SG188734A1 - Etching solution for copper and copper alloy - Google Patents
Etching solution for copper and copper alloy Download PDFInfo
- Publication number
- SG188734A1 SG188734A1 SG2012065843A SG2012065843A SG188734A1 SG 188734 A1 SG188734 A1 SG 188734A1 SG 2012065843 A SG2012065843 A SG 2012065843A SG 2012065843 A SG2012065843 A SG 2012065843A SG 188734 A1 SG188734 A1 SG 188734A1
- Authority
- SG
- Singapore
- Prior art keywords
- copper
- etching
- copper alloy
- layer
- acid
- Prior art date
Links
- 238000005530 etching Methods 0.000 title claims abstract description 180
- 239000010949 copper Substances 0.000 title claims abstract description 129
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 92
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 91
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000000203 mixture Substances 0.000 claims abstract description 79
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 46
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000005001 laminate film Substances 0.000 claims abstract description 39
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims abstract description 30
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 26
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 25
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 17
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005751 Copper oxide Substances 0.000 claims abstract description 15
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 118
- 239000000758 substrate Substances 0.000 claims description 61
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 9
- -1 copper-magnesium- aluminum Chemical group 0.000 claims description 9
- JZBWUTVDIDNCMW-UHFFFAOYSA-L dipotassium;oxido sulfate Chemical compound [K+].[K+].[O-]OS([O-])(=O)=O JZBWUTVDIDNCMW-UHFFFAOYSA-L 0.000 claims description 9
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- KASGZKMAZIEEHX-UHFFFAOYSA-N aluminum copper magnesium oxygen(2-) Chemical compound [O-2].[Al+3].[Mg+2].[Cu+2] KASGZKMAZIEEHX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- 239000012935 ammoniumperoxodisulfate Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- JXSJBGJIGXNWCI-UHFFFAOYSA-N diethyl 2-[(dimethoxyphosphorothioyl)thio]succinate Chemical compound CCOC(=O)CC(SP(=S)(OC)OC)C(=O)OCC JXSJBGJIGXNWCI-UHFFFAOYSA-N 0.000 abstract 1
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 abstract 1
- 229940061319 ovide Drugs 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 52
- 239000010408 film Substances 0.000 description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 27
- 238000012360 testing method Methods 0.000 description 15
- 238000004090 dissolution Methods 0.000 description 14
- 239000007921 spray Substances 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 229910003023 Mg-Al Inorganic materials 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229940045803 cuprous chloride Drugs 0.000 description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 5
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 5
- 235000019838 diammonium phosphate Nutrition 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 229910016027 MoTi Inorganic materials 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- 229910017767 Cu—Al Inorganic materials 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RCITVHFNWJIDNA-UHFFFAOYSA-K [NH4+].[NH4+].[NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O Chemical compound [NH4+].[NH4+].[NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O RCITVHFNWJIDNA-UHFFFAOYSA-K 0.000 description 2
- FVTRDWMTAVVDCU-UHFFFAOYSA-N acetic acid;hydrogen peroxide Chemical compound OO.CC(O)=O FVTRDWMTAVVDCU-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- BWKOZPVPARTQIV-UHFFFAOYSA-N azanium;hydron;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [NH4+].OC(=O)CC(O)(C(O)=O)CC([O-])=O BWKOZPVPARTQIV-UHFFFAOYSA-N 0.000 description 2
- XEPNJJFNSJKTSO-UHFFFAOYSA-N azanium;zinc;chloride Chemical compound [NH4+].[Cl-].[Zn] XEPNJJFNSJKTSO-UHFFFAOYSA-N 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- AUTNMGCKBXKHNV-UHFFFAOYSA-P diazanium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [NH4+].[NH4+].O1B([O-])OB2OB([O-])OB1O2 AUTNMGCKBXKHNV-UHFFFAOYSA-P 0.000 description 2
- YMGGAHMANIOXGP-UHFFFAOYSA-L disodium;oxido sulfate Chemical compound [Na+].[Na+].[O-]OS([O-])(=O)=O YMGGAHMANIOXGP-UHFFFAOYSA-L 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- IFABLCIRROMTAN-MDZDMXLPSA-N (e)-1-chlorooctadec-9-ene Chemical compound CCCCCCCC\C=C\CCCCCCCCCl IFABLCIRROMTAN-MDZDMXLPSA-N 0.000 description 1
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
- TXQJIMNDEHCONN-UHFFFAOYSA-N 3-(2-methoxyphenoxy)propanoic acid Chemical compound COC1=CC=CC=C1OCCC(O)=O TXQJIMNDEHCONN-UHFFFAOYSA-N 0.000 description 1
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 1
- HSEYYGFJBLWFGD-UHFFFAOYSA-N 4-methylsulfanyl-2-[(2-methylsulfanylpyridine-3-carbonyl)amino]butanoic acid Chemical compound CSCCC(C(O)=O)NC(=O)C1=CC=CN=C1SC HSEYYGFJBLWFGD-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 239000004251 Ammonium lactate Substances 0.000 description 1
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 description 1
- 241000566113 Branta sandvicensis Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241000722721 Capparis Species 0.000 description 1
- 235000017336 Capparis spinosa Nutrition 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000019743 Choline chloride Nutrition 0.000 description 1
- 229910021554 Chromium(II) chloride Inorganic materials 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910017566 Cu-Mn Inorganic materials 0.000 description 1
- 229910017758 Cu-Si Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910017818 Cu—Mg Inorganic materials 0.000 description 1
- 229910017871 Cu—Mn Inorganic materials 0.000 description 1
- 229910017931 Cu—Si Inorganic materials 0.000 description 1
- 229910017985 Cu—Zr Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910017262 Mo—B Inorganic materials 0.000 description 1
- XHAFPKVCDCRTLV-UHFFFAOYSA-L N.S(=O)(=O)([O-])[O-].[Mn+2] Chemical compound N.S(=O)(=O)([O-])[O-].[Mn+2] XHAFPKVCDCRTLV-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- UGLUPDDGTQHFKU-UHFFFAOYSA-M [NH4+].S(=O)(=O)([O-])[O-].[Mg+] Chemical compound [NH4+].S(=O)(=O)([O-])[O-].[Mg+] UGLUPDDGTQHFKU-UHFFFAOYSA-M 0.000 description 1
- NHMRYEHMYUEXTN-UHFFFAOYSA-L [NH4+].[Cl-].[Cl-].[Cl-].[Co++] Chemical compound [NH4+].[Cl-].[Cl-].[Cl-].[Co++] NHMRYEHMYUEXTN-UHFFFAOYSA-L 0.000 description 1
- LXFUCSMCVAEMCD-UHFFFAOYSA-N acetic acid;nitric acid;phosphoric acid Chemical compound CC(O)=O.O[N+]([O-])=O.OP(O)(O)=O LXFUCSMCVAEMCD-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- XGGLLRJQCZROSE-UHFFFAOYSA-K ammonium iron(iii) sulfate Chemical compound [NH4+].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGGLLRJQCZROSE-UHFFFAOYSA-K 0.000 description 1
- 229940059265 ammonium lactate Drugs 0.000 description 1
- 235000019286 ammonium lactate Nutrition 0.000 description 1
- DAPUDVOJPZKTSI-UHFFFAOYSA-L ammonium nickel sulfate Chemical compound [NH4+].[NH4+].[Ni+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DAPUDVOJPZKTSI-UHFFFAOYSA-L 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 description 1
- RAGLTCMTCZHYEJ-UHFFFAOYSA-K azanium;chromium(3+);disulfate Chemical compound [NH4+].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RAGLTCMTCZHYEJ-UHFFFAOYSA-K 0.000 description 1
- KVTQOXMLIFVKOK-UHFFFAOYSA-K azanium;iron(3+);oxalate Chemical compound [NH4+].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O KVTQOXMLIFVKOK-UHFFFAOYSA-K 0.000 description 1
- URGYLQKORWLZAQ-UHFFFAOYSA-N azanium;periodate Chemical compound [NH4+].[O-]I(=O)(=O)=O URGYLQKORWLZAQ-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- KLOIYEQEVSIOOO-UHFFFAOYSA-N carbocromen Chemical compound CC1=C(CCN(CC)CC)C(=O)OC2=CC(OCC(=O)OCC)=CC=C21 KLOIYEQEVSIOOO-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 1
- 229960003178 choline chloride Drugs 0.000 description 1
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 1
- FIHCMDIDYDOFDJ-UHFFFAOYSA-L copper;azane;sulfate Chemical compound N.[Cu+2].[O-]S([O-])(=O)=O FIHCMDIDYDOFDJ-UHFFFAOYSA-L 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- NUHXWPRATKOXDB-UHFFFAOYSA-L diazanium;cobalt(2+);disulfate Chemical compound [NH4+].[NH4+].[Co+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O NUHXWPRATKOXDB-UHFFFAOYSA-L 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- MQLVWQSVRZVNIP-UHFFFAOYSA-L ferrous ammonium sulfate hexahydrate Chemical compound [NH4+].[NH4+].O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MQLVWQSVRZVNIP-UHFFFAOYSA-L 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- ATADHKWKHYVBTJ-UHFFFAOYSA-N hydron;4-[1-hydroxy-2-(methylamino)ethyl]benzene-1,2-diol;chloride Chemical compound Cl.CNCC(O)C1=CC=C(O)C(O)=C1 ATADHKWKHYVBTJ-UHFFFAOYSA-N 0.000 description 1
- WTDHULULXKLSOZ-UHFFFAOYSA-N hydroxylamine hydrochloride Substances Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 1
- WCYJQVALWQMJGE-UHFFFAOYSA-M hydroxylammonium chloride Chemical compound [Cl-].O[NH3+] WCYJQVALWQMJGE-UHFFFAOYSA-M 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- IQUGDGIIAQZHGL-UHFFFAOYSA-L iron(2+);dichloride;hydrochloride Chemical compound Cl.[Cl-].[Cl-].[Fe+2] IQUGDGIIAQZHGL-UHFFFAOYSA-L 0.000 description 1
- QTBFPMKWQKYFLR-UHFFFAOYSA-N isobutyl chloride Chemical compound CC(C)CCl QTBFPMKWQKYFLR-UHFFFAOYSA-N 0.000 description 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- BDRTVPCFKSUHCJ-UHFFFAOYSA-N molecular hydrogen;potassium Chemical compound [K].[H][H] BDRTVPCFKSUHCJ-UHFFFAOYSA-N 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- LLXFMGCWJYTHRF-UHFFFAOYSA-I potassium platinum(4+) pentachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[K+].[Pt+4] LLXFMGCWJYTHRF-UHFFFAOYSA-I 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- JOQGJRQKCIJIDB-UHFFFAOYSA-M tin;chloride Chemical compound [Cl-].[Sn] JOQGJRQKCIJIDB-UHFFFAOYSA-M 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 239000001393 triammonium citrate Substances 0.000 description 1
- 235000011046 triammonium citrate Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
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- Microelectronics & Electronic Packaging (AREA)
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- Mechanical Engineering (AREA)
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Abstract
It is an object of the present invention to ovide anetching solution composition that etches with good precision a pattern in a metal laminate film containing a cnper layer and a copper oxide layer and/or a copper alloy layer, forms an excellent cross-sectional shape, has excel nt practicability, is stable, and has a long solution lift ime, and an etchingmethod employing such an etching solut n composition. [Solving means]The present invention rel es to an etching solution composition for etching a meta laminate film having a copper layer and a copper oxide later and/or a copper alloy layer, the composition containi 0.1 to 80 wt% of a persulfate and/or a persulfuric acid solution, 0.1 to 80 wt% of phosphoric acid, and 0.1 to 50 wt% of nitric acid and/orsulfuric acid an furthermore, to an etching solutioncomposition tha enables the etching rate or the cross sectional shap to be easily controlled by adding chloride ion or ammonium on, or an etching method. It is an object of the present invention to provide an etching solution composition that etches with good precision a pattern in a metal laminate film containing a copper layer and a copper oxide layer and/or a copper alloy layer, forms an excellent cross-sectional shape, has excellent practicability, is stable, and has a long solution lifetime, and an etchingmethod employing such an etching solution composition. [Solving means]The present invention relates to an etching solution composition for etching a metal laminate film having a copper layer and a copper oxide layer and/or a copper alloy layer,the composition containing 0.1 to 80 wt% of a persulfate and/or a persulfuric acid solution, 0.1 to 80 wt% of phosphoric acid, and 0.1 to 50 wt% of nitric acid and/or sulfuric acid and, furthermore, to an etching solution composition that enables the etching rate or the cross sectional shape to be easily controlled by adding chloride ion or ammonium ion, or an etching method.
Description
ETCHING SOLUTION FOR COPPER AND COPPER ALLOY
[0001]
The present invention relates to an etching composition for etching a metal laminate film of copper and a copper alloy containing copper as a main component used in production of a flat panel display, etc., and an etching method employing the etching solution. [Background Art]
[0002]
As a fine wiring material for liquid crystal displays, an aluminum thin film has conventionally been used, and the use of copper or a copper alloy containing copper as a main component in order to form a flat panel display drive transistor electrode and a fine pattern having a line width of a few microns or less has not been seen until recently.
Therefore, copper thin film etching technology for line widths of a few microns or less that is suitable for production of a flat panel has been limited up until now.
[0003]
When a copper thin film is used as an electrode, the copper is not used as a single layer; it is necessary to use a metal such as Ti, Mo, or MoTi as an adhesive layer or a barrier layer for the purpose of improving adhesion to a glass substrate or providing a barrier to the diffusion of copper.
In this case, as a rule, the use of a laminate film such as
Ti/Cu/Ti, Cu/Ti, Mo/Cu/Mo, Cu/Mo, MoTi/Cu/MoTi, or Cu/MoTi as an electrode has been tried, and methods for etching various types of films have been examined.
[0004]
Patent Document 1 describes an aqueous hydrogen peroxide- acetic acid type etching solution as an etching solution for a copper single film or a copper molybdenum multiple film, but the aqueous hydrogen peroxide-acetic acid type has the problem that control is difficult since the concentration and the etching rate change greatly over time. Furthermecre, aqueous hydrogen peroxide has a short solution lifetime, it is necessary to dissolve copper therein as a pretreatment in order tc stabilize the performance and, moreover, since liquid waste after etching generates a gas due to decomposition of aqueous hydrogen peroxide, there is a possibility of explosion of a container during storage. Furthermore, the aqueous hydrogen peroxide type is often used for simultaneously etching of a laminate film such as Cu/Ti or Cu/Mo, but since it contains a fluorine compound, due to corrosion of glass the substrate cannot be reused, and there is a problem with increased materials cost.
[0005]
A phosphoric acid-nitric acid-acetic acid type etching solution used for etching of an aluminum film conventionally used as a wiring material can also dissolve a copper film, but the solution tends to penetrate between the resist and the Cu, the copper beneath the resist tends to be etched, and there is also the problem that, since the higher the spray flow rate, the lower the etching rate, it is difficult to use in a spray device. Furthermore, when it is used for a laminate film such as for example Cu/Mo, one of the metals is very easily dissolved because of the Galvanic effect due to a difference in corrosion potential between the laminate film layers, and it is difficult to obtain a good pattern shape.
[0006]
With an etching solution of a copper <chloride- hydrochloric acid type or an iron chloride-hydrochloric acid type as described in Patent Document 2, the cross-sectional shape of the copper becomes substantially vertical, and when there is a copper alloy as a lower layer, there is the problem that, since the etching rate therefor is higher than that for copper, etching of the lower layer progresses, and the shape tends to become a reverse taper (i.e., a taper angle is 90° or mere To 180° or less).
[0007]
Furthermore, Patent Documents 2 to 5 examine etching of a 9 copper single layer or a laminate film such as Cu/Ti or Cu/Mo by means of an etching solution containing a persulfate.
[0008]
In recent years, laminate films containing a copper alloy have been developed as laminate films for replacing a Cu/Ti or
Cu/Mo laminate film. Unlike conventional laminate films that employ films of different types of metal, they are laminate films of a copper layer and a copper alloy layer, and they not only have excellent performance as a base film, but they also have the merit that each layer of the laminate film can be formed during a film formation step using the same device. [COC9]
However, hardly any examination has been carried out of methods that can etch effectively a laminate film having a copper layer and a copper oxide layer and/or a copper alloy layer or of etching solutions used therein. Patent Document 6 discloses an etching solution, containing a peroxide and an organic acid, for a laminate film having a copper oxide layer and a copper alloy oxide layer, and persulfuric acid and a persulfate are cited as the peroxide. However, since a composition containing persulfuric acid or a persulfate and an organic acid has greatly reduced solubility for copper due to the effect of the organic acid, it is difficult to adjust for a target treatment time. In order to deal with this, it is necessary to increase the amount of persulfuric acid or persulfate to thus promote the solubility, but if the amount thereof is increased, the etching solution tends to penetrate between a resist and the copper or copper alloy, the resist will peel off, and patterning becomes difficult. When a copper/copper alloy substrate was actually etched by preparing an example described in Patent Document 6, that is, a composition containing ammonium persulfate, acetic acid, and ammonium acetate, the resist peeled off before etching of the copper was completed, and patterning was impossible. Since it was a copper alloy/copper alloy substrate such as a CuMg/CuMgQ® 9 substrate that could be treated with the compcsition described in Patent Document 6, it 1s surmised that a simultaneously etching treatment was possible because a copper alloy is a laminate film having higher solubility than copper. It is also surmised that since the solubilities of a copper alloy/copper alloy substrate are similar to each other compared with those of a copper/copper alloy substrate, it is easy to carry out a simultaneously etching treatment. As described above, due to the etching properties {solubilities) in a copper/copper alloy laminate film being different, a desired shape cannot be obtained when using a generally known etching solution. [Related Art Documents] [Patent Documents]
[0010] [Patent Document 1] JP, A, 2004-19%3620 [Patent Document 2] JP, A, 2010-87213 [Patent Document 3] JP, A, 2010-265547 [Patent Document 4] Japanese Patent No. 39874305 [Patent Document 5] JP, A, 11-140669 [Patent Document 6] JP, A, 2010-265524 [Summary of the Invention] [Problems to be Solved by the Invention]
[0011]
That 1s, it is an object of the present invention to provide an etching solution composition for etching of a laminate film having copper and a copper alloy, the composition enabling impertant factors for simultaneously etching of a laminate film to be controlled.
[Means for Solving the Problems]
[0012]
While carrying out an intensive investigation in order to solve the above-mentioned problems, the present inventors 5 found that a good cross-sectional shape can be obtained by etching a metal laminate film having a copper thin film and an adhesive layer or a barrier layer of a copper alloy containing copper as the main component by using an etching solution composition in which phosphoric acid and nitric acid and/or sulfuric acid are added to a persulfate and/or persulfuric acid solution, and as a result of further research the present invention has been accomplished.
[0013]
That is, the present invention relates to the following. (1) An etching solution composition for etching a metal laminate film having a copper layer and a copper oxide layer and/or a copper alloy layer (excluding copper alloys consisting of copper and molybdenum, copper and titanium, and copper and chromium), the composition containing 0.1 to 80 wt% of a persulfate solution and/or a persulfuric acid solution, 0.1 to 80 wt% of phosphoric acid, and 0.1 to 50 wt% of nitric acid and/or sulfuric acid. (2) The etching solution composition according to (1) above, wherein the persulfate solution is an aqueous solution containing one or more of potassium peroxomonosulfate, potassium hydrogen peroxysuifate (KHSOs) , ammonium peroxodisulfate and potassium peroxodisulfate. (3) The etching solution composition according to (1) or (2} above, wherein the persulfate solution and/or the persulfuric acid solution contain potassium hydrogen peroxysulfate (KHSOs).
[0014] {4) The etching solution composition according to any one of (1) to (3) above, wherein the persulfuric acid solution contains one or more of potassium peroxomonosulfate, potassium hydrogen peroxysulfate (KHSOs), ammonium peroxodisulfate and potassium peroxodisulfate, and has an active oxygen content of 0.01 to 5 wt%. (5) The etching sclution composition according to any one of (l} to {4) above, wherein it does not contain nitric acid. {6) The etching solution composition according to any one of {l) to (5) above, wherein it further contains 0.00001 to 30 wt% of chloride ion. (7) The etching solution composition according to any one of (1) to (6) above, wherein it further contains 0.1 to 50 wt% of ammonium ion.
[0015] (8) The etching sclution composition according to any one of (1) to (7) above, wherein the metal laminate film is a copper/copper alloy or copper alloy/copper/copper alloy layer structure, the copper alloy being in contact with a substrate. (2) The etching sclution composition according to any one of (1) to (8) above, wherein the copper alloy is copper- magnesium-aluminum or copper-magnesium-aluminum oxide. {10) The etching solution composition according to any one of {l) to (9) above, wherein it is for etching a drive transistor electrode in a flat panel display.
[0016] (11) An etching method for a metal laminate film having a copper layer and a copper oxide layer and/or a copper alloy layer (excluding copper alloys consisting of copper and molybdenum, copper and titanium, and copper and chromium), the method including a step of carrying out etching using the etching solution composition according to any one of (1) to (10) above. (12) The etching method according to (11) above, wherein the metal laminate film is a copper/copper alloy or copper alloy/copper/copper alloy layer structure, the copper alloy being in contact with a substrate.
(13) The etching method according to (11) or (12) above, wherein the copper alloy is copper-magnesium-aluminum or copper-magnesium-aluminum oxide. (14d) The etching method according to any one of (11) to (13) above, wherein it is for etching a drive transistor electrode in a flat panel display. [Effects of the Invention]
[0017] i0 In accordance with the above-mentioned constitution, the etching method of the present invention can carry out etching of a metal laminate film of copper and a copper oxide layer and/or a copper alloy containing copper as a main component with good precision even for a metal thin film fine pattern having a line width of on the order of 0.5 to 5 pm. With a persulfate and/or persulfuric acid solution there is the problem that the cross-sectional shape tends to become vertical or the surface of the cross section becomes roughened and the problem that, due to the low solubility of the copper alloy as the lower layer, the lower layer tends to project, but with the etching solution composition of the present invention, in accordance with the synergistic effects of the persulfate and/or persulfuric acid solution and phosphoric acid and nitric acid and/or sulfuric acid, a metal laminate film containing a copper layer and a copper oxide layer and/or a copper alloy layer can be etched into a good forward taper shape, (i.e., a taper angle is (0° or more to 90° or less).
[0018]
Furthermore, it is possible to control the etching rate and the taper angle, and it is possible to carry out etching with high in-plane uniformity in which side etching and generation of residue are suppressed.
Moreover, a good cross-secticnal shape is obtained even using a dip system or a spray system, and in the case of a spray system since the etching rate increases accompanying an increase in the spray flow rate, 1t is easy to use and has excellent practicability.
[0019]
In particular, a laminate film in which the copper alloy is copper-magnesium-aluminum {(Cu-Mg-Al) or copper-magnesium- aluminum oxide (Cu~Mg=-Al-O) is a copper laminate film that has received the most attention from the present inventors from the viewpoint of adhesion and barrier properties, and in accordance with the etching solution composition of the present invention a fine pattern can be formed successfully by etching. [Brief Description of Drawings] [C020] [FIG. 1] FIG. 1 shows SEM photographs of substrate cross- sections after an etching treatment in Examples 1 to 8. [FIG. 2] FIG. 2 shows SEM photographs of substrate cross- sections after an etching treatment in Examples 9 to 19. [FIG. 3] FIG. 3 shows SEM photographs of substrate cross- sections after an etching treatment in Examples 20 to 36. [FIG. 4] FIG. 4 shows SEM photographs of two types of substrate having different film thicknesses after an etching treatment in Example 54. [FIG. 5] FIG. 5 shows SEM photographs of substrate cross- sections after an etching treatment in Examples 55 to 58. [FIG. 6] FIG. © shows SEM photographs of substrate cross-— sections after an etching treatment in Examples 59 to 62. [FTG. 7] FIG. 7 shows SEM photographs of substrate cross- sections after an etching treatment in Examples 63 to 66.
FFIG. 8] FIG. 8 shows SEM photographs of substrate cross- sections after an etching treatment in Examples 67 and
Comparative Example 1. [Modes for Carrying Out the Invention]
One aspect of the present invention relates to an etching solution composition for etching a metal laminate film having a copper layer and a copper oxide layer and/or a copper alloy layer (excluding copper alloys consisting of copper and 9 molybdenum, copper and titanium, and copper and chromium), the composition containing 0.1 to 80 wt% of a persulfate solution and/or a persulfuric acid solution, 0.1 to 80 wt% of phosphoric acid, and 0.1 to 50 wt$% of nitric acid and/or sulfuric acid.
[0022]
The copper alloy in the present invention is a copper alloy containing copper and any metal, copper being the main component, and includes a copper alloy oxide. It preferably contains copper in an amount of at least B80 atom %, and examples thereof include Cu-Ca, Cu-Mg, Cu-Ca-0, Cu-Mg-0, Cu-Al,
Cu-Zr, Cu-Mn, Cu-Ni-B, Cu-Mn-B, Cu-Ni-B, Cu-Si, Cu-2l, Cu-Mo,
Cu-Al, Cu-Mg-B, Cu-Ti-B, Cu-Mo-B, Cu-Al-B, Cu-S$i-B, Cu-Mg-Al, and Cu-Mg-41-0. Here, copper alloys consisting of copper and molybdenum, copper and titanium, and copper and chromium are excluded. Cu-Mg-Al and Cu-Mg-Al-O are preferable since a particularly good taper shape is obtained.
[0023]
The metal laminate film in the present invention has a copper layer and a copper oxide layer and/or a copper alloy layer (here, copper alloys consisting of copper and molybdenum, copper and titanium, and copper and chromium are excluded).
The laminate is typically formed from two layers, but even one having three or more layers can be etched simultaneously by the etching solution composition of the present invention. & two layer substrate typically has a copper/copper alloy layer structure, and a three layer substrate has a copper alloy/copper/copper alloy layer structure, both being a layer structure in which a copper alloy is in contact with a substrate. The substrate here is not limited but may contain any material, such as glass, silicon, ceramic, or a resin such as polyimide, that is required as an insulating material or a semiconductor to have a pattern formed on the surface thereof, and is preferably glass or silicon.
[0024]
In the present invention, the persulfate solution is an aqueous solution containing the persulfate, such as a peroxomonosulfate and/or a peroxodisulfate, and examples of the persulfate include, but are not limited to, potassium percxomonosulfate, potassium hydrogen peroxysulfate (KHSOs), sodium peroxomonosulfate (NaHSOs), ammonium peroxodisulfate ( (NH) 23205), potassium peroxocdisulfate (K235208), and sodium peroxodisulfate (Na 5;0g) .
[0025]
From the viewpoint of solubility, the persulfuric acid solution is preferably an aqueous solution containing potassium peroxcmonosulfate, ammonium peroxodisulfate ( (NH4) 25208) , or potassium hydrogen peroxysulfate (KHSOs).
The term 'potassium peroxomonosulfate' is generally used in commercial transactions, and it is used to mean the mixed triple salt 2KHSOs;:-KHS04:Kz30; in the present specification.
The term 'KHSOs' is used in the present specification to mean potassium hydrogen peroxysulfate in particular.
Potassium peroxomonosulfate is known under the product name of Oxone, and this persulfate is preferable in terms of 256 high solution stability.
[0026]
In the present invention, the persulfuric acid solution is an aqueous solution containing a persulfate such as potassium peroxomonosulfate, potassium hydrogen peroxysulfate (KHSOs) , sodium peroxomonosulfate {NaHSQs) , ammonium peroxodisulfate ((NHy)2S5:0¢), potassium peroxodisulfate {K:S5,0s), or sodium peroxodisulfate (Na;S;04) and having 0.01 to 5 wt$ active oxygen, preferably 0.3 to 3 wt%, and more preferably 0.5 to 2 wt%.
Potassium peroxomonosulfate as a solid theoretically has 5.2% active oxygen, but a commercial solid triple salt typically has about 4.7% active oxygen. The purity of a commercial potassium peroxomonosulfate is known to be about 9 95% to 98% due to trace amounts of impurities, trace amounts of additives, and variations in the production process.
[0028] "Active oxygen' is defined as the amount of oxygen in a potassium peroxomonosulfate triple salt that exceeds the amount of oxygen required to form the corresponding hydrogen sulfate salt. It may be calculated as a percentage from the equation for the decomposition of potassium peroxomonosulfate.
[0029] [Equation 1]
KH505 — KHSO, + [0]
Active oxygen 3% = Weight of [0] x 100
Weight of KHSOs
In the Formula, [0] is the oxygen released in the decomposition shown above. When applying the given equation, the weight of KHSOs is replaced by the weight of a sample that contains an impurity material. The active oxygen can of course be determined from many reactions, for example, the quantitative displacement of iodine from potassium iodide.
[0030] (Measurement of active oxygen)
A measurement method for active oxygen is carried out in accordance with published Japanese translation 2009-539740 of a PCT application, it being determined by standard iodine titration. A solution to be analyzed is diluted with cold deionized water, made acidic, treated with potassium iodide, and titrated using a standardized 0.1 N sodium thiosulfate reagent until an end point that is visually indicated by a starch indicator. The active oxygen content is calculated as follows.
[0031] % active oxygen = (mLtitration solution * NOYMalitVeirration solution X 0.8)/(gramgample)
The % KHSOs concentration may similarly be calculated as follows. % KHSOs = % active oxygen/0.105 {0032]
The concentration of the persulfate and/or persulfuric acid solution is 0.1 to 80 wt%, and preferably 5 to 35 wif%.
When the concentration is in the above-mentioned range, the etching rate or side etching can each be controlled by a combination with another component, but when the concentration is smaller than or larger than the above range, the etching rate becomes extremely low or high, and control becomes difficult.
[0033]
The etching solution composition of the present invention contains phosphoric acid. The concentration of phosphoric acid is 0.1 to 80 wt%, and preferably 5 to 50 wt%. When the phosphoric acid 1s less than or greater than the above- mentioned range, in-plane uniformity becomes poor, side etching tends to be serious, and it becomes difficult to carry out control only by the use of another component. The etching solution composition may contain either one or both of nitric acid and sulfuric acid. An etching solution containing sulfuric acid is preferable. The total concentration of nitric acid and sulfuric acid when the two are contained is 0.1 to 50 wt%, with preferably nitric acid being 1 to 20 wt% or sulfuric acid being 1 to 30 wt%. When only nitric acid is contained, the concentration cof nitric acid is 0.1 to 50 wt%, and preferably 1 to 20 wt. When only sulfuric acid is contained, the concentration cof sulfuric acid is 0.1 to 50 wt%, 39 and preferably 1 to 30 wi%.
[0034]
In one embodiment of the present invention, the etching solution composition of the present invention does not contain nitric acid. A composition containing a persulfuric acid 9 solution, phosphoric acid, and sulfuric acid can enhance solution stability of persulfate anion because of the large sulfate ion content compared with a composition containing a persulfuric acid sclution, phosphoric acid, and nitric acid.
Furthermore, with a persulfuric acid solution-based etching solution composition, when nitric acid is added, variation in the etching rate is small, but when phosphoric acid is added the speed increases, and when sulfuric acid is added the speed decreases, and there is the advantage that the etching rate is easily controlled by adjusting the amounts of phosphoric acid and sulfuric acid.
[0035]
In one embodiment of the present invention, the etching solution composition of the present invention may contain chloride ion. The chloride ion may be present in the etching solution composition by adding hydrochloric acid or a compound that dissolves in water and easily generates chloride ion.
Examples of the compound that generates chloride ion include chlorides such as zinc chloride, zinc ammonium chloride, aluminum chloride, ammonium chloride, cobalt (II) chloride, copper (II) chloride, palladium chloride, isobutyl chloride, isopropyl chloride, indium (III} chloride, ethylene chloride, oleyl chloride, potassium chloride, calcium chloride, silver chloride, chromium (II) chloride, cobalt {T1) chloride, choline chloride, zirconium {IV} chloride, mercury (I) chloride, tin (IV) chloride, tin (II) chloride, tin (VI) chloride, strontium chloride, caesium chloride, cerium (III) chloride, tungsten (VI) chloride, tantalum (V) chloride, titanium (IV) chloride, titanium (III) chloride, iron (II) chloride, iron (III) chloride, tetraethylammeonium c<¢hloride, copper (I) chloride, copper (II) chloride, sodium chloride,
lead (II) chloride, nickel (II) chloride, platinum (II) chloride, platinum (IV) potassium chloride, barium chloride, palladium (II) chloride, methylene chloride, ethylene chloride, and lithium chloride. In particular, from the viewpoint of solution stability in an acidic solution and wettability on a microfabricated part, hydrochloric acid is preferable. It has been found that chloride ion contributes to the speed of dissolution of a copper alloy in particular, and it makes it possible to control the speed and control the taper angle.
Furthermore, since chloride ion has a high migration rate in aqueous solution, it promotes uniform dissolution of the surface of a processed article, and the in-plane uniformity improves, thus resulting in suppression of side etching.
[0036]
The chloride ion concentration may be set appropriately in accordance with the type of copper alloy film and the film thickness, and although it is not limited thereto it is 0.00001 to 30 wt%, preferably 0.00003 to 2 wt%, and more preferably 0.00003 to 0.05 wt%. When the chloride ion is less than the above-mentioned range there is hardly any effect in improving the in-plane uniformity, and when it is larger since dissolution of a copper alloy is faster than that of copper, the cross-sectional shape tends to become poor. Furthermore, a residue that is thought to be cuprous chloride tends to be formed. It is surmised that this is due to chlorine reacting with the surface of the copper, sparingly soluble cuprous chloride being formed on the copper surface, and this cuprous chloride inhibiting etching. However, adding ammonium ion to the etching solution composition of the present invention suppresses formation of cuprous chloride, thus suppressing formation of the residue.
[0037]
Ammonium ion may be made to be present in the etching solution composition by adding a compound that dissolves in water and easily generates ammonium ion. Examples of the compound that generates ammonium ion include diammonium hydrogenphosphate, ammonium sulfamate, zinc ammonium chloride, ammonium chloride, cobalt (II) ammonium chloride, copper (II) armonium chloride, palladium (II) ammonium chloride,
9 tetraethylammonium chloride, tetrabutylammonium chloride, tetrapropylammonium chloride, hydroxylammonium chloride, ammonium perchlorate, ammonium periodate, ammonium formate, ammonium citrate, iron (III) ammonium citrate, monoammonium citrate, triammonium citrate, diammonium hydrogen citrate,
iron (III) ammonium citrate, ammonium dihydrogen citrate, ammonium acetate, ammonium tetraborate, ammonium bromide, ammonium oxalate, hydrogen ammonium oxalate, iron (III) ammonium oxalate, ammonium tartarate, ammonium nitrate, cerium
(IV) ammonium nitrate, tetraethylammonium hydroxide,
tetrabutylammonium hydroxide, tetrapropylammonium hydroxide, tetramethylammonium hydroxide, ammonium bicarbonate, ammonium carbonate, ammonium thiosulfate, ammonium trifluorcacetate, ammonium lactate, ammonium hydrofluoride, ammonium borate, ammonium icdide, ammonium sulfate, aluminum ammonium sulfate,
chromium (III) ammonium sulfate, cobalt (II) ammonium sulfate, iron (II) ammonium sulfate, iron (III) ammonium sulfate, copper (II) ammonium sulfate, nickel (II) ammonium sulfate, magnesium ammonium sulfate, manganese (II) ammonium sulfate, monoammonium phosphate, triammonium phosphate, sodium ammonium hydrogen phosphate, and ammonium dihydrogenphosphate, and from the viewpoint of solubility in particular ammonium dihydrogenphosphate or diammonium hydrogenphosphate is preferable.
The concentration of ammonium ion may be set appropriately according to the type of the copper alloy film and the film thickness and the concentration of the persulfuric acid solution, nitric acid, sulfuric acid, or chloride ion, and although it is not limited thereto it is 0.1 to 50 wt3, and preferably 1 to 5 wt%. When the ammonium ion is less than the above-mentioned range it becomes difficult to suppress formation of a residue that occurs when chloride ion is added or to control the speed of dissolution of a copper alloy, and when it is greater, since the speed of dissolution of a copper alloy becomes too low, the cross-sectional shape tends to become poor.
[0038]
By adjusting the concentrations of chloride ion and ammonium ion, the speed of dissolution of copper and a copper alloy can be controlled, and the taper angle can also be easily controlled by utilizing this. The taper angie is in 100 the range of 20 to 100 degrees, and preferably 30 to 60 degrees.
[0039]
Furthermore, chloride ion and ammonium ion have a further effect in etching of a three layer substrate. That is, in the case of a three layer substrate, since penetration of a solution between the resist and the copper alloy progresses to a greater extent, there is the problem that the taper angle becomes small compared with the case of a two layer substrate, but adding chloride ion and ammonium ion enables penetration between the resist and the copper alloy and between the copper alloy and the glass to be adjusted, thus enabling the taper angle of the three layer substrate to be controlled.
[0040]
The etching solution composition of the present invention may contain one or more surfactants in order to improve the wettability toward a surface that 1s to be etched. The surfactant is preferably an anionic or nonionic surfactant.
[0041]
In accordance with use of the etching solution composition of the present invention, it is possible to carry out etching safely with high precision by a simple etching treatment without using aqueous hydrogen peroxide or a flucrine compound. Furthermore, unlike the case of a composition employing agueous hydrogen peroxide it is not necessary to dissolve copper prior to treatment of a substrate in order to stabilize the rate of etching of copper.
Furthermore, since etching can be carried out without an organic acid being present, it is unnecessary to take into ccnsideration problems such as peeling off of a resist.
[0042]
With regard to the etching solution composition of the present invention, a replenisher may be prepared using a persulfate and/or persulfuric acid solution, phosphoric acid, nitric acid, sulfuric acid, chloride ion, and ammonium ion: for example, the solution lifespan may be increased by adding only a required amount of persulfuric acid solution commensurate with a decrease in the etching rate, but it is also possible to further increase the solution lifespan by adding another component at the same time. This enables the cost of use to be reduced.
[0043]
Another aspect of the present invention relates to an etching method for a metal laminate film having a copper layer and a copper oxide layer and/or a copper alloy layer (excluding copper alloys consisting of copper and molybdenum, copper and titanium, and copper and chromium), the method including a step of carrying out etching using an etching solution composition containing 0.1 to 80 wt% of a persulfate solution and/or a persulfuric acid solution, 0.1 to 80 wt% of phosphoric acid, and 0.1 to 50 wt% of nitric acid and/or 0.1 to 50 wt% of sulfuric acid.
[0044]
In accordance with the etching method of the present invention, since the speeds of dissolution of copper and a copper alloy vary according to temperature, it is possible to control the taper angle by changing the temperature while taking into consideration the above. From the viewpoint of temperature conditions that can be set for etching equipment, the temperature is preferably 20 to 80 °C, and more preferably 25 to 40 °C.
[0045]
The etching composition and the etching method of the present invention exhibit particularly good etching properties for a laminate film having a novel copper alloy, that is, a copper-magnesium-aluminum alloy and/or a copper-magnesium- aluminum oxide alloy. Here, the copper-magnesium-aluminum alloy is preferably an alloy obtained by sputtering a target material containing 0.1 to 10.0 atom% of Mg and 0.1 to 10.0 atom% of Al, the remainder being Cu and inevitable impurities, and is a Cu alloy film for a wiring film. The copper- magnesium-aluminum oxide alloy 1s an alloy obtained by sputtering the target material under conditions of an oxygen partial pressure of 0.1% to 20%. A film formed from the copper-magnesium-aluminum oxide allcy does not have a problem with adhesion being degraded by reduction of an oxide film by a hydrogen plasma treatment carried out during a step of producing a TFT in production of a flat panel display (ULVAC
TECHNICAL JOURNAL, No. 71, 2009, pp 24 tc 28).
[0046]
In one embodiment of the present invention, the etching solution compesition and the etching method of the present invention relate to an etching solution composition and an etching method for etching a drive transistor electrode in a flat panel display. [Examples]
[0047]
The present invention is explained in further detail below by reference to Examples and Comparative Examples, but the present invention is not limited by these examples and may be modified appropriately as long as the spirit and scope thereof are maintained.
[0048]
Examples 1 toc 53
A Cu alloy (Cu-Mg-Al) with a film thickness of 500 A and
Cu with a film thickness of 3000 A were formed as films on a glass substrate, a resist pattern was then formed, and the sample was immersed in an etching solution from Tables 1 to 4 9 at a solution temperature of 30°C for a time of 1.5 times the just-etching time. Subsequently, the sample was washed with water and dried, and was evaluated for residue. As persulfuric acid solution, DuPont LD100 {a solution containing
KH505 as the main component) was used.
The results are shown in Tables 1 to 4. The results of
SEM photography of Tables 1 to 3 are shown in FIGS. 1 to 3 respectively.
[0049] [Table 1]
Evaluation results for various compositions [J.E.T. x 1.5]
Cu/CuMghl substrate
Amount of
LD100 H»50, H4PO, side . (Wt) (WES) (wt) etching Taper shape Residue (yr)
Example 1| 11.9 | 4.5 | 82 | 0.65 | Forward taper | Wome [example 2| 13.7 | 4.5 | 155 | 0.495 | Forward taper | tome [Example 5] 11.7 | 98 | 82 | 0.51 | Forward taper | None [Bxample 8] 11.7 | 9.8 | 42.0 | 0.66 | Forward taper | Wome [Table 2]
Evaluation results for various compositions [J.E.T. x 1.5]
Cu/CuMgAl substrate
Amount of
LDi0C HSC, H4PO, side . (WES) (wt) (Wks) etching Taper shape Residue (pm)
Example 17] 17.5 | 19.6 | 42.0 | 0.55 | Foruard taper | ons
[0050] [Table 3]
Evaluation results for various compositions {J.E.T. x 1.5]
Cu/CuMgAhl substrate
Amount of
LD1OG 5 H4P0, side , (WES) HNO; (wi%) (wt 2) etching Taper shape Residue (pm)
Pomple 20] 5.6 | 63 | 6.2 | 0.10 | vorwazd taper | None _
Banple 50] 5.6 | 18.9 | 42.0 | 185 | Forward taper | tome
Bample 32] 5.8 | 26.2 | ©.2 | 1065 | Forward taper | Nene
[0051] [Table 4]
Evaluation results for various compositions [J.E.T. x 1.5]
Cu/CuMgAl substrate
Amount of
LD1GO a HPO, side . (WES) HNO, (wt%} (ts) etching Taper shape Residue {pm}
[0052]
The cross-sectional shape of the Cu/CuMgAl substrate was examined when the concentration of LD100 (KHSOs) was fixed but the concentrations of nitric acid or sulfuric acid and phosphoric acid were changed; it was found that since the amount of side etching changed depending on the concentration of each type, the amount of side etching could be suppressed by optimizing the concentration of each type. The amount of side etching is sufficient for use when it is no greater than 10 times the film thickness of the substrate, preferably no greater than 7 to 4 times, more preferably no greater than three types, and yet more preferably no greater than twice. 18 Furthermore, since the etching rate changes at the same time, by adjusting the concentrations of phosphoric acid and nitric acid and/or sulfuric acid it becomes possible to control the amount of side etching and the etching rate at the same time. [C053]
Example 54
Resist patterns were formed on each of a substrate in which a Cu alloy (Cu-Mg-Al) with a film thickness of 500 A and
Cu with a film thickness of 3000 A were formed as films on a glass substrate and a substrate in which a Cu alloy (Cu-Mg-Al) with a film thickness of 300 A and Cu with a film thickness of 4000 A were formed as films on a glass substrate, and the samples were immersed in the etching solution from Table 5 at solution temperatures of 30°C, 40°C, and 50°C for a time of
1.5 times the Jjust=-etching time. Subsequently, the samples were washed with water and dried, and ware evaluated for residue. As persulfuric acid solution, DuPont LDI100 (a solution containing KHSOs as the main component) was used.
The results are shown in Table 6, and the results of SEM photographs of Table 6 are shown in FIG. 4. [00541 [Table 5]
Composition
Tew | mew [wm 10055] (Table 6]
Evaluation results for various compositions [J.E.T. x 1.5] 16 Cu/CuMgAl substrate
Substrate pr etching |angle (°) Taper shape Residue (yam) cunt 1200 I
Cu 000 &)
[0056]
The cross-sectional shape when the solution temperature was changed was examined using two types of substrate having different film thicknesses, and it was confirmed for both that the taper angle increased as the temperature increased.
Furthermore, it was confirmed that the range of change in taper angle was larger for the Cu (4000 A)/CuMgAl (300 A) substrate than for the Cu(3000 A)/CuMgAl (500 A) substrate. A main factor for the change in taper angle is the change in speed of dissolution of Cu and CuMgAl, and for CuMgAl in particular this depends greatly on the solution temperature.
Moreover, the film thickness of the substrate is also involved; the thinner the CuMgAl film thickness, the higher the speed of dissolution of the lower layer, the greater the effect on the taper angle, and the greater the range for controlling this. [C057]
Examples 55 to 58
A Cu alloy (Cu-Mg-Al) with a film thickness of 500 A and
Cu with a film thickness of 3000 A were formed as films on a glass substrate, a resist pattern was then formed, and the cross-sectional shape and the residue when hydrochloric acid was added were evaluated using the etching solution of Example 55 in Table 7 as a base. The solution temperature was 30°C, and the immersion time was 1.5 times the just-etching time.
Furthermore, as persulfuric acid solution, DuPont LD100 (a solution containing KHSOs; as the main component) was used.
The results are shown in Table 8, and the results of SEM photographs of Table 8 are shown in FIG. 5.
[0058] [Takle 7]
Various compositions (Teo [me [mew [mo
Cmemwpless | mi 52 | ez | 0] [C059] [Table 8]
Evaluation results for various compositions [J.E.T. x 1.5]
Cu/CuMghl substrate
TEE ee [oe | ie Bemple 55 | 0.45 | 20 | Forward taper | wom manele 55 | 035 | 60 | forward caper | Nome
[0060]
The cross-sectional shape when the concentration of hydrochloric acid was changed was examined using the composition of Example 55 as a base, and it was confirmed that 9 the taper angle increased as the concentration increased.
Furthermore, it was found that the amount of side etching could be suppressed as the concentration of hydrochloric acid increased.
[0061]
This is because the reactivity of chloride ion with
CuMgAl is higher than with Cu, and this enables the taper angle or the «cross-sectional shape to be controlled.
Furthermore, it is surmised that since chloride ion has a high migration rate in aqueous solution, it promotes uniform dissolution of the surface of a processed article, and the in-~ plane uniformity improves, thus enabling side etching to be suppressed.
[0062]
Examples 59 to 62
A Cu alloy (Cu-Mg-Al) with a film thickness of 500 A, Cu with a film thickness of 3000 A, and a Cu alloy {Cu-Mg-Al) with a film thickness of 500 A were formed as films on a glass substrate, a resist pattern was then formed, and the cross- sectional shape and the residue when hydrochloric acid was added were evaluated using the etching solution of Example 59 in Table 9 as a base. Evaluation of the addition of diammonium hydrogenphosphate together with hydrochloric acid was also carried out. The solution temperature was 30°C, and the immersion time was 1.5 times the Jjust-etching time.
Furthermore, as persulfuric acid solution, DuPont LD100 (a solution containing KHSOs as the main component) was used.
The results are shown in Table 10, and the results of SEM photographs of Table 10 are shown in FIG. 6.
[0063] [Table 9]
Various compositions
Tow wn [von Jorn [oe (Beemple 59 | 31.7 | 52 | sz | soooose | - [Example e0 | 117 | 52 | aa | o.oo | = [(eremple 61 | 17 | 52 | woos | =
[0064] [Table 10] 9 Evaluation results for various compositions [J.E.T. x 1.5]
CuMgAl/Cu/CuMgAl substrate
TEE fee a | wee [Grample 59 | 0.45 | 30 | Forward taper | Noms ample 62 | 0.65 | 55 | voruard taper | Wome
[0065]
Examples 63 to 66
A Cu alloy (Cu-Mg-Al) with a film thickness of 500 A, Cu with a film thickness of 3000 A, and a Cu alloy (Cu-Mg-Al) with a film thickness of 500 A were formed as films on a glass substrate, a resist pattern was then formed, and the cross- sectional shape and the residue when hydrochloric acid was added were evaluated using the etching solution of Example 63 in Table 11 as a base. Evaluation of the addition of diammonium hydrogenphosphate together with hydrochloric acid was also carried out. The sclution temperature was 30°C, and the immersion time was 1.5 times the just-etching time.
Furthermore, as persulfuric acid solution, DuPont LD100 (a solution containing KHSOs; as the main component) was used.
The results are shown in Table 12, and the results of SEM photographs of Table 12 are shown in FIG. 7.
[0066] [Table 11]
Various compositions or or] wes)
Ero oa
TEwamole 61 | 117 | 49 | 52 | ooo | -
[0067] [Table 12]
Evaluation results for various compositions [J.E.T. x 1.5]
CuMgAl/Cu/CuMgAl substrate
EE eee] oe |e
[0068]
The taper angle tended to be smaller for the three layer (CuMgAl/Cu/CuMgAl} substrate than for the two layer (Cu/CuMghl) substrate. Because of this, the amount of side etching was small, and etching while maintaining forward taper was possible, but it was difficult to control the taper angle with good precision only by the concentration of hydrochloric acid added. It was possible to change the cross-sectional shape to some extent by increasing the concentration of hydrochloric acid, but when the concentration of hydrochloric acid was too high, a residue that was thought to be cuprous chloride tended to form the surface of the substrate. On the other hand, when the concentrations of hydrochloric acid and diammonium hydrogenphosphate added were controlled, it became possible to carry out etching with a large taper angle while suppressing the formation of residue and maintaining a forward taper, and it was confirmed that the taper angle could be controlled.
[0069]
Example 67 and Comparative Example 1
A Cu alloy (Cu-Mg-Al) with a film thickness of 50C A and
Cu with a film thickness of 3000 A were formed as films on a glass substrate, a resist pattern was then formed, and evaluation of etching was carried out using an etching solution from Table 13. As the test method, two types of tests, that 1s, a dip test in which a substrate was etched by immersing it in a beaker and a spray test in which the substrate was etched by spraying an etching solution in a mist state, were employed. The solution temperature was 30°C for both, and the treatment time was 1.5 times the Jjust-etching time; subsequently washing with water and drying were carried i0 cut, and residue was evaluated. As persulfuric acid solution,
DuPont LDI1OO (a solution containing KHSOs; as the main component) was used.
The results are shown in Table 14, and the results of SEM photographs of Table 14 are shown in FIG. 8. [00701 [Table 13]
Various compositions
To on [an [oo om oo fm (Sample 67 | 225 | 4s | esq | = | = marl | ee [ee | me
[0071] [Table 14]
Evaluation results for various compositions [J.E.T. x 1.5]
Cu/CuMgAl substrate
Amount of [Ee (am) come [pte [oe The Tron baer | None [C072]
Evaluation was carried out by the dip test and the spray test using Example 67, which contained persulfate, phosphoric acid, and sulfuric acid, and Comparative Example 1, which was of the phosphoric acid + nitric acid + acetic acid type. In the dip test, the cross-sectional shape was forward taper for both and there was no residue, the results obtained thus being good, but in the spray test it was found that the cross- sectional shape of Comparative Example 1 was a shape similar to the tip of an arrow (referred to as an arrow shape) in which both ends were tapered. [00731
The cause therefor is thought to be difference in solubility in the two solutions. For the etching solution of the present invention. containing persulfate, phosphoric acid, and sulfuric acid, the etching rate for Cu increased as the stirring speed increased in the beaker test, but for the phosphoric acid + nitric acid + acetic acid type, the etching rate for Cu tended to decrease as the stirring speed increased.
The flow rate cof fhe spray test showed the same trend as the stirring speed of the beaker test; for the phosphoric acid + nitric acid + acetic acid type, the etching rate decreased as the spray flow rate increased. Furthermore, the flow rate of the spray test is harder fo control than the stirring speed of the beaker test, and the flow rate tends to increase (difficult to decrease).
[0074]
Therefore, dissolution by the composition of Comparative
Example 1 hardly proceeds by spraying alone. It is surmised that although dissolution is possible by a sprayed solution building up on the substrate, since the etching rate of the solution built up on the substrate is higher than the etching rate by spraying, dissolution of the lower layer that is in contact with the built up solution progresses more quickly than dissolution of the upper layer, and the cross-sectional shape becomes an arrow shape.
[0075]
Furthermore, in the spray test of Comparative Example 1, 3% there is the problem that residue tends to form on an end part of a substrate, and even if the flow rate of a spray device can be set finely, since the control range is small, it is difficult to use.
Compared with this, with regard to the composition used in the Examples, a composition can be prepared that does not require fine setting of conditions in both the dip test and the spray test, gives a good cross-
sectional shape, and does not form a residue.
Claims (14)
1. An etching solution composition for etching a metal laminate film having a copper layer and a copper oxide layer 9 and/or a copper alloy layer (excluding copper alloys consisting of copper and molybdenum, copper and titanium, and copper and chromium), the composition comprising C.1 to B80 wt% of a persulfate solution and/or a persulfuric acid solution, 0.1 te 80 wt% of phosphoric acid, and 0.1 to 50 wt% of nitric acid and/or sulfuric acid.
2. The etching solution composition according to Claim 1, wherein the persulfate sclution is an aqueous solution comprising one or more of potassium peroxomonosulfate, potassium hydrogen peroxysulfate {KHSOs) , ammonium peroxodisulfate and potassium peroxodisulfate.
3. The etching solution composition according to Claim 1 or 2, wherein the persulfate solution and/or the persulfuric acid solution comprise potassium hydrogen peroxysulfate (KHSOs).
4. The etching solution composition according to any one of Claims 1 to 3, wherein the persuifuric acid sclution comprises one or more of potassium peroxomcnosulfate, potassium hydrogen peroxysulfate (KHSOs), ammonium peroxodisulfate and potassium peroxodisulfate, and has an active oxygen content of 0.01 to 5 wt.
5. The etching sclution composition according to any one of Claims 1 to 4, wherein it dees not comprise nitric acid.
6. The etching solution composition according to any one of Claims 1 to 5, wherein it further comprises 0.00001 to 30 wt$ of chloride ion.
7. The etching solution composition according to any one of Claims 1 to 6, wherein it further comprises 0.1 to 50 wt% of ammonium ion.
8. The etching solution composition according to any one of Claims 1 to 7, wherein the metal laminate film is a copper/copper alloy or copper alloy/copper/copper alloy layer structure, the copper alloy being in contact with a substrate.
9. The etching solution composition according to any one of Claims 1 to 8, wherein the copper alloy is copper-magnesium- aluminum or copper-magnesium-aluminum oxide.
10. The etching solution composition according to any one of Claims 1 to 9, wherein it is for etching a drive transistor electrode in a flat panel display.
11. An etching method for a metal laminate film having a copper layer and a copper oxide layer and/or a copper alloy layer (excluding copper alloys consisting of copper and molybdenum, copper and titanium, and copper and chromium), the method comprising a step of carrying out etching using the etching solution composition according to any one of Claims 1 to 10.
12. The etching method according to Claim 11, wherein the metal laminate film is a copper/copper alloy or copper alloy/copper/copper alloy layer structure, the copper alloy being in contact with a substrate.
13. The etching method according to Claim 11 or 12, wherein the copper alloy is copper-magnesium-aluminum or copper- magnesium-aluminum oxide.
14. The etching method according to any one of Claims 11 to 13, wherein it is for etching a drive transistor electrode in a flat panel display.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011196394A JP5885971B2 (en) | 2011-09-08 | 2011-09-08 | Etching solution for copper and copper alloy |
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| SG188734A1 true SG188734A1 (en) | 2013-04-30 |
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| Application Number | Title | Priority Date | Filing Date |
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| SG2012065843A SG188734A1 (en) | 2011-09-08 | 2012-09-05 | Etching solution for copper and copper alloy |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5885971B2 (en) |
| KR (1) | KR20130028014A (en) |
| CN (1) | CN102995021A (en) |
| SG (1) | SG188734A1 (en) |
| TW (1) | TW201323661A (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6777420B2 (en) * | 2016-04-21 | 2020-10-28 | 関東化学株式会社 | Etching composition of single-layer film or laminated film or etching method using the composition |
| CN105887092B (en) * | 2016-04-28 | 2019-01-15 | 华南理工大学 | A kind of PCB acidic etching liquid suitable for ozone absorption method |
| WO2019135338A1 (en) * | 2018-01-05 | 2019-07-11 | 株式会社Adeka | Composition and etching method |
| KR102205628B1 (en) | 2019-02-12 | 2021-01-21 | 김진호 | Etchant composition for copper or copper-containing metal films |
| CN110093606A (en) * | 2019-06-14 | 2019-08-06 | 大连亚太电子有限公司 | A kind of etching solution and preparation method thereof for pcb board |
| CN110938822A (en) * | 2019-11-14 | 2020-03-31 | 浙江工业大学 | Etching solution, etching method and application of molybdenum/copper composite metal layer |
| CN111041489B (en) * | 2020-01-03 | 2021-10-15 | 易安爱富(武汉)科技有限公司 | Molybdenum/titanium alloy film etching solution composition and application thereof |
| CN111809183B (en) * | 2020-07-14 | 2022-08-09 | 北京航空航天大学宁波创新研究院 | Metallographic corrosive liquid of copper-gallium alloy and metallographic display method |
| CN112635553B (en) * | 2020-12-25 | 2022-09-16 | 广东省科学院半导体研究所 | Manufacturing method of thin film transistor and display device |
| CN113667979A (en) * | 2021-08-05 | 2021-11-19 | Tcl华星光电技术有限公司 | Copper-molybdenum metal etching solution and application thereof |
| WO2024107260A1 (en) * | 2022-11-14 | 2024-05-23 | Tokyo Electron Limited | Methods for wet etching of noble metals |
| CN116573782B (en) * | 2023-04-03 | 2023-11-03 | 迁安市宏奥工贸有限公司 | Method for treating desulfurization waste liquid |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4706081B2 (en) * | 2001-06-05 | 2011-06-22 | メック株式会社 | Etching agent and etching method for copper or copper alloy |
| JP4069387B2 (en) * | 2003-08-27 | 2008-04-02 | 上村工業株式会社 | Etching solution |
| JP4093147B2 (en) * | 2003-09-04 | 2008-06-04 | 三菱電機株式会社 | Etching solution and etching method |
| US7442323B2 (en) * | 2006-06-02 | 2008-10-28 | E. I. Du Pont De Nemours And Company | Potassium monopersulfate solutions |
| JP4973231B2 (en) * | 2006-09-05 | 2012-07-11 | 日立化成工業株式会社 | Copper etching method and wiring board and semiconductor package using this method |
| KR101310310B1 (en) * | 2007-03-15 | 2013-09-23 | 주식회사 동진쎄미켐 | Etchant for thin film transistor-liquid crystal displays |
| JP5559956B2 (en) * | 2007-03-15 | 2014-07-23 | 東進セミケム株式会社 | Etching solution composition for thin film transistor liquid crystal display device |
| US8518281B2 (en) * | 2008-06-03 | 2013-08-27 | Kesheng Feng | Acid-resistance promoting composition |
| KR101520921B1 (en) * | 2008-11-07 | 2015-05-18 | 삼성디스플레이 주식회사 | Etchant composition, method for forming metal patterns and method for manufacturing thin film transistor array panel using the same |
| JP5604056B2 (en) * | 2009-05-15 | 2014-10-08 | 関東化学株式会社 | Etching solution for copper-containing laminated film |
| CN101807572A (en) * | 2010-02-25 | 2010-08-18 | 友达光电股份有限公司 | Etching solution, active component array substrate and method for manufacturing active component array substrate |
| KR20120066950A (en) * | 2010-12-15 | 2012-06-25 | 삼성전자주식회사 | Echtant, display device and method for manufacturing display device using the same |
-
2011
- 2011-09-08 JP JP2011196394A patent/JP5885971B2/en not_active Expired - Fee Related
-
2012
- 2012-09-05 SG SG2012065843A patent/SG188734A1/en unknown
- 2012-09-07 CN CN2012103305021A patent/CN102995021A/en active Pending
- 2012-09-07 TW TW101132768A patent/TW201323661A/en unknown
- 2012-09-07 KR KR1020120099231A patent/KR20130028014A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013058629A (en) | 2013-03-28 |
| KR20130028014A (en) | 2013-03-18 |
| JP5885971B2 (en) | 2016-03-16 |
| TW201323661A (en) | 2013-06-16 |
| CN102995021A (en) | 2013-03-27 |
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