KR102468320B1 - Etching composition for metal layer - Google Patents
Etching composition for metal layer Download PDFInfo
- Publication number
- KR102468320B1 KR102468320B1 KR1020150110168A KR20150110168A KR102468320B1 KR 102468320 B1 KR102468320 B1 KR 102468320B1 KR 1020150110168 A KR1020150110168 A KR 1020150110168A KR 20150110168 A KR20150110168 A KR 20150110168A KR 102468320 B1 KR102468320 B1 KR 102468320B1
- Authority
- KR
- South Korea
- Prior art keywords
- weight
- metal film
- acid
- etchant composition
- sulfate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 59
- 239000002184 metal Substances 0.000 title claims abstract description 59
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 238000005530 etching Methods 0.000 title claims description 64
- -1 thiophene compound Chemical class 0.000 claims abstract description 22
- QMHIMXFNBOYPND-UHFFFAOYSA-N 4-methylthiazole Chemical compound CC1=CSC=N1 QMHIMXFNBOYPND-UHFFFAOYSA-N 0.000 claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 13
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 11
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 11
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 10
- 229930192474 thiophene Natural products 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 33
- 239000010949 copper Substances 0.000 claims description 33
- 229910052802 copper Inorganic materials 0.000 claims description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 235000002639 sodium chloride Nutrition 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 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
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 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
- 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 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- JXRVKYBCWUJJBP-UHFFFAOYSA-L calcium;hydrogen sulfate Chemical compound [Ca+2].OS([O-])(=O)=O.OS([O-])(=O)=O JXRVKYBCWUJJBP-UHFFFAOYSA-L 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 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
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- AVRWEULSKHQETA-UHFFFAOYSA-N Thiophene-2 Chemical compound S1C=2CCCCCC=2C(C(=O)OC)=C1NC(=O)C1=C(F)C(F)=C(F)C(F)=C1F AVRWEULSKHQETA-UHFFFAOYSA-N 0.000 claims description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 235000011132 calcium sulphate Nutrition 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 2
- 239000003352 sequestering agent Substances 0.000 claims description 2
- 230000021148 sequestering of metal ion Effects 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 claims description 2
- GBNRIMMKLMTDLW-UHFFFAOYSA-N thiolan-3-amine Chemical compound NC1CCSC1 GBNRIMMKLMTDLW-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 229910052755 nonmetal Inorganic materials 0.000 abstract description 13
- 150000007522 mineralic acids Chemical class 0.000 abstract description 11
- 150000007524 organic acids Chemical class 0.000 abstract description 9
- 239000010408 film Substances 0.000 description 51
- 230000000052 comparative effect Effects 0.000 description 35
- 238000001514 detection method Methods 0.000 description 20
- 238000001556 precipitation Methods 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 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 description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004140 cleaning Methods 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
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 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 description 2
- ZMPRRFPMMJQXPP-UHFFFAOYSA-N 2-sulfobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1S(O)(=O)=O ZMPRRFPMMJQXPP-UHFFFAOYSA-N 0.000 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 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 description 2
- 239000005711 Benzoic acid Substances 0.000 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 description 2
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 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 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 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 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000000174 gluconic acid Substances 0.000 description 2
- 235000012208 gluconic acid Nutrition 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- ODBLHEXUDAPZAU-UHFFFAOYSA-N isocitric acid Chemical compound OC(=O)C(O)C(C(O)=O)CC(O)=O ODBLHEXUDAPZAU-UHFFFAOYSA-N 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000003577 thiophenes Chemical class 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- VPSXHKGJZJCWLV-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(1-ethylpiperidin-4-yl)oxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OC1CCN(CC1)CC VPSXHKGJZJCWLV-UHFFFAOYSA-N 0.000 description 1
- KNDAEDDIIQYRHY-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(piperazin-1-ylmethyl)pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CN1CCNCC1 KNDAEDDIIQYRHY-UHFFFAOYSA-N 0.000 description 1
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- YMZZPMVKABUEBL-UHFFFAOYSA-N 2-methylthiolan-3-one Chemical compound CC1SCCC1=O YMZZPMVKABUEBL-UHFFFAOYSA-N 0.000 description 1
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 1
- IEZCKZKVXLOVPU-UHFFFAOYSA-N 4-methyl-1,3-thiazole Chemical compound CC=1N=CSC1.CC=1N=CSC1 IEZCKZKVXLOVPU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
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Abstract
본 발명은 (a) 과황산염, (b) 불소 화합물, (c) 무기산, (d) 4-메틸싸이아졸, (e) 염소 화합물, (f) 비금속 황산염, (g) 싸이오펜화합물, (h) 유기산 또는 그의 염, 및 (i) 물을 포함하는, 금속막 식각액 조성물을 제공한다.(a) a persulfate, (b) a fluorine compound, (c) an inorganic acid, (d) 4-methylthiazole, (e) a chlorine compound, (f) a non-metal sulfate, (g) a thiophene compound, (h) ) It provides a metal film etchant composition comprising an organic acid or a salt thereof, and (i) water.
Description
본 발명은, 금속막 식각액 조성물에 관한 것이다.The present invention relates to a metal film etchant composition.
일반적으로 박막 트랜지스터 표시판(Thin Firm Transistor, TFT)은 액정 표시 장치나 유기 EL(Electro Luminescence) 표시 장치 등에서 각 화소를 독립적으로 구동하기 위한 회로 기판으로써 사용된다. 박막 트랜지스터 표시판은 주사 신호를 전달하는 주사 신호 배선 또는 게이트 배선과, 화상 신호를 전달하는 화상 신호선 또는 데이터 배선이 형성되어 있고, 게이트 배선 및 데이터 배선과 연결되어 있는 박막 트랜지스터, 박막 트랜지스터와 연결되어 있는 화소 전극 등으로 이루어져 있다.In general, a thin film transistor display (TFT) is used as a circuit board for independently driving each pixel in a liquid crystal display or an organic electroluminescence (EL) display. The thin film transistor array panel includes a scan signal line or gate line that transmits a scan signal, an image signal line or data line that transmits an image signal, a thin film transistor connected to the gate line and the data line, and a thin film transistor connected to the thin film transistor. It consists of a pixel electrode and the like.
이러한 박막 트랜지스터 표시판의 제조 시에 기판 위에 게이트 배선 및 데이터 배선용 금속층을 적층시키고, 이들 금속층을 식각하는 과정이 그 뒤를 따르게 된다.In manufacturing such a thin film transistor array panel, a process of stacking metal layers for gate wiring and data wiring on a substrate, followed by etching these metal layers.
게이트 배선 및 데이터 배선은 전기 전도도가 좋고, 저항이 낮은 구리를 사용하는데, 구리의 경우, 포토레지스트를 도포하고, 패터닝하는 공정 상 어려운 점이 있으므로, 게이트 배선 및 데이터 배선은 구리 단일막을 적용하지 않고, 다중 금속막을 적용한다.Gate wiring and data wiring use copper with good electrical conductivity and low resistance. In the case of copper, there are difficulties in the process of applying and patterning photoresist, so the gate wiring and data wiring do not apply a copper single film, Apply multiple metal films.
다중 금속막 중에서 일반적으로 널리 사용되는 것이 티타늄/구리의 이중막이다. 이러한 티타늄/구리의 이중막을 동시에 식각하는 경우, 식각액에 석출물 발생하여 TFT 구동 수율이 저하되며, 장비내 석출 문제에 따른 주기적인 청소에 대한 공정상 비용 발생하는 문제가 있다. Among the multi-metal films, a titanium/copper double film is generally widely used. When such a titanium/copper double layer is simultaneously etched, there is a problem in that precipitates are generated in the etchant, which lowers the TFT drive yield, and incurs process costs for periodic cleaning due to the precipitation problem in the equipment.
이와 관련하여, 대한민국 공개특허 제 2010-0123131 호에는 구리계, 몰리브덴계 금속막에 대한 식각액 조성물이 개시되어 있으나, 처리매수가 진행될수록 식각 특성(Etch Profile)이 불량하며, 식각 속도(Etch Rate) 성능 저하를 줄이기 위해 무기산 도입에 따른 과침식의 문제가 있다. In this regard, Korean Patent Publication No. 2010-0123131 discloses an etchant composition for a copper-based, molybdenum-based metal film, but the etching characteristics (Etch Profile) are poor as the number of treated sheets progresses, and the etching rate (Etch Rate) In order to reduce performance degradation, there is a problem of over-erosion due to the introduction of inorganic acid.
따라서, 식각액의 보존안정성을 늘리면서 식각 초기 단계에서 식각 특성(Etch Profile)을 유지하게 할 뿐 아니라, 금속막의 처리매수가 늘어나더라도 배선부의 식각 특성 (Etch profile)이 우수하면서, 식각액에 석출물 발생이 되지 않는 금속막 식각액 조성물의 개발이 필요하다.Therefore, while increasing the storage stability of the etchant, the etching characteristics (Etch Profile) are maintained at the initial stage of etching, and the etching characteristics (Etch profile) of the wiring part is excellent even when the number of metal films processed increases, and precipitates are not generated in the etchant. It is necessary to develop a metal film etchant composition that does not
본 발명은 식각액의 보존안정성을 늘리면서 식각 초기 단계에서 식각 특성(Etch Profile)을 유지하게 할 뿐 아니라, 금속막의 처리매수가 늘어나더라도 배선부의 식각 특성 (Etch profile)이 우수하면서, 식각액에 석출물 발생이 되지 않는 금속막 식각액 조성물을 제공하는 것을 목적으로 한다.The present invention not only maintains the etching characteristics (Etch Profile) at the initial stage of etching while increasing the storage stability of the etching solution, but also maintains the etching characteristics (Etch profile) of the wiring part even when the number of processed metal films increases, and prevents the formation of precipitates in the etching solution. It is an object to provide a metal film etchant composition that does not become.
본 발명은, (a) 과황산염, (b) 불소 화합물, (c) 무기산, (d) 4-메틸싸이아졸, (e) 염소 화합물, (f) 비금속 황산염, (g) 싸이오펜화합물, (h) 유기산 또는 그의 염, 및 (i) 물을 포함하는, 금속막 식각액 조성물을 제공한다.(a) a persulfate, (b) a fluorine compound, (c) an inorganic acid, (d) 4-methylthiazole, (e) a chlorine compound, (f) a non-metal sulfate, (g) a thiophene compound, ( h) an organic acid or salt thereof, and (i) providing a metal film etchant composition comprising water.
본 발명의 금속막 식각액 조성물은, 식각액에 석출물 발생을 방지하여 TFT 구동 수율을 향상시킬 뿐 아니라 장비내 석출 문제에 따른 주기적인 청소에 대한 공정상 비용을 절감시키는 효과를 갖는다. 또한, 식각액의 보존안정성을 늘리면서 식각 초기 단계에서 식각 특성(Etch Profile)을 유지하게 할 뿐 아니라, 금속막의 처리매수가 늘어나더라도 배선부의 식각 특성 (Etch profile) 중 직진성이 우수하다.The metal film etchant composition of the present invention has an effect of preventing the formation of precipitates in the etchant to improve the TFT driving yield and reducing process costs for periodic cleaning due to precipitation problems in the equipment. In addition, while increasing the storage stability of the etchant, the etching characteristics (Etch Profile) are maintained in the initial stage of etching, and even if the number of processed metal films increases, the straightness of the etching characteristics (Etch profile) of the wiring part is excellent.
도 1은 고리형 아민화합물의 유무에 따른 석출여부를 확인하기 위하여, 비교예 2와 실시예 1의 금속막 식각액 조성물을 대상으로 석출여부를 평가한 결과이다.
도 2는 비교예 10 및 12와 실시예 1의 금속막 식각액 조성물을 대상으로, 비금속 황산염 첨가에 따른 처리매수에 따른 식각특성 (Profile)을 확인한 결과이다.1 is a result of evaluating the precipitation of the metal film etchant compositions of Comparative Example 2 and Example 1 in order to confirm precipitation according to the presence or absence of a cyclic amine compound.
2 is a result of confirming the etching characteristics (Profile) according to the number of treated sheets according to the addition of non-metal sulfate, for the metal film etchant compositions of Comparative Examples 10 and 12 and Example 1.
본 발명은, (a) 과황산염, (b) 불소 화합물, (c) 무기산, (d) 4-메틸싸이아졸, (e) 염소 화합물, (f) 비금속 황산염, (g) 싸이오펜화합물, (h) 유기산 또는 그의 염, 및 (i) 물을 포함하는, 금속막 식각액 조성물에 대한 것이다. (a) a persulfate, (b) a fluorine compound, (c) an inorganic acid, (d) 4-methylthiazole, (e) a chlorine compound, (f) a non-metal sulfate, (g) a thiophene compound, ( h) an organic acid or a salt thereof, and (i) to a metal film etchant composition comprising water.
본 발명의 금속막 식각액 조성물은, 종래 식각액 조성물에 사용되던 고리형 아민화합물을 대체하여 4-메틸싸이아졸을 사용함으로, 식각액에 석출물 발생을 방지하여 TFT 구동 수율을 향상시킬 뿐 아니라 장비내 석출 문제에 따른 주기적인 청소에 대한 공정상 비용을 절감시키는 효과를 갖는다. 또한, 종래 식각액 조성물에 사용되던 구리염을 대체하여 싸이오펜화합물을 사용함으로, 식각액의 보존안정성을 늘리면서 식각 초기 단계에서 식각 특성(Etch Profile)을 유지하게 할 뿐 아니라, 비금속 황산염을 사용하여, 금속막의 처리매수가 늘어나더라도 배선부의 식각 특성 (Etch profile) 중 직진성이 우수하다.The metal film etchant composition of the present invention uses 4-methylthiazole instead of the cyclic amine compound used in the conventional etchant composition, thereby preventing the formation of precipitates in the etchant to improve the TFT drive yield and the precipitation problem in the equipment It has the effect of reducing the process cost for periodic cleaning according to. In addition, by using a thiophene compound in place of the copper salt used in the conventional etchant composition, the preservation stability of the etchant is increased and the etching characteristics (Etch Profile) are maintained at the initial stage of etching. Even if the number of layers processed increases, straightness is excellent among the etching characteristics (Etch profile) of the wiring part.
이하, 본 발명의 내용을 각 구성별로 상세히 설명한다. Hereinafter, the content of the present invention will be described in detail for each component.
(a) 과황산염(a) Persulfate
본 발명의 과황산염은 구리 또는 구리를 포함하는 금속막을 식각하는 주성분이다. The persulfate of the present invention is a main component for etching copper or a metal film containing copper.
본 발명의 과황산염은 과황산칼륨(K2S2O8), 과황산나트륨(Na2S2O8), 과황산암모늄((NH4)2S2O8) 중에서 적어도 하나의 물질이 사용될 수 있다.For the persulfate of the present invention, at least one 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 ) is used. can
본 발명의 과황산염은 식각액의 총 함량에 대하여 0.5 내지 20 중량%로 포함되는 것이 바람직하다. 과황산염의 함량이 0.5 중량% 미만이면 구리 또는 구리를 포함하는 금속막의 식각이 안되거나 식각속도가 아주 느리고, 20 중량%를 초과할 경우에는 식각 속도가 전체적으로 빨라지기 때문에 공정을 컨트롤하는 것이 어려워진다.The persulfate of the present invention is preferably included in an amount of 0.5 to 20% by weight based on the total amount of the etchant. If the content of persulfate is less than 0.5% by weight, copper or metal film containing copper cannot be etched or the etching rate is very slow, and if it exceeds 20% by weight, it becomes difficult to control the process because the etching rate increases overall. .
(b) 불소 화합물(b) fluorine compounds
본 발명의 불소화합물은 티타늄 또는 티타늄을 포함하는 금속막을 식각하는 주성분으로서, 식각시 발생할 수 있는 잔사를 제거하여 주는 역할을 한다.The fluorine compound of the present invention is a main component for etching titanium or a metal film containing titanium, and serves to remove residues that may occur during etching.
본 발명의 불소화합물은 불화암모늄, 불화나트륨, 불화칼륨, 중불화암모늄, 중불화나트륨 및 중불화칼륨 중에서 적어도 하나의 물질이 사용될 수 있다.At least one of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride and potassium bifluoride may be used as the fluorine compound of the present invention.
본 발명의 불소화합물은 식각액의 총 함량에 대하여 0.01 내지 2 중량%로 포함되는 것이 바람직하다. 불소화합물이 0.01 중량% 미만이면 티타늄 또는 티타늄을 포함하는 티타늄계 금속막의 식각속도가 저하되어 잔사가 발생할 수 있으며, 2 중량%를 초과하면 금속배선이 형성되는 유리 등의 기판 및 금속 배선과 함께 형성되는 실리콘을 포함하는 절연막에 손상을 일으킬 수 있다. 또한, 구리 식각시간을 미세하게 늦추게 되어, 공정상의 문제를 야기시킨다.The fluorine compound of the present invention is preferably included in an amount of 0.01 to 2% by weight based on the total content of the etching solution. If the fluorine compound is less than 0.01% by weight, the etching rate of titanium or a titanium-based metal film containing titanium may decrease, resulting in residues. If it exceeds 2% by weight, it is formed together with a substrate such as glass and metal wiring on which metal wiring is formed may cause damage to the insulating film containing silicon. In addition, the copper etching time is finely delayed, causing process problems.
(c) 무기산(c) inorganic acids;
본 발명의 무기산은 구리 또는 구리를 포함하는 금속막을 식각하는 보조 산화제로써 식각속도 및 테이퍼의 각도를 조절하는 역할을 한다. 또한 식각액의 용해도를 증가시켜 구리기판의 처리매수를 증가 시킨다. The inorganic acid of the present invention is an auxiliary oxidizing agent for etching copper or a metal film containing copper, and serves to control the etching rate and the taper angle. In addition, the solubility of the etchant is increased to increase the number of copper substrates processed.
본 발명의 무기산은 질산, 황산, 인산 및 과염소산 중에서 선택되는 적어도 하나일 수 있다. The inorganic acid of the present invention may be at least one selected from nitric acid, sulfuric acid, phosphoric acid and perchloric acid.
본 발명의 무기산은 식각액의 총 함량에 대하여 1 내지 10 중량%로 포함되는 것이 바람직하다. 상기 무기산의 함량이 1 중량% 미만이면 구리 또는 구리를 포함하는 구리계 금속막 및 티타늄 또는 티타늄을 포함하는 티타늄계 금속막의 식각속도가 저하되어 식각 프로파일 불량 및 잔사가 발생할 수 있으며, 10 중량%를 초과하면 과식각 및 포토레지스트 균열이 발생하여 약액 침투에 의하여 배선이 단락될 수 있다.The inorganic acid of the present invention is preferably included in an amount of 1 to 10% by weight based on the total content of the etching solution. If the content of the inorganic acid is less than 1% by weight, the etching rate of copper or a copper-based metal film containing copper and titanium or a titanium-based metal film containing titanium may decrease, resulting in poor etching profiles and residues. If it is exceeded, over-etching and cracking of the photoresist may occur, and the wiring may be short-circuited by chemical penetration.
(d) 4-메틸싸이아졸(d) 4-methylthiazole
본 발명의 4-메틸 싸이아졸(4-Methylthiazole)은 환경규제물질일 시안화물(Cyanide)을 포함하고, 석출물 발생 문제가 있던 기존 고리형 아민 화합물을 대체하여 사용되며, 구리 또는 구리를 포함하는 금속막의 균일 식각 및 식각 속도를 조절하는 역할을 한다. 4-Methylthiazole of the present invention contains cyanide, which is an environmental regulatory substance, and is used in place of existing cyclic amine compounds that have a precipitate generation problem, and is used to replace copper or metal containing copper. It serves to uniformly etch the film and control the etch rate.
본 발명의 4-메틸싸이아졸 4-메틸 싸이아졸은 0.1 내지 5 중량%로 포함되는 것이 바람직하다. 0.1 중량% 미만이면 식각(Etch)이 되지 않으며, 5 중량%를 초과하여도 식각(Etch)이 되지 않는다.4-methylthiazole 4-methylthiazole of the present invention is preferably included in an amount of 0.1 to 5% by weight. If it is less than 0.1% by weight, it is not etched, and even if it exceeds 5% by weight, it is not etched.
(e) 염소 화합물(e) chlorine compounds
본 발명의 염소화합물은 구리 또는 구리를 포함하는 금속막을 식각하는 식각조절제, 테이퍼의 각도를 조절, 및 수율을 떨어뜨리는 Open현상이 일어나지 않게 하는 역할을 한다. The chlorine compound of the present invention serves as an etching control agent for etching copper or a metal film containing copper, adjusting the angle of the taper, and preventing an open phenomenon that reduces yield.
본 발명의 염소화합물은 염산, 염화나트륨, 염화칼륨 및 염화암모늄 중에서 선택되는 적어도 하나일 수 있다. The chlorine compound of the present invention may be at least one selected from hydrochloric acid, sodium chloride, potassium chloride and ammonium chloride.
본 발명의 염소화합물은 식각액의 총 함량에 대하여 0.1 내지 5 중량%로 포함되는 것이 바람직하다. 상기 염소 화합물의 함량이 0.1 중량% 미만이면 구리 또는 구리를 포함하는 구리계 금속막의 식각 속도가 저하되어 식각 프로파일이 불량하게 되며, 5 중량%를 초과하면 과식각이 발생하여 금속 배선이 소실될 수 있다.The chlorine compound of the present invention is preferably included in an amount of 0.1 to 5% by weight based on the total content of the etching solution. If the content of the chlorine compound is less than 0.1% by weight, the etching rate of copper or a copper-based metal film containing copper decreases, resulting in a poor etching profile, and if it exceeds 5% by weight, over-etching may occur and metal wiring may be lost. have.
(f) 비금속 황산염(f) non-metal sulfates;
본 발명의 비금속 황산염은 금속막의 처리매수가 진행될수록 식각액이 갖는 단점인 좋지 않은 Etch profile 직진성의 개선 효과를 갖는다. The non-metal sulfate of the present invention has an effect of improving the straightness of the etch profile, which is a disadvantage of etching solutions, as the number of metal films treated increases.
본 발명의 비금속 황산염은 황산암모늄 (ammonium sulfate), 황산나트륨 (sodium sulfate), 황산칼륨 (potassium sulfate), 황산칼슘 (calcium sulfate), 황산수소암모늄 (ammonium bisulfate), 황산수소나트륨 (sodium bisulfate), 중황산칼륨 (potassium bisulfate) 및 황산수소칼슘 (calcium bisulfate) 중에서 선택되는 적어도 하나 이상의 화합물을 포함할 수 있다.The non-metallic sulfates of the present invention include ammonium sulfate, sodium sulfate, potassium sulfate, calcium sulfate, ammonium bisulfate, sodium bisulfate, bisulfite It may include at least one compound selected from potassium bisulfate and calcium bisulfate.
본 발명의 비금속 황산염은 조성함량은, 0.5 내지 10 중량%로 포함되는 것이 바람직하다. 0.5 중량% 미만이면 Etch profile 직진성 개선 효과를 갖지 못하며, 10 중량%을 초과하게 될 경우는 과식각이 일어날 수 있다.The compositional content of the non-metal sulfate of the present invention is preferably 0.5 to 10% by weight. If it is less than 0.5% by weight, it does not have an effect of improving the straightness of the etch profile, and if it exceeds 10% by weight, over-etching may occur.
(g) 싸이오펜화합물(g) thiophene compounds
본 발명의 싸이오펜화합물은 구리 또는 구리를 포함하는 금속막을 식각하는 경우, 초기 식각의 불량이 발생하게 되는데, 이 현상을 막아주는 역할을 한다. 또한 기존의 구리염이 들어가는 경우는, 보관안정성이 떨어지는데 이를 보완하기 위해 싸이오펜화합물을 사용된다.When copper or a metal film containing copper is etched, the thiophene compound of the present invention causes initial etching defects, and serves to prevent this phenomenon. In addition, when the existing copper salt is used, the storage stability is poor, and a thiophene compound is used to compensate for this.
본 발명의 싸이오펜화합물은 술포란 (sulfolane), 테트라하이드로-3-싸이오펜아민 (tetrahydro-3-thiophenamine), 테트라하이드로 싸이오펜 1-옥사이드 (tetrahydro thiophene 1-oxide) 및 2-메틸테트라히드로 싸이오펜-3-온 (2-methyltetrahydro thiophen-3-one) 중에서 선택되는 적어도 하나 이상의 화합물을 포함할 수 있다.The thiophene compound of the present invention is sulfolane, tetrahydro-3-thiophenamine, tetrahydro thiophene 1-oxide and 2-methyltetrahydro It may include at least one compound selected from phen-3-one (2-methyltetrahydro thiophen-3-one).
본 발명의 싸이오펜화합물의 함유량이 0.01 내지 3 중량%인 것이 바람직하다. 함유량이 0.01 중량% 미만일 경우에는 초기 식각이 균일하지 않게 되며, 3 중량%를 초과할 경우에는 식각 성능의 하락을 일으킨다. It is preferable that the content of the thiophene compound of the present invention is 0.01 to 3% by weight. When the content is less than 0.01% by weight, the initial etching is not uniform, and when it exceeds 3% by weight, the etching performance is deteriorated.
(h) 유기산 또는 그의 염(h) organic acids or salts thereof;
본 발명의 유기산 및 유기산염은 식각된 금속이온과의 킬레이팅 작용에 의해 식각액에 영향을 주는 것을 방지해 줌으로써 결과적으로 처리매수를 증가시켜주는 역할을 한다. The organic acid and organic acid salt of the present invention prevent the etchant from being affected by a chelating action with the etched metal ion, thereby increasing the number of treated sheets.
본 발명의 유기산은 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 중에서 선택되는 적어도 하나의 화합물을 포함하고,The organic acid of the present invention is 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, benzoic acid, lactic acid, glyceric acid , It contains at least one compound selected from succinic acid, malic acid, tartaric acid, isocitrate acid, propenoic acid, iminodiacetic acid and ethylenediaminetetraacetic acid,
상기 유기산염은 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 중에서 선택되는 화합물의 칼륨염, 나트륨염 및 암모늄염 중에서 선택되는 적어도 하나의 화합물을 포함하는 것 일 수 있다. The organic acid salt is 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, benzoic acid, lactic acid, glyceric acid, It may contain at least one compound selected from potassium salt, sodium salt and ammonium salt of a compound selected from succinic acid, malic acid, tartaric acid, isocitrate acid, propenoic acid, iminodiacetic acid and ethylenediaminetetraacetic acid.
상기 유기산 또는 유기산염은 식각액 조성물 총 중량에 대하여 1 내지 20 중량%로 포함된다. 상기 유기산 또는 유기산염의 함량이 1 중량% 미만이면 처리매수 증가 효과가 없고, 20 중량%를 초과하면 과식각이 되어 배선의 단락이 발생할 수 있다.The organic acid or organic acid salt is included in 1 to 20% by weight based on the total weight of the etchant composition. If the content of the organic acid or organic acid salt is less than 1% by weight, there is no effect of increasing the number of treated cells, and if it exceeds 20% by weight, over-etching may occur, resulting in a short circuit of the wiring.
(i) 물(i) water
본 발명의 물은 탈이온수일 수 있으며, 반도체 공정용을 사용하며, 바람직하게는 18㏁/㎝이상의 물을 사용한다. The water of the present invention may be deionized water, used for semiconductor processing, and preferably water of 18 MΩ/cm or more.
본 발명의 식각액의 총 함량에 대하여 물은 금속막 식각액 조성물 총 중량이 100 중량%가 되도록 잔량 포함된다.With respect to the total content of the etchant of the present invention, water is included in the remaining amount so that the total weight of the metal film etchant composition is 100% by weight.
본 발명의 금속막 식각액 조성물은 공지의 식각조절제, 계면활성제, 금속 이온 봉쇄제, 부식방지제 및 pH 조절제로 이루어진 군으로부터 선택되는 1종 또는 2종 이상을 더 포함할 수 있다. The metal film etchant composition of the present invention may further include one or two or more selected from the group consisting of known etching control agents, surfactants, metal ion sequestering agents, corrosion inhibitors, and pH adjusting agents.
본 발명의 금속막은 티타늄 또는 티타늄 합금 및 구리 또는 구리 합금 중 하나 이상을 포함하는 단일막, 또는 이중막 이상의 다중막 일 수 있다. 바람직하게는 티타늄 또는 티타늄 합금 및 구리 또는 구리 합금의 이중막 일 수 있다. The metal film of the present invention may be a single film including at least one of titanium or a titanium alloy and copper or a copper alloy, or a multi-layer of a double film or more. It may preferably be a double layer of titanium or titanium alloy and copper or copper alloy.
이하에서, 본 발명을 실시예에 기초하여 더욱 상세하게 설명한다. 그러나, 하기에 개시되는 본 발명의 실시 형태는 본 발명의 예시하기 위한 것으로서, 본 발명의 범위는 이들의 실시 형태에 한정되지 않는다. 본 발명의 범위는 특허청구범위에 표시되었고, 더욱이 특허청구범위 기록과 균등한 의미 및 범위 내에서의 모든 변경을 포함한다. Hereinafter, the present invention will be described in more detail based on examples. However, the embodiments of the present invention disclosed below are intended to illustrate the present invention, and the scope of the present invention is not limited to these embodiments. The scope of the present invention has been indicated in the claims, and further includes all changes within the meaning and range equivalent to the written claims.
이하의 실시예, 비교예에서 함유량을 나타내는 "%" 및 "부"는 특별히 언급하지 않는 한 중량 기준이다.In the following Examples and Comparative Examples, "%" and "parts" indicating content are based on weight unless otherwise specified.
실시예 및 비교예: 금속막 식각액 조성물의 제조 Examples and Comparative Examples: Preparation of metal film etchant composition
하기 표 1에 기재된 구성 및 함량대로, 실시예 및 비교예의 금속막 식각액 조성물을 제조하였다. According to the configuration and content shown in Table 1 below, metal film etchant compositions of Examples and Comparative Examples were prepared.
※SPS: 과황산나트륨(sodium persulfate)※SPS: sodium persulfate
※ABF: 불화암모늄 (ammonium bifluoride)※ABF: ammonium bifluoride
※ATZ: 5-아미노테트라졸 (5-aminotetrazole) ※ATZ: 5-aminotetrazole
※AcOH: 아세트산 (acetic acid) ※AcOH: acetic acid
※NaCl: 염화나트륨 (sodium chloride)※NaCl: sodium chloride
※CuSO4: Copper(II) Sulfate 5-hydrate※CuSO4: Copper(II) Sulfate 5-hydrate
※A.SO4: 황산암모늄 (ammonium sulfate)※A.SO4: ammonium sulfate
※A.NO3: Ammonium nitrate※A.NO3: Ammonium nitrate
실험예 1. 금속막 식각 특성 평가Experimental Example 1. Evaluation of metal film etching characteristics
실시예와 비교예의 금속막에 대한 식각 특성을 평가 하기 위하여, 다음과 같은 방법으로, 석출여부, 시안화물(Cyanide) 검출 여부, (Cu/Ti 이중막에 대한) 식각여부, 식각 초기 안정성 및 보관 안정성을 평가하여 그 결과를 표 2에 나타내었다. In order to evaluate the etching characteristics of the metal films of Examples and Comparative Examples, in the following ways, whether or not precipitation, cyanide detection, etching (for Cu / Ti double film), initial stability of etching and storage The stability was evaluated and the results are shown in Table 2.
석출여부Precipitation
실제 공정설비와 유사조건[Cu Powder 3000ppm과 식각액의 혼합 후 -8℃ 보관]시, 용기 벽면에 생기는 난용성 물질의 유무를 육안으로 확인하였다. Under conditions similar to the actual process equipment [after mixing Cu Powder 3000ppm and etchant and storing at -8 ° C], the presence or absence of poorly soluble substances generated on the container wall was visually confirmed.
시안화물(Cyanide) 검출 여부Whether cyanide is detected
환경유해물질인 시안화물의 검출여부를 확인하였다. It was confirmed whether cyanide, an environmentally harmful substance, was detected.
금속막 식각여부Metal film etching
식각액이 스프레이 형식으로 뿌려지는데, 이곳에 기판을 넣고 막질이 식각되는 시간의 두배를 식각시간으로 갖고, 금속막 식각여부를 전자주사현미경을 사용하여 확인하였다.The etchant is sprayed in the form of a spray, where the substrate is placed and the etching time is twice as long as the film is etched, and whether or not the metal film is etched is confirmed using a scanning electron microscope.
식각 초기 안정성 Etch Initial Stability
식각액이 스프레이 형식으로 뿌려지는데, 이곳에 기판을 넣고 막질이 식각되는 시간의 두배를 식각시간으로 갖고 결과를 전자주사현미경을 사용하여 확인하였다. 이때, 식각되는 정도를 비교하여, 성능미달 여부를 판단하였다.The etchant is sprayed in the form of a spray, where the substrate is placed and the etching time is twice the time the film is etched, and the results are confirmed using a scanning electron microscope. At this time, the degree of etching was compared to determine whether performance was insufficient.
보관 안정성storage stability
실제 공정설비와 유사조건[12℃ 보관]시, 식각액의 식각성능이 유지되는 시간을 측정하여 나타내었다. 구체적으로, 12℃ 냉장고에 식각액을 보관하다가, 1일 단위로 식각액 성능실험을 하였다. 식각되는 정도가 0일차 기준으로 식각되는 정도의 ±10%를 벗어나면 성능미달이 되는 날로 판단하였다.In the case of actual process equipment and similar conditions [12 ℃ storage], the time for maintaining the etching performance of the etching solution was measured and indicated. Specifically, while storing the etchant in a refrigerator at 12 ° C, the performance test of the etchant was performed on a daily basis. If the degree of etching deviated from ±10% of the degree of etching based on the 0th day, it was judged as a day with insufficient performance.
발생 유무precipitation
Occurrence or not
안정성keep
stability
석출발생Day 1
precipitation
석출발생Day 1
precipitation
불량Profile
error
Un-Etch : 비패턴부의 Cu가 Etch되지 않아 패턴이 형성되지 않음.Un-Etch: No pattern is formed because Cu in the non-patterned area is not etched.
실험예 2. 고리형 아민화합물 유무에 따른 석출여부 확인Experimental Example 2. Confirmation of precipitation according to the presence or absence of cyclic amine compounds
고리형 아민화합물의 유무에 따른 석출여부를 확인하기 위하여, 비교예 2와 실시예 1의 금속막 식각액 조성물을 대상으로 상기 실험예 1과 동일한 방법으로 석출여부를 평가하였다. 그 결과를 도 1에 나타내었다. In order to confirm precipitation according to the presence or absence of the cyclic amine compound, the metal film etchant compositions of Comparative Example 2 and Example 1 were evaluated for precipitation in the same manner as in Experimental Example 1. The results are shown in Figure 1.
도 1의 실험결과를 참고하면, 고리형 아민화합물(ATZ)이 포함된 종래 조성물인 비교예 2의 금속막 식각액 조성물의 경우, 1일차에 석출이 발생한 반면, 종래 고리형 아민화합물(ATZ) 대신 4-메틸싸이아졸이 포함된 실시예 1의 본 발명의 금속막 식각액 조성물은 40일 경과시까지 석출이 발생하지 않음을 확인하였다. Referring to the experimental results of FIG. 1, in the case of the metal film etchant composition of Comparative Example 2, which is a conventional composition containing a cyclic amine compound (ATZ), precipitation occurred on the first day, whereas instead of the conventional cyclic amine compound (ATZ) It was confirmed that the metal film etchant composition of Example 1 containing 4-methylthiazole did not precipitate until 40 days had elapsed.
실험예Experimental example 3. 비금속 황산염 첨가에 따른, 처리매수에 따른 3. According to the addition of non-metal sulfate, according to the number of sheets treated 식각특성Etch characteristics (Profile) 평가 (Profile) evaluation
비금속 황산염 첨가에 따른, 처리매수에 따른 식각특성 (Profile)을 확인하기 위하여, 비교예 10 및 12와 실시예 1의 금속막 식각액 조성물을 대상으로 티타늄/구리 금속막의 레퍼런스 식각(reference etch) 테스트를 진행하여 처리매수 평가를 하였다. 처리매수 불량 기준은 구리 분말을 일정량씩 첨가하였을 때의 씨디 스큐 값이 레퍼런스 식각 테스트 값, 즉 구리 분말이 첨가되지 않았을 때(Cu 0ppm)의 씨디 스큐값을 편측 기준으로 ±10% 값을 초과하면 불량이라고 판정하였고, 첨가된 구리 분말의 농도로 처리매수를 평가하여 도 2에 나타내었다. In order to confirm the etching characteristics (Profile) according to the number of treated sheets according to the addition of non-metal sulfate, a reference etch test of titanium / copper metal films was performed for the metal film etchant compositions of Comparative Examples 10 and 12 and Example 1 The number of treatments was evaluated by proceeding. The processing quantity defect criterion is when the CDS skew value when a certain amount of copper powder is added exceeds the reference etching test value, that is, the CDS skew value when copper powder is not added (Cu 0ppm) on a one-sided basis. It was judged to be defective, and the number of treated sheets was evaluated based on the concentration of the added copper powder, and is shown in FIG. 2 .
도 2의 실험결과를 참고하면, 비금속 황산염이 포함되지 않은 비교예 10 및 비금속 질산염(ammonium nitrate)이 포함된 비교예 12의 금속막 식각액 조성물의 경우, 처리매수가 진행됨에 따라 식각 특성(Etch Profile)에 큰 차이가 발생하였으나, 비금속 황산염이 포함된 실시예 1의 본 발명의 금속막 식각액 조성물은 처리매수가 진행되더라도 식각 특성(Etch Profile)이 초기 값과 비슷함을 확인할 수 있다.Referring to the experimental results of FIG. 2, in the case of the metal film etchant composition of Comparative Example 10 without non-metal sulfate and Comparative Example 12 containing non-metal nitrate (ammonium nitrate), the etching characteristics (Etch Profile) as the number of treatments progressed. ), but it can be confirmed that the metal film etchant composition of the present invention of Example 1 containing non-metal sulfate has an etching characteristic (Etch Profile) similar to the initial value even if the number of treated sheets is progressed.
Claims (11)
(a) 0.5중량% 내지 20중량%의 과황산염,
(b) 0.01중량% 내지 2중량%의 불소 화합물,
(c) 1 중량% 내지 10중량%의 질산,
(d) 0.1 중량% 내지 5 중량%의 4-메틸싸이아졸,
(e) 0.1 중량% 내지 5 중량%의 염소 화합물,
(f) 0.5 중량% 내지 10 중량%의 황산염,
(g) 0.01 중량% 내지 3 중량%의 싸이오펜화합물,
(h) 1 중량% 내지 20중량%의 아세트산 또는 그의 염, 및
(i) 전체 조성물의 총 중량이 100중량%가 되도록 하는 물을 포함하며,
상기 (f) 황산염은 황산암모늄 (ammonium sulfate), 황산나트륨 (sodium sulfate), 황산칼륨 (potassium sulfate), 황산칼슘 (calcium sulfate), 황산수소암모늄 (ammonium bisulfate), 황산수소나트륨 (sodium bisulfate), 중황산칼륨 (potassium bisulfate) 및 황산수소칼슘 (calcium bisulfate)에서 선택되는 하나 이상인, 금속막 식각액 조성물.
With respect to the total weight of the etchant composition,
(a) 0.5% to 20% persulfate;
(b) 0.01% to 2% by weight of a fluorine compound;
(c) 1% to 10% by weight of nitric acid;
(d) 0.1% to 5% by weight of 4-methylthiazole;
(e) 0.1% to 5% by weight of a chlorine compound;
(f) 0.5% to 10% by weight of a sulfate;
(g) 0.01% to 3% by weight of a thiophene compound;
(h) 1% to 20% by weight of acetic acid or a salt thereof, and
(i) water to make up to 100% by weight of the total composition;
The sulfate (f) is ammonium sulfate, sodium sulfate, potassium sulfate, calcium sulfate, ammonium bisulfate, sodium bisulfate, bisulfite At least one selected from potassium acid (potassium bisulfate) and calcium hydrogen sulfate (calcium bisulfate), a metal film etchant composition.
상기 (a) 과황산염은 과황산칼륨(K2S2O8), 과황산나트륨(Na2S2O8) 및 과황산암모늄((NH4)2S2O8)에서 선택되는 하나 이상인, 금속막 식각액 조성물.
The method of claim 1,
The (a) persulfate is at least one selected from 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 ), Metal film etchant composition.
상기 (b) 불소 화합물은 불화암모늄, 불화나트륨, 불화칼륨, 중불화암모늄, 중불화나트륨 및 중불화칼륨에서 선택되는 하나 이상인, 금속막 식각액 조성물.
The method of claim 1,
The (b) fluorine compound is at least one selected from ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride and potassium bifluoride, a metal film etchant composition.
상기 (e) 염소 화합물은 염산, 염화나트륨, 염화칼륨 및 염화암모늄에서 선택되는 하나 이상인, 금속막 식각액 조성물.
The method of claim 1,
The (e) chlorine compound is at least one selected from hydrochloric acid, sodium chloride, potassium chloride and ammonium chloride, a metal film etchant composition.
상기 (g) 싸이오펜화합물은 술포란 (sulfolane), 테트라하이드로-3-싸이오펜아민 (tetrahydro-3-thiophenamine), 테트라하이드로 싸이오펜 1-옥사이드 (tetrahydro thiophene 1-oxide) 및 2-메틸테트라히드로 싸이오펜-3-온 (2-methyltetrahydro thiophen-3-one)에서 선택되는 하나 이상인, 금속막 식각액 조성물.
The method of claim 1,
The (g) thiophene compound is sulfolane, tetrahydro-3-thiophenamine, tetrahydro thiophene 1-oxide and 2-methyltetrahydro At least one selected from thiophene-3-one (2-methyltetrahydro thiophen-3-one), a metal film etchant composition.
상기 금속막은 구리 또는 구리 합금 및 티타늄 또는 티타늄 합금으로 구성된 단일막 또는 상기 금속을 포함하는 이중막 이상의 다중막인, 금속막 식각액 조성물.
The method of claim 1,
The metal film is a single film composed of copper or a copper alloy and titanium or a titanium alloy, or a multi-layer of a double film or more containing the metal, a metal film etchant composition.
식각조절제, 계면활성제, 금속 이온 봉쇄제, 부식방지제 및 pH 조절제로 이루어진 군으로부터 선택되는 1종 또는 2종 이상을 함유하는 금속막 식각액 조성물. The method of claim 1,
A metal film etchant composition containing one or two or more selected from the group consisting of an etching regulator, a surfactant, a metal ion sequestering agent, a corrosion inhibitor, and a pH adjusting agent.
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