KR102245660B1 - Etchant composition for molybdenum alloy layer and indium oxide layer and method for manufacturing an array substrate for liquid crystal display - Google Patents
Etchant composition for molybdenum alloy layer and indium oxide layer and method for manufacturing an array substrate for liquid crystal display Download PDFInfo
- Publication number
- KR102245660B1 KR102245660B1 KR1020140184420A KR20140184420A KR102245660B1 KR 102245660 B1 KR102245660 B1 KR 102245660B1 KR 1020140184420 A KR1020140184420 A KR 1020140184420A KR 20140184420 A KR20140184420 A KR 20140184420A KR 102245660 B1 KR102245660 B1 KR 102245660B1
- Authority
- KR
- South Korea
- Prior art keywords
- indium oxide
- molybdenum alloy
- oxide film
- film
- alloy film
- Prior art date
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- 229910001182 Mo alloy Inorganic materials 0.000 title claims abstract description 74
- 229910003437 indium oxide Inorganic materials 0.000 title claims abstract description 67
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 239000000758 substrate Substances 0.000 title claims abstract description 30
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 230000007797 corrosion Effects 0.000 claims abstract description 14
- 238000005260 corrosion Methods 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003112 inhibitor Substances 0.000 claims abstract description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 11
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical class O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010408 film Substances 0.000 claims description 143
- 238000005530 etching Methods 0.000 claims description 46
- 239000010949 copper Substances 0.000 claims description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 19
- -1 HBF 4 Inorganic materials 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 11
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 150000005846 sugar alcohols Polymers 0.000 claims description 6
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 239000012964 benzotriazole Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-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
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 claims description 3
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 3
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 claims description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 3
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 150000003536 tetrazoles Chemical class 0.000 claims description 3
- 150000003852 triazoles Chemical class 0.000 claims description 3
- 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
- VMSBGXAJJLPWKV-UHFFFAOYSA-N 2-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=C VMSBGXAJJLPWKV-UHFFFAOYSA-N 0.000 claims description 2
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 claims description 2
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 2
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- YZMHQCWXYHARLS-UHFFFAOYSA-N naphthalene-1,2-disulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C21 YZMHQCWXYHARLS-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical class 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 10
- 239000010936 titanium Substances 0.000 description 7
- 229920002120 photoresistant polymer Polymers 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910000846 In alloy Inorganic materials 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- HIMXGTXNXJYFGB-UHFFFAOYSA-N alloxan Chemical compound O=C1NC(=O)C(=O)C(=O)N1 HIMXGTXNXJYFGB-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VFPFQHQNJCMNBZ-UHFFFAOYSA-N ethyl gallate Chemical compound CCOC(=O)C1=CC(O)=C(O)C(O)=C1 VFPFQHQNJCMNBZ-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- FBSFWRHWHYMIOG-UHFFFAOYSA-N methyl 3,4,5-trihydroxybenzoate Chemical compound COC(=O)C1=CC(O)=C(O)C(O)=C1 FBSFWRHWHYMIOG-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- 239000004262 Ethyl gallate Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- AFTDTIZUABOECB-UHFFFAOYSA-N [Co].[Mo] Chemical compound [Co].[Mo] AFTDTIZUABOECB-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XTKDAFGWCDAMPY-UHFFFAOYSA-N azaperone Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCN(C=2N=CC=CC=2)CC1 XTKDAFGWCDAMPY-UHFFFAOYSA-N 0.000 description 1
- XOPOEBVTQYAOSV-UHFFFAOYSA-N butyl 3,4,5-trihydroxybenzoate Chemical compound CCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 XOPOEBVTQYAOSV-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 235000019277 ethyl gallate Nutrition 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 229960005150 glycerol Drugs 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002596 lactones Chemical group 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 229960001855 mannitol Drugs 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- IBKQQKPQRYUGBJ-UHFFFAOYSA-N methyl gallate Natural products CC(=O)C1=CC(O)=C(O)C(O)=C1 IBKQQKPQRYUGBJ-UHFFFAOYSA-N 0.000 description 1
- ZPZCREMGFMRIRR-UHFFFAOYSA-N molybdenum titanium Chemical compound [Ti].[Mo] ZPZCREMGFMRIRR-UHFFFAOYSA-N 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
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000010388 propyl gallate Nutrition 0.000 description 1
- 239000000473 propyl gallate Substances 0.000 description 1
- 229940075579 propyl gallate Drugs 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 230000021148 sequestering of metal ion Effects 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229960002920 sorbitol Drugs 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 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
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- C23F1/30—Acidic compositions for etching other metallic material
-
- 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
- G02F1/1333—Constructional arrangements; Manufacturing methods
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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Abstract
본 발명은 조성물 총 중량에 대하여, A) 과산화수소(H2O2) 5 내지 25중량%; B) 함불소화합물 0.1 내지 2중량%; C) 히드록시기 함유 감마부티로락톤 유도체 0.5 내지 5중량%; D) 술폰산계 화합물 0.01 내지 5중량%; E) 부식방지제 0.1 내지 3중량%; 및 F) 물 잔량을 포함하는 것을 특징으로 하는 몰리브덴 합금막, 인듐 산화막, 또는 몰리브덴 합금막과 인듐 산화막의 다중막용 식각액 조성물 및 상기 조성물을 이용한 액정표시장치용 어레이 기판의 제조방법을 제공한다.The present invention is based on the total weight of the composition, A) hydrogen peroxide (H2O2) 5 to 25% by weight; B) 0.1 to 2% by weight of a fluorinated compound; C) 0.5 to 5% by weight of a gammabutyrolactone derivative containing a hydroxy group; D) 0.01 to 5% by weight of a sulfonic acid-based compound; E) 0.1 to 3% by weight of a corrosion inhibitor; And F) a molybdenum alloy film, an indium oxide film, or an etchant composition for a multilayer of a molybdenum alloy film and an indium oxide film comprising the remaining amount of water, and a method of manufacturing an array substrate for a liquid crystal display device using the composition.
Description
본 발명은 초박막 액정표시장치(TFT-LCD)의 화소전극에 사용되는 몰리브덴 합금막, 인듐 산화막 또는 몰리브덴 합금막과 인듐 산화막의 다중막의 식각 공정 시 사용되는 식각액 조성물 및 상기 식각액 조성물을 사용하는 액정표시장치용 어레이 기판의 제조방법에 관한 것이다.The present invention provides an etchant composition used in the etching process of a molybdenum alloy film, an indium oxide film, or a multilayer of a molybdenum alloy film and an indium oxide film used for a pixel electrode of an ultra-thin liquid crystal display (TFT-LCD), and a liquid crystal display using the etchant composition. It relates to a method of manufacturing an array substrate for an apparatus.
반도체 장치 및 TFT-LCD 등의 액정표시장치의 화소전극에는 몰리브덴 합금막 및 인듐 산화막의 단일막 또는 몰리브덴 합금막과 인듐 산화막의 다중막이 사용된다. 상기 화소전극은 일반적으로 스퍼터링 등의 방법을 통해 기판상에 적층시키고, 그 위에 포토레지스트를 균일하게 도포한 다음, 패턴이 새겨진 마스크를 통하여 빛을 조사한 후 현상을 통하여 원하는 패턴의 포토레지스트를 형성시킨 다음, 건식 또는 습식 식각으로 포토레지스트 하부에 있는 금속막에 패턴을 전사한 후, 필요없는 포토레지스트를 박리 공정에 의해 제거하는, 일련의 리소그래피(lithography) 공정을 거쳐 완성된다.A single film of a molybdenum alloy film and an indium oxide film, or a multiple film of a molybdenum alloy film and an indium oxide film is used for the pixel electrode of a semiconductor device and a liquid crystal display device such as a TFT-LCD. The pixel electrode is generally laminated on a substrate through a method such as sputtering, a photoresist is uniformly applied thereon, and then a photoresist having a desired pattern is formed through development after irradiating light through a pattern-engraved mask. Next, after the pattern is transferred to the metal film under the photoresist by dry or wet etching, unnecessary photoresist is removed by a stripping process, which is completed through a series of lithography processes.
상기 몰리브덴 합금막 및 인듐 산화막의 식각을 동일한 식각액으로 실시하는 경우 제조 공정을 간소화시킬 수 있으나, 일반적으로 몰리브덴 합금막은 내화학성이 우수하여 습식 식각이 용이하지 않다는 문제점이 있으며, 또한 인듐 산화막을 식각하기 위한 옥살산 계열의 식각액으로는 몰리브덴 합금막을 식각하지 못한다는 문제점이 있다.When the molybdenum alloy layer and the indium oxide layer are etched with the same etching solution, the manufacturing process can be simplified, but in general, the molybdenum alloy layer has a problem that wet etching is not easy due to excellent chemical resistance, and the indium oxide layer is etched. There is a problem in that the molybdenum alloy film cannot be etched with an oxalic acid-based etchant for this purpose.
종래 기술로서 대한민국 공개특허 제10-2014-0025817호는 과산화수소 5 내지 25중량%; 불소화합물 0.1 내지 2 중량%; 술폰산기를 갖는 화합물 0.001 내지 2 중량%; 부식방지제 0.1 내지 2 중량%; 보조산화제 0.01 내지 1 중량%; 과수안정제 0.1 내지 5 중량% 및 전체 조성물 총 중량이 100중량%가 되도록 물을 포함하는 몰리브덴 합금막, 인듐 산화막 또는 몰리브덴 합금막과 인듐 산화막의 다중막용 식각액 조성물을 개시하고 있다. 그러나 상기 조성물은 몰리브덴 합금막과 인듐 산화막에 대한 식각속도가 충분하지 못하다는 단점을 갖는다. As a prior art, Korean Patent Application Publication No. 10-2014-0025817 discloses 5 to 25% by weight of hydrogen peroxide; 0.1 to 2% by weight of a fluorine compound; 0.001 to 2% by weight of a compound having a sulfonic acid group; 0.1 to 2% by weight of a corrosion inhibitor; 0.01 to 1% by weight of a co-oxidizing agent; Disclosed is an etchant composition for a multilayer of a molybdenum alloy film, an indium oxide film, or a molybdenum alloy film and an indium oxide film containing water so that 0.1 to 5% by weight of a fruit water stabilizer and a total weight of the total composition is 100% by weight. However, the composition has a disadvantage in that the etching rate for the molybdenum alloy film and the indium oxide film is insufficient.
대한민국 공개특허 제10-2014-0025817호Republic of Korea Patent Publication No. 10-2014-0025817
본 발명은 종래기술의 상기와 같은 문제를 해결하기 위하여 안출된 것으로서, 몰리브덴 합금막과 인듐 산화막에 대한 식각속도가 우수하며, 하부의 구리계 금속막을 어텍하지 않는 몰리브덴 합금막, 인듐 산화막, 또는 몰리브덴 합금막과 인듐 산화막의 다중막용 식각액 조성물을 제공하는 것을 목적으로 한다. The present invention has been devised to solve the above problems of the prior art, has excellent etch rates for the molybdenum alloy film and the indium oxide film, and does not attack the lower copper-based metal film, a molybdenum alloy film, indium oxide film, or molybdenum An object of the present invention is to provide an etchant composition for a multilayer of an alloy film and an indium oxide film.
또한, 본 발명은 몰리브덴 합금막과 인듐 산화막의 다중막을 일괄식각이 가능한 몰리브덴 합금막, 인듐 산화막, 또는 몰리브덴 합금막과 인듐 산화막의 다중막용 식각액 조성물을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide an etchant composition for a molybdenum alloy film, an indium oxide film, or a multilayer of a molybdenum alloy film and an indium oxide film capable of batch etching a multilayer of a molybdenum alloy film and an indium oxide film.
또한, 본 발명은 상기 식각액 조성물을 사용하는 액정표시장치용 어레이 기판의 제조방법을 제공하는 것을 목적으로 한다.Another object of the present invention is to provide a method of manufacturing an array substrate for a liquid crystal display device using the etchant composition.
본 발명은, 조성물 총 중량에 대하여,The present invention, based on the total weight of the composition,
A) 과산화수소(H2O2) 5 내지 25중량%;A) 5 to 25% by weight of hydrogen peroxide (H2O2);
B) 함불소화합물 0.1 내지 2중량%;B) 0.1 to 2% by weight of a fluorinated compound;
C) 히드록시기 함유 감마부티로락톤 유도체 0.5 내지 5중량%;C) 0.5 to 5% by weight of a gammabutyrolactone derivative containing a hydroxy group;
D) 술폰산계 화합물 0.01 내지 5중량%; D) 0.01 to 5% by weight of a sulfonic acid-based compound;
E) 부식방지제 0.1 내지 3중량%; 및E) 0.1 to 3% by weight of a corrosion inhibitor; And
F) 물 잔량을 포함하는 것을 특징으로 하는 몰리브덴 합금막, 인듐 산화막, 또는 몰리브덴 합금막과 인듐 산화막의 다중막용 식각액 조성물을 제공한다. F) It provides an etchant composition for a multilayer of a molybdenum alloy film, an indium oxide film, or a molybdenum alloy film and an indium oxide film, comprising the remaining amount of water.
또한, 본 발명은In addition, the present invention
a)기판 상에 게이트 배선을 형성하는 단계;a) forming a gate wiring on the substrate;
b)상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;b) forming a gate insulating layer on the substrate including the gate wiring;
c)상기 게이트 절연층 상에 반도체층을 형성하는 단계;c) forming a semiconductor layer on the gate insulating layer;
d)상기 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및d) forming source and drain electrodes on the semiconductor layer; And
e)상기 드레인 전극에 연결된 화소전극을 형성하는 단계를 포함하는 액정표시장치용 어레이 기판의 제조방법에 있어서,e) In a method of manufacturing an array substrate for a liquid crystal display device comprising the step of forming a pixel electrode connected to the drain electrode,
상기 e)단계는 기판 상에 몰리브덴 합금막, 인듐 산화막, 또는 몰리브덴 합금막과 인듐 산화막의 다중막을 형성하고 상기 형성된 막을 상기 본 발명의 식각액 조성물로 식각하는 단계를 포함하는 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조방법을 제공한다.
The step e) comprises forming a molybdenum alloy film, an indium oxide film, or a multilayer of a molybdenum alloy film and an indium oxide film on a substrate, and etching the formed film with the etchant composition of the present invention. It provides a method of manufacturing an array substrate for use.
또한, 본 발명은In addition, the present invention
상기 본 발명의 식각액 조성물을 사용하여 식각된 화소전극을 포함하는 액정표시장치용 어레이 기판을 제공한다.An array substrate for a liquid crystal display device including a pixel electrode etched using the etchant composition of the present invention is provided.
본 발명의 식각액 조성물은 몰리브덴 합금막과 인듐 산화막에 대한 식각속도가 우수하며, 하부의 구리계 금속막을 어텍하지 않으므로 화소전극의 형성에 유용하게 사용될 수 있다. The etchant composition of the present invention has excellent etch rates for the molybdenum alloy film and the indium oxide film, and does not attack the lower copper-based metal film, so it can be usefully used for forming a pixel electrode.
또한, 본 발명의 몰리브덴 합금막, 인듐 산화막, 또는 몰리브덴 합금막과 인듐 산화막의 다중막용 식각액 조성물은 몰리브덴 합금막과 인듐 산화막의 다중막을 일괄식각할 수 있기 때문에 화소전극의 형성시 공정효율을 크게 향상시키는 효과를 제공한다. In addition, the etchant composition for a multilayer of a molybdenum alloy film, an indium oxide film, or a molybdenum alloy film and an indium oxide film of the present invention can etch a multilayer of a molybdenum alloy film and an indium oxide film at a time, thus greatly improving process efficiency when forming a pixel electrode. Provides a lethal effect.
본 발명은 조성물 총 중량에 대하여, A) 과산화수소(H2O2) 5 내지 25중량%; B) 함불소화합물 0.1 내지 2중량%; C) 히드록시기 함유 감마부티로락톤 유도체 0.5 내지 5중량%; D) 술폰산계 화합물 0.01 내지 5중량%; E) 부식방지제 0.1 내지 3중량%; 및 F) 물 잔량을 포함하는 것을 특징으로 하는 몰리브덴 합금막, 인듐 산화막, 또는 몰리브덴 합금막과 인듐 산화막의 다중막용 식각액 조성물에 관한 것이다.
The present invention is based on the total weight of the composition, A) hydrogen peroxide (H2O2) 5 to 25% by weight; B) 0.1 to 2% by weight of a fluorinated compound; C) 0.5 to 5% by weight of a gammabutyrolactone derivative containing a hydroxy group; D) 0.01 to 5% by weight of a sulfonic acid-based compound; E) 0.1 to 3% by weight of a corrosion inhibitor; And F) an etchant composition for a multilayer of a molybdenum alloy film, an indium oxide film, or a molybdenum alloy film and an indium oxide film comprising the remaining amount of water.
본 발명에 있어서, 상기 몰리브덴 합금막은 예컨대, 티타늄(Ti), 탄탈륨(Ta), 크롬(Cr), 니켈(Ni) 및 네오디늄(Nd) 등으로 이루어진 군에서 선택되는 하나 이상과 몰리브덴의 합금막을 의미한다. 구체적으로 몰리브덴-티타늄 합금막 또는 몰리브덴-코발트 합금막을 들 수 있다. 상기 인듐 산화막으로는 투명전도막으로서 인듐아연산화막(IZO) 또는 인듐주석산화막(ITO)을 들 수 있다.In the present invention, the molybdenum alloy film comprises, for example, an alloy film of molybdenum and at least one selected from the group consisting of titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni) and neodymium (Nd). it means. Specifically, a molybdenum-titanium alloy film or a molybdenum-cobalt alloy film may be mentioned. The indium oxide film may be an indium zinc oxide film (IZO) or an indium tin oxide film (ITO) as a transparent conductive film.
상기 몰리브덴 합금막과 인듐 산화막의 다중막은 몰리브덴 합금막과 인듐 산화막으로 이루어지는 이중막 이상의 막을 의미한다.
The multilayer of the molybdenum alloy layer and the indium oxide layer refers to a double layer or more formed of a molybdenum alloy layer and an indium oxide layer.
본 발명에서 있어서, 상기 A) 과산화수소는 주 산화제로 작용한다. 상기 과산화수소는 조성물의 총 중량에 대하여 5 내지 25중량%로 포함될 수 있으며, 바람직하게는 10 내지 20중량%, 더욱 바람직하게는 12 내지 18중량%로 포함된다.In the present invention, A) hydrogen peroxide acts as a main oxidizing agent. The hydrogen peroxide may be included in an amount of 5 to 25% by weight, preferably 10 to 20% by weight, more preferably 12 to 18% by weight based on the total weight of the composition.
과산화수소가 5 중량% 미만으로 포함될 경우 몰리브덴 합금의 산화력이 충분하지 못하여 식각이 이루어지지 않을 수 있고, 25중량%를 초과하여 포함되는 경우 화소전극 하부막 등에 과도한 식각을 발생시킬 수 있으며, 식각속도가 너무 빨라져 공정상 제어가 어려워져 바람직하지 못하다.
If hydrogen peroxide is contained in an amount of less than 5% by weight, etching may not be performed due to insufficient oxidizing power of the molybdenum alloy. If it is contained in an amount exceeding 25% by weight, excessive etching may occur on the lower layer of the pixel electrode, etc. It is too fast, and it is difficult to control in the process, which is not preferable.
상기 B) 함불소화합물은 몰리브덴 합금막, 인듐 산화막 또는 몰리브덴 합금막과 인듐 산화막의 다중막에 대해 주 식각제로서 작용하며 식각 속도 증가 및 잔사 제거의 작용을 한다. The fluorinated compound B) acts as a main etchant for a molybdenum alloy film, an indium oxide film, or a multilayer of a molybdenum alloy film and an indium oxide film, and functions to increase an etching rate and remove residues.
상기 함불소화합물은 해리되어 F-나 HF2 -를 낼 수 있는 화합물이며, 예컨대, HF, NaF, KF, AlF3, HBF4, NH4F, NH4HF2, NaHF2, KHF2 및 NH4BF4 등으로 이루어진 군으로부터 선택될 수 있으며, 이들은 1종 단독으로 또는 2종 이상을 조합하여 사용할 수 있다. The fluorinated compound is a compound that can dissociate to give F - or HF 2 - , for example, HF, NaF, KF, AlF 3 , HBF 4 , NH 4 F, NH 4 HF 2 , NaHF 2 , KHF 2 and NH 4 BF 4 It may be selected from the group consisting of, and the like, and these may be used alone or in combination of two or more.
상기 함불소화합물은 조성물의 총 중량에 대하여 0.1 내지 2중량%로 포함될수 있으며, 바람직하게는 0.1 내지 1.5중량%로 포함된다. 함불소화합물이 0.1중량% 미만으로 포함되는 경우 식각 속도가 느려지고 식각 후 몰리브덴 합금막, 인듐 산화막, 또는 몰리브덴 합금막과 인듐 산화막의 다중막의 잔사가 발생할 수 있고, 2 중량%를 초과하여 포함되는 경우 하부막인 절연막 및 소스 드레인 전극을 이루는 구리막에 대해 과도하게 식각 작용을 할 수 있으므로 바람직하지 못하다.
The fluorinated compound may be included in an amount of 0.1 to 2% by weight, preferably 0.1 to 1.5% by weight, based on the total weight of the composition. When the fluorine-containing compound is contained in an amount of less than 0.1% by weight, the etching rate is slowed, and after etching, a residue of a molybdenum alloy film, an indium oxide film, or a multilayer of a molybdenum alloy film and an indium oxide film may occur, and if it contains more than 2% by weight It is not preferable because an excessive etching action may be performed on the insulating layer, which is the lower layer, and the copper layer forming the source and drain electrode.
상기 C) 히드록시기 함유 감마부티로락톤 유도체는 몰리브덴 합금막, 인듐 산화막, 또는 몰리브덴 합금막과 인듐 산화막의 다중막의 식각속도를 향상시키는 기능을 한다. The C) hydroxy group-containing gamma butyrolactone derivative functions to improve the etching rate of a molybdenum alloy film, an indium oxide film, or a multilayer of a molybdenum alloy film and an indium oxide film.
상기 히드록시기 함유 감마부티로락톤 유도체는 조성물 총 중량에 대하여 0.5 내지 5중량%로 포함될 수 있으며, 바람직하게는 1 내지 3중량%로 포함될 수 있다. 상기 히드록시기 함유 감마부티로락톤 유도체가 0.5중량% 미만으로 포함되는 경우, 몰리브덴 합금막, 인듐 산화막, 또는 몰리브덴 합금막과 인듐 산화막의 다중막의 식각속도 증가를 기대하기 어려우며, 5중량%를 초과하여 포함되는 경우는 인듐산화막의 식각속도가 지나치게 증가하여 패턴균일성을 확보하기 어려운 문제가 야기될 수 있어 바람직하지 않다.The hydroxy group-containing gamma butyrolactone derivative may be included in an amount of 0.5 to 5% by weight, preferably 1 to 3% by weight, based on the total weight of the composition. When the gamma butyrolactone derivative containing the hydroxy group is contained in an amount of less than 0.5% by weight, it is difficult to expect an increase in the etch rate of the molybdenum alloy film, the indium oxide film, or the multilayer of the molybdenum alloy film and the indium oxide film, and contains more than 5% by weight. In this case, the etching rate of the indium oxide layer is excessively increased, which may cause a problem in which it is difficult to secure pattern uniformity, which is not preferable.
상기 C) 히드록시기 함유 감마부티로락톤 유도체는 하기 화학식 1로 표시되는 화합물일 수 있다:The C) hydroxy group-containing gamma butyrolactone derivative may be a compound represented by the following formula (1):
[화학식 1][Formula 1]
상기 식에서In the above formula
R1, R2 및 R3는, 각각 독립적으로, 수소; 히드록시기; C1~C5의 알킬기; C1~C5의 알콕시기; 또는 C1~C5의 알콕시기, 아세톡시기 및 히드록시기로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환된 C1~C5의 알킬기이며, 상기에서 R2 및 R3 중 어느 하나는 부존재일 수 있으며; R1, R2 and R3 are each independently hydrogen; Hydroxy group; C1-C5 alkyl group; C1-C5 alkoxy group; Or a C1-C5 alkyl group substituted with one or more substituents selected from the group consisting of a C1-C5 alkoxy group, an acetoxy group, and a hydroxy group, wherein any one of R2 and R3 may be absent;
R4는 수소, C1~C5의 알킬기, 또는 C1~C5의 아세틸기일 수 있다.R4 may be hydrogen, a C1-C5 alkyl group, or a C1-C5 acetyl group.
상기에서 R2 및 R3 중 어느 하나가 부존재인 경우는 R2 및 R3가 결합되어 있는 탄소가 락톤고리 내의 인접 탄소와 이중결합을 형성하는 경우이다.
In the above, when any one of R2 and R3 is absent, the carbon to which R2 and R3 are bonded forms a double bond with an adjacent carbon in the lactone ring.
구체적으로, 상기 화학식 1의 화합물은 하기 화학식들로부터 선택되는 어느 하나일 수 있다:Specifically, the compound of Formula 1 may be any one selected from the following formulas:
상기 D) 술폰산계 화합물은 몰리브덴 합금막, 인듐합금막, 구리막 및 글라스의 식각속도를 향상시키는 역할을 하나, 구리막 및 글라스 대비, 상대적으로 몰리브덴 합금막 및 인듐합금막의 식각속도를 보다 향상시키는 역할을 수행한다. The D) sulfonic acid-based compound serves to improve the etching rate of the molybdenum alloy layer, the indium alloy layer, the copper layer, and the glass, but relatively improves the etching rate of the molybdenum alloy layer and the indium alloy layer compared to the copper layer and the glass. Play a role.
상기 술폰산계 화합물로는 알킬술폰산, 알킬디술폰산, 알킬벤젠술폰산, 알킬페닐에테르디술폰산, 알킬나프탈렌술폰산, 나프탈렌술폰산, 나프탈렌디술폰산, 포름알데히드와 나프탈렌 술폰산의 중합체, 아크릴아미도메틸프로판술폰산의 중합체, 아크릴산과 아크릴아미도메틸프로판술폰산의 공중합체 및 비닐벤젠술폰산중합체로부터 선택되는 술폰산기 또는 그 염을 갖고 있는 화합물을 들 수 있으며, 이들은 1종 단독으로 또는 2종 이상의 조합으로 사용될 수 있다. 상기 술폰산계 화합물중에서, 조성물내의 안정성, 식각 성능 및 경제적인 면에서 파라톨루엔술폰산 및 메탄술폰산이 바람직하다.Examples of the sulfonic acid-based compound include alkylsulfonic acid, alkyldisulfonic acid, alkylbenzenesulfonic acid, alkylphenyl ether disulfonic acid, alkylnaphthalenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid, polymer of formaldehyde and naphthalene sulfonic acid, and polymer of acrylamidomethylpropanesulfonic acid. , A sulfonic acid group selected from a copolymer of acrylic acid and acrylamidomethylpropane sulfonic acid and a vinylbenzene sulfonic acid polymer, or a compound having a salt thereof, and these may be used alone or in combination of two or more. Among the sulfonic acid-based compounds, paratoluenesulfonic acid and methanesulfonic acid are preferred in terms of stability, etching performance, and economical efficiency in the composition.
상기 술폰산계 화합물은 0.01 내지 5중량%로 포함될 수 있으며, 바람직하게는 0.1 내지 3중량%로 포함될 수 있다. 상기 술폰산계 화합물이 0.01중량% 미만으로 포함되는 경우에는 몰리브덴 합금막의 식각속도가 충분히 향상되지 못하며, 5중량%를 초과하는 경우는 인듐산화막의 지나친 식각에 의해 패턴 균일성 확보가 곤란해질 수 있어 바람직하지 않다.
The sulfonic acid-based compound may be included in an amount of 0.01 to 5% by weight, preferably 0.1 to 3% by weight. When the sulfonic acid-based compound is contained in an amount of less than 0.01% by weight, the etching rate of the molybdenum alloy layer cannot be sufficiently improved, and when it exceeds 5% by weight, it may be difficult to secure pattern uniformity due to excessive etching of the indium oxide layer. I don't.
상기 E) 부식방지제는 화소전극 식각 공정 중에서 화소전극과 소스/드레인 전극의 컨택홀과 절연막의 크랙에 의해서 발생할 수 있는, 소스/ 드레인 전극 등 하부막으로 사용되는 구리막의 식각을 방지하는 작용을 한다.The E) corrosion inhibitor acts to prevent etching of the copper layer used as a lower layer such as the source/drain electrode, which may be caused by cracks of the contact hole between the pixel electrode and the source/drain electrode and the insulating layer during the pixel electrode etching process. .
상기 부식방지제로는 고리 헤테로 방향족 화합물, 고리 헤테로 지방족 화합물, 방향족 다가알콜 및 직쇄구조 다가알콜류로 이루어진 군으로부터 선택되는 것을 들 수 있으며, 이들은 1종 단독으로 또는 2종 이상의 조합으로 사용될 수 있다.Examples of the corrosion inhibitor include those selected from the group consisting of cyclic heteroaromatic compounds, cyclic heteroaliphatic compounds, aromatic polyhydric alcohols and linear polyhydric alcohols, and these may be used alone or in combination of two or more.
상기 고리 헤테로 방향족 화합물로는 퓨란, 티오펜, 피롤, 옥사졸, 티아졸, 이미다졸, 피라졸, 트리아졸, 테트라졸, 벤조퓨란, 벤조티오펜, 인돌, 벤조티아졸, 벤조이미다졸, 벤조피라졸, 아미노테트라졸, 메틸테트라졸, 톨루트리아졸, 하이드로톨루트리아졸, 하이드록시톨루트리아졸 등을 들 수 있으며; 상기 고리 헤테로 지방족 화합물로는 피페라진, 메틸피페라진, 하이드록실에틸피페라진, 피롤리딘, 알록산 등을 들 수 있다. The cyclic heteroaromatic compounds include furan, thiophene, pyrrole, oxazole, thiazole, imidazole, pyrazole, triazole, tetrazole, benzofuran, benzothiophene, indole, benzothiazole, benzoimidazole, benzo Pyrazole, aminotetrazole, methyltetrazole, tolutriazole, hydrotolutriazole, hydroxytolutriazole, and the like; Examples of the cyclic heteroaliphatic compound include piperazine, methyl piperazine, hydroxylethyl piperazine, pyrrolidine, and alloxane.
상기 방향족 다가알코올로는 갈산, 메틸갈레이트, 에틸갈레이트, 프로필갈레이트, 부틸갈레이트 등을 들 수 있으며, 상기 직쇄구조 다가알코올로는 글리세롤, 에리스리톨, 솔비톨, 마니톨, 자일리톨 등을 들 수 있다. The aromatic polyhydric alcohol may include gallic acid, methyl gallate, ethyl gallate, propyl gallate, butyl gallate, and the like, and the linear polyhydric alcohol may include glycerol, erythritol, sorbitol, mannitol, xylitol, and the like. have.
상기 부식방지제는 조성물 총 중량에 대하여, 0.1 내지 3중량%로 포함될 수일 수있으며, 바람직하게는 0.5 내지 1.5 중량%로 포함될 수 있다. 부식방지제가 0.1 중량% 미만으로 포함될 경우 구리막에 대한 부식방지 성능이 충분하지 않아 하부 구리막의 부식을 막기 어렵고, 3중량%를 초과하여 포함되는 경우 구리막에 대한 부식방지 성능은 우수하나 화소전극을 이루는 몰리브덴 합금막, 인듐 산화막, 또는 몰리브덴합금막과 인듐 산화막의 다중막에 대한 식각 속도가 저하될 수 있다. The corrosion inhibitor may be included in an amount of 0.1 to 3% by weight, preferably 0.5 to 1.5% by weight, based on the total weight of the composition. If the corrosion inhibitor is contained in an amount of less than 0.1% by weight, it is difficult to prevent corrosion of the lower copper film because the corrosion prevention performance for the copper film is insufficient. The etching rate of the molybdenum alloy layer, the indium oxide layer, or the multiple layers of the molybdenum alloy layer and the indium oxide layer forming the may be reduced.
본 발명에서 부식방지제로는 이미다졸, 피라졸, 트리아졸, 테트라졸, 벤조퓨란, 벤조티오펜, 인돌, 벤조티아졸, 벤조이미다졸, 벤조트리아졸, 벤조피라졸, 아미노테트라졸, 메틸테트라졸, 톨루트리아졸, 하이드로톨루트리아졸 및 하이드록시톨루트리아졸로 이루어진 군으로부터 선택되는 1종 이상의 아졸계 화합물이 바람직하게 사용될 수 있다. 특히, 구리의 부식방지성, 용해성, 식각균일성, 조성물의 안정성을 고려할 때, 벤조트리아졸 및 그의 유도체가 가장 바람직하게 사용될 수 있다.As a corrosion inhibitor in the present invention, imidazole, pyrazole, triazole, tetrazole, benzofuran, benzothiophene, indole, benzothiazole, benzoimidazole, benzotriazole, benzopyrazole, aminotetrazole, methyltetrasol One or more azole-based compounds selected from the group consisting of sol, tolutriazole, hydrotolutriazole, and hydroxytolutriazole may be preferably used. In particular, in consideration of the corrosion protection, solubility, uniformity of etching, and stability of the composition of copper, benzotriazole and derivatives thereof may be most preferably used.
상기 E)물은 조성물 총 중량이 100 중량%가 되도록 잔량으로 포함된다. 상기 물은 특별히 한정되지 않으나, 탈이온수를 이용하는 것이 바람직하다. 그리고, 상기 물은 물속에 이온이 제거된 정도를 보여주는 물의 비저항값이 18㏁·㎝ 이상인 탈이온수를 이용하는 것이 좋다.
The E) water is included in the balance so that the total weight of the composition is 100% by weight. The water is not particularly limited, but it is preferable to use deionized water. In addition, it is preferable to use deionized water having a specific resistance value of 18㏁·cm or more, which shows the degree to which ions have been removed from the water.
본 발명의 식각액 조성물은 전술한 성분 외에 G) 인산을 더 포함할 수 있다. 상기 인산은 몰리브덴 합금 및 인듐산화막의 식각 속도를 향상시켜주는 기능을 수행한다. 상기 인산은 조성물 총 중량에 대하여 0.1 내지 2중량%로 포함될 수 있다. 인산이 0.1중량% 미만으로 포함되는 경우에는 목적하는 효과를 얻기 어려우며, 2중량%를 초과하여 포함되는 경우에는 몰리브덴 합금 및 인듐산화막의 식각 속도는 추가로 향상시키지 못하는 반면, 부작용으로 PH를 낮추어 글라스의 식각속도가 향상될 수 있어 바람직하지 않다.
The etchant composition of the present invention may further include G) phosphoric acid in addition to the above-described components. The phosphoric acid functions to improve the etching rate of the molybdenum alloy and the indium oxide layer. The phosphoric acid may be included in an amount of 0.1 to 2% by weight based on the total weight of the composition. When phosphoric acid is contained in an amount of less than 0.1% by weight, it is difficult to obtain the desired effect, and when it is contained in an amount exceeding 2% by weight, the etching rate of the molybdenum alloy and indium oxide film cannot be further improved. It is not preferable because the etch rate of can be improved.
본 발명에 따른 식각액 조성물에는 전술한 성분 이외에 통상의 첨가제를 더 첨가할 수 있으며, 첨가제로는 금속이온 봉쇄제, 계면활성제 등을 들 수 있다. 또한, 상기 첨가제는 이에만 한정되는 것이 아니라, 본 발명의 효과를 더욱 양호하게 하기 위하여, 당 업계에 공지되어 있는 여러 다른 첨가제들을 선택하여 첨가할 수도 있다.
In addition to the above-described components, conventional additives may be further added to the etchant composition according to the present invention, and examples of the additives include metal ion sequestering agents and surfactants. In addition, the additive is not limited thereto, and in order to further improve the effect of the present invention, various other additives known in the art may be selected and added.
본 발명에서 사용되는 A) 과산화수소(H2O2), B) 함불소화합물, C) 히드록시기 함유 감마부티로락톤 유도체, D) 술폰산계 화합물, E) 부식방지제 등은 통상적으로 공지된 방법에 의해서 제조가 가능하며, 본 발명의 식각액 조성물은 반도체 공정용의 순도를 가지는 것이 바람직하다.
A) hydrogen peroxide (H 2 O 2 ), B) a fluorinated compound, C) a gamma butyrolactone derivative containing a hydroxy group, D) a sulfonic acid compound, E) a corrosion inhibitor, etc. It is possible to manufacture, and it is preferable that the etchant composition of the present invention has a purity for semiconductor processing.
본 발명에 따른 몰리브덴 합금막, 인듐 산화막, 또는 몰리브덴 합금막과 인듐 산화막의 다중막용 식각액 조성물은 몰리브덴 합금막, 인듐 산화막, 및 몰리브덴 합금막과 인듐 산화막의 다중막을 일괄 식각할 수 있다.
The etchant composition for a molybdenum alloy film, an indium oxide film, or a multilayer of a molybdenum alloy film and an indium oxide film according to the present invention may collectively etch a molybdenum alloy film, an indium oxide film, and a multilayer of a molybdenum alloy film and an indium oxide film.
또한, 본 발명은,In addition, the present invention,
a)기판 상에 게이트 배선을 형성하는 단계;a) forming a gate wiring on the substrate;
b)상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;b) forming a gate insulating layer on the substrate including the gate wiring;
c)상기 게이트 절연층 상에 반도체층을 형성하는 단계;c) forming a semiconductor layer on the gate insulating layer;
d)상기 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및d) forming source and drain electrodes on the semiconductor layer; And
e)상기 드레인 전극에 연결된 화소전극을 형성하는 단계를 포함하는 액정표시장치용 어레이 기판의 제조방법에 있어서,e) In a method of manufacturing an array substrate for a liquid crystal display device comprising the step of forming a pixel electrode connected to the drain electrode,
상기 e)단계는 기판 상에 몰리브덴 합금막, 인듐 산화막, 또는 몰리브덴 합금막과 인듐 산화막의 다중막을 형성하고 상기 형성된 막을 상기 본 발명의 식각액 조성물로 식각하는 단계를 포함하는 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조방법을 제공한다.The step e) comprises forming a molybdenum alloy film, an indium oxide film, or a multilayer of a molybdenum alloy film and an indium oxide film on a substrate, and etching the formed film with the etchant composition of the present invention. It provides a method of manufacturing an array substrate for use.
상기 액정표시장치용 어레이 기판은 박막트랜지스터(TFT) 어레이 기판일 수 있다. The liquid crystal display array substrate may be a thin film transistor (TFT) array substrate.
또한, 본 발명은In addition, the present invention
식각액 조성물을 사용하여 식각된 화소전극을 포함하는 액정표시장치용 어레이 기판을 제공한다.
An array substrate for a liquid crystal display device including a pixel electrode etched using an etchant composition is provided.
이하에서, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나, 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다. 하기의 실시예는 본 발명의 범위 내에서 당업자에 의해 적절히 수정, 변경될 수 있다.
Hereinafter, the present invention will be described in more detail through examples. However, the following examples are for explaining the present invention more specifically, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
실시예Example 1 내지 1 to 실시예Example 2 및 2 and 비교예Comparative example 1 내지 1 to 비교예Comparative example 6: 6: 식각액Etchant 조성물의 제조 Preparation of the composition
하기 표 1에 나타낸 조성에 따라 실시예 1 내지 2, 비교예 1 내지 6의 식각액 조성물을 제조하였다. 하기 표 1에서 표기한 성분 이외에 잔량의 물을 포함하여 전체 조성물이 100중량부가 되는 조성임. The etchant compositions of Examples 1 to 2 and Comparative Examples 1 to 6 were prepared according to the compositions shown in Table 1 below. In addition to the components indicated in Table 1 below, the total composition including the remaining amount of water is 100 parts by weight.
유리기판(100mmⅩ100mm)상에 몰리브덴합금막(Mo-Ti)을 증착시키고 상기 몰리브덴합금막 상에 포토리소그래피(photolithography) 공정을 통하여 소정의 패턴을 가진 포토레지스트가 형성되게 하였다.A molybdenum alloy film (Mo-Ti) was deposited on a glass substrate (100mm×100mm), and a photoresist having a predetermined pattern was formed on the molybdenum alloy film through a photolithography process.
실시예 1 내지 2 및 비교예 1 내지 6의 조성물을 각각 사용하여 몰리브덴합금막에 대하여 식각공정을 실시하였다. 분사식 식각 방식의 실험장비(모델명 : ETCHER(TFT), SEMES사)를 이용하였고, 식각공정시 식각액 조성물의 온도는 약 35℃로 하고, 72초 간 식각을 진행하였다. 육안으로 EPD(End Point Detection, 금속 식각 시점)를 측정하여 시간에 따른 식각 속도(etching rate)를 평가하였다. An etching process was performed on the molybdenum alloy film using the compositions of Examples 1 to 2 and Comparative Examples 1 to 6, respectively. Experimental equipment (model name: ETCHER(TFT), SEMES) was used in the spray etching method, and during the etching process, the temperature of the etchant composition was about 35°C, and etching was performed for 72 seconds. Etching rate over time was evaluated by measuring EPD (End Point Detection, metal etching time point) with the naked eye.
또한, 유리기판(100mmⅩ100mm)상에 구리막을 증착시킨 후, 상기 구리막상에 포토리소그래피(photolithography) 공정을 통하여 소정의 패턴을 가진 포토레지스트를 형성하고 상기와 동일한 식각 방법으로 식각하여 구리막의 손상을 SEM(Hitachi사 제품, 모델명 S-4700)을 사용하여 검사하고, side etch 길이/72sec로 계산하여 그 결과를 하기 표 1에 기재하였다.In addition, after depositing a copper film on a glass substrate (100mm x 100mm), a photoresist having a predetermined pattern is formed on the copper film through a photolithography process, and the copper film is etched by the same etching method as above to reduce damage to the copper film by SEM. (Hitachi's product, model name S-4700) was used to inspect, side etch length/72sec was calculated, and the results are shown in Table 1 below.
(단위:중량%)(Unit:% by weight)
주)week)
AF: 불화암모늄AF: ammonium fluoride
BTA: 벤조트리아졸BTA: benzotriazole
PTSA: 파라톨루엔술폰산 PTSA: paratoluenesulfonic acid
< < MoMo -- TiTi 식각속도Etching speed 평가 기준 > Evaluation Criteria>
◎: 35℃ 72초 간 식각에 의한 side etch가 0.3um이상 ◎: The side etch by etching for 72 seconds at 35℃ is more than 0.3um
○: 35℃ 72초 간 식각에 의한 side etch가 0.2~0.3um.○: Side etch by etching for 72 seconds at 35℃ is 0.2~0.3um.
△: 35℃ 72초 간 식각에 의한 side etch가 0.1~0.2um.△: Side etch by etching for 72 seconds at 35℃ is 0.1~0.2um.
Х: 35℃ 72초 간 식각에 의한 side etch가 0.1um이하Х: Side etch by etching for 72 seconds at 35℃ is less than 0.1um
< < CuCu 막 손상 평가 기준 >Membrane damage evaluation criteria>
◎:구리막 식각속도가 2 Å/sec 미만 ◎: Copper film etching rate is less than 2 Å/sec
○: 구리막 식각속도가 2~5 미만 Å/sec○: Copper film etching rate is less than 2 ~ 5 Å/sec
△: 구리막 식각속도가 5~10 미만 Å/sec△: copper film etching rate is less than 5 ~ 10 Å/sec
Х: 구리막 식각속도가 10 Å/sec 초과 Х: copper film etching rate exceeds 10 Å/sec
상기 표 1에서 확인되는 바와 같이, 아스코르브산을 포함한 본 발명의 식각액 조성물은 모두 몰리브덴합금막(Mo-Ti)의 식각속도가 우수하였으며, 하부막인 구리막의 어텍 방지력도 우수하였다. 반면, 인용발명의 식각액 조성물들은 모두 몰리브덴합금막(Mo-Ti)의 식각속도 면에서 부족한 특성을 보였다. As can be seen in Table 1, all of the etchant compositions of the present invention including ascorbic acid had excellent etch rates of the molybdenum alloy film (Mo-Ti), and the attack preventing power of the lower film, the copper film, was also excellent. On the other hand, all of the etchant compositions of the cited invention showed insufficient characteristics in terms of the etching rate of the molybdenum alloy film (Mo-Ti).
Claims (11)
A) 과산화수소(H2O2) 5 내지 25중량%;
B) 함불소화합물 0.1 내지 2중량%;
C) 히드록시기 함유 감마부티로락톤 유도체 0.5 내지 5중량%;
D) 술폰산계 화합물 0.01 내지 5중량%;
E) 부식방지제 0.1 내지 3중량%; 및
F) 물 잔량을 포함하며,
구리막의 손상을 방지하는 것을 특징으로 하는 몰리브덴 합금막, 인듐 산화막, 또는 몰리브덴 합금막과 인듐 산화막의 다중막용 식각액 조성물. Based on the total weight of the composition,
A) 5 to 25% by weight of hydrogen peroxide (H2O2);
B) 0.1 to 2% by weight of a fluorinated compound;
C) 0.5 to 5% by weight of a gammabutyrolactone derivative containing a hydroxy group;
D) 0.01 to 5% by weight of a sulfonic acid-based compound;
E) 0.1 to 3% by weight of a corrosion inhibitor; And
F) contains the remaining amount of water,
A molybdenum alloy film, an indium oxide film, or a multilayer etchant composition of a molybdenum alloy film and an indium oxide film, characterized in that preventing damage to the copper film.
상기 C) 히드록시기 함유 감마부티로락톤 유도체는 하기 화학식 1로 표시되는 화합물인 것을 특징으로 하는 몰리브덴 합금막, 인듐 산화막, 또는 몰리브덴 합금막과 인듐 산화막의 다중막용 식각액 조성물:
[화학식 1]
상기 식에서
R1, R2 및 R3는, 각각 독립적으로, 수소; 히드록시기; C1~C5의 알킬기; C1~C5의 알콕시기; 또는 C1~C5의 알콕시기, 아세톡시기 및 히드록시기로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환된 C1~C5의 알킬기이며, 상기에서 R2 및 R3 중 어느 하나는 부존재일 수 있으며;
R4는 수소이다.The method according to claim 1,
The C) hydroxy group-containing gamma butyrolactone derivative is a compound represented by the following formula (1), characterized in that a molybdenum alloy film, an indium oxide film, or a multilayer etchant composition of a molybdenum alloy film and an indium oxide film
[Formula 1]
In the above formula
R1, R2 and R3 are each independently hydrogen; Hydroxy group; C1-C5 alkyl group; C1-C5 alkoxy group; Or a C1-C5 alkyl group substituted with one or more substituents selected from the group consisting of a C1-C5 alkoxy group, an acetoxy group, and a hydroxy group, wherein any one of R2 and R3 may be absent;
R4 is hydrogen.
상기 화학식 1의 화합물은 하기 화학식들로부터 선택되는 어느 하나인 것을 특징으로 하는 몰리브덴 합금막, 인듐 산화막, 또는 몰리브덴 합금막과 인듐 산화막의 다중막용 식각액 조성물:
The compound of Formula 1 is any one selected from the following formulas:
상기 B) 함불소화합물은 HF, NaF, KF, AlF3, HBF4, NH4F, NH4HF2, NaHF2, KHF2 및 NH4BF4로 이루어진 군으로부터 선택되는 1종 이상의 것인 것을 특징으로 하는 몰리브덴 합금막, 인듐 산화막, 또는 몰리브덴 합금막과 인듐 산화막의 다중막용 식각액 조성물.The method according to claim 1,
The B) fluorinated compound is one or more selected from the group consisting of HF, NaF, KF, AlF 3 , HBF 4 , NH 4 F, NH 4 HF 2 , NaHF 2 , KHF 2 and NH 4 BF 4 A molybdenum alloy film, an indium oxide film, or a multilayer etchant composition of a molybdenum alloy film and an indium oxide film, characterized in that.
상기 D) 술폰산계 화합물은 알킬술폰산, 알킬디술폰산, 알킬벤젠술폰산, 알킬페닐에테르디술폰산, 알킬나프탈렌술폰산, 나프탈렌술폰산, 나프탈렌디술폰산, 포름알데히드와 나프탈렌 술폰산의 중합체, 아크릴아미도메틸프로판술폰산의 중합체, 아크릴산과 아크릴아미도메틸프로판술폰산의 공중합체 및 비닐벤젠술폰산중합체로부터 선택되는 술폰산기 또는 그 염을 갖고 있는 1종 이상의 화합물인 것을 특징으로 하는 몰리브덴 합금막, 인듐 산화막, 또는 몰리브덴 합금막과 인듐 산화막의 다중막용 식각액 조성물.The method according to claim 1,
The D) sulfonic acid-based compound is an alkyl sulfonic acid, an alkyl disulfonic acid, an alkylbenzene sulfonic acid, an alkylphenyl ether disulfonic acid, an alkyl naphthalene sulfonic acid, a naphthalene sulfonic acid, a naphthalene disulfonic acid, a polymer of formaldehyde and naphthalene sulfonic acid, an acrylamidomethylpropane sulfonic acid. A molybdenum alloy film, an indium oxide film, or a molybdenum alloy film, characterized in that it is at least one compound having a sulfonic acid group selected from a polymer, a copolymer of acrylic acid and acrylamidomethylpropanesulfonic acid, and a vinylbenzene sulfonic acid polymer, or a salt thereof. Etching solution composition for multiple layers of indium oxide film.
상기 E) 부식방지제는 고리 헤테로 방향족 화합물, 고리 헤테로 지방족 화합물, 방향족 다가알콜 및 직쇄구조 다가알콜류로 이루어진 군으로부터 선택되는 1종 이상의 것인 것을 특징으로 하는 몰리브덴 합금막, 인듐 산화막, 또는 몰리브덴 합금막과 인듐 산화막의 다중막용 식각액 조성물.The method according to claim 1,
The E) corrosion inhibitor is a molybdenum alloy film, an indium oxide film, or a molybdenum alloy film, characterized in that at least one selected from the group consisting of cyclic heteroaromatic compounds, cyclic heteroaliphatic compounds, aromatic polyhydric alcohols, and linear polyhydric alcohols. Etching solution composition for a multilayer of and indium oxide film.
상기 고리 헤테로 방향족 화합물은 이미다졸, 피라졸, 트리아졸, 테트라졸, 벤조퓨란, 벤조티오펜, 인돌, 벤조티아졸, 벤조이미다졸, 벤조트리아졸, 벤조피라졸, 아미노테트라졸, 메틸테트라졸, 톨루트리아졸, 하이드로톨루트리아졸 및 하이드록시톨루트리아졸로 이루어진 군으로부터 선택되는 1종 이상의 아졸계 화합물인 것을 특징으로 하는 몰리브덴 합금막, 인듐 산화막, 또는 몰리브덴 합금막과 인듐 산화막의 다중막용 식각액 조성물.The method of claim 6,
The cyclic heteroaromatic compound is imidazole, pyrazole, triazole, tetrazole, benzofuran, benzothiophene, indole, benzothiazole, benzoimidazole, benzotriazole, benzopyrazole, aminotetrazole, methyltetrazole , A molybdenum alloy film, an indium oxide film, or a multiple of a molybdenum alloy film and an indium oxide film, characterized in that it is at least one azole-based compound selected from the group consisting of tolutriazole, hydrotolutriazole, and hydroxytolutriazole. Membrane etchant composition.
G) 인산 0.1 내지 2중량%를 더 포함하는 것을 특징으로 하는 몰리브덴 합금막, 인듐 산화막, 또는 몰리브덴 합금막과 인듐 산화막의 다중막용 식각액 조성물.The method according to claim 1,
G) A molybdenum alloy film, an indium oxide film, or a multilayer etchant composition of a molybdenum alloy film and an indium oxide film, further comprising 0.1 to 2% by weight of phosphoric acid.
b)상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;
c)상기 게이트 절연층 상에 반도체층을 형성하는 단계;
d)상기 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및
e)상기 드레인 전극에 연결된 화소전극을 형성하는 단계를 포함하는 액정표시장치용 어레이 기판의 제조방법에 있어서,
상기 e)단계는 기판 상에 몰리브덴 합금막, 인듐 산화막, 또는 몰리브덴 합금막과 인듐 산화막의 다중막을 형성하고 상기 형성된 막을 청구항 1 내지 8 중의 어느 한 항의 식각액 조성물로 식각하는 단계를 포함하는 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조방법.a) forming a gate wiring on the substrate;
b) forming a gate insulating layer on the substrate including the gate wiring;
c) forming a semiconductor layer on the gate insulating layer;
d) forming source and drain electrodes on the semiconductor layer; And
e) In a method of manufacturing an array substrate for a liquid crystal display device comprising the step of forming a pixel electrode connected to the drain electrode,
The step e) comprises forming a molybdenum alloy film, an indium oxide film, or a multilayer of a molybdenum alloy film and an indium oxide film on a substrate, and etching the formed film with the etchant composition of any one of claims 1 to 8. Method of manufacturing an array substrate for a liquid crystal display device.
상기 액정표시장치용 어레이 기판이 박막트랜지스터(TFT) 어레이 기판인 것을 특징으로 하는 액정표시장치용 어레이 기판의 제조방법.The method of claim 9,
The method of manufacturing an array substrate for a liquid crystal display device, wherein the array substrate for a liquid crystal display device is a thin film transistor (TFT) array substrate.
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