CN114016098B - Copper-clad plate electroplated Ni-Co-Ce film plating solution for PCB and film preparation method - Google Patents
Copper-clad plate electroplated Ni-Co-Ce film plating solution for PCB and film preparation method Download PDFInfo
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- CN114016098B CN114016098B CN202111226368.6A CN202111226368A CN114016098B CN 114016098 B CN114016098 B CN 114016098B CN 202111226368 A CN202111226368 A CN 202111226368A CN 114016098 B CN114016098 B CN 114016098B
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- Prior art keywords
- copper
- electroplating
- clad plate
- printed circuit
- sulfate
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- 238000007747 plating Methods 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000009713 electroplating Methods 0.000 claims abstract description 48
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 31
- 229910052802 copper Inorganic materials 0.000 claims abstract description 29
- 239000010949 copper Substances 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 25
- 229910000636 Ce alloy Inorganic materials 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims abstract description 12
- 229940044175 cobalt sulfate Drugs 0.000 claims abstract description 12
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims abstract description 12
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000002482 conductive additive Substances 0.000 claims abstract description 10
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 claims abstract description 9
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 claims abstract description 8
- 239000006174 pH buffer Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 54
- 229910045601 alloy Inorganic materials 0.000 claims description 21
- 239000000956 alloy Substances 0.000 claims description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- 235000002639 sodium chloride Nutrition 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- -1 ceric sulfate compound Chemical class 0.000 claims description 13
- 229910002058 ternary alloy Inorganic materials 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical group OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000011241 protective layer Substances 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- 239000006179 pH buffering agent Substances 0.000 claims 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 230000006872 improvement Effects 0.000 abstract description 9
- 239000011229 interlayer Substances 0.000 abstract description 7
- 239000010410 layer Substances 0.000 description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 238000005260 corrosion Methods 0.000 description 14
- 230000007797 corrosion Effects 0.000 description 14
- 229910052684 Cerium Inorganic materials 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000011135 tin Substances 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910001297 Zn alloy Inorganic materials 0.000 description 3
- GZSJSGZGZXGFOW-UHFFFAOYSA-N [Zn].[Ce].[Cu] Chemical compound [Zn].[Ce].[Cu] GZSJSGZGZXGFOW-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000008054 signal transmission Effects 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 150000000703 Cerium Chemical class 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910001313 Cobalt-iron alloy Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WITQLILIVJASEQ-UHFFFAOYSA-N cerium nickel Chemical compound [Ni].[Ce] WITQLILIVJASEQ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical group C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- WVCWZRQYDQZQHD-UHFFFAOYSA-N [Zn].[Sn].[Ce] Chemical compound [Zn].[Sn].[Ce] WVCWZRQYDQZQHD-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910001453 nickel ion Inorganic materials 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
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- FZUJWWOKDIGOKH-UHFFFAOYSA-N sulfuric acid hydrochloride Chemical compound Cl.OS(O)(=O)=O FZUJWWOKDIGOKH-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003466 welding Methods 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
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention provides a plating solution formula and a preparation method of a printed circuit copper-clad plate copper surface electrodeposited Ni-Co-Ce alloy film, and a method for manufacturing the Ni-Co-Ce alloy film on the copper-clad plate surface by using the plating solution. The plating solution formula comprises: nickel chloride 0.03-0.05 mol/L, cobalt sulfate 0.03-0.05 mol/L, conductive additive 0.1-0.2 mol/L, pH buffer 0.1-0.2 mol/L, electroplating additive 0.1-0.2 mol/L, ceric sulfate 0.005-0.03 mol/L, deionized water and the like, and the Ni-Co-Ce alloy film obtained by electroplating can be used for protecting electronic circuits of multilayer printed circuit boards, improving interlayer binding force and high-frequency signal integrity and the like. Meanwhile, the plating solution formula is simple and convenient to prepare, does not corrode the printed circuit board, has good compatibility with the existing conditions in the field of printed circuit manufacturing, and greatly reduces the technical improvement investment and the product manufacturing cost.
Description
Technical Field
The invention belongs to the technical field of surface modification of printed circuit substrates, and particularly relates to a plating solution for electroplating a Ni-Co-Ce film on a copper-clad plate for a PCB and a film preparation method.
Background
The printed circuit board is a basic component for manufacturing electronic equipment, the FR-4 copper-clad plate is one of the most used substrate materials at present, and the surface protection treatment of the printed circuit board is one of important procedures in the field of manufacturing the printed circuit board in order to avoid the problems of oxidization, pollution and the like of the printed circuit board before packaging components.
The conventional surface treatment technology in the industry comprises hot air leveling, electroless nickel gold/silver/tin plating, organic protective film coating, tin/nickel gold electroplating and the like. For example, the high-phthalocyanine remote control introduces a tin plating technology of a printed circuit board in the paper of research and application of the tin plating technology of a copper surface of the printed circuit board, and the tin plating prepared by the technology can improve the etching quality of an electronic circuit, the welding reliability of components, the interlayer bonding force of a multilayer board and the like. The method for improving the surface performance of the prepared circuit board by adopting the electroplated nickel layer in the field of printed circuits is based on the characteristics that a nickel simple substance has better corrosion resistance and high temperature resistance, the nickel plating layer can be easily passivated in air, and has slow action with common strong alkali, strong acid, hydrochloric acid, sulfuric acid and the like, so that the protection effect on copper electronic circuits can be effectively exerted. Therefore, developing the technology for manufacturing the alloy plating layer on the surface of the printed circuit board becomes a hot spot in industry research. The patent "nickel-cerium alloy plating annealed copper wire production process" (publication No. CN 101556846A) proposes an annealed copper wire production process for electroplating nickel-cerium alloy on the surface of a copper wire, and the obtained nickel-cerium alloy plating layer has the characteristics of good adhesiveness, good toughness, excellent extensibility and the like on the surface of the annealed copper wire, and is suitable for manufacturing aviation wires and cables and special installation conductive cores; the patent 'a nickel-gold electroplating process of a printed circuit board' (application publication number CN 101835346A) adopts a design electroplating connection line to lead the electric brush position on the process edge of the printed circuit board to be communicated with a non-edge nickel-gold area to be electroplated, thereby realizing nickel-gold electroplating in the non-edge area on the printed circuit board, ensuring the reliability of nickel-gold electroplating layer of the printed circuit board, effectively reducing the waste of noble metal nickel and gold resources, reducing the cost and being more environment-friendly; the patent 'a plating solution for electroplating a nickel cobalt iron alloy layer on a crystallizer copper plate' (application publication No. CN 105442002A) discloses a plating solution for electroplating a nickel cobalt iron alloy layer on a crystallizer copper plate, wherein the plating solution comprises 220-240g/L of nickel sulfate, 17-19g/L of nickel chloride, 4.5-5.5g/L of cobalt sulfate, 7.5-8.5g/L of ferric sulfate, 23-27g/L of boric acid, 5-7g/L of potassium sulfate, 30-40g/L of sodium chloride, 0.2-0.4g/L of sodium dodecyl sulfate and 20-22m1/L of additive (wherein the additive is sodium gluconate, ascorbic acid and dextrin).
In order to solve the corrosion resistance problem of the copper foil, some copper foil manufacturers develop a ternary and quaternary alloy corrosion resistance process of metals such as zinc, nickel, cobalt, tin, iron, arsenic and tungsten, so that the corrosion resistance of the copper foil is greatly improved, but the process is complex, the process parameter range is narrow, and the problems of inadvisable operation, high cost, difficult recovery of plating solution and waste water treatment, inadvisable environment protection and the like exist. Based on the fact that the cerium atomic structure is provided with electrons with a 4f layer which is not filled, electronegativity is small, and strong chemical affinity can effectively improve the performance of plating solution in the traditional electroplating process, so that the structure of a metal plating layer is changed, and the like, the copper-based electroplating technology added with cerium salt is paid attention to. The patent 'a surface treating agent for improving the corrosion resistance of electrolytic copper foil' (application publication number CN 111304709A) realizes the improvement of the corrosion resistance of the copper foil by forming a uniform and fine tin-zinc-cerium ternary alloy composite coating on the surface of the copper foil by electroplating, and the hydrochloric acid cracking resistance rate of the copper foil can be lower than 2%; the patent 'a rare earth cerium-copper-zinc alloy electroplating solution and an electroplating method thereof' (application publication No. CN 105483772A) discloses a rare earth cerium-copper-zinc alloy electroplating solution and an electroplating method thereof, wherein the electroplating solution comprises 10-80g/L of copper sulfate, 4-60g/L of zinc sulfate, 0.1-1g/L of dioxygen, 4-40g/L of amino acid, 100-200g/L of sodium pyrophosphate and 3-8g/L of brightening agent, and a cerium-copper-zinc alloy plating layer electroplated by using the electroplating solution is attractive in color and luster, and excellent in compactness and corrosion resistance. The result of this document further improves the stability of the electronic circuit in the environment, but the key problems of multi-layer printed circuit board manufacture such as interlayer bonding force, electromagnetic compatibility and the like are not involved. In the prior art, the improvement of interlayer bonding force mostly needs to be performed with palm-oxidation treatment, and the treatment means can improve the roughness of the copper surface and increase the insertion loss. With the development of higher density and multilayering of circuit boards, particularly the recent development of higher frequency signal transmission of electric products, the production of metal plating on the copper-based surface of printed circuits has been required to not only improve the corrosion resistance and wear resistance of copper electronic circuits, but also to improve the interlayer bonding force of multilayering boards, and to solve the problems of signal loss and electromagnetic interference of protected electronic circuits during the transmission of high frequency signals. In addition, in practice, it is found that some alloy layers obtained by electroplating have insufficient and uniform crystallization, and the corrosion resistance of the alloy layers cannot achieve an ideal effect, so that the phenomenon of edge corrosion occurs when the copper foil circuit board etches high-definition circuits, and the quality of manufactured finished products is seriously affected.
Therefore, developing a new plating solution formula and realizing good protection of the protective plating layer of the printed circuit copper-clad plate become a research hot spot.
Disclosure of Invention
Aiming at the problems of weak bonding force between a protective coating prepared by the prior plating solution formula in the background art and a printed circuit copper-clad plate, signal transmission influence and the like, the invention aims to provide a plating solution for electroplating a Ni-Co-Ce film on the copper-clad plate for a PCB and a film preparation method. According to the formula of the plating solution, cerium ions are added into the plating solution to increase the cathode polarization in the copper surface plating process of the copper-clad plate, the electrodeposition speed of nickel ions and cobalt ions on the copper surface is controlled, the regulation and control of the performances of the prepared Ni-Co-Ce alloy, such as the surface compactness and the like are realized, the peel strength of high polymer materials such as epoxy resin and the like on the surface of the prepared alloy layer is effectively improved, and the improvement of the interlayer bonding force of the multilayer printed circuit board is facilitated. In addition, the compact alloy plating layer is very beneficial to high-frequency electronic signal transmission, thereby realizing the combination of improving the bonding force between layers and reducing the insertion loss of high-frequency transmission signals in the manufacturing of the multi-layer high-frequency printed circuit board. Meanwhile, the plating solution formula does not contain noble metals such as gold, highly toxic substances and the like, the plating solution is simple and convenient to prepare, the organic materials of the printed circuit board are not corroded, the equipment for manufacturing the alloy layer on the surface of the copper-clad plate by using the plating solution has better compatibility with the existing electroplating equipment in the field of printed circuit manufacturing, the technical improvement investment is less, and the production and manufacturing cost is low.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a plating solution for electroplating Ni-Co-Ce film on a copper-clad plate for a PCB comprises the following components: 0.03 to 0.05mol/L of nickel chloride, 0.03 to 0.05mol/L of cobalt sulfate, 0.1 to 0.2mol/L of conductive additive, 0.1 to 0.2mol/L of pH buffer, 0.1 to 0.2mol/L of electroplating additive, 0.005 to 0.03mol/L of ceric sulfate and deionized water.
Further, the conductive additive may be sodium chloride, sodium sulfate, potassium chloride or potassium sulfate, preferably sodium chloride.
Further, the pH buffer may be a weak acid, a weak acid salt or an ammonium salt, the weak acid being acetic acid, citric acid, boric acid, etc., the weak acid salt being oxalate, tartrate, phosphate, etc., preferably boric acid.
Further, the plating additive is sodium dodecyl sulfate, thiourea, sodium polydithio-dipropyl sulfonate (SPS), etc., preferably thiourea and sodium polydithio-dipropyl sulfonate (SPS).
The method for preparing the Ni-Co-Ce ternary alloy film based on the plating solution comprises the following steps of:
step 1, preparing plating solution: adding a certain amount of deionized water into a container, sequentially adding a pH buffer, a conductive additive, nickel salt, cobalt salt, an electroplating additive and a rare earth cerium compound under continuous stirring, then adjusting the pH value of the system to a preset pH value by using dilute sulfuric acid or dilute NaOH solution, and finally obtaining plating solution by using deionized water with a preset pH value to fix the volume; wherein, nickel chloride is 0.03-0.05 mol/L, cobalt sulfate is 0.03-0.05 mol/L, ceric sulfate is 0.005-0.03 mol/L, conductive additive is 0.1-0.2 mol/L, pH buffer is 0.1-0.2 mol/L, electroplating additive is 0.1-0.2 mol/L, pH value is 5-7;
step 2, pretreatment of plating pieces: removing surface stains such as surface oxide layers and dirt from a printed circuit copper-clad plate to be electroplated by using a brush plate, immersing the printed circuit copper-clad plate in 5% dilute sulfuric acid for washing for 1-10 min, taking out the printed circuit copper-clad plate, washing the printed circuit copper-clad plate by using deionized water, carrying out microetching treatment by using a mixed solution of 5% dilute sulfuric acid and 5% sodium persulfate for 1-50 s, and finally washing the printed circuit copper-clad plate by using deionized water and drying the printed circuit copper-clad plate for later use;
step 3, preparing a Ni-Co-Ce alloy film: the pretreated plating piece is placed into a plating bath, an alloy film is prepared by adopting a constant potential deposition method at room temperature, the pH value of the solution is kept to be 5-7 in the plating process, and the plating time is 10-40min, and current density of 15-20 mA/cm 2 The temperature of the electroplating solution is 15-40 ℃, and stirring is continuously carried out in the electroplating process to reduce concentration polarization, so that the Ni-Co-Ce alloy film covered on the copper surface of the copper-clad plate can be prepared.
The invention also provides an application of the Ni-Co-Ce alloy film obtained by the method as a protective layer on the surface of an electronic circuit in the manufacture of a printed board, and the Ni-Co-Ce alloy film can be used for manufacturing a corrosion-resistant layer, an anticorrosive layer and the like.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. by adding cerium salt into the plating solution, the Ni-Co-Ce alloy plating layer can be obtained, the electrodeposition speed of nickel and cobalt on the surface of the copper-clad plate and the microstructure of the plating layer are changed through the characteristic adsorption of cerium ions on the copper surface, the plating layer with compact surface and good bonding force with matrix copper is formed, and the technical problem of poor bonding force of the plating layer in the prior art is solved. The existence of the simple substance cerium in the plating layer can not only promote the binding force between the alloy plating layer and the copper surface of the matrix, but also promote the corrosion resistance of the prepared alloy plating layer because the active metal cerium is passivated in the air. In addition, under the condition that the surface roughness of an electronic circuit and a plating layer is not increased, the ultrathin layer high oxidation state substance generated by the passivation of the simple substance cerium increases the wettability (or affinity) of an alloy layer to organic materials special for manufacturing printed circuit boards such as epoxy resin and the like, and effectively improves the peeling strength of the organic resin materials for manufacturing the printed circuit boards on the surface of the plating layer, thereby realizing the compromise of three aims of electronic circuit protection, improvement of the interlayer bonding force of a multilayer board and reduction of the insertion loss (improvement of the signal integrity) of a transmission high-frequency signal.
2. The plating solution provided by the invention does not contain noble metals such as Au and the like, cyanide and the like, and has the advantages of easily obtained plating solution raw materials, good stability, convenience in maintenance, cost saving and environmental friendliness. Meanwhile, the plating solution provided by the invention belongs to a weak acid system, can not generate corrosion action with the substrate organic material of the copper-clad plate, simplifies the preparation operation of the alloy film, reduces the process controllability and the process complexity, simplifies the requirements on equipment and process, and can better realize large-scale application.
3. Preparation of Ni-Co-Ce ternary alloy thin based on plating solution formula of the inventionThe film has excellent electromagnetic performance and cerium special chemical performance, and can realize better compatibility of the bonding force between layers and the improvement of signal integrity in the manufacture of the multi-layer high-frequency printed circuit board. The bonding force between the plating layer and the copper-clad plate substrate is as high as 57.47N/cm 2 Far above industry technical standards.
Drawings
FIG. 1 is an SEM image of a copper substrate prior to plating an alloy after pretreatment in accordance with the present invention.
FIG. 2 is an SEM image of a copper-based Ni-Co-Ce alloy film prepared by the invention.
FIG. 3 is an EDS diagram of a copper-based Ni-Co-Ce alloy film prepared by the invention.
Detailed Description
The present invention will be described in further detail with reference to the embodiments and the accompanying drawings, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent.
According to the characteristic that the nickel-cobalt alloy is a typical magnetic metal alloy and has a synergistic effect, and the property that cerium ions are adsorbed on the surface of copper to help nickel and cobalt cathode deposition potential to negatively move, the invention provides electroplating solution for electrodeposition manufacture of a printed circuit copper-clad plate copper surface Ni-Co-Ce ternary alloy and a method for manufacturing an alloy layer by using the electroplating solution. The nickel source of the plating solution selects nickel chloride, the cobalt source selects cobalt sulfate, the cerium source selects cerium sulfate with the oxidation number of +4, and then the ratio of the concentration of chloride ions to the concentration of sulfate ions in the solution is controlled by adding the conductive material containing chloride ions and sulfate ions, so that the purpose of controlling the conductivity of the plating solution system is achieved, and the plating solution for plating Ni-Co-Ce sulfate-chloride on the copper surface of the copper-clad plate has the advantages of high deposition speed, low plating stress and the like, thereby not only improving the plating quality, but also improving the plating efficiency.
The substrate for selecting the electrodeposited Ni-Co-Ce alloy film is a copper-clad plate for manufacturing a printed circuit board. Firstly, the printed circuit copper-clad plate needs to be cleaned in advance, so that the copper surface of the plated part is ensured to be clean. In the electroplating process, the pretreated printed circuit copper-clad plate is used as a negative electrode to be placed in a plating solution, metal ions in the plating solution are deposited on the surface of a substrate through electroplating, an alloy plating layer is formed on the copper surface of the copper-clad plate, and the alloy is proved to be a Ni-Co-Ce alloy film through EDS.
If the flexible copper clad laminate is used, reinforcement treatment is needed in advance.
Example 1
A method for electroplating a Ni-Co-Ce film on a copper-clad plate for a PCB comprises the following steps:
step 1: preparing a plating solution: taking a certain amount of deionized water in a container, sequentially adding boric acid, sodium chloride, nickel chloride, cobalt sulfate, thiourea, sodium polydithio-dipropyl sulfonate and ceric sulfate under continuous stirring, fully stirring to dissolve all components, then regulating the pH value of the system to pH value=6 by using dilute sulfuric acid or dilute NaOH solution, and finally, fixing the volume by using deionized water with pH value=6 to obtain plating solution; wherein, nickel chloride is 0.04mol/L, cobalt sulfate is 0.035mol/L, sodium chloride is 0.1mol/L, boric acid is 0.2mol/L, thiourea is 0.1mol/L, polydithio-dipropyl sodium sulfonate is 0.1mol/L, ceric sulfate is 0.005mol/L;
step 2: pretreatment of plating parts: cutting an FR-4 copper-clad plate into a size of 1cm multiplied by 1cm, removing surface stains such as surface oxide layers and dirt by using a brush plate, flushing with tap water, airing, immersing in 5% dilute sulfuric acid for 5min, taking out, washing, drying, microetching with a 5% dilute sulfuric acid and 5% sodium persulfate mixed solution for 5 seconds, and finally cleaning with deionized water, and drying for later use;
step 3: preparing a Ni-Co-Ce ternary alloy film: using an AUT85266 electrochemical workstation, adopting a constant potential deposition method to prepare an alloy film, using the copper-clad plate cleaned in the step 2 as a working electrode, using a pure platinum electrode as a counter electrode and a saturated potassium sulfate electrode as a reference electrode, electroplating in the plating solution prepared in the step 1, wherein the temperature is kept at 25 ℃, the pH value of the solution is kept at 6, the electroplating time is kept constant for 5min, and the current density is 20mA/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Stirring is continuously carried out in the electroplating process to reduce concentration polarization, and the required Ni-Co-Ce ternary alloy film can be prepared.
The peel strength of the resin layer on the surface of the copper-clad plate prepared in the embodiment is 47.02N/cm 2 。
Example 2
A Ni-Co-Ce ternary alloy film was prepared following the procedure of example 1, with only the plating bath formulation of step 1 adjusted to: nickel chloride 0.04mol/L, cobalt sulfate 0.035mol/L, sodium chloride 0.1mol/L, boric acid 0.2mol/L, thiourea 0.1mol/L, sodium polydithio-dipropyl sulfonate 0.1mol/L, ceric sulfate 0.01mol/L, pH value=6, and other steps are unchanged.
The peel strength of the resin layer on the surface of the copper-clad plate prepared in the embodiment is 49.21N/cm 2 。
Example 3
A Ni-Co-Ce ternary alloy film was prepared following the procedure of example 1, with only the plating bath formulation of step 1 adjusted to: nickel chloride 0.04mol/L, cobalt sulfate 0.035mol/L, sodium chloride 0.1mol/L, boric acid 0.2mol/L, thiourea 0.1mol/L, sodium polydithio-dipropyl sulfonate 0.1mol/L, ceric sulfate 0.02mol/L, pH value=6, and other steps are unchanged.
The peel strength of the resin layer on the surface of the copper-clad plate prepared in the embodiment is 57.47N/cm 2 。
FIG. 1 is an SEM image of a copper substrate prior to plating an alloy after pretreatment in accordance with the present invention. As can be seen from the figure, the substrate surface is very rough with many faults and gaps.
FIG. 2 is an SEM image of a copper-based Ni-Co-Ce alloy film prepared by the invention. As can be seen from the graph, the alloy film prepared by the method has the advantages of flat and compact surface, fine grains, reduced granular feel, improved brightness of the plating layer, easily changed surface pH value and chemical property, and favorable improvement of the corrosion resistance of the alloy layer by such surface modification, and reduction of the surface roughness.
FIG. 3 is an EDS diagram of a copper-based Ni-Co-Ce alloy film prepared by the invention. As can be seen from the graph, the active ingredients of the alloy film prepared by the method comprise Co, ni and Ce, wherein the Co accounts for 41.45%, the Ni accounts for 50.13% and the Ce accounts for 8.42%.
While the invention has been described in terms of specific embodiments, any feature disclosed in this specification may be replaced by alternative features serving the equivalent or similar purpose, unless expressly stated otherwise; all of the features disclosed, or all of the steps in a method or process, except for mutually exclusive features and/or steps, may be combined in any manner.
Claims (3)
1. The plating solution for electroplating the Ni-Co-Ce film on the copper-clad plate for the PCB is characterized by comprising the following components: 0.03 to 0.05mol/L of nickel chloride, 0.03 to 0.05mol/L of cobalt sulfate, 0.1 to 0.2mol/L of conductive additive, 0.1 to 0.2mol/L of pH buffer, 0.1 to 0.2mol/L of electroplating additive, 0.005 to 0.03mol/L of cerous sulfate and deionized water;
the plating solution is prepared according to the following preparation process: taking a certain amount of deionized water in a container, sequentially adding a pH buffer, a conductive additive, nickel chloride, cobalt sulfate, an electroplating additive and a ceric sulfate compound under continuous stirring, then adding an acid solution or an alkali solution to adjust the pH value of the system to pH value=5-7, and finally, using deionized water with the same pH value as the system to fix the volume to obtain the required plating solution;
the conductive additive is sodium chloride, sodium sulfate, potassium chloride or potassium sulfate; the pH buffering agent is weak acid, weak acid salt or ammonium salt; the electroplating additive is thiourea and sodium polydithio-dipropyl sulfonate or sodium dodecyl sulfate;
the Ni-Co-Ce alloy film obtained based on the plating solution is used as a protective layer for the surface of an electronic circuit in the manufacturing of a printed board.
2. The plating solution of claim 1, wherein the weak acid is acetic acid, citric acid, or boric acid, and the weak acid salt is an oxalate or a tartrate.
3. The preparation method of the electroplated Ni-Co-Ce alloy film of the copper-clad plate for the PCB is characterized by comprising the following steps of:
step 1: pretreatment of a copper matrix: removing surface stains on the printed circuit copper-clad plate to be electroplated, immersing the printed circuit copper-clad plate in 5% dilute sulfuric acid for 1-10 min, taking out the printed circuit copper-clad plate, cleaning the printed circuit copper-clad plate by using deionized water, carrying out microetching treatment by using a mixed solution of 5% dilute sulfuric acid and 5% sodium persulfate for 1-50 s, cleaning the printed circuit copper-clad plate by using deionized water, and drying the printed circuit copper-clad plate for later use;
step 2: preparing a Ni-Co-Ce ternary alloy film: taking the printed circuit copper-clad plate to be electroplated after the cleaning in the step 1 as a cathode, taking a platinum or titanium net as an anode, adopting a constant potential deposition method to prepare an alloy film by electroplating on the copper surface of the copper-clad plate, wherein the electroplating time is 10-40 min, and the current density is 15-20 mA/cm 2 The temperature of the electroplating solution is 15-40 ℃, and stirring is continuously carried out in the electroplating process; wherein, the electroplating solution comprises the following components: 0.03 to 0.05mol/L of nickel chloride, 0.03 to 0.05mol/L of cobalt sulfate, 0.1 to 0.2mol/L of conductive additive, 0.1 to 0.2mol/L of pH buffer, 0.1 to 0.2mol/L of electroplating additive, 0.005 to 0.03mol/L of ceric sulfate and deionized water; wherein the conductive additive is sodium chloride, sodium sulfate, potassium chloride or potassium sulfate; the pH buffering agent is weak acid, weak acid salt or ammonium salt; the electroplating additive is thiourea and sodium polydithio-dipropyl sulfonate or sodium dodecyl sulfate.
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| CN105562637B (en) * | 2015-12-31 | 2018-03-23 | 永春琦承茶叶专业合作社 | A kind of preparation method for the copper plate of crystallizer for being plated with nickel cobalt (alloy) layer |
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