US3589916A - Autocatalytic gold plating solutions - Google Patents
Autocatalytic gold plating solutions Download PDFInfo
- Publication number
- US3589916A US3589916A US877052A US3589916DA US3589916A US 3589916 A US3589916 A US 3589916A US 877052 A US877052 A US 877052A US 3589916D A US3589916D A US 3589916DA US 3589916 A US3589916 A US 3589916A
- Authority
- US
- United States
- Prior art keywords
- gold
- water soluble
- amount
- catalytic
- baths
- 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.)
- Expired - Lifetime
Links
- 229910052737 gold Inorganic materials 0.000 title abstract description 47
- 239000010931 gold Substances 0.000 title abstract description 47
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title abstract description 39
- 238000007747 plating Methods 0.000 title abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 33
- -1 CYANIDE COMPOUND Chemical class 0.000 abstract description 23
- 239000008139 complexing agent Substances 0.000 abstract description 18
- 239000003638 chemical reducing agent Substances 0.000 abstract description 17
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 abstract description 12
- 229910000085 borane Inorganic materials 0.000 abstract description 10
- 230000000087 stabilizing effect Effects 0.000 abstract description 7
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 27
- 230000003197 catalytic effect Effects 0.000 description 22
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 14
- 238000000151 deposition Methods 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 7
- 150000002825 nitriles Chemical class 0.000 description 7
- 230000008021 deposition Effects 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000003352 sequestering agent Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 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 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
- 239000011521 glass Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 3
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical class [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- ZTQYEZDTWTZXPF-UHFFFAOYSA-N boron;propan-2-amine Chemical compound [B].CC(C)N ZTQYEZDTWTZXPF-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000000454 electroless metal deposition Methods 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 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
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 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
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- LTYRAPJYLUPLCI-UHFFFAOYSA-N glycolonitrile Chemical compound OCC#N LTYRAPJYLUPLCI-UHFFFAOYSA-N 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000001476 sodium potassium tartrate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XYYVDQWGDNRQDA-UHFFFAOYSA-K trichlorogold;trihydrate;hydrochloride Chemical compound O.O.O.Cl.Cl[Au](Cl)Cl XYYVDQWGDNRQDA-UHFFFAOYSA-K 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
Definitions
- the present invention relates to a new and improved process for the autocatalytic deposition of gold, and to novel and improved autocatalytic plating solutions capable of electrolessly depositing gold on catalytic surfaces in contact therewith.
- the present invention has for its object the provision of novel and improved processes and compositions for the electroless plating or deposition of bright layers of gold on various surfaces.
- a further object of this invention is the provisions of novel and improved electroless plating baths for the deposition of gold which are simple to use, operate with certainty, have improved stability against spontaneous decomposition and which are economical.
- the invention consists in the novel steps, processes, compositions and improvements herein shown and described.
- Electroless metal deposition is also to be distinguished from displacement metal plating of the type described in Metals Finishing Guide Book, 27th Edition, 1959, page 469 et seq., and metal mirroring procedures, wherein the metal plating desired and achieved is only a few millionths of an inch in thickness.
- autocatalytic solutions for depositing gold electrolessly which comprise an aqueous alkaline solution of a water soluble salt of gold, a borohydride or amine borane reducing agent, a complexing agent for gold and a small, stabilizing amount of a cyanide compound.
- Electroless gold baths of the type known in the prior art until now have a tendency to decompose after rela- Patented June 29, 1971 tively short periods of time. Further, such baths tend to produce deposits of gold which are brittle and exhibit poor ductility.
- water soluble cyanide compounds may be added to the bath.
- the amount to be added appears to be somewhat critical; especially the upper limit is critical.
- the water soluble cyanide compounds may be mentioned alkali cyanides, such as sodium and potassium cyanide, and nitriles, such as alpha-hydroxynitriles, e.g., glycolnitrile and lacton'itrile, and a-hydroxyisobutyronitrile.
- alkali cyanides such as sodium and potassium cyanide
- nitriles such as alpha-hydroxynitriles, e.g., glycolnitrile and lacton'itrile, and a-hydroxyisobutyronitrile.
- the cyanide compound will be added in an amount of between about 5 micrograms and 500 milligrams per liter. Care should be used in adding the cyanide compound to insure that an excess, i.e., more than 500 mg./l., is not employed.
- the present plating baths will not function, i.e., they will slow down to the point where' they will not .autocataly-tically deposit gold from solution when
- the gold deposits produced by autocatalytic baths containing cyanide compounds of the type described are bright and ductile. Additionally, as has been mentioned, the baths are more stable and have a longer useful life than the baths in which cyanide is not used.
- the reducing agent may consist of any water soluble borohydride or amine borane having a good degree of solubility and stability in aqueous solutions.
- Sodium and potassium borohydrides are preferred.
- substituted borohydrides such as sodium trimethoxy borohydride, NaB(OCH H.
- Useful too are the amine boranes, such as monoand di-lower alkyl, e.g., up to C alkyl, amine boranes, e.g., isopropyl amine borane and dirnethyl amine borane.
- the plating solution described herein will ordinarily be operated at high pH, preferably at between pH 10 and 14. It is preferred to use an alkali metal hydroxide, e.g., sodium or potassium hydroxide to atain this pH.
- an alkali metal hydroxide e.g., sodium or potassium hydroxide to atain this pH.
- the pH will ordinarily be in the vicinity of 13-14.
- the pH will generally be maintained between about 11 and 12.
- the pH will be between about 10 and 14.
- the water soluble sulfates chlorides, acetates, or nitrates of gold will ordinarily be utilized as the water soluble salts.
- Other water soluble salts may be utilized, however, the choice being primarily a question of economics.
- the sequestering or complexing agent used has to form a sufficiently strong complex with the gold ions to pre vent the precipitation of metallic gold or salts of gold. Further, the complexing agent must be capable of forming a complex with gold ions which is soluble in the plating solution, and also which is sufficiently stable so that it will not react with the reducing agent in the main body of the plating solution, but only at or in the vicinity of the catalytic surface to be plated.
- Among such agents may be mentioned etheylene diamine, diethylene triamine, triethylene tetramine, ethylenediamine tetraacetic acid, citric acid, tartaric acid, 1,3-propane diamine, and ammonia. Rochelle salts can be used.
- Related polyamines and N-carboxymethyl derivatives thereof may also be used.
- Rochelle salts are preferred for gold baths.
- the complexing agent it is therefore preferred to first add the complexing agent to the aqueous solution of the metal salt to form the water soluble complex of the gold cations. If the reducing agent is added before the metal complex is formed, there will be a tendency for it to react instantaneously with the gold salt to precipitate the metal or a salt of the metal. After forming the metal complex, the pH is adjusted to the proper value before adding the reducing agent.
- the reducing agent will ordinarily be added in the form of an alkaline aqueous solution.
- the catalytic surfaces which may be plated with the baths of this invention include metals such as nickel, cobalt, iron, steel, palladium, platinum, copper, brass, manganese, chromium, molybdenum, tungsten, titanium, tin or silver. All such metals are catalytic to the reduction of the metal cations dissolved in the solution described. In some cases, it is useful to sensitize the substrate by treatments well known to those skilled in the art.
- Non-catalytic materials such as glass, ceramic, and various plastics are, in general, non-catalytic.
- the surfaces of such non-catalytic materials can be rendered catalytic by producing a film of particles of one of the catalytic materials thereon. This can be accomplished by a variety of techniques known to those skilled in the art.
- One suitable sensitization procedure involves dipping non-catalytic materials in an acidic solution of stannous chloride, Washing with Water, and then contacting the material with an acidic solution of a precious metal salt, e.g., palladium chloride. A mono-layer of precious metal is thus produced, which mono-layer is catalytic to reduction of the metal ions in the electroless metal plating solutions.
- a precious metal salt e.g., palladium chloride
- such materials as glass, ceramic, and plastic may be sensitized or rendered catalytic by treatment with an acidic aqueous solution containing, in combination, stannous tin ions and precious metal ions.
- a further sensitization procedure involves adhering to the normally non-catalytic surface, finely divided particles of metals or metal oxides which are catalytic to electroless metal solutions.
- catalytic surface refers to the surface of any article composed of the catalytic material described hereinabove or covered therewith or to the surface of a non-catalytic material which has been sensitized by producing a film of particles of said catalytic materials on its surface.
- the baths of this invention will deposit gold electrolessly on the catalytic surfaces of metals and non-metals, such as paper, glass, ceramic, synthetic resins and plastics, including but not limited to silicones, phenolics, alkyds, epoxies, styrenes, acrylics, vinyl chlorides, nylon, mylar, acrylonitrile-butadiene-styrene, and the like.
- metals and non-metals such as paper, glass, ceramic, synthetic resins and plastics, including but not limited to silicones, phenolics, alkyds, epoxies, styrenes, acrylics, vinyl chlorides, nylon, mylar, acrylonitrile-butadiene-styrene, and the like.
- gold deposition occurs autocatalytically at a uniform rate wherever there is contact between the catalytic surface being plated and the plating solution. There is no substantial variation in the plate thickness even for the most complicated shapes. Thus, gold may be uniformly deposited in recesses, as well as on exposed parts of the object being plated, and there is no build-up of coating at points or edges. These conditions are difficult or impossible to achieve by electroplating. Becasuse of the uniform deposition achieved, the plating process described is particularly suitable for plating objects of irregular or complicated shapes which are diflicult or impossible to metallize by conventional techniques.
- the process of this invention permits gold to be deposited on practically any conceivable substratum and to practically any thickness desired.
- the gold salt, and the reducing agent may be replenished from time to time, and also that it may be advisable to monitor the pH, and the solution ingredients, and to adjust them to their optimum value as the bath is used.
- surfactants in an amount of less than about 5 grams per liter are added to the baths disclosed herein.
- suitable surfactants are organic phosphate esters, and oxyethylated sodium salts.
- Such surfactants may be obtained under the trade names Gefac RE 610 and Triton QS-lS, respectively.
- the surface to be plated must be free of grease and other contaminating material.
- the surface areas to receive the deposit should first be sensitized as described hereinabove.
- a metal surface such as stainless steel
- it should be degreased, and then treated with acid, such as hydrochloric or phosphoric acid, to free the surface of oxides.
- the surface to be plated is immersed in the autocatalytic bath, and permitted to remain in the bath until a gold deposit of the desired thickness has been built up.
- Metallized surfaces produced by utilizing the autocatalytic gold deposition solutions of this invention are useful as ornamental designs, markings, and the like. Similarly, using these baths gold may be deposited in predetermined patterns on substrata and serve as electrical conductors. Electrically conductive circuit patterns, e.g., printed circuits, may thus be selectively plated on the activated areas of an inexpensive sheet of a wide variety of insulating material.
- An aqueous alkaline chemical plating solution capable of autocatalytically depositing gold on a substratum in contact therewith, comprising, in combination, water; a water soluble salt of gold in an amount of from about 0.002 to 0.60 mole per liter; a complexing agent for said gold wherein said complexing agent is a member selected from the group consisting of ammonia and compounds containing at least one of an amine group, carboxy group and hydroxy group, said complexing agent forming a stable, water soluble complex with gold in an amount of between 0.7 and times the moles of gold salt; as a reducing agent, a member selected from the group consisting of water soluble alkali metal borohydrides and water soluble amine boranes in an amount of between 0.0002 and 2.5 moles per liter and a small effective stabilizing amount of a water soluble cyanide compound in an amount of between about 5 micrograms and 500 milligrams per liter and wherein the pH is between about 10 and 14.
- a process for electrolessly depositing gold on a catalytic surface which comprises contacting the surface with an aqueous alkaline solution comprising a Water soluble salt of gold in an amount of from about 0.002 to 0.60 mole per liter; a complexing agent for said gold wherein said complexing agent is a member selected from the group consisting of ammonia and compounds containing at least one of an amine group, carboxy group and hydroxy group, said complexing agent forming a stable water soluble complex with gold in an amount of between about 0.7 and 10 times the moles of gold salt; as a reducing agent, a member selected from the group consisting of a water soluble alkali metal borohydride and a water soluble amine borane in an amount of between about 0.0002 and 2.5 moles per liter and a small effective stabilizing amount of a water soluble cyanide compound in an amount of between about 5 micrograms per liter and 500 milligrams per liter and wherein the pH is between about 10 and 14.
- cyanide compound is a member selected from the group consisting of water soluble inorganic cyanides and water soluble organic nitriles.
- said cyanide compound is selected from the group consisting of potassium cyanide, sodium cyanide and alpha-hydroxynitriles and wherein said compound is present in an amount low enough to permit the bath to function.
- An aqueous alkaline electroless gold plating bath solution comprising water, gold ions in the form of a water soluble gold salt in an amount of between about 0.002 to 0.60 mole per liter, a complexing agent for said gold ions which is a member selected from the group consisting of ammonia and compounds containing at least one of an amine group, carboxy group and hydroxy group, said complexing agent being capable of forming a stable water soluble complex with said gold ions in an amount of between about 0.7 and 10 times the moles of gold salt, a reducing agent for said gold ions which is a member selected from the group consisting of sodium borohydride, potassium borohydride, sodium trimethoxy borohydride, isopropyl amine borane and dimethyl amine borane, said reducing agent being present in an amount of between about 0.0002 and 2.5 moles per liter and a small elfective stabilizing amount of a compound which is a member selected from the group consisting of water soluble inorganic
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Abstract
IMPROVED ELECTROLESS GOLD PLATING BATHS ARE PROVIDED BY FORMULATING IN AQUEOUS ALKALINE MEDIA, A WATER SOLUBLE GOLD SALT; A COMPLEXING AGENT FOR GOLD, A WATER SOLUBLE BOROHYDRIDE OR AMINE BORANE REDUCING AGENT FOR GOLD, AND A SMALL EFFECTIVE STABILIZING AMOUNT OF A CYANIDE COMPOUND IN AN AMOUNT OF BETWEEN ABOUT 5 MICROGRAMS AND 500 MILLIGRAMS.
Description
United States Patent 3,589,916 AUTOCATALYTIC GOLD PLATING SOLUTIONS John F. McCormack, Roslyn Heights, N.Y., assignor to Photocircuits Corporation, Glen Cove, NY.
No Drawing. Continuation-impart of abandoned application Ser. No. 768,575, Aug. 20, 1968, which is a continuation-in-part of abandoned application Ser. No. 377,509, June 24, 1964. This application Nov. 14, 1969, Ser. No. 877,052
Int. Cl. C230 3/02 US. Cl. 106-1 9 Claims ABSTRACT OF THE DISCLOSURE Improved electroless gold plating baths are provided by formulating in aqueous alkaline media, a water soluble gold salt; a complexing agent for gold, a water soluble borohydride or amine borane reducing agent for gold, and a small elfective stabilizing amount of a cyanide compound in an amount of between about micrograms and 500 milligrams.
CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of copending application, Ser. No. 768,575, filed Aug. 20, 1968, now abandoned, which, in turn is a continuation of Ser. No. 377,509, filed June 24, 1964, now abandoned.
The present invention relates to a new and improved process for the autocatalytic deposition of gold, and to novel and improved autocatalytic plating solutions capable of electrolessly depositing gold on catalytic surfaces in contact therewith.
The present invention has for its object the provision of novel and improved processes and compositions for the electroless plating or deposition of bright layers of gold on various surfaces.
A further object of this invention is the provisions of novel and improved electroless plating baths for the deposition of gold which are simple to use, operate with certainty, have improved stability against spontaneous decomposition and which are economical.
The invention consists in the novel steps, processes, compositions and improvements herein shown and described.
Chemical plating solutions for continuously depositing gold by autocatalytic chemical reduction of gold ions dissolved in the solutions and in contact with a catalytic surface of an article to be plated are well known. Such solutions, which do not utilize electricity, are sometimes referred to in the art as electroless metal plating solutions, to distinguish them from electroplating solutions, which do require the use of electricity. Electroless metal deposition is also to be distinguished from displacement metal plating of the type described in Metals Finishing Guide Book, 27th Edition, 1959, page 469 et seq., and metal mirroring procedures, wherein the metal plating desired and achieved is only a few millionths of an inch in thickness.
DESCRIPTION OF THE INVENTION According to this invention, there are provided autocatalytic solutions for depositing gold electrolessly which comprise an aqueous alkaline solution of a water soluble salt of gold, a borohydride or amine borane reducing agent, a complexing agent for gold and a small, stabilizing amount of a cyanide compound.
Electroless gold baths of the type known in the prior art until now have a tendency to decompose after rela- Patented June 29, 1971 tively short periods of time. Further, such baths tend to produce deposits of gold which are brittle and exhibit poor ductility.
To enhance the useful life of the bath and improve the ductility of the deposit, it has now been found that water soluble cyanide compounds may be added to the bath. The amount to be added appears to be somewhat critical; especially the upper limit is critical.
Among the water soluble cyanide compoundsmay be mentioned alkali cyanides, such as sodium and potassium cyanide, and nitriles, such as alpha-hydroxynitriles, e.g., glycolnitrile and lacton'itrile, and a-hydroxyisobutyronitrile. -In general, the cyanide compound will be added in an amount of between about 5 micrograms and 500 milligrams per liter. Care should be used in adding the cyanide compound to insure that an excess, i.e., more than 500 mg./l., is not employed. When too much cyanide is used, the present plating baths will not function, i.e., they will slow down to the point where' they will not .autocataly-tically deposit gold from solution when in contact with a catalytic surface.
The gold deposits produced by autocatalytic baths containing cyanide compounds of the type described are bright and ductile. Additionally, as has been mentioned, the baths are more stable and have a longer useful life than the baths in which cyanide is not used.
The reducing agent may consist of any water soluble borohydride or amine borane having a good degree of solubility and stability in aqueous solutions. Sodium and potassium borohydrides are preferred. Also may be mentioned substituted borohydrides, such as sodium trimethoxy borohydride, NaB(OCH H. Useful too are the amine boranes, such as monoand di-lower alkyl, e.g., up to C alkyl, amine boranes, e.g., isopropyl amine borane and dirnethyl amine borane.
In order to prevent spontaneous decomposition of the baths, the plating solution described herein will ordinarily be operated at high pH, preferably at between pH 10 and 14. It is preferred to use an alkali metal hydroxide, e.g., sodium or potassium hydroxide to atain this pH.
When sodium borohydride is used as the complexing agent, the pH will ordinarily be in the vicinity of 13-14. With potassium borohydride, the pH will generally be maintained between about 11 and 12. With the amine boranes, the pH will be between about 10 and 14.
In preparing the solution, the water soluble sulfates chlorides, acetates, or nitrates of gold will ordinarily be utilized as the water soluble salts. Other water soluble salts may be utilized, however, the choice being primarily a question of economics.
The sequestering or complexing agent used has to form a sufficiently strong complex with the gold ions to pre vent the precipitation of metallic gold or salts of gold. Further, the complexing agent must be capable of forming a complex with gold ions which is soluble in the plating solution, and also which is sufficiently stable so that it will not react with the reducing agent in the main body of the plating solution, but only at or in the vicinity of the catalytic surface to be plated.
The complexing or sequestering agents suitable for use include ammonia and organic complex-forming agents containing one or more of the following functional groups: primary amino group (-NH), secondary amino group NH), tertiary amino group N-), imino group (=NH), carboxy group (COOH), and hydroxy group (OH). Among such agents may be mentioned etheylene diamine, diethylene triamine, triethylene tetramine, ethylenediamine tetraacetic acid, citric acid, tartaric acid, 1,3-propane diamine, and ammonia. Rochelle salts can be used. Related polyamines and N-carboxymethyl derivatives thereof may also be used.
Generally, Rochelle salts are preferred for gold baths.
In preparing the electroless metal deposition baths, it is desirable to combine the bath ingredients in such a manner as to avoid reaction between the soluble metal salt and the reducing agent.
It is therefore preferred to first add the complexing agent to the aqueous solution of the metal salt to form the water soluble complex of the gold cations. If the reducing agent is added before the metal complex is formed, there will be a tendency for it to react instantaneously with the gold salt to precipitate the metal or a salt of the metal. After forming the metal complex, the pH is adjusted to the proper value before adding the reducing agent. The reducing agent will ordinarily be added in the form of an alkaline aqueous solution.
The catalytic surfaces which may be plated with the baths of this invention include metals such as nickel, cobalt, iron, steel, palladium, platinum, copper, brass, manganese, chromium, molybdenum, tungsten, titanium, tin or silver. All such metals are catalytic to the reduction of the metal cations dissolved in the solution described. In some cases, it is useful to sensitize the substrate by treatments well known to those skilled in the art.
Materials such as glass, ceramic, and various plastics are, in general, non-catalytic. However, the surfaces of such non-catalytic materials can be rendered catalytic by producing a film of particles of one of the catalytic materials thereon. This can be accomplished by a variety of techniques known to those skilled in the art. One suitable sensitization procedure involves dipping non-catalytic materials in an acidic solution of stannous chloride, Washing with Water, and then contacting the material with an acidic solution of a precious metal salt, e.g., palladium chloride. A mono-layer of precious metal is thus produced, which mono-layer is catalytic to reduction of the metal ions in the electroless metal plating solutions.
Alternatively, such materials as glass, ceramic, and plastic may be sensitized or rendered catalytic by treatment with an acidic aqueous solution containing, in combination, stannous tin ions and precious metal ions.
A further sensitization procedure involves adhering to the normally non-catalytic surface, finely divided particles of metals or metal oxides which are catalytic to electroless metal solutions. 7
The term catalytic surface as used herein refers to the surface of any article composed of the catalytic material described hereinabove or covered therewith or to the surface of a non-catalytic material which has been sensitized by producing a film of particles of said catalytic materials on its surface.
The baths of this invention will deposit gold electrolessly on the catalytic surfaces of metals and non-metals, such as paper, glass, ceramic, synthetic resins and plastics, including but not limited to silicones, phenolics, alkyds, epoxies, styrenes, acrylics, vinyl chlorides, nylon, mylar, acrylonitrile-butadiene-styrene, and the like.
The quantities of the various ingredients in the baths of this invention are subject to wide variation. Typically, however, the bath constituents will be as follows:
Water soluble gold salt: 0.002 to 0.60 moles/liter Reducing agent: 0.0002 to 2.5 moles/liter Complexing agent: 0.7 to 10 times the moles of metal salt Cyanide stabilizer: micrograms to 500 milligrams/liter Alkali metal hydroxide: sufficient to provide a pH of to 14 The amount of sequestering agent to be added to the plating solution depends upon the nature of the sequestering agent and the amount of the gold salt present in the bath. In alkaline solutions, the preferred ratio of the gold salt to complexing agent lies between about 1:1 and 1:10. A small excess of the sequestering agent, based upon the gold salt, generally is advantageous.
With the baths disclosed, gold deposition occurs autocatalytically at a uniform rate wherever there is contact between the catalytic surface being plated and the plating solution. There is no substantial variation in the plate thickness even for the most complicated shapes. Thus, gold may be uniformly deposited in recesses, as well as on exposed parts of the object being plated, and there is no build-up of coating at points or edges. These conditions are difficult or impossible to achieve by electroplating. Becasuse of the uniform deposition achieved, the plating process described is particularly suitable for plating objects of irregular or complicated shapes which are diflicult or impossible to metallize by conventional techniques.
The process of this invention permits gold to be deposited on practically any conceivable substratum and to practically any thickness desired.
It should be understood that as the baths are used up in plating, the gold salt, and the reducing agent may be replenished from time to time, and also that it may be advisable to monitor the pH, and the solution ingredients, and to adjust them to their optimum value as the bath is used.
For best results, surfactants in an amount of less than about 5 grams per liter are added to the baths disclosed herein. Typical of suitable surfactants are organic phosphate esters, and oxyethylated sodium salts. Such surfactants may be obtained under the trade names Gefac RE 610 and Triton QS-lS, respectively.
In using the autocatalytic or electroless gold solutions the surface to be plated must be free of grease and other contaminating material.
Where a non-metallic surface is to be plated, the surface areas to receive the deposit should first be sensitized as described hereinabove.
Where a metal surface, such as stainless steel, is to be treated, it should be degreased, and then treated with acid, such as hydrochloric or phosphoric acid, to free the surface of oxides.
Following pre-treatment and/or sensitization, the surface to be plated is immersed in the autocatalytic bath, and permitted to remain in the bath until a gold deposit of the desired thickness has been built up.
DESCRIPTION OF THE PREFERRED EMBODIMENTS A typical plating bath made in accordance with teachings contained herein is given below:
EXAMPLE 1 Gold chloride hydrochloride trihydrate (AuCl -HCl- 3H 0) 0.01 moles/ liter Sodium potassium tartrate: 0.014 moles liter Dimethyl amine borane: 0.013 moles/liter Sodium cyanide: 400 milligrams/liter Water: q.s.a.d.
pH (adjusted with NaOH): 13 Temperature: 60 C.
Metallized surfaces produced by utilizing the autocatalytic gold deposition solutions of this invention are useful as ornamental designs, markings, and the like. Similarly, using these baths gold may be deposited in predetermined patterns on substrata and serve as electrical conductors. Electrically conductive circuit patterns, e.g., printed circuits, may thus be selectively plated on the activated areas of an inexpensive sheet of a wide variety of insulating material.
The invention in its broader aspects is not limited to the specific steps, processes and compositions described but departures may be made therefrom within the scope of the accompanying claims without departing from the principles of the invention and without sacrificing its chief advantages.
What is claimed is:
1. An aqueous alkaline chemical plating solution capable of autocatalytically depositing gold on a substratum in contact therewith, comprising, in combination, water; a water soluble salt of gold in an amount of from about 0.002 to 0.60 mole per liter; a complexing agent for said gold wherein said complexing agent is a member selected from the group consisting of ammonia and compounds containing at least one of an amine group, carboxy group and hydroxy group, said complexing agent forming a stable, water soluble complex with gold in an amount of between 0.7 and times the moles of gold salt; as a reducing agent, a member selected from the group consisting of water soluble alkali metal borohydrides and water soluble amine boranes in an amount of between 0.0002 and 2.5 moles per liter and a small effective stabilizing amount of a water soluble cyanide compound in an amount of between about 5 micrograms and 500 milligrams per liter and wherein the pH is between about 10 and 14.
2. A solution as defined in claim 1 wherein the pH is between about 12.0 to 14.0.
3. A process for electrolessly depositing gold on a catalytic surface 'which comprises contacting the surface with an aqueous alkaline solution comprising a Water soluble salt of gold in an amount of from about 0.002 to 0.60 mole per liter; a complexing agent for said gold wherein said complexing agent is a member selected from the group consisting of ammonia and compounds containing at least one of an amine group, carboxy group and hydroxy group, said complexing agent forming a stable water soluble complex with gold in an amount of between about 0.7 and 10 times the moles of gold salt; as a reducing agent, a member selected from the group consisting of a water soluble alkali metal borohydride and a water soluble amine borane in an amount of between about 0.0002 and 2.5 moles per liter and a small effective stabilizing amount of a water soluble cyanide compound in an amount of between about 5 micrograms per liter and 500 milligrams per liter and wherein the pH is between about 10 and 14.
4. A process as defined in claim 3 wherein the pH of the solution is maintained between about 12 and 14.
5. A process as defined in claim 3 wherein the cyanide compound is a member selected from the group consisting of water soluble inorganic cyanides and water soluble organic nitriles.
6. A process as defined in claim 5 wherein said cyanide compound is selected from the group consisting of potassium cyanide, sodium cyanide and alpha-hydroxynitriles and wherein said compound is present in an amount low enough to permit the bath to function.
7. An aqueous alkaline electroless gold plating bath solution comprising water, gold ions in the form of a water soluble gold salt in an amount of between about 0.002 to 0.60 mole per liter, a complexing agent for said gold ions which is a member selected from the group consisting of ammonia and compounds containing at least one of an amine group, carboxy group and hydroxy group, said complexing agent being capable of forming a stable water soluble complex with said gold ions in an amount of between about 0.7 and 10 times the moles of gold salt, a reducing agent for said gold ions which is a member selected from the group consisting of sodium borohydride, potassium borohydride, sodium trimethoxy borohydride, isopropyl amine borane and dimethyl amine borane, said reducing agent being present in an amount of between about 0.0002 and 2.5 moles per liter and a small elfective stabilizing amount of a compound which is a member selected from the group consisting of water soluble inorganic cyanide compounds and water soluble organic nitrile compounds, said compounds being present in an amount of about 5 micrograms to 500 milligrams per liter and wherein the pH is between 10 and 14.
8. A solution as defined in claim 7 wherein said reducing agent is dimethyl amine borane.
9. A solution as defined in claim 7 wherein the stabilizing compound is a member selected from the group consisting of potassium cyanide, sodium cyanide and alphahydroxynitriles.
References Cited UNITED STATES PATENTS 3,300,328 l/1967 Luce 1l7130X 3,468,676 9/1969 Schneble et al 106-1 LORENZO B. HAYES, Primary Examiner U.S. Cl. X.R.
@2 33 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION D d June 29, 1971 John F. McCormack Patent No.
Inventofla) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 2, line 42, "complexing"- should read reducing Column 2, line 67, "etheylene" should read ethylene Column 4, line 10, "Becasuse" should read Because Column 4, line 28, "Gefac" should read Gafac Signed and sealed this 28th day of November 1972.
(SEAL) Attast:
ROBERT GOTTSCHALK
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US37750964A | 1964-06-24 | 1964-06-24 | |
US87705269A | 1969-11-14 | 1969-11-14 |
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US877052A Expired - Lifetime US3589916A (en) | 1964-06-24 | 1969-11-14 | Autocatalytic gold plating solutions |
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Cited By (30)
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US3862850A (en) * | 1973-06-08 | 1975-01-28 | Ceramic Systems | Electroless gold plating on refractory metals |
US3890455A (en) * | 1972-06-23 | 1975-06-17 | Ibm | Method of electrolessly plating alloys |
US3917885A (en) * | 1974-04-26 | 1975-11-04 | Engelhard Min & Chem | Electroless gold plating process |
US3922400A (en) * | 1972-08-25 | 1975-11-25 | Hitachi Ltd | Chemical plating method |
US3993808A (en) * | 1971-08-13 | 1976-11-23 | Hitachi, Ltd. | Method for electroless plating gold directly on tungsten or molybdenum |
US4005229A (en) * | 1975-06-23 | 1977-01-25 | Ppg Industries, Inc. | Novel method for the rapid deposition of gold films onto non-metallic substrates at ambient temperatures |
US4082908A (en) * | 1976-05-05 | 1978-04-04 | Burr-Brown Research Corporation | Gold plating process and product produced thereby |
US4091128A (en) * | 1976-10-08 | 1978-05-23 | Ppg Industries, Inc. | Electroless gold plating bath |
US4307136A (en) * | 1978-11-16 | 1981-12-22 | Engelhard Minerals & Chemicals Corp. | Process for the chemical deposition of gold by autocatalytic reduction |
US4337091A (en) * | 1981-03-23 | 1982-06-29 | Hooker Chemicals & Plastics Corp. | Electroless gold plating |
US4374876A (en) * | 1981-06-02 | 1983-02-22 | Occidental Chemical Corporation | Process for the immersion deposition of gold |
US4798626A (en) * | 1986-09-30 | 1989-01-17 | Lamerie, N.V. | Solutions and creams for silver plating and polishing |
US4832743A (en) * | 1986-12-19 | 1989-05-23 | Lamerie, N.V. | Gold plating solutions, creams and baths |
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US3993808A (en) * | 1971-08-13 | 1976-11-23 | Hitachi, Ltd. | Method for electroless plating gold directly on tungsten or molybdenum |
US3890455A (en) * | 1972-06-23 | 1975-06-17 | Ibm | Method of electrolessly plating alloys |
US3922400A (en) * | 1972-08-25 | 1975-11-25 | Hitachi Ltd | Chemical plating method |
US3862850A (en) * | 1973-06-08 | 1975-01-28 | Ceramic Systems | Electroless gold plating on refractory metals |
US3917885A (en) * | 1974-04-26 | 1975-11-04 | Engelhard Min & Chem | Electroless gold plating process |
US4005229A (en) * | 1975-06-23 | 1977-01-25 | Ppg Industries, Inc. | Novel method for the rapid deposition of gold films onto non-metallic substrates at ambient temperatures |
US4082908A (en) * | 1976-05-05 | 1978-04-04 | Burr-Brown Research Corporation | Gold plating process and product produced thereby |
US4091128A (en) * | 1976-10-08 | 1978-05-23 | Ppg Industries, Inc. | Electroless gold plating bath |
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Also Published As
Publication number | Publication date |
---|---|
DE1521439B2 (en) | 1975-03-06 |
DE1521439A1 (en) | 1970-03-26 |
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