CN107630219A - The manufacture method of metal film etchant and array substrate for display device - Google Patents
The manufacture method of metal film etchant and array substrate for display device Download PDFInfo
- Publication number
- CN107630219A CN107630219A CN201710585309.5A CN201710585309A CN107630219A CN 107630219 A CN107630219 A CN 107630219A CN 201710585309 A CN201710585309 A CN 201710585309A CN 107630219 A CN107630219 A CN 107630219A
- Authority
- CN
- China
- Prior art keywords
- metal film
- acid
- film etchant
- weight
- etching
- 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
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 106
- 239000002184 metal Substances 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000000758 substrate Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000005530 etching Methods 0.000 claims abstract description 87
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000003851 azoles Chemical class 0.000 claims abstract description 18
- -1 imidazole compound Chemical class 0.000 claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 13
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 13
- 229920005862 polyol Polymers 0.000 claims abstract description 13
- 150000003077 polyols Chemical class 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims description 43
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 39
- 229910052802 copper Inorganic materials 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 26
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 21
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims description 16
- 239000011733 molybdenum Substances 0.000 claims description 16
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 150000002460 imidazoles Chemical class 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- PMZBHPUNQNKBOA-UHFFFAOYSA-N 5-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC(C(O)=O)=CC(C(O)=O)=C1 PMZBHPUNQNKBOA-UHFFFAOYSA-N 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 239000004065 semiconductor Substances 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- 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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- AYDQIZKZTQHYIY-UHFFFAOYSA-N OC(=O)C1(C)CC(C(O)=O)=CC=C1 Chemical compound OC(=O)C1(C)CC(C(O)=O)=CC=C1 AYDQIZKZTQHYIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000012212 insulator Substances 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 3
- 229910017665 NH4HF2 Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 235000004279 alanine Nutrition 0.000 claims description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 235000013922 glutamic acid Nutrition 0.000 claims description 3
- 239000004220 glutamic acid Substances 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical group [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 229910000597 tin-copper alloy Inorganic materials 0.000 claims description 3
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 2
- XGIDEUICZZXBFQ-UHFFFAOYSA-N 1h-benzimidazol-2-ylmethanethiol Chemical compound C1=CC=C2NC(CS)=NC2=C1 XGIDEUICZZXBFQ-UHFFFAOYSA-N 0.000 claims description 2
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 claims description 2
- 150000004941 2-phenylimidazoles Chemical class 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- PNWSHHILERSSLF-UHFFFAOYSA-N 4-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC=C(C(O)=O)C=C1C(O)=O PNWSHHILERSSLF-UHFFFAOYSA-N 0.000 claims description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- 229910004039 HBF4 Inorganic materials 0.000 claims description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
- 229910017971 NH4BF4 Inorganic materials 0.000 claims description 2
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 239000004094 surface-active agent Substances 0.000 claims 2
- GTKOKCQMHAGFSM-UHFFFAOYSA-O 1-methyl-2h-tetrazol-1-ium-5-amine Chemical compound C[N+]=1NN=NC=1N GTKOKCQMHAGFSM-UHFFFAOYSA-O 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 229940124277 aminobutyric acid Drugs 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 claims 1
- 230000003628 erosive effect Effects 0.000 abstract description 17
- 238000012545 processing Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 15
- 238000001514 detection method Methods 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 127
- 239000010410 layer Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000004973 liquid crystal related substance Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 4
- IOQLGFCIMRCCNA-UHFFFAOYSA-N 2-(carboxymethylamino)acetic acid Chemical compound OC(=O)CNCC(O)=O.OC(=O)CNCC(O)=O IOQLGFCIMRCCNA-UHFFFAOYSA-N 0.000 description 3
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 2
- 239000003352 sequestering agent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 2
- 150000000178 1,2,4-triazoles Chemical class 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- XOHZHMUQBFJTNH-UHFFFAOYSA-N 1-methyl-2h-tetrazole-5-thione Chemical compound CN1N=NN=C1S XOHZHMUQBFJTNH-UHFFFAOYSA-N 0.000 description 1
- GTKOKCQMHAGFSM-UHFFFAOYSA-N 1-methyltetrazol-5-amine Chemical compound CN1N=NN=C1N GTKOKCQMHAGFSM-UHFFFAOYSA-N 0.000 description 1
- OMAFFHIGWTVZOH-UHFFFAOYSA-N 1-methyltetrazole Chemical group CN1C=NN=N1 OMAFFHIGWTVZOH-UHFFFAOYSA-N 0.000 description 1
- GBIBYNIYVUFTIT-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O.OC(=O)CN(CC(O)=O)CC(O)=O GBIBYNIYVUFTIT-UHFFFAOYSA-N 0.000 description 1
- LPMKADABKPYRHE-UHFFFAOYSA-N 2-aminobutanoic acid Chemical compound CCC(N)C(O)=O.CCC(N)C(O)=O LPMKADABKPYRHE-UHFFFAOYSA-N 0.000 description 1
- YCIRHAGYEUJTFH-UHFFFAOYSA-N 2-imidazol-1-ylethanamine Chemical compound NCCN1C=CN=C1 YCIRHAGYEUJTFH-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 150000008614 2-methylimidazoles Chemical class 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- UDQCDDZBBZNIFA-UHFFFAOYSA-N 4-methyl-1,3-dihydrobenzimidazole-2-thione Chemical compound CC1=CC=CC2=C1NC(=S)N2 UDQCDDZBBZNIFA-UHFFFAOYSA-N 0.000 description 1
- HHDRWGJJZGJSGZ-UHFFFAOYSA-N 5-benzyl-2h-tetrazole Chemical compound C=1C=CC=CC=1CC=1N=NNN=1 HHDRWGJJZGJSGZ-UHFFFAOYSA-N 0.000 description 1
- HYMWOIHFTWVIRV-UHFFFAOYSA-N 5-phenyl-2H-tetrazole Chemical compound C1=CC=CC=C1C1=NN=NN1.C1=CC=CC=C1C1=NN=NN1 HYMWOIHFTWVIRV-UHFFFAOYSA-N 0.000 description 1
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 1
- BFBSNVIURQHDCS-UHFFFAOYSA-N C(COCCOCCO)O.C=C.C=C.C=C Chemical compound C(COCCOCCO)O.C=C.C=C.C=C BFBSNVIURQHDCS-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 108010077895 Sarcosine Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229940049706 benzodiazepine Drugs 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000003244 pro-oxidative effect Effects 0.000 description 1
- 229940043230 sarcosine Drugs 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/34—Alkaline compositions for etching copper or alloys thereof
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/136227—Through-hole connection of the pixel electrode to the active element through an insulation layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
-
- C11D2111/22—
Abstract
The present invention provides a kind of manufacture method of metal film etchant and array substrate for display device, and above-mentioned metal film etchant includes A) hydrogen peroxide (H2O2), B) fluorochemical, C) four azole compounds of alkyl, D) imidazole compound, E) intramolecular have the water soluble compound of nitrogen-atoms and carboxyl, F) sulfate and G) EPE polyol EPE, so as to (End Point Detection the time required to terminating with the etching for making to change with the increase of processing number；EPD), the effect that lateral erosion (Side etch), the variable quantity of cone angle (Taper angle) minimize.
Description
Technical field
Filled the present invention relates to a kind of metal film etchant and using the display of above-mentioned metal film etchant
Put the manufacture method with array base palte.
Background technology
In semiconductor device, on substrate formed metal wiring process generally include to utilize following process the step of：Profit
With the metal film formation process of sputtering etc.；Coated using photoresist, be in exposed and developed selective area photic anti-
Lose agent formation process；And etching work procedure, and it is included in matting before and after Individual cells process etc..Such etching work procedure
Refer to, using photoresist as mask, the process that metal film is left in selective area is usually used to utilize plasma
Deng dry-etching or using metal film etchant Wet-type etching.
In general, liquid crystal display device includes by thin film transistor base plate, filter substrate and is infused in two substrates
Between liquid crystal layer formed liquid crystal panel.
Liquid crystal layer is by the edge surrounding for being printed on two substrates and the sealing agent combination for surrounding liquid crystal layer.Because liquid crystal panel is
Non-luminescent element, therefore back light unit is provided with behind thin film transistor base plate.The light that backlight is irradiated is according to liquid crystal molecule
Ordered state and adjust light transmission capacity.
In order to transmit signal to liquid crystal layer, formed with distribution on thin film transistor base plate.The distribution of thin film transistor base plate
Including gate wirings and data wiring.
Here, gate wirings include the gate electrode of the gate line and thin film transistor (TFT) that apply signal, data wiring bag
Apply drain electrode and the source of the data wire of data-signal and the data electrode of composition thin film transistor (TFT) containing being insulated with gate wirings
Electrode.
Such distribution can be made up of metal single layer or alloy individual layer, but the shortcomings that in order to make up each metal or alloy and
Desired physical property is obtained, can also be formed by multilayer.
The multilayer being vaporized on baseplate material is and patterned distribution by etching.For etching, there is dry-etching
And Wet-type etching, it is more using being capable of uniform etching and the high Wet-type etching of productivity ratio.
Korean Patent Laid the 10-2007-0055259th proposes the etching solution that can etch copper-molybdenum alloy film
And its engraving method, but have not been able to solve to lower with etching (Etch) performance caused by processing number increase, and lateral erosion
(End Point Detection the time required to (Side etch), etching terminate；EPD), cone angle (Taper angle) variable quantity
Increased phenomenon.
In order to solve the above problems, applicant has developed for when manufacturing array substrate for display device by metal foil
Film and thick film etch and solve the composition with above mentioned problem caused by processing number increase in the lump.
Prior art literature
Patent document
Patent document 1：Korean Patent Laid the 10-2007-0055259th
The content of the invention
Problem to be solved
It is an object of the present invention to provide the processing number variable quantity of conventional etching solution (Etchant) to be improved, and with
(END POINT DETECTION the time required to the etching that processing number increases and changed terminates；EPD), lateral erosion (Side
Etch), the small metal film etchant that can etch metal film in the lump of cone angle (Taper angle) variable quantity.
It is further an object that, there is provided the metal film etching solution of metal film or copper system metal film can be etched in the lump
Composition, it includes hydrogen peroxide (H2O2), fluorochemical, 5- methyl isophthalic acid H- tetrazoliums (5-Methyl-1H-tetrazole),
Imidazoles (Imidazole), iminodiacetic acid (Iminodiacetic acid), sulfate and water.
It is further an object that, there is provided the etching solution of identical metal film or copper system metal film combines in use
Thing etches the engraving method of metal film or copper system metal film.
It is further an object that, there is provided use the etching solution group of above-mentioned identical metal film or copper system metal film
The manufacture method of the array substrate for display device of compound.
The method for solving problem
The present invention provides a kind of metal film etchant, and it includes A) hydrogen peroxide (H2O2), B) fluorochemical,
C) azole compounds of alkyl four, D) imidazole compound, E) intramolecular have nitrogen-atoms and carboxyl water soluble compound,
F) sulfate and G) EPE polyol EPE.
In addition, the present invention provides a kind of manufacture method of array substrate for display device, it is characterised in that including：A) exist
The step of gate electrode is formed on substrate；B) on the substrate comprising above-mentioned gate electrode formed gate insulator the step of；C) upper
State the step of semiconductor layer is formed on gate insulator；D) source electrode is being formed on above-mentioned semiconductor layer and the step of drain electrode；
And the step of e) forming the pixel electrode being connected with above-mentioned drain electrode, above-mentioned a) step are included on substrate profit after formation metal film
The step of etching above-mentioned metal film with metal film etchant and forming gate wirings, above-mentioned d) step include forming metal
The step of above-mentioned metal film being etched after film using the metal film etchant of the present invention and forming source electrode and drain electrode.
Invention effect
The present invention metal film etchant when manufacture array substrate for display device can by metallic film with
Thick film etches in the lump, so as to which process extremely simplifies and can maximize process yield.
Further, metal film etchant of the invention can terminate the etching changed with the increase of processing number
Required time, lateral erosion, cone angle variable quantity minimize and effectively manufacture array substrate for display device.
Embodiment
Hereinafter, the metal film etchant of the present invention and the manufacturer of array substrate for display device are described in detail
Method.
The present invention relates to a kind of metal film etchant, and it includes A) hydrogen peroxide (H2O2), B) fluorochemical,
C) azole compounds of alkyl four, D) imidazole compound, E) intramolecular have nitrogen-atoms and carboxyl water soluble compound,
F) sulfate and G) EPE polyol EPE.Particularly, by including C) four azole compounds of alkyl, D) imidazoles system
Compound, so as to the effect for minimizing the EDP, lateral erosion and the cone angle variable quantity that change with the increase of processing number.
In the present invention, the concept of so-called metal film includes：The monofilm of copper or copper alloy；With comprising selected from copper film and copper conjunction
More than one layer of film in golden film and more than one layer in the group being made up of molybdenum film, molybdenum alloy film, titanium film and titanium alloy film
Film multilayer film.
Copper system metal film described in this specification is the concept for including copper in the constituent of film.
Alloy film described in this specification is the concept also comprising nitride film or oxide-film.
As the example of above-mentioned multilayer film, can enumerate copper/molybdenum film, copper/molybdenum alloy film, copper alloy/molybdenum alloy film, copper/
The duplicatures such as titanium film or trilamellar membrane.Above-mentioned copper/molybdenum film refers to the film comprising molybdenum layer and the layers of copper formed on above-mentioned molybdenum layer, above-mentioned
Copper/molybdenum alloy film refers to the film comprising Mo alloy and the layers of copper formed on above-mentioned Mo alloy, and copper alloy/molybdenum alloy film is
Refer to comprising Mo alloy and formed the film of copper alloy layer on above-mentioned Mo alloy, above-mentioned copper/titanium film refer to comprising titanium layer and
The film of the layers of copper formed on above-mentioned titanium layer.
In addition, above-mentioned Mo alloy refer to by selected from by such as titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd) and
The layer that the alloy of one or more of the groups of composition such as indium (In) metal and molybdenum is formed.
Particularly, metal film etchant of the invention preferably can apply to by copper or tin-copper alloy film and molybdenum or molybdenum
The multilayer film that alloy film is formed.
In the present invention, the thickness of copper system metal film is at leastAnd reached including thicknessMetal film above.With
Thickness isThe film of degree is different, in thicknessIn the case of thick film above, if using conventional etching
Liquid, then corrosion rate is slow, therefore activity time (Process Time) increase.Therefore need compared with conventional etching solution faster
Corrosion rate (/ more than sec), thus conventional etching solution can not be used.In addition, cone angle in the characteristic of thick film is big
In the case of (more than 60 ° of cone angle), when carrying out subsequent handling, it may occur that Step Coverage (Step Coverage) is bad, therefore must
Cone angle must be reduced, but in the past in the case of etching solution, be difficult to apply because cone angle is big.
Hereinafter, the metal film etchant of the present invention is illustrated by inscape.
A) hydrogen peroxide
A included in the metal film etchant of the present invention) hydrogen peroxide (H2O2) it is to influence copper system metal film
The primary oxidant of etching, the copper system metal film are characterised by, are the copper comprising molybdenum layer and the layers of copper formed on above-mentioned molybdenum layer
Molybdenum film or the copper-molybdenum alloy film comprising Mo alloy and the layers of copper formed on above-mentioned Mo alloy.
Relative to composition total weight, above-mentioned A) hydrogen peroxide (H2O2) content be 15~25.0 weight %, be preferably
18.0~24.0 weight %.If content is less than above range, the possible deficiency of etching power of copper system metal film and molybdenum alloy film
And sufficient etching can not be realized, in the case where content is more than 25.0 weight %, because of hydrogen peroxide (H2O2) excessive concentration and lose
Carving the stability of liquid reduces.
B) fluorochemical
The present invention metal film etchant included in B) fluorochemical be refer to dissociate in water and
Discharge the compound of F ion.Above-mentioned B) fluorochemical be influence molybdenum alloy film etching speed pro-oxidant, regulation molybdenum close
The etching speed of golden film.
Relative to composition total weight, above-mentioned B) content of fluorochemical is 0.01~3.0 weight %, preferably 0.05
~1.0 weight %.If content is less than above range, the etching speed of molybdenum system metal film and metal oxide film is slack-off.Such as
Fruit content exceedes above range, although then the etching performance of molybdenum alloy film improves, etching speed accelerates on the whole, therefore can be bright
Explict occurrence undercuts the etch damage (Damage) of the Si systems lower layer of (under cut) phenomenon or lower layer.
Above-mentioned B) as long as fluorochemical material used in the art is just not particularly limited.But above-mentioned B)
Fluorochemical is preferably selected from by HF, NaF, NH4F、NH4BF4、NH4HF2(ammonium acid fluoride (ammonium bifluoride)；
ABF)、KF、KHF2、AlF3And HBF4The group of composition, from SiO2Damage from the aspect of (Damage), preferably NH4F、NH4HF2
Deng.
C) the azole compounds of alkyl four
The present invention metal film etchant included in C) alkyl four azole compounds play regulation copper systems gold
Belong to the etching speed of film and reduce the CD losses (CD Loss) of pattern and improve the effect of operation allowance.
Relative to composition total weight, above-mentioned C) alkyl four the contents of azole compounds be 0.05~3.0 weight %, especially
Preferred content is 0.05~1.0 weight % composition.In above-mentioned C) alkyl four the contents of azole compounds be less than above range
In the case of, overetch can substantially occur and change with the etching performance (etching outline (Etch Profile)) of processing number change
Become.In above-mentioned C) alkyl four azole compounds content exceed above range in the case of, because the etching speed of copper became
Slowly, thus can occur activity time loss.
Above-mentioned C) alkyl four azole compounds can include be selected from by 5- methyl isophthalic acid H- tetrazoliums (5-Methyl-1H-
Tetrazole), 5- phenyl -1H-TETRAZOLE (5-Phenyl-1H-tetrazole), 5- amino -1- methyl tetrazoliums (5-Amino-1-
Methyltetrazole), 5- benzyls -1H-TETRAZOLE (5-Benzyl-1H-tetrazole), 5- sulfydryl -1- methyl tetrazoliums (5-
Mercapto-1-methyltetrazole) and the composition such as 1- methyl isophthalic acid H- tetrazoliums (1-Methyl-1H-tetrazole) group
One or more of, more preferably 5- methyl isophthalic acids H- tetrazoliums (5-Methyl-1H-tetrazole).
D) imidazole compound
D included in the metal film etchant of the present invention) imidazole compound plays regulation metal film or copper
It is the etching speed of metal film and makes to change with the etching performance (etching outline) of processing number change and reduce and improve more than process
The effect of amount.
Relative to composition total weight, D) content of imidazole compound is 0.05~3.0 weight %, particularly preferably
0.05~1.0 weight % scopes.In above-mentioned D) in the case that the content of imidazole compound is less than above range, can substantially occur
Overetch and etching performance (etching outline) change with processing number change.In above-mentioned D) content of imidazole compound exceedes
In the case of above range, because the etching speed of copper becomes too slow, therefore activity time loss can occur.Above-mentioned D) imidazoles system
Compound can be included and is selected from by imidazoles (Imidazole), benzimidazole (Benzimidazole), 2- phenylimidazoles (2-
Phenyl-1H-Imidazole), 1- methyl isophthalic acids H- imidazoles (1-Methyl-1H-Imidazole), 2- methyl isophthalic acid H- imidazoles (2-
Methyl-1H-imidazole), 4- methyl isophthalic acids H- imidazoles (4-Methyl-1H-Imidazole), 1H- imidazoles -1- propylamine (1H-
Imidzole-1-propylamine), 1H- imidazoles -1- ethamine (1H-Imidazole-1-ethanamine), 2- sulfydryl benzos
Imidazoles (2-Mercaptobenzimidazole), 2 mercaptomethyl benzimidazole (2-Mercaptotoluimidazole) and 1,
One or more of groups of composition such as 2- methylimidazoles (1,2-Dimethyl imidazole), more preferably comprising imidazoles
(Imidazole)。
In the present invention, C) alkyl four azole compounds and D) ratio of content of imidazole compound can be 1:20~
20:1, more preferably content ratio is 1:5~5:1 situation.If the ratio of the azole compounds of alkyl four and imidazole compound
Meet above range, then have processing number variable quantity small, there is required quick etch-rate (Etch Rate) during thick film
Effect.
E) intramolecular has the water soluble compound of nitrogen-atoms and carboxyl
E included in the metal film etchant of the present invention) intramolecular have the water of nitrogen-atoms and carboxyl
Soluble compound prevent keeping metal film etchant when may occur aquae hydrogenii dioxidi selfdecomposition reaction and
Prevent etching characteristic from changing when etching multiple substrates.In general, in the metal film etchant using aquae hydrogenii dioxidi
In the case of, selfdecomposition occurs for aquae hydrogenii dioxidi when taking care of and its storage time is not grown, and also tool is there is a possibility that the danger of container explosion
Dangerous factor.
But including above-mentioned E) and in the case that an intramolecular have the water soluble compound of nitrogen-atoms and carboxyl, mistake
The decomposition rate of hydrogen oxide water reduces nearly 10 times, it is advantageously ensured that storage time and stability.Particularly, in the situation of layers of copper
Under, when remaining a large amount of copper ions in metal film etchant, can often occur formed passivation (passivation) film and
Situation about can not be further etched after oxidation blackening, but in the case where adding above-claimed cpd, such a phenomenon can be prevented.
Above-mentioned E) to have the content of the water soluble compound of nitrogen-atoms and carboxyl be 0.5~5.0 weight % to an intramolecular,
Particularly preferably 1.0~3.0 weight % scopes.
In above-mentioned E) intramolecular have nitrogen-atoms and carboxyl water soluble compound content less than above range
In the case of, it can be not easy to obtain sufficient operation allowance because forming passivating film after etching mass substrate (about 500).In addition,
In above-mentioned E) intramolecular have in the case that the content of the water soluble compound of nitrogen-atoms and carboxyl exceedes above range, by
It is slack-off in the etching speed of molybdenum or molybdenum alloy, therefore molybdenum or molybdenum alloy film can occur in the case of copper-molybdenum film or copper-molybdenum alloy film
Scrap problems.
Above-mentioned E) there is an intramolecular water soluble compound of nitrogen-atoms and carboxyl can enumerate alanine
(alanine), aminobutyric acid (aminobutyric acid), glutamic acid (glutamic acid), glycine (glycine),
Iminodiacetic acid (iminodiacetic acid), nitrilotriacetic acid (nitrilotriacetic acid) and methyl amimoacetic acid
(sarcosine) etc..And wherein it is most preferably iminodiacetic acid (iminodiacetic acid).
F) sulfate
F included in the metal film etchant of the present invention) sulfate be adjust Cu surfaces oxidizing potential and
The composition for increasing the etching speed of copper film.If above-mentioned F is not present in the metal film etchant of the present invention) sulfuric acid
Salt, then etching speed is very slow and etching outline may be bad.
Relative to composition total weight, above-mentioned F) content of sulfate is 0.05~5.0 weight %, particularly preferred content is
The composition of 0.10~3.0 weight % scopes.In above-mentioned F) in the case that the content of sulfate is less than above range, etching speed
It is very slow and may occur that etching performance (etching outline) is bad and activity time loss.
In above-mentioned F) in the case that the content of sulfate exceedes above range, the etching speed of copper or tin-copper alloy film became
Fast or cone angle value becomes much and easily occurs that Step Coverage is bad, and it is dfficult to apply to thick film.
Above-mentioned F) sulfate can enumerate ammonium sulfate (Ammonium sulfate), sodium sulphate (Sodium sulfate),
Potassium sulfate (Potassium sulfate), magnesium sulfate (Magnesium sulfate), lithium sulfate (Lithium sulfate)
Deng.
G) EPE polyol EPE
G included in the metal film etchant of the present invention) EPE polyol EPE plays makes surface
Power reduces and improves the effect of etch uniformity.
In addition, above-mentioned G) EPE polyol EPE by surround the copper of the dissolution in etching solution after etching from
Son, so as to suppress the activity of copper ion, suppress the decomposition reaction of hydrogen peroxide.If so reducing the activity of copper ion,
Process can stably be carried out by using during etching solution.
Relative to composition total weight, above-mentioned G) content of EPE polyol EPE is 1.0~5.0 weight %, it is excellent
Elect 1.5~3.0 weight % as.In above-mentioned G) in the case that the content of EPE polyol EPE is less than above range, may
The problem of generation etch uniformity reduces, and the decomposition of hydrogen peroxide is accelerated.If above-mentioned G) EPE polyol EPE contains
Amount exceedes above range, then the shortcomings that producing a large amount of foams be present.
Above-mentioned G) EPE polyol EPE can enumerate glycerine (glycerol), triethylene glycol (triethylene
) and polyethylene glycol (polyethylene glycol) etc. glycol.And wherein it is preferably triethylene glycol (triethylene
glycol)。
H) the water of surplus
The content of water included in the metal film etchant of the present invention is to make metal film etchant total
Weight turns into 100 weight % surplus.The water of above-mentioned surplus is meant, so as to include A) hydrogen peroxide (H2O2), B) containing fluorination
Compound, C) 5- methyl isophthalic acid H- tetrazoliums, D) imidazoles, E) intramolecular have the water soluble compound of nitrogen-atoms and carboxyl, F) sulphur
Hydrochlorate and G) EPE polyol EPE metal film etchant gross weight turn into 100 weight % mode bag
Contain, in the case where further includeing machine acid and/or additive, also turned into the gross weight of metal film etchant
100 weight % mode includes.Above-mentioned water is not particularly limited, preferably using deionized water.In addition, more preferably using embodiment water
The deionized water that the resistivity value that intermediate ion removes the water of degree is more than 18M Ω cm.
I) organic acid
The metal film etchant of the present invention can further include I) organic acid, play the good work for removing residue
With.
Relative to composition total weight, above-mentioned I) content of organic acid is 0.01~5.0 weight %, particularly preferably 0.01
~3.0 weight %.In above-mentioned I) in the case that the content of organic acid exceedes above range, having increases processing number variable quantity
Effect, in the case of less than above range, remove residue when there is no positive effect.
Above-mentioned I) organic acid can enumerate acetic acid, butyric acid, citric acid, formic acid, gluconic acid, malonic acid, valeric acid, lactic acid and grass
Acid etc., more preferably citric acid.
The pH of the metal film etchant of the present invention can be 1.0~3.0, more preferably 1.5~2.5.In metal
In the case that the pH scopes of film etchant are above range, there is excellent effect when removing residue.
In addition, in the present invention, in addition to mentioned component, common additive can be further added, is added as above-mentioned
Add agent, sequestering agent and anticorrosive etc. can be enumerated.Above-mentioned additive can be added in sequestering agent and anticorrosive
More than one.
Relative to composition total weight, the content of above-mentioned metallic addition is 0.001~10 weight %, in above-mentioned additive
Content be above range in the case of, further improve etching performance (etching outline).
Each constituent used in the present invention can be manufactured using commonly known method, metal film of the invention
Etchant preferably has the purity for semiconductor process.
Hereinafter, the present invention is described in more detail by embodiment.But following embodiments are used to further illustrate this hair
Bright, the scope of the present invention is not limited to following embodiments.Following embodiments can be within the scope of the invention by this area
Technical staff suitably change, changed.
<Embodiment and comparative example>The manufacture of metal film etchant
Composition described in table 1 below and the water of surplus are mixed with corresponding ratio of components, embodiment is manufactured and compares
The ㎏ of metal film etchant 180 of example.
[table 1]
Unit：Weight %
(note) ABF：Ammonium acid fluoride；5-MTZ：5- methyl isophthalic acid H- tetrazoliums；IMZ：Imidazoles；IDA：Iminodiacetic acid；AS：Sulphur
Sour ammonium；TEG：Triethylene glycol；5-ATZ：5- Aminotetrazoles；TRZ：1,2,4- triazoles；PTZ：5- phenyl -1H-TETRAZOLE；MIMZ：1-
Methyl isophthalic acid H- imidazoles
<Experimental example>Etching characteristic confirms experiment
Implement etching work procedure using the metal film etchant of embodiment 1~12, comparative example 1~9 respectively.Use spray
Penetrate the experimental facilities (model name of formula etching mode：ETCHER (TFT), SEMES companies), during etching work procedure, metal film etching solution
The temperature of composition is set to about 32 DEG C or so.Etching period can be different according to etch temperature, but in LCD etching work procedures generally
Carried out with 50~80 seconds degree.Detect what above-mentioned etching work procedure was etched using SEM (Hitachi, Ltd's product, model name S-4700)
The section of outline of copper system metal film, result is documented in table 2 below.For the copper system metal film used in etching work procedure,
Use Cu/Mo-Ti 6500/Film substrate.
Determine lateral erosion (μm) variable quantity with Cu change in concentration.Cone angle refers to the slope on Cu metal films inclined-plane, and lateral erosion refers to
The distance between photoresist end and lower metal end for being determined after etching.If side etching quantity changes, TFT
During driving signal transmission speed can be made to change and produce speckle, therefore preferably minimize lateral erosion variable quantity.In this evaluation,
When lateral erosion variable quantity is ± 0.1 μm, cone angle meets 45~55 ° of scopes, and cone angle variable quantity meets minimum zone i.e. close to 0
It is preferred during condition, and is set to and metal film etchant be can be used for into etching work procedure.After being etched on metal film not
It is etched and remains in the residue measure part on surface, by SEM to being measured between distribution and distribution, and with residue
Number carries out metewand definition with measure area ratio and implements to test.
[table 2]
(note) ◎：It is very good, zero：Well, △：Commonly, Х：Difference,
[etching speed metewand]
◎：Very good (/ sec≤etching speed≤/sec)
○：Well (/ sec≤etching speed</sec,/sec<Etching speed≤/sec)
△：Commonly (/ sec≤etching speed</sec,/sec<Etching speed≤/sec)
Х：Poor (etching speed</sec,/sec<Etching speed)
[residue removal metewand]
◎：Very good (residue number=0)
○：Well (residue number≤1)
△：Commonly (1<Residue number≤5)
Х：Difference (5<Residue number, or (Un Etch) can not be etched)
[etching rectilinear propagation metewand]
◎：It is very good, zero：Well, △：Commonly, Х：Difference or can not etch
[lateral erosion variable quantity metewand]
◎：Very good (lateral erosion variable quantity<0.05μm)
○：Well (0.05 μm≤lateral erosion variable quantity<0.1μm)
△：Commonly (0.1 μm≤lateral erosion variable quantity<0.2μm)
Х：Poor (0.2 μm≤lateral erosion variable quantity)
[cone angle metewand]
◎：Very good (cone angle variable quantity<5 °, the cone angle of formation is 45~55 °)
○：Well (5 °≤cone angle variable quantity<10 °, the cone angle of formation is 45~55 °)
△：Commonly (10 °≤cone angle variable quantity<15 °, the cone angle of formation is 40~60 °)
Х：Poor (15 °≤cone angle variable quantity, the cone angle of formation<40 °, 60 °<The cone angle of formation)
As known from Table 2, the metal film etchant of embodiment 1~8 shows excellent etching characteristic.In detail and
Speech, the etching outline and straight that copper system film metal film is etched and obtained using the metal film etchant of embodiment 3
Property is excellent.In addition, understanding that lateral erosion variable quantity meets ± 0.1 μm, cone angle meets 45~55 ° for 49.3 °, and cone angle variable quantity is
2.4 ° of conditions for also meeting minimum.It is same as Example 3 in the case of embodiment 7, lateral erosion variable quantity, cone angle, cone angle change
Amount is peer-level and excellent, and for other characteristics, in residue evaluation, compared with Example 3, residue removes very excellent
It is different.In the case of embodiment 9~12, even if including the other kinds of azole compounds of alkyl four and imidazole compound, side
Erosion variable quantity and cone angle variable quantity also meet excellent scope.Particularly, confirm comprising 5- methyl isophthalic acid H- tetrazoliums and during imidazoles
Composition it is most excellent.
On the other hand, it is known that in the case where not including the comparative example 1 of azole compounds, etching speed is very fast, etching wheel
It is wide excessively poor.Show that processing number variable quantity is also very big, cone angle also shows that more than 65 ° of level.Only including 5-MTZ
Comparative example 2 in the case of, although showing that processing number variable quantity and etching outline are normal, cone angle is more than 55 °.Only
In the case of comparative example 3 comprising IMZ, although showing that etching outline is excellent, processing number variable quantity is very big, cone angle
For more than 60 degree.In the case where azole compounds 5-MTZ is changed into 5-ATZ comparative example 4, although showing that etching outline is excellent
It is different, but it is big to handle number variable quantity.In the case of comparative example 5, handle number variable quantity and cone angle variable quantity aspect is excellent, but
Cone angle is unsatisfactory for 45~55 °.In the case of comparative example 6, processing number variable quantity is more than 0.1, determines cone angle variable quantity
Up to 12.6 °.In the case of comparative example 7, cone angle can not be made to meet 45~55 °, in the case of comparative example 8, show source
It is larger to manage number variable quantity, cone angle, cone angle variable quantity.In the case of comparative example 9, etching speed is slow, the cone angle formed
Also it is very small, it is also unexcellent that number variable quantity is handled in addition.
Claims (17)
1. a kind of metal film etchant, it includes A) hydrogen peroxide, B) fluorochemical, C) alkyl tetrazolium system chemical combination
Thing, D) imidazole compound, E) intramolecular have the water soluble compound of nitrogen-atoms and carboxyl, F) sulfate and G) it is more
First alcohol type surfactant.
2. metal film etchant according to claim 1, it is characterised in that the B) fluorochemical be selected from
By HF, NaF, NH4F、NH4BF4、NH4HF2、KF、KHF2、AlF3And HBF4One or more of group of composition.
3. metal film etchant according to claim 1, it is characterised in that the C) four azole compounds of alkyl
For selected from by 5- methyl isophthalic acid H- tetrazoliums, 5- phenyl -1H-TETRAZOLE, 5- amino -1- methyl tetrazolium, 5- benzyls -1H-TETRAZOLE, 5- mercaptos
One or more of group of base -1- methyl tetrazolium and 1- methyl isophthalic acid H- tetrazoliums composition.
4. metal film etchant according to claim 1, it is characterised in that the D) imidazole compound for choosing
Free imidazoles, benzimidazole, 2- phenylimidazoles, 1- methyl isophthalic acid H- imidazoles, 2- methyl isophthalic acid H- imidazoles, 4- methyl isophthalic acid H- imidazoles, 1H-
Imidazoles -1- propylamine, 1H- imidazoles -1- ethamine, 2-mercaptobenzimidazole, 2 mercaptomethyl benzimidazole and DMIZ 1,2 dimethylimidazole
One or more of group of composition.
5. metal film etchant according to claim 1, it is characterised in that the E) intramolecular have nitrogen
The water soluble compound of atom and carboxyl is selected from by alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, ammonia
It is more than one or both of group of triacetic acid and methyl amimoacetic acid composition.
6. metal film etchant according to claim 1, it is characterised in that the G) polyol type surface-active
Agent is selected from one or more of group being made up of glycerine, triethylene glycol and polyethylene glycol.
7. metal film etchant according to claim 1, it is characterised in that the F) sulfate be selected from by sulphur
One or more of group that sour ammonium, sodium sulphate, potassium sulfate, magnesium sulfate and lithium sulfate form.
8. metal film etchant according to claim 1, it is characterised in that further include machine acid.
9. metal film etchant according to claim 8, it is characterised in that the organic acid is selected from by second
One or more of group that acid, butyric acid, citric acid, formic acid, gluconic acid, malonic acid, valeric acid, lactic acid and oxalic acid form.
10. metal film etchant according to claim 1, it is characterised in that C) alkyl four azole compounds with
D) content ratio of imidazole compound is 1:20~20:1.
11. metal film etchant according to claim 1, it is characterised in that further comprising additive.
12. metal film etchant according to claim 11, it is characterised in that the additive chelates for multivalence
One or more of agent and anticorrosive.
13. the metal film etchant according to any one of claim 1~12, it is characterised in that the metal
Film is made up of the monofilm or multilayer film of copper or copper alloy, and the multilayer film includes one in copper film or tin-copper alloy film
Film more than layer and more than one layer of the film in the group being made up of molybdenum film, molybdenum alloy film, titanium film and titanium alloy film.
14. metal film etchant according to claim 1, it is characterised in that relative to composition total weight, institute
Metal film etchant is stated to include：
A) hydrogen peroxide (H2O2) 15~25 weight %；
B) the weight % of fluorochemical 0.01~3.0；
C) the weight % of four azole compounds of alkyl 0.05~3.0；
D) the weight % of imidazole compound 0.05~3.0；
E) intramolecular has the weight % of water soluble compound 0.5~5.0 of nitrogen-atoms and carboxyl；
F) the weight % of sulfate 0.05~5.0；
G) the weight % of EPE polyol EPE 1.0~5.0；With
H) the water of surplus.
15. metal film etchant according to claim 14, it is characterised in that further include machine acid 0.01
~5.0 weight %.
16. metal film etchant according to claim 14, it is characterised in that further comprising additive
0.001~10 weight %.
17. a kind of manufacture method of array substrate for display device, it includes：
A) on substrate formed gate electrode the step of；
B) on the substrate comprising the gate electrode formed gate insulator the step of；
C) on the gate insulator formed semiconductor layer the step of；
D) source electrode is being formed on the semiconductor layer and the step of drain electrode；And
E) the step of forming the pixel electrode being connected with the drain electrode,
A) the step be included on substrate formed after metal film etch the metal film using metal film etchant and
The step of forming gate wirings,
D) the step includes etching the metal film after forming metal film using metal film etchant and forming source electricity
The step of pole and drain electrode,
The metal film etchant is the metal film etchant any one of claim 1~12.
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| KR1020170035892A KR102400343B1 (en) | 2016-07-19 | 2017-03-22 | Metal film etchant composition and manufacturing method of an array substrate for display device |
| KR10-2017-0035892 | 2017-03-22 |
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| Publication number | Publication date |
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| KR20180009687A (en) | 2018-01-29 |
| KR102400343B1 (en) | 2022-05-23 |
| CN107630219B (en) | 2020-01-24 |
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