CN110546741A - Etching solution and use thereof - Google Patents
Etching solution and use thereof Download PDFInfo
- Publication number
- CN110546741A CN110546741A CN201780087436.0A CN201780087436A CN110546741A CN 110546741 A CN110546741 A CN 110546741A CN 201780087436 A CN201780087436 A CN 201780087436A CN 110546741 A CN110546741 A CN 110546741A
- Authority
- CN
- China
- Prior art keywords
- copper
- etching
- hydrogen
- conductive film
- etching solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005530 etching Methods 0.000 title claims abstract description 166
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 112
- 229910052802 copper Inorganic materials 0.000 claims abstract description 112
- 239000010949 copper Substances 0.000 claims abstract description 112
- 238000004090 dissolution Methods 0.000 claims abstract description 35
- 239000003112 inhibitor Substances 0.000 claims abstract description 30
- 239000003085 diluting agent Substances 0.000 claims abstract description 29
- 239000007800 oxidant agent Substances 0.000 claims abstract description 27
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 25
- 150000005309 metal halides Chemical class 0.000 claims abstract description 25
- 229910000039 hydrogen halide Inorganic materials 0.000 claims abstract description 22
- 239000012433 hydrogen halide Substances 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 239000004020 conductor Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 31
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 14
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 8
- 150000001451 organic peroxides Chemical class 0.000 claims description 8
- 230000000737 periodic effect Effects 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 7
- 150000004820 halides Chemical class 0.000 claims description 7
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 7
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 7
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000010408 film Substances 0.000 description 102
- 239000000243 solution Substances 0.000 description 94
- 239000007864 aqueous solution Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- WTDHULULXKLSOZ-UHFFFAOYSA-N hydroxylamine hydrochloride Substances Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 235000011007 phosphoric acid Nutrition 0.000 description 9
- 239000012452 mother liquor Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000001110 calcium chloride Substances 0.000 description 6
- 229910001628 calcium chloride Inorganic materials 0.000 description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 6
- WCYJQVALWQMJGE-UHFFFAOYSA-M hydroxylammonium chloride Chemical compound [Cl-].O[NH3+] WCYJQVALWQMJGE-UHFFFAOYSA-M 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- -1 halogen ions Chemical class 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000010413 mother solution Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- YVBCULSIZWMTFY-UHFFFAOYSA-N 4-Heptanol Natural products CCCC(O)CCC YVBCULSIZWMTFY-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- COWKRCCNQSQUGJ-UHFFFAOYSA-N 1,1,2,2,3-pentafluoropropan-1-ol Chemical compound OC(F)(F)C(F)(F)CF COWKRCCNQSQUGJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 239000005968 1-Decanol Substances 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- NBUKAOOFKZFCGD-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropan-1-ol Chemical compound OCC(F)(F)C(F)F NBUKAOOFKZFCGD-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- YALMXYPQBUJUME-UHFFFAOYSA-L calcium chlorate Chemical compound [Ca+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O YALMXYPQBUJUME-UHFFFAOYSA-L 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- CRJZNQFRBUFHTE-UHFFFAOYSA-N hydroxylammonium nitrate Chemical compound O[NH3+].[O-][N+]([O-])=O CRJZNQFRBUFHTE-UHFFFAOYSA-N 0.000 description 1
- VGYYSIDKAKXZEE-UHFFFAOYSA-L hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Weting (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention provides an etching solution which selectively dissolves a transparent conductive film without corroding copper, the etching solution comprises (a) hydrogen halide, (b) metal halide, (c) copper dissolution inhibitor selected from hydroxylamine and salts thereof, and (d) diluent, and optionally (e) oxidant.
Description
Technical Field
The present invention relates to an etching technique of a transparent conductive film containing indium oxide used for a liquid crystal display or the like, and more particularly to an etching solution for etching a transparent conductive film having a pattern containing a copper conductor on a surface thereof, and use thereof.
Background
Transparent conductive films typified by ITO (indium-tin oxide) films are widely used in the field of electronic devices such as antistatic films, heat reflective films, photoelectric conversion elements, and transparent electrodes of various flat panel displays. In recent years, with the spread of portable information terminals, notebook computers, small televisions, and the like, there has been an increasing demand for Liquid Crystal Displays (LCDs).
Sensors using ITO films are widely used in touch panels, and in recent years, improvements such as increasing the screen size have been rapidly developed in addition to improvements in sensitivity and reactivity. As a method for forming a fine electrode pattern on a transparent conductive film typified by such an ITO film, a wet pre-process method is used, that is, a method for removing a portion of the transparent electrode film which is not masked by an etching solution containing an acidic aqueous solution containing halogen ions (patent document 1).
In recent years, the mainstream of the metal used for the circuit for supplying power to the circuit of the ITO film is to use copper which is relatively inexpensive and has excellent conductivity. However, since the conventional etching solutions have an oxidizing action on the metal layer and a corrosive action on copper, they cannot be directly applied to etching of a transparent conductive film having a pattern including a copper conductor.
the etching solution (patent document 2) completed by the present applicant is a chemical agent which contains a halogen acid, a halogen metal salt, an oxidizing agent, and a remaining amount of a diluting solution and which causes a small amount of corrosion of a copper conductor in the currently used etching solution for an ITO film. However, even if the etching solution is used for etching, the dissolution of the copper conductor cannot be ignored, and damage to a high-definition copper circuit pattern cannot be avoided.
in addition, in the method of collectively etching the copper conductor and the ITO film using an etching solution containing ferric chloride, hydrochloric acid, and an oxidizing agent (patent document 3 and patent document 4), although there is an advantage that the manufacturing process of the transparent electrode pattern can be made effective, there is a problem that the etching of the copper conductor in the upper layer of the ITO film is excessively performed, and the resistance value of the power feeding circuit increases.
Further, a method of separately using different etching solutions for etching a copper film and etching a transparent conductor layer has been proposed (patent document 5), but the composition of each etching solution has not been studied in detail here, and it cannot be said that the composition has reached a practical level.
Conventionally, it has been pointed out that an etching rate of an etching solution for an ITO film changes with time (patent documents 6 and 7).
documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2015-60937
Patent document 2: japanese patent No. 4897148
Patent document 3: japanese patent laid-open publication No. 2011-114194
Patent document 4: japanese patent laid-open publication No. 2013-89731
patent document 5: japanese patent laid-open No. 2014-52737
Patent document 6: japanese patent laid-open publication No. 2017-10996
Patent document 7: japanese patent laid-open publication No. 2002-241968
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above problems, and an object thereof is to realize a technique for selectively etching an ITO circuit without corroding a conductor mainly composed of copper while maintaining a high etching rate for a crystalline transparent conductive film. Another object of the present invention is to provide a method for etching a transparent conductive film, which can suppress dissolution of a copper conductor and can etch only an ITO conductor. Further, another object of the present invention is to provide an etching solution which is less likely to change with time.
Means for solving the problems
In order to solve the above-described problems, the present inventors have made an effort to provide a novel and high-performance etching solution capable of selectively dissolving a transparent conductive film without corroding a conductor mainly composed of copper and suppressing a change with time. Namely, the present invention is as follows.
(1)
An etching solution, comprising: (a) a hydrogen halide, (b) a metal halide, (c) a copper dissolution inhibitor and (d) a diluent, and optionally (e) an oxidizing agent,
The hydrogen halide (a) contains 1 or more selected from hydrogen chloride, hydrogen bromide and hydrogen iodide,
The (b) metal halide comprises 1 or more halides selected from the group consisting of group 1,2, and 13 elements of the periodic Table of the elements,
the copper dissolution inhibitor (c) contains 1 or more selected from hydroxylamine and salts thereof,
the (d) diluent comprises water and/or an organic solvent, and may optionally comprise a phosphoric acid,
the oxidant (e) contains more than 1 selected from chlorate, nitrate or nitrite of alkali metal and/or alkaline earth metal, perchloric acid, nitric acid, hydrogen peroxide and organic peroxide, and
the etching solution is used for etching a transparent conductive film having a conductive pattern containing copper as a main component on the surface.
(2)
A method for etching a transparent conductive film having a conductor pattern containing copper as a main component on a surface thereof, comprising:
A step of bringing a transparent conductive film having a conductive pattern mainly composed of copper on the surface thereof into contact with an etching solution containing (a) a hydrogen halide, (b) a metal halide, (c) a copper dissolution inhibitor, and (d) a diluent, and optionally (e) an oxidizing agent, and
the hydrogen halide (a) contains 1 or more selected from hydrogen chloride, hydrogen bromide and hydrogen iodide,
the (b) metal halide comprises 1 or more halides selected from the group consisting of group 1,2, and 13 elements of the periodic Table of the elements,
The copper dissolution inhibitor (c) contains 1 or more selected from hydroxylamine and salts thereof,
The (d) diluent comprises water and/or an organic solvent, and may optionally comprise a phosphoric acid,
the oxidant (e) contains 1 or more selected from chlorate of alkali metal and/or alkaline earth metal, nitrate or nitrite, perchloric acid, nitric acid, hydrogen peroxide, and organic peroxide.
(3)
A method for forming a transparent electrode pattern having a conductive pattern mainly composed of copper on a surface thereof, comprising the following steps 1 to 4:
A step of forming a transparent conductive film on a substrate (step 1);
(step 2) forming a conductive film containing copper as a main component on the transparent conductive film;
(step 3) a step of etching the conductive film mainly composed of copper to form a conductive pattern mainly composed of copper on the transparent conductive film; and
(step 4) a step of forming a transparent electrode pattern by bringing a transparent conductive film having a conductive pattern mainly composed of copper obtained in step 3 on the surface thereof into contact with an etching solution containing (a) a hydrogen halide, (b) a metal halide, (c) a copper dissolution inhibitor and (d) a diluent, optionally containing (e) an oxidizing agent, and forming a transparent electrode pattern by etching the transparent conductive film
in the above-mentioned step (4), the resin,
The hydrogen halide (a) contains 1 or more selected from hydrogen chloride, hydrogen bromide and hydrogen iodide,
The (b) metal halide comprises 1 or more halides selected from the group consisting of group 1,2, and 13 elements of the periodic Table of the elements,
The copper dissolution inhibitor (c) contains 1 or more selected from hydroxylamine and salts thereof,
The (d) diluent comprises water and/or an organic solvent, and may optionally comprise a phosphoric acid,
The oxidant (e) contains 1 or more selected from chlorate of alkali metal and/or alkaline earth metal, nitrate or nitrite, perchloric acid, nitric acid, hydrogen peroxide, and organic peroxide.
Effects of the invention
The present invention has succeeded in significantly reducing the corrosive action of an etching solution on metallic copper by newly adding (c) a copper dissolution inhibitor to an etching solution obtained by dissolving a main component including the components (a) and (b) and an optional component (d) in a diluent (d).
By using the etching solution of the present invention, the transparent conductive film can be etched in a fine manner in accordance with the resist pattern without corroding the copper conductor pattern adjacent to the transparent conductive film. With this etching method, the copper conductor and the transparent electrode can be patterned with higher precision.
Drawings
fig. 1 schematically shows a transparent conductive film having a conductive pattern containing copper as a main component on the surface immediately before etching.
fig. 2 schematically shows a transparent electrode having a conductor pattern mainly composed of copper on the surface thereof, which is formed using the etching solution of the present invention. Here, the resist pattern has been removed.
fig. 3 schematically shows a transparent electrode having a conductor pattern mainly composed of copper on the surface thereof, which is formed using a comparative etching solution not containing (c) a copper dissolution inhibitor. Here, the resist pattern has been removed.
Detailed Description
(etching solution)
the etching solution of the present invention comprises (a) a hydrogen halide, (b) a metal halide, (c) a copper dissolution inhibitor and (d) a diluent, and optionally (e) an oxidizing agent.
The hydrogen halide (a) contains 1 or more selected from hydrogen chloride, hydrogen bromide and hydrogen iodide. Among them, hydrogen chloride (hydrochloric acid) is preferable. The (a) hydrogen halide is used in the form of being dissolved in the (d) diluent, and is preferably used in the form of an aqueous solution. The concentration of the hydrogen halide (a) in the etching solution of the present invention can be suitably adjusted depending on the desired etching rate, but is usually in the range of 0.1 to 7 mol%, preferably 1.0 to 5.0 mol%.
the metal halide (b) contains 1 or more elements selected from the group consisting of halides of group 1,2, and 13 elements of the periodic table. The metal halide (b) is usually 1 or more selected from chlorides, bromides, and iodides of sodium, potassium, magnesium, calcium, and aluminum, and chlorides of group 2 elements (alkaline earth metals) of the periodic table of elements are preferable from the viewpoint of increasing the etching rate, and calcium chloride is particularly preferable. Calcium chloride and other metal halides can also be combined. As calcium chloride, a hydrate which is easily available can be used. The (b) metal halide is used in a form dissolved in the (d) diluent, preferably in a form of an aqueous solution. The concentration of the metal halide (b) in the etching solution of the present invention can be suitably adjusted depending on the desired etching rate, but is usually in the range of 0.01 to 6 mol%, preferably 0.1 to 5.0 mol%.
The copper dissolution inhibitor (c) contains 1 or more selected from hydroxylamine and salts thereof. As the salt of hydroxylamine, hydroxylammonium chloride, hydroxylammonium nitrate and hydroxylammonium sulfate can be used, and hydroxylammonium chloride is preferable. The (c) copper dissolution inhibitor is used in a form dissolved in the (d) diluent, preferably in a form of an aqueous solution. The concentration of the copper dissolution inhibitor (c) in the etching solution of the present invention is not limited as long as it is a concentration at least capable of providing an effect of inhibiting the copper solubility of the etching solution of the present invention.
when hydroxylammonium chloride is used as the copper dissolution inhibitor (c), it is common to adjust an aqueous solution of hydroxylammonium chloride of 20 wt% based on the weight, and to add 1ml or more of the aqueous solution to 1L of a mother solution of an etching solution which may contain (a) hydrogen halide, (b) a metal halide, (d) a diluent, and optionally (e) an oxidizing agent, and it is preferable to add 1ml to 20ml of the aqueous solution in view of cost.
The (d) diluent comprises water and/or an organic solvent, and may optionally comprise a phosphoric acid. The diluent (d) functions as a solvent for the hydrogen halide (a), the metal halide (b), and the copper dissolution inhibitor (c) contained in the etching solution of the present invention, and also functions as a solvent for the oxidizing agent (e) which is an optional component of the etching solution of the present invention.
as water used as the diluent (d), ion-exchanged water or distilled water can be generally used. The organic solvent used as the diluent (d) can be used without limitation as long as it can dissolve the components of the etching solution of the present invention, exhibits relatively low conductivity, and does not affect the etching treatment. Examples of such organic solvents include alcohols such as methanol, ethanol, isopropanol, 1-propanol, 1-butanol, 2-butanol, tert-butanol, 2-methyl-1-propanol, 1-pentanol, 1-hexanol, 1-heptanol, 4-heptanol, 1-octanol, 1-nonanol, 1-decanol, and 1-dodecanol; diols or triols such as ethylene glycol, 1, 2-propylene glycol, butylene glycol, and glycerin; ketones such as acetone, acetylacetone, and methyl ethyl ketone; nitriles such as acetonitrile, propionitrile, butyronitrile, isobutyronitrile, and benzonitrile; aldehydes such as acetaldehyde and propionaldehyde; lower alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and propylene glycol monoethyl ether; ethers such as tetrahydrofuran and dioxane, fluorine-containing alcohols such as trifluoroethanol, pentafluoropropanol and 2,2,3, 3-tetrafluoropropanol, and organic solvents such as sulfolane. Among such organic solvents, lower alcohols such as methanol, ethanol, isopropanol, and 1-propanol are preferable from the viewpoint of ease of handling. As such an organic solvent, a mixture of 2 or more kinds can also be used. The diluent (d) of the present invention may be the water, the organic solvent, or a mixture of the water and the organic solvent in an arbitrary ratio.
Further, the phosphoric acid compound may be dissolved in the diluent (d). The phosphoric acid used herein includes any of phosphoric acid, phosphorous acid and hypophosphorous acid. By adding 1 or more of these phosphoric acids to the diluent (d), the ionization balance of the aqueous solution constituting the etching solution of the present invention can be adjusted. These phosphoric acids can be added at an appropriate concentration according to the characteristics of the material to be etched, such as a metal species represented by copper, in the transparent electrode film, the substrate in contact with the transparent electrode film, and the conductor to which the etching solution of the present invention is applied.
as such diluent (d) of the present invention, water and/or alcohol may be typically used.
The oxidizing agent (e) is a component that can be used as needed in order to increase the etching rate of the etching solution of the present invention and reduce corrosion of device materials caused by (a) hydrogen halide and (b) metal halide contained in the etching solution of the present invention. The oxidant (e) is at least 1 selected from alkali metal and/or alkaline earth metal chlorate, nitrate or nitrite, perchloric acid, nitric acid, hydrogen peroxide, and organic peroxide, preferably sodium or calcium chlorate, nitrate, hydrogen peroxide, and organic peroxide. When the oxidizing agent (e) is used, the amount of the oxidizing agent (e) is not limited as long as the amount of the oxidizing agent does not exceed the saturation amount, but is preferably 0.01 mol% or more, and more preferably 0.01 mol% to 2.0 mol% with respect to the total amount of the etching solution.
In addition, in view of the etching rate, it is preferable that the halogen concentration of the etching solution of the present invention is 1 mol to a saturation amount per 1L of the etching solution, and the metal halide (b) is supplied to 10 wt% to 90 wt% of the total amount of halogen contained in the etching solution.
(etching method)
By bringing the etching solution of the present invention into contact with the transparent conductive film having a conductive pattern mainly composed of copper on the surface thereof, the transparent conductive film having a conductive pattern mainly composed of copper on the surface thereof can be etched without causing dissolution of the copper conductor.
The "conductor mainly composed of copper" in the present invention includes not only the case where the conductor is composed of a copper single body but also the case where the conductor is composed of a copper single body layer and a layer containing a copper composite oxide or alloy.
the transparent conductive film having a conductor pattern mainly composed of copper on the surface thereof is typically a film in which a circuit pattern including a conductor mainly composed of copper is formed on an ITO (indium-tin oxide) film. Such a circuit pattern is formed in an electrode region connected to the display region. Therefore, a typical example of the transparent conductive film having a conductor pattern mainly composed of copper on the surface in the present invention is a portion having a so-called lead electrode.
When such a transparent conductive film having a conductive pattern mainly composed of copper on the surface is brought into contact with the etching solution of the present invention, a resist pattern corresponding to the pattern of the transparent electrode is formed on the film. By the etching method of the present invention, the portion of the transparent conductive film not covered with the resist pattern is etched to form the transparent electrode pattern. Since the etching solution of the present invention cannot dissolve copper, only the transparent conductive film is etched in the etching method while the copper pattern formed on the transparent conductive film is kept well. As a result, a high-definition copper pattern and a transparent electrode pattern can be formed.
The method of contacting the etching solution of the present invention with the transparent conductive film having a conductive pattern containing copper as a main component on the surface thereof follows a conventional method of etching treatment. Usually, the etching solution of the present invention heated to 30 to 70 ℃ is brought into contact with a transparent conductive film having a conductive pattern containing copper as a main component on the surface thereof at the temperature by a dipping method or a spraying method. The immersion time in the immersion method, the amount of the liquid jet in the jet method, and the like are appropriately set in consideration of the etching rate. In this case, by performing etching while blowing a gaseous oxidizing agent such as oxygen, chlorine, nitrogen monoxide, or ozone, corrosion of the device material can be reduced, and the life of the device can be prolonged.
(method of Forming transparent electrode Pattern)
by a method including the following steps using the etching method of the present invention, a transparent electrode pattern can be formed.
the step (step 1) is a step of forming a transparent conductive film on a substrate according to a conventional method. As the substrate, a substrate including glass, quartz, polyethylene terephthalate (PET), polyether sulfone (PES), or the like, which is used for an LCD (liquid crystal display), a touch panel, or the like, can be used, and a glass substrate or a PET substrate can be generally used. Examples of the transparent conductive film include films containing ITO (indium tin oxide), indium oxide, tin oxide, and zinc oxide. The transparent conductive film of the present invention is preferably an ITO film, and particularly preferably a crystalline ITO film. As a method for forming a transparent conductive film on a substrate, any of sputtering, thin film deposition, vacuum deposition using ion assist or the like, CVD (chemical vapor deposition), coating, spin coating, and spraying can be used. The thickness of the transparent conductive film may be selected according to the thickness corresponding to the target device, but is generally within the range.
the step (step 2) is a step of forming a conductor film containing copper as a main component on the transparent conductive film according to a conventional method. As a method for forming a conductive film containing copper as a main component, there are methods such as sputtering, CVD, and plating, but sputtering is generally used.
The step (step 3) is a step of etching the conductive film containing copper as a main component to form a conductive pattern containing copper as a main component on the transparent conductive film. In step 3, a resist material is applied to a conductive film mainly composed of copper, and a photomask having a pattern drawn on the surface of the resist material is formed. Next, an energy ray such as an electromagnetic wave or an electron beam is irradiated onto the resist material through a photomask. The resist material is developed to form a resist pattern.
Next, the conductive film containing copper as a main component is etched. The etching solution used in step 3 is an etching solution that does not corrode the transparent conductive film. As such an etching solution, an acidic etching solution such as a persulfate-based or hydrogen peroxide-based etching solution can be used. After selectively etching the copper, the film is cleaned.
the step (step 4) is a step of etching the transparent conductive film having the conductive pattern mainly composed of copper on the surface obtained in the step 3, by using the etching solution of the present invention. In step 4, a resist material is applied to the transparent conductive film having the conductive pattern mainly composed of copper on the surface obtained in step 3, and a photomask having a pattern drawn on the surface of the resist material is formed. Then, energy rays such as electromagnetic waves and electron beams are irradiated onto the resist material through the photomask. The resist material is developed to form a resist pattern. As described above, the transparent conductive film thus obtained is brought into contact with the etching solution of the present invention, and portions of the transparent conductive film not protected by the resist are selectively etched while the conductor pattern formed on the transparent conductive film is well preserved. After selectively etching the ITO film, the film is cleaned.
Examples
Examples 1 to 6 and comparative example 1
As described below, using 2 types of the etching solution of the present invention and the comparative etching solution not containing (c) the copper dissolution inhibitor, the ITO film having the conductor pattern containing copper on the surface was etched, and the pattern formation of each of the conductor containing copper and the ITO electrode after etching was compared.
(preparation of etching solution)
A mother solution of an etching solution was prepared by mixing (a) hydrochloric acid as a hydrogen halide, (b) calcium chloride as a metal halide, (d) water as a diluent, and optionally (e) calcium nitrate as an oxidizing agent in the formulation shown in table 1. The concentrations (mol%) shown in table 1 are the concentrations of the above (a), (b), and (e) obtained by dilution with (d) water. An etching solution obtained by adding and mixing (c) a 20 wt% aqueous solution of hydroxylammonium hydrochloride as a copper dissolution inhibitor in an amount shown in table 1 to 1L of the mother solution and then allowing the mixture to stand for a certain time (t) shown in table 1 was used as the etching solution of the present invention (examples 1 to 6). When t is 0, it represents that the copper dissolution inhibitor (c) shown in table 1 is used for etching immediately after the copper dissolution inhibitor (c) is added to the mother liquor and mixed.
On the other hand, the mother liquor to which the copper dissolution inhibitor (c) was not added was used as the comparative etching solution (comparative example 1).
In addition, dihydrate was used as calcium chloride shown in table 1, and the concentration thereof indicates the calcium chloride concentration in the mother liquor. Dihydrate was used as calcium nitrate shown in table 1, and the concentration thereof indicates the calcium nitrate concentration in the mother liquor.
(formation of etching and transparent electrode Pattern)
(step 1) an ITO film having a thickness of 0.25mm was formed on a PET substrate having a thickness of 0.25mm by sputtering. (step 2) A copper film having a thickness of 1 μm was formed on the obtained ITO film by sputtering. (step 3) a resist material is applied to the copper film, and the resist material is exposed to light through a photomask and developed. Thus, a resist pattern was formed on the copper film. For this, the copper film was etched using a commercially available acidic etching solution. Thus, a conductor pattern containing copper was formed on the ITO film. (step 4) a resist material is applied to the ITO film on which the conductor pattern containing copper is formed, and the resist material is exposed to light through a photomask and developed. Thus, a conductor pattern containing copper and a resist pattern on the ITO film are formed. The resist pattern was formed with a resist line width of about 40 μm and a resist line interval of about 20 μm.
the ITO film having the thus obtained conductor pattern containing copper was immersed in the etching solution of the present invention and the etching solution for comparison prepared in the following manner.
Further, an ITO film having a thickness of 0.25mm was formed on a PET substrate by sputtering, and this film was set as a standard film for determining the dipping time. In advance, the standard film was immersed in each of the etching solutions shown in table 1, and the time from the start of immersion to the time when dissolution of the ITO coating film was completed was set as the standard time (T). In addition, the completion of the dissolution of the ITO coating was confirmed by showing that the surface resistance value of the standard coating measured by a tester is infinite. The smaller T represents the higher etching rate for each etching solution.
The ITO film having a conductor pattern containing copper was immersed in each of the etching solutions shown in table 1 over a time equivalent to T × 1.5. During immersion, the temperature of each etching solution was maintained at 30 ℃.
Thus, etching was performed for a sufficient time. After the immersion, the ITO film having the conductor pattern including copper was cleaned and dried. Thus, an ITO electrode pattern was formed by an etching method using the etching solution of the present invention and the comparative etching solution.
(evaluation)
It was verified how much the shape of the resist pattern formed in step 3 was reproduced as an ITO electrode pattern by etching using the etching solutions of examples 1 to 6 and comparative example 1 (step 4).
Fig. 1 schematically shows an ITO film having a conductor pattern containing copper on the surface immediately before etching in step 4.
The resist line interval immediately before etching was measured at 4 different points (S1), and the average of 4 values (S11, S12, S13, S14) was determined (S1 av).
The resist line width immediately before etching was measured at 4 different points (L1), and the average (L1av) of 4 values (L11, L12, L13, L14) was determined.
Fig. 2 schematically shows ITO electrode patterns having a conductor pattern including copper on the surface, which are formed using the etching solutions (examples 1 to 6) of the present invention. Fig. 3 schematically shows an ITO pattern having a conductor pattern containing copper on the surface thereof, which was formed using a comparative etchant (comparative example 1).
at 4 points where S1 was measured, the line width of the ITO pattern after etching was measured (S2), and the average of 4 values (S21, S22, S23, S24) was determined (S2 av).
At 4 points where L1 was measured, the line width of the ITO pattern after etching was measured (L2), and the average (L2av) of 4 values (L21, L22, L23, L24) was obtained.
By the formula: the difference (Δ S) between the resist line spacing and the ITO electrode pattern line spacing in the etching using the etching solutions of examples 1 to 6 and comparative example 1 was determined as Δ S1av-S2 av. Table 1 shows Δ S values corresponding to example 1, example 2, example 3, example 4, and comparative example 1. The smaller the absolute value of Δ S means that the resist pattern line interval is more faithfully reproduced in the ITO electrode pattern line interval by suppressing the corrosion of the copper conductor pattern on the ITO film.
by the formula: the difference (Δ L) between the resist line width and the ITO electrode pattern line width in the etching using the etching solutions of examples 1 to 6 and comparative example 1 was determined as Δ L — L1av-L2 av. Table 1 shows the values of Δ L corresponding to example 1, example 2, example 3, example 4, and comparative example 1. The smaller the absolute value of Δ L, the more faithfully the resist pattern line width is reproduced in the ITO electrode pattern line width by suppressing the corrosion of the copper conductor pattern on the ITO film.
[ Table 1]
As shown in table 1, since the ITO film was selectively etched by the etching solution of the present invention containing (c) the copper dissolution inhibitor, the resist pattern could be reproduced on the ITO electrode pattern with high accuracy. This selective etching effect of the etching solution of the present invention is stable until at least 5 hours have elapsed after the preparation of the etching solution. In addition, in the etching using the etching solution of the present invention, the etching rate was not decreased as compared with the case of comparative example 1 in which the copper dissolution inhibitor (c) was not used.
Example 7, example 8 and comparative example 2
The etching solutions were produced under the conditions shown in table 1. In examples 8 and 9, etching was performed after 24 hours had elapsed after the addition of (c) a 20 wt% aqueous solution of hydroxylammonium hydrochloride. In comparative example 2, the mother liquor after 24 hours from the preparation was used for etching.
The etching solutions of example 8 and comparative example 2 were used, and etching was performed under the same conditions as in example 1, and evaluation was performed. In the etching using the etching solution of example 9, the ITO film was etched under the same conditions as in example 1 except that the contact method of the etching solution was changed from the immersion method to the spray method, and the evaluation was performed. The results are shown in table 2.
[ Table 2]
as shown in table 2, regarding the selective etching effect of the etching solution of the present invention, it was maintained even if 24 hours passed after the preparation of the etching solution, or even if the contact method of the etching solution with the ITO film was changed.
[ example 9]
Example 9 is an example in which (c) a 20 wt% aqueous solution of hydroxylammonium hydrochloride was added to an etching solution in portions. In example 9, after 24 hours had elapsed after 2ml of a 20 wt% aqueous solution of (c) hydroxylammonium hydrochloride was added to 1L of the mother liquor shown in table 1, a 20 wt% aqueous solution of (c) hydroxylammonium hydrochloride in the same amount as described above was added again. The ITO film was etched under the same conditions as in example 1 using an etching solution at a time when 72 hours had elapsed after the initial addition of hydroxylammonium chloride (c), and evaluated. The results are shown in table 3.
[ example 10]
example 10 also shows an example in which (c) a 20 wt% aqueous solution of hydroxylammonium hydrochloride was added to the etching solution in portions. In example 10, 2ml of a 20 wt% aqueous solution of (c) hydroxylammonium hydrochloride was added to 1L of the mother liquor shown in table 1, and then after 24 hours and 48 hours, the same amount of the 20 wt% aqueous solution of (c) hydroxylammonium hydrochloride was again added. The ITO film was etched under the same conditions as in example 1 using an etching solution at a time when 72 hours had elapsed after the initial addition of hydroxylammonium chloride (c), and evaluated. The results are shown in table 3.
[ Table 3]
As shown in table 3, by adding the copper dissolution inhibitor (c) to the etching solution of the present invention in portions, the deterioration of the selective etching effect on the ITO film with time can be suppressed.
[ examples 11 and 12]
Examples 11 and 12 are examples in which the oxidizing agent (e) was not added. To 1L of the mother liquor shown in Table 4, 2ml of a 20 wt% aqueous solution of (c) hydroxylammonium hydrochloride was added to prepare an etching solution of the present invention, and the ITO film was etched under the same conditions as in example 1 and evaluated. The results are shown in table 4.
[ Table 4]
as shown in table 4, even when the etching solution of the present invention does not contain the oxidizing agent (e), the etching solution of the present invention exhibits a high etching rate and selective etching of ITO by blending (a) hydrogen halide, (b) metal halide, (c) copper dissolution inhibitor, and (d) diluent.
Industrial applicability
The etching solution of the present invention is epoch-making from the viewpoint of having both an etching rate and selective etching of an ITO film and little deterioration with time. By using the etching solution of the present invention, a transparent electrode pattern having copper wiring can be efficiently and highly accurately produced. The present invention can contribute to the manufacture of liquid crystal displays and touch panels that require thinner and high-definition image display.
Description of the symbols
1: substrate
2: ITO film
3: conductor pattern comprising copper
4: resist pattern
5: ITO electrode pattern
Claims (3)
1. An etching solution, comprising: (a) a hydrogen halide, (b) a metal halide, (c) a copper dissolution inhibitor and (d) a diluent, and optionally (e) an oxidizing agent,
The hydrogen halide (a) contains 1 or more selected from hydrogen chloride, hydrogen bromide and hydrogen iodide,
The (b) metal halide comprises 1 or more halides selected from the group consisting of group 1,2, and 13 elements of the periodic Table of the elements,
the copper dissolution inhibitor (c) contains 1 or more selected from hydroxylamine and salts thereof,
the (d) diluent comprises water and/or an organic solvent, and may optionally comprise a phosphoric acid,
The oxidant (e) contains more than 1 selected from chlorate, nitrate or nitrite of alkali metal and/or alkaline earth metal, perchloric acid, nitric acid, hydrogen peroxide and organic peroxide, and
The etching solution is used for etching a transparent conductive film having a conductive pattern containing copper as a main component on the surface.
2. A method for etching a transparent conductive film having a conductor pattern containing copper as a main component on a surface thereof, comprising:
A step of bringing a transparent conductive film having a conductive pattern mainly composed of copper on the surface thereof into contact with an etching solution containing (a) a hydrogen halide, (b) a metal halide, (c) a copper dissolution inhibitor, and (d) a diluent, and optionally (e) an oxidizing agent, and
The hydrogen halide (a) contains 1 or more selected from hydrogen chloride, hydrogen bromide and hydrogen iodide,
The (b) metal halide comprises 1 or more halides selected from the group consisting of group 1,2, and 13 elements of the periodic Table of the elements,
The copper dissolution inhibitor (c) contains 1 or more selected from hydroxylamine and salts thereof,
The (d) diluent comprises water and/or an organic solvent, and may optionally comprise a phosphoric acid,
The oxidant (e) contains 1 or more selected from chlorate of alkali metal and/or alkaline earth metal, nitrate or nitrite, perchloric acid, nitric acid, hydrogen peroxide, and organic peroxide.
3. A method for forming a transparent electrode pattern having a conductive pattern mainly composed of copper on a surface thereof, comprising the following steps 1 to 4:
A step of forming a transparent conductive film on a substrate (step 1);
(step 2) forming a conductive film containing copper as a main component on the transparent conductive film;
(step 3) a step of etching the conductive film mainly composed of copper to form a conductive pattern mainly composed of copper on the transparent conductive film; and
(step 4) a step of forming a transparent electrode pattern by bringing a transparent conductive film having a conductive pattern mainly composed of copper obtained in step 3 on the surface thereof into contact with an etching solution containing (a) a hydrogen halide, (b) a metal halide, (c) a copper dissolution inhibitor and (d) a diluent, optionally containing (e) an oxidizing agent, and forming a transparent electrode pattern by etching the transparent conductive film
In the above-mentioned step (4), the resin,
The hydrogen halide (a) contains 1 or more selected from hydrogen chloride, hydrogen bromide and hydrogen iodide,
The (b) metal halide comprises 1 or more halides selected from the group consisting of group 1,2, and 13 elements of the periodic Table of the elements,
the copper dissolution inhibitor (c) contains 1 or more selected from hydroxylamine and salts thereof,
The (d) diluent comprises water and/or an organic solvent, and may optionally comprise a phosphoric acid,
The oxidant (e) contains 1 or more selected from chlorate of alkali metal and/or alkaline earth metal, nitrate or nitrite, perchloric acid, nitric acid, hydrogen peroxide, and organic peroxide.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2017/007466 WO2018154775A1 (en) | 2017-02-27 | 2017-02-27 | Etching liquid and use of same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110546741A true CN110546741A (en) | 2019-12-06 |
Family
ID=63253611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780087436.0A Pending CN110546741A (en) | 2017-02-27 | 2017-02-27 | Etching solution and use thereof |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6817655B2 (en) |
| CN (1) | CN110546741A (en) |
| WO (1) | WO2018154775A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112064027A (en) * | 2020-09-14 | 2020-12-11 | 深圳市志凌伟业光电有限公司 | Etching solution for composite copper film structure |
| CN114182258A (en) * | 2021-12-09 | 2022-03-15 | 上海天承化学有限公司 | Copper and copper alloy surface roughening etching solution and preparation method and application thereof |
| CN116024574A (en) * | 2022-12-28 | 2023-04-28 | 广州微纳芯材料科技有限公司 | ITO etching solution and preparation and use methods thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6033993A (en) * | 1997-09-23 | 2000-03-07 | Olin Microelectronic Chemicals, Inc. | Process for removing residues from a semiconductor substrate |
| CN102177219A (en) * | 2008-11-12 | 2011-09-07 | 韩国泰科诺赛美材料株式会社 | Etching solution for a transparent conductive film |
| CN102732254A (en) * | 2011-04-11 | 2012-10-17 | 关东化学株式会社 | Etching solution composition for transparent conductive film |
| JP2016178103A (en) * | 2015-03-18 | 2016-10-06 | 株式会社Adeka | Etchant composition and etching method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010538167A (en) * | 2007-09-06 | 2010-12-09 | イー．ケー．シー．テクノロジー．インコーポレーテッド | Compositions and methods for treating copper surfaces |
-
2017
- 2017-02-27 JP JP2019500999A patent/JP6817655B2/en active Active
- 2017-02-27 CN CN201780087436.0A patent/CN110546741A/en active Pending
- 2017-02-27 WO PCT/JP2017/007466 patent/WO2018154775A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6033993A (en) * | 1997-09-23 | 2000-03-07 | Olin Microelectronic Chemicals, Inc. | Process for removing residues from a semiconductor substrate |
| CN102177219A (en) * | 2008-11-12 | 2011-09-07 | 韩国泰科诺赛美材料株式会社 | Etching solution for a transparent conductive film |
| CN102732254A (en) * | 2011-04-11 | 2012-10-17 | 关东化学株式会社 | Etching solution composition for transparent conductive film |
| JP2016178103A (en) * | 2015-03-18 | 2016-10-06 | 株式会社Adeka | Etchant composition and etching method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112064027A (en) * | 2020-09-14 | 2020-12-11 | 深圳市志凌伟业光电有限公司 | Etching solution for composite copper film structure |
| CN114182258A (en) * | 2021-12-09 | 2022-03-15 | 上海天承化学有限公司 | Copper and copper alloy surface roughening etching solution and preparation method and application thereof |
| CN116024574A (en) * | 2022-12-28 | 2023-04-28 | 广州微纳芯材料科技有限公司 | ITO etching solution and preparation and use methods thereof |
| CN116024574B (en) * | 2022-12-28 | 2023-12-05 | 广州微纳芯材料科技有限公司 | ITO etching solution and preparation and use methods thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6817655B2 (en) | 2021-01-20 |
| WO2018154775A1 (en) | 2018-08-30 |
| JPWO2018154775A1 (en) | 2019-12-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5030403B2 (en) | Etching composition for indium oxide based transparent conductive film and etching method using the same | |
| KR101310310B1 (en) | Etchant for thin film transistor-liquid crystal displays | |
| JP5788701B2 (en) | Etching composition for transparent conductive film | |
| JP2008227508A (en) | Etching liquid composition of thin film transistor liquid crystal display | |
| KR20100053175A (en) | Etchant for transparent conductive ito films | |
| CN110546741A (en) | Etching solution and use thereof | |
| CN109797396B (en) | Silver film etching liquid composition, etching method using the same and metal pattern forming method | |
| CN109750292B (en) | Silver etchant composition, etching method using the same, and method for forming metal pattern | |
| KR20000017470A (en) | ITO etchant composition | |
| KR101369946B1 (en) | Etchant for thin film transistor-liquid crystal displays | |
| KR101941289B1 (en) | Manufacturing method of an array substrate for liquid crystal display | |
| KR100761602B1 (en) | Wet etching agent composition | |
| TWI673344B (en) | Etching solution composition for indium oxide layer and method for manufacturing array substrate for liquid crystal display device using the same | |
| CN111755461A (en) | Method for manufacturing array substrate for liquid crystal display device and copper-based metal film etching solution composition used for same | |
| JP4897148B2 (en) | Etching solution for transparent conductive film | |
| CN107365996B (en) | Etching solution composition for copper-based metal film and application thereof | |
| KR20160116943A (en) | Etchant composition for copper-containing metal layer and preparing method of an array substrate for liquid crystal display using same | |
| KR20190057018A (en) | Etchant composition for silver thin layer and ehting method and mehtod for fabrication metal pattern using the same | |
| KR20050066395A (en) | Etchant for indium oxide film etching, and etching method using the same | |
| JP3406079B2 (en) | Manufacturing method of oxide etching products | |
| KR100415319B1 (en) | Etchant formulation for ITO film | |
| CN107475716B (en) | Etching solution composition for copper-based metal film and application thereof | |
| CN111748816B (en) | Silver thin film etching solution composition, etching method and metal pattern forming method | |
| KR101796784B1 (en) | Manufacturing method of an array substrate for liquid crystal display | |
| JP2009267115A (en) | Etching method and producing method of substrate for semiconductor device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20191206 |
|
| WD01 | Invention patent application deemed withdrawn after publication |