CN109385634A - Metal film etchant and the conductive pattern forming method for utilizing it - Google Patents
Metal film etchant and the conductive pattern forming method for utilizing it Download PDFInfo
- Publication number
- CN109385634A CN109385634A CN201810813657.8A CN201810813657A CN109385634A CN 109385634 A CN109385634 A CN 109385634A CN 201810813657 A CN201810813657 A CN 201810813657A CN 109385634 A CN109385634 A CN 109385634A
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- Prior art keywords
- acid
- metal film
- mentioned
- conductive pattern
- film
- Prior art date
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- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 94
- 239000002184 metal Substances 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000005530 etching Methods 0.000 claims abstract description 75
- 150000007524 organic acids Chemical class 0.000 claims abstract description 37
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 24
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010408 film Substances 0.000 claims description 151
- 230000003647 oxidation Effects 0.000 claims description 40
- 238000007254 oxidation reaction Methods 0.000 claims description 40
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 23
- 150000003839 salts Chemical class 0.000 claims description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 14
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 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 12
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 10
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 10
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000004323 potassium nitrate Substances 0.000 claims description 7
- 235000010333 potassium nitrate Nutrition 0.000 claims description 7
- 239000004317 sodium nitrate Substances 0.000 claims description 7
- 235000010344 sodium nitrate Nutrition 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 6
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 5
- 239000004471 Glycine Substances 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229960001484 edetic acid Drugs 0.000 claims description 5
- 239000000174 gluconic acid Substances 0.000 claims description 5
- 235000012208 gluconic acid Nutrition 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 238000004073 vulcanization Methods 0.000 claims description 4
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 3
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 3
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 230000008859 change Effects 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims 1
- 240000000203 Salix gracilistyla Species 0.000 claims 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims 1
- 235000015165 citric acid Nutrition 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 claims 1
- 235000006408 oxalic acid Nutrition 0.000 claims 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 18
- 239000000126 substance Substances 0.000 description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 230000003628 erosive effect Effects 0.000 description 9
- 229920002120 photoresistant polymer Polymers 0.000 description 9
- 229910052709 silver Inorganic materials 0.000 description 9
- 239000004332 silver Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000009413 insulation Methods 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 230000001976 improved effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 229950006191 gluconic acid Drugs 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- VHBSECWYEFJRNV-UHFFFAOYSA-N 2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1O.OC(=O)C1=CC=CC=C1O VHBSECWYEFJRNV-UHFFFAOYSA-N 0.000 description 2
- FZIPCQLKPTZZIM-UHFFFAOYSA-N 2-oxidanylpropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O FZIPCQLKPTZZIM-UHFFFAOYSA-N 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- OVYQSRKFHNKIBM-UHFFFAOYSA-N butanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCC(O)=O OVYQSRKFHNKIBM-UHFFFAOYSA-N 0.000 description 2
- PASOAYSIZAJOCT-UHFFFAOYSA-N butanoic acid Chemical compound CCCC(O)=O.CCCC(O)=O PASOAYSIZAJOCT-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- XVVLAOSRANDVDB-UHFFFAOYSA-N formic acid Chemical compound OC=O.OC=O XVVLAOSRANDVDB-UHFFFAOYSA-N 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- NIFHFRBCEUSGEE-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O.OC(=O)C(O)=O NIFHFRBCEUSGEE-UHFFFAOYSA-N 0.000 description 2
- HUPQYPMULVBQDL-UHFFFAOYSA-N pentanoic acid Chemical compound CCCCC(O)=O.CCCCC(O)=O HUPQYPMULVBQDL-UHFFFAOYSA-N 0.000 description 2
- -1 phosphoric acid Salt Chemical class 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- HJSRRUNWOFLQRG-UHFFFAOYSA-N propanedioic acid Chemical compound OC(=O)CC(O)=O.OC(=O)CC(O)=O HJSRRUNWOFLQRG-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-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
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910004882 Na2S2O8 Inorganic materials 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 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
- 230000003287 optical effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003244 pro-oxidative effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000009711 regulatory function Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000005019 vapor deposition process Methods 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
-
- 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
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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
- C23F1/02—Local etching
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1343—Electrodes
- G02F1/13439—Electrodes characterised by their electrical, optical, physical properties; materials therefor; method of making
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- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/136286—Wiring, e.g. gate line, drain line
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- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
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Abstract
The present invention provides a kind of metal film etchant and the conductive pattern forming method using it, which includes the water of etching initiator, inorganic acid, organic acid, polyalcohol system profile improver and surplus, and pH is 2 or less.By using metal film etchant, it is capable of forming the conductive pattern for etching the bad fine sizes reduced.
Description
Technical field
The present invention relates to metal film etchant and utilize its conductive pattern forming method.More specifically, it relates to
And metal film etchant comprising sour component and the conductive pattern forming method using it.
Background technique
For example, utilizing thin film transistor (TFT) (Thin as a part in semiconductor device and the driving circuit of display device
Film Transistor:TFT).TFT is for example in organic light emitting display (OLED) device or the substrate of liquid crystal display device (LCD)
On according to each pixel arrangement, pixel electrode, to the wirings such as electrode, source electrode, drain electrode, data line, power supply line can with it is upper
State TFT electrical connection.
In order to form above-mentioned electrode or wiring, metal film can be formed on display base plate, the shape on above-mentioned metal film
After photoresist, above-mentioned metal film portion is removed using etchant.
Signal propagation delay is prevented to reduce wiring resistance, and ensures the chemical resistance of wiring, stability, above-mentioned gold
The multilayer film comprising dissimilar metal or xenogenesis conductive materials each other with different chemical characteristics can be formed as by belonging to film.
For example, in order to which low resistance characteristic is presented argentiferous (Ag) film can be formed, and in order to improve chemical resistance, stability
And permeability, the transparent conductive oxides film to form tin indium oxide (Indium Tin Oxide:ITO) etc can be added.
About above-mentioned etchant, as disclosed in Ebrean Registered Patent bulletin the 10-0579421st,
Use inorganic system's strong acid of phosphoric acid, sulfuric acid or the like as basic ingredient.But in the case where stating inorganic system's strong acid in use,
Non-uniform etching outline caused by the rate of etch difference of xenogenesis conductive film, overetch (over-etch) may be caused, overflow and hang
(over-hang) etc. bad, and be difficult to adjust the rate of etch for being used to form fine pattern.
Existing technical literature
Patent document
Ebrean Registered Patent bulletin 10-0579421 (2006.05.08.)
Summary of the invention
Project to be solved
A project of the invention is that providing has the etch uniformity improved, high-resolution metal film etching solution
Composition.
A project of the invention is, provides the conductive pattern forming method using above-mentioned metal film etchant.
A project of the invention is, provides the manufacturer of the display base plate using above-mentioned metal film etchant
Method.
Solve project method
1. a kind of metal film etchant, it includes etching initiators, inorganic acid, organic acid, polyalcohol system profile
The water of improver and surplus, and pH is 2 or less.
2. the metal film etchant as described in 1, above-mentioned etching initiator includes selected from by vulcanization peroxide, mistake
At least one of hydrogen oxide, persulfate and group of peroxy-nitrate composition.
3. the metal film etchant as described in 2, above-mentioned etching initiator includes oxone
(oxone)。
4. the metal film etchant as described in 1, above-mentioned inorganic acid includes nitric acid.
5. the metal film etchant as described in 1, above-mentioned organic acid includes the first organic acid and acidity than above-mentioned
The second weak organic acid of first organic acid.
6. the metal film etchant as described in 5, above-mentioned first organic acid includes acetic acid,
Above-mentioned second organic acid includes selected from by iminodiacetic acid (iminodiacetic acid:IDA), ethylenediamine tetraacetic
Acetic acid (ethylenediaminetetraacetic acid:EDTA), glycine (glycine), salicylic acid (salicylic
Acid), citric acid (citric acid), formic acid (formic acid), oxalic acid (oxalic acid), malonic acid (malonic
Acid), succinic acid (succinic acid), butyric acid (butyric acid), gluconic acid (gluconicacid), glycolic
At least one of the group of (glycolic acid) and valeric acid (pentanic acid) composition.
7. the metal film etchant as described in 1, polyalcohol system profile improver includes selected from by glycerol
(glycerol), ethylene glycol (ethylene glycol), diethylene glycol (diethylene glycol), triethylene glycol
At least one of the group of (triethylene glycol) and polyethylene glycol (polyethylene glycol) composition.
8. the metal film etchant as described in 1, further includes metal salt.
9. the metal film etchant as described in 8, above-mentioned metal salt includes selected from by ferric nitrate
(ferricnitrate), in the group of sodium nitrate (sodium nitrate) and potassium nitrate (potassium nitrate) composition
It is at least one.
10. the metal film etchant as described in 1, in composition total weight, include:
Above-mentioned 1~20 weight % of etching initiator；Above-mentioned 1~15 weight % of inorganic acid；Above-mentioned 0.1~20 weight of organic acid
Measure %；Above-mentioned 1~20 weight % of polyalcohol system profile improver；And the water of surplus.
11. the metal film etchant as described in 10 further includes 0.1~5 weight % of metal salt.
12. the metal film etchant as described in 1 does not include phosphoric acid or phosphoric acid based compound.
13. a kind of conductive pattern forming method comprising:
In the step of forming metal film on substrate；And
The step of above-mentioned metal film is etched using metal film etchant described in above-mentioned any one of 1~12.
14. the conductive pattern forming method as described in 13, the step of forming above-mentioned metal film includes forming the step containing silverskin
Suddenly.
15. the conductive pattern forming method as described in 14, the step of forming above-mentioned metal film further comprise to be formed it is transparent
The step of electric conductivity oxidation film.
16. the conductive pattern forming method as described in 15, above-mentioned transparent conductivity oxidation film includes to contain silverskin across above-mentioned
The the first transparent conductivity oxidation film and the second transparent conductivity oxidation film formed.
17. the conductive pattern forming method as described in 15, above-mentioned transparent conductivity oxidation film includes selected from by tin indium oxide
(ITO), the group of indium zinc oxide (IZO), indium tin zinc oxide (ITZO), gallium oxide zinc (GZO) and indium gallium zinc (IGZO) composition
At least one of.
18. the conductive pattern forming method as described in 13, further comprising: forming thin film transistor (TFT) on aforesaid substrate
The step of；The step of forming the pixel electrode being electrically connected with above-mentioned thin film transistor (TFT)；And it is formed in pixel electrodes aobvious
The step of showing layer, above-mentioned metal film is formed on above-mentioned display layer.
19. the conductive pattern forming method as described in 18, above-mentioned conductive pattern as image display device public electrode,
Reflecting electrode or wiring and provide.
Invention effect
The metal film etchant of embodiments of the invention described above may include etching initiator, inorganic acid, organic
Acid and polyalcohol system profile improver, and there are 2 pH below.In above-mentioned pH range, rate of etch and etching effect can be improved
Rate, and by the effect of above-mentioned organic acid and above-mentioned polyalcohol system profile improver, it can be improved on the side wall of conductive pattern
Etch uniformity.
According to exemplary embodiments, above-mentioned inorganic acid includes nitric acid, due to excluding or reducing the strong of phosphoric acid, sulfuric acid or the like
The content of acid, therefore can be realized the etching characteristic adjusting for being used to form fine pattern.
In addition, in the case where above-mentioned metal film includes containing silverskin and transparent conductivity oxidation film, above-mentioned etching initiator
Metal oxide displacement reaction can be caused, made above-mentioned containing silverskin and transparent conductivity oxidation film quilt while uniform etching.It is above-mentioned
Etchant further includes metal salt, in this case, can further increase above-mentioned containing silverskin and above-mentioned electrically conducting transparent
The etch uniformity of property oxidation film.
By using above-mentioned etchant, the electrode of reflecting electrode of such as display device etc can be made or matched
Line, the induction electrode of touch sensor, trace or weld pad etc. are formed to have desired aspect ratio and profile.
Detailed description of the invention
Fig. 1 and Fig. 2 is the sectional view for illustrating the conductive pattern side of being formed of exemplary embodiments.
Fig. 3 is the sectional view for illustrating the manufacturing method of the display base plate of exemplary embodiments.
Symbol description
100,200: substrate 110: lower insulating film
115: lower conducting pattern 120: metal film
120a: 121: the first transparent conductivity oxidation film of conductive pattern
122,262,272: the first transparent conductivity oxide film pattern
123: containing silverskin 124,264,274: argentiferous pattern
125: the second transparent conductivity oxidation films
126,266,276: the second transparent conductivity oxide film pattern
210: active layer 225: gate electrode
233: source electrode 237: drain electrode
245: pixel electrode 260: to electrode
270: wiring
Specific embodiment
According to an embodiment of the invention, providing a kind of metal film etchant (hreinafter referred to as " etching solution combination
Object "), it includes etching initiator, inorganic acid, organic acid and polyalcohol system profile improvers, and pH is 2 or less.Further it is provided that
Utilize the conductive pattern forming method of above-mentioned metal film etchant, the manufacturing method of display base plate.
Term " metal film " used herein is as including metal single layer film and above-mentioned metal single layer film and transparent
The term of the stepped construction of electric conductivity oxidation film and use.In addition, above-mentioned metal film may include formed by dissimilar metal it is more
Kind metal single layer film.
In exemplary embodiments, above-mentioned metal film may include containing silverskin.It is above-mentioned to can be finger comprising silver-colored or silver-colored containing silverskin
The film of alloy.In addition, the above-mentioned multilayered structure that also may include 2 layers or more containing silverskin.
For example, above-mentioned silver alloy may include: neodymium (Nd), copper (Cu), palladium (Pd), niobium (Nb), nickel (Ni), molybdenum (Mo), chromium
(Cr), the alloy of magnesium (Mg), tungsten (W), protactinium (Pa), titanium (Ti) or their two or more combinations and silver-colored (Ag)；Containing nitrogen (N),
The silver compound of the doped chemicals such as silicon (Si), carbon (C)；Or their two or more combinations.
Above-mentioned transparent conductivity oxidation film may include transparent metal oxide.Such as above-mentioned transparent metal oxide can be with
Include tin indium oxide (ITO), indium zinc oxide (IZO), indium tin zinc oxide (ITZO), gallium oxide zinc (GZO), indium gallium zinc
(IGZO) or their combination.
It include to contain silverskin and transparent conductivity with above-mentioned metal film hereinafter, the embodiment of the present invention is described in detail
It is illustrated in case where oxidation film.But this belongs to preferred illustration, and thought of the invention and range are not necessarily limited to this.
<etchant>
Above-mentioned etching initiator, which can be used as, contained in the etchant of the embodiment of the present invention can promote silver
(Ag) etc. it etching speed and improves the ingredient of etch uniformity and provides.Furthermore, it is possible to as aoxidizing/going back compared with silver
The relatively low transparent conductivity oxidation film of former characteristic causes or inducing metal displacement is reacted and promotes the ingredient of etching and includes.
In addition, promoting the activity of aftermentioned inorganic acid by the inclusion of above-mentioned etching initiator, thus, it is possible to opposite reduction nothings
The content of machine acid.Caused overetch, etching are uneven etc. when being therefore able to suppress comprising excessive inorganic acid.
According to exemplary embodiments, above-mentioned etching initiator may include vulcanization peroxide, hydrogen peroxide, persulfate
And/or peroxy-nitrate, it preferably may include the vulcanization peroxide of oxone (oxone) etc.
As above-mentioned persulfate, potassium peroxydisulfate (K can be used2S2O8), sodium peroxydisulfate (Na2S2O8) and ammonium persulfate
((NH4)2S2O8) at least one of substance potassium per nitrate (KNO can be used as above-mentioned peroxy-nitrate4), pernitric acid sodium
(NaNO4) and pernitric acid ammonium (NH4NO4) at least one of substance.
In a part of the embodiment, in composition total weight, the content of above-mentioned etching initiator can be 1~20 weight %.
The content of above-mentioned etching initiator be lower than 1 weight % in the case where, etching speed excessive descent and uneven etching may be caused.
Furthermore, it is possible to the short circuit of the wiring as caused by silver-colored residue occur, and the etching facilitation effect of transparent conductivity oxidation film may be micro-
Its is micro-.In the case where the content of above-mentioned etching initiator is more than 20 weight %, the oxidation of inorganic acid may be hindered instead.
In one embodiment, from minimizing the above-mentioned etching speed difference containing silverskin and transparent conductivity oxidation film, and it is real
From the aspect of existing excellent etch uniformity, the adjustable content of above-mentioned etching initiator is 3~10 weight %.
Above-mentioned inorganic acid can interact with above-mentioned etching initiator and play oxidant effect.For example, above-mentioned inorganic
Acid can play the main oxidant effect for the transparent conductivity oxidation film of ITO etc.Pass through above-mentioned inorganic acid and above-mentioned erosion
It carves initiator to play a role together, thus can be by uniform etching simultaneously containing silverskin and transparent conductivity oxidation film.
According to exemplary embodiments, above-mentioned inorganic acid may include nitric acid.In a part of the embodiment, above-mentioned inorganic acid can be with
It simultaneously include nitrate.As the example of above-mentioned nitrate, sodium nitrate (sodium nitrate), potassium nitrate can be enumerated
(potassium nitrate) or ammonium nitrate (ammonium nitrate) etc..They can be individually or by two or more combinations
It uses.
In a part of the embodiment, in composition total weight, the content of above-mentioned inorganic acid can be 1~15 weight %.Upper
The content of inorganic acid is stated lower than in the case where 1 weight %, etching speed excessive descent and may cause for example by ITO residue, silver
The short circuit of wiring caused by residue.In addition, because of above-mentioned ITO residue or there may be stain (dark spot or blind due to silver-colored residue
spot).In the case where the content of above-mentioned inorganic acid is more than 15 weight %, it is possible to create the erosion of the metal film of overetch or the like
It is bad to carve control.
In one embodiment, it is contemplated that the above-mentioned uniform etching speed containing silverskin and transparent conductivity oxidation film and control are special
Property, the content of above-mentioned inorganic acid can be adjusted to 3~10 weight %.
Above-mentioned organic acids can such as reduce acquired to suitably promote or adjust the above-mentioned etching speed containing silverskin
Conductive pattern critical dimension loss (CD Loss), and promote fine pattern formed and include.
In a part of the embodiment, above-mentioned organic acid may include the first organic acid and acidity is weaker than above-mentioned first organic acid
The second organic acid.
For example, above-mentioned first organic acid includes acetic acid, it can be used as pro-oxidant or function played to silver-colored main oxidant
Energy.Above-mentioned second organic acid may include iminodiacetic acid (iminodiacetic acid:IDA), ethylenediamine tetra-acetic acid
(ethylenediaminetetraacetic acid:EDTA), glycine (glycine), salicylic acid (salicylic
Acid), citric acid (citric acid), formic acid (formic acid), oxalic acid (oxalic acid), malonic acid (malonic
Acid), succinic acid (succinic acid), butyric acid (butyric acid), gluconic acid (gluconic acid), glycolic
(glycolic acid), valeric acid (pentanic acid) etc..They can be independent or be used in combination of two or more.
Above-mentioned second organic acid can be used as etching outline promotor and function.By utilizing above-mentioned second organic acid
And inhibit or control a part of oxidation as caused by above-mentioned first organic acid, the CD loss of conductive pattern can be substantially reduced
Or CD deviation.
In a part of the embodiment, in composition total weight, the content of above-mentioned organic acid can be 0.1~20 weight %.?
In the case that the content of above-mentioned organic acid is lower than 0.1 weight %, the CD loss of conductive pattern can be can increase.In above-mentioned organic acid
In the case that content is more than 20 weight %, the ageing stability of composition may decline.
In view of the profile characteristic of above-mentioned conductive pattern improves, in a preferred embodiment, the content of above-mentioned organic acid can
Think 10~20 weight %.
In exemplary embodiments, includes also above-mentioned polyalcohol system profile improver, further can fine control conduction
The etching outline of pattern.
For example, above-mentioned polyalcohol system profile improver is due to that can make above-mentioned etching solution combine comprising multiple hydroxyls
The pH of object slightly rises, to inhibit overetch, tip (tip) phenomenon.In addition, above-mentioned polyalcohol system profile improver can be made
It is functioned for the surfactant of above-mentioned etchant or the surface protectant of conductive pattern, so that pattern be inhibited to damage
It loses.
Above-mentioned polyalcohol system profile improver may include such as glycerol (glycerol), ethylene glycol (ethylene
Glycol), diethylene glycol (diethylene glycol), triethylene glycol (triethylene glycol), polyethylene glycol
(polyethylene glycol) etc..They can be independent or be used in combination of two or more
Preferably, the etching performance of composition is overly hindered in order to prevent, as above-mentioned polyalcohol system profile improver,
Diatomic alcohol compounds can be used.
In a part of the embodiment, in composition total weight, the content of above-mentioned polyalcohol system profile improver can be 1~20
Weight %.In the case where the content of above-mentioned polyalcohol system profile improver is lower than 1 weight %, sufficient table may be cannot achieve
Face protection, pH regulatory function may excessively hinder etching performance or composition pH mistake more than 20 weight %
Degree increases.
In one embodiment, from the aspect of the fine adjustments for realizing etching characteristic, above-mentioned polyalcohol system profile can be changed
The content of kind agent is adjusted to 1~10 weight %.
In a part of exemplary embodiments, above-mentioned etchant can further include metal salt.Above-mentioned metal salt
It can be in order to further increase the above-mentioned etch uniformity containing silverskin and transparent conductivity oxidation film and addition includes.On for example,
Metal salt is stated by removing or dissociating the silver being formed in above-mentioned transparent conductivity oxidation film surface from the above-mentioned desorption containing silverskin
Natural oxide film, can prevent the etching speed of above-mentioned transparent conductivity oxidation film from declining.In addition, by means of above-mentioned metal
Salt can improve whole etching speed while maintaining etch uniformity.
In a part of the embodiment, above-mentioned metal salt can further include metal nitrate, such as may include ferric nitrate
(ferric nitrate), sodium nitrate (sodium nitrate), potassium nitrate (potassium nitrate) etc..It is preferred that can be with
Use ferric nitrate.
In a part of the embodiment, in composition total weight, the content of above-mentioned metal salt can be 0.1~5 weight %.Upper
The content of metal salt is stated lower than in the case where 0.1 weight %, silver may be adsorbed in above-mentioned transparent conductivity oxidation film again, super
In the case where crossing 5 weight %, the etching speed containing silverskin is excessively increased and may cause overetch, tip phenomenon.
In view of the above-mentioned uniform etching containing silverskin and transparent conductivity oxidation film, the content of preferably above-mentioned metal salt can
Think 0.1~3 weight %.
Above-mentioned etchant may include the water of surplus in addition to the above ingredients, such as may include deionization
Water.In the case where above-mentioned deionized water, such as it can have the resistivity value of 18M Ω/㎝ or more.
Term " surplus " used herein refers to, comprising other additives, comprising in addition to it is above-mentioned at
Divide the variable amount with the amount other than above-mentioned additive.
It, can be in the work for not hindering mentioned component in order to improve etching efficiency or etch uniformity in a part of the embodiment
It include above-mentioned additive in the range of.It is widely used for preventing in the art for example, above-mentioned additive may include
Only burn into prevents the preparation etc. of etch byproducts absorption, the cone angle for adjusting etched pattern etc..
In a part of the embodiment, above-mentioned etchant substantially can be by above-mentioned etching initiator, inorganic acid, organic
Acid, polyalcohol system profile improver, metal salt and water are constituted.
In a part of the embodiment, above-mentioned etchant can not include phosphoric acid or phosphoric acid based compound (for example, phosphoric acid
Salt).In the case where above-mentioned phosphoric acid or phosphoric acid based compound, possible initiation loss as caused by the overetch of above-mentioned metal film,
The damage of substructure object, silver adsorb again.In addition, may make to etch in the case where above-mentioned phosphoric acid or phosphoric acid based compound
The excess stickiness of liquid composition increases and causes the etch bias in each region of etch target film.
But above-mentioned etchant is by excluding phosphoric acid or above-mentioned phosphoric acid based compound, it is above-mentioned so as to prevent
Overetch containing silverskin and it is capable of forming the conductive pattern with fine pattern size.
Above-mentioned inorganic acid contained in the etchant of a part of exemplary embodiments is substantially made of nitric acid, can
Not include hydrochloric acid and sulfuric acid.Thereby, it is possible to realize the etching work procedure for reducing problem of environmental pollution and silver-colored precipitation problem.
The pH of the etchant of exemplary embodiments adjustable is 2 or less.The content of above-mentioned composition ingredient can
To be adjusted in 2 or less range of pH.For example, being improved in the range of 2 or less pH by above-mentioned polyalcohol system profile
Agent, being capable of subtle control pH.Due to pH be adjusted to 2 hereinafter, therefore can reduce do not etch, silver is precipitated, silver adsorbs etc. no again
It is good, and etching speed, etch uniformity are improved by the interaction of mentioned component.
<conductive pattern forming method>
Fig. 1 and Fig. 2 is the schematically sectional view for illustrating the wiring side of being formed of exemplary embodiments.
Referring to Fig.1, lower conducting pattern 115 and lower insulating film 110 can be formed on the substrate 100.
Substrate 100 may include glass substrate, macromolecule resin or plastic base, inorganic insulation substrate etc..
Lower conducting pattern 115 can be formed as including, for example, aluminium (Al), copper (Cu), molybdenum (Mo), tungsten (W), titanium (Ti), tantalum
(Ta), the transparent conductive oxides etc. of ITO etc.Lower insulating film 110 can be formed as including acrylic resin, poly- silicon
The inorganic insulation substance of the organic insulation substance, and/or silica of oxygen alkane or the like, silicon nitride, silicon oxynitride or the like.
Lower conducting pattern 115 can be used as such as conductive channel or conductive contact piece and provide.
According to exemplary embodiments, can be formed on lower insulating film 110 and lower conducting pattern 115 comprising successively layer
The first folded transparent conductivity oxidation film 121, the metal film 120 containing silverskin 123 and the second transparent conductivity oxidation film 125.
First and second transparent conductivity oxidation films 121,125 can be formed as comprising ITO, IZO, GZO, IGZO or the like
Transparent metal oxide.It can be formed as described above containing silverskin 123 comprising silver and/or silver alloy.First transparent conductivity
Oxidation film 121, can be for example, by sputtering (sputtering) process containing silverskin 123 and the second transparent conductivity oxidation film 125
Etc vapor deposition process formed.
Mask pattern 130 can be formed on metal film 120.For example, can be on the second transparent conductivity oxidation film 125
After forming photoresist film, by exposure and imaging process, above-mentioned photoresist film is partly removed and forms mask
Pattern 130.
Referring to Fig. 2, the metal film etchant of above-mentioned exemplary embodiments can be used, metal film 120 is etched
And form conductive pattern 120a.Conductive pattern 120a for example may be embodied in first stacked gradually on lower insulating film 110 thoroughly
Bright electric conductivity oxide film pattern 122, argentiferous pattern 124 and the first transparent conductivity oxide film pattern 126.
Conductive pattern 120a for example may be used as the weld pad, electrode or wiring of image display device.Due to by low resistance, believing
Number relatively excellent argentiferous pattern 124 of transmission characteristic is formed in the first and second transparent conductivity oxidation films of excellent corrosion resistance
Between pattern 122,126, therefore it can be realized low resistance and conductive pattern that machinery, chemical reliability improve.
Further, since using above-mentioned etching initiator, inorganic acid, organic acid, polyalcohol system profile improver, metal is included
Salt etc. and the etchant for excluding or reducing phosphoric acid, therefore the overetch of argentiferous pattern 124 can be prevented, formation has
The conductive pattern 120a of substantially uniform and continuous side wall profile.
In a part of the embodiment, containing silverskin 123 or argentiferous pattern 124 with a thickness of aboutMore than, in an embodiment,
It can be aboutMore than.The thickness of first and second transparent conductivity oxide film patterns 122,126 can be about
In order to realize low resistance, it will increase the thickness of argentiferous pattern 124, increase the aspect ratio of conductive pattern 120a, therefore
It is bad to may cause the etching as caused by silver-colored residue, overetch.But it is combined by using the etching solution of exemplary embodiments
Object can be realized and inhibit the above-mentioned undesirable wet etching process of etching.
Fig. 3 is the sectional view for illustrating the manufacturing method of the display base plate of exemplary embodiments.For example, scheming in Fig. 3
The display base plate comprising the wiring, electrode structure object that are formed by above-mentioned conductive pattern forming method is shown.
Referring to Fig. 3, thin film transistor (TFT) (TFT) can be formed on substrate 200.For example, above-mentioned TFT may include active layer
210, gate insulating film 220 and gate electrode 225.
According to exemplary embodiments, after active layer 210 being formed on substrate 200, the grid of covering active layer 210 are formed
Pole insulating film 220.
Active layer 210 can be formed as partly leading comprising the oxide of polysilicon or such as indium gallium zinc (IGZO) etc
Body.Gate insulating film 220 can be formed as including silica, silicon nitride and/or silicon oxynitride.
Gate electrode 225 can be formed in a manner of Chong Die with active layer 210 on gate insulating film 220.Gate electrode 225 can
To be formed as the metal comprising Al, Ti, Cu, W, Ta, Ag or the like.
After the interlayer dielectric 230 of covering grid electrode 225 being formed on gate insulating film 220, perforation interlayer is formed
Insulating film 230 and gate insulating film 220 and the source electrode 233 and drain electrode 237 contacted with active layer 210.Source electrode 233 and leakage
Electrode 237 can be formed as the metal comprising Al, Ti, Cu, W, Ta, Ag or the like.
Channel (via) insulating film of covering source electrode 233 and drain electrode 237 can be formed on interlayer dielectric 230
240.Channel insulation film 240 can be used the organic insulation substance of acrylic acid series, siloxane-based resin or the like and be formed.
The pixel electrode 245 being electrically connected with drain electrode 237 can be formed on channel insulation film 240.Pixel electrode 245 can
With the channel part (via portion) contacted comprising through channel insulating film 240 with drain electrode 237.Pixel electrode 245 can be with
Be formed as metal and/or transparent conductive oxides comprising Al, Ti, Cu, W, Ta, Ag or the like.
Pixel can be formed on channel insulation film 240 and limits film 250, in the pixel exposed because pixel limits film 250
It limits film 250 and forms display layer 255 above.Display layer 255 can be formed as organic luminous layer contained in such as OLED device
(EML) or liquid crystal layer contained in LCD device.
Shape paired electrode 260 on film 250 and display layer 255 can be limited in pixel.It is aobvious that image can be used as to electrode 260
Public electrode, reflecting electrode or the cathode (cathode) of showing device and provide.
According to exemplary embodiments, to electrode 260 can by the first transparent conductivity oxidation film, containing silverskin and second thoroughly
After bright electric conductivity oxidation film stacks gradually, patterned and shape by using the wet etching process of above-mentioned etchant
At.
It is transparent to may be embodied in first stacked gradually on pixel restriction film 250 and display layer 255 to electrode 260 as a result,
Electric conductivity oxide film pattern 262, argentiferous pattern 264 and the second transparent conductivity oxide film pattern 266.
In a part of the embodiment, above-mentioned image display device may include display area I and non-display area II.It is above-mentioned
TFT, pixel electrode 245, display layer 255 and electrode 260 can be formed on the I of display area.It can on non-display area II
To form wiring 270.Wiring 270 can be electrically connected with above-mentioned TFT or to electrode 260.
Also the first transparent conductivity oxide film pattern including, for example, being stacked gradually on channel insulation film 240 of wiring 270
272, argentiferous pattern 274 and the second transparent conductivity oxide film pattern 276, and the etching solution group of exemplary embodiments can be used
It closes object and patterns.
In one embodiment, wiring 270 can also by with the wet type substantially the same to electrode 260 on the I of display area
Etching work procedure and be formed together.
As noted previously, as image display device is formed as transparent comprising first to electrode 260 and/or wiring 270
Electric conductivity oxide film pattern-argentiferous pattern the-the second transparent conductivity oxide film pattern stepped construction, therefore low electricity can be presented
Characteristic is hindered and at the same time improving mechanical/chemical stability and optical characteristics.Further, since using above-mentioned etchant, because
This is able to suppress the bad of silver-colored residue, side damage, tip phenomenon or the like.
In a part of the embodiment, it can use above-mentioned etchant or conductive pattern forming method and implement gate electrode
225, source electrode 233, drain electrode 237, pixel electrode 245 patterning.
In addition, above-mentioned etchant can be used for being formed by the image display device of aforementioned display device substrate
The various conductive patterns of contained touch sensor.It is, for example, possible to use above-mentioned etchants to pass to form above-mentioned touch
Induction electrode, trace, weld pad of sensor etc..
Hereinafter, providing the experimental example including specific embodiment and comparative example, still to help to understand the present invention
This only illustrates the present invention, is not intended to limit this appended claims range, can be in scope of the invention and technical idea model
Enclose it is interior numerous variations and modification are carried out to embodiment, this is will be obvious to those skilled in the art that certainly in this way
Change and modification also belong to the ranges of appended claims.
Embodiment and comparative example
According to the composition and content (weight %) recorded in following table 1, the metal film etching of embodiment and comparative example is manufactured
Liquid composition.
[table 1]
Experimental example
It is formed on the glass substrateTrilamellar membrane uses diamond tool
Cut into 10cm × 10cm size and the perparation of specimen.
The metal film of injection embodiment and comparative example in injecting type etching machines (manufacture of ETCHER, K.C.Tech company)
Etchant.The temperature of metal film etchant is set as 40 DEG C, then when temperature reaches 40 ± 0.1 DEG C,
85 seconds etching work procedures are implemented to above-mentioned sample metal injection film etchant.
After etching work procedure, above-mentioned sample is cleaned with deionized water, after air drier drying, is resisted with photic
Erosion agent stripping machine (PR stripper) removes photoresist.
(1) etching speed (Etch Rate:ER) is evaluated
It, will be through losing using the thickness of electronic scanner microscope (SU-8010, Hitachi, Ltd's manufacture) the etched sample of measurement
The thickness of the sample at quarter implements the time divided by etching and measures longitudinal etching speed.Later, according to following benchmark, implement etching speed
Degree evaluation, and the results are shown in table 2.
<evaluation criteria>
◎: longitudinal etching speed is more than
Zero: longitudinal etching speed is
X: longitudinal etching speed is less than
(2) lateral erosion (Side Etch) is evaluated
For etched sample, using electronic scanner microscope (SU-8010, Hitachi, Ltd's manufacture), measurement is formed
Conductive pattern lateral erosion and substrate top and the bottom between etching range distribution.
Lateral erosion (S/E) is calculated by following mathematical expressions 1, and is evaluated as follows.
[mathematical expression 1]
Lateral erosion (S/E)=((width of photoresist both ends part)-(difference of the width of etched wiring))/2
◎: outstanding (0.5 μm or less)
Zero: good (more than 0.5 μm and 1.0 μm or less)
X: bad (more than 1.0 μm)
(3) critical dimension variations (CD bias) measure
Substrate will be cut off after etched sample clean and drying, for section, utilizes electronic scanner microscope (SEM；
Model: SU-8010, Hitachi, Ltd's manufacture) it is measured.It is evaluated about critical dimension variations, after etching, measurement and light
The upper width of wiring that causes resist pattern to connect and evaluated.Evaluation criteria is as follows.
◎: the width of the wiring to connect with photoresist pattern is more than 31 μm and 34 μm or less
Zero: the width of the wiring to connect with photoresist pattern is more than 23 μm and 31 μm or less
△: the width of the wiring to connect with photoresist pattern is more than 9 μm and 23 μm or less
The width for the wiring that X: not being etched or connects with photoresist pattern is 9 μm or less
The evaluation result of above-mentioned experimental example is recorded in following table 2 together.
[table 2]
| It distinguishes | ER evaluation | Lateral erosion | CD deviation |
| Embodiment 1 | ◎ | ◎ | ◎ |
| Embodiment 2 | ◎ | ◎ | ◎ |
| Embodiment 3 | ◎ | ◎ | ◎ |
| Embodiment 4 | ◎ | ○ | ○ |
| Embodiment 5 | ○ | ○ | ○ |
| Comparative example 1 | X | X | △ |
| Comparative example 2 | X | X | X |
| Comparative example 3 | X | ○ | △ |
Referring to table 2, the etchant of the embodiment of pH range and ingredient comprising exemplary embodiments is shown on the whole
Outstanding etching characteristic is shown.In particular, showing etching speed in the Examples 1 to 3 comprising metal salt and the second organic acid
Degree and the outstanding result of etch uniformity.
On the other hand, pH be more than 2 or be omitted etching initiator etc ingredient comparative example etching speed under
Drop, lateral erosion or CD deviation are also deteriorated together.
Claims (19)
1. a kind of metal film etchant, it includes etching initiator, inorganic acid, organic acid, polyalcohol system profiles to improve
The water of agent and surplus, and pH is 2 or less.
2. metal film etchant according to claim 1, the etching initiator includes selected from by vulcanization peroxide
At least one of compound, hydrogen peroxide, persulfate and group of peroxy-nitrate composition.
3. metal film etchant according to claim 2, the etching initiator includes oxone.
4. metal film etchant according to claim 1, the inorganic acid includes nitric acid.
5. metal film etchant according to claim 1, the organic acid includes the first organic acid and acidity
Second organic acid weaker than first organic acid.
6. metal film etchant according to claim 5, first organic acid includes acetic acid,
Second organic acid includes selected from by iminodiacetic acid (IDA), ethylenediamine tetra-acetic acid (EDTA), glycine, bigcatkin willow
At least one in group that acid, citric acid, formic acid, oxalic acid, malonic acid, succinic acid, butyric acid, gluconic acid, glycolic and valeric acid form
Kind.
7. metal film etchant according to claim 1, the polyalcohol system profile improver include selected from by
At least one of glycerol, ethylene glycol, diethylene glycol, triethylene glycol and group of polyethylene glycol composition.
8. metal film etchant according to claim 1, further includes metal salt.
9. metal film etchant according to claim 8, the metal salt includes selected from by ferric nitrate, sodium nitrate
With at least one of the group of potassium nitrate composition.
10. metal film etchant according to claim 1, in composition total weight, include:
1~20 weight % of etching initiator；
1~15 weight % of inorganic acid；
0.1~20 weight % of organic acid；
1~20 weight % of polyalcohol system profile improver；And
The water of surplus.
11. metal film etchant according to claim 10 further includes 0.1~5 weight % of metal salt.
12. metal film etchant according to claim 1 does not include phosphoric acid or phosphoric acid based compound.
13. a kind of conductive pattern forming method comprising:
In the step of forming metal film on substrate；And
The step of metal film is etched using metal film etchant described in any one of claim 1~12.
14. conductive pattern forming method according to claim 13, the step of forming the metal film includes forming argentiferous
The step of film.
15. conductive pattern forming method according to claim 14, the step of forming the metal film further comprises shape
The step of at transparent conductivity oxidation film.
16. conductive pattern forming method according to claim 15, the transparent conductivity oxidation film includes across described
The the first transparent conductivity oxidation film and the second transparent conductivity oxidation film formed containing silverskin.
17. conductive pattern forming method according to claim 15, the transparent conductivity oxidation film includes selected from by oxygen
Change indium tin (ITO), indium zinc oxide (IZO), indium tin zinc oxide (ITZO), gallium oxide zinc (GZO) and indium gallium zinc (IGZO) group
At at least one of group.
18. conductive pattern forming method according to claim 13, further comprising:
The step of forming thin film transistor (TFT) on the substrate；
The step of forming the pixel electrode being electrically connected with the thin film transistor (TFT)；And
On the pixel electrode formed display layer the step of,
The metal film is formed on the display layer.
19. conductive pattern forming method according to claim 18, public affairs of the conductive pattern as image display device
Common electrode, reflecting electrode or wiring and provide.
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| US11639470B2 (en) | 2020-12-28 | 2023-05-02 | Samsung Display Co., Ltd. | Etching composition for thin film containing silver, method for forming pattern and method for manufacturing a display device using the same |
| US12031076B2 (en) | 2020-12-28 | 2024-07-09 | Samsung Display Co., Ltd. | Etching composition for thin film containing silver, method for forming pattern and method for manufacturing a display device using the same |
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| KR20210128383A (en) * | 2019-02-19 | 2021-10-26 | 디아이씨 가부시끼가이샤 | Etching liquid for silver and manufacturing method of a printed wiring board using the same |
| KR102590529B1 (en) * | 2019-05-14 | 2023-10-16 | 주식회사 엘지화학 | Etchant composition for metal layer and etching method of metal layer using the same |
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