CN114016098A - Copper-clad plate electroplating Ni-Co-Ce film plating solution for PCB and film preparation method - Google Patents
Copper-clad plate electroplating Ni-Co-Ce film plating solution for PCB and film preparation method Download PDFInfo
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- CN114016098A CN114016098A CN202111226368.6A CN202111226368A CN114016098A CN 114016098 A CN114016098 A CN 114016098A CN 202111226368 A CN202111226368 A CN 202111226368A CN 114016098 A CN114016098 A CN 114016098A
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- Prior art keywords
- copper
- electroplating
- clad plate
- mol
- plating solution
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Links
- 238000009713 electroplating Methods 0.000 title claims abstract description 61
- 238000007747 plating Methods 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052802 copper Inorganic materials 0.000 claims abstract description 33
- 239000010949 copper Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 31
- 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
- 230000008569 process Effects 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 11
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims abstract description 11
- 229940044175 cobalt sulfate Drugs 0.000 claims abstract description 11
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims abstract description 11
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 9
- 239000002482 conductive additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 53
- 229910045601 alloy Inorganic materials 0.000 claims description 21
- 239000000956 alloy Substances 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- -1 ceric sulfate compound Chemical class 0.000 claims description 12
- 235000002639 sodium chloride Nutrition 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 claims description 9
- 229910002058 ternary alloy Inorganic materials 0.000 claims 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 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 239000011780 sodium chloride 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
- 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
- 239000006179 pH buffering agent Substances 0.000 claims description 6
- 238000011282 treatment Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 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
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000002791 soaking Methods 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
- 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 compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 238000000861 blow drying Methods 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 31
- 238000004519 manufacturing process Methods 0.000 abstract description 22
- 239000000758 substrate Substances 0.000 abstract description 10
- 239000011229 interlayer Substances 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000009472 formulation Methods 0.000 abstract description 4
- 239000006174 pH buffer Substances 0.000 abstract description 3
- 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 abstract description 2
- 230000009466 transformation Effects 0.000 abstract description 2
- 239000010409 thin film Substances 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 32
- 229910052759 nickel Inorganic materials 0.000 description 16
- 238000005260 corrosion Methods 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 13
- 238000000576 coating method Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 229910052684 Cerium Inorganic materials 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 8
- 230000006872 improvement Effects 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 group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 230000008054 signal transmission Effects 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-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
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000001878 scanning electron micrograph 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
- WITQLILIVJASEQ-UHFFFAOYSA-N cerium nickel Chemical compound [Ni].[Ce] WITQLILIVJASEQ-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 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
- 230000009471 action Effects 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
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008199 coating composition Substances 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
- 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
- 239000013078 crystal Substances 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
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 231100000614 poison Toxicity 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer 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
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000035807 sensation 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
- 235000019333 sodium laurylsulphate Nutrition 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
- 238000010301 surface-oxidation reaction 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
- 239000011135 tin 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
本发提供一种印制电路覆铜板铜面电沉积Ni‑Co‑Ce合金薄膜的镀液配方与制备方法、以及使用该镀液在覆铜板表面制作Ni‑Co‑Ce合金薄膜方法。镀液配方包含：氯化镍0.03～0.05mol/L、硫酸钴0.03～0.05mol/L、导电添加物0.1～0.2mol/L、pH缓冲剂0.1～0.2mol/L、电镀添加剂0.1～0.2mol/L、硫酸高铈0.005～0.03mol/L、去离子水等，电镀获得的Ni‑Co‑Ce合金薄膜可用于多层印制电路板电子线路防护、层间结合力及高频信号完整性提升等。同时镀液配方配制简便且不腐蚀印制电路基板、电镀工艺与设备与印制电路制造领域现有条件兼容性较好，极大降低技术改造投入与产品制造成本。
The invention provides a plating solution formulation and preparation method for electrodepositing Ni-Co-Ce alloy thin film on the copper surface of a printed circuit copper clad laminate, and a method for producing the Ni-Co-Ce alloy thin film on the surface of a copper clad laminate by using the plating solution. The plating solution formula includes: nickel chloride 0.03～0.05mol/L, cobalt sulfate 0.03～0.05mol/L, conductive additive 0.1～0.2mol/L, pH buffer 0.1～0.2mol/L, electroplating additive 0.1～0.2mol /L, cerium sulfate 0.005～0.03mol/L, deionized water, etc. The Ni-Co-Ce alloy film obtained by electroplating can be used for electronic circuit protection, interlayer adhesion and high-frequency signal integrity of multilayer printed circuit boards boost etc. At the same time, the formulation of the plating solution is simple and does not corrode the printed circuit substrate, and the electroplating process and equipment are compatible with the existing conditions in the printed circuit manufacturing field, which greatly reduces the investment in technological transformation and the cost of product manufacturing.
Description
Technical Field
The invention belongs to the technical field of surface modification of printed circuit boards, and particularly relates to a Ni-Co-Ce film electroplating solution for a copper-clad plate for a PCB (printed circuit board) 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 substrate materials with the largest use amount at present, and the surface protection treatment of the printed circuit board is one of the important processes in the field of printed circuit board manufacturing in order to avoid the problems of oxidation, pollution and the like of the printed circuit board before components are packaged.
The surface treatment techniques commonly used in the industry at present include hot air leveling, chemical immersion of nickel gold/silver/tin, coating of organic protective film, electroplating of tin/nickel gold and the like. For example, Gaoban is introduced in the treatise on the research and application of the tin plating technology for the copper surface of the printed circuit board, and the tin plating layer prepared by adopting the technology can improve the etching quality of an electronic circuit and the welding reliability of components and parts, enhance 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 nickel electroplating layer in the field of printed circuits is based on the fact that a nickel simple substance has better corrosion resistance and high temperature resistance, a nickel plating layer can be easily passivated in the air and can effectively play a role in protecting copper electronic circuits by the characteristics of slow action with common strong base, strong acid, hydrochloric acid and sulfuric acid, and the like, and the patent 'a method for electroplating nickel on the surface of the printed circuit board by using ionic liquid' (application publication No. CN105018975A) realizes the preparation of the nickel electroplating layer on the surface of the printed circuit board by using the ionic liquid as electrolyte, but a pure nickel plating layer on the surface of copper has the defects of poor stability, easy peeling of the plating layer, non-bright surface and the like. Therefore, the development of the technique for manufacturing the alloy coating on the surface of the printed circuit board becomes an industrial research hotspot. The patent 'production process of nickel-cerium alloy plated annealed copper wire' (publication number CN101556846A) proposes a production process of nickel-cerium alloy plated annealed copper wire on the surface of copper wire, and the obtained nickel-cerium alloy plated coating has the characteristics of good adhesiveness, good toughness, excellent extensibility and the like on the surface of annealed copper wire, and is suitable for manufacturing aviation wire and cable and special installation conductive cores; the patent 'a printed circuit board electroplating nickel gold technology' (application publication No. CN101835346A) adopts the design of electroplating connecting line to conduct the electric brush position on the edge of the printed circuit board technology and the non-edge region to be electroplated with nickel and gold, thus realizing the electroplating of nickel and gold on the non-edge region on the printed circuit board, ensuring the reliability of the electroplating nickel layer on the printed circuit board, effectively reducing the waste of precious metal nickel and gold resources, reducing the cost and being more environment-friendly; the patent 'plating solution for electroplating a nickel-cobalt-iron alloy layer on a crystallizer copper plate' (application publication No. CN105442002A) discloses a plating solution for electroplating a nickel-cobalt-iron alloy layer on a crystallizer copper plate, which comprises 240g/L of nickel sulfate 220-.
In order to solve the corrosion resistance problem of the copper foil, some copper foil manufacturers develop ternary and quaternary alloy corrosion resistant processes of metals such as zinc, nickel, cobalt, tin, iron, arsenic, tungsten and the like, so that the corrosion resistance of the copper foil is greatly improved, but the processes are complex, the process parameter range is narrow, and the problems of difficult operation, high cost, difficult plating solution recovery and wastewater treatment, environmental protection and the like exist. Based on the cerium atom structure with 4f unfilled electrons and small electronegativity, the copper-based electroplating technology added with cerium salt has attracted attention. The patent 'surface treating agent for improving the corrosion resistance of electrolytic copper foil' (application publication No. CN 111304709A) realizes the improvement of the corrosion resistance of the copper foil by electroplating the surface of the copper foil to form a uniform and fine tin-zinc-cerium ternary alloy composite plating layer, and the hydrochloric acid cracking resistance of the copper foil can be realized to be less than 2%; the patent 'a rare earth cerium-copper-zinc alloy electroplating solution and an electroplating method thereof' (application publication number CN105483772A) 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 dioxide decorations, 4-40g/L of amino acid, 100 g/L of sodium pyrophosphate and 200g/L of brightener, and a cerium-copper-zinc alloy coating electroplated by using the electroplating solution has the advantages of beautiful color, compactness and corrosion resistance. The document results in further improvement of the stability of electronic circuits in the environment, but the core problems of interlayer bonding force, electromagnetic compatibility and the like in the manufacture of multilayer printed circuit boards are not involved. The existing interlayer bonding force is mostly improved by treatments such as browning, and the treatment means can improve the roughness of the copper surface and increase the insertion loss. With the development of high density and multi-layer circuit boards, especially the development of high frequency signal transmission of electronic products in recent years, the production of metal coatings on copper-based surfaces of printed circuits not only needs to consider the improvement of corrosion resistance and wear resistance of copper electronic circuits, but also needs to consider the improvement of interlayer bonding force of multilayer boards, and the problems of signal loss, electromagnetic interference and the like of protected electronic circuits during high frequency signal transmission. In addition, in practice, it is found that some alloy layers obtained by electroplating are not fine and uniform enough in crystallization, and the corrosion resistance of the alloy layers does not achieve an ideal effect, so that the edge corrosion phenomenon occurs when a copper foil circuit board is etched on a high-precision circuit, and the quality of a manufactured finished product is seriously affected.
Therefore, developing a new plating solution formula and realizing good protection of the protective coating of the copper-clad plate of the printed circuit become research hotspots.
Disclosure of Invention
Aiming at the problems of weak bonding force between a protective coating prepared by the prior coating formula and a printed circuit copper-clad plate, influence on signal transmission and the like in the prior art, the invention aims to provide a coating 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 effect in the copper surface electroplating 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 composition, the surface compactness and other properties of the prepared Ni-Co-Ce alloy are realized, the peel strength of high polymer materials such as epoxy resin 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, so that the interlayer bonding force is improved and the insertion loss of high-frequency transmission signals is reduced in the manufacturing process of the multilayer high-frequency printed circuit board. Meanwhile, the formula of the plating solution does not contain precious metals such as gold and the like and highly toxic substances and the like, the plating solution is simple and convenient to prepare and does not corrode organic materials of the printed circuit substrate, equipment for manufacturing an 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 transformation investment is less, and the production and manufacturing cost is low.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a plating solution for electroplating a Ni-Co-Ce film on a copper-clad plate for a PCB comprises the following components: 0.03-0.05 mol/L of nickel chloride, 0.03-0.05 mol/L of cobalt sulfate, 0.1-0.2 mol/L of conductive additive, 0.1-0.2 mol/L of pH buffering agent, 0.1-0.2 mol/L of electroplating additive, 0.005-0.03 mol/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, which is acetic acid, citric acid, boric acid, or the like, a weak acid salt, which is oxalate, tartrate, phosphate, or the like, preferably boric acid, or an ammonium salt.
Further, the plating additive is sodium lauryl sulfate, thiourea, sodium polydithio-dipropyl sulfonate (SPS), and the like, 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:
step 1, preparing plating solution: putting a certain amount of deionized water into a container, sequentially adding a pH buffering agent, a conductive additive, a nickel salt, a 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 a dilute NaOH solution, and finally performing constant volume by using the deionized water with the preset pH value to obtain a plating solution; 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 agent is 0.1-0.2 mol/L, electroplating additive is 0.1-0.2 mol/L, and pH value is 5-7;
step 2, pretreatment of the plated part: 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, then soaking and washing the printed circuit copper-clad plate in 5% dilute sulfuric acid 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, finally cleaning the printed circuit copper-clad plate by using deionized water, and blow-drying the cleaned printed circuit copper-clad plate for later use;
step 3, preparing the Ni-Co-Ce alloy film: putting the pretreated plating piece into an electroplating bath, preparing the alloy film by adopting a constant potential deposition method at room temperature, keeping the pH value of the solution at 5-7 in the electroplating process, and keeping the electroplating time at 10-40 min and the current density at 15-20 mA/cm2And continuously stirring the electroplating solution at the temperature of 15-40 ℃ in the electroplating process to reduce concentration polarization, thus preparing the Ni-Co-Ce alloy film covering the copper surface of the copper-clad plate.
The invention also provides the application of the Ni-Co-Ce alloy film obtained by the method as a surface protective layer of an electronic circuit in the manufacture of a printed board, and the Ni-Co-Ce alloy film can be used for manufacturing an anti-corrosion layer, an anti-corrosion layer and the like.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the Ni-Co-Ce alloy plating layer can be obtained by adding cerium salt into the plating solution, the electrodeposition speed of nickel and cobalt on the surface of the copper-clad plate and the microstructure of the plating layer are changed by the characteristic adsorption of cerium ions on the copper surface, the formation of the plating layer with compact surface and good binding force with matrix copper is facilitated, and the technical problem of poor binding force of the plating layer in the prior art is broken through. The existence of the simple substance cerium in the plating layer can not only improve the binding force between the alloy plating layer and the substrate copper surface, but also improve the corrosion resistance of the prepared alloy plating layer because the active metal cerium generates passivation in the air. In addition, under the condition that the surface roughness of an electronic circuit and a coating is not increased, the wettability (or affinity) of an alloy layer to organic materials special for manufacturing printed circuit boards such as epoxy resin is increased by using an extremely thin layer of high-oxidation-state substances generated by elementary cerium passivation, and the peel strength of the organic resin materials for manufacturing the printed circuit on the surface of the coating is effectively improved, so that the three aims of electronic circuit protection, multi-layer board interlayer bonding force improvement and high-frequency signal transmission insertion loss reduction (signal integrity improvement) are fulfilled.
2. The plating solution provided by the invention does not contain precious metals such as Au and the like, cyanide and the like, is easy to obtain the plating solution raw materials, has good stability, is convenient to maintain, saves the cost and is environment-friendly. Meanwhile, the plating solution provided by the invention belongs to a weak acid system, does not generate a corrosion effect with a substrate organic material of a copper-clad plate, simplifies the preparation operation of an alloy film, reduces the controllability of the process and the complexity of the process, simplifies the requirements of equipment and process, and can better realize large-scale application.
3. The Ni-Co-Ce ternary alloy film prepared based on the plating solution formula has excellent electromagnetic performance and cerium specific chemical performance, and can realize better compatibility of interlayer bonding force and signal integrity improvement in the manufacture of multilayer high-frequency printed circuit boards. The bonding force between the plating layer and the copper-clad plate substrate is as high as 57.47N/cm2And is far higher than the technical standard of the industry.
Drawings
FIG. 1 is an SEM image of a copper substrate prior to alloy plating after pretreatment in accordance with the present invention.
FIG. 2 is an SEM image of the copper-based Ni-Co-Ce alloy film prepared by the invention.
FIG. 3 is an EDS diagram of the copper-based Ni-Co-Ce alloy film prepared by the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following embodiments and accompanying drawings.
The invention provides electroplating solution prepared by electroplating ternary Ni-Co-Ce alloy on the copper surface of a copper-clad plate of a printed circuit and a method for preparing an alloy layer by using the electroplating solution, according to the characteristic that nickel-cobalt alloy is a typical magnetic metal alloy and has a synergistic effect and the characteristic that cerium ions are adsorbed on the surface of copper and contribute to negative displacement of the deposition potential of nickel and cobalt cathodes. The nickel source of the electroplating solution is selected from nickel chloride, the cobalt source is selected from cobalt sulfate, the cerium source is selected from cerium sulfate with the oxidation number of +4, and then a conductive substance containing chloride ions and sulfate ions is added to control the ratio of the concentration of the chloride ions to the concentration of the sulfate ions in the solution, so that the aim of controlling the conductivity of the electroplating solution system is fulfilled, and the Ni-Co-Ce sulfate-chloride electroplating solution system for electroplating the copper surface of the copper-clad plate has the advantages of high deposition speed, low coating stress and the like, so that the coating quality can be improved, and the electroplating efficiency can be improved.
The substrate of the electrodeposited Ni-Co-Ce alloy film is selected to be a copper-clad plate for manufacturing the printed circuit board. Firstly, the printed circuit copper-clad plate needs to be cleaned in advance, so that the copper surface of a plated part is clean. In the electroplating process, the printed circuit copper-clad plate after pretreatment is used as a negative electrode and placed in a plating solution, metal ions in the plating solution are deposited on the surface of a matrix through electroplating, an alloy plating layer is formed on the copper surface of the copper-clad plate, and EDS proves that the alloy becomes a Ni-Co-Ce alloy film.
If the copper clad laminate is a flexible copper clad laminate, reinforcement treatment needs to be carried out 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: putting a certain amount of deionized water into 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 adjusting the pH value of the system to 6 by using dilute sulfuric acid or dilute NaOH solution, and finally performing constant volume by using the deionized water with the pH value of 6 to obtain a 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, sodium polydithio-dipropyl sulfonate is 0.1mol/L, and ceric sulfate is 0.005 mol/L;
step 2: pretreatment of a plated part: cutting the FR-4 copper-clad plate into a size of 1cm multiplied by 1cm, removing surface stains such as surface oxidation layers, dirt and the like by using a brush plate, then washing with tap water, airing, soaking in 5% dilute sulfuric acid for 5min, taking out, washing, drying, then carrying out micro-etching for 5 seconds by using a mixed solution of 5% dilute sulfuric acid and 5% sodium persulfate, finally cleaning with deionized water, and drying for later use;
and step 3: preparing a Ni-Co-Ce ternary alloy film: preparing an alloy film by using an AUT85266 electrochemical workstation and adopting a constant potential deposition method, electroplating in the plating solution prepared in the step 1 by using the copper-clad plate cleaned in the step 2 as a working electrode, a pure platinum electrode as a counter electrode and a saturated potassium sulfate electrode as a reference electrode, keeping the temperature at 25 ℃, the pH value of the solution at 6, the electroplating time at 5min and the current density at 20mA/cm in the electroplating process2(ii) a And continuously stirring in the electroplating process to reduce concentration polarization, thus preparing the required Ni-Co-Ce ternary alloy film.
The peel strength of the resin layer on the surface of the copper-clad plate prepared by the embodiment is 47.02N/cm2。
Example 2
A Ni-Co-Ce ternary alloy film was prepared according to the procedure of example 1, with only the bath formulation of step 1 adjusted to: 0.04mol/L of nickel chloride, 0.035mol/L of cobalt sulfate, 0.1mol/L of sodium chloride, 0.2mol/L of boric acid, 0.1mol/L of thiourea, 0.1mol/L of sodium polydithio-dipropyl sulfonate, 0.01mol/L of ceric sulfate, pH value of 6 and other steps are not changed.
The peel strength of the resin layer on the surface of the copper-clad plate prepared by the embodiment is 49.21N/cm2。
Example 3
A Ni-Co-Ce ternary alloy film was prepared according to the procedure of example 1, with only the bath formulation of step 1 adjusted to: 0.04mol/L of nickel chloride, 0.035mol/L of cobalt sulfate, 0.1mol/L of sodium chloride, 0.2mol/L of boric acid, 0.1mol/L of thiourea, 0.1mol/L of sodium polydithio-dipropyl sulfonate, 0.02mol/L of ceric sulfate, pH value of 6 and other steps are not changed.
The peel strength of the resin layer on the surface of the copper-clad plate prepared by the embodiment is 57.47N/cm2。
FIG. 1 is an SEM image of a copper substrate prior to alloy plating after pretreatment in accordance with the present invention. As can be seen from the figure, the surface of the substrate is very rough with many faults and gaps.
FIG. 2 is an SEM image of the copper-based Ni-Co-Ce alloy film prepared by the invention. As can be seen from the figure, the alloy film prepared by the method has the advantages of smooth and compact surface, refined crystal grains, reduced granular sensation, improved coating brightness, easily changed surface pH value and chemical properties, and the surface modification is favorable for improving the corrosion resistance of the alloy layer and reducing the surface roughness.
FIG. 3 is an EDS diagram of the copper-based Ni-Co-Ce alloy film prepared by the invention. As can be seen from the figure, the effective components of the alloy film prepared by the method comprise Co, Ni and Ce, wherein the ratio of Co is 41.45%, the ratio of Ni is 50.13% and the ratio of Ce is 8.42%.
While the invention has been described with reference to specific embodiments, any feature disclosed in this specification may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise; all of the disclosed features, or all of the method or process steps, may be combined in any combination, except mutually exclusive features and/or steps.
Claims (6)
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: 0.03-0.05 mol/L of nickel chloride, 0.03-0.05 mol/L of cobalt sulfate, 0.1-0.2 mol/L of conductive additives, 0.1-0.2 mol/L of pH buffering agents, 0.1-0.2 mol/L of electroplating additives, 0.005-0.03 mol/L of ceric sulfate and deionized water;
the plating solution is prepared according to the following preparation process: and (2) putting a certain amount of deionized water into a container, sequentially adding a pH buffering agent, 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 5-7, and finally performing constant volume by using the deionized water with the same pH value as the system to obtain the required plating solution.
2. The plating solution of claim 1, wherein the conductive additive is sodium chloride, sodium sulfate, potassium chloride, or potassium sulfate.
3. The plating solution of claim 1, wherein the pH buffering agent is a weak acid, a weak acid salt, or an ammonium salt.
4. The plating solution of claim 3, wherein the weak acid is acetic acid, citric acid, or boric acid and the salt of the weak acid is an oxalate, tartrate, or phosphate.
5. The plating solution of claim 1, wherein the plating additives are sodium dodecyl sulfate, thiourea, and sodium polydithio dipropane sulfonate.
6. A preparation method of a Ni-Co-Ce alloy film electroplated on a copper-clad plate for a PCB is characterized by comprising the following steps:
step 1: copper matrix pretreatment: removing surface stains on the printed circuit copper-clad plate to be electroplated, soaking and washing the printed circuit copper-clad plate in 5% dilute sulfuric acid for 1-10 min, taking out the printed circuit copper-clad plate, washing the printed circuit copper-clad plate with deionized water, carrying out microetching treatment on the copper-clad plate with a mixed solution of 5% dilute sulfuric acid and 5% sodium persulfate for 1-50 s, finally cleaning the copper-clad plate with deionized water, and blow-drying the 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 cleaned in the step 1 as a cathode and a platinum or titanium net as an anode, and electroplating the copper surface of the copper-clad plate at room temperature by adopting a constant potential deposition method to prepare an alloy film, wherein the electroplating time is 10-40 min, and the current density is 15-20 mA/cm2Continuously stirring the electroplating solution at the temperature of 15-40 ℃ in the electroplating process; wherein, the electroplating solution comprises the following components: 0.03-0.05 mol/L of nickel chloride, 0.03-0.05 mol/L of cobalt sulfate, 0.1-0.2 mol/L of conductive additive, 0.1-0.2 mol/L of pH buffering agent, 0.1-0.2 mol/L of electroplating additive, 0.005-0.03 mol/L of ceric sulfate and deionized water.
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