JP6164614B2 - エッチング液、補給液及び銅配線の形成方法 - Google Patents
エッチング液、補給液及び銅配線の形成方法 Download PDFInfo
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- JP6164614B2 JP6164614B2 JP2014069448A JP2014069448A JP6164614B2 JP 6164614 B2 JP6164614 B2 JP 6164614B2 JP 2014069448 A JP2014069448 A JP 2014069448A JP 2014069448 A JP2014069448 A JP 2014069448A JP 6164614 B2 JP6164614 B2 JP 6164614B2
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- heteroaromatic
- etching
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- ring
- etching solution
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- 238000005530 etching Methods 0.000 title claims description 163
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 87
- 229910052802 copper Inorganic materials 0.000 title claims description 85
- 239000010949 copper Substances 0.000 title claims description 85
- 238000000034 method Methods 0.000 title claims description 16
- 239000000243 solution Substances 0.000 claims description 69
- 150000002390 heteroarenes Chemical class 0.000 claims description 66
- 125000001072 heteroaryl group Chemical group 0.000 claims description 53
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 125000005842 heteroatom Chemical group 0.000 claims description 18
- -1 aliphatic heterocyclic compound Chemical class 0.000 claims description 16
- 150000001875 compounds Chemical group 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 229910021645 metal ion Inorganic materials 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229940126062 Compound A Drugs 0.000 claims description 14
- 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 description 14
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
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- 125000003277 amino group Chemical group 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
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- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 3
- 229910001447 ferric ion Inorganic materials 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 125000005647 linker group Chemical group 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 230000000694 effects Effects 0.000 description 12
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- 238000011156 evaluation Methods 0.000 description 7
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- 229930195733 hydrocarbon Natural products 0.000 description 4
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
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- 125000003710 aryl alkyl group Chemical group 0.000 description 3
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 3
- MVXVYAKCVDQRLW-UHFFFAOYSA-N 1h-pyrrolo[2,3-b]pyridine Chemical compound C1=CN=C2NC=CC2=C1 MVXVYAKCVDQRLW-UHFFFAOYSA-N 0.000 description 2
- UYWWLYCGNNCLKE-UHFFFAOYSA-N 2-pyridin-4-yl-1h-benzimidazole Chemical compound N=1C2=CC=CC=C2NC=1C1=CC=NC=C1 UYWWLYCGNNCLKE-UHFFFAOYSA-N 0.000 description 2
- PEHVGBZKEYRQSX-UHFFFAOYSA-N 7-deaza-adenine Chemical compound NC1=NC=NC2=C1C=CN2 PEHVGBZKEYRQSX-UHFFFAOYSA-N 0.000 description 2
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- BVIAOQMSVZHOJM-UHFFFAOYSA-N N(6),N(6)-dimethyladenine Chemical compound CN(C)C1=NC=NC2=C1N=CN2 BVIAOQMSVZHOJM-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
- 229960000643 adenine Drugs 0.000 description 2
- OIRDTQYFTABQOQ-KQYNXXCUSA-N adenosine Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O OIRDTQYFTABQOQ-KQYNXXCUSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- LMEKQMALGUDUQG-UHFFFAOYSA-N azathioprine Chemical compound CN1C=NC([N+]([O-])=O)=C1SC1=NC=NC2=C1NC=N2 LMEKQMALGUDUQG-UHFFFAOYSA-N 0.000 description 2
- 229960002170 azathioprine Drugs 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- GLVAUDGFNGKCSF-UHFFFAOYSA-N mercaptopurine Chemical compound S=C1NC=NC2=C1NC=N2 GLVAUDGFNGKCSF-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- YPZWRUGCMKMBHR-UHFFFAOYSA-N (7-methyl-5-phenylpyrazolo[3,4-e][1,2,4]triazin-3-yl)hydrazine Chemical compound C12=NC(NN)=NN=C2C(C)=NN1C1=CC=CC=C1 YPZWRUGCMKMBHR-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
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- 125000003363 1,3,5-triazinyl group Chemical group N1=C(N=CN=C1)* 0.000 description 1
- HIVSZDCEZUMRNG-UHFFFAOYSA-N 1,3,6,8,10,12-hexazatricyclo[7.3.0.02,6]dodeca-2,7,9,11-tetraene Chemical compound C1=NC2=NC=NN2C2=NCCN21 HIVSZDCEZUMRNG-UHFFFAOYSA-N 0.000 description 1
- FQUYSHZXSKYCSY-UHFFFAOYSA-N 1,4-diazepane Chemical group C1CNCCNC1 FQUYSHZXSKYCSY-UHFFFAOYSA-N 0.000 description 1
- VHZYOSMVUSWWLN-UHFFFAOYSA-N 1-(2-phenylethyl)imidazo[4,5-c]pyridine Chemical compound C1=NC2=CN=CC=C2N1CCC1=CC=CC=C1 VHZYOSMVUSWWLN-UHFFFAOYSA-N 0.000 description 1
- MKNNPOHQZOTMHM-UHFFFAOYSA-N 1-pyridin-2-ylpyrazol-4-amine Chemical compound C1=C(N)C=NN1C1=CC=CC=N1 MKNNPOHQZOTMHM-UHFFFAOYSA-N 0.000 description 1
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- VJGXVQYLRZDTLP-UHFFFAOYSA-N 7-methyl-1h-pyrrolo[2,3-c]pyridine Chemical compound CC1=NC=CC2=C1NC=C2 VJGXVQYLRZDTLP-UHFFFAOYSA-N 0.000 description 1
- NSKBIOGKGMWUQC-UHFFFAOYSA-N 7-methyl-[1,2,4]triazolo[4,3-a]pyridine Chemical compound C1=C(C)C=CN2C=NN=C21 NSKBIOGKGMWUQC-UHFFFAOYSA-N 0.000 description 1
- CDMRMPWJHYFXJJ-UHFFFAOYSA-N 7-methylpyrazolo[1,5-a][1,3,5]triazine-2,4-diamine Chemical compound N1=C(N)N=C(N)N2N=C(C)C=C21 CDMRMPWJHYFXJJ-UHFFFAOYSA-N 0.000 description 1
- LQJWKIHMMHGNCX-UHFFFAOYSA-N 8-methyltetrazolo[1,5-b]pyridazine Chemical compound CC1=CC=NN2N=NN=C12 LQJWKIHMMHGNCX-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000002126 C01EB10 - Adenosine Substances 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NWBJYWHLCVSVIJ-UHFFFAOYSA-N N-benzyladenine Chemical compound N=1C=NC=2NC=NC=2C=1NCC1=CC=CC=C1 NWBJYWHLCVSVIJ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- JZRWCGZRTZMZEH-UHFFFAOYSA-N Thiamine Natural products CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N JZRWCGZRTZMZEH-UHFFFAOYSA-N 0.000 description 1
- BGVGAKUIJCKCEN-UHFFFAOYSA-N [1,2,4]triazolo[1,5-a]pyridin-6-amine Chemical compound C1=C(N)C=CC2=NC=NN21 BGVGAKUIJCKCEN-UHFFFAOYSA-N 0.000 description 1
- KMZCSSCUBKHIJS-UHFFFAOYSA-N [1,2,4]triazolo[4,3-a][1,3,5]triazine-3,5,7-triamine Chemical compound N1=C(N)N=C(N)N2C(N)=NN=C21 KMZCSSCUBKHIJS-UHFFFAOYSA-N 0.000 description 1
- YRACHDVMKITFAZ-UHFFFAOYSA-N [1,2,4]triazolo[4,3-b]pyridazine Chemical compound C1=CC=NN2C=NN=C21 YRACHDVMKITFAZ-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229960005305 adenosine Drugs 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000004419 alkynylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 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
- NJJPSFAJAKVSST-UHFFFAOYSA-N bumepidil Chemical compound CC1=NC2=NC=NN2C2=C1CCN2C(C)(C)C NJJPSFAJAKVSST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 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
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004050 homopiperazines Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- INSWZAQOISIYDT-UHFFFAOYSA-N imidazo[1,2-a]pyrimidine Chemical compound C1=CC=NC2=NC=CN21 INSWZAQOISIYDT-UHFFFAOYSA-N 0.000 description 1
- VTVRXITWWZGKHV-UHFFFAOYSA-N imidazo[1,2-b]pyridazine Chemical compound N1=CC=CC2=NC=CN21 VTVRXITWWZGKHV-UHFFFAOYSA-N 0.000 description 1
- JMANUKZDKDKBJP-UHFFFAOYSA-N imidazo[1,5-a]pyridine Chemical compound C1=CC=CC2=CN=CN21 JMANUKZDKDKBJP-UHFFFAOYSA-N 0.000 description 1
- UFDFAMUXKRGTJE-UHFFFAOYSA-N imidazo[1,5-a]pyridine-3-carbaldehyde Chemical compound C1=CC=CN2C(C=O)=NC=C21 UFDFAMUXKRGTJE-UHFFFAOYSA-N 0.000 description 1
- QDZGZPRWPPKMSE-UHFFFAOYSA-N imidazo[5,1-f][1,2,4]triazine-2,7-diamine Chemical compound C1=NC(N)=NN2C(N)=NC=C21 QDZGZPRWPPKMSE-UHFFFAOYSA-N 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
- 229960001428 mercaptopurine Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- GYNLUADYDUGREZ-UHFFFAOYSA-N n-(3-methylbut-2-enyl)-1h-pyrazolo[3,4-d]pyrimidin-4-amine Chemical compound CC(C)=CCNC1=NC=NC2=C1C=NN2 GYNLUADYDUGREZ-UHFFFAOYSA-N 0.000 description 1
- HPZHFGBKCGWNGN-UHFFFAOYSA-N n-benzyl-2-methyl-7h-pyrrolo[2,3-d]pyrimidin-4-amine Chemical compound C=12C=CNC2=NC(C)=NC=1NCC1=CC=CC=C1 HPZHFGBKCGWNGN-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 150000003216 pyrazines Chemical class 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- KVFXLYYEDRTNLK-UHFFFAOYSA-N pyrazolo[5,1-c][1,2,4]benzotriazin-8-ol Chemical compound N1=CC=C2N=NC3=C(N21)C=C(C=C3)O KVFXLYYEDRTNLK-UHFFFAOYSA-N 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
- 150000004892 pyridazines Chemical class 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- JBKICBDXAZNSKA-UHFFFAOYSA-N tcmdc-123507 Chemical compound C1=CC=C2NC(C=3C=CC=C(N=3)C=3NC4=CC=CC=C4N=3)=NC2=C1 JBKICBDXAZNSKA-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical group 0.000 description 1
- FCBRQZIPVWCKKL-UHFFFAOYSA-N tetrazolo[1,5-b]pyridazin-6-amine Chemical compound N1=C(N)C=CC2=NN=NN21 FCBRQZIPVWCKKL-UHFFFAOYSA-N 0.000 description 1
- LWFUGGGWLUMXQZ-UHFFFAOYSA-N tetrazolo[1,5-b]pyridazine Chemical compound C1=CC=NN2N=NN=C21 LWFUGGGWLUMXQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011721 thiamine Substances 0.000 description 1
- KYMBYSLLVAOCFI-UHFFFAOYSA-N thiamine Chemical compound CC1=C(CCO)SCN1CC1=CN=C(C)N=C1N KYMBYSLLVAOCFI-UHFFFAOYSA-N 0.000 description 1
- 229960003495 thiamine Drugs 0.000 description 1
- 235000019157 thiamine Nutrition 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
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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- ing And Chemical Polishing (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Description
前記エッチング液は、酸と、酸化性金属イオンと、複素芳香族化合物とを含む水溶液であり、
前記複素芳香族化合物は、環を構成するヘテロ原子として窒素を1つ以上有する複素芳香5員環と、環を構成するヘテロ原子として窒素を1つ以上有する複素芳香6員環とを分子内に含むことを特徴とする。
前記補給液は、酸と、複素芳香族化合物とを含む水溶液であり、
前記複素芳香族化合物は、環を構成するヘテロ原子として窒素を1つ以上有する複素芳香5員環と、環を構成するヘテロ原子として窒素を1つ以上有する複素芳香6員環とを分子内に含むことを特徴とする。
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、銅層の総厚みを22.5μmとした。得られた電解銅めっき膜の表面を厚み15μmの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)で被覆した。その後、ライン/スペース(L/S)=33μm/27μmのガラスマスクを使用して露光し、現像処理により未露光部を除去することでL/S=33μm/27μmのエッチングレジストパターンを作製した。
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、エッチング後の銅配線の底部幅(W1)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。
エッチング処理した各試験基板の一部を切断し、これをポリエステル製冷間埋め込み樹脂に埋め込み、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、銅配線の底部幅(W1)が30μmであることを確認するとともに頂部幅(W2)を計測して、エッチングレジストパターン幅との差(33−W2)をサイドエッチング量(μm)とした(図1参照)。結果を表1〜3に示す。
エッチング処理した各試験基板を50℃の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:ISVV9020)で、スプレー圧0.12MPa、処理温度30℃、処理時間10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、銅配線頂部の配線幅(W2)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1〜3に示す。
エッチングレジストパターンを作製する際、L/S=33μm/27μmのパターン領域と、L/S=60μm/150μmのパターン領域とが混在したエッチングレジストパターンを作製したこと以外は、上記と同様の試験基板を用意した。
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=33μm/27μmのエッチングレジストパターン領域における銅配線の底部幅(W1)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。
エッチング処理した各試験基板の一部を切断し、これをポリエステル製冷間埋め込み樹脂に埋め込み、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、L/S=33μm/27μmのエッチングレジストパターン領域と、L/S=60μm/150μmのエッチングレジストパターン領域のそれぞれの銅配線の頂部幅(W2)を計測して、エッチングレジストパターン幅との差をサイドエッチング量(μm)とした。つまり、L/S=33μm/27μmのエッチングレジストパターン領域のサイドエッチング量は、33−W2(μm)となり、L/S=60μm/150μmのエッチングレジストパターン領域のサイドエッチング量は、60−W2(μm)となる。結果を表4に示す。
エッチング処理した各試験基板を50℃の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:ISVV9020)で、スプレー圧0.12MPa、処理温度30℃、処理時間10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=33μm/27μmのエッチングレジストパターン領域に形成された銅配線頂部の配線幅(W2)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4に示す。
2 エッチングレジスト
3 保護皮膜
Claims (7)
- 銅のエッチング液であって、
前記エッチング液は、酸と、酸化性金属イオンと、複素芳香族化合物とを含む水溶液であり、
前記複素芳香族化合物は、環を構成するヘテロ原子として窒素を1つ以上有する複素芳香5員環と、環を構成するヘテロ原子として窒素を1つ以上有する複素芳香6員環とを分子内に含み、
前記酸は塩酸であり、
前記酸化性金属イオンは第二銅イオンおよび/または第二鉄イオンであり、
前記酸の濃度が、5〜180g/Lであり、
前記酸化性金属イオンの濃度が、10〜300g/Lであり、
前記複素芳香族化合物の濃度が、0.01〜100g/Lであるエッチング液。 - 前記酸化性金属イオンは、第二銅イオンである請求項1記載のエッチング液。
- 前記複素芳香族化合物は、前記複素芳香5員環と前記複素芳香6員環とが縮合して縮合環を形成した複素芳香族化合物A、及び前記複素芳香5員環と前記複素芳香6員環とが単結合又は二価の連結基で連結した複素芳香族化合物Bから選ばれる1種以上である請求項1または2に記載のエッチング液。
- 前記複素芳香族化合物Aは、複素芳香族化合物A1及び複素芳香族化合物A2から選ばれる1種以上であり、
前記複素芳香族化合物A1は、分子中に含まれる前記複素芳香5員環及び/又は前記複素芳香6員環が、アミノ基、アルキル基、ヒドロキシル基、アルコキシ基、ハロゲン基及びチオール基から選ばれる1種以上の置換基で置換されている化合物であり、
前記複素芳香族化合物A2は、分子中に含まれる前記複素芳香5員環及び前記複素芳香6員環を構成する窒素の数の合計が3つ以下の化合物である請求項3に記載のエッチング液。 - 5〜7員環の脂肪族複素環を有する脂肪族複素環式化合物をさらに含む請求項1〜4のいずれか1項に記載のエッチング液。
- 請求項1〜5のいずれか1項に記載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、酸と、複素芳香族化合物とを含む水溶液であり、
前記酸は塩酸であり、
前記複素芳香族化合物は、環を構成するヘテロ原子として窒素を1つ以上有する複素芳香5員環と、環を構成するヘテロ原子として窒素を1つ以上有する複素芳香6員環とを分子内に含む、補給液。 - 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、
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。
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