於，所述(a)胺基烷基矽烷系化合物為(2-胺基乙基)三乙氧基矽烷、(3-胺基丙基)三甲氧基矽烷和(3-胺基丙基)三乙氧基矽烷中的一種以上。
- 如請求項1~4中任一項所述的抗蝕劑剝離液組合物，其特徵在於，所述(b)烷醇胺為單乙醇胺、二乙醇胺、三乙醇胺、單丙醇胺、2-胺基乙醇、2-(乙基胺基)乙醇、2-(甲基胺基)乙醇、N-甲基二乙醇胺、N,N-二甲基乙醇胺、N,N-二乙基胺基乙醇、2-(2-胺基乙基胺基)-1-乙醇、1-胺基-2-丙醇、2-胺基-1-丙醇、3-胺基-1-丙醇、4-胺基-1-丁醇、二丁醇胺、(甲氧基甲基)二乙醇胺、(羥基乙基氧基甲基)二乙基胺、甲基(甲氧基甲基)胺基乙醇、甲基(丁氧基甲基)胺基乙醇、2-(2-胺基乙氧基)乙醇、1-(2-羥基乙基)哌嗪、1-(2-羥基乙基)甲基哌嗪、N-(2-羥基乙基)嗎啉和N-(3-羥基丙基)嗎啉中的一種以上。
- 如請求項1~4中任一項所述的抗蝕劑剝離液組合物，其特徵在於，所述(c)極性有機溶劑為質子性極性溶劑和非質子性極性溶劑中的一種以上。
- 如請求項6所述的抗蝕劑剝離液組合物，其特徵在於，所述質子性極性溶劑為乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單異丙基醚、乙二醇單丁基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單異丙基醚、二乙二醇單丁基醚、三乙二醇單甲基醚、三乙二醇單乙基醚、三乙二醇單異丙基醚、三乙二醇單丁基醚、聚乙二醇單甲基醚、聚乙二醇單丁基醚、丙二醇單甲基醚、二丙二醇單甲基醚、三丙二醇單甲基醚、丙二醇單甲基醚乙酸酯和四氫糠醇中的一種以上。
- 如請求項6所述的抗蝕劑剝離液組合物，其特徵在於，所述非質子性極性溶劑為N-甲基吡咯烷酮、N-乙基吡咯烷酮、1,3-二甲基-2-咪唑烷酮、1,3-二丙基-2-咪唑烷酮、γ-丁內酯、二甲基亞碸、環丁碸、磷酸三乙酯、磷酸三丁酯、碳酸二甲酯、碳酸亞乙酯、甲醯胺、N-甲基甲醯胺、N,N-二甲基甲醯胺、乙醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、N-(2-羥基乙基)乙醯胺、3-甲氧基-N,N-二甲基丙醯胺、3-(2-乙基己基氧基)-N,N-二甲基丙醯胺和3-丁氧基-N,N-二甲基丙醯胺中的一種以上。
- 如請求項2所述的抗蝕劑剝離液組合物，其特徵在於，(d)防腐蝕劑為甲酸、乙酸、丙酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、馬來酸、富馬酸、戊烯二酸、偏苯三酸、丙三羧酸、羥基乙酸、乳酸、水楊酸、蘋果酸、酒石酸、檸檬酸、葡糖酸、羥基羧酸、琥珀酸醯胺酯、蘋果酸醯胺酯、馬來酸醯胺酯、富馬酸醯胺酯、草酸醯胺酯、丙二酸醯胺酯、戊二酸醯胺酯、乙酸醯胺酯、乳酸醯胺酯、檸檬酸醯胺酯、酒石酸醯胺酯、葡糖酸醯胺酯、甲酸醯胺酯、尿酸醯胺酯、苯并三唑、甲苯基三唑、甲基甲苯基三唑、2,2'-[[[苯并三唑]甲基]亞胺基]雙乙醇、2,2'-[[[甲基-1氫-苯并三唑-1-基]甲基]亞胺基]雙甲醇、2,2'-[[[乙基-1氫-苯并三唑-1-基]甲基]亞胺基]雙乙醇、2,2'-[[[甲基-1氫-苯并三唑-1-基]甲基]亞胺基]雙乙醇、2,2'-[[[甲基-1氫-苯并三唑-1-基]甲基]亞胺基]雙羧酸、2,2'-[[[甲基-1氫-苯并三唑-1-基]甲基]亞胺基]雙甲胺、2,2'-[[[胺-1氫-苯并三唑-1-基]甲基]亞胺基]雙乙醇、4-甲基-1-氫-苯并三唑、6-甲基-4,5,6,7-四氫-1H-苯并[1,2,3]三唑、4-甲基-4,5,6,7-四氫-1H-苯并[1,2,3]三唑、5-甲基-4,5,6,7-四氫-1H-苯并[1,2,3]三唑、5,6-二甲基-4,5,6,7-四氫-1H-苯并[1,2,3]三唑、4,6-二甲基-4,5,6,7-四氫-1H-苯并[1,2,3]三唑、5-甲基-1-氫-苯并三唑、2,6-二甲基苯酚、2,4,6-三甲基苯酚、2,6-二乙基苯酚、2,6-二乙基-4-甲基苯酚、2,6-二丙基苯酚、2,6-二丙基-4-甲基苯酚、2,6-二叔丁基苯酚、2,4,6-三叔丁基苯酚和2,6-二叔丁基-4-甲基苯酚中的一種以上。
- 如請求項1所述的抗蝕劑剝離液組合物，相對於組合物總重量，包含： (a)胺基烷基矽烷系化合物0.001~3.0重量%、 (b)烷醇胺化合物0.1~20.0重量%、和 (c)極性有機溶劑75.0~99.8重量%。
- 如請求項10所述的抗蝕劑剝離液組合物，其進一步包含(d)防腐蝕劑0.001~1.0重量%。
- 一種顯示器基板的製造方法，其包括使用請求項1~11中任一項所述的抗蝕劑剝離液組合物來清洗顯示器基板的工序。
- 一種顯示器基板，其由請求項12所述的製造方法來製造。
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