CN111755461B - Method for manufacturing array substrate for liquid crystal display device and copper-based metal film etching liquid composition for same - Google Patents
Method for manufacturing array substrate for liquid crystal display device and copper-based metal film etching liquid composition for same Download PDFInfo
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- CN111755461B CN111755461B CN202010231299.7A CN202010231299A CN111755461B CN 111755461 B CN111755461 B CN 111755461B CN 202010231299 A CN202010231299 A CN 202010231299A CN 111755461 B CN111755461 B CN 111755461B
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- Prior art keywords
- acid
- copper
- metal film
- based metal
- liquid composition
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- 238000005530 etching Methods 0.000 title claims abstract description 103
- 239000010949 copper Substances 0.000 title claims abstract description 77
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 76
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 68
- 239000002184 metal Substances 0.000 title claims abstract description 68
- 239000007788 liquid Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000000758 substrate Substances 0.000 title claims abstract description 24
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- -1 azole compound Chemical class 0.000 claims abstract description 28
- 239000004065 semiconductor Substances 0.000 claims abstract description 25
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004094 surface-active agent Substances 0.000 claims abstract description 20
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 19
- 239000011737 fluorine Substances 0.000 claims abstract description 19
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 19
- 150000007524 organic acids Chemical class 0.000 claims abstract description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 19
- 239000010452 phosphate Substances 0.000 claims abstract description 19
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920005862 polyol Polymers 0.000 claims abstract description 18
- 150000003077 polyols Chemical class 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 16
- 150000001860 citric acid derivatives Chemical class 0.000 claims abstract description 11
- 239000010408 film Substances 0.000 claims description 129
- 239000010410 layer Substances 0.000 claims description 33
- 229910052750 molybdenum Inorganic materials 0.000 claims description 22
- 239000011733 molybdenum Substances 0.000 claims description 22
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 21
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 18
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002356 single layer Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 6
- 235000019263 trisodium citrate Nutrition 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 5
- HWPKGOGLCKPRLZ-UHFFFAOYSA-M monosodium citrate Chemical compound [Na+].OC(=O)CC(O)(C([O-])=O)CC(O)=O HWPKGOGLCKPRLZ-UHFFFAOYSA-M 0.000 claims description 5
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 5
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 5
- 150000003536 tetrazoles Chemical class 0.000 claims description 5
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229940038773 trisodium citrate Drugs 0.000 claims description 5
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002526 disodium citrate Substances 0.000 claims description 4
- 235000019262 disodium citrate Nutrition 0.000 claims description 4
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 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
- 239000002524 monosodium citrate Substances 0.000 claims description 4
- 235000018342 monosodium citrate Nutrition 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-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
- 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 3
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 239000000174 gluconic acid Substances 0.000 claims description 3
- 235000012208 gluconic acid Nutrition 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 239000006012 monoammonium phosphate Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 3
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 150000003852 triazoles Chemical class 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
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 2
- ZMPRRFPMMJQXPP-UHFFFAOYSA-N 2-sulfobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1S(O)(=O)=O ZMPRRFPMMJQXPP-UHFFFAOYSA-N 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
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 claims description 2
- ODBLHEXUDAPZAU-ZAFYKAAXSA-N D-threo-isocitric acid Chemical compound OC(=O)[C@H](O)[C@@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-ZAFYKAAXSA-N 0.000 claims description 2
- 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
- 239000005696 Diammonium phosphate Substances 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- ODBLHEXUDAPZAU-FONMRSAGSA-N Isocitric acid Natural products OC(=O)[C@@H](O)[C@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-FONMRSAGSA-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
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-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
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 235000019253 formic 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
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- ODBLHEXUDAPZAU-UHFFFAOYSA-N threo-D-isocitric acid Natural products OC(=O)C(O)C(C(O)=O)CC(O)=O ODBLHEXUDAPZAU-UHFFFAOYSA-N 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- 150000003851 azoles Chemical class 0.000 claims 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims 1
- 150000003854 isothiazoles Chemical class 0.000 claims 1
- WUHLVXDDBHWHLQ-UHFFFAOYSA-N pentazole Chemical compound N=1N=NNN=1 WUHLVXDDBHWHLQ-UHFFFAOYSA-N 0.000 claims 1
- 150000003557 thiazoles Chemical class 0.000 claims 1
- 230000008569 process Effects 0.000 description 20
- 230000008859 change Effects 0.000 description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 239000011651 chromium Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 239000011698 potassium fluoride Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- DEPDDPLQZYCHOH-UHFFFAOYSA-N 1h-imidazol-2-amine Chemical compound NC1=NC=CN1 DEPDDPLQZYCHOH-UHFFFAOYSA-N 0.000 description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- MREIFUWKYMNYTK-UHFFFAOYSA-N 1H-pyrrole Chemical compound C=1C=CNC=1.C=1C=CNC=1 MREIFUWKYMNYTK-UHFFFAOYSA-N 0.000 description 1
- HUEXNHSMABCRTH-UHFFFAOYSA-N 1h-imidazole Chemical class C1=CNC=N1.C1=CNC=N1 HUEXNHSMABCRTH-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-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
- MKBBSFGKFMQPPC-UHFFFAOYSA-N 2-propyl-1h-imidazole Chemical compound CCCC1=NC=CN1 MKBBSFGKFMQPPC-UHFFFAOYSA-N 0.000 description 1
- GEHBUYNXWNQEIU-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC=1N=NNN=1.NC=1N=NNN=1 GEHBUYNXWNQEIU-UHFFFAOYSA-N 0.000 description 1
- GVSNQMFKEPBIOY-UHFFFAOYSA-N 4-methyl-2h-triazole Chemical compound CC=1C=NNN=1 GVSNQMFKEPBIOY-UHFFFAOYSA-N 0.000 description 1
- NJQHZENQKNIRSY-UHFFFAOYSA-N 5-ethyl-1h-imidazole Chemical compound CCC1=CNC=N1 NJQHZENQKNIRSY-UHFFFAOYSA-N 0.000 description 1
- HPSJFXKHFLNPQM-UHFFFAOYSA-N 5-propyl-1h-imidazole Chemical compound CCCC1=CNC=N1 HPSJFXKHFLNPQM-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Chemical group 0.000 description 1
- 150000001342 alkaline earth metals Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 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
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004544 sputter deposition Methods 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
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
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- C09K13/00—Etching, surface-brightening or pickling compositions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
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- 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
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- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1259—Multistep manufacturing methods
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- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1259—Multistep manufacturing methods
- H01L27/127—Multistep manufacturing methods with a particular formation, treatment or patterning of the active layer specially adapted to the circuit arrangement
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Abstract
The invention provides a method for manufacturing an array substrate for a liquid crystal display device and a copper-based metal film etching liquid composition used for the same, wherein the copper-based metal film etching liquid composition comprises hydrogen peroxide; fluorine-containing compounds or inorganic acids; an azole compound; an organic acid; a citrate salt; more than one of sulfate and phosphate; a polyol type surfactant; and water, the above-mentioned method for manufacturing array base plate for liquid crystal display device, by etching the copper-based metal film and forming the source electrode/drain electrode by using the above-mentioned etchant composition, can etch the copper-based metal film together under the condition of not damaging the oxide semiconductor layer.
Description
Technical Field
The present invention relates to a method for manufacturing an array substrate for a liquid crystal display device and a copper-based metal film etching liquid composition used for the same.
Background
With the formal entry into the information age, the field of displays that process and display a large amount of information has been rapidly developed, and accordingly, various flat panel displays have been developed and attracting attention.
Examples of such flat panel display devices include Liquid crystal display devices (Liquid CRYSTAL DISPLAY DEVICE: LCD), plasma display devices (PLASMA DISPLAY PANEL DEVICE: PDP), field Emission display devices (Field Emission DISPLAY DEVICE: FED), electroluminescent display devices (Electroluminescence DISPLAY DEVICE: ELD), organic LIGHT EMITTING Diodes (OLED), and the like, and such flat panel display devices are used in various applications in the fields of home appliances such as televisions and video recorders, and in computers and mobile phones such as notebooks. In practice, these flat panel display devices are rapidly replacing the conventional Cathode Ray Tube (NIT) devices due to their excellent performances such as thickness reduction, light weight, and low power consumption.
In a liquid crystal display device, a process of forming a metal wiring on a substrate generally includes steps of: a metal film forming step using sputtering or the like; a photoresist forming step in a selective region by photoresist coating, exposure and development; and an etching step, and includes a cleaning step before and after the individual unit steps, and the like. Such etching step is a step of leaving a metal film in a selective region using a photoresist as a mask, and generally uses dry etching using plasma or the like or wet etching using an etchant composition.
In such a liquid crystal display device, in recent years, attention has been paid mainly to the resistance of the metal wiring. This is because the resistance is a major factor inducing RC signal delay, and in a thin film transistor liquid crystal display (thin film transistor-liquid CRYSTAL DISPLAY, TFT-LCD), solving the RC signal delay problem is a key to increase the panel size and achieve high resolution. Therefore, in order to reduce the RC signal delay required for the large-scale TFT-LCD, low-resistance materials have to be developed.
Chromium (Cr, resistivity: 12.7x -8 Ω m), molybdenum (Mo, resistivity: 5 x 10 -8 Ω m), aluminum (Al, resistivity: 2.65x -8 Ω m) and alloys thereof, which have been mainly used in the past, have large resistances, and thus are difficult to be used for gate lines, data lines, and the like, which are used in large-sized TFT-LCDs. Therefore, attention has been paid to copper-based metal films such as copper films and copper-molybdenum films, which are low-resistance metal films, and etching liquid compositions therefor. However, the hitherto known copper-based metal film etchant compositions still fail to satisfy the performance required by users, and thus research and development for improving the performance have been required.
In connection with this, korean laid-open patent No. 10-2015-0004971 discloses a copper-based metal film etching liquid composition comprising a polyol surfactant, citric acid, hydrogen peroxide, a fluorine-containing compound and an azole compound, but in the case of the above etching liquid composition, when an oxide semiconductor is used as a semiconductor layer, there are the following problems: when the process is performed, the etching liquid composition is concentrated by the exhaust gas, and the degree of damage of the oxide semiconductor is changed, so that it is difficult to control the process, and thus it is difficult to maintain the performance of the liquid crystal display device.
Prior art literature
Patent literature
Korean laid-open patent No. 10-2015-0004971
Disclosure of Invention
Problems to be solved
In order to solve the above-described problems of the prior art, an object of the present invention is to provide a method for manufacturing an array substrate for a liquid crystal display device, which uses an etchant composition capable of etching copper-based metal films simultaneously without damaging an oxide semiconductor layer.
Means for solving the problems
In order to achieve the above object, the present invention provides a method for manufacturing an array substrate for a liquid crystal display device, comprising: a) A step of forming a gate electrode on a substrate; b) Forming a gate insulating layer on a substrate including the gate electrode; c) A step of forming an oxide semiconductor layer (IGZO) on the gate insulating layer; d) Forming a source electrode/drain electrode on the oxide semiconductor layer; and e) forming a pixel electrode connected to the source electrode and the drain electrode, wherein in the d), a copper-based metal film is formed on the oxide semiconductor layer, and the copper-based metal film is etched by using an etchant composition, the etchant composition including hydrogen peroxide; fluorine-containing compounds or inorganic acids; an azole compound; an organic acid; a citrate salt; more than one of sulfate and phosphate; a polyol type surfactant; and water.
The present invention also provides a copper-based metal film etching liquid composition comprising (A) 5.0 to 30.0 wt% of hydrogen peroxide, based on the total weight of the composition; 0.001 to 1.0 wt% of a fluorine-containing compound or an inorganic acid; (C) 0.01 to 2.0% by weight of an azole compound; (D) 1.0 to 10.0% by weight of an organic acid; (E) 0.1 to 5% by weight of citrate; (F) More than 0.01 to 5 weight percent of one of sulfate and phosphate; (G) 0.001 to 5.0 wt% of a polyol surfactant; and (H) water.
Effects of the invention
The method for manufacturing an array substrate for a liquid crystal display device according to the present invention can simultaneously etch a copper-based metal film without damaging an oxide semiconductor layer, and can reduce the generation of a tip (tip) of a molybdenum film or a molybdenum alloy film including the copper-based metal film by using an etching liquid composition excellent in etching profile and etching straightness, and can suppress the change of Side etching (Side etching) by reducing the change of the damage rate (DAMAGE RATE) of the oxide semiconductor layer caused by outgas during etching by using equipment, thereby providing an effect of easy control of a process.
Detailed Description
The present invention relates to a composition comprising hydrogen peroxide; fluorine-containing compounds or inorganic acids; an azole compound; an organic acid; a citrate salt; more than one of sulfate and phosphate; a polyol type surfactant; and an etching liquid composition of water, and a method for manufacturing an array substrate for a liquid crystal display device using the etching liquid composition, wherein the etching liquid composition can etch a copper-based metal film without damaging an oxide semiconductor layer, and the etching profile and the etching straightness are excellent, so that the generation of tips of a molybdenum film or a molybdenum alloy film containing the copper-based metal film is reduced, and the damage rate variation of the oxide semiconductor layer caused by exhaust gas is low in the etching process using equipment, so that the side etching variation is suppressed, thereby providing the effect of easy control of the process.
The constitution of the present invention will be specifically described below.
< Method for manufacturing array substrate for liquid Crystal display device >
The invention provides a method for manufacturing an array substrate for a liquid crystal display device, which is characterized by comprising the following steps: a) A step of forming a gate electrode on a substrate; b) Forming a gate insulating layer on a substrate including the gate electrode; c) A step of forming an oxide semiconductor layer (IGZO) on the gate insulating layer; d) Forming a source electrode/drain electrode on the oxide semiconductor layer; and e) forming a pixel electrode connected to the source electrode and the drain electrode, wherein in the d), a copper-based metal film is formed on the oxide semiconductor layer, and the copper-based metal film is etched by using an etchant composition, the etchant composition including hydrogen peroxide; fluorine-containing compounds or inorganic acids; an azole compound; an organic acid; a citrate salt; more than one of sulfate and phosphate; a polyol type surfactant; and water.
The copper-based metal film is a metal film containing copper in the constituent components of the film, and specifically may be a single-layer film composed of copper or a copper alloy, or a multilayer film such as a double-layer film and a three-layer film including the single-layer film and a film composed of molybdenum or a molybdenum alloy.
For example, the copper-based metal film may include a copper film and a copper alloy film as a single layer film, may include a copper film-molybdenum film, a copper film-molybdenum alloy film, a copper alloy film-molybdenum alloy film, and a molybdenum film-copper alloy film-molybdenum alloy film, a molybdenum film-copper alloy film-molybdenum film, a molybdenum alloy film-copper alloy film-molybdenum alloy film, a molybdenum alloy film-copper alloy film-molybdenum alloy film, and the like as a three-layer film.
The alloy film may be an alloy film of copper or molybdenum and at least one selected from the group consisting of titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), and the like, or may be a nitride film or an oxide film of copper or molybdenum.
When the copper-based metal film is etched by using the etching liquid composition of the present invention, the copper-based metal film can be etched simultaneously without damaging (damage) the oxide semiconductor layer.
As an embodiment of the etching liquid composition of the present invention, hydrogen peroxide is preferably contained; a fluorine-containing compound; an azole compound; an organic acid; a citrate salt; more than one of sulfate and phosphate; a polyol type surfactant; and water, as another embodiment of the etching liquid composition of the present invention, preferably contains hydrogen peroxide; an inorganic acid; an azole compound; an organic acid; a citrate salt; more than one of sulfate and phosphate; a polyol type surfactant; and water.
The etching liquid composition of the present invention will be described in detail below.
< Copper-based Metal film etchant composition >
The copper-based metal film etching liquid composition of the present invention may contain hydrogen peroxide; fluorine-containing compounds or inorganic acids; an azole compound; an organic acid; a citrate salt; more than one of sulfate and phosphate; a polyol type surfactant; and water.
As an embodiment of the etching liquid composition of the present invention, hydrogen peroxide is preferably contained; a fluorine-containing compound; an azole compound; an organic acid; a citrate salt; more than one of sulfate and phosphate; a polyol type surfactant; and water, as another embodiment of the etching liquid composition of the present invention, preferably contains hydrogen peroxide; an inorganic acid; an azole compound; an organic acid; a citrate salt; more than one of sulfate and phosphate; a polyol type surfactant; and water.
(A) Hydrogen peroxide
The hydrogen peroxide (H 2O2) contained in the etching solution composition of the present invention can be used as a main oxidizing agent for the copper-based metal film.
The content of the hydrogen peroxide may be 5.0 to 30.0 wt%, and preferably may be 8.0 to 25.0 wt%, with respect to the total weight of the composition. When the content of hydrogen peroxide is less than 5.0 wt%, the copper-based metal film may not be etched or the etching rate may be very slow, and when the content is more than 30.0 wt%, the etching rate becomes fast as a whole, and the process may not be easily controlled.
(B-1) fluorine-containing Compound
The fluorine-containing compound contained in the etching liquid composition of the present invention is a compound capable of dissociating in water to release fluorine ions. The fluorine-containing compound is a main component of etching the copper-based metal film, and serves to remove residues inevitably generated in the molybdenum film or the molybdenum alloy film.
The fluorine-containing compound is not particularly limited as long as it is a compound which is used in the art and can be dissociated into fluoride ions or polyatomic fluoride ions in a solution, and is preferably at least one selected from the group consisting of ammonium fluoride (ammonium fluoride: NH 4 F), sodium fluoride (sodium fluoride: naF), potassium fluoride (potassium fluoride: KF), ammonium bifluoride (ammonium bifluoride: NH 4 F. HF), sodium bifluoride (sodium bifluoride: naF. HF) and potassium bifluoride (potassium bifluoride: KF. HF), more preferably at least one selected from the group consisting of ammonium bifluoride and ammonium fluoride.
The content of the fluorine-containing compound may be 0.001 to 1.0% by weight, and preferably may be 0.02 to 0.20% by weight, based on the total weight of the composition. When the content of the fluorine-containing compound is less than 0.001 wt%, the etching rate of the molybdenum film or the molybdenum alloy film may be reduced, and an etching residue may be generated, and when the content is more than 1.0 wt%, the etching rate of the oxide semiconductor layer in the lower portion of the copper-based metal film may be increased.
(B-2) mineral acid
The inorganic acid contained in the etching liquid composition of the present invention can be used as a co-oxidizing agent for the copper-based metal film. When the etching liquid composition does not contain the above-mentioned inorganic acid, there is a problem that the etching rate is lowered and the process time is increased. In addition, if the tip of the molybdenum film or the molybdenum alloy film is generated on the upper portion of the copper-based metal film as the etching rate of the molybdenum film or the molybdenum alloy film decreases, defects may be induced in the subsequent steps.
In one embodiment, the inorganic acid may be one or more selected from the group consisting of nitric acid, sulfuric acid, and phosphoric acid.
The content of the inorganic acid may be 0.001 to 1.0 wt%, and preferably may be 0.005 to 0.5 wt%, with respect to the total weight of the composition. In the case where the content of the inorganic acid is less than 0.001 wt%, the etching rate is decreased and the process time is increased, and in the case where the content is more than 1.0 wt%, there is a possibility that the etching rate of the copper film or the copper alloy film is significantly faster than that of the molybdenum film or the molybdenum alloy film, thereby causing a problem that the tip of the molybdenum film or the molybdenum alloy film located on the upper portion of the copper film or the copper alloy film is located.
(C) Azole compounds
The azole compound contained in the etching solution composition of the present invention serves to adjust the etching rate and reduce the variation of the etching (Etch) profile due to the number of processed sheets, thereby improving the process margin.
In one or more embodiments, the azole compound may be selected from pyrrole (pyrrole) based compounds; pyrazole (pyrazol) compound; imidazole (imidazole) compounds including imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-aminoimidazole, 4-methylimidazole, 4-ethylimidazole, and 4-propylimidazole; triazole (triazole) compounds including benzotriazole (benzotriazole), methylbenzotriazole (tolyltriazole), and methyltriazole; tetrazole (tetrazole) compounds including aminotetrazole (aminotetrazole) and methyltetrazole; a pentazole (pentazole) compound; an azole (oxazole) compound; different species An azole (isoxazole) compound; more than one kind of thiazole (thiazole) compound and isothiazole (isothiazole) compound is preferably tetrazole (tetrazole) compound.
The azole compound may be contained in an amount of 0.01 to 2.0 wt%, preferably 0.05 to 1.0 wt%, based on the total weight of the composition. When the content of the azole compound is less than 0.01 wt%, the etching rate becomes high, and a CD Loss (CD Loss) may occur excessively, and when the content is more than 2.0 wt%, the etching rate of the copper-based metal film is too low, and an etching residue may occur.
(D) Organic acid
The organic acid contained in the etching solution composition of the present invention is a treatment number improver, and can chelate copper ions to improve the treatment number of the copper-based metal film.
In one embodiment, the organic acid may be one or more selected from the group consisting of acetic acid, iminodiacetic acid, ethylenediamine tetraacetic acid, butyric acid, citric acid, isocitric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, valeric acid, sulfobenzoic acid, succinic acid, sulfosuccinic acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, malic acid, tartaric acid, and acrylic acid, and preferably one or more selected from the group consisting of citric acid, gluconic acid, and iminodiacetic acid.
The content of the organic acid may be 1.0 to 10.0% by weight, and preferably may be 2.0 to 7.0% by weight, relative to the total weight of the composition. When the content of the organic acid is less than 1.0 wt%, the etching rate of the copper-based metal film may be reduced to generate etching residues as the number of processed sheets increases, and when the content is more than 10.0 wt%, overetching of the copper-based metal film may be caused.
(E) Citrate salt
The citrate contained in the etching solution composition of the present invention assists the action of the organic acid to chelate copper ions, thereby suppressing the decomposition reaction of the hydrogen peroxide. In addition, when the copper-based metal film is etched by using the apparatus, the citrate can serve to minimize a change in etching characteristics of the etchant composition due to concentration of the etchant composition by the exhaust gas. In the case where the etching solution composition does not contain the citrate, as the exhaust time increases, the etching Rate (Etch Rate) changes more, and thus the Rate of change of the undercut (SideEtch) may become more.
In one embodiment, the Citrate may be in the form of a salt of citric acid, and may be at least one selected from the group consisting of monosodium Citrate (Monosodium Citrate), disodium Citrate (Disodium Citrate), and trisodium Citrate (Trisodium Citrate), and preferably may be trisodium Citrate.
The citrate may be contained in an amount of 0.1 to 5.0 wt%, preferably 0.5 to 3 wt%, based on the total weight of the composition. When the content of the citrate is less than 0.1 wt%, the damage rate of the oxide semiconductor layer increases as the exhaust time increases, and the element characteristics may be lowered, and when the content is more than 5.0 wt%, the etching rate of the copper film may be lowered due to an increase in pH, which may cause difficulty in the process.
When the citrate is used in the above-described range, the damage rate of the oxide semiconductor layer is constantly maintained even if the exhaust time increases, and thus, even if the process is performed, the deterioration of the element characteristics does not occur, and the process can be easily controlled.
(F) More than one of sulfate and phosphate
The sulfate and the phosphate contained in the etching solution composition of the present invention are components for increasing the etching rate of the molybdenum film or the molybdenum alloy film, and can realize a fine pattern by adjusting the etching rate. In particular, when the copper-based metal film is formed as a multilayer film, the etching rates of the upper and lower metal films of the multilayer film can be simultaneously made to realize a fine pattern.
The sulfate is not particularly limited as long as one or two hydrogens selected from the group consisting of sulfuric acid are replaced with ammonium, alkali metal or alkaline earth metal, and may be, for example, one or more selected from the group consisting of ammonium sulfate, ammonium persulfate, sodium sulfate, sodium persulfate, potassium sulfate and potassium persulfate, and preferably may be sodium sulfate.
The phosphate may be, for example, at least one selected from the group consisting of monoammonium phosphate and diammonium phosphate.
The content of one or more of the sulfate and the phosphate is not particularly limited, and may be, for example, 0.01 to 5% by weight, preferably 0.01 to 1.0% by weight, based on the total weight of the etching liquid composition. When the content of one or more of the sulfate and the phosphate is within the above range, the etching rate of the copper-based metal film can be adjusted to realize a fine pattern. In particular, by increasing the etching rate of the molybdenum film or the molybdenum alloy film, the phenomenon that the copper film or the copper alloy film is excessively etched to form a stepped tapered profile during etching of the molybdenum film or the molybdenum alloy film can be prevented. When the content of one or more of the sulfate and the phosphate is out of the above range, the CD loss of the upper copper film or the copper alloy film becomes serious and the line width becomes narrow, so that the resistance becomes large and the advantage of the low-resistance metal is lost.
(G) Polyol type surfactant
The above-mentioned polyol type surfactant contained in the etching liquid composition of the present invention plays a role of reducing the surface tension and improving the etching uniformity. The polyol surfactant can also surround copper ions dissolved in the etchant composition after etching the copper-based metal film, thereby suppressing the activity of the copper ions and suppressing the decomposition reaction of the hydrogen peroxide. If the activity of copper ions is lowered, the process can be stably performed during the use of the etching liquid composition.
In one embodiment, the polyol-type surfactant may be one or more selected from the group consisting of glycerol (glycerol), diethylene glycol (DIETHYLENE GLYCOL), triethylene glycol (TRIETHYLENE GLYCOL), tetraethylene glycol (tetraethyleneglycol) and polyethylene glycol (polyethylene glycol), and more preferably one or more selected from the group consisting of triethylene glycol, diethylene glycol and tetraethylene glycol.
The content of the above-mentioned polyol type surfactant may be 0.001 to 5.0% by weight, preferably 0.1 to 3.0% by weight, relative to the total weight of the composition. When the content of the polyol surfactant is less than 0.001 wt%, there is a possibility that etching uniformity is lowered, and the decomposition of the hydrogen peroxide is accelerated, and when the content is more than 5.0 wt%, there is a disadvantage that a large amount of bubbles are generated.
(H) Water and its preparation method
The water contained in the copper-based metal film etching liquid composition of the present invention may be deionized water for a semiconductor process, and preferably 18mΩ·cm or more.
The water may be contained in an amount of 100% by weight based on the total weight of the composition. Specifically, in the present invention, the term "balance" means that the total weight of the composition containing the essential components of the present invention and other additional components is set to 100% by weight, and the composition of the present invention does not contain additional components in the meaning of "balance".
Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are provided to more specifically illustrate the present invention, and the scope of the present invention is not limited by the following examples. The scope of the present invention is indicated in the claims, and all changes that come within the meaning and range of equivalency of the claims are intended to be embraced therein. In the following examples and comparative examples, "%" and "parts" indicating the content are based on mass unless otherwise specified.
Production of copper-based Metal film etchant composition of examples and comparative examples
Copper-based metal film etchant compositions of examples and comparative examples were prepared with reference to the following [ table 1].
TABLE 1
(Unit: wt%)
(A) : hydrogen peroxide
(B-1): ammonium fluoride
(B-2): nitric acid
(C) : methyltetrazole
(D1) : glycolic acid
(D2) : citric acid
(D3) : iminodiacetic acid
(E1) : citric acid trisodium salt
(E2) : citric acid monosodium salt
(E3) : citric acid disodium salt
(F1) : sodium sulfate
(F2) : monoammonium phosphate
(G) : triethylene glycol
Test example 1: etch profile and etch straightness evaluation
A Mo-Ti film is deposited on an IGZO active layer (ACTIVE LAYER) on a glass substrate (100 mm x 100 mm), a copper film is deposited on the Mo-Ti film, and then a photoresist having a predetermined pattern is formed on the substrate by a photolithography (photolithography) process. Then, etching steps were performed on the Cu/mo—ti bilayer films using the etching liquid compositions of examples and comparative examples, respectively.
In the etching step, a jet etching type experimental apparatus (model name: ETCHER (TFT), SEMES) was used, and the etching time was 150 seconds at a temperature of about 32℃in the etching step. The cross section of the copper-based metal film etched by the etching step was photographed using SEM (model name S-4700 of Hitachi) and then evaluated according to the following evaluation criteria, and the results are shown in table 2 below.
< Etching Profile evaluation criterion >
O: cone angle of 30 DEG or more and less than 65 DEG
Delta: the taper angle is 25 DEG or more and less than 30 DEG or 65 DEG or more and 70 DEG or less
X: cone angle of 25 deg. or less or more than 70 deg
Unetch: failure to etch
< Evaluation criterion of etching straightness >
O: the pattern is formed in a straight line
Delta: the curve form in the pattern is below 20%
X: the curve form in the pattern is more than 20 percent
Unetch: failure to etch
Test example 2: measurement of change in damage ratio (DAMAGERATE) of oxide semiconductor layer (IGZO) with change in exhaust time
The copper-based metal film was etched in the same etching process as in test example 1, and the amount of change in the damage rate of the etching solution composition with respect to the oxide semiconductor layer (IGZO) immediately after the production was measured for 72 hours, and the results are shown in table 2 below.
TABLE 2
When the etching process was performed using the copper-based metal film etching solution composition of the example, it was confirmed that the etching profile, etching straightness, and the change amount characteristics of the IGZO rate with the change in the exhaust time were excellent.
On the other hand, when the etching step was performed using the copper-based metal film etching solution composition of the comparative example, it was confirmed that the etching profile and etching straightness were poor, and the amount of change in the damage rate of IGZO with the change in the exhaust time exceededSec, the process is not easily controlled, and the characteristics of the element are degraded.
Claims (12)
1. A method for manufacturing an array substrate for a liquid crystal display device, comprising:
a) A step of forming a gate electrode on a substrate;
b) A step of forming a gate insulating layer on a substrate including the gate electrode;
c) A step of forming an oxide semiconductor layer IGZO on the gate insulating layer;
d) A step of forming a source electrode/drain electrode on the oxide semiconductor layer; and
E) A step of forming a pixel electrode connected to the source/drain electrode,
In the step d), a copper-based metal film is formed on the oxide semiconductor layer, and the copper-based metal film is etched by an etchant composition including hydrogen peroxide to form the source/drain electrodes; fluorine-containing compounds or inorganic acids; an azole compound; an organic acid; comprises one or more citrates selected from the group consisting of monosodium citrate, disodium citrate, and trisodium citrate; more than one of sulfate and phosphate; a polyol type surfactant; and water.
2. The method of manufacturing an array substrate for a liquid crystal display device according to claim 1, wherein the copper-based metal film is a single-layer film made of copper or a copper alloy, or a multilayer film including the single-layer film and a film made of molybdenum or a molybdenum alloy.
3. The method of manufacturing an array substrate for a liquid crystal display device according to claim 1, wherein the array substrate for a liquid crystal display device is a thin film transistor TFT array substrate.
4.A copper-based metal film etching liquid composition comprising, relative to the total weight of the composition:
(A) 5.0 to 30.0 weight percent of hydrogen peroxide;
(B) 0.001 to 1.0 wt% of a fluorine-containing compound or an inorganic acid;
(C) 0.01 to 2.0 wt% of an azole compound;
(D) 1.0 to 10.0 wt% of an organic acid;
(E) 0.1 to 5% by weight of one or more citrates selected from the group consisting of monosodium citrate, disodium citrate and trisodium citrate;
(F) More than 0.01 to 5 weight percent of one of sulfate and phosphate;
(G) 0.001 to 5.0 wt% of a polyol surfactant; and
(H) And (3) water.
5. The copper-based metal film etchant composition according to claim 4, wherein the copper-based metal film is a single-layer film made of copper or copper alloy, or a multi-layer film comprising the single-layer film and a molybdenum-based single-layer film made of molybdenum or molybdenum alloy.
6. The copper-based metal film etching liquid composition according to claim 4, wherein the fluorine-containing compound is at least one selected from the group consisting of ammonium fluoride (NH 4 F), sodium fluoride (NaF), potassium fluoride (KF), ammonium bifluoride (NH 4 F-HF), sodium bifluoride (NaF-HF) and potassium bifluoride (KF-HF).
7. The copper-based metal film etching liquid composition according to claim 4, wherein the inorganic acid is at least one selected from the group consisting of nitric acid, sulfuric acid and phosphoric acid.
8. The copper-based metal film etching liquid composition according to claim 4, wherein the azole compound is selected from the group consisting of pyrrole-based compounds, pyrazole-based compounds, imidazole-based compounds, triazole-based compounds, tetrazole-based compounds, and pentazole-based compounds,Azole compounds, iso-compoundsAt least one kind selected from the group consisting of azole compounds, thiazole compounds and isothiazole compounds.
9. The copper-based metal film etching liquid composition according to claim 4, wherein the organic acid is at least one selected from the group consisting of acetic acid, iminodiacetic acid, ethylenediamine tetraacetic acid, butyric acid, citric acid, isocitric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, valeric acid, sulfobenzoic acid, succinic acid, sulfosuccinic acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, malic acid, tartaric acid, and acrylic acid.
10. The copper-based metal film etching liquid composition according to claim 4, wherein the sulfate is at least one selected from the group consisting of ammonium sulfate, ammonium persulfate, sodium sulfate, sodium persulfate, potassium sulfate and potassium persulfate.
11. The copper-based metal film etching liquid composition according to claim 4, wherein the phosphate is at least one selected from the group consisting of monoammonium phosphate and diammonium phosphate.
12. The copper-based metal film etching liquid composition according to claim 4, wherein the polyhydric alcohol-type surfactant comprises at least one selected from the group consisting of glycerol, diethylene glycol, triethylene glycol, tetraethylene glycol and polyethylene glycol.
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