TWI444488B - Etchant compositions for metal laminated films having titanium and aluminum layer - Google Patents
Etchant compositions for metal laminated films having titanium and aluminum layer Download PDFInfo
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- TWI444488B TWI444488B TW095106422A TW95106422A TWI444488B TW I444488 B TWI444488 B TW I444488B TW 095106422 A TW095106422 A TW 095106422A TW 95106422 A TW95106422 A TW 95106422A TW I444488 B TWI444488 B TW I444488B
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- Prior art keywords
- acid
- titanium
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- ammonium
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 47
- 239000010936 titanium Substances 0.000 title claims description 47
- 229910052719 titanium Inorganic materials 0.000 title claims description 45
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 38
- 229910052782 aluminium Inorganic materials 0.000 title claims description 35
- 229910052751 metal Inorganic materials 0.000 title claims description 32
- 239000002184 metal Substances 0.000 title claims description 32
- 239000000203 mixture Substances 0.000 title claims description 25
- 238000005530 etching Methods 0.000 claims description 74
- 239000000758 substrate Substances 0.000 claims description 41
- 239000007788 liquid Substances 0.000 claims description 35
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 32
- 239000007800 oxidant agent Substances 0.000 claims description 26
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 23
- 229910045601 alloy Inorganic materials 0.000 claims description 23
- 239000000956 alloy Substances 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 19
- 229910017604 nitric acid Inorganic materials 0.000 claims description 19
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 18
- 150000002222 fluorine compounds Chemical class 0.000 claims description 16
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 16
- 239000004065 semiconductor Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 11
- MBAKFIZHTUAVJN-UHFFFAOYSA-I hexafluoroantimony(1-);hydron Chemical compound F.F[Sb](F)(F)(F)F MBAKFIZHTUAVJN-UHFFFAOYSA-I 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- BNZCDZDLTIHJAC-UHFFFAOYSA-N 2-azaniumylethylazanium;sulfate Chemical compound NCC[NH3+].OS([O-])(=O)=O BNZCDZDLTIHJAC-UHFFFAOYSA-N 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000004973 liquid crystal related substance Substances 0.000 claims description 7
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012935 ammoniumperoxodisulfate Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 3
- 230000002411 adverse Effects 0.000 claims description 3
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 239000010408 film Substances 0.000 description 34
- 239000000243 solution Substances 0.000 description 16
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 8
- 229910000838 Al alloy Inorganic materials 0.000 description 6
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- -1 ammonium hexafluoroantimonate Chemical compound 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 4
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 238000001020 plasma etching Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910001182 Mo alloy Inorganic materials 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- NILMKXZBKQLWCT-UHFFFAOYSA-N 2-methylpiperazin-1-amine Chemical compound CC1CNCCN1N NILMKXZBKQLWCT-UHFFFAOYSA-N 0.000 description 1
- ASZZHBXPMOVHCU-UHFFFAOYSA-N 3,9-diazaspiro[5.5]undecane-2,4-dione Chemical compound C1C(=O)NC(=O)CC11CCNCC1 ASZZHBXPMOVHCU-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/20—Acidic compositions for etching aluminium or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
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- 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/067—Etchants
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
Description
本發明係有關於一種金屬層積膜的蝕刻液組成物，該金屬層積膜係使用於液晶顯示器的閘極、源極及汲極電極。 The present invention relates to an etching liquid composition for a metal laminated film which is used for a gate, a source and a drain electrode of a liquid crystal display.
因為鋁或是在鋁中添加釹或矽或銅等不純物而成的合金，價廉且電阻非常低，被使用作為液晶顯示器的閘極、源極及汲極電極的材料。 Aluminum or an alloy in which an impurity such as tantalum or niobium or copper is added to aluminum is inexpensive and has a very low electrical resistance, and is used as a material for a gate, a source, and a drain electrode of a liquid crystal display.
但是，因為鋁或是鋁合金與基底膜之玻璃基板的黏著性稍差、容易因藥液、熱而被腐蝕，所以在鋁或鋁合金的上部及/或下部使用鉬或是鉬合金膜，以層積膜的形式使用於電極材料，藉由使用磷酸等之蝕刻液，對層積膜進行總括地蝕刻。 However, since aluminum or an aluminum alloy is slightly inferior in adhesion to a glass substrate of a base film and is easily corroded by a chemical solution or heat, a molybdenum or molybdenum alloy film is used on the upper and/or lower portions of the aluminum or aluminum alloy. The laminated film is used in the form of a laminated film for the electrode material, and the laminated film is collectively etched by using an etching solution such as phosphoric acid.
近年來，為了鉬或是鉬合金的價格高漲，及更進一步改良因藥液、熱所造成的腐蝕性之目的，鈦或是鈦合金正受到注目。蝕刻鉬所使用的磷酸等，無法用來蝕刻鈦或鈦合金，半導體基板係進行使用鹵素系氣體之反應性離子蝕刻(Reactive Ion Etch；RIE)等乾式蝕刻，來作為蝕刻鈦-鋁系金屬層積膜的方法。RIE藉由異方向性蝕刻而能夠控制於具有錐形形狀的程度，但是必須有昂貴的真空裝置或高頻產生裝置，就成本面而言係不利的，因此，希望開發一種總括蝕刻液，能夠更價廉、且亦能夠縮短處理時間。 In recent years, titanium or titanium alloys have attracted attention for the purpose of increasing the price of molybdenum or molybdenum alloys and further improving the corrosiveness caused by chemical liquids and heat. The phosphoric acid or the like used for etching molybdenum cannot be used to etch titanium or a titanium alloy, and the semiconductor substrate is subjected to dry etching such as reactive ion etching (Reactive Ion Etch; RIE) using a halogen-based gas as an etching titanium-aluminum-based metal layer. The method of film accumulation. RIE can be controlled to have a tapered shape by anisotropic etching, but an expensive vacuum device or a high-frequency generating device is required, which is disadvantageous in terms of cost. Therefore, it is desired to develop a collective etching solution capable of It is cheaper and can also reduce processing time.
另一方面，在半導體裝置的製程，在蝕刻以鈦作主成分之金屬薄膜時，已知通常是使用氫氟酸系蝕刻液(例如專利文獻1)。又，亦已知能夠藉由使用氨水-過氧化氫水的蝕刻液，來蝕刻鈦或是鈦合金(例如專利文獻2)。 On the other hand, in the process of a semiconductor device, when a metal thin film containing titanium as a main component is etched, it is known that a hydrofluoric acid-based etching liquid is generally used (for example, Patent Document 1). Further, it is also known that titanium or a titanium alloy can be etched by using an etching solution of ammonia water-hydrogen peroxide water (for example, Patent Document 2).
但是，使用氫氟酸系蝕刻液時，因為會使基底的玻璃基板、矽基板及化合物半導體基板遭受損傷，故無法使用。又，使用氨水-過氧化氫水時，因過氧化氫水的分解會產生氣泡，會有因氣泡附著在基板上而使蝕刻不完全、而且蝕刻液壽命短，導致難以使用之情形。 However, when a hydrofluoric acid-based etching liquid is used, the glass substrate, the tantalum substrate, and the compound semiconductor substrate of the substrate are damaged, and thus cannot be used. Further, when ammonia water-hydrogen peroxide water is used, bubbles are generated due to decomposition of hydrogen peroxide water, and the bubbles are adhered to the substrate to make the etching incomplete, and the life of the etching liquid is short, which makes it difficult to use.
另外，雖然與本發明作為玻璃基板等的蝕刻液之用途不同，有揭示一種組成物(專利文獻3)係以過氧化氫、氟化物、無機酸類及氟系界面活性劑作為必要成分，其目的係使用於裝飾品或電子零件之鈦及鈦合金的表面進行結垢去除或是平滑化，但是關於蝕刻金屬層積膜(含有鈦或以鈦作為主成分之合金所構成的層、及鋁或以鋁作為主成分的之合金所構成的層)，沒有任何教導。又，有揭示一種含有過氧二硫酸鹽和氟化物之水溶液，其係作為蝕刻由鈦層和銅層所構成的金屬層積膜之蝕刻液(專利文獻4)，但是並非有關於蝕刻由鋁層和鈦層所構成的金屬層積膜之物。 In addition, unlike the use of the etching liquid of the present invention as a glass substrate or the like, it is disclosed that a composition (Patent Document 3) contains hydrogen peroxide, a fluoride, an inorganic acid, and a fluorine-based surfactant as essential components. It is used for the scale removal or smoothing of titanium and titanium alloys used for decorative or electronic parts, but for etching metal laminated films (layers containing titanium or alloys containing titanium as a main component, and aluminum or There is no teaching of a layer composed of an alloy containing aluminum as a main component. Further, an aqueous solution containing peroxodisulfate and fluoride as an etching solution for etching a metal laminated film composed of a titanium layer and a copper layer is disclosed (Patent Document 4), but it is not related to etching by an aluminum layer. A metal laminated film made of a titanium layer.
因此，總括地蝕刻鈦-鋁金屬層積膜之適當手段，尚未被開發。 Therefore, a suitable means for collectively etching a titanium-aluminum metal laminated film has not been developed.
[專利文獻1]特開昭59-124726號公報 [Patent Document 1] JP-A-59-124726
[專利文獻2]特開平6-310492號公報 [Patent Document 2] JP-A-6-310492
[專利文獻3]特開2004-43850號公報 [Patent Document 3] JP-A-2004-43850
[專利文獻4]特開2001-59191號公報 [Patent Document 4] JP-A-2001-59191
亦即，本發明的課題係提供一種蝕刻液，能夠總括地蝕刻鈦-鋁系金屬層積膜而解決上述問題點。 That is, an object of the present invention is to provide an etching solution capable of collectively etching a titanium-aluminum-based metal laminated film to solve the above problems.
在專心檢討解決上述問題當中，發現組合除了氫氟酸以外的氟化合物及氧化劑而成的蝕刻液，適合總括地蝕刻金屬層積膜，該金屬層積膜含有鈦或以鈦作為主成分之合金所構成的層、及鋁或以鋁作為主成分之合金所構成的層，進一步研究的結果，完成了本發明。 In an effort to review and solve the above problems, it has been found that an etching solution in which a fluorine compound other than hydrofluoric acid and an oxidizing agent are combined is suitable for collectively etching a metal laminated film containing titanium or an alloy containing titanium as a main component. The layer composed of the layer and the alloy of aluminum or an alloy containing aluminum as a main component has been studied as a result of further investigation.
亦即，本發明係有關於前述蝕刻液組成物，係一種含有氟化合物(但是除了氫氟酸以外)及氧化劑之蝕刻液組成物，用以總括地蝕刻金屬層積膜，該金屬層積膜含有鈦或以鈦作為主成分之合金所構成的層、及鋁或以鋁作為主成分之合金所構成的層。 That is, the present invention relates to the etching liquid composition, which is an etching liquid composition containing a fluorine compound (except for hydrofluoric acid) and an oxidizing agent for collectively etching a metal laminated film, the metal laminated film A layer composed of a layer containing titanium or an alloy containing titanium as a main component, and a layer composed of aluminum or an alloy containing aluminum as a main component.
又，本發明係有關於前述蝕刻液組成物，其中該氟化合物係1種或2種以上選自六氟矽酸、及氫氟酸或六氟矽酸與金屬或是氨的鹽中者。 Further, the present invention relates to the etchant composition, wherein the fluorine compound is one or more selected from the group consisting of hexafluoroantimonic acid, hydrofluoric acid or hexafluoroantimonic acid and a metal or ammonia salt.
本發明係有關於前述蝕刻液組成物，其中該氧化劑係1種或2種以上選自硝酸、硝酸銨、硫酸銨、過氧二硫酸銨、過氧二硫酸鉀、過氯酸、過氯酸銨、過氯酸鈉、過氯 酸鉀、過碘酸、過碘酸鈉、過碘酸鉀、甲磺酸、過氧化氫水、硫酸及硫酸乙二胺中者。 The present invention relates to the above etching liquid composition, wherein the oxidizing agent is one or more selected from the group consisting of nitric acid, ammonium nitrate, ammonium sulfate, ammonium peroxodisulfate, potassium peroxydisulfate, perchloric acid, and perchloric acid. Ammonium, sodium perchlorate, perchlorine Potassium acid, periodic acid, sodium periodate, potassium periodate, methanesulfonic acid, hydrogen peroxide water, sulfuric acid and ethylenediamine sulfate.
本發明係有關於前述蝕刻液組成物，其中該氟化物的濃度為0.01~5重量%，該氧化劑濃度為0.1~50重量%。 The present invention relates to the aforementioned etching liquid composition, wherein the concentration of the fluoride is 0.01 to 5% by weight, and the concentration of the oxidizing agent is 0.1 to 50% by weight.
本發明係有關於前述蝕刻液組成物，其中該氧化劑係硝酸或甲磺酸。 The present invention relates to the aforementioned etching liquid composition, wherein the oxidizing agent is nitric acid or methanesulfonic acid.
又，本發明係有關於前述蝕刻液組成物，更含有至少1種選自硝酸銨、硫酸銨、過氧二硫酸銨、過氧二硫酸鉀、過氯酸、過氯酸銨、過氯酸鈉、過氯酸鉀、過碘酸、過碘酸鈉、過碘酸鉀、過氧化氫水、硫酸及硫酸乙二胺中者來作為氧化劑。 Furthermore, the present invention relates to the etching liquid composition, and further comprises at least one selected from the group consisting of ammonium nitrate, ammonium sulfate, ammonium peroxodisulfate, potassium peroxydisulfate, perchloric acid, ammonium perchlorate, and perchloric acid. As an oxidizing agent, sodium, potassium perchlorate, periodic acid, sodium periodate, potassium periodate, hydrogen peroxide water, sulfuric acid and ethylenediamine sulfate are used.
本發明係有關於前述蝕刻液組成物，更含有至少1種選自胺基磺酸、乙酸及鹽酸中者。 The present invention relates to the etching liquid composition, and further contains at least one selected from the group consisting of aminosulfonic acid, acetic acid, and hydrochloric acid.
本發明係有關於前述蝕刻液組成物，其中該基底基板係液晶顯示器用玻璃基板。 The present invention relates to the aforementioned etching liquid composition, wherein the base substrate is a glass substrate for a liquid crystal display.
又，本發明係有關於前述蝕刻液組成物，其中該基底基板係半導體裝置用矽基板或是化合物半導體基板。 Moreover, the present invention relates to the etching liquid composition, wherein the base substrate is a tantalum substrate or a compound semiconductor substrate for a semiconductor device.
而且，本發明係有關於前述蝕刻液組成物，係用以對金屬層積膜(含有由鈦或是以鈦為主成分之合金構成的層、及由鋁或是以鋁為主成分之合金構成的層)進行蝕刻，使蝕刻後的錐形角度為30~90度。 Further, the present invention relates to the etching liquid composition for a metal laminated film (a layer containing an alloy mainly composed of titanium or titanium, and an alloy mainly composed of aluminum or aluminum). The layer formed is etched so that the taper angle after etching is 30 to 90 degrees.
本發明之蝕刻液因為不會對作為基底的基板造成不良影響，能總括地蝕刻金屬層積膜，該金屬層積膜含有鈦或 以鈦作為主成分之合金所構成的層、及鋁或以鋁作為主成分之合金所構成的層，所以該蝕刻液係具有特別優良的經濟性之物。又，因為容易控制錐形角度，藉由更提升閘極電極的被覆性，能夠製造高品質的製品。 Since the etching liquid of the present invention does not adversely affect the substrate as a substrate, the metal laminated film can be collectively etched, and the metal laminated film contains titanium or Since a layer composed of an alloy containing titanium as a main component and a layer composed of aluminum or an alloy containing aluminum as a main component, the etching liquid system is particularly excellent in economical efficiency. Moreover, since it is easy to control the taper angle, it is possible to manufacture a high-quality product by further improving the coverage of the gate electrode.
[實施發明的較佳形態] [Preferred form of implementing the invention]
以下詳述本發明實施形態。 The embodiments of the present invention are described in detail below.
本發明之蝕刻液組成物的要點，係由氟化合物(但是，氫氟酸除外)、氧化劑、及水所構成。 The point of the etching liquid composition of the present invention is composed of a fluorine compound (except hydrofluoric acid), an oxidizing agent, and water.
本發明之蝕刻液所使用的氟化合物，可以認為係藉溶解金屬層積膜上被本蝕刻液成分中之氧化劑氧化的氧化鈦，來進行主要的蝕刻。本發明之蝕刻液所使用的氟化合物可以使用氫氟酸以外之任何氟化合物，係1種或2種以上選自六氟矽酸，及氫氟酸或六氟矽酸與金屬或氨的鹽中者，例如，較佳是氟化銨、氟化鉀、氟化鈣、氟化氫銨、氟化氫鉀、氟化鈉、氟化鎂、氟化鋰、六氟矽酸、六氟矽酸銨、六氟矽酸鈉、六氟矽酸鉀，特佳是氟化銨、氟化氫銨。 The fluorine compound used in the etching liquid of the present invention is considered to be mainly etched by dissolving titanium oxide which is oxidized by the oxidizing agent in the etching liquid component on the metal laminated film. The fluorine compound used in the etching solution of the present invention may be any fluorine compound other than hydrofluoric acid, and one or more selected from the group consisting of hexafluoroantimonic acid and hydrofluoric acid or a salt of hexafluoroantimonic acid and metal or ammonia. Among them, for example, ammonium fluoride, potassium fluoride, calcium fluoride, ammonium hydrogen fluoride, potassium hydrogen fluoride, sodium fluoride, magnesium fluoride, lithium fluoride, hexafluoroantimonic acid, ammonium hexafluoroantimonate, or preferably Sodium fluoroantimonate or potassium hexafluoroantimonate, particularly preferably ammonium fluoride or ammonium hydrogen fluoride.
又，本發明之蝕刻液所使用的氧化劑，係藉由氧化金屬層積膜上的鈦或是鈦合金，來擔任作為蝕刻引發劑的任務。本發明之蝕刻液所使用的氧化劑，係1種或2種以上選自硝酸、硝酸銨、硫酸銨、過氧二硫酸銨、過氧二硫酸 鉀、過氯酸、過氯酸銨、過氯酸鈉、過氯酸鉀、過碘酸、過碘酸鈉、過碘酸鉀、甲磺酸、過氧化氫水、硫酸及硫酸乙二胺中者，其中以硝酸、過氧二硫酸銨、甲磺酸為佳。 Further, the oxidizing agent used in the etching liquid of the present invention serves as an etching initiator by using titanium or a titanium alloy on the metal oxide film. The oxidizing agent used in the etching solution of the present invention is one or more selected from the group consisting of nitric acid, ammonium nitrate, ammonium sulfate, ammonium peroxodisulfate, and peroxydisulfuric acid. Potassium, perchloric acid, ammonium perchlorate, sodium perchlorate, potassium perchlorate, periodate, sodium periodate, potassium periodate, methanesulfonic acid, hydrogen peroxide, sulfuric acid and ethylenediamine sulfate Among them, nitric acid, ammonium peroxodisulfate, and methanesulfonic acid are preferred.
亦可以使用硫酸銨、硫酸乙二胺以外的含氮有機化合物硫酸鹽，例如，哌嗪(piperazine)、1-(2-胺基乙基)哌嗪、1-胺基-甲基哌嗪等硫酸鹽作為氧化劑，就容易取得性而言，以硫酸銨、硫酸乙二胺為佳。 It is also possible to use a nitrogen-containing organic compound sulfate other than ammonium sulfate or ethylenediamine sulfate, for example, piperazine, 1-(2-aminoethyl)piperazine, 1-amino-methylpiperazine, etc. Sulfate is preferred as an oxidizing agent, and ammonium sulfate or ethylenediamine sulfate is preferred.
特佳是硝酸或是甲磺酸，因為即使低濃度亦能夠降低錐形角度，例如40度以下。雖然硝酸或是甲磺酸以外的氧化劑，降低錐形角度的效果較差，但是因為對光阻的損傷較小、能夠控制側面蝕刻的量，故較佳。含有前述氟化合物及硝酸或是甲磺酸之蝕刻液，能夠將錐形角度控制在40度以下，進而藉由添加至少1種以上選自硝酸及甲磺酸以外的氧化劑、或是胺基硫酸、乙酸、鹽酸中者，能夠將錐形角度控制在30~90度之間。 Particularly preferred is nitric acid or methanesulfonic acid because the cone angle can be lowered even at low concentrations, for example below 40 degrees. Although nitric acid or an oxidizing agent other than methanesulfonic acid has a poor effect of lowering the taper angle, it is preferable because the damage to the photoresist is small and the amount of side etching can be controlled. The etching solution containing the fluorine compound, nitric acid or methanesulfonic acid can control the taper angle to 40 degrees or less, and further add at least one type of oxidizing agent other than nitric acid and methanesulfonic acid or amine sulfuric acid. In acetic acid or hydrochloric acid, the taper angle can be controlled between 30 and 90 degrees.
本發明之蝕刻液組成物之較佳組合，除了氟化銨與硝酸、氟化銨與甲磺酸之外，組合使用2種以上氧化劑時，以下述為佳：氟化銨與硝酸及過氯酸；氟化銨與硝酸及硫酸；氟化銨與硝酸、過氯酸及甲磺酸；氟化銨與硝酸、過氯酸及硫酸。 In a preferred combination of the etching liquid composition of the present invention, in addition to ammonium fluoride and nitric acid, ammonium fluoride and methanesulfonic acid, when two or more kinds of oxidizing agents are used in combination, the following are preferred: ammonium fluoride and nitric acid and perchloric acid Acid; ammonium fluoride and nitric acid and sulfuric acid; ammonium fluoride and nitric acid, perchloric acid and methanesulfonic acid; ammonium fluoride and nitric acid, perchloric acid and sulfuric acid.
又，為了提高與基板之潤濕性的目的，亦可以在本蝕刻液中，添加使用通常所用的界面活性劑或有機溶劑。 Further, in order to improve the wettability with the substrate, a commonly used surfactant or organic solvent may be added to the etching solution.
本發明之蝕刻液係適合使用來蝕刻金屬層積膜，該金屬層積膜含有鈦或以鈦作為主成分之合金所構成的層、及 鋁或以鋁作為主成分之合金所構成的層，係在由玻璃基板等所構成的絕緣基板及矽基板、化合物半導體基板上，藉由濺鍍法所形成，例如鈦/鋁、鋁/鈦、鈦/鋁/鈦所構成的金屬積層膜，該蝕刻液之氟化合物的濃度為0.01~5重量%，以0.1~1重量%為佳，氧化劑的濃度為0.1~50重量%，以0.5~10重量%為佳。 The etching liquid of the present invention is suitably used for etching a metal laminated film containing titanium or a layer composed of an alloy containing titanium as a main component, and A layer made of aluminum or an alloy containing aluminum as a main component is formed on a insulating substrate made of a glass substrate or the like, a tantalum substrate, or a compound semiconductor substrate by sputtering, for example, titanium/aluminum, aluminum/titanium. a metal laminated film made of titanium/aluminum/titanium, wherein the concentration of the fluorine compound in the etching solution is 0.01 to 5% by weight, preferably 0.1 to 1% by weight, and the concentration of the oxidizing agent is 0.1 to 50% by weight, 0.5 to 0.5% 10% by weight is preferred.
氟化合物濃度小於5重量%時，不會對基底玻璃造成傷害，又，能夠抑制對金屬層積膜(含有鈦或以鈦作為主成分之合金所構成的層、及鋁或以鋁作為主成分之合金所構成的層)之側面蝕刻的量，高於0.01重量%時，可以降低對鈦或鈦的合金之蝕刻不均，蝕刻後的形狀較佳。氧化劑的含量低於50重量%時，能夠抑制對金屬層積膜(含有鈦或以鈦作為主成分之合金所構成的層、及鋁或以鋁作為主成分之合金所構成的層)之側面蝕刻的量，而且，不會產生對光阻的傷害，高於0.1重量%時，對鈦或鈦合金的蝕刻速度較快、較有效率。 When the concentration of the fluorine compound is less than 5% by weight, the base glass is not damaged, and the metal laminated film (a layer composed of titanium or an alloy containing titanium as a main component, and aluminum or aluminum as a main component can be suppressed as a main component. When the amount of side etching of the layer formed of the alloy is more than 0.01% by weight, the etching unevenness of the alloy of titanium or titanium can be lowered, and the shape after etching is preferable. When the content of the oxidizing agent is less than 50% by weight, it is possible to suppress the side of a metal laminated film (a layer composed of an alloy containing titanium or titanium as a main component, and a layer composed of aluminum or an alloy containing aluminum as a main component) The amount of etching, and no damage to the photoresist, is higher than 0.1% by weight, and the etching speed of titanium or titanium alloy is faster and more efficient.
又，適當地控制錐形角度，特別是為了使其成為30~90度，可以藉由單獨使用或適當組合使用硝酸或甲磺酸與其他的氧化劑來進行。此時，硝酸或甲磺酸為0.1~30重量%、特別是以0.5~15質量%為佳，其他的氧化劑為0.1~20重量%、特別是以0.5~15質量%為佳。 Further, the taper angle is appropriately controlled, and particularly, in order to make it 30 to 90 degrees, nitric acid or methanesulfonic acid and another oxidizing agent can be used alone or in appropriate combination. In this case, nitric acid or methanesulfonic acid is preferably 0.1 to 30% by weight, particularly preferably 0.5 to 15% by mass, and the other oxidizing agent is preferably 0.1 to 20% by weight, particularly preferably 0.5 to 15% by mass.
特別是，為了使錐形角度為40度以下，以使用硝酸或是甲磺酸為佳。 In particular, in order to make the taper angle 40 degrees or less, it is preferable to use nitric acid or methanesulfonic acid.
又，更含有至少1種選自胺基磺酸、乙酸或是鹽酸中 者時，其等的濃度以0.01~10質量%、特別是0.5~5質量%為佳。 Further, at least one selected from the group consisting of aminosulfonic acid, acetic acid or hydrochloric acid When the concentration is equal to 0.01 to 10% by mass, particularly 0.5 to 5% by mass.
本發明之蝕刻液，所蝕刻金屬層積膜的基底基板沒有特別限定，其中鈦、鋁金屬層積膜使用於液晶顯示器時，以玻璃基板為佳，使用於半導體裝置時，以矽基板和化合物半導體基板為佳。 In the etching liquid of the present invention, the base substrate on which the metal laminated film is etched is not particularly limited. When a titanium or aluminum metal laminated film is used for a liquid crystal display, a glass substrate is preferred, and when used in a semiconductor device, a germanium substrate and a compound are used. A semiconductor substrate is preferred.
以下，更詳細地舉出實施例與比較例來說明本發明，但是本發明不限定於此等實施例。 Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited thereto.
[實施例] [Examples]
實施例1~25 Example 1~25
如第1圖所示，準備一藉由濺鍍法使鈦(700Å)/鋁(2500Å)/鈦(200Å)成膜在玻璃基板(1)上而成的基板。 As shown in Fig. 1, a substrate obtained by depositing titanium (700 Å) / aluminum (2500 Å) / titanium (200 Å) on a glass substrate (1) by sputtering was prepared.
接著，在鈦/鋁/鈦金屬層積膜上使用光阻(4)進行圖案化，浸漬於表1之實施例1~25的蝕刻液(蝕刻溫度30℃)。隨後，使用超純水洗滌，吹氮氣使其乾燥後，藉由電子顯微鏡觀察基板形狀。結果如表1所示。 Next, the titanium/aluminum/titanium metal laminated film was patterned using a photoresist (4), and immersed in the etching liquids of Examples 1 to 25 of Table 1 (etching temperature: 30 ° C). Subsequently, it was washed with ultrapure water, and after drying with nitrogen, the shape of the substrate was observed by an electron microscope. The results are shown in Table 1.
比較例1~2 Comparative example 1~2
將實施例所使用之在玻璃基板上藉由濺鍍法所形成的鈦/鋁/鈦，浸漬於比較例1~2各成分所構成的蝕刻液中，與實施例同樣地進行處理。結果一併如表1所示。 Titanium/aluminum/titanium formed by a sputtering method on the glass substrate used in the examples was immersed in an etching liquid composed of the components of Comparative Examples 1 and 2, and treated in the same manner as in the examples. The results are shown in Table 1.
從表1可以清楚知道，使用本發明之蝕刻液進行蝕刻，能夠在短時間內，總括地蝕刻藉由濺鍍法所形成的鈦/鋁/鈦層積膜。 As is clear from Table 1, the etching using the etching liquid of the present invention can collectively etch the titanium/aluminum/titanium laminated film formed by the sputtering method in a short time.
[產業上利用的可能性] [Possibility of industrial use]
在半導體裝置及液晶顯示器等電子裝置的製程中，形成配線或是電極等時，本發明之蝕刻液能夠使用作為金屬層積膜的蝕刻液。 When a wiring or an electrode or the like is formed in a process of an electronic device such as a semiconductor device or a liquid crystal display, an etching liquid as a metal laminated film can be used as the etching liquid of the present invention.
(a)‧‧‧藉由本發明之蝕刻液蝕刻後之閘極電極(大致同樣的錐狀和40度以下的錐狀) (a) ‧ ‧ gate electrode etched by the etching solution of the present invention (substantially the same tapered shape and tapered shape of 40 degrees or less)
(b)‧‧‧藉由本發明之蝕刻液蝕刻後之源極或汲極電極(90度的錐形角度) (b) ‧‧‧ Source or gate electrode etched by the etching solution of the present invention (90 degree taper angle)
第1圖係在絕緣性基板上形成之金屬層積膜之配線製程，該金屬層積膜係含有鈦或以鈦作為主成分之合金所構成的層、及鋁或以鋁作為主成分之合金所構成的層。 Fig. 1 is a wiring process of a metal laminated film formed on an insulating substrate containing a layer composed of titanium or an alloy containing titanium as a main component, and an alloy of aluminum or aluminum as a main component. The layer formed.
(1)‧‧‧玻璃基板 (1) ‧‧‧glass substrate
(2)‧‧‧鈦或鈦合金膜 (2) ‧‧‧Titanium or titanium alloy film
(3)‧‧‧鋁或鋁合金膜 (3) ‧‧‧Aluminum or aluminum alloy film
(4)‧‧‧光阻 (4) ‧‧‧Light resistance
(a)‧‧‧藉由本發明之蝕刻液蝕刻後之閘極電極(大致同樣的錐狀和40度以下的錐狀) (a) ‧ ‧ gate electrode etched by the etching solution of the present invention (substantially the same tapered shape and tapered shape of 40 degrees or less)
(b)‧‧‧藉由本發明之蝕刻液蝕刻後之源極或汲極電極(90度的錐形角度) (b) ‧‧‧ Source or gate electrode etched by the etching solution of the present invention (90 degree taper angle)
Claims (5)
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| KR101341708B1 (en) * | 2006-12-05 | 2013-12-16 | 동우 화인켐 주식회사 | Etchant composition for multi layers thin film comprising titanium or titanium alloy layer, and aluminum or aluminum alloy layer |
| KR101456930B1 (en) * | 2008-06-27 | 2014-10-31 | 동우 화인켐 주식회사 | Etching solution composition |
| KR101122698B1 (en) | 2009-05-25 | 2012-03-09 | 한국기계연구원 | Etchant composition of nickle-based superalloy and method of etching the alloy |
| CN102471686B (en) * | 2009-07-22 | 2014-08-27 | 东友Fine-Chem股份有限公司 | Etchant composition for the formation of a metal line |
| WO2012017819A1 (en) * | 2010-08-05 | 2012-02-09 | 昭和電工株式会社 | Composition for removal of nickel-platinum alloy metal |
| KR102179756B1 (en) | 2013-12-18 | 2020-11-18 | 동우 화인켐 주식회사 | Etching solution composition for a metal nitride layer |
| KR101584937B1 (en) | 2015-04-03 | 2016-01-14 | 한양대학교 산학협력단 | Method of manufacturing superhydrophobic titanium structure and superhydrophobic titanium structure manufactured thereby |
| CN114293056B (en) * | 2021-12-20 | 2022-12-23 | 富联裕展科技(深圳)有限公司 | Metal workpiece, metal product, etching solution and method for manufacturing metal workpiece |
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| KR100419071B1 (en) * | 2001-06-20 | 2004-02-19 | 엘지.필립스 엘시디 주식회사 | Etching solution for copper titanium layer and etching method thereof |
| KR20030079740A (en) * | 2002-04-02 | 2003-10-10 | 동우 화인켐 주식회사 | Etchant composition for aluminum (or aluminum alloy) single layer and multi layers |
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| KR101149003B1 (en) | 2012-05-23 |
| TW200641168A (en) | 2006-12-01 |
| KR20100080761A (en) | 2010-07-12 |
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