EP3023520B1 - Environmentally friendly gold electroplating compositions and corresponding method - Google Patents
Environmentally friendly gold electroplating compositions and corresponding method Download PDFInfo
- Publication number
- EP3023520B1 EP3023520B1 EP15193859.4A EP15193859A EP3023520B1 EP 3023520 B1 EP3023520 B1 EP 3023520B1 EP 15193859 A EP15193859 A EP 15193859A EP 3023520 B1 EP3023520 B1 EP 3023520B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gold
- electroplating
- antimony
- cyanide
- ions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910052737 gold Inorganic materials 0.000 title claims description 149
- 239000010931 gold Substances 0.000 title claims description 149
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims description 130
- 238000009713 electroplating Methods 0.000 title claims description 78
- 239000000203 mixture Substances 0.000 title claims description 62
- 238000000034 method Methods 0.000 title claims description 19
- -1 gold ions Chemical class 0.000 claims description 63
- WOFVPNPAVMKHCX-UHFFFAOYSA-N N#C[Au](C#N)C#N Chemical class N#C[Au](C#N)C#N WOFVPNPAVMKHCX-UHFFFAOYSA-N 0.000 claims description 12
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 11
- 239000001476 sodium potassium tartrate Substances 0.000 claims description 11
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 11
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 claims description 7
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 6
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 6
- 150000003009 phosphonic acids Chemical class 0.000 claims description 6
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 6
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 5
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 229910052716 thallium Inorganic materials 0.000 claims description 4
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 150000003973 alkyl amines Chemical class 0.000 claims description 3
- 229910000379 antimony sulfate Inorganic materials 0.000 claims description 3
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 3
- MVMLTMBYNXHXFI-UHFFFAOYSA-H antimony(3+);trisulfate Chemical compound [Sb+3].[Sb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MVMLTMBYNXHXFI-UHFFFAOYSA-H 0.000 claims description 3
- IQXHAJSMTNDJGA-UHFFFAOYSA-O azanium;gold(1+);dicyanide Chemical compound [NH4+].[Au+].N#[C-].N#[C-] IQXHAJSMTNDJGA-UHFFFAOYSA-O 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- 125000004437 phosphorous atom Chemical group 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- VMDSWYDTKFSTQH-UHFFFAOYSA-N sodium;gold(1+);dicyanide Chemical compound [Na+].[Au+].N#[C-].N#[C-] VMDSWYDTKFSTQH-UHFFFAOYSA-N 0.000 claims description 3
- AFWAHDXCIBPFNW-UHFFFAOYSA-J sodium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [Na+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O AFWAHDXCIBPFNW-UHFFFAOYSA-J 0.000 claims 2
- 238000007747 plating Methods 0.000 description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 239000004094 surface-active agent Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- TXTQARDVRPFFHL-UHFFFAOYSA-N [Sb].[H][H] Chemical compound [Sb].[H][H] TXTQARDVRPFFHL-UHFFFAOYSA-N 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 150000001204 N-oxides Chemical class 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 150000002343 gold Chemical class 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical class 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 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 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 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 239000003139 biocide Substances 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- DKPHLYCEFBDQKM-UHFFFAOYSA-H hexapotassium;1-phosphonato-n,n-bis(phosphonatomethyl)methanamine Chemical compound [K+].[K+].[K+].[K+].[K+].[K+].[O-]P([O-])(=O)CN(CP([O-])([O-])=O)CP([O-])([O-])=O DKPHLYCEFBDQKM-UHFFFAOYSA-H 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 150000002903 organophosphorus compounds Chemical class 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Chemical class 0.000 description 3
- 125000003821 2-(trimethylsilyl)ethoxymethyl group Chemical group [H]C([H])([H])[Si](C([H])([H])[H])(C([H])([H])[H])C([H])([H])C(OC([H])([H])[*])([H])[H] 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 239000001472 potassium tartrate Substances 0.000 description 2
- 229940111695 potassium tartrate Drugs 0.000 description 2
- 235000011005 potassium tartrates Nutrition 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 229940095064 tartrate Drugs 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- XHAZMZWXAOBLQG-UHFFFAOYSA-N (1-hydroxy-1-phosphonopropyl)phosphonic acid Chemical compound CCC(O)(P(O)(O)=O)P(O)(O)=O XHAZMZWXAOBLQG-UHFFFAOYSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- UUWJHAWPCRFDHZ-UHFFFAOYSA-N 1-dodecoxydodecane;phosphoric acid Chemical compound OP(O)(O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC UUWJHAWPCRFDHZ-UHFFFAOYSA-N 0.000 description 1
- OWWOMIFQTFZNGK-UHFFFAOYSA-N 1-phosphonobutylphosphonic acid Chemical compound CCCC(P(O)(O)=O)P(O)(O)=O OWWOMIFQTFZNGK-UHFFFAOYSA-N 0.000 description 1
- MXYOPVWZZKEAGX-UHFFFAOYSA-N 1-phosphonoethylphosphonic acid Chemical compound OP(=O)(O)C(C)P(O)(O)=O MXYOPVWZZKEAGX-UHFFFAOYSA-N 0.000 description 1
- HSWSQPDMHQDRSF-UHFFFAOYSA-N 16-methyl-N-[3-(1-oxidopyridin-1-ium-2-yl)propyl]heptadecanamide Chemical compound C(CCCCCCCCCCCCCCC(C)C)(=O)NCCCC1=[N+](C=CC=C1)[O-] HSWSQPDMHQDRSF-UHFFFAOYSA-N 0.000 description 1
- PEWFHTFASPEWFH-UHFFFAOYSA-N 16-methyl-N-[3-(4-oxidomorpholin-4-ium-4-yl)propyl]heptadecanamide Chemical compound C(CCCCCCCCCCCCCCC(C)C)(=O)NCCC[N+]1(CCOCC1)[O-] PEWFHTFASPEWFH-UHFFFAOYSA-N 0.000 description 1
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 description 1
- ROPQINLWRARCTM-UHFFFAOYSA-N 2-phosphonopropan-2-ylphosphonic acid Chemical compound OP(=O)(O)C(C)(C)P(O)(O)=O ROPQINLWRARCTM-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- WWXQUHIKHRDKRT-UHFFFAOYSA-N P1(=O)OC(C)(O)OP(O1)=O.[K].[K].[K].[K] Chemical compound P1(=O)OC(C)(O)OP(O1)=O.[K].[K].[K].[K] WWXQUHIKHRDKRT-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RXSPKSMQHLNUSU-UHFFFAOYSA-H [Na+].[Na+].[Na+].[Au+3].[O-]S([O-])(=O)=S.[O-]S([O-])(=O)=S.[O-]S([O-])(=O)=S Chemical compound [Na+].[Na+].[Na+].[Au+3].[O-]S([O-])(=O)=S.[O-]S([O-])(=O)=S.[O-]S([O-])(=O)=S RXSPKSMQHLNUSU-UHFFFAOYSA-H 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- KQNKJJBFUFKYFX-UHFFFAOYSA-N acetic acid;trihydrate Chemical compound O.O.O.CC(O)=O KQNKJJBFUFKYFX-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229940026189 antimony potassium tartrate Drugs 0.000 description 1
- SZXAQBAUDGBVLT-UHFFFAOYSA-H antimony(3+);2,3-dihydroxybutanedioate Chemical compound [Sb+3].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O SZXAQBAUDGBVLT-UHFFFAOYSA-H 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ZRKZFNZPJKEWPC-UHFFFAOYSA-N decylamine-N,N-dimethyl-N-oxide Chemical compound CCCCCCCCCC[N+](C)(C)[O-] ZRKZFNZPJKEWPC-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- ADPOBOOHCUVXGO-UHFFFAOYSA-H dioxido-oxo-sulfanylidene-$l^{6}-sulfane;gold(3+) Chemical class [Au+3].[Au+3].[O-]S([O-])(=O)=S.[O-]S([O-])(=O)=S.[O-]S([O-])(=O)=S ADPOBOOHCUVXGO-UHFFFAOYSA-H 0.000 description 1
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 229940076131 gold trichloride Drugs 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Chemical class 0.000 description 1
- 229910052749 magnesium Chemical class 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- MBKDYNNUVRNNRF-UHFFFAOYSA-N medronic acid Chemical compound OP(O)(=O)CP(O)(O)=O MBKDYNNUVRNNRF-UHFFFAOYSA-N 0.000 description 1
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
- LVJGHGOKXKNASI-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)-3-(8-methylnonoxy)propan-1-amine oxide Chemical compound CC(C)CCCCCCCOCCC[N+]([O-])(CCO)CCO LVJGHGOKXKNASI-UHFFFAOYSA-N 0.000 description 1
- RSVIRMFSJVHWJV-UHFFFAOYSA-N n,n-dimethyloctan-1-amine oxide Chemical compound CCCCCCCC[N+](C)(C)[O-] RSVIRMFSJVHWJV-UHFFFAOYSA-N 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
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000004302 potassium sorbate Substances 0.000 description 1
- 235000010241 potassium sorbate Nutrition 0.000 description 1
- 229940069338 potassium sorbate Drugs 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229950005425 sodium myristyl sulfate Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- 229940071240 tetrachloroaurate Drugs 0.000 description 1
- KWXLCDNSEHTOCB-UHFFFAOYSA-J tetrasodium;1,1-diphosphonatoethanol Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P(=O)([O-])C(O)(C)P([O-])([O-])=O KWXLCDNSEHTOCB-UHFFFAOYSA-J 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- ILAVZBMETAVWCZ-UHFFFAOYSA-H tripotassium dioxido-oxo-sulfanylidene-lambda6-sulfane gold(3+) Chemical compound [K+].[K+].[K+].[Au+3].[O-]S([O-])(=O)=S.[O-]S([O-])(=O)=S.[O-]S([O-])(=O)=S ILAVZBMETAVWCZ-UHFFFAOYSA-H 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
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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- 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
- C25D3/48—Electroplating: Baths therefor from solutions of gold
-
- 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
- C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
-
- 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
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- 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
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
-
- 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
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
- C25D5/611—Smooth layers
-
- 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
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/617—Crystalline layers
-
- 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
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/623—Porosity of the layers
-
- 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
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
-
- 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
-
- 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
- C25D7/005—Jewels; Clockworks; Coins
Definitions
- the present invention is directed to environmentally friendly gold electroplating compositions and methods. More specifically, the present invention is directed to environmentally friendly gold electroplating compositions and methods where soft gold may be electroplated over broad current density ranges to provide bright soft gold deposits even under jet and pulse current plating conditions.
- Electrolytic gold is typically used in connectors and electronic finishing because of the exceptional performance of gold for these particular uses.
- Gold is one of the most reliable materials for electronic components because of its anticorrosion properties, electrical conductivity and thermal stability.
- Substantially pure gold is generally electroplated from cyanide electrolytic plating baths containing several additives and metallic brighteners. Some of those additives such as hydrazine are toxic and are now restricted by many national and international regulations.
- Most commercial pure gold baths contain free-cyanide and one or more grain refiner such as arsenic, thallium and lead which are known to be toxic to the environment, thus disposal of waste from such gold plating baths must be discrete and is also time consuming and costly to the industry.
- such gold electroplating baths present undue hazards to workers using the baths.
- U.S. 5,277,790 to Morrissey discloses a cyanide-free gold electroplating bath where gold is provided as a soluble sulfite complex.
- the gold electroplating bath is cyanide-free, it undesirably generates sulfur dioxide at elevated temperatures. Sulfur dioxide is a toxic gas with a pungent odor. To address the problem even more sulfites are added to the plating solution.
- the gold is plated at relatively low plating rates from near 0 to 30 mA/cm 2 . Accordingly, there is a need for an improved gold electroplating bath which is environmentally friendly and can plate over broad current density ranges.
- DE2723910 discloses a gold electroplating bath free of free cyanide, said bath comprising a gold cyanide salt, a source of phosphate ions, potassium tartrate and antimony potassium tartrate.
- Gold electroplating compositions including one or more sources of gold ions from gold-cyanide salts, one or more sources of phosphate ions, one or more sources of phosphonic acids or salts thereof, sodium potassium tartrate in amounts of 10 g/L to 50 g/L and one or more sources of antimony (III) ions to provide antimony (III) ions in amounts of 1 mg/L to 20 mg/L, the gold electroplating compositions are free of free-cyanide.
- Method of electroplating gold include providing a gold electroplating composition including one or more sources of gold ions from gold-cyanide salts, one or more sources of phosphate ions, one or more sources of phosphonic acids or salts thereof, sodium potassium tartrate in amounts of 10 g/L to 50 g/L and one or more sources of antimony (III) ions to provide antimony (III) ions in amounts of 1 mg/L to 20 mg/L, the gold electroplating compositions are free of free-cyanide; contacting a substrate with the gold electroplating composition; and electroplating gold on the substrate using direct current or pulse current at a current density of 0.03 ASD or greater.
- the gold electroplating compositions are environmentally friendly and may plate bright soft gold deposits over broad current density ranges including under high speed jet plating conditions.
- the soft gold deposits also have fine grain structures.
- the electroplating gold compositions may be used to plate gold strike layers on electronic components and may be used to electroplate soft gold layers in the formation of contacts for connectors and gold layers on switches or printed circuit boards.
- the gold electroplating compositions may also be used to deposit soft gold layers on decorative articles.
- the gold deposits also have fine grain structures. Small grain size reduces porosity in thin film.
- the brightness of the deposits is also a direct consequence of this small grain size. Generally, the roughness of matte or semi bright deposit is high as compared to bright deposits which are smooth.
- °C degrees Centigrade
- Compositions include gold ions from one or more gold-cyanide salts such as alkali gold cyanide compounds such as potassium gold cyanide, sodium gold cyanide and ammonium gold cyanide.
- alkali gold cyanide compound is potassium gold cyanide.
- gold ions are provided by gold-cyanide salts, there is no free-cyanide added in the gold electroplating compositions such as cyanide alkali metal salts or any salt, except gold salts, which may provide free cyanide ligands.
- additional gold ions may be provided by alkali gold thiosulfate compounds such as trisodium gold thiosulfate and tripotassium gold thiosulfate, gold halides such as gold chloride, hydrogen tetrachloroaurate and gold trichloride.
- gold ions are provided only from gold-cyanide salts.
- gold compounds are generally commercially available from a variety of suppliers or may be prepared by methods well known in the art.
- the amount of gold salts added to the compositions is in amounts which provide gold ions at desired concentrations.
- gold ions are in amounts of 4 g/L to 20 g/L, preferably from 8 g/L to 20 g/L, more preferably from 15 g/L to 20 g/L.
- the amount of gold ions in the electroplating compositions depends on the type of plating, such as jet, rack or barrel plating.
- Conducting inorganic acid and salts thereof are included in the gold electroplating compositions.
- the inorganic acid and salts thereof are chosen from phosphoric acid and potassium dihydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, sodium phosphate and mixtures thereof.
- phosphoric acid is added when using potassium phosphate.
- Alkaline compounds also may be added to maintain the pH of the compositions at desired levels of 5 to 6.8, preferably 5.8 to 6.7, more preferably from 6 to 6.3.
- Such alkaline compounds include, but are not limited to, hydroxides, carbonates, and other salts of sodium, potassium and magnesium.
- NaOH, KOH, K 2 CO 3 , Na 2 CO 3 , NaHCO 3 and mixtures thereof are suitable alkaline compounds.
- the alkaline materials are included in amounts of 1 g/L to 100 g/L.
- Organophosphorus compounds are included as chelating agents for the gold ions in the gold electroplating compositions. They deprotonate and chelate with gold ions in the pH range of the gold electroplating compositions and the chelating capabilities of these compounds is good enough such that free cyanide from potassium cyanide or sodium cyanide is not added to stabilize the gold compositions.
- the organophosphorus compounds include those compounds having the following formulation: wherein n is an integer from 2 to 3, inclusive, M 1 and M 2 may be the same or different and are chosen from hydrogen, ammonium, lower alkyl amine having 1-9 carbons atoms, preferably 1-5 carbon atoms or an alkali metal cation such as sodium, potassium and lithium, preferably the alkali metal cation is potassium or sodium, and Z is a radical equal in valence to n and is a linear or branched, substituted or unsubstituted (C 1 -C 12 )alkyl or an N-substituted (C 2 -C 3 )alkyl where the Z radical has a carbon atom linked to a phosphorus atom of formula (I).
- Z is a linear or branched, substituted or unsubstituted (C 1 -C 4 )alkyl where the substituent group is hydroxyl.
- Such compounds are included in amounts of 5 g/l to 200 g/L, preferably from 20 g/L to 150 g/L, more preferably from 50 g/l to 120 g/L.
- a class of compounds falling within the above general formula includes aminotri (lower alkylidene phosphonic acids).
- examples of such compounds include aminotri(methylene phosphonic acid), aminotri(ethylidene phosphonic acid), aminotri(isopropyllidene phosphonic acid), aminodi(methylene phosphonic acid) mono (ethylidene phosphonic acid), aminodi(methylene phosphonic acid) mono(isopropylidene phosphonic acid), aminomono(methylene phosphonic acid) di(ethylidene phosphonic acid) and aminomono(methylene phosphonic acid) diisopropylidene phosphonic acid.
- Lower alkylidene diphosphonic acid compounds within the scope of the above formula are methylene diphosphonic acid, ethylidene diphosphonic acid, isopropylene diphosphonic acid, isopropylidene diphosphonic acid, 1-hydroxyethylidene diphosphonic acid, 1-hydroxypropylidene diphosphonic acid, butylidene diphosphonic acid.
- organophosphorus compounds are tetrapotassium 1-hydroxyethylidene diphosphonate, tetrasodium 1-hydroxyethylidene diphosphonate and hydroxyethylene-1,1-diphosphonic acid.
- Antimony (III) ions are included as potassium antimony tartrate in combination with sodium potassium tartrate. Although antimony (III) ions may be added as antimony chloride or antimony sulfate, antimony (III) is preferably added as antimony tartrate.
- the salts of antimony (III) are added to the gold electroplating compositions in amounts to provide 1 mg/L to 20 mg/L, preferably 5 mg/L to 15 mg/L of antimony (III) ions.
- Sodium potassium tartrate is added to the gold electroplating compositions in amounts of 10 g/l to 50 g/L, preferably from 15 g/l to 35 g/L.
- Additional tartrate may be added to the gold electroplating compositions as tartaric acid, potassium tartrate or other water soluble tartrate salts and compounds in the amounts specified for the sodium potassium tartrate; however, the most preferred source of tartrate is sodium potassium tartrate for preventing the antimony (III) ions from oxidizing to antimony (V) ions. While not being bound by theory, the presence of the antimony (III) ions may provide for a bright gold deposit even under jet plating conditions. In addition, antimony may provide for a soft gold deposit.
- the gold plating compositions may include one or more organic acids, such as citric acid, malic acid, oxalic acid, formic acid or polyethylene amino acetic acid or inorganic acids such as phosphoric acid.
- organic acids such as citric acid, malic acid, oxalic acid, formic acid or polyethylene amino acetic acid or inorganic acids such as phosphoric acid.
- Such acids help maintain the pH of the compositions in the desired range.
- the acids are included in amounts of 1 g/L to 200 g/L.
- Suitable gold complexing agents include, but are not limited to thiosulfuric acid, thiosulfate salts such as sodium thiosulfate, potassium thiosulfate, potassium sorbate and ammonium thiosulfate, ethylenediamine tetraacetic acid and its salts, iminodiacetic acid and nitrilotriacetic acid.
- the one or more additional chelating or complexing agents may be added in conventional amounts, or such as in amounts of 1 g/L to 100 g/L, or such as 10 g/L to 50 g/L.
- the one or more complexing agents are generally commercially available or may be prepared from methods well known in the art.
- compositions also may include one or more surfactants.
- Any suitable surfactant may be used in the compositions.
- Such surfactants include, but are not limited to, alkoxyalkyl sulfates (alkyl ether sulfates) and alkoxyalkyl phosphates (alkyl ether phosphates).
- the alkyl and alkoxy groups typically contain from 10 to 20 carbon atoms.
- Examples of such surfactants are sodium lauryl sulfate, sodium capryl sulfate, sodium myristyl sulfate, sodium ether sulfate of a C 12 -C 18 straight chain alcohol, sodium lauryl ether phosphate and corresponding potassium salts.
- N-oxide surfactants include, but are not limited to, cocodimethylamine N-oxide, lauryldimethylamine N-oxide, oleyldimethylamine N-oxide, dodecyldimethylamine N-oxide, octyldimethylamine N-oxide, bis-(hydroxyethyl)isodecyloxypropylamine N-oxide, decyldimethylamine N-oxide, cocamidopropyldimethylamine N-oxide, bis(hydroxyethyl) C 12 -C 15 alkoxypropylamine N-oxide, lauramine N-oxide, laurami-dopropyldimethylamine N-oxide, C 14 -C 16 alkyldimethylamine N-oxide, N,N-diemthyl (hydrogenated tallow alkyl) amine N-oxide
- surfactants include, but are not limited to, betaines, and alkoxylates such as the ethylene oxide/propylene oxide (EO/PO) compounds. Such surfactants are well known in the art.
- surfactants may be commercially obtained or made by methods described in the literature. Typically, the surfactants are included in the compositions in amounts of 0.1 g/L to 20 g/L.
- the components of the compositions may be combined by any suitable method known in the art. Typically, the components are mixed in any order and the compositions are brought to a desired volume by adding sufficient water. Some heating may be necessary to solubilize certain composition components.
- the gold electroplating compositions are substantially free of arsenic, lead, thallium, hydrazine and sulfites. In general, substantially free means that the metals, hydrazine and sulfites are not readily detectable with most conventional analytical apparatus or, if they are detectable, they are at levels of 100 ppb or less.
- Current density ranges from 0.03 ASD and higher using DC or pulse plating.
- current densities may be from 0.05 ASD to 2.5 ASD using DC current.
- Gold ion concentrations preferably range from 4 g/L to 8 g/L.
- current densities may range from 0.05 ASD to 4 ASD using DC current.
- Gold ion concentrations preferably range from 8 g/L to 12 g/L; however, the applicable current density may be extend to 6 ASD for rack plating when using pulse current with ON: OFF times of 1: 3 ms.
- gold ion concentrations preferably range from 12 g/L to 20 g/L.
- Bright deposit may be obtained from 2 ASD to 70 ASD pulse peak current and ON:OFF pulse parameter of 1:1 to 1:4 ms.
- the jet agitation can be varied from 100 L/hour to 1000 L/hour depending on the applied current density. It is preferable to use high agitation at higher pulse peak current.
- the soft gold electroplating compositions may be used in rack plating, barrel plating and high speed jet plating by adjusting the gold concentration and the plating parameters. Unlike many conventional pure gold electroplating compositions, the gold electroplating compositions can be used with jet plating equipment for high speed gold deposition. Jet plating or plating at higher current densities is fast and provides increased electroplating efficiency on production lines than plating at lower current densities. Such high speed jet plating methods are highly desirable for mass production.
- the soft gold electroplating compositions deposit substantially uniform soft gold deposits.
- Gold hardness is typically expressed as knoop hardness values and represents the average of a number of tests using a 25 gram indenting tool.
- the knoop hardness is from 91 to 129 a gold class B according to ASTM B488-11 as plated. After annealing the knoop hardness is 78 or a gold class A.
- the purity of the gold deposits is 99.9% and is type III purity.
- Plating times may vary. The amount of time depends on the desired thickness of the gold on the substrate. Typically, the thickness of the gold is from 0.01 microns to 50 microns, or such as from 0.1 microns to 2 microns, or such as from 0.2 microns to 0.5 microns.
- the anodes are insoluble anodes such as stainless steel, platinum, platinum-clad tantalum, platinized titanium and graphite.
- the anode is a platinized titanium anode.
- the soft gold electroplating compositions may be used to electroplate gold layers on metals such as nickel, nickel alloys, copper, copper alloys, tin and tin alloys.
- the gold electroplating compositions are used to electroplate gold on nickel and nickel alloys such as contacts, connectors, switches and printed circuit boards.
- the gold electroplating compositions may also be used to plate gold layers on decorative articles such as jewelry.
- the gold electroplating compositions may also be used to plate strike layers on substrates to improve adhesion between metal layers.
- the soft gold electroplating compositions are environmentally friendly and may plate bright gold deposits over the applicable current density ranges using DC or pulse current and under barrel, rack or jet plating conditions.
- the gold deposits also have fine grain structures. Small grain size reduces porosity in thin film.
- the brightness of the deposits is also a direct consequence of this small grain size.
- the roughness of matte or semi-bright deposit is high as compared to bright deposits which are smooth.
- An aqueous soft gold electroplating bath having the following composition was prepared: Table 1 COMPONENT AMOUNT Gold from potassium gold cyanide 8 g/L Potassium dihydrogen phosphate 79 g/L Hydroxyethylene-1,1-diphosphonic acid 113 g/L Potassium hydroxide 64 g/L KATHONETM LXE Biocide 1 50 mg/L Sodium potassium tartrate 20 g/L Antimony (III) from potassium antimony tartrate 8 mg/L (antimony (III)) 1 5-Chlor-2 methyl-4-isothiazol-3-on, magnesium nitrate, copper nitrate and 2-methyl-2H-isothiazol-3-one available from The Dow Chemical Company, Midland, MI.
- aqueous gold electroplating bath having the following formula was prepared: Table 2 COMPONENT AMOUNT Gold from potassium gold cyanide 8 g/L Potassium dihydrogen phosphate 79 g/L Hydroxyethylene-1,1-diphosphonic acid 113 g/L Potassium hydroxide 64 g/L KATHONETM LXE Biocide 50 mg/L Acetic acid 5 g/L Lead acetate trihydrate 6 mg/L as lead
- Figure 2 shows one of the SEMs taken with the microscope.
- the SEM showed coarse grain structure. This microstructure was in agreement with the optical appearance of the deposit which was semi-bright.
- the grain structure and the optical appearance of gold plated from Table 2 were inferior to that of the gold electroplating composition of Example 1 where the test panels were electroplated with gold from an electroplating bath containing antimony (III) from potassium antimony tartrate with sodium potassium tartrate and free of lead.
- the electroplating process described above was repeated except that the gold electroplating bath of Table 2 of Example 2 was used. After plating, the gold deposits electroplated from 0.5 ASD to 3 ASD had semi-bright deposits; however, the gold plated at 3.5 ASD and 4 ASD had a dull-matte appearance. The results showed that the gold electroplating bath of Table 1 had an improved plating performance in terms of applicable current density and appearance over the lead containing gold electroplating bath of Table 2.
- a soft gold electrolytic plating bath as shown in the table below was prepared: Table 3 COMPONENT AMOUNT Gold from potassium gold cyanide 20 g/L Potassium dihydrogen phosphate 79 g/L Hydroxyethylene-1,1-diphosphonic acid 113 g/L Potassium hydroxide 64 g/L KATHONETM LXE Biocide 50 mg/L Sodium potassium tartrate 20 g/L Antimony (III) from potassium antimony tartrate 10 mg/L (antimony (III))
- a double sided nickel pre-plated copper test panel 15 x 20mm 2 was mounted on jet plating equipment containing 1000 mL of the soft gold electroplating bath of Table 3.
- the anode was a platinized titanium electrode.
- the baths had a pH of 6.2 and the temperature of the bath was 60 °C.
- Pulse current was applied with a peak current density of 50 ASD with an ON:OFF time of 1:3 ms. This corresponded to an average current density of 12.5 ASD.
- the jet agitation or flow rate was set to 800 L/hour. After the 10 second plating period, the panels were removed from the bath, rinsed with deionized water and air dried. All of the panels had a bright gold deposit.
- the process was repeated with the gold electroplating bath of Table 2 except the amount of gold ions was 20 g/L gold. The same jet agitation and plating parameters described above were used. The gold deposits were strongly matte or burned in appearance. The test was repeated except the pulse peak current density was 30 ASD with the same flow rate as above. This corresponded to the average current density of 7.5 ASD. All of the deposits were matte.
- the electroplating bath of table 2 did not provide a bright or even a semi-bright gold deposit at high current density under jet agitation, thus the gold bath was inferior in performance to the gold plating bath of Table 3.
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Description
- The present invention is directed to environmentally friendly gold electroplating compositions and methods. More specifically, the present invention is directed to environmentally friendly gold electroplating compositions and methods where soft gold may be electroplated over broad current density ranges to provide bright soft gold deposits even under jet and pulse current plating conditions.
- Electrolytic gold is typically used in connectors and electronic finishing because of the exceptional performance of gold for these particular uses. Gold is one of the most reliable materials for electronic components because of its anticorrosion properties, electrical conductivity and thermal stability. Substantially pure gold is generally electroplated from cyanide electrolytic plating baths containing several additives and metallic brighteners. Some of those additives such as hydrazine are toxic and are now restricted by many national and international regulations. Most commercial pure gold baths contain free-cyanide and one or more grain refiner such as arsenic, thallium and lead which are known to be toxic to the environment, thus disposal of waste from such gold plating baths must be discrete and is also time consuming and costly to the industry. In addition, such gold electroplating baths present undue hazards to workers using the baths.
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U.S. 5,277,790 to Morrissey discloses a cyanide-free gold electroplating bath where gold is provided as a soluble sulfite complex. Although the gold electroplating bath is cyanide-free, it undesirably generates sulfur dioxide at elevated temperatures. Sulfur dioxide is a toxic gas with a pungent odor. To address the problem even more sulfites are added to the plating solution. In addition, the gold is plated at relatively low plating rates from near 0 to 30 mA/cm2. Accordingly, there is a need for an improved gold electroplating bath which is environmentally friendly and can plate over broad current density ranges. -
DE2723910 discloses a gold electroplating bath free of free cyanide, said bath comprising a gold cyanide salt, a source of phosphate ions, potassium tartrate and antimony potassium tartrate. - Gold electroplating compositions including one or more sources of gold ions from gold-cyanide salts, one or more sources of phosphate ions, one or more sources of phosphonic acids or salts thereof, sodium potassium tartrate in amounts of 10 g/L to 50 g/L and one or more sources of antimony (III) ions to provide antimony (III) ions in amounts of 1 mg/L to 20 mg/L, the gold electroplating compositions are free of free-cyanide.
- Method of electroplating gold include providing a gold electroplating composition including one or more sources of gold ions from gold-cyanide salts, one or more sources of phosphate ions, one or more sources of phosphonic acids or salts thereof, sodium potassium tartrate in amounts of 10 g/L to 50 g/L and one or more sources of antimony (III) ions to provide antimony (III) ions in amounts of 1 mg/L to 20 mg/L, the gold electroplating compositions are free of free-cyanide; contacting a substrate with the gold electroplating composition; and electroplating gold on the substrate using direct current or pulse current at a current density of 0.03 ASD or greater.
- The gold electroplating compositions are environmentally friendly and may plate bright soft gold deposits over broad current density ranges including under high speed jet plating conditions. The soft gold deposits also have fine grain structures. The electroplating gold compositions may be used to plate gold strike layers on electronic components and may be used to electroplate soft gold layers in the formation of contacts for connectors and gold layers on switches or printed circuit boards. The gold electroplating compositions may also be used to deposit soft gold layers on decorative articles. The gold deposits also have fine grain structures. Small grain size reduces porosity in thin film. The brightness of the deposits is also a direct consequence of this small grain size. Generally, the roughness of matte or semi bright deposit is high as compared to bright deposits which are smooth.
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Figure 1 is a SEM at 20,000 magnification showing the microstructure of a soft gold deposit electroplated with a gold electroplating composition containing antimony (III) ions. -
Figure 2 is a SEM at 20,000 magnification showing the microstructure of a gold deposit electroplated with a conventional gold electroplating bath containing lead as a grain refiner. - As used throughout this specification, the following abbreviations shall have the following meanings, unless the context clearly indicates otherwise: °C = degrees Centigrade; g = gram; mg = milligrams; L = liter; mL = milliliters; cm = centimeters; mm = millimeters; µm = microns = micrometers; ppb = parts per billion; ms = milliseconds; DC = direct current; ASD = amperes/decimeter squared = A/dm2 and ASTM = American Standard Testing Method.
- The terms "electroplating" and "plating" are used interchangeably throughout this specification. The terms "composition", "solution" and "bath" are used interchangeably throughout the specification. The terms "a" and "an" refer to both the singular and the plural.
- All percentages are by weight, unless otherwise noted. All numerical ranges are inclusive and combinable in any order, except where it is logical that such numerical ranges are constrained to add up to 100%.
- Compositions include gold ions from one or more gold-cyanide salts such as alkali gold cyanide compounds such as potassium gold cyanide, sodium gold cyanide and ammonium gold cyanide. Preferably the alkali gold cyanide compound is potassium gold cyanide. Although gold ions are provided by gold-cyanide salts, there is no free-cyanide added in the gold electroplating compositions such as cyanide alkali metal salts or any salt, except gold salts, which may provide free cyanide ligands.
- In addition to the gold-cyanide salts, additional gold ions may be provided by alkali gold thiosulfate compounds such as trisodium gold thiosulfate and tripotassium gold thiosulfate, gold halides such as gold chloride, hydrogen tetrachloroaurate and gold trichloride. Preferably gold ions are provided only from gold-cyanide salts. Such gold compounds are generally commercially available from a variety of suppliers or may be prepared by methods well known in the art.
- The amount of gold salts added to the compositions is in amounts which provide gold ions at desired concentrations. In general, gold ions are in amounts of 4 g/L to 20 g/L, preferably from 8 g/L to 20 g/L, more preferably from 15 g/L to 20 g/L. The amount of gold ions in the electroplating compositions depends on the type of plating, such as jet, rack or barrel plating.
- Conducting inorganic acid and salts thereof are included in the gold electroplating compositions. The inorganic acid and salts thereof are chosen from phosphoric acid and potassium dihydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, sodium phosphate and mixtures thereof. Preferably, phosphoric acid is added when using potassium phosphate.
- Alkaline compounds also may be added to maintain the pH of the compositions at desired levels of 5 to 6.8, preferably 5.8 to 6.7, more preferably from 6 to 6.3. Such alkaline compounds include, but are not limited to, hydroxides, carbonates, and other salts of sodium, potassium and magnesium. For example, NaOH, KOH, K2CO3, Na2CO3, NaHCO3 and mixtures thereof are suitable alkaline compounds. Typically, the alkaline materials are included in amounts of 1 g/L to 100 g/L.
- Organophosphorus compounds are included as chelating agents for the gold ions in the gold electroplating compositions. They deprotonate and chelate with gold ions in the pH range of the gold electroplating compositions and the chelating capabilities of these compounds is good enough such that free cyanide from potassium cyanide or sodium cyanide is not added to stabilize the gold compositions.
- The organophosphorus compounds include those compounds having the following formulation:
- A class of compounds falling within the above general formula includes aminotri (lower alkylidene phosphonic acids). Examples of such compounds include aminotri(methylene phosphonic acid), aminotri(ethylidene phosphonic acid), aminotri(isopropyllidene phosphonic acid), aminodi(methylene phosphonic acid) mono (ethylidene phosphonic acid), aminodi(methylene phosphonic acid) mono(isopropylidene phosphonic acid), aminomono(methylene phosphonic acid) di(ethylidene phosphonic acid) and aminomono(methylene phosphonic acid) diisopropylidene phosphonic acid.
- Lower alkylidene diphosphonic acid compounds within the scope of the above formula are methylene diphosphonic acid, ethylidene diphosphonic acid, isopropylene diphosphonic acid, isopropylidene diphosphonic acid, 1-hydroxyethylidene diphosphonic acid, 1-hydroxypropylidene diphosphonic acid, butylidene diphosphonic acid.
- Particularly preferred organophosphorus compounds are tetrapotassium 1-hydroxyethylidene diphosphonate, tetrasodium 1-hydroxyethylidene diphosphonate and hydroxyethylene-1,1-diphosphonic acid.
- Antimony (III) ions are included as potassium antimony tartrate in combination with sodium potassium tartrate. Although antimony (III) ions may be added as antimony chloride or antimony sulfate, antimony (III) is preferably added as antimony tartrate. The salts of antimony (III) are added to the gold electroplating compositions in amounts to provide 1 mg/L to 20 mg/L, preferably 5 mg/L to 15 mg/L of antimony (III) ions. Sodium potassium tartrate is added to the gold electroplating compositions in amounts of 10 g/l to 50 g/L, preferably from 15 g/l to 35 g/L. Additional tartrate may be added to the gold electroplating compositions as tartaric acid, potassium tartrate or other water soluble tartrate salts and compounds in the amounts specified for the sodium potassium tartrate; however, the most preferred source of tartrate is sodium potassium tartrate for preventing the antimony (III) ions from oxidizing to antimony (V) ions. While not being bound by theory, the presence of the antimony (III) ions may provide for a bright gold deposit even under jet plating conditions. In addition, antimony may provide for a soft gold deposit.
- Optionally, the gold plating compositions may include one or more organic acids, such as citric acid, malic acid, oxalic acid, formic acid or polyethylene amino acetic acid or inorganic acids such as phosphoric acid. Such acids help maintain the pH of the compositions in the desired range. Typically, the acids are included in amounts of 1 g/L to 200 g/L.
- Optionally, a wide variety of additional gold chelating or complexing agents may be included in the compositions. Suitable gold complexing agents include, but are not limited to thiosulfuric acid, thiosulfate salts such as sodium thiosulfate, potassium thiosulfate, potassium sorbate and ammonium thiosulfate, ethylenediamine tetraacetic acid and its salts, iminodiacetic acid and nitrilotriacetic acid.
- The one or more additional chelating or complexing agents may be added in conventional amounts, or such as in amounts of 1 g/L to 100 g/L, or such as 10 g/L to 50 g/L. The one or more complexing agents are generally commercially available or may be prepared from methods well known in the art.
- The compositions also may include one or more surfactants. Any suitable surfactant may be used in the compositions. Such surfactants include, but are not limited to, alkoxyalkyl sulfates (alkyl ether sulfates) and alkoxyalkyl phosphates (alkyl ether phosphates). The alkyl and alkoxy groups typically contain from 10 to 20 carbon atoms. Examples of such surfactants are sodium lauryl sulfate, sodium capryl sulfate, sodium myristyl sulfate, sodium ether sulfate of a C12-C18 straight chain alcohol, sodium lauryl ether phosphate and corresponding potassium salts.
- Other suitable surfactants which may be used include, but are not limited to, N-oxide surfactants. Such N-oxide surfactants include, but are not limited to, cocodimethylamine N-oxide, lauryldimethylamine N-oxide, oleyldimethylamine N-oxide, dodecyldimethylamine N-oxide, octyldimethylamine N-oxide, bis-(hydroxyethyl)isodecyloxypropylamine N-oxide, decyldimethylamine N-oxide, cocamidopropyldimethylamine N-oxide, bis(hydroxyethyl) C12-C15 alkoxypropylamine N-oxide, lauramine N-oxide, laurami-dopropyldimethylamine N-oxide, C14-C16 alkyldimethylamine N-oxide, N,N-diemthyl (hydrogenated tallow alkyl) amine N-oxide, isostearamidopropyl morpholine N-oxide, and isostearamidopropyl pyridine N-oxide.
- Other suitable surfactants include, but are not limited to, betaines, and alkoxylates such as the ethylene oxide/propylene oxide (EO/PO) compounds. Such surfactants are well known in the art.
- Many of the surfactants may be commercially obtained or made by methods described in the literature. Typically, the surfactants are included in the compositions in amounts of 0.1 g/L to 20 g/L.
- The components of the compositions may be combined by any suitable method known in the art. Typically, the components are mixed in any order and the compositions are brought to a desired volume by adding sufficient water. Some heating may be necessary to solubilize certain composition components. The gold electroplating compositions are substantially free of arsenic, lead, thallium, hydrazine and sulfites. In general, substantially free means that the metals, hydrazine and sulfites are not readily detectable with most conventional analytical apparatus or, if they are detectable, they are at levels of 100 ppb or less.
- Current density ranges from 0.03 ASD and higher using DC or pulse plating. For barrel plating applications, current densities may be from 0.05 ASD to 2.5 ASD using DC current. Gold ion concentrations preferably range from 4 g/L to 8 g/L. For rack plating applications, current densities may range from 0.05 ASD to 4 ASD using DC current. Gold ion concentrations preferably range from 8 g/L to 12 g/L; however, the applicable current density may be extend to 6 ASD for rack plating when using pulse current with ON: OFF times of 1: 3 ms. When jet plating with jet plating equipment, gold ion concentrations preferably range from 12 g/L to 20 g/L. Bright deposit may be obtained from 2 ASD to 70 ASD pulse peak current and ON:OFF pulse parameter of 1:1 to 1:4 ms. The jet agitation can be varied from 100 L/hour to 1000 L/hour depending on the applied current density. It is preferable to use high agitation at higher pulse peak current. The soft gold electroplating compositions may be used in rack plating, barrel plating and high speed jet plating by adjusting the gold concentration and the plating parameters. Unlike many conventional pure gold electroplating compositions, the gold electroplating compositions can be used with jet plating equipment for high speed gold deposition. Jet plating or plating at higher current densities is fast and provides increased electroplating efficiency on production lines than plating at lower current densities. Such high speed jet plating methods are highly desirable for mass production.
- In addition to providing a bright deposit at high current densities, the soft gold electroplating compositions deposit substantially uniform soft gold deposits. Gold hardness is typically expressed as knoop hardness values and represents the average of a number of tests using a 25 gram indenting tool. The knoop hardness is from 91 to 129 a gold class B according to ASTM B488-11 as plated. After annealing the knoop hardness is 78 or a gold class A. The purity of the gold deposits is 99.9% and is type III purity.
- Plating times may vary. The amount of time depends on the desired thickness of the gold on the substrate. Typically, the thickness of the gold is from 0.01 microns to 50 microns, or such as from 0.1 microns to 2 microns, or such as from 0.2 microns to 0.5 microns.
- Conventional gold plating apparatus may be used to electroplate gold on substrates. The anodes are insoluble anodes such as stainless steel, platinum, platinum-clad tantalum, platinized titanium and graphite. Preferably, the anode is a platinized titanium anode.
- The soft gold electroplating compositions may be used to electroplate gold layers on metals such as nickel, nickel alloys, copper, copper alloys, tin and tin alloys. Preferably, the gold electroplating compositions are used to electroplate gold on nickel and nickel alloys such as contacts, connectors, switches and printed circuit boards. The gold electroplating compositions may also be used to plate gold layers on decorative articles such as jewelry. The gold electroplating compositions may also be used to plate strike layers on substrates to improve adhesion between metal layers.
- The soft gold electroplating compositions are environmentally friendly and may plate bright gold deposits over the applicable current density ranges using DC or pulse current and under barrel, rack or jet plating conditions. The gold deposits also have fine grain structures. Small grain size reduces porosity in thin film. The brightness of the deposits is also a direct consequence of this small grain size. Generally, the roughness of matte or semi-bright deposit is high as compared to bright deposits which are smooth.
- The following examples are intended to illustrate the invention, but are not intended to limit its scope.
- An aqueous soft gold electroplating bath having the following composition was prepared:
Table 1 COMPONENT AMOUNT Gold from potassium gold cyanide 8 g/L Potassium dihydrogen phosphate 79 g/L Hydroxyethylene-1,1-diphosphonic acid 113 g/L Potassium hydroxide 64 g/L KATHONE™ LXE Biocide1 50 mg/L Sodium potassium tartrate 20 g/L Antimony (III) from potassium antimony tartrate 8 mg/L (antimony (III)) 15-Chlor-2 methyl-4-isothiazol-3-on, magnesium nitrate, copper nitrate and 2-methyl-2H-isothiazol-3-one available from The Dow Chemical Company, Midland, MI. - Five double sided nickel pre-plated copper test panels 15 x 20 mm2 were immersed in 500 mL baths of the soft gold electroplating bath for 3 minutes to plate gold on nickel. The anode was a platinized titanium electrode. The baths were agitated using a magnetic stirrer during the entire 3 minutes. The baths had a pH of 6.2 and the temperatures of the baths were 55 °C. DC current was applied with a current density of 1 ASD. After the 3 minute period, the coupons were removed from the baths, rinsed with deionized water and air dried. The gold deposits were bright. The thickness of the gold deposits was measured with a FISHERSCOPE™ X-ray apparatus, model XDV-SD, and was determined to be 1.7 microns. The panels were then analyzed for the microstructure of the gold deposit using a SEM microscope at 20,000 magnification.
Figure 1 shows one of the SEMs taken with the microscope. The SEM showed small grain structure. - An aqueous gold electroplating bath having the following formula was prepared:
Table 2 COMPONENT AMOUNT Gold from potassium gold cyanide 8 g/L Potassium dihydrogen phosphate 79 g/L Hydroxyethylene-1,1-diphosphonic acid 113 g/L Potassium hydroxide 64 g/L KATHONE™ LXE Biocide 50 mg/L Acetic acid 5 g/L Lead acetate trihydrate 6 mg/L as lead - Five double sided nickel pre-plated copper test panels 15 x 20 mm2 were immersed in a 500 mL bath of the gold electroplating baths for 3 minutes to plate gold on nickel. The anode was a platinized titanium electrode. The baths were agitated using a magnetic stirrer during the entire 3 minutes. The baths had a pH of 6.2 and the temperatures of the baths were 55 °C. DC current was applied with a current density of 1 ASD. After the 3 minute period, the coupons were removed from the baths, rinsed with deionized water and air dried. The thickness of the gold deposits was 1.7 microns. The panels were then analyzed for the microstructure of the gold deposit using a SEM microscope at 20,000 magnification.
Figure 2 shows one of the SEMs taken with the microscope. The SEM showed coarse grain structure. This microstructure was in agreement with the optical appearance of the deposit which was semi-bright. The grain structure and the optical appearance of gold plated from Table 2 were inferior to that of the gold electroplating composition of Example 1 where the test panels were electroplated with gold from an electroplating bath containing antimony (III) from potassium antimony tartrate with sodium potassium tartrate and free of lead. - Eight double sided nickel pre-plated copper test panels 15 x 20 mm2 were immersed separately in 500 mL baths containing gold electroplating baths having the formulation in Table 1 of Example 1. The anode was a platinized titanium electrode. Electroplating gold on nickel was done for 3 minutes for each bath. The baths were agitated using a magnetic stirrer during the entire plating time. The baths had a pH of 6.2 and the temperatures of the baths were 55 °C. DC current was applied with varying current densities from one panel to another. The current densities were 0.5 ASD, 1.2 ASD, 1.5 ASD, 2 ASD, 2.5 ASD, 3 ASD, 3.5 ASD and 4 ASD. After plating, the panels were removed from the baths, rinsed with deionized water and air dried. All of the gold deposits had a bright appearance.
- The electroplating process described above was repeated except that the gold electroplating bath of Table 2 of Example 2 was used. After plating, the gold deposits electroplated from 0.5 ASD to 3 ASD had semi-bright deposits; however, the gold plated at 3.5 ASD and 4 ASD had a dull-matte appearance. The results showed that the gold electroplating bath of Table 1 had an improved plating performance in terms of applicable current density and appearance over the lead containing gold electroplating bath of Table 2.
- A soft gold electrolytic plating bath as shown in the table below was prepared:
Table 3 COMPONENT AMOUNT Gold from potassium gold cyanide 20 g/L Potassium dihydrogen phosphate 79 g/L Hydroxyethylene-1,1-diphosphonic acid 113 g/L Potassium hydroxide 64 g/L KATHONE™ LXE Biocide 50 mg/L Sodium potassium tartrate 20 g/L Antimony (III) from potassium antimony tartrate 10 mg/L (antimony (III)) - A double sided nickel pre-plated copper test panel 15 x 20mm2 was mounted on jet plating equipment containing 1000 mL of the soft gold electroplating bath of Table 3. The anode was a platinized titanium electrode. The baths had a pH of 6.2 and the temperature of the bath was 60 °C. Pulse current was applied with a peak current density of 50 ASD with an ON:OFF time of 1:3 ms. This corresponded to an average current density of 12.5 ASD. The jet agitation or flow rate was set to 800 L/hour. After the 10 second plating period, the panels were removed from the bath, rinsed with deionized water and air dried. All of the panels had a bright gold deposit.
- The process was repeated with the gold electroplating bath of Table 2 except the amount of gold ions was 20 g/L gold. The same jet agitation and plating parameters described above were used. The gold deposits were strongly matte or burned in appearance. The test was repeated except the pulse peak current density was 30 ASD with the same flow rate as above. This corresponded to the average current density of 7.5 ASD. All of the deposits were matte. The electroplating bath of table 2 did not provide a bright or even a semi-bright gold deposit at high current density under jet agitation, thus the gold bath was inferior in performance to the gold plating bath of Table 3.
Claims (14)
- A gold electroplating composition comprising one or more sources of gold ions from gold-cyanide salts, one or more sources of phosphate ions, one or more sources of phosphonic acids or salts thereof, sodium potassium tartrate in amounts of 10 g/L to 50 g/L and one or more sources of antimony (III) ions to provide antimony (III) ions in amounts of 1 mg/L to 20 mg/L, the gold electroplating composition is free of free-cyanide.
- The gold electroplating composition of claim 1, wherein the gold-cyanide salts are chosen from potassium gold cyanide, sodium gold cyanide, and ammonium gold cyanide.
- The gold electroplating composition of claim 1, wherein the one or more sources of phosphate ions are chosen from phosphoric acid, sodium dihydrogen phosphate and potassium dihydrogen phosphate.
- The gold electroplating composition of claim 1, wherein the one or more phosphonic acids have a formula:
- The gold electroplating composition of claim 1, wherein the one or more sources of antimony (III) ions are chosen from potassium antimony tartrate, sodium antimony tartrate, antimony sulfate and antimony chloride.
- The gold electroplating composition of claim 1, wherein the gold electroplating composition is free of lead, arsenic, thallium, hydrazine and sulfites.
- A method of electroplating gold comprising:a. providing a gold electroplating composition comprising one or more sources of gold ions from gold-cyanide salts, one or more sources of phosphate ions, one or more sources of phosphonic acids or salts thereof, sodium potassium tartrate in amounts of 10 g/L to 50 g/L and one or more sources of antimony (III) ions to provide antimony (III) ions in amounts of 1 mg/L to 20 mg/L, the gold electroplating composition is free of free-cyanide;b. contacting a substrate with the gold electroplating composition; andc. electroplating gold on the substrate using direct current or pulse current at a current density of 0.03 ASD or greater.
- The method of electroplating gold of claim 7, wherein the current density is from 1 ASD to 50 ASD.
- The method of electroplating gold of claim 7, wherein the gold-cyanide salts are chosen from potassium gold cyanide, sodium gold cyanide, and ammonium gold cyanide.
- The method of electroplating gold of claim 7, wherein the one or more sources of phosphate ions are chosen from phosphoric acid, sodium dihydrogen phosphate and potassium dihydrogen phosphate.
- The method of electroplating gold of claim 7, wherein the one or more phosphonic acids have a formula:
- The method of electroplating gold of claim 7, wherein the one or more sources of antimony (III) ions are chosen from potassium antimony tartrate, sodium antimony tartrate, antimony sulfate and antimony chloride.
- The method of electroplating gold of claim 7, wherein the gold electroplating composition is free of lead, arsenic, thallium, hydrazine and sulfites.
- The method of electroplating gold of claim 7, wherein the substrate is a printed circuit board, a contact for a connector, switch or decorative article.
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CN109778270A (en) * | 2019-03-18 | 2019-05-21 | 杭州埃迷丽珠宝有限公司 | Mist gold process is electroplated |
CN110129843A (en) * | 2019-06-05 | 2019-08-16 | 深圳市华乐珠宝首饰有限公司 | A kind of hard golden mirror photoelectricity casting process of no cyanogen |
CN110205654A (en) * | 2019-06-05 | 2019-09-06 | 深圳市尚美金品有限公司 | A kind of manufacture craft of hollow jewelry piece |
CN110106537A (en) * | 2019-06-26 | 2019-08-09 | 浙江金卓首饰有限公司 | A kind of preparation method of the electroforming solution being used to prepare the hard gold of 3D and the hard gold of 3D |
CN110306211A (en) * | 2019-08-06 | 2019-10-08 | 深圳市凯恩特珠宝首饰有限公司 | A kind of electromoulding K gold technique |
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TWI600805B (en) | 2017-10-01 |
JP6073450B2 (en) | 2017-02-01 |
EP3023520A1 (en) | 2016-05-25 |
KR20160061268A (en) | 2016-05-31 |
JP2016117946A (en) | 2016-06-30 |
CN105624745B (en) | 2018-11-06 |
KR101712970B1 (en) | 2017-03-08 |
TW201619446A (en) | 2016-06-01 |
CN105624745A (en) | 2016-06-01 |
US20160145756A1 (en) | 2016-05-26 |
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