KR20180103535A - Etching solution composition and manufacturing method of an array substrate for display device using the same - Google Patents
Etching solution composition and manufacturing method of an array substrate for display device using the same Download PDFInfo
- Publication number
- KR20180103535A KR20180103535A KR1020170030601A KR20170030601A KR20180103535A KR 20180103535 A KR20180103535 A KR 20180103535A KR 1020170030601 A KR1020170030601 A KR 1020170030601A KR 20170030601 A KR20170030601 A KR 20170030601A KR 20180103535 A KR20180103535 A KR 20180103535A
- Authority
- KR
- South Korea
- Prior art keywords
- acid
- weight
- etchant composition
- etching
- copper
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 238000005530 etching Methods 0.000 title claims abstract description 66
- 239000000758 substrate Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- -1 cyclic azole compound Chemical class 0.000 claims abstract description 20
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 13
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 12
- 150000007524 organic acids Chemical class 0.000 claims abstract description 12
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 12
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 59
- 238000000034 method Methods 0.000 claims description 23
- 229910052802 copper Inorganic materials 0.000 claims description 22
- 239000010949 copper Substances 0.000 claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
- 235000002639 sodium chloride Nutrition 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000004065 semiconductor Substances 0.000 claims description 11
- 239000005749 Copper compound Substances 0.000 claims description 10
- 150000001880 copper compounds Chemical class 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 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 4
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-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
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- 235000015165 citric acid Nutrition 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 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
- 239000011780 sodium chloride Substances 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- 239000011698 potassium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 239000011775 sodium fluoride Substances 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
- WGPNLKPTYJCEKI-UHFFFAOYSA-N 1-ethyltetrazol-5-amine Chemical compound CCN1N=NN=C1N WGPNLKPTYJCEKI-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
- 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
- SDGNNLQZAPXALR-UHFFFAOYSA-N 3-sulfophthalic acid Chemical compound OC(=O)C1=CC=CC(S(O)(=O)=O)=C1C(O)=O SDGNNLQZAPXALR-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
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 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
- 239000012359 Methanesulfonyl chloride Substances 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 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
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 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
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 239000010409 thin film Substances 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
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims 2
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 claims 1
- ZQMUTZKOOPWXJE-UHFFFAOYSA-L copper silver sulfate Chemical compound S(=O)(=O)([O-])[O-].[Cu+2].[Ag+] ZQMUTZKOOPWXJE-UHFFFAOYSA-L 0.000 claims 1
- FRYHCSODNHYDPU-UHFFFAOYSA-N ethanesulfonyl chloride Chemical compound CCS(Cl)(=O)=O FRYHCSODNHYDPU-UHFFFAOYSA-N 0.000 claims 1
- 239000004310 lactic acid Substances 0.000 claims 1
- 235000014655 lactic acid Nutrition 0.000 claims 1
- 239000011664 nicotinic acid Substances 0.000 claims 1
- 229960003512 nicotinic acid Drugs 0.000 claims 1
- 235000001968 nicotinic acid Nutrition 0.000 claims 1
- 159000000001 potassium salts Chemical class 0.000 claims 1
- 159000000000 sodium salts Chemical class 0.000 claims 1
- 239000002244 precipitate Substances 0.000 abstract description 16
- 230000000052 comparative effect Effects 0.000 description 26
- 230000008569 process Effects 0.000 description 16
- 238000011282 treatment Methods 0.000 description 6
- 229920002120 photoresistant polymer Polymers 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- DBGSRZSKGVSXRK-UHFFFAOYSA-N 1-[2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]acetyl]-3,6-dihydro-2H-pyridine-4-carboxylic acid Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CCC(=CC1)C(=O)O DBGSRZSKGVSXRK-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- GTKOKCQMHAGFSM-UHFFFAOYSA-N 1-methyltetrazol-5-amine Chemical compound CN1N=NN=C1N GTKOKCQMHAGFSM-UHFFFAOYSA-N 0.000 description 1
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 1
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 description 1
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010020710 Hyperphagia Diseases 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 235000020830 overeating Nutrition 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 230000021148 sequestering of metal ion Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
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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
-
- 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
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Abstract
Description
본 발명은 식각액 조성물 및 이를 이용한 디스플레이 장치용 어레이 기판의 제조방법에 관한 것이다.The present invention relates to an etching liquid composition and a method of manufacturing an array substrate for a display device using the same.
일반적으로 반도체장치 및 평판표시장치에서 기판 위에 금속배선을 형성하는 과정은 스퍼터링에 의한 금속막 형성공정; 포토레지스트 도포, 노광 및 현상에 의한 선택적인 영역에서의 포토레지스트 형성공정; 및 식각공정에 의한 단계로 구성되며, 개별적인 단위 공정 전후의 세정공정 등을 포함한다.Generally, a process of forming a metal wiring on a substrate in a semiconductor device and a flat panel display device includes a metal film formation process by sputtering; A photoresist forming step in a selective region by photoresist application, exposure and development; And an etching process, and includes a cleaning process before and after the individual unit process.
상기 식각공정은 포토레지스트를 마스크로 사용하여 선택적인 영역에 금속막을 남기는 공정을 의미하며, 통상적으로 플라즈마 등을 이용한 건식 식각 또는 식각액을 사용하는 습식 식각이 사용된다.The etching process refers to a process of leaving a metal film in a selective region by using a photoresist as a mask. Typically, dry etching using plasma or wet etching using an etching solution is used.
근래 들어, 반도체장치나 평판표시장치에서 금속배선의 저항이 주요한 관심사로 떠오르고 있다. 저항은 RC 신호지연을 유발하는 주요 인자이므로, 평판표시장치에서 패널 크기를 증가시키고 고해상도를 실현하는데 있어 매우 중요하다.In recent years, the resistance of metal wiring has become a major concern in semiconductor devices and flat panel displays. Since resistance is a major factor in causing RC signal delay, it is very important to increase the panel size and achieve high resolution in flat panel displays.
평판표시장치에서 필수적으로 요구되는 RC 신호지연의 감소를 실현하기 위해서는 저저항의 물질개발이 필수적이며, 종래에 주로 사용되었던 크롬(Cr 비저항:12.7 x 10- 8Ωm), 몰리브덴(Mo 비저항: 5 x 10- 8Ωm), 알루미늄(Al 비저항: 2.65 x10-8Ωm) 및 이들의 합금은 대형 TFT LCD에 사용되는 게이트 및 데이터 배선 등으로 이용하기 어려운 실정이다.In order to realize a reduction in the RC signal delay that is necessarily required in a flat panel display device, and the essential material development of low resistance, chromium was mainly used conventionally (Cr resistivity: 12.7 x 10 - 8 Ωm) , molybdenum (Mo resistivity: 5 x 10 - 8 Ωm), aluminum (Al resistivity: 2.65 × 10 -8 Ωm), and alloys thereof are difficult to be used for gate and data wiring used in a large-sized TFT LCD.
이와 같은 배경하에서, 새로운 저저항 금속막 중 하나인 구리막에 대한 관심이 높다. 구리막은 알루미늄막이나 크롬막보다 저항이 현저하게 낮고, 환경적으로도 큰 문제가 없는 장점이 있는 것으로 알려져 있기 때문이다. 그러나, 구리막은 포토레지스트를 도포하고 패터닝하는 공정상 어려운 점들이 많으며, 실리콘 절연막과의 접착력이 나쁜 단점이 발견되었다.Under these circumstances, interest in copper films, one of the new low resistance metal films, is high. Copper films are known to have a lower resistance than aluminum and chrome films, and are environmentally benign. However, the copper film has many disadvantages in the process of applying and patterning the photoresist, and has a disadvantage that the adhesion to the silicon insulating film is poor.
이에 따라, 저저항 구리 단일막의 단점을 보완하는 다중 금속막에 대한 연구가 진행되고 있으며, 그 중에서도 특히 각광받는 물질이 구리-티타늄 이중막이다.Accordingly, studies on multi-metal films that complement the disadvantages of the low-resistance copper single films are under way, and among them, the copper-titanium double films are particularly popular.
대한민국 공개특허 제10-2010-0123131호에는 티타늄 및 구리를 포함하는 금속막을 식각하는 식각액 조성물에 대하여 게재하고 있으나, 상기 식각액 조성물은 식각 성능을 유지하는 기간이 짧으며, 식각 속도 성능 저하를 줄이기 위한 무기산 도입에 따른 과침식 등의 문제점을 지니고 있는 바, 구리-티타늄 이중막을 식각하기 위한 식각액 조성물의 개발이 여전히 필요한 상황이다.Korean Patent Laid-Open No. 10-2010-0123131 discloses an etchant composition for etching a metal film containing titanium and copper. However, the etchant composition has a short period of time to maintain the etchant performance, It is still necessary to develop an etchant composition for etching a copper-titanium double-layer film.
본 발명은 식각 프로파일이 우수하며, 금속막 식각시 석출물이 발생하지 않는 식각액 조성물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide an etching composition which has an excellent etching profile and does not generate precipitates when a metal film is etched.
또한, 본 발명은 상기 식각액 조성물을 사용하여 디스플레이 장치용 어레이 기판을 제조하는 방법 및 상기 제조방법으로 제조된 디스플레이 장치용 어레이 기판을 제공하는 것을 목적으로 한다.It is another object of the present invention to provide a method of manufacturing an array substrate for a display device using the etchant composition and an array substrate for a display device manufactured by the method.
상기 목적을 달성하기 위하여,In order to achieve the above object,
본 발명은 조성물 총 중량에 대하여,The present invention relates to a composition,
과황산염 0.5 내지 20 중량%;From 0.5 to 20% by weight persulfate;
불소 화합물 0.01 내지 2 중량%;0.01 to 2% by weight of a fluorine compound;
무기산 1 내지 10 중량%;1 to 10% by weight of an inorganic acid;
고리형 아민 화합물 0.5 내지 5 중량%;0.5 to 5% by weight of a cyclic amine compound;
염소 화합물 0.01 내지 0.1 중량% 미만;0.01 to less than 0.1% by weight of a chlorine compound;
유기산 또는 유기산염 1 내지 20 중량%; 및1 to 20% by weight of an organic acid or an organic acid salt; And
식각액 조성물 총 중량이 100 중량%가 되도록 잔량의 물을 포함하는 식각액 조성물을 제공한다.Wherein the etchant composition comprises a residual amount of water such that the total weight of the etchant composition is 100% by weight.
또한, 본 발명은 (a) 기판 상에 게이트 배선을 형성하는 단계;The present invention also provides a method of manufacturing a semiconductor device, comprising: (a) forming a gate wiring on a 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; 및(d) forming source and drain electrodes on the semiconductor layer; And
(e) 상기 드레인 전극에 연결된 화소전극을 형성하는 단계; 를 포함하는 디스플레이 장치용 어레이 기판의 제조방법에 있어서,(e) forming a pixel electrode connected to the drain electrode; The method comprising the steps of:
상기 (a) 단계 및 (d) 단계 중 어느 한 단계 이상이, 상기 본 발명의 식각액 조성물로 식각하여 각각의 게이트 배선, 소스 및 드레인 전극을 형성하는 공정을 포함하는 것을 특징으로 하는 디스플레이 장치용 어레이 기판의 제조방법을 제공한다.Wherein at least one of the steps (a) and (d) includes a step of etching each of the gate wirings, the source and the drain electrodes with the etching solution composition of the present invention A method of manufacturing a substrate is provided.
또한, 본 발명은 상기 본 발명의 제조방법으로 제조된 디스플레이 장치용 어레이 기판을 제공한다.The present invention also provides an array substrate for a display device manufactured by the manufacturing method of the present invention.
본 발명의 식각액 조성물은 식각 프로파일이 우수한 효과를 지니고 있다.The etchant composition of the present invention has an excellent etching profile.
또한, 본 발명의 식각액 조성물은 금속막 식각시 석출물 생성을 억제하여, 석출물로 인한 식각 성능 저하, 배선 불량률 증가, 장비 및 배관 내 석출 문제에 따른 공정상 비용 증가, 폐수 처리 비용 증가 등의 문제점을 예방할 수 있는 효과를 지니고 있다.In addition, the etching composition of the present invention suppresses the formation of precipitates in the case of metal film etching, thereby causing problems such as deterioration of etching performance due to precipitates, increase in wiring defect rate, increase in process cost due to problems in equipment and piping, It has a preventive effect.
도 1은 테이퍼 앵글이 우수한 SEM 사진이다.
도 2는 테이퍼 앵글이 불량한 SEM 사진이다.
도 3은 테이퍼 앵글이 불량한 SEM 사진이다.
도 4는 사면 직진성이 우수한 SEM 사진이다.
도 5는 사면 직진성이 불량한 SEM 사진이다.
도 6은 석출물이 발생하지 않은 SEM 사진이다.
도 7은 석출물이 발생한 SEM 사진이다.1 is an SEM photograph showing an excellent taper angle.
2 is a SEM photograph showing a poor taper angle.
3 is a SEM photograph showing a tapered angle is poor.
4 is an SEM photograph showing excellent slope straightness.
5 is a SEM photograph showing poor slope straightness.
Fig. 6 is a SEM photograph showing no precipitate.
Fig. 7 is a SEM photograph showing a precipitate.
이하, 본 발명을 보다 자세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 조성물 총 중량에 대하여,The present invention relates to a composition,
과황산염 0.5 내지 20 중량%;From 0.5 to 20% by weight persulfate;
불소 화합물 0.01 내지 2 중량%;0.01 to 2% by weight of a fluorine compound;
무기산 1 내지 10 중량%;1 to 10% by weight of an inorganic acid;
고리형 아민 화합물 0.5 내지 5 중량%;0.5 to 5% by weight of a cyclic amine compound;
염소 화합물 0.01 내지 0.1 중량% 미만;0.01 to less than 0.1% by weight of a chlorine compound;
유기산 또는 유기산염 1 내지 20 중량%; 및1 to 20% by weight of an organic acid or an organic acid salt; And
식각액 조성물 총 중량이 100 중량%가 되도록 잔량의 물을 포함하는 식각액 조성물에 관한 것이다.To an etchant composition comprising a residual amount of water such that the total weight of the etchant composition is 100% by weight.
디스플레이 장치용 어레이 기판 위에는 다수의 층이 적층되어 상기 층 간에 원치않는 전기적 단락이 발생하게 된다. 상기 전기적 단락 발생을 방지하기 위해서는 식각 기판의 절단 측면, 즉 식각 프로파일의 표면이 매끄러우면서도 하방이 상방보다 더 넓은 완만한 테이퍼 형상인 것이 바람직하다. 특히, 최근에는 응답속도를 높이기 위하여 두께가 두꺼운 후막을 사용하기 때문에 식각액 조성물의 우수한 프로파일이 요구되고 있다.On the array substrate for a display device, a plurality of layers are stacked to cause an unwanted electrical short between the layers. In order to prevent the occurrence of the electrical short, it is preferable that the etching side surface of the etching substrate, that is, the surface of the etching profile is smooth and the downside is a gentle taper shape wider than the upper side. Particularly, in recent years, a thicker thick film is used in order to increase the response speed, and thus an excellent profile of the etching liquid composition is required.
또한, 금속막 식각시 발생하는 석출물은 식각 성능 저하, 배선 불량률 증가, 장비 및 배관 내 석출 문제에 따른 공정상 비용 증가, 폐수 처리 비용 증가 등의 문제를 발생시킨다.In addition, the precipitates generated when the metal film is etched cause problems such as a decrease in etching performance, an increase in wiring defect rate, an increase in process cost due to problems in equipment and piping precipitation, and an increase in waste water treatment cost.
따라서, 본 발명에서는 상기 문제점을 해결하기 위하여 식각 프로파일이 우수하며, 금속막 식각시 석출물이 발생하지 않는 식각액 조성물을 제공하고자 하였다.Accordingly, in order to solve the above problems, the present invention provides an etchant composition having an excellent etch profile and free of precipitates during metal film etching.
본 발명의 식각액 조성물은 티타늄계 금속막의 단일막, 구리계 금속막의단일막 또는 티타늄계 금속막/구리계 금속막의 이중막을 식각할 수 있으며, 바람직하게는 티타늄계 금속막/구리계 금속막의 이중막을 식각하며, 상기 이중막을 동시에 일괄식각할 수 있다.The etchant composition of the present invention can etch a single film of a titanium-based metal film, a single film of a copper-based metal film or a double film of a titanium-based metal film / a copper-based metal film, and preferably a double film of a titanium- And the double films can be simultaneously etched simultaneously.
이하, 본 발명의 식각액 조성물을 구성하는 성분에 대하여 설명한다.Hereinafter, components constituting the etchant composition of the present invention will be described.
(A)(A) 과황산염Persulfate
본 발명의 식각액 조성물에 포함되는 과황산염은 구리계 금속막을 식각하는 주성분이다.The persulfate contained in the etchant composition of the present invention is the main component for etching the copper-based metal film.
상기 과황산염은 과황산칼륨(K2S2O8), 과황산나트륨(Na2S2O8) 및 과황산암모늄((NH4)2S2O8)으로 이루어진 군으로부터 선택되는 1종 이상을 사용할 수 있다.Wherein the persulfate is at least one selected from the group consisting of potassium persulfate (K 2 S 2 O 8 ), sodium persulfate (Na 2 S 2 O 8 ) and ammonium persulfate ((NH 4 ) 2 S 2 O 8 ) Can be used.
상기 과황산염은 본 발명의 식각액 조성물 총 중량에 대하여 0.5 내지 20 중량%로 포함되며, 바람직하게 8 내지 15 중량%로 포함된다. The persulfate is contained in an amount of 0.5 to 20% by weight, preferably 8 to 15% by weight based on the total weight of the etchant composition of the present invention.
상기 과황산염을 0.5 중량% 미만으로 포함하면 구리계 금속막의 식각이 이루어지지 않거나 매우 느린 식각속도를 보이고, 20 중량%를 초과하여 포함하면 식각 속도가 전체적으로 빨라져 공정을 컨트롤하는 것이 어려워진다.If the persulfate is contained in an amount of less than 0.5% by weight, the copper-based metal film is not etched or exhibits a very slow etching rate. If the persulfate is contained in an amount exceeding 20% by weight, the etch rate is generally accelerated.
(B)불소 화합물(B) Fluorine compound
본 발명의 식각액 조성물에 포함되는 불소 화합물은 티타늄계 금속막을 식각하는 주성분이며, 식각 시 발생하는 잔사를 제거하여 주는 역할을 한다.The fluorine compound contained in the etchant composition of the present invention is a main component for etching the titanium-based metal film and serves to remove residues generated during etching.
상기 불소 화합물은 용액 내에서 불소 이온 또는 다원자 불소이온이 해리되는 화합물이라면 그 종류를 특별히 한정하지는 않으나, 바람직하게는 불화암모늄(ammonium fluoride), 불화나트륨(sodium fluoride), 불화칼륨(potassium fluoride), 중불화암모늄(ammonium bifluoride), 중불화나트륨(sodium bifluoride) 및 중불화칼륨(potassium bifluoride)으로 이루어진 군으로부터 선택되는 1종 이상을 사용할 수 있다.The fluorine compound is not particularly limited as long as it is a compound in which fluorine ion or polyatomic fluorine ion is dissociated in a solution. Preferably, the fluorine compound is ammonium fluoride, sodium fluoride, potassium fluoride, , Ammonium bifluoride, sodium bifluoride, and potassium bifluoride may be used.
상기 불소 화합물은 본 발명의 식각액 조성물 총 중량에 대하여 0.01 내지 2 중량%로 포함되며, 바람직하게는 0.1 내지 0.6 중량%로 포함된다. The fluorine compound is contained in an amount of 0.01 to 2% by weight, preferably 0.1 to 0.6% by weight based on the total weight of the etchant composition of the present invention.
상기 불소 화합물을 0.01 중량% 미만으로 포함하면 티타늄계 금속막의 식각속도가 저하되어 잔사가 발생할 수 있으며, 2 중량%를 초과하여 포함하면 금속 배선이 형성되는 유리 등의 기판 및 금속 배선과 함께 형성되는 실리콘을 포함하는 절연막에 손상을 일으킬 수 있다.When the fluorine compound is contained in an amount of less than 0.01% by weight, the etching rate of the titanium-based metal film may be lowered to cause residues. If the fluorine compound is contained in an amount exceeding 2% by weight, It may cause damage to the insulating film containing silicon.
(C)무기산(C)
본 발명의 식각액 조성물에 포함되는 무기산은 구리계 금속막 및 티타늄계 금속막의 식각을 위한 보조산화제의 역할을 한다.The inorganic acid included in the etchant composition of the present invention serves as a copper-based metal film and a co-oxidant for etching the titanium-based metal film.
상기 무기산은 질산, 황산, 인산 및 과염소산으로 이루어진 군으로부터 선택되는 1종 이상을 사용할 수 있다.The inorganic acid may be at least one selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid and perchloric acid.
또한, 상기 무기산은 본 발명의 식각액 조성물 총 중량에 대하여 1 내지 10 중량%로 포함되며, 바람직하게는 1 내지 5 중량%로 포함된다.The inorganic acid is contained in an amount of 1 to 10% by weight, preferably 1 to 5% by weight based on the total weight of the etching solution composition of the present invention.
상기 무기산을 1 중량% 미만으로 포함하면 구리계 금속막 및 티타늄계 금속막의 식각속도가 저하되어 식각 프로파일 불량해지며, 잔사가 발생할 수 있으며, 10 중량%를 초과하여 포함하면 과식각 및 포토레지스트 균열이 발생하여 약액 침투에 의하여 배선이 단락될 수 있다.If the inorganic acid is contained in an amount of less than 1% by weight, the etching rate of the copper-based metal film and the titanium-based metal film may be lowered and the etching profile may become poor and residues may be formed. And the wiring may be short-circuited by the penetration of the chemical liquid.
(D)고리형 (D) Ring type 아민Amine 화합물 compound
본 발명의 식각액 조성물에 포함되는 고리형 아민 화합물은 구리계 금속막의 식각 속도를 조절하는 역할을 한다.The cyclic amine compound contained in the etchant composition of the present invention has a role of controlling the etching rate of the copper-based metal film.
상기 고리형 아민 화합물은 5-아미노테트라졸(5-aminotetrazole), 이미다졸(imidazole), 인돌(indole), 푸린(purine), 피라졸(pyrazole), 피리딘(pyridine), 피리미딘(pyrimidine), 피롤(pyrrole), 피롤리딘(pyrrolidine), 피롤린(pyrroline), 5-메틸테트라졸(5-methyltetrazole), 1-메틸-5-아미노테트라졸(1-Methyl-5-Aminotetrazole) 및, 1-에틸-5-아미노테트라졸(1-Ethyl-5-Aminotetrazole)로 이루어진 군으로부터 선택되는 1종 이상을 사용할 수 있다.The cyclic amine compound may be selected from the group consisting of 5-aminotetrazole, imidazole, indole, purine, pyrazole, pyridine, pyrimidine, Pyrrole, pyrrolidine, pyrroline, 5-methyltetrazole, 1-methyl-5-aminotetrazole, and 1 (1-ethyl-5-aminotetrazole) may be used.
또한, 상기 고리형 아민 화합물은 본 발명의 식각액 조성물 총 중량에 대하여 0.5 내지 5 중량%로 포함되며, 바람직하게는 0.5 내지 3.0 중량%로 포함된다.The cyclic amine compound is contained in an amount of 0.5 to 5% by weight, preferably 0.5 to 3.0% by weight based on the total weight of the etchant composition of the present invention.
상기 고리형 아민 화합물을 0.5 중량% 미만으로 포함하면 구리의 식각 속도를 조절할 수 없어 과식각 및 불균일 식각이 일어날 수 있으며, 5 중량%를 초과하여 포함하면 식각 프로파일이 불량해져 생산 효율이 감소할 수 있다.If the amount of the cyclic amine compound is less than 0.5% by weight, the etching rate of copper can not be controlled, which may result in overeating and non-uniform etching. If the amount exceeds 5% by weight, the etching profile may become poor, have.
(E)염소 화합물(E) Chlorine compound
본 발명의 식각액 조성물에 포함되는 염소 화합물은 구리계 금속막을 식각하는 보조 산화제 역할을 한다.The chlorine compound contained in the etchant composition of the present invention serves as a co-oxidant for etching the copper-based metal film.
일반적으로 금속 배선의 각도가 높으면 금속막 적층시 전기적 과부하가 발생하여 디스플레이 장치용 어레기 기판의 배선이 터지는 현상이 발생하므로, 너무 높지 않은 배선의 각도와 균일한 식각 프로파일이 요구된다. In general, when the angle of the metal wiring is high, electrical overload occurs during the lamination of the metal film, and wiring of the array substrate substrate for the display device is blown. Therefore, the wiring angle and the etching profile that are not too high are required.
본 발명에서는 염소 화합물을 극소량 포함함으로써 금속 배선의 각도 및 균일한 식각 프로파일을 제공할 수 있으며, 배선 단락 불량률을 최소화할 수 있어 디스플레이 장치용 어레이 기판의 구동 수율을 향상시킬 수 있다.In the present invention, it is possible to provide the angle of the metal wiring and the uniform etching profile by including a very small amount of the chlorine compound, minimize the wiring shortage defect rate, and improve the driving yield of the array substrate for a display device.
상기 염소 화합물은 염소 이온으로 해리될 수 있는 화합물을 의미하며, 염산(HCl), 염화나트륨(NaCl), 염화칼륨(KCl), 염화암모늄(NH4Cl), 염화에탄술포닐(C2H5ClO2S) 및 염화메탄술포닐(CH3ClO2S)으로 이루어진 군으로부터 선택되는 1종 이상을 사용할 수 있다.The chlorine compound is meant a compound which can be dissociated into chloride ion and hydrochloric acid (HCl), sodium chloride (NaCl), potassium chloride (KCl), ammonium chloride (NH 4 Cl), chlorinated ethane sulfonyl (C 2 H 5 ClO 2 S) and methanesulfonyl chloride (CH 3 ClO 2 S) can be used.
상기 염소 화합물은 본 발명의 식각액 조성물 총 중량에 대하여 0.01 내지 0.1 중량% 미만으로 포함되며, 바람직하게는 0.01 내지 0.09 중량%로 포함된다.The chlorine compound is contained in an amount of 0.01 to less than 0.1% by weight, preferably 0.01 to 0.09% by weight based on the total weight of the etchant composition of the present invention.
상기 염소 화합물을 0.01 중량% 미만으로 포함하면 구리계 금속막의 식각 속도가 저하되어 공정상 적용할 수 없게 되며, 너무 적은 함량으로 인하여 대량 제조를 할 수 없는 단점이 있다. 또한, 0.1 중량%를 초과하여 포함하면 식각 프로파일이 불량해져 생산 효율이 감소할 수 있으며, 석출물이 발생할 수 있다.If the chlorine compound is contained in an amount of less than 0.01% by weight, the etching rate of the copper-based metal film is lowered, so that the process can not be applied to the process. If it is contained in an amount exceeding 0.1% by weight, the etching profile may become poor and the production efficiency may decrease, and precipitates may be formed.
(F)유기산 또는 (F) an organic acid or 유기산염Organic acid salt
본 발명의 식각액 조성물에 포함되는 유기산 또는 유기산염은 식각된 금속 이온과의 킬레이팅 작용으로 식각액에 영향을 주는 것을 방지해 줌으로써 결과적으로 처리매수를 증가시켜주는 역할을 한다. The organic acid or organic acid salt contained in the etchant composition of the present invention prevents the etchant from affecting the etchant by chelating with the etched metal ions, thereby increasing the number of treatments.
상기 유기산은 니코틴산, 아세트산, 부탄산, 시트르산, 포름산, 글루콘산, 글리콜산, 말론산, 옥살산, 펜탄산, 설포벤조산, 설포석신산, 설포프탈산, 살리실산, 설포살리실산, 벤조산, 락트산, 글리세르산, 석신산, 말산, 타르타르산, 이소시트르산, 프로펜산, 이미노디아세트산 및 에틸렌디아민테트라아세트산(EDTA)으로 이루어진 군으로부터 선택되는 1종 이상을 사용할 수 있으며, 상기 유기산염은 상기 유기산의 나트륨염, 칼륨염 및 암모늄염으로 이루어진 군으로부터 선택되는 1종 이상을 사용할 수 있다.The organic acid may be selected from the group consisting of citric acid, acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, pentanoic acid, sulfobenzoic acid, sulfosuccinic acid, sulfophthalic acid, salicylic acid, sulfosalicylic acid, At least one selected from the group consisting of citric acid, succinic acid, malic acid, tartaric acid, isocitric acid, propenoic acid, iminodiacetic acid and ethylenediaminetetraacetic acid (EDTA) At least one selected from the group consisting of salts and ammonium salts can be used.
상기 유기산 또는 유기산염은 본 발명의 식각액 조성물 총 중량에 대하여 1 내지 20 중량%로 포함되며, 바람직하게는 1.0 내지 10.0 중량%로 포함된다. 상기 유기산 또는 유기산염을 1 중량% 미만으로 포함하면 처리매수 증가 효과가 없고, 20 중량%를 초과하여 포함하면 과식각이 되어 배선의 단락이 발생할 수 있다.The organic acid or organic acid salt is contained in an amount of 1 to 20% by weight, preferably 1.0 to 10.0% by weight based on the total weight of the etching solution composition of the present invention. If the organic acid or the organic acid salt is contained in an amount less than 1% by weight, the effect of increasing the number of treatments is not exhibited. If the organic acid or the organic acid salt is contained in an amount exceeding 20% by weight, overcorrection may occur.
(G)물(G) Water
본 발명의 식각액 조성물에 포함되는 물은 특별히 한정하지 않으나, 탈이온수를 이용하는 것이 바람직하며, 상기 탈이온수는 반도체 공정용으로 비저항값이 18 ㏁/㎝ 이상인 것을 사용하는 것이 바람직하다.The water contained in the etchant composition of the present invention is not particularly limited, but it is preferable to use deionized water. It is preferable that the deionized water has a resistivity value of 18 M? / Cm or more for semiconductor processing.
(H)구리 화합물(H) Copper compound
본 발명의 식각액 조성물은 추가로 구리 화합물을 포함할 수 있으며, 상기 구리 화합물을 포함함으로써 금속막 식각시 씨디스큐(CD skew)가 변동되지 않고 유지될 수 있다.The etchant composition of the present invention may further contain a copper compound, and the CD skew can be kept unchanged when the metal film is etched by including the copper compound.
상기 구리 화합물은 황산 구리, 염화 구리 및 질산 구리로 이루어진 군으로부터 선택되는 1종 이상을 사용할 수 있다.The copper compound may be at least one selected from the group consisting of copper sulfate, copper chloride, and copper nitrate.
상기 구리 화합물은 본 발명의 식각액 조성물 총 중량에 대하여 0.01 내지 3 중량%로 포함되며, 바람직하게는 0.05 내지 1.0 중량%로 포함된다. 상기 구리 화합물을 0.01 중량% 미만으로 포함하면 씨디 스큐(CD Skew)를 일관되게 식각하는 능력이 없고, 3 중량%를 초과하여 포함하면 한계 식각 능력이 떨어져 식각액의 성능이 저하된다.The copper compound is contained in an amount of 0.01 to 3% by weight, preferably 0.05 to 1.0% by weight based on the total weight of the etching solution composition of the present invention. If the copper compound is contained in an amount of less than 0.01 wt%, the CD skew can not be consistently etched. If the copper compound is contained in an amount exceeding 3 wt%, the etchant may deteriorate due to the limited etching capability.
본 발명의 식각액 조성물은 상기에 언급한 성분들 외에 식각 조절제, 계면활성제, 금속 이온 봉쇄제, pH 조절제 및 이에 국한되지 않는 다른 첨가제로부터 선택되는 1종 이상을 추가로 포함할 수 있다. 상기 첨가제는, 본 발명의 범위 내에서 본 발명의 효과를 더욱 양호하게 하기 위하여, 당해 분야에서 통상적으로 사용하는 첨가제들로부터 선택하여 사용할 수 있다.The etchant composition of the present invention may further include at least one selected from the above-mentioned components, etchants, surfactants, metal ion sequestering agents, pH adjusting agents, and other additives not limited thereto. The above additives can be selected from additives commonly used in the art in order to further improve the effects of the present invention within the scope of the present invention.
본 발명의 식각액 조성물을 구성하는 성분들은 반도체 공정용의 순도를 가지는 것이 바람직하다.The components constituting the etchant composition of the present invention preferably have purity for semiconductor processing.
또한, 본 발명은In addition,
(a) 기판 상에 게이트 배선을 형성하는 단계;(a) forming a gate wiring on a 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; 및(d) forming source and drain electrodes on the semiconductor layer; And
(e) 상기 드레인 전극에 연결된 화소전극을 형성하는 단계; 를 포함하는 디스플레이 장치용 어레이 기판의 제조방법에 있어서,(e) forming a pixel electrode connected to the drain electrode; The method comprising the steps of:
상기 (a) 단계 및 (d) 단계 중 어느 한 단계 이상이, 상기 본 발명의 식각액 조성물로 식각하여 각각의 게이트 배선, 소스 및 드레인 전극을 형성하는 공정을 포함하는 것을 특징으로 하는 디스플레이 장치용 어레이 기판의 제조방법에 관한 것이다.Wherein at least one of the steps (a) and (d) includes a step of etching each of the gate wirings, the source and the drain electrodes with the etching solution composition of the present invention And a method of manufacturing a substrate.
상기 게이트 배선, 소스전극 또는 드레인 전극은 바람직하게는 티타늄계 금속막의 단일막, 또는 티타늄계 금속막/구리계 금속막의 이중막일 수 있으며, 상기 금속막을 본 발명의 식각액 조성물로 식각하여 게이트 배선, 소스전극 또는 드레인 전극을 제조할 수 있다.The gate wiring, the source electrode, or the drain electrode may preferably be a single film of a titanium-based metal film or a double film of a titanium-based metal film / copper-based metal film. The metal film is etched by the etching solution composition of the present invention, An electrode or a drain electrode can be manufactured.
상기 티타늄계 금속막 및 구리계 금속막에 대한 내용은 상술한 내용이 동일하게 적용될 수 있다.The contents of the titanium-based metal film and the copper-based metal film can be applied in the same manner as described above.
또한, 상기 디스플레이 장치용 어레이 기판은 박막트랜지스터(TFT) 어레이 기판일 수 있다.In addition, the array substrate for a display device may be a thin film transistor (TFT) array substrate.
또한, 본 발명은 상기 본 발명의 제조방법으로 제조된 디스플레이 장치용 어레이 기판에 관한 것이다.The present invention also relates to an array substrate for a display device manufactured by the manufacturing method of the present invention.
이하, 본 발명을 실시예 및 비교예를 이용하여 더욱 상세하게 설명한다. 그러나 하기 실시예는 본 발명을 예시하기 위한 것으로서 본 발명은 하기 실시예에 의해 한정되지 않으며, 다양하게 수정 및 변경될 수 있다. 본 발명의 범위는 후술하는 특허청구범위의 기술적 사상에 의해 정해질 것이다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples illustrate the present invention and the present invention is not limited by the following examples, and various modifications and changes may be made. The scope of the present invention will be determined by the technical idea of the following claims.
실시예Example 1 내지 9 및 1 to 9 and 비교예Comparative Example 1 내지 6. 1 to 6. 식각액Etchant 조성물 제조 Composition manufacturing
하기 표 1에 나타낸 조성 및 함량으로 실시예 1 내지 7 및 비교예 1 내지 6의 식각액 조성물을 제조하였으며, 조성물 총 중량이 100 중량%가 되도록 잔량의 탈이온수를 포함하였다.The etchant compositions of Examples 1 to 7 and Comparative Examples 1 to 6 were prepared by the compositions and contents shown in Table 1 below, and the remaining amount of deionized water was included so that the total weight of the composition was 100% by weight.
SPS : 과황산염,SPS: persulfate,
ABF : 중불화암모늄ABF: Ammonium fluoride
ATZ : 5-아미노 테트라졸ATZ: 5-Aminotetrazole
AcOH : 초산AcOH: acetic acid
실험예Experimental Example 1. One. 식각액Etchant 조성물의 특성 평가 Evaluation of composition characteristics
유리기판(100mm100mm)상에 티타늄막/구리막의 이중막을 증착시키고 포토리소그래피(photolithography) 공정을 통하여 기판 상에 소정의 패턴을 가진 포토레지스트가 형성되도록 한 후, 실시예 1 내지 9 및 비교예 1 내지 6의 식각액 조성물을 각각 사용하여 식각공정을 실시하였다.A double layer film of titanium film / copper film was deposited on a glass substrate (100 mm 100 mm), and a photoresist having a predetermined pattern was formed on the substrate through a photolithography process. Then, in Examples 1 to 9 and Comparative Examples 1 to 3, 6 were used for the etching process.
분사식 식각 방식의 실험장비(모델명 : ETCHER(TFT), SEMES사)를 이용하였고, 식각공정시 식각액 조성물의 온도는 약 30℃ 내외로 하였으나, 적정온도는 다른 공정조건과 기타 요인에 의해 필요에 따라 변경될 수 있다. 식각시간은 식각 온도에 따라서 다를 수 있으나, 통상 100초 정도로 진행하였다. 상기 식각공정에서 식각된 티타늄막/구리막의 이중막의 배선 단락과 식각 프로파일인 사면 직진성 및 테이퍼 앵글을 SEM(Hitachi사 제품, 모델명 S-4700)을 사용하여 검사하였고, 결과를 하기 표 2에 나타내었으며, 평가 기준은 하기와 같다. (ETCHER (TFT), manufactured by SEMES) was used as the etchant, and the temperature of the etchant composition was set at about 30 ° C. during the etching process. However, the optimum temperature was determined according to other process conditions and other factors can be changed. The etching time may vary depending on the etching temperature, but is usually about 100 seconds. The wiring short-circuit of the double-layered titanium film / copper film etched in the above etching process and the etching profile, slope straightness and taper angle were examined using an SEM (product name: S-4700, manufactured by Hitachi). The results are shown in Table 2 , And the evaluation criteria are as follows.
<테이퍼 앵글 평가 기준><Evaluation Criteria of Taper Angle>
O : 우수(도 1)O: Excellent (Figure 1)
X : 불량(도 2, 3)X: defective (Figs. 2 and 3)
<사면 직진성 평가 기준><Slope Straightness Evaluation Standard>
O : 우수(도 4)O: Excellent (FIG. 4)
X : 불량(도 5)X: Bad (Figure 5)
공정 특성상 테이퍼 앵글이 너무 낮으면 응답 효율이 떨어지며, 너무 높으면 전기적 과부하가 걸려 배선 터짐이 발생하여 불량의 원인이 되므로, 적정 수준의 우수한 테이퍼 앵글은 55 내지 70°이다.If the taper angle is too low, the response efficiency is low. If the taper angle is too high, electrical overload is applied, which causes wire breakage and causes defects. Therefore, the proper taper angle is 55 to 70 degrees.
또한, 상기 실시예 1 내지 9 및 비교예 1 내지 6의 식각액 조성물에 구리 3000ppm을 녹인 후, -9에서 최장 90일 까지 저온 보관하면서 석출물 발생 유무를 관찰하였으며, 그 결과를 하기 표 2에 나타내었다. 석출물이 발생하지 않은 것은 도 6과 같이 관찰되었으며, 석출물이 발생한 것은 도 7과 같이 관찰되었다.In addition, 3000 ppm of copper was dissolved in the etchant compositions of Examples 1 to 9 and Comparative Examples 1 to 6, and the presence or absence of precipitates was observed while keeping the temperature low from -9 to 90 days. The results are shown in Table 2 below . It was observed as in FIG. 6 that the precipitate did not occur, and the occurrence of the precipitate was observed as in FIG.
(배선 끊김)Wiring short
(Wiring break)
상기 표 2의 결과에서, 본 발명의 식각액 조성물인 실시예 1 내지 9는 배선 단락 및 석출물이 발생하지 않았으며, 사면 직진성 및 테이퍼 앵글 등의 식각 프로파일이 매우 우수한 것으로 관찰되었다.In the results of Table 2, it was observed that the etching compositions of Examples 1 to 9 of the present invention did not cause short-circuiting of wiring and precipitates, and had excellent etching profiles such as slope straightness and taper angle.
반면, 염소 화합물을 포함하지 않은 비교예 1의 식각액 조성물은 배선 단락이 발생하였으며, 염소 화합물의 함량이 본 발명의 함량 범위보다 초과하여 포함된 비교예 2 내지 6의 식각액 조성물은 배선 단락, 석출물, 사면 직진성 및 테이퍼 앵글 중 하나 이상이 불량한 결과를 보였으며, 그 중에서도 특히 석출물이 발생하는 결과를 보였다.On the other hand, the etchant composition of Comparative Example 1, which did not contain a chlorine compound, caused a short-circuit in the wiring, and the etchant compositions of Comparative Examples 2 to 6 containing a chlorine compound in an amount exceeding the content range of the present invention, At least one of slope straightness and taper angle showed poor results, and in particular, precipitate was observed.
따라서, 본 발명의 식각액 조성물은 식각 프로파일이 우수하며, 식각 시 석출물이 발생하지 않는다는 것을 알 수 있다.Thus, it can be seen that the etchant composition of the present invention has an excellent etching profile and no precipitates are formed during etching.
또한, 처리매수 진행에 따른 CD skew 변화를 확인하였다. In addition, the change of CD skew according to the progress of the number of processing was confirmed.
상기 처리매수는 1500ppm으로 진행하였으며, Ti 및 Cu 파우더를 동일한 비율로 첨가하였고, 200, 400, 600, 800, 1000 및 1500ppm에서의 처리매수 진행에 따른 CD skew를 측정하였으며, 결과를 하기 표 3에 나타내었다.The number of treatments proceeded to 1500 ppm, Ti and Cu powders were added in the same ratio, and CD skew according to the number of treatments at 200, 400, 600, 800, 1000 and 1500 ppm was measured. Respectively.
상기 표 3의 결과에서, 황산구리를 포함하지 않는 실시예 1 내지 7 및 비교예 1 내지 6의 식각액 조성물은 처리매수 400 및 600ppm에서 초기 CD skew를 유지하지 못하는 것을 확인할 수 있었다.From the results shown in Table 3, it can be seen that the etching solution compositions of Examples 1 to 7 and Comparative Examples 1 to 6 which do not contain copper sulfate can not maintain the initial CD skew at 400 and 600 ppm of the treatment number.
반면, 황산구리를 포함한 실시예 8 및 9의 식각액 조성물은 처리매수가 증가하더라도 초기 CD skew를 유지하였다.On the other hand, the etchant compositions of Examples 8 and 9 containing copper sulfate maintained the initial CD skew even when the number of treatments increased.
따라서, 식각액 조성물에 구리 화합물을 추가로 포함하였을 경우, CD skew가 변동되지 않고, 초기의 값을 유지하는 것을 알 수 있었다.Therefore, when the etching solution composition further contains a copper compound, it was found that the CD skew did not fluctuate and maintained the initial value.
Claims (13)
과황산염 0.5 내지 20 중량%;
불소 화합물 0.01 내지 2 중량%;
무기산 1 내지 10 중량%;
고리형 아민 화합물 0.5 내지 5 중량%;
염소 화합물 0.01 내지 0.1 중량% 미만;
유기산 또는 유기산염 1 내지 20 중량%; 및
식각액 조성물 총 중량이 100 중량%가 되도록 잔량의 물을 포함하는 식각액 조성물.With respect to the total weight of the composition,
From 0.5 to 20% by weight persulfate;
0.01 to 2% by weight of a fluorine compound;
1 to 10% by weight of an inorganic acid;
0.5 to 5% by weight of a cyclic amine compound;
0.01 to less than 0.1% by weight of a chlorine compound;
1 to 20% by weight of an organic acid or an organic acid salt; And
Wherein the etchant composition comprises a residual amount of water such that the total weight of the etchant composition is 100% by weight.
상기 유기산염은 상기 유기산의 나트륨염, 칼륨염 및 암모늄염으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는 식각액 조성물. The method of claim 1, wherein the organic acid is selected from the group consisting of nicotinic acid, acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, pentanoic acid, sulfobenzoic acid, sulfosuccinic acid, sulfophthalic acid, salicylic acid, sulfosalicylic acid, At least one compound selected from the group consisting of lactic acid, glyceric acid, succinic acid, malic acid, tartaric acid, isocitric acid, propenoic acid, iminodiacetic acid and ethylenediaminetetraacetic acid,
Wherein the organic acid salt comprises at least one selected from the group consisting of sodium salts, potassium salts and ammonium salts of the organic 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 단계; 를 포함하는 디스플레이 장치용 어레이 기판의 제조방법에 있어서,
상기 (a) 단계 및 (d) 단계 중 어느 한 단계 이상이, 청구항 1 내지 10 중 어느 한 항의 식각액 조성물로 식각하여 각각의 게이트 배선, 소스 및 드레인 전극을 형성하는 공정을 포함하는 것을 특징으로 하는 디스플레이 장치용 어레이 기판의 제조방법.(a) forming a gate wiring on a 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) forming a pixel electrode connected to the drain electrode; The method comprising the steps of:
Wherein at least one of the steps (a) and (d) comprises the step of forming the gate wiring, the source and the drain electrode by etching with the etching liquid composition according to any one of claims 1 to 10 A method of manufacturing an array substrate for a display device.
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| KR20160115715A (en) * | 2015-03-26 | 2016-10-06 | 동우 화인켐 주식회사 | Etchant composition and manufacturing method of an array substrate for liquid crystal display |
| KR20170015703A (en) * | 2015-07-30 | 2017-02-09 | 삼성디스플레이 주식회사 | Etchant and manufacturing method of thin film transistor substrate using the same |
| KR20170016715A (en) * | 2015-08-04 | 2017-02-14 | 동우 화인켐 주식회사 | Etching composition for metal layer |
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| Publication number | Publication date |
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| CN108570679A (en) | 2018-09-25 |
| KR102368382B1 (en) | 2022-02-28 |
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