JP2023176435A - Electroless nickel-phosphorus plating bath for electroless silver plating and method for applying electroless silver plating on sulfur compound-free nickel plating - Google Patents
Electroless nickel-phosphorus plating bath for electroless silver plating and method for applying electroless silver plating on sulfur compound-free nickel plating Download PDFInfo
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- JP2023176435A JP2023176435A JP2022088711A JP2022088711A JP2023176435A JP 2023176435 A JP2023176435 A JP 2023176435A JP 2022088711 A JP2022088711 A JP 2022088711A JP 2022088711 A JP2022088711 A JP 2022088711A JP 2023176435 A JP2023176435 A JP 2023176435A
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- Prior art keywords
- plating
- nickel
- electroless
- bath
- phosphorus
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- 238000007747 plating Methods 0.000 title claims abstract description 302
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 71
- 239000004332 silver Substances 0.000 title claims abstract description 71
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 51
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title abstract description 86
- 229910052759 nickel Inorganic materials 0.000 title abstract description 37
- 229910052717 sulfur Inorganic materials 0.000 title abstract description 17
- 239000011593 sulfur Substances 0.000 title abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 91
- 239000002184 metal Substances 0.000 claims abstract description 91
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229910018104 Ni-P Inorganic materials 0.000 description 112
- 229910018536 Ni—P Inorganic materials 0.000 description 112
- 238000005260 corrosion Methods 0.000 description 16
- 230000007797 corrosion Effects 0.000 description 16
- 238000007654 immersion Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- 239000003381 stabilizer Substances 0.000 description 15
- 239000000654 additive Substances 0.000 description 14
- 239000003638 chemical reducing agent Substances 0.000 description 14
- 239000008139 complexing agent Substances 0.000 description 14
- -1 nickel fluoroborate Chemical compound 0.000 description 12
- 229910001453 nickel ion Inorganic materials 0.000 description 12
- 229910000679 solder Inorganic materials 0.000 description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 239000012190 activator Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000005476 soldering Methods 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 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 1
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- XXSPKSHUSWQAIZ-UHFFFAOYSA-L 36026-88-7 Chemical compound [Ni+2].[O-]P=O.[O-]P=O XXSPKSHUSWQAIZ-UHFFFAOYSA-L 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- RZDZTERVDXYFJM-UHFFFAOYSA-L S(=O)(=O)(O)C(C(=O)[O-])CC(=O)[O-].[Ag+2] Chemical compound S(=O)(=O)(O)C(C(=O)[O-])CC(=O)[O-].[Ag+2] RZDZTERVDXYFJM-UHFFFAOYSA-L 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MFIHOCAEOJNSOL-UHFFFAOYSA-N [Ag]C#N Chemical class [Ag]C#N MFIHOCAEOJNSOL-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229940053195 antiepileptics hydantoin derivative Drugs 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 1
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- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
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- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- GQZXNSPRSGFJLY-UHFFFAOYSA-N hydroxyphosphanone Chemical compound OP=O GQZXNSPRSGFJLY-UHFFFAOYSA-N 0.000 description 1
- 229940005631 hypophosphite ion Drugs 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 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
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical group 0.000 description 1
- FYWSTUCDSVYLPV-UHFFFAOYSA-N nitrooxythallium Chemical compound [Tl+].[O-][N+]([O-])=O FYWSTUCDSVYLPV-UHFFFAOYSA-N 0.000 description 1
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- HKSGQTYSSZOJOA-UHFFFAOYSA-N potassium argentocyanide Chemical compound [K+].[Ag+].N#[C-].N#[C-] HKSGQTYSSZOJOA-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000011347 resin Chemical class 0.000 description 1
- 229920005989 resin Chemical class 0.000 description 1
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 description 1
- 229940082569 selenite Drugs 0.000 description 1
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical compound [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 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
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- WYCFMBAHFPUBDS-UHFFFAOYSA-L silver sulfite Chemical compound [Ag+].[Ag+].[O-]S([O-])=O WYCFMBAHFPUBDS-UHFFFAOYSA-L 0.000 description 1
- LMEWRZSPCQHBOB-UHFFFAOYSA-M silver;2-hydroxypropanoate Chemical compound [Ag+].CC(O)C([O-])=O LMEWRZSPCQHBOB-UHFFFAOYSA-M 0.000 description 1
- TZMGLOFLKLBEFW-UHFFFAOYSA-M silver;sulfamate Chemical compound [Ag+].NS([O-])(=O)=O TZMGLOFLKLBEFW-UHFFFAOYSA-M 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 150000003498 tellurium compounds Chemical class 0.000 description 1
- 150000003476 thallium compounds Chemical class 0.000 description 1
- YTQVHRVITVLIRD-UHFFFAOYSA-L thallium sulfate Chemical compound [Tl+].[Tl+].[O-]S([O-])(=O)=O YTQVHRVITVLIRD-UHFFFAOYSA-L 0.000 description 1
- 229940119523 thallium sulfate Drugs 0.000 description 1
- 229910000374 thallium(I) sulfate Inorganic materials 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
Images
Abstract
Description
本発明は、無電解銀めっき用無電解ニッケル－リンめっき浴、及び、硫黄化合物を含まないニッケルめっき上への無電解銀めっきを施す方法に関する。 The present invention relates to an electroless nickel-phosphorus plating bath for electroless silver plating, and a method for electroless silver plating on nickel plating that does not contain sulfur compounds.
特許文献1は、無電解ニッケルめっきを施す工程及び銀めっきを施す工程を含む金属表面を処理する方法において、無電解ニッケルめっき溶液が0.0005重量%～0.1重量%の硫黄を含む方法を開示する。 Patent Document 1 discloses a method for treating a metal surface including a step of applying electroless nickel plating and a step of applying silver plating, in which the electroless nickel plating solution contains 0.0005% to 0.1% by weight of sulfur.
本発明は、新たに、硫黄化合物を含まないニッケルめっき上への無電解銀めっきを施す方法を提供する事を目的とする。 An object of the present invention is to provide a new method for electroless silver plating on nickel plating that does not contain sulfur compounds.
本発明者は、鋭意検討した結果、無電解銀めっき用無電解ニッケル－リンめっき浴は、硫黄化合物を含まない事に依り、金属表面に、先ず、無電解銀めっき用無電解ニッケル－リンめっき浴を用いて無電解ニッケルめっきを施し、次いで、前記ニッケルめっきが施された金属表面に、無電解銀めっきを施すと、ニッケル腐食が減少した為、ニッケル（Ni）めっきと銀（Ag）めっきとの間の密着性が良好であり、はんだ濡れ性や焼結銀による接合性も良好になるという技術を開発した。 As a result of extensive studies, the inventor of the present invention discovered that the electroless nickel-phosphorus plating bath for electroless silver plating does not contain sulfur compounds. When electroless nickel plating was applied using a bath, and then electroless silver plating was applied to the nickel-plated metal surface, nickel corrosion was reduced, so nickel (Ni) plating and silver (Ag) plating were applied. We have developed a technology that provides good adhesion between the metal and the metal, and also improves solder wettability and bondability with sintered silver.
即ち、本発明は、次の無電解銀めっき用無電解ニッケル－リンめっき浴、及び、硫黄化合物を含まないニッケルめっき上への無電解銀めっきを施す方法を包含する。 That is, the present invention includes the following electroless nickel-phosphorus plating bath for electroless silver plating, and a method for electroless silver plating on nickel plating that does not contain sulfur compounds.
項１．
無電解銀めっき用無電解ニッケル－リンめっき浴であって、
ニッケル－リン皮膜中に硫黄化合物を含まない、無電解銀めっき用無電解ニッケル－リンめっき浴。
Item 1.
An electroless nickel-phosphorus plating bath for electroless silver plating,
Electroless nickel-phosphorus plating bath for electroless silver plating that does not contain sulfur compounds in the nickel-phosphorus film.
項２．
金属表面を処理する方法であって、
（1）金属表面に、無電解銀めっき用無電解ニッケル－リンめっき浴を用いて無電解ニッケル－リンめっきを施す工程、及び
（2）前記ニッケル－リンめっきが施された金属表面に、無電解銀めっきを施す工程
を含み、
前記無電解銀めっき用無電解ニッケル－リンめっき浴は、硫黄化合物を含まない、
方法。
Item 2.
A method of treating a metal surface, the method comprising:
(1) Applying electroless nickel-phosphorus plating to the metal surface using an electroless nickel-phosphorus plating bath for electroless silver plating, and (2) Applying electroless nickel-phosphorus plating to the metal surface that has been subjected to the nickel-phosphorus plating. Including the process of applying electrolytic silver plating,
The electroless nickel-phosphorus plating bath for electroless silver plating does not contain sulfur compounds,
Method.
項３．
めっき皮膜の製造方法であって、
（1）金属表面に、無電解銀めっき用無電解ニッケル－リンめっき浴を用いて無電解ニッケル－リンめっきを施す工程、
を含み、
前記無電解銀めっき用無電解ニッケル－リンめっき浴は、硫黄化合物を含まない、
製造方法。
Item 3.
A method for producing a plating film, the method comprising:
(1) A process of applying electroless nickel-phosphorus plating to the metal surface using an electroless nickel-phosphorus plating bath for electroless silver plating,
including;
The electroless nickel-phosphorus plating bath for electroless silver plating does not contain sulfur compounds,
Production method.
項４．
更に、
（2）前記工程（1）の後、前記ニッケル－リンめっきが施された金属表面に、無電解銀めっきを施す工程、
を含む、
前記項３に記載のめっき皮膜の製造方法。
Item 4.
Furthermore,
(2) After the step (1), applying electroless silver plating to the metal surface that has been subjected to the nickel-phosphorus plating,
including,
The method for producing a plating film according to item 3 above.
項５．
前記項３又は４に記載の製造方法に依って得られるめっき皮膜。
Item 5.
A plating film obtained by the manufacturing method according to item 3 or 4 above.
本発明の無電解銀めっき用無電解ニッケル－リンめっき浴は、硫黄化合物を含まない事から、金属表面に、先ず、無電解銀めっき用無電解ニッケル-リンめっき浴を用いて無電解ニッケル-リンめっきを施し、次いで、前記ニッケル-リンめっきが施された金属表面に、無電解銀めっきを施すと、ニッケル腐食が減少した為、ニッケル（Ni）めっきと銀（Ag）めっきとの間の密着性が良好であり、はんだ濡れ性や焼結銀による接合性が良好になる。 Since the electroless nickel-phosphorus plating bath for electroless silver plating of the present invention does not contain sulfur compounds, the electroless nickel-phosphorus plating bath for electroless silver plating is first applied to the metal surface using the electroless nickel-phosphorus plating bath for electroless silver plating. When phosphor plating was applied and then electroless silver plating was applied to the nickel-phosphorus plated metal surface, nickel corrosion was reduced, so there was a difference between nickel (Ni) plating and silver (Ag) plating. Adhesion is good, and solder wettability and bondability with sintered silver are also good.
本発明は、新たに、硫黄化合物を含まないニッケルめっき上への無電解銀めっきを施す方法を提供する事が出来る。 The present invention can provide a new method for electroless silver plating on nickel plating that does not contain sulfur compounds.
以下に本発明を詳細に説明する。 The present invention will be explained in detail below.
本発明を表す実施の形態は、発明の趣旨がより良く理解出来る説明であり、特に指定のない限り、発明内容を限定するものではない。 The embodiments representing the present invention are explanations that enable a better understanding of the gist of the invention, and do not limit the content of the invention unless otherwise specified.
本明細書において、「含む」及び「含有」は、「含む（comprise）」、「実質的にのみから成る（consist essentially of）」、及び「のみから成る（consist of）」のいずれも包含する概念である。 As used herein, "comprise" and "containing" include "comprise," "consist essentially of," and "consist of." It is a concept.
本明細書において、数値範囲を「A～B」で示す場合、A以上B以下を意味する。 In this specification, when a numerical range is expressed as "A to B", it means from A to B.
［1］無電解銀めっき用無電解ニッケル－リンめっき浴
本発明の無電解銀めっき用無電解ニッケル－リンめっき浴（Ni-Pめっき浴）は、硫黄化合物を含まない。
[1] Electroless nickel-phosphorus plating bath for electroless silver plating The electroless nickel-phosphorus plating bath (Ni-P plating bath) for electroless silver plating of the present invention does not contain sulfur compounds.
硫黄化合物（図1）
本発明のNi-Pめっき浴は、硫黄化合物を含まない。Ni-Pめっき浴が「硫黄化合物を含まない」は、添加剤として、「硫黄化合物を実質的に含まない」（硫黄フリー）事を含む。本発明は、Ni-Pめっき浴に、添加剤として硫黄化合物を実質的に含まない事に依り、硫黄フリーの無電解Ni-P皮膜を作成する事が出来る。
Sulfur compounds (Figure 1)
The Ni-P plating bath of the present invention does not contain sulfur compounds. When the Ni-P plating bath "does not contain sulfur compounds", it includes "substantially no sulfur compounds" (sulfur-free) as additives. The present invention makes it possible to create a sulfur-free electroless Ni-P film by substantially not containing a sulfur compound as an additive in the Ni-P plating bath.
「硫黄化合物」とは、無電解ニッケル－リンめっき（Ni-Pめっき）処理を行った際に、めっき皮膜中に硫黄が共析する性質を有する化合物を意味する。一方、硫酸ニッケル（硫酸イオン）やpH調整剤として用いられる硫酸は、めっき処理後に皮膜中に硫黄が共析する性質を有していない事から、本発明が表す「硫黄化合物」には該当しない。 The term "sulfur compound" refers to a compound that has the property of eutectoiding sulfur into a plating film when electroless nickel-phosphorus plating (Ni-P plating) is performed. On the other hand, nickel sulfate (sulfate ions) and sulfuric acid used as a pH adjuster do not fall under the category of "sulfur compounds" as defined in the present invention because they do not have the property of eutectoiding sulfur into the film after plating. .
硫黄化合物を「実質的に」含まないとは、無電解Ni-Pめっき浴を用いた場合に作成できる無電解ニッケル－リンめっき皮膜（Ni-Pめっき皮膜）皮膜中における硫黄含有率が0.0005質量%未満となる事を意味する。本発明では、無電解Ni-Pめっき浴に硫黄化合物が全く含まれない事のみを意味するものではない。 "Substantially" containing no sulfur compounds means that the sulfur content in the electroless nickel-phosphorus plating film (Ni-P plating film) that can be created using an electroless Ni-P plating bath is 0.0005 mass. It means less than %. The present invention does not only mean that the electroless Ni--P plating bath does not contain any sulfur compounds.
無電解Ni-Pめっき皮膜中における硫黄含有率は、燃焼法による炭素・硫黄分析装置等に依り測定する事が出来る。 The sulfur content in the electroless Ni-P plating film can be measured using a carbon/sulfur analyzer using a combustion method.
硫黄化合物は、例えば、促進剤として用いられるチオ硫酸又はその塩（例えば、ナトリウム塩等）、安定剤として用いられるチオ尿素等である。 Examples of the sulfur compound include thiosulfuric acid or a salt thereof (eg, sodium salt, etc.) used as a promoter, and thiourea used as a stabilizer.
本発明のNi-Pめっき浴は、硫黄化合物を含まない事から、金属表面に、先ず、Ni-Pめっき浴を用いて無電解ニッケル－リンめっき（以下「Ni-Pめっき」とも記す）を施し、次いで、前記ニッケル-リンめっきが施された金属表面に、無電解銀めっき（以下「Agめっき」とも記す）を施すと、ニッケル腐食が減少した為、Ni-PめっきとAgめっきとの間の密着性が良好となり、はんだ濡れ性や焼結銀による接合性も良好になる。 Since the Ni-P plating bath of the present invention does not contain sulfur compounds, first electroless nickel-phosphorus plating (hereinafter also referred to as "Ni-P plating") is applied to the metal surface using the Ni-P plating bath. Then, when electroless silver plating (hereinafter also referred to as "Ag plating") was applied to the metal surface that had been subjected to the nickel-phosphorus plating, nickel corrosion was reduced, so the difference between Ni-P plating and Ag plating was The adhesion between the two is good, and the solder wettability and bondability with sintered silver are also good.
ニッケルイオン源
本発明のNi-Pめっき浴は、好ましくは、ニッケルイオン源を含む。
Nickel Ion Source The Ni-P plating bath of the present invention preferably includes a nickel ion source.
ニッケルイオン源は、好ましくは、臭化ニッケル、フルオロホウ酸ニッケル、スルホン酸ニッケル、スルファミン酸ニッケル、アルキルスルホン酸ニッケル、硫酸ニッケル、塩化ニッケル、酢酸ニッケル、及び次亜リン酸ニッケルから成る群から選ばれる少なくとも1種のニッケルイオン源（ニッケル塩）である。ニッケルイオン源（ニッケル塩）は、より好ましくは、スルファミン酸ニッケル、硫酸ニッケル等である。 The nickel ion source is preferably selected from the group consisting of nickel bromide, nickel fluoroborate, nickel sulfonate, nickel sulfamate, nickel alkyl sulfonate, nickel sulfate, nickel chloride, nickel acetate, and nickel hypophosphite. At least one nickel ion source (nickel salt). The nickel ion source (nickel salt) is more preferably nickel sulfamate, nickel sulfate, or the like.
ニッケルイオン源は、これらのニッケルイオン源を1種単独で用いても良く、或は2種以上を混合（ブレンド）して用いても良い。 As the nickel ion source, one type of these nickel ion sources may be used alone, or two or more types may be mixed (blended) and used.
ニッケルイオンは、工程において酸化される化学還元剤の作用によって、Ni-Pめっき浴中でニッケルに還元される。触媒は、基材であっても基材上の金属表面であってもよく、これに依り、最終的に基材上にニッケルが析出すると同時に還元-酸化反応が生じることを可能とする。 Nickel ions are reduced to nickel in the Ni-P plating bath by the action of a chemical reducing agent that is oxidized in the process. The catalyst may be the substrate or a metal surface on the substrate, allowing the reduction-oxidation reaction to occur simultaneously with the final deposition of nickel on the substrate.
Ni-Pめっき浴におけるニッケルイオン源の濃度は、良好にNi-Pめっき皮膜を形成する上で、適宜調整する。Ni-Pめっき浴におけるニッケルイオン源の濃度は、ニッケル金属として、好ましくは、0.01g／L～100g／Lであり、より好ましくは、0.5g／L～50g／Lであり、更に好ましくは、1g／L～10g／Lである。Ni-Pめっき浴におけるニッケルイオン源の濃度を、ニッケル金属として、0.01g／L～100g／Lに調整する事に依り、析出速度は良好であり、Ni-Pめっき浴の安定性は良好である。 The concentration of the nickel ion source in the Ni-P plating bath is adjusted as appropriate to form a good Ni-P plating film. The concentration of the nickel ion source in the Ni-P plating bath is preferably 0.01 g/L to 100 g/L, more preferably 0.5 g/L to 50 g/L, still more preferably, as nickel metal. It is 1g/L to 10g/L. By adjusting the concentration of the nickel ion source in the Ni-P plating bath to 0.01g/L to 100g/L as nickel metal, the deposition rate is good and the stability of the Ni-P plating bath is good. be.
還元剤
本発明のNi-Pめっき浴は、好ましくは、還元剤を含む。
Reducing Agent The Ni-P plating bath of the present invention preferably contains a reducing agent.
還元剤は、好ましくは、ヒドリドホウ酸イオン、及び次亜リン酸イオンから成る群から選ばれる少なくとも1種の還元剤である。還元剤は、より好ましくは、次亜リン酸イオン等の次亜リン酸を用い、更に好ましくは、次亜リン酸ナトリウム等の次亜リン酸塩である。還元剤は、その他、好ましくは、水素化ホウ素ナトリウム、ジメチルアミンボラン、Ｎ－ジエチルアミンボラン、ヒドラジン、及び水素から成る群から選ばれる少なくとも1種の還元剤である。 The reducing agent is preferably at least one reducing agent selected from the group consisting of hydridoborate ions and hypophosphite ions. The reducing agent is more preferably hypophosphorous acid such as hypophosphite ion, and even more preferably a hypophosphite salt such as sodium hypophosphite. In addition, the reducing agent is preferably at least one reducing agent selected from the group consisting of sodium borohydride, dimethylamine borane, N-diethylamine borane, hydrazine, and hydrogen.
還元剤は、これらの還元剤を1種単独で用いても良く、或は2種以上を混合（ブレンド）して用いても良い。 As the reducing agent, these reducing agents may be used alone or in a mixture (blend) of two or more.
Ni-Pめっき浴における還元剤の濃度は、良好にNi-Pめっき皮膜を形成する上で、適宜調整する。Ni-Pめっき浴における還元剤（次亜リン酸、次亜リン酸塩、及びその水和物等）の濃度は、好ましくは、0.1g／L～100g／Lであり、より好ましくは、1g／L～50g／Lであり、更に好ましくは、5g／L～35g／Lである。Ni-Pめっき浴における還元剤の濃度を、0.1g／L～100g／Lに調整する事に依り、析出速度は良好であり、Ni-Pめっき浴の安定性は良好である。 The concentration of the reducing agent in the Ni-P plating bath is adjusted as appropriate to form a good Ni-P plating film. The concentration of the reducing agent (hypophosphorous acid, hypophosphite, its hydrate, etc.) in the Ni-P plating bath is preferably 0.1 g/L to 100 g/L, more preferably 1 g /L to 50g/L, more preferably 5g/L to 35g/L. By adjusting the concentration of the reducing agent in the Ni-P plating bath to 0.1 g/L to 100 g/L, the deposition rate is good and the stability of the Ni-P plating bath is good.
錯化剤
本発明のNi-Pめっき浴は、好ましくは、錯化剤を含む。
Complexing Agent The Ni-P plating bath of the present invention preferably contains a complexing agent.
錯化剤は、好ましくは、グリシン等のアミノ酸、クエン酸、乳酸、及びリンゴ酸から成る群から選ばれる少なくとも1種の錯化剤である。 The complexing agent is preferably at least one complexing agent selected from the group consisting of amino acids such as glycine, citric acid, lactic acid, and malic acid.
錯化剤は、これらの錯化剤を1種単独で用いても良く、或は2種以上を混合（ブレンド）して用いても良い。 These complexing agents may be used alone or in a mixture (blend) of two or more.
Ni-Pめっき浴における錯化剤の濃度は、良好にNi-Pめっき皮膜を形成する上で、適宜調整する。Ni-Pめっき浴における錯化剤の濃度は、好ましくは、0.5g／L～100g／Lである。Ni-Pめっき浴における錯化剤の濃度を、0.5g／L～100g／Lに調整する事に依り、析出速度は良好であり、Ni-Pめっき浴の安定性は良好である。 The concentration of the complexing agent in the Ni-P plating bath is adjusted as appropriate to form a good Ni-P plating film. The concentration of the complexing agent in the Ni-P plating bath is preferably 0.5 g/L to 100 g/L. By adjusting the concentration of the complexing agent in the Ni-P plating bath to 0.5 g/L to 100 g/L, the deposition rate is good and the stability of the Ni-P plating bath is good.
浴安定剤
本発明のNi-Pめっき浴は、好ましくは、浴安定剤を含む。
Bath Stabilizer The Ni-P plating bath of the present invention preferably contains a bath stabilizer.
浴安定剤は、好ましくは、金属（無機）安定剤、及び有機安定剤から成る群から選ばれる少なくとも1種の浴安定剤である。 The bath stabilizer is preferably at least one bath stabilizer selected from the group consisting of metal (inorganic) stabilizers and organic stabilizers.
金属安定剤は、例えば、鉛化合物（例えば、硝酸鉛、酢酸鉛等）、カドミウム化合物（例えば、硝酸カドミウム、酢酸カドミウム等）、タリウム化合物（例えば、硫酸タリウム、硝酸タリウム等）、アンチモン化合物（例えば、塩化アンチモン、酒石酸アンチモニルカリウム等）、テルル化合物（例えば、テルル酸、塩化テルル等）、クロム化合物（例えば、酸化クロム、硫酸クロム）、鉄化合物（例えば、硫酸鉄、塩化鉄等）、マンガン化合物（例えば、硫酸マンガン、硝酸マンガン）、ビスマス化合物（例えば、硝酸ビスマス、酢酸ビスマス等）、スズ化合物（例えば、硫酸スズ、塩化スズ等）、セレン化合物（例えば、セレン酸、亜セレン酸等）、シアン化物（例えば、メチルシアニド、イソプロピルシアニド等）等が挙げられる。 Metal stabilizers include, for example, lead compounds (e.g., lead nitrate, lead acetate, etc.), cadmium compounds (e.g., cadmium nitrate, cadmium acetate, etc.), thallium compounds (e.g., thallium sulfate, thallium nitrate, etc.), antimony compounds (e.g. , antimony chloride, antimonyl potassium tartrate, etc.), tellurium compounds (e.g., telluric acid, tellurium chloride, etc.), chromium compounds (e.g., chromium oxide, chromium sulfate), iron compounds (e.g., iron sulfate, iron chloride, etc.), manganese compounds (e.g., manganese sulfate, manganese nitrate), bismuth compounds (e.g., bismuth nitrate, bismuth acetate, etc.), tin compounds (e.g., tin sulfate, tin chloride, etc.), selenium compounds (e.g., selenic acid, selenite, etc.) , cyanide (eg, methyl cyanide, isopropyl cyanide, etc.).
本発明は、Ni-Pめっき浴に、前記説明の通り、添加剤として硫黄化合物を実質的に含まない場合において、有機安定剤を含んでも良い。有機安定剤は、好ましくは、窒素化合物であり、例えば、チオ尿素等が挙げられる。 In the present invention, the Ni-P plating bath may contain an organic stabilizer in the case where it does not substantially contain a sulfur compound as an additive, as explained above. The organic stabilizer is preferably a nitrogen compound, such as thiourea.
浴安定剤は、これらの浴安定剤を1種単独で用いても良く、或は2種以上を混合（ブレンド）して用いても良い。 As the bath stabilizer, these bath stabilizers may be used alone or in a mixture (blend) of two or more.
Ni-Pめっき浴における浴安定剤の濃度は、良好にNi-Pめっき皮膜を形成する上で、適宜調整する。Ni-Pめっき浴における浴安定剤の濃度は、好ましくは、0.10mg／L～100mg／Lである。Ni-Pめっき浴における浴安定剤の濃度を、0.10mg／L～100mg／Lに調整する事に依り、Ni-Pめっき浴の安定性は向上し、良好に被処理物のめっき皮膜が形成され、Ni-Pめっき浴の安定性は良好である。被処理物のめっき皮膜の未析出箇所が発生しない。 The concentration of the bath stabilizer in the Ni-P plating bath is adjusted as appropriate to form a good Ni-P plating film. The concentration of bath stabilizer in the Ni-P plating bath is preferably 0.10 mg/L to 100 mg/L. By adjusting the concentration of bath stabilizer in the Ni-P plating bath to 0.10mg/L to 100mg/L, the stability of the Ni-P plating bath is improved and a plating film is formed on the object to be treated. The stability of the Ni-P plating bath is good. There are no undeposited areas of the plating film on the object to be treated.
添加剤
本発明のNi-Pめっき浴は、好ましくは、添加剤を含む。
Additives The Ni-P plating bath of the present invention preferably contains additives.
Ni-Pめっき浴の溶液のpHを維持する為に、好ましくは、添加剤として、塩酸、硫酸、リン酸等の酸；水酸化ナトリウム、水酸化カリウム、アンモニア水等のアルカリから成る群から選ばれる少なくとも1種のpH調整剤を含む。 In order to maintain the pH of the solution in the Ni-P plating bath, an additive is preferably selected from the group consisting of acids such as hydrochloric acid, sulfuric acid, phosphoric acid, etc.; alkalis such as sodium hydroxide, potassium hydroxide, aqueous ammonia, etc. Contains at least one pH adjusting agent.
本発明のNi-Pめっき浴のpHは、pH調整剤を用いて調整する事が出来、好ましくは、pH3～pH12であり、より好ましくは、pH4～pH9である。Ni-Pめっき浴のpHを、pH3～pH12に調整する事に依り、良好に被処理物のめっき皮膜が形成される。被処理物のめっき皮膜の未析出箇所が発生しない。pHが、3未満であると未析出が発生する場合があり、12を超えると浴安定性が低下する場合がある為、上記した範囲とすることが好ましい。 The pH of the Ni-P plating bath of the present invention can be adjusted using a pH adjuster, and is preferably pH 3 to pH 12, more preferably pH 4 to pH 9. By adjusting the pH of the Ni-P plating bath to pH 3 to pH 12, a plating film can be formed on the object to be treated. There are no undeposited areas of the plating film on the object to be treated. If the pH is less than 3, non-precipitation may occur, and if it exceeds 12, the bath stability may decrease, so it is preferably within the above range.
本発明の金属表面にめっきされるニッケルは、浸漬銀析出物を得る点で、好ましくは、0.1質量%～14質量%のリンを含む。 The nickel plated on the metal surface of the present invention preferably contains 0.1% to 14% by weight of phosphorus in order to obtain immersion silver deposits.
添加剤は、これらの添加剤を1種単独で用いても良く、或は2種以上を混合（ブレンド）して用いても良い。 As for the additives, these additives may be used alone or in a mixture (blend) of two or more types.
［2］金属表面を処理する方法、及びめっき皮膜の製造方法
本発明の金属表面を処理する方法は、
（1）金属表面に、無電解銀めっき用無電解ニッケル－リンめっき浴（Ni-Pめっき浴）を用いて無電解ニッケル－リンめっき（Ni-Pめっき）を施す工程、及び
（2）前記ニッケル－リンめっき（Ni-Pめっき）が施された金属表面に、無電解銀めっき（Agめっき）を施す工程を含み、
前記無電解銀めっき用無電解ニッケル－リンめっき浴（Ni-Pめっき浴）は、硫黄化合物（S化合物）を含まない、方法である。
[2] Method of treating a metal surface and method of manufacturing a plating film The method of treating a metal surface of the present invention includes:
(1) A step of applying electroless nickel-phosphorus plating (Ni-P plating) to the metal surface using an electroless nickel-phosphorus plating bath (Ni-P plating bath) for electroless silver plating, and (2) the above-mentioned step. Including the process of applying electroless silver plating (Ag plating) to the metal surface that has been subjected to nickel-phosphorus plating (Ni-P plating),
The electroless nickel-phosphorus plating bath (Ni-P plating bath) for electroless silver plating does not contain sulfur compounds (S compounds).
本発明の金属表面を処理する方法は、言い換えると、めっき皮膜の製造方法であり、
（1）金属表面に、無電解銀めっき用無電解ニッケル－リンめっき浴を用いて無電解ニッケル－リンめっきを施す工程を含み、
前記無電解銀めっき用無電解ニッケル－リンめっき浴は、硫黄化合物を含まない、
製造方法である。
In other words, the method for treating a metal surface of the present invention is a method for producing a plating film,
(1) Including the process of applying electroless nickel-phosphorus plating to the metal surface using an electroless nickel-phosphorus plating bath for electroless silver plating,
The electroless nickel-phosphorus plating bath for electroless silver plating does not contain sulfur compounds,
This is the manufacturing method.
本発明のめっき皮膜の製造方法は、好ましくは、更に、
（2）前記工程（1）の後、前記ニッケル－リンめっきが施された金属表面に、無電解銀めっきを施す工程を含む。
The method for producing a plating film of the present invention preferably further includes:
(2) After the step (1), the method includes a step of applying electroless silver plating to the metal surface that has been subjected to the nickel-phosphorus plating.
金属表面に、Ni-Pめっき浴を用いてNi-Pめっきを施す工程は、好ましくは、金属表面に、Ni-Pめっき浴を浸漬する。 In the step of applying Ni-P plating to a metal surface using a Ni-P plating bath, the metal surface is preferably immersed in the Ni-P plating bath.
Ni-Pめっきが施された金属表面に、Agめっきを施す工程は、好ましくは、Ni-Pめっきが施された金属表面に、Agめっき浴を浸漬する。 The step of applying Ag plating to the Ni-P-plated metal surface preferably involves immersing the Ni-P-plated metal surface in an Ag plating bath.
本発明は、本発明の金属表面を処理する方法、及びめっき皮膜の製造方法に依って得られるめっき皮膜を包含する。 The present invention includes a plating film obtained by the method of treating a metal surface and the method of manufacturing a plating film of the present invention.
（1）金属表面に、Ni-Pめっき浴を用いてNi-Pめっきを施す工程
金属表面
本発明の金属表面を処理する方法、及び前記めっき皮膜の製造方法は、（1）金属表面にNi-Pめっき浴を用いてNi-Pめっきを施す工程を含む。
(1) Process of applying Ni-P plating to the metal surface using a Ni-P plating bath
Metal Surface The method of treating a metal surface and the method of manufacturing the plated film of the present invention include the steps of (1) applying Ni-P plating to the metal surface using a Ni-P plating bath.
前記Ni-Pめっき浴は、硫黄化合物（S化合物）を含まない。 The Ni-P plating bath does not contain sulfur compounds (S compounds).
金属表面は、好ましくは、鉄、ニッケル、アルミ、銅、及びこれらの合金（アルミ合金等）等である。 The metal surface is preferably made of iron, nickel, aluminum, copper, alloys thereof (aluminum alloy, etc.), and the like.
金属表面とめっき組成物とを接触させる前に、好ましくは、金属表面を洗浄する。洗浄は、酸性、又はアルカリ性洗浄組成物等の洗浄組成物を用いる。 The metal surface is preferably cleaned before contacting the metal surface with the plating composition. For cleaning, a cleaning composition such as an acidic or alkaline cleaning composition is used.
ニッケルめっきは、好ましくは、無電解で行われる。無電解ニッケル－リンめっき（Ni-Pめっき）では、ニッケルイオンがニッケルに自己触媒的に又は化学的に還元され、次いで、基材上に析出するものであり、ニッケルでめっきし得る任意の金属表面上で用いる事が出来る。 Nickel plating is preferably performed electrolessly. In electroless nickel-phosphorus plating (Ni-P plating), nickel ions are autocatalytically or chemically reduced to nickel and then deposited on the substrate, and any metal that can be plated with nickel Can be used on surfaces.
鉄、ニッケル等の金属表面上において、良好にNi-Pめっきを行う為に、好ましくは、金属表面と無電解ニッケルめっき浴（Ni-Pめっき浴）とを接触させる前に、前処理方法として、金属表面を、塩酸、硫酸等を用いて酸活性処理を行う。 In order to perform Ni-P plating well on metal surfaces such as iron and nickel, it is preferable to use a pretreatment method before bringing the metal surface into contact with an electroless nickel plating bath (Ni-P plating bath). , the metal surface is subjected to acid activation treatment using hydrochloric acid, sulfuric acid, etc.
アルミ等の金属表面上において、良好にNi-Pめっきを行う為に、好ましくは、金属表面と無電解ニッケルめっき浴（Ni-Pめっき浴）とを接触させる前に、前処理方法として、金属表面を貴金属活性化剤又は金属活性化剤で活性化させたり、金属表面をダブルジンケート法（アルミの酸化皮膜を亜鉛皮膜に置換させる処理）で処理したりする。貴金属活性化剤は、好ましくは、コロイド状又はイオン状の白金、金、パラジウム、銀等を含む。金属活性化剤は、好ましくは、コロイド状又はイオン状のニッケル、コバルト等を含む。貴金属活性化剤又は金属活性化剤で活性化に依る活性化は、無電解工程の前に実施する。 In order to perform Ni-P plating well on a metal surface such as aluminum, it is preferable to apply a pretreatment method to the metal before bringing the metal surface into contact with an electroless nickel plating bath (Ni-P plating bath). The surface is activated with a noble metal activator or a metal activator, or the metal surface is treated with a double zincate method (a process in which the aluminum oxide film is replaced with a zinc film). The noble metal activator preferably includes colloidal or ionic platinum, gold, palladium, silver, and the like. The metal activator preferably includes colloidal or ionic nickel, cobalt, and the like. Activation by activation with noble metal activators or metal activators is carried out before the electroless process.
金属表面には、好ましくは、金属表面をマイクロエッチングして、接着の強度を高める。銅又は銅合金の金属表面の場合、マイクロエッチングは、好ましくは、硫黄過酸化物マイクロエッチング、塩化第二銅マイクロエッチング、過硫酸塩マイクロエッチング等である。マイクロエッチングに依り、金属表面を均一に粗化する。マイクロエッチング液と接触させる時間及び温度は、均一に粗い金属表面を得る目的で、用いるマイクロエッチング液の種類及び金属表面の特徴に応じて、適宜調整する。 The metal surface is preferably micro-etched to increase the strength of the bond. In the case of copper or copper alloy metal surfaces, the microetch is preferably a sulfur peroxide microetch, a cupric chloride microetch, a persulfate microetch, or the like. The metal surface is uniformly roughened by micro-etching. The time and temperature of contact with the micro-etching solution are adjusted as appropriate depending on the type of micro-etching solution used and the characteristics of the metal surface, in order to obtain a uniformly rough metal surface.
金属表面に対して、マイクロエッチングの後、且つNi-Pめっきとの接触前、金属表面を、貴金属活性化剤で活性化して、好ましくは、Ni-Pめっきを開始させる事が出来る触媒性貴金属部位で、金属表面をコーティングする。 A catalytic noble metal that can preferably be activated with a noble metal activator to initiate Ni-P plating after micro-etching the metal surface and before contact with the Ni-P plating. Coating the metal surface at the site.
無電解めっき（Ni-Pめっき）の析出速度は、適切な温度、pH、及び金属イオン／還元剤の濃度を選択する事に依り制御する。また、錯化剤を触媒阻害剤として用いて、無電解浴の自然分解能を低下させることもできる。 The deposition rate of electroless plating (Ni-P plating) is controlled by selecting the appropriate temperature, pH, and metal ion/reducing agent concentration. Complexing agents can also be used as catalyst inhibitors to reduce the natural decomposition capacity of electroless baths.
Ni-Pめっき皮膜
金属表面とNi-Pめっき浴とを接触させる。金属表面上における無電解ニッケル－リンめっき（Ni-Pめっき皮膜）の総厚みは、時間及び温度好を適宜調整して、好ましくは、0.1μm～50μm、より好ましくは、1μm～25μmのニッケルをめっきする。
The Ni-P plating film metal surface is brought into contact with the Ni-P plating bath. The total thickness of the electroless nickel-phosphorus plating (Ni-P plating film) on the metal surface is preferably 0.1 μm to 50 μm, more preferably 1 μm to 25 μm, by adjusting the time and temperature appropriately. Plate.
Ni-Pめっき皮膜の層が金属表面上に析出すると、次いで、Ni-Pめっきが施された金属表面に浸漬銀めっき（Agめっき）を施して、銀の層を提供する。 Once the layer of Ni-P plating film is deposited on the metal surface, the Ni-P plated metal surface is then subjected to immersion silver plating (Ag plating) to provide a layer of silver.
浸漬銀析出物は、優れたはんだ付け性保存剤であり、また、焼結銀による接合性に優れる点から、プリント基板やセラミック基板の製造において特に有用である。 Immersion silver deposits are particularly useful in the manufacture of printed circuit boards and ceramic substrates because they are excellent solderability preservatives and provide excellent bondability with sintered silver.
Ni-Pめっきを施す工程
Ni-Pめっき浴の浴温は、めっき浴の組成等に応じて適宜決定する。めっき工程におけるNi-Pめっき浴の浴温は、好ましくは、25℃以上であり、より好ましくは、40℃～100℃であり、更に好ましくは、60℃～95℃である。Ni-Pめっき浴の浴温を、25℃以上に調整する事に依り、良好にめっき皮膜が析出し、生産効率は良好である。
Process of applying Ni-P plating
The bath temperature of the Ni-P plating bath is appropriately determined depending on the composition of the plating bath. The bath temperature of the Ni-P plating bath in the plating step is preferably 25°C or higher, more preferably 40°C to 100°C, and even more preferably 60°C to 95°C. By adjusting the bath temperature of the Ni-P plating bath to 25°C or higher, a plating film is deposited well and production efficiency is good.
めっき工程における処理時間は、めっき浴の組成等に応じて適宜決定し、被めっき物に必要な膜厚のNi-Pめっき皮膜が形成されるまでの時間とする。めっき工程における処理時間は、めっき浴の組成、被めっき物の種類等に応じて適宜決定し、好ましくは、1分～1,000分であり、より好ましくは、5分～180分である。 The processing time in the plating step is appropriately determined depending on the composition of the plating bath, etc., and is the time required to form a Ni-P plating film of the thickness required for the object to be plated. The treatment time in the plating step is appropriately determined depending on the composition of the plating bath, the type of the object to be plated, etc., and is preferably 1 minute to 1,000 minutes, more preferably 5 minutes to 180 minutes.
（2）Ni-Pめっきが施された金属表面に、Agめっきを施す工程
本発明のNi-Pめっき及び浸漬Agめっき後に得られるはんだ付け性は、回路表面のガルバニック腐食を大きく低減し、変色及び腐食し易い銅孔を減少させ、且つボンディング用途のプロセスウインドウを広げる。これは、プリント基板用途において、例えば、表面がワイヤボンディング可能に成る点、また、焼結銀による接合性に優れる点から、有益である。
(2) Process of applying Ag plating to the Ni-P plated metal surface The solderability obtained after the Ni-P plating and immersion Ag plating of the present invention greatly reduces galvanic corrosion on the circuit surface and discolors. and reduce corrosion-prone copper holes and widen the process window for bonding applications. This is useful in printed circuit board applications, for example, since the surface can be wire bonded and the bonding properties of sintered silver are excellent.
本発明の金属表面を処理する方法、及びめっき皮膜の製造方法に依って、均一な銀皮膜が得られる。 A uniform silver film can be obtained by the method of treating a metal surface and the method of manufacturing a plating film of the present invention.
浸漬銀（Ag）めっき浴
本発明の金属表面を処理する方法、及びめっき皮膜の製造方法は、前記（1）の後、（2）前記Ni-Pめっきが施された金属表面に、Agめっきを施す工程を含む。
Immersion silver (Ag) plating bath The method for treating a metal surface and the method for producing a plating film of the present invention includes, after (1) above, (2) applying Ag plating to the Ni-P plated metal surface. including the step of applying.
Agめっきを施す工程で用いる浸漬銀（Ag）めっき浴は、好ましくは、可溶性銀イオン源、酸、錯化剤、任意で、イミダゾール又はイミダゾール誘導体を含む。 The immersion silver (Ag) plating bath used in the step of applying Ag plating preferably contains a soluble silver ion source, an acid, a complexing agent, and optionally an imidazole or imidazole derivative.
可溶性銀イオン源
浸漬Agめっき浴は、好ましくは、可溶性銀イオン源及び酸水性マトリクスを含む。可溶性銀イオン源は、好ましくは、有機又は無機の銀塩を含む。可溶性銀イオン源は、例えば、硝酸銀、ヨウ化銀、酸化銀、硫酸銀、塩化銀、亜硫酸銀、炭酸銀、酢酸銀、乳酸銀、スルホコハク酸銀、スルホン酸銀、スルファミン酸銀、シュウ酸銀、シアン化銀カリウム等のシアン化銀化合物等が挙げられる。
The soluble silver ion source immersion Ag plating bath preferably includes a soluble silver ion source and an acidic aqueous matrix. The soluble silver ion source preferably includes an organic or inorganic silver salt. Soluble silver ion sources include, for example, silver nitrate, silver iodide, silver oxide, silver sulfate, silver chloride, silver sulfite, silver carbonate, silver acetate, silver lactate, silver sulfosuccinate, silver sulfonate, silver sulfamate, silver oxalate. , silver cyanide compounds such as silver potassium cyanide, and the like.
浸漬Agめっき浴における銀の濃度は、銀金属として、好ましくは、0.01g／L～25g／Lであり、より好ましくは、0.1g／L～5g／Lである。 The concentration of silver in the immersion Ag plating bath is preferably 0.01 g/L to 25 g/L, more preferably 0.1 g/L to 5 g/L as silver metal.
酸
浸漬Agめっき浴に、好ましくは、フルオロホウ酸、塩酸、リン酸、メタンスルホン酸、及び硝酸から成る群から選ばれる少なくとも1種の酸を使用する。酸は、好ましくは、メタンスルホン酸、硝酸等を用いる。
The acid immersion Ag plating bath preferably uses at least one acid selected from the group consisting of fluoroboric acid, hydrochloric acid, phosphoric acid, methanesulfonic acid, and nitric acid. As the acid, methanesulfonic acid, nitric acid, etc. are preferably used.
浸漬Agめっき浴における酸の濃度は、好ましくは、0.01g／L～150g／Lであり、より好ましくは、0.05g／L～50g／Lである。 The concentration of acid in the immersion Ag plating bath is preferably 0.01 g/L to 150 g/L, more preferably 0.05 g/L to 50 g/L.
錯化剤
浸漬Agめっき浴は、Ni-Pめっきが施された金属表面（基材）を、均一に銀で被覆する為に、好ましくは、錯化剤を含む。錯化剤は、好ましくは、亜硫酸塩、コハク酸イミド、ヒダントイン誘導体、エチレンジアミン、エチレンジアミン四酢酸（EDTA）、シアン化合物、アンモニア塩、チオ硫酸塩、チオシアン酸塩、ヨウ化物塩から成る群から選ばれる少なくとも1種の化合物である。
The complexing agent -immersed Ag plating bath preferably contains a complexing agent in order to uniformly coat the Ni-P plated metal surface (substrate) with silver. The complexing agent is preferably selected from the group consisting of sulfites, succinimides, hydantoin derivatives, ethylenediamine, ethylenediaminetetraacetic acid (EDTA), cyanide compounds, ammonia salts, thiosulfates, thiocyanates, iodide salts. At least one compound.
浸漬Agめっき浴における錯化剤の濃度は、好ましくは、0.1g／L～200g／Lであり、より好ましくは、0.5g／L～150g／Lである。 The concentration of the complexing agent in the immersion Ag plating bath is preferably 0.1 g/L to 200 g/L, more preferably 0.5 g/L to 150 g/L.
添加剤
浸漬Agめっきが電気移動する傾向を更に低減する為に、好ましくは、めっき浴に添加剤を配合したり、めっきが施された表面を後に添加剤で処理したりしても良い。添加剤をめっき析出物中に含めても良い。添加剤は、好ましくは、脂肪族アミン、脂肪酸、脂肪族アミド、第四級塩、両性塩、樹脂質アミン、樹脂質アミド、樹脂酸、及びこれらの混合物から成る群から選ばれる少なくとも1種の添加剤である。
To further reduce the tendency of additive- soaked Ag plating to electromigrate, additives may preferably be included in the plating bath or the plated surface may be subsequently treated with additives. Additives may also be included in the plating deposit. The additive preferably contains at least one selected from the group consisting of aliphatic amines, fatty acids, aliphatic amides, quaternary salts, amphoteric salts, resinous amines, resinous amides, resin acids, and mixtures thereof. It is an additive.
浸漬Agめっき浴における添加剤の濃度は、好ましくは、0.01g／L～15g／Lであり、より好ましくは、0.05g／L～10g／Lである。 The concentration of the additive in the immersion Ag plating bath is preferably from 0.01 g/L to 15 g/L, more preferably from 0.05 g/L to 10 g/L.
イミダゾール又はイミダゾール誘導体
浸漬Agめっき浴は、好ましくは、イミダゾール又はイミダゾール誘導体を含み、めっきをより明るく、より滑らかに、且つより凝集性にしても良い。
The imidazole or imidazole derivative immersion Ag plating bath preferably contains imidazole or an imidazole derivative to make the plating brighter, smoother, and more cohesive.
Agめっきを施す工程
浸漬Agめっき浴の浴温は、好ましくは、室温～100℃であり、より好ましくは、25℃～90℃の温度である。めっきが施される製品は、望ましいめっき厚みの析出物を得るのに適した時間は、好ましくは、1分間～60分間において、めっき溶液に浸漬する。
The bath temperature of the immersion Ag plating bath in the step of applying Ag plating is preferably room temperature to 100°C, more preferably 25°C to 90°C. The product to be plated is immersed in the plating solution for a time suitable for obtaining a precipitate of the desired plating thickness, preferably from 1 minute to 60 minutes.
浸漬Ag溶液は、金属表面上に銀の薄層をめっきする。 The immersion Ag solution will plate a thin layer of silver on the metal surface.
得られる銀コーティングの厚みは、表面のはんだ付け性を有効に強化及び保持する為の厚みであり、好ましくは、0.01μm～5μmであり、より好ましくは、0.05μm～1.5μmである。 The thickness of the resulting silver coating is such that it effectively strengthens and maintains the solderability of the surface, and is preferably from 0.01 μm to 5 μm, more preferably from 0.05 μm to 1.5 μm.
本発明の金属表面を処理する方法、及びめっき皮膜の製造方法の有用性
本発明の金属表面を処理する方法、及びめっき皮膜の製造方法は、様々な金属表面のはんだ付けにおいて有効であり、特に、プリント基板等の電子パッケージデバイスにおける接続領域等の銅表面のはんだ付けにおいて特に有用である。プリント基板における腐食を防ぐ事に依って、デバイスの耐用寿命を延ばす事が出来る。更に、腐食を無くす事が出来、基板、回路、コンポーネント、焼結銀による接合、パワーモジュール等の製造に有用である。
Usefulness of the method for treating metal surfaces and the method for producing plated films of the present invention The method for treating metal surfaces and the method for producing plated films of the present invention are effective in soldering various metal surfaces, and are particularly effective. It is particularly useful in soldering copper surfaces, such as connection areas in electronic package devices such as printed circuit boards. By preventing corrosion on printed circuit boards, the useful life of the device can be extended. Furthermore, it eliminates corrosion and is useful for manufacturing substrates, circuits, components, sintered silver bonding, power modules, etc.
本発明の金属表面を処理する方法、及びめっき皮膜の製造方法は、例えば、プリント基板を含む電子パッケージデバイスのはんだ付けにおいて有用である。 The method of treating a metal surface and the method of manufacturing a plating film of the present invention are useful, for example, in soldering electronic package devices including printed circuit boards.
本発明の金属表面を処理する方法、及びめっき皮膜の製造方法を用いて、半導体チップ上にニッケルを無電解で析出させる事が出来る。本発明の金属表面を処理する方法、及びめっき皮膜の製造方法を用いて、透明基板上に第1の伝導性層、活性層、及び第2の伝導性層をこの順序で積層する事に依り、半導体上に、無電解ニッケル及び浸漬銀めっきを析出させる事が出来る。 By using the method for treating a metal surface and the method for producing a plating film of the present invention, nickel can be electrolessly deposited on a semiconductor chip. By using the method for treating a metal surface and the method for producing a plating film of the present invention, the first conductive layer, the active layer, and the second conductive layer are laminated in this order on a transparent substrate. , electroless nickel and immersion silver plating can be deposited on semiconductors.
本発明の金属表面を処理する方法、及びめっき皮膜の製造方法は、下層の銅基板に起因するガルバニック腐食を実質的に無くす事が出来る。 The method of treating a metal surface and the method of manufacturing a plating film of the present invention can substantially eliminate galvanic corrosion caused by the underlying copper substrate.
本発明の金属表面を処理する方法、及びめっき皮膜の製造方法は、変色腐食を受け易い銀析出物における銅孔を実質的に無くし、更に、銀析出物を通じた銅の移動を実質的に無くす事が可能である。 The method of treating a metal surface and the method of producing a plating film of the present invention substantially eliminates copper pores in silver deposits that are susceptible to discoloration corrosion, and further substantially eliminates copper migration through the silver deposits. things are possible.
本発明の金属表面を処理する方法、及びめっき皮膜の製造方法は、ワイヤボンディング中に遭遇する任意の酸化された銅に依りボンディング不可能な表面が生じるので、ワイヤボンディング用途に有用である。 The methods of treating metal surfaces and producing plated films of the present invention are useful in wire bonding applications because any oxidized copper encountered during wire bonding results in non-bondable surfaces.
本発明の金属表面を処理する方法、及びめっき皮膜の製造方法は、Ni-Pめっきを利用しており、Ni-Pめっき析出物を用いてニッケルバリアを提供しても良く、Ni-Pめっき浴がニッケル合金を含んでいても良い。 The method for treating a metal surface and the method for producing a plating film of the present invention utilizes Ni-P plating, and Ni-P plating deposits may be used to provide a nickel barrier, and the method for producing a plating film uses Ni-P plating. The bath may also contain a nickel alloy.
以下に、実施例を示して本発明を具体的に説明する。 EXAMPLES The present invention will be specifically described below with reference to Examples.
本発明は、以下の具体的な実施例に限定されない。 The present invention is not limited to the following specific examples.
［1］金属表面を処理する方法
（1）金属表面に、Ni-Pめっき浴を用いてNi-Pめっきを施す工程
実施例の無電解Ni-Pめっき浴を、表1に記載の組成に従って、調整した。
[1] Method of treating metal surfaces
(1) Step of applying Ni-P plating to a metal surface using a Ni-P plating bath The electroless Ni-P plating bath of the example was prepared according to the composition shown in Table 1.
被めっき物としてCu板を用い、調整した無電解Ni-Pめっき浴中（浴温：90℃）に被めっき物を浸漬することで、膜厚3μm～5μmのNi-Pめっき皮膜を形成した。 A Cu plate was used as the object to be plated, and a Ni-P plating film with a thickness of 3 μm to 5 μm was formed by immersing the object in a prepared electroless Ni-P plating bath (bath temperature: 90°C). .
形成しためっき皮膜のP含有率を蛍光X線分析装置で測定した。 The P content of the formed plating film was measured using a fluorescent X-ray analyzer.
硫黄含有率を燃焼法による炭素・硫黄分析装置で測定した。 The sulfur content was measured using a carbon/sulfur analyzer using the combustion method.
実施例で使用した皮膜
硫黄フリーNi-P／Agめっき皮膜：硫黄フリーNi-Pめっき皮膜中に、硫黄は含有しない。
Sulfur-free Ni-P/Ag plating film used in Examples : The sulfur-free Ni-P plating film does not contain sulfur.
比較例で使用した皮膜
硫黄含有Ni-P／Agめっき皮膜：硫黄含有Ni-Pめっき皮膜中に、1質量%～12質量%のリン（P）を含み、及び0.0005質量%～0.1質量%の硫黄を含む。
Sulfur-containing Ni-P/Ag plating film used in comparative example : The sulfur-containing Ni-P plating film contains 1% by mass to 12% by mass of phosphorus (P), and 0.0005% by mass to 0.1% by mass. Contains sulfur.
リン（P）含有率
低リン：めっき皮膜に含まれるP含有率が0.1質量%～5質量%程度である。
中リン：めっき皮膜に含まれるP含有率が6質量%～9質量%程度である。
高リン：めっき皮膜に含まれるP含有率が10質量%～14質量%程度である。
Low phosphorus (P) content : The P content contained in the plating film is approximately 0.1% by mass to 5% by mass.
Medium phosphorus: The P content contained in the plating film is approximately 6% by mass to 9% by mass.
High phosphorus: The P content in the plating film is approximately 10% to 14% by mass.
（2）Ni-Pめっきが施された金属表面に、Agめっきを施す工程
前記工程（1）でNi-Pめっきを行っためっき物を用い、無電解Agめっき浴中（浴温：70℃～80℃）にNi-Pめっき物を浸漬する事で、膜厚0.1μm～1μmのAgめっき皮膜を形成した。
(2) Process of applying Ag plating to the metal surface that has been subjected to Ni-P plating. Using the plated material that has undergone Ni-P plating in the above step (1), place it in an electroless Ag plating bath (bath temperature: 70°C). By immersing the Ni-P plated material in temperatures (~80°C), an Ag plating film with a thickness of 0.1 μm to 1 μm was formed.
形成したAgめっきの膜厚を、蛍光X線分析装置で測定した。 The film thickness of the formed Ag plating was measured using a fluorescent X-ray analyzer.
［2］めっき皮膜の評価
（1）密着性
無電解Agめっき後、碁盤目状にカッターで切り込みをいれ、テープを用いて評価を行った。
◎～〇評価：剥がしたテープをマイクロスコープにて観察し、テープにめっき皮膜が全く付着していない場合。
△評価：剥がしたテープをマイクロスコープにて観察し、テープにめっき皮膜が少し付着した場合。
×評価：剥がしたテープをマイクロスコープにて観察し、テープにめっき皮膜が多量に付着した場合。
[2] Evaluation of plating film
(1) Adhesion After electroless Ag plating, cuts were made in a grid pattern using a cutter, and evaluation was performed using tape.
◎～〇 Evaluation: When the peeled tape is observed under a microscope and no plating film is attached to the tape.
△ Evaluation: When the peeled tape was observed with a microscope, a small amount of plating film was observed on the tape.
× Evaluation: When the peeled tape was observed under a microscope, a large amount of plating film was attached to the tape.
実施例の硫黄フリーNi-Pめっき皮膜をAgめっきの下地として使用すると、Agめっき皮膜の剥がれは認められなかった。 When the sulfur-free Ni-P plating film of the example was used as a base for Ag plating, no peeling of the Ag plating film was observed.
実施例の硫黄フリーNi-Pめっき皮膜は、中リン～高リンの時に最も良好な密着性を示した。 The sulfur-free Ni-P plating film of the example showed the best adhesion when the phosphorus was medium to high.
（2）無電解AgめっきによるNi-P皮膜の腐食度合い
無電解Agめっき後、剥離液にてAgめっき皮膜を剥離し、Ni-P皮膜表面をFE-SEMにて観察した。
(2) Corrosion degree of Ni-P film due to electroless Ag plating After electroless Ag plating , the Ag plating film was peeled off using a stripping solution, and the surface of the Ni-P film was observed using FE-SEM.
実施例の硫黄フリーNi-Pめっき皮膜を使用した場合、皮膜中に硫黄が含有していない為、耐食性が向上し、Ag剥離後においてもNi腐食が減少した。 When the sulfur-free Ni-P plating film of the example was used, corrosion resistance was improved because the film did not contain sulfur, and Ni corrosion was reduced even after Ag was removed.
実施例の硫黄フリーNi-Pめっき皮膜は、中リン～高リンの時に最もNi腐食が減少する傾向であった。 In the sulfur-free Ni-P plating film of the example, Ni corrosion tended to decrease most when the phosphorus was medium to high.
（3）はんだ濡れ性
はんだボール（Sn-3Ag-0.5Cu、Φ0.76mm）を用いて、窒素雰囲気化にて、Agめっき皮膜上にはんだ付けを行い、はんだ濡れ広がり性の評価を行った。はんだをマイクロスコープにて観察し、濡れ広がった長さ（μm）を測定した。
(3) Solder wettability Using solder balls (Sn-3Ag-0.5Cu, Φ0.76 mm), soldering was performed on the Ag plating film in a nitrogen atmosphere, and the solder wettability was evaluated. The solder was observed with a microscope and the length (μm) of the solder spread was measured.
比較例の硫黄含有Ni-Pめっき皮膜を使用した場合、濡れ広がり性は約2500μm～2800μmであった。 When the sulfur-containing Ni-P plating film of the comparative example was used, the wetting and spreading properties were approximately 2500 μm to 2800 μm.
一方、実施例の硫黄フリーNi-Pめっき皮膜を使用した場合、濡れ広がり性は約3100μm～3600μmとなり、Ag剥離後のNi腐食が少なく、Ni-Pめっき皮膜の耐食性が向上した為、濡れ広がり性が向上する結果となった。 On the other hand, when the sulfur-free Ni-P plating film of the example was used, the wetting and spreading property was approximately 3100 μm to 3600 μm, and there was less Ni corrosion after Ag peeling, and the corrosion resistance of the Ni-P plating film was improved, so it spread easily. This resulted in improved performance.
実施例の硫黄フリーNi-Pめっき皮膜が中リン～高リンの時に最も良好なはんだ濡れ性を示した。 The sulfur-free Ni-P plating film of the example exhibited the best solder wettability when the phosphorus content was medium to high.
本発明のNi-Pめっき浴は、硫黄化合物を含まない事から、金属表面に、先ず、Ni-Pめっき浴を用いてNi-Pめっきを施し、次いで、前記Ni-Pめっきが施された金属表面に、Agめっきを施すと、ニッケル腐食が減少するためNi-PめっきとAgめっきとの間の密着性が良好であり、はんだ濡れ性や焼結銀による接合性も良好になる。 Since the Ni-P plating bath of the present invention does not contain sulfur compounds, the metal surface is first plated with Ni-P using the Ni-P plating bath, and then the Ni-P plating is applied. When Ag plating is applied to the metal surface, nickel corrosion is reduced, so the adhesion between Ni-P plating and Ag plating is good, and the solder wettability and bondability with sintered silver are also good.
［3］産業上の利用可能性
本発明のNi-Pめっき浴は、硫黄化合物を含まない事から、金属表面に、先ず、Ni-Pめっき浴を用いてNi-Pめっきを施し、次いで、前記Ni-Pめっきが施された金属表面に、Agめっきを施すと、ニッケル腐食が減少したためNi-PめっきとAgめっきとの間の密着性が良好であり、はんだ濡れ性や焼結銀による接合性も良好になる。
[3] Industrial applicability Since the Ni-P plating bath of the present invention does not contain sulfur compounds, the metal surface is first plated with Ni-P using the Ni-P plating bath, and then, When Ag plating is applied to the Ni-P-plated metal surface, the adhesion between the Ni-P plating and Ag plating is good because nickel corrosion is reduced, and the solder wettability and sintered silver Bondability also improves.
Claims (5)
ニッケル－リン皮膜中に硫黄化合物を含まない、
無電解銀めっき用無電解ニッケル－リンめっき浴。 An electroless nickel-phosphorus plating bath for electroless silver plating,
Does not contain sulfur compounds in the nickel-phosphorus coating.
Electroless nickel-phosphorus plating bath for electroless silver plating.
（1）金属表面に、無電解銀めっき用無電解ニッケル－リンめっき浴を用いて無電解ニッケル－リンめっきを施す工程、及び
（2）前記ニッケル－リンめっきが施された金属表面に、無電解銀めっきを施す工程
を含み、
前記無電解銀めっき用無電解ニッケル－リンめっき浴は、硫黄化合物を含まない、
方法。 A method of treating a metal surface, the method comprising:
(1) Applying electroless nickel-phosphorus plating to the metal surface using an electroless nickel-phosphorus plating bath for electroless silver plating, and (2) Applying electroless nickel-phosphorus plating to the metal surface that has been subjected to the nickel-phosphorus plating. Including the process of applying electrolytic silver plating,
The electroless nickel-phosphorus plating bath for electroless silver plating does not contain sulfur compounds,
Method.
（1）金属表面に、無電解銀めっき用無電解ニッケル－リンめっき浴を用いて無電解ニッケル－リンめっきを施す工程、
を含み、
前記無電解銀めっき用無電解ニッケル－リンめっき浴は、硫黄化合物を含まない、
製造方法。 A method for producing a plating film, the method comprising:
(1) A process of applying electroless nickel-phosphorus plating to the metal surface using an electroless nickel-phosphorus plating bath for electroless silver plating,
including;
The electroless nickel-phosphorus plating bath for electroless silver plating does not contain sulfur compounds,
Production method.
（2）前記工程（1）の後、前記ニッケル－リンめっきが施された金属表面に、無電解銀めっきを施す工程、
を含む、
請求項３に記載のめっき皮膜の製造方法。 Furthermore,
(2) After the step (1), applying electroless silver plating to the metal surface that has been subjected to the nickel-phosphorus plating,
including,
The method for producing a plating film according to claim 3.
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