WO2024096006A1 - Composition aqueuse pour gravure, procédé de gravure l'utilisant et procédé de fabrication de substrat semi-conducteur - Google Patents
Composition aqueuse pour gravure, procédé de gravure l'utilisant et procédé de fabrication de substrat semi-conducteur 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
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
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- JEOSMYVMLZTQOH-UHFFFAOYSA-M 1-hexylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCC[N+]1=CC=CC=C1 JEOSMYVMLZTQOH-UHFFFAOYSA-M 0.000 description 1
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- URVSXZLUUCVGQM-UHFFFAOYSA-M 1-methyl-3-octylimidazol-1-ium;bromide Chemical compound [Br-].CCCCCCCCN1C=C[N+](C)=C1 URVSXZLUUCVGQM-UHFFFAOYSA-M 0.000 description 1
- ZKPSZHWFVLHSJM-UHFFFAOYSA-M 1-methyl-3-tetradecylimidazol-1-ium;bromide Chemical compound [Br-].CCCCCCCCCCCCCC[N+]=1C=CN(C)C=1 ZKPSZHWFVLHSJM-UHFFFAOYSA-M 0.000 description 1
- SDXDXENAFAXVMX-UHFFFAOYSA-M 1-methyl-3-tetradecylimidazol-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCN1C=C[N+](C)=C1 SDXDXENAFAXVMX-UHFFFAOYSA-M 0.000 description 1
- ZLBVJFYDSJGQAN-UHFFFAOYSA-N 1-octadecylisoquinolin-2-ium;chloride Chemical compound [Cl-].C1=CC=C2C(CCCCCCCCCCCCCCCCCC)=[NH+]C=CC2=C1 ZLBVJFYDSJGQAN-UHFFFAOYSA-N 0.000 description 1
- JDASKPRUFDKACZ-UHFFFAOYSA-M 1-octadecylpyridin-1-ium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 JDASKPRUFDKACZ-UHFFFAOYSA-M 0.000 description 1
- WJDJWDHXZBNQNE-UHFFFAOYSA-M 1-octadecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 WJDJWDHXZBNQNE-UHFFFAOYSA-M 0.000 description 1
- OVIYAWWBKPWUOH-UHFFFAOYSA-M 1-octylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCC[N+]1=CC=CC=C1 OVIYAWWBKPWUOH-UHFFFAOYSA-M 0.000 description 1
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- YFVBASFBIJFBAI-UHFFFAOYSA-M 1-tetradecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+]1=CC=CC=C1 YFVBASFBIJFBAI-UHFFFAOYSA-M 0.000 description 1
- WTLZRZPWBYWOME-UHFFFAOYSA-M 1-tetradecylquinolin-1-ium;chloride Chemical compound [Cl-].C1=CC=C2[N+](CCCCCCCCCCCCCC)=CC=CC2=C1 WTLZRZPWBYWOME-UHFFFAOYSA-M 0.000 description 1
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
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- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 1
- XHKUWVGCDOVIAI-UHFFFAOYSA-M 3-decyl-1,3-thiazol-3-ium;chloride Chemical compound [Cl-].CCCCCCCCCC[N+]=1C=CSC=1 XHKUWVGCDOVIAI-UHFFFAOYSA-M 0.000 description 1
- WYPWADKIUJBMEI-UHFFFAOYSA-M 3-dodecyl-1,3-oxazol-3-ium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]=1C=COC=1 WYPWADKIUJBMEI-UHFFFAOYSA-M 0.000 description 1
- OXFBEEDAZHXDHB-UHFFFAOYSA-M 3-methyl-1-octylimidazolium chloride Chemical compound [Cl-].CCCCCCCCN1C=C[N+](C)=C1 OXFBEEDAZHXDHB-UHFFFAOYSA-M 0.000 description 1
- IFKUFILIBIXFKQ-UHFFFAOYSA-M 3-octadecyl-1,3-oxazol-3-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+]=1C=COC=1 IFKUFILIBIXFKQ-UHFFFAOYSA-M 0.000 description 1
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- 229910001316 Ag alloy Inorganic materials 0.000 description 1
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- QUVFFLVBYJHIGS-UHFFFAOYSA-M CCCCCCCCCCCCCCCC[N+]1=COC=C1.[Cl-] Chemical compound CCCCCCCCCCCCCCCC[N+]1=COC=C1.[Cl-] QUVFFLVBYJHIGS-UHFFFAOYSA-M 0.000 description 1
- FXUWZKXITKVRRC-UHFFFAOYSA-M CCCCCCCCCCCCCCCC[N+]1=CSC=C1.[Cl-] Chemical compound CCCCCCCCCCCCCCCC[N+]1=CSC=C1.[Cl-] FXUWZKXITKVRRC-UHFFFAOYSA-M 0.000 description 1
- NEXOEEFWXRGIAA-UHFFFAOYSA-M CCCCCCCCCCCCCC[N+]1=CN=CC=C1.[Cl-] Chemical compound CCCCCCCCCCCCCC[N+]1=CN=CC=C1.[Cl-] NEXOEEFWXRGIAA-UHFFFAOYSA-M 0.000 description 1
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- VZFREXGFQGIDPD-UHFFFAOYSA-M CCCCCC[N+]1=CN=CC=C1.[Cl-] Chemical compound CCCCCC[N+]1=CN=CC=C1.[Cl-] VZFREXGFQGIDPD-UHFFFAOYSA-M 0.000 description 1
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
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- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 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
- TTZLKXKJIMOHHG-UHFFFAOYSA-M benzyl-decyl-dimethylazanium;chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 TTZLKXKJIMOHHG-UHFFFAOYSA-M 0.000 description 1
- 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
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- 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
La présente invention concerne une composition aqueuse pour gravure, la composition aqueuse comprenant un agent oxydant, un acide et un inhibiteur de corrosion et ayant un pH de 0 à 3. La composition aqueuse selon un aspect de la présente invention comprend de préférence, par rapport à la quantité totale de la composition aqueuse : 0,001 à 20 % en masse de l'agent oxydant ; 0,1 à 50 % en masse de l'acide ; et 0,00001 à 5,0 % en masse de l'inhibiteur de corrosion.
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| PCT/JP2023/039251 WO2024096006A1 (fr) | 2022-11-01 | 2023-10-31 | Composition aqueuse pour gravure, procédé de gravure l'utilisant et procédé de fabrication de substrat semi-conducteur |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4998731A (fr) * | 1973-01-30 | 1974-09-18 | ||
| JPS57134563A (en) * | 1981-02-12 | 1982-08-19 | Nippon Peroxide Co Ltd | Etching agent for electroless plated thin nickel film |
| JP2003519286A (ja) * | 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 | 基板に結合するための銅表面の粗面化方法 |
| JP2005350708A (ja) * | 2004-06-09 | 2005-12-22 | Okuno Chem Ind Co Ltd | エッチング処理用組成物 |
| JP2009079284A (ja) * | 2007-09-04 | 2009-04-16 | Mec Kk | エッチング液及び導体パターンの形成方法 |
| JP2012012654A (ja) * | 2010-06-30 | 2012-01-19 | Adeka Corp | 銅含有材料粗面化剤及び銅含有材料の粗面化方法 |
| JP2013245401A (ja) * | 2012-05-30 | 2013-12-09 | Shikoku Chem Corp | 銅のエッチング液およびエッチング方法 |
| JP2022181453A (ja) * | 2021-05-26 | 2022-12-08 | 東京応化工業株式会社 | エッチング処理に用いられる薬液 |
-
2023
- 2023-10-31 WO PCT/JP2023/039251 patent/WO2024096006A1/fr unknown
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4998731A (fr) * | 1973-01-30 | 1974-09-18 | ||
| JPS57134563A (en) * | 1981-02-12 | 1982-08-19 | Nippon Peroxide Co Ltd | Etching agent for electroless plated thin nickel film |
| JP2003519286A (ja) * | 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 | 基板に結合するための銅表面の粗面化方法 |
| JP2005350708A (ja) * | 2004-06-09 | 2005-12-22 | Okuno Chem Ind Co Ltd | エッチング処理用組成物 |
| JP2009079284A (ja) * | 2007-09-04 | 2009-04-16 | Mec Kk | エッチング液及び導体パターンの形成方法 |
| JP2012012654A (ja) * | 2010-06-30 | 2012-01-19 | Adeka Corp | 銅含有材料粗面化剤及び銅含有材料の粗面化方法 |
| JP2013245401A (ja) * | 2012-05-30 | 2013-12-09 | Shikoku Chem Corp | 銅のエッチング液およびエッチング方法 |
| JP2022181453A (ja) * | 2021-05-26 | 2022-12-08 | 東京応化工業株式会社 | エッチング処理に用いられる薬液 |
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