JP4157985B2 - Pre-treatment type copper plating method - Google Patents
Pre-treatment type copper plating method Download PDFInfo
- Publication number
- JP4157985B2 JP4157985B2 JP2003163417A JP2003163417A JP4157985B2 JP 4157985 B2 JP4157985 B2 JP 4157985B2 JP 2003163417 A JP2003163417 A JP 2003163417A JP 2003163417 A JP2003163417 A JP 2003163417A JP 4157985 B2 JP4157985 B2 JP 4157985B2
- Authority
- JP
- Japan
- Prior art keywords
- copper plating
- benzotriazole
- mol
- acid
- polyethoxylate
- 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.)
- Expired - Fee Related
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 104
- 239000010949 copper Substances 0.000 title claims description 104
- 229910052802 copper Inorganic materials 0.000 title claims description 104
- 238000007747 plating Methods 0.000 title claims description 101
- 238000000034 method Methods 0.000 title claims description 33
- 238000002203 pretreatment Methods 0.000 title claims description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 69
- 239000007788 liquid Substances 0.000 claims description 46
- 239000012964 benzotriazole Substances 0.000 claims description 32
- OVCXRBARSPBVMC-UHFFFAOYSA-N triazolopyridine Chemical compound C=1N2C(C(C)C)=NN=C2C=CC=1C=1OC=NC=1C1=CC=C(F)C=C1 OVCXRBARSPBVMC-UHFFFAOYSA-N 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 150000001879 copper Chemical class 0.000 claims description 7
- 235000012431 wafers Nutrition 0.000 claims description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 58
- -1 nitrogenous organic compounds Chemical class 0.000 description 33
- 239000010408 film Substances 0.000 description 30
- 230000015572 biosynthetic process Effects 0.000 description 26
- 238000003786 synthesis reaction Methods 0.000 description 25
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 24
- 125000002947 alkylene group Chemical group 0.000 description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 239000000126 substance Substances 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 238000009713 electroplating Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 229910000365 copper sulfate Inorganic materials 0.000 description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- 239000011734 sodium Chemical group 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000011800 void material Substances 0.000 description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- 229960003237 betaine Drugs 0.000 description 7
- 238000007654 immersion Methods 0.000 description 7
- VQNDBXJTIJKJPV-UHFFFAOYSA-N 2h-triazolo[4,5-b]pyridine Chemical compound C1=CC=NC2=NNN=C21 VQNDBXJTIJKJPV-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 150000003585 thioureas Chemical class 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000005702 oxyalkylene group Chemical group 0.000 description 4
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000012312 sodium hydride Substances 0.000 description 4
- 229910000104 sodium hydride Inorganic materials 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- LMPMFQXUJXPWSL-UHFFFAOYSA-N 3-(3-sulfopropyldisulfanyl)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCSSCCCS(O)(=O)=O LMPMFQXUJXPWSL-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 3
- VLCDUOXHFNUCKK-UHFFFAOYSA-N N,N'-Dimethylthiourea Chemical compound CNC(=S)NC VLCDUOXHFNUCKK-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
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000000987 azo dye Substances 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- FFYRIXSGFSWFAQ-UHFFFAOYSA-N 1-dodecylpyridin-1-ium Chemical class CCCCCCCCCCCC[N+]1=CC=CC=C1 FFYRIXSGFSWFAQ-UHFFFAOYSA-N 0.000 description 2
- WMQUKDQWMMOHSA-UHFFFAOYSA-N 1-pyridin-4-ylethanone Chemical compound CC(=O)C1=CC=NC=C1 WMQUKDQWMMOHSA-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- KJWMCPYEODZESQ-UHFFFAOYSA-N 4-Dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=C(O)C=C1 KJWMCPYEODZESQ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- CETBSQOFQKLHHZ-UHFFFAOYSA-N Diethyl disulfide Chemical compound CCSSCC CETBSQOFQKLHHZ-UHFFFAOYSA-N 0.000 description 2
- XYWDPYKBIRQXQS-UHFFFAOYSA-N Diisopropyl sulfide Chemical compound CC(C)SC(C)C XYWDPYKBIRQXQS-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000008431 aliphatic amides Chemical class 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 2
- 150000001556 benzimidazoles Chemical class 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002462 imidazolines Chemical class 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- OIRKGXWQBSPXLQ-UHFFFAOYSA-N isobutyl ethyl sulfide Natural products CCSCC(C)C OIRKGXWQBSPXLQ-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- UPHWVVKYDQHTCF-UHFFFAOYSA-N octadecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCCCCCCCN UPHWVVKYDQHTCF-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 150000003248 quinolines Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- SOUHUMACVWVDME-UHFFFAOYSA-N safranin O Chemical compound [Cl-].C12=CC(N)=CC=C2N=C2C=CC(N)=CC2=[N+]1C1=CC=CC=C1 SOUHUMACVWVDME-UHFFFAOYSA-N 0.000 description 2
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
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- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 108700003601 dimethylglycine Proteins 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229960000735 docosanol Drugs 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BPSQMWSZGQGXHF-UHFFFAOYSA-N dodecyl-ethyl-dimethylazanium Chemical class CCCCCCCCCCCC[N+](C)(C)CC BPSQMWSZGQGXHF-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- HBRNMIYLJIXXEE-UHFFFAOYSA-N dodecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCN HBRNMIYLJIXXEE-UHFFFAOYSA-N 0.000 description 1
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical class CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- WUUOYCPDGWDPRO-UHFFFAOYSA-N ethyl-dimethyl-octadecylazanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)CC WUUOYCPDGWDPRO-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- BPMFZUMJYQTVII-UHFFFAOYSA-N guanidinoacetic acid Chemical compound NC(=N)NCC(O)=O BPMFZUMJYQTVII-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000002537 isoquinolines Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 125000002911 monocyclic heterocycle group Chemical group 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- OVLGNUHSJCCFPG-UHFFFAOYSA-N nonoxybenzene;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCOC1=CC=CC=C1 OVLGNUHSJCCFPG-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229960003104 ornithine Drugs 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Chemical group 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- KZOJQMWTKJDSQJ-UHFFFAOYSA-M sodium;2,3-dibutylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CCCC)C(CCCC)=CC2=C1 KZOJQMWTKJDSQJ-UHFFFAOYSA-M 0.000 description 1
- WUWHFEHKUQVYLF-UHFFFAOYSA-M sodium;2-aminoacetate Chemical compound [Na+].NCC([O-])=O WUWHFEHKUQVYLF-UHFFFAOYSA-M 0.000 description 1
- NJZLKINMWXQCHI-UHFFFAOYSA-N sodium;3-(3-sulfopropyldisulfanyl)propane-1-sulfonic acid Chemical compound [Na].[Na].OS(=O)(=O)CCCSSCCCS(O)(=O)=O NJZLKINMWXQCHI-UHFFFAOYSA-N 0.000 description 1
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 description 1
- MWZFQMUXPSUDJQ-KVVVOXFISA-M sodium;[(z)-octadec-9-enyl] sulfate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCCOS([O-])(=O)=O MWZFQMUXPSUDJQ-KVVVOXFISA-M 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
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- HNONEKILPDHFOL-UHFFFAOYSA-M tolonium chloride Chemical compound [Cl-].C1=C(C)C(N)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 HNONEKILPDHFOL-UHFFFAOYSA-M 0.000 description 1
- 150000008523 triazolopyridines Chemical class 0.000 description 1
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
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- Electroplating Methods And Accessories (AREA)
- Electrodes Of Semiconductors (AREA)
- Manufacturing Of Printed Wiring (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は前処理式の銅メッキ方法に関して、銅メッキ皮膜のレベリング性を良好に確保しながら、銅メッキ皮膜にボイド（空洞）が発生するのを有効に防止できるものを提供する。
【０００２】
【発明の背景】
一般に、実用水準を満たす銅メッキ皮膜の条件としては、光沢性に優れることに加えて、被メッキ物の素地表面を微視観察した場合、その凹部には比較的厚く、逆に、凸部には比較的薄く夫々皮膜形成されて、皮膜表面が平滑に仕上げられていることが重要である。
この平滑仕上げ(レベリング性：Leveling)を確保する目的で添加されるのがレベラーであり、塩化ナトリウム、エピクロルヒドリンなどの塩化物、高分子界面活性剤、アゾ染料などの窒素系有機化合物、或はイオウ化合物などがレベラーとして使用されている(例えば、特開平７−３１６８７６号公報、特公昭４７−２８５８１号公報、特開昭５２−１０８３４０号公報などを参照)。
【０００３】
ところが、従来の銅メッキ浴で電気メッキを行うと、メッキ皮膜にボイドが発生することが多く、各種レベラーを含有した上記公報の銅メッキ浴においても、その例外ではない。
プリント基板などに形成した銅メッキ皮膜にボイドが発生すると、配線抵抗の増大やＥＭ（Electric Migration）耐性の低減などの悪影響をもたらすため、銅メッキ皮膜のレベリング性などを良好に確保しながら、ボイドを有効に防止することが強く要請される。
【０００４】
【従来の技術】
本出願人は、特許文献１で、界面活性剤、塩化物、窒素系有機化合物よりなる群から選ばれたレベラーの少なくとも一種を含有するボイドフリー銅メッキ用の前処理液に被メッキ物を浸漬し、水洗した後、界面活性剤を含有しない銅メッキ液で電気銅メッキを施すことにより、銅メッキ皮膜のレベリング性とボイド発生防止能を良好に確保できるボイドフリー銅メッキ方法を開示した。
【０００５】
特許文献２には、上記レベリング性の確保を主目的として、
(1)基板の表面とビアホールの底面を含む壁面に銅皮膜を形成する銅皮膜形成工程と、
(2)３−メルカプト−１−プロパンスルホン酸ナトリウム、２−メルカプトエタンスルホン酸ナトリウム、ビス−(３−スルホプロピル)−ジスルフィドジナトリウムなどのめっき促進剤を添加した水溶液中に、前記銅皮膜が形成された基板を浸漬して、前記銅皮膜表面にめっき促進剤を付着させる浸漬工程と、
(3)ビアホールの底面を含む内壁面を除く前記銅皮膜表面に付着しためっき促進剤を除去する剥離工程と、
(4)前記剥離工程の後、絶縁層表面に形成された銅皮膜とビアホールの底面を含む壁面に形成された銅皮膜上に電解銅めっきを施して、ビアホール内にめっき金属を充填する電解銅めっき工程とからなり、
めっき促進剤をビアホール内に偏在付着させて電流を集中させることで、ビアホール内を銅めっきで充分に埋め切るようにしたビアフィリング銅めっき方法が開示されている(請求項１、請求項３〜４、段落１３〜１４)。
【０００６】
また、特許文献３には、プリント配線板やウエハーのビアホールや溝部に空隙などの析出不良を起こさず、良好に銅を埋設することを目的として、
ビス(３−スルホプロピル)ジスルフィド又はその２ナトリウム塩、ビス(２−スルホプロピル)ジスルフィド又はその２ナトリウム塩、ビス(３−スル−２−ヒドロキシプロピル)ジスルフィド又はその２ナトリウム塩などのブライトナー成分を、プリント配線板又はウエハー等のビアホールや回路溝部などに予め吸着させた後、ブライトナー成分を含まない銅メッキ浴中で電気銅メッキを行う方法が開示されている(請求項１〜２、段落８〜１０参照)。
上記予備吸着は浸漬やスプレー噴霧などの方式で行い(段落１６)、予備吸着に際しては、アセトアミド、ベンズアミド、アクリルアミドなどの有機酸アミド、アミン化合物からなるレベラー成分、或は、ポリビニルアルコール、ポリエチレングリコール、ポリプロピレングリコールなどのポリマー成分を併用可能であることが記載されている(請求項２、段落１４〜１５)。
【０００７】
【特許文献１】
特開２００１−１５２３８７号公報
【特許文献２】
特開２００１−２９１９５４号公報
【特許文献３】
特許第３１２４５２３号公報
【０００８】
【発明が解決しようとする課題】
上記特許文献１の方法は前処理を行わない通常の銅メッキ方法に比べるとボイドの発生を円滑に防止できるが、最近の基板、各種ウエハーなどを初めとする電子部品の高密度化、多機能化、高実装化などが進み、一層の信頼性向上が要求される現状に鑑みると、レベリング性とボイド防止能のさらなる向上が期待されるところである。
また、上記特許文献２〜３は、レベリング性の確保を主目的としており、ボイドを有効に防止する面では効果が不充分である。
本発明は、電子部品を初めとする銅メッキにおいて、レベリング性の確保とボイドの発生防止能のさらなる改善を技術的課題とする。
【０００９】
【課題を解決するための手段】
本発明者らは、新規の含窒素有機化合物であるベンゾトリアゾール、トリアゾロピリジンのＣ2〜Ｃ4アルキレンオキシド付加物を合成して、この新規化合物を電気銅メッキの前処理に適用すると、銅メッキ皮膜のレベリング性に優れるとともに、ボイドの発生を円滑に防止できることを見い出し、本発明を完成した。
【００１０】
即ち、本発明１は、ベンゾトリアゾール、トリアゾロピリジンのＣ2〜Ｃ4アルキレンオキシド付加物をレベラーとして含有する前処理液に被メッキ物を浸漬した後、被メッキ物に電気銅メッキを施すことを特徴とする前処理式の銅メッキ方法である。
【００１１】
本発明２は、上記本発明１において、レベラーが、１,２,３−ベンゾトリアゾールポリエトキシレート、ω,ω′−ビス(１,２,３−ベンゾトリアゾール)ポリエトキシレートであることを特徴とする前処理式の銅メッキ方法である。
【００１２】
本発明３は、上記本発明１又は２において、前処理液のレベラーの含有量が ０.１ｍｇ／Ｌ〜５０ｇ／Ｌであることを特徴とする前処理式の銅メッキ方法である。
【００１３】
本発明４は、上記本発明１〜３のいずれかの前処理液に、さらに可溶性銅塩、酸を含有することを特徴とする前処理式の銅メッキ方法である。
【００１４】
本発明５は、上記本発明４の前処理液に浸漬する替わりに、前処理液により被メッキ物に予備の電気銅メッキを施すことを特徴とする前処理式の銅メッキ方法である。
【００１５】
本発明６は、上記本発明１〜５のいずれかの被メッキ物が、ビルドアップ構造を有する基板、各種ウエハーであることを特徴とする前処理式の銅メッキ方法である。
【００１６】
【発明の実施の形態】
本発明は、第一に、新規の含窒素有機化合物であるベンゾトリアゾール、トリアゾロピリジンのＣ2〜Ｃ4アルキレンオキシド付加物をレベラーとして含有する前処理液に、ビルドアップ基板、各種ウエハーなどの被メッキ物を浸漬した後、被メッキ物に電気銅メッキを施す前処理式のボイドフリー銅メッキ方法であり、第二に、前処理液に浸漬する替わりに、前処理液を用いて被メッキ物に予備メッキを施してから電気銅メッキを行う方法である。
【００１７】
本発明の新規の含窒素有機化合物であるベンゾトリアゾール又はトリアゾロピリジンのＣ2〜Ｃ4アルキレンオキシド付加物は、下記の一般式(1)又は一般式(2)で表される。
Ａｒ−(ＡＯ)n−Ｈ …(1)
Ａｒ−(ＡＯ)n−Ａｒ …(2)
（式(1)又は(2)において、Ａｒは下記の原子団(ａ)又は(ｂ)である；ＡＯはオキシエチレン、オキシプロピレン、オキシブチレンである；ｎは２〜３００の整数である。）
【化１】
【化２】
【００１８】
上記ベンゾトリアゾールのＣ2〜Ｃ4アルキレンオキシド付加物（以下、ベンゾトリアゾール系付加物という）は、上式(ａ)又は(ｂ)のＸがＣＨである場合に相当し、例えば、下記の化学式(Ａ)〜(Ｃ)で表される。
【化３】
このアルキレンオキシド鎖は同じ種類のオキシアルキレンの繰り返しでも良いし、例えば、オキシエチレンとオキシプロピレンの共重合鎖のように、異なる種類のオキシアルキレンが共存する繰り返しでも良い。
また、このベンゾトリアゾール系付加物においては、アルキレンオキシド鎖がベンゾトリアゾール環の１位に結合しても良いし(上式(ａ)参照)、同環の２位に結合しても良い(上式(ｂ)参照)。
例えば、ベンゾトリアゾール系付加物のうち、両端のベンゾトリアゾール骨格同士をアルキレンオキシド鎖が結合する形態の化合物では、アルキレンオキシド鎖がベンゾトリアゾール骨格の２位同士に結合する場合に限らず、両骨格の１位同士に結合しても良いし、一方の骨格の１位と他方の骨格の２位に結合しても差し支えない。
【００１９】
上式(ａ)又は(ｂ)に示すように、ベンゾトリアゾール系付加物におけるベンゾトリアゾール骨格のベンゼン環には、Ｃ1〜Ｃ6アルキル、ＯＣ1〜ＯＣ6アルキル、ハロゲン、アミノ基(又は置換アミノ基)、ニトロ基、スルホン酸基(又はスルホン酸塩基)、カルボキシル基(又はカルボン酸塩基)よりなる群から選ばれた置換基が１〜３個結合することができる。置換基の結合数が２〜３の場合、置換基の種類は同じでも異なっても良い。
【００２０】
上記トリアゾロピリジンのＣ2〜Ｃ4アルキレンオキシド付加物(以下、トリアゾロピリジン系付加物という)は、上式(ａ)又は(ｂ)のＸがＮの場合に相当し（即ち、基本的に上記ベンゾトリアゾール系付加物の母骨格がトリアゾロピリジン環に置き換えられ）、トリアゾロピリジン骨格の窒素原子にエチレンオキシド、プロピレンオキシド又はブチレンオキシドの鎖が２〜３００の繰り返しで結合したものであり、アルキレンオキシド鎖の一端にトリアゾロピリジン骨格が配置しても良いし(上式(1)参照)、アルキレンオキシド鎖の両端にトリアゾロピリジン骨格が配置しても良い(上式(2)参照)。
このトリアゾロピリジン系付加物は、例えば、下記の化学式(Ｄ)〜(Ｅ)で表され、アルキレンオキシド鎖の繰り返し単位の種類は同じでも異なっても良い点、トリアゾロピリジン骨格のピリジン環に各種置換基が結合できる点、或は、アルキレンオキシド鎖がトリアゾロピリジン骨格に対して結合位置を変えられる(骨格の１位又は２位に結合できる)点は、上記ベンゾトリアゾール系付加物と同様である。
【化６】
本発明のベンゾトリアゾール系付加物の一般的な合成方法は、概ね次の３通りに分けられる。
(イ)合成方法１
１,２,３−ベンゾトリアゾールとω−置換ポリアルコキシレートを反応物とし、アルキレンオキシド鎖の一端にベンゾトリアゾール骨格が配置する化合物を生成するもので、下記の反応式(イ)で表される。
【化８】
反応条件は次の通りである。
(1)溶媒：水、メタノール、エタノール、イソプロパノール、ｔ−ブタノール、ＴＨＦ、ジオキサン、ＤＭＦ、ＤＭＳＯ、Ｎ−メチルピロリドン等
(2)反応温度：室温〜１００℃
(3)反応時間：０.５〜５０時間
(4)塩基：水酸化ナトリウム、水酸化カリウム、ナトリウムメトキシド、カリウムエトキシド、水素化ナトリウム、金属ナトリウム、炭酸ナトリウム、炭酸カリウム等
(5)後処理：通常の方法、例えば、溶媒抽出の後、水洗し、溶媒留去する。
【００２２】
(ロ)合成方法２
１,２,３−ベンゾトリアゾールとω,ω′−ジ置換ポリアルコキシレートを反応物とし、アルキレンオキシド鎖の両端にベンゾトリアゾール骨格が配置する化合物を生成するもので、下記の反応式(ロ)で表される。
【化９】
反応条件は次の通りである。
(1)溶媒：水、メタノール、エタノール、イソプロパノール、ｔ−ブタノール、ＴＨＦ、ジオキサン、ＤＭＦ、ＤＭＳＯ、Ｎ−メチルピロリドン等
(2)反応温度：室温〜１００℃
(3)反応時間：０.５〜５０時間
(4)塩基：水酸化ナトリウム、水酸化カリウム、ナトリウムメトキシド、カリウムエトキシド、水素化ナトリウム、金属ナトリウム、炭酸ナトリウム、炭酸カリウム等
(5)後処理：通常の方法、例えば、溶媒抽出の後、水洗し、溶媒留去する。
【００２３】
(ハ)合成方法３
１,２,３−ベンゾトリアゾールとアルキレンオキシドを反応物とするもので、下記の反応式(ハ)で表される。
【化１０】
(1)溶媒：水酸化ナトリウム、水酸化カリウム、ナトリウムメトキサイド、カリウムエトキサイド、水素化ナトリウム等の水溶性溶媒、無溶媒又は、トルエン、キシレン等の有機溶媒
(2)反応温度：１００〜２００℃
(3)触媒量：(通常０.００１〜０.０５当量の)塩基性物質、例えば、金属ナトリウム、水酸化ナトリウム、水酸化カリウム、ナトリウムメトキサイド、カリウムエトキサイド、水素化ナトリウムの存在下で行う。
【００２４】
本発明のトリアゾロピリジン系付加物の合成方法は上記ベンゾトリアゾール系付加物に準じる。
本発明のベンゾトリアゾール系付加物又はトリアゾロピリジン系付加物の具体例としては、下記の化合物が挙げられる。
・１,２,３−ベンゾトリアゾールポリエトキシレート(ＥＯ３モル)
・１,２,３−ベンゾトリアゾールポリエトキシレート(ＥＯ４５モル)
・１,２,３−ベンゾトリアゾールポリエトキシレート(ＥＯ７０モル)
・１,２,３−ベンゾトリアゾールポリエトキシレート(ＥＯ２００モル)
・１,２,３−ベンゾトリアゾールポリエトキシレート(ＥＯ３００モル)
・ω,ω′−ビス(１,２,３−ベンゾトリアゾール)ポリエトキシレート(ＥＯ２２モル)
・ω,ω′−ビス(１,２,３−ベンゾトリアゾール)ポリエトキシレート(ＥＯ１００モル)
・１,２,３−ベンゾトリアゾールポリエトキシレート(ＥＯ３モル)ポリプロポキシレート(ＰＯ２モル)
・５−メチル(１,２,３−ベンゾトリアゾール)ポリエトキシレート(ＥＯ５モル)ポリプロポキシレート(ＰＯ２モル)
・１,２,３−ベンゾトリアゾールポリエトキシレート(ＥＯ３モル)ポリプロポキシレート(ＰＯ２モル)
・１,２,３−ベンゾトリアゾールポリプロポキシレート(ＰＯ４モル)ポリエトキシレート(ＥＯ１０モル)
・１,２,３−ベンゾトリアゾールポリエトキシレート(ＥＯ１０モル)ポリプロポキシレート(ＰＯ８モル)ポリエトキシレート(ＥＯ１０モル)
・ω,ω′−ビス(１,２,３−ベンゾトリアゾール)ポリエトキシレート(ＥＯ２０モル)ポリプロポキシレート(ＰＯ３０モル)ポリエトキシレート(ＥＯ２０モル)
・ω,ω′−ビス［５,６−ジメチル(１,２,３−ベンゾトリアゾール)］ポリエトキシレート(ＥＯ２５モル)ポリプロポキシレート(ＰＯ２５モル)ポリエトキシレート(ＥＯ２５モル)
・１,２,３−ベンゾトリアゾールポリエトキシレート(ＥＯ１０モル)ポリプロポキシレート(ＰＯ８モル)ポリエトキシレート(ＥＯ１０モル)
・１,２,３−ベンゾトリアゾールポリプロポキシレート(ＰＯ３０モル)ポリエトキシレート(ＥＯ２６モル)
・１,２,３−ベンゾトリアゾールポリエトキシレート(ＥＯ１０モル)ポリプロポキシレート(ＰＯ８モル)ポリエトキシレート(ＥＯ１０モル)
・ω,ω′−ビス(１,２,３−ベンゾトリアゾール)ポリエトキシレート(ＥＯ４０モル)ポリプロポキシレート(ＰＯ３０モル)
・１,２,３−ベンゾトリアゾールポリエトキシレート(ＥＯ２５モル)ポリプロポキシレート(ＰＯ２０モル)ポリエトキシレート(ＥＯ２５モル)
・ω,ω′−ビス（１,２,３−ベンゾトリアゾール）ポリエトキシレート(ＥＯ２５モル)ポリプロポキシレート(ＰＯ２０モル)ポリエトキシレート(ＥＯ２５モル）
・１,２,３−ベンゾトリアゾールポリエトキシレート(ＥＯ１２モル)ポリブトキシレート(ＢＯ８モル)ポリエトキシレート(ＥＯ１２モル)
・５−クロロ(１,２,３−ベンゾトリアゾール)ポリエトキシレート(ＥＯ１５モル)ポリブトキシレート(ＢＯ１０モル)ポリエトキシレート(ＥＯ１５モル)
・ω,ω′−ビス(１,２,３−ベンゾトリアゾール)ポリエトキシレート(ＥＯ１５モル)ポリブトキシレート(ＢＯ１０モル)ポリエトキシレート(ＥＯ１５モル)
・１,２,３−トリアゾロ［４,５−ｂ］ピリジンポリエトキシレート(ＥＯ１３モル)ポリプロポキシレート(ＰＯ４モル)
・１,２,３−トリアゾロ［４,５−ｂ］ピリジンポリエトキシレート(ＥＯ１８モル)
・１,２,３−トリアゾロ［４,５−ｂ］ピリジンポリエトキシレート(ＥＯ８０モル)
・１,２,３−トリアゾロ［４,５−ｂ］ピリジンポリエトキシレート(ＥＯ３０モル)ポリプロポキシレート(ＰＯ２０モル)ポリエトキシレート(ＥＯ３０モル)
・ω,ω′−ビス(１,２,３−トリアゾロ［４,５−ｂ］ピリジン)ポリエトキシレート(ＥＯ５０モル)
・ω,ω′−ビス(１,２,３−トリアゾロ［４,５−ｂ］ピリジン)ポリエトキシレート(ＥＯ３０モル)ポリプロポキシレート(ＰＯ２０モル)ポリエトキシレート(ＥＯ３０モル)
上記化合物のうちでも、本発明２に示すように、１,２,３−ベンゾトリアゾールポリエトキシレート(ＥＯ３モル付加物、ＥＯ７０モル付加物)、ω,ω′−ビス(１,２,３−ベンゾトリアゾール)ポリエトキシレート(ＥＯ２２モル付加物)が好ましい。
【００２５】
本発明のベンゾトリアゾール系又はトリアゾロピリジン系付加物は夫々の付加物を単用又は併用でき、また、ベンゾトリアゾール系付加物とトリアゾロピリジン系付加物を複用できることは勿論である。
上記付加物はＣ2〜Ｃ4オキシアルキレン鎖が分子内に存在するため、水に比較的円滑に溶解し、水に添加するだけで水溶液形態の前処理液を容易に調製することができる。
上記付加物の前処理液に対する含有量は０.１ｍｇ／Ｌ〜５０ｇ／Ｌであり、好ましくは、１ｍｇ／Ｌ〜１０ｇ／Ｌである。０.１ｍｇ／Ｌより少ないとボイドフリー能とレベリング性の効果が得られず、５０ｇ／Ｌを越えても効果は余り変わらず、コストの無駄である。
【００２６】
本発明は、新規のベンゾトリアゾール系又はトリアゾロピリジン系付加物をレベラーとして含有した液で前処理することを特徴とするが、この前処理においては、上記従来技術に記載された化合物を初め、公知のレベラーを併用できることはいうまでもない。
上記公知のレベラーには、上記特許文献１にも示すように、塩化物、窒素系有機化合物、イオウ化合物、界面活性剤を挙げることができる。
上記塩化物は前処理液中で塩化物イオンを供給可能な化合物であり、塩化ナトリウム、塩化水素、塩化カリウム、塩化アンモニウム、塩化銅などが挙げられる。第４アルキルアンモニウムクロリド、クロル酢酸などの塩素系有機化合物などであっても良い。
【００２７】
上記窒素系有機化合物は、染料或はその誘導体、アミド系化合物、チオアミド系化合物、アニリン又はピリジン環を有する化合物、各種複素単環式化合物、各種縮合複素環式化合物、アミノカルボン酸類などであり、具体的には、Ｃ.Ｉ.(Color Index)ベーシックレッド２、トルイジンブルーなどのトルイジン系染料、Ｃ.Ｉ.ダイレクトイエロー１、Ｃ.Ｉ.ヤーナスグリーンＢ、Ｃ.Ｉ.ベーシックブラック２などのアゾ系染料、３−アミノ−６−ジメチルアミノ−２−メチルフェナジン一塩酸などのフェナジン系染料、コハク酸イミド、２′−ビス(２−イミダゾリン)などのイミダゾリン類、イミダゾール類、ベンゾイミダゾール類、インドール類、２−ビニルピリジン、４−アセチルピリジン、４−メルカプト−２−カルボキシルピリジン、２，２′−ビピリジル、フェナントロリンなどのピリジン類、キノリン類、イソキノリン類、アニリン、チオ尿素、ジメチルチオ尿素などのチオ尿素類、３,３′,３′′−ニトリロ三プロピオン酸、ジアミノメチレンアミノ酢酸、グリシン、Ｎ−メチルグリシン、ジメチルグリシン、β−アラニン、システイン、グルタミン酸、アスパラギン酸、アミノ吉草酸、オルニチンなどが挙げられる。
なかでも、Ｃ.Ｉ.ベーシックレッド２などのトルイジン染料、Ｃ.Ｉ.ダイレクトイエロー１、Ｃ.Ｉ.ヤーナスグリーンＢなどのアゾ染料、３−アミノ−６−ジメチルアミノ−２−メチルフェナジン一塩酸などのフェナジン系染料、２′−ビス(２−イミダゾリン)などのイミダゾリン類、ベンゾイミダゾール類、２−ビニルピリジン、４−アセチルピリジン、２，２′−ビピリジル、フェナントロリンなどのピリジン類、キノリン類、アニリン、チオ尿素、ジメチルチオ尿素などのチオ尿素類、アミノメチレンアミノ酢酸などのアミノカルボン酸類が好ましい。
【００２８】
上記イオウ化合物は、チオ尿素類、メルカプタン類、メルカプトスルホン酸類、ベンゾチアゾール類、スルフィド類、チオフェン類、ベンゾチオフェン類などであり、具体的には、チオ尿素、１,３―ジメチルチオ尿素、トリメチルチオ尿素、ジエチルチオ尿素、Ｎ,Ｎ′―ジイソプロピルチオ尿素、アリルチオ尿素、アセチルチオ尿素、エチレンチオ尿素、１,３―ジフェニルチオ尿素、二酸化チオ尿素、チオセミカルバジドなどのチオ尿素誘導体、チオフェノール、ｏ、ｍ又はｐ−ジメルカプトベンゼン、２−メルカプトベンゾオキサゾール、２−メルカプトベンゾイミダゾール、２−メルカプトベンゾチアゾール、ｔ−ブチルメルカプタン、チオグリコール、チオグリコール酸、３−メルカプトプロピオン酸などのメルカプタン類、ビス(３−スルホプロピル)ジスルフィド、２,２′−(又は４,４′−)ジピリジルスルフィド、２,２′−ジチオジアニリン、ビス(４−アミノフェニル)スルフィド、ジエチルスルフィド、イソプロピルスルフィド、ジフェニルスルフィド、イソブチルエチルスルフィド、２,２′−チオジグリコール酸、３,３′−チオジプロピオン酸、２,２′−チオジグリコール、ジメチルジスルフィド、ジエチルジスルフィド、ジフェニルジスルフィド、ジ−ｎ−プロピル−チオエーテル−ジ−３−スルホン酸(２ナトリウム塩)、ビス(３−スルホプロピル)ジスルフィド(２ナトリウム塩)、３−(ベンゾチアゾリル−２−チオ)プロピルスルホン酸(ナトリウム塩)などのスルフィド類、３−メルカプトプロパン−１−スルホン酸ナトリウム、２−メルカプトエタンスルホン酸ナトリウムなどのメルカプトスルホン酸類などが挙げられる。
なかでも、チオ尿素類、ベンゾチアゾール類、メルカプタン類、メルカプトスルホン酸類、スルフィド類などが好ましい。
【００２９】
上記界面活性剤としては、ノニオン系、アニオン系、カチオン系、或は両性の各種界面活性剤が挙げられ、特にノニオン系界面活性剤が好ましい。
当該ノニオン系界面活性剤は高分子界面活性剤を包含する概念であり、具体的には、ポリビニルアルコール(ＰＶＡ)、カルボキシメチルセルロース(ＣＭＣ)、ポリエチレングリコール(ＰＥＧ)、ポリプロピレングリコール(ＰＰＧ)、ポリアクリルアミドなどであり、また、Ｃ1〜Ｃ20アルカノール、フェノール、ナフトール、ビスフェノール類、Ｃ1〜Ｃ25アルキルフェノール、アリールアルキルフェノール、Ｃ1〜Ｃ25アルキルナフトール、Ｃ1〜Ｃ25アルコキシル化リン酸(塩)、ソルビタンエステル、スチレン化フェノール、ポリアルキレングリコール、Ｃ1〜Ｃ22脂肪族アミン、Ｃ1〜Ｃ22脂肪族アミドなどにエチレンオキシド(ＥＯ)及び／又はプロピレンオキシド(ＰＯ)を２〜３００モル付加縮合したものである。但し、上記付加縮合物では、所定のアルカノール、フェノール、ナフトールなどのＥＯ単独の付加物、ＰＯ単独の付加物、或は、ＥＯとＰＯが共存した付加物のいずれでも良い。
【００３０】
エチレンオキシド(ＥＯ)及び／又はプロピレンオキシド(ＰＯ)を付加縮合させるＣ1〜Ｃ20アルカノールとしては、オクタノール、デカノール、ラウリルアルコール、テトラデカノール、ヘキサデカノール、ステアリルアルコール、エイコサノール、セチルアルコール、オレイルアルコール、ドコサノールなどが挙げられる。
同じくビスフェノール類としては、ビスフェノールＡ、ビスフェノールＢなどが挙げられる。
Ｃ1〜Ｃ25アルキルフェノールとしては、モノ、ジ、若しくはトリアルキル置換フェノール、例えば、ｐ−ブチルフェノール、ｐ−イソオクチルフェノール、ｐ−ノニルフェノール、ｐ−ヘキシルフェノール、２,４−ジブチルフェノール、２,４,６−トリブチルフェノール、ｐ−ドデシルフェノール、ｐ−ラウリルフェノール、ｐ−ステアリルフェノールなどが挙げられる。
アリールアルキルフェノールとしては、２−フェニルイソプロピルフェニルなどが挙げられる。
【００３１】
Ｃ1〜Ｃ25アルキルナフトールのアルキル基としては、メチル、エチル、プロピル、ブチルヘキシル、オクチル、デシル、ドデシル、オクタデシルなどが挙げられ、ナフタレン核の任意の位置にあって良い。
Ｃ1〜Ｃ25アルコキシル化リン酸(塩)は、下記の一般式(a)で表されるものである。
Ｒａ・Ｒｂ・(ＭＯ)Ｐ＝Ｏ …(ａ)
(式(ａ)中、Ｒa及びＲbは同一又は異なるＣ1〜Ｃ25アルキル、但し、一方がＨであっても良い。ＭはＨ又はアルカリ金属を示す。)
【００３２】
ソルビタンエステルとしては、モノ、ジ又はトリエステル化した１,４−、１,５−又は３,６−ソルビタン、例えばソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンジステアレート、ソルビタンジオレエート、ソルビタン混合脂肪酸エステルなどが挙げられる。
Ｃ1〜Ｃ22脂肪族アミンとしては、プロピルアミン、ブチルアミン、ヘキシルアミン、オクチルアミン、デシルアミン、ラウリルアミン、ステアリルアミン、エチレンジアミン、プロピレンジアミンなどの飽和及び不飽和脂肪酸アミンなどが挙げられる。
Ｃ1〜Ｃ22脂肪族アミドとしては、プロピオン酸、酪酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘン酸などのアミドが挙げられる。
【００３３】
上記カチオン系界面活性剤としては、下記の一般式(ｂ)で表される第４級アンモニウム塩
(Ｒ1・Ｒ2・Ｒ3・Ｒ4Ｎ)+・Ｘ- …(ｂ)
(式(ｂ)中、Ｘはハロゲン、ヒドロキシ、Ｃ1〜Ｃ5アルカンスルホン酸又は硫酸、Ｒ1、Ｒ2及びＲ3は同一又は異なるＣ1〜Ｃ20アルキル、Ｒ4はＣ1〜Ｃ10アルキル又はベンジルを示す。)
或は、下記の一般式(ｃ)で表されるピリジニウム塩などが挙げられる。
Ｒ6−(Ｃ6Ｈ4Ｎ−Ｒ5)+・Ｘ- …(ｃ)
(式(ｃ)中、Ｃ6Ｈ4Ｎはピリジル基、Ｘはハロゲン、ヒドロキシ、Ｃ1〜Ｃ5アルカンスルホン酸又は硫酸、Ｒ5はＣ1〜Ｃ20アルキル、Ｒ6はＨ又はＣ1〜Ｃ10アルキルを示す。)
【００３４】
塩の形態のカチオン系界面活性剤の例としては、ラウリルトリメチルアンモニウム塩、ステアリルトリメチルアンモニウム塩、ラウリルジメチルエチルアンモニウム塩、オクタデシルジメチルエチルアンモニウム塩、ジメチルベンジルラウリルアンモニウム塩、セチルジメチルベンジルアンモニウム塩、オクタデシルジメチルベンジルアンモニウム塩、トリメチルベンジルアンモニウム塩、トリエチルベンジルアンモニウム塩、ヘキサデシルピリジニウム塩、ラウリルピリジニウム塩、ドデシルピリジニウム塩、ステアリルアミンアセテート、ラウリルアミンアセテート、オクタデシルアミンアセテートなどが挙げられる。
【００３５】
上記アニオン系界面活性剤としては、アルキル硫酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸塩、アルキルベンゼンスルホン酸塩、(モノ、ジ、トリ)アルキルナフタレンスルホン酸塩などが挙げられる。アルキル硫酸塩としては、ラウリル硫酸ナトリウム、オレイル硫酸ナトリウムなどが挙げられる。ポリオキシエチレンアルキルエーテル硫酸塩としては、ポリオキシエチレン(ＥＯ１２)ノニルエーテル硫酸ナトリウム、ポリオキシエチレン(ＥＯ１５)ドデシルエーテル硫酸ナトリウムなどが挙げられる。ポリオキシエチレンアルキルフェニルエーテル硫酸塩としては、ポリオキシエチレン(ＥＯ１５)ノニルフェニルエーテル硫酸塩などが挙げられる。アルキルベンゼンスルホン酸塩としては、ドデシルベンゼンスルホン酸ナトリウムなどが挙げられる。また、(モノ、ジ、トリ)アルキルナフタレンスルホン酸塩としては、ジブチルナフタレンスルホン酸ナトリウムなどが挙げられる。
【００３６】
上記両性界面活性剤としては、カルボキシベタイン、イミダゾリンベタイン、スルホベタイン、アミノカルボン酸などが挙げられる。また、エチレンオキシド及び／又はプロピレンオキシドとアルキルアミン又はジアミンとの縮合生成物の硫酸化、或はスルホン酸化付加物も使用できる。
【００３７】
代表的なカルボキシベタイン、或はイミダゾリンベタインとしては、ラウリルジメチルアミノ酢酸ベタイン、ミリスチルジメチルアミノ酢酸ベタイン、ステアリルジメチルアミノ酢酸ベタイン、ヤシ油脂肪酸アミドプロピルジメチルアミノ酢酸ベタイン、２−ウンデシル−１−カルボキシメチル−１−ヒドロキシエチルイミダゾリニウムベタイン、２−オクチル−１−カルボキシメチル−１−カルボキシエチルイミダゾリニウムベタインなどが挙げられ、硫酸化及びスルホン酸化付加物としてはエトキシル化アルキルアミンの硫酸付加物、スルホン酸化ラウリル酸誘導体ナトリウム塩などが挙げられる。
【００３８】
上記スルホベタインとしては、ヤシ油脂肪酸アミドプロピルジメチルアンモニウム−２−ヒドロキシプロパンスルホン酸、Ｎ−ココイルメチルタウリンナトリウム、Ｎ−パルミトイルメチルタウリンナトリウムなどが挙げられる。
アミノカルボン酸としては、ジオクチルアミノエチルグリシン、Ｎ−ラウリルアミノプロピオン酸、オクチルジ(アミノエチル)グリシンナトリウム塩などが挙げられる。
【００３９】
また、ボイドフリー銅メッキ用の前処理液には、本発明３に示すように、さらに可溶性銅塩及び酸を含有させることができる。
上記可溶性銅塩は、安定な銅の水溶液が得られる化合物を意味し、硫酸銅、塩化銅、酸化銅、炭酸銅、酢酸銅、ピロリン酸銅、シュウ酸銅などが挙げられ、硫酸銅、酸化銅などが好ましい。
上記酸は、硫酸、塩酸、シュウ酸、酢酸、ピロリン酸などである。
可溶性銅塩の含有量は０.０１〜３ｍｏｌ／Ｌであり、好ましくは、０.１〜１.５ｍｏｌ／Ｌである。
【００４０】
本発明１の前処理式のボイドフリー銅メッキ方法は、被メッキ物を上記前処理液に浸漬した後に、銅メッキ液で電気メッキを施すものである。浸漬処理に替えて、前処理液を塗布又は噴霧しても良い。
また、本発明３に示すように、可溶性銅塩と酸を含む前処理液で予備メッキを施した後に、銅メッキ液で電気メッキを施すこともできる。即ち、本発明の前処理は、浸漬処理と予備メッキ処理の両方を包含する概念である。
【００４１】
本発明のベンゾトリアゾール系又はトリアゾロピリジン系付加物を含有する液で前処理された被メッキ物は、次工程で銅メッキ液により通常の銅メッキを施される。
前処理後の銅メッキでは、公知の銅メッキ浴を任意に適用でき、特段の制限はない。従って、銅メッキ浴には、可溶性銅塩と酸以外にも、ｐＨ調整剤、緩衝剤などの各種添加剤を含有できることはいうまでもない。
銅メッキ浴における陰極電流密度、浴温、メッキ時間などの電気メッキ条件も、特には限定されない。
本発明のベンゾトリアゾール系又はトリアゾロピリジン系付加物については、銅メッキ浴への含有の有無は問わない。従って、本発明の付加物を含有する前処理液で予備吸着した後、当該付加物を含む銅メッキ浴で電気メッキを行っても良いし、含まない浴で電気銅メッキを行っても良い。また、公知のレベラーについては、同様に、銅メッキ浴への含有の有無は問わない。
【００４２】
本発明の前処理式のボイドフリー銅メッキ方法は任意の被メッキ物に適用できるが、本発明６に示すように、各種ウエハー、プリント基板(特に、マザーボードやＣＳＰ(Chip Size Package)等のビルドアップ構造を有する基板など)に好適である。
即ち、殊に、ビルドアップ基板はその構造上ビア(ブラインドビアと呼ばれる有底状の孔)を多く有することから、従来の銅メッキ方法ではこのビアにボイドが発生し易いが、本発明を適用することで、基板のレベリング性を良好に確保しながら、ボイドを確実に防止できる。
【００４３】
【発明の効果】
新規のベンゾトリアゾール系又はトリアゾロピリジン系付加物を添加した前処理液で予め前処理してから被メッキ物に電気銅メッキを施すため、銅メッキ皮膜のレベリング性を良好に確保しながら、ボイドを有効に防止できる。この場合、当該付加物の銅メッキ浴への含有の有無は問わない。
上記前処理は上記特定成分を含む水溶液に被メッキ物を浸漬するだけなので、処理が簡便であるうえ、浸漬処理に替えて予備メッキを行っても、同様にレベリング性とボイドフリー能を有効に担保できる。
また、上記付加物はＣ2〜Ｃ4オキシアルキレン鎖が分子内に存在することから、水に比較的円滑に溶解するため、この付加物を水に添加するだけで水溶液形態の前処理液を容易に調製することができる。
【００４４】
【実施例】
以下、本発明のベンゾトリアゾール系付加物の合成例、当該合成例の付加物を含む前処理液を用いた本発明のボイドフリー銅メッキ方法の実施例、当該実施例で得られた銅メッキ皮膜についてのボイドの発生度合、並びにレベリング性の各種評価試験例を順次説明する。
尚、本発明は下記の実施例及び試験例に拘束されるものではなく、本発明の技術的思想の範囲内で任意の変形をなし得ることは勿論である。
【００４５】
《ベンゾトリアゾール系付加物の合成例》
(1)合成例１（１,２,３−ベンゾトリアゾールポリエトキシレート(EO3モル)の合成例；前記化学式(Ａ)参照）
四つ口フラスコに１,２,３−ベンゾトリアゾールを５ｇ加えた。次いで、攪拌下に、水酸化ナトリウム２.２ｇを水４０ｍｌに溶解した溶液を滴下し、６５℃に加熱して、２−［２−(２−クロロエトキシ)エトキシ］エタノール７.１ｇを水１０ｍｌに溶解した溶液を滴下した。
滴下後１０時間、７０℃にて加熱攪拌した。反応終了後、反応液を塩化メチレンで抽出した。塩化メチレン抽出液をアルカリ水で洗浄した後、十分水洗し、ぼう硝乾燥した。乾燥後、塩化メチレンを留去して、目的物としての油状物８.３ｇを得た。
上記油状物を赤外分光分析に付したところ、ＩＲチァートに現れた特徴的な吸収ピークの波数は次の通りであった。
２８７２ｃｍ-1（ヘテロ芳香族のＣ−Ｈ)、１４５６ｃｍ-1、１３３０ｃｍ-1、１２８３ｃｍ-1、１１２０ｃｍ-1（−ＣＨ2−Ｏ−ＣＨ2−)、１０７０ｃｍ-1、７５０ｃｍ-1（ヘテロ芳香族のＣ−Ｈ)
上記結果によると、得られた化合物の分子内にはヘテロ芳香族であるベンゾトリアゾール環とアルキレンオキシドのエーテル結合が存在することから、１,２,３−ベンゾトリアゾールポリエトキシレート(以下、ＢＴＡＰという)(EO3モル)の生成が確認できた。
【００４６】
(2)合成例２（ω,ω′−ビス(１,２,３−ベンゾトリアゾール)ポリエトキシレート(EO22モル)の合成例；前記化学式(Ｂ)参照）
四つ口フラスコに１,２,３−ベンゾトリアゾールを９.２ｇ加えた。次いで、攪拌下に、ジオキサンを１００ｍｌ加えた後、無水炭酸カリウムを１２ｇ加え、９０℃に加熱して、ポリエチレングリコール(ＥＯ２２モル)ジ−ｐ−トシレート５０ｇをジオキサン２００ｍｌに溶解した溶液を滴下した。
滴下後２０時間、９０℃にて加熱攪拌した。反応終了後、反応液を塩化メチレンで抽出した。塩化メチレン抽出液をアルカリ水で洗浄した後、十分水洗し、ぼう硝乾燥した。乾燥後、塩化メチレンを留去して、目的物としての油状物３２.２ｇを得た。
上記油状物を赤外分光分析に付したところ、ＩＲチァートに特徴的な吸収ピークの波数は次の通りであったため、上記合成例１の分析例に準じて、ω,ω′−ビス(１,２,３−ベンゾトリアゾール)ポリエトキシレート(EO22モル)の生成が確認できた。
２８７２ｃｍ-1、１４６８ｃｍ-1、１３６０ｃｍ-1、１２８０ｃｍ-1、１１５０ｃｍ-1、１１１６ｃｍ-1、１０６０ｃｍ-1、９５０ｃｍ-1、８４２ｃｍ-1
【００４７】
(3)合成例３（ＢＴＡＰ(EO70モル)の合成例；前記化学式(Ｃ)参照）
オートクレーブに１,２,３−ベンゾトリアゾールを５０ｇ仕込み、触媒量の水酸化カリウムを加えた。次いで、攪拌下にオートクレーブを１７０℃に加熱し、エチレンオキサイドを７０モル付加させて茶褐色の固体１３１０ｇを得た。
得られた茶褐色の固体を赤外分光分析に付したところ、下記の分析結果を得たことから、前記合成例１の分析例に準じて、ＢＴＡＰ(EO70モル)の生成が確認できた。
２８７２ｃｍ-1、１４６８ｃｍ-1、１３６０ｃｍ-1、１２８０ｃｍ-1、１１５０ｃｍ-1、１１１６ｃｍ-1、１０６０ｃｍ-1、９５０ｃｍ-1、８４２ｃｍ-1
【００４８】
そこで、上記合成例１〜２のベンゾトリアゾール系付加物を用いた前処理式のボイドフリー銅メッキ方法の実施例を述べる。
下記の実施例１〜５は合成例１のＢＴＡＰを水に溶解して前処理液とした例であり、このうち、実施例１はＢＴＡＰを銅メッキ浴に含有しない例、実施例２はＢＴＡＰを銅メッキ浴にも含有した例、実施例３は銅メッキ浴にＢＴＡＰを含有せずに、公知のレベラーを含有した例、実施例４は前処理液に公知のレベラーを併用した例、実施例５は前処理液に公知のレベラーを併用し、銅メッキ浴にＢＴＡＰを含有した例である。また、実施例６は、実施例１を基本として、ベンゾトリアゾール系付加物を合成例１から合成例２のビス化合物に変更した例である。
一方、比較例１は銅メッキ液で通常の電気銅メッキのみを行った例である。
【００４９】
以下の実施例及び比較例において、前処理液での浸漬条件、銅メッキ液での電気メッキ条件は夫々下記の(ａ)〜(ｂ)の通りに設定した。
(ａ)前処理液での浸漬条件
浴温 ３０℃
浸漬時間 ５分
(ｂ)銅メッキ液での電気メッキ条件
陰極電流密度 ５.０Ａ／ｄｍ2
浴温 ３０℃
メッキ時間 ３０分
但し、実施例と比較例では、銅の電着皮膜におけるボイドの発生状況とレベリング性を観察する必要があるため、後述の試験例に示すように、ボイドの評価試験ではチタン板の素地上に電気銅メッキを行い、レベリング性試験では予め約２０μｍの溝を刻設した銅パネルを素地として電気銅メッキを行った。
【００５０】
《実施例１》
(1)前処理液
合成例１のＢＴＡＰ ０.２ｇ／Ｌ
(2)銅メッキ液
硫酸銅 ２００ｇ／Ｌ
硫酸 ５０ｇ／Ｌ
【００５１】
《実施例２》
(1)前処理液
合成例１のＢＴＡＰ ０.２ｇ／Ｌ
(2)銅メッキ液
硫酸銅 ２００ｇ／Ｌ
硫酸 ５０ｇ／Ｌ
合成例１のＢＴＡＰ ０.２ｇ／Ｌ
【００５２】
《実施例３》
(1)前処理液
合成例１のＢＴＡＰ ０.２ｇ／Ｌ
(2)銅メッキ液
硫酸銅 ２００ｇ／Ｌ
硫酸 ５０ｇ／Ｌ
２−メルカプトベンゾチアゾール ０.００１ｇ／Ｌ
Ｃ.Ｉ.ヤーナスグリーンＢ ０.００２ｇ／Ｌ
塩化ナトリウム ０.１ｇ／Ｌ
ポリエチレングリコール(平均分子量2,000) ０.１ｇ／Ｌ
【００５３】
《実施例４》
(1)前処理液
合成例１のＢＴＡＰ ０.２ｇ／Ｌ
Ｃ.Ｉ.ヤーナスグリーンＢ ０.００２ｇ／Ｌ
塩化ナトリウム ０.１ｇ／Ｌ
ポリエチレングリコール(平均分子量2,000) ０.１ｇ／Ｌ
(2)銅メッキ液
硫酸銅 ２００ｇ／Ｌ
硫酸 ５０ｇ／Ｌ
【００５４】
《実施例５》
(1)前処理液
合成例１のＢＴＡＰ ０.２ｇ／Ｌ
２−メルカプトベンゾチアゾール ０.００１ｇ／Ｌ
Ｃ.Ｉ.ヤーナスグリーンＢ ０.００２ｇ／Ｌ
塩化ナトリウム ０.１ｇ／Ｌ
ポリエチレングリコール(平均分子量2,000) ０.１ｇ／Ｌ
(2)銅メッキ液
硫酸銅 ２００ｇ／Ｌ
硫酸 ５０ｇ／Ｌ
合成例１のＢＴＡＰ ０.２ｇ／Ｌ
【００５５】
《実施例６》
(1)前処理液
合成例２のビス化合物 ０.２ｇ／Ｌ
(2)銅メッキ液
硫酸銅 ２００ｇ／Ｌ
硫酸 ５０ｇ／Ｌ
【００５６】
《比較例１》
下記の組成で銅メッキ液を調製し、電気メッキを行った。
硫酸銅 ２００ｇ／Ｌ
硫酸 ５０ｇ／Ｌ
２−メルカプトベンゾチアゾール ０.００１ｇ／Ｌ
Ｃ.Ｉ.ヤーナスグリーンＢ ０.００２ｇ／Ｌ
塩化ナトリウム ０.１ｇ／Ｌ
ポリエチレングリコール(平均分子量2,000) ０.１ｇ／Ｌ
【００５７】
《ボイド発生状況とレベリング性に関する評価試験例》
(1)ボイド評価試験
前述したように、チタン板を素地として、上記実施例１〜６び比較例１の各メッキ方法でチタン板の素地上に２０μｍの膜厚で銅メッキ皮膜を形成し、得られた各銅メッキ皮膜を集束イオンビームで薄膜状の試料に加工し、透過電子顕微鏡を用いてボイドの発生状況を微視観察した。
上記ボイド発生度合に関する評価基準は、次の通りである。
○：ボイドは観察されなかった。
×：１視野当たりのボイド数が５個以上観察された。
【００５８】
(2)レベリング性評価試験
前述したように、溝を刻んだ銅パネルの素地上に、上記実施例１〜６及び比較例１の各メッキ方法で銅メッキ皮膜を形成し、得られた銅の各電着皮膜の表面を顕微鏡を用いて目視観察した。
上記レベリング性の評価基準は、次の通りである。
○：皮膜表面に微小凹凸は観察されず、優れた平滑性を示した。
△：溝周辺で凹凸が観察された。
×：溝周辺で顕著な凹凸が観察された。
【００５９】
下表はその試験結果である。
(1)ボイドの評価
上記実施例１〜６は全て○の評価であったが、比較例１は×であった。
これにより、ボイドフリーの銅メッキ皮膜を形成するに当たり、本発明の新規のベンゾトリアゾール系付加物を含有する前処理液で予め予備吸着を施すことの顕著な実効性が明らかになった。合成例１のＢＴＡＰを使用した実施例１〜５、並びに合成例２のビス化合物を使用した実施例６は共に同様の有効性を示したことから、ベンゾトリアゾール骨格にアルキレンオキシド鎖が結合する化合物であれば、ベンゾトリアゾール構造の配置はアルキレンオキシド鎖の一端又は両端を問わず、良好にボイドフリーの銅皮膜を形成できることが判った。さらには、ベンゾトリアゾール系付加物の含有液で前処理するという条件さえ満たせば、銅メッキ浴への当該ベンゾトリアゾール系付加物の含有の有無、或は、公知のレベラーを前処理液に併用することの有無を問わず、銅メッキ皮膜のボイドフリー化を円滑に達成できることが確認できた。
【００６１】
(2)レベリング性の評価
上記実施例１〜６は全て○の評価であったが、比較例１は△であった。
実施例１〜６は前処理液にベンゾトリアゾール系付加物をレベラーとして含有しており、特に、実施例１と６は前処理液のみにベンゾトリアゾール系付加物を含有し、銅メッキ浴にはレベラーを含有しなかったにも拘わらず、銅メッキ皮膜のレベリング性は良好であった。
また、銅メッキ浴に公知のレベラーを含有した比較例１では、レベリング性の評価は実施例より後退していた。これにより、実施例１〜６で使用した新規のベンゾトリアゾール系化合物は、レベリング性付与の面で公知のレベラーに対する優位性が示された。
以上のように、本発明のベンゾトリアゾール系付加物を含有する前処理液で被メッキ物を予備吸着すると、銅メッキ浴へのレベラーの含有の有無を問わず、銅メッキ皮膜のレベリング性を良好に確保でき、且つ、当該ベンゾトリアゾール系付加物はレベラーとして優れた働きをすることが確認できた。[0001]
BACKGROUND OF THE INVENTION
The present invention provides a pretreatment type copper plating method that can effectively prevent voids (cavities) from being generated in a copper plating film while ensuring good leveling properties of the copper plating film.
[0002]
BACKGROUND OF THE INVENTION
In general, as a condition of the copper plating film that satisfies the practical level, in addition to being excellent in glossiness, when microscopically observing the substrate surface of the object to be plated, the concave portion is relatively thick, and conversely, the convex portion It is important that the film is formed to be relatively thin and the surface of the film is smooth.
Levelers are added to ensure this smooth finish (leveling), chlorides such as sodium chloride and epichlorohydrin, polymeric surfactants, nitrogenous organic compounds such as azo dyes, or sulfur. Compounds and the like are used as levelers (see, for example, JP-A-7-316876, JP-B-47-28581, JP-A-52-108340, etc.).
[0003]
However, when electroplating is performed in a conventional copper plating bath, voids are often generated in the plating film, and the copper plating bath disclosed in the above publication containing various levelers is no exception.
If voids occur in the copper plating film formed on a printed circuit board, etc., it causes adverse effects such as increased wiring resistance and reduced EM (Electric Migration) resistance. There is a strong demand for effective prevention.
[0004]
[Prior art]
In the patent document 1, the present applicant immerses an object to be plated in a pretreatment liquid for void-free copper plating containing at least one leveler selected from the group consisting of surfactants, chlorides, and nitrogen-based organic compounds. Then, after washing with water, a void-free copper plating method is disclosed in which the leveling property of the copper plating film and the ability to prevent void generation can be satisfactorily secured by performing electrolytic copper plating with a copper plating solution containing no surfactant.
[0005]
In Patent Document 2, for the purpose of ensuring the leveling property,
(1) a copper film forming step of forming a copper film on the wall surface including the surface of the substrate and the bottom surface of the via hole;
(2) The copper film is in an aqueous solution to which a plating accelerator such as sodium 3-mercapto-1-propanesulfonate, sodium 2-mercaptoethanesulfonate, disodium bis- (3-sulfopropyl) -disulfide is added. Dipping the formed substrate and attaching a plating accelerator to the copper film surface; and
(3) a peeling step of removing the plating accelerator attached to the surface of the copper film excluding the inner wall surface including the bottom surface of the via hole;
(4) After the peeling step, electrolytic copper plating is performed on the copper film formed on the wall surface including the copper film formed on the insulating layer surface and the bottom surface of the via hole, and the plated copper is filled with the plating metal in the via hole. Consisting of a plating process,
A via filling copper plating method is disclosed in which a plating accelerator is unevenly attached in a via hole and current is concentrated to fully fill the via hole with copper plating (claims 1 and 3). 4, paragraphs 13-14).
[0006]
In addition, in Patent Document 3, for the purpose of burying copper well without causing a deposition defect such as a void in a printed wiring board or a via hole or a groove of a wafer,
Brightener components such as bis (3-sulfopropyl) disulfide or its disodium salt, bis (2-sulfopropyl) disulfide or its disodium salt, bis (3-sulf-2-hydroxypropyl) disulfide or its disodium salt , A method of performing electrolytic copper plating in a copper plating bath that does not contain a brightener component after pre-adsorbed to a via hole or a circuit groove portion of a printed wiring board or a wafer (claims 1 and 2). (See paragraphs 8-10).
The pre-adsorption is carried out by a method such as immersion or spraying (paragraph 16). In the pre-adsorption, organic acid amides such as acetamide, benzamide and acrylamide, a leveler component comprising an amine compound, or polyvinyl alcohol, polyethylene glycol, It is described that a polymer component such as polypropylene glycol can be used in combination (claim 2, paragraphs 14 to 15).
[0007]
[Patent Document 1]
JP 2001-152387 A
[Patent Document 2]
Japanese Patent Laid-Open No. 2001-291554
[Patent Document 3]
Japanese Patent No. 3124523
[0008]
[Problems to be solved by the invention]
Although the method of Patent Document 1 can smoothly prevent the generation of voids as compared with a normal copper plating method in which pretreatment is not performed, the density of electronic components such as recent substrates and various wafers is increased and the functions are increased. In view of the current situation where higher reliability and higher reliability are required, further improvement in leveling and void prevention capability is expected.
Moreover, the said patent documents 2-3 are mainly aimed at ensuring leveling property, and an effect is inadequate in the surface which prevents a void effectively.
The present invention has a technical problem of ensuring leveling properties and further improving the ability to prevent voids in copper plating including electronic parts.
[0009]
[Means for Solving the Problems]
The present inventors have developed a novel nitrogen-containing organic compound, benzotriazole, triazolopyridine C.2~ CFourBy synthesizing an alkylene oxide adduct and applying this new compound to the pretreatment of the copper electroplating, it was found that the leveling property of the copper plating film was excellent and the generation of voids could be prevented smoothly, thereby completing the present invention.
[0010]
That is, the present invention 1 relates to C of benzotriazole and triazolopyridine.2~ CFourA pretreatment-type copper plating method characterized in that after an object to be plated is immersed in a pretreatment liquid containing an alkylene oxide adduct as a leveler, electrolytic copper plating is applied to the object to be plated.
[0011]
Invention 2 is characterized in that, in the Invention 1, the leveler is 1,2,3-benzotriazole polyethoxylate, ω, ω′-bis (1,2,3-benzotriazole) polyethoxylate. This is a pretreatment type copper plating method.
[0012]
The present invention 3 is the pretreatment type copper plating method according to the present invention 1 or 2, wherein the leveler content of the pretreatment liquid is 0.1 mg / L to 50 g / L.
[0013]
The present invention 4 is a pretreatment-type copper plating method, wherein the pretreatment liquid according to any one of the present inventions 1 to 3 further contains a soluble copper salt and an acid.
[0014]
The present invention 5 is a pretreatment type copper plating method characterized in that preliminary electrolytic copper plating is applied to an object to be plated with the pretreatment liquid instead of being immersed in the pretreatment liquid of the present invention 4.
[0015]
The present invention 6 is a pretreatment type copper plating method, wherein the object to be plated according to any one of the present inventions 1 to 5 is a substrate having a build-up structure and various wafers.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, first, the novel nitrogen-containing organic compounds benzotriazole and triazolopyridine C2~ CFourThis is a pre-treatment type void-free copper plating method in which an object to be plated such as a build-up substrate and various wafers is immersed in a pretreatment liquid containing an alkylene oxide adduct as a leveler, and then the object to be plated is subjected to electrolytic copper plating. Secondly, instead of immersing in the pretreatment liquid, the copper plating is performed after preliminarily plating the object to be plated using the pretreatment liquid.
[0017]
C of benzotriazole or triazolopyridine which is a novel nitrogen-containing organic compound of the present invention2~ CFourThe alkylene oxide adduct is represented by the following general formula (1) or general formula (2).
Ar- (AO)n-H (1)
Ar- (AO)n-Ar (2)
(In the formula (1) or (2), Ar is the following atomic group (a) or (b); AO is oxyethylene, oxypropylene, or oxybutylene; n is an integer of 2 to 300. )
[Chemical 1]
[Chemical 2]
[0018]
C of the above benzotriazole2~ CFourAn alkylene oxide adduct (hereinafter referred to as a benzotriazole-based adduct) corresponds to the case where X in the above formula (a) or (b) is CH, and is represented by, for example, the following chemical formulas (A) to (C). Is done.
[Chemical 3]
This alkylene oxide chain may be a repetition of the same type of oxyalkylene, or may be a repetition in which different types of oxyalkylene coexist, such as a copolymer chain of oxyethylene and oxypropylene.
In this benzotriazole-based adduct, the alkylene oxide chain may be bonded to the 1-position of the benzotriazole ring (see the above formula (a)) or may be bonded to the 2-position of the same ring (above). (See formula (b)).
For example, among the benzotriazole-based adducts, a compound in which alkylene oxide chains are bonded to each other at both ends of the benzotriazole skeletons is not limited to the case where the alkylene oxide chains are bonded to the 2-positions of the benzotriazole skeletons. They may be bonded to the 1-position, or may be bonded to the 1-position of one skeleton and the 2-position of the other skeleton.
[0019]
As shown in the above formula (a) or (b), the benzene ring of the benzotriazole skeleton in the benzotriazole-based adduct has C1~ C6Alkyl, OC1~ OC61 to 3 substituents selected from the group consisting of alkyl, halogen, amino group (or substituted amino group), nitro group, sulfonic acid group (or sulfonic acid group), carboxyl group (or carboxylic acid group) are bonded. be able to. When the number of bonds of the substituent is 2 to 3, the type of the substituent may be the same or different.
[0020]
C of the above triazolopyridine2~ CFourThe alkylene oxide adduct (hereinafter referred to as triazolopyridine adduct) corresponds to the case where X in the above formula (a) or (b) is N (that is, basically the mother skeleton of the benzotriazole adduct). Is replaced with a triazolopyridine ring), a chain of ethylene oxide, propylene oxide or butylene oxide is bonded to the nitrogen atom of the triazolopyridine skeleton in a repetition of 2 to 300, and the triazolopyridine skeleton is attached to one end of the alkylene oxide chain. May be arranged (see the above formula (1)), or a triazolopyridine skeleton may be arranged at both ends of the alkylene oxide chain (see the above formula (2)).
This triazolopyridine-based adduct is represented by, for example, the following chemical formulas (D) to (E), and the type of repeating unit of the alkylene oxide chain may be the same or different. The point that various substituents can be bonded, or that the alkylene oxide chain can change the bonding position with respect to the triazolopyridine skeleton (can be bonded to the 1st or 2nd position of the skeleton) is the same as the above benzotriazole adduct It is.
[Chemical 6]
The general synthesis method of the benzotriazole-based adduct of the present invention can be roughly divided into the following three methods.
(A) Synthesis method 1
1,2,3-benzotriazole and ω-substituted polyalkoxylate are used as reactants to produce a compound in which a benzotriazole skeleton is arranged at one end of an alkylene oxide chain, and is represented by the following reaction formula (A) .
[Chemical 8]
The reaction conditions are as follows.
(1) Solvent: water, methanol, ethanol, isopropanol, t-butanol, THF, dioxane, DMF, DMSO, N-methylpyrrolidone, etc.
(2) Reaction temperature: room temperature to 100 ° C
(3) Reaction time: 0.5 to 50 hours
(4) Base: sodium hydroxide, potassium hydroxide, sodium methoxide, potassium ethoxide, sodium hydride, metallic sodium, sodium carbonate, potassium carbonate, etc.
(5) Post-treatment: After usual method, for example, solvent extraction, water washing and solvent distillation.
[0022]
(B) Synthesis method 2
A reaction product of 1,2,3-benzotriazole and ω, ω′-disubstituted polyalkoxylate to produce a compound in which a benzotriazole skeleton is arranged at both ends of an alkylene oxide chain. The following reaction formula (b) It is represented by
[Chemical 9]
The reaction conditions are as follows.
(1) Solvent: water, methanol, ethanol, isopropanol, t-butanol, THF, dioxane, DMF, DMSO, N-methylpyrrolidone, etc.
(2) Reaction temperature: room temperature to 100 ° C
(3) Reaction time: 0.5 to 50 hours
(4) Base: sodium hydroxide, potassium hydroxide, sodium methoxide, potassium ethoxide, sodium hydride, metallic sodium, sodium carbonate, potassium carbonate, etc.
(5) Post-treatment: After usual method, for example, solvent extraction, water washing and solvent distillation.
[0023]
(C) Synthesis method 3
The reaction product is 1,2,3-benzotriazole and alkylene oxide, and is represented by the following reaction formula (c).
[Chemical Formula 10]
(1) Solvent: Water-soluble solvent such as sodium hydroxide, potassium hydroxide, sodium methoxide, potassium ethoxide and sodium hydride, no solvent, or organic solvent such as toluene and xylene
(2) Reaction temperature: 100-200 ° C
(3) Catalytic amount: in the presence of a basic substance (usually 0.001 to 0.05 equivalents) such as metallic sodium, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium ethoxide, sodium hydride. Do.
[0024]
The method for synthesizing the triazolopyridine adduct of the present invention is in accordance with the above benzotriazole adduct.
Specific examples of the benzotriazole adduct or triazolopyridine adduct of the present invention include the following compounds.
1,2,3-benzotriazole polyethoxylate (EO 3 mol)
1,2,3-benzotriazole polyethoxylate (EO 45 mol)
1,2,3-benzotriazole polyethoxylate (EO 70 mol)
1,2,3-benzotriazole polyethoxylate (EO 200 mol)
1,2,3-benzotriazole polyethoxylate (EO 300 mol)
.Omega.,. Omega .'- bis (1,2,3-benzotriazole) polyethoxylate (EO 22 mol)
.Omega.,. Omega .'- bis (1,2,3-benzotriazole) polyethoxylate (EO 100 mol)
1,2,3-benzotriazole polyethoxylate (EO 3 mol) polypropoxylate (PO 2 mol)
5-methyl (1,2,3-benzotriazole) polyethoxylate (EO 5 mol) polypropoxylate (PO 2 mol)
1,2,3-benzotriazole polyethoxylate (EO 3 mol) polypropoxylate (PO 2 mol)
1,2,3-benzotriazole polypropoxylate (PO4 mol) polyethoxylate (EO 10 mol)
1,2,3-benzotriazole polyethoxylate (EO 10 mol) polypropoxylate (PO 8 mol) polyethoxylate (EO 10 mol)
Ω, ω'-bis (1,2,3-benzotriazole) polyethoxylate (EO 20 mol) polypropoxylate (PO 30 mol) polyethoxylate (EO 20 mol)
Ω, ω′-bis [5,6-dimethyl (1,2,3-benzotriazole)] polyethoxylate (EO 25 mol) polypropoxylate (PO25 mol) polyethoxylate (EO 25 mol)
1,2,3-benzotriazole polyethoxylate (EO 10 mol) polypropoxylate (PO 8 mol) polyethoxylate (EO 10 mol)
1,2,3-benzotriazole polypropoxylate (PO 30 mol) polyethoxylate (EO 26 mol)
1,2,3-benzotriazole polyethoxylate (EO 10 mol) polypropoxylate (PO 8 mol) polyethoxylate (EO 10 mol)
Ω, ω′-bis (1,2,3-benzotriazole) polyethoxylate (EO 40 mol) polypropoxylate (PO 30 mol)
1,2,3-benzotriazole polyethoxylate (EO 25 mol) polypropoxylate (PO 20 mol) polyethoxylate (EO 25 mol)
Ω, ω'-bis (1,2,3-benzotriazole) polyethoxylate (EO 25 mol) polypropoxylate (PO 20 mol) polyethoxylate (EO 25 mol)
1,2,3-benzotriazole polyethoxylate (EO 12 mol) polybutoxylate (BO 8 mol) polyethoxylate (EO 12 mol)
5-chloro (1,2,3-benzotriazole) polyethoxylate (EO 15 mol) polybutoxylate (BO 10 mol) polyethoxylate (EO 15 mol)
Ω, ω'-bis (1,2,3-benzotriazole) polyethoxylate (EO 15 mol) polybutoxylate (BO 10 mol) polyethoxylate (EO 15 mol)
1,2,3-triazolo [4,5-b] pyridine polyethoxylate (EO 13 mol) polypropoxylate (PO 4 mol)
1,2,3-triazolo [4,5-b] pyridine polyethoxylate (EO 18 mol)
1,2,3-triazolo [4,5-b] pyridine polyethoxylate (EO 80 mol)
1,2,3-triazolo [4,5-b] pyridine polyethoxylate (EO 30 mol) polypropoxylate (PO 20 mol) polyethoxylate (EO 30 mol)
Ω, ω′-bis (1,2,3-triazolo [4,5-b] pyridine) polyethoxylate (EO 50 mol)
Ω, ω′-bis (1,2,3-triazolo [4,5-b] pyridine) polyethoxylate (EO 30 mol) polypropoxylate (PO 20 mol) polyethoxylate (EO 30 mol)
Among the above compounds, as shown in the present invention 2, 1,2,3-benzotriazole polyethoxylate (EO 3 mol adduct, EO 70 mol adduct), ω, ω′-bis (1,2,3- Benzotriazole) polyethoxylate (EO 22 mole adduct) is preferred.
[0025]
The benzotriazole-based or triazolopyridine-based adduct of the present invention can be used singly or in combination, and of course, a benzotriazole-based adduct and a triazolopyridine-based adduct can be used in combination.
The above adduct is C2~ CFourSince the oxyalkylene chain is present in the molecule, the pretreatment liquid in the form of an aqueous solution can be easily prepared by dissolving in water relatively smoothly and simply adding to water.
Content with respect to the pre-processing liquid of the said adduct is 0.1 mg / L-50 g / L, Preferably, it is 1 mg / L-10 g / L. If it is less than 0.1 mg / L, the effects of void-free ability and leveling properties cannot be obtained, and even if it exceeds 50 g / L, the effect does not change so much that the cost is wasted.
[0026]
The present invention is characterized by pretreatment with a liquid containing a novel benzotriazole-based or triazolopyridine-based adduct as a leveler. In this pretreatment, the compounds described in the above-mentioned prior art are firstly used. Needless to say, a known leveler can be used in combination.
Examples of the known levelers include chlorides, nitrogen-based organic compounds, sulfur compounds, and surfactants as shown in Patent Document 1 described above.
The chloride is a compound capable of supplying chloride ions in the pretreatment liquid, and examples thereof include sodium chloride, hydrogen chloride, potassium chloride, ammonium chloride, and copper chloride. Chlorinated organic compounds such as quaternary alkyl ammonium chloride and chloroacetic acid may also be used.
[0027]
The nitrogen-based organic compound is a dye or a derivative thereof, an amide compound, a thioamide compound, a compound having an aniline or pyridine ring, various heteromonocyclic compounds, various condensed heterocyclic compounds, aminocarboxylic acids, and the like. Specifically, CI (Color Index) Basic Red 2, Toluidine dyes such as Toluidine Blue, CI Direct Yellow 1, CI Yanas Green B, CI Basic Black 2, etc. Azo dyes, phenazine dyes such as 3-amino-6-dimethylamino-2-methylphenazine monohydrochloride, imidazolines such as succinimide and 2'-bis (2-imidazoline), imidazoles, and benzimidazoles , Indoles, 2-vinylpyridine, 4-acetylpyridine, 4-mercapto-2-carboxylpyridine, 2,2 -Pyridines such as bipyridyl and phenanthroline, quinolines, isoquinolines, thioureas such as aniline, thiourea and dimethylthiourea, 3,3 ', 3 "-nitrilotripropionic acid, diaminomethyleneaminoacetic acid, glycine, N -Methylglycine, dimethylglycine, β-alanine, cysteine, glutamic acid, aspartic acid, aminovaleric acid, ornithine and the like.
Among them, toluidine dyes such as CI Basic Red 2, azo dyes such as CI Direct Yellow 1 and CI Yanas Green B, 3-amino-6-dimethylamino-2-methylphenazine Phenazine dyes such as hydrochloric acid, imidazolines such as 2'-bis (2-imidazoline), benzimidazoles, 2-vinylpyridine, 4-acetylpyridine, pyridines such as 2,2'-bipyridyl, phenanthroline, and quinolines Preferred are thioureas such as aniline, thiourea and dimethylthiourea, and aminocarboxylic acids such as aminomethyleneaminoacetic acid.
[0028]
Examples of the sulfur compounds include thioureas, mercaptans, mercaptosulfonic acids, benzothiazoles, sulfides, thiophenes, benzothiophenes, and the like, specifically, thiourea, 1,3-dimethylthiourea, trimethylthio. Thiourea derivatives such as urea, diethylthiourea, N, N′-diisopropylthiourea, allylthiourea, acetylthiourea, ethylenethiourea, 1,3-diphenylthiourea, thiourea dioxide, thiosemicarbazide, thiophenol, o, m or Mercaptans such as p-dimercaptobenzene, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, t-butylmercaptan, thioglycol, thioglycolic acid, 3-mercaptopropionic acid, bis (3 -Sulfopropyl) disulfide, 2,2 '-(or 4,4'-) dipyridyl sulfide, 2,2'-dithiodianiline, bis (4-aminophenyl) sulfide, diethyl sulfide, isopropyl sulfide, diphenyl sulfide, isobutyl Ethyl sulfide, 2,2'-thiodiglycolic acid, 3,3'-thiodipropionic acid, 2,2'-thiodiglycol, dimethyl disulfide, diethyl disulfide, diphenyl disulfide, di-n-propyl-thioether-di Sulfides such as -3-sulfonic acid (disodium salt), bis (3-sulfopropyl) disulfide (disodium salt), 3- (benzothiazolyl-2-thio) propylsulfonic acid (sodium salt), 3-mercaptopropane -1-sodium sulfonate, 2-mercaptoethanesulfonic acid Such as mercaptopurine sulfonic acids such as thorium, and the like.
Of these, thioureas, benzothiazoles, mercaptans, mercaptosulfonic acids, sulfides and the like are preferable.
[0029]
Examples of the surfactant include various nonionic, anionic, cationic, and amphoteric surfactants, and nonionic surfactants are particularly preferable.
The nonionic surfactant is a concept including a polymer surfactant, and specifically, polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), polyethylene glycol (PEG), polypropylene glycol (PPG), polyacrylamide. And C1~ C20Alkanol, phenol, naphthol, bisphenols, C1~ Ctwenty fiveAlkylphenol, arylalkylphenol, C1~ Ctwenty fiveAlkyl naphthol, C1~ Ctwenty fiveAlkoxylated phosphoric acid (salt), sorbitan ester, styrenated phenol, polyalkylene glycol, C1~ Ctwenty twoAliphatic amine, C1~ Ctwenty twoAn aliphatic amide or the like is obtained by addition condensation of 2-300 mol of ethylene oxide (EO) and / or propylene oxide (PO). However, the addition condensate may be an EO-only adduct such as a predetermined alkanol, phenol, or naphthol, an PO-only adduct, or an adduct in which EO and PO coexist.
[0030]
C for addition condensation of ethylene oxide (EO) and / or propylene oxide (PO)1~ C20Examples of the alkanol include octanol, decanol, lauryl alcohol, tetradecanol, hexadecanol, stearyl alcohol, eicosanol, cetyl alcohol, oleyl alcohol, docosanol and the like.
Similarly, bisphenols include bisphenol A and bisphenol B.
C1~ Ctwenty fiveAlkylphenols include mono, di, or trialkyl substituted phenols such as p-butylphenol, p-isooctylphenol, p-nonylphenol, p-hexylphenol, 2,4-dibutylphenol, 2,4,6-tributylphenol, Examples include p-dodecylphenol, p-laurylphenol, p-stearylphenol.
Examples of the arylalkylphenol include 2-phenylisopropylphenyl.
[0031]
C1~ Ctwenty fiveExamples of the alkyl group of the alkyl naphthol include methyl, ethyl, propyl, butylhexyl, octyl, decyl, dodecyl, octadecyl and the like, which may be at any position of the naphthalene nucleus.
C1~ Ctwenty fiveThe alkoxylated phosphoric acid (salt) is represented by the following general formula (a).
Ra · Rb · (MO) P = O (a)
(In formula (a), RaAnd RbAre the same or different C1~ Ctwenty fiveAlkyl, one of which may be H. M represents H or an alkali metal. )
[0032]
Sorbitan esters include mono-, di- or triesterized 1,4-, 1,5- or 3,6-sorbitan, such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan distearate, sorbitan dioleate, Examples include sorbitan mixed fatty acid esters.
C1~ Ctwenty twoExamples of the aliphatic amine include saturated and unsaturated fatty acid amines such as propylamine, butylamine, hexylamine, octylamine, decylamine, laurylamine, stearylamine, ethylenediamine, and propylenediamine.
C1~ Ctwenty twoExamples of the aliphatic amide include amides such as propionic acid, butyric acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid.
[0033]
As the cationic surfactant, a quaternary ammonium salt represented by the following general formula (b)
(R1・ R2・ RThree・ RFourN)+・ X- ... (b)
(In the formula (b), X is halogen, hydroxy, C1~ CFiveAlkanesulfonic acid or sulfuric acid, R1, R2And RThreeAre the same or different C1~ C20Alkyl, RFourIs C1~ CTenIndicates alkyl or benzyl. )
Or the pyridinium salt etc. which are represented with the following general formula (c) are mentioned.
R6-(C6HFourN-RFive)+・ X- ... (c)
(In formula (c), C6HFourN is a pyridyl group, X is halogen, hydroxy, C1~ CFiveAlkanesulfonic acid or sulfuric acid, RFiveIs C1~ C20Alkyl, R6Is H or C1~ CTenIndicates alkyl. )
[0034]
Examples of cationic surfactants in the form of salts include lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, lauryl dimethyl ethyl ammonium salt, octadecyl dimethyl ethyl ammonium salt, dimethyl benzyl lauryl ammonium salt, cetyl dimethyl benzyl ammonium salt, octadecyl dimethyl Examples include benzylammonium salt, trimethylbenzylammonium salt, triethylbenzylammonium salt, hexadecylpyridinium salt, laurylpyridinium salt, dodecylpyridinium salt, stearylamine acetate, laurylamine acetate, and octadecylamine acetate.
[0035]
Examples of the anionic surfactant include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl benzene sulfonates, (mono, di, tri) alkyl naphthalene sulfonates, and the like. It is done. Examples of the alkyl sulfate include sodium lauryl sulfate and sodium oleyl sulfate. Examples of the polyoxyethylene alkyl ether sulfate include sodium polyoxyethylene (EO12) nonyl ether sulfate and sodium polyoxyethylene (EO15) dodecyl ether sulfate. Examples of the polyoxyethylene alkylphenyl ether sulfate include polyoxyethylene (EO15) nonylphenyl ether sulfate. Examples of the alkyl benzene sulfonate include sodium dodecylbenzene sulfonate. Examples of the (mono, di, tri) alkyl naphthalene sulfonate include sodium dibutyl naphthalene sulfonate.
[0036]
Examples of the amphoteric surfactant include carboxybetaine, imidazoline betaine, sulfobetaine, and aminocarboxylic acid. Further, sulfation of a condensation product of ethylene oxide and / or propylene oxide and an alkylamine or diamine, or a sulfonated adduct can also be used.
[0037]
Representative carboxybetaines or imidazoline betaines include lauryl dimethylaminoacetic acid betaine, myristyldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, 2-undecyl-1-carboxymethyl- 1-hydroxyethyl imidazolinium betaine, 2-octyl-1-carboxymethyl-1-carboxyethyl imidazolinium betaine, and the like. Examples of sulfated and sulfonated adducts include sulfated adducts of ethoxylated alkylamines, sulfones. Examples include sodium lauric acid derivative sodium salt.
[0038]
Examples of the sulfobetaines include coconut oil fatty acid amidopropyldimethylammonium-2-hydroxypropanesulfonic acid, N-cocoylmethyl taurine sodium, and N-palmitoylmethyl taurine sodium.
Examples of the aminocarboxylic acid include dioctylaminoethylglycine, N-laurylaminopropionic acid, octyldi (aminoethyl) glycine sodium salt, and the like.
[0039]
In addition, as shown in the present invention 3, the pretreatment liquid for void-free copper plating can further contain a soluble copper salt and an acid.
The above-mentioned soluble copper salt means a compound from which a stable aqueous solution of copper is obtained, and examples thereof include copper sulfate, copper chloride, copper oxide, copper carbonate, copper acetate, copper pyrophosphate, and copper oxalate. Copper or the like is preferable.
Examples of the acid include sulfuric acid, hydrochloric acid, oxalic acid, acetic acid, pyrophosphoric acid, and the like.
Content of soluble copper salt is 0.01-3 mol / L, Preferably, it is 0.1-1.5 mol / L.
[0040]
In the pretreatment type void-free copper plating method of the first aspect of the invention, an object to be plated is immersed in the pretreatment liquid and then electroplated with a copper plating liquid. Instead of the immersion treatment, a pretreatment liquid may be applied or sprayed.
Further, as shown in the present invention 3, after pre-plating with a pretreatment liquid containing a soluble copper salt and an acid, electroplating can be performed with a copper plating liquid. That is, the pretreatment of the present invention is a concept including both immersion treatment and pre-plating treatment.
[0041]
The object to be plated pretreated with the liquid containing the benzotriazole-based or triazolopyridine-based adduct of the present invention is subjected to normal copper plating with a copper plating liquid in the next step.
In the copper plating after the pretreatment, a known copper plating bath can be arbitrarily applied, and there is no particular limitation. Therefore, it goes without saying that the copper plating bath can contain various additives such as a pH adjusting agent and a buffering agent in addition to the soluble copper salt and the acid.
Electroplating conditions such as cathode current density, bath temperature, and plating time in the copper plating bath are not particularly limited.
The benzotriazole-based or triazolopyridine-based adduct of the present invention may or may not be contained in a copper plating bath. Therefore, after pre-adsorption with the pretreatment liquid containing the adduct of the present invention, electroplating may be performed in a copper plating bath containing the adduct, or electrolytic copper plating may be performed in a bath not containing the adduct. Moreover, about a well-known leveler, the presence or absence to the copper plating bath is not ask | required similarly.
[0042]
The pretreatment type void-free copper plating method of the present invention can be applied to any object to be plated. However, as shown in the present invention 6, various wafers, printed boards (particularly, builds such as a mother board and a CSP (Chip Size Package)) It is suitable for a substrate having an up structure.
That is, in particular, the build-up board has many vias (bottomed holes called blind vias) due to its structure, so that voids are easily generated in the conventional copper plating method, but the present invention is applied. By doing so, voids can be reliably prevented while ensuring the leveling properties of the substrate.
[0043]
【The invention's effect】
Pre-treatment with a pre-treatment solution with a new benzotriazole or triazolopyridine adduct is added before electrolytic copper plating is applied to the object to be plated, ensuring a good level of copper plating film while ensuring good voids. Can be effectively prevented. In this case, it does not matter whether the adduct is contained in the copper plating bath.
Since the pretreatment simply involves immersing the object to be plated in the aqueous solution containing the specific component, the treatment is simple, and even if pre-plating is performed in place of the immersion treatment, leveling properties and void-free ability are also effective. Can be secured.
The adduct is C2~ CFourSince the oxyalkylene chain is present in the molecule, it dissolves relatively smoothly in water. Therefore, a pretreatment liquid in the form of an aqueous solution can be easily prepared simply by adding this adduct to water.
[0044]
【Example】
Examples of synthesis of benzotriazole-based adducts of the present invention, examples of the void-free copper plating method of the present invention using a pretreatment liquid containing the adducts of the synthesis examples, and copper plating films obtained in the examples Various evaluation test examples of the degree of occurrence of voids and leveling properties will be sequentially described.
It should be noted that the present invention is not limited to the following examples and test examples, and can of course be modified arbitrarily within the scope of the technical idea of the present invention.
[0045]
<Synthesis example of benzotriazole adduct>
(1) Synthesis Example 1 (Synthesis example of 1,2,3-benzotriazole polyethoxylate (EO3 mol); see the chemical formula (A))
5 g of 1,2,3-benzotriazole was added to the four-necked flask. Next, with stirring, a solution of 2.2 g of sodium hydroxide dissolved in 40 ml of water was added dropwise and heated to 65 ° C., and 7.1 g of 2- [2- (2-chloroethoxy) ethoxy] ethanol was added to 10 ml of water. The solution dissolved in was dropped.
The mixture was stirred with heating at 70 ° C. for 10 hours after the dropping. After completion of the reaction, the reaction solution was extracted with methylene chloride. The methylene chloride extract was washed with alkaline water, then sufficiently washed with water and dried with sodium nitrate. After drying, methylene chloride was distilled off to obtain 8.3 g of an oily product as the target product.
When the above oily substance was subjected to infrared spectroscopic analysis, the wave number of a characteristic absorption peak appearing in the IR chart was as follows.
2872cm-1(Heteroaromatic C—H), 1456 cm-1, 1330cm-1, 1283cm-11120cm-1(-CH2-O-CH2-) 1070cm-1750cm-1(Heteroaromatic C—H)
According to the above results, since there is a heteroaromatic benzotriazole ring and an alkylene oxide ether bond in the molecule of the obtained compound, 1,2,3-benzotriazole polyethoxylate (hereinafter referred to as BTAP). ) (EO3 mol) was confirmed.
[0046]
(2) Synthesis Example 2 (Synthesis example of ω, ω′-bis (1,2,3-benzotriazole) polyethoxylate (EO22 mol); see the chemical formula (B))
To a four-necked flask, 9.2 g of 1,2,3-benzotriazole was added. Next, 100 ml of dioxane was added under stirring, 12 g of anhydrous potassium carbonate was added, and the mixture was heated to 90 ° C., and a solution of 50 g of polyethylene glycol (EO 22 mol) di-p-tosylate dissolved in 200 ml of dioxane was added dropwise.
The mixture was heated and stirred at 90 ° C. for 20 hours after the dropping. After completion of the reaction, the reaction solution was extracted with methylene chloride. The methylene chloride extract was washed with alkaline water, then sufficiently washed with water and dried with sodium nitrate. After drying, methylene chloride was distilled off to obtain 32.2 g of an oily product as the target product.
When the oily substance was subjected to infrared spectroscopic analysis, the wave number of the absorption peak characteristic of IR chart was as follows. Therefore, according to the analysis example of Synthesis Example 1, ω, ω′-bis (1 , 2,3-Benzotriazole) polyethoxylate (EO22 mol) was confirmed.
2872cm-1, 1468cm-1, 1360cm-11280cm-11150cm-11116cm-11060cm-1950cm-1842cm-1
[0047]
(3) Synthesis Example 3 (BTAP (EO 70 mol) synthesis example; see the chemical formula (C))
An autoclave was charged with 50 g of 1,2,3-benzotriazole, and a catalytic amount of potassium hydroxide was added. Subsequently, the autoclave was heated to 170 ° C. with stirring, and 70 mol of ethylene oxide was added to obtain 1310 g of a brown solid.
When the obtained brown solid was subjected to infrared spectroscopic analysis, the following analysis results were obtained. Thus, the formation of BTAP (EO 70 mol) was confirmed according to the analysis example of Synthesis Example 1.
2872cm-1, 1468cm-1, 1360cm-11280cm-11150cm-11116cm-11060cm-1950cm-1842cm-1
[0048]
Therefore, an example of a pretreatment type void-free copper plating method using the benzotriazole-based adduct of Synthesis Examples 1 and 2 will be described.
Examples 1 to 5 below are examples in which BTAP of Synthesis Example 1 was dissolved in water to prepare a pretreatment solution. Among these, Example 1 was an example in which BTAP was not contained in a copper plating bath, and Example 2 was a BTAP. Example 3 also contains a known leveler without containing BTAP in the copper plating bath, Example 4 is an example in which a known leveler is used in combination with the pretreatment liquid, Example 3 Example 5 is an example in which a known leveler is used in combination with the pretreatment liquid and BTAP is contained in the copper plating bath. Example 6 is an example in which the benzotriazole-based adduct was changed from Synthesis Example 1 to the bis compound of Synthesis Example 2 on the basis of Example 1.
On the other hand, Comparative Example 1 is an example in which only normal electrolytic copper plating was performed with a copper plating solution.
[0049]
In the following examples and comparative examples, the immersion conditions in the pretreatment liquid and the electroplating conditions in the copper plating liquid were set as follows (a) to (b), respectively.
(a) Immersion conditions in pretreatment liquid
Bath temperature 30 ° C
Immersion time 5 minutes
(b) Electroplating conditions with copper plating solution
Cathode current density 5.0A / dm2
Bath temperature 30 ° C
Plating time 30 minutes
However, in the examples and comparative examples, it is necessary to observe the occurrence of voids and leveling in the electrodeposition film of copper, so as shown in the test examples described later, the void evaluation test is performed on the titanium plate surface. Copper electroplating was performed, and in the leveling test, copper electroplating was performed using a copper panel with grooves of about 20 μm in advance as a base.
[0050]
Example 1
(1) Pretreatment liquid
BTAP of Synthesis Example 1 0.2 g / L
(2) Copper plating solution
Copper sulfate 200g / L
Sulfuric acid 50g / L
[0051]
Example 2
(1) Pretreatment liquid
BTAP of Synthesis Example 1 0.2 g / L
(2) Copper plating solution
Copper sulfate 200g / L
Sulfuric acid 50g / L
BTAP of Synthesis Example 1 0.2 g / L
[0052]
Example 3
(1) Pretreatment liquid
BTAP of Synthesis Example 1 0.2 g / L
(2) Copper plating solution
Copper sulfate 200g / L
Sulfuric acid 50g / L
2-mercaptobenzothiazole 0.001 g / L
CI Yanas Green B 0.002g / L
Sodium chloride 0.1g / L
Polyethylene glycol (average molecular weight 2,000) 0.1g / L
[0053]
Example 4
(1) Pretreatment liquid
BTAP of Synthesis Example 1 0.2 g / L
CI Yanas Green B 0.002g / L
Sodium chloride 0.1g / L
Polyethylene glycol (average molecular weight 2,000) 0.1g / L
(2) Copper plating solution
Copper sulfate 200g / L
Sulfuric acid 50g / L
[0054]
Example 5
(1) Pretreatment liquid
BTAP of Synthesis Example 1 0.2 g / L
2-mercaptobenzothiazole 0.001 g / L
CI Yanas Green B 0.002g / L
Sodium chloride 0.1g / L
Polyethylene glycol (average molecular weight 2,000) 0.1g / L
(2) Copper plating solution
Copper sulfate 200g / L
Sulfuric acid 50g / L
BTAP of Synthesis Example 1 0.2 g / L
[0055]
Example 6
(1) Pretreatment liquid
Bis compound of Synthesis Example 2 0.2 g / L
(2) Copper plating solution
Copper sulfate 200g / L
Sulfuric acid 50g / L
[0056]
<< Comparative Example 1 >>
A copper plating solution was prepared with the following composition and electroplated.
Copper sulfate 200g / L
Sulfuric acid 50g / L
2-mercaptobenzothiazole 0.001 g / L
CI Yanas Green B 0.002g / L
Sodium chloride 0.1g / L
Polyethylene glycol (average molecular weight 2,000) 0.1g / L
[0057]
《Evaluation test example regarding the occurrence of voids and leveling properties》
(1) Void evaluation test
As described above, using a titanium plate as a base, a copper plating film having a film thickness of 20 μm is formed on the base of the titanium plate by the plating methods of Examples 1 to 6 and Comparative Example 1 above, and each obtained copper plating is obtained. The film was processed into a thin film sample with a focused ion beam, and the state of voids was observed microscopically using a transmission electron microscope.
The evaluation criteria regarding the void generation degree are as follows.
○: No void was observed.
X: Five or more voids per field of view were observed.
[0058]
(2) Leveling evaluation test
As described above, a copper plating film is formed by the plating methods of Examples 1 to 6 and Comparative Example 1 on the surface of a copper panel having a groove, and the surface of each obtained electrodeposition film of copper is formed. Visual observation was performed using a microscope.
The evaluation criteria for the leveling property are as follows.
○: No minute irregularities were observed on the surface of the film, and excellent smoothness was exhibited.
Δ: Unevenness was observed around the groove.
X: Remarkable unevenness was observed around the groove.
[0059]
The table below shows the test results.
(1) Evaluation of voids
Although the said Examples 1-6 were all (circle) evaluation, the comparative example 1 was x.
Thereby, in forming a void-free copper plating film, the remarkable effectiveness of preliminarily adsorbing with a pretreatment liquid containing the novel benzotriazole-based adduct of the present invention was revealed. Since Examples 1 to 5 using BTAP of Synthesis Example 1 and Example 6 using the bis compound of Synthesis Example 2 showed the same effectiveness, a compound in which an alkylene oxide chain is bonded to the benzotriazole skeleton. Then, it was found that the arrangement of the benzotriazole structure can form a void-free copper film satisfactorily regardless of one or both ends of the alkylene oxide chain. Furthermore, as long as the pretreatment with the benzotriazole adduct-containing liquid is satisfied, the presence or absence of the benzotriazole adduct in the copper plating bath or a known leveler is used in the pretreatment liquid. It was confirmed that void-free copper plating film can be achieved smoothly regardless of the presence or absence.
[0061]
(2) Leveling evaluation
Although the said Examples 1-6 were all evaluation of (circle), the comparative example 1 was (triangle | delta).
Examples 1 to 6 contain a benzotriazole-based adduct as a leveler in the pretreatment liquid. In particular, Examples 1 and 6 contain a benzotriazole-based adduct only in the pretreatment liquid. Despite not containing a leveler, the leveling property of the copper plating film was good.
Moreover, in the comparative example 1 which contained the well-known leveler in the copper plating bath, evaluation of leveling property was set back from the Example. Thereby, the novel benzotriazole type compound used in Examples 1-6 showed the predominance over a known leveler in terms of imparting leveling properties.
As described above, when pre-adsorbing the object to be plated with the pretreatment liquid containing the benzotriazole-based adduct of the present invention, the leveling property of the copper plating film is good regardless of whether the leveler is contained in the copper plating bath. It was also confirmed that the benzotriazole-based adduct works excellently as a leveler.
Claims (6)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9598787B2 (en) | 2013-03-14 | 2017-03-21 | Rohm And Haas Electronic Materials Llc | Method of filling through-holes |
| US10508357B2 (en) | 2016-02-15 | 2019-12-17 | Rohm And Haas Electronic Materials Llc | Method of filling through-holes to reduce voids and other defects |
| US10512174B2 (en) | 2016-02-15 | 2019-12-17 | Rohm And Haas Electronic Materials Llc | Method of filling through-holes to reduce voids and other defects |
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| JP5022529B2 (en) * | 2006-10-11 | 2012-09-12 | 石原薬品株式会社 | Copper filling method |
| JP2011179085A (en) * | 2010-03-02 | 2011-09-15 | C Uyemura & Co Ltd | Electroplating pretreatment agent, electroplating pretreatment method and electroplating method |
| US20140299476A1 (en) * | 2013-04-09 | 2014-10-09 | Ebara Corporation | Electroplating method |
| JP2015078443A (en) * | 2015-01-14 | 2015-04-23 | 上村工業株式会社 | Pretreatment agent for electrolytic copper plating, pretreatment method for electrolytic copper plating, and electrolytic copper plating method |
| JP6550585B2 (en) * | 2016-01-29 | 2019-07-31 | トヨタ自動車株式会社 | Method of forming copper film |
| CN116536719A (en) * | 2023-04-25 | 2023-08-04 | 安徽立德半导体材料有限公司 | Identification code for lead frame and silver plating process thereof |
| JP2025181416A (en) | 2024-05-31 | 2025-12-11 | 三星電子株式会社 | Ammonium salt compound, additive for electrolytic copper plating, electrolytic copper plating solution composition, and electrolytic copper plating method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US9598787B2 (en) | 2013-03-14 | 2017-03-21 | Rohm And Haas Electronic Materials Llc | Method of filling through-holes |
| US10508357B2 (en) | 2016-02-15 | 2019-12-17 | Rohm And Haas Electronic Materials Llc | Method of filling through-holes to reduce voids and other defects |
| US10512174B2 (en) | 2016-02-15 | 2019-12-17 | Rohm And Haas Electronic Materials Llc | Method of filling through-holes to reduce voids and other defects |
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