JP5618340B1 - Etching solution, replenisher, and method for forming copper wiring - Google Patents
Etching solution, replenisher, and method for forming copper wiring Download PDFInfo
- Publication number
- JP5618340B1 JP5618340B1 JP2013252799A JP2013252799A JP5618340B1 JP 5618340 B1 JP5618340 B1 JP 5618340B1 JP 2013252799 A JP2013252799 A JP 2013252799A JP 2013252799 A JP2013252799 A JP 2013252799A JP 5618340 B1 JP5618340 B1 JP 5618340B1
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- JP
- Japan
- Prior art keywords
- etching
- aliphatic heterocyclic
- compound
- etching solution
- ring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000005530 etching Methods 0.000 title claims abstract description 146
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 82
- 239000010949 copper Substances 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 19
- -1 aliphatic heterocyclic compound Chemical class 0.000 claims abstract description 74
- 239000000243 solution Substances 0.000 claims abstract description 70
- 125000003277 amino group Chemical group 0.000 claims abstract description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229940126062 Compound A Drugs 0.000 claims abstract description 19
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 18
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 9
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 125000001424 substituent group Chemical group 0.000 claims description 35
- 150000002390 heteroarenes Chemical class 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 18
- 230000001590 oxidative effect Effects 0.000 claims description 14
- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- 150000004050 homopiperazines Chemical class 0.000 claims 1
- 150000004885 piperazines Chemical class 0.000 claims 1
- 150000003053 piperidines Chemical class 0.000 claims 1
- 150000003235 pyrrolidines Chemical class 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 19
- 150000002430 hydrocarbons Chemical class 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 11
- 229930195733 hydrocarbon Natural products 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 8
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Natural products C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- LKLLNYWECKEQIB-UHFFFAOYSA-N 1,3,5-triazinane Chemical group C1NCNCN1 LKLLNYWECKEQIB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 2
- 125000003363 1,3,5-triazinyl group Chemical group N1=C(N=CN=C1)* 0.000 description 2
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 description 2
- FQUYSHZXSKYCSY-UHFFFAOYSA-N 1,4-diazepane Chemical group C1CNCCNC1 FQUYSHZXSKYCSY-UHFFFAOYSA-N 0.000 description 2
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- UNRBEYYLYRXYCG-UHFFFAOYSA-N (1-ethylpyrrolidin-2-yl)methanamine Chemical compound CCN1CCCC1CN UNRBEYYLYRXYCG-UHFFFAOYSA-N 0.000 description 1
- FBXRCTMIDHCRDT-UHFFFAOYSA-N 1,3,5-tri(propan-2-yl)-1,3,5-triazinane Chemical compound CC(C)N1CN(C(C)C)CN(C(C)C)C1 FBXRCTMIDHCRDT-UHFFFAOYSA-N 0.000 description 1
- VWVZIRPJPFJGFE-UHFFFAOYSA-N 1,3,5-tribenzyl-1,3,5-triazinane Chemical compound C=1C=CC=CC=1CN(CN(CC=1C=CC=CC=1)C1)CN1CC1=CC=CC=C1 VWVZIRPJPFJGFE-UHFFFAOYSA-N 0.000 description 1
- XYRTVIAPRQLSOW-UHFFFAOYSA-N 1,3,5-triethyl-1,3,5-triazinane Chemical compound CCN1CN(CC)CN(CC)C1 XYRTVIAPRQLSOW-UHFFFAOYSA-N 0.000 description 1
- DPMZXMBOYHBELT-UHFFFAOYSA-N 1,3,5-trimethyl-1,3,5-triazinane Chemical compound CN1CN(C)CN(C)C1 DPMZXMBOYHBELT-UHFFFAOYSA-N 0.000 description 1
- HFWOSHMLDRSIDN-UHFFFAOYSA-N 1,3,5-trinitroso-1,3,5-triazinane Chemical compound O=NN1CN(N=O)CN(N=O)C1 HFWOSHMLDRSIDN-UHFFFAOYSA-N 0.000 description 1
- DPHBVWJGMBYPMK-UHFFFAOYSA-N 1,3,5-tripropyl-1,3,5-triazinane Chemical compound CCCN1CN(CCC)CN(CCC)C1 DPHBVWJGMBYPMK-UHFFFAOYSA-N 0.000 description 1
- QDVBKXJMLILLLB-UHFFFAOYSA-N 1,4'-bipiperidine Chemical compound C1CCCCN1C1CCNCC1 QDVBKXJMLILLLB-UHFFFAOYSA-N 0.000 description 1
- CBBKKVPJPRZOCM-UHFFFAOYSA-N 1,4-diacetylpiperazine-2,5-dione Chemical compound CC(=O)N1CC(=O)N(C(C)=O)CC1=O CBBKKVPJPRZOCM-UHFFFAOYSA-N 0.000 description 1
- RNNVQNMOFQXXTH-UHFFFAOYSA-N 1,4-diazepane-1-carbaldehyde Chemical compound O=CN1CCCNCC1 RNNVQNMOFQXXTH-UHFFFAOYSA-N 0.000 description 1
- XZOJPXWWMZWPSJ-UHFFFAOYSA-N 1,4-diethylpiperazin-2-one Chemical compound CCN1CCN(CC)C(=O)C1 XZOJPXWWMZWPSJ-UHFFFAOYSA-N 0.000 description 1
- YQWYNMOCRRYVCE-UHFFFAOYSA-N 1,4-dimethyl-1,4-diazepane Chemical compound CN1CCCN(C)CC1 YQWYNMOCRRYVCE-UHFFFAOYSA-N 0.000 description 1
- NFTWWHSKWXOTLL-UHFFFAOYSA-N 1,4-dimethylpiperazin-2-one Chemical compound CN1CCN(C)C(=O)C1 NFTWWHSKWXOTLL-UHFFFAOYSA-N 0.000 description 1
- WWBHDWHAIVWDMT-UHFFFAOYSA-N 1,4-dimethylpiperazine-2,3-dione Chemical compound CN1CCN(C)C(=O)C1=O WWBHDWHAIVWDMT-UHFFFAOYSA-N 0.000 description 1
- NBOOZXVYXHATOW-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-ylmethyl)piperazine Chemical compound C=1C=C2OCOC2=CC=1CN1CCNCC1 NBOOZXVYXHATOW-UHFFFAOYSA-N 0.000 description 1
- TWJPZMYNUBAUGA-UHFFFAOYSA-N 1-(1,4-diazepan-1-yl)ethanone Chemical compound CC(=O)N1CCCNCC1 TWJPZMYNUBAUGA-UHFFFAOYSA-N 0.000 description 1
- FLNQAPQQAZVRDA-UHFFFAOYSA-N 1-(2-(2-Hydroxyethoxy)ethyl)piperazine Chemical compound OCCOCCN1CCNCC1 FLNQAPQQAZVRDA-UHFFFAOYSA-N 0.000 description 1
- YLBWRMSQRFEIEB-UHFFFAOYSA-N 1-(2-Pyrrolidinylmethyl)pyrrolidine Chemical compound C1CCCN1CC1CCCN1 YLBWRMSQRFEIEB-UHFFFAOYSA-N 0.000 description 1
- BMEMBBFDTYHTLH-UHFFFAOYSA-N 1-(2-methoxyethyl)piperazine Chemical compound COCCN1CCNCC1 BMEMBBFDTYHTLH-UHFFFAOYSA-N 0.000 description 1
- HUUQNWZMQSLPMX-UHFFFAOYSA-N 1-(2-methylpropyl)piperazine Chemical compound CC(C)CN1CCNCC1 HUUQNWZMQSLPMX-UHFFFAOYSA-N 0.000 description 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
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- VCVPSRADUBPOKJ-UHFFFAOYSA-N 1-[(1-methylpyrrolidin-2-yl)methyl]piperidine Chemical compound CN1CCCC1CN1CCCCC1 VCVPSRADUBPOKJ-UHFFFAOYSA-N 0.000 description 1
- REUAXQZIRFXQML-UHFFFAOYSA-N 1-azabicyclo[2.2.2]octan-3-amine Chemical compound C1CC2C(N)CN1CC2 REUAXQZIRFXQML-UHFFFAOYSA-N 0.000 description 1
- SOTUMZCQANFRAM-UHFFFAOYSA-N 1-benzyl-n,n-dimethylpyrrolidin-3-amine Chemical compound C1C(N(C)C)CCN1CC1=CC=CC=C1 SOTUMZCQANFRAM-UHFFFAOYSA-N 0.000 description 1
- ZSIUSRJKSLXIJH-UHFFFAOYSA-N 1-benzyl-n-ethylpyrrolidin-3-amine Chemical compound C1C(NCC)CCN1CC1=CC=CC=C1 ZSIUSRJKSLXIJH-UHFFFAOYSA-N 0.000 description 1
- UEAYAIWNQQWSBK-UHFFFAOYSA-N 1-benzyl-n-methylpyrrolidin-3-amine Chemical compound C1C(NC)CCN1CC1=CC=CC=C1 UEAYAIWNQQWSBK-UHFFFAOYSA-N 0.000 description 1
- YUBDLZGUSSWQSS-UHFFFAOYSA-N 1-benzylpiperidin-4-amine Chemical compound C1CC(N)CCN1CC1=CC=CC=C1 YUBDLZGUSSWQSS-UHFFFAOYSA-N 0.000 description 1
- HBVNLKQGRZPGRP-UHFFFAOYSA-N 1-benzylpyrrolidin-3-amine Chemical compound C1C(N)CCN1CC1=CC=CC=C1 HBVNLKQGRZPGRP-UHFFFAOYSA-N 0.000 description 1
- HEARQVUKBKMUPY-UHFFFAOYSA-N 1-benzylpyrrolidine-3,4-diamine Chemical compound C1C(N)C(N)CN1CC1=CC=CC=C1 HEARQVUKBKMUPY-UHFFFAOYSA-N 0.000 description 1
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- LQOASEHNECNLNM-UHFFFAOYSA-N 1-ethylpyrrolidine-2-carboxamide Chemical compound CCN1CCCC1C(N)=O LQOASEHNECNLNM-UHFFFAOYSA-N 0.000 description 1
- FXHRAKUEZPSMLJ-UHFFFAOYSA-N 1-methyl-1,4-diazepane Chemical compound CN1CCCNCC1 FXHRAKUEZPSMLJ-UHFFFAOYSA-N 0.000 description 1
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- VVNRVKMOTTTYKS-UHFFFAOYSA-N 1-methyl-4-(1-piperidin-4-ylpiperidin-4-yl)piperazine Chemical compound C1CN(C)CCN1C1CCN(C2CCNCC2)CC1 VVNRVKMOTTTYKS-UHFFFAOYSA-N 0.000 description 1
- ALOCUZOKRULSAA-UHFFFAOYSA-N 1-methylpiperidin-4-amine Chemical compound CN1CCC(N)CC1 ALOCUZOKRULSAA-UHFFFAOYSA-N 0.000 description 1
- PKDPUENCROCRCH-UHFFFAOYSA-N 1-piperazin-1-ylethanone Chemical compound CC(=O)N1CCNCC1 PKDPUENCROCRCH-UHFFFAOYSA-N 0.000 description 1
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- ZRQQXFMGYSOKDF-UHFFFAOYSA-N 1-propan-2-ylpiperidin-4-amine Chemical compound CC(C)N1CCC(N)CC1 ZRQQXFMGYSOKDF-UHFFFAOYSA-N 0.000 description 1
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- FTVFPPFZRRKJIH-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CC1(C)CC(N)CC(C)(C)N1 FTVFPPFZRRKJIH-UHFFFAOYSA-N 0.000 description 1
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- PNHGJPJOMCXSKN-UHFFFAOYSA-N 2-(1-methylpyrrolidin-2-yl)ethanamine Chemical compound CN1CCCC1CCN PNHGJPJOMCXSKN-UHFFFAOYSA-N 0.000 description 1
- BWSIKGOGLDNQBZ-UHFFFAOYSA-N 2-(methoxymethyl)pyrrolidin-1-amine Chemical compound COCC1CCCN1N BWSIKGOGLDNQBZ-UHFFFAOYSA-N 0.000 description 1
- HUHGPYXAVBJSJV-UHFFFAOYSA-N 2-[3,5-bis(2-hydroxyethyl)-1,3,5-triazinan-1-yl]ethanol Chemical compound OCCN1CN(CCO)CN(CCO)C1 HUHGPYXAVBJSJV-UHFFFAOYSA-N 0.000 description 1
- 125000003006 2-dimethylaminoethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- JOMNTHCQHJPVAZ-UHFFFAOYSA-N 2-methylpiperazine Chemical compound CC1CNCCN1 JOMNTHCQHJPVAZ-UHFFFAOYSA-N 0.000 description 1
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- CLBJZAWCBRAMRZ-UHFFFAOYSA-N 2-piperidin-2-ylpiperidine Chemical compound N1CCCCC1C1NCCCC1 CLBJZAWCBRAMRZ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- WRXNJTBODVGDRY-UHFFFAOYSA-N 2-pyrrolidin-1-ylethanamine Chemical compound NCCN1CCCC1 WRXNJTBODVGDRY-UHFFFAOYSA-N 0.000 description 1
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- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- FZQMJOOSLXFQSU-UHFFFAOYSA-N 3-[3,5-bis[3-(dimethylamino)propyl]-1,3,5-triazinan-1-yl]-n,n-dimethylpropan-1-amine Chemical compound CN(C)CCCN1CN(CCCN(C)C)CN(CCCN(C)C)C1 FZQMJOOSLXFQSU-UHFFFAOYSA-N 0.000 description 1
- VPBWZBGZWHDNKL-UHFFFAOYSA-N 3-pyrrolidin-1-ylpropan-1-amine Chemical compound NCCCN1CCCC1 VPBWZBGZWHDNKL-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- MOZNZNKHRXRLLF-UHFFFAOYSA-N 4-(4-methylpiperazin-1-yl)aniline Chemical compound C1CN(C)CCN1C1=CC=C(N)C=C1 MOZNZNKHRXRLLF-UHFFFAOYSA-N 0.000 description 1
- DPBWFNDFMCCGGJ-UHFFFAOYSA-N 4-Piperidine carboxamide Chemical compound NC(=O)C1CCNCC1 DPBWFNDFMCCGGJ-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- UMRORFKGYQPUGR-UHFFFAOYSA-N 4-methyl-1,4-diazepan-4-ium-1-carbodithioate Chemical compound CN1CCCN(C(S)=S)CC1 UMRORFKGYQPUGR-UHFFFAOYSA-N 0.000 description 1
- RJWLLQWLBMJCFD-UHFFFAOYSA-N 4-methylpiperazin-1-amine Chemical compound CN1CCN(N)CC1 RJWLLQWLBMJCFD-UHFFFAOYSA-N 0.000 description 1
- PRNRUOJLUPUJDN-UHFFFAOYSA-N 4-piperidin-4-ylpiperidine Chemical compound C1CNCCC1C1CCNCC1 PRNRUOJLUPUJDN-UHFFFAOYSA-N 0.000 description 1
- STWODXDTKGTVCJ-UHFFFAOYSA-N 4-pyrrolidin-1-ylpiperidine Chemical compound C1CCCN1C1CCNCC1 STWODXDTKGTVCJ-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 0 CC1*(*2CC2)C(*)C(*)C1** Chemical compound CC1*(*2CC2)C(*)C(*)C1** 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical class [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Chemical class 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Natural products C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001956 copper hydroxide Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- NWVNXDKZIQLBNM-UHFFFAOYSA-N diphenylmethylpiperazine Chemical compound C1CNCCN1C(C=1C=CC=CC=1)C1=CC=CC=C1 NWVNXDKZIQLBNM-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LNOQURRKNJKKBU-UHFFFAOYSA-N ethyl piperazine-1-carboxylate Chemical compound CCOC(=O)N1CCNCC1 LNOQURRKNJKKBU-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- XHOADYKJSBCVBJ-UHFFFAOYSA-N n,n-diethylpyrrolidin-3-amine Chemical compound CCN(CC)C1CCNC1 XHOADYKJSBCVBJ-UHFFFAOYSA-N 0.000 description 1
- AVAWMINJNRAQFS-UHFFFAOYSA-N n,n-dimethylpyrrolidin-3-amine Chemical compound CN(C)C1CCNC1 AVAWMINJNRAQFS-UHFFFAOYSA-N 0.000 description 1
- PXKZVCOKJFOTQY-UHFFFAOYSA-N n-(1-benzylpiperidin-4-yl)acetamide Chemical compound C1CC(NC(=O)C)CCN1CC1=CC=CC=C1 PXKZVCOKJFOTQY-UHFFFAOYSA-N 0.000 description 1
- CMSWETNAAPYFSH-UHFFFAOYSA-N n-(1-benzylpyrrolidin-3-yl)acetamide Chemical compound C1C(NC(=O)C)CCN1CC1=CC=CC=C1 CMSWETNAAPYFSH-UHFFFAOYSA-N 0.000 description 1
- NHMWGGURJSUYGU-UHFFFAOYSA-N n-ethyl-n-pyrrolidin-3-ylacetamide Chemical compound CCN(C(C)=O)C1CCNC1 NHMWGGURJSUYGU-UHFFFAOYSA-N 0.000 description 1
- OPCPWFHLFKAUEA-UHFFFAOYSA-N n-ethylpyrrolidin-3-amine Chemical compound CCNC1CCNC1 OPCPWFHLFKAUEA-UHFFFAOYSA-N 0.000 description 1
- KOEKUQRWTOSZOR-UHFFFAOYSA-N n-methyl-n-pyrrolidin-3-ylacetamide Chemical compound CC(=O)N(C)C1CCNC1 KOEKUQRWTOSZOR-UHFFFAOYSA-N 0.000 description 1
- NGZYRKGJWYJGRS-UHFFFAOYSA-N n-methylpyrrolidin-3-amine Chemical compound CNC1CCNC1 NGZYRKGJWYJGRS-UHFFFAOYSA-N 0.000 description 1
- BCXSCZDWARFWAW-UHFFFAOYSA-N n-piperidin-3-ylacetamide Chemical compound CC(=O)NC1CCCNC1 BCXSCZDWARFWAW-UHFFFAOYSA-N 0.000 description 1
- YLWUSMHZABTZGP-UHFFFAOYSA-N n-piperidin-4-ylacetamide Chemical compound CC(=O)NC1CCNCC1 YLWUSMHZABTZGP-UHFFFAOYSA-N 0.000 description 1
- HDCCJUCOIKLZNM-UHFFFAOYSA-N n-pyrrolidin-3-ylacetamide Chemical compound CC(=O)NC1CCNC1 HDCCJUCOIKLZNM-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- YZTJYBJCZXZGCT-UHFFFAOYSA-N phenylpiperazine Chemical compound C1CNCCN1C1=CC=CC=C1 YZTJYBJCZXZGCT-UHFFFAOYSA-N 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- IWELDVXSEVIIGI-UHFFFAOYSA-N piperazin-2-one Chemical compound O=C1CNCCN1 IWELDVXSEVIIGI-UHFFFAOYSA-N 0.000 description 1
- CBLGQEBXWDKYDI-UHFFFAOYSA-N piperazine-1,4-dicarbaldehyde Chemical compound O=CN1CCN(C=O)CC1 CBLGQEBXWDKYDI-UHFFFAOYSA-N 0.000 description 1
- RFIOZSIHFNEKFF-UHFFFAOYSA-N piperazine-1-carboxylic acid Chemical compound OC(=O)N1CCNCC1 RFIOZSIHFNEKFF-UHFFFAOYSA-N 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- LWMPFIOTEAXAGV-UHFFFAOYSA-N piperidin-1-amine Chemical compound NN1CCCCC1 LWMPFIOTEAXAGV-UHFFFAOYSA-N 0.000 description 1
- RHPBLLCTOLJFPH-UHFFFAOYSA-N piperidin-2-ylmethanamine Chemical compound NCC1CCCCN1 RHPBLLCTOLJFPH-UHFFFAOYSA-N 0.000 description 1
- PEUGKEHLRUVPAN-UHFFFAOYSA-N piperidin-3-amine Chemical compound NC1CCCNC1 PEUGKEHLRUVPAN-UHFFFAOYSA-N 0.000 description 1
- IPOVLZSJBYKHHU-UHFFFAOYSA-N piperidin-3-ylmethanamine Chemical compound NCC1CCCNC1 IPOVLZSJBYKHHU-UHFFFAOYSA-N 0.000 description 1
- BCIIMDOZSUCSEN-UHFFFAOYSA-N piperidin-4-amine Chemical compound NC1CCNCC1 BCIIMDOZSUCSEN-UHFFFAOYSA-N 0.000 description 1
- LTEKQAPRXFBRNN-UHFFFAOYSA-N piperidin-4-ylmethanamine Chemical compound NCC1CCNCC1 LTEKQAPRXFBRNN-UHFFFAOYSA-N 0.000 description 1
- XIMBESZRBTVIOD-UHFFFAOYSA-N piperidine-2-carboxamide Chemical compound NC(=O)C1CCCCN1 XIMBESZRBTVIOD-UHFFFAOYSA-N 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- NGXSWUFDCSEIOO-UHFFFAOYSA-N pyrrolidin-3-amine Chemical compound NC1CCNC1 NGXSWUFDCSEIOO-UHFFFAOYSA-N 0.000 description 1
- VLJNHYLEOZPXFW-UHFFFAOYSA-N pyrrolidine-2-carboxamide Chemical compound NC(=O)C1CCCN1 VLJNHYLEOZPXFW-UHFFFAOYSA-N 0.000 description 1
- IQHXABCGSFAKPN-UHFFFAOYSA-N pyrrolidine-3-carboxamide Chemical compound NC(=O)C1CCNC1 IQHXABCGSFAKPN-UHFFFAOYSA-N 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- CMIBWIAICVBURI-UHFFFAOYSA-N tert-butyl 3-aminopyrrolidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCC(N)C1 CMIBWIAICVBURI-UHFFFAOYSA-N 0.000 description 1
- DQQJBEAXSOOCPG-UHFFFAOYSA-N tert-butyl n-pyrrolidin-3-ylcarbamate Chemical compound CC(C)(C)OC(=O)NC1CCNC1 DQQJBEAXSOOCPG-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical group 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005406 washing Methods 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
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/067—Etchants
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
- H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
- H05K2203/0789—Aqueous acid solution, e.g. for cleaning or etching
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
【課題】銅配線の直線性を損なうことなくサイドエッチングを抑制できるエッチング液とその補給液、及び銅配線の形成方法を提供する。【解決手段】本発明のエッチング液は、銅のエッチング液であって、環を構成するヘテロ原子として窒素のみを有する５〜７員環の脂肪族複素環を含む脂肪族複素環式化合物と、酸と、酸化性金属イオンとを含む水溶液であり、前記脂肪族複素環式化合物は、環を構成するヘテロ原子として窒素を２つ以上有する脂肪族複素環式化合物Ａ、及びアミノ基を有する置換基で置換された脂肪族複素環式化合物Ｂから選ばれる１種以上であることを特徴とする。本発明の銅配線（１）の形成方法は、銅層のエッチングレジスト（２）で被覆されていない部分をエッチングする銅配線（１）の形成方法であって、前記本発明のエッチング液を用いてエッチングすることを特徴とする。【選択図】図１An etching solution capable of suppressing side etching without impairing the linearity of a copper wiring, a replenisher thereof, and a method for forming a copper wiring. An etching solution of the present invention is an etching solution of copper, an aliphatic heterocyclic compound containing a 5- to 7-membered aliphatic heterocyclic ring having only nitrogen as a hetero atom constituting the ring, and An aqueous solution containing an acid and an oxidizable metal ion, wherein the aliphatic heterocyclic compound is an aliphatic heterocyclic compound A having two or more nitrogen atoms as a hetero atom constituting the ring, and a substitution having an amino group It is one or more selected from aliphatic heterocyclic compounds B substituted with a group. The method for forming a copper wiring (1) of the present invention is a method for forming a copper wiring (1) for etching a portion of a copper layer not covered with an etching resist (2), using the etching solution of the present invention. And etching. [Selection] Figure 1
Description
本発明は、銅のエッチング液とその補給液、及び銅配線の形成方法に関する。 The present invention relates to a copper etching solution, a replenisher thereof, and a method for forming a copper wiring.
プリント配線板の製造において、フォトエッチング法で銅配線パターンを形成する場合、エッチング液として塩化鉄系エッチング液、塩化銅系エッチング液、アルカリ性エッチング液などが用いられている。これらのエッチング液を使用すると、サイドエッチングとよばれるエッチングレジスト下の銅が配線パターンの側面から溶解する場合があった。即ち、エッチングレジストでカバーされることによって、本来エッチングで除去されないことが望まれる部分（即ち、銅配線部分）が、エッチング液により除去されて、当該銅配線の底部から頂部になるに従い幅が細くなる現象が生じていた。特に銅配線パターンが微細な場合、このようなサイドエッチングはできる限り少なくしなければならない。このサイドエッチングを抑制するために、アゾール化合物が配合されたエッチング液が提案されている（例えば下記特許文献１参照）。 In the production of a printed wiring board, when a copper wiring pattern is formed by a photoetching method, an iron chloride etching solution, a copper chloride etching solution, an alkaline etching solution or the like is used as an etching solution. When these etching solutions are used, copper under an etching resist called side etching sometimes dissolves from the side surface of the wiring pattern. That is, by covering with an etching resist, a portion that is originally not desired to be removed by etching (that is, a copper wiring portion) is removed by an etching solution, and the width becomes narrower from the bottom to the top of the copper wiring. The phenomenon that occurred. Especially when the copper wiring pattern is fine, such side etching must be minimized. In order to suppress this side etching, an etching solution containing an azole compound has been proposed (see, for example, Patent Document 1 below).
特許文献１に記載のエッチング液によれば、サイドエッチングについては抑制できるが、特許文献１に記載のエッチング液を通常の方法で使用すると、銅配線の側面にがたつきが生じるおそれがあった。銅配線の側面にがたつきが生じると、銅配線の直線性が低下して、プリント配線板の上方から銅配線幅を光学的に検査する際に、誤認識を引き起こすおそれがあった。また、極端に直線性が悪化するとプリント配線板のインピーダンス特性が低下するおそれがあった。 According to the etching solution described in Patent Document 1, side etching can be suppressed. However, when the etching solution described in Patent Document 1 is used in a normal method, there is a possibility that the side surface of the copper wiring may be rattled. . When the side surface of the copper wiring is rattled, the linearity of the copper wiring is lowered, and there is a possibility of causing erroneous recognition when optically inspecting the width of the copper wiring from above the printed wiring board. Further, when the linearity is extremely deteriorated, the impedance characteristic of the printed wiring board may be deteriorated.
このように、従来のエッチング液では、銅配線の直線性を損なうことなくサイドエッチングを抑制するのは困難であった。 Thus, it has been difficult to suppress side etching with a conventional etching solution without impairing the linearity of the copper wiring.
本発明は、前記実情に鑑みてなされたものであり、銅配線の直線性を損なうことなくサイドエッチングを抑制できるエッチング液とその補給液、及び銅配線の形成方法を提供する。 This invention is made | formed in view of the said situation, and provides the etching liquid which can suppress side etching, without impairing the linearity of copper wiring, its replenisher, and the formation method of copper wiring.
本発明のエッチング液は、銅のエッチング液であって、
前記エッチング液は、環を構成するヘテロ原子として窒素のみを有する５〜７員環の脂肪族複素環を含む脂肪族複素環式化合物と、酸と、酸化性金属イオンとを含む水溶液であり、
前記脂肪族複素環式化合物は、環を構成するヘテロ原子として窒素を２つ以上有する脂肪族複素環式化合物Ａ、及びアミノ基を有する置換基で置換された脂肪族複素環式化合物Ｂから選ばれる１種以上であることを特徴とする。
The etching solution of the present invention is a copper etching solution,
The etching solution is an aqueous solution containing an aliphatic heterocyclic compound containing a 5- to 7-membered aliphatic heterocyclic ring having only nitrogen as a hetero atom constituting the ring, an acid, and an oxidizing metal ion.
The aliphatic heterocyclic compound is selected from an aliphatic heterocyclic compound A having two or more nitrogen atoms as a hetero atom constituting the ring, and an aliphatic heterocyclic compound B substituted with a substituent having an amino group It is characterized by being 1 or more types.
本発明の補給液は、前記本発明のエッチング液を連続又は繰り返し使用する際に、前記エッチング液に添加する補給液であって、
前記補給液は、環を構成するヘテロ原子として窒素のみを有する５〜７員環の脂肪族複素環を含む脂肪族複素環式化合物と、酸とを含む水溶液であり、
前記脂肪族複素環式化合物は、環を構成するヘテロ原子として窒素を２つ以上有する脂肪族複素環式化合物Ａ、及びアミノ基を有する置換基で置換された脂肪族複素環式化合物Ｂから選ばれる１種以上であることを特徴とする。
The replenisher of the present invention is a replenisher that is added to the etchant when the etchant of the present invention is used continuously or repeatedly,
The replenisher is an aqueous solution containing an aliphatic heterocyclic compound containing a 5- to 7-membered aliphatic heterocyclic ring having only nitrogen as a hetero atom constituting the ring, and an acid.
The aliphatic heterocyclic compound is selected from an aliphatic heterocyclic compound A having two or more nitrogen atoms as a hetero atom constituting the ring, and an aliphatic heterocyclic compound B substituted with a substituent having an amino group It is characterized by being 1 or more types.
本発明の銅配線の形成方法は、銅層のエッチングレジストで被覆されていない部分をエッチングする銅配線の形成方法であって、前記本発明のエッチング液を用いてエッチングすることを特徴とする。 The method for forming a copper wiring according to the present invention is a method for forming a copper wiring in which a portion of the copper layer not covered with the etching resist is etched, which is characterized by etching using the etching solution of the present invention.
なお、前記本発明における「銅」は、銅からなるものであってもよく、銅合金からなるものであってもよい。また、本明細書において「銅」は、銅又は銅合金を指す。 The “copper” in the present invention may be made of copper or a copper alloy. In this specification, “copper” refers to copper or a copper alloy.
本発明によれば、銅配線の直線性を損なうことなくサイドエッチングを抑制できるエッチング液とその補給液、及び銅配線の形成方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the etching liquid which can suppress side etching, without impairing the linearity of copper wiring, its replenisher, and the formation method of copper wiring can be provided.
本発明の銅のエッチング液は、環を構成するヘテロ原子として窒素のみを有する５〜７員環の脂肪族複素環を含む脂肪族複素環式化合物と、酸と、酸化性金属イオンとを含む水溶液である。本発明の銅のエッチング液には、前記脂肪族複素環式化合物として、環を構成するヘテロ原子として窒素を２つ以上有する脂肪族複素環式化合物Ａ（以下、単に「化合物Ａ」ともいう）、及びアミノ基を有する置換基（以下、アミノ基含有置換基ともいう）で置換された脂肪族複素環式化合物Ｂ（以下、単に「化合物Ｂ」ともいう）から選ばれる１種以上が配合される。図１は、本発明のエッチング液によりエッチングした後の銅配線の一例を示す部分断面図である。銅配線１上には、エッチングレジスト２が形成されている。そして、エッチングレジスト２の端部の直下における銅配線１の側面に、保護皮膜３が形成されている。この保護皮膜３は、エッチングの進行とともにエッチング液中に生成する第一銅イオン及びその塩と、化合物Ａ及び／又は化合物Ｂとにより主に形成されると考えられる。本発明のエッチング液によれば、前記化合物Ａ及び／又は化合物Ｂを含むため、均一な保護皮膜３が形成されると考えられる。これにより、銅配線１のがたつきが軽減されるため、銅配線１の直線性を損なうことなくサイドエッチングを抑制できると考えられる。よって、本発明のエッチング液によれば、プリント配線板の製造工程における歩留まりを改善できる。なお、保護皮膜３はエッチング処理後に除去液による処理で簡単に除去することができる。前記除去液としては、過酸化水素と硫酸の混合液、塩酸などの酸性液、あるいはジプロピレングリコールモノメチルエーテルなどの有機溶媒などが好ましい。
The copper etching solution of the present invention contains an aliphatic heterocyclic compound containing a 5- to 7-membered aliphatic heterocyclic ring having only nitrogen as a hetero atom constituting the ring, an acid, and an oxidizing metal ion. It is an aqueous solution. In the copper etching solution of the present invention, as the aliphatic heterocyclic compound, an aliphatic heterocyclic compound A (hereinafter also simply referred to as “compound A”) having two or more nitrogen atoms as hetero atoms constituting the ring. And one or more selected from aliphatic heterocyclic compounds B (hereinafter also simply referred to as “compound B”) substituted with a substituent having an amino group (hereinafter also referred to as an amino group-containing substituent). The FIG. 1 is a partial cross-sectional view showing an example of a copper wiring after etching with the etching solution of the present invention. An
なお、前記特許文献１のエッチング液で銅配線を形成すると、本発明のエッチング液でエッチングしたときよりも不均一な保護皮膜が厚く形成されると考えられるため、銅配線の直線性が損なわれると推測される。 In addition, since it is thought that when a copper wiring is formed with the etching solution of the above-mentioned Patent Document 1, a non-uniform protective film is formed thicker than when etching with the etching solution of the present invention, the linearity of the copper wiring is impaired. It is guessed.
また、前記特許文献１のエッチング液を用いる場合、エッチング速度が遅いため、処理速度の低下を招き、生産性が低下していたが、本発明のエッチング液は、一般的な塩化鉄系エッチング液又は塩化銅系エッチング液と同等のエッチング速度を維持できるため、生産性を低下させずに歩留まりを改善できる。 In addition, when the etching solution of Patent Document 1 is used, the etching rate is slow, so that the processing rate is reduced and the productivity is reduced. However, the etching solution of the present invention is a general iron chloride etching solution. Alternatively, since the etching rate equivalent to that of the copper chloride-based etching solution can be maintained, the yield can be improved without reducing the productivity.
本発明のエッチング液に用いられる酸は、無機酸及び有機酸から適宜選択可能である。前記無機酸としては、硫酸、塩酸、硝酸、リン酸などが挙げられる。前記有機酸としては、ギ酸、酢酸、シュウ酸、マレイン酸、安息香酸、グリコール酸などが挙げられる。前記酸の中では、エッチング速度の安定性及び銅の溶解安定性の観点から、塩酸が好ましい。 The acid used in the etching solution of the present invention can be appropriately selected from inorganic acids and organic acids. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and the like. Examples of the organic acid include formic acid, acetic acid, oxalic acid, maleic acid, benzoic acid, and glycolic acid. Among the acids, hydrochloric acid is preferable from the viewpoints of etching rate stability and copper dissolution stability.
前記酸の濃度は、好ましくは５〜１８０ｇ／Ｌであり、より好ましくは７〜１１０ｇ／Ｌである。酸の濃度が５ｇ／Ｌ以上の場合は、エッチング速度が速くなるため、銅を速やかにエッチングすることができる。また、酸の濃度が１８０ｇ／Ｌ以下の場合は、銅の溶解安定性が維持されるとともに、作業環境の悪化を抑制できる。 The acid concentration is preferably 5 to 180 g / L, more preferably 7 to 110 g / L. When the acid concentration is 5 g / L or more, the etching rate increases, so that copper can be etched quickly. Moreover, when the density | concentration of an acid is 180 g / L or less, while melt | dissolving stability of copper is maintained, the deterioration of a working environment can be suppressed.
本発明のエッチング液に用いられる酸化性金属イオンは、金属銅を酸化できる金属イオンであればよく、例えば第二銅イオン、第二鉄イオン等が挙げられる。サイドエッチングを抑制する観点、及びエッチング速度の安定性の観点から、酸化性金属イオンとして第二銅イオンを用いることが好ましい。 The oxidizing metal ions used in the etching solution of the present invention may be metal ions that can oxidize metallic copper, and examples thereof include cupric ions and ferric ions. From the viewpoint of suppressing side etching and the stability of etching rate, it is preferable to use cupric ions as the oxidizing metal ions.
前記酸化性金属イオンは、酸化性金属イオン源を配合することによって、エッチング液中に含有させることができる。例えば、酸化性金属イオン源として第二銅イオン源を用いる場合、その具体例としては、塩化銅、硫酸銅、臭化銅、有機酸の銅塩、水酸化銅などが挙げられる。例えば、酸化性金属イオン源として第二鉄イオン源を用いる場合、その具体例としては、塩化鉄、臭化鉄、ヨウ化鉄、硫酸鉄、硝酸鉄、有機酸の鉄塩などが挙げられる。 The oxidizing metal ion can be contained in the etching solution by blending an oxidizing metal ion source. For example, when using a cupric ion source as the oxidizing metal ion source, specific examples thereof include copper chloride, copper sulfate, copper bromide, copper salts of organic acids, and copper hydroxide. For example, when a ferric ion source is used as the oxidizing metal ion source, specific examples thereof include iron chloride, iron bromide, iron iodide, iron sulfate, iron nitrate, and iron salts of organic acids.
前記酸化性金属イオンの濃度は、好ましくは１０〜２５０ｇ／Ｌであり、より好ましくは１０〜２００ｇ／Ｌであり、更に好ましくは１５〜１６０ｇ／Ｌであり、更により好ましくは３０〜１６０ｇ／Ｌである。酸化性金属イオンの濃度が１０ｇ／Ｌ以上の場合は、エッチング速度が速くなるため、銅を速やかにエッチングすることができる。また、酸化性金属イオンの濃度が２５０ｇ／Ｌ以下の場合は、銅の溶解安定性が維持される。 The concentration of the oxidizing metal ion is preferably 10 to 250 g / L, more preferably 10 to 200 g / L, still more preferably 15 to 160 g / L, and still more preferably 30 to 160 g / L. It is. When the concentration of the oxidizing metal ions is 10 g / L or more, the etching rate is increased, so that copper can be etched quickly. Moreover, when the concentration of the oxidizing metal ion is 250 g / L or less, the dissolution stability of copper is maintained.
本発明のエッチング液には、銅配線の直線性を損なうことなくサイドエッチングを抑制するために、環を構成するヘテロ原子として窒素を２つ以上有する脂肪族複素環式化合物Ａ（化合物Ａ）、及びアミノ基含有置換基で置換された脂肪族複素環式化合物Ｂ（化合物Ｂ）から選ばれる１種以上が配合される。上述したように化合物Ａ及び化合物Ｂは、環を構成するヘテロ原子として窒素のみを有し、かつ５〜７員環の脂肪族複素環を含む脂肪族複素環式化合物であるため、構造安定性及び酸性液に対する溶解性が高い。なお、前記アミノ基とは、−ＮＨ２、−ＮＨＲ、及び−ＮＲＲ’のいずれかを指し、前記Ｒ、Ｒ’はそれぞれ独立に炭素数１〜６の炭化水素誘導基を指し、ＲとＲ’は互いに結合して飽和環構造を形成していてもよい。前記アミノ基含有置換基とは、アミノ基からなる置換基、及び炭素数１〜６の炭化水素誘導基にて一部の水素がアミノ基に置き換わった置換基のいずれかを指す。サイドエッチングを効果的に抑制し、かつ銅配線の直線性をより向上させる観点から、アミノ基からなる置換基、又は炭素、水素及び窒素からなるアミノ基含有置換基が好ましい。 In the etching solution of the present invention, an aliphatic heterocyclic compound A (compound A) having two or more nitrogen atoms as heteroatoms constituting the ring in order to suppress side etching without impairing the linearity of the copper wiring, And one or more selected from aliphatic heterocyclic compound B (compound B) substituted with an amino group-containing substituent. As described above, since compound A and compound B are aliphatic heterocyclic compounds having only nitrogen as a hetero atom constituting the ring and containing a 5- to 7-membered aliphatic heterocyclic ring, structural stability And the solubility with respect to an acidic liquid is high. The amino group refers to any of —NH 2 , —NHR, and —NRR ′, and R and R ′ each independently represent a hydrocarbon-derived group having 1 to 6 carbon atoms, and R and R 'May be bonded to each other to form a saturated ring structure. The amino group-containing substituent refers to either a substituent composed of an amino group or a substituent in which part of hydrogen is replaced with an amino group in a hydrocarbon derivative having 1 to 6 carbon atoms. From the viewpoint of effectively suppressing the side etching and further improving the linearity of the copper wiring, a substituent composed of an amino group or an amino group-containing substituent composed of carbon, hydrogen and nitrogen is preferable.
なお、前記炭化水素誘導基とは、炭化水素基にて一部の炭素又は水素が他の原子又は置換基に置き換わっていてもよいものを指す。炭化水素誘導基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、アリル基、アセチル基、フェニル基、ヒドロキシエトキシメチル基、ヒドロキシエトキシエチル基、ヒドロキシエトキシプロピル基等が例示でき、サイドエッチングを効果的に抑制し、かつ銅配線の直線性をより向上させる観点から、炭素及び水素からなる炭化水素誘導基が好ましい。以下の炭化水素誘導基も同様である。 The hydrocarbon-derived group refers to a hydrocarbon group in which part of carbon or hydrogen may be replaced with another atom or substituent. Examples of hydrocarbon-derived groups include methyl group, ethyl group, propyl group, butyl group, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, allyl group, acetyl group, phenyl group, hydroxyethoxymethyl group, hydroxyethoxyethyl. A hydrocarbon-derived group consisting of carbon and hydrogen is preferable from the viewpoint of effectively suppressing side etching and further improving the linearity of the copper wiring. The same applies to the following hydrocarbon-derived groups.
前記化合物Ａ及び／又は化合物Ｂは、環を構成するヘテロ原子として窒素のみを有する５〜７員環の脂肪族複素環を含む脂肪族複素環式化合物の中から適宜選択することができるが、エッチング液中の安定性の観点から、環を構成する窒素の数が１〜３の脂肪族複素環式化合物が好ましい。なお、化合物Ａ又は化合物Ｂとして、化合物Ａ及び化合物Ｂの双方の特徴を備えた脂肪族複素環式化合物を配合してもよい。そのような脂肪族複素環式化合物としては、1-(2-アミノエチル)ピペラジン、1-アミノ-4-メチルピペラジン、ヘキサヒドロ-1,3,5-トリス(3-ジメチルアミノプロピル)-1,3,5-トリアジン等が例示できる。 The compound A and / or compound B can be appropriately selected from aliphatic heterocyclic compounds containing a 5- to 7-membered aliphatic heterocyclic ring having only nitrogen as a hetero atom constituting the ring, From the viewpoint of stability in the etching solution, an aliphatic heterocyclic compound having 1 to 3 nitrogen atoms constituting the ring is preferable. In addition, you may mix | blend the aliphatic heterocyclic compound provided with the characteristic of both the compound A and the compound B as the compound A or the compound B. Such aliphatic heterocyclic compounds include 1- (2-aminoethyl) piperazine, 1-amino-4-methylpiperazine, hexahydro-1,3,5-tris (3-dimethylaminopropyl) -1, Examples include 3,5-triazine.
なかでも、銅配線の直線性向上の観点、及びサイドエッチングを効果的に抑制する観点から、化合物Ａ及び／又は化合物Ｂとして、ピロリジン化合物、ピペリジン化合物、ピペラジン化合物、ホモピペラジン化合物及びヘキサヒドロ-1,3,5-トリアジン化合物から選ばれる１種以上を配合することが好ましい。 Among them, from the viewpoint of improving the linearity of the copper wiring and effectively suppressing side etching, as the compound A and / or compound B, pyrrolidine compound, piperidine compound, piperazine compound, homopiperazine compound and hexahydro-1, It is preferable to blend at least one selected from 3,5-triazine compounds.
前記ピロリジン化合物は、ピロリジン骨格を有する化合物であれば特に限定されないが、例えば下記式（Ｉ）に示すピロリジン化合物が例示できる。
〔化１〕
[Chemical formula 1]
前記ピロリジン化合物の具体例としては、1-(3-アミノプロピル)ピロリジン、1-(2-アミノエチル)ピロリジン、3-アミノピロリジン、2-アミノメチル-1-エチルピロリジン、2-(2-アミノエチル)-1-メチルピロリジン、3-(ジメチルアミノ)ピロリジン、3-(メチルアミノ)ピロリジン、1-(2-ピロリジニルメチル)ピロリジン、3-(ジエチルアミノ)ピロリジン、1,1’-ジメチル-3-アミノピロリジン、3-(エチルアミノ)ピロリジン、1-メチル-2-(1-ピペリジノメチル)ピロリジン、4-(1-ピロリジニル)ピペリジン、3-(N-アセチル-N-メチルアミノ)ピロリジン、3-(N-アセチル-N-エチルアミノ)ピロリジン、2-ピロリジンカルボキサミド、3-ピロリジンカルボキサミド、3-アセトアミドピロリジン、1-エチル-2-ピロリジンカルボキサミド、3-アミノ-1-(tert-ブトキシカルボニル)ピロリジン、3-(tert-ブトキシカルボニルアミノ)ピロリジン、1-アミノ-2-(メトキシメチル)ピロリジン、1-ベンジル-3-アミノピロリジン、1-ベンジル-3-(ジメチルアミノ)ピロリジン、1-ベンジル-3-(メチルアミノ)ピロリジン、1-ベンジル-3-(エチルアミノ)ピロリジン、3,4-ジアミノ-1-ベンジルピロリジン、1-ベンジル-3-アセトアミドピロリジン、(1s,6s)-2,8-ジアザビシクロ[4.3.0]ノナン等が挙げられる。 Specific examples of the pyrrolidine compound include 1- (3-aminopropyl) pyrrolidine, 1- (2-aminoethyl) pyrrolidine, 3-aminopyrrolidine, 2-aminomethyl-1-ethylpyrrolidine, 2- (2-amino Ethyl) -1-methylpyrrolidine, 3- (dimethylamino) pyrrolidine, 3- (methylamino) pyrrolidine, 1- (2-pyrrolidinylmethyl) pyrrolidine, 3- (diethylamino) pyrrolidine, 1,1'-dimethyl- 3-aminopyrrolidine, 3- (ethylamino) pyrrolidine, 1-methyl-2- (1-piperidinomethyl) pyrrolidine, 4- (1-pyrrolidinyl) piperidine, 3- (N-acetyl-N-methylamino) pyrrolidine, 3 -(N-acetyl-N-ethylamino) pyrrolidine, 2-pyrrolidinecarboxamide, 3-pyrrolidinecarboxamide, 3-acetamidopyrrolidine, 1-ethyl-2-pyrrolidinecarboxamide, 3-amino-1- (tert-butoxycarbonyl) pyrrolidine , 3- (tert-Butoxycarbonylamino) pyrrolidine, 1-amino-2- (methoxymethyl) pyrrolidine, 1-benzyl-3-aminopyrrolidine, 1-benzyl-3- (dimethylamino) pyrrolidine, 1-benzyl-3- (methyl Amino) pyrrolidine, 1-benzyl-3- (ethylamino) pyrrolidine, 3,4-diamino-1-benzylpyrrolidine, 1-benzyl-3-acetamidopyrrolidine, (1s, 6s) -2,8-diazabicyclo [4.3. 0] nonane and the like.
前記ピペリジン化合物は、ピペリジン骨格を有する化合物であれば特に限定されないが、例えば下記式（II）に示すピペリジン化合物が例示できる。
〔化２〕
[Chemical formula 2]
前記ピペリジン化合物の具体例としては、4-アミノピペリジン、1-アミノピペリジン、3-アミノピペリジン、4-(アミノメチル)ピペリジン、4-アミノ-1-メチルピペリジン、2-(アミノメチル)ピペリジン、3-(アミノメチル)ピペリジン、4-ピペリジンカルボキサミド、2-ピペリジンカルボキサミド、1-(2-アミノエチル)ピペリジン、4-アセトアミドピペリジン、3-アセトアミドピペリジン、4-アミノ-1-イソプロピルピペリジン、1-(3-アミノプロピル)-2-メチルピペリジン、4-アミノ-2,2,6,6-テトラメチルピペリジン、2,2’-ビピペリジン、4,4’-ビピペリジン、4-ピペリジノピペリジン、4-アミノ-1-ピペリジンカルボン酸エチル、4-アミノ-1-ベンジルピペリジン、4-(2-アミノエチル)-1-ベンジルピペリジン、4-アセトアミド-1-ベンシルピペリジン、3-アミノキヌクリジン等が挙げられる。 Specific examples of the piperidine compound include 4-aminopiperidine, 1-aminopiperidine, 3-aminopiperidine, 4- (aminomethyl) piperidine, 4-amino-1-methylpiperidine, 2- (aminomethyl) piperidine, 3 -(Aminomethyl) piperidine, 4-piperidinecarboxamide, 2-piperidinecarboxamide, 1- (2-aminoethyl) piperidine, 4-acetamidopiperidine, 3-acetamidopiperidine, 4-amino-1-isopropylpiperidine, 1- (3 -Aminopropyl) -2-methylpiperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 2,2'-bipiperidine, 4,4'-bipiperidine, 4-piperidinopiperidine, 4-amino Ethyl-1-piperidinecarboxylate, 4-amino-1-benzylpiperidine, 4- (2-aminoethyl) -1-benzylpiperidine, 4-acetamido-1-benzylpiperidine, 3-aminoquinuclidine And the like.
前記ピペラジン化合物は、ピペラジン骨格を有する化合物であれば特に限定されないが、例えば下記式（III）に示すピペラジン化合物が例示できる。
〔化３〕
[Chemical formula 3]
前記ピペラジン化合物の具体例としては、ピペラジン、1-メチルピペラジン、2-メチルピペラジン、1-アリルピペラジン、1-イソブチルピペラジン、1-ヒドロキシエトキシエチルピペラジン、1-フェニルピペラジン、1-アミノ-4-メチルピペラジン、1-エチルピペラジン、1-ピペラジンエタノール、1-ピペラジンカルボン酸エチル、1-ホルミルピペラジン、1-プロピルピペラジン、1-アセチルピペラジン、1-イソプロピルピペラジン、1-シクロペンチルピペラジン、1-シクロヘキシルピペラジン、1-（2-メトキシエチル）ピペラジン、1-ピペロニルピペラジン、1-(ジフェニルメチル)ピペラジン、2-ピペラジノン、1,4-ジメチルピペラジン、1-メチル-3-フェニルピペラジン、1,4-ビス（3-アミノプロピル）ピペラジン、1-(2-ジメチルアミノエチル）-4-メチルピペラジン、1-（2-アミノエチル）ピペラジン、1,4-ビス（3-アミノプロピル）ピペラジン、2,5-ジメチルピペラジン、2,6-ジメチルピペラジン、1,4-ジホルミルピペラジン、1-(4-アミノフェニル)-4-メチルピペラジン、1,4-ジアセチル-2,5-ピペラジンジオン、1-メチル-4-(1,4'-ビピペリジン-4-イル)ピペラジン、1-(4-アミノフェニル)-4-(4-メトキシフェニル)ピペラジン、1,4-ジメチルピペラジン-2-オン、1,4-ジエチルピペラジン-2-オン、1,4-ジメチルピペラジン-2,3-ジオン、2-ピペラジンカルボン酸、トリエチレンジアミン等が挙げられる。 Specific examples of the piperazine compound include piperazine, 1-methylpiperazine, 2-methylpiperazine, 1-allylpiperazine, 1-isobutylpiperazine, 1-hydroxyethoxyethylpiperazine, 1-phenylpiperazine, 1-amino-4-methyl. Piperazine, 1-ethylpiperazine, 1-piperazineethanol, ethyl 1-piperazinecarboxylate, 1-formylpiperazine, 1-propylpiperazine, 1-acetylpiperazine, 1-isopropylpiperazine, 1-cyclopentylpiperazine, 1-cyclohexylpiperazine, 1 -(2-methoxyethyl) piperazine, 1-piperonylpiperazine, 1- (diphenylmethyl) piperazine, 2-piperazinone, 1,4-dimethylpiperazine, 1-methyl-3-phenylpiperazine, 1,4-bis ( 3-aminopropyl) piperazine, 1- (2-dimethylaminoethyl) -4-methylpiperazi 1- (2-aminoethyl) piperazine, 1,4-bis (3-aminopropyl) piperazine, 2,5-dimethylpiperazine, 2,6-dimethylpiperazine, 1,4-diformylpiperazine, 1- ( 4-aminophenyl) -4-methylpiperazine, 1,4-diacetyl-2,5-piperazinedione, 1-methyl-4- (1,4'-bipiperidin-4-yl) piperazine, 1- (4-amino Phenyl) -4- (4-methoxyphenyl) piperazine, 1,4-dimethylpiperazin-2-one, 1,4-diethylpiperazin-2-one, 1,4-dimethylpiperazine-2,3-dione, 2- Examples include piperazine carboxylic acid and triethylenediamine.
前記ホモピペラジン化合物は、ホモピペラジン骨格を有する化合物であれば特に限定されないが、例えば下記式（IV）に示すホモピペラジン化合物が例示できる。
〔化４〕
[Chemical formula 4]
前記ホモピペラジン化合物の具体例としては、ホモピペラジン、1-メチルホモピペラジン、1-ホルミルホモピペラジン、1,4-ジメチルホモピペラジン、4-メチル-1-ホモピペラジンジチオカルボン酸、1-アセチルホモピペラジン、1-ブチリルホモピペラジン等が挙げられる。 Specific examples of the homopiperazine compound include homopiperazine, 1-methylhomopiperazine, 1-formylhomopiperazine, 1,4-dimethylhomopiperazine, 4-methyl-1-homopiperazine dithiocarboxylic acid, 1-acetylhomopiperazine 1-butyryl homopiperazine and the like.
前記ヘキサヒドロ-1,3,5-トリアジン化合物は、ヘキサヒドロ-1,3,5-トリアジン骨格を有する化合物であれば特に限定されないが、例えば下記式（Ｖ）に示すヘキサヒドロ-1,3,5-トリアジン化合物が例示できる。
〔化５〕
[Chemical formula 5]
前記ヘキサヒドロ-1,3,5-トリアジン化合物の具体例としては、ヘキサヒドロ-1,3,5-トリアジン、ヘキサヒドロ-1,3,5-トリメチル-1,3,5-トリアジン、ヘキサヒドロ-2,4,6-トリメチル-1,3,5-トリアジン、ヘキサヒドロ-1,3,5-トリス(3-ジメチルアミノプロピル)-1,3,5-トリアジン、ヘキサヒドロ-1,3,5-トリプロピル-1,3,5-トリアジン、ヘキサヒドロ-1,3,5-トリエチル-1,3,5-トリアジン、ヘキサヒドロ-1,3,5-トリイソプロピル-1,3,5-トリアジン、ヘキサヒドロ-1,3,5-トリベンジル-1,3,5-トリアジン、ヘキサヒドロ-1,3,5-トリス(2-ヒドロキシエチル)-1,3,5-トリアジン、ヘキサヒドロ-1,3,5-トリニトロ-1,3,5-トリアジン、ヘキサヒドロ-1,3,5-トリニトロソ-1,3,5-トリアジン、ヘキサヒドロ-2,4,6-トリメチル-1,3,5-トリニトロ-1,3,5-トリアジン、ヘキサヒドロ-1,3,5-トリアクリロイル-1,3,5-トリアジン、ヘキサメチレンテトラミン等が挙げられる。 Specific examples of the hexahydro-1,3,5-triazine compound include hexahydro-1,3,5-triazine, hexahydro-1,3,5-trimethyl-1,3,5-triazine, and hexahydro-2,4. , 6-Trimethyl-1,3,5-triazine, hexahydro-1,3,5-tris (3-dimethylaminopropyl) -1,3,5-triazine, hexahydro-1,3,5-tripropyl-1 , 3,5-triazine, hexahydro-1,3,5-triethyl-1,3,5-triazine, hexahydro-1,3,5-triisopropyl-1,3,5-triazine, hexahydro-1,3, 5-tribenzyl-1,3,5-triazine, hexahydro-1,3,5-tris (2-hydroxyethyl) -1,3,5-triazine, hexahydro-1,3,5-trinitro-1,3, 5-triazine, hexahydro-1,3,5-trinitroso-1,3,5-triazine, hexahydro-2,4,6-trimethyl-1,3,5-trinitro-1,3,5-triazine, hexahydro- 1,3,5-triacryloyl-1,3,5-tria Emissions, hexamethylenetetramine and the like.
前記化合物Ａ及び／又は化合物Ｂの濃度（合計濃度）は、０．０１〜１００ｇ／Ｌが好ましく、０．０２〜８０ｇ／Ｌがより好ましい。この範囲内であれば、銅配線の直線性をさらに向上させ、かつサイドエッチングをさらに効果的に抑制できる。 The concentration (total concentration) of Compound A and / or Compound B is preferably 0.01 to 100 g / L, and more preferably 0.02 to 80 g / L. Within this range, the linearity of the copper wiring can be further improved and side etching can be more effectively suppressed.
本発明のエッチング液は、サイドエッチング抑制効果及び直線性向上効果をさらに高めるために、６員環の複素芳香環を有する複素芳香族化合物（以下、「６員環複素芳香族化合物」という）を含んでいてもよい。６員環複素芳香族化合物としては、構造安定性及び酸性液に対する溶解性の観点から、環を構成するヘテロ原子として窒素のみを有するものが好ましい。６員環複素芳香族化合物の具体例としては、ピリジン骨格を有するピリジン化合物、ピラジン骨格を有するピラジン化合物、ピリミジン骨格を有するピリミジン化合物、ピリダジン骨格を有するピリダジン化合物、1,3,5-トリアジン骨格を有する1,3,5-トリアジン化合物等が例示できる。上記列挙した化合物は、６員環の複素芳香環を有する縮合環であってもよい。また、複素芳香環が、アミノ基含有置換基、アルキル基、アラルキル基、アリール基、ニトロ基、ニトロソ基、ヒドロキシル基、カルボキシル基、カルボニル基、アルコキシ基、ハロゲン基、アゾ基、シアノ基、イミノ基、ホスフィノ基、チオール基、スルホ基等の置換基で置換されていてもよい。本発明のエッチング液には、これらの６員環複素芳香族化合物の１種又は２種以上を配合できる。なかでも、サイドエッチングを効果的に抑制し、かつ直線性を効果的に向上させる観点から、アミノ基含有置換基で置換されたピリジン環を含む６員環複素芳香族化合物、及び環を構成するヘテロ原子として窒素を２つ以上有する複素芳香環を含む６員環複素芳香族化合物から選ばれる１種以上が好ましい。 In order to further enhance the side etching suppressing effect and the linearity improving effect, the etching liquid of the present invention is a heteroaromatic compound having a 6-membered heteroaromatic ring (hereinafter referred to as “6-membered heteroaromatic compound”). May be included. As the 6-membered ring heteroaromatic compound, those having only nitrogen as a hetero atom constituting the ring are preferable from the viewpoint of structural stability and solubility in an acidic liquid. Specific examples of the 6-membered heteroaromatic compound include a pyridine compound having a pyridine skeleton, a pyrazine compound having a pyrazine skeleton, a pyrimidine compound having a pyrimidine skeleton, a pyridazine compound having a pyridazine skeleton, and a 1,3,5-triazine skeleton. Examples thereof include 1,3,5-triazine compounds. The above-listed compounds may be condensed rings having a 6-membered heteroaromatic ring. In addition, the heteroaromatic ring is an amino group-containing substituent, alkyl group, aralkyl group, aryl group, nitro group, nitroso group, hydroxyl group, carboxyl group, carbonyl group, alkoxy group, halogen group, azo group, cyano group, imino group. It may be substituted with a substituent such as a group, phosphino group, thiol group or sulfo group. One or more of these 6-membered heteroaromatic compounds can be blended in the etching solution of the present invention. Among these, from the viewpoint of effectively suppressing side etching and effectively improving linearity, a 6-membered heteroaromatic compound including a pyridine ring substituted with an amino group-containing substituent, and a ring are formed. One or more kinds selected from 6-membered heteroaromatic compounds containing a heteroaromatic ring having two or more nitrogen atoms as heteroatoms are preferred.
本発明のエッチング液に６員環複素芳香族化合物を配合する場合、６員環複素芳香族化合物の濃度は、０．０１〜３０ｇ／Ｌが好ましく、０．０１〜２０ｇ／Ｌがより好ましい。この範囲内であれば、銅配線の直線性をさらに向上させ、かつサイドエッチングをさらに効果的に抑制できる。 When mix | blending a 6-membered ring heteroaromatic compound with the etching liquid of this invention, 0.01-30 g / L is preferable and, as for the density | concentration of a 6-membered heteroaromatic compound, 0.01-20 g / L is more preferable. Within this range, the linearity of the copper wiring can be further improved and side etching can be more effectively suppressed.
前記酸化性金属イオンとして第二銅イオンを使用すると、エッチングするうちに、第二銅イオンとエッチングされる金属銅との反応により第一銅イオンが生成し、この第一銅イオンの濃度が上昇することによってエッチング性能が低下する。このような場合、過酸化水素、塩素酸塩等の酸化剤をエッチング液に添加して、第一銅イオンを第二銅イオンへ再生することによって、エッチング性能の低下を防ぐことができる。しかし、過酸化水素、塩素酸塩等の酸化剤をエッチング液に添加すると、前記脂肪族複素環式化合物が分解するおそれがある。また、本発明のエッチング液に６員環複素芳香族化合物を配合する場合は、過酸化水素、塩素酸塩等の酸化剤をエッチング液に添加すると、６員環複素芳香族化合物が分解するおそれがある。本発明のエッチング液は、前記酸化剤の添加による前記脂肪族複素環式化合物及び／又は６員環複素芳香族化合物の分解を防ぐために、５員環の複素芳香環を有する複素芳香族化合物（以下、「５員環複素芳香族化合物」という）を含んでいてもよい。 When cupric ions are used as the oxidizing metal ions, cuprous ions are generated by the reaction between the cupric ions and the metallic copper being etched during etching, and the concentration of the cuprous ions increases. As a result, the etching performance decreases. In such a case, the etching performance can be prevented from being lowered by adding an oxidizing agent such as hydrogen peroxide or chlorate to the etching solution to regenerate the cuprous ions into cupric ions. However, when an oxidizing agent such as hydrogen peroxide or chlorate is added to the etching solution, the aliphatic heterocyclic compound may be decomposed. In addition, when a 6-membered ring heteroaromatic compound is added to the etching solution of the present invention, if an oxidizing agent such as hydrogen peroxide or chlorate is added to the etching solution, the 6-membered ring heteroaromatic compound may be decomposed. There is. In order to prevent the aliphatic heterocyclic compound and / or the 6-membered heteroaromatic compound from being decomposed by the addition of the oxidizing agent, the etching solution of the present invention is a heteroaromatic compound having a 5-membered heteroaromatic ring ( Hereinafter, it may be referred to as a “5-membered heteroaromatic compound”.
５員環複素芳香族化合物としては、構造安定性及び酸性液に対する溶解性の観点から、環を構成するヘテロ原子として窒素のみを有するものが好ましい。５員環複素芳香族化合物の具体例としては、イミダゾール骨格を有するイミダゾール化合物、ピラゾール骨格を有するピラゾール化合物、トリアゾール骨格を有するトリアゾール化合物、テトラゾール骨格を有するテトラゾール化合物等のアゾール化合物等が例示できる。上記列挙した化合物は、５員環の複素芳香環を有する縮合環であってもよい。また、複素芳香環が、アミノ基含有置換基、アルキル基、アラルキル基、アリール基、ニトロ基、ニトロソ基、ヒドロキシル基、カルボキシル基、カルボニル基、アルコキシ基、ハロゲン基、アゾ基、シアノ基、イミノ基、ホスフィノ基、チオール基、スルホ基等の置換基で置換されていてもよい。本発明のエッチング液には、これらの５員環複素芳香族化合物の１種又は２種以上を配合できる。 As the 5-membered ring heteroaromatic compound, those having only nitrogen as a hetero atom constituting the ring are preferable from the viewpoint of structural stability and solubility in an acidic liquid. Specific examples of the 5-membered heteroaromatic compound include imidazole compounds having an imidazole skeleton, pyrazole compounds having a pyrazole skeleton, triazole compounds having a triazole skeleton, and azole compounds such as a tetrazole compound having a tetrazole skeleton. The above-listed compounds may be condensed rings having a 5-membered heteroaromatic ring. In addition, the heteroaromatic ring is an amino group-containing substituent, alkyl group, aralkyl group, aryl group, nitro group, nitroso group, hydroxyl group, carboxyl group, carbonyl group, alkoxy group, halogen group, azo group, cyano group, imino group. It may be substituted with a substituent such as a group, phosphino group, thiol group or sulfo group. One or more of these five-membered ring heteroaromatic compounds can be blended in the etching solution of the present invention.
本発明のエッチング液に５員環複素芳香族化合物を配合する場合、５員環複素芳香族化合物の濃度は、０．０１〜５０ｇ／Ｌが好ましく、０．０５〜３０ｇ／Ｌがより好ましい。この範囲内であれば、前記酸化剤の添加による前記脂肪族複素環式化合物及び／又は６員環複素芳香族化合物の分解を容易に防ぐことができる。 When mix | blending a 5-membered ring heteroaromatic compound with the etching liquid of this invention, 0.01-50 g / L is preferable and, as for the density | concentration of a 5-membered heteroaromatic compound, 0.05-30 g / L is more preferable. Within this range, decomposition of the aliphatic heterocyclic compound and / or 6-membered heteroaromatic compound due to the addition of the oxidizing agent can be easily prevented.
本発明のエッチング液には、上述した成分以外にも、本発明の効果を妨げない程度に他の成分を添加してもよい。例えば、成分安定剤、消泡剤などを添加してもよい。前記他の成分を添加する場合、その濃度は０．００１〜５ｇ／Ｌ程度である。 In addition to the components described above, other components may be added to the etching solution of the present invention to the extent that the effects of the present invention are not hindered. For example, you may add a component stabilizer, an antifoamer, etc. When the other components are added, the concentration is about 0.001 to 5 g / L.
前記エッチング液は、前記の各成分を水に溶解させることにより、容易に調製することができる。前記水としては、イオン性物質及び不純物を除去した水が好ましく、例えばイオン交換水、純水、超純水などが好ましい。 The etching solution can be easily prepared by dissolving the components described above in water. As the water, water from which ionic substances and impurities have been removed is preferable. For example, ion-exchanged water, pure water, ultrapure water, and the like are preferable.
前記エッチング液は、各成分を使用時に所定の濃度になるように配合してもよく、濃縮液を調製しておき使用直前に希釈して使用してもよい。前記エッチング液の使用方法は、特に限定されないが、サイドエッチングを効果的に抑制するには、後述するようにスプレーを用いてエッチングすることが好ましい。また、使用時のエッチング液の温度は、特に制限はないが、生産性を高く維持した上で、サイドエッチングを効果的に抑制するには２０〜５５℃で使用することが好ましい。 The etching solution may be blended so that each component has a predetermined concentration when used, or a concentrated solution may be prepared and diluted immediately before use. Although the usage method of the said etching liquid is not specifically limited, In order to suppress side etching effectively, it is preferable to etch using a spray so that it may mention later. The temperature of the etching solution during use is not particularly limited, but it is preferably used at 20 to 55 ° C. in order to effectively suppress side etching while maintaining high productivity.
本発明の補給液は、本発明のエッチング液を連続又は繰り返し使用する際に、前記エッチング液に添加する補給液であって、酸と、化合物Ａ及び化合物Ｂから選ばれる１種以上とを含む水溶液である。前記補給液中の各成分は、上述した本発明のエッチング液に配合できる成分と同様である。前記補給液を添加することにより、前記エッチング液の各成分比が適正に保たれるため、上述した本発明のエッチング液の効果を安定して維持できる。なお、本発明の補給液には、更に塩化第二銅などの第二銅イオン源が第二銅イオン濃度で１４ｇ／Ｌの濃度を超えない範囲で含まれていてもよい。また、本発明の補給液には、前記成分以外に、エッチング液に添加する成分が配合されていてもよい。 The replenisher of the present invention is a replenisher added to the etching liquid when the etching liquid of the present invention is used continuously or repeatedly, and includes an acid and one or more selected from Compound A and Compound B. It is an aqueous solution. Each component in the replenisher is the same as the component that can be blended in the above-described etching solution of the present invention. By adding the replenisher, each component ratio of the etching solution is maintained appropriately, so that the effect of the etching solution of the present invention described above can be stably maintained. The replenisher of the present invention may further contain a cupric ion source such as cupric chloride in a range not exceeding a cupric ion concentration of 14 g / L. In addition to the above components, the replenisher of the present invention may contain components added to the etching solution.
前記補給液中の各成分の濃度は、エッチング液中の各成分の濃度に応じて適宜設定されるが、上述した本発明のエッチング液の効果を安定して維持するという観点から、酸の濃度が５〜３６０ｇ／Ｌ、化合物Ａ及び／又は化合物Ｂの濃度（合計濃度）が０．０１〜１００ｇ／Ｌであることが好ましい。 The concentration of each component in the replenisher is appropriately set according to the concentration of each component in the etching solution. From the viewpoint of stably maintaining the effect of the etching solution of the present invention described above, the concentration of acid Is preferably 5 to 360 g / L, and the concentration (total concentration) of Compound A and / or Compound B is preferably 0.01 to 100 g / L.
本発明の銅配線の形成方法は、銅層のエッチングレジストで被覆されていない部分をエッチングする銅配線の形成方法において、上述した本発明のエッチング液を用いてエッチングすることを特徴とする。これにより、上述したように、銅配線の直線性を損なうことなくサイドエッチングを抑制できる。また、本発明の銅配線の形成方法を採用した銅配線形成工程において、本発明のエッチング液を連続又は繰り返し使用する場合は、上述した本発明の補給液を添加しながらエッチングすることが好ましい。前記エッチング液の各成分比が適正に保たれるため、上述した本発明のエッチング液の効果を安定して維持できるからである。 The copper wiring forming method of the present invention is characterized in that in the copper wiring forming method of etching a portion of the copper layer not covered with the etching resist, etching is performed using the above-described etching solution of the present invention. Thereby, as above-mentioned, side etching can be suppressed without impairing the linearity of copper wiring. Moreover, in the copper wiring formation process which employ | adopted the formation method of the copper wiring of this invention, when using the etching liquid of this invention continuously or repeatedly, it is preferable to etch, adding the replenishing liquid of this invention mentioned above. This is because each component ratio of the etching solution is appropriately maintained, so that the effect of the etching solution of the present invention described above can be stably maintained.
本発明の銅配線の形成方法では、前記銅層のエッチングレジストで被覆されていない部分に、前記エッチング液をスプレーにより噴霧することが好ましい。サイドエッチングを効果的に抑制できるからである。スプレーする際、ノズルは特に限定されず、扇形ノズル又は充円錐ノズル等が使用できる。 In the method for forming a copper wiring according to the present invention, it is preferable that the etching solution is sprayed on a portion of the copper layer not covered with the etching resist. This is because side etching can be effectively suppressed. When spraying, the nozzle is not particularly limited, and a sector nozzle or a full cone nozzle can be used.
スプレーでエッチングする場合、スプレー圧は、０．０４ＭＰａ以上が好ましく、０．０８ＭＰａ以上がより好ましい。スプレー圧が０．０４ＭＰａ以上であれば、保護皮膜を適切な厚みで銅配線の側面に形成できる。これにより、サイドエッチングを効果的に防止できる。なお、前記スプレー圧は、エッチングレジストの破損防止の観点から０．３０ＭＰａ以下が好ましい。 When etching by spraying, the spray pressure is preferably 0.04 MPa or more, and more preferably 0.08 MPa or more. When the spray pressure is 0.04 MPa or more, the protective film can be formed on the side surface of the copper wiring with an appropriate thickness. Thereby, side etching can be effectively prevented. The spray pressure is preferably 0.30 MPa or less from the viewpoint of preventing damage to the etching resist.
次に、本発明の実施例について比較例と併せて説明する。なお、本発明は下記の実施例に限定して解釈されるものではない。 Next, examples of the present invention will be described together with comparative examples. In addition, this invention is limited to a following example and is not interpreted.
表１、２に示す組成の各エッチング液を調製し、後述する条件でエッチングを行い、後述する評価方法により各項目について評価した。なお、表１、２に示す組成の各エッチング液において、残部はイオン交換水である。また、表１、２に示す塩酸の濃度は、塩化水素としての濃度である。 Each etching solution having the composition shown in Tables 1 and 2 was prepared, etched under the conditions described later, and each item was evaluated by an evaluation method described later. In each etching solution having the composition shown in Tables 1 and 2, the balance is ion-exchanged water. Moreover, the concentration of hydrochloric acid shown in Tables 1 and 2 is the concentration as hydrogen chloride.
（使用した試験基板）
厚み１２μｍの電解銅箔（三井金属鉱業社製、商品名３ＥＣ−III）を積層した銅張積層板を用意し、前記銅箔をパラジウム触媒含有処理液（奥野製薬社製、商品名：アドカッパーシリーズ）で処理した後、無電解銅めっき液（奥野製薬社製、商品名：アドカッパーシリーズ）を用いて無電解銅めっき膜を形成した。次いで、電解銅めっき液（奥野製薬社製、商品名：トップルチナＳＦ）を用いて、前記無電解銅めっき膜上に厚み１０μｍの電解銅めっき膜を形成した。得られた電解銅めっき膜上に、ドライフィルムレジスト（旭化成イーマテリアルズ社製、商品名：ＳＵＮＦＯＲＴ ＳＰＧ−１５２）を用いて、厚み１５μｍのエッチングレジストパターンを形成した。この際、エッチングレジストパターンは、ライン／スペース（Ｌ／Ｓ）＝３０μｍ／３０μｍのレジストパターンと、Ｌ／Ｓ＝４０μｍ／１５０μｍのレジストパターンとが混在したパターンとした。
(Test board used)
A copper clad laminate was prepared by laminating a 12 μm thick electrolytic copper foil (trade name 3EC-III, manufactured by Mitsui Mining & Smelting Co., Ltd.), and the copper foil was treated with a palladium catalyst-containing treatment solution (Okuno Pharmaceutical Co., Ltd., trade name: Ad Copper). After treatment with an electroless copper plating solution (Okuno Pharmaceutical Co., Ltd., trade name: Adcopper series), an electroless copper plating film was formed. Next, an electrolytic copper plating film having a thickness of 10 μm was formed on the electroless copper plating film using an electrolytic copper plating solution (Okuno Pharmaceutical Co., Ltd., trade name: Top Lucina SF). On the obtained electrolytic copper plating film, an etching resist pattern having a thickness of 15 μm was formed using a dry film resist (trade name: SUNFORT SPG-152, manufactured by Asahi Kasei E-Materials Co., Ltd.). At this time, the etching resist pattern was a pattern in which a line / space (L / S) = 30 μm / 30 μm resist pattern and a L / S = 40 μm / 150 μm resist pattern were mixed.
（エッチング条件）
エッチングは扇形ノズル（いけうち社製、商品名：ＩＳＶＶ９０２０）を使用して、スプレー圧０．１２ＭＰａ、処理温度４５℃の条件で行った。エッチング加工時間は、Ｌ／Ｓ＝３０μｍ／３０μｍのレジストパターン領域におけるエッチング後の銅配線の底部幅が３０μｍに至る時点に設定した。エッチング後、水洗、乾燥を行って、以下に示す評価を行った。
(Etching conditions)
Etching was performed using a fan-shaped nozzle (manufactured by Ikeuchi Co., Ltd., trade name: ISVV9020) under conditions of a spray pressure of 0.12 MPa and a processing temperature of 45 ° C. The etching processing time was set at the time when the bottom width of the copper wiring after etching in the resist pattern region of L / S = 30 μm / 30 μm reached 30 μm. After etching, washing and drying were performed, and the following evaluation was performed.
（サイドエッチング量）
エッチング処理した各試験基板の一部を切断し、これを冷間埋め込み樹脂に埋め込み、Ｌ／Ｓ＝３０μｍ／３０μｍのレジストパターン領域における銅配線の断面を観察できるように研磨加工を行った。そして、光学顕微鏡を用いて２００倍で前記断面を観察し、銅配線の頂部幅（Ｗ１）及び銅配線の底部幅（Ｗ２）を計測して、その差（Ｗ２−Ｗ１）をサイドエッチング量（μｍ）とした。結果を表１、２に示す。
(Side etching amount)
A part of each etched test substrate was cut, embedded in a cold embedding resin, and polished so that a cross section of the copper wiring in the resist pattern region of L / S = 30 μm / 30 μm could be observed. Then, the cross section was observed at 200 times using an optical microscope, the top width (W1) of the copper wiring and the bottom width (W2) of the copper wiring were measured, and the difference (W2-W1) was calculated as the side etching amount ( μm). The results are shown in Tables 1 and 2.
（直線性）
エッチング処理した各試験基板を３重量％水酸化ナトリウム水溶液に６０秒間浸漬し、エッチングレジストを除去した。その後、塩酸（塩化水素濃度：７重量％）を用い、扇形ノズル（いけうち社製、商品名：ＶＰ９０２０）で、スプレー圧０．１２ＭＰａ、処理温度３０℃、処理時間３０秒で保護皮膜を除去した。そして、光学顕微鏡を用いて２００倍で試験基板上面を観察し、Ｌ／Ｓ＝４０μｍ／１５０μｍのレジストパターン領域における銅配線頂部の配線幅を２０μｍ間隔で１０箇所計測し、その標準偏差を直線性（μｍ）とした。結果を表１、２に示す。
(Linearity)
Each test substrate subjected to the etching treatment was immersed in a 3 wt% aqueous sodium hydroxide solution for 60 seconds to remove the etching resist. Then, using hydrochloric acid (hydrogen chloride concentration: 7% by weight), the protective film was removed with a fan-shaped nozzle (manufactured by Ikeuchi Co., Ltd., trade name: VP9020) at a spray pressure of 0.12 MPa, a treatment temperature of 30 ° C., and a treatment time of 30 seconds. . Then, the top surface of the test substrate is observed at 200 times using an optical microscope, and the wiring width at the top of the copper wiring in the resist pattern region of L / S = 40 μm / 150 μm is measured at 10 points at intervals of 20 μm, and the standard deviation is linearity. (Μm). The results are shown in Tables 1 and 2.
表１に示すように、本発明の実施例によれば、いずれの評価項目についても良好な結果が得られた。一方、表２に示すように、比較例については、一部の評価項目で実施例に比べ劣る結果が得られた。この結果から、本発明によれば、銅配線の直線性を損なうことなくサイドエッチングを抑制できることが分かった。 As shown in Table 1, according to the examples of the present invention, good results were obtained for any of the evaluation items. On the other hand, as shown in Table 2, the results of the comparative examples were inferior to those of the examples in some evaluation items. From this result, it was found that according to the present invention, the side etching can be suppressed without impairing the linearity of the copper wiring.
（脂肪族複素環式化合物と６員環複素芳香族化合物の併用）
上記実施例１１の組成に以下の表３に記載の各６員環複素芳香族化合物をさらに配合して、上記と同様の評価を行った。結果を表３に示す。
(Combination of aliphatic heterocyclic compound and 6-membered heterocyclic aromatic compound)
Each of the 6-membered ring heteroaromatic compounds described in Table 3 below was further added to the composition of Example 11 and evaluated in the same manner as described above. The results are shown in Table 3.
表３に示すように、６員環複素芳香族化合物をさらに配合した実施例１３〜１６は、実施例１１よりもサイドエッチング量が軽減され、かつ直線性も向上している。この結果から、脂肪族複素環式化合物と６員環複素芳香族化合物を併用することにより、サイドエッチングを効果的に抑制でき、かつ直線性を効果的に向上できることが分かった。 As shown in Table 3, in Examples 13 to 16 in which a 6-membered ring heteroaromatic compound was further blended, the side etching amount was reduced compared to Example 11, and the linearity was also improved. From this result, it was found that side etching can be effectively suppressed and linearity can be effectively improved by using an aliphatic heterocyclic compound and a 6-membered heteroaromatic compound in combination.
１ 銅配線
２ エッチングレジスト
３ 保護皮膜
1
Claims (8)
前記エッチング液は、環を構成するヘテロ原子として窒素のみを有する５〜７員環の脂肪族複素環を含む脂肪族複素環式化合物と、酸と、酸化性金属イオンとを含む水溶液であり、
前記酸は塩酸であり、塩酸の濃度は５〜１８０ｇ／Ｌであり、
前記脂肪族複素環式化合物は、環を構成するヘテロ原子として窒素を２つ以上有する脂肪族複素環式化合物Ａ、及びアミノ基を有する置換基で置換された脂肪族複素環式化合物Ｂから選ばれる１種以上である、エッチング液。 A copper etching solution for forming a copper wiring,
The etching solution is an aqueous solution containing an aliphatic heterocyclic compound containing a 5- to 7-membered aliphatic heterocyclic ring having only nitrogen as a hetero atom constituting the ring, an acid, and an oxidizing metal ion.
The acid is hydrochloric acid, the concentration of hydrochloric acid is 5 to 180 g / L,
The aliphatic heterocyclic compound is selected from an aliphatic heterocyclic compound A having two or more nitrogen atoms as a hetero atom constituting the ring, and an aliphatic heterocyclic compound B substituted with a substituent having an amino group An etchant that is one or more of the above.
前記脂肪族複素環式化合物の濃度が、０．０１〜１００ｇ／Ｌである請求項１〜３のいずれか１項に記載のエッチング液。 The concentration of the oxidizing metal ions is 10 to 250 g / L;
The concentration of the aliphatic heterocyclic compound, the etching solution according to any one of claims 1 to 3, which is 0.01 to 100 g / L.
前記補給液は、環を構成するヘテロ原子として窒素のみを有する５〜７員環の脂肪族複素環を含む脂肪族複素環式化合物と、塩酸とを含む水溶液であり、
前記脂肪族複素環式化合物は、環を構成するヘテロ原子として窒素を２つ以上有する脂肪族複素環式化合物Ａ、及びアミノ基を有する置換基で置換された脂肪族複素環式化合物Ｂから選ばれる１種以上である、補給液。 A replenisher that is added to the etchant when continuously or repeatedly using the etchant according to any one of claims 1 to 5 ,
The replenisher is an aqueous solution containing an aliphatic heterocyclic compound containing a 5- to 7-membered aliphatic heterocyclic ring having only nitrogen as a hetero atom constituting the ring, and hydrochloric acid ,
The aliphatic heterocyclic compound is selected from an aliphatic heterocyclic compound A having two or more nitrogen atoms as a hetero atom constituting the ring, and an aliphatic heterocyclic compound B substituted with a substituent having an amino group A replenisher that is one or more of
前記脂肪族複素環式化合物の濃度が、０．０１〜１００ｇ／Ｌである請求項６記載の補給液。The replenisher according to claim 6, wherein the concentration of the aliphatic heterocyclic compound is 0.01 to 100 g / L.
請求項１〜５のいずれか１項に記載のエッチング液を用いてエッチングする、銅配線の形成方法。 A method for forming a copper wiring for etching a portion of a copper layer not covered with an etching resist,
The formation method of copper wiring which etches using the etching liquid of any one of Claims 1-5 .
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| JP2017048462A (en) * | 2016-08-30 | 2017-03-09 | メック株式会社 | Etching solution, replenishment solution, and copper wiring formation method |
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| JP6736088B2 (en) * | 2017-05-22 | 2020-08-05 | メック株式会社 | Etching solution, replenishing solution and method for forming copper wiring |
| JP6333455B1 (en) * | 2017-08-23 | 2018-05-30 | メック株式会社 | Copper microetching agent and method of manufacturing wiring board |
| JP7129711B2 (en) * | 2020-01-24 | 2022-09-02 | メック株式会社 | Etching liquid, replenishing liquid and method for forming copper wiring |
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| JP2006111953A (en) * | 2004-10-18 | 2006-04-27 | Mec Kk | Etching agent for copper or copper alloy, its manufacturing method, replenishing liquid, and method for manufacturing wiring substrate |
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