US20090038950A1 - High speed method for plating palladium and palladium alloys - Google Patents
High speed method for plating palladium and palladium alloys Download PDFInfo
- Publication number
- US20090038950A1 US20090038950A1 US12/220,037 US22003708A US2009038950A1 US 20090038950 A1 US20090038950 A1 US 20090038950A1 US 22003708 A US22003708 A US 22003708A US 2009038950 A1 US2009038950 A1 US 2009038950A1
- Authority
- US
- United States
- Prior art keywords
- palladium
- ammonia
- bath
- plating
- high speed
- 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.)
- Abandoned
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 227
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 68
- 229910001252 Pd alloy Inorganic materials 0.000 title claims abstract description 51
- 238000007747 plating Methods 0.000 title description 60
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 208
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 95
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims description 54
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 25
- 239000004202 carbamide Substances 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- -1 ammonium ions Chemical class 0.000 claims description 19
- 238000005275 alloying Methods 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 5
- 238000000151 deposition Methods 0.000 abstract description 11
- 238000000576 coating method Methods 0.000 abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 46
- 238000009713 electroplating Methods 0.000 description 30
- 229910052759 nickel Inorganic materials 0.000 description 20
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 15
- 229910000990 Ni alloy Inorganic materials 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 239000010949 copper Substances 0.000 description 11
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 10
- 238000013019 agitation Methods 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 229910001369 Brass Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910001297 Zn alloy Inorganic materials 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 239000004327 boric acid Substances 0.000 description 6
- 239000010951 brass Substances 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 235000011130 ammonium sulphate Nutrition 0.000 description 5
- 229910002056 binary alloy Inorganic materials 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910001128 Sn alloy Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000003868 ammonium compounds Chemical class 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 230000001473 noxious effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229940124530 sulfonamide Drugs 0.000 description 3
- 229910002058 ternary alloy Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910000531 Co alloy Inorganic materials 0.000 description 2
- 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
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 2
- 239000006172 buffering agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000002941 palladium compounds Chemical class 0.000 description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 150000005041 phenanthrolines Chemical class 0.000 description 2
- 150000003248 quinolines Chemical class 0.000 description 2
- 238000005185 salting out Methods 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 239000011686 zinc sulphate Substances 0.000 description 2
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XDVOLDOITVSJGL-UHFFFAOYSA-N 3,7-dihydroxy-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B(O)OB2OB(O)OB1O2 XDVOLDOITVSJGL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical class [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical class [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 230000000368 destabilizing effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- LWHYKTAISUZRAD-UHFFFAOYSA-L palladium(2+);carbonate Chemical compound [Pd+2].[O-]C([O-])=O LWHYKTAISUZRAD-UHFFFAOYSA-L 0.000 description 1
- RFLFDJSIZCCYIP-UHFFFAOYSA-L palladium(2+);sulfate Chemical compound [Pd+2].[O-]S([O-])(=O)=O RFLFDJSIZCCYIP-UHFFFAOYSA-L 0.000 description 1
- 229910000364 palladium(II) sulfate Inorganic materials 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical class OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 150000003216 pyrazines Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical group C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 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
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/567—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of platinum group metals
Definitions
- the present invention is directed to high speed methods for plating palladium and palladium alloys using ammonia-based palladium and palladium alloy plating compositions. More specifically, the present invention is directed to high speed methods for plating palladium and palladium alloys using ammonia-based palladium and palladium alloy plating compositions where the level of free ammonia is reduced.
- Vigorous agitation may also be supplied without the jet stream by moving the solution very rapidly past the substrate being plated by use of a pump or by moving the substrate rapidly through the solution.
- Another form of high speed plating is selective plating. Such selective plating uses specialized plating equipment such as chemical or mechanical masks which limit metal deposits to specific required areas while leaving other areas free of the metal.
- the industry desires palladium and palladium alloy deposits that are crack-free at usable current densities in high speed plating from 10 to 100 Amps/dm 2 and higher.
- the industry desires palladium and palladium alloys which have high wear resistance, high corrosion resistance, low electrical resistance and good solderability, such as for use as coatings for electrical contacts.
- a number of process parameters must be addressed. Such parameters include, but are not limited to, the composition of the bath, bath temperature, agitation rate during plating and bath pH. The specific parameters to achieve an optimum process may vary widely depending on whether the process is for low speed or high speed plating. Many palladium and palladium alloy plating processes use ammonia as a ligand for metals. Ammonia based processes have many advantages over ammonia free processes.
- Such advantages include: 1) no detrimental decomposition products from organic ligands in contrast to other types of ligands, such as polyamine type ligands; 2) highly ductile deposits; and 3) palladium-ammonia salts are more economical and readily available than many exotic palladium salts which are required for ammonia free processes.
- ammonia-based processes operate from the low acidic to high alkaline pH range, such as from a pH of 6 and higher.
- free ammonia escapes from the baths as ammonia vapor. This alters the pH of the bath and destabilizes it to seriously compromise the bath performance. This is especially problematic at high speed plating where plating rates are faster and bath agitation is more vigorous than with low speed plating, thus causing a greater rate of free ammonia loss.
- plating at high temperatures or an increase in temperature during plating which is typical for high speed plating, causes ammonia loss from the bath, thus destabilizing the plating process.
- Ammonia-based plating processes require periodic replacement of ammonia to maintain the stability and optimum operation of the process.
- free ammonia levels are kept at 50 g/L to 150 g/L, more typically 100 g/L.
- ammonia replenishment is difficult.
- Ammonia is often replenished by adding ammonium salts, e.g. ammonium sulfate for sulfate-based solutions, to the plating bath; however, this results in an accumulation of anions in the plating bath which dramatically reduces the life of the bath due to salting out of bath components.
- Ammonia gas and ammonium hydroxide also may be added to the baths; however, such compounds are inconvenient and problematic to handle. Both present potential serious noxious and toxic hazards to workers using them.
- the more free ammonia added to the bath the greater the ammonia loss, thus presenting a hazard to the environment. Accordingly, the industry desires a high speed plating method where the free ammonia level is reduced.
- ammonia loss is greater, thus requiring a greater rate of ammonia replacement and increasing the difficulty of maintaining a stable plating process.
- the high temperatures and rapid agitation of the bath during high speed plating further increase the loss of ammonia and destabilize the bath.
- a rapid loss of ammonia results in an unstable bath and poor process performance. This reduces the overall efficiency of the process and increases the cost of plating.
- U.S. Pat. No. 5,415,685 discloses an ammonia-based palladium plating composition and process.
- the patent alleges that the ammonia-based palladium plating composition is both stable and provides a whiter palladium deposit over a wider range of plating thicknesses than conventional processes.
- the process described in the patent is a low speed process with current densities ranging from 0.1 Amps/ft 2 to 50 Amps/ft 2 (0.01 Amps/dm 2 to 5 Amps/dm 2 ).
- Such processes are not suitable in an industry where high speed plating is mandatory to achieve economic efficiency. Accordingly, there is a need for a high speed method for plating palladium and palladium alloys from an ammonia-based bath.
- a method includes: a) providing a composition consisting essentially of one or more sources of palladium, ammonium ions and urea; b) contacting a substrate with the composition; and c) generating a current density of at least 10 Amps/dm 2 to deposit palladium on the substrate.
- a method includes: a) providing a composition consisting essentially of one or more sources of palladium, one or more sources of alloying metals, ammonium ions and urea; b) contacting a substrate with the composition; and c) generating a current density of at least 10 Amps/dm 2 to deposit a palladium alloy on the substrate.
- the high speed methods provide stable palladium and palladium alloy baths and eliminate the need to add ammonium sulfates, ammonium hydroxide, ammonia gas or other ammonium compounds to replenish the free ammonia levels in the bath. Thus, the hazards and other disadvantages of adding such compounds to the plating baths are eliminated.
- the high speed methods also reduce the amount of free ammonia in the bath in contrast to many conventional high speed palladium and palladium alloy processes. Accordingly, the vapor level of ammonia is reduced.
- the high speed methods provide bright, ductile and crack free palladium and palladium alloy deposits on substrates at high current densities.
- the high speed methods may be used to plate palladium and palladium alloys on any substrate where palladium and palladium alloy coatings are desired.
- substrates include electronic components as well as jewelry.
- Electronic components may include electrical contacts where high wear resistance, high corrosion resistance and low electrical contact resistance and good solderability are desired.
- ° C. degrees Centigrade
- g gram
- mg milligrams
- L liter
- mL milliliter
- Amp amperes
- dm decimeter
- rpm revolutions per minute.
- MTO Metal turnover
- the methods are high speed electroplating methods for depositing palladium and palladium alloys with low levels of free ammonia, thus reducing the generation of ammonia vapor during high speed electroplating and vigorous bath agitation.
- the free ammonia in the electroplating baths is less than 50 g/L.
- the reduction in free ammonia also provides for a more environmentally friendly bath since less ammonia vapor is generated during electroplating in contrast to many conventional ammonia-based baths. The unpleasant and annoying odor of ammonia is eliminated or at least reduced.
- ammonia is continuously added in metered quantities to maintain an optimum pH.
- ammonium sulfate, ammonium hydroxide and ammonia gas are used.
- Such compounds are difficult to handle are noxious and are hazardous to workers.
- adding such compounds to the baths often cause the salting out of bath components, thus compromising bath performance.
- the high speed methods eliminate the need to add such compounds to the plating baths.
- Urea is included in the baths to stabilize the baths by compensating for the reduced free ammonia and for preventing changes in the pH due to the loss of ammonia.
- the high speed electroplating baths have a pH range of 6 to 10, typically, from 7 to 8.
- Including urea in the baths eliminates the need to replenish ammonia by the addition of ammonium compounds or ammonia.
- Urea is easier to handle than ammonia or ammonium compounds.
- Urea is a weak complexing agent and addition of large quantities of urea to ammonia-based plating baths does not detrimentally affect the microstructure of palladium and palladium alloy deposits. Further, there is no accumulation of decomposition products which limit the bath life.
- one of the hydrolysis products of urea is ammonia and this ammonia is used to replenish the loss of free-ammonia and help maintain the desired pH and the bath stability.
- Urea is included in the baths in amounts such that the total amount of urea and free ammonia in the baths are from 100 g/L to 150 g/L.
- palladium compounds may be used as a source of palladium in the high speed electroplating methods provided that they are compatible with the high speed process and other bath components.
- Such palladium compounds include, but are not limited to, palladium complex ion compounds with ammonia as the complexing agent.
- Such compounds include, but are not limited to, dichlorodiammine palladium (II), dinitrodiammine palladium (II), tetrammine palladium (II) chloride, tetrammine palladium (II) sulfate, tetrammine palladium tetrachloropalladate, tetramine palladium carbonate and tetramine palladium hydrogen carbonate.
- Additional sources of palladium include, but are not limited to, palladium dichloride, palladium dibromide, palladium sulfate, palladium nitrate, palladium monoxide-hydrate, palladium acetates, palladium propionates, palladium oxalates and palladium formates.
- One or more sources of palladium may be mixed together in the bath.
- the ammonia palladium complexes are used in the bath.
- Sufficient amounts of one or more sources of palladium are added to the bath to provide 10 g/L to 50 g/L of palladium for deposition, or such as from 20 g/L to 40 g/L of palladium.
- Ammonia may be added to the bath by water soluble ammonium salts.
- ammonium salts include, but are not limited to, ammonium halides, such as ammonium chloride and ammonium bromides, ammonium sulfates and ammonium nitrates.
- Sources of ammonia are added to the baths in sufficient amounts to provide free ammonia in amounts of less than 50 g/L, or such as from 10 g/L to 45 g/L, or such as from 15 g/L to 35 g/L.
- Alloying metals which may be added to the high speed electroplating baths to form palladium alloys include, but are not limited to, one or more of nickel, cobalt, iron and zinc.
- the alloys may be binary alloys or ternary alloys.
- the alloys are binary alloys such as palladium/nickel, palladium/cobalt and palladium/zinc. More typically, the binary alloy is palladium/nickel.
- the ternary alloy is palladium/nickel/zinc.
- One or more alloying metals may be added to the baths as a water soluble salt.
- Such salts include, but are not limited to, halides, sulfates, sulfites, phosphates, pyrophosphates, nitrates and salts with organic acids, such as acetates, propionates, oxalates and formates.
- the halide and sulfate salts are used.
- Sufficient amounts of one or more alloying metal salts are added to the baths to provide alloying metal ions in amounts of 0.1 g/L to 15 g/L, or such as from 1 g/L to 10 g/L.
- Palladium alloys made by the high speed methods are stable. Stability means that the alloy composition remains substantially constant over a wide current density as well as changes in the pH of the bath, temperature fluctuations and bath agitation rates.
- the weight ranges of palladium in the binary alloys range from 50wt % to 90wt % with the balance being the alloying metal.
- An example of such a binary alloy which is used for coatings on electrical contacts is palladium/nickel (80 wt %/20 wt %).
- the weight ranges of palladium in a ternary alloy range from 40 wt % to 80 wt % with the balance being the two alloying metals in equal or unequal proportions.
- the palladium electroplating baths used in the high speed methods consist essentially of one or more sources of palladium, ammonium ions, free ammonia and urea.
- the bath is used for depositing a palladium alloy, one or more alloying metal ions are added to the bath.
- the palladium and palladium alloys deposited by the high speed methods are bright, crack free and adhere to substrates.
- One or more conventional additives also may be added to the bath.
- Such conventional additives include, but are not limited to, buffers, brighteners, surfactants and mixtures thereof. Such additives may be included in the bath in conventional amounts.
- surfactants which do not compromise the performance of the bath may be included.
- surfactants include, but are not limited to, non-ionic surfactants, cationic surfactants and anionic surfactants.
- non-ionic surfactants include polyethylene glycols, alkyl quaternary ammonium salts and sulfopropylated alkylalkoxylates.
- Buffering agents include, but are not limited to, one or more of acetic acid, boric acid, carbonic acid, citric acid, tetraboric acid, maleic acid, itaconic acid and salts thereof. Other conventional water soluble acids also may be included as buffering agents.
- Mineral acids and bases also may be added to the baths to help maintain the pH.
- Such mineral acids include sulfuric acid, hydrochloric acid and nitric acid.
- Bases include, but are not limited to, sodium hydroxide and potassium hydroxide. Typically, sulfuric acid or sodium hydroxide is used.
- Suitable brighteners are those compounds which provide a bright palladium or palladium alloy deposit.
- Such brighteners include conventional organic brighteners.
- organic brighteners include, but are not limited to, succinimide, maleimide, quinolines, substituted quinolines, phenanthrolines and substituted phenanthrolines and quaternized derivatives thereof, pyridine and its derivatives, such as pyridine carboxylic acids, pyridine carboxylic acid amines, and polypyridines, such as bipyridines, nicotinic acid and its derivatives, pyridinium alkyl sulfobetaine, piperidine and its derivatives, piperazine and its derivatives, pyrazine and its derivatives and mixtures thereof.
- the brighteners used in the high speed baths are organic brighteners which have nitrogen containing heterocyclic rings, however, excluding aromatic sulfonamides. More typically, the brighteners used are pyridine derivatives, pyrazine derivatives or mixtures thereof.
- stress reducing agents are, in general, excluded from the baths.
- An example of such stress reducing agents are the aromatic sulfonamides.
- a typical aromatic sulfonamide which is used as a stress reducing agent is saccharin.
- Bath temperatures may be maintained by conventional heating apparatus. Bath temperatures range from 40 to 70° C., or such as from 50 to 60° C. Maintaining the bath temperature within the ranges, in particular at the higher end of the range, is highly desirable because as the temperature increases the amount of ammonia vapor leaving the bath also increases. Accordingly, temperature maintenance is important.
- the high speed electroplating methods use current densities from 10 Amps/dm2 and higher. Typically, current densities range from 10 Amps/dm 2 to 100 Amps/dm 2 , or such as from 20 Amps/dm 2 to 80 Amps/dm 2 . Such current densities are controlled using conventional rectifiers.
- Conventional high speed plating apparatus may be used to electroplate palladium metal and palladium metal alloys.
- the palladium and palladium alloys are electroplated using reel-to-reel plating apparatus; however, any apparatus which maintains a high speed plating rate may be used.
- insoluble anodes may be used with the high speed methods.
- insoluble anodes include, but are not limited to, platinized titanium, mixed oxide coated titanium and stainless steel.
- anodes with the above mentioned materials with the shield design as described in U.S. Ser. No. 2006/0124451 may be used.
- Cathodes include any substrate which may be plated with palladium or a palladium alloy.
- the palladium or palladium alloy is deposited on copper, copper alloy or nickel-plated copper substrates.
- Such substrates may be electrical contacts where high wear resistance, high corrosion resistance, low electrical contact resistance, high ductility and good solderability are required. Examples of an electrical contact are lead frames and electrical connectors.
- Electronic devices which include such electrical contacts include, but are not limited to, printed circuit boards, semi-conductor devices, optoelectronic devices, electrical components and automobile components. Additionally, the high speed methods may be used to deposit palladium or palladium alloys on components for solar cell devices and jewelry as well as any article which may accept a palladium or palladium alloy coating.
- the thicknesses of the palladium and palladium alloy coatings deposited by the high speed methods may vary and depend on the function of the substrate. In general, thicknesses range from 0.1 ⁇ m to 100 ⁇ m. Typically, the thicknesses range from 0.5 ⁇ m to 20 ⁇ m.
- the rate of deposit depends on the current density used. In general, the rate may range from 1 ⁇ m/min to 30 ⁇ m/min.
- palladium/nickel alloy may be plated at 3 ⁇ m/min at 10 Amps/dm 2 and 18 ⁇ m/min at 60 Amps/dm 2 .
- the ammonia-based palladium/nickel alloy composition was added to a 1000 ml beaker with a magnetic stirrer to maintain agitation of the composition during electroplating.
- the anode was a platinzed titanium insoluble anode and the cathode was a brass substrate.
- the temperature of the composition was maintained at 50° C. and the initial pH was 7.2. Electroplating was done at a high current density of 10 Amps/dm 2 . The experiment was run until 20 MTO with respect to palladium metals was achieved.
- Free ammonia in the bath was analyzed every MTO for the first 5 MTOs, then reduced to a frequency of every 3 to 5 MTOs.
- the content of the ammonia in the bath was monitored by a pH titration method using 809 TitrandoTM from Metrohm. It was observed that the bath was chemically unstable once the deposition began with the initial low free ammonia concentration of 35 g/L. Bath destabilization was noticeable by a white precipitate forming at the bottom of the beaker. In order to maintain the stability and operation of the bath and achieve a bright and ductile deposit, the white precipitate was removed from the bath by filtration, and the free ammonia content was increased to 100 g/L by adding ammonium sulfate.
- the following palladium/nickel alloy aqueous, ammonia-based composition was prepared for depositing a bright and ductile palladium/nickel alloy (80/20% w/w):
- the ammonia-based palladium/nickel alloy composition was added to a 1000 ml beaker with a magnetic stirrer to maintain agitation of the composition during electroplating.
- the anode was a platinized titanium insoluble anode and the cathode was a brass substrate.
- the temperature of the composition was maintained at 50° C. and the pH was 7.2. Electroplating was done at a high current density of 10 Amps/dm 2 . The experiment was run until 20 MTO with respect to palladium metal was achieved.
- Free ammonia in the bath was analyzed every MTO for the first 5 MTOs then analysis was reduced to a frequency of every 3 to 5 MTOs.
- the content of the ammonia in the bath was monitored by a pH titration method using 809 TitrandoTM from Metrohm.
- Urea levels were analyzed using Genesis II FTIR SpectrometerTM from Mattson Instruments. Electroplating bath analysis showed that the ammonia/ammonium level and the pH remained stable throughout the electroplating (20 metal turnover with respect to palladium). There was no noticeable white precipitate.
- Urea replenishment was 0.7 to 0.8 g/g of palladium metal deposited.
- ammonia-based/urea electroplating composition eliminated the need to replenish ammonia during electroplating with undesirable and hazardous compounds such as NH 4 OH and ammonia gas.
- Low levels of free ammonia were easily maintained during electroplating in contrast to the bath of Example 1.
- noxious vapors were reduced due to the low free ammonia.
- the frequency and amount of urea replenishment was less than the ammonia replenishment in comparative Example 1 using NH 4 OH and ammonia gas, thus providing a more economical and cost effective process than the conventional method.
- Example 2 The palladium/nickel method described in Example 2 was repeated except that the amount of urea added to the electroplating composition was 80 g/L. The rate of urea replenishment was 0.7 to 0.8 g/g of palladium metal deposited on the brass substrate. The bath was stable throughout electroplating. The performance of this method was the same as in Example 2. A bright and ductile palladium/nickel alloy was deposited on the brass substrate.
- the following palladium/nickel alloy aqueous, ammonia-based composition was prepared for depositing a bright and ductile palladium/nickel alloy (80/20% w/w):
- the ammonia-based palladium/nickel alloy composition was added to a 1000 ml beaker.
- the cathode was a rotating cylinder pre-plated with bright nickel. During plating the cathode was rotated at 1000 rpm.
- the pH of the ammonia-based composition was maintained at 7.2 during electroplating and the temperature was 50° C. Electroplating was done at a current density of 20 Amps/dm 2 . The bath was stable during the electroplating process.
- the palladium/nickel deposits were bright, ductile and adhered to the bright nickel.
- Example 4 Four bright nickel coated brass substrates were electroplated with the aqueous, ammonia-based palladium/nickel composition as described in Example 4. Each substrate was plated with the composition at different current densities. The current densities were 20 Amps/dm 2 , 40 Amps/dm 2 , 60 Amps/dm 2 and 80 amps/dm 2 . The pH of the plating composition was 7.2 with a temperature of 50° C. The high speed method was done using jet plating equipment designed for laboratory testing. The plating composition was applied to the substrates at a flow rate of 800 liters/hour. All of the palladium/nickel deposits on the bright nickel coated brass substrates were bright, ductile and adhered to the substrates.
- aqueous, ammonia-based palladium metal composition is prepared for depositing a palladium coating on a copper substrate:
- the aqueous, ammonia-based palladium composition is deposited on the copper substrate using jet plating equipment as described in Example 5.
- the pH of the composition is maintained at 8 and the temperature of the composition is maintained at 40° C.
- the current density is 20 Amps/dm 2 .
- the bath is expected to be stable during electroplating.
- the resulting palladium coatings on the substrates are expected to be semi-bright and crack-free.
- aqueous, ammonia-based palladium/cobalt alloy composition is prepared for depositing a palladium/cobalt alloy on a copper substrate:
- the aqueous, ammonia-based palladium alloy composition is deposited on the copper substrate using jet plating equipment as described in Example 5.
- the pH of the bath is maintained at 7.5 and the temperature is maintained at 60° C.
- the current density is 90 Amps/dm 2 .
- the bath is expected to be stable during electroplating.
- the palladium/cobalt deposit is expected to be bright and crack-free.
- aqueous, ammonia-based palladium/zinc alloy composition is used to deposit a palladium zinc alloy on a copper/tin alloy substrate:
- the aqueous, ammonia-based palladium alloy composition is deposited on the copper/tin alloy substrate using jet plating equipment as described in Example 5.
- the pH of the composition is maintained at 7 and the temperature of the composition is maintained at 60° C.
- the current density is 30 Amps/dm 2 .
- the bath is expected to be stable during electroplating.
- a bright and crack-free palladium/zinc alloy is deposited on the copper/tin alloy.
- aqueous, ammonia-based palladium/nickel/zinc alloy composition is used to deposit a palladium/nickel/zinc alloy on a copper substrate:
- the aqueous, ammonia-based palladium alloy composition is deposited on the copper substrate using the jet plating equipment as described in Example 5.
- the pH of the composition is maintained at 7 and the temperature of the composition is maintained at 60° C.
- the current density is 85 Amps/dm 2 .
- the bath is expected to be stable during electroplating.
- the palladium/nickel/zinc alloy is expected to be bright and crack-free.
Abstract
Description
- The present invention is directed to high speed methods for plating palladium and palladium alloys using ammonia-based palladium and palladium alloy plating compositions. More specifically, the present invention is directed to high speed methods for plating palladium and palladium alloys using ammonia-based palladium and palladium alloy plating compositions where the level of free ammonia is reduced.
- The dramatic increase in the price of gold over the past several years has given rise to new methods and equipment in the metal plating field and attempts to use substitute metals such as palladium and its alloys through, for example, reel-to-reel plating. The use of such plating processes requires high speed plating and high speed requires current densities of 10 Amps/dm2 and above. In addition, the industry desires high speed plating to achieve metal deposition in as short a time as possible to be more efficient in the manufacturing of metal plated articles. High speed plating equipment may employ the jet plating principle where the plating solution is sprayed out onto a substrate being plated with a jet stream to provide vigorous agitation. Vigorous agitation may also be supplied without the jet stream by moving the solution very rapidly past the substrate being plated by use of a pump or by moving the substrate rapidly through the solution. Another form of high speed plating is selective plating. Such selective plating uses specialized plating equipment such as chemical or mechanical masks which limit metal deposits to specific required areas while leaving other areas free of the metal.
- Attempts have been made to plate palladium and its alloys from high speed plating equipment with various baths; however, the deposits are either burned or matte gray or they are bright to semi-bright and highly stressed and exhibit surface micro-cracks which are visible only under a microscope at high power. Such cracks can be visible in the deposit right out of the plating bath or they become visible later after the deposit has been permitted to stand at room temperature for a day or more. There is a large amount of literature about the cracks. It is attributed to the co-deposition of hydrogen with palladium. After the hydrogen is emitted from the deposit, the cracks appear. The industry desires palladium and palladium alloy deposits that are crack-free at usable current densities in high speed plating from 10 to 100 Amps/dm2 and higher. In addition the industry desires palladium and palladium alloys which have high wear resistance, high corrosion resistance, low electrical resistance and good solderability, such as for use as coatings for electrical contacts.
- To achieve a palladium or palladium alloy deposit from a plating process with the desired properties, a number of process parameters must be addressed. Such parameters include, but are not limited to, the composition of the bath, bath temperature, agitation rate during plating and bath pH. The specific parameters to achieve an optimum process may vary widely depending on whether the process is for low speed or high speed plating. Many palladium and palladium alloy plating processes use ammonia as a ligand for metals. Ammonia based processes have many advantages over ammonia free processes. Such advantages include: 1) no detrimental decomposition products from organic ligands in contrast to other types of ligands, such as polyamine type ligands; 2) highly ductile deposits; and 3) palladium-ammonia salts are more economical and readily available than many exotic palladium salts which are required for ammonia free processes.
- Such ammonia-based processes operate from the low acidic to high alkaline pH range, such as from a pH of 6 and higher. During bath operation free ammonia escapes from the baths as ammonia vapor. This alters the pH of the bath and destabilizes it to seriously compromise the bath performance. This is especially problematic at high speed plating where plating rates are faster and bath agitation is more vigorous than with low speed plating, thus causing a greater rate of free ammonia loss. Also, plating at high temperatures or an increase in temperature during plating, which is typical for high speed plating, causes ammonia loss from the bath, thus destabilizing the plating process. Ammonia-based plating processes require periodic replacement of ammonia to maintain the stability and optimum operation of the process. Typically, free ammonia levels are kept at 50 g/L to 150 g/L, more typically 100 g/L. However, ammonia replenishment is difficult. Ammonia is often replenished by adding ammonium salts, e.g. ammonium sulfate for sulfate-based solutions, to the plating bath; however, this results in an accumulation of anions in the plating bath which dramatically reduces the life of the bath due to salting out of bath components. Ammonia gas and ammonium hydroxide also may be added to the baths; however, such compounds are inconvenient and problematic to handle. Both present potential serious noxious and toxic hazards to workers using them. The more free ammonia added to the bath the greater the ammonia loss, thus presenting a hazard to the environment. Accordingly, the industry desires a high speed plating method where the free ammonia level is reduced.
- At high speed plating, such as reel-to-reel plating, ammonia loss is greater, thus requiring a greater rate of ammonia replacement and increasing the difficulty of maintaining a stable plating process. Also, the high temperatures and rapid agitation of the bath during high speed plating further increase the loss of ammonia and destabilize the bath. A rapid loss of ammonia results in an unstable bath and poor process performance. This reduces the overall efficiency of the process and increases the cost of plating.
- U.S. Pat. No. 5,415,685 discloses an ammonia-based palladium plating composition and process. The patent alleges that the ammonia-based palladium plating composition is both stable and provides a whiter palladium deposit over a wider range of plating thicknesses than conventional processes. The process described in the patent is a low speed process with current densities ranging from 0.1 Amps/ft2 to 50 Amps/ft2 (0.01 Amps/dm2 to 5 Amps/dm2). Such processes are not suitable in an industry where high speed plating is mandatory to achieve economic efficiency. Accordingly, there is a need for a high speed method for plating palladium and palladium alloys from an ammonia-based bath.
- In one aspect a method includes: a) providing a composition consisting essentially of one or more sources of palladium, ammonium ions and urea; b) contacting a substrate with the composition; and c) generating a current density of at least 10 Amps/dm2 to deposit palladium on the substrate.
- In another aspect a method includes: a) providing a composition consisting essentially of one or more sources of palladium, one or more sources of alloying metals, ammonium ions and urea; b) contacting a substrate with the composition; and c) generating a current density of at least 10 Amps/dm2 to deposit a palladium alloy on the substrate.
- The high speed methods provide stable palladium and palladium alloy baths and eliminate the need to add ammonium sulfates, ammonium hydroxide, ammonia gas or other ammonium compounds to replenish the free ammonia levels in the bath. Thus, the hazards and other disadvantages of adding such compounds to the plating baths are eliminated. The high speed methods also reduce the amount of free ammonia in the bath in contrast to many conventional high speed palladium and palladium alloy processes. Accordingly, the vapor level of ammonia is reduced.
- The high speed methods provide bright, ductile and crack free palladium and palladium alloy deposits on substrates at high current densities. The high speed methods may be used to plate palladium and palladium alloys on any substrate where palladium and palladium alloy coatings are desired. Such substrates include electronic components as well as jewelry. Electronic components may include electrical contacts where high wear resistance, high corrosion resistance and low electrical contact resistance and good solderability are desired.
- As used throughout the specification, the following abbreviations have the following meaning unless the context clearly indicates otherwise: ° C.=degrees Centigrade; g=gram; mg=milligrams; L=liter; mL=milliliter; Amp=amperes; dm=decimeter; μm=microns=micrometer; and rpm=revolutions per minute.
- The terms “depositing”, “plating” and “electroplating” are used interchangeably throughout this specification. The term “burnt” means a dull or coarse finish. The term “bright” means an optical reflective finish. The term “ductile” or “ductility” is the resistance of metal deposits to cracking during distortion, such as bending or stretching. “Metal turnover (MTO)”=total palladium deposited in grams divided by the palladium content in the solution in grams. All amounts are percent by weight unless otherwise noted. All numerical ranges are inclusive and combinable in any order except where it is logical that such numerical ranges are constrained to add up to 100%.
- The methods are high speed electroplating methods for depositing palladium and palladium alloys with low levels of free ammonia, thus reducing the generation of ammonia vapor during high speed electroplating and vigorous bath agitation. Typically, the free ammonia in the electroplating baths is less than 50 g/L. The reduction in free ammonia also provides for a more environmentally friendly bath since less ammonia vapor is generated during electroplating in contrast to many conventional ammonia-based baths. The unpleasant and annoying odor of ammonia is eliminated or at least reduced.
- Also, constantly evaporating ammonia causes considerable difficulties in controlling the pH value. In conventional ammonia-based baths ammonia is continuously added in metered quantities to maintain an optimum pH. Typically, ammonium sulfate, ammonium hydroxide and ammonia gas are used. Such compounds are difficult to handle are noxious and are hazardous to workers. Further, adding such compounds to the baths often cause the salting out of bath components, thus compromising bath performance. The high speed methods eliminate the need to add such compounds to the plating baths.
- Urea is included in the baths to stabilize the baths by compensating for the reduced free ammonia and for preventing changes in the pH due to the loss of ammonia. The high speed electroplating baths have a pH range of 6 to 10, typically, from 7 to 8. Including urea in the baths eliminates the need to replenish ammonia by the addition of ammonium compounds or ammonia. Urea is easier to handle than ammonia or ammonium compounds. Urea is a weak complexing agent and addition of large quantities of urea to ammonia-based plating baths does not detrimentally affect the microstructure of palladium and palladium alloy deposits. Further, there is no accumulation of decomposition products which limit the bath life. Additionally, one of the hydrolysis products of urea is ammonia and this ammonia is used to replenish the loss of free-ammonia and help maintain the desired pH and the bath stability. Urea is included in the baths in amounts such that the total amount of urea and free ammonia in the baths are from 100 g/L to 150 g/L.
- A wide variety of palladium compounds may be used as a source of palladium in the high speed electroplating methods provided that they are compatible with the high speed process and other bath components. Such palladium compounds include, but are not limited to, palladium complex ion compounds with ammonia as the complexing agent. Such compounds include, but are not limited to, dichlorodiammine palladium (II), dinitrodiammine palladium (II), tetrammine palladium (II) chloride, tetrammine palladium (II) sulfate, tetrammine palladium tetrachloropalladate, tetramine palladium carbonate and tetramine palladium hydrogen carbonate. Additional sources of palladium include, but are not limited to, palladium dichloride, palladium dibromide, palladium sulfate, palladium nitrate, palladium monoxide-hydrate, palladium acetates, palladium propionates, palladium oxalates and palladium formates. One or more sources of palladium may be mixed together in the bath. Typically, the ammonia palladium complexes are used in the bath. Sufficient amounts of one or more sources of palladium are added to the bath to provide 10 g/L to 50 g/L of palladium for deposition, or such as from 20 g/L to 40 g/L of palladium.
- Ammonia may be added to the bath by water soluble ammonium salts. Such ammonium salts include, but are not limited to, ammonium halides, such as ammonium chloride and ammonium bromides, ammonium sulfates and ammonium nitrates. Sources of ammonia are added to the baths in sufficient amounts to provide free ammonia in amounts of less than 50 g/L, or such as from 10 g/L to 45 g/L, or such as from 15 g/L to 35 g/L.
- Alloying metals which may be added to the high speed electroplating baths to form palladium alloys include, but are not limited to, one or more of nickel, cobalt, iron and zinc. The alloys may be binary alloys or ternary alloys. Typically, the alloys are binary alloys such as palladium/nickel, palladium/cobalt and palladium/zinc. More typically, the binary alloy is palladium/nickel. Typically, the ternary alloy is palladium/nickel/zinc. One or more alloying metals may be added to the baths as a water soluble salt. Such salts include, but are not limited to, halides, sulfates, sulfites, phosphates, pyrophosphates, nitrates and salts with organic acids, such as acetates, propionates, oxalates and formates. Typically, the halide and sulfate salts are used. Sufficient amounts of one or more alloying metal salts are added to the baths to provide alloying metal ions in amounts of 0.1 g/L to 15 g/L, or such as from 1 g/L to 10 g/L.
- Palladium alloys made by the high speed methods are stable. Stability means that the alloy composition remains substantially constant over a wide current density as well as changes in the pH of the bath, temperature fluctuations and bath agitation rates. The weight ranges of palladium in the binary alloys range from 50wt % to 90wt % with the balance being the alloying metal. An example of such a binary alloy which is used for coatings on electrical contacts is palladium/nickel (80 wt %/20 wt %). The weight ranges of palladium in a ternary alloy range from 40 wt % to 80 wt % with the balance being the two alloying metals in equal or unequal proportions.
- The palladium electroplating baths used in the high speed methods consist essentially of one or more sources of palladium, ammonium ions, free ammonia and urea. When the bath is used for depositing a palladium alloy, one or more alloying metal ions are added to the bath. The palladium and palladium alloys deposited by the high speed methods are bright, crack free and adhere to substrates.
- One or more conventional additives also may be added to the bath. Such conventional additives include, but are not limited to, buffers, brighteners, surfactants and mixtures thereof. Such additives may be included in the bath in conventional amounts.
- One or more surfactants which do not compromise the performance of the bath may be included. Typically, such surfactants include, but are not limited to, non-ionic surfactants, cationic surfactants and anionic surfactants. Examples of such surfactants are polyethylene glycols, alkyl quaternary ammonium salts and sulfopropylated alkylalkoxylates.
- Buffering agents include, but are not limited to, one or more of acetic acid, boric acid, carbonic acid, citric acid, tetraboric acid, maleic acid, itaconic acid and salts thereof. Other conventional water soluble acids also may be included as buffering agents.
- Mineral acids and bases also may be added to the baths to help maintain the pH. Such mineral acids include sulfuric acid, hydrochloric acid and nitric acid. Bases include, but are not limited to, sodium hydroxide and potassium hydroxide. Typically, sulfuric acid or sodium hydroxide is used.
- Suitable brighteners are those compounds which provide a bright palladium or palladium alloy deposit. Such brighteners include conventional organic brighteners. Such organic brighteners include, but are not limited to, succinimide, maleimide, quinolines, substituted quinolines, phenanthrolines and substituted phenanthrolines and quaternized derivatives thereof, pyridine and its derivatives, such as pyridine carboxylic acids, pyridine carboxylic acid amines, and polypyridines, such as bipyridines, nicotinic acid and its derivatives, pyridinium alkyl sulfobetaine, piperidine and its derivatives, piperazine and its derivatives, pyrazine and its derivatives and mixtures thereof. Typically, the brighteners used in the high speed baths are organic brighteners which have nitrogen containing heterocyclic rings, however, excluding aromatic sulfonamides. More typically, the brighteners used are pyridine derivatives, pyrazine derivatives or mixtures thereof.
- Since the palladium and palladium alloys deposited by the high speed methods are typically crack free, stress reducing agents are, in general, excluded from the baths. An example of such stress reducing agents are the aromatic sulfonamides. A typical aromatic sulfonamide which is used as a stress reducing agent is saccharin.
- Bath temperatures may be maintained by conventional heating apparatus. Bath temperatures range from 40 to 70° C., or such as from 50 to 60° C. Maintaining the bath temperature within the ranges, in particular at the higher end of the range, is highly desirable because as the temperature increases the amount of ammonia vapor leaving the bath also increases. Accordingly, temperature maintenance is important.
- The high speed electroplating methods use current densities from 10 Amps/dm2 and higher. Typically, current densities range from 10 Amps/dm2 to 100 Amps/dm2, or such as from 20 Amps/dm2 to 80 Amps/dm2. Such current densities are controlled using conventional rectifiers.
- Conventional high speed plating apparatus may be used to electroplate palladium metal and palladium metal alloys. Typically, the palladium and palladium alloys are electroplated using reel-to-reel plating apparatus; however, any apparatus which maintains a high speed plating rate may be used.
- Conventional insoluble anodes may be used with the high speed methods. Examples of insoluble anodes include, but are not limited to, platinized titanium, mixed oxide coated titanium and stainless steel. Also, anodes with the above mentioned materials with the shield design as described in U.S. Ser. No. 2006/0124451 may be used.
- Cathodes include any substrate which may be plated with palladium or a palladium alloy. In general, the palladium or palladium alloy is deposited on copper, copper alloy or nickel-plated copper substrates. Such substrates may be electrical contacts where high wear resistance, high corrosion resistance, low electrical contact resistance, high ductility and good solderability are required. Examples of an electrical contact are lead frames and electrical connectors. Electronic devices which include such electrical contacts include, but are not limited to, printed circuit boards, semi-conductor devices, optoelectronic devices, electrical components and automobile components. Additionally, the high speed methods may be used to deposit palladium or palladium alloys on components for solar cell devices and jewelry as well as any article which may accept a palladium or palladium alloy coating.
- The thicknesses of the palladium and palladium alloy coatings deposited by the high speed methods may vary and depend on the function of the substrate. In general, thicknesses range from 0.1 μm to 100 μm. Typically, the thicknesses range from 0.5 μm to 20 μm.
- The rate of deposit depends on the current density used. In general, the rate may range from 1 μm/min to 30 μm/min. For example, palladium/nickel alloy may be plated at 3 μm/min at 10 Amps/dm2 and 18 μm/min at 60 Amps/dm2.
- The following examples are intended to further illustrate the high speed methods, but are not intended to limit the scope of the invention.
- The following conventional palladium/nickel alloy aqueous, ammonia-based composition was prepared to deposit a palladium/nickel alloy (80/20% w/w):
-
TABLE 1 COMPONENT AMOUNT (g/L) Palladium as Pd(NH3)4SO4 15 Nickel as NiSO4 6 Boric acid 26 Free NH3 as (NH4)2SO4 35 Nitrogen containing heterocyclic brightener 0.1 NH4OH Sufficient amount to achieve pH - The ammonia-based palladium/nickel alloy composition was added to a 1000 ml beaker with a magnetic stirrer to maintain agitation of the composition during electroplating. The anode was a platinzed titanium insoluble anode and the cathode was a brass substrate.
- The temperature of the composition was maintained at 50° C. and the initial pH was 7.2. Electroplating was done at a high current density of 10 Amps/dm2. The experiment was run until 20 MTO with respect to palladium metals was achieved.
- Free ammonia in the bath was analyzed every MTO for the first 5 MTOs, then reduced to a frequency of every 3 to 5 MTOs. The content of the ammonia in the bath was monitored by a pH titration method using 809 Titrando™ from Metrohm. It was observed that the bath was chemically unstable once the deposition began with the initial low free ammonia concentration of 35 g/L. Bath destabilization was noticeable by a white precipitate forming at the bottom of the beaker. In order to maintain the stability and operation of the bath and achieve a bright and ductile deposit, the white precipitate was removed from the bath by filtration, and the free ammonia content was increased to 100 g/L by adding ammonium sulfate. The strong odor of ammonia was noticeable during electroplating. Additionally, free ammonia lost during electroplating had to be replenished to maintain a stable pH. 3-4 g of ammonia as ammonia gas and NH4OH were added to the bath per gram of palladium plated in addition to the amount of ammonia added through Pd(NH3)4SO4 replenishment. Ammonia concentrations of 100 g/L were needed to maintain the stability of the bath. Although a bright and ductile deposit was plated, stability varied over the 20 MTO and required elimination of the white precipitate in addition to adding 3-4 g of ammonia/g of palladium plated to replenish the bath and maintain bath stability.
- The following palladium/nickel alloy aqueous, ammonia-based composition was prepared for depositing a bright and ductile palladium/nickel alloy (80/20% w/w):
-
TABLE 2 COMPONENT AMOUNT (g/L) Palladium as Pd(NH3)4SO4 15 Nickel as NiSO4 6 Boric acid 26 Free NH3 as (NH4)2SO4 35 Urea 100 Nitrogen containing heterocyclic brightener 0.1 NH4OH Sufficient amount to achieve pH - The ammonia-based palladium/nickel alloy composition was added to a 1000 ml beaker with a magnetic stirrer to maintain agitation of the composition during electroplating. The anode was a platinized titanium insoluble anode and the cathode was a brass substrate.
- The temperature of the composition was maintained at 50° C. and the pH was 7.2. Electroplating was done at a high current density of 10 Amps/dm2. The experiment was run until 20 MTO with respect to palladium metal was achieved.
- Free ammonia in the bath was analyzed every MTO for the first 5 MTOs then analysis was reduced to a frequency of every 3 to 5 MTOs. The content of the ammonia in the bath was monitored by a pH titration method using 809 Titrando™ from Metrohm. Urea levels were analyzed using Genesis II FTIR Spectrometer™ from Mattson Instruments. Electroplating bath analysis showed that the ammonia/ammonium level and the pH remained stable throughout the electroplating (20 metal turnover with respect to palladium). There was no noticeable white precipitate. Urea replenishment was 0.7 to 0.8 g/g of palladium metal deposited.
- Using the ammonia-based/urea electroplating composition eliminated the need to replenish ammonia during electroplating with undesirable and hazardous compounds such as NH4OH and ammonia gas. Low levels of free ammonia were easily maintained during electroplating in contrast to the bath of Example 1. Also, noxious vapors were reduced due to the low free ammonia. Additionally, the frequency and amount of urea replenishment was less than the ammonia replenishment in comparative Example 1 using NH4OH and ammonia gas, thus providing a more economical and cost effective process than the conventional method.
- This method was repeated except that the pH of the bath was 8. The results were substantially the same as at a pH of 7.2.
- The palladium/nickel method described in Example 2 was repeated except that the amount of urea added to the electroplating composition was 80 g/L. The rate of urea replenishment was 0.7 to 0.8 g/g of palladium metal deposited on the brass substrate. The bath was stable throughout electroplating. The performance of this method was the same as in Example 2. A bright and ductile palladium/nickel alloy was deposited on the brass substrate.
- EXAMPLE 4
- The following palladium/nickel alloy aqueous, ammonia-based composition was prepared for depositing a bright and ductile palladium/nickel alloy (80/20% w/w):
-
TABLE 3 COMPONENT AMOUNT (g/L) Palladium as Pd(NH3)4SO4 25 Nickel as NiSO4 10 Boric acid 26 Free NH3 as (NH4)2SO4 35 Urea 80 Nitrogen containing heterocyclic brightener 02 - The ammonia-based palladium/nickel alloy composition was added to a 1000 ml beaker. The cathode was a rotating cylinder pre-plated with bright nickel. During plating the cathode was rotated at 1000 rpm. The pH of the ammonia-based composition was maintained at 7.2 during electroplating and the temperature was 50° C. Electroplating was done at a current density of 20 Amps/dm2. The bath was stable during the electroplating process. The palladium/nickel deposits were bright, ductile and adhered to the bright nickel.
- The method described above was repeated twice with the same parameters except that they were done at current densities of 40 Amps/dm2 and 60 Amps/dm2. The results were the same as at 20 Amps/dm2. Bright and ductile palladium/nickel deposits were deposited on the nickel at the high current densities and adhered to the nickel.
- Four bright nickel coated brass substrates were electroplated with the aqueous, ammonia-based palladium/nickel composition as described in Example 4. Each substrate was plated with the composition at different current densities. The current densities were 20 Amps/dm2, 40 Amps/dm2, 60 Amps/dm2 and 80 amps/dm2. The pH of the plating composition was 7.2 with a temperature of 50° C. The high speed method was done using jet plating equipment designed for laboratory testing. The plating composition was applied to the substrates at a flow rate of 800 liters/hour. All of the palladium/nickel deposits on the bright nickel coated brass substrates were bright, ductile and adhered to the substrates.
- The following aqueous, ammonia-based palladium metal composition is prepared for depositing a palladium coating on a copper substrate:
-
TABLE 4 COMPONENT AMOUNT (g/L) Palladium as [Pd(NH3)4]Cl2 10 Free NH3 as (NH4)Cl 30 Boric acid 20 Urea 100 Nitrogen containing heterocyclic brightener 0.2 - The aqueous, ammonia-based palladium composition is deposited on the copper substrate using jet plating equipment as described in Example 5. The pH of the composition is maintained at 8 and the temperature of the composition is maintained at 40° C. The current density is 20 Amps/dm2. The bath is expected to be stable during electroplating. The resulting palladium coatings on the substrates are expected to be semi-bright and crack-free.
- The following aqueous, ammonia-based palladium/cobalt alloy composition is prepared for depositing a palladium/cobalt alloy on a copper substrate:
-
TABLE 5 COMPONENT AMOUNT (g/L) Palladium as [Pd(NH3)4]Cl2 10 Cobalt as CoSO4 5 Free NH3 as NH4Cl 30 Urea 90 Boric acid 20 Nitrogen containing heterocyclic brightener 1 - The aqueous, ammonia-based palladium alloy composition is deposited on the copper substrate using jet plating equipment as described in Example 5. The pH of the bath is maintained at 7.5 and the temperature is maintained at 60° C. The current density is 90 Amps/dm2. The bath is expected to be stable during electroplating. The palladium/cobalt deposit is expected to be bright and crack-free.
- The following aqueous, ammonia-based palladium/zinc alloy composition is used to deposit a palladium zinc alloy on a copper/tin alloy substrate:
-
TABLE 6 COMPONENT AMOUNT (g/L) Palladium as [Pd(NH3)4]Cl2 15 Zinc as ZnSO4 5 Free NH3 as (NH4)2SO4 40 citric acid 15 Urea 100 Nitrogen containing heterocyclic brightener 0.3 - The aqueous, ammonia-based palladium alloy composition is deposited on the copper/tin alloy substrate using jet plating equipment as described in Example 5. The pH of the composition is maintained at 7 and the temperature of the composition is maintained at 60° C. The current density is 30 Amps/dm2. The bath is expected to be stable during electroplating. A bright and crack-free palladium/zinc alloy is deposited on the copper/tin alloy.
- The following aqueous, ammonia-based palladium/nickel/zinc alloy composition is used to deposit a palladium/nickel/zinc alloy on a copper substrate:
-
TABLE 7 COMPONENT AMOUNT (g/L) Palladium as Pd(NH3)4SO4 20 Nickel as NiSO4 5 Zinc as ZnSO4 1 Free NH3 as (NH4)2SO4 40 Urea 70 Citric acid 15 Nitrogen containing heterocyclic brightener 0.5 - The aqueous, ammonia-based palladium alloy composition is deposited on the copper substrate using the jet plating equipment as described in Example 5. The pH of the composition is maintained at 7 and the temperature of the composition is maintained at 60° C. The current density is 85 Amps/dm2. The bath is expected to be stable during electroplating. The palladium/nickel/zinc alloy is expected to be bright and crack-free.
Claims (10)
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/220,037 US20090038950A1 (en) | 2007-07-20 | 2008-07-21 | High speed method for plating palladium and palladium alloys |
US12/912,400 US20110147225A1 (en) | 2007-07-20 | 2010-10-26 | High speed method for plating palladium and palladium alloys |
US13/924,553 US9435046B2 (en) | 2007-07-20 | 2013-06-22 | High speed method for plating palladium and palladium alloys |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US96139307P | 2007-07-20 | 2007-07-20 | |
US12/220,037 US20090038950A1 (en) | 2007-07-20 | 2008-07-21 | High speed method for plating palladium and palladium alloys |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/912,400 Continuation-In-Part US20110147225A1 (en) | 2007-07-20 | 2010-10-26 | High speed method for plating palladium and palladium alloys |
Publications (1)
Publication Number | Publication Date |
---|---|
US20090038950A1 true US20090038950A1 (en) | 2009-02-12 |
Family
ID=39942904
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/220,037 Abandoned US20090038950A1 (en) | 2007-07-20 | 2008-07-21 | High speed method for plating palladium and palladium alloys |
Country Status (4)
Country | Link |
---|---|
US (1) | US20090038950A1 (en) |
EP (1) | EP2017373B1 (en) |
CN (1) | CN101348928B (en) |
TW (1) | TWI391533B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100300888A1 (en) * | 2009-05-27 | 2010-12-02 | Ponnuswamy Thomas A | Pulse sequence for plating on thin seed layers |
US20120244276A1 (en) * | 2009-11-10 | 2012-09-27 | Doduco Gmbh | Method for depositing a palladium layer suitable for wire bonding on conductors of a printed circuit board, and palladium bath for use in said method |
US9385035B2 (en) | 2010-05-24 | 2016-07-05 | Novellus Systems, Inc. | Current ramping and current pulsing entry of substrates for electroplating |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101838830B (en) * | 2010-05-07 | 2012-08-15 | 厦门大学 | Electrolyte of electroplating palladium-nickel alloy |
CN105401182B (en) * | 2015-10-14 | 2017-06-23 | 佛山科学技术学院 | A kind of electroplate liquid formulation and its electro-plating method of the palladium of plating thick on stainless steel |
CN105543913A (en) * | 2016-02-25 | 2016-05-04 | 盈昌集团有限公司 | Palladium-cobalt alloy electroplating liquid and technology of electroplating spectacle frame with same |
GB202020071D0 (en) | 2020-12-18 | 2021-02-03 | Johnson Matthey Plc | Electroplating solutions |
Citations (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3458409A (en) * | 1964-10-12 | 1969-07-29 | Shinichi Hayashi | Method and electrolyte for thick,brilliant plating of palladium |
US3580820A (en) * | 1967-01-11 | 1971-05-25 | Suwa Seikosha Kk | Palladium-nickel alloy plating bath |
US3637474A (en) * | 1967-09-08 | 1972-01-25 | Sel Rex Corp | Electrodeposition of palladium |
US3920526A (en) * | 1974-03-12 | 1975-11-18 | Ibm | Process for the electrodeposition of ductile palladium and electroplating bath useful therefor |
US3925170A (en) * | 1974-01-23 | 1975-12-09 | American Chem & Refining Co | Method and composition for producing bright palladium electrodepositions |
US3933602A (en) * | 1973-04-27 | 1976-01-20 | Oxy Metal Industries Corporation | Palladium electroplating bath, process, and preparation |
US4066517A (en) * | 1976-03-11 | 1978-01-03 | Oxy Metal Industries Corporation | Electrodeposition of palladium |
US4076599A (en) * | 1975-10-30 | 1978-02-28 | International Business Machines Corporation | Method and composition for plating palladium |
US4092225A (en) * | 1976-11-17 | 1978-05-30 | Amp Incorporated | High efficiency palladium electroplating process, bath and composition therefor |
US4098656A (en) * | 1976-03-11 | 1978-07-04 | Oxy Metal Industries Corporation | Bright palladium electroplating baths |
US4100039A (en) * | 1976-11-11 | 1978-07-11 | International Business Machines Corporation | Method for plating palladium-nickel alloy |
US4224115A (en) * | 1975-12-03 | 1980-09-23 | Mitsubishi Denki Kabushiki Kaisha | Process for forming electrode on semiconductor device |
US4242180A (en) * | 1976-12-21 | 1980-12-30 | Siemens Aktiengesellschaft | Ammonia free palladium electroplating bath using aminoacetic acid |
US4297177A (en) * | 1980-09-19 | 1981-10-27 | American Chemical & Refining Company Incorporated | Method and composition for electrodepositing palladium/nickel alloys |
US4428802A (en) * | 1980-09-19 | 1984-01-31 | Kabushiki Kaisha Suwa Seikosha | Palladium-nickel alloy electroplating and solutions therefor |
US4454010A (en) * | 1982-08-30 | 1984-06-12 | At & T Bell Laboratories | Palladium plating procedure |
US4545868A (en) * | 1981-10-06 | 1985-10-08 | Learonal, Inc. | Palladium plating |
US4545869A (en) * | 1985-01-29 | 1985-10-08 | Omi International Corporation | Bath and process for high speed electroplating of palladium |
US4552628A (en) * | 1982-09-09 | 1985-11-12 | Engelhard Corporation | Palladium electroplating and bath thereof |
US4564426A (en) * | 1985-04-15 | 1986-01-14 | International Business Machines Corporation | Process for the deposition of palladium-nickel alloy |
US4622110A (en) * | 1981-10-06 | 1986-11-11 | Learonal, Inc. | Palladium plating |
US4673472A (en) * | 1986-02-28 | 1987-06-16 | Technic Inc. | Method and electroplating solution for deposition of palladium or alloys thereof |
US4715935A (en) * | 1985-01-25 | 1987-12-29 | Omi International Corporation | Palladium and palladium alloy plating |
US4849303A (en) * | 1986-07-01 | 1989-07-18 | E. I. Du Pont De Nemours And Company | Alloy coatings for electrical contacts |
US4911799A (en) * | 1989-08-29 | 1990-03-27 | At&T Bell Laboratories | Electrodeposition of palladium films |
US4911798A (en) * | 1988-12-20 | 1990-03-27 | At&T Bell Laboratories | Palladium alloy plating process |
US5342504A (en) * | 1992-03-30 | 1994-08-30 | Yazaki Corporation | Palladium-nickel alloy plating solution |
US5415685A (en) * | 1993-08-16 | 1995-05-16 | Enthone-Omi Inc. | Electroplating bath and process for white palladium |
US5750016A (en) * | 1995-09-16 | 1998-05-12 | Moon; Sung-Soo | Process for plating palladium or palladium alloy onto iron-nickel alloy substrate |
US5976344A (en) * | 1996-05-10 | 1999-11-02 | Lucent Technologies Inc. | Composition for electroplating palladium alloys and electroplating process using that composition |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0711475A (en) * | 1993-06-23 | 1995-01-13 | Kojima Kagaku Yakuhin Kk | Palladium plating solution |
US6251249B1 (en) * | 1996-09-20 | 2001-06-26 | Atofina Chemicals, Inc. | Precious metal deposition composition and process |
US7566390B2 (en) | 2004-12-15 | 2009-07-28 | Lam Research Corporation | Wafer support apparatus for electroplating process and method for using the same |
-
2008
- 2008-03-17 CN CN2008100868593A patent/CN101348928B/en active Active
- 2008-07-14 TW TW097126599A patent/TWI391533B/en active
- 2008-07-21 US US12/220,037 patent/US20090038950A1/en not_active Abandoned
- 2008-07-21 EP EP08160839.0A patent/EP2017373B1/en active Active
Patent Citations (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3458409A (en) * | 1964-10-12 | 1969-07-29 | Shinichi Hayashi | Method and electrolyte for thick,brilliant plating of palladium |
US3580820A (en) * | 1967-01-11 | 1971-05-25 | Suwa Seikosha Kk | Palladium-nickel alloy plating bath |
US3677909A (en) * | 1967-01-11 | 1972-07-18 | Katsumi Yamamura | Palladium-nickel alloy plating bath |
US3637474A (en) * | 1967-09-08 | 1972-01-25 | Sel Rex Corp | Electrodeposition of palladium |
US3933602A (en) * | 1973-04-27 | 1976-01-20 | Oxy Metal Industries Corporation | Palladium electroplating bath, process, and preparation |
US3925170A (en) * | 1974-01-23 | 1975-12-09 | American Chem & Refining Co | Method and composition for producing bright palladium electrodepositions |
US3920526A (en) * | 1974-03-12 | 1975-11-18 | Ibm | Process for the electrodeposition of ductile palladium and electroplating bath useful therefor |
US4076599A (en) * | 1975-10-30 | 1978-02-28 | International Business Machines Corporation | Method and composition for plating palladium |
US4224115A (en) * | 1975-12-03 | 1980-09-23 | Mitsubishi Denki Kabushiki Kaisha | Process for forming electrode on semiconductor device |
US4066517A (en) * | 1976-03-11 | 1978-01-03 | Oxy Metal Industries Corporation | Electrodeposition of palladium |
US4098656A (en) * | 1976-03-11 | 1978-07-04 | Oxy Metal Industries Corporation | Bright palladium electroplating baths |
US4100039A (en) * | 1976-11-11 | 1978-07-11 | International Business Machines Corporation | Method for plating palladium-nickel alloy |
US4092225A (en) * | 1976-11-17 | 1978-05-30 | Amp Incorporated | High efficiency palladium electroplating process, bath and composition therefor |
US4242180A (en) * | 1976-12-21 | 1980-12-30 | Siemens Aktiengesellschaft | Ammonia free palladium electroplating bath using aminoacetic acid |
US4297177A (en) * | 1980-09-19 | 1981-10-27 | American Chemical & Refining Company Incorporated | Method and composition for electrodepositing palladium/nickel alloys |
US4428802A (en) * | 1980-09-19 | 1984-01-31 | Kabushiki Kaisha Suwa Seikosha | Palladium-nickel alloy electroplating and solutions therefor |
US4622110A (en) * | 1981-10-06 | 1986-11-11 | Learonal, Inc. | Palladium plating |
US4545868A (en) * | 1981-10-06 | 1985-10-08 | Learonal, Inc. | Palladium plating |
US4454010A (en) * | 1982-08-30 | 1984-06-12 | At & T Bell Laboratories | Palladium plating procedure |
US4552628A (en) * | 1982-09-09 | 1985-11-12 | Engelhard Corporation | Palladium electroplating and bath thereof |
US4715935A (en) * | 1985-01-25 | 1987-12-29 | Omi International Corporation | Palladium and palladium alloy plating |
US4545869A (en) * | 1985-01-29 | 1985-10-08 | Omi International Corporation | Bath and process for high speed electroplating of palladium |
US4564426A (en) * | 1985-04-15 | 1986-01-14 | International Business Machines Corporation | Process for the deposition of palladium-nickel alloy |
US4673472A (en) * | 1986-02-28 | 1987-06-16 | Technic Inc. | Method and electroplating solution for deposition of palladium or alloys thereof |
US4849303A (en) * | 1986-07-01 | 1989-07-18 | E. I. Du Pont De Nemours And Company | Alloy coatings for electrical contacts |
US4911798A (en) * | 1988-12-20 | 1990-03-27 | At&T Bell Laboratories | Palladium alloy plating process |
US4911799A (en) * | 1989-08-29 | 1990-03-27 | At&T Bell Laboratories | Electrodeposition of palladium films |
US5342504A (en) * | 1992-03-30 | 1994-08-30 | Yazaki Corporation | Palladium-nickel alloy plating solution |
US5415685A (en) * | 1993-08-16 | 1995-05-16 | Enthone-Omi Inc. | Electroplating bath and process for white palladium |
US5750016A (en) * | 1995-09-16 | 1998-05-12 | Moon; Sung-Soo | Process for plating palladium or palladium alloy onto iron-nickel alloy substrate |
US5976344A (en) * | 1996-05-10 | 1999-11-02 | Lucent Technologies Inc. | Composition for electroplating palladium alloys and electroplating process using that composition |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100300888A1 (en) * | 2009-05-27 | 2010-12-02 | Ponnuswamy Thomas A | Pulse sequence for plating on thin seed layers |
US8500983B2 (en) * | 2009-05-27 | 2013-08-06 | Novellus Systems, Inc. | Pulse sequence for plating on thin seed layers |
US20120244276A1 (en) * | 2009-11-10 | 2012-09-27 | Doduco Gmbh | Method for depositing a palladium layer suitable for wire bonding on conductors of a printed circuit board, and palladium bath for use in said method |
US9385035B2 (en) | 2010-05-24 | 2016-07-05 | Novellus Systems, Inc. | Current ramping and current pulsing entry of substrates for electroplating |
Also Published As
Publication number | Publication date |
---|---|
CN101348928A (en) | 2009-01-21 |
EP2017373A3 (en) | 2013-09-11 |
CN101348928B (en) | 2012-07-04 |
TW200923140A (en) | 2009-06-01 |
TWI391533B (en) | 2013-04-01 |
EP2017373B1 (en) | 2018-09-26 |
EP2017373A2 (en) | 2009-01-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1009869B1 (en) | Cyanide-free monovalent copper electroplating solutions | |
EP2017373B1 (en) | High speed method for plating palladium alloys | |
CN102037162B (en) | Pd and Pd-Ni electrolyte baths | |
US9435046B2 (en) | High speed method for plating palladium and palladium alloys | |
EP2980279B1 (en) | Zinc-nickel alloy plating solution and plating method | |
US4911799A (en) | Electrodeposition of palladium films | |
JP2012504701A (en) | Method for depositing a palladium-rhodium layer with improved whiteness | |
US6743346B2 (en) | Electrolytic solution for electrochemical deposit of palladium or its alloys | |
JP5583896B2 (en) | High-speed plating method of palladium and palladium alloy | |
US20020112966A1 (en) | High current density zinc sulfate electrogalvanizing process and composition | |
KR20110032540A (en) | Nickel flash plating solutions, zinc-electroplated steel sheet and manufacturing method thereof | |
EP0112561B1 (en) | Aqueous electroplating solutions and process for electrolytically plating palladium-silver alloys | |
EP0892087A2 (en) | Electroplating of low-stress nickel | |
TWI784601B (en) | Platinum electroplating baths and platinum-plated products | |
EP3686319A1 (en) | Indium electroplating compositions and methods for electroplating indium on nickel | |
JP7121390B2 (en) | Tin alloy electroplating bath and plating method using the same | |
KR101491980B1 (en) | High speed method for plating palladium and palladium alloys | |
JPH1060683A (en) | Electroplating with ternary system zinc alloy, and its method | |
US4545869A (en) | Bath and process for high speed electroplating of palladium | |
TW201333275A (en) | Selective hard gold deposition | |
US4470886A (en) | Gold alloy electroplating bath and process | |
JP4740528B2 (en) | Nickel-molybdenum alloy plating solution, plating film and plated article | |
US11280014B2 (en) | Silver/tin electroplating bath and method of using the same | |
JPH0347988A (en) | Production of galvanized steel sheet |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: UNITED TECHNOLOGIES CORPORATION, CONNECTICUT Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:VONTELL SR., JOHN H.;REEL/FRAME:021337/0416 Effective date: 20080718 |
|
AS | Assignment |
Owner name: ROHM AND HAAS ELECTRONIC MATERIALS LLC, MASSACHUSE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ZHANG-BEGLINGER, WAN;CLAUSS, MARGIT;GUEBEY, JONAS;AND OTHERS;REEL/FRAME:021723/0705;SIGNING DATES FROM 20080918 TO 20081006 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- AFTER EXAMINER'S ANSWER OR BOARD OF APPEALS DECISION |