KR102707397B1 - Etchant composition for silver thin layer and etching method and method for fabrication metal pattern using the same - Google Patents
Etchant composition for silver thin layer and etching method and method for fabrication metal pattern using the same Download PDFInfo
- Publication number
- KR102707397B1 KR102707397B1 KR1020190115615A KR20190115615A KR102707397B1 KR 102707397 B1 KR102707397 B1 KR 102707397B1 KR 1020190115615 A KR1020190115615 A KR 1020190115615A KR 20190115615 A KR20190115615 A KR 20190115615A KR 102707397 B1 KR102707397 B1 KR 102707397B1
- Authority
- KR
- South Korea
- Prior art keywords
- silver
- etching
- film
- transparent conductive
- composition
- Prior art date
Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 238000005530 etching Methods 0.000 title claims abstract description 118
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 115
- 239000004332 silver Substances 0.000 title claims abstract description 115
- 239000000203 mixture Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 24
- 239000002184 metal Substances 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title 1
- 239000010409 thin film Substances 0.000 claims abstract description 54
- -1 azole compound Chemical class 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims abstract description 12
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 12
- 239000010408 film Substances 0.000 claims description 101
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 3
- 159000000014 iron salts Chemical class 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 150000003233 pyrroles Chemical class 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical class C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 150000002545 isoxazoles Chemical class 0.000 claims description 2
- 150000002916 oxazoles Chemical class 0.000 claims description 2
- 150000003853 pentazoles Chemical class 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 2
- 150000003557 thiazoles Chemical class 0.000 claims description 2
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 2
- TYHJXGDMRRJCRY-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) tin(4+) Chemical compound [O-2].[Zn+2].[Sn+4].[In+3] TYHJXGDMRRJCRY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims 1
- 230000008569 process Effects 0.000 description 14
- 238000001179 sorption measurement Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- 229920002120 photoresistant polymer Polymers 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- DOYOPBSXEIZLRE-UHFFFAOYSA-N pyrrole-3-carboxylic acid Natural products OC(=O)C=1C=CNC=1 DOYOPBSXEIZLRE-UHFFFAOYSA-N 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- DEPDDPLQZYCHOH-UHFFFAOYSA-N 1h-imidazol-2-amine Chemical compound NC1=NC=CN1 DEPDDPLQZYCHOH-UHFFFAOYSA-N 0.000 description 2
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- XKVUYEYANWFIJX-UHFFFAOYSA-N 5-methyl-1h-pyrazole Chemical compound CC1=CC=NN1 XKVUYEYANWFIJX-UHFFFAOYSA-N 0.000 description 2
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 description 2
- TVNDPZYOQCCHTJ-UHFFFAOYSA-N 5-thiophen-2-yl-1h-pyrazole Chemical compound C1=CSC(C=2NN=CC=2)=C1 TVNDPZYOQCCHTJ-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- WRHZVMBBRYBTKZ-UHFFFAOYSA-N pyrrole-2-carboxylic acid Chemical compound OC(=O)C1=CC=CN1 WRHZVMBBRYBTKZ-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XMGWNAIPGOPSNX-UHFFFAOYSA-N 1,5-diaminotetrazole Chemical compound NC1=NN=NN1N XMGWNAIPGOPSNX-UHFFFAOYSA-N 0.000 description 1
- PWIXZDJDBSEIOY-UHFFFAOYSA-N 1-(benzotriazol-1-yl)propane-1,2-diol Chemical compound C1=CC=C2N(C(O)C(O)C)N=NC2=C1 PWIXZDJDBSEIOY-UHFFFAOYSA-N 0.000 description 1
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 1
- ZHPSBMQVLQEIIC-UHFFFAOYSA-N 1-methoxybenzotriazole Chemical compound C1=CC=C2N(OC)N=NC2=C1 ZHPSBMQVLQEIIC-UHFFFAOYSA-N 0.000 description 1
- GTKOKCQMHAGFSM-UHFFFAOYSA-N 1-methyltetrazol-5-amine Chemical compound CN1N=NN=C1N GTKOKCQMHAGFSM-UHFFFAOYSA-N 0.000 description 1
- CAMZCCDMGNIZTA-UHFFFAOYSA-N 1-naphthalen-1-yltetrazol-5-amine Chemical compound NC1=NN=NN1C1=CC=CC2=CC=CC=C12 CAMZCCDMGNIZTA-UHFFFAOYSA-N 0.000 description 1
- ULIDRMKBVYYVIQ-UHFFFAOYSA-N 1-phenyltetrazol-5-amine Chemical compound NC1=NN=NN1C1=CC=CC=C1 ULIDRMKBVYYVIQ-UHFFFAOYSA-N 0.000 description 1
- NEUWPDLMDVINSN-UHFFFAOYSA-N 1h-pyrazol-5-ylboronic acid Chemical compound OB(O)C=1C=CNN=1 NEUWPDLMDVINSN-UHFFFAOYSA-N 0.000 description 1
- IYSPNYLFKSTATA-UHFFFAOYSA-N 1h-pyrazol-5-ylmethanamine Chemical compound NCC=1C=CNN=1 IYSPNYLFKSTATA-UHFFFAOYSA-N 0.000 description 1
- CZHBXDSQJOQIHE-UHFFFAOYSA-N 2-(benzotriazol-1-yl)ethane-1,1-diol Chemical compound C1=CC=C2N(CC(O)O)N=NC2=C1 CZHBXDSQJOQIHE-UHFFFAOYSA-N 0.000 description 1
- ZUHDIDYOAZNPBV-UHFFFAOYSA-N 2-[2-hydroxyethyl-[(4-methylbenzotriazol-1-yl)methyl]amino]ethanol Chemical compound CC1=CC=CC2=C1N=NN2CN(CCO)CCO ZUHDIDYOAZNPBV-UHFFFAOYSA-N 0.000 description 1
- HHYPDQBCLQZKLI-UHFFFAOYSA-N 2-[2-hydroxyethyl-[(5-methylbenzotriazol-1-yl)methyl]amino]ethanol Chemical compound CC1=CC=C2N(CN(CCO)CCO)N=NC2=C1 HHYPDQBCLQZKLI-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- MKBBSFGKFMQPPC-UHFFFAOYSA-N 2-propyl-1h-imidazole Chemical compound CCCC1=NC=CN1 MKBBSFGKFMQPPC-UHFFFAOYSA-N 0.000 description 1
- GDMZHPUPLWQIBD-UHFFFAOYSA-N 2-pyrrol-1-ylaniline Chemical compound NC1=CC=CC=C1N1C=CC=C1 GDMZHPUPLWQIBD-UHFFFAOYSA-N 0.000 description 1
- GUOVBFFLXKJFEE-UHFFFAOYSA-N 2h-benzotriazole-5-carboxylic acid Chemical compound C1=C(C(=O)O)C=CC2=NNN=C21 GUOVBFFLXKJFEE-UHFFFAOYSA-N 0.000 description 1
- WVIXTJQLKOLKTQ-UHFFFAOYSA-N 3-(benzotriazol-1-yl)propane-1,2-diol Chemical compound C1=CC=C2N(CC(O)CO)N=NC2=C1 WVIXTJQLKOLKTQ-UHFFFAOYSA-N 0.000 description 1
- RZJWSGHNRLPGHP-UHFFFAOYSA-N 3-pyrrol-1-ylpropanoic acid Chemical compound OC(=O)CCN1C=CC=C1 RZJWSGHNRLPGHP-UHFFFAOYSA-N 0.000 description 1
- XORHNJQEWQGXCN-UHFFFAOYSA-N 4-nitro-1h-pyrazole Chemical compound [O-][N+](=O)C=1C=NNC=1 XORHNJQEWQGXCN-UHFFFAOYSA-N 0.000 description 1
- NJQHZENQKNIRSY-UHFFFAOYSA-N 5-ethyl-1h-imidazole Chemical compound CCC1=CNC=N1 NJQHZENQKNIRSY-UHFFFAOYSA-N 0.000 description 1
- KYRMPMCAOPMOIR-UHFFFAOYSA-N 5-ethyl-2h-tetrazole Chemical compound CCC=1N=NNN=1 KYRMPMCAOPMOIR-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- OEDUIFSDODUDRK-UHFFFAOYSA-N 5-phenyl-1h-pyrazole Chemical compound N1N=CC=C1C1=CC=CC=C1 OEDUIFSDODUDRK-UHFFFAOYSA-N 0.000 description 1
- HPSJFXKHFLNPQM-UHFFFAOYSA-N 5-propyl-1h-imidazole Chemical compound CCCC1=CNC=N1 HPSJFXKHFLNPQM-UHFFFAOYSA-N 0.000 description 1
- JAHCQVVOKAFXQU-UHFFFAOYSA-N 5-propyl-2h-tetrazole Chemical compound CCCC=1N=NNN=1 JAHCQVVOKAFXQU-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/30—Acidic compositions for etching other metallic material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/02—Local etching
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
Abstract
본 발명은 (A) 은식각촉진제; (B) 무기산; (C) 중황산염; (D) 아졸 화합물; 및 (E) 물을 포함하는 은 박막 식각액 조성물 및 이를 이용한 식각 방법 및 금속 패턴의 형성 방법에 관한 것이다. The present invention relates to a silver thin film etchant composition comprising (A) a silver etching accelerator; (B) an inorganic acid; (C) a bisulfate; (D) an azole compound; and (E) water, and to an etching method and a method for forming a metal pattern using the same.
Description
본 발명은 은 박막 식각액 조성물, 이를 이용한 식각 방법 및 금속 패턴의 형성 방법에 관한 것이다.The present invention relates to a thin film etching composition, an etching method using the same, and a method for forming a metal pattern.
본격적인 정보화 시대로 접어들게 됨에 따라 대량의 정보를 처리 및 표시하는 디스플레이 분야가 급속도로 발전해 왔으며, 이에 부응하여 다양한 평판 디스플레이가 개발되어 각광받고 있다.As we enter the full-fledged information age, the display field that processes and displays large amounts of information has developed rapidly, and in response, various flat panel displays have been developed and are receiving attention.
이러한 평판디스플레이 장치의 예로는 액정디스플레이장치(Liquid crystal display device: LCD), 플라즈마디스플레이장치(Plasma Display Panel device: PDP), 전계방출디스플레이장치(Field Emission Display device: FED), 전기발광디스플레이장치(Electroluminescence Display device: ELD), 유기발광디스플레이(Organic Light Emitting Diodes: OLED) 등을 들 수 있으며, 이러한 평판디스플레이 장치는 텔레비전이나 비디오 등의 가전분야 뿐만 아니라 노트북과 같은 컴퓨터 및 핸드폰 등에 다양한 용도로 사용되고 있다. 이들 평판디스플레이 장치는 박형화, 경량화, 및 저소비전력화 등의 우수한 성능으로 인하여 기존에 사용되었던 브라운관(Cathode Ray Tube: CRT)을 빠르게 대체하고 있는 실정이다. Examples of such flat panel display devices include liquid crystal display devices (LCD), plasma display panel devices (PDP), field emission display devices (FED), electroluminescence display devices (ELD), and organic light emitting diodes (OLED). These flat panel display devices are used for a variety of purposes, not only in home appliances such as televisions and videos, but also in computers such as laptops and cell phones. These flat panel display devices are rapidly replacing the previously used cathode ray tubes (CRT) due to their superior performances such as thinning, weight reduction, and low power consumption.
특히 OLED는 소자 자체적으로 빛을 발광하며 저전압에서도 구동될 수 있기 때문에 최근 휴대기기 등의 소형 디스플레이 시장에 빠르게 적용되고 있다. 또한 OLED는 소형 디스플레이를 넘어서 대형 TV의 상용화를 목전에 둔 상태이다.In particular, OLEDs are rapidly being applied to the small display market for mobile devices, etc., because they emit light by themselves and can be operated at low voltages. In addition, OLEDs are on the verge of commercialization in large TVs beyond small displays.
한편, 반사판의 경우 과거 알루미늄(Al) 반사판을 주로 제품에 이용해왔으나, 휘도 향상을 통한 저전력 소비실현을 위해서는 반사율이 더 높은 금속으로의 재료변경을 모색하고 있는 상태이다. 이를 위해 평판디스플레이장치에 적용되고 있는 금속들에 비해 낮은 비저항과 높은 휘도를 가지고 있는 은(Ag: 비저항 약 1.59μΩ㎝)막, 은합금 또는 이를 포함한 다층막을 칼라필터의 전극, LCD 또는 OLED 배선 및 반사판에 적용, 평판표시장치의 대형화와 고 해상도 및 저전력 소비 등을 실현하고자 하여, 이 재료의 적용을 위한 식각액의 개발이 요구되었다.Meanwhile, in the case of reflectors, aluminum (Al) reflectors have been mainly used in products in the past, but in order to realize low power consumption through improved brightness, a change in material to a metal with higher reflectivity is being sought. To this end, silver (Ag: resistivity approximately 1.59 μΩ cm) films, silver alloys, or multilayer films containing them, which have lower resistivity and higher brightness than the metals used in flat panel display devices, are being applied to electrodes of color filters, LCD or OLED wiring, and reflectors to realize large-scale flat panel display devices, high resolution, and low power consumption, and therefore, the development of an etchant for the application of these materials has been required.
그러나, 은(Ag)은 유리 등의 절연 기판 또는 진성 비정질 규소나 도핑된 비정질 규소 등으로 이루어진 반도체 기판 등의 하부 기판에 대해 접착성(adhesion)이 극히 불량하여 증착이 용이하지 않고, 배선의 들뜸(lifting) 또는 벗겨짐(Peeling)이 쉽게 유발된다. 또한, 은(Ag)도전층이 기판에 증착된 경우에도 이를 패터닝하기 위해 식각액을 사용하게 된다. 이러한 식각액으로서 종래의 식각액을 사용하는 경우 은(Ag)이 과도하게 식각되거나, 불균일하게 식각되어 배선의 들뜸 또는 벗겨짐 현상이 발생하고, 배선의 측면 프로파일이 불량하게 된다.However, silver (Ag) has extremely poor adhesion to insulating substrates such as glass or semiconductor substrates made of intrinsic amorphous silicon or doped amorphous silicon, making deposition difficult and easily causing lifting or peeling of the wiring. In addition, even when a silver (Ag) conductive layer is deposited on a substrate, an etchant is used to pattern it. When a conventional etchant is used as this etchant, the silver (Ag) is excessively or unevenly etched, causing lifting or peeling of the wiring and a poor side profile of the wiring.
또한 고해상도 구현을 위한 낮은 스큐(LOW Skew)구현이 공정을 하는데 있어 어려움이 있다.Additionally, there are difficulties in implementing low skew for high resolution implementation.
특히, 은(Ag)은 쉽게 환원이 되는 금속으로 식각 속도가 빨라야 잔사 유발 없이 식각이 되게 되는데 이때 식각 속도가 빨라 상하부 간 식각 속도의 차이가 발생하지 않아 식각 후 테이퍼 각(taper angle) 형성이 어렵고 식각 패턴의 직진성 확보에 어려움이 있어서, 배선 및 패턴 형성 시 많은 한계점을 가지고 있다. 또한, 은 식각액 조성물을 사용하여 은 박막 식각시, 기판 내 노출된 S/D 부의 금속막에 식각된 은 입자가 다시 흡착되는 문제가 발생하며, 이 경우 후속 공정에서의 전기적 쇼트가 발생할 수 있어 불량 발생의 원인이 될 수 있다는 점에서 문제가 있다. In particular, silver (Ag) is a metal that is easily reduced, so the etching speed must be fast so that etching can be performed without causing residue. However, since the etching speed is fast and there is no difference in the etching speed between the upper and lower parts, it is difficult to form a taper angle after etching and it is difficult to secure the straightness of the etching pattern, so there are many limitations when forming wiring and patterns. In addition, when etching a silver thin film using a silver etchant composition, there is a problem that the etched silver particles are re-adsorbed to the metal film of the exposed S/D part in the substrate, and in this case, an electrical short may occur in the subsequent process, which can become the cause of defects, which is problematic.
이와 관련하여, 대한민국 공개특허 제 2008-0009866호와 같이 주 은식각촉진제로써 인산이 필수적으로 사용되는 인산계 은 식각액 조성물이 주로 개발되어 왔으나, 인산에 의한 하부막 손상 등 인산계 식각액 조성물의 문제점 발생하고 있다. 따라서, 인산이 포함되지 않으면서도 은 식각 특성이 우수한 식각액 조성물의 개발이 필요하며, 특히, 당해 기술분야의 주요한 문제점인 잔사 및 은 재흡착 문제 및 처리매수 증가에 따른 식각액 조성물의 성능 저하 문제를 완전히 해결할 수 있는 비인산계 은 식각액 조성물의 개발이 필요한 실정이다.In this regard, phosphoric acid-based silver etchant compositions have been mainly developed, such as those disclosed in Korean Patent Publication No. 2008-0009866, which essentially use phosphoric acid as a primary silver etching accelerator; however, problems with the phosphoric acid-based etchant compositions, such as damage to the underlying film caused by phosphoric acid, are occurring. Therefore, there is a need for the development of an etchant composition having excellent silver etching characteristics even without phosphoric acid, and in particular, there is a need for the development of a non-phosphoric acid-based silver etchant composition that can completely solve the major problems in the relevant technical field, such as residue and silver re-adsorption problems and the performance degradation of the etchant composition due to an increase in the number of treatments.
본 발명은 상술한 종래 기술의 문제점을 개선하기 위한 것으로, 은(Ag) 또는 은 합금으로 이루어진 단일막 및 상기 단일막과 투명전도막으로 구성되는 다층막의 식각에 사용되며, 잔사(예를 들어, 은 잔사 및/또는 투명전도막 잔사 등) 및 은 재흡착 문제가 발생하지 않는 것을 특징으로 하는 은 박막 식각액 조성물을 제공하는 것을 목적으로 한다.The present invention is intended to improve the problems of the above-described prior art, and aims to provide a silver thin film etching composition which is used for etching a single film made of silver (Ag) or a silver alloy and a multilayer film composed of the single film and a transparent conductive film, and which is characterized in that no residue (e.g., silver residue and/or transparent conductive film residue, etc.) and silver re-adsorption problems occur.
또한, 본 발명은 상기 단일막 및 상기 다층막을 동시에 식각할 수 있는 은 박막 식각액 조성물을 제공하는 것을 목적으로 한다.In addition, the present invention aims to provide a silver thin film etching composition capable of etching the single film and the multilayer film simultaneously.
또한, 본발명은 식각 공정 초반에도 잔사 및 은 재흡착 문제가 발생하지 않을 뿐만 아니라, 장시간 식각공정을 진행하여 처리매수 높은 시점에도 잔사가 발생하지 않으며 은 재흡착 방지 효과가 우수하게 유지될 수 있는 은 박막 식각액 조성물을 제공하는 것을 목적으로 한다. In addition, the present invention aims to provide a silver thin film etchant composition that not only does not generate residue and silver re-adsorption problems even at the beginning of the etching process, but also does not generate residue and maintains an excellent silver re-adsorption prevention effect even at a high processing point during a long-term etching process.
또한, 본 발명은 하부막의 손상 없이 식각 균일성을 나타내는 습식 식각에 유용하게 사용될 수 있는 은 박막 식각액 조성물을 제공하는 것을 목적으로 한다.In addition, the present invention aims to provide a silver thin film etchant composition that can be usefully used in wet etching that exhibits etching uniformity without damaging the underlying film.
또한, 본 발명은 상기 은 박막 식각액 조성물을 이용하는 식각 방법을 제공하는 것을 목적으로 한다.In addition, the present invention aims to provide an etching method using the silver thin film etching solution composition.
또한, 본 발명은 상기 은 박막 식각액 조성물을 이용하는 금속 패턴의 형성 방법을 제공하는 것을 목적으로 한다.In addition, the present invention aims to provide a method for forming a metal pattern using the silver thin film etching composition.
상기 목적을 달성하기 위해, 본 발명은, (A) 은식각촉진제; (B) 무기산; (C) 중황산염; (D) 아졸 화합물; 및 (E) 물을 포함하는 은 박막 식각액 조성물을 제공한다.To achieve the above object, the present invention provides a silver thin film etching composition comprising: (A) a silver etching accelerator; (B) an inorganic acid; (C) a bisulfate; (D) an azole compound; and (E) water.
또한, 본 발명은, 상기 은 박막 식각액 조성물을 사용하는 식각 방법을 제공한다.In addition, the present invention provides an etching method using the silver thin film etching solution composition.
또한, 본 발명은 상기 은 박막 식각액 조성물을 사용하는 금속 패턴의 형성 방법을 제공한다.In addition, the present invention provides a method for forming a metal pattern using the silver thin film etching composition.
본 발명의 은 박막 식각액 조성물은 은(Ag) 또는 은 합금으로 이루어진 단일막 및 상기 단일막과 투명전도막으로 구성되는 다층막의 식각에 사용되어, 잔사(예를 들어, 은 잔사 및/또는 투명전도막 잔사 등) 및 은 재흡착 문제가 발생하지 않는 효과를 제공한다.The silver thin film etchant composition of the present invention is used for etching a single film made of silver (Ag) or a silver alloy and a multilayer film composed of the single film and a transparent conductive film, thereby providing an effect in which residue (e.g., silver residue and/or transparent conductive film residue, etc.) and silver re-adsorption problems do not occur.
또한, 본 발명의 은 박막 식각액 조성물은 상기 단일막 및 상기 다층막을 동시에 식각하여, 식각 효율을 향상시키는 효과를 제공한다.In addition, the silver thin film etching composition of the present invention provides an effect of improving etching efficiency by simultaneously etching the single film and the multilayer film.
또한, 본발명은 식각 공정 초반에도 잔사 및 은 재흡착 문제가 발생하지 않을 뿐만 아니라, 장시간 식각공정을 진행하여 처리매수 높은 시점에도 잔사가 발생하지 않으며 은 재흡착 방지 효과가 우수하게 유지될 수 있는 은 박막 식각액 조성물을 제공한다. In addition, the present invention provides a silver thin film etchant composition that not only does not generate residue and silver re-adsorption problems even at the beginning of the etching process, but also does not generate residue and maintains an excellent silver re-adsorption prevention effect even when the etching process is performed for a long time and the processing amount is high.
또한, 본 발명의 은 박막 식각액 조성물은 상기 단일막 및 상기 다층막의 과식각을 방지하여 편측 식각(Side etch)량을 감소시킬 수 있어 미세패턴을 형성할 수 있다.In addition, the silver thin film etching composition of the present invention can prevent overetching of the single film and the multilayer film, thereby reducing the side etch amount, thereby forming a fine pattern.
본 발명은(A) 은식각촉진제; (B) 무기산; (C) 중황산염; (D) 아졸 화합물; 및 (E) 물을 포함하는 은 박막 식각액 조성물 및 이를 이용한 식각 방법 및 금속 패턴의 형성 방법에 대한 것이다.The present invention relates to a silver thin film etchant composition comprising (A) a silver etching accelerator; (B) an inorganic acid; (C) a bisulfate; (D) an azole compound; and (E) water, and to an etching method and a method for forming a metal pattern using the same.
본 발명의 은 박막 식각액 조성물 및 이를 이용한 식각 방법 및 금속 패턴의 형성 방법은 은(Ag) 또는 은 합금으로 이루어진 단일막 및 상기 단일막과 투명전도막으로 구성되는 다층막의 식각에 사용될 수 있으며, 특히 중황산염 및 아졸 화합물을 포함함으로, 잔사(예를 들어, 은 잔사 및/또는 투명전도막 잔사 등) 및 은 재흡착 문제가 발생하지 않는 것을 특징으로 한다. 상기 재흡착은 기판 내 노출된 S/D(소스/드레인) 부의 금속막에, 식각된 은 입자가 부착되는 현상을 의미하는 것일 수 있으며, 상기 기판 내 노출된 S/D 부의 금속막은 Mo, Cu, 및 이들의 합금으로 구성된 단일막 또는 다층막일 수 있고, 삼중막 상부 Ti, 중앙의 Al, 하부의 Ti 의 일부 또는 모든 부분에서 은의 재흡착일수 있다. 특히 Ti/Al/Ti의 삼중막의 상부 Ti에의 은의 재흡착 일 수 있다.The silver thin film etchant composition of the present invention and the etching method and the metal pattern forming method using the same can be used for etching a single film made of silver (Ag) or a silver alloy and a multilayer film made of the single film and a transparent conductive film, and is particularly characterized in that, since it contains a bisulfate and an azole compound, residues (for example, silver residues and/or transparent conductive film residues, etc.) and silver readsorption problems do not occur. The readsorption may mean a phenomenon in which etched silver particles are attached to a metal film of an S/D (source/drain) portion exposed within a substrate, and the metal film of the S/D portion exposed within the substrate may be a single film or multilayer film made of Mo, Cu, and an alloy thereof, and silver may be readsorbed on some or all of the upper Ti, the central Al, and the lower Ti of the triple film. In particular, it may be readsorbed on the upper Ti of the triple film of Ti/Al/Ti.
또한, 본발명은 식각 공정 초반에도 잔사 및 은 재흡착 문제가 발생하지 않을 뿐만 아니라, 장시간 식각공정을 진행하여 처리매수 높은 시점에도 잔사가 발생하지 않으며 은 재흡착 방지 효과가 우수하게 유지될 수 있는 은 박막 식각액 조성물을 제공한다. In addition, the present invention provides a silver thin film etchant composition that not only does not generate residue and silver re-adsorption problems even at the beginning of the etching process, but also does not generate residue and maintains an excellent silver re-adsorption prevention effect even when the etching process is performed for a long time and the processing amount is high.
본 발명의 은 박막 식각액 조성물 및 이를 이용한 식각 방법 및 금속 패턴의 형성 방법은 상기 단일막 및 상기 다층막을 동시에 식각에 사용될 수 있다.The silver thin film etchant composition of the present invention and the etching method and metal pattern forming method using the same can be used to etch the single film and the multilayer film simultaneously.
또한, 본 발명의 은 박막 식각액 조성물은 상기 단일막 및 상기 다층막의 과식각을 방지하여 편측 식각(Side etch)량을 감소시킬 수 있어 미세패턴을 형성할 수 있다.In addition, the silver thin film etching composition of the present invention can prevent overetching of the single film and the multilayer film, thereby reducing the side etch amount, thereby forming a fine pattern.
본 발명의 은 박막 식각액 조성물 및 이를 이용한 식각 방법 및 금속 패턴의 형성 방법은 side etch를 조절할 수 있는 효과를 제공할 수 있다. 신액 및 구액의 side etch가 0.3㎛ 미만인 경우 우수하게 side etch가 조절되었다고 볼 수 있다. The silver thin film etchant composition of the present invention and the etching method and metal pattern forming method using the same can provide an effect capable of controlling side etch. When the side etch of the new solution and the old solution is less than 0.3 ㎛, it can be considered that the side etch is excellently controlled.
상기 은 합금은 은을 주성분으로 하여 Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W, Pa, In, Zn, Sn, Al 및 Ti 등의 다른 금속을 포함하는 합금 형태와; 은의 질화물, 규화물, 탄화물, 산화물 등을 포함할 수 있으며, 이에 한정되지 않는다.The above silver alloy may include, but is not limited to, an alloy form containing silver as a main component and other metals such as Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W, Pa, In, Zn, Sn, Al, and Ti; and silver nitrides, silicides, carbides, oxides, etc.
상기 투명전도막은 산화주석인듐(ITO), 산화아연인듐(IZO), 산화주석아연인듐(ITZO) 및 산화갈륨아연인듐(IGZO)으로 이루어진 군으로부터 선택되는 1종 이상을 포함할 수 있다.The above transparent conductive film may include at least one selected from the group consisting of indium tin oxide (ITO), indium zinc oxide (IZO), indium tin zinc oxide (ITZO), and indium gallium zinc oxide (IGZO).
상기 다층막은 투명전도막/은, 투명전도막/은 합금, 투명전도막/은/투명전도막 또는 투명전도막/은 합금/투명전도막으로 형성되는 것을 포함할 수 있다.The above multilayer film may include one formed of transparent conductive film/silver, transparent conductive film/silver alloy, transparent conductive film/silver/transparent conductive film, or transparent conductive film/silver alloy/transparent conductive film.
본 발명의 은 박막 식각액 조성물 및 이를 이용한 식각 방법 및 금속 패턴의 형성 방법은 반사막용 OLED TFT 어레이 기판, 터치스크린 패널용 trace 배선 또는 나노와이어(nanowire) 배선의 형성에 사용될 수 있으며, 이에 한정되지 않고 상기 단일막 및 상기 다층막을 포함하는 전자 부품 소재에 사용될 수 있다. The silver thin film etchant composition of the present invention and the etching method using the same and the method for forming a metal pattern can be used for forming an OLED TFT array substrate for a reflective film, a trace wiring or nanowire wiring for a touch screen panel, and is not limited thereto, and can be used for electronic component materials including the single film and the multilayer film.
<은 박막 식각액 조성물> <Silver thin film etching solution composition>
본 발명의 식각액 조성물은, (A) 은식각촉진제, (B) 무기산 및 (C) 아졸화합물을 포함하며, 용제로써 (D) 물을 포함할 수 있다. The etchant composition of the present invention comprises (A) a silver etching accelerator, (B) an inorganic acid, and (C) an azole compound, and may comprise (D) water as a solvent.
(A) 은식각촉진제(A) Silver etching accelerator
본 발명의 은 박막 식각액 조성물에 포함되는 은식각촉진제는 은 박막 및/또는 투명전도막을 산화시키는 데 사용될 수 있다.The silver etching accelerator included in the silver thin film etching composition of the present invention can be used to oxidize a silver thin film and/or a transparent conductive film.
본 발명의 은식각촉진제는 과산화수소 및 철염으로 이루어진 군으로부터 선택되는 1종 이상을 포함할 수 있다. The silver etching accelerator of the present invention may include at least one selected from the group consisting of hydrogen peroxide and iron salts.
철염으로는, 예를 들면, 질산철, 질산 제이철, 황산철 및 황산 제이철 등을 들 수 있고, 질산제이철이 가장 바람직하다.Examples of iron salts include iron nitrate, ferric nitrate, iron sulfate, and ferric sulfate, with ferric nitrate being most preferred.
다만, 상기 철염이 FeCl3와 같이 염소화합물(즉, 염소이온)을 포함하는 경우, 이를 사용하는 본 발명의 인 박막 식각액 조성물로 은 박막을 식각하게 되면 은 석출이 발생하는 문제점을 야기 시킨다. 따라서, 본 발명에서 철염은 FeCl3 등의 염소화합물을 포함하지 않는 것이 바람직하다However, if the iron salt contains a chlorine compound (i.e., chlorine ion) such as FeCl 3 , when etching a silver thin film with the thin film etchant composition of the present invention using it, a problem occurs in which silver precipitation occurs. Therefore, it is preferable that the iron salt in the present invention does not contain a chlorine compound such as FeCl 3 .
상기 은식각촉진제의 함량은 조성물 총 중량에 대하여, 0.01 내지 20 중량%로 포함되며, 바람직하게는 1 내지 5 중량%로 포함될 수 있다. 은식각촉진제의 함량이 상기 함량범위 내로 포함되는 경우, 은의 식각 속도와 은 잔사 발생 방지 효과가 우수하고, 다층막 식각 시 은 박막과 투명전도막에 대한 식각 밸런스가 양호한 이점이 있다.The content of the above silver etching accelerator is included in an amount of 0.01 to 20 wt%, and preferably 1 to 5 wt%, based on the total weight of the composition. When the content of the silver etching accelerator is included within the above content range, the silver etching speed and the effect of preventing silver residue generation are excellent, and the etching balance for the silver thin film and the transparent conductive film is good during the etching of the multilayer film.
(B) 무기산(B) Weapon acid
본 발명의 무기산은 상기 은 박막에 대한 식각제로서, 상기 은식각촉진제 의해 산화된 상기 은 박막을 식각하는 데 사용될 수 있다. The inorganic acid of the present invention can be used as an etchant for the silver thin film, and can be used to etch the silver thin film oxidized by the silver etching accelerator.
상기 무기산은 보다 구체적으로, 질산 및 황산 등으로 이루어진 군으로부터 선택되는 1종 이상을 포함할 수 있으며, 바람직하게는 2종 이상을 포함하고, 가장 바람직하게는 질산 및 황산을 포함할 수 있다. The above inorganic acid may more specifically include at least one selected from the group consisting of nitric acid and sulfuric acid, preferably at least two, and most preferably nitric acid and sulfuric acid.
상기 무기산의 함량은 조성물 총 중량에 대하여, 0.1 내지 20 중량%로 포함되며, 3 내지 8 중량%가 보다 바람직하다. The content of the above inorganic acid is included in an amount of 0.1 to 20 wt% based on the total weight of the composition, and is more preferably 3 to 8 wt%.
무기산의 함량이 상기 함량범위 내로 포함되는 경우, 식각 속도 및 식각 균일성(Uniformity)이 우수하여 미세패턴을 형성할 수 있다.When the content of the inorganic acid is within the above content range, the etching speed and etching uniformity are excellent, so that a fine pattern can be formed.
(C) 중황산염(C) Bisulfate
본 발명의 식각액 조성물에 포함되는 중황산염은 처리매수 향상제로 사용되는 성분으로서, 은 박막 식각시 Ag+ 이온이 증가됨에 따른 Etch 특성 변화를 억제하는 역할을 수행한다.The bisulfate included in the etchant composition of the present invention is a component used as a treatment water improvement agent, and plays a role in suppressing changes in etch characteristics due to an increase in Ag + ions during etching of a silver thin film.
상기 중황산염은 양이온이 암모늄, 칼륨, 나트륨으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것으로, 예를 들면, 중황산칼륨, 중황산나트륨, 중황산암모늄 등을 들 수 있다. 바람직하게는 중황산칼륨을 포함할 수 있다. The above bisulfate salt contains at least one cation selected from the group consisting of ammonium, potassium, and sodium, and examples thereof include potassium bisulfate, sodium bisulfate, and ammonium bisulfate. Potassium bisulfate is preferable.
상기 중황산염의 함량은 조성물 총 중량에 대하여, 0.1 내지 30 중량%로 포함되며, 바람직하게는 3 내지 8 중량%로 포함될 수 있다. 본 발명에서 중황산염의 함량이 상기 함량범위 내인 경우, Ag+ 이온을 킬레이팅(Chelating)하는 효과가 우수하고, 은 박막 식각 속도 증가에 의한 과식각을 방지할 수 있다. The content of the above bisulfate may be included in an amount of 0.1 to 30 wt%, and preferably 3 to 8 wt%, based on the total weight of the composition. In the present invention, when the content of the bisulfate is within the above content range, the effect of chelating Ag + ions is excellent, and overetching due to an increase in the etching rate of a silver thin film can be prevented.
(D) 아졸 화합물(D) Azole compound
본 발명에서 아졸화합물은 은합금의 식각속도를 조절한다. 상기 D) 아졸화합물은 예를 들어, 피롤(pyrrole)계, 피라졸(pyrazol)계, 이미다졸(imidazole)계, 트리아졸(triazole)계, 테트라졸(tetrazole)계, 펜타졸(pentazole)계, 옥사졸(oxazole)계, 이소옥사졸(isoxazole)계, 디아졸(thiazole)계, 이소디아졸(isothiazole)계 등을 들 수 있으며, 이들은 1종 단독으로 또는 2종 이상이 함께 사용될 수 있다.In the present invention, the azole compound controls the etching rate of the silver alloy. Examples of the D) azole compound include pyrrole compounds, pyrazol compounds, imidazole compounds, triazole compounds, tetrazole compounds, pentazole compounds, oxazole compounds, isoxazole compounds, thiazole compounds, isodiazole compounds, etc., and these may be used alone or in combination of two or more.
보다 구체적으로, 상기 피롤계 화합물 피롤-2-카르복실산, 피롤-3-카르복실산, 1-(2-아미노페닐)피롤, 1H-피롤-1-프로피온산 등을 들 수 있다. 상기 피라졸계 화합물은 3-페닐-1H-피라졸, 3-(아미노메틸)피라졸, 5-(2-씨에닐)피라졸, 1-(2-하이드로에틸)-피라졸, 3-(2-씨에닐)피라졸, 5-메틸-1H-피라졸, 5-메틸-1H-피라졸, 4-니트로-1H-피라졸, 1H-피라졸-5-붕소산 등을 들 수 있다. 상기 이미다졸계 화합물은 이미다졸, 2-메틸이미다졸, 2-에틸이미다졸, 2-프로필이미다졸, 2-아미노이미다졸, 4-메틸이미다졸, 4-에틸이미다졸, 4-프로필이미다졸 등을 들 수 있다. 상기 트리아졸계 화합물은 1,2,3-벤조트리아졸, 5-메틸벤조트리아졸, 벤조트리아졸, 1-(2,2-디히드록시에틸)벤조트리아졸, 1-히드록시벤조트리아졸, 1-메톡시벤조트리아졸, 1-(1,2-디히드록시프로필)벤조트리아졸, 1-(2,3-디히드록시프로필)벤조트리아졸, N,N-비스-(2-에틸헥실)-아릴메틸-1H-벤조트리아졸-1-메탄아민, 2,2'-{[(4-메틸-1H-벤조트리아졸-1-일)메틸]이미노}비스에탄올, 2,2'-{[(5-메틸-1H-벤조트리아졸-1-일)메틸]이미노}비스에탄올, 5-카르복시벤조트리아졸부틸에스테르, 5-카르복시벤조트리아졸옥틸에스테르, 5-카르복시벤조트리아졸 도데실 에스테르 등을 들 수 있다. 상기 테트라졸계 화합물은 아미노테트라졸, 5-아미노테트라졸, 5-아미노-1-페닐테트라졸, 5-아미노-1(1-나프틸)테트라졸, 1-메틸-5-아미노테트라졸, 1,5-디아미노테트라졸, 5-메틸 테트라졸, 5-에틸 테트라졸 및 5-프로필 테트라졸 등을 들 수 있다. 본 발명은 상술한 화합물로 이루어진 군으로부터 선택되는 1종 이상의 화합물을 포함할 수 있다. More specifically, the pyrrole compounds include pyrrole-2-carboxylic acid, pyrrole-3-carboxylic acid, 1-(2-aminophenyl)pyrrole, 1H-pyrrole-1-propionic acid, etc. The pyrazole compounds include 3-phenyl-1H-pyrazole, 3-(aminomethyl)pyrazole, 5-(2-thienyl)pyrazole, 1-(2-hydroethyl)-pyrazole, 3-(2-thienyl)pyrazole, 5-methyl-1H-pyrazole, 5-methyl-1H-pyrazole, 4-nitro-1H-pyrazole, 1H-pyrazole-5-boronic acid, etc. The above imidazole compounds include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-aminoimidazole, 4-methylimidazole, 4-ethylimidazole, 4-propylimidazole, etc. The above triazole compounds are 1,2,3-benzotriazole, 5-methylbenzotriazole, benzotriazole, 1-(2,2-dihydroxyethyl)benzotriazole, 1-hydroxybenzotriazole, 1-methoxybenzotriazole, 1-(1,2-dihydroxypropyl)benzotriazole, 1-(2,3-dihydroxypropyl)benzotriazole, N,N-bis-(2-ethylhexyl)-arylmethyl-1H-benzotriazole-1-methanamine, 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}bisethanol, 2,2'-{[(5-methyl-1H-benzotriazol-1-yl)methyl]imino}bisethanol, Examples thereof include 5-carboxybenzotriazole butyl ester, 5-carboxybenzotriazole octyl ester, and 5-carboxybenzotriazole dodecyl ester. Examples of the tetrazole compounds include aminotetrazole, 5-aminotetrazole, 5-amino-1-phenyltetrazole, 5-amino-1(1-naphthyl)tetrazole, 1-methyl-5-aminotetrazole, 1,5-diaminotetrazole, 5-methyl tetrazole, 5-ethyl tetrazole, and 5-propyl tetrazole. The present invention may include at least one compound selected from the group consisting of the compounds described above.
상기 D) 아졸화합물은 조성물 총 중량에 대하여, 0.05 내지 5.0중량%으로 포함되고, 바람직하게는 0.1 내지 3.0중량%로 포함된다. 상술한 범위 미만이면 은합금의 식각속도를 조절이 불가햐여 S/E가 증가하여 미세패턴 구현 효과가 떨어지게 된다. 상술한 범위를 초과하여 포함되면, 은합금의 식각속도가 감소하게 되므로 잔사가 발생하여 불량이 나타날 수 있다.The above D) azole compound is contained in an amount of 0.05 to 5.0 wt%, and preferably 0.1 to 3.0 wt%, based on the total weight of the composition. If it is contained in an amount less than the above-described range, the etching speed of the silver alloy cannot be controlled, so that S/E increases and the effect of implementing a fine pattern deteriorates. If it is contained in an amount exceeding the above-described range, the etching speed of the silver alloy decreases, so that residues may be generated and defects may occur.
(E)물(E)Water
본 발명의 은 박막 식각액 조성물에 포함되는 상기 물은 반도체 공정용 탈이온수일 수 있으며, 바람직하게는 18㏁/㎝ 이상의 상기 탈이온수를 사용할 수 있다.The water included in the silver thin film etching composition of the present invention may be deionized water for semiconductor processes, and preferably, deionized water having a density of 18 MΩ/cm or more may be used.
본 발명에서 물은 잔량으로 포함될 수 있으며, 상기 잔량은, 본 발명의 필수 성분 및 그 외 다른 성분들을 더 포함한 총 조성물의 중량이 100중량%가 되도록 하는 잔량을 의미한다. In the present invention, water may be included as a residual amount, and the residual amount means a residual amount such that the weight of the total composition including the essential components of the present invention and other components becomes 100% by weight.
예를 들면, 본 발명은 조성물의 총 중량대비 30 내지 99 중량 %로 포함될 수 있다. For example, the present invention may be included in an amount of 30 to 99 weight % based on the total weight of the composition.
본 발명의 은 박막 식각액 조성물은 유발시키는 인산을 포함하지 않는 것을 특징으로 하여, 은(Ag) 또는 은합금으로 이루어진 단일막 및 상기 단일막과 투명전도막으로 구성된 다층막 식각시에 하부막을 손상시키지 않으면서 우수한 식각 균일성을 나타낼 수 있다The silver thin film etchant composition of the present invention is characterized by not containing phosphoric acid that causes oxidation, and thus can exhibit excellent etching uniformity without damaging the underlying film when etching a single film made of silver (Ag) or a silver alloy and a multilayer film made of the single film and a transparent conductive film.
<은 박막 식각액 조성물을 이용한 식각 방법><Etching method using a thin film etchant composition>
또한, 본 발명은, 본 발명에 따른 은 박막 식각액 조성물을 이용하는 식각 방법을 제공한다. 본 발명의 식각 방법은, 본 발명의 상기 은 박막 식각액 조성물을 사용하는 점을 제외하고는, 공지의 금속 식각 방법에 따라 패턴을 형성 할 수 있다. In addition, the present invention provides an etching method using the silver thin film etching composition according to the present invention. The etching method of the present invention can form a pattern according to a known metal etching method, except that the silver thin film etching composition of the present invention is used.
일 예로, 상기 식각 방법은, i) 기판 상에, 은 또는 은 합금으로 이루어진 단일막, 또는 상기 단일막과 투명전도막으로 구성되는 다층막을 형성하는 단계; ii) 상기 단일막 또는 상기 다층막 위에 선택적으로 광 반응 물질을 남기는 단계; 및 iii) 본 발명에 따른 은 박막 식각액 조성물을 사용하여, 상기 단일막 또는 상기 다층막을 식각하는 단계를 포함한다.For example, the etching method comprises: i) forming a single film made of silver or a silver alloy on a substrate, or a multilayer film composed of the single film and a transparent conductive film; ii) selectively leaving a photo-reactive material on the single film or the multilayer film; and iii) etching the single film or the multilayer film using a silver thin film etching composition according to the present invention.
<< 은 박막 식각액 조성물을 이용한 금속 패턴의 형성 방법>>Method for forming a metal pattern using a thin film etching composition
또한, 본 발명은, 본 발명에 따른 은 박막 식각액 조성물을 이용하는 금속 패턴의 형성 방법을 제공한다. 본 발명의 금속 패턴의 형성 방법은, 본 발명의 상기 은 박막 식각액 조성물을 사용하는 점을 제외하고는, 공지의 금속 패턴 형성 방법에 따라 패턴을 형성 할 수 있다. In addition, the present invention provides a method for forming a metal pattern using the silver thin film etching composition according to the present invention. The method for forming a metal pattern according to the present invention can form a pattern according to a known metal pattern forming method, except that the silver thin film etching composition according to the present invention is used.
일 예로, 상기 금속 패턴의 형성 방법은, i) 기판 상에, 은 또는 은 합금으로 이루어진 단일막, 또는 상기 단일막과 투명전도막으로 구성되는 다층막을 형성하는 단계; 및 ii) 본 발명에 따른 은 박막 식각액 조성물을 사용하여, 상기 단일막 또는 상기 다층막을 식각하는 단계를 포함한다.For example, the method for forming the metal pattern includes: i) a step of forming a single film made of silver or a silver alloy, or a multilayer film composed of the single film and a transparent conductive film, on a substrate; and ii) a step of etching the single film or the multilayer film using a silver thin film etching composition according to the present invention.
이하, 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. 본 발명의 범위는 특허청구범위에 표시되었고, 더욱이 특허 청구범위 기록과 균등한 의미 및 범위 내에서의 모든 변경을 함유하고 있다. 또한, 이하의 실시예, 비교예에서 함유량을 나타내는 "%" 및 "부"는 특별히 언급하지 않는 한 중량% 기준이다.Hereinafter, the present invention will be described in more detail through examples. However, the following examples are intended to further explain the present invention, and the scope of the present invention is not limited by the following examples. The scope of the present invention is indicated in the claims, and furthermore, it includes all changes within the meaning and scope equivalent to the claims. In addition, "%" and "part" indicating the content in the following examples and comparative examples are based on weight % unless specifically stated otherwise.
실시예 1 내지 7, 참조예 1 내지 2 및 비교예 1 내지 4에 따른 은 박막 식각액 조성물의 제조Preparation of silver thin film etching compositions according to Examples 1 to 7, Reference Examples 1 to 2 and Comparative Examples 1 to 4
하기 표 1에 나타낸 조성 및 함량에 따라 실시예1 내지 실시예6 및 비교예1 내지 비교예5의 식각액 조성물을 제조하였으며, 식각액 조성물 총 중량이 100 중량%가 되도록 잔량의 물을 포함하였다.Etching compositions of Examples 1 to 6 and Comparative Examples 1 to 5 were prepared according to the compositions and contents shown in Table 1 below, and the remaining amount of water was included so that the total weight of the etching composition became 100 wt%.
[표 1][Table 1]
-PBS: Potassium bisulfate-PBS: Potassium bisulfate
-MTZ: 5-Methyltetrazole-MTZ: 5-Methyltetrazole
본 발명의 실시를 위해 상기 식각액 조성물을 신액 및 구액으로 구분하여 평가를 실시하였으며, 본 발명에서 신액이란 식각액 조성물이 제조된 바로 직후의 상태를 신액이라 하며, 상기 제조된 식각액을 장시간 식각 공정을 진행했다는 가정 하에 인위적으로 은 파우더 1000ppm을 녹인 상태(처리매수 평가)를 구액이라고 한다. In order to carry out the present invention, the etchant composition was divided into a fresh solution and an old solution and evaluated. In the present invention, the fresh solution refers to the state immediately after the etchant composition is manufactured, and the state in which 1000 ppm of silver powder is artificially dissolved under the assumption that the manufactured etchant has undergone an etching process for a long period of time (evaluation of the number of treatments) is referred to as the old solution.
실험예 1. Side Etch 측정Experimental Example 1. Side Etch Measurement
기판 상에 ITO(산화주석인듐)/은/ITO 삼중막을 형성한 뒤, 상기 삼중막 상에 포토레지스트를 패터닝하였다. 상기 기판을 실시예 및 비교예에 따른 은 박막 식각액 조성물을이용하여 식각 공정을 수행하였다.After forming an ITO (indium tin oxide)/silver/ITO triple film on a substrate, a photoresist was patterned on the triple film. An etching process was performed on the substrate using a silver thin film etchant composition according to examples and comparative examples.
포토레지스트가 덮여 있지 않은 부분의 투명전도막/은/투명전도막 삼중막의 에치가 끝난 시점으로부터 추가적으로 Over Etch를 100% 진행하여 패터닝 된 포토레지스트 끝단으로부터 식각 된 은(Ag)막까지의 거리를 전자주사현미경 (SEM; 모델명: SU-8010, HITACHI)을 이용하여 측정 하였으며, 하기의 기준으로 평가하여 그 결과를 표 2에 나타내었다. From the point at which the etching of the transparent conductive film/silver/transparent conductive film triple layer was completed in the area not covered by the photoresist, an additional 100% Over Etch was performed, and the distance from the edge of the patterned photoresist to the etched silver (Ag) film was measured using a scanning electron microscope (SEM; model name: SU-8010, HITACHI), and the results were evaluated based on the following criteria, and are shown in Table 2.
<편측식각 거리 측정 평가기준><Evaluation criteria for measuring distance of unilateral etching>
양호: 편측식각(S/E) ≤ 0.25㎛ Good: Single-sided etching (S/E) ≤ 0.25㎛
보통: 0.25㎛ < 편측식각(S/E)≤0.50㎛Normal: 0.25㎛ < Single-sided etching (S/E) ≤ 0.50㎛
불량: 0.50㎛ < 편측식각(S/E)Defect: 0.50㎛ < Single-sided etching (S/E)
실험예 2. 은 잔사 측정Experimental Example 2. Measurement of silver residue
분사식 식각 방식의 실험장비(모델명: ETCHER(TFT), SEMES사) 내에 상기 실시예 1 내지 6 및 비교예 1 내지 5의 은 식각액 조성물을 각각 넣고, 온도를 40℃로 설정하여 가온한 후, 온도가 40±0.1℃에 도달하였을 때 상기 시편의 식각 공정을 수행하였다. 총 식각 시간은 85초로 실시하였다. 기판을 넣고 분사를 시작하여 85초의 식각 시간이 다 되면 꺼내어 탈이온수로 세정한 후, 열풍건조장치를 이용하여 건조하고, 포토레지스트 박리기(PR stripper)를 이용하여 포토레지스트를 제거하였다. 세정 및 건조 후 전자주사현미경(SEM; 모델명: SU-8010, HITACHI사 제조)을 이용하여 포토레지스트가 덮여 있지 않은 부분에 은(Ag)이 식각 되지 않고 남아 있는 현상인 잔사를 측정하였으며, 하기의 기준으로 평가하여, 결과를 표2 에 나타내었다. The silver etchant compositions of Examples 1 to 6 and Comparative Examples 1 to 5 were each placed into a spray-type etching experiment device (model name: ETCHER (TFT), manufactured by SEMES), the temperature was set to 40°C, and the device was heated. When the temperature reached 40±0.1°C, the etching process of the specimens was performed. The total etching time was 85 seconds. The substrate was placed and spraying started, and when the etching time of 85 seconds was reached, it was taken out, washed with deionized water, dried using a hot air dryer, and the photoresist was removed using a photoresist stripper. After washing and drying, the residue, which is a phenomenon in which silver (Ag) remains unetched in areas not covered by the photoresist, was measured using a scanning electron microscope (SEM; model name: SU-8010, manufactured by HITACHI), and the results are shown in Table 2.
<잔사 측정 평가 기준><Residue Measurement Evaluation Criteria>
양호: [잔사 미발생]Good: [No residue]
불량: [잔사 발생]Defective: [residue occurs]
실험예 3. 은 재흡착 평가Experimental Example 3. Silver re-adsorption evaluation
분사식 식각 방식의 실험장비(모델명: ETCHER(TFT), SEMES사) 내에 상기 실시예 1 내지 6 및 비교예 1 내지 5의 은 식각액 조성물을 각각 넣고, 온도를 40℃로 설정하여 승온한 후, 온도가 40±0.1℃에 도달하였을 때 상기 시편의 식각 공정을 수행하였다. 총 식각 시간은 85초로 실시하였다. 기판을 넣고 분사를 시작하여 85초의 식각 시간이 다 되면 꺼내어 탈이온수로 세정한 후, 열풍건조장치를 이용하여 건조하였다. 세정 및 건조 후 기판을 절단하고 단면을 전자주사현미경(SEM; 모델명: SU-8010, HITACHI사 제조)을 이용하여 측정하였다. 상기 식각 공정으로 인해, 상기 기판 내 노출된 S/D 부의 Ti/Al/Ti 삼중막의 상부 Ti에 흡착된 은 입자의 개수를 측정하고, 하기의 기준으로 평가하여, 결과를 표2 에 나타내었다.The silver etchant compositions of Examples 1 to 6 and Comparative Examples 1 to 5 were each placed into a spray-type etching experiment device (model name: ETCHER (TFT), SEMES), the temperature was set to 40°C and increased, and when the temperature reached 40±0.1°C, the etching process of the specimens was performed. The total etching time was 85 seconds. The substrate was placed and spraying was started, and when the etching time of 85 seconds was reached, it was taken out, washed with deionized water, and dried using a hot air dryer. After washing and drying, the substrate was cut and the cross-section was measured using a scanning electron microscope (SEM; model name: SU-8010, manufactured by HITACHI). The number of silver particles adsorbed on the upper Ti of the Ti/Al/Ti triple film of the S/D portion exposed in the substrate due to the etching process was measured, and the results are shown in Table 2.
<은 재흡착 평가 기준><Silver resorption evaluation criteria>
양호: [5개 미만]Good: [Less than 5]
보통: [5개 이상 50개 미만]Normal: [5 or more but less than 50]
불량: [50개 이상]Bad: [50 or more]
[표 2][Table 2]
본원발명의 식각액 조성물의 구성을 전부 포함하는 실시예 1 내지 7의 경우 신액 및 구액 모두가 사이드 에치, 은 잔사 및 은 재흡착 효과가 우수함을 확인하였다. 그러나, 질산제이철을 포함하지 않는 비교예 1 의 경우 식각자체가 불가능 하였으며, 본원발명의 식각액 조성물의 필수 구성 중, 무기산, 중황산염 및 아졸화합물 중 하나라도 포함하지 않는 비교예 2 내지 4의 경우 신액 및 구액의 은 재흡착 효과가 불량하였고, 사이드 에치 변화량 또한 신액 및 구액의 효과차이가 현저히 발생함을 확인하였다. 또한, 은을 식각함에 있어서 무기산으로 인산을 포함하는 참조예 1의 경우 신액 및 구액의 은 잔사 및 재흡착 방지 능력이 불량함을 확인하였고, 철염이라도 염소를 포함하는 철염을 사용하는 참조예의 경우 은 잔사 능력은 양호하더라도, 은 재흡착 효과가 불량함을 확인 하였다. In the case of Examples 1 to 7 including all of the components of the etchant composition of the present invention, it was confirmed that both the new solution and the old solution were excellent in side etch, silver residue, and silver re-adsorption effects. However, in the case of Comparative Example 1 which did not include ferric nitrate, etching itself was impossible, and in the case of Comparative Examples 2 to 4 which did not include even one of the essential components of the etchant composition of the present invention, namely, inorganic acid, bisulfate, and azole compound, the silver re-adsorption effects of the new solution and the old solution were poor, and it was confirmed that there was a significant difference in the effect of the side etch change amount between the new solution and the old solution. In addition, in the case of Reference Example 1 which included phosphoric acid as an inorganic acid in etching silver, it was confirmed that the silver residue and re-adsorption prevention capabilities of the new solution and the old solution were poor, and in the case of the Reference Example which used an iron salt including chlorine even as an iron salt, it was confirmed that although the silver residue capability was good, the silver re-adsorption effect was poor.
Claims (14)
(A) 은식각촉진제 0.01 내지 20 중량%;
(B) 무기산 0.1 내지 20 중량%;
(C) 중황산염 0.1 내지 30 중량%;
(D) 아졸 화합물 0.05 내지 5.0 중량%; 및
(E) 조성물 총 중량이 100중량%가 되게 하는 물을 포함하는, 은 박막 식각액 조성물로,
상기 (A)은식각촉진제는 과산화수소 및 철염으로 이루어진 군으로부터 선택되는 1종 이상을 포함하며, 상기 철염은 염소 화합물을 포함하지 않는 것이고,
상기 (B) 무기산은 질산, 및 황산으로 이루어진 군으로부터 선택되는 1종 이상을 포함하며, 인산을 포함하지 않는 것이고,
상기 (C) 중황산염은 중황산칼륨, 중황산나트륨 및 중황산암모늄으로 이루어진 군으로부터 선택되는 1종 이상을 포함하며, 과산화물을 포함하지 않는 것을 특징으로 하는, 은 박막 식각액 조성물.Regarding the total weight of the composition,
(A) 0.01 to 20 wt% of silver etching accelerator;
(B) 0.1 to 20 wt% of inorganic acid;
(C) 0.1 to 30 wt% of bisulfate;
(D) 0.05 to 5.0 wt% of an azole compound; and
(E) A silver thin film etching composition containing water so that the total weight of the composition becomes 100 wt%,
The above (A) etching accelerator comprises at least one selected from the group consisting of hydrogen peroxide and iron salts, wherein the iron salt does not contain a chlorine compound,
The above (B) inorganic acid comprises at least one selected from the group consisting of nitric acid and sulfuric acid, and does not contain phosphoric acid.
A silver thin film etching composition, characterized in that the (C) bisulfate comprises at least one selected from the group consisting of potassium bisulfate, sodium bisulfate and ammonium bisulfate, and does not contain a peroxide.
상기 철염은 질산철, 질산제이철, 황산철 및 황산제이철로 이루어진 군으로부터 선택되는 1종 이상을 포함하는, 은 박막 식각액 조성물.In claim 1,
A silver thin film etching composition, wherein the iron salt comprises at least one selected from the group consisting of iron nitrate, ferric nitrate, iron sulfate, and ferric sulfate.
상기 (D) 아졸 화합물은, 피롤(pyrrole)계, 피라졸(pyrazol)계, 이미다졸(imidazole)계, 트리아졸(triazole)계, 테트라졸(tetrazole)계, 펜타졸(pentazole)계, 옥사졸(oxazole)계, 이소옥사졸(isoxazole)계, 디아졸(thiazole)계 및 이소디아졸(isothiazole)계로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것인, 은 박막 식각액 조성물.In claim 1,
A silver thin film etching composition, wherein the (D) azole compound comprises at least one selected from the group consisting of pyrrole compounds, pyrazol compounds, imidazole compounds, triazole compounds, tetrazole compounds, pentazole compounds, oxazole compounds, isoxazole compounds, thiazole compounds, and isodiazole compounds.
상기 은 박막 식각액 조성물은 은 또는 은 합금으로 이루어진 단일막, 또는 상기 단일막과 투명전도막으로 구성되는 다층막을 동시에 식각할 수 있는 것을 특징으로 하는 은 박막 식각액 조성물.In claim 1,
The above silver thin film etching composition is characterized in that it can simultaneously etch a single film made of silver or a silver alloy, or a multilayer film made of the single film and a transparent conductive film.
상기 투명전도막은 산화주석인듐(ITO), 산화아연인듐(IZO), 산화주석아연인듐(ITZO) 및 산화갈륨아연인듐(IGZO)으로 이루어진 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 은 박막 식각액 조성물.In claim 9,
A silver thin film etching composition, characterized in that the transparent conductive film is at least one selected from the group consisting of indium tin oxide (ITO), indium zinc oxide (IZO), indium tin zinc oxide (ITZO), and indium gallium zinc oxide (IGZO).
상기 다층막은 투명전도막/은, 투명전도막/은 합금, 투명전도막/은/투명전도막 또는 투명전도막/은 합금/투명전도막으로 형성되는 것을 포함하는 은 박막 식각액 조성물.In claim 9,
A silver thin film etching composition including the multilayer film formed by transparent conductive film/silver, transparent conductive film/silver alloy, transparent conductive film/silver/transparent conductive film or transparent conductive film/silver alloy/transparent conductive film.
은 박막 식각액 조성물은 인산을 포함하지 않는 것인, 은 박막 식각액 조성물. In claim 1,
A silver thin film etching composition, wherein the silver thin film etching composition does not contain phosphoric acid.
상기 단일막 또는 상기 다층막 위에 선택적으로 광 반응 물질을 남기는 단계; 및
청구항 1의 조성물을 사용하여, 상기 단일막 또는 상기 다층막을 식각하는 단계를 포함하는 식각 방법.A step of forming a single film made of silver or a silver alloy, or a multilayer film composed of the single film and a transparent conductive film, on a substrate;
A step of selectively leaving a photo-responsive material on the single film or the multilayer film; and
An etching method comprising a step of etching the single film or the multilayer film using the composition of claim 1.
청구항 1의 조성물을 사용하여, 상기 단일막 또는 상기 다층막을 식각하는 단계를 포함하는 금속 패턴의 형성 방법.
A step of forming a single film made of silver or a silver alloy, or a multilayer film composed of the single film and a transparent conductive film on a substrate; and
A method for forming a metal pattern, comprising the step of etching the single film or the multilayer film using the composition of claim 1.
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