US3917885A - Electroless gold plating process - Google Patents
Electroless gold plating process Download PDFInfo
- Publication number
- US3917885A US3917885A US464666A US46466674A US3917885A US 3917885 A US3917885 A US 3917885A US 464666 A US464666 A US 464666A US 46466674 A US46466674 A US 46466674A US 3917885 A US3917885 A US 3917885A
- Authority
- US
- United States
- Prior art keywords
- group
- alkali metal
- gold
- bath
- plating bath
- 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 claims abstract description 64
- 239000010931 gold Substances 0.000 title claims abstract description 64
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000007747 plating Methods 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000007772 electroless plating Methods 0.000 claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 46
- 239000000758 substrate Substances 0.000 claims abstract description 45
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 41
- 150000003949 imides Chemical class 0.000 claims abstract description 41
- -1 alkali metal cyanide Chemical class 0.000 claims abstract description 40
- 230000008021 deposition Effects 0.000 claims abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 150000002739 metals Chemical class 0.000 claims abstract description 14
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 13
- 239000002738 chelating agent Substances 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 150000001340 alkali metals Chemical class 0.000 claims description 23
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 16
- 125000000732 arylene group Chemical group 0.000 claims description 14
- 125000002947 alkylene group Chemical group 0.000 claims description 13
- 235000019846 buffering salt Nutrition 0.000 claims description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 239000004332 silver Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910000085 borane Inorganic materials 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 8
- 229960002317 succinimide Drugs 0.000 claims description 8
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 5
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 5
- 150000001860 citric acid derivatives Chemical class 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 150000003892 tartrate salts Chemical class 0.000 claims description 5
- LTJMHCGDSFTOHA-UHFFFAOYSA-N 2-carbamoylbenzenesulfonic acid Chemical compound NC(=O)C1=CC=CC=C1S(O)(=O)=O LTJMHCGDSFTOHA-UHFFFAOYSA-N 0.000 claims description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000013522 chelant Substances 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000007654 immersion Methods 0.000 abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 4
- 239000006172 buffering agent Substances 0.000 abstract description 4
- 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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 24
- 239000000243 solution Substances 0.000 description 14
- 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 11
- 229910052708 sodium Inorganic materials 0.000 description 11
- 239000011734 sodium Substances 0.000 description 9
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 6
- 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 5
- 150000002825 nitriles Chemical class 0.000 description 5
- 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 description 5
- 239000001476 sodium potassium tartrate Substances 0.000 description 5
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229960001484 edetic acid Drugs 0.000 description 4
- 239000001508 potassium citrate Substances 0.000 description 4
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 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 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229960003975 potassium Drugs 0.000 description 3
- QMKIMYFCMFAFAH-UHFFFAOYSA-J potassium;gold(3+);5-oxo-3,4-dihydropyrrol-2-olate Chemical compound [K+].[Au+3].[O-]C1=NC(=O)CC1.[O-]C1=NC(=O)CC1.[O-]C1=NC(=O)CC1.[O-]C1=NC(=O)CC1 QMKIMYFCMFAFAH-UHFFFAOYSA-J 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 235000015424 sodium Nutrition 0.000 description 3
- 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 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- VDNXILQBKLFION-UHFFFAOYSA-N [K].[Cu] Chemical compound [K].[Cu] VDNXILQBKLFION-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229960002635 potassium citrate Drugs 0.000 description 2
- 235000011082 potassium citrates Nutrition 0.000 description 2
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 2
- 229940083542 sodium Drugs 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000015870 tripotassium citrate Nutrition 0.000 description 2
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 1
- ZRXHLJNBNWVNIM-UHFFFAOYSA-N 3-methyl-1-benzofuran Chemical compound C1=CC=C2C(C)=COC2=C1 ZRXHLJNBNWVNIM-UHFFFAOYSA-N 0.000 description 1
- 241000132028 Bellis Species 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- RVLVPYVRHBEOJW-UHFFFAOYSA-N C1(C=2C(C(N1)=O)=CC=CC2)=O.[Ag].[Na] Chemical compound C1(C=2C(C(N1)=O)=CC=CC2)=O.[Ag].[Na] RVLVPYVRHBEOJW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical class NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- WOFVPNPAVMKHCX-UHFFFAOYSA-N N#C[Au](C#N)C#N Chemical class N#C[Au](C#N)C#N WOFVPNPAVMKHCX-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GGXDMBXZYQSZRM-UHFFFAOYSA-N [Au].O=C1NC(=O)C2=CC=CC=C12 Chemical compound [Au].O=C1NC(=O)C2=CC=CC=C12 GGXDMBXZYQSZRM-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- ZTQYEZDTWTZXPF-UHFFFAOYSA-N boron;propan-2-amine Chemical compound [B].CC(C)N ZTQYEZDTWTZXPF-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- JYHGLOJFYPBKGI-UHFFFAOYSA-L dipotassium phosphono phosphate phosphoric acid Chemical compound [O-]P([O-])(=O)OP(=O)(O)O.[K+].P(=O)(O)(O)O.[K+] JYHGLOJFYPBKGI-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- KPQDSKZQRXHKHY-UHFFFAOYSA-N gold potassium Chemical compound [K].[Au] KPQDSKZQRXHKHY-UHFFFAOYSA-N 0.000 description 1
- DXONONHRBADGKK-UHFFFAOYSA-N gold;isoindole-1,3-dione;potassium Chemical compound [K].[Au].C1=CC=C2C(=O)NC(=O)C2=C1 DXONONHRBADGKK-UHFFFAOYSA-N 0.000 description 1
- MIZQMGYIIBZNEB-UHFFFAOYSA-N gold;pyrrolidine-2,5-dione Chemical compound [Au].O=C1CCC(=O)N1 MIZQMGYIIBZNEB-UHFFFAOYSA-N 0.000 description 1
- 229910021482 group 13 metal Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 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
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 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 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000001472 potassium tartrate Substances 0.000 description 1
- 229940111695 potassium tartrate Drugs 0.000 description 1
- 235000011005 potassium tartrates Nutrition 0.000 description 1
- JVUYWILPYBCNNG-UHFFFAOYSA-N potassium;oxido(oxo)borane Chemical compound [K+].[O-]B=O JVUYWILPYBCNNG-UHFFFAOYSA-N 0.000 description 1
- WQMVVOKCUPKPKL-UHFFFAOYSA-L potassium;silver;5-oxo-3,4-dihydropyrrol-2-olate Chemical compound [K+].[Ag+].[O-]C1=NC(=O)CC1.[O-]C1=NC(=O)CC1 WQMVVOKCUPKPKL-UHFFFAOYSA-L 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- KIIUTKAWYISOAM-UHFFFAOYSA-N silver sodium Chemical compound [Na].[Ag] KIIUTKAWYISOAM-UHFFFAOYSA-N 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 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
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 electroless plating bath disclosed includes an aqueous solution of an imide complex of the Group lB metal to be plated, an alkali metal cyanide, and a reducing agent, and is maintained at a pH of from about 1 1 to 14 by the addition of alkali metal hydroxides.
- an electroless gold plating bath is disclosed, including an aqueous solution of an alkali metal gold imide complex.
- non-metallic substrates are to be plated
- the surfaces are rendered catalytically active prior to immersion in the electroless plating baths
- metallic substrates are plated, they are preferably pre-coated with a thin plate by immersion in an aqueous plating bath including a soluble gold salt, an ammonium buffering agent, and an organic chelating agent, prior to immersion in the electroless plating baths of the present invention.
- the present invention relates to improved electroless plating baths for the autocatalytic deposition of Group [B metals upon substrates.
- the present invention relates to improved electroless silver, copper and gold plating baths for autocatalytic deposition upon catalytic surfaces, which baths provide improved palting characteristics, including improved plating rates.
- the present invention relates to improved methods of plating various substrates utilizing electroless plating baths of the Group IB metal to be plated thereon.
- electroless plating baths for the autocatalytic deposition of gold and other Group [B metals upon various substrates has become widely known.
- Such baths as compared to conventional electroplating baths, are characterized by an ability to deposit these metals on a wide variety of metallic and nonmetalic substrates without requiring the use of electricity.
- Dr. Okinaka has described the electroless deposition of gold using as reducing agents borohydride and dimethylamine borane, and alkali metal cyanides as the source of gold, with a demonstrable deterioration in the baths with increased cyanide concentrations, particularly upon replenishment with additional alkali metal gold cyanide.
- borohydride and dimethylamine borane as the source of gold
- alkali metal cyanides as the source of gold
- an electroless gold plating bath including a water-soluble gold salt and a complexing agent for the gold, in addition to the water-soluble borohydride or amine borane reducing agent, and a stabi lizing amount of a cyanide compound, all maintained at a pH of between 10 and 14.
- This disclosure thus teaches the use of a complexing agent of form a gold complex in an attempt to prevent gold precipitation during plating.
- This disclosure also teaches that the amount of water-soluble cyanide compound, between 5 micrograms and 500 milligrams per liter, is critical.
- electroless plating baths for autocatalytic deposition upon various substrates are provided, resulting in the deposition of thick silver, copper and gold plates.
- the electroless plating baths of this invention comprise an aqueous so lution of an imide complex of the Group IB metal to be plated, an alkali metal cyanide in an amount sufficient to stabilize the bath, and a reducing agent selected from the group consisting of water soluble alkali metal borohydrides, water soluble amine boranes and formaldehyde.
- the pH of the bath is maintained from about 1 l to 14. It has thus been found that these electroless plating baths exhibit superior plating rates, without concomitant bath decomposition. Specifically, plating rates of greater than 2.5 microns per hour, and preferably greater than 2.7 microns per hour are obtainable therewith.
- the required pH level is maintained by the addition of alkali metal hydroxides to the bath, and preferably alkali metal buffering salts are added thereto in addition to the alkali metal hydroxides, in order to obtain a superior degree of pH control.
- organic chelating agents may be added to these electroless plating baths, particularly when metallic substrates are to be plated therewith, in order to form complexes with the replaced metals, and prevent the precipitation thereof.
- improved methods for plating various substrates are provided, in which the metallic or non-metallic substrates are rendered catalytically active prior to immersion to the improved electroless plating baths hereof.
- Ductile silver, copper and gold plates are thus provided, having strong adherence to the substrates employed, and of relatively uniform thicknesses as compared to the plates obtainable by the prior art plating baths.
- the imides of the present invention which are capable of forming particularly strong complexes with the Group ID metals to be plated, such as gold, have a general formula as follows:
- R is a radical selected from the group consisting of alkylene, substituted alkylene, arylene, and substituted arylene.
- R will be a substituted arylene, such as sulfonyl-o-phenylene (SO C H in which case the imide formed will be sulphobenzoic imide, (i.e., saccharin, or o-benzosulfimide) C H (S0 (C .))--Nl-l.
- SO C H sulfonyl-o-phenylene
- S0 (C .) o-benzosulfimide
- the imides with which the Group 18 metals to be plated are complexed will have a general formula as follows:
- R is a radical selected from the group consisting of alkylene, substituted alkylene, arylene, and substituted arylene.
- R will be alkylene.
- the imide will be succinimide
- R is an arylene radical such as C l-i (o-phenylene)
- the imide will be phthalimide.
- these two compounds, succinimide and phthalimide will be particularly preferred, thus forming complexes with the gold in the form of alkali metal gold succinimide, particularly potassium gold succinimide, and alkali metal gold phthalimide, particularly potassium gold phthalimide.
- the electroless plating baths of this invention include soluble cyanide compounds in critical amounts in order to maintain the stability of the bath.
- water soluble cyanide compounds are the alkali metal cyanides, such as sodium, potassium and lithium cyanide. Among these, sodium and potassium cyanide are particularly preferred. Other such compounds may, however, be employed, such as nitriles, including alpha-hydroxynitriles, etc. as described in U.S. Pat. No. 3,589,916 which compounds are thus incorporated herein by reference. It is critical, however, that the water-soluble cyanide compounds be used in specific amounts, generally from between about 2 and 20 grams per liter, and preferably from about 5 to grams per liter.
- the reducing agents employed in connection with the present electroless plating baths include any of the borohydrides or amine boranes which are soluble and stable in aqueous solution.
- alkali metal borohydrides preferably sodium and potassium borohydrides
- substituted borohydrodes such as sodium or potassium trimethoxyborohydride, Na[K]B(OCH I-l
- amine boranes such as monoand dilower alkyl, e.g., up to C alkyl-amine boranes, preferably isopropyl amine borane and dimethylamine borane.
- formaldehyde is also an excellent reducing agent for use in these baths, particularly for the deposition of copper and silver.
- the electroless plating baths of the present invention be maintained at a pH of between about 11 and 14, principally to prevent spontaneous decomposition thereof. It is thus preferred that an alkali metal hydroxide, such as sodium or potassium hydroxide, be employed to maintain the pH at this level. It has, however, been discovered that pH control is considerably easier when alkali metal buffering salts are employed in addition to the alkali metal hydroxide. Thus, while the alkali metal hydroxide is necessary in order to maintain the present electroless baths at the required pH level during plating, as the pH tends to drop, the ease of pH control is considerably facilitated by the addition of such alkali metal buffering salts.
- an alkali metal hydroxide such as sodium or potassium hydroxide
- alkali metal buffering salts thus include the alkali metal phosphates, citrates, tartrates, borates, metaborates, etc.
- the alkali metal buffering salts may this include sodium or potassium phosphate potassium pyrophosphate, sodium or potassium citrate, sodium potassium tartrate, sodium or potassium borate, sodium or potassium metaborate, etc.
- the preferred alkali metal buffering salts are sodium or potassium citrate and sodium or potassium tartrate. in order to further improve the electroless plating baths of this invention, it is preferred to add an organic chelating agent thereto.
- Such chelating agents combine with the replaced surface metal ions, thus preventing their interference with the plating process, and the consequent deterioration of the color characteristics of the deposited plates, as well as other plate properties such as adherence and thickness.
- These organic chelating agents thus include ethylenediamine tetraacetic acid, and the di-sodium, tri-sodium and tetra-sodium and potassium salts of ethylenediamine tetraacetic acid, di-ethylene triamine pentacetic acid, nitrilotriacetic acid.
- the ethylenediamine tetraacetic acid and its di-, tri-, and tetrasodium salts are the preferred chelating agents, with the triand tetra-sodium salts being particularly preferred.
- non-metallic substrates With the use of non-metallic substrates, however, these surfaces must be rendered catalytically active by producing a film of particles of catalytic material thereon. This may be done in the method described in U.S. Pat. No. 3,589,916, upon such surfaces as glass, ceramics, various plastics. etc.
- a plastic substrate is to be plated according to the present invention, it is initially etched, preferably in a solution of chromic and sulfuric acid. After rinsing, the substrate is immersed in an acidic solution of stannous chloride, such as stannous chloride and hydrochloric acid, rinsed with water and then contacted with an acid solution of a precious metal, such as paladium chloride in hydrochloric acid. Subsequently, the now catalytically acitve non-metallic substrate may be contacted with the electroless plating solutions of this invention in order to autocatalytically deposite Group 18 metal plates thereon.
- stannous chloride such as stannous chlor
- a preplating step is employed.
- a rapid contamination of the plating bath with the base metals replaced by the Group lB metals plated thereon occurs, thus affecting the purity of the deposit obtained, and the stability of the electroless plating solution.
- a pre-plating step for the provision of a thin plate of gold be carried out. This may be accomplished by using the Atomex process as described in US. Pat. No.
- the plated substrate may be immersed in the electroless plating baths of the present invention in order to provide a thick, ductile plate of the Group 18 metal having the improved properties obtainable in accordance with the present invention.
- a gold solution is obtained by dissolving potassium gold succinimade in water, and heating to between about 70 and 95C. Potassium cyanide, tripotassium citrate, potassium hydroxide, and ethylene diamine tetraacetic acid are added thereto, the pH being maintained at about 13 and the temperature at about 80C. Dimethylamine borane is then dissolved in water, and added to this solution. In order to continue the gold plating, gold is replenished from an aqueous solution containing gold, as potassium gold succinimide. Additional amounts of dimethylamine borane may be required, as well as potassium hydroxide in order to maintain the proper pH.
- the initial plating bath thus prepared has the following composition:
- the silver plating bath thus prepared has the following composition:
- the copper bath thus prepared has the following composition:
- An electroless plating bath for autocatalytic deposition of Group IB metals upon a substrate comprising an aqueous solution of an imide complex of the Group 13 metal to be plated, said imide complex of the Group IB metal to be plated including an imide selected from the group consisting of imides having the formula H O, and cyclic imides having the formula R NH 0, wherein R is selected from the group consisting of alkylene, substituted alkylene, arylene, and substituted arylene, an alkali metal cyanide in an amount ranging from about 2 to 20 grams per liter, suf ficient to stabilize said bath, and a reducing agent selected from the group consisting of water soluble alkali metal borohydrides, water soluble amine boranes and formaldehyde, said bath maintained at a pH of from about 11 to 14.
- the electroless plating bath of claim 3 including an alkali metal buffering salt selected from the group consisting of alkali metal phosphates, citrates, tartrates, borates, metaborates, and mixtures thereof.
- An electroless gold plating bath for the autocatalytic deposition of gold upon a substrate comprising an aqueous solution of an alkali metal gold imide complex, said alkali metal gold imide complex including an imide selected from the group consisting of imides having the formula RNHQO, and cyclic imides having the formula lECONHCO, wherein R is selected from the group consisting of alkylene, substituted alkylene, arylene, and substituted arylene, an alkali metal cyanide in an amount sufficient to stabilize said bath, a reducing agent selected from the group consisting of water soluble alkali metal borohydrides, water soluble amine boranes, and formaldehyde, said bath maintained at a pH of from about 11 to 14.
- the electroless gold plating bath of claim 6 including an organic chelating agent capable of forming a chelate with the metal of said substrate.
- the electroless gold platng bath of claim 10 including an alkali metal buffering salt selected from the group consisting of an alkali metal phosphates, citrates, tartrates, borates, metaborates, and mixtures thereof.
- a method of plating a metallic substrate with a Group [B metal comprising:
- aqueous gold plating bath comprising a soluble gold salt selected from the group consisting of the alkali metal gold cyanides, an ammonium buffering agent capable of maintaining the pH of said bath between about 5.5 and 14, an organic chelating agent capable of chelating the metal ions of said substrate, for sufficient time to place said substrate with a thin layer of gold; and
- step (a) is from about 2 to 10 microinches.
- said electroless plating bath includes an alkali metal buffering salt.
- said electroless plating bath includes an organic chelating agent capable of forming a chelate with the metal of said substrate.
- said imide comprises an imide selected from the group consisting of succinimide and phthalimide.
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Metallurgy (AREA)
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- Chemically Coating (AREA)
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US464666A US3917885A (en) | 1974-04-26 | 1974-04-26 | Electroless gold plating process |
MX157698A MX146110A (es) | 1974-04-26 | 1975-04-09 | Mejoras en bano para producir un electrochapado de plata cobre y oro sobre substratos metalicos |
CA225,269A CA1038559A (en) | 1974-04-26 | 1975-04-23 | Electroless gold plating process |
FR7512789A FR2268595B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1974-04-26 | 1975-04-24 | |
IT49280/75A IT1035454B (it) | 1974-04-26 | 1975-04-24 | Metod e bagno di placcatura chimica |
GB1712775A GB1448659A (en) | 1974-04-26 | 1975-04-24 | Electroless deposition of copper silver and gold |
JP50050163A JPS5818430B2 (ja) | 1974-04-26 | 1975-04-24 | 無電解メツキ浴およびメツキ方法 |
AU80523/75A AU488780B2 (en) | 1975-04-24 | electroless GOLD SILVER AND COPPER PLATING PROCESS | |
BR3224/75A BR7502540A (pt) | 1974-04-26 | 1975-04-25 | Banho de deposicao nao eletrolitica e processo de deposicao de um substrato metalico com um metal do grupo ib |
DD185707A DD117488A5 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1974-04-26 | 1975-04-25 | |
DE19752518559 DE2518559A1 (de) | 1974-04-26 | 1975-04-25 | Stromloses plattierungsverfahren und plattierungsbad |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US464666A US3917885A (en) | 1974-04-26 | 1974-04-26 | Electroless gold plating process |
Publications (1)
Publication Number | Publication Date |
---|---|
US3917885A true US3917885A (en) | 1975-11-04 |
Family
ID=23844812
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US464666A Expired - Lifetime US3917885A (en) | 1974-04-26 | 1974-04-26 | Electroless gold plating process |
Country Status (10)
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4082908A (en) * | 1976-05-05 | 1978-04-04 | Burr-Brown Research Corporation | Gold plating process and product produced thereby |
US4162337A (en) * | 1977-11-14 | 1979-07-24 | Bell Telephone Laboratories, Incorporated | Process for fabricating III-V semiconducting devices with electroless gold plating |
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 |
US4340451A (en) * | 1979-12-17 | 1982-07-20 | Bell Telephone Laboratories, Incorporated | Method of replenishing gold/in plating baths |
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 |
US4822641A (en) * | 1985-04-30 | 1989-04-18 | Inovan Gmbh & Co. Kg | Method of manufacturing a contact construction material structure |
US4863766A (en) * | 1986-09-02 | 1989-09-05 | General Electric Company | Electroless gold plating composition and method for plating |
US4919720A (en) * | 1988-06-30 | 1990-04-24 | Learonal, Inc. | Electroless gold plating solutions |
US4925491A (en) * | 1986-09-30 | 1990-05-15 | Lamerie, N.V. | Solutions and creams for silver plating and polishing |
EP0369545A1 (en) * | 1988-11-15 | 1990-05-23 | H.B.T. Holland Biotechnology B.V. | Process for the preparation of elemental sols |
US4978559A (en) * | 1989-11-03 | 1990-12-18 | General Electric Company | Autocatalytic electroless gold plating composition |
US4979988A (en) * | 1989-12-01 | 1990-12-25 | General Electric Company | Autocatalytic electroless gold plating composition |
US5130168A (en) * | 1988-11-22 | 1992-07-14 | Technic, Inc. | Electroless gold plating bath and method of using same |
US5206055A (en) * | 1991-09-03 | 1993-04-27 | General Electric Company | Method for enhancing the uniform electroless deposition of gold onto a palladium substrate |
US5338343A (en) * | 1993-07-23 | 1994-08-16 | Technic Incorporated | Catalytic electroless gold plating baths |
US20040069641A1 (en) * | 2002-09-30 | 2004-04-15 | Shinko Electric Industries Co., Ltd. | Non-cyanogen type electrolytic solution for plating gold |
US20060141149A1 (en) * | 2004-12-29 | 2006-06-29 | Industrial Technology Research Institute | Method for forming superparamagnetic nanoparticles |
US20060165909A1 (en) * | 2002-07-17 | 2006-07-27 | Hans-Jurgen Schreier | Immersion plating of silver |
US20090139264A1 (en) * | 2007-11-30 | 2009-06-04 | Rachel Brown | Antique jewelry articles and methods of making same |
CN102925933A (zh) * | 2012-11-05 | 2013-02-13 | 福州大学 | 一种Au-FeNi两段式合金纳米马达及其制备方法 |
US20150345039A1 (en) * | 2015-07-20 | 2015-12-03 | National Institute Of Standards And Technology | Composition having alkaline ph and process for forming superconformation therewith |
US11579344B2 (en) | 2012-09-17 | 2023-02-14 | Government Of The United States Of America, As Represented By The Secretary Of Commerce | Metallic grating |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2747562A1 (de) * | 1977-10-20 | 1979-05-03 | Schering Ag | Verfahren und anlage zur wiedergewinnung von im abwasser von anlagen zur chemischen oberflaechenbehandlung befindlichen metallen und anderen wertstoffen |
DE3029785A1 (de) * | 1980-08-04 | 1982-03-25 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Saures goldbad zur stromlosen abscheidung von gold |
US4474838A (en) * | 1982-12-01 | 1984-10-02 | Omi International Corporation | Electroless direct deposition of gold on metallized ceramics |
JPS60179127U (ja) * | 1984-05-09 | 1985-11-28 | ヤンマー農機株式会社 | コンバイン |
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US3294578A (en) * | 1963-10-22 | 1966-12-27 | Gen Aniline & Film Corp | Deposition of a metallic coat on metal surfaces |
US3482974A (en) * | 1966-12-27 | 1969-12-09 | Gen Electric | Method of plating gold films onto oxide-free silicon substrates |
US3506462A (en) * | 1966-10-29 | 1970-04-14 | Nippon Electric Co | Electroless gold plating solutions |
US3515571A (en) * | 1963-07-02 | 1970-06-02 | Lockheed Aircraft Corp | Deposition of gold films |
US3589916A (en) * | 1964-06-24 | 1971-06-29 | Photocircuits Corp | Autocatalytic gold plating solutions |
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US3700469A (en) * | 1971-03-08 | 1972-10-24 | Bell Telephone Labor Inc | Electroless gold plating baths |
-
1974
- 1974-04-26 US US464666A patent/US3917885A/en not_active Expired - Lifetime
-
1975
- 1975-04-09 MX MX157698A patent/MX146110A/es unknown
- 1975-04-23 CA CA225,269A patent/CA1038559A/en not_active Expired
- 1975-04-24 IT IT49280/75A patent/IT1035454B/it active
- 1975-04-24 GB GB1712775A patent/GB1448659A/en not_active Expired
- 1975-04-24 FR FR7512789A patent/FR2268595B1/fr not_active Expired
- 1975-04-24 JP JP50050163A patent/JPS5818430B2/ja not_active Expired
- 1975-04-25 DE DE19752518559 patent/DE2518559A1/de not_active Ceased
- 1975-04-25 DD DD185707A patent/DD117488A5/xx unknown
- 1975-04-25 BR BR3224/75A patent/BR7502540A/pt unknown
Patent Citations (8)
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US3230098A (en) * | 1962-10-09 | 1966-01-18 | Engelhard Ind Inc | Immersion plating with noble metals |
US3515571A (en) * | 1963-07-02 | 1970-06-02 | Lockheed Aircraft Corp | Deposition of gold films |
US3294578A (en) * | 1963-10-22 | 1966-12-27 | Gen Aniline & Film Corp | Deposition of a metallic coat on metal surfaces |
US3589916A (en) * | 1964-06-24 | 1971-06-29 | Photocircuits Corp | Autocatalytic gold plating solutions |
US3506462A (en) * | 1966-10-29 | 1970-04-14 | Nippon Electric Co | Electroless gold plating solutions |
US3482974A (en) * | 1966-12-27 | 1969-12-09 | Gen Electric | Method of plating gold films onto oxide-free silicon substrates |
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US3697296A (en) * | 1971-03-09 | 1972-10-10 | Du Pont | Electroless gold plating bath and process |
Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4082908A (en) * | 1976-05-05 | 1978-04-04 | Burr-Brown Research Corporation | Gold plating process and product produced thereby |
US4162337A (en) * | 1977-11-14 | 1979-07-24 | Bell Telephone Laboratories, Incorporated | Process for fabricating III-V semiconducting devices with electroless gold plating |
US4307136A (en) * | 1978-11-16 | 1981-12-22 | Engelhard Minerals & Chemicals Corp. | Process for the chemical deposition of gold by autocatalytic reduction |
US4340451A (en) * | 1979-12-17 | 1982-07-20 | Bell Telephone Laboratories, Incorporated | Method of replenishing gold/in plating baths |
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 |
US4822641A (en) * | 1985-04-30 | 1989-04-18 | Inovan Gmbh & Co. Kg | Method of manufacturing a contact construction material structure |
US4863766A (en) * | 1986-09-02 | 1989-09-05 | General Electric Company | Electroless gold plating composition and method for plating |
US4798626A (en) * | 1986-09-30 | 1989-01-17 | Lamerie, N.V. | Solutions and creams for silver plating and polishing |
US4925491A (en) * | 1986-09-30 | 1990-05-15 | Lamerie, N.V. | Solutions and creams for silver plating and polishing |
US4919720A (en) * | 1988-06-30 | 1990-04-24 | Learonal, Inc. | Electroless gold plating solutions |
EP0369545A1 (en) * | 1988-11-15 | 1990-05-23 | H.B.T. Holland Biotechnology B.V. | Process for the preparation of elemental sols |
US5130168A (en) * | 1988-11-22 | 1992-07-14 | Technic, Inc. | Electroless gold plating bath and method of using same |
US4978559A (en) * | 1989-11-03 | 1990-12-18 | General Electric Company | Autocatalytic electroless gold plating composition |
US4979988A (en) * | 1989-12-01 | 1990-12-25 | General Electric Company | Autocatalytic electroless gold plating composition |
US5206055A (en) * | 1991-09-03 | 1993-04-27 | General Electric Company | Method for enhancing the uniform electroless deposition of gold onto a palladium substrate |
US5338343A (en) * | 1993-07-23 | 1994-08-16 | Technic Incorporated | Catalytic electroless gold plating baths |
US20060165909A1 (en) * | 2002-07-17 | 2006-07-27 | Hans-Jurgen Schreier | Immersion plating of silver |
US7479305B2 (en) | 2002-07-17 | 2009-01-20 | Atotech Deutschland Gmbh | Immersion plating of silver |
US7261803B2 (en) * | 2002-09-30 | 2007-08-28 | Shinko Electric Industries Co., Ltd. | Non-cyanogen type electrolytic solution for plating gold |
US20070029206A1 (en) * | 2002-09-30 | 2007-02-08 | Shinko Electric Industries Co., Ltd. | Non-cyanogen type electrolytic solution for plating gold |
US20040069641A1 (en) * | 2002-09-30 | 2004-04-15 | Shinko Electric Industries Co., Ltd. | Non-cyanogen type electrolytic solution for plating gold |
US20060141149A1 (en) * | 2004-12-29 | 2006-06-29 | Industrial Technology Research Institute | Method for forming superparamagnetic nanoparticles |
US20090139264A1 (en) * | 2007-11-30 | 2009-06-04 | Rachel Brown | Antique jewelry articles and methods of making same |
US11579344B2 (en) | 2012-09-17 | 2023-02-14 | Government Of The United States Of America, As Represented By The Secretary Of Commerce | Metallic grating |
US11733439B2 (en) | 2012-09-17 | 2023-08-22 | Government Of The United States Of America. As Represented By The Secretary Of Commerce | Process for making a metallic grating |
CN102925933A (zh) * | 2012-11-05 | 2013-02-13 | 福州大学 | 一种Au-FeNi两段式合金纳米马达及其制备方法 |
CN102925933B (zh) * | 2012-11-05 | 2015-03-04 | 福州大学 | 一种Au-FeNi两段式合金纳米马达及其制备方法 |
US20150345039A1 (en) * | 2015-07-20 | 2015-12-03 | National Institute Of Standards And Technology | Composition having alkaline ph and process for forming superconformation therewith |
Also Published As
Publication number | Publication date |
---|---|
AU8052375A (en) | 1976-10-28 |
MX146110A (es) | 1982-05-18 |
JPS5818430B2 (ja) | 1983-04-13 |
GB1448659A (en) | 1976-09-08 |
FR2268595A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1975-11-21 |
JPS50149542A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1975-11-29 |
DE2518559A1 (de) | 1975-11-13 |
FR2268595B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1981-03-20 |
BR7502540A (pt) | 1976-03-03 |
IT1035454B (it) | 1979-10-20 |
DD117488A5 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1976-01-12 |
CA1038559A (en) | 1978-09-19 |
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Owner name: ENGELHARD CORPORATION 70 WOOD AVENUE SOUTH, METRO Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:PHIBRO CORPORATION, A CORP. OF DE;REEL/FRAME:003968/0801 Effective date: 19810518 |