WO2024096006A1 - Aqueous composition for etching, etching method using same, and semiconductor substrate manufacturing method - Google Patents
Aqueous composition for etching, etching method using same, and semiconductor substrate manufacturing method Download PDFInfo
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- WO2024096006A1 WO2024096006A1 PCT/JP2023/039251 JP2023039251W WO2024096006A1 WO 2024096006 A1 WO2024096006 A1 WO 2024096006A1 JP 2023039251 W JP2023039251 W JP 2023039251W WO 2024096006 A1 WO2024096006 A1 WO 2024096006A1
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- aqueous composition
- carbon atoms
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- acid
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- 239000000203 mixture Substances 0.000 title claims abstract description 124
- 238000005530 etching Methods 0.000 title claims abstract description 62
- 239000000758 substrate Substances 0.000 title claims description 48
- 239000004065 semiconductor Substances 0.000 title claims description 43
- 238000000034 method Methods 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 238000005260 corrosion Methods 0.000 claims abstract description 28
- 230000007797 corrosion Effects 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 25
- 239000003112 inhibitor Substances 0.000 claims abstract description 19
- 239000007800 oxidant agent Substances 0.000 claims abstract description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 164
- -1 nitrogen-containing heterocyclic compound Chemical class 0.000 claims description 86
- 125000000217 alkyl group Chemical group 0.000 claims description 82
- 239000010949 copper Substances 0.000 claims description 54
- 125000003118 aryl group Chemical group 0.000 claims description 52
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 40
- 229910052802 copper Inorganic materials 0.000 claims description 40
- 125000004474 heteroalkylene group Chemical group 0.000 claims description 40
- 150000003839 salts Chemical class 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000003093 cationic surfactant Substances 0.000 claims description 16
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 8
- 125000001072 heteroaryl group Chemical group 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 35
- 150000003863 ammonium salts Chemical class 0.000 description 22
- 235000011007 phosphoric acid Nutrition 0.000 description 16
- 229910000881 Cu alloy Inorganic materials 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 14
- 229910052759 nickel Inorganic materials 0.000 description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- 125000000547 substituted alkyl group Chemical group 0.000 description 11
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 10
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 10
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 10
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 8
- 229910000990 Ni alloy Inorganic materials 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 7
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 7
- 125000004093 cyano group Chemical group *C#N 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 125000001624 naphthyl group Chemical group 0.000 description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 7
- 150000003016 phosphoric acids Chemical class 0.000 description 7
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 150000004693 imidazolium salts Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000004965 peroxy acids Chemical class 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 229910001020 Au alloy Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 5
- 229910001128 Sn alloy Inorganic materials 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 229960001950 benzethonium chloride Drugs 0.000 description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000003353 gold alloy Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000003107 substituted aryl group Chemical group 0.000 description 5
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 229910007637 SnAg Inorganic materials 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229940006460 bromide ion Drugs 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000006353 oxyethylene group Chemical group 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 150000004715 keto acids Chemical class 0.000 description 3
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 2
- HJUPHPDWOUZDKH-UHFFFAOYSA-M 1-decylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCC[N+]1=CC=CC=C1 HJUPHPDWOUZDKH-UHFFFAOYSA-M 0.000 description 2
- GKQHIYSTBXDYNQ-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]1=CC=CC=C1 GKQHIYSTBXDYNQ-UHFFFAOYSA-M 0.000 description 2
- NKRASMXHSQKLHA-UHFFFAOYSA-M 1-hexyl-3-methylimidazolium chloride Chemical compound [Cl-].CCCCCCN1C=C[N+](C)=C1 NKRASMXHSQKLHA-UHFFFAOYSA-M 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 2
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229960003872 benzethonium Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003901 ceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- SXPWTBGAZSPLHA-UHFFFAOYSA-M cetalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SXPWTBGAZSPLHA-UHFFFAOYSA-M 0.000 description 2
- 229960000228 cetalkonium chloride Drugs 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- SIYLLGKDQZGJHK-UHFFFAOYSA-N dimethyl-(phenylmethyl)-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethyl]ammonium Chemical compound C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 SIYLLGKDQZGJHK-UHFFFAOYSA-N 0.000 description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- 229940006461 iodide ion Drugs 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 2
- 125000002463 lignoceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000015654 memory Effects 0.000 description 2
- 125000002819 montanyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001802 myricyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
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- JDASKPRUFDKACZ-UHFFFAOYSA-M 1-octadecylpyridin-1-ium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 JDASKPRUFDKACZ-UHFFFAOYSA-M 0.000 description 1
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
- PLUHAVSIMCXBEX-UHFFFAOYSA-N azane;dodecyl benzenesulfonate Chemical compound N.CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 PLUHAVSIMCXBEX-UHFFFAOYSA-N 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- UMISEVUFAORUTM-UHFFFAOYSA-M benzyl-butyl-dimethylazanium;chloride Chemical compound [Cl-].CCCC[N+](C)(C)CC1=CC=CC=C1 UMISEVUFAORUTM-UHFFFAOYSA-M 0.000 description 1
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- PXFDQFDPXWHEEP-UHFFFAOYSA-M benzyl-dimethyl-octylazanium;chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(C)CC1=CC=CC=C1 PXFDQFDPXWHEEP-UHFFFAOYSA-M 0.000 description 1
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 description 1
- BNDXNEVHWSOJGV-UHFFFAOYSA-M benzyl-hexyl-dimethylazanium;chloride Chemical compound [Cl-].CCCCCC[N+](C)(C)CC1=CC=CC=C1 BNDXNEVHWSOJGV-UHFFFAOYSA-M 0.000 description 1
- 159000000004 beryllium salts Chemical class 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
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- YGGIZRRNXQJOTI-UHFFFAOYSA-M butyl(trimethyl)azanium;bromide Chemical compound [Br-].CCCC[N+](C)(C)C YGGIZRRNXQJOTI-UHFFFAOYSA-M 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical compound OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 159000000006 cesium salts Chemical class 0.000 description 1
- DVBJBNKEBPCGSY-UHFFFAOYSA-M cetylpyridinium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 DVBJBNKEBPCGSY-UHFFFAOYSA-M 0.000 description 1
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
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- 150000001879 copper Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 description 1
- PSLWZOIUBRXAQW-UHFFFAOYSA-M dimethyl(dioctadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC PSLWZOIUBRXAQW-UHFFFAOYSA-M 0.000 description 1
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- VUFOSBDICLTFMS-UHFFFAOYSA-M ethyl-hexadecyl-dimethylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)CC VUFOSBDICLTFMS-UHFFFAOYSA-M 0.000 description 1
- KSCHLNBLIAOANF-UHFFFAOYSA-M ethyl-hexadecyl-dimethylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC KSCHLNBLIAOANF-UHFFFAOYSA-M 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 1
- MZMRZONIDDFOGF-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.CCCCCCCCCCCCCCCC[N+](C)(C)C MZMRZONIDDFOGF-UHFFFAOYSA-M 0.000 description 1
- WJLUBOLDZCQZEV-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCC[N+](C)(C)C WJLUBOLDZCQZEV-UHFFFAOYSA-M 0.000 description 1
- YRBKSJIXFZPPGF-UHFFFAOYSA-N hexazine Chemical compound N1=NN=NN=N1 YRBKSJIXFZPPGF-UHFFFAOYSA-N 0.000 description 1
- JYVPKRHOTGQJSE-UHFFFAOYSA-M hexyl(trimethyl)azanium;bromide Chemical compound [Br-].CCCCCC[N+](C)(C)C JYVPKRHOTGQJSE-UHFFFAOYSA-M 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- GEOVEUCEIQCBKH-UHFFFAOYSA-N hypoiodous acid Chemical compound IO GEOVEUCEIQCBKH-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- SRPSOCQMBCNWFR-UHFFFAOYSA-N iodous acid Chemical compound OI=O SRPSOCQMBCNWFR-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical class C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002829 nitrogen Chemical group 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- XCOHAFVJQZPUKF-UHFFFAOYSA-M octyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](C)(C)C XCOHAFVJQZPUKF-UHFFFAOYSA-M 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- LLYCMZGLHLKPPU-UHFFFAOYSA-N perbromic acid Chemical compound OBr(=O)(=O)=O LLYCMZGLHLKPPU-UHFFFAOYSA-N 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- IDXKTTNFXPPXJY-UHFFFAOYSA-N pyrimidin-1-ium;chloride Chemical compound Cl.C1=CN=CN=C1 IDXKTTNFXPPXJY-UHFFFAOYSA-N 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 159000000005 rubidium salts Chemical class 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
- AQZSPJRLCJSOED-UHFFFAOYSA-M trimethyl(octyl)azanium;chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(C)C AQZSPJRLCJSOED-UHFFFAOYSA-M 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
Definitions
- the present invention relates to an aqueous etching composition, in particular an aqueous etching composition capable of selectively etching a layer containing copper or a copper alloy.
- the present invention also relates to an etching method using a specific aqueous etching composition and a method for manufacturing a semiconductor substrate.
- Patent Documents 1 and 2 etching solutions for etching layers containing copper, copper alloys, etc. are known (for example, Patent Documents 1 and 2).
- Patent Document 1 International Publication No. 2017/188108
- Patent Document 2 International Publication No. 2020/105605
- the present invention provides the aqueous etching composition shown below.
- An aqueous composition for etching comprising: Contains an oxidizer, an acid and a corrosion inhibitor; The aqueous composition has a pH of 0 or more and 3 or less. [2] 0.001 to 20% by mass of the oxidizing agent based on the total amount of the aqueous composition; 0.1 to 50% by mass of the acid based on the total amount of the aqueous composition; The aqueous composition according to [1] above, comprising 0.00001 to 5.0 mass% of the corrosion inhibitor based on the total amount of the aqueous composition.
- aqueous composition according to [1] above, wherein the corrosion inhibitor comprises at least one of (i) a nitrogen-containing heterocyclic compound, (ii) a cationic surfactant or salt, and (iii) an alkyl sulfate/sulfonate or a salt thereof.
- the content of the nitrogen-containing heterocyclic compound (i) is 0.01 to 5.0 mass% based on the total amount of the aqueous composition;
- the content of the (ii) cationic surfactant or its salt is 0.00001 to 0.2 mass% based on the total amount of the aqueous composition, or
- the (ii) cationic surfactant is represented by the following formula (4):
- R 6 is a substituted or unsubstituted alkyl group having 10 to 30 carbon atoms, a substituted or unsubstituted alkyl (poly)heteroalkylene group having 10 to 30 carbon atoms, or a substituted or unsubstituted aryl (poly)heteroalkylene group having 10 to 30 carbon atoms
- R 7 is independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms
- X ⁇ is a halide ion, a hydroxide ion, an organic sulfonate ion, a tetrafluoroborate anion, or a hexafluorophosphate anion.
- An etching method comprising the step of etching a copper-containing seed layer of a semiconductor substrate having the seed layer, using the aqueous composition according to any one of [1] to [10] above.
- a method for producing a semiconductor substrate comprising the step of etching a copper-containing seed layer of a semiconductor substrate, using the aqueous composition according to any one of [1] to [10] above.
- an aqueous composition that selectively etches layers containing copper, copper alloys, etc., and that is also effective in suppressing undercuts.
- an etching method and a method for manufacturing a semiconductor substrate that use the aqueous composition.
- FIG. 2 is a schematic diagram showing a side surface of a semiconductor substrate before etching treatment used in evaluation in Examples and Comparative Examples. 2 is an enlarged schematic view showing a part of the semiconductor substrate of FIG. 1; FIG. 1 is a diagram showing the amount of undercut generated by etching treatment in an example and a comparative example.
- aqueous etching composition of the present invention will be described in detail below, but the present invention is not limited thereto, and various modifications are possible without departing from the gist of the invention.
- the aqueous composition of the present invention contains at least an oxidizing agent, an acid, and a corrosion inhibitor, and the pH of the aqueous composition is not less than 0 and not more than 3.
- the aqueous composition preferably contains 0.001 to 20 mass % of an oxidizing agent based on the total amount of the aqueous composition, 0.1 to 50 mass % of an acid based on the total amount of the aqueous composition, and 0.00001 to 5.0 mass % of a corrosion inhibitor based on the total amount of the aqueous composition.
- the aqueous composition of the present invention contains one or more wiring materials selected from the group consisting of nickel and nickel alloys, and one or more wiring materials selected from the group consisting of tin, tin alloys, gold, and gold alloys, it is possible to selectively etch copper and copper alloys while suppressing the dissolution of these metals.
- nickel alloy is not particularly limited as long as it is made by adding one or more metal elements or nonmetal elements to nickel and has metallic properties. The same applies to "tin alloy", “gold alloy” and "copper alloy”.
- targets to be etched with the aqueous composition of the present invention include laminates of a layer mainly composed of copper and a layer mainly composed of nickel or a nickel alloy; and laminates including a layer mainly composed of copper, a layer mainly composed of nickel or a nickel alloy, and a layer mainly composed of tin, a tin alloy, gold or a gold alloy.
- the oxidizing agent is a component that mainly oxidizes copper.
- the oxidizing agent include peracids, halogen oxoacids, and salts thereof.
- the peracids include hydrogen peroxide, persulfuric acid, percarbonic acid, perphosphoric acid, peracetic acid, perbenzoic acid, and metachloroperbenzoic acid.
- halogen oxoacids examples include oxoacids of chlorine such as hypochlorous acid, chlorous acid, chloric acid, and perchloric acid; oxoacids of bromine such as hypobromous acid, bromous acid, bromic acid, and perbromic acid; and oxoacids of iodine such as hypoiodous acid, iodous acid, iodic acid, and periodic acid.
- the salt examples include alkali metal salts such as lithium salts, sodium salts, potassium salts, rubidium salts, and cesium salts of the above-mentioned peracids or halogen oxoacids; alkaline earth metal salts such as beryllium salts, magnesium salts, calcium salts, strontium salts, and barium salts of the above-mentioned peracids or halogen oxoacids; metal salts such as aluminum salts, copper salts, zinc salts, and silver salts of the above-mentioned peracids or halogen oxoacids; and ammonium salts of the above-mentioned peracids or halogen oxoacids.
- oxidizing agents hydrogen peroxide is preferred. In general, it is preferred to use an aqueous solution of hydrogen peroxide as an oxidizing agent in terms of availability and operability.
- the concentration of the oxidizing agent in the aqueous composition is preferably 0.001 to 20 mass% relative to the total mass of the aqueous composition, more preferably 0.1 to 10.0 mass%, even more preferably 0.02 to 5.0 mass%, and particularly preferably 0.1 to 3 mass%, 0.5 to 2.0 mass%, or 0.5 to 1.5 mass%, etc.
- An aqueous composition in which the concentration of the oxidizing agent is adjusted in this way can achieve a good etching rate and suppress unnecessary dissolution of the wiring material.
- the acid in the aqueous composition mainly acts as an etching agent for copper and copper alloys oxidized by the oxidizing agent.
- acids that can be used include phosphoric acids such as phosphoric acid (H 3 PO 4 ), phosphonic acid (H 3 PO 3 ), pyrophosphoric acid (H 4 P 2 O 7 ), and metaphosphoric acid (HPO 3 ); sulfuric acid, hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, and nitric acid.
- phosphoric acids, particularly phosphoric acid are preferably used.
- etching equipment exposed to nitric acid for a long period of time may become corroded
- the acid in the aqueous composition preferably contains 50% or more phosphoric acids or phosphoric acid based on the total mass of the acid, more preferably 70% or more phosphoric acids or phosphoric acid, and more preferably 90% or more phosphoric acids or phosphoric acid, and particularly preferably, phosphoric acids or phosphoric acid are used alone as the acid.
- the concentration of the acid in the aqueous composition is preferably 0.1 to 50% by mass, more preferably 1.0 to 30% by mass, even more preferably 3.0 to 20% by mass, and particularly preferably 5.0 to 10% by mass.
- An aqueous composition in which the acid concentration is adjusted within the above range can achieve a good etching rate while suppressing unnecessary dissolution of the wiring material.
- the corrosion inhibitor in the aqueous composition can effectively suppress corrosion, particularly galvanic corrosion, of a layer containing a metal that has a higher ionization tendency than copper, such as nickel, mainly by reacting with or adsorbing to the surface of copper, nickel, etc., and can also suppress undercutting, which is excessive etching of a layer containing copper, etc.
- the corrosion inhibitor preferably contains at least one of (i) a nitrogen-containing heterocyclic compound, (ii) a cationic surfactant, and (iii) an alkyl sulfuric acid/sulfonic acid or a salt thereof.
- the total concentration of the corrosion inhibitor in the aqueous composition is preferably 0.00001 to 5.0 mass% based on the total amount of the aqueous composition, more preferably 0.0001 to 3.0 mass%, even more preferably 0.0005 to 1.0 mass%, and particularly preferably 0.001 to 0.2 mass%.
- An aqueous composition in which the concentration of the corrosion inhibitor is adjusted to fall within the above range can effectively suppress corrosion, particularly galvanic corrosion, of layers containing metals such as nickel that have a higher ionization tendency than copper, and can also suppress undercutting, which is excessive etching of layers containing copper, etc.
- Nitrogen-containing heterocyclic compound preferably used as a corrosion inhibitor preferably contains at least a nitrogen-containing five-membered ring compound.
- the nitrogen-containing five-membered ring compound may have one or more substituents selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an amino group, and a substituted amino group having one or more substituents selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and a phenyl group.
- the nitrogen-containing heterocyclic compound may also contain a ring other than the nitrogen-containing five-membered ring, for example, an aliphatic ring having 5 to 30 carbon atoms, an aromatic ring having 6 to 30 carbon atoms, etc., and these rings may be condensed rings with the nitrogen-containing five-membered ring.
- the nitrogen-containing five-membered ring compound is, for example, one or more selected from the group consisting of pyrrole, pyrazole, imidazole, triazole, and tetrazole.
- the nitrogen-containing five-membered ring compound may be only one type, or two or more types may be combined.
- the nitrogen-containing five-membered ring compound is preferably represented by the following formula (1), formula (2) or formula (3):
- R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from the group consisting of (a) a hydrogen atom, (b) an alkyl group having 1 to 6 carbon atoms, (c) an amino group and (d) a substituted amino group having one or more substituents selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and a phenyl group, or R 2 and R 3 may be bonded to each other to form an aliphatic ring having 5 to 30 carbon atoms or an aromatic ring having 6 to 30 carbon atoms; R 4 and R 5 may be bonded to each other to form an aliphatic ring having 5 to 30 carbon atoms or an aromatic ring having 6 to 30 carbon atoms.
- the number of carbon atoms in the aliphatic ring is preferably 6 to 24, more preferably 6 to 16 or 8 to 12, and the number of carbon atoms in the aromatic ring is preferably 6 to 24, more preferably 6 to 16 or 8 to 12.
- alkyl group having 1 to 6 carbon atoms examples include linear or branched alkyl groups and cycloalkyl groups.
- linear or branched alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl groups.
- Examples of the cycloalkyl group include cycloalkyl groups having 3 to 6 carbon atoms, such as cyclopropyl, cyclopentyl, and cyclohexyl groups. Among these, methyl and ethyl groups are preferred, with methyl being particularly preferred.
- the substituted amino group is not particularly limited as long as it has one or more substituents selected from the group consisting of alkyl groups having 1 to 6 carbon atoms and phenyl groups.
- the alkyl groups having 1 to 6 carbon atoms are as described above.
- nitrogen-containing five-membered ring compound examples include 5-methyltetrazole, 5-aminotetrazole, 1,2,4-triazole, 1,2,3-triazole, and tetrazole.
- at least one selected from the group consisting of 1,2,4-triazole, 3-amino-1,2,4-triazole, 5-methyltetrazole, and 5-aminotetrazole is particularly preferred.
- pyrrole, pyrazole, and compounds containing the substituents represented by R 1 to R 5 in the ring skeleton of these compounds are also preferred.
- the nitrogen-containing heterocyclic compound is preferably a compound other than a nitrogen-containing five-membered ring compound, for example, a nitrogen-containing six-membered ring compound such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, tetrazine, pentazidine, hexazine, or a compound having the substituents represented by R 1 to R 5 in the ring skeleton of the compound.
- the nitrogen-containing heterocyclic compound (i) may be used alone or in combination of two or more kinds.
- the concentration of the nitrogen-containing heterocyclic compound (i) in the aqueous composition is, for example, 0.0001 to 5.0 mass% based on the total amount of the aqueous composition, preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, even more preferably 0.07 to 1.0 mass%, and particularly preferably 0.1 to 0.5 mass%.
- Cationic surfactant suitably used as a corrosion inhibitor preferably contains an alkyl group-containing quaternary ammonium hydroxide or a salt thereof, and an alkyl group-containing heteroaryl hydroxide or a salt thereof.
- a preferred example of the alkyl group-containing ammonium hydroxide or a salt thereof is represented by the following formula (4).
- R6 is a substituted or unsubstituted alkyl group having 4 to 30 carbon atoms, a substituted or unsubstituted alkyl (poly)heteroalkylene group having 4 to 30 carbon atoms, or a substituted or unsubstituted aryl (poly)heteroalkylene group having 4 to 30 carbon atoms.
- Alkyl groups having 4 to 30 carbon atoms are not particularly limited, but include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, docosyl, tetracosyl, hexacosyl, octacosyl, and triacontyl groups.
- the substituent is not particularly limited, but may include halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; aryl groups having 6 to 20 carbon atoms such as phenyl and naphthyl; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and propyloxy; hydroxyl groups; cyano groups; and nitro groups.
- the number of substituents may be one or more.
- a substituted alkyl group having 4 to 30 carbon atoms means that the total number of carbon atoms in the substituent and the number of carbon atoms in the alkyl group is 4 to 30.
- a substituted alkyl group having 4 to 30 carbon atoms may include an alkyl group having 4 or more carbon atoms (for example, an alkyl group having 4 to 13 carbon atoms such as a butyl group, a hexyl group, an octyl group, a decyl group, or a dodecyl group) so that the total number of carbon atoms in the substituent falls within the above-mentioned range.
- the alkyl (poly) heteroalkylene group having 4 to 30 carbon atoms is represented by -(C n H 2n -Z-) m -R 3.
- n is independently 1 to 5, preferably 1 to 3, and more preferably 1 to 2.
- m is 1 to 5, preferably 1 to 2.
- Z is independently an oxygen atom (O), a sulfur atom (S), or a phosphorus atom (P), and is preferably an oxygen atom (O).
- R 7 is an alkyl group having 1 to 30 carbon atoms, and examples of such groups include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an icosyl group.
- the substituent is not particularly limited, but includes halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; aryl groups having 6 to 20 carbon atoms such as phenyl group and naphthyl group; alkoxy groups having 1 to 6 carbon atoms such as methoxy group, ethoxy group, and propyloxy group; hydroxy group; cyano group; and nitro group.
- the substituent is usually substituted with the hydrogen atom of R 7.
- the number of the substituent may be one or more.
- the substituted alkyl(poly)heteroalkylene group having 4 to 30 carbon atoms means that the total number of carbon atoms of the substituent and the number of carbon atoms of the alkyl(poly)heteroalkylene group is 4 to 30.
- a substituted alkyl(poly)heteroalkylene group having 4 to 30 carbon atoms can include an alkyl(poly)heteroalkylene group having 4 or more carbon atoms (e.g., an alkyl group having 4 to 13 carbon atoms, such as a butyl group, a hexyl group, an octyl group, a decyl group, or a dodecyl group) so that the total carbon number of the substituents falls within the above-mentioned range.
- an alkyl(poly)heteroalkylene group having 4 or more carbon atoms e.g., an alkyl group having 4 to 13 carbon atoms, such as a butyl group, a hexyl group, an octyl group, a decyl group, or a dodecyl group
- An aryl(poly)heteroalkylene group having 4 to 30 carbon atoms is represented by -(C n H 2n -Z-) m -Ar.
- n is independently 1 to 5, preferably 1 to 3, and more preferably 1 to 2.
- m is 1 to 5, and preferably 1 to 2.
- Z is independently an oxygen atom (O), a sulfur atom (S), or a phosphorus atom (P), and is preferably an oxygen atom (O).
- Ar is an aryl group having 6 to 18 carbon atoms, and examples of such groups include a phenyl group, a naphthyl group, and an anthracenyl group.
- a substituted or unsubstituted aryl(poly)heteroalkylene group having 4 to 30 carbon atoms has a substituent (a substituted aryl(poly)heteroalkylene group having 4 to 30 carbon atoms)
- the substituent is not particularly limited, but includes halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, and 1,1,3,3-tetramethylbutyl group; alkoxy groups having 1 to 6 carbon atoms such as methoxy group, ethoxy group, and propyloxy group; hydroxy group; cyano group; and nitro group.
- the substituent is usually substituted with a hydrogen atom of Ar.
- the number of the substituent may be one or more.
- a substituted aryl(poly)heteroalkylene group having 4 to 30 carbon atoms means that the total number of carbon atoms of the substituent and the number of carbon atoms of the aryl(poly)heteroalkylene group is 4 to 30.
- a substituted aryl(poly)heteroalkylene group having 4 to 30 carbon atoms can include an aryl(poly)heteroalkylene group having 4 or more carbon atoms (e.g., an alkyl group having 4 to 13 carbon atoms, such as a butyl group, a hexyl group, an octyl group, a decyl group, or a dodecyl group) so that the total carbon number of the substituents falls within the above range.
- an alkyl group having 4 to 13 carbon atoms such as a butyl group, a hexyl group, an octyl group, a decyl group, or a dodecyl group
- R 6 is preferably a substituted or unsubstituted alkyl(poly)heteroalkylene group having 4 to 30 carbon atoms, or a substituted or unsubstituted aryl(poly)heteroalkylene group having 4 to 30 carbon atoms, more preferably a substituted or unsubstituted aryl(poly)heteroalkylene group having 6 to 20 carbon atoms, even more preferably a substituted or unsubstituted aryl(poly)heteroalkylene group having 8 to 20 carbon atoms, particularly preferably a substituted or unsubstituted aryl(poly)heteroalkylene group having 10 to 18 carbon atoms, and most preferably a p-(1,1,3,3-tetramethylbutyl)phenyldi(oxyethylene) (p-CH 3 C(CH 3 ) 2 CH 2 C(CH 3 ) 2 -Ph-(O-C 2 H 4
- R 6 is preferably a substituted or unsubstituted alkyl group having 4 to 25 carbon atoms or a substituted or unsubstituted aryl (poly)heteroalkylene group having 4 to 25 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 6 to 20 carbon atoms or a substituted or unsubstituted aryl (poly)heteroalkylene group having 6 to 20 carbon atoms, and further preferably a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, or a p-(1,1,3,3-tetramethylbutyl)phenyldi(oxyethylene) (p-CH 3 C(CH 3 ) 2 CH 2 C(CH 3 ) 2 -Ph-(O-C 2 H 4 ) 2 -) group, and more preferably a hex
- each R 7 is independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
- Alkyl groups having 1 to 30 carbon atoms include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, nonadecyl, and icosyl groups.
- a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms has a substituent (a substituted alkyl group having 1 to 30 carbon atoms)
- substituents include halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; aryl groups having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; alkoxy groups having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, and a propyloxy group; a hydroxy group; a cyano group; and a nitro group.
- the number of substituents may be one or more.
- a substituted alkyl group having 1 to 30 carbon atoms means that the total number of carbon atoms in the substituent and the alkyl group is 1 to 30.
- Aryl groups having 6 to 30 carbon atoms include, but are not limited to, phenyl groups, naphthyl groups, biphenyl groups, etc.
- a substituted or unsubstituted aryl group having 6 to 30 carbon atoms has a substituent (a substituted aryl group having 6 to 30 carbon atoms)
- substituents include halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl, and isopropyl; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and propyloxy; hydroxyl groups; cyano groups; and nitro groups.
- the number of substituents may be one or more.
- a substituted aryl group having 6 to 30 carbon atoms means that the total number of carbon atoms in the substituent and the number of carbon atoms in the alkyl group is 6 to 30.
- R 7 is preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, a benzyl group, a hydroxymethyl group, or a 2-hydroxyethyl group, even more preferably a methyl group, an ethyl group, a benzyl group, or a 2-hydroxyethyl group, particularly preferably a methyl group or a benzyl group, and most preferably a methyl group.
- R 7 is preferably an alkyl group having 1 to 10 carbon atoms substituted with an aryl group having 6 to 20 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms substituted with a phenyl group, even more preferably a benzyl group or a phenylethyl group, and particularly preferably a benzyl group.
- X is a halide ion (fluoride ion, chloride ion, bromide ion, iodide ion, etc.), hydroxide ion, organic sulfonate ion (methanesulfonate ion, p-toluenesulfonate ion, etc.), tetrafluoroborate anion, or hexafluorophosphate anion.
- X is preferably a halide ion, and more preferably a chloride ion or bromide ion.
- ammonium salt represented by formula (1) in which R 6 is a substituted or unsubstituted alkyl group having 4 to 30 carbon atoms include ammonium salts having a butyl group, such as butyltrimethylammonium bromide and benzyldimethylbutylammonium chloride; ammonium salts having a hexyl group, such as hexyltrimethylammonium bromide and benzyldimethylhexylammonium chloride; ammonium salts having an octyl group, such as octyltrimethylammonium bromide and benzyldimethyloctylammonium chloride; ammonium salts having a decyl group, such as decyltrimethylammonium bromide and benzyldimethyldecylammonium chloride; ammonium salts having a dodecyl group, such as dodecyltrimethylammonium
- ammonium salt represented by formula (1) in which R 6 is a substituted or unsubstituted alkyl(poly)heteroalkylene group having 4 to 30 carbon atoms include trimethylpropyldi(oxyethylene)ammonium chloride, trimethylpropyloxyethylenethioethyleneammonium chloride, and the like.
- ammonium salt represented by formula (1) in which R 6 is a substituted or unsubstituted aryl(poly)heteroalkylene group having 4 to 30 carbon atoms include benzyldimethyl-2- ⁇ 2-[4-(1,1,3,3-tetramethylbutyl)phenoxy]ethoxy ⁇ ethylammonium chloride (benzethonium chloride) and benzyldimethylphenyldi(oxyethylene)ammonium chloride.
- the ammonium salt represented by the above formula (1) is preferably such that R 6 is a substituted or unsubstituted aryl (poly)heteroalkylene group having 4 to 30 carbon atoms, and at least one of the R 7 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, more preferably such that R 6 is a substituted or unsubstituted aryl (poly)heteroalkylene group having 8 to 20 carbon atoms, and at least one of the R 7 is a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, even more preferably such that R 6 is a substituted or unsubstituted aryl (poly)heteroalkylene group having 10 to 18 carbon atoms, and at least one of the R 7 is a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and particularly preferably benzyldimethyl-2- ⁇
- heteroaryl salts having a substituted or unsubstituted alkyl group having 4 to 30 carbon atoms include, but are not limited to, salts of heteroaryl cations in which at least one nitrogen atom in a substituted or unsubstituted nitrogen atom-containing heteroaryl ring is bonded to a substituted or unsubstituted alkyl group having 4 to 30 carbon atoms.
- the nitrogen atom-containing heteroaryl ring is not particularly limited, but examples thereof include imidazole, pyrazole, oxazole, isoxazole (isoxazole), thiazole, isothiazole, pyridine, pyrazine, pyridazine, pyrimidine, quinoline, and isoquinoline rings.
- the nitrogen atom-containing heteroaryl ring has a substituent
- substituents include halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, and isopropyl groups; aryl groups having 6 to 20 carbon atoms such as phenyl and naphthyl groups; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and propyloxy groups; hydroxy groups; cyano groups; and nitro groups.
- halogen atoms such as fluorine, chlorine, bromine, and iodine atoms
- alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, and isopropyl groups
- aryl groups having 6 to 20 carbon atoms such as phenyl and naphthyl groups
- Alkyl groups having 4 to 30 carbon atoms are not particularly limited, but include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, docosyl, tetracosyl, hexacosyl, octacosyl, and triacontyl groups.
- a substituted or unsubstituted alkyl group having 4 to 30 carbon atoms has a substituent (a substituted alkyl group having 4 to 30 carbon atoms)
- substituents include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, and isopropyl; aryl groups having 6 to 20 carbon atoms such as phenyl and naphthyl; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and propyloxy; hydroxyl groups; cyano groups; and nitro groups.
- the number of substituents may be one or more.
- a substituted alkyl group having 4 to 30 carbon atoms means that the total number of carbon atoms in the substituent and the number of carbon atoms in the alkyl group is 4 to 30.
- a substituted alkyl group having 4 to 30 carbon atoms can include an alkyl group having 4 or more carbon atoms (for example, an alkyl group having 4 to 13 carbon atoms such as a butyl group, a hexyl group, an octyl group, a decyl group, and a dodecyl group) so that the total number of carbon atoms in the substituent falls within the above-mentioned range.
- the substituted or unsubstituted alkyl group having 4 to 30 carbon atoms is preferably a substituted or unsubstituted alkyl group having 8 to 20 carbon atoms, more preferably an alkyl group having 12 to 18 carbon atoms, even more preferably a dodecyl group, a tetradecyl group, a hexadecyl group, or an octadecyl group, and from the viewpoint of suppressing undercut, a dodecyl group, a tetradecyl group, or a hexadecyl group is particularly preferable.
- the counter anion of a heteroaryl cation having a substituted or unsubstituted alkyl group having 4 to 30 carbon atoms is not particularly limited, but examples thereof include halide ions such as fluoride ion, chloride ion, bromide ion, and iodide ion; hydroxide ion; organic sulfonate ions such as methanesulfonate ion and p-toluenesulfonate ion; tetrafluoroborate anion; and hexafluorophosphate anion.
- the counter anion is preferably a halide ion, and more preferably a chloride ion or bromide ion.
- heteroaryl salts having a substituted or unsubstituted alkyl group having 4 to 30 carbon atoms include 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium bromide, 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium bromide, 1-octyl-3-methylimidazolium chloride, 1-octyl-3-methylimidazolium bromide, 1-decyl-3-methylimidazolium chloride, 1-decyl-3-methylimidazolium bromide, 1-dodecyl-3-methylimidazolium chloride, 1-dodecyl-3-methylimidazolium bromide, 1-tetradecyl-3-methylimidazolium chloride, 1-tetradecyl-3-methylimidazolium bromide, 1-hexadecane, 1- ...
- Imidazolium salts such as 1-hexyl-3-methylimidazolium chloride, 1-hexadecyl-3-methylimidazolium bromide, 1-octadecyl 3-methylimidazolium chloride, and 1-octadecyl 3-methylimidazolium bromide;
- oxazolium salts such as 3-butyloxazolium chloride, 3-hexyloxazolium chloride, 3-octyloxazolium chloride, 3-decyloxazolium chloride, 3-dodecyloxazolium chloride, 3-tetradecyloxazolium chloride, 3-hexadecyloxazolium chloride, and 3-octadecyloxazolium chloride; 3-butylthiazolium chloride, 3-hexylthiazolium chloride, 3-octylthiazolium chloride, 3-decylthiazolium chloride, and 3-dodecylthi
- the (ii) cationic surfactant is preferably an ammonium salt represented by formula (4) (wherein R 6 is a substituted or unsubstituted alkyl group having 8 to 20 carbon atoms, or a substituted or unsubstituted aryl (poly)heteroalkylene group having 8 to 20 carbon atoms), an imidazolium salt having a substituted or unsubstituted alkyl group having 8 to 20 carbon atoms, or a pyridinium salt having a substituted or unsubstituted alkyl group having 8 to 20 carbon atoms; more preferably an ammonium salt represented by formula (4) (wherein R 6 is a substituted or unsubstituted aryl (poly)heteroalkylene group having 12 to 20 carbon atoms, and at least one of R 7 is a substituted or unsubstituted aryl group having 6 to 12 carbon atoms), an imidazolium salt having a substituted
- the cationic surfactant or its salt preferably includes at least one selected from the group consisting of an ammonium salt represented by formula (4) (wherein R 6 is a substituted or unsubstituted alkyl group having 10 to 20 carbon atoms, or a substituted or unsubstituted aryl (poly)heteroalkylene group having 10 to 20 carbon atoms), an imidazolium salt having a substituted or unsubstituted alkyl group having 10 to 20 carbon atoms, and a pyridinium salt having a substituted or unsubstituted alkyl group having 10 to 20 carbon atoms, and more preferably includes at least one selected from the group consisting of an ammonium salt represented by formula (4) (wherein R 6 is a substituted or unsubstituted ary
- cationic surfactants include dodecylpyridinium chloride, benzyldimethylhexadecylammonium chloride, benzethonium chloride, 1-hexadecyl-3-methylimidazolium chloride, and octyltrimethylammonium chloride.
- the cationic surfactant may be one type only, or two or more types may be combined.
- the concentration of (ii) the cationic surfactant or its salt in the aqueous composition is, for example, 0.00001 to 0.2 mass%, preferably 0.0001 to 0.1 mass%, more preferably 0.0005 to 0.08 mass%, even more preferably 0.0007 to 0.03 mass%, and particularly preferably 0.001 to 0.01 mass%, based on the total amount of the aqueous composition.
- alkyl Sulfuric Acid/Sulfonic Acid or Salt thereof Although there are no particular limitations on the type of (iii) alkyl sulfuric acid/sulfonic acid or salt thereof (hereinafter also referred to as alkyl sulfuric acid/alkyl sulfonic acid, etc.) in the aqueous composition, it is preferable that the aqueous composition contains an alkyl sulfuric acid/alkyl sulfonic acid, etc. having an alkyl group having at least 6 to 30 carbon atoms. (iii) The alkyl sulfate/alkyl sulfonate etc.
- aryl group having 6 to 20 carbon atoms may have an aryl group having 6 to 20 carbon atoms, preferably has an alkyl group having 8 to 20 carbon atoms and/or an aryl group having 6 to 16 carbon atoms, and more preferably has an alkyl group having 10 to 16 carbon atoms and/or an aryl group having 6 to 12 carbon atoms.
- alkyl sulfates/sulfonic acids or their salts include dodecyl sulfate, sodium dodecyl sulfate, ammonium dodecyl sulfate, dodecylbenzenesulfonic acids such as 4-dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, and ammonium dodecylbenzenesulfonate.
- the alkyl sulfates/alkyl sulfonic acids, etc. may be of one type only, or may be of two or more types in combination.
- the concentration of (iii) alkyl sulfate/alkyl sulfonate, etc. in the aqueous composition is, for example, 0.001 to 2.0 mass% based on the total amount of the aqueous composition, preferably 0.002 to 1.0 mass%, preferably 0.005 to 0.5 mass%, more preferably 0.007 to 0.05 mass%, even more preferably 0.007 to 0.03 mass%, and particularly preferably 0.008 to 0.02 mass%.
- the aqueous composition may contain, as additives (D), hydrogen peroxide stabilizers, organic solvents, surfactants other than cationic surfactants and alkyl sulfates/sulfonic acids or salts thereof, chelating agents, antifoaming agents, acids other than (B), alkalis, silicon-containing compounds, etc.
- additives (D) hydrogen peroxide stabilizers, organic solvents, surfactants other than cationic surfactants and alkyl sulfates/sulfonic acids or salts thereof, chelating agents, antifoaming agents, acids other than (B), alkalis, silicon-containing compounds, etc.
- hydrogen peroxide stabilizers known ones such as alcohols, urea, phenylurea, organic carboxylic acids, organic phosphonic acids, and organic phosphoric acids may be appropriately added.
- the aqueous composition of the present invention may contain water and, as necessary, one or more of various additives that are commonly used in other aqueous compositions, within a range that does not impair the effects of the aqueous composition of the present invention.
- the water is preferably water from which metal ions, organic impurities, particles, etc. have been removed by distillation, ion exchange treatment, filtration, various adsorption treatments, etc., and is more preferably pure water, and particularly preferably ultrapure water.
- the content of water in the aqueous composition is appropriately adjusted depending on the contents of other components in the aqueous composition, and is not particularly limited, but is, for example, 70 to 99 mass%, preferably 75 to 98 mass%, and more preferably 85 to 95 mass% based on the total mass of the aqueous composition.
- the aqueous composition is preferably a solution and preferably does not contain solid particles such as abrasive particles.
- the total content of the oxidizing agent (component (A)), the acid (component (B)), the corrosion inhibitor (component (C)) and water, or the total content of these plus the additive (component (D)), is preferably 70 to 100% by mass, more preferably 85 to 100% by mass, even more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass, based on the total mass of the aqueous composition.
- the pH range of the aqueous composition is 0.0 or more and 3.0 or less, and the pH is preferably 0.3 to 3.0, more preferably 0.5 to 2.0, even more preferably 0.7 to 1.8, and particularly preferably 0.7 to 1.4.
- the aqueous composition has an excellent effect of suppressing undercut. Specifically, it can efficiently prevent undercut, which is mainly caused by excessive etching of the ends of a seed layer that contains copper or a copper alloy and is formed on the underside of a plating layer containing a metal with a greater ionization tendency than copper, such as nickel or a nickel alloy, i.e., on the substrate side, and is essentially made of a copper alloy.
- the aqueous composition can be prepared by uniformly stirring the components (A), (B), (C), (D), and water, and, if necessary, other components.
- the method of stirring these components is not particularly limited, and any stirring method commonly used in the preparation of aqueous compositions can be used.
- the aqueous composition can be used for etching copper and copper alloys.
- materials for processes using bumps include at least one selected from the group consisting of nickel and nickel alloys, and optionally at least one selected from the group consisting of tin, tin alloys, gold and gold alloys
- the aqueous composition can be suitably used as an aqueous composition for selectively etching at least one selected from copper and copper alloys while suppressing dissolution of these metals.
- the etching method of the present invention is a method mainly for semiconductor substrates, and includes a step of etching a seed layer of an intermediate product having a copper-containing seed layer of a semiconductor substrate using the above-mentioned aqueous composition.
- the semiconductor substrate to be etched by the etching method is preferably laminated in contact with the above-mentioned seed layer and has a layer containing a metal having a higher ionization tendency than copper above the seed layer.
- the temperature at which the aqueous composition is used in the etching process there are no particular limitations on the temperature at which the aqueous composition is used in the etching process, but a temperature of 10 to 50°C is preferred, more preferably 20 to 45°C, and even more preferably 25 to 40°C. If the temperature of the aqueous composition is 10°C or higher, the etching rate is good, resulting in excellent production efficiency. On the other hand, if the temperature of the aqueous composition is 50°C or lower, changes in the liquid composition can be suppressed and the etching conditions can be kept constant. Increasing the temperature of the aqueous composition increases the etching rate, but the optimal processing temperature can be determined appropriately, taking into consideration factors such as minimizing changes in the composition of the aqueous composition (decomposition of hydrogen peroxide).
- the processing time may be appropriately selected depending on various conditions such as the surface condition of the object to be etched, the concentration of the aqueous composition, the temperature, and the processing method.
- the processing time can be the moment when the color of the seed layer disappears and it can be determined that only the area overlapping with the plating layer remains (just etching time (JET)).
- the method of contacting the aqueous composition with the etching target is not particularly limited.
- a wet etching method such as a method of contacting the aqueous composition with the etching target by dropping (single-wafer spin processing) or spraying, or a method of immersing the etching target in the aqueous composition, can be used. Either method may be used in the present invention.
- the method for producing a semiconductor substrate of the present invention includes at least the etching step described above.
- the method for producing a semiconductor substrate may further include the following steps. That is, a step of preparing a semiconductor substrate having a copper seed layer on a surface thereof, the copper seed layer including one or more selected from the group consisting of copper and copper alloys; forming a resist pattern having an opening pattern exposing a portion of the copper seed layer; forming, in this order, a metal layer A containing one or more selected from the group consisting of nickel and nickel alloys, and a metal layer B containing one or more selected from the group consisting of tin, tin alloys, gold and gold alloys, on a surface of the copper seed layer exposed in the openings of the opening pattern of the resist pattern; and removing the resist pattern.
- the method for manufacturing a semiconductor substrate essentially includes a step of contacting an exposed portion of the copper seed layer, which is produced in the step of removing the resist pattern and in which metal layer A and metal layer B are not formed, with an aqueous composition to etch the exposed portion of the copper seed layer.
- Example 1 (A) hydrogen peroxide (H 2 O 2 ), (B) phosphoric acid as an inorganic acid, and (C) 1,2,4-triazole as a corrosion inhibitor were added to pure water and stirred to produce a semiconductor substrate cleaning composition. At this time, the addition rates of hydrogen peroxide, phosphoric acid, and 1,2,4-triazole were 0.75 mass%, 8 mass%, and 0.2 mass%, respectively, relative to the total mass of the semiconductor substrate cleaning composition.
- the pH of the semiconductor substrate cleaning composition was 0.9.
- the pH of the pretreatment agent was measured at 23° C. using a tabletop pH meter (F-71) and a pH electrode (9615S-10D) manufactured by Horiba, Ltd.
- Examples 2 to 13, Comparative Example 1 and Reference Example 1 The aqueous compositions of Examples 2 to 13, Comparative Example 1, and Reference Example 1 were produced in the same manner as in Example 1, except for changing the components to be added as shown in Table 1 below.
- a semiconductor substrate 10 having the structure shown in Fig. 1 was used as an evaluation substrate.
- the semiconductor substrate 10 includes an upper SnAg layer 14, a Ni layer 16 laminated below the SnAg layer 14, and a Cu layer 12 laminated below the Ni layer 16. Furthermore, in the semiconductor substrate 10, a Ti layer 18 is laminated below the Cu layer 12, and the Ti layer 18 is provided on a substrate 20.
- Fig. 1 and Fig. 2 which is an enlarged view of the area enclosed by the dashed square in Fig.
- a semiconductor substrate 10 was used which was provided with a Cu layer 12 (thickness: 0.2 ⁇ m) as a seed layer, a SnAg layer 14 (thickness: 6 ⁇ m) as an upper metal layer, a Ni layer 16 (thickness: 3 ⁇ m) as a lower metal layer (plating layer), and a Ti layer 18 (thickness: 0.1 ⁇ m) as a barrier metal layer.
- the diameter of the cylindrical bump shown in Fig. 1 was 12.5 ⁇ m, and the height was 9 ⁇ m.
- the evaluation sample was cut into a size of 1 cm x 1 cm (immersion treatment area: 1 cm 2 ). Next, the evaluation sample was immersed in 50 g of the aqueous composition for etching semiconductor substrates produced in each of Examples 1 to 13, Comparative Example 1, and Reference Example 1 at 25°C for a predetermined time while stirring with a stirrer at 350 rpm. During the immersion treatment, the evaluation sample was held with tweezers and placed above the stirrer.
- the aqueous composition of the present invention can be suitably used in forming wiring on a semiconductor substrate. According to a preferred embodiment of the present invention, the aqueous composition can suppress dissolution of wiring materials including nickel and nickel alloys, selectively etch copper and copper alloys, and prevent undercut of a seed layer of copper and copper alloys.
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Abstract
According to the present invention, it is possible to provide an aqueous composition for etching, the aqueous composition comprising an oxidizing agent, an acid, and a corrosion inhibitor, and having a pH of 0 to 3. The aqueous composition according to an aspect of the present invention preferably includes, with respect to the total amount of the aqueous composition: 0.001-20 mass% of the oxidizing agent; 0.1-50 mass% of the acid; and 0.00001-5.0 mass% of the corrosion inhibitor.
Description
本発明は、エッチング用水性組成物、特に、銅または銅合金を含む層を選択的にエッチング可能なエッチング用の水性組成物に関する。また、本発明は、所定のエッチング用の水性組成物を用いたエッチング方法及び半導体基板の製造方法に関する。
The present invention relates to an aqueous etching composition, in particular an aqueous etching composition capable of selectively etching a layer containing copper or a copper alloy. The present invention also relates to an etching method using a specific aqueous etching composition and a method for manufacturing a semiconductor substrate.
半導体基板の配線形成において、銅、銅合金などを含む層をエッチングするためのエッチング液が知られている（例えば、特許文献１および２）。
In forming wiring on a semiconductor substrate, etching solutions for etching layers containing copper, copper alloys, etc. are known (for example, Patent Documents 1 and 2).
特許文献１：国際公開第２０１７／１８８１０８号
特許文献２：国際公開第２０２０／１０５６０５号 Patent Document 1: International Publication No. 2017/188108 Patent Document 2: International Publication No. 2020/105605
特許文献２：国際公開第２０２０／１０５６０５号 Patent Document 1: International Publication No. 2017/188108 Patent Document 2: International Publication No. 2020/105605
従来のエッチング液を用いると、例えば、バンプ構造を有する半導体基板の銅、銅合金などを含む層の主として端部などが過剰にエッチングされ、アンダーカットが生じるといった問題が生じ得る。そこで、銅を含む層を選択的にエッチング可能であり、なおかつアンダーカットを抑制する性能に優れたエッチング用の水性組成物の提供が求められている。
When conventional etching solutions are used, problems can arise, such as excessive etching of layers containing copper or copper alloys on semiconductor substrates having bump structures, mainly at the edges, resulting in undercuts. There is therefore a demand for an aqueous etching composition that is capable of selectively etching layers containing copper and that also has excellent performance in suppressing undercuts.
本発明者らは、上記課題について鋭意検討した結果、以下に示すエッチング用水性組成物が、上記課題を解決し得ることを見出した。本発明は、以下に示すエッチング用の水性組成物等を提供する。
As a result of intensive research into the above-mentioned problems, the inventors have found that the aqueous etching composition shown below can solve the above-mentioned problems. The present invention provides the aqueous etching composition shown below.
［１］エッチング用の水性組成物であって、
酸化剤、酸及び腐食抑制剤を含み、
前記水性組成物のｐＨが０以上かつ３以下である、水性組成物。
［２］前記水性組成物の全量基準で０．００１～２０質量％の前記酸化剤と、
前記水性組成物の全量基準で０．１～５０質量％の前記酸と、
前記水性組成物の全量基準で０．００００１～５．０質量％の前記腐食抑制剤とを含む、上記［１］に記載の水性組成物。
［３］前記腐食抑制剤が、（ｉ）含窒素複素環化合物、（ｉｉ）カチオン性界面活性剤または塩及び（ｉｉｉ）アルキル硫酸／スルホン酸またはその塩の少なくともいずれかを含む、上記［１］に記載の水性組成物。
［４］前記（ｉ）含窒素複素環化合物の含有量が、前記水性組成物の全量基準で０．０１～５．０質量％であり、
前記（ｉｉ）カチオン性界面活性剤またはその塩の含有量が、前記水性組成物の全量基準で０．００００１～０．２質量％であり、又は、
前記（ｉｉｉ）アルキル硫酸／スルホン酸またはその塩の含有量が、前記水性組成物の全量基準で０．００１～２．０質量％である、上記［３］に記載の水性組成物。
［５］前記（ｉ）含窒素複素環式化合物が、少なくとも含窒素５員環化合物を含む、上記［３］に記載の水性組成物。
［６］前記（ｉｉ）カチオン性界面活性剤が、下記式（４）：
（上記式（４）中、
Ｒ６は、炭素数１０～３０の置換もしくは非置換アルキル基、炭素数１０～３０の置換もしくは非置換アルキル（ポリ）ヘテロアルキレン基、または炭素数１０～３０の置換もしくは非置換アリール（ポリ）ヘテロアルキレン基であり、
Ｒ７は、それぞれ独立して、炭素数１～３０の置換もしくは非置換アルキル基、または炭素数６～３０の置換もしくは非置換アリール基であり、
Ｘ－は、ハロゲン化物イオン、水酸化物イオン、有機スルホン酸イオン、テトラフルオロボレートアニオン、またはヘキサフルオロフォスファートアニオンである）
で表されるアンモニウム塩、および
炭素数１０～３０の置換もしくは非置換アルキル基を有するヘテロアリール塩からなる群から選択される少なくとも１つを含む、上記［３］に記載の水性組成物。
［７］前記（ｉｉｉ）アルキル硫酸／スルホン酸またはその塩が、少なくとも炭素数６～３０のアルキル基を有する、上記［３］に記載の水性組成物。
［８］前記酸が、硝酸を除く無機酸を含む、上記［１］に記載の水性組成物。
［９］前記酸が、少なくともリン酸を含む、上記［８］に記載の水性組成物。
［１０］前記酸化剤が、少なくとも過酸化水素を含む、上記［１］に記載の水性組成物。 [1] An aqueous composition for etching, comprising:
Contains an oxidizer, an acid and a corrosion inhibitor;
The aqueous composition has a pH of 0 or more and 3 or less.
[2] 0.001 to 20% by mass of the oxidizing agent based on the total amount of the aqueous composition;
0.1 to 50% by mass of the acid based on the total amount of the aqueous composition;
The aqueous composition according to [1] above, comprising 0.00001 to 5.0 mass% of the corrosion inhibitor based on the total amount of the aqueous composition.
[3] The aqueous composition according to [1] above, wherein the corrosion inhibitor comprises at least one of (i) a nitrogen-containing heterocyclic compound, (ii) a cationic surfactant or salt, and (iii) an alkyl sulfate/sulfonate or a salt thereof.
[4] The content of the nitrogen-containing heterocyclic compound (i) is 0.01 to 5.0 mass% based on the total amount of the aqueous composition;
The content of the (ii) cationic surfactant or its salt is 0.00001 to 0.2 mass% based on the total amount of the aqueous composition, or
The aqueous composition according to [3] above, wherein the content of the (iii) alkyl sulfuric acid/sulfonic acid or a salt thereof is 0.001 to 2.0% by mass based on the total amount of the aqueous composition.
[5] The aqueous composition according to the above [3], wherein the nitrogen-containing heterocyclic compound (i) contains at least a nitrogen-containing five-membered ring compound.
[6] The (ii) cationic surfactant is represented by the following formula (4):
(In the above formula (4),
R 6 is a substituted or unsubstituted alkyl group having 10 to 30 carbon atoms, a substituted or unsubstituted alkyl (poly)heteroalkylene group having 10 to 30 carbon atoms, or a substituted or unsubstituted aryl (poly)heteroalkylene group having 10 to 30 carbon atoms;
R 7 is independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms;
X − is a halide ion, a hydroxide ion, an organic sulfonate ion, a tetrafluoroborate anion, or a hexafluorophosphate anion.
and heteroaryl salts having a substituted or unsubstituted alkyl group having 10 to 30 carbon atoms.
[7] The aqueous composition according to the above [3], wherein the (iii) alkyl sulfuric acid/sulfonic acid or salt thereof has an alkyl group having at least 6 to 30 carbon atoms.
[8] The aqueous composition described in [1] above, wherein the acid includes an inorganic acid other than nitric acid.
[9] The aqueous composition described in [8] above, wherein the acid includes at least phosphoric acid.
[10] The aqueous composition described in [1] above, wherein the oxidizing agent contains at least hydrogen peroxide.
酸化剤、酸及び腐食抑制剤を含み、
前記水性組成物のｐＨが０以上かつ３以下である、水性組成物。
［２］前記水性組成物の全量基準で０．００１～２０質量％の前記酸化剤と、
前記水性組成物の全量基準で０．１～５０質量％の前記酸と、
前記水性組成物の全量基準で０．００００１～５．０質量％の前記腐食抑制剤とを含む、上記［１］に記載の水性組成物。
［３］前記腐食抑制剤が、（ｉ）含窒素複素環化合物、（ｉｉ）カチオン性界面活性剤または塩及び（ｉｉｉ）アルキル硫酸／スルホン酸またはその塩の少なくともいずれかを含む、上記［１］に記載の水性組成物。
［４］前記（ｉ）含窒素複素環化合物の含有量が、前記水性組成物の全量基準で０．０１～５．０質量％であり、
前記（ｉｉ）カチオン性界面活性剤またはその塩の含有量が、前記水性組成物の全量基準で０．００００１～０．２質量％であり、又は、
前記（ｉｉｉ）アルキル硫酸／スルホン酸またはその塩の含有量が、前記水性組成物の全量基準で０．００１～２．０質量％である、上記［３］に記載の水性組成物。
［５］前記（ｉ）含窒素複素環式化合物が、少なくとも含窒素５員環化合物を含む、上記［３］に記載の水性組成物。
［６］前記（ｉｉ）カチオン性界面活性剤が、下記式（４）：
Ｒ６は、炭素数１０～３０の置換もしくは非置換アルキル基、炭素数１０～３０の置換もしくは非置換アルキル（ポリ）ヘテロアルキレン基、または炭素数１０～３０の置換もしくは非置換アリール（ポリ）ヘテロアルキレン基であり、
Ｒ７は、それぞれ独立して、炭素数１～３０の置換もしくは非置換アルキル基、または炭素数６～３０の置換もしくは非置換アリール基であり、
Ｘ－は、ハロゲン化物イオン、水酸化物イオン、有機スルホン酸イオン、テトラフルオロボレートアニオン、またはヘキサフルオロフォスファートアニオンである）
で表されるアンモニウム塩、および
炭素数１０～３０の置換もしくは非置換アルキル基を有するヘテロアリール塩からなる群から選択される少なくとも１つを含む、上記［３］に記載の水性組成物。
［７］前記（ｉｉｉ）アルキル硫酸／スルホン酸またはその塩が、少なくとも炭素数６～３０のアルキル基を有する、上記［３］に記載の水性組成物。
［８］前記酸が、硝酸を除く無機酸を含む、上記［１］に記載の水性組成物。
［９］前記酸が、少なくともリン酸を含む、上記［８］に記載の水性組成物。
［１０］前記酸化剤が、少なくとも過酸化水素を含む、上記［１］に記載の水性組成物。 [1] An aqueous composition for etching, comprising:
Contains an oxidizer, an acid and a corrosion inhibitor;
The aqueous composition has a pH of 0 or more and 3 or less.
[2] 0.001 to 20% by mass of the oxidizing agent based on the total amount of the aqueous composition;
0.1 to 50% by mass of the acid based on the total amount of the aqueous composition;
The aqueous composition according to [1] above, comprising 0.00001 to 5.0 mass% of the corrosion inhibitor based on the total amount of the aqueous composition.
[3] The aqueous composition according to [1] above, wherein the corrosion inhibitor comprises at least one of (i) a nitrogen-containing heterocyclic compound, (ii) a cationic surfactant or salt, and (iii) an alkyl sulfate/sulfonate or a salt thereof.
[4] The content of the nitrogen-containing heterocyclic compound (i) is 0.01 to 5.0 mass% based on the total amount of the aqueous composition;
The content of the (ii) cationic surfactant or its salt is 0.00001 to 0.2 mass% based on the total amount of the aqueous composition, or
The aqueous composition according to [3] above, wherein the content of the (iii) alkyl sulfuric acid/sulfonic acid or a salt thereof is 0.001 to 2.0% by mass based on the total amount of the aqueous composition.
[5] The aqueous composition according to the above [3], wherein the nitrogen-containing heterocyclic compound (i) contains at least a nitrogen-containing five-membered ring compound.
[6] The (ii) cationic surfactant is represented by the following formula (4):
R 6 is a substituted or unsubstituted alkyl group having 10 to 30 carbon atoms, a substituted or unsubstituted alkyl (poly)heteroalkylene group having 10 to 30 carbon atoms, or a substituted or unsubstituted aryl (poly)heteroalkylene group having 10 to 30 carbon atoms;
R 7 is independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms;
X − is a halide ion, a hydroxide ion, an organic sulfonate ion, a tetrafluoroborate anion, or a hexafluorophosphate anion.
and heteroaryl salts having a substituted or unsubstituted alkyl group having 10 to 30 carbon atoms.
[7] The aqueous composition according to the above [3], wherein the (iii) alkyl sulfuric acid/sulfonic acid or salt thereof has an alkyl group having at least 6 to 30 carbon atoms.
[8] The aqueous composition described in [1] above, wherein the acid includes an inorganic acid other than nitric acid.
[9] The aqueous composition described in [8] above, wherein the acid includes at least phosphoric acid.
[10] The aqueous composition described in [1] above, wherein the oxidizing agent contains at least hydrogen peroxide.
［１１］上記［１］～［１０］のいずれかに記載の水性組成物を用いて、銅を含むシード層を有する半導体基板の前記シード層をエッチングする工程を含む、エッチング方法。
［１２］前記半導体基板が、前記シード層に接するように積層されていて、銅よりもイオン化傾向の大きい金属を含む層をさらに有する、上記［１１］に記載のエッチング方法。
［１３］上記［１］～［１０］のいずれかに記載の水性組成物を用いて、銅を含むシード層を有する半導体基板の前記シード層をエッチングする工程を含む、半導体基板の製造方法。
［１４］前記半導体基板が、前記シード層に接するように積層されていて、銅よりもイオン化傾向の大きい金属を含む層をさらに有する、上記［１３］に記載の半導体基板の製造方法。 [11] An etching method comprising the step of etching a copper-containing seed layer of a semiconductor substrate having the seed layer, using the aqueous composition according to any one of [1] to [10] above.
[12] The etching method according to [11] above, wherein the semiconductor substrate further has a layer that is stacked in contact with the seed layer and contains a metal having a higher ionization tendency than copper.
[13] A method for producing a semiconductor substrate, comprising the step of etching a copper-containing seed layer of a semiconductor substrate, using the aqueous composition according to any one of [1] to [10] above.
[14] The method for producing a semiconductor substrate according to [13] above, wherein the semiconductor substrate further has a layer that is stacked in contact with the seed layer and contains a metal having a higher ionization tendency than copper.
［１２］前記半導体基板が、前記シード層に接するように積層されていて、銅よりもイオン化傾向の大きい金属を含む層をさらに有する、上記［１１］に記載のエッチング方法。
［１３］上記［１］～［１０］のいずれかに記載の水性組成物を用いて、銅を含むシード層を有する半導体基板の前記シード層をエッチングする工程を含む、半導体基板の製造方法。
［１４］前記半導体基板が、前記シード層に接するように積層されていて、銅よりもイオン化傾向の大きい金属を含む層をさらに有する、上記［１３］に記載の半導体基板の製造方法。 [11] An etching method comprising the step of etching a copper-containing seed layer of a semiconductor substrate having the seed layer, using the aqueous composition according to any one of [1] to [10] above.
[12] The etching method according to [11] above, wherein the semiconductor substrate further has a layer that is stacked in contact with the seed layer and contains a metal having a higher ionization tendency than copper.
[13] A method for producing a semiconductor substrate, comprising the step of etching a copper-containing seed layer of a semiconductor substrate, using the aqueous composition according to any one of [1] to [10] above.
[14] The method for producing a semiconductor substrate according to [13] above, wherein the semiconductor substrate further has a layer that is stacked in contact with the seed layer and contains a metal having a higher ionization tendency than copper.
本発明によれば、銅、銅合金などを含む層を選択的にエッチングし、なおかつアンダーカット抑制の効果に優れた水性組成物を提供することができる。また、本発明によれば、該水性組成物を用いたエッチング方法及び半導体基板の製造方法を提供できる。
According to the present invention, it is possible to provide an aqueous composition that selectively etches layers containing copper, copper alloys, etc., and that is also effective in suppressing undercuts. In addition, according to the present invention, it is possible to provide an etching method and a method for manufacturing a semiconductor substrate that use the aqueous composition.
以下、本発明のエッチング用水性組成物等について具体的に説明するが、本発明はこれに限定されるものではなく、その要旨を逸脱しない範囲で様々な変形が可能である。
The aqueous etching composition of the present invention will be described in detail below, but the present invention is not limited thereto, and various modifications are possible without departing from the gist of the invention.
＜１．エッチング用水性組成物＞
本発明の水性組成物は、少なくとも、酸化剤、酸及び腐食抑制剤を含み、水性組成物のｐＨは０以上かつ３以下である。水性組成物は、好ましくは、水性組成物の全量基準で０．００１～２０質量％の酸化剤、水性組成物の全量基準で０．１～５０質量％の酸、及び、水性組成物の全量基準で０．００００１～５．０質量％の腐食抑制剤を含む。 <1. Aqueous Etching Composition>
The aqueous composition of the present invention contains at least an oxidizing agent, an acid, and a corrosion inhibitor, and the pH of the aqueous composition is not less than 0 and not more than 3. The aqueous composition preferably contains 0.001 to 20 mass % of an oxidizing agent based on the total amount of the aqueous composition, 0.1 to 50 mass % of an acid based on the total amount of the aqueous composition, and 0.00001 to 5.0 mass % of a corrosion inhibitor based on the total amount of the aqueous composition.
本発明の水性組成物は、少なくとも、酸化剤、酸及び腐食抑制剤を含み、水性組成物のｐＨは０以上かつ３以下である。水性組成物は、好ましくは、水性組成物の全量基準で０．００１～２０質量％の酸化剤、水性組成物の全量基準で０．１～５０質量％の酸、及び、水性組成物の全量基準で０．００００１～５．０質量％の腐食抑制剤を含む。 <1. Aqueous Etching Composition>
The aqueous composition of the present invention contains at least an oxidizing agent, an acid, and a corrosion inhibitor, and the pH of the aqueous composition is not less than 0 and not more than 3. The aqueous composition preferably contains 0.001 to 20 mass % of an oxidizing agent based on the total amount of the aqueous composition, 0.1 to 50 mass % of an acid based on the total amount of the aqueous composition, and 0.00001 to 5.0 mass % of a corrosion inhibitor based on the total amount of the aqueous composition.
本発明の好ましい態様によれば、本発明の水性組成物は、配線材料として、ニッケルおよびニッケル合金からなる群より選択される１種以上と、錫、錫合金、金および金合金からなる群より選択される１種以上とを含む場合に、これらの金属の溶解を抑えながら、銅および銅合金を選択的にエッチングすることが可能である。なお、本明細書において「ニッケル合金」とは、ニッケルに１種以上の金属元素または非金属元素を加えたものであって金属的性質を有するものであれば特に限定されない。「錫合金」、「金合金」および「銅合金」についても同様である。
本発明の水性組成物によるエッチングの対象として、好ましくは、銅を主成分とする層とニッケルまたはニッケル合金を主成分とする層との積層体；銅を主成分とする層、ニッケルまたはニッケル合金を主成分とする層、錫、錫合金、金または金合金を主成分とする層を含む積層体などが挙げられる。 According to a preferred embodiment of the present invention, when the aqueous composition of the present invention contains one or more wiring materials selected from the group consisting of nickel and nickel alloys, and one or more wiring materials selected from the group consisting of tin, tin alloys, gold, and gold alloys, it is possible to selectively etch copper and copper alloys while suppressing the dissolution of these metals. In this specification, the term "nickel alloy" is not particularly limited as long as it is made by adding one or more metal elements or nonmetal elements to nickel and has metallic properties. The same applies to "tin alloy", "gold alloy" and "copper alloy".
Preferred examples of targets to be etched with the aqueous composition of the present invention include laminates of a layer mainly composed of copper and a layer mainly composed of nickel or a nickel alloy; and laminates including a layer mainly composed of copper, a layer mainly composed of nickel or a nickel alloy, and a layer mainly composed of tin, a tin alloy, gold or a gold alloy.
本発明の水性組成物によるエッチングの対象として、好ましくは、銅を主成分とする層とニッケルまたはニッケル合金を主成分とする層との積層体；銅を主成分とする層、ニッケルまたはニッケル合金を主成分とする層、錫、錫合金、金または金合金を主成分とする層を含む積層体などが挙げられる。 According to a preferred embodiment of the present invention, when the aqueous composition of the present invention contains one or more wiring materials selected from the group consisting of nickel and nickel alloys, and one or more wiring materials selected from the group consisting of tin, tin alloys, gold, and gold alloys, it is possible to selectively etch copper and copper alloys while suppressing the dissolution of these metals. In this specification, the term "nickel alloy" is not particularly limited as long as it is made by adding one or more metal elements or nonmetal elements to nickel and has metallic properties. The same applies to "tin alloy", "gold alloy" and "copper alloy".
Preferred examples of targets to be etched with the aqueous composition of the present invention include laminates of a layer mainly composed of copper and a layer mainly composed of nickel or a nickel alloy; and laminates including a layer mainly composed of copper, a layer mainly composed of nickel or a nickel alloy, and a layer mainly composed of tin, a tin alloy, gold or a gold alloy.
［１－１．エッチング用の水性組成物の成分］
以下、本発明の水性組成物に含まれる各成分について詳細に説明する。 [1-1. Components of aqueous etching composition]
Each component contained in the aqueous composition of the present invention will be described in detail below.
以下、本発明の水性組成物に含まれる各成分について詳細に説明する。 [1-1. Components of aqueous etching composition]
Each component contained in the aqueous composition of the present invention will be described in detail below.
１－１（Ａ）酸化剤
酸化剤は、主として銅を酸化させる成分である。酸化剤としては、過酸、ハロゲンオキソ酸、およびこれらの塩が挙げられる。前記過酸としては、過酸化水素、過硫酸、過炭酸、過リン酸、過酢酸、過安息香酸、メタクロロ過安息香酸等が挙げられる。前記ハロゲンオキソ酸としては、次亜塩素酸、亜塩素酸、塩素酸、過塩素酸等の塩素のオキソ酸；次亜臭素酸、亜臭素酸、臭素酸、過臭素酸等の臭素のオキソ酸；次亜ヨウ素酸、亜ヨウ素酸、ヨウ素酸、過ヨウ素酸等のヨウ素のオキソ酸等が挙げられる。前記塩としては、上記過酸またはハロゲンオキソ酸のリチウム塩、ナトリウム塩、カリウム塩、ルビジウム塩、セシウム塩等のアルカリ金属塩；上記過酸またはハロゲンオキソ酸のベリリウム塩、マグネシウム塩、カルシウム塩、ストロンチウム塩、バリウム塩等のアルカリ土類金属塩；上記過酸またはハロゲンオキソ酸のアルミニウム塩、銅塩、亜鉛塩、銀塩等の金属塩；上記過酸またはハロゲンオキソ酸のアンモニウム塩等が挙げられる。これらの酸化剤のうち、過酸化水素が好ましい。一般的には、過酸化水素の水溶液を酸化剤として用いることが、入手性および操作性の点で好ましい。 1-1 (A) Oxidizing Agent The oxidizing agent is a component that mainly oxidizes copper. Examples of the oxidizing agent include peracids, halogen oxoacids, and salts thereof. Examples of the peracids include hydrogen peroxide, persulfuric acid, percarbonic acid, perphosphoric acid, peracetic acid, perbenzoic acid, and metachloroperbenzoic acid. Examples of the halogen oxoacids include oxoacids of chlorine such as hypochlorous acid, chlorous acid, chloric acid, and perchloric acid; oxoacids of bromine such as hypobromous acid, bromous acid, bromic acid, and perbromic acid; and oxoacids of iodine such as hypoiodous acid, iodous acid, iodic acid, and periodic acid. Examples of the salt include alkali metal salts such as lithium salts, sodium salts, potassium salts, rubidium salts, and cesium salts of the above-mentioned peracids or halogen oxoacids; alkaline earth metal salts such as beryllium salts, magnesium salts, calcium salts, strontium salts, and barium salts of the above-mentioned peracids or halogen oxoacids; metal salts such as aluminum salts, copper salts, zinc salts, and silver salts of the above-mentioned peracids or halogen oxoacids; and ammonium salts of the above-mentioned peracids or halogen oxoacids. Among these oxidizing agents, hydrogen peroxide is preferred. In general, it is preferred to use an aqueous solution of hydrogen peroxide as an oxidizing agent in terms of availability and operability.
酸化剤は、主として銅を酸化させる成分である。酸化剤としては、過酸、ハロゲンオキソ酸、およびこれらの塩が挙げられる。前記過酸としては、過酸化水素、過硫酸、過炭酸、過リン酸、過酢酸、過安息香酸、メタクロロ過安息香酸等が挙げられる。前記ハロゲンオキソ酸としては、次亜塩素酸、亜塩素酸、塩素酸、過塩素酸等の塩素のオキソ酸；次亜臭素酸、亜臭素酸、臭素酸、過臭素酸等の臭素のオキソ酸；次亜ヨウ素酸、亜ヨウ素酸、ヨウ素酸、過ヨウ素酸等のヨウ素のオキソ酸等が挙げられる。前記塩としては、上記過酸またはハロゲンオキソ酸のリチウム塩、ナトリウム塩、カリウム塩、ルビジウム塩、セシウム塩等のアルカリ金属塩；上記過酸またはハロゲンオキソ酸のベリリウム塩、マグネシウム塩、カルシウム塩、ストロンチウム塩、バリウム塩等のアルカリ土類金属塩；上記過酸またはハロゲンオキソ酸のアルミニウム塩、銅塩、亜鉛塩、銀塩等の金属塩；上記過酸またはハロゲンオキソ酸のアンモニウム塩等が挙げられる。これらの酸化剤のうち、過酸化水素が好ましい。一般的には、過酸化水素の水溶液を酸化剤として用いることが、入手性および操作性の点で好ましい。 1-1 (A) Oxidizing Agent The oxidizing agent is a component that mainly oxidizes copper. Examples of the oxidizing agent include peracids, halogen oxoacids, and salts thereof. Examples of the peracids include hydrogen peroxide, persulfuric acid, percarbonic acid, perphosphoric acid, peracetic acid, perbenzoic acid, and metachloroperbenzoic acid. Examples of the halogen oxoacids include oxoacids of chlorine such as hypochlorous acid, chlorous acid, chloric acid, and perchloric acid; oxoacids of bromine such as hypobromous acid, bromous acid, bromic acid, and perbromic acid; and oxoacids of iodine such as hypoiodous acid, iodous acid, iodic acid, and periodic acid. Examples of the salt include alkali metal salts such as lithium salts, sodium salts, potassium salts, rubidium salts, and cesium salts of the above-mentioned peracids or halogen oxoacids; alkaline earth metal salts such as beryllium salts, magnesium salts, calcium salts, strontium salts, and barium salts of the above-mentioned peracids or halogen oxoacids; metal salts such as aluminum salts, copper salts, zinc salts, and silver salts of the above-mentioned peracids or halogen oxoacids; and ammonium salts of the above-mentioned peracids or halogen oxoacids. Among these oxidizing agents, hydrogen peroxide is preferred. In general, it is preferred to use an aqueous solution of hydrogen peroxide as an oxidizing agent in terms of availability and operability.
水性組成物中の酸化剤の濃度は、好ましくは、水性組成物の全質量に対して０．００１～２０質量％であり、より好ましくは０．１～１０．０質量％であり、さらに好ましくは０．０２～５．０質量％であり、特に好ましくは、０．１～３質量％、０．５～２．０質量％、あるいは０．５～１．５質量％などである。酸化剤の濃度をこのように調整されている水性組成物によれば、良好なエッチング速度を実現できるとともに、配線材料の不必要な溶解を抑制することができる。
The concentration of the oxidizing agent in the aqueous composition is preferably 0.001 to 20 mass% relative to the total mass of the aqueous composition, more preferably 0.1 to 10.0 mass%, even more preferably 0.02 to 5.0 mass%, and particularly preferably 0.1 to 3 mass%, 0.5 to 2.0 mass%, or 0.5 to 1.5 mass%, etc. An aqueous composition in which the concentration of the oxidizing agent is adjusted in this way can achieve a good etching rate and suppress unnecessary dissolution of the wiring material.
１－１（Ｂ）酸
水性組成物における酸は、主として、酸化剤によって酸化された銅および銅合金のエッチング剤として作用する。酸としては、リン酸（Ｈ３ＰＯ４）、ホスホン酸（Ｈ３ＰＯ３）、ピロリン酸（Ｈ４Ｐ２Ｏ７）、メタリン酸（ＨＰＯ３）、などのリン酸類；硫酸、塩化水素酸、フッ化水素酸、臭化水素酸、ヨウ化水素酸、硝酸などが用いられ得る。これらの酸のうち、リン酸類、特に、リン酸が好適に用いられる。
また、硝酸に長い期間さらされたエッチング装置には腐食が生じる可能性もあるため、硝酸、亜硝酸を除く無機酸、少なくとも硝酸を除く無機酸を酸成分として用いることが好ましい。 1-1(B) Acid The acid in the aqueous composition mainly acts as an etching agent for copper and copper alloys oxidized by the oxidizing agent. Examples of acids that can be used include phosphoric acids such as phosphoric acid (H 3 PO 4 ), phosphonic acid (H 3 PO 3 ), pyrophosphoric acid (H 4 P 2 O 7 ), and metaphosphoric acid (HPO 3 ); sulfuric acid, hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, and nitric acid. Among these acids, phosphoric acids, particularly phosphoric acid, are preferably used.
Furthermore, since etching equipment exposed to nitric acid for a long period of time may become corroded, it is preferable to use an inorganic acid other than nitric acid or nitrous acid, or at least an inorganic acid other than nitric acid, as the acid component.
水性組成物における酸は、主として、酸化剤によって酸化された銅および銅合金のエッチング剤として作用する。酸としては、リン酸（Ｈ３ＰＯ４）、ホスホン酸（Ｈ３ＰＯ３）、ピロリン酸（Ｈ４Ｐ２Ｏ７）、メタリン酸（ＨＰＯ３）、などのリン酸類；硫酸、塩化水素酸、フッ化水素酸、臭化水素酸、ヨウ化水素酸、硝酸などが用いられ得る。これらの酸のうち、リン酸類、特に、リン酸が好適に用いられる。
また、硝酸に長い期間さらされたエッチング装置には腐食が生じる可能性もあるため、硝酸、亜硝酸を除く無機酸、少なくとも硝酸を除く無機酸を酸成分として用いることが好ましい。 1-1(B) Acid The acid in the aqueous composition mainly acts as an etching agent for copper and copper alloys oxidized by the oxidizing agent. Examples of acids that can be used include phosphoric acids such as phosphoric acid (H 3 PO 4 ), phosphonic acid (H 3 PO 3 ), pyrophosphoric acid (H 4 P 2 O 7 ), and metaphosphoric acid (HPO 3 ); sulfuric acid, hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, and nitric acid. Among these acids, phosphoric acids, particularly phosphoric acid, are preferably used.
Furthermore, since etching equipment exposed to nitric acid for a long period of time may become corroded, it is preferable to use an inorganic acid other than nitric acid or nitrous acid, or at least an inorganic acid other than nitric acid, as the acid component.
水性組成物中の酸においては、酸の全質量を基準として５０％以上のリン酸類あるいはリン酸が含まれることが好ましく、７０％以上のリン酸類あるいはリン酸が含まれることがより好ましく、９０％以上のリン酸類あるいはリン酸が含まれることが好ましく、特に好ましくは、リン酸類あるいはリン酸のみが酸として用いられる。
The acid in the aqueous composition preferably contains 50% or more phosphoric acids or phosphoric acid based on the total mass of the acid, more preferably 70% or more phosphoric acids or phosphoric acid, and more preferably 90% or more phosphoric acids or phosphoric acid, and particularly preferably, phosphoric acids or phosphoric acid are used alone as the acid.
水性組成物における酸の濃度は、好ましくは０．１～５０質量％であり、より好ましくは１．０～３０質量％であり、さらに好ましくは３．０～２０質量％であり、特に好ましくは５．０～１０質量％である。酸の濃度が上記範囲内に調整された水性組成物によれば、エッチング速度が良好なものとなりつつ、配線材料の不必要な溶解を抑制できる。
The concentration of the acid in the aqueous composition is preferably 0.1 to 50% by mass, more preferably 1.0 to 30% by mass, even more preferably 3.0 to 20% by mass, and particularly preferably 5.0 to 10% by mass. An aqueous composition in which the acid concentration is adjusted within the above range can achieve a good etching rate while suppressing unnecessary dissolution of the wiring material.
１－１（Ｃ）腐食抑制剤
水性組成物における腐食抑制剤は、主として、銅やニッケルなどの表面との反応または表面への吸着によって、ニッケルなどの銅よりもイオン化傾向の高い金属を含む層の腐食、特にガルバニック腐食を効果的に抑えることができ、銅などを含む層の過剰なエッチングであるアンダーカットも抑制できる。腐食抑制剤は、（ｉ）含窒素複素環化合物、（ｉｉ）カチオン性界面活性剤及び（ｉｉｉ）アルキル硫酸／スルホン酸またはその塩の少なくともいずれかを含むことが好ましい。 1-1(C) Corrosion Inhibitor The corrosion inhibitor in the aqueous composition can effectively suppress corrosion, particularly galvanic corrosion, of a layer containing a metal that has a higher ionization tendency than copper, such as nickel, mainly by reacting with or adsorbing to the surface of copper, nickel, etc., and can also suppress undercutting, which is excessive etching of a layer containing copper, etc. The corrosion inhibitor preferably contains at least one of (i) a nitrogen-containing heterocyclic compound, (ii) a cationic surfactant, and (iii) an alkyl sulfuric acid/sulfonic acid or a salt thereof.
水性組成物における腐食抑制剤は、主として、銅やニッケルなどの表面との反応または表面への吸着によって、ニッケルなどの銅よりもイオン化傾向の高い金属を含む層の腐食、特にガルバニック腐食を効果的に抑えることができ、銅などを含む層の過剰なエッチングであるアンダーカットも抑制できる。腐食抑制剤は、（ｉ）含窒素複素環化合物、（ｉｉ）カチオン性界面活性剤及び（ｉｉｉ）アルキル硫酸／スルホン酸またはその塩の少なくともいずれかを含むことが好ましい。 1-1(C) Corrosion Inhibitor The corrosion inhibitor in the aqueous composition can effectively suppress corrosion, particularly galvanic corrosion, of a layer containing a metal that has a higher ionization tendency than copper, such as nickel, mainly by reacting with or adsorbing to the surface of copper, nickel, etc., and can also suppress undercutting, which is excessive etching of a layer containing copper, etc. The corrosion inhibitor preferably contains at least one of (i) a nitrogen-containing heterocyclic compound, (ii) a cationic surfactant, and (iii) an alkyl sulfuric acid/sulfonic acid or a salt thereof.
水性組成物における腐食抑制剤の合計の濃度は、好ましくは、水性組成物の全量基準で０．００００１～５．０質量％であり、より好ましくは０．０００１～３．０質量％であり、さらに好ましくは、０．０００５～１．０質量％であり、特に好ましくは、０．００１～０．２質量％である。腐食抑制剤の濃度が上記範囲内に調整された水性組成物によれば、例えばニッケルなどの銅よりもイオン化傾向の高い金属を含む層の腐食、特にガルバニック腐食を効果的に抑えることができ、銅などを含む層の過剰なエッチングであるアンダーカットも抑制できる。
The total concentration of the corrosion inhibitor in the aqueous composition is preferably 0.00001 to 5.0 mass% based on the total amount of the aqueous composition, more preferably 0.0001 to 3.0 mass%, even more preferably 0.0005 to 1.0 mass%, and particularly preferably 0.001 to 0.2 mass%. An aqueous composition in which the concentration of the corrosion inhibitor is adjusted to fall within the above range can effectively suppress corrosion, particularly galvanic corrosion, of layers containing metals such as nickel that have a higher ionization tendency than copper, and can also suppress undercutting, which is excessive etching of layers containing copper, etc.
（ｉ）含窒素複素環化合物
腐食抑制剤として好適に用いられる（ｉ）含窒素複素環化合物は、少なくとも含窒素５員環化合物を含むことが好ましい。含窒素５員環化合物は、炭素数１～６のアルキル基、アミノ基、ならびに炭素数１～６のアルキル基およびフェニル基からなる群より選択される１種以上の置換基を有する置換アミノ基からなる群より選択される１種以上の置換基を有していてもよい。また、含窒素複素環化合物は、含窒素５員環以外の環、例えば、炭素数が５～３０の脂肪族環、炭素数が６～３０の芳香環などを含んでいてもよく、これらの環が含窒素５員環との縮合環であってもよい。含窒素５員環化合物は、例えば、ピロール、ピラゾール、イミダゾール、トリアゾール、テトラゾール、からなる群より選択される１種以上である。含窒素５員環化合物は、１種のみであってもよく、２種以上を組み合わせてもよい。 (i) Nitrogen-containing heterocyclic compound The (i) nitrogen-containing heterocyclic compound preferably used as a corrosion inhibitor preferably contains at least a nitrogen-containing five-membered ring compound. The nitrogen-containing five-membered ring compound may have one or more substituents selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an amino group, and a substituted amino group having one or more substituents selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and a phenyl group. The nitrogen-containing heterocyclic compound may also contain a ring other than the nitrogen-containing five-membered ring, for example, an aliphatic ring having 5 to 30 carbon atoms, an aromatic ring having 6 to 30 carbon atoms, etc., and these rings may be condensed rings with the nitrogen-containing five-membered ring. The nitrogen-containing five-membered ring compound is, for example, one or more selected from the group consisting of pyrrole, pyrazole, imidazole, triazole, and tetrazole. The nitrogen-containing five-membered ring compound may be only one type, or two or more types may be combined.
腐食抑制剤として好適に用いられる（ｉ）含窒素複素環化合物は、少なくとも含窒素５員環化合物を含むことが好ましい。含窒素５員環化合物は、炭素数１～６のアルキル基、アミノ基、ならびに炭素数１～６のアルキル基およびフェニル基からなる群より選択される１種以上の置換基を有する置換アミノ基からなる群より選択される１種以上の置換基を有していてもよい。また、含窒素複素環化合物は、含窒素５員環以外の環、例えば、炭素数が５～３０の脂肪族環、炭素数が６～３０の芳香環などを含んでいてもよく、これらの環が含窒素５員環との縮合環であってもよい。含窒素５員環化合物は、例えば、ピロール、ピラゾール、イミダゾール、トリアゾール、テトラゾール、からなる群より選択される１種以上である。含窒素５員環化合物は、１種のみであってもよく、２種以上を組み合わせてもよい。 (i) Nitrogen-containing heterocyclic compound The (i) nitrogen-containing heterocyclic compound preferably used as a corrosion inhibitor preferably contains at least a nitrogen-containing five-membered ring compound. The nitrogen-containing five-membered ring compound may have one or more substituents selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an amino group, and a substituted amino group having one or more substituents selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and a phenyl group. The nitrogen-containing heterocyclic compound may also contain a ring other than the nitrogen-containing five-membered ring, for example, an aliphatic ring having 5 to 30 carbon atoms, an aromatic ring having 6 to 30 carbon atoms, etc., and these rings may be condensed rings with the nitrogen-containing five-membered ring. The nitrogen-containing five-membered ring compound is, for example, one or more selected from the group consisting of pyrrole, pyrazole, imidazole, triazole, and tetrazole. The nitrogen-containing five-membered ring compound may be only one type, or two or more types may be combined.
含窒素５員環化合物としては、好ましくは、下記式（１）、式（２）または式（３）：
［式（１）～式（３）中、Ｒ １、Ｒ２、Ｒ ３、Ｒ ４およびＲ ５は、それぞれ独立して、（ａ）水素原子、（ｂ）炭素数１～６のアルキル基、（ｃ）アミノ基及び（ｄ）炭素数１～６のアルキル基およびフェニル基からなる群より選択される１種以上の置換基を有する置換アミノ基からなる群より選択されるか、又は、
Ｒ２とＲ３とが互いに結合して、炭素数が５～３０の脂肪族環あるいは炭素数が６～３０の芳香族環を形成してもよく、
Ｒ４とＲ５とが互いに結合して、炭素数が５～３０の脂肪族環あるいは炭素数が６～３０の芳香族環を形成してもよい。］
で示される化合物を挙げることができる。
上述の脂肪族環の炭素数は、好ましくは６～２４であり、より好ましくは、６～１６あるいは８～１２であり、芳香族環の炭素数は、好ましくは６～２４であり、より好ましくは、６～１６あるいは８～１２である。 The nitrogen-containing five-membered ring compound is preferably represented by the following formula (1), formula (2) or formula (3):
[In formulas (1) to (3), R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from the group consisting of (a) a hydrogen atom, (b) an alkyl group having 1 to 6 carbon atoms, (c) an amino group and (d) a substituted amino group having one or more substituents selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and a phenyl group, or
R 2 and R 3 may be bonded to each other to form an aliphatic ring having 5 to 30 carbon atoms or an aromatic ring having 6 to 30 carbon atoms;
R 4 and R 5 may be bonded to each other to form an aliphatic ring having 5 to 30 carbon atoms or an aromatic ring having 6 to 30 carbon atoms.
Examples of the compound include those represented by the following formula:
The number of carbon atoms in the aliphatic ring is preferably 6 to 24, more preferably 6 to 16 or 8 to 12, and the number of carbon atoms in the aromatic ring is preferably 6 to 24, more preferably 6 to 16 or 8 to 12.
Ｒ２とＲ３とが互いに結合して、炭素数が５～３０の脂肪族環あるいは炭素数が６～３０の芳香族環を形成してもよく、
Ｒ４とＲ５とが互いに結合して、炭素数が５～３０の脂肪族環あるいは炭素数が６～３０の芳香族環を形成してもよい。］
で示される化合物を挙げることができる。
上述の脂肪族環の炭素数は、好ましくは６～２４であり、より好ましくは、６～１６あるいは８～１２であり、芳香族環の炭素数は、好ましくは６～２４であり、より好ましくは、６～１６あるいは８～１２である。 The nitrogen-containing five-membered ring compound is preferably represented by the following formula (1), formula (2) or formula (3):
R 2 and R 3 may be bonded to each other to form an aliphatic ring having 5 to 30 carbon atoms or an aromatic ring having 6 to 30 carbon atoms;
R 4 and R 5 may be bonded to each other to form an aliphatic ring having 5 to 30 carbon atoms or an aromatic ring having 6 to 30 carbon atoms.
Examples of the compound include those represented by the following formula:
The number of carbon atoms in the aliphatic ring is preferably 6 to 24, more preferably 6 to 16 or 8 to 12, and the number of carbon atoms in the aromatic ring is preferably 6 to 24, more preferably 6 to 16 or 8 to 12.
炭素数１～６のアルキル基としては、直鎖または分岐のアルキル基およびシクロアルキル基が挙げられる。直鎖または分岐のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基等が挙げられる。シクロアルキル基としては炭素数３～６のシクロアルキル基が挙げられ、例えば、シクロプロピル基、シクロペンチル基、シクロヘキシル基等が挙げられる。これらの中でも、メチル基またはエチル基が好ましく、メチル基が特に好ましい。
Examples of the alkyl group having 1 to 6 carbon atoms include linear or branched alkyl groups and cycloalkyl groups. Examples of the linear or branched alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl groups. Examples of the cycloalkyl group include cycloalkyl groups having 3 to 6 carbon atoms, such as cyclopropyl, cyclopentyl, and cyclohexyl groups. Among these, methyl and ethyl groups are preferred, with methyl being particularly preferred.
置換アミノ基としては、炭素数１～６のアルキル基およびフェニル基からなる群より選択される１種以上の置換基を有するアミノ基であればよく特に制限されない。炭素数１～６のアルキル基については、上述のとおりである。
The substituted amino group is not particularly limited as long as it has one or more substituents selected from the group consisting of alkyl groups having 1 to 6 carbon atoms and phenyl groups. The alkyl groups having 1 to 6 carbon atoms are as described above.
含窒素５員環化合物の好ましい具体例としては、５－メチルテトラゾール、５－アミノテトラゾール、１，２，４－トリアゾール、１，２，３－トリアゾール、およびテトラゾールを挙げることができる。これらの中でも、１，２，４－トリアゾール、３－アミノ－１，２，４－トリアゾール、５－メチルテトラゾール、５－アミノテトラゾールおよびからなる群より選択される１種以上が特に好ましい。
また、上記式（１）～（３）で表されるものの他にも、ピロール、ピラゾール、及びこれらの化合物の環骨格に上記Ｒ１～Ｒ ５で示される置換基を含むものが好ましい。 Specific preferred examples of the nitrogen-containing five-membered ring compound include 5-methyltetrazole, 5-aminotetrazole, 1,2,4-triazole, 1,2,3-triazole, and tetrazole. Among these, at least one selected from the group consisting of 1,2,4-triazole, 3-amino-1,2,4-triazole, 5-methyltetrazole, and 5-aminotetrazole is particularly preferred.
In addition to those represented by the above formulas (1) to (3), pyrrole, pyrazole, and compounds containing the substituents represented by R 1 to R 5 in the ring skeleton of these compounds are also preferred.
また、上記式（１）～（３）で表されるものの他にも、ピロール、ピラゾール、及びこれらの化合物の環骨格に上記Ｒ１～Ｒ ５で示される置換基を含むものが好ましい。 Specific preferred examples of the nitrogen-containing five-membered ring compound include 5-methyltetrazole, 5-aminotetrazole, 1,2,4-triazole, 1,2,3-triazole, and tetrazole. Among these, at least one selected from the group consisting of 1,2,4-triazole, 3-amino-1,2,4-triazole, 5-methyltetrazole, and 5-aminotetrazole is particularly preferred.
In addition to those represented by the above formulas (1) to (3), pyrrole, pyrazole, and compounds containing the substituents represented by R 1 to R 5 in the ring skeleton of these compounds are also preferred.
また、（ｉ）含窒素複素環化合物として、含窒素５員環化合物以外のもの、例えば、含窒素６員環化合物として、ピリジン、ピラジン、ピリミジン、ピリダジン、トリアジン、テトラジン、ペンタジジン、ヘキサジン、及びこれらの化合物の環骨格に上記Ｒ１～Ｒ ５で示される置換基を含むものが好ましい。
（ｉ）含窒素複素環化合物は、１種のみであってもよく、２種以上を組み合わせてもよい。 In addition, (i) the nitrogen-containing heterocyclic compound is preferably a compound other than a nitrogen-containing five-membered ring compound, for example, a nitrogen-containing six-membered ring compound such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, tetrazine, pentazidine, hexazine, or a compound having the substituents represented by R 1 to R 5 in the ring skeleton of the compound.
The nitrogen-containing heterocyclic compound (i) may be used alone or in combination of two or more kinds.
（ｉ）含窒素複素環化合物は、１種のみであってもよく、２種以上を組み合わせてもよい。 In addition, (i) the nitrogen-containing heterocyclic compound is preferably a compound other than a nitrogen-containing five-membered ring compound, for example, a nitrogen-containing six-membered ring compound such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, tetrazine, pentazidine, hexazine, or a compound having the substituents represented by R 1 to R 5 in the ring skeleton of the compound.
The nitrogen-containing heterocyclic compound (i) may be used alone or in combination of two or more kinds.
水性組成物中の（ｉ）含窒素複素環化合物の濃度は、例えば、水性組成物の全量基準で０．０００１～５．０質量％であり、好ましくは０．０１～５．０質量％であり、より好ましくは０．０５～２．０質量％、さらに好ましくは０．０７～１．０質量％、特に好ましくは０．１～０．５質量％である。
The concentration of the nitrogen-containing heterocyclic compound (i) in the aqueous composition is, for example, 0.0001 to 5.0 mass% based on the total amount of the aqueous composition, preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, even more preferably 0.07 to 1.0 mass%, and particularly preferably 0.1 to 0.5 mass%.
（ｉｉ）カチオン性界面活性剤
腐食抑制剤として好適に用いられる（ｉｉ）カチオン性界面活性剤は、アルキル基含有４級アンモニウム水酸化物またはその塩、ならびにアルキル基含有ヘテロアリール水酸化物またはその塩を含むことが好ましい。
アルキル基含有アンモニウム水酸化物またはその塩の好ましい具体例は、以下の式（４）で表される。
(ii) Cationic Surfactant (ii) Cationic surfactant suitably used as a corrosion inhibitor preferably contains an alkyl group-containing quaternary ammonium hydroxide or a salt thereof, and an alkyl group-containing heteroaryl hydroxide or a salt thereof.
A preferred example of the alkyl group-containing ammonium hydroxide or a salt thereof is represented by the following formula (4).
腐食抑制剤として好適に用いられる（ｉｉ）カチオン性界面活性剤は、アルキル基含有４級アンモニウム水酸化物またはその塩、ならびにアルキル基含有ヘテロアリール水酸化物またはその塩を含むことが好ましい。
アルキル基含有アンモニウム水酸化物またはその塩の好ましい具体例は、以下の式（４）で表される。
A preferred example of the alkyl group-containing ammonium hydroxide or a salt thereof is represented by the following formula (4).
上記式（４）中、Ｒ６は、炭素数４～３０の置換もしくは非置換アルキル基、炭素数４～３０の置換もしくは非置換アルキル（ポリ）ヘテロアルキレン基、または炭素数４～３０の置換もしくは非置換アリール（ポリ）ヘテロアルキレン基である。
In the above formula (4), R6 is a substituted or unsubstituted alkyl group having 4 to 30 carbon atoms, a substituted or unsubstituted alkyl (poly)heteroalkylene group having 4 to 30 carbon atoms, or a substituted or unsubstituted aryl (poly)heteroalkylene group having 4 to 30 carbon atoms.
炭素数４～３０のアルキル基としては、特に制限されないが、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基、ドコシル基、テトラコシル基、ヘキサコシル基、オクタコシル基、トリアコンチル基等が挙げられる。
Alkyl groups having 4 to 30 carbon atoms are not particularly limited, but include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, docosyl, tetracosyl, hexacosyl, octacosyl, and triacontyl groups.
炭素数４～３０の置換もしくは非置換アルキル基が置換基を有する場合（炭素数４～３０の置換アルキル基）の置換基としては、特に制限されないが、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；フェニル基、ナフチル基等の炭素数６～２０のアリール基；メトキシ基、エトキシ基、プロピルオキシ基等の炭素数１～６のアルコキシ基；ヒドロキシ基；シアノ基；ニトロ基等が挙げられる。なお、置換基は１つであってもよいし、２以上有していてもよい。また、炭素数４～３０の置換アルキル基は、置換基の炭素数およびアルキル基の炭素数の総数が４～３０であることを意味する。すなわち、炭素数４～３０の置換アルキル基においては、当該置換基の合計の炭素数が上述の範囲内となるように、炭素数が４以上のアルキル基（例えば、ブチル基、ヘキシル基、オクチル基、デシル基、ドデシル基等の炭素数４～１３のアルキル基）を含めることができる。
When a substituted or unsubstituted alkyl group having 4 to 30 carbon atoms has a substituent (a substituted alkyl group having 4 to 30 carbon atoms), the substituent is not particularly limited, but may include halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; aryl groups having 6 to 20 carbon atoms such as phenyl and naphthyl; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and propyloxy; hydroxyl groups; cyano groups; and nitro groups. The number of substituents may be one or more. A substituted alkyl group having 4 to 30 carbon atoms means that the total number of carbon atoms in the substituent and the number of carbon atoms in the alkyl group is 4 to 30. In other words, a substituted alkyl group having 4 to 30 carbon atoms may include an alkyl group having 4 or more carbon atoms (for example, an alkyl group having 4 to 13 carbon atoms such as a butyl group, a hexyl group, an octyl group, a decyl group, or a dodecyl group) so that the total number of carbon atoms in the substituent falls within the above-mentioned range.
炭素数４～３０のアルキル（ポリ）ヘテロアルキレン基は、－（ＣｎＨ２ｎ－Ｚ－）ｍ－Ｒ３で表される。この際、ｎは、それぞれ独立して、１～５であり、好ましくは１～３であり、より好ましくは１～２である。ｍは１～５であり、好ましくは１～２である。Ｚは、それぞれ独立して、酸素原子（Ｏ）、硫黄原子（Ｓ）、リン原子（Ｐ）であり、好ましくは酸素原子（Ｏ）である。Ｒ７は炭素数１～３０のアルキル基であり、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基等が挙げられる。
The alkyl (poly) heteroalkylene group having 4 to 30 carbon atoms is represented by -(C n H 2n -Z-) m -R 3. In this case, n is independently 1 to 5, preferably 1 to 3, and more preferably 1 to 2. m is 1 to 5, preferably 1 to 2. Z is independently an oxygen atom (O), a sulfur atom (S), or a phosphorus atom (P), and is preferably an oxygen atom (O). R 7 is an alkyl group having 1 to 30 carbon atoms, and examples of such groups include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an icosyl group.
炭素数４～３０の置換もしくは非置換アルキル（ポリ）ヘテロアルキレン基が置換基を有する場合（炭素数４～３０の置換アルキル（ポリ）ヘテロアルキレン基）の置換基としては、特に制限されないが、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；フェニル基、ナフチル基等の炭素数６～２０のアリール基；メトキシ基、エトキシ基、プロピルオキシ基等の炭素数１～６のアルコキシ基；ヒドロキシ基；シアノ基；ニトロ基等が挙げられる。なお、当該置換基は通常Ｒ７の水素原子と置換される。また、置換基は１つであってもよいし、２以上有していてもよい。さらに、炭素数４～３０の置換アルキル（ポリ）ヘテロアルキレン基は、置換基の炭素数およびアルキル（ポリ）ヘテロアルキレン基の炭素数の総数が４～３０であることを意味する。すなわち、炭素数４～３０の置換アルキル（ポリ）ヘテロアルキレン基においては、当該置換基の合計の炭素数が上述の範囲内となるように、炭素数が４以上のアルキル（ポリ）ヘテロアルキレン基（例えば、ブチル基、ヘキシル基、オクチル基、デシル基、ドデシル基等の炭素数４～１３のアルキル基を有するもの）を含めることができる。
In the case where the substituted or unsubstituted alkyl(poly)heteroalkylene group having 4 to 30 carbon atoms has a substituent (substituted alkyl(poly)heteroalkylene group having 4 to 30 carbon atoms), the substituent is not particularly limited, but includes halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; aryl groups having 6 to 20 carbon atoms such as phenyl group and naphthyl group; alkoxy groups having 1 to 6 carbon atoms such as methoxy group, ethoxy group, and propyloxy group; hydroxy group; cyano group; and nitro group. The substituent is usually substituted with the hydrogen atom of R 7. The number of the substituent may be one or more. Furthermore, the substituted alkyl(poly)heteroalkylene group having 4 to 30 carbon atoms means that the total number of carbon atoms of the substituent and the number of carbon atoms of the alkyl(poly)heteroalkylene group is 4 to 30. That is, a substituted alkyl(poly)heteroalkylene group having 4 to 30 carbon atoms can include an alkyl(poly)heteroalkylene group having 4 or more carbon atoms (e.g., an alkyl group having 4 to 13 carbon atoms, such as a butyl group, a hexyl group, an octyl group, a decyl group, or a dodecyl group) so that the total carbon number of the substituents falls within the above-mentioned range.
炭素数４～３０のアリール（ポリ）ヘテロアルキレン基は、－（ＣｎＨ２ｎ－Ｚ－）ｍ－Ａｒで表される。この際、ｎは、それぞれ独立して、１～５であり、好ましくは１～３であり、より好ましくは１～２である。ｍは１～５であり、好ましくは１～２である。Ｚは、それぞれ独立して、酸素原子（Ｏ）、硫黄原子（Ｓ）、リン原子（Ｐ）であり、好ましくは酸素原子（Ｏ）である。Ａｒは、炭素数６～１８のアリール基であり、フェニル基、ナフチル基、アントラセニル基等が挙げられる。
An aryl(poly)heteroalkylene group having 4 to 30 carbon atoms is represented by -(C n H 2n -Z-) m -Ar. In this case, n is independently 1 to 5, preferably 1 to 3, and more preferably 1 to 2. m is 1 to 5, and preferably 1 to 2. Z is independently an oxygen atom (O), a sulfur atom (S), or a phosphorus atom (P), and is preferably an oxygen atom (O). Ar is an aryl group having 6 to 18 carbon atoms, and examples of such groups include a phenyl group, a naphthyl group, and an anthracenyl group.
炭素数４～３０の置換もしくは非置換アリール（ポリ）ヘテロアルキレン基が置換基を有する場合（炭素数４～３０の置換アリール（ポリ）ヘテロアルキレン基）の置換基としては、特に制限されないが、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、１，１－ジメチルブチル基、２，２－ジメチルブチル基、１，１，３，３－テトラメチルブチル基等の炭素数１～１０のアルキル基；メトキシ基、エトキシ基、プロピルオキシ基等の炭素数１～６のアルコキシ基；ヒドロキシ基；シアノ基；ニトロ基等が挙げられる。なお、当該置換基は通常Ａｒの水素原子と置換される。また、置換基は１つであってもよいし、２以上有していてもよい。さらに、炭素数４～３０の置換アリール（ポリ）ヘテロアルキレン基は、置換基の炭素数およびアリール（ポリ）ヘテロアルキレン基の炭素数の総数が４～３０であることを意味する。すなわち、炭素数４～３０の置換アリール（ポリ）ヘテロアルキレン基においては、当該置換基の合計の炭素数が上述の範囲内となるように、炭素数が４以上のアリール（ポリ）ヘテロアルキレン基（例えば、ブチル基、ヘキシル基、オクチル基、デシル基、ドデシル基等の炭素数４～１３のアルキル基を有するもの）を含めることができる。
When a substituted or unsubstituted aryl(poly)heteroalkylene group having 4 to 30 carbon atoms has a substituent (a substituted aryl(poly)heteroalkylene group having 4 to 30 carbon atoms), the substituent is not particularly limited, but includes halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, and 1,1,3,3-tetramethylbutyl group; alkoxy groups having 1 to 6 carbon atoms such as methoxy group, ethoxy group, and propyloxy group; hydroxy group; cyano group; and nitro group. The substituent is usually substituted with a hydrogen atom of Ar. The number of the substituent may be one or more. Furthermore, a substituted aryl(poly)heteroalkylene group having 4 to 30 carbon atoms means that the total number of carbon atoms of the substituent and the number of carbon atoms of the aryl(poly)heteroalkylene group is 4 to 30. That is, a substituted aryl(poly)heteroalkylene group having 4 to 30 carbon atoms can include an aryl(poly)heteroalkylene group having 4 or more carbon atoms (e.g., an alkyl group having 4 to 13 carbon atoms, such as a butyl group, a hexyl group, an octyl group, a decyl group, or a dodecyl group) so that the total carbon number of the substituents falls within the above range.
一実施形態において、Ｒ６は、炭素数４～３０の置換もしくは非置換アルキル（ポリ）ヘテロアルキレン基、または炭素数４～３０の置換もしくは非置換アリール（ポリ）ヘテロアルキレン基であることが好ましく、炭素数６～２０の置換または非置換アリール（ポリ）ヘテロアルキレン基であることがより好ましく、炭素数８～２０の置換または非置換アリール（ポリ）ヘテロアルキレン基であることがさらに好ましく、炭素数１０～１８の置換または非置換アリール（ポリ）ヘテロアルキレン基であることが特に好ましく、ｐ－（１，１，３，３－テトラメチルブチル）フェニルジ（オキシエチレン）（ｐ－ＣＨ３Ｃ（ＣＨ３）２ＣＨ２Ｃ（ＣＨ３）２－Ｐｈ－（Ｏ－Ｃ２Ｈ４）２－）基であることが最も好ましい。
In one embodiment, R 6 is preferably a substituted or unsubstituted alkyl(poly)heteroalkylene group having 4 to 30 carbon atoms, or a substituted or unsubstituted aryl(poly)heteroalkylene group having 4 to 30 carbon atoms, more preferably a substituted or unsubstituted aryl(poly)heteroalkylene group having 6 to 20 carbon atoms, even more preferably a substituted or unsubstituted aryl(poly)heteroalkylene group having 8 to 20 carbon atoms, particularly preferably a substituted or unsubstituted aryl(poly)heteroalkylene group having 10 to 18 carbon atoms, and most preferably a p-(1,1,3,3-tetramethylbutyl)phenyldi(oxyethylene) (p-CH 3 C(CH 3 ) 2 CH 2 C(CH 3 ) 2 -Ph-(O-C 2 H 4 ) 2 -) group.
また、別の一実施形態において、Ｒ６は、炭素数４～２５の置換もしくは非置換アルキル基、炭素数４～２５の置換もしくは非置換アリール（ポリ）ヘテロアルキレン基であることが好ましく、炭素数６～２０の置換もしくは非置換アルキル基、炭素数６～２０の置換もしくは非置換アリール（ポリ）ヘテロアルキレン基であることがより好ましく、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、ｐ－（１，１，３，３－テトラメチルブチル）フェニルジ（オキシエチレン）（ｐ－ＣＨ３Ｃ（ＣＨ３）２ＣＨ２Ｃ（ＣＨ３）２－Ｐｈ－（Ｏ－Ｃ２Ｈ４）２－）基であることがさらに好ましく、ヘキサデシル基、オクタデシル基、ｐ－（１，１，３，３－テトラメチルブチル）フェニルジ（オキシエチレン）（ｐ－ＣＨ３Ｃ（ＣＨ３）２ＣＨ２Ｃ（ＣＨ３）２－Ｐｈ－（Ｏ－Ｃ２Ｈ４）２－）基であることが特に好ましく、ｐ－（１，１，３，３－テトラメチルブチル）フェニルジ（オキシエチレン）（ｐ－ＣＨ３Ｃ（ＣＨ３）２ＣＨ２Ｃ（ＣＨ３）２－Ｐｈ－（Ｏ－Ｃ２Ｈ４）２－）基であることが最も好ましい。
In another embodiment, R 6 is preferably a substituted or unsubstituted alkyl group having 4 to 25 carbon atoms or a substituted or unsubstituted aryl (poly)heteroalkylene group having 4 to 25 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 6 to 20 carbon atoms or a substituted or unsubstituted aryl (poly)heteroalkylene group having 6 to 20 carbon atoms, and further preferably a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, or a p-(1,1,3,3-tetramethylbutyl)phenyldi(oxyethylene) (p-CH 3 C(CH 3 ) 2 CH 2 C(CH 3 ) 2 -Ph-(O-C 2 H 4 ) 2 -) group, and more preferably a hexadecyl group, an octadecyl group, or a p-(1,1,3,3-tetramethylbutyl)phenyldi(oxyethylene) (p-CH 3 C(CH 3 ) 2 CH 2 C(CH 3 ) 2 Particularly preferred is the -Ph-(O-C 2 H 4 ) 2 - group, and most preferred is the p-(1,1,3,3-tetramethylbutyl)phenyldi(oxyethylene) (p-CH 3 C(CH 3 ) 2 CH 2 C(CH 3 ) 2 -Ph-(O-C 2 H 4 ) 2 -) group.
また、Ｒ７は、それぞれ独立して、炭素数１～３０の置換もしくは非置換アルキル基、または炭素数６～３０の置換もしくは非置換アリール基である。
Furthermore, each R 7 is independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
炭素数１～３０のアルキル基としては、特に限定されないが、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、ノナデシル基、イコシル基等が挙げられる。
Alkyl groups having 1 to 30 carbon atoms include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, nonadecyl, and icosyl groups.
炭素数１～３０の置換もしくは非置換アルキル基が置換基を有する場合（炭素数１～３０の置換アルキル基）の置換基としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；フェニル基、ナフチル基等の炭素数６～２０のアリール基；メトキシ基、エトキシ基、プロピルオキシ基等の炭素数１～６のアルコキシ基；ヒドロキシ基；シアノ基；ニトロ基等が挙げられる。なお、置換基は１つであってもよいし、２以上有していてもよい。また、炭素数１～３０の置換アルキル基は、置換基の炭素数およびアルキル基の炭素数の総数が１～３０であることを意味する。
When a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms has a substituent (a substituted alkyl group having 1 to 30 carbon atoms), examples of the substituent include halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; aryl groups having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; alkoxy groups having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, and a propyloxy group; a hydroxy group; a cyano group; and a nitro group. The number of substituents may be one or more. A substituted alkyl group having 1 to 30 carbon atoms means that the total number of carbon atoms in the substituent and the alkyl group is 1 to 30.
炭素数６～３０のアリール基としては、特に制限されないが、フェニル基、ナフチル基、ビフェニル基等が挙げられる。
Aryl groups having 6 to 30 carbon atoms include, but are not limited to, phenyl groups, naphthyl groups, biphenyl groups, etc.
炭素数６～３０の置換もしくは非置換アリール基が置換基を有する場合（炭素数６～３０の置換アリール基）の置換基としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；メチル基、エチル基、プロピル基、イソプロピル基等の炭素数１～１０のアルキル基；メトキシ基、エトキシ基、プロピルオキシ基等の炭素数１～６のアルコキシ基；ヒドロキシ基；シアノ基；ニトロ基等が挙げられる。なお、置換基は１つであってもよいし、２以上有していてもよい。また、炭素数６～３０の置換アリール基は、置換基の炭素数およびアルキル基の炭素数の総数が６～３０であることを意味する。
When a substituted or unsubstituted aryl group having 6 to 30 carbon atoms has a substituent (a substituted aryl group having 6 to 30 carbon atoms), examples of the substituent include halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl, and isopropyl; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and propyloxy; hydroxyl groups; cyano groups; and nitro groups. The number of substituents may be one or more. A substituted aryl group having 6 to 30 carbon atoms means that the total number of carbon atoms in the substituent and the number of carbon atoms in the alkyl group is 6 to 30.
これらのうち、Ｒ７は、炭素数１～３０の置換もしくは非置換アルキル基であることが好ましく、メチル基、エチル基、プロピル基、イソプロピル基、ヘキシル基、オクチル基、デシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、ベンジル基、ヒドロキシメチル基、２－ヒドロキシエチル基であることがより好ましく、メチル基、エチル基、ベンジル基、２－ヒドロキシエチル基であることがさらに好ましく、メチル基、ベンジル基であることが特に好ましく、メチル基であることが最も好ましい。また、別の一実施形態において、Ｒ７は、炭素数６～２０のアリール基で置換された炭素数１～１０のアルキル基であることが好ましく、フェニル基で置換された炭素数１～５のアルキル基であることがより好ましく、ベンジル基、フェニルエチル基であることがさらに好ましく、ベンジル基であることが特に好ましい。
Among these, R 7 is preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, a benzyl group, a hydroxymethyl group, or a 2-hydroxyethyl group, even more preferably a methyl group, an ethyl group, a benzyl group, or a 2-hydroxyethyl group, particularly preferably a methyl group or a benzyl group, and most preferably a methyl group. In another embodiment, R 7 is preferably an alkyl group having 1 to 10 carbon atoms substituted with an aryl group having 6 to 20 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms substituted with a phenyl group, even more preferably a benzyl group or a phenylethyl group, and particularly preferably a benzyl group.
Ｘは、ハロゲン化物イオン（フッ化物イオン、塩化物イオン、臭化物イオン、ヨウ化物イオン等）、水酸化物イオン、有機スルホン酸イオン（メタンスルホン酸イオン、ｐ－トルエンスルホン酸イオン等）、テトラフルオロボレートアニオン、ヘキサフルオロフォスファートアニオンである。これらのうち、Ｘは、ハロゲン化物イオンであることが好ましく、塩化物イオン、臭化物イオンであることがより好ましい。
X is a halide ion (fluoride ion, chloride ion, bromide ion, iodide ion, etc.), hydroxide ion, organic sulfonate ion (methanesulfonate ion, p-toluenesulfonate ion, etc.), tetrafluoroborate anion, or hexafluorophosphate anion. Of these, X is preferably a halide ion, and more preferably a chloride ion or bromide ion.
Ｒ６が炭素数４～３０の置換もしくは非置換アルキル基である式（１）で表されるアンモニウム塩の具体例としては、ブチルトリメチルアンモニウムブロミド、ベンジルジメチルブチルアンモニウムクロリド等のブチル基を有するアンモニウム塩；ヘキシルトリメチルアンモニウムブロミド、ベンジルジメチルヘキシルアンモニウムクロリド等のヘキシル基を有するアンモニウム塩；オクチルトリメチルアンモニウムブロミド、ベンジルジメチルオクチルアンモニウムクロリド等のオクチル基を有するアンモニウム塩；デシルトリメチルアンモニウムブロミド、ベンジルジメチルデシルアンモニウムクロリド等のデシル基を有するアンモニウム塩；ドデシルトリメチルアンモニウムブロミド、ベンジルジメチルドデシルアンモニウムクロリド等のドデシル基を有するアンモニウム塩；テトラデシルトリメチルアンモニウムブロミド、ベンジルジメチルテトラデシルアンモニウムクロリド等のテトラデシル基を有するアンモニウム塩；ヘキサデシルトリメチルアンモニウムクロリド、ヘキサデシルトリメチルアンモニウムブロミド、ヘキサデシルトリメチルアンモニウムｐ－トルエンスルホネート、ヘキサデシルトリメチルアンモニウムヒドロキシド、エチルヘキサデシルジメチルアンモニウムクロリド、エチルヘキサデシルジメチルアンモニウムブロミド、ベンジルジメチルヘキサデシルアンモニウムクロリド等のヘキサデシル基を有するアンモニウム塩；トリメチルオクタデシルアンモニウムクロリド、トリメチルオクタデシルアンモニウムブロミド、ジメチルジオクタデシルアンモニウムクロリド、ジメチルジオクタデシルアンモニウムブロミド、ベンジルジメチルオクタデシルアンモニウムクロリド等のオクタデシル基を有するアンモニウム塩が挙げられる。
Specific examples of the ammonium salt represented by formula (1) in which R 6 is a substituted or unsubstituted alkyl group having 4 to 30 carbon atoms include ammonium salts having a butyl group, such as butyltrimethylammonium bromide and benzyldimethylbutylammonium chloride; ammonium salts having a hexyl group, such as hexyltrimethylammonium bromide and benzyldimethylhexylammonium chloride; ammonium salts having an octyl group, such as octyltrimethylammonium bromide and benzyldimethyloctylammonium chloride; ammonium salts having a decyl group, such as decyltrimethylammonium bromide and benzyldimethyldecylammonium chloride; ammonium salts having a dodecyl group, such as dodecyltrimethylammonium bromide and benzyldimethyldodecylammonium chloride; ammonium salts having a dodecyl group, such as dodecyltrimethylammonium bromide and benzyldimethyldodecylammonium chloride; tetradecyltrimethylammonium bromide and benzyldimethyldodecylammonium chloride; ammonium salts having a tetradecyl group, such as benzyldimethyltetradecylammonium chloride; ammonium salts having a hexadecyl group, such as hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium p-toluenesulfonate, hexadecyltrimethylammonium hydroxide, ethylhexadecyldimethylammonium chloride, ethylhexadecyldimethylammonium bromide, and benzyldimethylhexadecylammonium chloride; and ammonium salts having an octadecyl group, such as trimethyloctadecylammonium chloride, trimethyloctadecylammonium bromide, dimethyldioctadecylammonium chloride, dimethyldioctadecylammonium bromide, and benzyldimethyloctadecylammonium chloride.
Ｒ６が炭素数４～３０の置換もしくは非置換アルキル（ポリ）ヘテロアルキレン基である式（１）で表されるアンモニウム塩の具体例としては、トリメチルプロピルジ（オキシエチレン）アンモニウムクロリド、トリメチルプロピルオキシエチレンチオエチレンアンモニウムクロリド等が挙げられる。
Specific examples of the ammonium salt represented by formula (1) in which R 6 is a substituted or unsubstituted alkyl(poly)heteroalkylene group having 4 to 30 carbon atoms include trimethylpropyldi(oxyethylene)ammonium chloride, trimethylpropyloxyethylenethioethyleneammonium chloride, and the like.
Ｒ６が炭素数４～３０の置換もしくは非置換アリール（ポリ）ヘテロアルキレン基である式（１）で表されるアンモニウム塩の具体例としては、ベンジルジメチル－２－｛２－［４－（１，１，３，３－テトラメチルブチル）フェノキシ］エトキシ｝エチルアンモニウムクロリド（ベンゼトニウムクロリド）、ベンジルジメチルフェニルジ（オキシエチレン）アンモニウムクロリド等が挙げられる。
Specific examples of the ammonium salt represented by formula (1) in which R 6 is a substituted or unsubstituted aryl(poly)heteroalkylene group having 4 to 30 carbon atoms include benzyldimethyl-2-{2-[4-(1,1,3,3-tetramethylbutyl)phenoxy]ethoxy}ethylammonium chloride (benzethonium chloride) and benzyldimethylphenyldi(oxyethylene)ammonium chloride.
一実施形態において、上記式（１）で表されるアンモニウム塩は、Ｒ６が、炭素数４～３０の置換または非置換アリール（ポリ）ヘテロアルキレン基であり、Ｒ７の少なくとも１つが、炭素数６～３０の置換もしくは非置換アリール基であることが好ましく、Ｒ６が、炭素数８～２０の置換または非置換アリール（ポリ）ヘテロアルキレン基であり、Ｒ７の少なくとも１つが、炭素数６～１５の置換もしくは非置換アリール基であることがより好ましく、Ｒ６が、炭素数１０～１８の置換または非置換アリール（ポリ）ヘテロアルキレン基であり、Ｒ７の少なくとも１つが、炭素数６～１２の置換もしくは非置換アリール基であることがさらに好ましく、ベンジルジメチル－２－｛２－［４－（１，１，３，３－テトラメチルブチル）フェノキシ］エトキシ｝エチルアンモニウムクロリド（ベンゼトニウムクロリド）であることが特に好ましい。
In one embodiment, the ammonium salt represented by the above formula (1) is preferably such that R 6 is a substituted or unsubstituted aryl (poly)heteroalkylene group having 4 to 30 carbon atoms, and at least one of the R 7 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, more preferably such that R 6 is a substituted or unsubstituted aryl (poly)heteroalkylene group having 8 to 20 carbon atoms, and at least one of the R 7 is a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, even more preferably such that R 6 is a substituted or unsubstituted aryl (poly)heteroalkylene group having 10 to 18 carbon atoms, and at least one of the R 7 is a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and particularly preferably benzyldimethyl-2-{2-[4-(1,1,3,3-tetramethylbutyl)phenoxy]ethoxy}ethylammonium chloride (benzethonium chloride).
また、炭素数４～３０の置換もしくは非置換アルキル基を有するヘテロアリール塩としては、特に制限されないが、置換または非置換の窒素原子含有ヘテロアリール環が有する窒素原子の少なくとも１つが、炭素数４～３０の置換もしくは非置換アルキル基と結合してなるヘテロアリールカチオンの塩が挙げられる。
In addition, examples of heteroaryl salts having a substituted or unsubstituted alkyl group having 4 to 30 carbon atoms include, but are not limited to, salts of heteroaryl cations in which at least one nitrogen atom in a substituted or unsubstituted nitrogen atom-containing heteroaryl ring is bonded to a substituted or unsubstituted alkyl group having 4 to 30 carbon atoms.
前記窒素原子含有ヘテロアリール環としては、特に制限されないが、イミダゾール、ピラゾール、オキサゾール、イソキサゾール（イソオキサゾール）、チアゾール、イソチアゾール、ピリジン、ピラジン、ピリダジン、ピリミジン、キノリン、イソキノリン等の環が挙げられる。
The nitrogen atom-containing heteroaryl ring is not particularly limited, but examples thereof include imidazole, pyrazole, oxazole, isoxazole (isoxazole), thiazole, isothiazole, pyridine, pyrazine, pyridazine, pyrimidine, quinoline, and isoquinoline rings.
この際、窒素原子含有ヘテロアリール環が置換基を有する場合の置換基としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；メチル基、エチル基、プロピル基、イソプロピル基等の炭素数１～４のアルキル基；フェニル基、ナフチル基等の炭素数６～２０のアリール基；メトキシ基、エトキシ基、プロピルオキシ基等の炭素数１～６のアルコキシ基；ヒドロキシ基；シアノ基；ニトロ基等が挙げられる。
In this case, when the nitrogen atom-containing heteroaryl ring has a substituent, examples of the substituent include halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, and isopropyl groups; aryl groups having 6 to 20 carbon atoms such as phenyl and naphthyl groups; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and propyloxy groups; hydroxy groups; cyano groups; and nitro groups.
炭素数４～３０のアルキル基としては、特に制限されないが、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基、ドコシル基、テトラコシル基、ヘキサコシル基、オクタコシル基、トリアコンチル基等が挙げられる。
Alkyl groups having 4 to 30 carbon atoms are not particularly limited, but include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, docosyl, tetracosyl, hexacosyl, octacosyl, and triacontyl groups.
炭素数４～３０の置換もしくは非置換アルキル基が置換基を有する場合（炭素数４～３０の置換アルキル基）の置換基としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；メチル基、エチル基、プロピル基、イソプロピル基等の炭素数１～４のアルキル基；フェニル基、ナフチル基等の炭素数６～２０のアリール基；メトキシ基、エトキシ基、プロピルオキシ基等の炭素数１～６のアルコキシ基；ヒドロキシ基；シアノ基；ニトロ基等が挙げられる。なお、置換基は１つであってもよいし、２以上有していてもよい。また、炭素数４～３０の置換アルキル基は、置換基の炭素数およびアルキル基の炭素数の総数が４～３０であることを意味する。すなわち、炭素数４～３０の置換アルキル基においては、当該置換基の合計の炭素数が上述の範囲内となるように、炭素数が４以上のアルキル基（例えば、ブチル基、ヘキシル基、オクチル基、デシル基、ドデシル基等の炭素数４～１３のアルキル基）を含めることができる。
When a substituted or unsubstituted alkyl group having 4 to 30 carbon atoms has a substituent (a substituted alkyl group having 4 to 30 carbon atoms), examples of the substituent include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, and isopropyl; aryl groups having 6 to 20 carbon atoms such as phenyl and naphthyl; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and propyloxy; hydroxyl groups; cyano groups; and nitro groups. The number of substituents may be one or more. A substituted alkyl group having 4 to 30 carbon atoms means that the total number of carbon atoms in the substituent and the number of carbon atoms in the alkyl group is 4 to 30. In other words, a substituted alkyl group having 4 to 30 carbon atoms can include an alkyl group having 4 or more carbon atoms (for example, an alkyl group having 4 to 13 carbon atoms such as a butyl group, a hexyl group, an octyl group, a decyl group, and a dodecyl group) so that the total number of carbon atoms in the substituent falls within the above-mentioned range.
これらのうち、炭素数４～３０の置換もしくは非置換アルキル基は、炭素数８～２０の置換もしくは非置換アルキル基であることが好ましく、炭素数１２～１８のアルキル基であることがより好ましく、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基であることがさらに好ましく、アンダーカットを抑制できる観点から、ドデシル基、テトラデシル基、ヘキサデシル基であることが特に好ましい。
Among these, the substituted or unsubstituted alkyl group having 4 to 30 carbon atoms is preferably a substituted or unsubstituted alkyl group having 8 to 20 carbon atoms, more preferably an alkyl group having 12 to 18 carbon atoms, even more preferably a dodecyl group, a tetradecyl group, a hexadecyl group, or an octadecyl group, and from the viewpoint of suppressing undercut, a dodecyl group, a tetradecyl group, or a hexadecyl group is particularly preferable.
炭素数４～３０の置換もしくは非置換アルキル基を有するヘテロアリールカチオンの対アニオンは、特に制限されないがフッ化物イオン、塩化物イオン、臭化物イオン、ヨウ化物イオン等のハロゲン化物イオン；水酸化物イオン；メタンスルホン酸イオン、ｐ－トルエンスルホン酸イオン等の有機スルホン酸イオン；テトラフルオロボレートアニオン；ヘキサフルオロフォスファートアニオン等が挙げられる。これらのうち、前記対アニオンは、ハロゲン化物イオンであることが好ましく、塩化物イオン、臭化物イオンであることがより好ましい。
The counter anion of a heteroaryl cation having a substituted or unsubstituted alkyl group having 4 to 30 carbon atoms is not particularly limited, but examples thereof include halide ions such as fluoride ion, chloride ion, bromide ion, and iodide ion; hydroxide ion; organic sulfonate ions such as methanesulfonate ion and p-toluenesulfonate ion; tetrafluoroborate anion; and hexafluorophosphate anion. Of these, the counter anion is preferably a halide ion, and more preferably a chloride ion or bromide ion.
炭素数４～３０の置換もしくは非置換アルキル基を有するヘテロアリール塩の具体例としては、１－ブチル－３－メチルイミダゾリウムクロリド、１－ブチル－３－メチルイミダゾリウムブロミド、１－ヘキシル－３－メチルイミダゾリウムクロリド、１－ヘキシル－３－メチルイミダゾリウムブロミド、１－オクチル－３－メチルイミダゾリウムクロリド、１－オクチル－３－メチルイミダゾリウムブロミド、１－デシル－３－メチルイミダゾリウムクロリド、１－デシル－３－メチルイミダゾリウムブロミド、１－ドデシル－３－メチルイミダゾリウムクロリド、１－ドデシル－３－メチルイミダゾリウムブロミド、１－テトラデシル－３－メチルイミダゾリウムクロリド、１－テトラデシル－３－メチルイミダゾリウムブロミド、１－ヘキサデシル－３－メチルイミダゾリウムクロリド、１－ヘキサデシル－３－メチルイミダゾリウムブロミド、１－オクタデシル３－メチルイミダゾリウムクロリド、１－オクタデシル３－メチルイミダゾリウムブロミド等のイミダゾリウム塩；３－ブチルオキサゾリウムクロリド、３－ヘキシルオキサゾリウムクロリド、３－オクチルオキサゾリウムクロリド、３－デシルオキサゾリウムクロリド、３－ドデシルオキサゾリウムクロリド、３－テトラデシルオキサゾリウムクロリド、３－ヘキサデシルオキサゾリウムクロリド、３－オクタデシルオキサゾリウムクロリド等のオキサゾリウム塩；３－ブチルチアゾリウムクロリド、３－ヘキシルチアゾリウムクロリド、３－オクチルチアゾリウムクロリド、３－デシルチアゾリウムクロリド、３－ドデシルチアゾリウムクロリド、３－テトラデシルチアゾリウムクロリド、３－ヘキサデシルチアゾリウムクロリド、３－オクタデシルチアゾリウムクロリド等のチアゾリウム塩；１－ブチルピリジニウムクロリド、１－ヘキシルピリジニウムクロリド、１－オクチルピリジニウムクロリド、１－デシルピリジニウムクロリド、１－ドデシルピリジニウムクロリド、１－テトラデシルピリジニウムクロリド、１－テトラデシルピリジニウムブロミド、１－ヘキサデシルピリジニウムクロリド、１－ヘキサデシルピリジニウムブロミド、１－オクタデシルピリジニウムクロリド、１－オクタデシルピリジニウムブロミド等のピリジニウム塩；１－ブチルピリミジニウムクロリド、１－ヘキシルピリミジニウムクロリド、１－オクチルピリミジニウムクロリド、１－デシルピリミジニウムクロリド、１－ドデシルピリミジニウムクロリド、１－テトラデシルピリミジニウムクロリド、１－ヘキサデシルピリミジニウムクロリド、１－オクタデシルピリミジニウムクロリド等のピリミジニウム塩；ブチルキノリニウムクロリド、ヘキシルキノリニウムクロリド、オクチルキノリニウムクロリド、デシルキノリニウムクロリド、ドデシルキノリニウムクロリド、テトラデシルキノリニウムクロリド、ヘキサデシルキノリニウムクロリド、オクタデシルキノリニウムクロリド等のキノリニウム塩；デシルイソキノリニウムクロリド、ドデシルイソキノリニウムクロリド、テトラデシルイソキノリニウムクロリド、ヘキサデシルイソキノリニウムクロリド、オクタデシルイソキノリニウムクロリド等のイソキノリニウム塩等が挙げられる。さらに、これらは水和物として用いてもよい。
Specific examples of heteroaryl salts having a substituted or unsubstituted alkyl group having 4 to 30 carbon atoms include 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium bromide, 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium bromide, 1-octyl-3-methylimidazolium chloride, 1-octyl-3-methylimidazolium bromide, 1-decyl-3-methylimidazolium chloride, 1-decyl-3-methylimidazolium bromide, 1-dodecyl-3-methylimidazolium chloride, 1-dodecyl-3-methylimidazolium bromide, 1-tetradecyl-3-methylimidazolium chloride, 1-tetradecyl-3-methylimidazolium bromide, 1-hexadecane, 1- ... Imidazolium salts such as 1-hexyl-3-methylimidazolium chloride, 1-hexadecyl-3-methylimidazolium bromide, 1-octadecyl 3-methylimidazolium chloride, and 1-octadecyl 3-methylimidazolium bromide; oxazolium salts such as 3-butyloxazolium chloride, 3-hexyloxazolium chloride, 3-octyloxazolium chloride, 3-decyloxazolium chloride, 3-dodecyloxazolium chloride, 3-tetradecyloxazolium chloride, 3-hexadecyloxazolium chloride, and 3-octadecyloxazolium chloride; 3-butylthiazolium chloride, 3-hexylthiazolium chloride, 3-octylthiazolium chloride, 3-decylthiazolium chloride, and 3-dodecylthiazo thiazolium chloride, 3-tetradecyl thiazolium chloride, 3-hexadecyl thiazolium chloride, 3-octadecyl thiazolium chloride, and other thiazolium salts; pyridinium salts such as 1-butyl pyridinium chloride, 1-hexyl pyridinium chloride, 1-octyl pyridinium chloride, 1-decyl pyridinium chloride, 1-dodecyl pyridinium chloride, 1-tetradecyl pyridinium chloride, 1-tetradecyl pyridinium bromide, 1-hexadecyl pyridinium chloride, 1-hexadecyl pyridinium bromide, 1-octadecyl pyridinium chloride, and 1-octadecyl pyridinium bromide; 1-butyl pyrimidinium chloride, 1-hexyl pyrimidinium chloride, 1-octyl pyrimidinium chloride, 1-decyl pyridinium chloride, and other pyridinium salts; Examples of suitable quinolinium salts include pyrimidinium chloride, 1-dodecylpyrimidinium chloride, 1-tetradecylpyrimidinium chloride, 1-hexadecylpyrimidinium chloride, and 1-octadecylpyrimidinium chloride; quinolinium salts include butylquinolinium chloride, hexylquinolinium chloride, octylquinolinium chloride, decylquinolinium chloride, dodecylquinolinium chloride, tetradecylquinolinium chloride, hexadecylquinolinium chloride, and octadecylquinolinium chloride; and isoquinolinium salts include decylisoquinolinium chloride, dodecylisoquinolinium chloride, tetradecylisoquinolinium chloride, hexadecylisoquinolinium chloride, and octadecylisoquinolinium chloride. These may also be used as hydrates.
これらのうち、（ｉｉ）カチオン性界面活性剤としては、式（４）で表されるアンモニウム塩（ここで、Ｒ６は、炭素数８～２０の置換もしくは非置換アルキル基、または炭素数８～２０の置換もしくは非置換アリール（ポリ）ヘテロアルキレン基である）、炭素数８～２０の置換もしくは非置換アルキル基を有するイミダゾリウム塩、炭素数８～２０の置換もしくは非置換アルキル基を有するピリジニウム塩であることが好ましく、式（４）で表されるアンモニウム塩（ここで、Ｒ６は、炭素数１２～２０の置換もしくは非置換アリール（ポリ）ヘテロアルキレン基であり、Ｒ７の少なくとも１つが、炭素数６～１２の置換もしくは非置換アリール基である）、炭素数１０～１８の置換もしくは非置換アルキル基を有するイミダゾリウム塩、炭素数１０～１８の置換もしくは非置換アルキル基を有するピリジニウム塩であることがより好ましく、式（４）で表されるアンモニウム塩（ここで、Ｒ６は、炭素数１２～１８の置換もしくは非置換アリール（ポリ）ヘテロアルキレン基であり、Ｒ７の少なくとも１つが、炭素数６～１２の置換もしくは非置換アリール基である）、炭素数１２～１８の置換もしくは非置換アルキル基を有するイミダゾリウム塩、炭素数１２～１８の置換もしくは非置換アルキル基を有するピリジニウム塩であることがさらに好ましく、式（４）で表されるアンモニウム塩（ここで、Ｒ６は、炭素数１２～１６の置換もしくは非置換アリール（ポリ）ヘテロアルキレン基であり、Ｒ７の少なくとも１つが、炭素数６～１２の置換もしくは非置換アリール基である）、炭素数１２～１６の置換もしくは非置換アルキル基を有するピリジニウム塩であることが特に好ましく、ベンゼトニウムクロリド、ベンゼトニウムブロミドであることが最も好ましい。
Of these, the (ii) cationic surfactant is preferably an ammonium salt represented by formula (4) (wherein R 6 is a substituted or unsubstituted alkyl group having 8 to 20 carbon atoms, or a substituted or unsubstituted aryl (poly)heteroalkylene group having 8 to 20 carbon atoms), an imidazolium salt having a substituted or unsubstituted alkyl group having 8 to 20 carbon atoms, or a pyridinium salt having a substituted or unsubstituted alkyl group having 8 to 20 carbon atoms; more preferably an ammonium salt represented by formula (4) (wherein R 6 is a substituted or unsubstituted aryl (poly)heteroalkylene group having 12 to 20 carbon atoms, and at least one of R 7 is a substituted or unsubstituted aryl group having 6 to 12 carbon atoms), an imidazolium salt having a substituted or unsubstituted alkyl group having 10 to 18 carbon atoms, or a pyridinium salt having a substituted or unsubstituted alkyl group having 10 to 18 carbon atoms; and more preferably an ammonium salt represented by formula (4) (wherein R 6 is a substituted or unsubstituted aryl (poly)heteroalkylene group having 12 to 18 carbon atoms, and and more preferably an ammonium salt represented by formula (4) (wherein R 6 is a substituted or unsubstituted aryl (poly)heteroalkylene group having 12 to 16 carbon atoms, and at least one of R 7 is a substituted or unsubstituted aryl group having 6 to 12 carbon atoms), or a pyridinium salt having a substituted or unsubstituted alkyl group having 12 to 18 carbon atoms; and most preferably benzethonium chloride or benzethonium bromide.
なお、上述の（ｉｉ）カチオン性界面活性剤またはその塩は単独で用いても、２種以上を組み合わせて用いてもよい。すなわち、好ましい一実施形態において、（ｉｉ）カチオン性界面活性剤またはその塩は、式（４）で表されるアンモニウム塩（ここで、Ｒ６は、炭素数１０～２０の置換もしくは非置換アルキル基、または炭素数１０～２０の置換もしくは非置換アリール（ポリ）ヘテロアルキレン基である）、炭素数１０～２０の置換もしくは非置換アルキル基を有するイミダゾリウム塩、および炭素数１０～２０の置換もしくは非置換アルキル基を有するピリジニウム塩からなる群から選択される少なくとも1つを含むことが好ましく、式（４）で表されるアンモニウム塩（ここで、Ｒ６は、炭素数１６～２０の置換もしくは非置換アリール（ポリ）ヘテロアルキレン基であり、Ｒ７の少なくとも１つが、炭素数６～１２の置換もしくは非置換アリール基である）、炭素数１０～１６の置換もしくは非置換アルキル基を有するイミダゾリウム塩、および炭素数１０～１６の置換もしくは非置換アルキル基を有するピリジニウム塩からなる群から選択される少なくとも1つを含むことがより好ましく、式（４）で表されるアンモニウム塩（ここで、Ｒ６は、炭素数１８～２０の置換もしくは非置換アリール（ポリ）ヘテロアルキレン基であり、Ｒ７の少なくとも１つが、炭素数６～１２の置換もしくは非置換アリール基である）、炭素数１０～１４の置換もしくは非置換アルキル基を有するイミダゾリウム塩、および炭素数１０～１４の置換もしくは非置換アルキル基を有するピリジニウム塩からなる群から選択される少なくとも1つを含むことがさらに好ましく、式（４）で表されるアンモニウム塩（ここで、Ｒ６は、炭素数１８～２０の置換もしくは非置換アリール（ポリ）ヘテロアルキレン基であり、Ｒ７の少なくとも１つが、炭素数６～１２の置換もしくは非置換アリール基である）、および炭素数１０～１４の置換もしくは非置換アルキル基を有するピリジニウム塩からなる群から選択される少なくとも1つを含むことが特に好ましく、ベンゼトニウムクロリドおよびベンゼトニウムブロミドからなる群から選択される少なくとも1つを含むことが最も好ましい。
The above-mentioned (ii) cationic surfactants or salts thereof may be used alone or in combination of two or more kinds. That is, in a preferred embodiment, (ii) the cationic surfactant or its salt preferably includes at least one selected from the group consisting of an ammonium salt represented by formula (4) (wherein R 6 is a substituted or unsubstituted alkyl group having 10 to 20 carbon atoms, or a substituted or unsubstituted aryl (poly)heteroalkylene group having 10 to 20 carbon atoms), an imidazolium salt having a substituted or unsubstituted alkyl group having 10 to 20 carbon atoms, and a pyridinium salt having a substituted or unsubstituted alkyl group having 10 to 20 carbon atoms, and more preferably includes at least one selected from the group consisting of an ammonium salt represented by formula (4) (wherein R 6 is a substituted or unsubstituted aryl (poly)heteroalkylene group having 16 to 20 carbon atoms, and at least one of R 7 is a substituted or unsubstituted aryl group having 6 to 12 carbon atoms), an imidazolium salt having a substituted or unsubstituted alkyl group having 10 to 16 carbon atoms, and a pyridinium salt having a substituted or unsubstituted alkyl group having 10 to 16 carbon atoms, and It is more preferable that the compound contains at least one selected from the group consisting of an ammonium salt represented by formula (4) (wherein R 6 is a substituted or unsubstituted aryl (poly)heteroalkylene group having 18 to 20 carbon atoms, and at least one of R 7 is a substituted or unsubstituted aryl group having 6 to 12 carbon atoms), an imidazolium salt having a substituted or unsubstituted alkyl group having 10 to 14 carbon atoms, and a pyridinium salt having a substituted or unsubstituted alkyl group having 10 to 14 carbon atoms, and it is particularly preferable that the compound contains at least one selected from the group consisting of an ammonium salt represented by formula (4) (wherein R 6 is a substituted or unsubstituted aryl (poly)heteroalkylene group having 18 to 20 carbon atoms, and at least one of R 7 is a substituted or unsubstituted aryl group having 6 to 12 carbon atoms), and a pyridinium salt having a substituted or unsubstituted alkyl group having 10 to 14 carbon atoms, and it is most preferable that the compound contains at least one selected from the group consisting of benzethonium chloride and benzethonium bromide.
（ｉｉ）カチオン性界面活性剤の好ましい具体例として、ドデシルピリジニウムクロリド，ベンジルジメチルヘキサデシルアンモニウムクロリド，ベンゼトニウムクロリド，１－ヘキサデシル－３－メチルイミダゾリウムクロリド，オクチルトリメチルアンモニウムクロリドなどが挙げられる。（ｉｉ）カチオン性界面活性剤は、１種のみであってもよく、２種以上を組み合わせてもよい。
(ii) Preferred specific examples of cationic surfactants include dodecylpyridinium chloride, benzyldimethylhexadecylammonium chloride, benzethonium chloride, 1-hexadecyl-3-methylimidazolium chloride, and octyltrimethylammonium chloride. (ii) The cationic surfactant may be one type only, or two or more types may be combined.
水性組成物中の（ｉｉ）カチオン性界面活性剤またはその塩の濃度は、例えば、水性組成物の全量基準で０．００００１～０．２質量％であり、好ましくは０．０００１～０．１質量％であり、より好ましくは０．０００５～０．０８質量％、さらに好ましくは０．０００７～０．０３質量％、特に好ましくは０．００１～０．０１質量％である。
The concentration of (ii) the cationic surfactant or its salt in the aqueous composition is, for example, 0.00001 to 0.2 mass%, preferably 0.0001 to 0.1 mass%, more preferably 0.0005 to 0.08 mass%, even more preferably 0.0007 to 0.03 mass%, and particularly preferably 0.001 to 0.01 mass%, based on the total amount of the aqueous composition.
（ｉｉｉ）アルキル硫酸／スルホン酸またはその塩
水性組成物における（ｉｉｉ）アルキル硫酸／スルホン酸またはその塩（以下、アルキル硫酸／アルキルスルホン酸等ともいう）の種類について特に制限はないものの、水性組成物は、少なくとも炭素数６～３０のアルキル基を有するアルキル硫酸／アルキルスルホン酸等を含むことが好ましい。
（ｉｉｉ）アルキル硫酸／アルキルスルホン酸等は、炭素数６～２０のアリール基を有していてもよく、好ましくは、炭素数８～２０のアルキル基及び／又は炭素数６～１６のアリール基を有し、より好ましくは、炭素数１０～１６のアルキル基及び／又は炭素数６～１２のアリール基を有する。 (iii) Alkyl Sulfuric Acid/Sulfonic Acid or Salt thereof Although there are no particular limitations on the type of (iii) alkyl sulfuric acid/sulfonic acid or salt thereof (hereinafter also referred to as alkyl sulfuric acid/alkyl sulfonic acid, etc.) in the aqueous composition, it is preferable that the aqueous composition contains an alkyl sulfuric acid/alkyl sulfonic acid, etc. having an alkyl group having at least 6 to 30 carbon atoms.
(iii) The alkyl sulfate/alkyl sulfonate etc. may have an aryl group having 6 to 20 carbon atoms, preferably has an alkyl group having 8 to 20 carbon atoms and/or an aryl group having 6 to 16 carbon atoms, and more preferably has an alkyl group having 10 to 16 carbon atoms and/or an aryl group having 6 to 12 carbon atoms.
水性組成物における（ｉｉｉ）アルキル硫酸／スルホン酸またはその塩（以下、アルキル硫酸／アルキルスルホン酸等ともいう）の種類について特に制限はないものの、水性組成物は、少なくとも炭素数６～３０のアルキル基を有するアルキル硫酸／アルキルスルホン酸等を含むことが好ましい。
（ｉｉｉ）アルキル硫酸／アルキルスルホン酸等は、炭素数６～２０のアリール基を有していてもよく、好ましくは、炭素数８～２０のアルキル基及び／又は炭素数６～１６のアリール基を有し、より好ましくは、炭素数１０～１６のアルキル基及び／又は炭素数６～１２のアリール基を有する。 (iii) Alkyl Sulfuric Acid/Sulfonic Acid or Salt thereof Although there are no particular limitations on the type of (iii) alkyl sulfuric acid/sulfonic acid or salt thereof (hereinafter also referred to as alkyl sulfuric acid/alkyl sulfonic acid, etc.) in the aqueous composition, it is preferable that the aqueous composition contains an alkyl sulfuric acid/alkyl sulfonic acid, etc. having an alkyl group having at least 6 to 30 carbon atoms.
(iii) The alkyl sulfate/alkyl sulfonate etc. may have an aryl group having 6 to 20 carbon atoms, preferably has an alkyl group having 8 to 20 carbon atoms and/or an aryl group having 6 to 16 carbon atoms, and more preferably has an alkyl group having 10 to 16 carbon atoms and/or an aryl group having 6 to 12 carbon atoms.
（ｉｉｉ）アルキル硫酸／スルホン酸またはその塩の好ましい具体例として、ドデシル硫酸、ドデシル硫酸ナトリウム、ドデシル硫酸アンモニウム、４－ドデシルベンゼンスルホン酸などのドデシルベンゼンスルホン酸、ドデシルベンゼンスルホン酸ナトリウム、ドデシルベンゼンスルホン酸アンモニウムなどが挙げられる。（ｉｉｉ）アルキル硫酸／アルキルスルホン酸等は、１種のみであってもよく、２種以上を組み合わせてもよい。
(iii) Preferred specific examples of alkyl sulfates/sulfonic acids or their salts include dodecyl sulfate, sodium dodecyl sulfate, ammonium dodecyl sulfate, dodecylbenzenesulfonic acids such as 4-dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, and ammonium dodecylbenzenesulfonate. (iii) The alkyl sulfates/alkyl sulfonic acids, etc. may be of one type only, or may be of two or more types in combination.
水性組成物中の（ｉｉｉ）アルキル硫酸／アルキルスルホン酸等の濃度は、例えば、水性組成物の全量基準で０．００１～２．０質量％であり、好ましくは０．００２～１．０質量％であり、好ましくは０．００５～０．５質量％であり、より好ましくは０．００７～０．０５質量％、さらに好ましくは０．００７～０．０３質量％、特に好ましくは０．００８～０．０２質量％である。
The concentration of (iii) alkyl sulfate/alkyl sulfonate, etc. in the aqueous composition is, for example, 0.001 to 2.0 mass% based on the total amount of the aqueous composition, preferably 0.002 to 1.0 mass%, preferably 0.005 to 0.5 mass%, more preferably 0.007 to 0.05 mass%, even more preferably 0.007 to 0.03 mass%, and particularly preferably 0.008 to 0.02 mass%.
（Ｄ）添加剤
水性組成物においては、添加剤（Ｄ）として、過酸化水素安定化剤、有機溶媒、カチオン性界面活性剤及びアルキル硫酸／スルホン酸またはその塩を除く界面活性剤、キレート剤、消泡剤、（Ｂ）を除く酸、アルカリ、ケイ素含有化合物等を含んでいても良い。特に過酸化水素安定化剤に関しては、アルコール類、尿素、フェニル尿素、有機カルボン酸類、有機ホスホン酸類、有機リン酸類等の公知のものを適宜添加してもよい。 (D) Additives
The aqueous composition may contain, as additives (D), hydrogen peroxide stabilizers, organic solvents, surfactants other than cationic surfactants and alkyl sulfates/sulfonic acids or salts thereof, chelating agents, antifoaming agents, acids other than (B), alkalis, silicon-containing compounds, etc. In particular, with regard to hydrogen peroxide stabilizers, known ones such as alcohols, urea, phenylurea, organic carboxylic acids, organic phosphonic acids, and organic phosphoric acids may be appropriately added.
水性組成物においては、添加剤（Ｄ）として、過酸化水素安定化剤、有機溶媒、カチオン性界面活性剤及びアルキル硫酸／スルホン酸またはその塩を除く界面活性剤、キレート剤、消泡剤、（Ｂ）を除く酸、アルカリ、ケイ素含有化合物等を含んでいても良い。特に過酸化水素安定化剤に関しては、アルコール類、尿素、フェニル尿素、有機カルボン酸類、有機ホスホン酸類、有機リン酸類等の公知のものを適宜添加してもよい。 (D) Additives
The aqueous composition may contain, as additives (D), hydrogen peroxide stabilizers, organic solvents, surfactants other than cationic surfactants and alkyl sulfates/sulfonic acids or salts thereof, chelating agents, antifoaming agents, acids other than (B), alkalis, silicon-containing compounds, etc. In particular, with regard to hydrogen peroxide stabilizers, known ones such as alcohols, urea, phenylurea, organic carboxylic acids, organic phosphonic acids, and organic phosphoric acids may be appropriately added.
［その他の成分］
本発明の水性組成物は、上述の各成分のほかに、水および必要に応じてその他の水性組成物に通常用いられる各種添加剤の１種以上を、本発明の水性組成物の効果を害しない範囲で含むことができる。
水としては、蒸留、イオン交換処理、フイルター処理、各種吸着処理などによって、金属イオンや有機不純物、パーテイクルなどが除去されたものが好ましく、純水がより好ましく、特に超純水が好ましい。水性組成物における水の含有量は、水性組成物におけるその他の成分の含有量などに応じて適宜、調整され、特に制限はないものの、水性組成物の全質量に対して、例えば、７０～９９質量％であり、７５～９８質量％であることが好ましく、８５～９５質量％であることがより好ましい。 [Other ingredients]
In addition to the above-mentioned components, the aqueous composition of the present invention may contain water and, as necessary, one or more of various additives that are commonly used in other aqueous compositions, within a range that does not impair the effects of the aqueous composition of the present invention.
The water is preferably water from which metal ions, organic impurities, particles, etc. have been removed by distillation, ion exchange treatment, filtration, various adsorption treatments, etc., and is more preferably pure water, and particularly preferably ultrapure water. The content of water in the aqueous composition is appropriately adjusted depending on the contents of other components in the aqueous composition, and is not particularly limited, but is, for example, 70 to 99 mass%, preferably 75 to 98 mass%, and more preferably 85 to 95 mass% based on the total mass of the aqueous composition.
本発明の水性組成物は、上述の各成分のほかに、水および必要に応じてその他の水性組成物に通常用いられる各種添加剤の１種以上を、本発明の水性組成物の効果を害しない範囲で含むことができる。
水としては、蒸留、イオン交換処理、フイルター処理、各種吸着処理などによって、金属イオンや有機不純物、パーテイクルなどが除去されたものが好ましく、純水がより好ましく、特に超純水が好ましい。水性組成物における水の含有量は、水性組成物におけるその他の成分の含有量などに応じて適宜、調整され、特に制限はないものの、水性組成物の全質量に対して、例えば、７０～９９質量％であり、７５～９８質量％であることが好ましく、８５～９５質量％であることがより好ましい。 [Other ingredients]
In addition to the above-mentioned components, the aqueous composition of the present invention may contain water and, as necessary, one or more of various additives that are commonly used in other aqueous compositions, within a range that does not impair the effects of the aqueous composition of the present invention.
The water is preferably water from which metal ions, organic impurities, particles, etc. have been removed by distillation, ion exchange treatment, filtration, various adsorption treatments, etc., and is more preferably pure water, and particularly preferably ultrapure water. The content of water in the aqueous composition is appropriately adjusted depending on the contents of other components in the aqueous composition, and is not particularly limited, but is, for example, 70 to 99 mass%, preferably 75 to 98 mass%, and more preferably 85 to 95 mass% based on the total mass of the aqueous composition.
水性組成物は溶解液であることが好ましく、研磨粒子等の固形粒子は含有しないことが好ましい。
The aqueous composition is preferably a solution and preferably does not contain solid particles such as abrasive particles.
水性組成物において、成分（Ａ）の酸化剤、成分（Ｂ）の酸、成分（Ｃ）の腐食抑制剤および水の合計含有量、あるいは、これにさらに成分（Ｄ）の添加剤を加えた合計含有量は、水性組成物の全質量に対して、７０～１００質量％であることが好ましく、より好ましくは８５～１００質量％、さらに好ましくは９０～１００質量％、特に好ましくは９５～１００質量％である。
In the aqueous composition, the total content of the oxidizing agent (component (A)), the acid (component (B)), the corrosion inhibitor (component (C)) and water, or the total content of these plus the additive (component (D)), is preferably 70 to 100% by mass, more preferably 85 to 100% by mass, even more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass, based on the total mass of the aqueous composition.
［１－２．エッチング用の水性組成物の性状および性能］
水性組成物におけるｐＨ値の範囲としては、０．０以上かつ３．０以下であり、ｐＨ値は好ましくは０．３～３．０であり、より好ましくは０．５～２．０であり、さらに好ましくは０．７～１．８であり、特に好ましくは０．７～１．４である。 [1-2. Properties and performance of aqueous etching composition]
The pH range of the aqueous composition is 0.0 or more and 3.0 or less, and the pH is preferably 0.3 to 3.0, more preferably 0.5 to 2.0, even more preferably 0.7 to 1.8, and particularly preferably 0.7 to 1.4.
水性組成物におけるｐＨ値の範囲としては、０．０以上かつ３．０以下であり、ｐＨ値は好ましくは０．３～３．０であり、より好ましくは０．５～２．０であり、さらに好ましくは０．７～１．８であり、特に好ましくは０．７～１．４である。 [1-2. Properties and performance of aqueous etching composition]
The pH range of the aqueous composition is 0.0 or more and 3.0 or less, and the pH is preferably 0.3 to 3.0, more preferably 0.5 to 2.0, even more preferably 0.7 to 1.8, and particularly preferably 0.7 to 1.4.
水性組成物は、優れたアンダーカット抑制効果を奏する。具体的には、銅よりもイオン化傾向の大きい金属、例えばニッケル、またはニッケル合金を含むめっき層の下側、すなわち基板側に形成された銅または銅合金を含み、例えば実質的には銅合金によって形成されたシード層に対して、主として端部が過剰にエッチングされてしまうアンダーカットを効率的に防止できる。具体的には、後述する測定方法において、アンダーカットを１．５μｍ以下に抑えることができ、より好ましくは１．０μｍ以下に抑えることができ、さらに好ましくは、０．７μｍ以下に抑えることが可能である。
The aqueous composition has an excellent effect of suppressing undercut. Specifically, it can efficiently prevent undercut, which is mainly caused by excessive etching of the ends of a seed layer that contains copper or a copper alloy and is formed on the underside of a plating layer containing a metal with a greater ionization tendency than copper, such as nickel or a nickel alloy, i.e., on the substrate side, and is essentially made of a copper alloy. Specifically, in the measurement method described below, it is possible to suppress undercut to 1.5 μm or less, more preferably to suppress it to 1.0 μm or less, and even more preferably to suppress it to 0.7 μm or less.
［１－３．水性組成物の調製］
水性組成物は、成分（Ａ）、成分（Ｂ）、成分（Ｃ）、成分（Ｄ）および水、さらには必要に応じてその他の成分を均一に攪拌することで調製することができる。これらの成分の攪拌方法は特に制限されなく、水性組成物の調製において通常用いられる撹拌方法を採用することができる。 [1-3. Preparation of aqueous composition]
The aqueous composition can be prepared by uniformly stirring the components (A), (B), (C), (D), and water, and, if necessary, other components. The method of stirring these components is not particularly limited, and any stirring method commonly used in the preparation of aqueous compositions can be used.
水性組成物は、成分（Ａ）、成分（Ｂ）、成分（Ｃ）、成分（Ｄ）および水、さらには必要に応じてその他の成分を均一に攪拌することで調製することができる。これらの成分の攪拌方法は特に制限されなく、水性組成物の調製において通常用いられる撹拌方法を採用することができる。 [1-3. Preparation of aqueous composition]
The aqueous composition can be prepared by uniformly stirring the components (A), (B), (C), (D), and water, and, if necessary, other components. The method of stirring these components is not particularly limited, and any stirring method commonly used in the preparation of aqueous compositions can be used.
［１－４．水性組成物の用途］
水性組成物は、銅および銅合金のエッチングに用いることができる。特に、次世代のＤＲＡＭメモリやＮＡＮＤメモリなどのパッケージングの用途において、バンプを使用したプロセス向けの材料として、ニッケルおよびニッケル合金からなる群より選択される１種以上と、任意選択的に錫、錫合金、金および金合金からなる群より選択される１種以上とを含む場合に、これらの金属の溶解を抑制しつつ、銅および銅合金から選ばれる少なくとも１種を選択的にエッチングするための水性組成物として好適に用いることができる。 [1-4. Uses of the aqueous composition]
The aqueous composition can be used for etching copper and copper alloys. In particular, in packaging applications such as next-generation DRAM memories and NAND memories, when materials for processes using bumps include at least one selected from the group consisting of nickel and nickel alloys, and optionally at least one selected from the group consisting of tin, tin alloys, gold and gold alloys, the aqueous composition can be suitably used as an aqueous composition for selectively etching at least one selected from copper and copper alloys while suppressing dissolution of these metals.
水性組成物は、銅および銅合金のエッチングに用いることができる。特に、次世代のＤＲＡＭメモリやＮＡＮＤメモリなどのパッケージングの用途において、バンプを使用したプロセス向けの材料として、ニッケルおよびニッケル合金からなる群より選択される１種以上と、任意選択的に錫、錫合金、金および金合金からなる群より選択される１種以上とを含む場合に、これらの金属の溶解を抑制しつつ、銅および銅合金から選ばれる少なくとも１種を選択的にエッチングするための水性組成物として好適に用いることができる。 [1-4. Uses of the aqueous composition]
The aqueous composition can be used for etching copper and copper alloys. In particular, in packaging applications such as next-generation DRAM memories and NAND memories, when materials for processes using bumps include at least one selected from the group consisting of nickel and nickel alloys, and optionally at least one selected from the group consisting of tin, tin alloys, gold and gold alloys, the aqueous composition can be suitably used as an aqueous composition for selectively etching at least one selected from copper and copper alloys while suppressing dissolution of these metals.
＜２．エッチング方法＞
本発明のエッチング方法は、主として半導体基板を対象とする方法であり、上述の水性組成物を用いて、銅を含む半導体基板のシード層を有する中間製品のシード層をエッチングする工程を含む。エッチング方法の対象とされる半導体基板は、上述のシード層に接するように積層されていて、銅よりもイオン化傾向の大きい金属を含む層をシード層よりも上方側に有することが好ましい。 2. Etching method
The etching method of the present invention is a method mainly for semiconductor substrates, and includes a step of etching a seed layer of an intermediate product having a copper-containing seed layer of a semiconductor substrate using the above-mentioned aqueous composition. The semiconductor substrate to be etched by the etching method is preferably laminated in contact with the above-mentioned seed layer and has a layer containing a metal having a higher ionization tendency than copper above the seed layer.
本発明のエッチング方法は、主として半導体基板を対象とする方法であり、上述の水性組成物を用いて、銅を含む半導体基板のシード層を有する中間製品のシード層をエッチングする工程を含む。エッチング方法の対象とされる半導体基板は、上述のシード層に接するように積層されていて、銅よりもイオン化傾向の大きい金属を含む層をシード層よりも上方側に有することが好ましい。 2. Etching method
The etching method of the present invention is a method mainly for semiconductor substrates, and includes a step of etching a seed layer of an intermediate product having a copper-containing seed layer of a semiconductor substrate using the above-mentioned aqueous composition. The semiconductor substrate to be etched by the etching method is preferably laminated in contact with the above-mentioned seed layer and has a layer containing a metal having a higher ionization tendency than copper above the seed layer.
エッチング工程における水性組成物の使用温度に特に制限はないが、１０～５０℃の温度が好ましく、より好ましくは２０～４５℃であり、さらに好ましくは２５～４０℃である。水性組成物の温度が１０℃以上であれば、エッチング速度が良好となるため、優れた生産効率が得られる。一方、水性組成物の温度が５０℃以下であれば、液組成変化を抑制し、エッチング条件を一定に保つことができる。水性組成物の温度を高くすることで、エッチング速度は上昇するが、水性組成物の組成変化（過酸化水素の分解）を小さく抑えることなども考慮した上で、適宜最適な処理温度を決定すればよい。
There are no particular limitations on the temperature at which the aqueous composition is used in the etching process, but a temperature of 10 to 50°C is preferred, more preferably 20 to 45°C, and even more preferably 25 to 40°C. If the temperature of the aqueous composition is 10°C or higher, the etching rate is good, resulting in excellent production efficiency. On the other hand, if the temperature of the aqueous composition is 50°C or lower, changes in the liquid composition can be suppressed and the etching conditions can be kept constant. Increasing the temperature of the aqueous composition increases the etching rate, but the optimal processing temperature can be determined appropriately, taking into consideration factors such as minimizing changes in the composition of the aqueous composition (decomposition of hydrogen peroxide).
また、エッチング処理時間に特に制限はないが、１０～６００秒が好ましく、３０～１２０秒がより好ましい。処理時間は、エッチング対象物の表面の状態、水性組成物の濃度、温度および処理方法等の種々の条件により適宜選択すればよい。例えば、ニッケルなどの銅よりもイオン化傾向の大きい金属を主成分とするめっき層のすぐ下に積層されている、銅合金などによって形成されたシード層に対するエッチング処理においては、シード層の色が消失してめっき層と重なる領域のみが残存していると判断できる瞬間（ジャストエッチングタイム（Ｊ．Ｅ．Ｔ.ともいう））までを処理時間とすることができる。
There is no particular limit to the etching time, but 10 to 600 seconds is preferable, and 30 to 120 seconds is more preferable. The processing time may be appropriately selected depending on various conditions such as the surface condition of the object to be etched, the concentration of the aqueous composition, the temperature, and the processing method. For example, in the case of an etching process for a seed layer made of a copper alloy or the like that is laminated immediately below a plating layer whose main component is a metal such as nickel that has a higher ionization tendency than copper, the processing time can be the moment when the color of the seed layer disappears and it can be determined that only the area overlapping with the plating layer remains (just etching time (JET)).
エッチング対象物に水性組成物を接触させる方法は特に制限されない。例えば水性組成物の滴下（枚葉スピン処理）またはスプレーなどの形式によりエッチング対象物に接触させる方法、またはエッチング対象物を水性組成物に浸漬させる方法などの湿式法（ウェット）エッチング方法を採用することができる。本発明においては、いずれの方法を採用してもよい。
The method of contacting the aqueous composition with the etching target is not particularly limited. For example, a wet etching method such as a method of contacting the aqueous composition with the etching target by dropping (single-wafer spin processing) or spraying, or a method of immersing the etching target in the aqueous composition, can be used. Either method may be used in the present invention.
＜３．半導体基板の製造方法＞
本発明の半導体基板の製造方法は、少なくとも上述のエッチング工程を含む。さらに、半導体基板の製造方法は、以下の工程を含んでいてもよい。
すなわち、銅および銅合金からなる群より選択される１種以上を含む銅シード層を表面に有する半導体基材を準備する工程；
銅シード層の一部を露出する開口パターンを有するレジストパターンを形成する工程；
レジストパターンの開口パターンの開口部に露出する銅シード層の表面にニッケルおよびニッケル合金からなる群より選択される１種以上を含む金属層Ａと、錫、錫合金、金および金合金からなる群より選択される１種以上を含む金属層Ｂとをこの順に配置するように形成する工程；および
上記レジストパターンを除去する工程を含み得る。
そして、半導体基板の製造方法は、上記レジストパターンを除去する工程で生じた、金属層Ａおよび金属層Ｂが形成されていない銅シード層の露出部を、水性組成物と接触させて、銅シード層の露出部をエッチングする工程を必須とする。
実施例 3. Manufacturing method of semiconductor substrate
The method for producing a semiconductor substrate of the present invention includes at least the etching step described above. The method for producing a semiconductor substrate may further include the following steps.
That is, a step of preparing a semiconductor substrate having a copper seed layer on a surface thereof, the copper seed layer including one or more selected from the group consisting of copper and copper alloys;
forming a resist pattern having an opening pattern exposing a portion of the copper seed layer;
forming, in this order, a metal layer A containing one or more selected from the group consisting of nickel and nickel alloys, and a metal layer B containing one or more selected from the group consisting of tin, tin alloys, gold and gold alloys, on a surface of the copper seed layer exposed in the openings of the opening pattern of the resist pattern; and removing the resist pattern.
The method for manufacturing a semiconductor substrate essentially includes a step of contacting an exposed portion of the copper seed layer, which is produced in the step of removing the resist pattern and in which metal layer A and metal layer B are not formed, with an aqueous composition to etch the exposed portion of the copper seed layer.
Example
本発明の半導体基板の製造方法は、少なくとも上述のエッチング工程を含む。さらに、半導体基板の製造方法は、以下の工程を含んでいてもよい。
すなわち、銅および銅合金からなる群より選択される１種以上を含む銅シード層を表面に有する半導体基材を準備する工程；
銅シード層の一部を露出する開口パターンを有するレジストパターンを形成する工程；
レジストパターンの開口パターンの開口部に露出する銅シード層の表面にニッケルおよびニッケル合金からなる群より選択される１種以上を含む金属層Ａと、錫、錫合金、金および金合金からなる群より選択される１種以上を含む金属層Ｂとをこの順に配置するように形成する工程；および
上記レジストパターンを除去する工程を含み得る。
そして、半導体基板の製造方法は、上記レジストパターンを除去する工程で生じた、金属層Ａおよび金属層Ｂが形成されていない銅シード層の露出部を、水性組成物と接触させて、銅シード層の露出部をエッチングする工程を必須とする。
実施例 3. Manufacturing method of semiconductor substrate
The method for producing a semiconductor substrate of the present invention includes at least the etching step described above. The method for producing a semiconductor substrate may further include the following steps.
That is, a step of preparing a semiconductor substrate having a copper seed layer on a surface thereof, the copper seed layer including one or more selected from the group consisting of copper and copper alloys;
forming a resist pattern having an opening pattern exposing a portion of the copper seed layer;
forming, in this order, a metal layer A containing one or more selected from the group consisting of nickel and nickel alloys, and a metal layer B containing one or more selected from the group consisting of tin, tin alloys, gold and gold alloys, on a surface of the copper seed layer exposed in the openings of the opening pattern of the resist pattern; and removing the resist pattern.
The method for manufacturing a semiconductor substrate essentially includes a step of contacting an exposed portion of the copper seed layer, which is produced in the step of removing the resist pattern and in which metal layer A and metal layer B are not formed, with an aqueous composition to etch the exposed portion of the copper seed layer.
Example
以下、実施例により本発明をさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.
［実施例１］
（Ａ）過酸化水素（Ｈ２Ｏ２）と、（Ｂ）無機酸であるリン酸と、（Ｃ）腐食抑制剤である１，２，４―トリアゾールとを純水に添加し、撹拌することで、半導体基板洗浄用組成物を製造した。この際、過酸化水素、リン酸、および１，２，４―トリアゾールの添加率は、それぞれ半導体基板洗浄用組成物の全質量に対して、０．７５質量％、８質量％、および０．２質量％であった。また、半導体基板洗浄用組成物のｐＨは０．９であった。ｐＨは、株式会社堀場製作所製卓上型ｐＨメーター（Ｆ―７１）とｐＨ電極（９６１５Ｓ－１０Ｄ）を用いて、２３℃における前処理剤のｐＨを測定した。 [Example 1]
(A) hydrogen peroxide (H 2 O 2 ), (B) phosphoric acid as an inorganic acid, and (C) 1,2,4-triazole as a corrosion inhibitor were added to pure water and stirred to produce a semiconductor substrate cleaning composition. At this time, the addition rates of hydrogen peroxide, phosphoric acid, and 1,2,4-triazole were 0.75 mass%, 8 mass%, and 0.2 mass%, respectively, relative to the total mass of the semiconductor substrate cleaning composition. The pH of the semiconductor substrate cleaning composition was 0.9. The pH of the pretreatment agent was measured at 23° C. using a tabletop pH meter (F-71) and a pH electrode (9615S-10D) manufactured by Horiba, Ltd.
（Ａ）過酸化水素（Ｈ２Ｏ２）と、（Ｂ）無機酸であるリン酸と、（Ｃ）腐食抑制剤である１，２，４―トリアゾールとを純水に添加し、撹拌することで、半導体基板洗浄用組成物を製造した。この際、過酸化水素、リン酸、および１，２，４―トリアゾールの添加率は、それぞれ半導体基板洗浄用組成物の全質量に対して、０．７５質量％、８質量％、および０．２質量％であった。また、半導体基板洗浄用組成物のｐＨは０．９であった。ｐＨは、株式会社堀場製作所製卓上型ｐＨメーター（Ｆ―７１）とｐＨ電極（９６１５Ｓ－１０Ｄ）を用いて、２３℃における前処理剤のｐＨを測定した。 [Example 1]
(A) hydrogen peroxide (H 2 O 2 ), (B) phosphoric acid as an inorganic acid, and (C) 1,2,4-triazole as a corrosion inhibitor were added to pure water and stirred to produce a semiconductor substrate cleaning composition. At this time, the addition rates of hydrogen peroxide, phosphoric acid, and 1,2,4-triazole were 0.75 mass%, 8 mass%, and 0.2 mass%, respectively, relative to the total mass of the semiconductor substrate cleaning composition. The pH of the semiconductor substrate cleaning composition was 0.9. The pH of the pretreatment agent was measured at 23° C. using a tabletop pH meter (F-71) and a pH electrode (9615S-10D) manufactured by Horiba, Ltd.
［実施例２～１３・比較例１及び参考例１］
下記表１に示される通りに添加する成分等を変更しする他、実施例１と同様の手法で、実施例２～１３・比較例１及び参考例１における水性組成物を製造した。
[Examples 2 to 13, Comparative Example 1 and Reference Example 1]
The aqueous compositions of Examples 2 to 13, Comparative Example 1, and Reference Example 1 were produced in the same manner as in Example 1, except for changing the components to be added as shown in Table 1 below.
下記表１に示される通りに添加する成分等を変更しする他、実施例１と同様の手法で、実施例２～１３・比較例１及び参考例１における水性組成物を製造した。
The aqueous compositions of Examples 2 to 13, Comparative Example 1, and Reference Example 1 were produced in the same manner as in Example 1, except for changing the components to be added as shown in Table 1 below.
［評価方法］
実施例１～１３、比較例１及び参考例１で製造した半導体基板洗浄用組成物のＣｕ Ｊ.Ｅ.Ｔ（Ｊｕｓｔ Ｅｔｃｈｉｎｇ Ｔｉｍｅ）およびＣｕアンダーカット量を評価した。 [Evaluation method]
The compositions for cleaning semiconductor substrates prepared in Examples 1 to 13, Comparative Example 1 and Reference Example 1 were evaluated for Cu JET (Just Etching Time) and Cu undercut amount.
実施例１～１３、比較例１及び参考例１で製造した半導体基板洗浄用組成物のＣｕ Ｊ.Ｅ.Ｔ（Ｊｕｓｔ Ｅｔｃｈｉｎｇ Ｔｉｍｅ）およびＣｕアンダーカット量を評価した。 [Evaluation method]
The compositions for cleaning semiconductor substrates prepared in Examples 1 to 13, Comparative Example 1 and Reference Example 1 were evaluated for Cu JET (Just Etching Time) and Cu undercut amount.
（評価用サンプル）
各実施例、比較例等では、図１の構造を有する半導体基板１０を評価用基板として使用した。半導体基板１０は、上層のＳｎＡｇ層１４、ＳｎＡｇ層１４の下に積層されたＮｉ層１６、Ｎｉ層１６の下に積層されたＣｕ層１２を含む。さらに、半導体基板１０においては、Ｃｕ層１２の下側にＴｉ層１８が積層されていて、Ｔｉ層１８は基板２０の上に設けられている。
実施例及び比較例においては、図１、及び図１の破線の四角で囲った領域の拡大図である図２にて示されるように、シード層としてのＣｕ層１２（厚み；０．２μｍ）、上側金属層としてのＳｎＡｇ層１４（厚み；６μｍ）、下側金属層（めっき層）としてのＮｉ層１６（厚み；３μｍ）、及び、バリアメタル層としてのＴｉ層１８（厚み；０．１μｍ）が設けられている半導体基板１０を用いた。なお、図１に示される円柱状のバンプの直径は１２．５μｍ、高さは９μｍであった。 (Evaluation sample)
In each of the examples and comparative examples, asemiconductor substrate 10 having the structure shown in Fig. 1 was used as an evaluation substrate. The semiconductor substrate 10 includes an upper SnAg layer 14, a Ni layer 16 laminated below the SnAg layer 14, and a Cu layer 12 laminated below the Ni layer 16. Furthermore, in the semiconductor substrate 10, a Ti layer 18 is laminated below the Cu layer 12, and the Ti layer 18 is provided on a substrate 20.
In the examples and comparative examples, as shown in Fig. 1 and Fig. 2, which is an enlarged view of the area enclosed by the dashed square in Fig. 1, asemiconductor substrate 10 was used which was provided with a Cu layer 12 (thickness: 0.2 μm) as a seed layer, a SnAg layer 14 (thickness: 6 μm) as an upper metal layer, a Ni layer 16 (thickness: 3 μm) as a lower metal layer (plating layer), and a Ti layer 18 (thickness: 0.1 μm) as a barrier metal layer. The diameter of the cylindrical bump shown in Fig. 1 was 12.5 μm, and the height was 9 μm.
各実施例、比較例等では、図１の構造を有する半導体基板１０を評価用基板として使用した。半導体基板１０は、上層のＳｎＡｇ層１４、ＳｎＡｇ層１４の下に積層されたＮｉ層１６、Ｎｉ層１６の下に積層されたＣｕ層１２を含む。さらに、半導体基板１０においては、Ｃｕ層１２の下側にＴｉ層１８が積層されていて、Ｔｉ層１８は基板２０の上に設けられている。
実施例及び比較例においては、図１、及び図１の破線の四角で囲った領域の拡大図である図２にて示されるように、シード層としてのＣｕ層１２（厚み；０．２μｍ）、上側金属層としてのＳｎＡｇ層１４（厚み；６μｍ）、下側金属層（めっき層）としてのＮｉ層１６（厚み；３μｍ）、及び、バリアメタル層としてのＴｉ層１８（厚み；０．１μｍ）が設けられている半導体基板１０を用いた。なお、図１に示される円柱状のバンプの直径は１２．５μｍ、高さは９μｍであった。 (Evaluation sample)
In each of the examples and comparative examples, a
In the examples and comparative examples, as shown in Fig. 1 and Fig. 2, which is an enlarged view of the area enclosed by the dashed square in Fig. 1, a
（Ｃｕ層のエッチングにおける Ｊ.Ｅ.Ｔの評価）
評価用サンプルを１ｃｍ×１ｃｍ（浸漬処理面積：１ｃｍ２）の大きさに切り出した。次いで、実施例１～１３、比較例１及び参考例１においてそれぞれ製造した半導体基板エッチング用の水性組成物５０ｇに、評価用サンプルを２５℃で所定時間、３５０ｒｐｍで攪拌子により攪拌しながら浸漬処理した。浸漬処理の際、評価用サンプルをピンセットで挟み、撹拌子の上部に位置させた状態で浸漬処理を実施した。 (Evaluation of JET in etching Cu layer)
The evaluation sample was cut into a size of 1 cm x 1 cm (immersion treatment area: 1 cm 2 ). Next, the evaluation sample was immersed in 50 g of the aqueous composition for etching semiconductor substrates produced in each of Examples 1 to 13, Comparative Example 1, and Reference Example 1 at 25°C for a predetermined time while stirring with a stirrer at 350 rpm. During the immersion treatment, the evaluation sample was held with tweezers and placed above the stirrer.
評価用サンプルを１ｃｍ×１ｃｍ（浸漬処理面積：１ｃｍ２）の大きさに切り出した。次いで、実施例１～１３、比較例１及び参考例１においてそれぞれ製造した半導体基板エッチング用の水性組成物５０ｇに、評価用サンプルを２５℃で所定時間、３５０ｒｐｍで攪拌子により攪拌しながら浸漬処理した。浸漬処理の際、評価用サンプルをピンセットで挟み、撹拌子の上部に位置させた状態で浸漬処理を実施した。 (Evaluation of JET in etching Cu layer)
The evaluation sample was cut into a size of 1 cm x 1 cm (immersion treatment area: 1 cm 2 ). Next, the evaluation sample was immersed in 50 g of the aqueous composition for etching semiconductor substrates produced in each of Examples 1 to 13, Comparative Example 1, and Reference Example 1 at 25°C for a predetermined time while stirring with a stirrer at 350 rpm. During the immersion treatment, the evaluation sample was held with tweezers and placed above the stirrer.
評価サンプルの浸漬時に、浸漬（エッチング処理）の開始時間から、目視で基板表面の色がオレンジから銀色に変化するのに要した時間、すなわちシード層の色が消失してめっき層と重なる領域のみが残存していると判断できた瞬間までに要した時間を、Ｃｕ Ｊ.Ｅ.Ｔと定義し、測定した。
When the evaluation sample was immersed, the time required from the start of immersion (etching process) until the color of the substrate surface visually changed from orange to silver, i.e., the time required until it was determined that the color of the seed layer had disappeared and only the area overlapping with the plating layer remained, was defined and measured as Cu J.E.T.
（Ｃｕアンダーカット量）
実施例１～１３、比較例１及び参考例１で製造した半導体基板エッチング用組成物にて、評価用サンプルを２５℃でＣｕ Ｊ.Ｅ.Ｔの１．５倍の時間、３５０ｒｐｍで攪拌子により攪拌しながら浸漬処理した。処理後の評価サンプルを、ＦＩＢ（集束イオンビーム）装置（Ｈｅｌｉｏｓ Ｇ４ ＵＸ（Thermo scientific社製）内で、バンプを上方から観察した際に円状から半円になるよう加工した。次いで、Ｈｅｌｉｏｓ Ｇ４ ＵＸ（Thermo scientific社製）を用いて加工した評価サンプルのＳＥＭ画像を得た。ＳＥＭ画像において、Ｎｉ端面からＣｕ端面までの水平方向の距離をＣｕアンダーカット量と定義し、測定した。 (Cu undercut amount)
In the compositions for etching semiconductor substrates produced in Examples 1 to 13, Comparative Example 1, and Reference Example 1, the evaluation samples were immersed at 25°C for 1.5 times the time of Cu JET while stirring with a stirrer at 350 rpm. The evaluation samples after the treatment were processed in a FIB (focused ion beam) device (Helios G4 UX (manufactured by Thermo Scientific) so that the bumps would change from circular to semicircular when observed from above. Next, an SEM image of the evaluation sample processed using Helios G4 UX (manufactured by Thermo Scientific) was obtained. In the SEM image, the horizontal distance from the Ni end face to the Cu end face was defined as the Cu undercut amount and measured.
実施例１～１３、比較例１及び参考例１で製造した半導体基板エッチング用組成物にて、評価用サンプルを２５℃でＣｕ Ｊ.Ｅ.Ｔの１．５倍の時間、３５０ｒｐｍで攪拌子により攪拌しながら浸漬処理した。処理後の評価サンプルを、ＦＩＢ（集束イオンビーム）装置（Ｈｅｌｉｏｓ Ｇ４ ＵＸ（Thermo scientific社製）内で、バンプを上方から観察した際に円状から半円になるよう加工した。次いで、Ｈｅｌｉｏｓ Ｇ４ ＵＸ（Thermo scientific社製）を用いて加工した評価サンプルのＳＥＭ画像を得た。ＳＥＭ画像において、Ｎｉ端面からＣｕ端面までの水平方向の距離をＣｕアンダーカット量と定義し、測定した。 (Cu undercut amount)
In the compositions for etching semiconductor substrates produced in Examples 1 to 13, Comparative Example 1, and Reference Example 1, the evaluation samples were immersed at 25°C for 1.5 times the time of Cu JET while stirring with a stirrer at 350 rpm. The evaluation samples after the treatment were processed in a FIB (focused ion beam) device (Helios G4 UX (manufactured by Thermo Scientific) so that the bumps would change from circular to semicircular when observed from above. Next, an SEM image of the evaluation sample processed using Helios G4 UX (manufactured by Thermo Scientific) was obtained. In the SEM image, the horizontal distance from the Ni end face to the Cu end face was defined as the Cu undercut amount and measured.
表１に示すとおり、実施例１～１３の水性組成物を用いた場合にはいずれも、ニッケル、および錫－銀合金の腐食を抑制しつつ、銅を選択的にエッチングすることが確認できた。
一方、成分組成が本発明に規定する範囲を外れた実施例以外の比較例１などにおいては、ニッケルのメッキ層１６（図２及び図３参照）にてガルバニック腐食が生じたことに起因するものと考えられるＣｕ層１２のアンダーカット量が大きくなった。
すなわち、概略的な図３（ａ）に示されるように、実施例の半導体基板の中間体１０ａにおいては、下側金属層（めっき層）１６ａの下面の端部領域におけるガルバニック腐食が防止され、Ｃｕのシード層である１２ａの端部におけるアンダーカットが抑制されたのに対し、図３（ｂ）にて示されるように、比較例の半導体基板の中間体１０ｂにおいては、下側金属層（めっき層）１６ｂの下面の端部領域におけるガルバニック腐食が進行してしまい、ガルバニック腐食の進行に伴って、Ｃｕのシード層である１２ｂの端部におけるアンダーカットも拡大してしまったものと考えられる。 As shown in Table 1, it was confirmed that when the aqueous compositions of Examples 1 to 13 were used, copper was selectively etched while suppressing the corrosion of nickel and tin-silver alloy.
On the other hand, in Comparative Example 1 and other examples other than the examples in which the component composition was outside the range specified in the present invention, the amount of undercut in theCu layer 12 increased, which is thought to be due to galvanic corrosion occurring in the nickel plating layer 16 (see Figures 2 and 3).
That is, as shown in the schematic diagram of FIG. 3(a), in the semiconductor substrate intermediate 10a of the embodiment, galvanic corrosion was prevented in the edge region of the underside of the lower metal layer (plated layer) 16a, and undercut at the edge of the Cu seed layer 12a was suppressed, whereas in the semiconductor substrate intermediate 10b of the comparative example, as shown in FIG. 3(b), galvanic corrosion progressed in the edge region of the underside of the lower metal layer (plated layer) 16b, and it is believed that as the galvanic corrosion progressed, the undercut at the edge of the Cu seed layer 12b also expanded.
一方、成分組成が本発明に規定する範囲を外れた実施例以外の比較例１などにおいては、ニッケルのメッキ層１６（図２及び図３参照）にてガルバニック腐食が生じたことに起因するものと考えられるＣｕ層１２のアンダーカット量が大きくなった。
すなわち、概略的な図３（ａ）に示されるように、実施例の半導体基板の中間体１０ａにおいては、下側金属層（めっき層）１６ａの下面の端部領域におけるガルバニック腐食が防止され、Ｃｕのシード層である１２ａの端部におけるアンダーカットが抑制されたのに対し、図３（ｂ）にて示されるように、比較例の半導体基板の中間体１０ｂにおいては、下側金属層（めっき層）１６ｂの下面の端部領域におけるガルバニック腐食が進行してしまい、ガルバニック腐食の進行に伴って、Ｃｕのシード層である１２ｂの端部におけるアンダーカットも拡大してしまったものと考えられる。 As shown in Table 1, it was confirmed that when the aqueous compositions of Examples 1 to 13 were used, copper was selectively etched while suppressing the corrosion of nickel and tin-silver alloy.
On the other hand, in Comparative Example 1 and other examples other than the examples in which the component composition was outside the range specified in the present invention, the amount of undercut in the
That is, as shown in the schematic diagram of FIG. 3(a), in the semiconductor substrate intermediate 10a of the embodiment, galvanic corrosion was prevented in the edge region of the underside of the lower metal layer (plated layer) 16a, and undercut at the edge of the Cu seed layer 12a was suppressed, whereas in the semiconductor substrate intermediate 10b of the comparative example, as shown in FIG. 3(b), galvanic corrosion progressed in the edge region of the underside of the lower metal layer (plated layer) 16b, and it is believed that as the galvanic corrosion progressed, the undercut at the edge of the Cu seed layer 12b also expanded.
産業上の利用可能性
本発明の水性組成物は、半導体基板の配線形成において好適に用いることができる。本発明の好ましい態様によれば、ニッケル、ニッケル合金などを含む配線材料の溶解を抑制し、銅および銅合金を選択的にエッチングしつつ、銅および銅合金のシード層のアンダーカットを防止することができる。 Industrial Applicability
The aqueous composition of the present invention can be suitably used in forming wiring on a semiconductor substrate. According to a preferred embodiment of the present invention, the aqueous composition can suppress dissolution of wiring materials including nickel and nickel alloys, selectively etch copper and copper alloys, and prevent undercut of a seed layer of copper and copper alloys.
本発明の水性組成物は、半導体基板の配線形成において好適に用いることができる。本発明の好ましい態様によれば、ニッケル、ニッケル合金などを含む配線材料の溶解を抑制し、銅および銅合金を選択的にエッチングしつつ、銅および銅合金のシード層のアンダーカットを防止することができる。 Industrial Applicability
The aqueous composition of the present invention can be suitably used in forming wiring on a semiconductor substrate. According to a preferred embodiment of the present invention, the aqueous composition can suppress dissolution of wiring materials including nickel and nickel alloys, selectively etch copper and copper alloys, and prevent undercut of a seed layer of copper and copper alloys.
１０ 半導体基板
１０ａ 実施例における半導体基板
１０ｂ 比較例における半導体基板
１２ Ｃｕ層（シード層）
１２ａ 実施例におけるＣｕ層
１２ｂ 比較例におけるＣｕ層
１４ ＳｎＡｇ層（上側金属層）
１６ Ｎｉ層（下側金属層）
１６ａ 実施例におけるＮｉ層
１６ｂ 比較例におけるＮｉ層
１８ Ｔｉ層（バリアメタル層）
１８ａ 実施例におけるＴｉ層
１８ｂ 比較例におけるＴｉ層
２０ 基板 10 Semiconductor substrate 10a Semiconductor substrate in the embodiment 10b Semiconductor substrate in the comparative example 12 Cu layer (seed layer)
12a Cu layer in the embodiment 12b Cu layer in the comparative example 14 SnAg layer (upper metal layer)
16 Ni layer (lower metal layer)
16a Ni layer in the embodiment 16b Ni layer in the comparative example 18 Ti layer (barrier metal layer)
18a Ti layer in the embodiment 18b Ti layer in the comparative example 20 Substrate
１０ａ 実施例における半導体基板
１０ｂ 比較例における半導体基板
１２ Ｃｕ層（シード層）
１２ａ 実施例におけるＣｕ層
１２ｂ 比較例におけるＣｕ層
１４ ＳｎＡｇ層（上側金属層）
１６ Ｎｉ層（下側金属層）
１６ａ 実施例におけるＮｉ層
１６ｂ 比較例におけるＮｉ層
１８ Ｔｉ層（バリアメタル層）
１８ａ 実施例におけるＴｉ層
１８ｂ 比較例におけるＴｉ層
２０ 基板 10 Semiconductor substrate 10a Semiconductor substrate in the embodiment 10b Semiconductor substrate in the comparative example 12 Cu layer (seed layer)
12a Cu layer in the embodiment 12b Cu layer in the comparative example 14 SnAg layer (upper metal layer)
16 Ni layer (lower metal layer)
16a Ni layer in the embodiment 16b Ni layer in the comparative example 18 Ti layer (barrier metal layer)
18a Ti layer in the embodiment 18b Ti layer in the comparative example 20 Substrate
Claims (14)
- エッチング用の水性組成物であって、
酸化剤、酸及び腐食抑制剤を含み、
前記水性組成物のｐＨが０以上かつ３以下である、水性組成物。 1. An aqueous etching composition comprising:
Contains an oxidizer, an acid and a corrosion inhibitor;
The aqueous composition has a pH of 0 or more and 3 or less. - 前記水性組成物の全量基準で０．００１～２０質量％の前記酸化剤と、
前記水性組成物の全量基準で０．１～５０質量％の前記酸と、
前記水性組成物の全量基準で０．００００１～５．０質量％の前記腐食抑制剤とを含む、請求項１に記載の水性組成物。 0.001 to 20% by mass of the oxidizing agent based on the total amount of the aqueous composition;
0.1 to 50% by mass of the acid based on the total amount of the aqueous composition;
The aqueous composition according to claim 1, comprising 0.00001 to 5.0 mass % of the corrosion inhibitor based on the total amount of the aqueous composition. - 前記腐食抑制剤が、（ｉ）含窒素複素環化合物、（ｉｉ）カチオン性界面活性剤またはその塩及び（ｉｉｉ）アルキル硫酸／スルホン酸またはその塩の少なくともいずれかを含む、請求項１に記載の水性組成物。 The aqueous composition according to claim 1, wherein the corrosion inhibitor comprises at least one of (i) a nitrogen-containing heterocyclic compound, (ii) a cationic surfactant or a salt thereof, and (iii) an alkyl sulfate/sulfonate or a salt thereof.
- 前記（ｉ）含窒素複素環化合物の含有量が、前記水性組成物の全量基準で０．０１～５．０質量％であり、
前記（ｉｉ）カチオン性界面活性剤またはその塩の含有量が、前記水性組成物の全量基準で０．００００１～０．２質量％であり、又は、
前記（ｉｉｉ）アルキル硫酸／スルホン酸またはその塩の含有量が、前記水性組成物の全量基準で０．００１～２．０質量％である、請求項３に記載の水性組成物。 The content of the nitrogen-containing heterocyclic compound (i) is 0.01 to 5.0% by mass based on the total amount of the aqueous composition,
The content of the (ii) cationic surfactant or its salt is 0.00001 to 0.2 mass% based on the total amount of the aqueous composition, or
The aqueous composition according to claim 3, wherein the content of the (iii) alkyl sulfuric acid/sulfonic acid or its salt is 0.001 to 2.0% by mass based on the total amount of the aqueous composition. - 前記（ｉ）含窒素複素環式化合物が、少なくとも含窒素５員環化合物を含む、請求項３に記載の水性組成物。 The aqueous composition according to claim 3, wherein the nitrogen-containing heterocyclic compound (i) includes at least a nitrogen-containing five-membered ring compound.
- 前記（ｉｉ）カチオン性界面活性剤が、下記式（４）：
Ｒ６は、炭素数１０～３０の置換もしくは非置換アルキル基、炭素数１０～３０の置換もしくは非置換アルキル（ポリ）ヘテロアルキレン基、または炭素数１０～３０の置換もしくは非置換アリール（ポリ）ヘテロアルキレン基であり、
Ｒ７は、それぞれ独立して、炭素数１～３０の置換もしくは非置換アルキル基、または炭素数６～３０の置換もしくは非置換アリール基であり、
Ｘ－は、ハロゲン化物イオン、水酸化物イオン、有機スルホン酸イオン、テトラフルオロボレートアニオン、またはヘキサフルオロフォスファートアニオンである）
で表されるアンモニウム塩、および
炭素数１０～３０の置換もしくは非置換アルキル基を有するヘテロアリール塩からなる群から選択される少なくとも１つを含む、請求項３に記載の水性組成物。 The (ii) cationic surfactant is represented by the following formula (4):
R 6 is a substituted or unsubstituted alkyl group having 10 to 30 carbon atoms, a substituted or unsubstituted alkyl (poly)heteroalkylene group having 10 to 30 carbon atoms, or a substituted or unsubstituted aryl (poly)heteroalkylene group having 10 to 30 carbon atoms;
R 7 is independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms;
X − is a halide ion, a hydroxide ion, an organic sulfonate ion, a tetrafluoroborate anion, or a hexafluorophosphate anion.
and a heteroaryl salt having a substituted or unsubstituted alkyl group having 10 to 30 carbon atoms. - 前記（ｉｉｉ）アルキル硫酸／スルホン酸またはその塩が、少なくとも炭素数６～３０のアルキル基を有する、請求項３に記載の水性組成物。 The aqueous composition according to claim 3, wherein the (iii) alkyl sulfate/sulfonate or salt thereof has an alkyl group having at least 6 to 30 carbon atoms.
- 前記酸が、硝酸を除く無機酸を含む、請求項１に記載の水性組成物。 The aqueous composition of claim 1, wherein the acid comprises an inorganic acid other than nitric acid.
- 前記酸が、少なくともリン酸を含む、請求項８に記載の水性組成物。 The aqueous composition of claim 8, wherein the acid comprises at least phosphoric acid.
- 前記酸化剤が、少なくとも過酸化水素を含む、請求項１に記載の水性組成物。 The aqueous composition of claim 1, wherein the oxidizing agent comprises at least hydrogen peroxide.
- 請求項１～１０のいずれかに記載の水性組成物を用いて、銅を含むシード層を有する半導体基板の前記シード層をエッチングする工程を含む、エッチング方法。 An etching method comprising a step of etching a copper-containing seed layer of a semiconductor substrate using the aqueous composition according to any one of claims 1 to 10.
- 前記半導体基板が、前記シード層に接するように積層されていて、銅よりもイオン化傾向の大きい金属を含む層をさらに有する、請求項１１に記載のエッチング方法。 The etching method according to claim 11, wherein the semiconductor substrate further includes a layer that is stacked in contact with the seed layer and contains a metal that has a higher ionization tendency than copper.
- 請求項１～１０のいずれかに記載の水性組成物を用いて、銅を含むシード層を有する半導体基板の前記シード層をエッチングする工程を含む、半導体基板の製造方法。 A method for manufacturing a semiconductor substrate, comprising the step of etching a copper-containing seed layer of a semiconductor substrate using the aqueous composition according to any one of claims 1 to 10.
- 前記半導体基板が、前記シード層に接するように積層されていて、銅よりもイオン化傾向の大きい金属を含む層をさらに有する、請求項１３に記載の半導体基板の製造方法。
The method for producing a semiconductor substrate according to claim 13 , wherein the semiconductor substrate further comprises a layer that is stacked in contact with the seed layer and contains a metal having a higher ionization tendency than copper.
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| JPS4998731A (en) * | 1973-01-30 | 1974-09-18 | ||
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| JP2003519286A (en) * | 2000-01-07 | 2003-06-17 | エレクトロケミカルズ インコーポレイティド | Method for roughening copper surface for bonding to substrate |
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| JP2009079284A (en) * | 2007-09-04 | 2009-04-16 | Mec Kk | Etching liquid, and method for forming conductor pattern |
| JP2012012654A (en) * | 2010-06-30 | 2012-01-19 | Adeka Corp | Surface roughening agent for copper-containing material and method for surface-roughening copper-containing material |
| JP2013245401A (en) * | 2012-05-30 | 2013-12-09 | Shikoku Chem Corp | Etching solution and etching method of copper |
| JP2022181453A (en) * | 2021-05-26 | 2022-12-08 | 東京応化工業株式会社 | Medical solution used for etching processing |
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| JPS4998731A (en) * | 1973-01-30 | 1974-09-18 | ||
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| JP2003519286A (en) * | 2000-01-07 | 2003-06-17 | エレクトロケミカルズ インコーポレイティド | Method for roughening copper surface for bonding to substrate |
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| JP2013245401A (en) * | 2012-05-30 | 2013-12-09 | Shikoku Chem Corp | Etching solution and etching method of copper |
| JP2022181453A (en) * | 2021-05-26 | 2022-12-08 | 東京応化工業株式会社 | Medical solution used for etching processing |
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