JP2020125539A - Electrolytic copper plating or copper alloy plating bath - Google Patents
Electrolytic copper plating or copper alloy plating bath Download PDFInfo
- Publication number
- JP2020125539A JP2020125539A JP2020002514A JP2020002514A JP2020125539A JP 2020125539 A JP2020125539 A JP 2020125539A JP 2020002514 A JP2020002514 A JP 2020002514A JP 2020002514 A JP2020002514 A JP 2020002514A JP 2020125539 A JP2020125539 A JP 2020125539A
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- JP
- Japan
- Prior art keywords
- acid
- copper
- nitrate
- plating
- chloride
- 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.)
- Pending
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- 238000007747 plating Methods 0.000 title claims abstract description 205
- 239000010949 copper Substances 0.000 title claims abstract description 117
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 86
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 45
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 64
- 239000003792 electrolyte Substances 0.000 claims abstract description 47
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 25
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 64
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 56
- 239000002253 acid Substances 0.000 claims description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 30
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 23
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 22
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 13
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 7
- 235000021317 phosphate Nutrition 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 6
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 4
- 229940005991 chloric acid Drugs 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- 159000000021 acetate salts Chemical class 0.000 claims description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 3
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 3
- 229940009827 aluminum acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001626 barium chloride Inorganic materials 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 235000010338 boric acid Nutrition 0.000 claims description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 239000001639 calcium acetate Substances 0.000 claims description 3
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- 229960005147 calcium acetate Drugs 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- 229910000009 copper(II) carbonate Inorganic materials 0.000 claims description 3
- 239000011646 cupric carbonate Substances 0.000 claims description 3
- 235000019854 cupric carbonate Nutrition 0.000 claims description 3
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 3
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 3
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 3
- 235000019800 disodium phosphate Nutrition 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- 229940071870 hydroiodic acid Drugs 0.000 claims description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 229940086066 potassium hydrogencarbonate Drugs 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 2
- 229940077239 chlorous acid Drugs 0.000 claims description 2
- 238000004070 electrodeposition Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 description 50
- 239000002202 Polyethylene glycol Substances 0.000 description 26
- 229920001223 polyethylene glycol Polymers 0.000 description 26
- 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 24
- 150000003839 salts Chemical class 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 14
- 229910001431 copper ion Inorganic materials 0.000 description 14
- 239000002659 electrodeposit Substances 0.000 description 14
- 230000002159 abnormal effect Effects 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 9
- 229910001316 Ag alloy Inorganic materials 0.000 description 8
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 7
- 239000005751 Copper oxide Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 229910000431 copper oxide Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000009713 electroplating Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 150000002823 nitrates Chemical class 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- -1 and for example Chemical compound 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000008139 complexing agent Substances 0.000 description 5
- 229940116318 copper carbonate Drugs 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 4
- ODDAWJGQWOGBCX-UHFFFAOYSA-N 1-[2-(dimethylazaniumyl)ethyl]tetrazole-5-thiolate Chemical compound CN(C)CCN1N=NN=C1S ODDAWJGQWOGBCX-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 4
- 229910001958 silver carbonate Inorganic materials 0.000 description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 230000005856 abnormality Effects 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 3
- 150000001556 benzimidazoles Chemical class 0.000 description 3
- 150000002462 imidazolines Chemical class 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 238000005304 joining Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 150000003248 quinolines Chemical class 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- UWMLNIDXSZYKTD-UHFFFAOYSA-N 1-n,1-n,7-trimethylphenazine-1,8-diamine Chemical compound CC1=C(N)C=C2N=C3C(N(C)C)=CC=CC3=NC2=C1 UWMLNIDXSZYKTD-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
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 2
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical compound CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 description 2
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- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- LLABTCPIBSAMGS-UHFFFAOYSA-L lead(2+);methanesulfonate Chemical compound [Pb+2].CS([O-])(=O)=O.CS([O-])(=O)=O LLABTCPIBSAMGS-UHFFFAOYSA-L 0.000 description 1
- 229960004635 mesna Drugs 0.000 description 1
- CXIHYTLHIDQMGN-UHFFFAOYSA-L methanesulfonate;nickel(2+) Chemical compound [Ni+2].CS([O-])(=O)=O.CS([O-])(=O)=O CXIHYTLHIDQMGN-UHFFFAOYSA-L 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- 229940098221 silver cyanide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- ULQFYBXXHIFWIQ-UHFFFAOYSA-M silver;2-hydroxyethanesulfonate Chemical compound [Ag+].OCCS([O-])(=O)=O ULQFYBXXHIFWIQ-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- ZWZLRIBPAZENFK-UHFFFAOYSA-J sodium;gold(3+);disulfite Chemical compound [Na+].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O ZWZLRIBPAZENFK-UHFFFAOYSA-J 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 229940007163 stannous tartrate Drugs 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- DWGGYBRHFHGTBF-UHFFFAOYSA-N sulfanylmethanesulfonic acid Chemical compound OS(=O)(=O)CS DWGGYBRHFHGTBF-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- ZPRVNEJJMJMSCN-UHFFFAOYSA-L tin(2+);disulfamate Chemical compound [Sn+2].NS([O-])(=O)=O.NS([O-])(=O)=O ZPRVNEJJMJMSCN-UHFFFAOYSA-L 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 229950003937 tolonium Drugs 0.000 description 1
- 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
- KRZKNIQKJHKHPL-UHFFFAOYSA-J tripotassium;gold(1+);disulfite Chemical compound [K+].[K+].[K+].[Au+].[O-]S([O-])=O.[O-]S([O-])=O KRZKNIQKJHKHPL-UHFFFAOYSA-J 0.000 description 1
- UCGZDNYYMDPSRK-UHFFFAOYSA-L trisodium;gold;hydroxy-oxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Na+].[Na+].[Na+].[Au].OS([S-])(=O)=O.OS([S-])(=O)=O UCGZDNYYMDPSRK-UHFFFAOYSA-L 0.000 description 1
- SNFLBFOWKDHQSB-UHFFFAOYSA-L zinc 2-hydroxypropane-1-sulfonate Chemical compound [Zn++].CC(O)CS([O-])(=O)=O.CC(O)CS([O-])(=O)=O SNFLBFOWKDHQSB-UHFFFAOYSA-L 0.000 description 1
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- OMSYGYSPFZQFFP-UHFFFAOYSA-J zinc pyrophosphate Chemical compound [Zn+2].[Zn+2].[O-]P([O-])(=O)OP([O-])([O-])=O OMSYGYSPFZQFFP-UHFFFAOYSA-J 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- MIPUHXODPDOHCI-UHFFFAOYSA-L zinc;2-hydroxyethanesulfonate Chemical compound [Zn+2].OCCS([O-])(=O)=O.OCCS([O-])(=O)=O MIPUHXODPDOHCI-UHFFFAOYSA-L 0.000 description 1
- MKRZFOIRSLOYCE-UHFFFAOYSA-L zinc;methanesulfonate Chemical compound [Zn+2].CS([O-])(=O)=O.CS([O-])(=O)=O MKRZFOIRSLOYCE-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
本発明は、電気銅メッキ又は銅合金メッキ浴に関する。さらに詳しくは、本発明は、例えば高アスペクトの突起電極群等の電着物を、非常に低い異常析出の発生頻度にて、高速でかつ均一な高さ又は厚さに形成することができる電気銅メッキ又は銅合金メッキ浴に関する。 The present invention relates to electrolytic copper plating or copper alloy plating baths. More specifically, the present invention relates to an electrolytic copper capable of forming an electrodeposit such as a high aspect projection electrode group at a high speed and a uniform height or thickness with a very low occurrence frequency of abnormal deposition. Plating or copper alloy plating bath.
電子部品に電気メッキを適用して突起電極（銅柱：Ｃｏｐｐｅｒ Ｐｉｌｌａｒ）、電着皮膜等の電着物を形成する場合、例えば半導体チップでは、小型化及び小スペース化に対応するために、パッケージ面積を縮小した３次元構造のＰｏＰ（パッケージオンパッケージ：Ｐａｃｋａｇｅ ｏｎ Ｐａｃｋａｇｅ）型の半導体部品等がある。 When applying electroplating to electronic parts to form electrodeposits such as bump electrodes (copper pillars) and electrodeposition coatings, for example, in semiconductor chips, in order to respond to downsizing and space saving, the package area There is a PoP (Package on Package) type semiconductor component having a three-dimensional structure that is a reduced size.
半導体チップを立体配置するためには、上部のチップを下部の配線と接合する必要があり、その際には、高アスペクトの突起電極を形成して接合する方法等を採用することが好ましい。 In order to arrange the semiconductor chips three-dimensionally, it is necessary to bond the upper chip to the lower wiring. At that time, it is preferable to adopt a method of forming and bonding a high aspect projection electrode.
前記のごとき突起電極を形成するための電気メッキ浴として、従来、例えば特許文献１〜３に開示のメッキ浴が提案されている。 Conventionally, for example, the plating baths disclosed in Patent Documents 1 to 3 have been proposed as electroplating baths for forming the protruding electrodes as described above.
ＬＳＩ、ＩＣ等のチップ部品を接合する場合、この接合を確実に担保するには、突起電極の形状、特に高さの均一性を確保することが重要である。この点は、突起電極を介して基板同士を接合する基板間接合についても同様である。 When joining chip parts such as LSI and IC, it is important to ensure the shape of the protruding electrodes, especially the uniformity of height, in order to ensure this joining. This point is the same for the inter-substrate bonding in which the substrates are bonded to each other via the bump electrodes.
ここで、従来の一般的な電解質、例えば硫酸やメタンスルホン酸は、溶解度に限界があるか、又はその特性上高速性を維持できない。よって、例えば前記特許文献１〜３に開示されているように、これらの電解質を含むメッキ浴に、前記メタンスルホン酸以外にも所定の有機酸を配合して、又は特定の有機化合物を添加剤として配合して、メッキ浴の特性の向上が試みられている。 Here, conventional general electrolytes, such as sulfuric acid and methanesulfonic acid, have a limited solubility or cannot maintain high speed due to their characteristics. Therefore, for example, as disclosed in Patent Documents 1 to 3, a plating bath containing these electrolytes is mixed with a predetermined organic acid other than the methanesulfonic acid, or a specific organic compound is added as an additive. Has been attempted to improve the characteristics of the plating bath.
しかしながら、前記のごとき従来のメッキ浴では、特にパッケージ面積を縮小した３次元構造のＰｏＰ型の半導体部品等の電子部品に、高速でかつ均一な高さに高アスペクトの電着物を形成することは非常に困難である。 However, in the conventional plating bath as described above, it is particularly difficult to form an electrodeposit having a high aspect at a high speed and at a uniform height on an electronic component such as a PoP type semiconductor component having a three-dimensional structure with a reduced package area. Very difficult.
本発明は、例えば高アスペクトの突起電極群等の電着物を高速でかつ均一な高さ又は厚さに形成することができる電気銅メッキ浴を提供することを課題とする。 An object of the present invention is to provide an electrolytic copper plating bath capable of forming an electrodeposit such as a high aspect projection electrode group at a high speed and at a uniform height or thickness.
本発明１は、
２種以上の電解質が配合されており、
前記電解質は、硝酸及び硝酸塩の少なくとも１つを含む、電気銅メッキ又は銅合金メッキ浴
に関する。
Invention 1
Two or more kinds of electrolytes are mixed,
The electrolyte relates to an electrolytic copper plating or copper alloy plating bath containing at least one of nitric acid and nitrate.
本発明２は、前記本発明１において、
高さが５μｍ以上の銅柱又は銅合金柱の形成に適用されるものである
ことを特徴とする。
The present invention 2 is the same as the above Invention 1,
It is characterized in that it is applied to the formation of copper columns or copper alloy columns having a height of 5 μm or more.
本発明３は、前記本発明２において、
前記銅柱又は銅合金柱は、ＳｉＰ（Ｓｙｓｔｅｍ ｉｎ Ｐａｃｋａｇｅ）型、ＦＯＷＬＰ（Ｆａｎ Ｏｕｔ Ｗａｆｅｒ Ｌｅｖｅｌ Ｐａｃｋａｇｅ）型、ＦＯＰＬＰ（Ｆａｎ Ｏｕｔ Ｐａｎｅｌ Ｌｅｖｅｌ Ｐａｃｋａｇｅ）型、ＳｏＣ（Ｓｙｓｔｅｍ ｏｎ ａ Ｃｈｉｐ）型、又はＰｏＰ（Ｐａｃｋａｇｅ ｏｎ Ｐａｃｋａｇｅ）型の電子部品に形成されるものであることを特徴とする。
The third aspect of the present invention is the same as the second aspect of the present invention.
The copper pillar or the copper alloy pillar is a SiP (System in Package) type, a FOWLP (Fan Out Wafer Level Package) type, a FOPLP (Fan Out Panel Level Package) type, a SoC (System Pegge type) or a SoC (System Pegge type). on Package) type electronic components.
本発明４は、前記本発明１において、
前記硝酸塩は、硝酸ナトリウム、硝酸カリウム、硝酸マグネシウム、硝酸カルシウム、硝酸バリウム、硝酸亜鉛、硝酸銀、硝酸銅（II）、硝酸ニッケル、硝酸アルミニウム、硝酸鉄（III）、及び硝酸アンモニウムからなる群より選ばれた少なくとも１つである
ことを特徴とする。
The present invention 4 is the same as the present invention 1,
The nitrate is selected from the group consisting of sodium nitrate, potassium nitrate, magnesium nitrate, calcium nitrate, barium nitrate, zinc nitrate, silver nitrate, copper (II) nitrate, nickel nitrate, aluminum nitrate, iron (III) nitrate, and ammonium nitrate. It is characterized in that it is at least one.
本発明５は、前記本発明１において、
前記電解質の含有量は、１ｇ／Ｌ〜５００ｇ／Ｌである
ことを特徴とする。
The present invention 5 is the same as the above Invention 1,
The content of the electrolyte is 1 g/L to 500 g/L.
本発明６は、前記本発明１において、
前記電解質として、前記硝酸以外の酸、塩化物、硫酸塩、炭酸塩、リン酸塩、酢酸塩、及び過塩素酸塩から選ばれた少なくとも１種がさらに配合されてなる
ことを特徴とする。
The present invention 6 is the same as the above Invention 1,
The electrolyte is characterized by further containing at least one selected from acids other than nitric acid, chlorides, sulfates, carbonates, phosphates, acetates, and perchlorates.
本発明７は、前記本発明６において、
前記硝酸以外の酸は、塩酸、硫酸、メタンスルホン酸、酢酸、炭酸、リン酸、ホウ酸、シュウ酸、乳酸、硫化水素、フッ化水素酸、ギ酸、過塩素酸、塩素酸、亜塩素酸、次亜塩素酸、臭化水素酸、ヨウ化水素酸、亜硝酸、及び亜硫酸からなる群より選ばれた少なくとも１つである
ことを特徴とする。
Invention 7 is the invention 6 according to
The acids other than nitric acid include hydrochloric acid, sulfuric acid, methanesulfonic acid, acetic acid, carbonic acid, phosphoric acid, boric acid, oxalic acid, lactic acid, hydrogen sulfide, hydrofluoric acid, formic acid, perchloric acid, chloric acid, chlorous acid. , At least one selected from the group consisting of hypochlorous acid, hydrobromic acid, hydroiodic acid, nitrous acid, and sulfurous acid.
本発明８は、前記本発明６において、
前記塩化物は、塩化リチウム、塩化ナトリウム、塩化カリウム、塩化マグネシウム、塩化カルシウム、塩化バリウム、塩化亜鉛、塩化銅（II）、塩化アルミニウム、塩化鉄（III）、及び塩化アンモニウムからなる群より選ばれた少なくとも１つである
ことを特徴とする。
Invention 8 is the invention 6 according to
The chloride is selected from the group consisting of lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, barium chloride, zinc chloride, copper (II) chloride, aluminum chloride, iron (III) chloride, and ammonium chloride. And at least one.
本発明９は、前記本発明６において、
前記炭酸塩は、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、炭酸水素カリウム、炭酸銅（II）、及び炭酸アンモニウムからなる群より選ばれた少なくとも１つである
ことを特徴とする。
Invention 9 is the invention 6 according to
The carbonate is at least one selected from the group consisting of sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, copper (II) carbonate, and ammonium carbonate.
本発明１０は、前記本発明６において、
前記リン酸塩は、リン酸ナトリウム、リン酸水素２ナトリウム、リン酸水素ナトリウム、リン酸カリウム、リン酸水素２カリウム、及びリン酸水素カリウムからなる群より選ばれた少なくとも１つである
ことを特徴とする。
The present invention 10 is the same as the present invention 6,
The phosphate is at least one selected from the group consisting of sodium phosphate, disodium hydrogen phosphate, sodium hydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, and potassium hydrogen phosphate. Characterize.
本発明１１は、前記本発明６において、
前記酢酸塩は、酢酸ナトリウム、酢酸カリウム、酢酸カルシウム、酢酸銅（II）、酢酸アルミニウム、及び酢酸アンモニウムからなる群より選ばれた少なくとも１つである
ことを特徴とする。
The present invention 11 is the same as the above Invention 6,
The acetate salt is characterized in that it is at least one selected from the group consisting of sodium acetate, potassium acetate, calcium acetate, copper (II) acetate, aluminum acetate, and ammonium acetate.
本発明１２は、前記本発明６において、
前記過塩素酸塩は、過塩素酸ナトリウム及び過塩素酸カリウムから選ばれた少なくとも１つである
ことを特徴とする。
Invention 12 is the invention 6 according to
The perchlorate is at least one selected from sodium perchlorate and potassium perchlorate.
本発明の電気銅メッキ又は銅合金メッキ浴を用いることにより、例えば高アスペクトの突起電極群等の電着物を、非常に低い異常析出の発生頻度にて、高速でかつ均一な高さ又は厚さに形成することができ、電子部品の生産性を向上させることができる。 By using the electrolytic copper plating or copper alloy plating bath of the present invention, an electrodeposit such as a high aspect protruding electrode group can be formed at a high speed and at a uniform height or thickness with a very low abnormal deposition frequency. It is possible to improve the productivity of electronic parts.
本発明の電気銅メッキ又は銅合金メッキ浴は、２種以上の電解質が配合されており、該電解質は、硝酸及び硝酸塩の少なくとも１つを含んでいる。 The electrolytic copper plating or copper alloy plating bath of the present invention contains two or more kinds of electrolytes, and the electrolyte contains at least one of nitric acid and nitrate.
前記硝酸塩は、例えば、硝酸ナトリウム、硝酸カリウム、硝酸マグネシウム、硝酸カルシウム、硝酸バリウム、硝酸亜鉛、硝酸銀、硝酸銅（II）、硝酸ニッケル、硝酸アルミニウム、硝酸鉄（III）、及び硝酸アンモニウムからなる群より選ばれた少なくとも１つであることが好ましい。これらの中でも、取扱いが容易であり、高速メッキ及び電着物の高さ又は厚さの均一性を向上させる効果が大きいという点で、硝酸銀及び硝酸銅（II）が好ましい。なお、これら硝酸塩のうち、硝酸銅（II）は、後述する銅イオン供給化合物としても作用し、硝酸亜鉛や硝酸銀は、後述する銅と共に合金を生成する金属の可溶性塩としても作用する。 The nitrate is, for example, selected from the group consisting of sodium nitrate, potassium nitrate, magnesium nitrate, calcium nitrate, barium nitrate, zinc nitrate, silver nitrate, copper nitrate (II), nickel nitrate, aluminum nitrate, iron nitrate (III), and ammonium nitrate. It is preferable that the number is at least one. Among these, silver nitrate and copper(II) nitrate are preferable because they are easy to handle and have a large effect of improving high-speed plating and uniformity of height or thickness of electrodeposit. Among these nitrates, copper (II) nitrate also acts as a copper ion supply compound described later, and zinc nitrate and silver nitrate also act as soluble salts of metals that form an alloy with copper described later.
前記２種以上の電解質の組み合わせには特に限定がなく、硝酸及び硝酸塩の少なくとも１つ（以下、硝酸類ともいう）を含んでいればよい。また、該２種以上の電解質として、いずれも該硝酸及び該硝酸塩の中から選ばれてもよく、該硝酸類以外に、硝酸以外の酸、塩化物、硫酸塩、炭酸塩、リン酸塩、酢酸塩、及び過塩素酸塩から選ばれた少なくとも１種（以下、他の電解質ともいう）が配合されてもよい。すなわち、該２種以上の電解質の組み合わせとしては、硝酸と硝酸塩の少なくとも１つ、硝酸塩の少なくとも２つ、硝酸と他の電解質の少なくとも１つ、硝酸塩の少なくとも１つと他の電解質の少なくとも１つ、及び、硝酸と硝酸塩の少なくとも１つと他の電解質の少なくとも１つが挙げられる。 The combination of the two or more types of electrolytes is not particularly limited as long as it contains at least one of nitric acid and nitrate (hereinafter, also referred to as nitric acid). The two or more electrolytes may be selected from the nitric acid and the nitrate, and in addition to the nitric acid, an acid other than nitric acid, a chloride, a sulfate, a carbonate, a phosphate, At least one selected from acetate and perchlorate (hereinafter, also referred to as other electrolyte) may be blended. That is, as a combination of the two or more electrolytes, at least one of nitric acid and nitrate, at least two of nitrate, at least one of nitric acid and other electrolytes, at least one of nitrates and at least one of the other electrolytes, And at least one of nitric acid and nitrate and at least one other electrolyte.
前記硝酸以外の酸は、例えば、塩酸、硫酸、メタンスルホン酸、酢酸、炭酸、リン酸、ホウ酸、シュウ酸、乳酸、硫化水素、フッ化水素酸、ギ酸、過塩素酸、塩素酸、亜塩素酸、次亜塩素酸、臭化水素酸、ヨウ化水素酸、亜硝酸、及び亜硫酸からなる群より選ばれた少なくとも１つであることが好ましい。これらの中では、硝酸及び硝酸塩との親和性が良好であるという点で、硫酸、メタンスルホン酸、及び塩酸が好ましい。なお、塩酸は、塩化物イオン供給源としても作用する。 Examples of the acid other than nitric acid include hydrochloric acid, sulfuric acid, methanesulfonic acid, acetic acid, carbonic acid, phosphoric acid, boric acid, oxalic acid, lactic acid, hydrogen sulfide, hydrofluoric acid, formic acid, perchloric acid, chloric acid, and It is preferably at least one selected from the group consisting of chloric acid, hypochlorous acid, hydrobromic acid, hydroiodic acid, nitrous acid, and sulfurous acid. Of these, sulfuric acid, methanesulfonic acid, and hydrochloric acid are preferable because they have good affinity with nitric acid and nitrates. Note that hydrochloric acid also acts as a chloride ion supply source.
前記塩化物は、前記塩酸と同様に塩化物イオン供給源として作用し、例えば、塩化リチウム、塩化ナトリウム、塩化カリウム、塩化マグネシウム、塩化カルシウム、塩化バリウム、塩化亜鉛、塩化銅（II）、塩化アルミニウム、塩化鉄（III）、及び塩化アンモニウムからなる群より選ばれた少なくとも１つであることが好ましい。 The chloride acts as a chloride ion source like the hydrochloric acid, and for example, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, barium chloride, zinc chloride, copper(II) chloride, aluminum chloride. It is preferably at least one selected from the group consisting of, iron (III) chloride, and ammonium chloride.
前記炭酸塩は、例えば、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、炭酸水素カリウム、炭酸銅（II）、及び炭酸アンモニウムからなる群より選ばれた少なくとも１つであることが好ましい。 The carbonate is preferably, for example, at least one selected from the group consisting of sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, copper (II) carbonate, and ammonium carbonate.
前記リン酸塩は、例えば、リン酸ナトリウム、リン酸水素２ナトリウム、リン酸水素ナトリウム、リン酸カリウム、リン酸水素２カリウム、及びリン酸水素カリウムからなる群より選ばれた少なくとも１つであることが好ましい。 The phosphate is, for example, at least one selected from the group consisting of sodium phosphate, disodium hydrogen phosphate, sodium hydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, and potassium hydrogen phosphate. It is preferable.
前記酢酸塩は、例えば、酢酸ナトリウム、酢酸カリウム、酢酸カルシウム、酢酸銅（II）、酢酸アルミニウム、及び酢酸アンモニウムからなる群より選ばれた少なくとも１つであることが好ましい。 The acetate salt is preferably at least one selected from the group consisting of sodium acetate, potassium acetate, calcium acetate, copper(II) acetate, aluminum acetate, and ammonium acetate.
前記過塩素酸塩は、例えば、過塩素酸ナトリウム及び過塩素酸カリウムから選ばれた少なくとも１つであることが好ましい。 The perchlorate is preferably at least one selected from sodium perchlorate and potassium perchlorate, for example.
本発明の電気銅メッキ又は銅合金メッキ浴における前記電解質の含有量は、１ｇ／Ｌ〜５００ｇ／Ｌであることが好ましく、５ｇ／Ｌ〜３００ｇ／Ｌであることがさらに好ましい。該電解質の含有量が前記下限値未満の場合には、高速メッキ及び電着物の高さ又は厚さの均一性を向上させる効果が充分に発揮されなくなる恐れがある。該電解質の含有量が前記上限値を超える場合には、例えば後述する他の成分との相溶性が低く、均質なメッキ浴を得ることが困難になる恐れがある。 The content of the electrolyte in the electrolytic copper plating or copper alloy plating bath of the present invention is preferably 1 g/L to 500 g/L, and more preferably 5 g/L to 300 g/L. If the content of the electrolyte is less than the lower limit, the effect of improving high-speed plating and uniformity of height or thickness of the electrodeposit may not be sufficiently exhibited. When the content of the electrolyte exceeds the upper limit, compatibility with other components described later is low, and it may be difficult to obtain a uniform plating bath.
また、前記硝酸類と前記他の電解質の少なくとも１つとを組み合わせて用いる場合、該硝酸類と該他の電解質との割合（硝酸類／他の電解質（重量比））は、硝酸類及び他の電解質双方の効果がバランスよく得られるという点から、０．００１／１〜１０００／１程度、さらには０．０１／１〜１００／１程度、特に０．１／１〜５０／１程度であることが好ましい。 When the nitric acid and at least one of the other electrolytes are used in combination, the ratio of the nitric acid to the other electrolyte (nitric acid/other electrolyte (weight ratio)) is From the viewpoint that the effects of both electrolytes are obtained in a well-balanced manner, it is about 0.001/1 to 1000/1, more preferably about 0.01/1 to 100/1, and particularly about 0.1/1 to 50/1. It is preferable.
前記硝酸類と前記他の電解質との組み合わせにおいて、硝酸類が硝酸の場合、すなわち、硝酸と他の電解質の少なくとも１つとを組み合わせて用いる場合、該硝酸と該他の電解質との割合（硝酸／他の電解質（重量比））は、硝酸及び他の電解質双方の効果がバランスよく得られるという点から、０．０５／１〜３０／１程度、さらには０．０８／１〜２０／１程度であることが好ましい。 In the combination of the nitric acid and the other electrolyte, when the nitric acid is nitric acid, that is, when the nitric acid and at least one of the other electrolytes are used in combination, the ratio of the nitric acid to the other electrolyte (nitric acid/nitric acid/ The other electrolyte (weight ratio) is about 0.05/1 to 30/1, more preferably about 0.08/1 to 20/1 from the viewpoint that the effects of both nitric acid and the other electrolyte are obtained in a balanced manner. Is preferred.
前記硝酸類と前記他の電解質との組み合わせにおいて、硝酸類が硝酸塩の場合、すなわち、硝酸塩の少なくとも１つと他の電解質の少なくとも１つとを組み合わせて用いる場合、該硝酸塩と該他の電解質との割合（硝酸塩／他の電解質（重量比））は、硝酸塩及び他の電解質双方の効果がバランスよく得られるという点から、０．０５／１〜２０／１程度、さらには０．０５／１〜１０／１程度であることが好ましい。 In the combination of the nitric acid and the other electrolyte, when the nitric acid is a nitrate, that is, when at least one of the nitrate and at least one of the other electrolytes are used in combination, the ratio of the nitrate to the other electrolyte (Nitrate/other electrolyte (weight ratio)) is about 0.05/1 to 20/1, and more preferably 0.05/1 to 10 from the viewpoint that the effects of both nitrate and other electrolyte are obtained in a well-balanced manner. It is preferably about /1.
さらに、硝酸と硝酸塩の少なくとも１つとを組み合わせて用いる場合、該硝酸と該硝酸塩との割合（硝酸／硝酸塩（重量比））は、硝酸及び硝酸塩双方の効果がバランスよく得られるという点から、０．２／１〜１０／１程度、さらには０．５／１〜５／１程度であることが好ましい。なお、硝酸塩の少なくとも２つを組み合わせて用いる場合は、用いる硝酸塩の種類に応じて適宜割合を調整することが好ましい。 Furthermore, when nitric acid and at least one of the nitrates are used in combination, the ratio of the nitric acid to the nitrate (nitric acid/nitrate (weight ratio)) is 0 from the viewpoint that the effects of both nitric acid and nitrate can be obtained in a well-balanced manner. It is preferably about 2/1 to 10/1, and more preferably about 0.5/1 to 5/1. When at least two nitrates are used in combination, it is preferable to adjust the ratio appropriately according to the type of nitrate used.
本発明の電気銅メッキ又は銅合金メッキ浴には、前記２種以上の電解質の他に、例えば、１種以上の銅イオン供給化合物が配合される。 In the electrolytic copper plating or copper alloy plating bath of the present invention, for example, one or more kinds of copper ion supplying compounds are blended in addition to the above two or more kinds of electrolytes.
前記銅イオン供給化合物は、基本的に水溶液中でＣｕ２＋を発生させる銅可溶性塩であればよく、特に限定がない。該銅イオン供給化合物としては、例えば、硫酸銅、酸化銅、硝酸銅、塩化銅、ピロリン酸銅、炭酸銅の他に、酢酸銅、シュウ酸銅、クエン酸銅等のカルボン酸銅塩；メタンスルホン酸銅、ヒドロキシエタンスルホン酸銅等のアルキルスルホン酸銅塩等が挙げられ、これらの中から１種以上を用いることができる。 The copper ion supply compound is basically any copper-soluble salt capable of generating Cu 2+ in an aqueous solution, and is not particularly limited. Examples of the copper ion supply compound include copper sulfate, copper oxide, copper nitrate, copper chloride, copper pyrophosphate, and copper carbonate, as well as carboxylic acid copper salts such as copper acetate, copper oxalate, and copper citrate; methane; Examples thereof include copper alkyl sulfonates such as copper sulfonate and copper hydroxyethane sulfonate, and at least one of them can be used.
本発明の電気銅メッキ浴における前記銅イオン供給化合物の含有量は、特に限定がないが、１ｇ／Ｌ〜３００ｇ／Ｌ程度、さらには３０ｇ／Ｌ〜２５０ｇ／Ｌ程度であることが好ましい。 The content of the copper ion supply compound in the electrolytic copper plating bath of the present invention is not particularly limited, but is preferably about 1 g/L to 300 g/L, and more preferably about 30 g/L to 250 g/L.
本発明のメッキ浴が電気銅メッキ浴の場合には、前記銅イオン供給化合物を配合すればよいが、電気銅合金メッキ浴の場合には、銅と共に合金を生成する金属の可溶性塩も１種以上配合すればよい。 When the plating bath of the present invention is an electrolytic copper plating bath, the above-mentioned copper ion supply compound may be blended, but in the case of an electrolytic copper alloy plating bath, a soluble salt of a metal which forms an alloy with copper is also one The above may be blended.
前記銅と共に合金を生成する金属には特に限定がなく、例えば、銀、亜鉛、ニッケル、ビスマス、コバルト、インジウム、アンチモン、スズ、金、鉛等が挙げられる。 The metal that forms an alloy with copper is not particularly limited, and examples thereof include silver, zinc, nickel, bismuth, cobalt, indium, antimony, tin, gold, and lead.
銀の可溶性塩としては、例えば、炭酸銀、硝酸銀、酢酸銀、塩化銀、酸化銀、シアン化銀、シアン化銀カリウム、メタンスルホン酸銀、２−ヒドロキシエタンスルホン酸銀、２−ヒドロキシプロパンスルホン酸銀等が挙げられる。 Examples of the soluble salt of silver include silver carbonate, silver nitrate, silver acetate, silver chloride, silver oxide, silver cyanide, potassium cyanide, silver methanesulfonate, silver 2-hydroxyethanesulfonate, and 2-hydroxypropanesulfone. Examples thereof include silver acid salt.
亜鉛の可溶性塩としては、例えば、酸化亜鉛、硫酸亜鉛、硝酸亜鉛、塩化亜鉛、ピロリン酸亜鉛、シアン化亜鉛、メタンスルホン酸亜鉛、２−ヒドロキシエタンスルホン酸亜鉛、２−ヒドロキシプロパンスルホン酸亜鉛等が挙げられる。 Examples of soluble salts of zinc include zinc oxide, zinc sulfate, zinc nitrate, zinc chloride, zinc pyrophosphate, zinc cyanide, zinc methanesulfonate, zinc 2-hydroxyethanesulfonate, zinc 2-hydroxypropanesulfonate and the like. Is mentioned.
ニッケルの可溶性塩としては、例えば、硫酸ニッケル、ギ酸ニッケル、塩化ニッケル、スルファミン酸ニッケル、ホウフッ化ニッケル、酢酸ニッケル、メタンスルホン酸ニッケル、２−ヒドロキシプロパンスルホン酸ニッケル等が挙げられる。 Examples of the soluble salt of nickel include nickel sulfate, nickel formate, nickel chloride, nickel sulfamate, nickel borofluoride, nickel acetate, nickel methanesulfonate, nickel 2-hydroxypropanesulfonate and the like.
ビスマスの可溶性塩としては、例えば、硫酸ビスマス、グルコン酸ビスマス、硝酸ビスマス、酸化ビスマス、炭酸ビスマス、塩化ビスマス、メタンスルホン酸ビスマス、２−ヒドロキシプロパンスルホン酸ビスマス等が挙げられる。 Examples of the soluble salt of bismuth include bismuth sulfate, bismuth gluconate, bismuth nitrate, bismuth oxide, bismuth carbonate, bismuth chloride, bismuth methanesulfonate, and bismuth 2-hydroxypropanesulfonate.
コバルトの可溶性塩としては、例えば、硫酸コバルト、塩化コバルト、酢酸コバルト、ホウフッ化コバルト、メタンスルホン酸コバルト、２−ヒドロキシプロパンスルホン酸コバルト等が挙げられる。 Examples of the soluble cobalt salt include cobalt sulfate, cobalt chloride, cobalt acetate, cobalt borofluoride, cobalt methanesulfonate, and cobalt 2-hydroxypropanesulfonate.
インジウムの可溶性塩としては、例えば、スルファミン酸インジウム、硫酸インジウム、ホウフッ化インジウム、酸化インジウム、メタンスルホン酸インジウム、２−ヒドロキシプロパンスルホン酸インジウム等が挙げられる。 Examples of the soluble salt of indium include indium sulfamate, indium sulfate, indium borofluoride, indium oxide, indium methanesulfonate, indium 2-hydroxypropanesulfonate and the like.
アンチモンの可溶性塩としては、例えば、ホウフッ化アンチモン、塩化アンチモン、酒石酸アンチモニルカリウム、ピロアンチモン酸カリウム、酒石酸アンチモン、メタンスルホン酸アンチモン、２−ヒドロキシプロパンスルホン酸アンチモン等が挙げられる。 Examples of the soluble salt of antimony include antimony borofluoride, antimony chloride, potassium antimonyl tartrate, potassium pyroantimonate, antimony tartrate, antimony methanesulfonate, antimony 2-hydroxypropanesulfonate, and the like.
スズの可溶性塩としては、例えば、硫酸第一スズ、酢酸第一スズ、ホウフッ化第一スズ、スルファミン酸第一スズ、ピロリン酸第一スズ、塩化第一スズ、グルコン酸第一スズ、酒石酸第一スズ、酸化第一スズ、スズ酸ナトリウム、スズ酸カリウム、メタンスルホン酸第一スズ、エタンスルホン酸第一スズ、２−ヒドロキシエタンスルホン酸第一スズ、２−ヒドロキシプロパンスルホン酸第一スズ、スルホコハク酸第一スズ等が挙げられる。 Examples of the soluble salt of tin include stannous sulfate, stannous acetate, stannous borofluoride, stannous sulfamate, stannous pyrophosphate, stannous chloride, stannous gluconate, and stannous tartrate. Stannous, stannous oxide, sodium stannate, potassium stannate, stannous methanesulfonate, stannous ethanesulfonate, stannous 2-hydroxyethanesulfonate, stannous 2-hydroxypropanesulfonate, Stannous sulfosuccinate etc. are mentioned.
金の可溶性塩としては、例えば、塩化金酸カリウム、塩化金酸ナトリウム、塩化金酸アンモニウム、亜硫酸金カリウム、亜硫酸金ナトリウム、亜硫酸金アンモニウム、チオ硫酸金カリウム、チオ硫酸金ナトリウム、チオ硫酸金アンモニウム等が挙げられる。 Examples of the soluble salts of gold include potassium chloroaurate, sodium chloroaurate, ammonium chloroaurate, potassium gold sulfite, sodium gold sulfite, ammonium gold sulfite, potassium gold thiosulfate, sodium gold thiosulfate, and ammonium gold thiosulfate. Etc.
鉛の可溶性塩としては、例えば、酢酸鉛、硝酸鉛、炭酸鉛、ホウフッ化鉛、スルファミン酸鉛、メタンスルホン酸鉛、エタンスルホン酸鉛、２−ヒドロキシエタンスルホン酸鉛、２−ヒドロキシプロパンスルホン酸鉛等が挙げられる。 Examples of the soluble salt of lead include lead acetate, lead nitrate, lead carbonate, lead borofluoride, lead sulfamate, lead methanesulfonate, lead ethanesulfonate, lead 2-hydroxyethanesulfonate, and 2-hydroxypropanesulfonate. Lead etc. are mentioned.
本発明の電気銅合金メッキ浴における、前記銅イオン供給化合物及び前記銅と共に合金を生成する金属の可溶性塩の合計含有量は、特に限定がないが、１ｇ／Ｌ〜２００ｇ／Ｌ程度、さらには１０ｇ／Ｌ〜１５０ｇ／Ｌ程度であることが好ましい。 In the electrolytic copper alloy plating bath of the present invention, the total content of the soluble salt of the metal that forms an alloy together with the copper ion supply compound and the copper is not particularly limited, but about 1 g/L to 200 g/L, and further It is preferably about 10 g/L to 150 g/L.
前記銅イオン供給化合物と、前記銅と共に合金を生成する金属の可溶性塩との組み合わせ及び割合には、特に限定がなく、本発明の電気銅合金メッキ浴から形成される電着物が所望の組成となるように、両化合物の組み合わせ及び割合を適宜調整すればよい。 The combination and ratio of the copper ion supply compound and the soluble salt of a metal that forms an alloy together with the copper are not particularly limited, and the electrodeposit formed from the electrolytic copper alloy plating bath of the present invention has a desired composition. Therefore, the combination and ratio of both compounds may be adjusted appropriately.
本発明の電気銅メッキ又は銅合金メッキ浴には、前記２種以上の電解質、並びに、前記１種以上の銅イオン供給化合物及び前記１種以上の銅と共に合金を生成する金属の可溶性塩の他に、例えば促進剤、高分子界面活性剤、レベラー等の各種添加剤を配合することができる。 In the electrolytic copper plating or copper alloy plating bath of the present invention, other than the two or more kinds of electrolytes, and the one or more kinds of copper ion-supplying compounds and the one or more kinds of soluble salts of metals that form an alloy with copper, Various additives such as accelerators, polymer surfactants, and levelers can be added to the composition.
前記促進剤は、メッキ析出において成長核の生成を促進する成分である。該促進剤としては、例えば、ビス（３−スルホプロピル）ジスルフィド（別名：３，３’−ジチオビス（１−プロパンスルホン酸））、ビス（２−スルホプロピル）ジスルフィド、ビス（３−スル−２−ヒドロキシプロピル）ジスルフィド、ビス（４−スルホプロピル）ジスルフィド、ビス（ｐ−スルホフェニル）ジスルフィド、３−ベンゾチアゾリル−２−チオ）プロパンスルホン酸、Ｎ，Ｎ−ジメチル−ジチオカルバミルプロパンスルホン酸、Ｎ，Ｎ−ジメチル−ジチオカルバミルプロパンスルホン酸、Ｎ，Ｎ−ジメチル−ジチオカルバミン酸−（３−スルホプロピル）−エステル、３−［（アミノイミノメチル）チオ］−１−プロパンスルホン酸、ｏ−エチル−ジエチル炭酸−Ｓ−（３−スルホプロピル）エステル、メルカプトメタンスルホン酸、メルカプトエタンスルホン酸、メルカプトプロパンスルホン酸、これらの塩等を用いることができる。 The promoter is a component that promotes the generation of growth nuclei during plating deposition. Examples of the accelerator include bis(3-sulfopropyl)disulfide (also known as 3,3′-dithiobis(1-propanesulfonic acid)), bis(2-sulfopropyl)disulfide and bis(3-sul-2). -Hydroxypropyl)disulfide, bis(4-sulfopropyl)disulfide, bis(p-sulfophenyl)disulfide, 3-benzothiazolyl-2-thio)propanesulfonic acid, N,N-dimethyl-dithiocarbamylpropanesulfonic acid, N , N-Dimethyl-dithiocarbamylpropanesulfonic acid, N,N-dimethyl-dithiocarbamic acid-(3-sulfopropyl)-ester, 3-[(aminoiminomethyl)thio]-1-propanesulfonic acid, o-ethyl -Diethyl carbonic acid-S-(3-sulfopropyl) ester, mercaptomethanesulfonic acid, mercaptoethanesulfonic acid, mercaptopropanesulfonic acid, salts thereof and the like can be used.
前記高分子界面活性剤としては、特にノニオン系界面活性剤が好ましく、例えば、ポリエチレングリコール、ポリプロピレングリコール、プルロニック型界面活性剤、テトロニック型界面活性剤、ポリエチレングリコール・グリセリルエーテル、スルホン酸基含有ポリアルキレンオキシド付加型アミン類、ノニオン性ポリエーテル系高分子界面活性剤等を用いることができる。 As the polymer surfactant, a nonionic surfactant is particularly preferable, and examples thereof include polyethylene glycol, polypropylene glycol, pluronic type surfactant, tetronic type surfactant, polyethylene glycol/glyceryl ether, and sulfonic acid group-containing poly Alkylene oxide addition type amines, nonionic polyether-based polymer surfactants and the like can be used.
前記レベラー（平滑化剤）は、電着抑制の機能を有し、電着皮膜を平滑にする作用を呈する。該レベラーは、例えば、アミン類、染料、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、ピリジン類、キノリン類、イソキノリン類、アニリン類、アミノカルボン酸類等から選択されることが好ましい。 The leveler (smoothing agent) has a function of suppressing electrodeposition and exhibits an effect of smoothing the electrodeposition coating. The leveler is preferably selected from amines, dyes, imidazolines, imidazoles, benzimidazoles, indoles, pyridines, quinolines, isoquinolines, anilines, aminocarboxylic acids and the like.
前記アミン類としては、スルホン酸基含有アルキレンオキシド付加型アミン類が好ましい。該スルホン酸基含有アルキレンオキシド付加型アミン類は、アルキレンオキシドが付加しているので、前記のとおり、高分子界面活性剤に分類されるが、アミン類として分類することもでき、レベラーとして有効である。 As the amines, sulfonic acid group-containing alkylene oxide addition type amines are preferable. The sulfonic acid group-containing alkylene oxide addition-type amines are classified as polymer surfactants as described above because alkylene oxide is added, but they can be classified as amines and are effective as a leveler. is there.
レベラーとして有効な、前記アミン類以外のその他の含窒素有機化合物の具体例としては、例えば、Ｃ．Ｉ．（Ｃｏｌｏｒ Ｉｎｄｅｘ）ベーシックレッド２、トルイジンブルー等のトルイジン系染料、Ｃ．Ｉ．ダイレクトイエロー１、Ｃ．Ｉ．ベーシックブラック２等のアゾ系染料、３−アミノ−６−ジメチルアミノ−２−メチルフェナジン１塩酸等のフェナジン系染料、ポリエチレンイミン、ジアリルアミンとアリルグアニジンメタンスルホン酸塩の共重合物、テトラメチルエチレンジアミンのＥＯ及び／又はＰＯ付加物、コハク酸イミド、２’−ビス（２−イミダゾリン）等のイミダゾリン類、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、フェナントロリン等のピリジン類、キノリン類、イソキノリン類、アニリン、３，３’，３”−ニトリロ３プロピオン酸、ジアミノメチレンアミノ酢酸等が挙げられる。これらの中でも、Ｃ．Ｉ．ベーシックレッド２等のトルイジン染料、Ｃ．Ｉ．ダイレクトイエロー１等のアゾ染料、３−アミノ−６−ジメチルアミノ−２−メチルフェナジン１塩酸等のフェナジン系染料、ポリエチレンイミン、ジアリルアミンとアリルグアニジンメタンスルホン酸塩との共重合物、テトラメチルエチレンジアミンのＥＯ及びＰＯ付加物、２’−ビス（２−イミダゾリン）等のイミダゾリン類、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、フェナントロリン等のピリジン類、キノリン類、アニリン類、並びにアミノメチレンアミノ酢酸等のアミノカルボン酸類が好ましい。 Specific examples of other nitrogen-containing organic compounds other than the amines which are effective as a leveler include C.I. I. (Color Index) Basic Red 2, toluidine dyes such as toluidine blue, C.I. I. Direct Yellow 1, C.I. I. Azo dyes such as Basic Black 2, phenazine dyes such as 3-amino-6-dimethylamino-2-methylphenazine 1 hydrochloric acid, polyethyleneimine, copolymers of diallylamine and allylguanidine methanesulfonate, tetramethylethylenediamine EO and/or PO adducts, succinimide, imidazolines such as 2'-bis(2-imidazoline), imidazoles, benzimidazoles, indoles, 2-vinylpyridine, 4-acetylpyridine, 4-mercapto- Pyridines such as 2-carboxylpyridine, 2,2′-bipyridyl and phenanthroline, quinolines, isoquinolines, aniline, 3,3′,3″-nitrilo-3propionic acid, diaminomethyleneaminoacetic acid and the like can be mentioned. Among them, toluidine dyes such as CI Basic Red 2, azo dyes such as CI Direct Yellow 1, phenazine dyes such as 3-amino-6-dimethylamino-2-methylphenazine 1 hydrochloric acid, polyethyleneimine, Copolymers of diallylamine and allylguanidine methanesulfonate, EO and PO adducts of tetramethylethylenediamine, imidazolines such as 2'-bis(2-imidazoline), benzimidazoles, 2-vinylpyridine, 4-acetyl Pyridines such as pyridine, 2,2′-bipyridyl, phenanthroline, quinolines, anilines, and aminocarboxylic acids such as aminomethyleneaminoacetic acid are preferable.
本発明の電気銅メッキ又は銅合金メッキ浴における前記各種添加剤の含有量は、特に限定がなく、該メッキ浴から目的とする電着物が形成されるように適宜調整すればよい。 The content of each of the various additives in the electrolytic copper plating or copper alloy plating bath of the present invention is not particularly limited, and may be appropriately adjusted so that the intended electrodeposit is formed from the plating bath.
本発明の電気銅メッキ又は銅合金メッキ浴は、硝酸及び硝酸塩の少なくとも１つを含む２種以上の電解質と、必要に応じて、これら硝酸類以外の、硝酸以外の酸、塩化物、硫酸塩、炭酸塩、リン酸塩、酢酸塩、及び過塩素酸塩から選ばれた少なくとも１種の電解質、１種以上の銅イオン供給化合物、１種以上の銅と共に合金を生成する金属の可溶性塩、各種添加剤等とを適宜配合して、建浴することができる。 The electrolytic copper plating or copper alloy plating bath of the present invention comprises two or more kinds of electrolytes containing at least one of nitric acid and nitrate, and if necessary, acids other than nitric acid, chlorides and sulfates other than nitric acid. A soluble salt of a metal which forms an alloy with at least one electrolyte selected from carbonates, phosphates, acetates, and perchlorates, one or more copper ion supply compounds, one or more copper, A bath can be prepared by appropriately mixing various additives and the like.
本発明の電気銅メッキ又は銅合金メッキ浴を用い、電気メッキにより所望の電着物を形成することができる。該電着物は、例えば、突起電極、電着皮膜等である。これらの電着物は、例えば、ウエハ、基板、リードフレーム等に形成され得る。 Using the electrolytic copper plating or copper alloy plating bath of the present invention, a desired electrodeposit can be formed by electroplating. The electrodeposit is, for example, a bump electrode, an electrodeposition coating or the like. These electrodeposits can be formed on, for example, a wafer, a substrate, a lead frame, or the like.
本発明の電気銅メッキ又は銅合金メッキ浴を用いることにより、高アスペクトの突起電極群（銅柱又は銅合金柱）を、高速でかつ均一な高さに形成することができる。該銅柱又は銅合金柱は、例えば、５μｍ以上、さらには３０μｍ〜４００μｍの高さに形成されることが好ましい。 By using the electrolytic copper plating or copper alloy plating bath of the present invention, a high aspect projection electrode group (copper pillar or copper alloy pillar) can be formed at a high speed and at a uniform height. The copper columns or copper alloy columns are preferably formed to have a height of, for example, 5 μm or more, further 30 μm to 400 μm.
また、本発明の電気銅メッキ又は銅合金メッキ浴を用いることにより、電着皮膜を、高速でかつ均一な厚さに形成することができ、例えばビアホールの充填では、ボイドの発生を円滑に防止することができる。 Further, by using the electrolytic copper plating or copper alloy plating bath of the present invention, the electrodeposition film can be formed at a high speed and with a uniform thickness. For example, in filling a via hole, the occurrence of voids can be prevented smoothly. can do.
前記電着物が形成される電子部品としては、例えば、ガラス基板、シリコン基板、サファイア基板、ウエハ、プリント配線板、半導体集積回路、抵抗、可変抵抗、コンデンサ、フィルタ、インダクタ、サーミスタ、水晶振動子、スイッチ、リード線、太陽電池等が挙げられる。本発明の電気銅メッキ又は銅合金メッキ浴を用いることにより、前記高アスペクトの突起電極群（銅柱又は銅合金柱）を、例えばＳｉＰ型、ＦＯＷＬＰ型、ＦＯＰＬＰ型、ＳｏＣ型、ＰｏＰ型等の電子部品に、特に、パッケージ面積を縮小した３次元構造のＰｏＰ型の半導体部品等の電子部品に、高速でかつ均一な高さに形成することができる。 Examples of electronic components on which the electrodeposit is formed include glass substrates, silicon substrates, sapphire substrates, wafers, printed wiring boards, semiconductor integrated circuits, resistors, variable resistors, capacitors, filters, inductors, thermistors, crystal oscillators, Examples include switches, lead wires, and solar cells. By using the electrolytic copper plating or copper alloy plating bath of the present invention, the high aspect projection electrode group (copper pillar or copper alloy pillar) can be formed into, for example, SiP type, FOWLP type, FOPLP type, SoC type, PoP type, etc. It is possible to form an electronic component at a high speed and at a uniform height, particularly in an electronic component such as a PoP type semiconductor component having a three-dimensional structure with a reduced package area.
本発明の電気銅メッキ又は銅合金メッキ浴を用いて電気メッキを行う際には、例えば、バレルメッキ、ラックメッキ、高速連続メッキ、ラックレスメッキ、カップメッキ、ディップメッキ等の各種メッキ方式を採用することができる。 When performing electroplating using the electrolytic copper plating or copper alloy plating bath of the present invention, various plating methods such as barrel plating, rack plating, high-speed continuous plating, rackless plating, cup plating, dip plating are adopted. can do.
電気メッキの条件には特に限定がないが、例えば、浴温は０℃以上、さらには１０℃〜５０℃程度であることが好ましい。陰極電流密度は、０．００１Ａ／ｄｍ２〜１００Ａ／ｄｍ２程度、さらには０．０１Ａ／ｄｍ２〜４０Ａ／ｄｍ２程度であることが好ましい。 The conditions for electroplating are not particularly limited, but for example, the bath temperature is preferably 0°C or higher, and more preferably about 10°C to 50°C. Cathode current density, 0.001A / dm 2 ~100A / dm 2 about, and more preferably from 0.01A / dm 2 ~40A / dm 2 about.
前記電気メッキの後に、析出した銅又は銅合金を、必要に応じてリフローして、目的とする突起電極、電着皮膜等の電着物を形成することができる。 After the electroplating, the deposited copper or copper alloy can be reflowed, if necessary, to form a desired electrodeposited product such as a protruding electrode or an electrodeposition coating.
以下、本発明の電気銅メッキ又は銅合金メッキ浴の実施例、該実施例で得られたメッキ浴を用いて突起電極群を形成した製造例、並びに、該製造例で得られた突起電極群についての、異常析出の発生頻度及び高さの均一性の評価試験例を順次記載する。 Hereinafter, examples of the electrolytic copper plating or copper alloy plating bath of the present invention, a production example in which a projection electrode group is formed using the plating bath obtained in the example, and a projection electrode group obtained in the production example The following describes the evaluation test examples of occurrence frequency of abnormal precipitation and uniformity of height.
しかしながら、本発明は、前記実施例、製造例、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で任意の変形をなし得ることは勿論である。 However, it is needless to say that the present invention is not limited to the above-described Examples, Production Examples, and Test Examples, and can be arbitrarily modified within the scope of the technical idea of the present invention.
≪電気銅メッキ又は銅合金メッキ浴の実施例≫
下記実施例１〜２１のうち、実施例１〜８及び実施例１１〜２１は、電気銅メッキ浴の例であり、実施例９〜１０は、電気銅−銀合金メッキ浴の例である。
<<Examples of electrolytic copper plating or copper alloy plating bath>>
Of the following Examples 1 to 21, Examples 1 to 8 and Examples 11 to 21 are examples of electrolytic copper plating baths, and Examples 9 to 10 are examples of electrolytic copper-silver alloy plating baths.
また、比較例１〜３は、電解質として硝酸及び硝酸塩の少なくとも１つを含まないブランク例である。 Further, Comparative Examples 1 to 3 are blank examples that do not contain at least one of nitric acid and nitrate as an electrolyte.
（１）実施例１
下記組成で電気銅メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
硫酸銅五水和物（Ｃｕ２＋として）：５０ｇ／Ｌ
硫酸（遊離酸として）：１００ｇ／Ｌ
硝酸：５０ｇ／Ｌ
塩酸（塩化物イオンとして）：５０ｍｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：１０ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１０００）：１００ｍｇ／Ｌ
［メッキ条件］
浴温：３０℃
陰極電流密度：１０Ａ／ｄｍ２
メッキ時間：約６５００秒
(1) Example 1
An electrolytic copper plating bath having the following composition was constructed. The plating conditions are also shown.
[composition]
Copper sulfate pentahydrate (as Cu 2+ ): 50 g/L
Sulfuric acid (as free acid): 100 g/L
Nitric acid: 50 g/L
Hydrochloric acid (as chloride ion): 50 mg/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 10 mg/L
Polyethylene glycol (average molecular weight 1000): 100 mg/L
[Plating conditions]
Bath temperature: 30℃
Cathode current density: 10 A/dm 2
Plating time: about 6500 seconds
（２）実施例２
下記組成で電気銅メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
硫酸銅五水和物（Ｃｕ２＋として）：６０ｇ／Ｌ
硫酸（遊離酸として）：８０ｇ／Ｌ
硝酸：５０ｇ／Ｌ
塩酸（塩化物イオンとして）：５０ｍｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：３０ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１００００）：２００ｍｇ／Ｌ
［メッキ条件］
浴温：３０℃
陰極電流密度：１５Ａ／ｄｍ２
メッキ時間：約４３５０秒
(2) Example 2
An electrolytic copper plating bath having the following composition was constructed. The plating conditions are also shown.
[composition]
Copper sulfate pentahydrate (as Cu 2+ ): 60 g/L
Sulfuric acid (as free acid): 80 g/L
Nitric acid: 50 g/L
Hydrochloric acid (as chloride ion): 50 mg/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 30 mg/L
Polyethylene glycol (average molecular weight 10,000): 200 mg/L
[Plating conditions]
Bath temperature: 30℃
Cathode current density: 15 A/dm 2
Plating time: about 4350 seconds
（３）実施例３
下記組成で電気銅メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
酸化銅（Ｃｕ２＋として）：７０ｇ／Ｌ
硫酸：１１０ｇ／Ｌ
硝酸：１４０ｇ／Ｌ
塩酸（塩化物イオンとして）：５０ｍｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：３０ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１００００）：２００ｍｇ／Ｌ
［メッキ条件］
浴温：３０℃
陰極電流密度：１５Ａ／ｄｍ２
メッキ時間：約４３５０秒
(3) Example 3
An electrolytic copper plating bath having the following composition was constructed. The plating conditions are also shown.
[composition]
Copper oxide (as Cu 2+ ): 70 g/L
Sulfuric acid: 110 g/L
Nitric acid: 140 g/L
Hydrochloric acid (as chloride ion): 50 mg/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 30 mg/L
Polyethylene glycol (average molecular weight 10,000): 200 mg/L
[Plating conditions]
Bath temperature: 30℃
Cathode current density: 15 A/dm 2
Plating time: about 4350 seconds
（４）実施例４
下記組成で電気銅メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
酸化銅（Ｃｕ２＋として）：７０ｇ／Ｌ
硫酸：１１０ｇ／Ｌ
硝酸：１４０ｇ／Ｌ
塩酸（塩化物イオンとして）：５０ｍｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：３０ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１００００）：２００ｍｇ／Ｌ
［メッキ条件］
浴温：３５℃
陰極電流密度：２０Ａ／ｄｍ２
メッキ時間：約３２５０秒
(4) Example 4
An electrolytic copper plating bath having the following composition was constructed. The plating conditions are also shown.
[composition]
Copper oxide (as Cu 2+ ): 70 g/L
Sulfuric acid: 110 g/L
Nitric acid: 140 g/L
Hydrochloric acid (as chloride ion): 50 mg/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 30 mg/L
Polyethylene glycol (average molecular weight 10,000): 200 mg/L
[Plating conditions]
Bath temperature: 35°C
Cathode current density: 20 A/dm 2
Plating time: about 3250 seconds
（５）実施例５
下記組成で電気銅メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
酸化銅（Ｃｕ２＋として）：６０ｇ／Ｌ
メタンスルホン酸：１１０ｇ／Ｌ
硝酸：１２０ｇ／Ｌ
塩酸（塩化物イオンとして）：５０ｍｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：３０ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１００００）：２００ｍｇ／Ｌ
［メッキ条件］
浴温：３５℃
陰極電流密度：１５Ａ／ｄｍ２
メッキ時間：約４３５０秒
(5) Example 5
An electrolytic copper plating bath having the following composition was constructed. The plating conditions are also shown.
[composition]
Copper oxide (as Cu 2+ ): 60 g/L
Methanesulfonic acid: 110 g/L
Nitric acid: 120 g/L
Hydrochloric acid (as chloride ion): 50 mg/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 30 mg/L
Polyethylene glycol (average molecular weight 10,000): 200 mg/L
[Plating conditions]
Bath temperature: 35°C
Cathode current density: 15 A/dm 2
Plating time: about 4350 seconds
（６）実施例６
下記組成で電気銅メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
酸化銅（Ｃｕ２＋として）：７０ｇ／Ｌ
硫酸：１１０ｇ／Ｌ
硝酸：１４０ｇ／Ｌ
塩酸（塩化物イオンとして）：５０ｍｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：３０ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１００００）：１５０ｍｇ／Ｌ
［メッキ条件］
浴温：４０℃
陰極電流密度：３５Ａ／ｄｍ２
メッキ時間：約１８５０秒
(6) Example 6
An electrolytic copper plating bath having the following composition was constructed. The plating conditions are also shown.
[composition]
Copper oxide (as Cu 2+ ): 70 g/L
Sulfuric acid: 110 g/L
Nitric acid: 140 g/L
Hydrochloric acid (as chloride ion): 50 mg/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 30 mg/L
Polyethylene glycol (average molecular weight 10,000): 150 mg/L
[Plating conditions]
Bath temperature: 40°C
Cathode current density: 35 A/dm 2
Plating time: about 1850 seconds
（７）実施例７
下記組成で電気銅メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
硝酸銅（Ｃｕ２＋として）：６０ｇ／Ｌ
硫酸：１１０ｇ／Ｌ
塩酸（塩化物イオンとして）：５０ｍｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：３０ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１００００）：２００ｍｇ／Ｌ
［メッキ条件］
浴温：３５℃
陰極電流密度：１５Ａ／ｄｍ２
メッキ時間：約４３５０秒
(7) Example 7
An electrolytic copper plating bath having the following composition was constructed. The plating conditions are also shown.
[composition]
Copper nitrate (as Cu 2+ ): 60 g/L
Sulfuric acid: 110 g/L
Hydrochloric acid (as chloride ion): 50 mg/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 30 mg/L
Polyethylene glycol (average molecular weight 10,000): 200 mg/L
[Plating conditions]
Bath temperature: 35°C
Cathode current density: 15 A/dm 2
Plating time: about 4350 seconds
（８）実施例８
下記組成で電気銅メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
硫酸銅五水和物（Ｃｕ２＋として）：６０ｇ／Ｌ
硫酸（遊離酸として）：８０ｇ／Ｌ
硝酸：５０ｇ／Ｌ
塩酸（塩化物イオンとして）：８０ｍｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：３０ｍｇ／Ｌ
２，２’−ビピリジル：３ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１００００）：１５０ｍｇ／Ｌ
［メッキ条件］
浴温：４０℃
陰極電流密度：４０Ａ／ｄｍ２
メッキ時間：約１６３０秒
(8) Example 8
An electrolytic copper plating bath having the following composition was constructed. The plating conditions are also shown.
[composition]
Copper sulfate pentahydrate (as Cu 2+ ): 60 g/L
Sulfuric acid (as free acid): 80 g/L
Nitric acid: 50 g/L
Hydrochloric acid (as chloride ion): 80 mg/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 30 mg/L
2,2'-bipyridyl: 3 mg/L
Polyethylene glycol (average molecular weight 10,000): 150 mg/L
[Plating conditions]
Bath temperature: 40°C
Cathode current density: 40 A/dm 2
Plating time: about 1630 seconds
（９）実施例９
下記組成で電気銅−銀合金メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
酸化銅（Ｃｕ２＋として）：７０ｇ／Ｌ
硫酸：１１０ｇ／Ｌ
硝酸：１４０ｇ／Ｌ
塩酸（塩化物イオンとして）：５０ｍｇ／Ｌ
炭酸銀（Ａｇ＋として）：０．１ｇ／Ｌ
１−（２−ジメチルアミノエチル）−５−メルカプトテトラゾール（錯化剤として）
：０．２ｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：３０ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１００００）：１５０ｍｇ／Ｌ
［メッキ条件］
浴温：３０℃
陰極電流密度：１５Ａ／ｄｍ２
メッキ時間：約４３５０秒
(9) Example 9
An electrolytic copper-silver alloy plating bath was constructed with the following composition. The plating conditions are also shown.
[composition]
Copper oxide (as Cu 2+ ): 70 g/L
Sulfuric acid: 110 g/L
Nitric acid: 140 g/L
Hydrochloric acid (as chloride ion): 50 mg/L
Silver carbonate (as Ag + ): 0.1 g/L
1-(2-dimethylaminoethyl)-5-mercaptotetrazole (as complexing agent)
: 0.2 g/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 30 mg/L
Polyethylene glycol (average molecular weight 10,000): 150 mg/L
[Plating conditions]
Bath temperature: 30℃
Cathode current density: 15 A/dm 2
Plating time: about 4350 seconds
（１０）実施例１０
下記組成で電気銅−銀合金メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
硫酸銅五水和物（Ｃｕ２＋として）：６０ｇ／Ｌ
硫酸（遊離酸として）：８０ｇ／Ｌ
硝酸：５０ｇ／Ｌ
塩酸（塩化物イオンとして）：５０ｍｇ／Ｌ
炭酸銀（Ａｇ＋として）：０．１ｇ／Ｌ
１−（２−ジメチルアミノエチル）−５−メルカプトテトラゾール（錯化剤として）
：０．２ｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：３０ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１００００）：１５０ｍｇ／Ｌ
［メッキ条件］
浴温：３０℃
陰極電流密度：１０Ａ／ｄｍ２
メッキ時間：約６５００秒
(10) Example 10
An electrolytic copper-silver alloy plating bath was constructed with the following composition. The plating conditions are also shown.
[composition]
Copper sulfate pentahydrate (as Cu 2+ ): 60 g/L
Sulfuric acid (as free acid): 80 g/L
Nitric acid: 50 g/L
Hydrochloric acid (as chloride ion): 50 mg/L
Silver carbonate (as Ag + ): 0.1 g/L
1-(2-dimethylaminoethyl)-5-mercaptotetrazole (as complexing agent)
: 0.2 g/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 30 mg/L
Polyethylene glycol (average molecular weight 10,000): 150 mg/L
[Plating conditions]
Bath temperature: 30℃
Cathode current density: 10 A/dm 2
Plating time: about 6500 seconds
（１１）実施例１１
下記組成で電気銅メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
硫酸銅五水和物（Ｃｕ２＋として）：５０ｇ／Ｌ
炭酸銅（Ｃｕ２＋として）：１０ｇ／Ｌ
硫酸（遊離酸として）：１００ｇ／Ｌ
硝酸：５０ｇ／Ｌ
塩酸（塩化物イオンとして）：５０ｍｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：１０ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１０００）：１００ｍｇ／Ｌ
［メッキ条件］
浴温：３０℃
陰極電流密度：１０Ａ／ｄｍ２
メッキ時間：約６５００秒
(11) Example 11
An electrolytic copper plating bath having the following composition was constructed. The plating conditions are also shown.
[composition]
Copper sulfate pentahydrate (as Cu 2+ ): 50 g/L
Copper carbonate (as Cu 2+ ): 10 g/L
Sulfuric acid (as free acid): 100 g/L
Nitric acid: 50 g/L
Hydrochloric acid (as chloride ion): 50 mg/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 10 mg/L
Polyethylene glycol (average molecular weight 1000): 100 mg/L
[Plating conditions]
Bath temperature: 30℃
Cathode current density: 10 A/dm 2
Plating time: about 6500 seconds
（１２）実施例１２
下記組成で電気銅メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
硫酸銅五水和物（Ｃｕ２＋として）：５０ｇ／Ｌ
酢酸銅一水和物（Ｃｕ２＋として）：１０ｇ／Ｌ
硫酸（遊離酸として）：１００ｇ／Ｌ
硝酸：５０ｇ／Ｌ
塩酸（塩化物イオンとして）：５０ｍｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：１０ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１０００）：１００ｍｇ／Ｌ
［メッキ条件］
浴温：３０℃
陰極電流密度：１０Ａ／ｄｍ２
メッキ時間：約６５００秒
(12) Example 12
An electrolytic copper plating bath having the following composition was constructed. The plating conditions are also shown.
[composition]
Copper sulfate pentahydrate (as Cu 2+ ): 50 g/L
Copper acetate monohydrate (as Cu 2+ ): 10 g/L
Sulfuric acid (as free acid): 100 g/L
Nitric acid: 50 g/L
Hydrochloric acid (as chloride ion): 50 mg/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 10 mg/L
Polyethylene glycol (average molecular weight 1000): 100 mg/L
[Plating conditions]
Bath temperature: 30℃
Cathode current density: 10 A/dm 2
Plating time: about 6500 seconds
（１３）実施例１３
下記組成で電気銅メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
硫酸銅五水和物（Ｃｕ２＋として）：５０ｇ／Ｌ
硫酸（遊離酸として）：１００ｇ／Ｌ
硝酸：５０ｇ／Ｌ
リン酸：２０ｇ／Ｌ
塩酸（塩化物イオンとして）：５０ｍｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：１０ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１０００）：１００ｍｇ／Ｌ
［メッキ条件］
浴温：３０℃
陰極電流密度：１０Ａ／ｄｍ２
メッキ時間：約６５００秒
(13) Example 13
An electrolytic copper plating bath having the following composition was constructed. The plating conditions are also shown.
[composition]
Copper sulfate pentahydrate (as Cu 2+ ): 50 g/L
Sulfuric acid (as free acid): 100 g/L
Nitric acid: 50 g/L
Phosphoric acid: 20 g/L
Hydrochloric acid (as chloride ion): 50 mg/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 10 mg/L
Polyethylene glycol (average molecular weight 1000): 100 mg/L
[Plating conditions]
Bath temperature: 30℃
Cathode current density: 10 A/dm 2
Plating time: about 6500 seconds
（１４）実施例１４
下記組成で電気銅メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
硝酸銅（Ｃｕ２＋として）：５０ｇ／Ｌ
炭酸銅（Ｃｕ２＋として）：１０ｇ／Ｌ
硫酸：１１０ｇ／Ｌ
塩酸（塩化物イオンとして）：５０ｍｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：３０ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１００００）：２００ｍｇ／Ｌ
［メッキ条件］
浴温：３５℃
陰極電流密度：１５Ａ／ｄｍ２
メッキ時間：約４３５０秒
(14) Example 14
An electrolytic copper plating bath having the following composition was constructed. The plating conditions are also shown.
[composition]
Copper nitrate (as Cu 2+ ): 50 g/L
Copper carbonate (as Cu 2+ ): 10 g/L
Sulfuric acid: 110 g/L
Hydrochloric acid (as chloride ion): 50 mg/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 30 mg/L
Polyethylene glycol (average molecular weight 10,000): 200 mg/L
[Plating conditions]
Bath temperature: 35°C
Cathode current density: 15 A/dm 2
Plating time: about 4350 seconds
（１５）実施例１５
下記組成で電気銅メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
硝酸銅（Ｃｕ２＋として）：６０ｇ／Ｌ
酢酸銅一水和物（Ｃｕ２＋として）：１０ｇ／Ｌ
硫酸：１１０ｇ／Ｌ
塩酸（塩化物イオンとして）：５０ｍｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：３０ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１００００）：２００ｍｇ／Ｌ
［メッキ条件］
浴温：３５℃
陰極電流密度：１５Ａ／ｄｍ２
メッキ時間：約４３５０秒
(15) Example 15
An electrolytic copper plating bath having the following composition was constructed. The plating conditions are also shown.
[composition]
Copper nitrate (as Cu 2+ ): 60 g/L
Copper acetate monohydrate (as Cu 2+ ): 10 g/L
Sulfuric acid: 110 g/L
Hydrochloric acid (as chloride ion): 50 mg/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 30 mg/L
Polyethylene glycol (average molecular weight 10,000): 200 mg/L
[Plating conditions]
Bath temperature: 35°C
Cathode current density: 15 A/dm 2
Plating time: about 4350 seconds
（１６）実施例１６
下記組成で電気銅メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
硝酸銅（Ｃｕ２＋として）：６０ｇ／Ｌ
硝酸銀（Ａｇ＋として）：０．１ｇ／Ｌ
硫酸（遊離酸として）：１００ｇ／Ｌ
塩酸（塩化物イオンとして）：５０ｍｇ／Ｌ
１−（２−ジメチルアミノエチル）−５−メルカプトテトラゾール（錯化剤として）
：０．２ｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：１０ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１０００）：１００ｍｇ／Ｌ
［メッキ条件］
浴温：３０℃
陰極電流密度：１０Ａ／ｄｍ２
メッキ時間：約６５００秒
(16) Example 16
An electrolytic copper plating bath having the following composition was constructed. The plating conditions are also shown.
[composition]
Copper nitrate (as Cu 2+ ): 60 g/L
Silver nitrate (as Ag + ): 0.1 g/L
Sulfuric acid (as free acid): 100 g/L
Hydrochloric acid (as chloride ion): 50 mg/L
1-(2-dimethylaminoethyl)-5-mercaptotetrazole (as complexing agent)
: 0.2 g/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 10 mg/L
Polyethylene glycol (average molecular weight 1000): 100 mg/L
[Plating conditions]
Bath temperature: 30℃
Cathode current density: 10 A/dm 2
Plating time: about 6500 seconds
（１７）実施例１７
下記組成で電気銅メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
硝酸銅（Ｃｕ２＋として）：１０ｇ／Ｌ
硝酸ニッケル六水和物（Ｎｉ＋として）：２０ｇ／Ｌ
硫酸（遊離酸として）：１００ｇ／Ｌ
塩酸（塩化物イオンとして）：５０ｍｇ／Ｌ
マロン酸（錯化剤として）：７５ｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：１０ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１０００）：１００ｍｇ／Ｌ
［メッキ条件］
浴温：３０℃
陰極電流密度：１０Ａ／ｄｍ２
メッキ時間：約６５００秒
(17) Example 17
An electrolytic copper plating bath having the following composition was constructed. The plating conditions are also shown.
[composition]
Copper nitrate (as Cu 2+ ): 10 g/L
Nickel nitrate hexahydrate (as Ni + ): 20 g/L
Sulfuric acid (as free acid): 100 g/L
Hydrochloric acid (as chloride ion): 50 mg/L
Malonic acid (as complexing agent): 75 g/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 10 mg/L
Polyethylene glycol (average molecular weight 1000): 100 mg/L
[Plating conditions]
Bath temperature: 30℃
Cathode current density: 10 A/dm 2
Plating time: about 6500 seconds
（１８）実施例１８
下記組成で電気銅メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
硝酸銅（Ｃｕ２＋として）：６０ｇ／Ｌ
硫酸（遊離酸として）：１００ｇ／Ｌ
硝酸：５０ｇ／Ｌ
塩酸（塩化物イオンとして）：５０ｍｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：１０ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１０００）：１００ｍｇ／Ｌ
［メッキ条件］
浴温：３０℃
陰極電流密度：１０Ａ／ｄｍ２
メッキ時間：約６５００秒
(18) Example 18
An electrolytic copper plating bath having the following composition was constructed. The plating conditions are also shown.
[composition]
Copper nitrate (as Cu 2+ ): 60 g/L
Sulfuric acid (as free acid): 100 g/L
Nitric acid: 50 g/L
Hydrochloric acid (as chloride ion): 50 mg/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 10 mg/L
Polyethylene glycol (average molecular weight 1000): 100 mg/L
[Plating conditions]
Bath temperature: 30℃
Cathode current density: 10 A/dm 2
Plating time: about 6500 seconds
（１９）実施例１９
下記組成で電気銅メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
硝酸銅（Ｃｕ２＋として）：６０ｇ／Ｌ
硫酸（遊離酸として）：１００ｇ／Ｌ
硝酸：１００ｇ／Ｌ
塩酸（塩化物イオンとして）：５０ｍｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：１０ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１０００）：１００ｍｇ／Ｌ
［メッキ条件］
浴温：３０℃
陰極電流密度：１０Ａ／ｄｍ２
メッキ時間：約６５００秒
(19) Example 19
An electrolytic copper plating bath having the following composition was constructed. The plating conditions are also shown.
[composition]
Copper nitrate (as Cu 2+ ): 60 g/L
Sulfuric acid (as free acid): 100 g/L
Nitric acid: 100 g/L
Hydrochloric acid (as chloride ion): 50 mg/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 10 mg/L
Polyethylene glycol (average molecular weight 1000): 100 mg/L
[Plating conditions]
Bath temperature: 30℃
Cathode current density: 10 A/dm 2
Plating time: about 6500 seconds
（２０）実施例２０
下記組成で電気銅メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
硝酸銅（Ｃｕ２＋として）：５０ｇ／Ｌ
炭酸銅（Ｃｕ２＋として）：１０ｇ／Ｌ
硫酸（遊離酸として）：１００ｇ／Ｌ
硝酸：５０ｇ／Ｌ
塩酸（塩化物イオンとして）：５０ｍｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：１０ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１０００）：１００ｍｇ／Ｌ
［メッキ条件］
浴温：３０℃
陰極電流密度：１０Ａ／ｄｍ２
メッキ時間：約６５００秒
(20) Example 20
An electrolytic copper plating bath having the following composition was constructed. The plating conditions are also shown.
[composition]
Copper nitrate (as Cu 2+ ): 50 g/L
Copper carbonate (as Cu 2+ ): 10 g/L
Sulfuric acid (as free acid): 100 g/L
Nitric acid: 50 g/L
Hydrochloric acid (as chloride ion): 50 mg/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 10 mg/L
Polyethylene glycol (average molecular weight 1000): 100 mg/L
[Plating conditions]
Bath temperature: 30℃
Cathode current density: 10 A/dm 2
Plating time: about 6500 seconds
（２１）実施例２１
下記組成で電気銅メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
硝酸銅（Ｃｕ２＋として）：５０ｇ／Ｌ
炭酸銅（Ｃｕ２＋として）：１０ｇ／Ｌ
硫酸（遊離酸として）：１００ｇ／Ｌ
硝酸：１００ｇ／Ｌ
塩酸（塩化物イオンとして）：５０ｍｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：１０ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１０００）：１００ｍｇ／Ｌ
［メッキ条件］
浴温：３０℃
陰極電流密度：１０Ａ／ｄｍ２
メッキ時間：約６５００秒
(21) Example 21
An electrolytic copper plating bath having the following composition was constructed. The plating conditions are also shown.
[composition]
Copper nitrate (as Cu 2+ ): 50 g/L
Copper carbonate (as Cu 2+ ): 10 g/L
Sulfuric acid (as free acid): 100 g/L
Nitric acid: 100 g/L
Hydrochloric acid (as chloride ion): 50 mg/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 10 mg/L
Polyethylene glycol (average molecular weight 1000): 100 mg/L
[Plating conditions]
Bath temperature: 30℃
Cathode current density: 10 A/dm 2
Plating time: about 6500 seconds
（２２）比較例１
下記組成で電気銅メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
硫酸銅五水和物（Ｃｕ２＋として）：５０ｇ／Ｌ
硫酸（遊離酸として）：１００ｇ／Ｌ
塩酸（塩化物イオンとして）：５０ｍｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：１０ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１０００）：１００ｍｇ／Ｌ
［メッキ条件］
浴温：３０℃
陰極電流密度：１０Ａ／ｄｍ２
メッキ時間：約６５００秒
(22) Comparative Example 1
An electrolytic copper plating bath having the following composition was constructed. The plating conditions are also shown.
[composition]
Copper sulfate pentahydrate (as Cu 2+ ): 50 g/L
Sulfuric acid (as free acid): 100 g/L
Hydrochloric acid (as chloride ion): 50 mg/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 10 mg/L
Polyethylene glycol (average molecular weight 1000): 100 mg/L
[Plating conditions]
Bath temperature: 30℃
Cathode current density: 10 A/dm 2
Plating time: about 6500 seconds
（２３）比較例２
下記組成で電気銅メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
酸化銅（Ｃｕ２＋として）：６０ｇ／Ｌ
メタンスルホン酸（遊離酸として）：１１０ｇ／Ｌ
塩酸（塩化物イオンとして）：５０ｍｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：３０ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１００００）：２００ｍｇ／Ｌ
［メッキ条件］
浴温：３５℃
陰極電流密度：１５Ａ／ｄｍ２
メッキ時間：約４３５０秒
(23) Comparative Example 2
An electrolytic copper plating bath having the following composition was constructed. The plating conditions are also shown.
[composition]
Copper oxide (as Cu 2+ ): 60 g/L
Methanesulfonic acid (as free acid): 110 g/L
Hydrochloric acid (as chloride ion): 50 mg/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 30 mg/L
Polyethylene glycol (average molecular weight 10,000): 200 mg/L
[Plating conditions]
Bath temperature: 35°C
Cathode current density: 15 A/dm 2
Plating time: about 4350 seconds
（２４）比較例３
下記組成で電気銅−銀合金メッキ浴を建浴した。また、メッキ条件も併せて示す。
［組成］
硫酸銅五水和物（Ｃｕ２＋として）：６０ｇ／Ｌ
硫酸（遊離酸として）：８０ｇ／Ｌ
塩酸（塩化物イオンとして）：５０ｍｇ／Ｌ
炭酸銀（Ａｇ＋として）：０．１ｇ／Ｌ
１−（２−ジメチルアミノエチル）−５−メルカプトテトラゾール（錯化剤として）
：０．２ｇ／Ｌ
３，３’−ジチオビス（１−プロパンスルホン酸）２ナトリウム：３０ｍｇ／Ｌ
ポリエチレングリコール（平均分子量１００００）：１５０ｍｇ／Ｌ
［メッキ条件］
浴温：３０℃
陰極電流密度：１０Ａ／ｄｍ２
メッキ時間：約６５００秒
(24) Comparative Example 3
An electrolytic copper-silver alloy plating bath was constructed with the following composition. The plating conditions are also shown.
[composition]
Copper sulfate pentahydrate (as Cu 2+ ): 60 g/L
Sulfuric acid (as free acid): 80 g/L
Hydrochloric acid (as chloride ion): 50 mg/L
Silver carbonate (as Ag + ): 0.1 g/L
1-(2-dimethylaminoethyl)-5-mercaptotetrazole (as complexing agent)
: 0.2 g/L
3,3′-Dithiobis(1-propanesulfonic acid) disodium: 30 mg/L
Polyethylene glycol (average molecular weight 10,000): 150 mg/L
[Plating conditions]
Bath temperature: 30℃
Cathode current density: 10 A/dm 2
Plating time: about 6500 seconds
次に、実施例１〜８、実施例１１〜２１、及び比較例１〜２の電気銅メッキ浴、並びに、実施例９〜１０及び比較例３の電気銅−銀合金メッキ浴を用いて、多数の突起電極（突起電極群）を形成し、突起電極の異常析出の発生頻度及び高さの均一性を評価した。 Next, using the electrolytic copper plating baths of Examples 1-8, Examples 11-21, and Comparative Examples 1-2, and the electrolytic copper-silver alloy plating baths of Examples 9-10 and Comparative Example 3, A large number of projection electrodes (projection electrode group) were formed, and the occurrence frequency of abnormal precipitation and the uniformity of height of the projection electrodes were evaluated.
≪突起電極群を形成した製造例≫
実施例１〜８、実施例１１〜２１、及び比較例１〜２の電気銅メッキ浴、並びに、実施例９〜１０及び比較例３の電気銅−銀合金メッキ浴を用いて、各メッキ条件にて電気メッキを行い、シリコン基板上に突起電極群（銅柱又は銅−銀合金柱、高さ：約２４０μｍ、個数：約５０００個）を形成した。
<<Production example in which bump electrode group is formed>>
Using the electrolytic copper plating baths of Examples 1-8, Examples 11-21, and Comparative Examples 1-2, and the electrolytic copper-silver alloy plating baths of Examples 9-10 and Comparative Example 3, each plating condition was used. Electroplating was performed to form a group of protruding electrodes (copper pillars or copper-silver alloy pillars, height: about 240 μm, number: about 5000 pieces) on a silicon substrate.
≪突起電極の異常析出の発生頻度の評価試験例≫
形成した突起電極群について、異常（ヤケ被膜、塗布したレジスト上に突出するように異常成長した突起電極、及び突起電極表面で瘤状に小さく突出した異常成長）の有無を観測し、異常が認められた突起電極数を計測した。下記式（ａ）にしたがって異常析出割合Ａ（％）を算出し、異常析出の発生頻度を、下記評価基準に基づいて定量評価した。
Ａ（％）＝［Ｎ（ａｂｎ）／Ｎ（ａｌｌ）］×１００ （ａ）
Ｎ（ａｂｎ）：異常が認められた突起電極数
Ｎ（ａｌｌ）：総突起電極数
［評価基準］
○：Ａが１％未満であった。
△：Ａが１％以上であり、５％未満であった。
×：Ａが５％以上であった。
<<Example of evaluation test of occurrence frequency of abnormal deposition of bump electrodes>>
Abnormality was recognized by observing the formed protruding electrode group for abnormalities (burnt coating, protruding electrode that abnormally grew so as to project on the applied resist, and abnormal growth that protruded in a bump shape on the protruding electrode surface). The number of protruding electrodes thus formed was measured. The abnormal precipitation rate A (%) was calculated according to the following formula (a), and the occurrence frequency of abnormal precipitation was quantitatively evaluated based on the following evaluation criteria.
A(%)=[N(abn)/N(all)]×100 (a)
N(abn): Number of protruding electrodes where abnormality was recognized N(all): Total number of protruding electrodes [Evaluation criteria]
◯: A was less than 1%.
Δ: A was 1% or more and less than 5%.
X: A was 5% or more.
≪突起電極の高さの均一性の評価試験例≫
形成した突起電極群について、各突起電極の高さを計測した。下記式（ｂ）にしたがってＷＩＤ（％）を算出し、高さの均一性を定量評価した。
ＷＩＤ（％）＝［（最大高さ−最小高さ）／平均高さ］×１／２×１００ （ｂ）
<<Example of evaluation test of height uniformity of bump electrodes>>
The height of each protruding electrode of the formed protruding electrode group was measured. WID (%) was calculated according to the following formula (b), and the uniformity of height was quantitatively evaluated.
WID (%)=[(maximum height-minimum height)/average height]×1/2×100 (b)
下記表１に、前記突起電極の異常析出の発生頻度及び高さの均一性についての評価試験の結果を示す。 Table 1 below shows the results of the evaluation test for the occurrence frequency and the height uniformity of the abnormal deposition of the bump electrodes.
前記表１に示す結果より、以下のことが分かる。 From the results shown in Table 1, the following can be seen.
比較例１は、本発明の電気銅メッキ又は銅合金メッキ浴に配合される硝酸類を含まないブランク例であり、この比較例１と実施例１〜２とを比較すると、実施例１〜２では、突起電極の高さの均一性が大幅に改善されていることが確認できる。 Comparative Example 1 is a blank example containing no nitric acid to be mixed in the electrolytic copper plating or copper alloy plating bath of the present invention. When Comparative Example 1 and Examples 1 and 2 are compared, Examples 1 and 2 are obtained. Then, it can be confirmed that the uniformity of the height of the bump electrode is significantly improved.
前記製造例では、約２４０μｍの高さの銅柱又は銅−銀合金柱を形成しており、１％の高さのバラツキは、約５μｍの膜厚差となる。接合時の信頼性を考慮した場合に、この膜厚差はできる限り小さい方が望ましく、実施例１〜２と比較例１とを比較すると、両者の差は顕著なものである。 In the above-mentioned manufacturing example, copper columns or copper-silver alloy columns having a height of about 240 μm are formed, and a variation of 1% in height results in a film thickness difference of about 5 μm. Considering the reliability at the time of joining, it is desirable that this film thickness difference be as small as possible, and comparing Examples 1 and 2 with Comparative Example 1, the difference between the two is remarkable.
また、比較例１のように、１０Ａ／ｄｍ２の陰極電流密度で約２４０μｍの高さの銅柱を形成した場合には、約６５００秒のメッキ時間が必要となる。これに対して、実施例６では、メッキ時間が約１８５０秒に短縮されており、本発明の電気銅メッキ又は銅合金メッキ浴を用いることで、高速メッキが可能となり、生産性の大幅な向上が期待できる。 Further, when a copper column having a height of about 240 μm is formed at a cathode current density of 10 A/dm 2 as in Comparative Example 1, a plating time of about 6500 seconds is required. On the other hand, in Example 6, the plating time was shortened to about 1850 seconds, and by using the electrolytic copper plating or copper alloy plating bath of the present invention, high-speed plating became possible and the productivity was greatly improved. Can be expected.
実施例３〜４では、硝酸を配合することで、高濃度の酸と銅イオンとの併用が実現されている。また実施例１１〜１３では、硝酸及び他の電解質を配合することで、実施例１４〜１５では、硝酸塩及び他の電解質を配合することで、高濃度の酸と銅イオンとの併用が実現されている。これに対して、比較例１のように、硝酸類を配合することなく、従来一般に使用されている硫酸を配合した場合には、高濃度の酸と銅イオンとの併用を実現することはできない。 In Examples 3 and 4, by using nitric acid, the combined use of high-concentration acid and copper ion was realized. Further, in Examples 11 to 13, by blending nitric acid and other electrolytes, and in Examples 14 to 15, by blending nitrates and other electrolytes, a high concentration of acid and copper ions can be used in combination. ing. On the other hand, as in Comparative Example 1, when sulfuric acid which is generally used in the past is blended without blending nitric acid, it is not possible to realize the combined use of a high concentration of acid and copper ion. ..
さらに、実施例１８〜１９では、硝酸と硝酸塩とを併用することで、実施例２０〜２１では、硝酸と硝酸塩とを併用し、他の電解質も配合することで、高濃度の酸と銅イオンとの併用が実現されており、併せて突起電極の高さの均一性も大幅に改善されていることが確認できる。 Furthermore, in Examples 18 to 19, by using nitric acid and nitrate together, in Examples 20 to 21, by using nitric acid and nitrate together, and by adding other electrolytes, high concentration of acid and copper ion It can be confirmed that the height uniformity of the protruding electrodes is also significantly improved in combination with the above.
同様に、比較例２のように、従来一般に使用されているメタンスルホン酸を配合し、高濃度の酸と銅イオンとの両立が試みられているが、高速メッキを行うと、異常析出が確認される。 Similarly, as in Comparative Example 2, it has been attempted to mix methanesulfonic acid, which has been generally used conventionally, to achieve both high-concentration acid and copper ions. However, when high-speed plating is performed, abnormal precipitation is confirmed. To be done.
ところが、実施例５のように、硝酸類とメタンスルホン酸とを併用した場合には、比較例２と同じメッキ時間の高速メッキであっても、前記のごとき異常析出を防ぐことが可能である。 However, when nitric acid and methanesulfonic acid are used in combination as in Example 5, it is possible to prevent abnormal precipitation as described above even with high-speed plating having the same plating time as in Comparative Example 2. ..
なお、実施例８のように、硝酸類を含む電解質と適切なレベラー成分とを組み合わせることで、より高速かつ高い均一性を達成することができる。 As in Example 8, by combining an electrolyte containing nitric acid with an appropriate leveler component, higher speed and higher uniformity can be achieved.
比較例３は、本発明の電気銅メッキ又は銅合金メッキ浴に配合される硝酸類を含まないブランク例であり、この比較例３と実施例９〜１０とを比較すると、実施例９〜１０では、突起電極の異常析出及び高さの均一性の改善、並びに、高速メッキについての有効性が確認できる。 Comparative Example 3 is a blank example containing no nitric acid to be mixed in the electrolytic copper plating or copper alloy plating bath of the present invention. When Comparative Example 3 and Examples 9 to 10 are compared, Examples 9 to 10 are compared. Then, it is possible to confirm the abnormal deposition of the bump electrodes, the improvement of the height uniformity, and the effectiveness of high-speed plating.
本発明の電気銅メッキ又は銅合金メッキ浴は、例えばＳｉＰ型、ＦＯＷＬＰ型、ＦＯＰＬＰ型、ＳｏＣ型、ＰｏＰ型等の各種電子部品、特にパッケージ面積を縮小した３次元構造のＰｏＰ型の半導体部品等の各種電子部品への電着物の形成に、効果的に利用することができる。 The electrolytic copper plating or copper alloy plating bath of the present invention is used for various electronic components such as SiP type, FOWLP type, FOPLP type, SoC type, and PoP type, particularly, PoP type semiconductor components having a three-dimensional structure with a reduced package area. Can be effectively used for forming an electrodeposit on various electronic components.
Claims (12)
前記電解質は、硝酸及び硝酸塩の少なくとも１つを含む、電気銅メッキ又は銅合金メッキ浴。 Two or more kinds of electrolytes are mixed,
The electrolyte is electrolytic copper plating or copper alloy plating bath containing at least one of nitric acid and nitrate.
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