CN102758230B - Gold electroplating solution and gold electroplating method - Google Patents
Gold electroplating solution and gold electroplating method Download PDFInfo
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- CN102758230B CN102758230B CN201210239390.9A CN201210239390A CN102758230B CN 102758230 B CN102758230 B CN 102758230B CN 201210239390 A CN201210239390 A CN 201210239390A CN 102758230 B CN102758230 B CN 102758230B
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- Prior art keywords
- gold
- plating
- plating solution
- solution
- acid
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- 239000010931 gold Substances 0.000 title claims abstract description 50
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000009713 electroplating Methods 0.000 title abstract description 14
- 238000007747 plating Methods 0.000 claims abstract description 78
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 238000005282 brightening Methods 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 54
- 239000007788 liquid Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 150000001413 amino acids Chemical class 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000006388 chemical passivation reaction Methods 0.000 claims description 5
- 235000011194 food seasoning agent Nutrition 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- 239000012487 rinsing solution Substances 0.000 claims description 5
- 238000005494 tarnishing Methods 0.000 claims description 5
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 3
- 150000003566 thiocarboxylic acids Chemical class 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 12
- -1 hydroxyl compound Chemical class 0.000 abstract description 12
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 abstract description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 abstract description 7
- 125000004434 sulfur atom Chemical group 0.000 abstract description 6
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 abstract description 6
- 229910001430 chromium ion Inorganic materials 0.000 abstract description 5
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract description 2
- 229910003803 Gold(III) chloride Inorganic materials 0.000 abstract 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 abstract 1
- 229940091173 hydantoin Drugs 0.000 abstract 1
- 150000002825 nitriles Chemical class 0.000 abstract 1
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract 1
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- 239000002253 acid Substances 0.000 description 9
- 229940024606 amino acid Drugs 0.000 description 9
- 235000001014 amino acid Nutrition 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229960003512 nicotinic acid Drugs 0.000 description 6
- 235000001968 nicotinic acid Nutrition 0.000 description 6
- 239000011664 nicotinic acid Substances 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 235000015320 potassium carbonate Nutrition 0.000 description 5
- 229910001020 Au alloy Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229940074355 nitric acid Drugs 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OTJFQRMIRKXXRS-UHFFFAOYSA-N (hydroxymethylamino)methanol Chemical compound OCNCO OTJFQRMIRKXXRS-UHFFFAOYSA-N 0.000 description 2
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- RLQMACPTWZLKDP-UHFFFAOYSA-N aminomethanediol Chemical compound NC(O)O RLQMACPTWZLKDP-UHFFFAOYSA-N 0.000 description 2
- 239000003429 antifungal agent Substances 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 2
- 229940043276 diisopropanolamine Drugs 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 150000002343 gold Chemical class 0.000 description 2
- 239000003353 gold alloy Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- KQIXMZWXFFHRAQ-UHFFFAOYSA-N 1-(2-hydroxybutylamino)butan-2-ol Chemical compound CCC(O)CNCC(O)CC KQIXMZWXFFHRAQ-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- WQNHWIYLCRZRLR-UHFFFAOYSA-N 2-(3-hydroxy-2,5-dioxooxolan-3-yl)acetic acid Chemical compound OC(=O)CC1(O)CC(=O)OC1=O WQNHWIYLCRZRLR-UHFFFAOYSA-N 0.000 description 1
- BZFGKBQHQJVAHS-UHFFFAOYSA-N 2-(trifluoromethyl)pyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C(F)(F)F)=C1 BZFGKBQHQJVAHS-UHFFFAOYSA-N 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- IOYAWJILOLWDLG-UHFFFAOYSA-N C(CC(O)(C(=O)O)CC(=O)O)(=O)O.N#CC#N Chemical compound C(CC(O)(C(=O)O)CC(=O)O)(=O)O.N#CC#N IOYAWJILOLWDLG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 1
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 1
- XUYPXLNMDZIRQH-LURJTMIESA-N N-acetyl-L-methionine Chemical compound CSCC[C@@H](C(O)=O)NC(C)=O XUYPXLNMDZIRQH-LURJTMIESA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- BIOSDDNUGLLZPN-UHFFFAOYSA-N O.[K].[K].[K].OC(=O)CC(O)(C(O)=O)CC(O)=O Chemical compound O.[K].[K].[K].OC(=O)CC(O)(C(O)=O)CC(O)=O BIOSDDNUGLLZPN-UHFFFAOYSA-N 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- RLUOETYSBXHPQQ-UHFFFAOYSA-N S(CC(=O)O)CC(=O)O.C(C)(=O)O Chemical compound S(CC(=O)O)CC(=O)O.C(C)(=O)O RLUOETYSBXHPQQ-UHFFFAOYSA-N 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 1
- 239000006035 Tryptophane Substances 0.000 description 1
- ITBPIKUGMIZTJR-UHFFFAOYSA-N [bis(hydroxymethyl)amino]methanol Chemical compound OCN(CO)CO ITBPIKUGMIZTJR-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- VQLYBLABXAHUDN-UHFFFAOYSA-N bis(4-fluorophenyl)-methyl-(1,2,4-triazol-1-ylmethyl)silane;methyl n-(1h-benzimidazol-2-yl)carbamate Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1.C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 VQLYBLABXAHUDN-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000005693 branched-chain amino acids Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- TVMUHOAONWHJBV-UHFFFAOYSA-N dehydroglycine Chemical compound OC(=O)C=N TVMUHOAONWHJBV-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229960002989 glutamic acid Drugs 0.000 description 1
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 description 1
- MXZVHYUSLJAVOE-UHFFFAOYSA-N gold(3+);tricyanide Chemical compound [Au+3].N#[C-].N#[C-].N#[C-] MXZVHYUSLJAVOE-UHFFFAOYSA-N 0.000 description 1
- 125000002349 hydroxyamino group Chemical group [H]ON([H])[*] 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Natural products OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- NRTDAKURTMLAFN-UHFFFAOYSA-N potassium;gold(3+);tetracyanide Chemical compound [K+].[Au+3].N#[C-].N#[C-].N#[C-].N#[C-] NRTDAKURTMLAFN-UHFFFAOYSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
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- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 229960004799 tryptophan Drugs 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention relates to a gold electroplating solution and a gold electroplating method. The gold electroplating solution comprises auric chloride, hydantoin, chromium ions, potassium pyrophosphate, potassium carbonate and brightening agent, wherein the brightening agent of the plating solution is a carboxyl or hydroxyl compound containing nitrogen atoms, or a carboxyl compound containing sulfur atoms. The gold electroplating solution provided by the invention is a non-cyanide gold-plating solution which can be used for plating a gold-plated layer on a metal substrate without cyanides; and moreover, the gold-plated layer has good brightness and high density.
Description
Technical field
The present invention relates to a kind of gold-plating solution and electro-plating method.
Background technology
Gold plate solidity to corrosion is strong, good conductivity, is easy to welding, high temperature resistant, and has certain wear resistance (as being mixed with the hard gold of other elements a small amount of).Thus, he is widely used in precision instrumentation, printing plate, unicircuit, electronics shell, electric contact etc. and requires that the part of electrical parameter performance long-term stability is electroplated.Gold plate as decorative coating also for electroplating jewellery, clock and watch part, artwork etc.Gold-platedly on silver prevent variable color.
In recent years, the electric property excellent due to gold and erosion resistance, in order to protect the surface of electronic component such as contact terminal, to be gold-platedly widely used on electron device and electronic component.The gold-plated surface treatment being used as the electrode terminal of semiconductor element, as the lead-in wire be formed in plastics film (lead), or is such as communicated with the surface treatment etc. of junctor of electron device as electronic component.Metal, plastics, pottery, semi-conductor etc. can be comprised by gold-plated material.
The junctor being communicated with electron device uses hard gold-plated, because according to the characteristic used, must have anti-corrosion, wear-resisting and conductivity as surface-treated gold coated films.Gold cobalt alloy plating and golden nickelalloy plating etc. are conventional hard gold-plated (such as, see DE1111897 and JP60-155696).In general, copper or copper alloy are used as the substrate of electronic component (as junctor).But in the surface of deposition of gold at copper, copper can be diffused in golden film.Therefore, in time using the gold-plated surface-treated as copper, usually carry out the blocking layer of nickel plating as copper substrate on copper surface.In general, carry out gold-plated on the surface of nickel coating subsequently.
Electronic component (such as junctor) carries out the gold-plated standard method of local hard and comprises a plating, by controlling the plating of liquid level, rack plating and barrel plating etc.
CN 101333671 discloses a kind of acidic gold alloy plating solution and solution and coating method thereof, and provide a kind of gold plating liquid with high depositing selective, this gold plating liquid contains gold tricyanide, cobalt ion, vulkacit H and special brightening agent.The brightening agent of described plating solution is the nitrogen atom compound with carboxyl or hydroxyl, or has the sulfur atom-containing compound of carboxyl.
In prior art, the gold plating solution of use has cyanide bath, low cyanogen Citrate trianion plating solution and sulphite plating solution.But, use traditional gold plating liquid, in the process of high current density plating, there are some problems, because so-called " burning " phenomenon can be there is on the golden film of deposition.In addition, use traditional gold plating liquid, Problems existing is when needing certain region of gold-plated film to carry out local electroplating at electronic component, and namely gold or au-alloy can not need gold-plated place deposition in the region around this yet yet.
In order to avoid gold is in unwanted place deposition, a variety of technology has been had to be suggested.The present inventor finds, by using a kind of acid golden cobalt plating bath, taking vulkacit H as additive, can control unnecessary deposition of gold, and having applied for patent (see JP2006-224465).By using these technology, unnecessary deposition of gold can be controlled, but needs the glossiness improving the gold coated films deposited further, and improves sedimentation velocity, and expands the current density range that can obtain good plating.
Prior art surface, the kind of coordination agent and content have larger impact for the outward appearance of coating.When coordination agent content is on the low side, coating surface has red floating ash; Along with the raising of coordination agent content, this floating ash obviously reduces, and even disappears, but when coordination agent too high levels, electroplate liquid is unstable, easy crystallize out.Thus, the present invention selects glycolylurea as coordination agent, and preferably 5,5-T10s (DMH) are as coordination agent.Preferably, the glycolylurea containing 30-100 weight part in gold-plating solution of the present invention.
Salt of wormwood is conducting salt of the present invention, can improve plating solution conductive capability.But the excessive concentration of sodium carbonate can crystallization in the plating solution, affects the stability of coating.Preferably, gold-plating solution of the present invention contains the sodium carbonate of 12-15 weight part, such as 12 parts, 12.4 parts, 13.5 parts, 14.7 parts, 15 parts.
Potassium pyrophosphate is auxiliary complex-former of the present invention, can improve the outward appearance of coating further, suppresses anode passivation.Preferably, gold-plating solution of the present invention contains the trisodium phosphate of 10-30 weight part, such as 10 parts, 10.3 parts, 16.6 parts, 21 parts, 25.5 parts, 29.6 parts, 30 parts.
Rare earth metal chromium can improve the stability of gold-plating solution.Preferably, gold-plating solution of the present invention contains the chromic salts of 12-18 weight part, such as 12 parts, 12.2 parts, 13.6 parts, 15 parts, 17.7 parts, 18 parts.The kind of the present invention to chromic salts does not limit, and what those skilled in the art can be known all can be used for the present invention by water-soluble chromic salts, and the typical but non-limiting example of described chromic salts has chromium chloride, chromium sulphate, chromium nitrate etc.
Brightening agent of the present invention is the nitrogen atom compound with carboxyl or hydroxyl, or has the sulfur atom-containing compound of carboxyl.The example with the nitrogen atom compound of carboxyl comprises: amino acid, such as neutral amino acids, acidic amino acid or basic aminoacids; Pyridine compounds containing carboxyl, such as, as pyridine carboxylic acid (such as 2-Pyridinecarboxylic Acid, Niacin Nicitinic Acid and 4-pyridine carboxylic acid) and its salt; Also can be imino-acetic acid; Nitrilotriacetic acid(NTA) (nitrillotriacetic acid); Diethylene triaminepentaacetic acid(DTPA); And ethylene dinitrilotetra-acetic acid.The example of neutral amino acids comprises: L-Ala, glycine, branched-chain amino acid as α-amino-isovaleric acid and L-LEU, sulfur-containing amino acid as Gelucystine, amidoamino acid as l-asparagine or glutamine, aliphatic amino acid as hydroxyamino acid, as Serine; Die aromatischen Aminosaeuren as phenylalanine, tyrosine and tryptophane, and imino-acid.The example of basic aminoacids comprises Methionin and arginine etc.The example of acidic amino acid comprises aspartic acid and L-glutamic acid etc.The example with the nitrogenous compound of hydroxyl comprises: alkanolamine is as carbinolamine, thanomin, Propanolamine, and α-amino isopropyl alcohol, two alkanolamines (dialkanolamine) are as dimethanolamine (dimethanolamine), diethanolamine, dipropanolamine (dipropanolamine), diisopropanolamine (DIPA) and two butanolamines (dibutanolamine), trialkanolamine (trialkanolamine) is as trimethanolamine, and trolamine, and aminodiol compound is as amino methylene glycol (aminomethanediol), 2-aminooxyethanol (aminoethanediol) etc.The example with the sulfur atom-containing compound of carboxyl comprises: thiolactic acid, thiobis acetic acid (thiodiacetic acid), and thiomalic acid etc.Brightening agent can be used alone, also can two or more combinationally use.
Preferably, the brightening agent containing 0-10 weight part in gold-plating solution of the present invention.
In addition, electroconductibility rising agent, anti-mycotic agent (antifungal agent) and tensio-active agent etc. also can add in gold alloy plating solution of the present invention, not depart from object of the present invention and effect for degree.
As optimal technical scheme, gold-plating solution of the present invention by weight component comprises:
Wherein, described " 0 ", for not comprise corresponding component, the content of such as brightening agent is 0-10, means can not contain brightening agent in gold-plating solution of the present invention.
Preferably, described gold-plating solution by weight component comprise:
Or described gold-plating solution by weight component comprises:
In addition, the invention provides a kind of method next gold-plated by electrolysis plating (electrolytic plating), the method uses gold-plating solution, gold-plating solution contains gold perchloride, glycolylurea, cobalt ion, sequestrant, vulkacit H and has the nitrogen atom compound of carboxyl or hydroxyl, or has the sulfur atom-containing compound of carboxyl.
Preferably, the pH value of plating solution of the present invention between 3 and 6.
Preferably, the method for the invention comprises the steps:
Metal base is polished through flint paper and fine sandpaper first; It is in 15%KOH solution that base material after polishing is immersed in massfraction, takes out after 10 ~ 20min; In rinsing solution, the oxide film of substrate surface is removed after washing; After washing, base material is connected with wire, puts into electroplate liquid, then gold-plated; Plate after washing, and put into chemical passivation liquid and carry out Anti-tarnishing process; Last seasoning in atmosphere.
In gold plating process, current density to the outward appearance of coating and character extremely important, when current density is lower than 0.5A/dm
2time, Deposit appearance is poor, but, when current density is more than 2A/dm
2time, the outward appearance of coating becomes again coarse.Therefore, in gold plating process of the present invention, current density is 0.5-2A/dm
2, preferred 0.7-1.8A/dm
2.In described gold plating process, the temperature of plating solution is between 20 DEG C to 80 DEG C, preferably 30 DEG C to 60 DEG C.
Gold-plating solution provided by the invention is a kind of cyanogen-less gold solution, can when not containing cyanogen, plated with gold coating on metal matrix, and described gold plate has good luminance brightness, and gold plate density is high.
Summary of the invention
An object of the present invention is to provide a kind of gold-plating solution, and two of object is a kind of method providing electrogilding.The glossiness electrogilding film with good covering and sedimentation velocity is obtained by described electro-plating method.The invention provides golden plating solution and gold plating method, maintain the performance of the gold coated films of connector surface, deposit relatively thick gold-plated film at higher current densities, the deposition that gold-plated film suppresses in unwanted region is simultaneously deposited in required region, which raises the sedimentation velocity of gold-plated film, and can in wide current density range plating.
Gold-plating solution of the present invention, contain: gold perchloride, glycolylurea, chromium ion, potassium pyrophosphate, salt of wormwood and brightening agent, wherein, the brightening agent of described plating solution is the nitrogen atom compound with carboxyl or hydroxyl, or has the sulfur atom-containing compound of carboxyl.
Gold perchloride in gold plating solution of the present invention is the main salt of gold plating solution.Gold salts contg has very large impact to sedimentation velocity and Deposit appearance.Generally, along with the raising of golden salts contg, cathode current density can improve, and sedimentation velocity can be accelerated.But if golden salts contg is too high, the cost of electrogilding increases, and coating can be made to produce the phenomenon of fragility increase; And gold content is too low, tint is poor, and cathode current density is lower, and sedimentation velocity is slower.Preferably, the gold perchloride containing 20-40 weight part in gold-plating solution of the present invention.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
A kind of gold-plating solution by weight component comprises:
Gold perchloride 20
Glycolylurea 100
Chromium ion 32
Potassium pyrophosphate 49
Salt of wormwood 77
Nicotinic acid (Niacin Nicitinic Acid) 10.
Electroplating process is: polished through flint paper and fine sandpaper first by metal base; It is in 7%KOH solution that base material after polishing is immersed in massfraction, takes out after 10min; In rinsing solution, the oxide film of substrate surface is removed after washing; After washing, base material is connected with wire, puts into electroplate liquid, then gold-plated; Plate after washing, and put into chemical passivation liquid and carry out Anti-tarnishing process; Last seasoning in atmosphere.In described gold plating process, current density is 2A/dm
2.In described gold plating process, the temperature of plating solution is 20 DEG C.
Embodiment 2
A kind of gold-plating solution by weight component comprises:
Gold perchloride 40
Glycolylurea 30
Chromium ion 44
Potassium pyrophosphate 20
Salt of wormwood 90
Electroplating process is: polished through flint paper and fine sandpaper first by metal base; It is in 17%KOH solution that base material after polishing is immersed in massfraction, takes out after 20min; In rinsing solution, the oxide film of substrate surface is removed after washing; After washing, base material is connected with wire, puts into electroplate liquid, then gold-plated; Plate after washing, and put into chemical passivation liquid and carry out Anti-tarnishing process; Last seasoning in atmosphere.In described gold plating process, current density is 0.5A/dm
2, preferred 1.8A/dm
2.In described gold plating process, the temperature of plating solution is 80 DEG C.
Embodiment 3
A kind of gold-plating solution by weight component comprises:
Gold perchloride 35
Glycolylurea 76
Chromium ion 40
Potassium pyrophosphate 29
Salt of wormwood 87
Imidazoles (Niacin Nicitinic Acid) 5.
Electroplating process is: polished through flint paper and fine sandpaper first by metal base; It is in 13%KOH solution that base material after polishing is immersed in massfraction, takes out after 13min; In rinsing solution, the oxide film of substrate surface is removed after washing; After washing, base material is connected with wire, puts into electroplate liquid, then gold-plated; Plate after washing, and put into chemical passivation liquid and carry out Anti-tarnishing process; Last seasoning in atmosphere.In described gold plating process, current density is 1.7A/dm
2, preferred 1.6A/dm
2.In described gold plating process, the temperature of plating solution is 56 DEG C.
Comparative example 1
Select embodiment that CN 101333671 provides as a comparison case, concrete operations are as follows:
Prepare a kind of golden cobalt plating solution be made up of following material, based on bath.
Gold potassium cyanide (I) 15g/L (10g/L gold)
Cobaltous dihydroxycarbonate 1.16g/L (0.5g/L cobalt)
Citric acid tri potassium monohydrate 116g/L
Citric anhydride 66.11g/L
Vulkacit H 0.5g/L
Water (deionized water) surplus
The pH value potassium hydroxide of above-mentioned plating solution is adjusted to 4.3.
By adding the nicotinic acid (Niacin Nicitinic Acid) of 0.5g/L as brightening agent before the pH value regulating the bath of above-mentioned basis, then adjust ph is prepared to 4.3.
Simultaneous test:
Embodiment 1-3 and comparative example 1 are tested, test event following "
(1) Deposit appearance.Requirement coating light, have golden colour lustre, and planarization is good, coating crystallization is careful not coarse.
(2) binding force of cladding material.Require after thermal shock test without bubbling and being separated sign.Thermal shock test: baking oven about 30min sample being put into 240 DEG C of constant temperature, immerse quenching in the water of 18 DEG C after taking out, optical microphotograph Microscopic observation is with or without foaming or separation phenomenon.
(3) corrosion resistance of coating.Require through the corrosion-free sign in nitric-acid test rear surface.Nitric acid is tested: sample is put into the moisture eliminator filling concentrated nitric acid, test period is 60 ± 10min, then puts into the baking oven 30min of 125 ± 5 DEG C, checks specimen surface corrosion condition under 10 times of magnifying glasses.
(5) bath stability.Require that nature places 45 days, muddiness, metachromatism do not occur; In load conditions, to the continuous plating 2.5h of plating solution, the not muddy variable color of plating solution.
Simultaneous test the results are shown in Table 1.
The comparative test result of table 1 embodiment 1-3 and comparative example
As shown in Table 1, the method for gold-plating solution provided by the invention and electrogilding can provide surfacing careful, glossiness coating, and strong with the bonding force of base material, has very strong erosion resistance, and gold-plating solution good stability.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (1)
1. a method for electrogilding, is characterized in that, described method comprises the steps:
Metal base is polished through flint paper and fine sandpaper first; It is in 15%KOH solution that base material after polishing is immersed in massfraction, takes out after 10 ~ 20min; In rinsing solution, the oxide film of substrate surface is removed after washing; After washing, base material is connected with wire, puts into gold-plating solution, then gold-plated; Plate after washing, and put into chemical passivation liquid and carry out Anti-tarnishing process; Last seasoning in atmosphere;
In described gold plating process, current density is 1.6-2A/dm
2;
Described gold-plating solution by weight component comprises:
The pH value of described plating solution is between 3 to 6;
Described brightening agent is selected from alkanolamine, two alkanolamines, trialkanolamine, amino acid, at least one compound of pyridine carboxylic acid and thiocarboxylic acid.
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| CN104342726A (en) * | 2013-07-23 | 2015-02-11 | 深圳中宇昭日科技有限公司 | Cyanide-free silver plating method |
| CN104726906A (en) * | 2013-12-24 | 2015-06-24 | 深圳中宇昭日科技有限公司 | Cyanide-free gold plating method |
| CN103741181B (en) * | 2014-01-10 | 2016-01-27 | 哈尔滨工业大学 | A kind of many coordination agents cyanide-free gold electroplating plating solution and electrogilding technique |
| CN104073845A (en) * | 2014-06-11 | 2014-10-01 | 安徽长青电子机械（集团）有限公司 | Gold plating method for PCB |
| CN104264195A (en) * | 2014-10-22 | 2015-01-07 | 华文蔚 | Mercaptoiminazole cyanide-free gold-electroplating solution and electroplating method thereof |
| CN105350035B (en) * | 2015-11-25 | 2018-11-09 | 广东致卓环保科技有限公司 | Organic amine system cyanide-free gold electroplating plating solution and method |
| CN106637307B (en) * | 2017-01-04 | 2019-01-01 | 中国地质大学（武汉） | A kind of additive for gold without cyanogen electroforming process |
| CN108385141A (en) * | 2018-03-27 | 2018-08-10 | 苏州东吴黄金文化发展有限公司 | A kind of non-cyanide plating gold formula and processing technology |
| CN109137012B (en) * | 2018-11-14 | 2021-03-16 | 江西旭昇电子有限公司 | PCB (printed circuit board) electrogilding liquid as well as preparation method and application thereof |
| CN110528031B (en) * | 2019-08-06 | 2020-12-11 | 国网山东省电力公司电力科学研究院 | Cyanide-free brush plating solution based on EDTA multi-coordination system and preparation method thereof |
| CN114108040A (en) * | 2020-08-25 | 2022-03-01 | 周大福珠宝文化产业园(武汉)有限公司 | Cyanide-free gold plating solution and gold electroforming part manufactured by cyanide-free electroplating process |
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