WO2013136624A1 - エッチング液組成物及びエッチング方法 - Google Patents
エッチング液組成物及びエッチング方法 Download PDFInfo
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- WO2013136624A1 WO2013136624A1 PCT/JP2012/083435 JP2012083435W WO2013136624A1 WO 2013136624 A1 WO2013136624 A1 WO 2013136624A1 JP 2012083435 W JP2012083435 W JP 2012083435W WO 2013136624 A1 WO2013136624 A1 WO 2013136624A1
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- Prior art keywords
- etching
- film
- group
- solution composition
- etching solution
- Prior art date
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- 238000005530 etching Methods 0.000 title claims abstract description 99
- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 20
- 229910003437 indium oxide Inorganic materials 0.000 claims abstract description 34
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 42
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 239000010949 copper Substances 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 12
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 11
- 229910001447 ferric ion Inorganic materials 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 239000002738 chelating agent Substances 0.000 claims description 2
- 230000005484 gravity Effects 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 abstract description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract 2
- 230000002265 prevention Effects 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 229910003336 CuNi Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- -1 halogen ions Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 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 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- HHAPGMVKBLELOE-UHFFFAOYSA-N 2-(2-methylpropoxy)ethanol Chemical compound CC(C)COCCO HHAPGMVKBLELOE-UHFFFAOYSA-N 0.000 description 1
- HRWADRITRNUCIY-UHFFFAOYSA-N 2-(2-propan-2-yloxyethoxy)ethanol Chemical compound CC(C)OCCOCCO HRWADRITRNUCIY-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- YJTIFIMHZHDNQZ-UHFFFAOYSA-N 2-[2-(2-methylpropoxy)ethoxy]ethanol Chemical compound CC(C)COCCOCCO YJTIFIMHZHDNQZ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910021576 Iron(III) bromide Inorganic materials 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229910002668 Pd-Cu Inorganic materials 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- NJWNEWQMQCGRDO-UHFFFAOYSA-N indium zinc Chemical compound [Zn].[In] NJWNEWQMQCGRDO-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 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 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- HEJPGFRXUXOTGM-UHFFFAOYSA-K iron(3+);triiodide Chemical compound [Fe+3].[I-].[I-].[I-] HEJPGFRXUXOTGM-UHFFFAOYSA-K 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
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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
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- 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
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- the present invention relates to an etching solution composition and an etching method using the etching solution composition, and more specifically, an etching solution composition used for collectively etching a laminated film composed of an indium oxide film and a metal film. And an etching method using the etching solution composition.
- Patent Document 1 discloses an etching solution composition for indium-tin oxide (hereinafter sometimes abbreviated as ITO) containing ferric chloride and hydrochloric acid.
- ITO indium-tin oxide
- Patent Document 2 discloses an aqueous solution containing cupric ions, organic acids, halogen ions, azoles, and polyalkylene glycols as copper or copper alloy etchants. Yes.
- polyalkylene glycol is used to suppress dissolution of the electrolytic copper plating layer and promote etching of the electroless copper plating layer which is the underlying conductive layer.
- the etching solution disclosed above is used to form a thin line with good linearity composed of an ITO film and a copper film by collectively etching a laminated film composed of an ITO film and a copper film, etching is performed.
- the speed cannot be controlled and a thin line with a desired width cannot be obtained, and that the thin line may meander.
- the etching rate differs greatly between the ITO film and the copper film, so that the width of etching the ITO film in the direction parallel to the substrate surface and the width of etching the copper film in the same direction are large.
- the present invention has been made to solve the above problems, and when a laminated film composed of an indium oxide-based film and a metal-based film is collectively etched, the present invention is provided between the indium oxide-based film and the metal-based film.
- An etching solution composition capable of performing etching with good linearity with a small width of a thin line made of an indium oxide-based coating and a metal coating without causing a large level difference, and an etching method using the etching solution composition The purpose is to provide.
- the present inventors have found that a ferric ion component; a hydrogen chloride component; and a compound represented by the following general formula (1) and a straight chain having 1 to 4 carbon atoms
- the etching liquid composition containing the at least 1 sort (s) or more of compound component chosen from the group which consists of branched alcohol can solve the said problem, and came to this invention:
- R 1 and R 3 each independently represents hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms; R 2 represents a linear or branched alkylene group having 1 to 4 carbon atoms; n represents a number of 1 to 3.
- the present invention provides an etching solution composition for collectively etching a laminated film composed of an indium oxide-based film and a metal-based film.
- a component Ferric ion component
- B component Hydrogen chloride component
- C component at least one compound component selected from the group consisting of the compound represented by the above general formula (1) and a linear or branched alcohol having 1 to 4 carbon atoms (hereinafter sometimes abbreviated as “C component”).
- An etching solution composition comprising an aqueous solution containing.
- the present invention also provides an etching method for collectively etching a laminated film composed of an indium oxide-based film and a metal-based film, characterized by using the above-mentioned etching solution composition.
- the etching solution composition of the present invention when a laminated film composed of an indium oxide-based film and a metal-based film is etched at once, a large step is not generated between the indium oxide-based film and the metal-based film.
- the thin line of the indium oxide-based film and the metal-based film has a small width and can be etched with good linearity. Therefore, the etching solution composition of the present invention can be suitably used for an etching method used for forming a fine line by etching an ITO film and a metal film at once.
- Evaluation is a schematic diagram showing the relationship of L 1, L 2 in the test.
- the “indium oxide-based film” described in the present specification is not particularly limited as long as it is a film containing indium oxide.
- indium oxide, indium-tin oxide, and indium-zinc A film made of at least one selected from oxides is generically named.
- the “metal-based coating” described in the present specification is not particularly limited as long as it is a coating made of a metal.
- a coating made of at least one selected from alloy coatings such as CuNi, CuNiTi, NiCr, Ag—Pd—Cu, etc. is generically named.
- the ferric ion component used in the etching solution composition of the present invention is a component constituting the main component of the etching solution composition of the present invention.
- the compound used as the ferric ion component is not particularly limited as long as it is a compound that can supply ferric ion.
- iron (III) chloride, iron (III) bromide examples thereof include iron (III) iodide, iron (III) sulfate, iron (III) nitrate, and iron (III) acetate, and they may be anhydrous or hydrated. Two or more compounds that can supply the ferric ion may be used in combination.
- the preferable (A) ferric ion concentration in the etching solution composition of the present invention may be adjusted as appropriate depending on the thickness and width of a laminated film composed of an indium oxide-based film and a metal-based film as a desired material to be etched. 0.1 to 15% by mass, preferably 1 to 10% by mass. (A) If the ferric ion concentration is less than 0.1% by mass, a sufficient etching rate may not be obtained, which is not preferable. On the other hand, when (A) the ferric ion concentration is higher than 15% by mass, the compound represented by the general formula (1) may be insolubilized as the component (C). Therefore, it is not preferable.
- the (B) hydrogen chloride component used in the etching solution composition of the present invention is a component constituting the main component of the etching solution composition of the present invention.
- the concentration of the preferred (B) hydrogen chloride component in the etching solution composition of the present invention may be appropriately adjusted depending on the thickness and width of the laminated film composed of an indium oxide-based film and a metal-based film, which is a desired material to be etched. Is 0.1 to 25% by mass, preferably 1 to 20% by mass.
- concentration of the hydrogen chloride component is less than 0.1% by mass, a sufficient etching rate may not be obtained, which is not preferable.
- the concentration of the (B) hydrogen chloride component is more than 25% by mass, the etching rate is not improved, and it may cause problems such as corrosion of the apparatus members.
- (C) used in the etching solution composition of the present invention is at least one compound selected from the group consisting of the compound represented by the above general formula (1) and a linear or branched alcohol having 1 to 4 carbon atoms.
- a ferric ion component and (B) a hydrogen chloride component are used in combination, a multilayer film composed of an indium oxide-based film and a metal-based film is collectively etched into the etching solution composition of the present invention.
- the hydrogen represented by R 1 and R 3 or the linear or branched alkyl group having 1 to 4 carbon atoms is, for example, Examples thereof include hydrogen, methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, isobutyl and the like.
- the linear or branched alkylene group having 1 to 4 carbon atoms represented by R 2 include methylene , Ethylene, propylene, isopropylene, butylene, second butylene, third butylene, isobutylene and the like.
- R 1 and R 3 hydrogen, methyl group, ethyl group, propyl group, butyl group and the like are preferable, and as R 2 , ethylene group, propylene group and the like are preferable.
- Specific examples of the compound represented by the general formula (1) include, for example, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, Diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol Nopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol
- the indium oxide-based film and the metal-based film are used. This is preferable because the level difference generated in the line is small, the narrow width of the fine line is small, and a fine line with good linearity can be obtained. Moreover, the case where dipropylene glycol monomethyl ether or isopropanol is used is particularly preferable because the effects as described above are particularly high. Further, when the etching solution composition of the present invention is used in an etching process using a resin resist, it is particularly preferable to use isopropanol because it does not affect the resin resist. Two or more kinds of the compound represented by the general formula (1) and the linear or branched alcohol having 1 to 4 carbon atoms may be used in combination.
- R 1, R 3 and n are R 1, R 3 and as defined n in the general formula (1).
- the preferable concentration of the component (C) in the etching solution composition of the present invention may be adjusted as appropriate depending on the thickness and width of the laminated film of the indium oxide-based film and the metal-based film, which is a desired material to be etched. 0.01 to 10% by mass, preferably 0.1 to 5% by mass. When the concentration of the component (C) is less than 0.01% by mass, the blending effect is not exhibited, which is not preferable. Even when the concentration exceeds 10% by mass, no further improvement in the blending effect is observed.
- the etching solution composition of the present invention is blended with known additives as long as the effects of the present invention are not impaired.
- the additive include an etchant composition stabilizer, a solubilizer for each component, an antifoaming agent, a pH adjuster, a specific gravity adjuster, a viscosity adjuster, a wettability improver, a chelating agent, an oxidizing agent, and a reduction agent.
- concentration when these additives are used is generally in the range of 0.001% by mass to 10% by mass, respectively.
- the etching rate of the etching solution composition of the present invention is too fast, it is preferable to use a reducing agent as an additive, specifically, copper chloride, ferrous chloride, copper powder, silver powder, and the like.
- a reducing agent specifically, copper chloride, ferrous chloride, copper powder, silver powder, and the like.
- the concentration is preferably in the range of 0.01 to 10% by mass.
- the etching solution composition of the present invention is used when collectively etching a laminated film composed of an indium oxide-based film and a metal-based film.
- the indium oxide-based film may be a single layer or a laminated film of two or more layers.
- the metal-based film may be a single layer or a laminated film of two or more layers.
- the metal-based film may be an upper layer, a lower layer, or an upper layer and a lower layer.
- the indium oxide-based film and the metal-based film may be alternately laminated.
- Examples of the device having a laminated film composed of an indium oxide-based film and a metal-based film as described above include a liquid crystal display, a plasma display, a touch panel, an organic EL, a solar battery, a lighting fixture, and the like.
- the etching solution composition of the present invention can be used.
- the etching method for collectively etching the laminated film of the indium oxide film and the metal film using the etching solution composition of the present invention is not particularly limited, and a well-known general etching method may be used. For example, there are dip type, spray type and spin type etching methods. Among these, for example, when etching a base material on which a CuNi / Cu / ITO layer is formed on a PET substrate by a dip etching method, the base material is used as the etching solution composition of the present invention.
- the CuNi / Cu / ITO layer on the PET substrate can be etched in a lump by dipping and pulling up after dipping under appropriate etching conditions.
- Etching conditions are not particularly limited, and can be arbitrarily set according to the shape or film thickness of the etching target.
- the etching temperature is preferably 10 ° C. to 60 ° C., particularly preferably 30 ° C. to 50 ° C. Since the temperature of the etching solution composition may be increased by heat of reaction, the temperature may be controlled by a known means so as to maintain it within the above temperature range if necessary.
- the etching time is not particularly limited because it may be a time sufficient for the object to be etched to be completely etched. For example, in the case of an etching target having a film thickness of about 500 to 2000 mm as in wiring manufacturing on an electronic circuit board, the etching may be performed for about 0.2 to 5 minutes within the above temperature range.
- Example 1 Using the compound shown in Table 1 as the component (C), the etching solution composition was formulated according to the formulation shown in Table 2, and Products 1 to 19 of the present invention were obtained. The balance of the content is water.
- Comparative Example 1 Comparative products 1 to 5 were obtained by blending an etching solution composition with the composition shown in Table 3. The balance of the content is water.
- Example 2 A substrate on which a resist pattern having a width of 75 ⁇ m and an opening of 25 ⁇ m was formed on a CuNi / Cu / ITO / PET using a positive liquid resist was cut into a test piece of 20 mm length ⁇ 20 mm width. This test piece was subjected to a dip etching process with stirring at 40 ° C. for 1 minute using the etching solution compositions of inventive products 1 to 19 prepared in Example 1.
- Comparative Example 2 A substrate on which a resist pattern having a width of 75 ⁇ m and an opening of 25 ⁇ m was formed on a CuNi / Cu / ITO / PET using a positive liquid resist was cut into a test piece of 20 mm length ⁇ 20 mm width. The test piece was subjected to a dip etching process at 40 ° C. for 1 minute with stirring using the etching solution compositions of Comparative Products 1 to 5 prepared in Comparative Example 1.
- the etching solution composition of the present invention can be used when etching the indium oxide-based film and the metal-based film in a lump, thereby reducing the thinning of the thin line and making a large step difference between the indium oxide-based film and the metal-based film. It turned out that it is an etching liquid composition which can obtain a thin line with good linearity, without generating.
Abstract
Description
(A)第二鉄イオン成分(以下、A成分と略す場合がある。);
(B)塩化水素成分(以下、B成分と略す場合がある。);
(C)上記一般式(1)で表される化合物及び炭素数1~4の直鎖または分岐状アルコールからなる群から選ばれる少なくとも1種以上の化合物成分(以下、C成分と略す場合がある。) を含む水溶液からなることを特徴とするエッチング液組成物を提供するものである。
したがって、本発明のエッチング液組成物は、特にITO被膜と金属系被膜を一括でエッチングすることにより細線を形成するために用いられるエッチング方法に好適に使用することができる。
まず、本明細書に記載する「酸化インジウム系被膜」とは、酸化インジウムを含む膜であればよく、特に限定されるものではないが、例えば、酸化インジウム、インジウム-スズ酸化物及びインジウム-亜鉛酸化物から選ばれる1種以上からなる被膜を総称するものとする。
また、本明細書に記載する「金属系被膜」とは、金属からなる被膜であれば特に限定されるものではないが、例えば、銅、ニッケル、チタン、クロム、銀、モリブデン、アルミニウム、白金及びパラジウム等からなる群から選択される金属被膜や、銅、ニッケル、チタン、クロム、銀、モリブデン、アルミニウム、白金及びパラジウムからなる群から選択される2種類以上の金属を含有する合金被膜、例えば、CuNi、CuNiTi、NiCr、Ag-Pd-Cu等の合金被膜から選ばれる1種以上からなる被膜を総称するものとする。
本発明のエッチング液組成物における好ましい(B)塩化水素成分の濃度は、所望とする被エッチング材である、酸化インジウム系被膜と金属系被膜からなる積層膜の厚みや幅によって適宜調節すればよいが、0.1~25質量%、好ましくは1~20質量%である。(B)塩化水素成分の濃度が0.1質量%よりも少ないと、充分なエッチング速度が得られないことがあるために好ましくない。一方、(B)塩化水素成分の濃度を25質量%より多くしても、エッチング速度の向上は図られず、かえって装置部材の腐食等の不具合を生じる場合があることがあるために好ましくない。
なお、前記一般式(1)で表される化合物及び炭素数1~4の直鎖または分岐状アルコールは2種以上を併用してもよい。
実施例1
表1に示す化合物を(C)成分として用いて、表2に示す配合でエッチング液組成物を配合し、本発明品1~19を得た。なお、含有量の残部は水である。
表3に示す配合でエッチング液組成物を配合し比較品1~5を得た。なお、含有量の残部は水である。
CuNi/Cu/ITO/PET上にポジ型液状レジストを用いて幅75μm、開口部25μmのレジストパターンを形成した基板を縦20mm×横20mmに切断してテストピースとした。このテストピースに対し、実施例1で調製した本発明品1~19のエッチング液組成物を用いて、40℃、1分間、撹拌下でディップ式によるエッチング処理を行った。
CuNi/Cu/ITO/PET上にポジ型液状レジストを用いて幅75μm、開口部25μmのレジストパターンを形成した基板を縦20mm×横20mmに切断してテストピースとした。このテストピースに対し、比較例1で調製した比較品1~5のエッチング液組成物を用いて、40℃、1分間、撹拌下でディップ式によるエッチング処理を行った。
実施例2及び比較例2で得られた細線について、細線の直線性、細線の幅(L1)、及びITOとCuの段差の大きさ(L2)をレーザー顕微鏡によって確認した。細線の直線性は、細線側面の蛇行の有無を確認することで評価した。具体的には、目視で細線に蛇行がみられるものを×、蛇行が見られないものを○とした。ITOとCuの段差の大きさ(L2)は、得られた配線の片側におけるITO膜とCu膜の線幅の差の絶対値を計算したものである。結果を表4に示す。
このことから、本発明のエッチング液組成物は、酸化インジウム系被膜と金属系被膜を一括でエッチング処理する際に用いることにより、細線の細りが少なく、酸化インジウム系被膜と金属系被膜に大きな段差が発生することなく、直線性の良い細線を得ることができるエッチング液組成物であることがわかった。
Claims (8)
- 前記(C)成分が、少なくともジプロピレングリコールモノメチルエーテルまたはイソプロパノールを含む、請求項1または2に記載のエッチング液組成物。
- 更に、安定化剤、(A)、(B)または(C)成分の可溶化剤、消泡剤、pH調整剤、比重調整剤、粘度調整剤、濡れ性改善剤、キレート剤、酸化剤、還元剤及び界面活性剤からなる群から選択される1種または2種以上の添加剤を含有する、請求項1ないし3のいずれか1項に記載のエッチング液組成物。
- 添加剤が、還元剤である、請求項4に記載のエッチング液組成物。
- 酸化インジウム系被膜と金属系被膜からなる積層膜を一括でエッチングするエッチング方法において、エッチング液組成物として請求項1ないし5のいずれか1項に記載のエッチング液組成物を用いることを特徴とするエッチング方法。
- 酸化インジウム系被膜が、酸化インジウム被膜、インジウム-スズ酸化物被膜及びインジウム-亜鉛酸化物被膜からなる群から選択される1層以上の膜である、請求項6に記載のエッチング方法。
- 金属系被膜が、銅、ニッケル、チタン、クロム、銀、モリブデン、アルミニウム、白金及びパラジウムからなる群から選択される金属被膜及び/または銅、ニッケル、チタン、クロム、銀、モリブデン、アルミニウム、白金及びパラジウムからなる群から選択される2種類以上の金属を含有する合金被膜からなる1層以上の膜である、請求項6または7のいずれか1項に記載のエッチング方法。
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KR20180012372A (ko) * | 2016-07-26 | 2018-02-06 | 삼성디스플레이 주식회사 | 식각액 조성물 및 이를 이용한 금속 패턴 제조 방법 |
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US11219583B2 (en) * | 2019-05-30 | 2022-01-11 | L'oreal | Compositions comprising alcohol-rich mixtures of alcohol and propylene glycol methyl ethers |
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JPWO2013136624A1 (ja) | 2015-08-03 |
TW201336972A (zh) | 2013-09-16 |
TWI550061B (zh) | 2016-09-21 |
JP6062418B2 (ja) | 2017-01-18 |
KR102058485B1 (ko) | 2019-12-23 |
KR20140134647A (ko) | 2014-11-24 |
EP2827363A1 (en) | 2015-01-21 |
EP2827363A4 (en) | 2015-11-11 |
US9068267B2 (en) | 2015-06-30 |
CN104160486B (zh) | 2016-11-02 |
US20150053888A1 (en) | 2015-02-26 |
CN104160486A (zh) | 2014-11-19 |
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