KR102400343B1 - Metal film etchant composition and manufacturing method of an array substrate for display device - Google Patents
Metal film etchant composition and manufacturing method of an array substrate for display device Download PDFInfo
- Publication number
- KR102400343B1 KR102400343B1 KR1020170035892A KR20170035892A KR102400343B1 KR 102400343 B1 KR102400343 B1 KR 102400343B1 KR 1020170035892 A KR1020170035892 A KR 1020170035892A KR 20170035892 A KR20170035892 A KR 20170035892A KR 102400343 B1 KR102400343 B1 KR 102400343B1
- Authority
- KR
- South Korea
- Prior art keywords
- metal film
- imidazole
- etchant composition
- acid
- film
- Prior art date
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 103
- 239000002184 metal Substances 0.000 title claims abstract description 103
- 239000000203 mixture Substances 0.000 title claims abstract description 76
- 239000000758 substrate Substances 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 73
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- -1 alkyl tetrazole compound Chemical class 0.000 claims abstract description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 238000005530 etching Methods 0.000 claims description 61
- 239000010949 copper Substances 0.000 claims description 40
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 36
- 229910052802 copper Inorganic materials 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 33
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 22
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 12
- 239000011733 molybdenum Substances 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 150000007524 organic acids Chemical class 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004065 semiconductor Substances 0.000 claims description 6
- 230000007797 corrosion Effects 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 5
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 5
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 5
- KSMBRKYAGMDASJ-UHFFFAOYSA-N 5-methyl-2H-tetrazole Chemical compound CC1=NN=NN1.CC1=NN=NN1 KSMBRKYAGMDASJ-UHFFFAOYSA-N 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- UDQCDDZBBZNIFA-UHFFFAOYSA-N 4-methyl-1,3-dihydrobenzimidazole-2-thione Chemical compound CC1=CC=CC2=C1NC(=S)N2 UDQCDDZBBZNIFA-UHFFFAOYSA-N 0.000 claims description 3
- ZAOSVPLMYOIGOB-UHFFFAOYSA-N 5-methyl-1H-imidazole Chemical compound CC=1N=CNC1.CC=1N=CNC1 ZAOSVPLMYOIGOB-UHFFFAOYSA-N 0.000 claims description 3
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 3
- 108010077895 Sarcosine Proteins 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
- 239000003112 inhibitor Substances 0.000 claims description 3
- 229940043230 sarcosine Drugs 0.000 claims description 3
- 239000003352 sequestering agent Substances 0.000 claims description 3
- MNWYQIUDIJSNBF-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound SC=1NC2=C(N1)C=CC=C2.SC=2NC1=C(N2)C=CC=C1 MNWYQIUDIJSNBF-UHFFFAOYSA-N 0.000 claims description 2
- JRSGMTIYAILZMO-UHFFFAOYSA-N 1-methyl-2h-tetrazole-5-thione Chemical compound CN1NN=NC1=S.CN1NN=NC1=S JRSGMTIYAILZMO-UHFFFAOYSA-N 0.000 claims description 2
- WOHOXHYMCWWJJH-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1.CC1=NC=CN1 WOHOXHYMCWWJJH-UHFFFAOYSA-N 0.000 claims description 2
- FLBUMFXTSUZXHH-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1.C1=CNC(C=2C=CC=CC=2)=N1 FLBUMFXTSUZXHH-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- HYMWOIHFTWVIRV-UHFFFAOYSA-N 5-phenyl-2H-tetrazole Chemical compound C1=CC=CC=C1C1=NN=NN1.C1=CC=CC=C1C1=NN=NN1 HYMWOIHFTWVIRV-UHFFFAOYSA-N 0.000 claims description 2
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 2
- CMTKWUZSCQDNBB-UHFFFAOYSA-N CN1C(=NC=C1)C.CN1C(=NC=C1)C Chemical compound CN1C(=NC=C1)C.CN1C(=NC=C1)C CMTKWUZSCQDNBB-UHFFFAOYSA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 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
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- 125000003295 alanine group Chemical group N[C@@H](C)C(=O)* 0.000 claims description 2
- 229940124277 aminobutyric acid Drugs 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 235000013922 glutamic acid Nutrition 0.000 claims description 2
- 239000004220 glutamic acid Substances 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 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
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- 150000003536 tetrazoles Chemical class 0.000 claims description 2
- HHDRWGJJZGJSGZ-UHFFFAOYSA-N 5-benzyl-2h-tetrazole Chemical compound C=1C=CC=CC=1CC=1N=NNN=1 HHDRWGJJZGJSGZ-UHFFFAOYSA-N 0.000 claims 1
- ZJJKZZQNPACYAG-UHFFFAOYSA-N CN1N=NN=C1.CN1N=NN=C1 Chemical compound CN1N=NN=C1.CN1N=NN=C1 ZJJKZZQNPACYAG-UHFFFAOYSA-N 0.000 claims 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims 1
- 238000011282 treatment Methods 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 8
- 150000002222 fluorine compounds Chemical class 0.000 abstract description 5
- 238000001514 detection method Methods 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 120
- 230000000052 comparative effect Effects 0.000 description 12
- 239000010409 thin film Substances 0.000 description 10
- 239000004973 liquid crystal related substance Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 3
- 238000001039 wet etching Methods 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- DTQZKOBDNLNBCU-UHFFFAOYSA-N 1-methylimidazole Chemical compound CN1C=CN=C1.CN1C=CN=C1 DTQZKOBDNLNBCU-UHFFFAOYSA-N 0.000 description 1
- OMAFFHIGWTVZOH-UHFFFAOYSA-N 1-methyltetrazole Chemical compound CN1C=NN=N1 OMAFFHIGWTVZOH-UHFFFAOYSA-N 0.000 description 1
- IOQLGFCIMRCCNA-UHFFFAOYSA-N 2-(carboxymethylamino)acetic acid Chemical compound OC(=O)CNCC(O)=O.OC(=O)CNCC(O)=O IOQLGFCIMRCCNA-UHFFFAOYSA-N 0.000 description 1
- GBIBYNIYVUFTIT-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O.OC(=O)CN(CC(O)=O)CC(O)=O GBIBYNIYVUFTIT-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
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- TTWYBNLBVHMTBZ-UHFFFAOYSA-N CN1N=NN=C1N.CN1N=NN=C1N Chemical compound CN1N=NN=C1N.CN1N=NN=C1N TTWYBNLBVHMTBZ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 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
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- 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
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
-
- C11D11/0047—
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- 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
-
- 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
- C23F1/32—Alkaline compositions
- C23F1/34—Alkaline compositions for etching copper or alloys thereof
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/136227—Through-hole connection of the pixel electrode to the active element through an insulation layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Nonlinear Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Weting (AREA)
- ing And Chemical Polishing (AREA)
Abstract
본 발명은 A)과산화 수소(H2O2), B)함 불소 화합물, C)알킬 테트라졸계 화합물, D)이미다졸계 화합물, E)한 분자 내에 질소원자와 카르복실기를 갖는 수용성화합물, F)황산염 화합물, 및 G)다가알코올 형 계면활성제를 포함하여, 처리매수가 증가함에 따른 식각완료소요시간 (End Point Detection; EPD), 사이드 엣치(Side etch), 테이퍼 각(Taper angle)의 변화량을 최소화하는 효과를 갖는 금속막 식각액 조성물 및 이를 사용한 표시장치용 어레이 기판의 제조방법에 관한 것이다. The present invention relates to A) hydrogen peroxide (H 2 O 2 ), B) a fluorine compound containing, C) an alkyl tetrazole compound, D) an imidazole compound, E) a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule, F) Including sulfate compound, and G) polyhydric alcohol-type surfactant, the amount of change in end point detection (EPD), side etch, and taper angle is minimized as the number of treatment sheets increases It relates to a metal film etchant composition having the effect of
Description
본 발명은 금속막 식각액 조성물 및 상기 금속막 식각액 조성물을 사용하는 표시장치용 어레이 기판의 제조방법에 관한 것이다. The present invention relates to a metal film etchant composition and a method of manufacturing an array substrate for a display device using the metal film etchant composition.
반도체 장치에서 기판 위에 금속 배선을 형성하는 과정은 통상적으로 스퍼터링 등에 의한 금속막 형성공정, 포토레지스트 도포, 노광 및 현상에 의한 선택적인 영역에서의 포토레지스트 형성공정, 및 식각공정에 의한 단계로 구성되고, 개별적인 단위 공정 전후의 세정 공정 등을 포함한다. 이러한 식각공정은 포토레지스트를 마스크로 하여 선택적인 영역에 금속막을 남기는 공정을 의미하며, 통상적으로 플라즈마 등을 이용한 건식식각 또는 금속막 식각액 조성물을 이용하는 습식식각이 사용된다.The process of forming a metal wiring on a substrate in a semiconductor device is usually composed of a metal film forming process by sputtering, etc., a photoresist forming process in a selective area by photoresist application, exposure and development, and an etching process. , and cleaning processes before and after individual unit processes. Such an etching process refers to a process of leaving a metal film in a selective area using a photoresist as a mask, and typically dry etching using plasma or wet etching using a metal film etchant composition is used.
일반적으로 액정표시장치는 박막트랜지스터 기판과 컬러필터 기판, 그리고 두 기판 사이에 주입되어 있는 액정층으로 이루어진 액정패널을 포함한다.In general, a liquid crystal display device includes a liquid crystal panel including a thin film transistor substrate, a color filter substrate, and a liquid crystal layer injected between the two substrates.
액정층은 두 기판의 가장자리 둘레에 인쇄되어 있으며 액정층을 가두는 봉인제로 결합되어 있다. 액정패널을 비발광소자이기 때문에 박막트렌지스터 기판의 후면에는 백라이트 유닛이 위치하고 있다. 백라이트에서 조사된 빛은 액정분자의 배열상태에 따라 투과량이 조절된다.A liquid crystal layer is printed around the edges of the two substrates and is bonded with a sealant that encloses the liquid crystal layer. Since the liquid crystal panel is a non-light emitting device, the backlight unit is located on the back side of the thin film transistor substrate. The amount of light irradiated from the backlight is adjusted according to the arrangement of liquid crystal molecules.
박막트랜지스터 기판에는 액정층에 신호를 전달하기 위해 배선이 형성되어 있다. 박막스트랜지스터 기판의 배선은 게이트 배선과 데이터 배선을 포함한다.A wiring is formed on the thin film transistor substrate to transmit a signal to the liquid crystal layer. The wiring of the thin film transistor substrate includes a gate wiring and a data wiring.
여기서, 게이트배선은 게이트 신호가 인가되는 게이트라인과 박막트랜지스터의 게이트전극을 포함하며, 데이터 배선은 게이트배선과 절연되어 데이터 신호를 인가하는 데이터라인과 박막트랜지스터의 데이터 전극을 구성하는 드레인전극과 소스전극을 포함한다.Here, the gate wiring includes a gate line to which a gate signal is applied and a gate electrode of the thin film transistor, and the data wiring is insulated from the gate wiring to apply a data signal and a drain electrode and a source constituting the data electrode of the thin film transistor. including electrodes.
이러한 배선은 금속 단일층 또는 합금 단일층으로 이루어질 수 있으나, 각 금속 도는 합금의 단점을 보완하고 원하는 물건을 얻기 위하여 다중층으로도 형성 가능하다.Such wiring may be formed of a single metal layer or a single alloy layer, but may also be formed in multiple layers in order to compensate for the shortcomings of each metal or alloy and to obtain a desired product.
기판 소재상에 증착된 다중층은 식각을 통하여 배선으로 패터닝된다. 식각에는 건식식각과 습식식각이 있는데, 균일하게 식각되고 생산성이 높은 습식식각이 많이 사용된다.The multilayer deposited on the substrate material is patterned into wiring through etching. There are two types of etching, dry etching and wet etching, and wet etching is widely used because it etches uniformly and has high productivity.
대한민국 공개특허공보 제 10-2007-0055259호는 구리 몰리브덴 합금막을 식각할 수 있는 식각용액 및 그 식각방법을 제공하는 것으로, 처리매수가 증가함에 따른 식각(Etch) 성능이 저하되면서, 사이드 엣치(Side etch), 식각완료소요시간 (End Point Detection; EPD), 테이퍼 각(Taper angle) 변화량이 증가되는 현상을 해결하지는 못하였다. Korean Patent Laid-Open Publication No. 10-2007-0055259 provides an etching solution capable of etching a copper molybdenum alloy film and an etching method thereof. As the etching performance decreases as the number of treatment sheets increases, the side etch etch), the etch completion time (End Point Detection; EPD), and the increase in the amount of change in the taper angle could not be solved.
전술한 문제점을 해결하기 위해, 본 출원인은 표시장치용 어레이 기판의 제조시 금속 박막 및 후막을 일괄 식각하여, 처리매수 증가에 따른 상기 문제점을 해결하기 위한 조성물을 개발하기에 이르렀다. In order to solve the above problems, the present applicant has developed a composition for solving the problems caused by an increase in the number of processing sheets by batch etching a metal thin film and a thick film when manufacturing an array substrate for a display device.
본 발명은 기존 식각액(Etchant)의 처리매수 변화량이 향상되고, 처리매수 증가에 따른 식각완료소요시간 (END POINT DETECTION; EPD), 사이드 엣치(Side etch), 테이퍼 각(Taper angle) 변화량이 작은 금속막의 일괄 금속막 식각액 조성물을 제공하는 것을 목적으로 한다.In the present invention, the amount of change in the number of treatments of the existing etchant is improved, and the amount of change in END POINT DETECTION (EPD), side etch, and taper angle is small according to the increase in the number of treatments. An object of the present invention is to provide a film batch metal film etchant composition.
또한, 본 발명은 과산화수소(H2O2), 함불소 화합물, 5-메틸-1H-테트라졸(5-Methyl-1H-tetrazole), 이미다졸(Imidazole), 이미노 디아세틱 산(Iminodiacetic acid), 황산염 및 물을 포함하는 금속막 또는 구리계 금속막의 일괄 금속막 식각액 조성물을 제공하는 것을 목적으로 한다.In addition, the present invention is hydrogen peroxide (H 2 O 2 ), a fluorine-containing compound, 5-methyl-1H-tetrazole (5-Methyl-1H-tetrazole), imidazole (Imidazole), imino diacetic acid (Iminodiacetic acid) An object of the present invention is to provide a metal film or copper-based metal film collective metal film etchant composition comprising , sulfate and water.
또한, 본 발명은 상기 동일한 금속막 또는 구리계 금속막의 식각액 조성물을 사용하는 금속막 또는 구리계 금속막의 식각방법을 제공하는 것을 목적으로 한다.Another object of the present invention is to provide a method for etching a metal film or a copper-based metal film using the same metal film or copper-based metal film etchant composition.
또한, 본 발명은 상기 동일한 금속막 또는 구리계 금속막의 식각액 조성물을 사용하는 표시장치용 어레이 기판의 제조방법을 제공하는 것을 목적으로 한다. Another object of the present invention is to provide a method of manufacturing an array substrate for a display device using the etchant composition of the same metal film or copper-based metal film.
본발명은, A)과산화 수소(H2O2), B)함 불소 화합물, C) 알킬 테트라졸계 화합물, D) 이미다졸계 화합물, E)한 분자 내에 질소원자와 카르복실기를 갖는 수용성화합물, F)황산염 화합물, 및 G)다가알코올 형 계면활성제를 포함하는, 금속막 식각액 조성물을 제공한다.The present invention provides A) hydrogen peroxide (H 2 O 2 ), B) containing fluorine compound, C) alkyl tetrazole compound, D) imidazole compound, E) water-soluble compound having a nitrogen atom and a carboxyl group in one molecule, F ) A sulfate compound, and G) provides a metal film etchant composition comprising a polyhydric alcohol-type surfactant.
또한, 본 발명은 a) 기판 상에 게이트 전극을 형성하는 단계; b) 상기 게이트 전극을 포함한 기판 상에 게이트 절연층을 형성하는 단계; c) 상기 게이트 절연층 상에 반도체 층을 형성하는 단계; d) 상기 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및 e) 상기 드레인 전극에 연결된 화소전극을 형성하는 단계를 포함하는 표시 장치용 어레이 기판의 제조방법에 있어서, 상기 a) 단계는 기판상에 금속막을 형성하고 상기 금속막을 금속막의 금속막 식각액 조성물로 식각하여 게이트 배선을 형성하는 단계를 포함하고, 상기 d) 단계는 금속막을 형성하고 상기 금속막을 본 발명의 금속막의 금속막 식각액 조성물로 식각하여 소스 및 드레인 전극을 형성하는 단계를 포함하는 것을 특징으로 하는 표시장치용 어레이 기판의 제조방법을 제공한다.In addition, the present invention comprises the steps of: a) forming a gate electrode on a substrate; b) forming a gate insulating layer on the substrate including the gate electrode; c) forming a semiconductor layer on the gate insulating layer; d) forming source and drain electrodes on the semiconductor layer; and e) forming a pixel electrode connected to the drain electrode, wherein the step a) comprises forming a metal film on the substrate and using the metal film as a metal film etchant composition of the metal film. and forming a gate wiring by etching, wherein step d) comprises forming a metal film and etching the metal film with the metal film etchant composition of the metal film of the present invention to form source and drain electrodes. It provides a method of manufacturing an array substrate for a display device.
본 발명에 따른 금속막의 금속막 식각액 조성물은 표시장치용 어레이 기판의 제조시, 금속 박막 및 후막을 일괄 식각 가능하여 공정이 매우 단순화 되어 공정 수율을 극대화 할 수 있다.The metal film etchant composition for a metal film according to the present invention can etch a metal thin film and a thick film in batches when manufacturing an array substrate for a display device, thereby greatly simplifying the process and maximizing the process yield.
더욱이, 본 발명에 따른 금속막의 금속막 식각액 조성물은 처리매수 증가에 따른 식각완료소요시간 (END POINT DETECTION; EPD), 사이드 엣치(Side etch), 테이퍼 각(Taper angle) 변화량을 최소화 하여 효율적인 표시장치용 어레이 기판의 제조를 가능하게 한다.Furthermore, the metal film etchant composition of the metal film according to the present invention is an efficient display device by minimizing changes in END POINT DETECTION (EPD), side etch, and taper angle according to the increase in the number of treatments. It enables the fabrication of array substrates for use.
이하 본 발명에 따른 금속막 식각액 조성물 및 표시장치용 어레이 기판의 제조방법을 상세히 설명한다.Hereinafter, a method for manufacturing a metal film etchant composition and an array substrate for a display device according to the present invention will be described in detail.
본발명은 A)과산화 수소(H2O2), B)함 불소 화합물, C) 알킬 테트라졸계 화합물, D) 이미다졸계 화합물, E)한 분자 내에 질소원자와 카르복실기를 갖는 수용성화합물, F)황산염 화합물, 및 G)다가알코올 형 계면활성제를 포함하는, 금속막 식각액 조성물에 관한 것이다. 특히, C) 알킬 테트라졸계 화합물, D) 이미다졸계 화합물을 포함하여, 처리매수가 증가함에 따른 EDP, 사이드 엣치(Side etch) 및 테이퍼 각(Taper angle) 변화량을 최소화 하는 효과를 갖는다.The present invention relates to A) hydrogen peroxide (H 2 O 2 ), B) containing fluorine compound, C) alkyl tetrazole-based compound, D) imidazole-based compound, E) water-soluble compound having a nitrogen atom and a carboxyl group in one molecule, F) It relates to a metal film etchant composition comprising a sulfate compound, and G) a polyalcohol-type surfactant. In particular, including C) an alkyl tetrazole-based compound and D) an imidazole-based compound, it has an effect of minimizing changes in EDP, side etch, and taper angle as the number of treatments increases.
본 발명에서 금속막이라 함은 구리 또는 구리 합금의 단일막; 및 구리막 및 구리 합금막 중에서 선택되는 하나 이상의 막과 몰리브덴막, 몰리브덴 합금막, 티타늄막 및 티타늄 합금막으로 이루어진 군으로부터 선택되는 하나 이상의 막을 포함하는 다층막을 포함하는 개념이다.In the present invention, the metal film refers to a single film of copper or copper alloy; and a multilayer film including one or more films selected from a copper film and a copper alloy film and one or more films selected from the group consisting of a molybdenum film, a molybdenum alloy film, a titanium film, and a titanium alloy film.
본 명세서에 개시된 구리계 금속막이라 함은 막의 구성성분 중에 구리가 포함되는 것을 의미한다.The copper-based metal film disclosed herein means that copper is included in a component of the film.
본 명세서에 개시된 합금막이라 함은 질화막 또는 산화막도 포함하는 개념이다.The alloy film disclosed herein is a concept including a nitride film or an oxide film.
상기 다층막의 예로는, 구리/몰리브덴막, 구리/몰리브덴 합금막, 구리 합금/몰리브덴 합금막, 구리/티타늄막 등의 2중막, 또는 3중막을 들 수 있다. 상기 구리/몰리브덴막은 몰리브덴층과 상기 몰리브덴층 상에 형성된 구리층을 포함하는 것을 의미하며, 상기 구리/몰리브덴 합금막은 몰리브덴 합금층과 상기 몰리브덴 합금층 상에 형성된 구리층을 포함하는 것을 의미하며, 구리 합금/몰리브덴 합금막은 몰리브덴 합금층과 상기 몰리브덴 합금층 상에 형성된 구리 합금층을 포함하는 것을 의미하며, 상기 구리/티타늄막은 티타늄층과 상기 티타늄층 상에 형성된 구리층을 포함하는 것을 의미한다.Examples of the multilayer film include a copper/molybdenum film, a copper/molybdenum alloy film, a copper alloy/molybdenum alloy film, a double film such as a copper/titanium film, or a triple film. The copper / molybdenum film means comprising a molybdenum layer and a copper layer formed on the molybdenum layer, and the copper / molybdenum alloy film includes a molybdenum alloy layer and a copper layer formed on the molybdenum alloy layer. The alloy/molybdenum alloy film means including a molybdenum alloy layer and a copper alloy layer formed on the molybdenum alloy layer, and the copper/titanium film includes a titanium layer and a copper layer formed on the titanium layer.
또한, 상기 몰리브덴 합금층은 예컨대, 티타늄(Ti), 탄탈륨(Ta), 크롬(Cr), 니켈(Ni), 네오디늄(Nd), 및 인듐(In) 등으로 이루어진 군에서 선택되는 1종 이상의 금속과 몰리브덴의 합금으로 이루어진 층을 의미한다.In addition, the molybdenum alloy layer is, for example, one or more selected from the group consisting of titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), and indium (In), etc. It means a layer made of an alloy of metal and molybdenum.
특히, 본 발명의 금속막 식각액 조성물은 구리 또는 구리 합금막과 몰리브덴 또는 몰리브덴 합금막으로 이루어진 다층막에 바람직하게 적용될 수 있다. In particular, the metal film etchant composition of the present invention can be preferably applied to a multilayer film consisting of a copper or copper alloy film and a molybdenum or molybdenum alloy film.
본 발명에서 구리계 금속막은 두께가 최소 3000Å 이며, 6500Å 이상 되는 금속막 까지를 일괄한다. 두께가 3000Å 정도인 박막에서와는 다르게 두께 6500Å 이상의 후막의 경우 기존의 식각액(Etchant)으로 부식속도가 느리므로 Process Time이 증가하게 된다. 따라서 기존 식각액(Etchant) 대비 빠른 부식속도(150Å/sec 이상)가 요구되므로 기존 식각액(Etchant)으로 적용이 불가하다. 또한 후막의 특성상 Taper angle이 높을 경우(테이퍼 각(Taper angle) 60°이상) 후속 공정 진행시 Step Coverage 불량이 발생할수 있으므로 테이퍼 각(Taper angle)감소가 필수적인데 기존 식각액(Etchant)의 경우 테이퍼 각(Taper angle)이 높아 적용에 어려움이 있다. In the present invention, the copper-based metal film has a minimum thickness of 3000 Å, and includes up to a metal film of 6500 Å or more. Unlike a thin film with a thickness of about 3000 Å, in the case of a thick film with a thickness of 6500 Å or more, the process time increases because the corrosion rate is slow with the conventional etchant. Therefore, a faster corrosion rate (150 Å/sec or more) is required compared to the existing etchant, so it cannot be applied to the existing etchant. In addition, due to the characteristics of the thick film, if the taper angle is high (taper angle 60° or more), step coverage defects may occur during the subsequent process, so it is essential to reduce the taper angle. (Taper angle) is high, so it is difficult to apply.
본 발명의 금속막 식각액 조성물을 구성요소 별로 설명하면 다음과 같다. The metal film etchant composition of the present invention will be described for each component as follows.
A)A) 과산화 수소hydrogen peroxide
본 발명의 금속막 식각액 조성물에 포함되는 A) 과산화수소(H2O2)는 몰리브덴층과 상기 몰리브덴층 상에 형성된 구리층을 포함하는 구리 몰리브덴막 또는 몰리브덴 합금층과 상기 몰리브덴 합금층 상에 형성된 구리층을 포함하는 구리 몰리브덴 합금막인 것을 특징으로 하는 구리계 금속막의 식각에 영향을 주는 주산화제이다.A) hydrogen peroxide (H 2 O 2 ) contained in the metal film etchant composition of the present invention is a copper molybdenum film or a molybdenum alloy layer including a molybdenum layer and a copper layer formed on the molybdenum layer and copper formed on the molybdenum alloy layer It is a main oxidizing agent affecting the etching of a copper-based metal film, characterized in that it is a copper molybdenum alloy film including a layer.
상기 A) 과산화수소(H2O2)는 조성물 총 중량에 대하여, 15 내지 25.0 중량%, 바람직하게는 18.0 내지 24.0 중량%로 포함된다. 상술한 범위 미만으로 포함되면, 구리계 금속막 및 몰리브덴 합금막의 식각력이 부족하여 충분한 식각이 이루어지지 않을 수 있으며, 25.0 중량%를 초과하여 포함될 경우, 과산화수소(H2O2) 농도가 너무 높아짐에 따라 식각액의 안정성이 감소된다.The A) hydrogen peroxide (H 2 O 2 ) is included in an amount of 15 to 25.0 wt%, preferably 18.0 to 24.0 wt%, based on the total weight of the composition. When included in less than the above range, sufficient etching may not be achieved due to insufficient etching power of the copper-based metal film and the molybdenum alloy film, and when included in excess of 25.0 wt%, hydrogen peroxide (H 2 O 2 ) concentration is too high Accordingly, the stability of the etchant is reduced.
B) 함 불소 화합물B) fluorine-containing compounds
본 발명의 금속막 식각액 조성물에 포함되는 B) 함 불소 화합물은물에 해리되어 F이온을 낼 수 있는 화합물을 의미한다. 상기 B) 함 불소화합물은 몰리브덴 합금막의 식각 속도에 영향을 주는 보조산화제이며, 몰리브덴 합금막의 식각 속도를 조절한다.B) fluorine-containing compound included in the metal film etchant composition of the present invention means a compound capable of dissociating in water to produce F ions. The B) fluorine-containing compound is an auxiliary oxidizing agent that affects the etching rate of the molybdenum alloy film, and controls the etching rate of the molybdenum alloy film.
상기 B) 함 불소화합물은 조성물 총 중량에 대하여, 0.01 내지 3.0 중량%, 바람직하게는 0.05 내지 1.0중량%로 포함된다. 상술한 범위 미만으로 포함되면, 몰리브덴계 금속막 및 금속산화물막의 식각 속도가 느려진다. 상술한 범위를 초과하여 포함되면, 몰리브덴 합금막의 시각 성능은 향상되지만, 식각 속도가 전체적으로 빨라지기 때문에 언더컷 현상이나 하부층 Si 계열의 하부층의 식각 손상(Damage)이 크게 나타난다.The B) fluorine-containing compound is included in an amount of 0.01 to 3.0 wt%, preferably 0.05 to 1.0 wt%, based on the total weight of the composition. When included below the above range, the etching rate of the molybdenum-based metal film and the metal oxide film is slowed. When the content exceeds the above-mentioned range, the visual performance of the molybdenum alloy film is improved, but the undercut phenomenon or the etch damage of the lower layer of the Si-based lower layer is greatly appeared because the etching rate is overall faster.
상기 B)함 불소화합물은 당업계에서 사용되는 것이라면 특별히 한정하지 않는다. 하지만, 상기 B)함 불소화합물은 HF, NaF, NH4F, NH4BF4, NH4HF2(ammonium bifluoride; ABF), KF, KHF2, AlF3 , 및 HBF4로 이루어진 군에서 선택되는 것이 바람직하나 SiO2 손상(Damage) 측면에서 NH4F, NH4HF2 등이 바람직하다.The fluorine-containing compound B) is not particularly limited as long as it is used in the art. However, the B) containing fluorine compound is selected from the group consisting of HF, NaF, NH 4 F, NH 4 BF 4 , NH 4 HF 2 (ammonium bifluoride; ABF), KF, KHF 2 , AlF 3 , and HBF 4 It is preferable, but in terms of SiO 2 Damage, NH 4 F, NH 4 HF 2 , etc. are preferable.
C) C) 알킬alkyl 테트라졸계tetrazole 화합물 compound
본 발명의 금속막 식각액 조성물에 포함되는 C)알킬 테트라졸계 화합물은 구리계 금속막의 식각 속도를 조절하며 패턴의 시디로스(CD Loss)를 줄여주어 공정상의 마진을 높이는 역할을 한다.C) Alkyl tetrazole-based compound included in the metal film etchant composition of the present invention controls the etching rate of the copper-based metal film and reduces the CD loss of the pattern, thereby increasing the process margin.
상기 C)알킬 테트라졸계 화합물의 함량은 조성물 총 중량에 대하여 0.05 내지 3.0 중량%로 포함되고, 0.05 내지 1.0 중량% 범위인 조성물이 특히 바람직하다. 상기 C)알킬 테트라졸계 화합물의 함량이 상술한 범위 미만인 경우, 과식각 및 처리매수에 따른 식각 성능(Etch Profile)변동이 크게 나타난다. 상기 C)알킬 테트라졸계 화합물의 함량이 상술한 범위 초과하는 경우, 구리의 식각속도가 너무 느려지기 때문에 공정시간 손실이 있을 수 있다.The C) content of the alkyl tetrazole-based compound is included in an amount of 0.05 to 3.0% by weight based on the total weight of the composition, and the composition is particularly preferably in the range of 0.05 to 1.0% by weight. When the content of the C) alkyl tetrazole-based compound is less than the above-mentioned range, the etching performance (Etch Profile) changes significantly according to over-etching and the number of treatment sheets. When the C) content of the alkyl tetrazole-based compound exceeds the above-described range, there may be a loss of process time because the etching rate of copper is too slow.
상기 C)알킬 테트라졸계 화합물은 5-메틸-1H-테트라졸(5-Methyl-1H-tetrazole), 5-페닐-1H-테트라졸(5-Phenyl-1H-tetrazole), 5-아미노-1-메틸테트라졸(5-Amino-1-methyltetrazole), 5-벤질-1H-테트라졸(5-Benzyl-1H-tetrazole), 5-머캅토-1메틸테트라졸(5-Mercapto-1-methyltetrazole) 및 1-메틸-1H-테트라졸(1-Methyl-1H-tetrazole)등으로 구성되는 군에서 선택되는 1종 이상을 포함할 수 있으며, 5-메틸-1H-테트라졸(5-Methyl-1H-tetrazole)이 보다 바람직 하다. The C) alkyl tetrazole compound is 5-methyl-1H-tetrazole (5-Methyl-1H-tetrazole), 5-phenyl-1H-tetrazole (5-Phenyl-1H-tetrazole), 5-amino-1- Methyltetrazole (5-Amino-1-methyltetrazole), 5-Benzyl-1H-tetrazole (5-Benzyl-1H-tetrazole), 5-Mercapto-1methyltetrazole (5-Mercapto-1-methyltetrazole) and It may include one or more selected from the group consisting of 1-methyl-1H-tetrazole, etc., and 5-methyl-1H-tetrazole (5-Methyl-1H-tetrazole). ) is more preferable.
D) 이미다졸계 화합물D) imidazole compounds
본 발명의 금속막 식각액 조성물에 포함되는 D) 이미다졸계 화합물은 금속막 또는 구리계 금속막의 식각 속도를 조절하며, 처리매수에 따른 식각 성능(Etch Profile)변동을 감소시켜주어 공정상의 마진을 높이는 역할을 한다. D) imidazole-based compound included in the metal film etchant composition of the present invention controls the etching rate of the metal film or copper-based metal film, and reduces the etching performance (Etch Profile) fluctuations according to the number of treatments to increase the margin in the process plays a role
D)이미다졸계 화합물의 함량은 조성물 총 중량에 대하여 0.05 내지 3.0 중량%로 포함되고, 0.05 내지 1.0 중량% 범위인 조성물이 특히 바람직하다. 상기 D)이미다졸계 화합물의 함량이 상술한 범위 미만인 경우, 과식각 및 처리매수에 따른 식각 성능(Etch Profile)변동이 크게 나타난다. 상기 D)이미다졸계 화합물의 함량이 상술한 범위 초과하는 경우, 구리의 식각속도가 너무 느려지기 때문에 공정시간 손실이 있을 수 있다. 상기 D)이미다졸계 화합물은 이미다졸(Imidazole), 벤조이미다졸(Benzimidazole), 2-페닐이미다졸(2-Phenyl-1H-Imidazole),1-메틸-1H-이미다졸(1-Methyl-1H-Imidazole),2-메틸-1H-이미다졸(2-Methyl-1H-imidazole) ,4-메틸-1H-이미다졸(4-Methyl-1H-Imidazole),1H-이미다졸-1-프로밀아민(1H-Imidzole-1-propylamine), 1H-이미다졸-1-에탄아민(1H-Imidazole-1-ethanamine), 2-메르캅토벤지이미다졸(2-Mercaptobenzimidazole), 2-메르캅토톨루이미다졸(2-Mercaptotoluimidazole) 및 1,2-디메틸 이미다졸(1,2-Dimethyl imidazole)등으로 이루어진 군으로부터 선택되는 1종 이상을 포함할 수 있으며, 이미다졸(Imidazole)을 포함 하는 것이 보다 바람직 하다.D) The content of the imidazole-based compound is included in an amount of 0.05 to 3.0% by weight based on the total weight of the composition, and a composition in the range of 0.05 to 1.0% by weight is particularly preferred. D) When the content of the imidazole-based compound is less than the above-mentioned range, there is a large change in etching performance (Etch Profile) according to over-etching and the number of treatments. D) When the content of the imidazole-based compound exceeds the above-described range, there may be a loss of process time because the etching rate of copper is too slow. The D) imidazole compound is imidazole (Imidazole), benzimidazole (Benzimidazole), 2-phenyl imidazole (2-Phenyl-1H-Imidazole), 1-methyl-1H- imidazole (1-Methyl- 1H-Imidazole), 2-methyl-1H-imidazole (2-Methyl-1H-imidazole), 4-methyl-1H-imidazole (4-Methyl-1H-Imidazole), 1H-imidazole-1-promyl Amine (1H-Imidzole-1-propylamine), 1H-imidazole-1-ethanamine (1H-Imidazole-1-ethanamine), 2-mercaptobenzimidazole (2-Mercaptobenzimidazole), 2-mercaptotoluimida It may include one or more selected from the group consisting of sol (2-Mercaptotoluimidazole) and 1,2-dimethyl imidazole (1,2-Dimethyl imidazole), and it is more preferable to include imidazole (Imidazole). .
본 발명에서, C)알킬 테트라졸계 화합물 및 D)이미다졸계 화합물은 1:20 내지 20:1의 비율로 포함될 수 있으며, 1:5 내지 5:1의 비율로 포함되는 경우 보다 바람직하다. 알킬 테트라졸계 화합물 및 이미다졸계 화합물의 비율이 상술한 범위를 만족하면 처리매수 변화량이 적고, 후막에서 필요한 빠른 Etch Rate를 갖는 효과가 있다. In the present invention, C) the alkyl tetrazole-based compound and D) the imidazole-based compound may be included in a ratio of 1:20 to 20:1, more preferably in a ratio of 1:5 to 5:1. When the ratio of the alkyl tetrazole-based compound and the imidazole-based compound satisfies the above-mentioned range, there is an effect of having a small amount of change in the number of treatment sheets and a fast etching rate required for a thick film.
E) 한 분자 내에 E) within one molecule 질소원자와nitrogen atom and 카르복실기를 갖는 수용성 화합물 Water-soluble compound having a carboxyl group
본 발명의 금속막 식각액 조성물에 포함되는 E)한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물은 금속막 식각액 조성물의 보관 시 발생할 수 있는 과산화수소수의 자체 분해 반응을 막아주고 많은 수의 기판을 식각할 시에 식각 특성이 변하는 것을 방지한다. 일반적으로 과산화수소수를 사용하는 금속막 식각액 조성물의 경우 보관시 과산화수소수가 자체 분해하여 그 보관기간이 길지가 못하고 용기가 폭발할 수 있는 위험요소까지 갖추고 있다. E) The water-soluble compound having a nitrogen atom and a carboxyl group in one molecule contained in the metal film etchant composition of the present invention prevents the self-decomposition reaction of hydrogen peroxide that may occur during storage of the metal film etchant composition and etches a large number of substrates. It prevents the etching characteristics from changing during the process. In general, in the case of a metal film etchant composition using hydrogen peroxide solution, the hydrogen peroxide solution self-decomposes during storage, so the storage period is not long and the container has a risk of explosion.
그러나 상기 E) 한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물이 포함될 경우 과산화수소수의 분해 속도가 10배 가까이 줄어들어 보관기간 및 안정성 확보에 유리하다. 특히 구리층의 경우 금속막 식각액 조성물 내에 구리 이온이 다량 잔존할 경우에 패시베이션(passivation) 막을 형성하여 까맣게 산화된 후 더 이상 식각되지 않는 경우가 많이 발생할 수 있으나 이 화합물을 첨가하였을 경우 이런 현상을 막을 수 있다. However, in case E) a water-soluble compound having a nitrogen atom and a carboxyl group is included in one molecule, the decomposition rate of the hydrogen peroxide solution is reduced by nearly 10 times, which is advantageous for securing storage period and stability. In particular, in the case of a copper layer, when a large amount of copper ions remain in the metal film etchant composition, a passivation film is formed and is oxidized to black, and there are many cases where it is not etched anymore. can
상기 E)한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물의 함량은 0.5 내지 5.0 중량%로 포함되고, 특히 바람직하게는 1.0 내지 3.0 중량% 범위로 포함된다. E) The content of the water-soluble compound having a nitrogen atom and a carboxyl group in one molecule is included in the range of 0.5 to 5.0% by weight, particularly preferably in the range of 1.0 to 3.0% by weight.
상기 E) 한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물의 함량이 상술한 범위 미만일 경우, 다량의 기판(약 500매)의 식각 후에는 패시베이션 막이 형성되어 충분한 공정 마진을 얻기가 어려워진다. 또한, 상기 E)한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물의 함량이 상술한 범위를 초과할 경우, 몰리브덴 또는 몰리브덴합금의 식각속도는 느려지므로 구리 몰리브덴막 또는 구리 몰리브덴합금막의 경우 몰리브덴 또는 몰리브덴합금막의 잔사 문제가 발생할수 있다.E) When the content of the water-soluble compound having a nitrogen atom and a carboxyl group in one molecule is less than the above range, a passivation film is formed after etching a large amount of substrates (about 500 sheets), making it difficult to obtain a sufficient process margin. In addition, E) when the content of the water-soluble compound having a nitrogen atom and a carboxyl group in one molecule exceeds the above-mentioned range, the etching rate of molybdenum or molybdenum alloy is slowed down. Residue problems may occur.
상기 E) 한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물은 알라닌(alanine), 아미노부티르산 (aminobutyric acid), 글루탐산(glutamic acid), 글리신(glycine), 이미노디아세트산(iminodiacetic acid), 니트릴로트리아세트산(nitrilotriacetic acid) 및 사르코신(sarcosine)등을 들 수 있다. 그리고 이중에서 이미노디아세트산(iminodiacetic acid)이 가장 바람직하다.E) A water-soluble compound having a nitrogen atom and a carboxyl group in one molecule is alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, nitrilotriacetic acid ( nitrilotriacetic acid) and sarcosine. And among them, iminodiacetic acid is most preferred.
F) 황산염F) sulfate
본 발명의 금속막 식각액 조성물에 포함되는 F) 황산염은 Cu 표면의 산화전위를 조절하여 구리막의 식각속도를 증가시켜주는 성분이다. 만약 상기 F) 황산염이 본 발명의 금속막 식각액 조성물에 존재하지 않으면 식각속도가 매우 낮아 식각프로파일이 불량하게 될 수 있다. F) sulfate contained in the metal film etchant composition of the present invention is a component that increases the etching rate of the copper film by controlling the oxidation potential of the Cu surface. If F) sulfate is not present in the metal film etchant composition of the present invention, the etch rate may be very low, resulting in a poor etch profile.
상기 F) 무기염의 함량은 조성물 총 중량에 대하여 0.05 내지 5.0 중량%로 포함되고, 특히 바람직하게는 0.10 내지 3.0 중량% 범위인 조성물로 포함된다. 상기 F) 황산염은 상술한 범위 미만일 경우, 식각속도가 매우 낮아 식각 성능(Etch Profile)불량 및 공정타임 손실이 발생할 수 있다. F) The content of the inorganic salt is included in the composition in an amount of 0.05 to 5.0% by weight, particularly preferably in the range of 0.10 to 3.0% by weight, based on the total weight of the composition. When the amount of F) sulfate is less than the above-mentioned range, the etching rate is very low, which may result in poor etching performance (Etch Profile) and loss of process time.
상기 F) 황산염은 상술한 범위를 초과하는 경우에는 구리 또는 구리합금막의 식각속도가 너무 빨라지거나 테이퍼 각(Taper angle)값이 너무 높아져 Step coverage 불량에 취약해지므로 후막 적용에 어려움이 있다.F) If the sulfate exceeds the above range, the etching rate of the copper or copper alloy film is too fast or the taper angle value is too high, which makes it vulnerable to poor step coverage, so it is difficult to apply a thick film.
상기 F) 황산염은 황산암모늄 (Ammonium sulfate), 황산나트륨 (Sodium sulfate), 황산칼륨 (Potassium sulfate), 황산마그네슘 (Magnesium sulfate), 황산리튬 (Lithium sulfate) 등을 들 수 있다.The F) sulfate may include ammonium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, lithium sulfate, and the like.
G) G) 다가알코올형polyhydric alcohol 계면활성제 Surfactants
본 발명의 금속막 식각액 조성물에 포함되는 G) 다가알코올형 계면활성제는 표면장력을 저하시켜 식각의 균일성을 증가시키는 역할을 한다. G) polyalcohol-type surfactant included in the metal film etchant composition of the present invention serves to increase the uniformity of the etching by reducing the surface tension.
또한, 상기 G) 다가알코올형 계면활성제는 구리막을 식각한 후 식각액에 녹아져 나오는 구리 이온을 둘러 쌈으로서 구리이온의 활동도를 억제하여 과산화수소의 분해 반응을 억제하게 된다. 이렇게 구리 이온의 활동도를 낮추게 되면 식각액을 사용하는 동안 안정적으로 공정을 진행 할 수 있게 된다. In addition, the G) polyalcohol-type surfactant suppresses the activity of copper ions by surrounding copper ions dissolved in the etchant after etching the copper film, thereby suppressing the decomposition reaction of hydrogen peroxide. If the activity of copper ions is lowered in this way, the process can be performed stably while using the etchant.
상기 G) 다가알코올형 계면활성제의 함량은 조성물 총 중량에 대하여 1.0 내지 5.0 중량%로 포함되고, 특히 바람직하게는 1.5 내지 3.0 중량% 범위로 포함된다. 상기 G)다가알코올형 계면활성제의 함량이 상술한 범위 미만인 경우, 식각 균일성이 저하되고 과산화수소의 분해가 가속화 되는 문제점이 생길 수 있다. 상기 G)다가알코올형 계면활성제의 함량이 상술한 범위 이상이면 거품이 많이 발생되는 단점이 있다.The content of the G) polyhydric alcohol-type surfactant is included in the range of 1.0 to 5.0% by weight, particularly preferably in the range of 1.5 to 3.0% by weight, based on the total weight of the composition. When the content of the G) polyalcohol-type surfactant is less than the above range, there may be problems in that the etching uniformity is lowered and the decomposition of hydrogen peroxide is accelerated. G) If the content of the polyhydric alcohol-type surfactant is above the above range, there is a disadvantage in that a lot of bubbles are generated.
상기 G)다가알코올형 계면활성제는 글리세롤(glycerol), 트리에틸렌글리콜(triethylene glycol) 및 폴리에틸렌 글리콜(polyethylene glycol)등을 들 수 있다. 그리고 이중에서 트리에틸렌글리콜(triethylene glycol)이 바람직하다. The G) polyhydric alcohol-type surfactant may include glycerol, triethylene glycol, and polyethylene glycol. And among them, triethylene glycol is preferable.
H)잔량의 물H) residual amount of water
본 발명의 금속막 식각액 조성물에 포함되는 물은 금속막 식각액 조성물 조성물 총 중량이 100중량%가 되도록 잔량 포함한다. 상기 잔량의 물은 A)과산화 수소(H2O2), B)함 불소 화합물, C) 5-메틸-1H-테트라졸(5-Methyl-1H-tetrazole), D) 이미다졸(Imidazole), E)한 분자 내에 질소원자와 카르복실기를 갖는 수용성화합물, F)황산염 화합물, 및 G)다가알코올 형 계면활성제를 포함하는 금속막 식각액 조성물의 총 중량이 100 중량%가 되도록 포함되며, 유기산 및/또는 첨가제를 더 포함하는 경우에도 금속막 식각액 조성물의 총 중량이 100중량% 되도록 포함되는 것을 의미한다. 상기 물은 특별히 한정하지 않으나, 탈이온수를 이용하는 것이 바람직하다. 또한, 물 속에 이온이 제거된 정도를 보여주는 물의 비저항값이 18㏁·cm이상인 탈 이온수를 이용하는 것이 보다 바람직 하다. The remaining amount of water included in the metal film etchant composition of the present invention is included so that the total weight of the metal film etchant composition composition is 100% by weight. The remaining amount of water is A) hydrogen peroxide (H 2 O 2 ), B) containing fluorine compound, C) 5-methyl-1H-tetrazole, D) imidazole, E) a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule, F) a sulfate compound, and G) a polyalcohol-type surfactant is included so that the total weight of the metal film etchant composition is 100% by weight, organic acid and/or Even when an additive is further included, it means that the total weight of the metal film etchant composition is included to be 100% by weight. The water is not particularly limited, but deionized water is preferably used. In addition, it is more preferable to use deionized water having a specific resistance value of 18 MΩ cm or more, which shows the degree to which ions are removed from the water.
I)유기산I) organic acid
본 발명의 금속막 식각액 조성물은 I)유기산을 더 포함할 수 있으며, 우수하게 잔사를 제거하는 역할을 한다. The metal film etchant composition of the present invention may further include I) an organic acid, and serves to excellently remove residues.
상기 I)유기산의 함량은 조성물 총 중량에 대하여 0.01 내지 5.0중량%로 포함되고, 특히 바람직하게는 0.01 내지 3.0중량% 범위로 포함된다. 상기 I)유기산의 함량이 상술한 범위 이상일 경우, 처리매수 변동량이 커지는 효과를 가지며, 상술한 미만인 경우, 잔사를 제거함에 있어 큰 효과가 없다.I) The content of the organic acid is included in the range of 0.01 to 5.0% by weight, particularly preferably in the range of 0.01 to 3.0% by weight, based on the total weight of the composition. I) When the content of the organic acid is greater than or equal to the above range, it has the effect of increasing the amount of variation in the number of treatments, and when it is less than the above, there is no significant effect in removing the residue.
상기 I)유기산은 아세트산, 부탄산, 시트르산, 포름산, 글루콘산, 말론산, 펜탄산, 젖산 및 옥살산 등일 수 있으며, 이 더욱 바람직 하다. I) The organic acid may be acetic acid, butanoic acid, citric acid, formic acid, gluconic acid, malonic acid, pentanoic acid, lactic acid and oxalic acid, and more preferably.
본발명의 금속막 식각액 조성물의 pH는 1.0내지 3.0일 수 있으며, 1.5내지 2.5일 경우 보다 바람직하다. 금속막 식각액 조성물의 pH범위가 상술한 범위일 경우 잔사 제거에 우수한 효과를 갖는다. The pH of the metal film etchant composition of the present invention may be 1.0 to 3.0, more preferably 1.5 to 2.5. When the pH range of the metal film etchant composition is within the above-mentioned range, it has an excellent effect in removing residues.
또한, 본 발명에서 전술한 성분 이외에 통상의 첨가제를 더 첨가할 수 있으며, 상기 첨가제로는 금속 이온 봉쇄제, 및 부식 방지제 등을 들 수 있다. 상기 첨가제는 금속이온 봉쇄제 및 부식방지제 중 하나이상 첨가 할 수 있다.In addition, in the present invention, in addition to the components described above, conventional additives may be further added, and the additives may include a metal ion sequestrant, a corrosion inhibitor, and the like. The additive may be added at least one of a metal ion sequestrant and a corrosion inhibitor.
상기 금속 첨가제의 함량은 조성물 총 중량에 대하여 0.001 내지 10 중량%로 포함되며, 상기 첨가제의 함량이 상술한 범위일 경우 식각 성능(Etch profile)이 더욱 향상된다. The content of the metal additive is included in an amount of 0.001 to 10% by weight based on the total weight of the composition, and when the content of the additive is in the above-described range, the etching performance (Etch profile) is further improved.
본 발명에서 사용되는 각 구성성분은 통상적으로 공지된 방법에 의해서 제조가 가능하며, 본 발명의 금속막 식각액 조성물은 반도체 공정용의 순도를 가지는 것이 바람직하다.Each component used in the present invention can be prepared by a conventionally known method, and the metal film etchant composition of the present invention preferably has a purity for semiconductor processing.
이하에서, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나, 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다. 하기의 실시예는 본 발명의 범위 내에서 당업자에 의해 적절히 수정, 변경될 수 있다.Hereinafter, the present invention will be described in more detail through examples. However, the following examples are provided to explain the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
<< 실시예Example 및 and 비교예comparative example > > 금속막metal film 식각액etchant 조성물의 제조 Preparation of the composition
하기 표 1에 기재된 성분 및 잔량의 물을 해당 조성비로 혼합하여 실시예 및 비교예의 금속막 식각액 조성물 180㎏을 제조하였다.180 kg of metal film etchant compositions of Examples and Comparative Examples were prepared by mixing the components shown in Table 1 and the remaining amount of water in the corresponding composition ratio.
[표 1] [Table 1]
단위: 중량%Unit: % by weight
(주) ABF : ammonium bifluoride ; 5-MTZ : 5-Methyl-1H-tetrazole; IMZ: imidazole; IDA: iminodiacetic acid; AS : ammonium sulfate ; TEG : triethylene glycol ; 5-ATZ : 5-aminotetrazole ; TRZ : 1,2,4-Triazole ; PTZ : 5-Phenyl-1H-tetrazole ; MIMZ : 1-Methyl-1H-Imidazole(Note) ABF : ammonium bifluoride ; 5-MTZ: 5-Methyl-1H-tetrazole; IMZ: imidazole; IDA: iminodiacetic acid; AS: ammonium sulfate; TEG: triethylene glycol; 5-ATZ: 5-aminotetrazole; TRZ: 1,2,4-Triazole; PTZ: 5-Phenyl-1H-tetrazole; MIMZ: 1-Methyl-1H-Imidazole
<< 실험예Experimental example > > 식각etching 특성 확인 실험 Characterization test
실시예 1 내지 10, 비교예 1 내지 13의 금속막 식각액 조성물을 각각 사용하여 식각 공정을 실시하였다. 분사식 식각 방식의 실험장비(모델명: ETCHER(TFT), SEMES사)를 이용하였고, 식각 공정시 금속막 식각액 조성물의 온도는 약 32℃ 내외로 하였다. 식각 시간은 식각 온도에 따라서 다를 수 있으나, LCD 식각(Etching) 공정에서 통상 50 내지 80초 정도로 진행하였다. 상기 식각 공정에서 식각된 구리계 금속막의 프로파일을 단면 SEM(Hitachi사 제품, 모델명 S-4700)을 사용하여 검사하였고, 결과를 하기 표2에 기재하였다. 식각공정에 사용된 구리계 금속막의 경우 Cu/Mo-Ti 6500/100Å 박막 기판을 사용하였다. The etching process was performed using the metal film etchant compositions of Examples 1 to 10 and Comparative Examples 1 to 13, respectively. Experimental equipment (model name: ETCHER (TFT), SEMES Co., Ltd.) of the spray-type etching method was used, and the temperature of the metal film etchant composition during the etching process was about 32°C. The etching time may vary depending on the etching temperature, but in the LCD etching process, it was usually performed for about 50 to 80 seconds. The profile of the copper-based metal film etched in the etching process was inspected using a cross-sectional SEM (manufactured by Hitachi, model name S-4700), and the results are shown in Table 2 below. For the copper-based metal film used in the etching process, a Cu/Mo-Ti 6500/100 Å thin film substrate was used.
Cu 농도에 따른 사이드 엣치(Side etch)(㎛) 변화량을 측정하였다. 테이퍼 각(Taper angle)은 Cu 사면의 기울기, 사이드 엣치(Side etch)는 식각 후에 측정된 포토레지스트 끝단과 하부 금속 끝단 사이의 거리를 말한다. 사이드 엣치(Side etch) 량이 변화 하면, TFT 구동 시 신호 전달 속도가 변화하게 되어 얼룩이 발생 될 수 있기 때문에, 사이드 엣치(Side etch) 변화량은 최소화 되는 것이 바람직하다. 본 평가에서는 사이드 엣치(Side etch) 변화량이 ±0.1 ㎛, 테이퍼 각(Taper angle) 45~55˚, 테이퍼 각(Taper angle) 변화량이 최소 범위, 즉, 0에 가까운 조건이 충족되는 경우가 바람직하고, 금속막 식각액 조성물을 식각 공정에 사용할 수 있는 것으로 정하였다. 금속막이 식각 후에도 표면에 식각이 되지 않고 남아있는 잔사 측정 부분은 배선과 배선 사이를 SEM으로 측정하였고 측정 면적대비 잔사의 개수로 수준 정의를 하고 실험을 실시하였다.Side etch (μm) variation according to Cu concentration was measured. The taper angle refers to the slope of the Cu slope, and the side etch refers to the distance between the end of the photoresist and the end of the lower metal measured after etching. If the amount of side etch changes, the signal transfer speed changes during TFT driving, which may cause staining. Therefore, it is desirable that the amount of change in side etch be minimized. In this evaluation, it is preferable that the side etch variation is ±0.1 μm, the taper angle 45 to 55˚, and the taper angle variation is within the minimum range, that is, close to zero. , it was determined that the metal film etchant composition can be used in the etching process. After the metal film was etched, the residual measurement part that was not etched on the surface was measured by SEM between the wirings, and the level was defined by the number of residues compared to the measurement area, and an experiment was conducted.
[표 2][Table 2]
(주) ◎:매우좋음, ○: 좋음, △: 보통, Х: 나쁨, Un Etch: 식각불가(Note) ◎: Very good, ○: Good, △: Normal, Х: Bad, Un Etch: Not etched
[[ 식각속도etch rate 평가 기준] Evaluation standard]
◎: 매우좋음(160Å/sec ≤ 식각속도 ≤ 180Å/sec)◎: Very good (160Å/sec ≤ Etch rate ≤ 180Å/sec)
○: 좋음(140Å/sec ≤ 식각속도 < 160Å/sec, 180Å/sec < 식각속도 ≤ 200Å/sec)○: good (140Å/sec ≤ etch rate < 160 Å/sec, 180 Å/sec < etch rate ≤ 200 Å/sec)
△: 보통(110Å/sec ≤ 식각속도 < 140Å/sec, 200Å/sec < 식각속도 ≤ 230Å/sec)△: normal (110Å/sec ≤ etch rate < 140 Å/sec, 200 Å/sec < etch rate ≤ 230 Å/sec)
Х: 나쁨(식각속도 < 110Å/sec, 230Å/sec < 식각속도)Х: bad (etch rate < 110 Å/sec, 230 Å/sec < etch rate)
[[ 잔사residue 제거 평가 기준] Removal Evaluation Criteria]
◎: 매우좋음( 잔사 개수 = 0) ◎: Very good (Number of residues = 0)
○: 좋음( 잔사 개수 ≤ 1)○: good (number of residues ≤ 1)
△: 보통( 1< 잔사 개수 ≤5)△: normal ( 1 < number of residues ≤ 5)
Х: 나쁨( 5< 잔사 개수 ≤unetch)Х: bad ( 5< number of residues ≤unetch)
[[ 식각직진성Etching straightness 평가기준] Evaluation standard]
◎:매우좋음 , ○: 좋음, △: 보통, Х: 나쁨, Un Etch: 식각불가 ◎: Very good , ○: Good, △: Normal, Х: Bad, Un Etch: Not etched
[[ 사이드엣치side etch 변화량 평가기준] Change amount evaluation criteria]
◎: 매우좋음(사이드엣치 변화량 <0.05㎛)◎: Very good (side etch change <0.05㎛)
○: 좋음(0.05㎛≤사이드엣치 변화량<0.1㎛), ○: good (0.05㎛≤side etch change <0.1㎛),
△: 보통(0.1㎛≤사이드엣치 변화량<0.2㎛),△: Normal (0.1㎛≤Side etch change <0.2㎛),
Х: 나쁨(0.2㎛≤사이드엣치 변화량) Х: bad (0.2㎛≤side etch change)
[[ 테이퍼각taper angle 평가기준] Evaluation standard]
◎: 매우좋음(테이퍼각 변화량 <5˚, 테이퍼각 형성 45~55˚)◎: Very good (change amount of taper angle <5˚, formation of taper angle 45~55˚)
○: 좋음(5˚ ≤테이퍼각 변화량 <10˚, 테이퍼각 형성 45~55˚)○: good (5˚ ≤ taper angle change <10˚, taper angle formation 45~55˚)
△: 보통(10˚ ≤테이퍼각 변화량 <15˚, 테이퍼각 형성 40~60˚)△: Normal (10˚ ≤ taper angle change <15˚, taper angle formation 40~60˚)
Х: 나쁨(15˚≤ 테이퍼각 변화량, 테이퍼각 형성 <40˚, 60˚< 테이퍼각 형성)Х: Bad (15˚≤ taper angle change, taper angle formation <40˚, 60˚< taper angle formation)
표 2에서 알 수 있듯이 실시예 1 내지 8의 금속막 식각액 조성물은 모두 우수한 식각 특성을 나타내었다. 세부적으로 실시예 3의 금속막 식각액 조성물을 이용하여 구리계 박막 금속막하여 얻어진 식각 프로파일 및 직진성은 우수하였다. 또한 사이드 엣치(Side etch) 변화량 ±0.1 ㎛, 테이퍼 각(Taper angle) 49.3˚으로 45~55˚에 만족하고, 테이퍼 각(Taper angle) 변화량도 2.4˚로 최소인 조건에 충족함을 알 수 있다. 실시예 7의 경우는 실시예 3과 같이 사이드 엣치 변화량, 테이퍼 각, 테티퍼 각 변화량이 동등수준으로 우수하며, 다른 특성으로는 잔사 평가에서 실시예 3에 비해 잔사 제거에 매우 우수하였다. 실시예 9 내지 12의 경우 다른 종류의 알킬테트라졸계 화합물과 이미다졸계 화합물을 포함할 경우에도 사이드 엣치 변화량 및 테이퍼 각 변화량이 우수한 범위를 만족하였다. 특히, 5-Methyl-1H-tetrazole 과 Imidazole를 포함할 경우의 조성물이 가장 우수함을 확인 하였다. As can be seen from Table 2, the metal film etchant compositions of Examples 1 to 8 all exhibited excellent etching properties. In detail, the etching profile and straightness obtained by forming a copper-based thin metal film using the metal film etchant composition of Example 3 were excellent. In addition, it can be seen that the side etch change amount is ±0.1 ㎛, the taper angle is 49.3˚, which is 45~55˚, and the taper angle change is also satisfied with the minimum condition of 2.4˚. . In the case of Example 7, as in Example 3, the amount of change in the side etch, the taper angle, and the taper angle was excellent at the same level, and in other characteristics, it was very excellent in removing the residue compared to Example 3 in the residue evaluation. In Examples 9 to 12, even when other types of alkyltetrazole-based compounds and imidazole-based compounds were included, the amount of change in the side etch and the amount of change in the taper angle were within excellent ranges. In particular, it was confirmed that the composition containing 5-Methyl-1H-tetrazole and Imidazole was the best.
반면, 아졸화합물이 포함되지 않는 비교예 1의 경우 식각 속도가 매우 빨라 식각 프로파일이 매우 불량함을 알 수 있었다. 처리매수 변화량도 매우 크게 나타났으며, 테이퍼 각(Taper angle)도 65˚ 이상 수준을 나타내었다. 5-MTZ만을 포함하는 비교예 2의 경우 처리매수 변화량과 식각 프로파일은 정상적이나 테이퍼 각(Taper angle)이 55˚ 이상을 나타내었다. IMZ만을 포함한 비교예 3의 경우 식각 프로파일은 우수하였으나, 처리매수 변화량이 매우 컸으며, 테이퍼 각(Taper angle)도 60도 이상을 나타내었다. 아졸화합물 5-MTZ를 5-ATZ로 변경한 비교예 4의 경우 식각 프로파일은 우수하지만 처리매수 변화량이 크게 나타내었다. 비교예 5의 경우 처리매수 변화량과 테이퍼 각(Taper angle) 변화량 측면에서는 우수하나, 테이퍼 각(Taper angle)이 45~55˚를 만족하지 않았다. 비교예 6의 경우 처리매수 변화량은 0.1 이상이며, 테이퍼 각(Taper angle) 변화량 12.6˚로 크게 측정되었다. 비교예 7의 경우 Taper angle을 45~55˚를 만족시키지 못하고, 비교예 8의 경우는 처리매수 변화량, 테이퍼 각(Taper angle), 테이퍼 각(Taper angle) 변화량 모두 크게 나타내었다. 비교예 9의 경우 식각 속도가 느리고 테이퍼각도 매우 낮게 형성이 되었고 또한 처리매수 변화량도 우수하지 않았다. On the other hand, in the case of Comparative Example 1 in which the azole compound was not included, the etching rate was very high, and it was found that the etching profile was very poor. The amount of change in the number of treated sheets was also very large, and the taper angle was 65˚ or higher. In Comparative Example 2 including only 5-MTZ, the amount of change in the number of treatments and the etch profile were normal, but the taper angle was 55° or more. In Comparative Example 3 including only IMZ, the etching profile was excellent, but the amount of change in the number of treatments was very large, and the taper angle was more than 60 degrees. In Comparative Example 4 in which the azole compound 5-MTZ was changed to 5-ATZ, the etching profile was excellent, but the amount of change in the number of treatments was large. Comparative Example 5 was excellent in terms of the amount of change in the number of sheets to be treated and the amount of change in the taper angle, but the taper angle did not satisfy 45 to 55˚. In the case of Comparative Example 6, the amount of change in the number of treatment sheets was 0.1 or more, and the amount of change in the taper angle was measured to be 12.6˚. In the case of Comparative Example 7, the taper angle did not satisfy 45 to 55˚, and in the case of Comparative Example 8, the amount of change in the number of treatments, the taper angle, and the change in the taper angle were all large. In the case of Comparative Example 9, the etching rate was slow, the taper angle was formed very low, and the amount of change in the number of treatment sheets was not excellent.
Claims (17)
A) 과산화수소(H2O2) 15 내지 25 중량 %;
B) 함 불소 화합물 0.01 내지 3.0 중량%;
C) 알킬 테트라졸계 화합물 0.05 내지 3.0 중량%;
D) 이미다졸계 화합물 0.05 내지 3.0 중량%;
E) 한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물 0.5 내지 5.0 중량%;
F) 황산염 화합물 0.05 내지 5.0 중량%;
G) 다가알코올형 계면 활성제 1.0 내지 5.0 중량%; 및
H) 잔량의 물을 포함하며,
상기 C)알킬 테트라졸계 화합물은 5-메틸-1H-테트라졸(5-Methyl-1H-tetrazole), 5-페닐-1H-테트라졸(5-Phenyl-1H-tetrazole), 5-벤질-1H-테트라졸(5-Benzyl-1H-tetrazole), 5-머캅토-1메틸테트라졸(5-Mercapto-1-methyltetrazole) 및 1-메틸-1H-테트라졸(1-Methyl-1H-tetrazole) 으로 이루어진 군에서 선택되는 1종 이상이며,
C)알킬 테트라졸계 화합물 및 D)이미다졸계 화합물은 1:20 내지 20:1의 비율로 포함되는 것을 특징으로 하는, 금속막 식각액 조성물.with respect to the total weight of the composition,
A) 15 to 25% by weight of hydrogen peroxide (H 2 O 2 );
B) 0.01 to 3.0 wt% of a fluorine-containing compound;
C) 0.05 to 3.0 wt% of an alkyl tetrazole-based compound;
D) 0.05 to 3.0 wt% of an imidazole-based compound;
E) 0.5 to 5.0 wt% of a water-soluble compound having a nitrogen atom and a carboxyl group in one molecule;
F) 0.05 to 5.0% by weight of a sulfate compound;
G) 1.0 to 5.0 wt% of a polyalcohol-type surfactant; and
H) the balance of water,
The C) alkyl tetrazole compound is 5-methyl-1H-tetrazole (5-Methyl-1H-tetrazole), 5-phenyl-1H-tetrazole (5-Phenyl-1H-tetrazole), 5-benzyl-1H- consisting of tetrazole (5-Benzyl-1H-tetrazole), 5-mercapto-1methyltetrazole (5-Mercapto-1-methyltetrazole) and 1-methyl-1H-tetrazole (1-Methyl-1H-tetrazole) It is at least one selected from the group,
C) The alkyl tetrazole-based compound and D) the imidazole-based compound are included in a ratio of 1:20 to 20:1, the metal film etchant composition.
b) 상기 게이트 전극을 포함한 기판 상에 게이트 절연층을 형성하는 단계;
c) 상기 게이트 절연층 상에 반도체 층을 형성하는 단계;
d) 상기 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및
e) 상기 드레인 전극에 연결된 화소 전극을 형성하는 단계를 포함하는 표시 장치용 어레이 기판의 제조방법에 있어서,
상기 a) 단계는 기판상에 금속막을 형성하고 상기 금속막을 금속막의 식각액 조성물로 식각하여 게이트 배선을 형성하는 단계를 포함하고,
상기 d) 단계는 금속막을 형성하고 상기 금속막을 금속막의 식각액 조성물로 식각하여 소스 및 드레인 전극을 형성하는 단계를 포함하고,
상기 금속막의 식각액 조성물은, 제 1항, 제 2항, 제 4항 내지 제 9항, 제 11항 및 제 12항 중 어느 한항의 금속막 식각액 조성물인, 표시장치용 어레이 기판의 제조방법.
a) forming a gate electrode on the substrate;
b) forming a gate insulating layer on the substrate including the gate electrode;
c) forming a semiconductor layer on the gate insulating layer;
d) forming source and drain electrodes on the semiconductor layer; and
In the method of manufacturing an array substrate for a display device comprising the step of e) forming a pixel electrode connected to the drain electrode,
Step a) includes forming a metal film on a substrate and etching the metal film with an etchant composition of the metal film to form a gate wiring,
Step d) comprises forming a metal film and etching the metal film with an etchant composition of the metal film to form source and drain electrodes,
The metal film etchant composition is the metal film etchant composition of any one of claims 1, 2, 4 to 9, 11 and 12, a method of manufacturing an array substrate for a display device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710585309.5A CN107630219B (en) | 2016-07-19 | 2017-07-18 | Metal film etching solution composition and method for manufacturing array substrate for display device |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160091531 | 2016-07-19 | ||
| KR20160091531 | 2016-07-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20180009687A KR20180009687A (en) | 2018-01-29 |
| KR102400343B1 true KR102400343B1 (en) | 2022-05-23 |
Family
ID=61028405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020170035892A KR102400343B1 (en) | 2016-07-19 | 2017-03-22 | Metal film etchant composition and manufacturing method of an array substrate for display device |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR102400343B1 (en) |
| CN (1) | CN107630219B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102459688B1 (en) * | 2018-02-13 | 2022-10-27 | 동우 화인켐 주식회사 | Etchant composition for silver thin layer and ehting method and mehtod for fabrication metal pattern using the same |
| KR102494016B1 (en) * | 2019-02-28 | 2023-02-01 | 주식회사 이엔에프테크놀로지 | Metal layer etchant composition |
| CN111748818B (en) * | 2020-06-30 | 2022-04-26 | 中国航发动力股份有限公司 | Solution and method for quickly removing nickel-cadmium diffusion layer on surface of structural steel |
| CN112080747B (en) * | 2020-09-02 | 2021-10-08 | Tcl华星光电技术有限公司 | Etching solution composition for etching molybdenum/copper/molybdenum or molybdenum alloy/copper/molybdenum alloy three-layer metal wiring structure and application thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070055259A (en) | 2005-11-25 | 2007-05-30 | 동우 화인켐 주식회사 | Etching solution of cu/ mo-alloy film and etching method thereof |
| KR101310310B1 (en) * | 2007-03-15 | 2013-09-23 | 주식회사 동진쎄미켐 | Etchant for thin film transistor-liquid crystal displays |
| KR101346976B1 (en) * | 2008-02-12 | 2014-01-03 | 동우 화인켐 주식회사 | Fabrication method of thin film transistor, etching solution composition used the method |
| US8088246B2 (en) * | 2009-01-08 | 2012-01-03 | Cordani Jr John L | Process for improving the adhesion of polymeric materials to metal surfaces |
| CN102472938B (en) * | 2009-07-23 | 2016-03-30 | 东友精细化工有限公司 | The manufacture method of array substrate for liquid crystal display device |
| CN102102206A (en) * | 2009-12-18 | 2011-06-22 | 鑫林科技股份有限公司 | Metal etching liquid composition and etching method |
| KR20140084417A (en) * | 2012-12-26 | 2014-07-07 | 동우 화인켐 주식회사 | Echaing composition for preparing a channel of thin film transistor and method of preparing a channel of thin film transistor |
| KR101960342B1 (en) * | 2013-02-28 | 2019-03-21 | 동우 화인켐 주식회사 | Echaing composition, method of preparing metal line and method of manufacturing array substrate using the same |
| KR20150035624A (en) * | 2013-09-27 | 2015-04-07 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for liquid crystal display |
| KR102279498B1 (en) * | 2013-10-18 | 2021-07-21 | 주식회사 동진쎄미켐 | Etchant composition for metal wire and method for preparing metal wire using the same |
| KR102160286B1 (en) * | 2013-11-04 | 2020-09-28 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for liquid crystal display |
-
2017
- 2017-03-22 KR KR1020170035892A patent/KR102400343B1/en active IP Right Grant
- 2017-07-18 CN CN201710585309.5A patent/CN107630219B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107630219B (en) | 2020-01-24 |
| CN107630219A (en) | 2018-01-26 |
| KR20180009687A (en) | 2018-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI524428B (en) | Method of fabricating array substrate for liquid crystal display | |
| KR102400343B1 (en) | Metal film etchant composition and manufacturing method of an array substrate for display device | |
| KR102137013B1 (en) | Manufacturing method of an array substrate for display device | |
| KR20120140481A (en) | Etchant for metal interconnects and method for preparing liquid crystal display devices using the same | |
| KR20230141720A (en) | Etching composition and etching method using the same | |
| KR102269327B1 (en) | Etchant composition and manufacturing method of an array for liquid crystal display | |
| TWI614550B (en) | Manufacturing method of array substrate for liquid crystal display and etching liquid compositions for multi film thereof | |
| KR102619627B1 (en) | Etching composition and etching method using the same | |
| KR20180077610A (en) | Metal film etchant composition manufacturing method of an array substrate for display device | |
| KR101560000B1 (en) | Manufacturing method of an array substrate for liquid crystal display | |
| CN103107130A (en) | Array substrate for liquid crystal display and manufacturing method thereof, etching liquid composition and method for forming metal routing | |
| KR101941289B1 (en) | Manufacturing method of an array substrate for liquid crystal display | |
| TWI673344B (en) | Etching solution composition for indium oxide layer and method for manufacturing array substrate for liquid crystal display device using the same | |
| KR102505196B1 (en) | Etchant composition for copper-containing metal layer and preparing method of an array substrate for liquid crystal display using same | |
| KR102282958B1 (en) | Etchant composition and manufacturing method of an array for liquid crystal display | |
| KR102459685B1 (en) | Etchant for cupper-based metat layer, manufacturing method of an array substrate for display using the same and an array substrate for display | |
| CN111755461A (en) | Method for manufacturing array substrate for liquid crystal display device and copper-based metal film etching solution composition used for same | |
| KR102459681B1 (en) | Etchant for cupper-based metat layer, manufacturing method of an array substrate for liquid crystal display using the same and an array substrate for liquid crystal display | |
| KR102265889B1 (en) | Etchant composition and manufacturing method of an array for liquid crystal display | |
| KR102282957B1 (en) | Etchant composition and manufacturing method of an array for liquid crystal display | |
| KR20130018531A (en) | Manufacturing method of an array substrate for liquid crystal display | |
| TWI840532B (en) | Etching composition and etching method using the same | |
| KR102368356B1 (en) | Etchant composition and manufacturing method of an array for liquid crystal display | |
| KR102368974B1 (en) | Etching solution composition, manufacturing method of an array substrate for display device using the same | |
| KR101845084B1 (en) | Manufacturing method of an array substrate for liquid crystal display |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| AMND | Amendment | ||
| E601 | Decision to refuse application | ||
| X091 | Application refused [patent] | ||
| AMND | Amendment | ||
| X701 | Decision to grant (after re-examination) | ||
| GRNT | Written decision to grant |