KR20180070474A - Etchant composition for metal wire - Google Patents
Etchant composition for metal wire Download PDFInfo
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- KR20180070474A KR20180070474A KR1020170170597A KR20170170597A KR20180070474A KR 20180070474 A KR20180070474 A KR 20180070474A KR 1020170170597 A KR1020170170597 A KR 1020170170597A KR 20170170597 A KR20170170597 A KR 20170170597A KR 20180070474 A KR20180070474 A KR 20180070474A
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- South Korea
- Prior art keywords
- compound
- group
- alloy
- copper
- film
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 57
- 239000002184 metal Substances 0.000 title claims abstract description 57
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 238000005530 etching Methods 0.000 claims abstract description 57
- -1 alcohol compound Chemical class 0.000 claims abstract description 54
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 125000003277 amino group Chemical group 0.000 claims abstract description 19
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 30
- 229910052802 copper Inorganic materials 0.000 claims description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 23
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 20
- 239000010936 titanium Substances 0.000 claims description 14
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 239000011733 molybdenum Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 10
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 9
- 150000002222 fluorine compounds Chemical class 0.000 claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 5
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 4
- 150000003467 sulfuric acid derivatives Chemical class 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
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 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
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 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
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- PFURGBBHAOXLIO-WDSKDSINSA-N cyclohexane-1,2-diol Chemical compound O[C@H]1CCCC[C@@H]1O PFURGBBHAOXLIO-WDSKDSINSA-N 0.000 claims description 2
- VKONPUDBRVKQLM-UHFFFAOYSA-N cyclohexane-1,4-diol Chemical compound OC1CCC(O)CC1 VKONPUDBRVKQLM-UHFFFAOYSA-N 0.000 claims description 2
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 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
- NGVNAUIRSOXAJB-UHFFFAOYSA-N prop-1-ene-1,2-diol Chemical compound CC(O)=CO NGVNAUIRSOXAJB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 229960002317 succinimide Drugs 0.000 claims description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims 2
- 150000000180 1,2-diols Chemical class 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 50
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 239000010409 thin film Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 34
- 238000011282 treatment Methods 0.000 description 11
- 230000008859 change Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 230000003679 aging effect Effects 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- MFEWNFVBWPABCX-UHFFFAOYSA-N 1,1,2,2-tetraphenylethane-1,2-diol Chemical compound C=1C=CC=CC=1C(C(O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(O)C1=CC=CC=C1 MFEWNFVBWPABCX-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-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
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- 125000002373 5 membered heterocyclic group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 206010020710 Hyperphagia Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RPJKYODNJDVOOO-UHFFFAOYSA-N [B].F Chemical compound [B].F RPJKYODNJDVOOO-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical compound [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- UYDJAHJCGZTTHB-UHFFFAOYSA-N cyclopentane-1,1-diol Chemical compound OC1(O)CCCC1 UYDJAHJCGZTTHB-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- IHPDTPWNFBQHEB-UHFFFAOYSA-N hydrobenzoin Chemical compound C=1C=CC=CC=1C(O)C(O)C1=CC=CC=C1 IHPDTPWNFBQHEB-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 235000020830 overeating Nutrition 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical class O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
-
- 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
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/067—Etchants
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Ceramic Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
- Weting (AREA)
- ing And Chemical Polishing (AREA)
Abstract
Description
본 발명은 금속 배선 식각액 조성물에 관한 것으로서, 더욱 상세하게는 금속막을 식각하여, 반도체 회로를 구성하는 박막 트랜지스터의 게이트 및 소스-드레인 영역을 형성하는 금속 배선 식각액 조성물에 관한 것이다.The present invention relates to a metal wiring etchant composition, and more particularly, to a metal wiring etchant composition which forms a gate and a source-drain region of a thin film transistor constituting a semiconductor circuit by etching a metal film.
액정표시장치(LCD) 등 디스플레이 산업에서 패널의 고품질화, 고화질화 및 대면적화에 따라, 액정표시장치(LCD) 패널의 응답속도를 증가시킬 필요가 있다. 이를 위하여, 디스플레이 패널의 반도체 회로를 구성하는 박막 트랜지스터(Thin film Transistor, TFT)의 게이트(Gate) 및 소스-드레인(Source Drain, S/D) 영역을, 종래의 크롬, 알루미늄 및 이들의 합금이 아닌, 저항이 낮은 구리 금속으로 형성함으로서, 게이트 전극 작동 시, 소스 드레인 사이의 채널 형성 속도를 증가시키는 방법이 사용되고 있다. 또한, 상기 구리 금속막과 하부의 유리 기판 또는 실리콘 절연막과의 접착력을 향상시키고, 실리콘 막으로의 구리 확산을 억제하기 위하여, 상기 구리 금속막의 하부에, 티타늄(Ti), 몰리브데늄(Mo), 티타늄 합금(Ti-alloy), 몰리브데늄 합금(Mo-alloy) 등의 중간 금속막을 혼용하고 있는데, 이와 같은 경우, 상기 중간 금속막의 두께에 따라 전자의 이동속도를 변화시킬 수 있기 때문에, 전자의 이동속도를 제어할 수 있는 장점이 있다. 또한, 상기 중간 금속막의 잔사를 제거하여, 후속 모듈 공정 시 배선의 합선으로 인한 구동 불량 등을 차단할 수 있어야 한다. 상기 금속막을 식각하여 금속 배선을 형성하는 식각액 조성물은 공정 마진을 극대화 하기 위하여, 식각된 금속 배선의 식각 프로파일이 우수하고, 기판의 처리 매수(경시성)가 많아야 한다. 따라서, 이러한 조건을 충족시킬 수 있고, 종래의 생산 수율(3,000 ppm)보다 우수한 조성물이 요구되고 있다.It is necessary to increase the response speed of the liquid crystal display (LCD) panel in accordance with the high quality, high image quality and large size of the panel in the display industry such as the liquid crystal display (LCD). For this purpose, the gate and source drain (S / D) regions of a thin film transistor (TFT) constituting a semiconductor circuit of a display panel are made of chromium, aluminum, A method of increasing the channel formation speed between the source and the drain in the operation of the gate electrode is used. In order to improve the adhesion between the copper metal film and the lower glass substrate or the silicon insulating film and to suppress copper diffusion into the silicon film, titanium (Ti), molybdenum (Mo) , A titanium alloy (Ti-alloy), and a molybdenum alloy (Mo-alloy). In this case, since the moving speed of electrons can be changed according to the thickness of the intermediate metal film, It is possible to control the moving speed of the motor. In addition, it is necessary to remove the residue of the intermediate metal film so as to block the driving failure due to the short circuit of the wiring in the subsequent module process. In order to maximize the process margin, the etching composition for forming the metal wiring by etching the metal film must have an excellent etching profile of the etched metal wiring and a large number of substrates to be processed (aging property). Therefore, there is a demand for a composition which can satisfy such a condition and is superior to the conventional production yield (3,000 ppm).
따라서, 본 발명의 목적은 식각 프로파일이 우수한 금속 배선 식각액 조성물을 제공하는 것이다. 본 발명의 다른 목적은 기판의 처리 매수(경시성)가 향상된 금속 배선 식각액 조성물을 제공하는 것이다.Accordingly, an object of the present invention is to provide a metal wiring etchant composition having an excellent etching profile. Another object of the present invention is to provide a metal wiring etchant composition improved in the number of processed substrates (aging property).
상기 목적을 달성하기 위하여, 본 발명은 산화제; 2가 알코올 화합물; 아미노기를 포함하지 않는 아졸계 화합물; 아민 화합물; 황산염 화합물, 불소계 화합물 및 이들의 혼합물로 이루어진 군으로부터 선택되는 화합물을 하나 이상 포함하는 식각제; 및 물;을 포함하는 금속 배선 식각액 조성물을 제공한다.In order to achieve the above object, Divalent alcohol compounds; An azole-based compound containing no amino group; Amine compounds; An etchant comprising at least one compound selected from the group consisting of sulfate compounds, fluorine compounds, and mixtures thereof; And water. The present invention provides a metal wiring etchant composition comprising:
또한, 본 발명은 산화제; 2가 알코올 화합물; 아미노기를 포함하지 않는 아졸계 화합물; 아민 화합물; 황산염 화합물, 불소계 화합물 및 이들의 혼합물로 이루어진 군으로부터 선택되는 화합물을 하나 이상 포함하는 식각제; 및 물; 을 포함하는 금속 배선 식각액 조성물을 제공한다.The present invention also relates to an oxidizing agent; Divalent alcohol compounds; An azole-based compound containing no amino group; Amine compounds; An etchant comprising at least one compound selected from the group consisting of sulfate compounds, fluorine compounds, and mixtures thereof; And water; Wherein the metal wiring etchant composition comprises:
본 발명에 따른 금속 배선 식각액 조성물은 구리/몰리브데늄 또는 티타늄 및 구리합금/몰리브데늄 합금의 이중막 및 다중막을 선택적으로 식각하여야 하는 구리 금속막의 배선 형성에 있어서, 빠른 식각 공정과 우수한 테이퍼 식각 프로파일을 얻을 수 있다. 또한, 식각액의 경시성을 향상시키기 위하여, 식각액을 구리이온으로부터 안정화 시켜, 생산 수율을 향상시킬 수 있다.The metal wiring etchant composition according to the present invention can be used for forming a wiring of a copper metal film which is to selectively etch a double film and a multiple film of copper / molybdenum or titanium and a copper alloy / molybdenum alloy, A profile can be obtained. Further, in order to improve the aging property of the etching solution, the etching yield can be improved by stabilizing the etching solution from the copper ions.
도 1은 식각 후 단면을 측정한 주사전자현미경 사진.1 is a scanning electron microscope photograph of a section after etching.
이하, 첨부된 도면을 참조하여 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.
본 발명에 따른 금속 배선 식각액 조성물은, 구리(Cu), 티타늄(Ti), 몰리브데늄(Mo), 구리 합금(Cu-alloy), 티타늄 합금(Ti-alloy) 및 몰리브데늄 합금(Mo-alloy) 등의 금속막을 식각하여, 반도체 회로의 금속 배선, 예를 들면, 박막 트랜지스터의 게이트 전극 및 소스-드레인 전극을 형성하는 조성물로서, 산화제, 아민 화합물, 2가 알코올 화합물, 아미노기를 포함하지 않는 아졸계 화합물, 및 물을 포함한다.The metal wiring etchant composition according to the present invention may further comprise at least one selected from the group consisting of copper (Cu), titanium (Ti), molybdenum (Mo), copper alloy, titanium alloy and molybdenum alloy (Mo- alloy or the like is etched to form a metal wiring of a semiconductor circuit, for example, a gate electrode and a source-drain electrode of a thin-film transistor. The composition includes an oxidizing agent, an amine compound, a divalent alcohol compound, An azole-based compound, and water.
상기 산화제는 금속막을 산화시키는 역할을 하는 것으로서, 구체적으로는 과산화수소(H2O2)를 사용할 수 있고, 예를 들면, 하기 반응식 1에 따라 구리(Cu)를 포함하는 금속막을 산화 및 식각하며, 하기 반응식 2에 따라, 과수분해 반응이 일어난다. 상기 산화제(과산화수소)의 함량은 전체 식각액 조성물에 대하여, 5 내지 25 중량%, 구체적으로는 10 내지 25 중량%, 더욱 구체적으로는 20 내지 25 중량%이다. 상기 산화제의 함량 범위 내에서는 목적하는 식각 속도를 얻을 수 있고, 과도하게 식각되지 않아 적정량으로 구리 금속막을 식각할 수 있다.Specifically, hydrogen peroxide (H 2 O 2 ) can be used. For example, a metal film containing copper (Cu) is oxidized and etched according to the following reaction formula 1, According to the following reaction formula 2, a hydrolysis reaction takes place. The content of the oxidizing agent (hydrogen peroxide) is 5 to 25% by weight, specifically 10 to 25% by weight, more specifically 20 to 25% by weight, based on the entire etchant composition. The desired etching rate can be obtained within the range of the content of the oxidizing agent, and the copper metal film can be etched at a proper amount because it is not excessively etched.
[반응식 1][Reaction Scheme 1]
M + H2O2 → MO + H2OM + H 2 O 2 - > MO + H 2 O
[반응식 2][Reaction Scheme 2]
H2O2 + M+ → ·OH + OH- + M2+ H 2 O 2 + M + - OH + OH - + M 2+
상기 반응식 1 및 2에서, M는 구리, 티타늄, 몰리브데늄, 구리 합금, 티타늄 합금 및 몰리브데늄 합금 등의 금속막을 의미한다.In the above Schemes 1 and 2, M means a metal film such as copper, titanium, molybdenum, a copper alloy, a titanium alloy, and a molybdenum alloy.
상기 아민 화합물은, 구리 금속의 식각시 2가 구리 이온과 리간드 결합을 함으로서(메탈 이온과의 배위결합), 구리 이온을 킬레이팅(chelating)하여, 구리 이온을 안정화시켜 식각 능력을 향상시키고, 처리 매수를 증가시키는 역할을 한다. 상기 아민 화합물은 예를 들면, 수용성 리간드제로서, 숙신산(succinic acid), 숙신이미드(succinimide), 이미노디아세트산(Iminodiacetic acid), 이미노디숙신산(Iminodisuccinic acid) 또는 이들의 혼합물 등이고, 구체적으로는 이미노디아세트산을 예시할 수 있다. 상기 아민 화합물의 함량은, 식각액 전체에 대하여, 0.01 내지 5 중량%, 구체적으로는 0.1 내지 3 중량%, 더욱 구체적으로는 2 내지 3 중량%이다. 상기 아민 화합물의 함량이 상기 범위 내에 있으면, 구리 이온을 안정화시킬 수 있어, 식각 능력을 향상시킬 수 있다.The amine compound can be prepared by chelating copper ions by ligand bonding with divalent copper ions (coordination bonding with metal ions) during etching of copper metal, stabilizing copper ions to improve etching ability, It increases the number of buyers. The amine compound may be, for example, succinic acid, succinimide, iminodiacetic acid, iminodisuccinic acid, or a mixture thereof, for example, as a water-soluble ligand agent, Iminodiacetic acid can be exemplified. The content of the amine compound is 0.01 to 5% by weight, specifically 0.1 to 3% by weight, more specifically 2 to 3% by weight, based on the whole etching solution. When the content of the amine compound is within the above range, the copper ion can be stabilized and the etching ability can be improved.
상기 2가 알코올 화합물은 식각액 내에서 산화제(과산화수소)를 안정화시키는 안정제의 역할을 하여 약액의 수명을 증가시키는 것으로서, 예를 들면, 종래의 알칼리 메탈의 오염 농도가 3,000 내지 4,000 ppm인 것을 7,000 ppm까지 수명을 증가시킬 수 있다. 상기 2가 알코올 화합물의 메커니즘을 간략하게 설명하면, 처리 매수가 증가함에 따라, 금속 오염 농도가 비례하여 증가하고, 알칼리 메탈(예를 들면 Cu2 + 등)에 의해 과산화수소의 라디칼 분해가 발생되는데, 상기 알칼리 메탈이 과잉 존재할 경우, 과산화수소와 지속적으로 반응하여 분해시키게 되고, 이는 과산화수소를 급속히 분해시키는 요인으로 작용하여, 발열 및 폭발 등의 위험 요인이 될 수 있기 때문에, 2가 알코올 화합물을 사용하여, 상기 알칼리 메탈이 과잉으로 존재하더라도, 정전기적으로 안정화시켜 과산화수소와 반응하는 것을 방지하여 생산 공정의 수율을 향상시킬 수 있다. 또한, 상기 2가 알코올 화합물은 EPD(End point detect), CD-Bias, Taper angle 등의 에칭 특성에 영향이 적기 때문에 이용가능하며, 1가 알코올 또는 3가 알코올 등을 사용하면 상기 에칭 특성에 영향을 끼칠 수 있는, 즉 변동성이 크기 때문에 이용이 어렵다.The divalent alcohol compound acts as a stabilizer for stabilizing the oxidizing agent (hydrogen peroxide) in the etching solution to increase the lifetime of the chemical solution. For example, when the contaminant concentration of the conventional alkali metal is 3,000 to 4,000 ppm, The life can be increased. The mechanism of the above-mentioned dihydric alcohol compound will be briefly described. As the number of treatments increases, the concentration of metal contaminant increases proportionally and radical decomposition of hydrogen peroxide occurs with an alkali metal (for example, Cu 2 + ). When the alkali metal is excessively present, the alkali metal is continuously reacted with the hydrogen peroxide to decompose, which acts as a factor for rapidly decomposing hydrogen peroxide, which may be a risk factor for generation of heat and explosion. Therefore, Even if the alkali metal is excessively present, it can be stabilized electrostatically to prevent it from reacting with hydrogen peroxide, thereby improving the yield of the production process. Further, the divalent alcohol compound can be used because it has little influence on etching characteristics such as EPD (End Point Detect), CD-Bias and Taper angle. When a monohydric alcohol or a trihydric alcohol is used, , That is, it is difficult to use because of its large variability.
상기 2가 알코올 화합물은 글리콜 화합물, 구체적으로는 1,2-에탄디올(1,2-ethanediol), 디에틸렌글리콜(Diethyleneglycol), 프로페인-1,2-다이올(propein-1,2-diol), 트리에틸렌글리콜(Triethyleneglycol), 트리메틸렌글리콜(Trimethyleneglycol), 1,3-프로판다이올(1,3-propanediol), 프로필렌글리콜, 1,4-부탄디올, 1,5-펜탄디올, 1,6-헥산디올, 1,7-헵탄디올, 1,8-옥탄디올, 1,9-노난디올, 1,10-데칸디올, 피나콜, 히드로벤조인, 벤즈피나콜, 시클로펜탄-1,2-디올, 시클로헥산-1,2-디올, 시클로헥산-1,4-디올 또는 이들의 혼합물 등이고, 더욱 구체적으로는 디에틸렌글리콜(DEG)이다. 상기 2가 알코올 화합물의 함량은, 식각액 전체에 대하여, 0.1 내지 10 중량%, 구체적으로는 1 내지 7 중량%, 더욱 구체적으로는 1 내지 5 중량%이다. 상기 2가 알코올 화합물의 함량이 상기 범위를 벗어나면, 생산 공정의 수율을 향상시키고자 하는 효과가 발생되지 않을 수 있다.The dihydric alcohol compound is a glycol compound, specifically, 1,2-ethanediol, diethyleneglycol, propene-1,2-diol ), Triethyleneglycol, trimethyleneglycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6 Hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, pinacol, hydrobenzoin, benzpinacol, cyclopentane- Diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol or a mixture thereof, and more specifically diethylene glycol (DEG). The content of the dihydric alcohol compound is 0.1 to 10% by weight, specifically 1 to 7% by weight, more specifically 1 to 5% by weight, based on the whole etching solution. If the content of the dihydric alcohol compound is out of the above range, the effect of improving the yield of the production process may not be generated.
상기 아미노기를 포함하지 않는 아졸계 화합물(고리형 아민 화합물)은, 구리를 포함하는 금속층의 상부 및 하부에 구리와 다른 금속층이 형성된 다층막에서 상기 구리와 다른 금속(예를 들면, 티타늄, 몰리브데늄, 티타늄 합금, 몰리브데늄 합금 등)사이의 식각 속도를 조절하는 역할을 한다. 또한, 상기 아졸계 화합물은, 식각에 의해 형성되는 금속 배선의 컷 디멘션 손실(cut dimension loss, CD loss)을 줄임으로서, 형성된 금속 배선이 게이트 및 데이터 배선으로 유용하게 사용될 수 있도록 한다. 상기 아졸계 화합물은 질소 원자를 포함하는 5원 헤테로고리(5-membered heterocyclic ring) 화합물로서, 예를 들면, 메틸테트라졸(5-methyltetrazole_MTZ), 벤조트리아졸(benzotriazole), 이미다졸(imidazole), 피라졸(pyrazole), 톨리트리아졸(tolytriazole) 또는 이들의 혼합물 등, 구체적으로는 메틸테트라졸이다. 또한, 상기 아졸계 화합물은 아미노기를 포함하지 않는다. 아졸계 화합물이 아미노기를 포함할 경우, 메탈 이온(Cu2 + 등)과의 반응으로 분해되어, 식각 억제제로서의 수명이 짧아지거나 불안정할 수 있기 때문에, 상기 아졸계 화합물은 아미노기를 포함하지 않아, 상기 메탈 이온과의 반응이 발생되지 않고, 그에 따라 식각 억제제로서의 수명을 향상시킬 수 있으며, 안정성이 우수하다.The azole compound (cyclic amine compound) that does not contain an amino group can be obtained by reacting the copper and another metal (for example, titanium, molybdenum and the like) in a multilayered film in which copper and another metal layer are formed on upper and lower portions of the metal layer containing copper , Titanium alloy, molybdenum alloy, etc.). In addition, the azole-based compound reduces the cut dimension loss (CD loss) of metal wiring formed by etching, so that the formed metal wiring can be usefully used as a gate and a data wiring. The azole-based compound is a 5-membered heterocyclic ring compound containing a nitrogen atom, for example, 5-methyltetrazole_MTZ, benzotriazole, imidazole, Pyrazole, tolytriazole, or a mixture thereof, and specifically methyltetrazole. In addition, the azole-based compound does not contain an amino group. When the azole-based compound contains an amino group, the azole-based compound does not contain an amino group and can be decomposed by reaction with a metal ion (Cu 2 + or the like) so that the lifetime as an etching inhibitor may be shortened or unstable. The reaction with the metal ion does not occur, thereby improving the lifetime of the etching inhibitor and providing excellent stability.
상기 아미노기를 포함하지 않는 아졸계 화합물의 함량은, 식각액 전체에 대하여, 0.01 내지 1.5 중량%, 구체적으로는 0.05 내지 1.0 중량%, 더욱 구체적으로는 0.08 내지 0.7 중량%이다. 상기 아미노기를 포함하지 않는 아졸계 화합물의 함량이 상기 범위 내에 포함되면, 적절한 식각 속도 및 우수한 배선의 직진성을 얻을 수 있다. 또한, 너무 적게 포함되면, 구리의 식각 속도를 조절할 수 없어 과도한 식각이 일어나거나, CD 손실이 커질 수 있으며, 배선의 직진성이 저하되어 양산 공정 적용 시 심각한 물제를 일으킬 수도 있고, 형성된 금속 배선의 식각 프로파일이 불량해질 우려가 있으며, 너무 많으면, 식각 속도가 저하되어 식각 공정의 시간이 길어질 수 있다.The content of the azole compound not containing an amino group is 0.01 to 1.5% by weight, specifically 0.05 to 1.0% by weight, more specifically 0.08 to 0.7% by weight, based on the whole etching solution. When the content of the azole compound not containing an amino group is within the above range, an appropriate etching rate and excellent linearity of wiring can be obtained. In addition, if the etching rate is too small, the etching rate of copper can not be controlled, excessive etching may occur, CD loss may be large, and the straightness of the wiring may be deteriorated, The profile may become poor, and if it is too much, the etching rate may be lowered and the etching process may take longer time.
상기, 금속 배선 식각액 조성물은 황산염 화합물, 불소계 화합물 및 이들의 혼합물로 이루어진 군으로부터 선택되는 화합물을 하나 이상 포함하는 식각제를 더 포함할 수 있다.The metal line etchant composition may further include an etchant containing at least one compound selected from the group consisting of a sulfate compound, a fluorine compound, and a mixture thereof.
상기 식각제는 구리 금속막의 보조 산화제로서, 구리의 식각 속도를 조절하는 역할을 하거나, 금속막의 배리어(barrier) 막인 티타늄, 몰리브덴늄, 티타늄 합금, 몰리브덴늄 합금의 식각시, 이중막 또는 다중막에서 테이퍼 각을 형성시키는 역할을 하는 것으로서, 황산염 화합물, 불소계 화합물 및 이들의 혼합물을 하나 이상, 구체적으로는 황산염 화합물 및 불소계 화합물을 동시에 포함한다.The etchant is a co-oxidant of a copper metal film. The etchant serves to control the etching rate of copper. In etching a titanium, molybdenum, titanium alloy or molybdenum alloy, which is a barrier film of a metal film, Which serves to form a taper angle, and contains at least one of a sulfate compound, a fluorine compound and a mixture thereof, concretely, a sulfate compound and a fluorine compound at the same time.
상기 황산염 화합물은 구리 금속막의 보조 산화제로서, 구리의 식각 속도를 조절하는 역할을 하는 것으로서, 예를 들면, 황산나트륨(sodium sulfate), 황산칼륨(potassium sulfate), 황산암모늄(ammonium sulfate), 과황산나트륨(sodium persulfate), 과황산칼륨(potassium persulfate), 과황산암모늄(ammonium persulfate), 질산 암모늄(ammonium nitrate), 벤젠술폰산(benzenesulfonic acid), p-톨루엔술폰산(p-toluenesulfonate), 암모늄술폰산(ammonium sulfate acid), 아미도술폰산(amidosulfonic acid), 메탄술폰산(methanesulfonic acid), 고리형 술폰산화합물(cyclic sulfonic acid), 탄화수소계 술폰산화합물 또는 이들의 혼합물 등일 수 있고, 구체적으로는 메탄술폰산이다.The sulphate compound serves as a co-oxidant for the copper metal film and serves to control the etching rate of copper. Examples of the sulphate compound include sodium sulfate, potassium sulfate, ammonium sulfate, sodium persulfate sodium persulfate, potassium persulfate, ammonium persulfate, ammonium nitrate, benzenesulfonic acid, p-toluenesulfonate, ammonium sulfate ), Amidosulfonic acid, methanesulfonic acid, cyclic sulfonic acid, hydrocarbon-based sulfonic acid compound or a mixture thereof, and specifically, it is methanesulfonic acid.
상기 불소계 화합물은, 금속막의 배리어(barrier) 막인 티타늄, 몰리브덴늄, 티타늄 합금, 몰리브덴늄 합금의 식각시, 이중막 또는 다중막에서 테이퍼 각을 형성시키는 역할을 한다. 상기 불소계 화합물의 구체적인 예로는, 불산(KF), 플루오린화 나트륨(NaF), 중불화 암모늄(NH4F), 플루오린화수소암모늄(NH4HF2), 헥사플루오로규산(H2SiF6), 붕불화수소산(HBF4), 불화티탄산(H2TiF6), 헥사플루오로지르코닉산(H2ZrF6) 또는 이들의 혼합물 등, 구체적으로는 플루오린화수소암모늄(NH4HF2)이다.The fluorine-based compound functions to form a taper angle in a bilayer or multilayer film when etching titanium, molybdenum, titanium alloy, or molybdenum alloy, which is a barrier film of a metal film. Specific examples of the fluorine-based compound include hydrofluoric acid (KF), sodium fluoride (NaF), ammonium fluoride (NH 4 F), ammonium fluoride (NH 4 HF 2 ), hexafluorosilicic acid (H 2 SiF 6 ) a boron hydrofluoric acid (HBF 4), fluorinated titanic acid (H 2 TiF 6), zirconyl hexafluoro-conic acid (H 2 ZrF 6), or the like and mixtures thereof, specifically, fluorine hydrogen, ammonium (NH 4 HF 2) .
상기 식각제의 함량은, 전체 식각액 조성물에 대하여, 0.01 내지 5 중량%, 구체적으로는 0.5 내지 3 중량%, 더욱 구체적으로는 1 내지 2 중량%이다. 상기 식각제의 함량이 상기 범위를 벗어나면, 식각제로서 효율이 좋지 않을 수 있다.The content of the etchant is 0.01 to 5% by weight, specifically 0.5 to 3% by weight, more specifically 1 to 2% by weight, based on the total etchant composition. If the content of the etching agent is out of the above range, the efficiency as an etching agent may not be good.
구체적으로는, 상기 황산염 화합물의 함량은, 전체 식각액 조성물에 대하여, 0.01 내지 5 중량%, 구체적으로는 0.5 내지 3 중량%, 더욱 구체적으로는 1 내지 2 중량%이다. 상기 황산염 화합물의 함량이 너무 적으면, 구리막의 식각이 어려울 수 있고, 상기 범위 내에서는, 구리막의 식각 속도가 빨라져, 공정상의 조절이 용이하다. 또한, 상기 불소계 화합물의 함량은, 전체 식각액 조성물에 대하여, 0.01 내지 1 중량%, 구체적으로는, 0.05 내지 0.2 중량%, 더욱 구체적으로는 0.07 내지 0.15 중량%이다. 상기 불소계 화합물의 함량이 너무 적으면, 배리어(barrier) 막의 식각 속도가 저하되어, 테이퍼 각이 불량이 되거나, 하부막의 잔막 불량이 나타날 수 있고, 너무 많으면, 금속막 하부의 유리막이 식각되거나, 배리어 막이 과도하게 식각될 수 있다. Specifically, the content of the sulfate compound is 0.01 to 5% by weight, specifically 0.5 to 3% by weight, more specifically 1 to 2% by weight, based on the total etching solution composition. If the content of the sulfate compound is too small, it may be difficult to etch the copper film, and within this range, the etching rate of the copper film is increased and the process can be easily controlled. The content of the fluorine-based compound is 0.01 to 1% by weight, specifically 0.05 to 0.2% by weight, more specifically 0.07 to 0.15% by weight, based on the total etchant composition. If the content of the fluorine-based compound is too small, the etching rate of the barrier film may be lowered and the taper angle may become defective or the defective film of the lower film may appear. If too much, the glass film under the metal film may be etched, The film may be excessively etched.
본 발명의 식각액 조성물에 있어서, 나머지 성분은 물로서, 구체적으로는 탈이온수(deionized water, DI), 증류수 등이다. 본 발명에 따른 식각액 조성물은, 발명의 목적 및 효과를 달성하는 한도 내에서, 필요에 따라, pH 조절제, 부식 방지제 등의 통상의 첨가제를 더욱 포함할 수 있다. 본 발명에 따른 식각액 조성물은, 공지된 임의의 방법으로 제조될 수 있다. 예를 들면, 상기 2가 알코올 화합물, 아미노기를 포함하지 않는 아졸계 화합물, 아민 화합물, 황산염 화합물 및 불소계 화합물 등을 탈이온수, 증류수 등의 수성매질에 필요한 농도로 첨가한 후, 상기 과산화수소를 원하는 농도만큼 첨가하여, 본 발명의 조성물을 제조할 수 있다.In the etchant composition of the present invention, the remaining components are water, specifically, deionized water (DI), distilled water and the like. The etchant composition according to the present invention may further contain conventional additives such as a pH adjuster and a corrosion inhibitor as necessary to the extent that the objects and effects of the invention are achieved. The etchant composition according to the present invention can be produced by any known method. For example, after the divalent alcohol compound, an azole compound containing no amino group, an amine compound, a sulfate compound and a fluorine compound are added to the aqueous medium such as deionized water and distilled water at a necessary concentration, the hydrogen peroxide is added to a desired concentration To thereby prepare the composition of the present invention.
본 발명에 따른 식각액 조성물은 게이트 및 소스-드레인(2종)의 일괄 에칭이 가능하고, 처리 매수를 종래에 비하여 2 배 이상 증가시킬 수 있어 생산 수율을 향상시킬 수 있으며, 개구율 증가에 따른 고해상도에 적용이 가능하다. 또한, 테이퍼의 변동이 낮아 TFT- 적층막 구성에 스택(stack) 불량을 최소화 할 수 있다.The etchant composition according to the present invention is capable of batch etching a gate and source-drain (two kinds), and can increase the number of treatments by more than two times as compared with the prior art, thereby improving production yield. It is applicable. In addition, since variations in the taper are low, it is possible to minimize the stack defect in the TFT-laminated film structure.
본 발명에 따른 식각액 조성물은, 금속막을 식각하여 반도체 회로의 금속 배선을 형성하는데 사용된다. 본 발명의 조성물에 의하여 식각되는 금속막으로는, 구리(Cu)를 포함하는 단일 금속막, 구리 합금막을 포함하는 합금막 및 상부막인 구리막을 포함하며 하부막으로는 적어도 하나 이상의 티타늄막, 티타늄 합금막, 몰리브데늄막 및 몰리브데늄 합금막 등을 포함하는 다중막 등을 예시할 수 있다. 또한, 상기 다중막을 식각할 시에는, 상기 상부막 및 상기 하부막을 일괄 또는 선택적으로 식각하는 것이 가능하다.The etchant composition according to the present invention is used for forming a metal wiring of a semiconductor circuit by etching a metal film. The metal film etched by the composition of the present invention includes a single metal film including copper (Cu), an alloy film including a copper alloy film, and a copper film as a top film, and the lower film includes at least one titanium film, An alloy film, a molybdenum film, a molybdenum alloy film, and the like. Further, when the multi-layer is etched, it is possible to collectively or selectively etch the upper layer and the lower layer.
본 발명에 따른 금속 배선 형성 방법은, 반도체 등의 집적회로의 제조에 있어서, 기판 위에 상기 구리 단일막 또는 구리/티타늄, 구리/몰리브데늄, 구리/티타늄 합금 및/또는 구리/몰리브데늄 합금으로 이루어진 다중막 등의 금속막을 형성하고, 상기 금속막의 위에 포토레지스트 패턴을 형성한다. 다음으로, 상기 포토레지스트 패턴을 마스크로 사용하여, 상기 금속막에 본 발명의 식각액 조성물을 접촉시켜 상기 금속막을 식각함으로써, 금속 배선, 예를 들면, 게이트 전극 또는 소스-드레인 전극을 형성할 수 있다.The method for forming a metal wiring according to the present invention is a method for forming an integrated circuit such as a semiconductor in which a copper single layer or a copper / titanium / copper / molybdenum / copper / titanium alloy and / or a copper / molybdenum alloy And a photoresist pattern is formed on the metal film. Next, a metal wiring, for example, a gate electrode or a source-drain electrode can be formed by etching the metal film by contacting the etchant composition of the present invention to the metal film using the photoresist pattern as a mask .
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하나, 본 발명이 하기 실시예에 의하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.
[실시예 1 내지 8 및 비교예 1 내지 11] 식각액 조성물의 제조 [Examples 1 to 8 and Comparative Examples 1 to 11] Preparation of etchant composition
식각액 조성물의 식각 성능을 평가하기 위하여, 하기 표 1에 나타낸 화합물 및 나머지 물(deionized)을 포함하는 식각액 조성물(실시예 1 내지 8, 비교예 1 내지 11)을 제조하였다. 여기서, 과수는 과산화수소를, IDA는 이미노디아세트산을, ABF는 중불화암모늄을, DEG는 디에틸렌글리콜을, MTZ는 5-메틸테트라졸을, ATZ는 5-아미노테트라졸을 의미한다.To evaluate the etching performance of the etchant compositions, the etchant compositions (Examples 1 to 8, Comparative Examples 1 to 11) comprising the compounds shown in Table 1 and the remainder of the deionized water were prepared. Here, the term "hydrogen peroxide" refers to hydrogen peroxide, "IDA" to "iminodiacetic acid", "ABF" to "ammonium bisphosphate", "DEG" to diethylene glycol, "MTZ" to "5-methyltetrazole" and "ATZ" to 5-aminotetrazole.
(H2O2)fruit tree
(H 2 O 2 )
((NH4)2SO4))Ammonium sulfate
((NH 4) 2 SO 4 ))
(C4H7NO4)IDA
(C 4 H 7 NO 4 )
(NH4HF2)ABF
(NH 4 HF 2)
(C4H10O3)DEG_2
(C 4 H 10 O 3 )
(CH4N4)MTZ
(CH 4 N 4 )
(CH4N5)ATZ
(CH 4 N 5 )
[실험예 1] 식각액 조성물의 평가 [Experimental Example 1] Evaluation of etchant composition
구리/몰리브데늄 및 구리/몰리브데늄 합금 이중막 위에 포토레지스트 패턴을 형성하고, 실시예 1 내지 8 및 비교예 1 내지 11의 식각액 조성물을 수직 단면으로 식각되는 시간을 측정(EPD: End Point Detection)하여, 이를 기준으로 과잉 식각(over etching)하였다. 식각된 금속막의 단면을 주사전자현미경으로 관찰하여, 식각 속도, 편측 CD 변화 range, 테이퍼 변화 range 및 처리매수를 하기 표 2에 나타내었다. 여기서, range 값은 경시성에 대한 판단 기준으로서, 약액의 처리매수를 판단하여, 생산 수율을 향상시킬 수 있고, CD skew(critical dimension skew)는 포토레지스트 패턴 말단과 하부막 또는 Barrier막 말단 사이의 거리를 의미하며, 단차가 적고 균일한 테이퍼 식각을 위하여, 편측 0.5 내지 0.8 ㎛가 되어야 한다. 또한, 테이퍼 각은 식각된 금속막의 측면에서 본 경사로서, 45 내지 60˚가 적절하다. 여기서, ◎는 "매우 우수"(식각속도: 170~180Å/sec / CD 변화 range: 편측 ≤≤0.1㎛ / Taper 변화 range: ≤≤5˚ / 처리매수: ≥≥7000ppm)를, ○는 "양호"(식각속도: 160 ~ 169Å/sec / CD 변화 range: 편측 0.11 ~ 0.20㎛ / Taper 변화 range: 6˚~ 9˚ / 처리매수: 4000 ~ 5000ppm)를, △는 "불량"(식각속도: ≤≤159Å/sec or ≥≥181Å/sec / CD 변화 range: 편측 ≥≥0.20㎛ / Taper 변화 range: ≥10˚ / 처리매수: ≤≤3000ppm)을 의미한다.A photoresist pattern was formed on copper / molybdenum and copper / molybdenum alloy double films, and the etchant compositions of Examples 1 to 8 and Comparative Examples 1 to 11 were etched at a vertical cross section (EPD: End Point Detection was performed and over-etching was performed based on this. The etching rate, the side CD variation range, the taper change range, and the number of treatments are shown in Table 2 by observing the cross section of the etched metal film with a scanning electron microscope. Here, the range value is a criterion for the aging property, and it is possible to improve the production yield by judging the number of treatments of the chemical solution. CD skew (critical dimension skew) is a distance between the end of the photoresist pattern and the end of the barrier film , And should be 0.5 to 0.8 [mu] m on one side for a tapered etching having a small step and a uniform taper. Further, the taper angle is an inclination viewed from the side of the etched metal film, and 45 to 60 degrees is suitable. Here, ⊚ represents "very good" (etching rate: 170 to 180 Å / sec / CD change range: one side ≤ ≤ 0.1 μm / Taper change range: ≤ 5 ˚ / number of processed sheets: ≥ ≥ 7000 ppm) (Etching rate: 160 to 169 Å / sec / CD change range: 0.11 to 0.20 μm on one side / taper change range: 6 ˚ to 9 ˚ / number of processed sheets: 4000 to 5000 ppm) ≤159 Å / sec or ≥ ≥ 181 Å / sec / CD change range: one side ≥≥0.20 ㎛ / Taper change range: ≥10 ˚ / number of processing: ≤ ≤3000 ppm).
(Å/sec)Etching rate
(Å / sec)
변화 range(μm)One side CD
Change range (μm)
변화 range(˚)Taper
Change range (˚)
(ppm)Number of processing
(ppm)
도 1은 식각 후 단면을 측정한 주사전자현미경 사진이다. 도 1은 실시예 및 비교예 평가의 기준이 되는 것으로서, 표 2에 나타낸 바와 같이, 과산화수소가 포함되지 않은 비교예 1의 경우, 실시예 1 내지 8에 비하여, 식각 속도, 편측CD, 테이퍼 각도 및 처리매수 모두 불량하다는 것을 알 수 있고, 아미노기를 포함하는 아졸계 화합물을 사용한 비교예 9의 경우, 아미노기를 포함하지 않는 아졸계 화합물을 사용한 실시예 1 내지 8에 비하여, 테이퍼 각도 및 처리 매수가 불량하게 나타나, 아미노기를 포함하지 않는 아졸계 화합물이 식각속도, 테이퍼 각도 및 처리 매수에 영향을 미친다는 것을 알 수 있다.1 is a scanning electron micrograph of a section after etching. As shown in Table 2, in the case of Comparative Example 1 containing no hydrogen peroxide, the etching rate, the side CD, the taper angle, and the taper angle were compared with those of Examples 1 to 8, It can be seen that the treatment number is poor and in the case of Comparative Example 9 using an azole compound containing an amino group as compared with Examples 1 to 8 using an azole compound not containing an amino group, , It can be seen that an azole compound not containing an amino group affects the etching rate, the taper angle and the number of treatments.
또한, 아미노기를 포함하지 않는 아졸계 화합물을 사용하고, 아민화합물(IDA)의 함량이 낮은 비교예 4의 경우, 테이퍼 각도 및 처리 매수뿐만 아니라, 편측CD도 불량하게 나타나, 아민화합물이 편측에 영향을 미친다는 것을 알 수 있고, 2가 알코올 화합물 대신 3가 알코올 화합물을 사용한 비교예 11의 경우, 식각 속도를 제외한 편측CD, 테이퍼 각도 및 처리매수가 불량하다는 것을 알 수 있다.In addition, in the case of Comparative Example 4 in which an azole compound not containing an amino group was used and the content of the amine compound (IDA) was low, not only the taper angle and the number of treatments but also the unidirectional CD were poor, And in Comparative Example 11 where a trivalent alcohol compound was used instead of a dihydric alcohol compound, it can be seen that the unidirectional CD, the taper angle, and the number of treatments except the etching rate were poor.
또한, 상기 실시예 6 및 7의 경우, 불소계 화합물 또는 황산염계 화합물을 포함하면, 편측, 테이퍼 각도 및 처리매수가 매우 우수한 것으로 나타났고, 불소계 화합물과 황산염 화합물을 동시에 포함하지 않는 실시예 8의 경우, 식각속도 또한 매우 우수한 것을 알 수 있었으며, 아민화합물을 포함하지 않는 비교예 4 및 2가 알코올을 포함하지 않는 비교예 5의 경우에는 식각속도는 양호한 것을 나타내었으나, 나머지 특성들이 불량으로 나타났고, 아미노기를 포함하는 아졸계 화합물을 포함하는 비교예 9의 경우, 식각속도가 불량으로 나타났다. 이를 통하여, 본 발명에 따른 식각액 조성물을 사용하면, 식각속도, 편측CD, 테이퍼 각도 및 처리매수가 우수한 것을 알 수 있고, 특히 처리매수가 우수함에 따라, 약액의 수명이 기존에 비해 증가됨을 알 수 있다.In the case of Examples 6 and 7, when the fluorine-based compound or the sulfate-based compound was included, the one side, the taper angle and the number of treatments were excellent, and in the case of Example 8 in which the fluorine- , And the etching rate was also excellent. In Comparative Example 4 in which the amine compound was not included and Comparative Example 5 in which the alcohol was not contained, the etching rate was good, but the remaining characteristics were poor. In the case of Comparative Example 9 comprising an azole compound containing an amino group, the etching rate was found to be poor. As a result, it can be seen that the etching rate, one side CD, taper angle and number of treatments are excellent when the etching solution composition according to the present invention is used, and that the lifetime of the chemical solution is increased as compared with the conventional one have.
또한, 황산암모늄 식각제를 수치한정 범위를 초과하여 사용한 비교예 3은 식각 속도, 편측CD, Taper range, 처리 매수 모두 양호한 수준이었으나, 과식각으로 인한 국부 침식이 발생하여, 식각제의 수치 범위가 5%를 초과하지 않아야함을 알 수 있으며, 2가 알코올을 수치한정 범위 초과하여 사용한 비교예 6은 수율이 좋지 않았다.Also, in Comparative Example 3 where the ammonium sulfate etchant was used in excess of the numerical limit range, the etch rate, unilateral CD, taper range, and the number of treatments were all at a satisfactory level. However, local erosion due to overeating occurred, 5%, and the yield of Comparative Example 6 in which the dihydric alcohol exceeded the numerical limit range was not good.
Claims (12)
아민 화합물;
2가 알코올 화합물; 및
아미노기를 포함하지 않는 아졸계 화합물;
을 포함하는 금속 배선 식각액 조성물.Oxidant;
Amine compounds;
Divalent alcohol compounds; And
An azole-based compound containing no amino group;
≪ / RTI >
2가 알코올 화합물;
아미노기를 포함하지 않는 아졸계 화합물;
아민 화합물;
황산염 화합물, 불소계 화합물 및 이들의 혼합물로 이루어진 군으로부터 선택되는 화합물을 하나 이상 포함하는 식각제; 및
물;
을 포함하는 금속 배선 식각액 조성물.Oxidant;
Divalent alcohol compounds;
An azole-based compound containing no amino group;
Amine compounds;
An etchant comprising at least one compound selected from the group consisting of sulfate compounds, fluorine compounds, and mixtures thereof; And
water;
≪ / RTI >
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| CN111876780A (en) * | 2020-08-31 | 2020-11-03 | 武汉迪赛新材料有限公司 | Ammonium persulfate system etching solution for etching TFT copper-molybdenum layer |
| CN115678439B (en) * | 2022-10-31 | 2024-04-23 | 上海应用技术大学 | Alkaline polishing solution for inhibiting copper-cobalt galvanic corrosion and preparation method thereof |
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| KR20150059602A (en) * | 2013-11-22 | 2015-06-01 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Composition for etching, and method for preparing printed wiring board by using same |
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| KR101608873B1 (en) * | 2010-03-18 | 2016-04-05 | 삼성디스플레이 주식회사 | Etchant for metal wire and method for manufacturing metal wire using the same |
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- 2017-12-15 CN CN201711347546.4A patent/CN108203830B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150039526A (en) * | 2013-10-02 | 2015-04-10 | 주식회사 이엔에프테크놀로지 | Etching composition for copper and molibdenum containing film |
| KR20150059602A (en) * | 2013-11-22 | 2015-06-01 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Composition for etching, and method for preparing printed wiring board by using same |
| KR20160112471A (en) * | 2015-03-19 | 2016-09-28 | 동우 화인켐 주식회사 | Etchant composition and manufacturing method of an array for liquid crystal display |
| KR20160114360A (en) * | 2015-03-24 | 2016-10-05 | 동우 화인켐 주식회사 | Etching solution composition for copper-based metal layer and method for etching copper-based metal layer using the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20230055735A1 (en) * | 2020-09-02 | 2023-02-23 | Tcl China Star Optoelectronics Technology Co., Ltd. | Etchant for etching triple layer metal wiring structures of molybdenum/copper/molybdenum or molybdenum alloy/copper/molybdenum, and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108203830B (en) | 2023-02-28 |
| TW201831726A (en) | 2018-09-01 |
| KR102568504B1 (en) | 2023-08-22 |
| CN108203830A (en) | 2018-06-26 |
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