KR20130008331A - An etching solution composition for copper layer/titanium layer - Google Patents
An etching solution composition for copper layer/titanium layer Download PDFInfo
- Publication number
- KR20130008331A KR20130008331A KR1020110069023A KR20110069023A KR20130008331A KR 20130008331 A KR20130008331 A KR 20130008331A KR 1020110069023 A KR1020110069023 A KR 1020110069023A KR 20110069023 A KR20110069023 A KR 20110069023A KR 20130008331 A KR20130008331 A KR 20130008331A
- Authority
- KR
- South Korea
- Prior art keywords
- acid
- film
- compound
- copper
- etching
- Prior art date
Links
- 238000005530 etching Methods 0.000 title claims abstract description 114
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000000203 mixture Substances 0.000 title claims abstract description 82
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 81
- 239000010949 copper Substances 0.000 title claims abstract description 80
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000010936 titanium Substances 0.000 title claims abstract description 66
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 66
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 150000007524 organic acids Chemical class 0.000 claims abstract description 15
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000010408 film Substances 0.000 claims description 160
- -1 cyclic amine compound Chemical class 0.000 claims description 34
- 235000002639 sodium chloride Nutrition 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 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
- 150000002222 fluorine compounds Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 150000007522 mineralic acids Chemical class 0.000 claims description 9
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 7
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N Valeric acid Natural products CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical class C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 5
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 5
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000011698 potassium fluoride Substances 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 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 3
- ZMPRRFPMMJQXPP-UHFFFAOYSA-N 2-sulfobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1S(O)(=O)=O ZMPRRFPMMJQXPP-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 3
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 claims description 3
- 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 3
- 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 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
- 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 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- KDCGOANMDULRCW-UHFFFAOYSA-N Purine Natural products N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-N benzopyrrole Natural products C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- 229910052790 beryllium Inorganic materials 0.000 claims description 3
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000000174 gluconic acid Substances 0.000 claims description 3
- 235000012208 gluconic acid Nutrition 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 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 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
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- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
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- 150000003230 pyrimidines Chemical class 0.000 claims 1
- 150000003233 pyrroles Chemical class 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract 1
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract 1
- 239000011707 mineral Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- 238000003860 storage Methods 0.000 description 13
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- 229920002120 photoresistant polymer Polymers 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
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- 239000007800 oxidant agent Substances 0.000 description 2
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 2
- 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
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 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
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 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
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- 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
- C23F1/02—Local etching
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
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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
- C09K13/10—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a boron compound
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- 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
- C23F1/26—Acidic compositions for etching refractory metals
-
- 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
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
Abstract
Description
본 발명은 구리막과 티타늄막으로 구성된 다중 금속막을 빠른 식각 속도로 균일하게 일괄 식각하여 우수한 식각 특성을 확보할 수 있는 구리막/티타늄막의 식각액 조성물에 관한 것이다.
The present invention relates to an etching liquid composition of a copper film / titanium film capable of ensuring excellent etching characteristics by uniformly batch-etching a multi-metal film composed of a copper film and a titanium film at a high etching rate.
반도체 장치 및 평판표시장치를 구동하는 전자 회로로서 대표적인 것은 박막 트랜지스터(thin film transistor, TFT)이다. TFT-LCD의 제조 과정은 통상 기판 위에 게이트와 소스/드레인 전극용 배선 재료로서 금속막을 형성하고, 이 금속막의 선택적인 영역에 포토레지스트를 형성한 후 이 포토레지스트를 마스크로 하여 위 금속막을 식각하는 공정으로 구성된다.Typical electronic circuits for driving semiconductor devices and flat panel displays are thin film transistors (TFTs). The manufacturing process of TFT-LCD typically forms a metal film as a wiring material for gate and source / drain electrodes on a substrate, forms a photoresist in an optional region of the metal film, and then etches the upper metal film using the photoresist as a mask. It consists of a process.
종래에는 게이트와 소스/드레인 전극용 배선 재료로 알루미늄 또는 이의 합금과 다른 금속이 적층된 금속막이 사용되었다. 알루미늄은 가격이 저렴하고 저항이 낮은 반면, 내화학성이 좋지 못하고 후 공정에서 힐락(hillock)과 같은 불량에 의해 다른 전도층과 쇼트(short) 현상을 일으키거나 산화물층과의 접촉에 의한 절연층을 형성시키는 등 액정패널의 동작 불량을 유발시킨다.Conventionally, as a wiring material for gate and source / drain electrodes, a metal film in which aluminum or an alloy thereof and another metal are laminated is used. While aluminum is inexpensive and low in resistance, it does not have good chemical resistance and causes short phenomena with other conductive layers due to defects such as hillocks in later processes, or insulating layers due to contact with oxide layers. It causes the malfunction of the liquid crystal panel.
이러한 점을 고려하여, 게이트와 소스/드레인 전극용 배선 재료로 구리막과 티타늄막의 이중 금속막이 제안되었다.In view of this, a double metal film of a copper film and a titanium film has been proposed as a wiring material for the gate and source / drain electrodes.
그러나, 구리막과 티타늄막의 이중 금속막을 식각하기 위해서는 각 금속막을 식각하기 위한 서로 다른 2종의 식각액을 이용해야 하는 단점이 있다. 특히, 구리를 포함하는 구리막을 식각하기 위해서는 과산화수소계 또는 옥손계 식각액이 주로 이용되는데, 과산화수소계 식각액은 불균등화 반응을 일으켜 조성물 자체가 분해되거나 경시에 따른 급격한 조성 변화로 인해 불안정한 단점이 있고, 옥손계 식각액은 식각 속도가 느리고 경시에 따른 불안정한 단점이 있다. 또한, 구리막용 식각액과 티타늄막용 식각액을 단순히 혼합한 식각액도 이용되었으나, 이 경우 식각 프로파일이 불량하고 후 공정에 어려움이 따르며, 특히 티타늄의 식각에 이용되는 불소 이온(F-)이 유리 기판과 실리콘층에 손상을 일으켜 실제 공정에 적용하기에 적합하지 않다.
However, in order to etch the double metal film of the copper film and the titanium film, there is a disadvantage in that two different etching solutions for etching each metal film must be used. In particular, a hydrogen peroxide-based or oxone-based etchant is mainly used to etch a copper film containing copper, and hydrogen peroxide-based etchant causes disproportionation reactions, resulting in instability due to decomposition of the composition itself or rapid change in composition over time. Hand-based etchant has a slow etching speed and unstable over time. In addition, an etching solution obtained by simply mixing an etching solution for a copper film and an etching solution for a titanium film was also used, but in this case, the etching profile was poor and difficulty in post-processing. In particular, the fluorine ion (F − ) used for etching titanium is a glass substrate and a silicon. It damages the layers and is not suitable for practical application.
본 발명은 조성물 자체가 분해되거나 경시에 따른 급격한 조성 변화가 없이 저장 안정성이 우수하고, 구리막과 티타늄막으로 구성된 다중 금속막을 빠른 식각 속도로 균일하게 일괄 식각할 수 있어 우수한 식각 특성을 확보할 수 있는 구리막/티타늄막의 식각액 조성물을 제공하는 것을 목적으로 한다.The present invention has excellent storage stability without degrading the composition itself or a sudden change in composition with time, and can uniformly batch-etch multiple metal films composed of a copper film and a titanium film at a high etching rate to secure excellent etching characteristics. It is an object to provide an etching liquid composition of a copper film / titanium film.
또한, 본 발명은 상기 구리막/티타늄막의 식각액 조성물을 이용한 박막 트랜지스터의 제조방법을 제공하는 것을 다른 목적으로 한다.
Another object of the present invention is to provide a method of manufacturing a thin film transistor using the etching solution composition of the copper film / titanium film.
1. 과황산염 5 내지 20중량%; 불소 화합물 0.01 내지 2중량%; 염소 화합물 0.001 내지 3중량%; 무기산, 이의 염 또는 이들의 혼합물 1 내지 10중량%; 고리형 아민 화합물 0.3 내지 5중량%; 유기산, 이의 염 또는 이들의 혼합물 1 내지 10중량%; p-톨루엔술폰산 0.1 내지 5중량%; 및 잔량의 물을 포함하는 구리막/티타늄막의 식각액 조성물.1. 5-20 wt% persulfate; 0.01 to 2% by weight of a fluorine compound; 0.001 to 3 weight percent of a chlorine compound; 1 to 10% by weight of inorganic acid, salts thereof or mixtures thereof; 0.3 to 5% by weight of the cyclic amine compound; 1 to 10% by weight of organic acid, salt thereof or mixture thereof; 0.1 to 5% by weight of p-toluenesulfonic acid; And a residual amount of water.
2. 위 1에 있어서, 과황산염은 과황산암모늄, 과황산나트륨 및 과황산칼륨으로 이루어진 군으로부터 선택된 1종 이상인 구리막/티타늄막의 식각액 조성물.2. The etching solution of claim 1, wherein the persulfate is at least one selected from the group consisting of ammonium persulfate, sodium persulfate and potassium persulfate.
3. 위 1에 있어서, 불소 화합물은 불산, 불화암모늄, 중불화암모늄, 붕불화암모늄, 불화칼륨, 중불화칼륨, 붕불화칼륨, 불화나트륨, 중불화나트륨, 불화알루미늄, 불화붕소산, 불화리튬 및 불화칼슘 이루어진 군으로부터 선택된 1종 이상인 구리막/티타늄막의 식각액 조성물.3. In the above 1, the fluorine compound is hydrofluoric acid, ammonium fluoride, ammonium bifluoride, ammonium fluoride, potassium fluoride, potassium bifluoride, potassium fluoride, sodium fluoride, sodium bifluoride, aluminum fluoride, boric fluoride, lithium fluoride And at least one copper film / titanium film selected from the group consisting of calcium fluoride.
4. 위 1에 있어서, 염소 화합물은 염산, 염화나트륨, 염화칼륨 및 염화암모늄으로 이루어진 군으로부터 선택된 1종 이상인 구리막/티타늄막의 식각액 조성물.4. In the above 1, wherein the chlorine compound is at least one selected from the group consisting of hydrochloric acid, sodium chloride, potassium chloride and ammonium chloride etching liquid composition of the copper film / titanium film.
5. 위 1에 있어서, 무기산은 질산, 황산, 인산 또는 과염소산으로 이루어진 군으로부터 선택된 1종 이상인 구리막/티타늄막의 식각액 조성물.5. The etching solution of claim 1, wherein the inorganic acid is at least one member selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, or perchloric acid.
6. 위 1에 있어서, 고리형 아민 화합물은 5-아미노테트라졸, 톨리트리아졸, 벤조트리아졸, 메틸벤조트리아졸, 이미다졸계 화합물, 인돌계 화합물, 푸린계 화합물, 피라졸계 화합물, 피리딘계 화합물, 피리미딘계 화합물, 피롤계 화합물, 피롤리딘계 화합물 및 피롤린계 화합물로 이루어진 군으로부터 선택된 1종 이상인 구리막/티타늄막의 식각액 조성물.6. In the above 1, the cyclic amine compound is 5-aminotetrazole, tolytriazole, benzotriazole, methylbenzotriazole, imidazole compound, indole compound, purine compound, pyrazole compound, pyridine An etching liquid composition of a copper film / titanium film of at least one selected from the group consisting of a compound, a pyrimidine compound, a pyrrole compound, a pyrrolidine compound and a pyrroline compound.
7. 위 1에 있어서, 유기산은 아세트산, 이미노디아세트산, 에틸렌디아민테트라아세트산, 부탄산, 시트르산, 이소시트르산, 포름산, 글루콘산, 글리콜산, 말론산, 옥살산, 펜탄산, 술포벤조산, 석신산, 술포석신산, 살리실산, 술포살리실산, 벤조산, 락트산, 글리세르산, 말산, 타르타르산 및 프로펜산으로 이루어진 군으로부터 선택된 1종 이상인 구리막/티타늄막의 식각액 조성물.7. In the above 1, the organic acid is acetic acid, imino diacetic acid, ethylenediamine tetraacetic acid, butanoic acid, citric acid, iso citric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, pentanic acid, sulfobenzoic acid, succinic acid, An etching solution composition of a copper film / titanium film of at least one member selected from the group consisting of sulfosuccinic acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, malic acid, tartaric acid, and propenoic acid.
8. 위 1에 있어서, 유기산의 염은 칼륨염, 나트륨염 또는 암모늄염인 구리막/티타늄막의 식각액 조성물.8. according to the above 1, wherein the salt of the organic acid is a potassium salt, sodium salt or ammonium salt etching liquid composition of the copper film / titanium film.
9. 위 1에 있어서, 구리막은 구리 단독막 또는 구리와 알루미늄, 마그네슘, 망간, 베릴륨, 하프늄, 나이오븀, 텅스텐 및 바나듐으로 이루어진 군으로부터 선택된 1종 이상을 함유하는 구리 합금막인 구리막/티타늄막의 식각액 조성물.9. The copper film according to the above 1, the copper film is a copper film or a copper alloy film containing at least one selected from the group consisting of copper and aluminum, magnesium, manganese, beryllium, hafnium, niobium, tungsten and vanadium. Etch solution composition of the membrane.
10. 위 1에 있어서, 티타늄막은 티타늄 단독막인 구리막/티타늄막의 식각액 조성물.10. In the above 1, the titanium film is a titanium film is an etching solution composition of the copper film / titanium film.
11. 위 1에 있어서, 구리막/티타늄막은 구리막과 티타늄막이 1회 이상 교대로 적층된 다중막인 구리막/티타늄막의 식각액 조성물.11. In the above 1, the copper film / titanium film is an etching liquid composition of the copper film / titanium film is a multilayer film in which the copper film and titanium film are alternately stacked one or more times.
12. 위 1 내지 11 중 어느 한 항의 식각액 조성물로 구리막/티타늄막을 식각하여 금속 배선의 패턴을 형성하는 공정을 포함하는 박막 트랜지스터의 제조방법.
12. Method of manufacturing a thin film transistor comprising the step of forming a pattern of metal wiring by etching the copper film / titanium film with the etching liquid composition of any one of 1 to 11.
본 발명의 식각액 조성물은 구리막과 티타늄막으로 구성된 다중 금속막을 빠른 식각 속도로 균일하게 일괄 식각할 수 있어, 식각 공정을 단순화하고 생산성을 향상시킬뿐만 아니라 우수한 식각 특성도 확보할 수 있다.The etchant composition of the present invention can uniformly etch multiple metal films composed of a copper film and a titanium film at a high etching rate, thereby simplifying an etching process and improving productivity, and also securing excellent etching characteristics.
또한, 본 발명의 식각액 조성물은 불균등화 반응을 일으키지 않아 조성물 자체가 분해되거나 경시에 따른 급격한 조성 변화가 없이 저장 안정성이 우수하다.In addition, the etchant composition of the present invention is excellent in storage stability without causing a disproportionation reaction so that the composition itself is degraded or there is no sudden composition change with time.
또한, 본 발명의 식각액 조성물은 식각 시 고가의 장비를 필요로 하지 않고 장비도 손상시키지 않을 뿐만 아니라 대면적화에 유리하여 경제적인 이점이 있다.
In addition, the etchant composition of the present invention does not require expensive equipment during etching and does not damage equipment as well, which is advantageous in terms of large area and thus has an economical advantage.
본 발명은 우수한 식각 특성을 확보할 수 있는 구리막/티타늄막의 식각액 조성물에 관한 것이다.
The present invention relates to an etching liquid composition of a copper film / titanium film that can secure excellent etching characteristics.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에서 '구리막/티타늄막'은 구리막과 티타늄막이 적층된 다중 금속막을 의미한다. 구체적으로, 구리막/티타늄막의 순으로 적층된 이중 금속막, 티타늄막/구리막의 순으로 적층된 이중 금속막을 포함한다. 또한, 구리막과 티타늄막이 3층 이상으로 교대로 적층된 다중 금속막, 예컨대 구리막/티타늄막/구리막의 삼중 금속막, 티타늄막/구리막/티타늄막의 삼중 금속막, 구리막/티타늄막/구리막/티타늄막/구리막의 다중 금속막 등도 포함한다. 이때, 구리막과 티타늄막의 두께는 특별히 한정되지 않는다.In the present invention, 'copper film / titanium film' means a multi-metal film in which a copper film and a titanium film are stacked. Specifically, a double metal film laminated in the order of the copper film / titanium film, and the double metal film stacked in the order of the titanium film / copper film. Further, a multi-metal film in which a copper film and a titanium film are alternately stacked in three or more layers, such as a triple metal film of a copper film / titanium film / copper film, a triple metal film of a titanium film / copper film / titanium film, and a copper film / titanium film / And multiple metal films of copper film / titanium film / copper film. At this time, the thickness of a copper film and a titanium film is not specifically limited.
또한, 본 발명에서 '구리막'은 구리만으로 구성된 구리 단독막일 수 있고, 구리와 함께 알루미늄(Al), 마그네슘(Mg), 망간(Mn), 베릴륨(Be), 하프늄(Hf), 나이오븀(Nb), 텅스텐(W) 및 바나듐(V)으로 이루어진 군으로부터 선택된 1종 이상을 함유하는 구리 합금으로 구성된 구리 합금막일 수도 있다.Further, in the present invention, the 'copper film' may be a copper monolayer composed of only copper, and together with copper, aluminum (Al), magnesium (Mg), manganese (Mn), beryllium (Be), hafnium (Hf), and niobium ( It may be a copper alloy film composed of a copper alloy containing at least one selected from the group consisting of Nb), tungsten (W) and vanadium (V).
또한, 본 발명에서 '티타늄막'은 티타늄 단독으로 구성된 티타늄 단독막일 수 있다.In addition, in the present invention, the 'titanium film' may be a titanium single film composed of titanium alone.
본 발명의 구리막/티타늄막의 식각액 조성물은 과황산염; 불소 화합물; 염소 화합물; 무기산, 이의 염 또는 이들의 혼합물; 고리형 아민 화합물; 유기산, 이의 염 또는 이들의 혼합물; p-톨루엔술폰산; 및 물을 최적의 함량비로 포함하는 것을 특징으로 한다.The etching liquid composition of the copper film / titanium film of this invention is a persulfate; Fluorine compounds; Chlorine compounds; Inorganic acids, salts thereof or mixtures thereof; Cyclic amine compounds; Organic acids, salts thereof or mixtures thereof; p-toluenesulfonic acid; And water in an optimal content ratio.
보다 상세하게, 과황산염 5 내지 20중량%; 불소 화합물 0.01 내지 2중량%; 염소 화합물 0.001 내지 3중량%; 무기산, 이의 염 또는 이들의 혼합물 1 내지 10중량%; 고리형 아민 화합물 0.3 내지 5중량%; 유기산, 이의 염 또는 이들의 혼합물 1 내지 10중량%; p-톨루엔술폰산 0.1 내지 5중량%; 및 잔량의 물을 포함한다.More specifically, 5 to 20% by weight persulfate; 0.01 to 2% by weight of a fluorine compound; 0.001 to 3 weight percent of a chlorine compound; 1 to 10% by weight of inorganic acid, salts thereof or mixtures thereof; 0.3 to 5% by weight of the cyclic amine compound; 1 to 10% by weight of organic acid, salt thereof or mixture thereof; 0.1 to 5% by weight of p-toluenesulfonic acid; And residual water.
과황산염은 구리막을 식각하는 주성분이다. 구체적인 예로는 과황산암모늄((NH4)2S2O8), 과황산나트륨(Na2S2O8), 과황산칼륨(K2S2O8) 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Persulfate is the main component for etching copper film. Specific examples thereof include ammonium persulfate ((NH 4 ) 2 S 2 O 8 ), sodium persulfate (Na 2 S 2 O 8 ), potassium persulfate (K 2 S 2 O 8 ), and the like. It can mix and use species.
과황산염은 식각액 조성물 총 100중량% 중에 5 내지 20중량%로 포함될 수 있고, 바람직하게는 7 내지 18중량%인 것이 좋다. 이 함량 범위에서는 구리막이 적정량으로 식각되고 우수한 식각 프로파일을 얻을 수 있다. 함량이 5중량% 미만인 경우 구리막이 식각되지 않거나 식각 속도가 느릴 수 있고, 20중량% 초과인 경우 식각 속도가 빨라져 공정을 제어하기 어려울 수 있다.Persulfate may be included in 5 to 20% by weight of the total 100% by weight of the etchant composition, preferably 7 to 18% by weight. In this content range, the copper film is etched in an appropriate amount and an excellent etching profile can be obtained. If the content is less than 5% by weight, the copper film may not be etched or the etching rate may be slow. If the content is more than 20% by weight, the etching rate may be difficult to control the process.
불소 화합물은 식각액 조성물 내에서 불소 이온 또는 다원자 불소 이온으로 해리될 수 있는 화합물로서, 티타늄막을 식각하는 주성분이며 식각 시 발생할 수 있는 잔사를 제거하는 역할을 한다. 불소 화합물의 종류는 특별히 한정되지 않으며, 구체적인 예로는 불산(HF), 불화암모늄(NH4F), 중불화암모늄(ammonium bifluoride, NH4HF2), 붕불화암모늄(NH4BF4), 불화칼륨(KF), 중불화칼륨(potassium bifluoride, KHF2), 붕불화칼륨(KBF4), 불화나트륨(NaF), 중불화나트륨(sodium bifluoride, NaHF2), 불화알루미늄(AlF3), 불화붕소산(HBF4), 불화리튬(LiF), 불화칼슘(CaF2) 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The fluorine compound is a compound capable of dissociating into fluorine ions or polyatomic fluorine ions in the etching liquid composition, and is a main component for etching the titanium film and removes residues that may occur during etching. The type of the fluorine compound is not particularly limited, and specific examples thereof include hydrofluoric acid (HF), ammonium fluoride (NH 4 F), ammonium bifluoride (NH 4 HF 2 ), ammonium fluoride (NH 4 BF 4 ), and fluoride Potassium (KF), Potassium Bifluoride (KHF 2 ), Potassium Borofluoride (KBF 4 ), Sodium Fluoride (NaF), Sodium Bifluoride (NaHF 2 ), Aluminum Fluoride (AlF 3 ), Boron Fluoride Acids (HBF 4 ), lithium fluoride (LiF), calcium fluoride (CaF 2 ), and the like, and these may be used alone or in combination of two or more thereof.
불소 화합물은 식각액 조성물 총 100중량% 중에 0.01 내지 2중량%로 포함될 수 있고, 바람직하게는 0.01 내지 1중량%인 것이 좋다. 이 함량 범위에서는 티타늄막이 적정량으로 식각되고 우수한 식각 프로파일을 얻을 수 있다. 함량이 0.01중량% 미만인 경우 티타늄막의 식각 속도가 저하되어 잔사가 발생할 수 있고, 2중량% 초과인 경우 유리 등의 기판과 실리콘막 등의 절연막에 손상을 일으킬 수 있다.The fluorine compound may be included in an amount of 0.01 to 2% by weight in 100% by weight of the etching liquid composition, preferably 0.01 to 1% by weight. In this content range, the titanium film is etched in an appropriate amount and an excellent etching profile can be obtained. If the content is less than 0.01% by weight, the etching rate of the titanium film may be lowered, and residues may occur. If the content is more than 2% by weight, the substrate may be damaged, such as glass, and the insulating film, such as a silicon film.
염소 화합물은 식각액 조성물 내에서 염소 이온으로 해리될 수 있는 화합물로서, 구리막을 식각하는 보조 산화제이자 과황산염과 구리막의 식각에 대하여 경쟁반응을 하여 과황산염의 구리막에 대한 국부적 과침식을 제어하는 제어하는 식각 속도 조절과 테이퍼 각도를 조절하는 성분이다. 구체적인 예로는 염산(HCl), 염화나트륨(NaCl), 염화칼륨(KCl), 염화암모늄(NH4Cl) 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The chlorine compound is a compound capable of dissociating into chlorine ions in the etching liquid composition. It is an auxiliary oxidant for etching the copper film and controls the local over-erosion of the persulphate copper film by competing reactions against the etching of the copper film with the persulfate. It is the component to control the etching speed and the taper angle. Specific examples include hydrochloric acid (HCl), sodium chloride (NaCl), potassium chloride (KCl), ammonium chloride (NH 4 Cl) and the like, these may be used alone or in combination of two or more.
염소 화합물은 식각액 조성물 총 100중량% 중에 0.001 내지 3중량%로 포함될 수 있고, 바람직하게는 0.001 내지 1.5중량%인 것이 좋다. 이 함량 범위에서는 구리막의 식각 속도를 최적화할 수 있다. 함량이 0.001중량% 미만인 경우 식각액에 의한 구리막의 국부적 과침식으로 불량을 유발시킬 수 있으며, 3중량% 초과인 경우 일정 함량에 대한 처리매수를 감소시키고 식각 속도가 과도하게 빨라져 식각 프로파일이 불량해질 수 있다.The chlorine compound may be included in 0.001 to 3% by weight in the total 100% by weight of the etching liquid composition, preferably 0.001 to 1.5% by weight. Within this content range, the etching rate of the copper film can be optimized. If the content is less than 0.001% by weight, it may cause defects by local erosion of the copper film by the etching solution.If the content is more than 3% by weight, the number of treatments for a certain content may be reduced, and the etching rate may be excessively increased, resulting in poor etching profiles. have.
무기산, 이의 염 또는 이들의 혼합물은 구리막과 티타늄의 식각을 위한 보조 산화제이다. 구체적인 예로는 질산, 황산, 인산, 과염소산 및 이들의 염을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Inorganic acids, salts thereof or mixtures thereof are auxiliary oxidants for etching copper films and titanium. Specific examples include nitric acid, sulfuric acid, phosphoric acid, perchloric acid and salts thereof, and these may be used alone or in combination of two or more thereof.
무기산, 이의 염 또는 이들의 혼합물은 식각액 조성물 총 100중량% 중에 1 내지 10중량%로 포함될 수 있고, 바람직하게는 2 내지 7중량%인 것이 좋다. 이 함량 범위에서는 구리막과 티타늄막이 적정량으로 식각되고 우수한 식각 프로파일을 얻을 수 있다. 함량이 1중량% 미만인 경우 식각 속도가 저하되어 식각 프로파일이 불량해질 수 있고 잔사가 발생할 수 있으며, 10중량% 초과인 경우 과식각이 발생할 수 있고 포토레지스트에 크랙(crack)이 발생하고 이 크랙으로 식각액 조성물이 침투하여 배선이 단락될 수 있다.The inorganic acid, salts thereof, or mixtures thereof may be included in an amount of 1 to 10% by weight, preferably 2 to 7% by weight, in 100% by weight of the total amount of the etchant composition. In this content range, the copper film and the titanium film are etched in an appropriate amount, and an excellent etching profile can be obtained. If the content is less than 1% by weight, the etching rate may be lowered, resulting in poor etching profiles and residues. If the content is more than 10% by weight, overetching may occur and cracks may occur in the photoresist. The etchant composition may penetrate and short the wiring.
고리형 아민 화합물은 구리막의 식각 시 식각 속도를 조절하고 프로파일을 형성하는 성분이다. 구체적인 예로는 5-아미노테트라졸, 톨리트리아졸, 벤조트리아졸, 메틸벤조트리아졸, 이미다졸계 화합물, 인돌계 화합물, 푸린계 화합물, 피라졸계 화합물, 피리딘계 화합물, 피리미딘계 화합물, 피롤계 화합물, 피롤리딘계 화합물, 피롤린계 화합물 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The cyclic amine compound is a component that controls the etching rate and forms a profile during etching of the copper film. Specific examples include 5-aminotetrazole, tolytriazole, benzotriazole, methylbenzotriazole, An imidazole compound, an indole compound, a purine compound, a pyrazole compound, a pyridine compound, a pyrimidine compound, a pyrrole compound, a pyrrolidine compound, a pyrroline compound, and the like. It can be mixed and used.
고리형 아민 화합물은 식각액 조성물 총 100중량% 중에 0.3 내지 5중량%로 포함될 수 있고, 바람직하게는 0.5 내지 3중량%인 것이 좋다. 이 함량 범위에서는 적정한 구리 식각율과 테이퍼 각도를 형성할 수 있고 측면 식각량을 조절할 수 있다. 함량이 0.3중량% 미만인 경우 구리의 식각 속도를 충분히 조절하기 어려워 과식각이 발생할 수 있고, 5중량% 초과인 경우 구리의 식각 속도가 저하되어 공정 상 식각 시간이 길어져 생산성을 저하시킬 수 있다.The cyclic amine compound may be included in 0.3 to 5% by weight in the total 100% by weight of the etchant composition, preferably 0.5 to 3% by weight. In this content range, it is possible to form an appropriate copper etch rate and taper angle, and to control the side etch amount. If the content is less than 0.3% by weight, it is difficult to sufficiently control the etching rate of copper, and overetching may occur. When the content is more than 5% by weight, the etching rate of copper may be lowered, thereby increasing the etching time in the process, thereby reducing productivity.
유기산, 이의 염 또는 이들의 혼합물은 구리막의 테이퍼 각도를 조절하고 식각 속도를 조절하여, 원하는 측면 식각(side etching)을 얻기 위하여 처리매수의 경시 진행 시 일정한 식각 프로파일을 유지할 수 있게 하는 성분이다. 또한, 식각된 금속 이온과의 킬레이팅 작용에 의해 식각액 조성물에 영향을 주는 것을 방지하여 일정 함량에 대한 처리매수를 증가시키는 역할도 한다.An organic acid, a salt thereof, or a mixture thereof is a component that can control a taper angle of the copper film and adjust an etching rate so that a constant etching profile can be maintained when the treated sheet is processed over time in order to obtain a desired side etching. In addition, the chelating action with the etched metal ions to prevent affecting the etching liquid composition also serves to increase the number of treatment for a certain amount.
유기산, 이의 염 또는 이들의 혼합물의 구체적인 예로는 아세트산, 이미노디아세트산, 에틸렌디아민테트라아세트산, 부탄산, 시트르산, 이소시트르산, 포름산, 글루콘산, 글리콜산, 말론산, 옥살산, 펜탄산, 술포벤조산, 석신산, 술포석신산, 살리실산, 술포살리실산, 벤조산, 락트산, 글리세르산, 말산, 타르타르산, 프로펜산 등을 들 수 있다. 또한, 유기산의 염으로는 위 유기산의 칼륨염, 나트륨염, 암모늄염 등을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Specific examples of organic acids, salts thereof, or mixtures thereof include acetic acid, imino diacetic acid, ethylenediaminetetraacetic acid, butanoic acid, citric acid, isocitric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, pentanic acid, sulfobenzoic acid, Succinic acid, sulfosuccinic acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, malic acid, tartaric acid, propenoic acid, and the like. In addition, examples of the salts of the organic acids include potassium salts, sodium salts and ammonium salts of the above organic acids. These can be used individually or in mixture of 2 or more types.
유기산, 이의 염 또는 이들의 혼합물은 식각액 조성물 총 100중량% 중에 1 내지 10중량%로 포함될 수 있고, 바람직하게는 2 내지 7중량%인 것이 좋다. 함량이 1중량% 미만인 경우 처리매수의 경시 진행 시 일정한 식각 프로파일의 유지가 어렵고 처리매수의 증가 효과가 미미하며, 10중량% 초과인 경우 과식각 현상이 발생하여 측면 식각이 커지는 현상이 발생하고 더 이상의 처리매수 증가 효과가 없어 비경제적이다.The organic acid, a salt thereof, or a mixture thereof may be included in an amount of 1 to 10% by weight, preferably 2 to 7% by weight, in 100% by weight of the total amount of the etchant composition. If the content is less than 1% by weight, it is difficult to maintain a constant etching profile over time, and the increase of the number of treatments is insignificant. If the content is more than 10% by weight, the side etching increases due to overetching and more. It is uneconomical because there is no effect of increasing the number of treatments above.
p-톨루엔술폰산은 식각액 조성물 제조 후 경시에 의한 자체 조성이 변하여 식각 특성이 변하게 되는 것을 방지하고 저장 안정성을 향상시켜 장기간 동안 보관할 수 있게 하는 성분이다.The p-toluenesulfonic acid is a component that can be stored for a long period of time to prevent the change in the etching properties by changing its composition over time after the preparation of the etching solution composition, improve the storage stability.
p-톨루엔술폰산은 식각액 조성물 총 100중량% 중에 0.1 내지 5중량%로 포함될 수 있고, 바람직하게 0.5 내지 3중량%로 포함되는 것이 좋다. 함량이 0.1중량% 미만인 경우 경시에 따른 자체 조성의 변화를 방지하기 어렵고, 5중량% 초과인 경우 과식각이 발생하여 식각 프로파일이 불량해질 수 있다.The p-toluenesulfonic acid may be included in an amount of 0.1 to 5% by weight in 100% by weight of the total etching solution composition, preferably 0.5 to 3% by weight. If the content is less than 0.1% by weight, it is difficult to prevent the change of its composition with time, and when the content is more than 5% by weight, overetching may occur, resulting in poor etching profiles.
물의 종류는 특별히 한정되지 않으며, 탈이온 증류수인 것이 바람직하고, 보다 바람직하게는 반도체 공정용 탈이온 증류수로서 비저항값이 18㏁/㎝ 이상인 것이 좋다.The kind of water is not specifically limited, It is preferable that it is deionized distilled water, More preferably, it is preferable that the specific resistance value is 18 kPa / cm or more as deionized distilled water for a semiconductor process.
물은 식각액 조성물 총 100중량% 중에 잔량으로 포함될 수 있다.Water may be included in the balance in a total of 100% by weight of the etchant composition.
본 발명의 식각액 조성물은 상기 성분과 함께 식각 조절제, 계면활성제, 금속 이온 봉쇄제, 부식방지제, pH 조절제 등의 첨가제를 1종 이상 더 포함할 수 있다.The etchant composition of the present invention may further include one or more additives such as an etching regulator, a surfactant, a metal ion sequestrant, a corrosion inhibitor, a pH regulator, etc. together with the above components.
이와 같이 구성된 본 발명의 식각액 조성물은 불균등화 반응을 일으키지 않아 조성물 자체가 분해되거나 경시에 따른 급격한 조성 변화가 없이 저장 안정성이 우수하며, 구리막과 티타늄막이 적층된 이중 금속막뿐만 아니라 이들이 2회 이상 적층된 다중 금속막을 빠른 식각 속도로 균일하게 일괄 식각하는데 특히 유용하다. 이를 통하여, 식각 공정을 단순화하고 생산성을 향상시킬 수 있으며 우수한 식각 특성도 확보할 수 있다.The etchant composition of the present invention configured as described above does not cause disproportionation reaction and thus has excellent storage stability without degrading the composition itself or sudden change of composition with time, and not only double metal film in which copper film and titanium film are laminated, but also these two or more times. It is particularly useful for uniformly batch etching multiple stacked metal films at a high etching rate. Through this, the etching process can be simplified and productivity can be improved, and excellent etching characteristics can be obtained.
또한, 본 발명의 식각액 조성물은 각각 구리막과 티타늄막을 식각하는 주성분이면서 동시에 금속 산화물막을 식각하는 성분인 과황산염과 불소 화합물을 포함하여, 구리막/티타늄막이 소스/드레인 전극으로 사용되고, a-ITO(indium tin oxide) 또는 IZO(indium zinc oxide)가 화소전극으로 사용되는 경우 이 소스/드레인 전극과 화소전극의 일괄 식각에도 이용될 수 있다.In addition, the etchant composition of the present invention comprises a persulfate and a fluorine compound, which is a main component for etching the copper film and the titanium film, and a component for etching the metal oxide film, respectively, and a copper film / titanium film is used as a source / drain electrode, and a-ITO Indium tin oxide (IZO) or indium zinc oxide (IZO) may be used for the batch etching of the source / drain electrode and the pixel electrode.
또한, 본 발명의 식각액 조성물은 액정표시장치와 같은 평판표시장치의 제조뿐만 아니라 메모리 반도체 표시판 등의 제조에도 이용될 수 있다.In addition, the etchant composition of the present invention can be used not only for the manufacture of flat panel displays such as liquid crystal displays but also for the manufacture of memory semiconductor displays and the like.
본 발명의 식각액 조성물을 이용하여 구리막/티타늄막의 다중 금속막을 식각하여 금속 배선의 패턴을 형성하는 공정을 포함하는 방법으로 TFT-LCD를 제조할 수 있다.The TFT-LCD may be manufactured by a method including etching a multiple metal film of a copper film / titanium film by using the etching solution composition of the present invention to form a pattern of a metal wiring.
TFT-LCD의 제조방법은 특별히 한정되지 않는다. 예컨대, 기판 위에 소스/드레인 전극용 배선 재료인 구리막/티타늄막으로 구성된 다중 금속막을 형성하는 단계; 형성된 구리막/티타늄막 상의 선택적인 영역에 포토레지스트를 형성하는 단계; 형성된 포토레지스트를 마스크로 하여 상기 구리막/티타늄막을 본 발명의 식각액 조성물로 식각하여 금속 배선의 패턴을 형성하는 단계를 포함할 수 있다.The manufacturing method of TFT-LCD is not specifically limited. For example, forming a multi-metal film composed of a copper film / titanium film which is a wiring material for the source / drain electrodes on the substrate; Forming a photoresist in an optional region on the formed copper film / titanium film; And etching the copper film / titanium film with the etchant composition of the present invention using the formed photoresist as a mask to form a pattern of a metal wiring.
이와 같이 구성된 TFT-LCD의 제조방법에 의하면 우수한 금속 배선, 즉 소스/드레인 배선을 용이하게 형성할 수 있어, TFT-LCD의 대형화를 달성할 수 있다.According to the TFT-LCD manufacturing method configured as described above, excellent metal wiring, that is, source / drain wiring, can be easily formed, and the size of the TFT-LCD can be achieved.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 이들 실시예는 본 발명을 예시하는 것일 뿐 첨부된 특허청구범위를 제한하는 것이 아니며, 본 발명의 범주 및 기술사상 범위 내에서 실시예에 대한 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.
Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.
실시예Example
실시예 1Example 1
과황산암모늄(ammonium persulfate, APS) 10중량%, 중불화암모늄(ammonium bifluoride, ABF) 0.5중량%, 염화암모늄(NH4Cl) 0.05중량%, 질산(HNO3) 3중량%, 5-아미노테트라졸(aminotetrazole, ATZ) 1중량%, 아세트산암모늄(ammonium acetate, AA) 3중량%와 아세트산(AcOH) 5중량%, p-톨루엔술폰산(p-toluene sulfonic acid, PTA) 2중량% 및 잔량의 물이 혼합된 식각액 조성물을 5㎏이 되도록 제조하였다.
10% by weight of ammonium persulfate (APS), 0.5% by weight of ammonium bifluoride (ABF), 0.05% by weight of ammonium chloride (NH 4 Cl), 3 % by weight of nitric acid (HNO 3 ), 5-aminotetra 1% by weight of azole (aminotetrazole (ATZ), 3% by weight of ammonium acetate (AA), 5% by weight of acOH, 2% by weight of p-toluene sulfonic acid (PTA) and residual water This mixed etchant composition was prepared to be 5 kg.
실시예Example 2, 2, 비교예Comparative example 1-6 1-6
상기 실시예 1과 동일하게 실시하되, 하기 표 1에 나타낸 바와 같은 성분 및 함량을 사용하였다.
The same procedure as in Example 1, except that the ingredients and contents as shown in Table 1 were used.
ABF: 중불화암모늄(ammonium bifluoride)
ATZ: 5-아미노테트라졸
AA: 암모늄아세테이트
AcOH: 아세트산
PTA: p-톨루엔술폰산APS: ammonium persulfate
ABF: ammonium bifluoride
ATZ: 5-aminotetrazole
AA: ammonium acetate
AcOH: acetic acid
PTA: p-toluenesulfonic acid
시험예Test Example
1. 식각 특성 평가1. Etch Characteristic Evaluation
유리 위에 실리콘층이 증착되어 있고, 실리콘층 위에 구리막과 티타늄막이 순서대로 적층되어 있으며, 티타늄막 상에 일정한 형태의 모양으로 포토레지스트가 패터닝된 기판을 다이아몬드 칼을 이용하여 550㎜×650㎜ 크기로 잘라 시편을 제작하였다.A silicon layer is deposited on glass, a copper film and a titanium film are stacked on the silicon layer in order, and a substrate is patterned on a titanium film in a uniform shape by using a diamond knife. The specimen was cut into pieces.
분사식 식각 방식의 실험장비(ETCHER(TFT), SEMES사) 내에 제조된 식각액 조성물을 넣고 온도를 30℃로 세팅하여 가온하였다. 그 후, 온도가 30±0.1℃에 도달한 후 식각 공정을 수행하였다. 총 식각 시간을 EPD 시간(Ending Point detector, EPD)를 기준으로 하여 50%를 주어 실시하였다. 시편을 넣고 분사를 시작하여 식각이 다 되면 꺼내어 탈이온수로 세정한 후, 열풍 건조장치를 이용하여 건조하고, 포토레지스트 박리기(stripper)를 이용하여 포토레지스트를 제거하였다. 세정 및 건조 후 전자주사현미경(SEM)(S-4700, HITACHI사)을 이용하여 측면 식각 손실(critical dimension, CD), 테이퍼 각도, 금속막 손상 등과 같은 식각 특성을 평가하였다.The etchant composition prepared in a spray-type etching system (ETCHER (TFT), manufactured by SEMES) was placed, and the temperature was set at 30 캜 and then heated. Thereafter, the etching process was performed after the temperature reached 30 占 0.1 占 폚. The total etching time was performed at 50% based on the EPD time (Ending Point detector, EPD). When the etching was completed, the specimen was injected. After the etching was completed, the substrate was washed with deionized water, dried using a hot air drier, and photoresist was removed using a photoresist stripper. After washing and drying, the electron scanning microscope (SEM) (S-4700, HITACHI Co., Ltd.) was used to evaluate the etching characteristics such as critical dimension (CD), taper angle, and metal film damage.
<평가 기준><Evaluation Criteria>
○: 우수(CD Skew ≤ 1㎛, 테이퍼 각도: 40-60°) ○: Excellent (CD Skew ≤ 1 μm, taper angle: 40-60 °)
△: 양호(1㎛ < CD Skew ≤ 2㎛, 테이퍼각: 30-70°)(Triangle | delta): Good (1 micrometer <CD Skew <2 micrometers, taper angle: 30-70 degrees)
×: 불량(금속막 소실 및 잔사 발생, 테이퍼각 : 80°이상)X: defective (metal film disappeared and residues generated, taper angle: 80 ° or more)
2. 저장 안정성(보관 특성) 평가2. Evaluation of Storage Stability (Storage Characteristics)
제조된 식각액 조성물로 레퍼런스 식각(reference etch) 테스트를 진행하고 남은 식각액 조성물을 25℃에서 계획된 날짜(5일 기준) 동안 보관하였다. 그 후, 보관된 식각액 조성물을 이용하여 위 테스트에서와 동일한 조건으로 다시 식각을 진행하여 레퍼런스 식각 테스트에서의 결과와 비교하고 저장 안정성을 평가하였다.A reference etch test was conducted with the prepared etchant composition, and the remaining etchant composition was stored at 25 ° C. for a planned date (based on 5 days). Thereafter, using the stored etchant composition was etched again under the same conditions as in the above test to compare with the results in the reference etching test and to evaluate the storage stability.
<평가 기준><Evaluation Criteria>
○: 우수(3일 경과 후 식각 프로파일 우수)○: Excellent (excellent etching profile after 3 days)
×: 불량(3일 경과 후 식각 프로파일 양호 이하 수준)X: Defective (less than or equal to etching profile after 3 days)
3. 처리매수 평가3. Valuation of treatment quantity
제조된 식각액 조성물을 이용하여 레퍼런스 식각(reference etch) 테스트를 진행하고 레퍼런스 테스트 식각액에 구리 분말을 4,000ppm 첨가하여 완전히 용해시켰다. 그 후, 다시 식각을 진행하여 레퍼런스 식각 테스트와 비교하여 측면 식각의 변화량이 10% 초과하여 차이가 발생할 경우 불량으로 평가하였다.A reference etch test was performed using the prepared etchant composition, and 4,000 ppm of copper powder was added to the reference test etchant to completely dissolve it. Subsequently, etching was performed again, and when the difference occurred because the variation of the side etching exceeded 10% compared to the reference etching test, the difference was evaluated as bad.
<평가 기준><Evaluation Criteria>
○: 우수 (측면 식각 변화량 10% 이하)○: excellent (10% or less of side etching variation)
×: 불량 (측면 식각 변화량 10% 초과)
×: defective (side etching amount more than 10%)
위 표 2와 같이, 본 발명에 따른 실시예 1 내지 2의 식각액 조성물은 구리막/티타늄막으로 구성된 이중 금속막의 일괄 식각 시 우수한 식각 프로파일을 얻을 수 있고, 유리 기판 및 실리콘층의 손상이 없고 금속막의 소실과 잔사가 없는 우수한 식각 특성을 나타내었다. 또한, 저장 안정성과 처리매수 특성도 우수한 것을 확인할 수 있었다.As shown in Table 2, the etching liquid composition of Examples 1 to 2 according to the present invention can obtain an excellent etching profile during batch etching of a double metal film composed of a copper film / titanium film, without damaging the glass substrate and the silicon layer and Excellent etching characteristics without loss of film and residue were shown. In addition, it was confirmed that the storage stability and treatment number characteristics were also excellent.
반면, 염소 화합물을 포함하지 않는 비교예 1은 식각 특성과 저장 안정성은 어느 정도 확보할 수 있었으나 처리매수가 불량이었고, 유기산/염과 p-톨루엔술폰산을 포함하지 않는 비교예 2는 저장 안정성과 처리매수 특성이 불량이었으며, 무기산을 포함하지 않는 비교예 3과 4는 식각 속도가 매우 느려져 식각 불량 및 잔사가 발생하고 이에 따라 처리매수 특성도 좋지 못하였다. 또한, p-톨루엔술폰산을 포함하지 않는 비교예 5는 저장 안정성과 처리매수 특성이 좋지 않았고, 염소 화합물을 과량 포함하는 비교예 6은 저장 안정성이 불량하고 식각 테이퍼 각도가 매우 커 식각 특성이 불량하였다.On the other hand, Comparative Example 1 containing no chlorine compound was able to secure some etching characteristics and storage stability, but the number of treatment was poor, Comparative Example 2 containing no organic acid / salt and p-toluenesulfonic acid storage stability and treatment The number of sheets was poor, and Comparative Examples 3 and 4, which did not contain an inorganic acid, had very low etching rates, resulting in poor etching and residues, and thus, poor number of sheets. In addition, Comparative Example 5, which does not contain p-toluenesulfonic acid, had poor storage stability and treatment number characteristics, and Comparative Example 6, which contained excessive amounts of chlorine compounds, had poor storage stability and very high etching taper angle, resulting in poor etching characteristics. .
Claims (12)
불소 화합물 0.01 내지 2중량%;
염소 화합물 0.001 내지 3중량%;
무기산, 이의 염 또는 이들의 혼합물 1 내지 10중량%;
고리형 아민 화합물 0.3 내지 5중량%;
유기산, 이의 염 또는 이들의 혼합물 1 내지 10중량%;
p-톨루엔술폰산 0.1 내지 5중량%; 및
잔량의 물을 포함하는 구리막/티타늄막의 식각액 조성물.
5-20 wt% persulfate;
0.01 to 2% by weight of a fluorine compound;
0.001 to 3 weight percent of a chlorine compound;
1 to 10% by weight of inorganic acid, salts thereof or mixtures thereof;
0.3 to 5% by weight of the cyclic amine compound;
1 to 10% by weight of organic acid, salt thereof or mixture thereof;
0.1 to 5% by weight of p-toluenesulfonic acid; And
Etching liquid composition of the copper film / titanium film containing a residual amount of water.
The etchant composition of claim 1, wherein the persulfate is at least one member selected from the group consisting of ammonium persulfate, sodium persulfate and potassium persulfate.
The fluorine compound of claim 1, wherein the fluorine compound is hydrofluoric acid, ammonium fluoride, ammonium bifluoride, ammonium fluoride, potassium fluoride, potassium bifluoride, potassium borofluoride, sodium fluoride, sodium bifluoride, aluminum fluoride, boric fluoride, lithium fluoride and fluoride An etching liquid composition of at least one copper film / titanium film selected from the group consisting of calcium.
The etchant composition of claim 1, wherein the chlorine compound is at least one selected from the group consisting of hydrochloric acid, sodium chloride, potassium chloride, and ammonium chloride.
The etchant composition of claim 1, wherein the inorganic acid is at least one selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, or perchloric acid.
The compound according to claim 1, wherein the cyclic amine compound is 5-aminotetrazole, tolytriazole, benzotriazole, methylbenzotriazole, imidazole compound, indole compound, purine compound, pyrazole compound, pyridine compound And pyrimidine compounds, pyrrole compounds, pyrrolidin compounds, and pyroline compounds. An etching liquid composition of at least one copper film / titanium film selected from the group consisting of compounds.
The method of claim 1, wherein the organic acid is acetic acid, imino diacetic acid, ethylenediamine tetraacetic acid, butanoic acid, citric acid, isocitric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, pentanic acid, sulfobenzoic acid, succinic acid, sulfostone An etching liquid composition of a copper film / titanium film which is at least one selected from the group consisting of citric acid, salicylic acid, sulfosalicylic acid, benzoic acid, lactic acid, glyceric acid, malic acid, tartaric acid and propene acid.
The etchant composition of claim 1, wherein the salt of the organic acid is a potassium salt, a sodium salt, or an ammonium salt.
The etchant of claim 1, wherein the copper film is a copper single film or a copper alloy film containing at least one selected from the group consisting of copper, aluminum, magnesium, manganese, beryllium, hafnium, niobium, tungsten, and vanadium. Composition.
The etchant composition of claim 1, wherein the titanium film is a titanium single film.
The etchant composition according to claim 1, wherein the copper film / titanium film is a multilayer film in which a copper film and a titanium film are alternately stacked one or more times.
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