EP2283170A1 - Pd and pd-ni electrolyte baths - Google Patents
Pd and pd-ni electrolyte bathsInfo
- Publication number
- EP2283170A1 EP2283170A1 EP08758401A EP08758401A EP2283170A1 EP 2283170 A1 EP2283170 A1 EP 2283170A1 EP 08758401 A EP08758401 A EP 08758401A EP 08758401 A EP08758401 A EP 08758401A EP 2283170 A1 EP2283170 A1 EP 2283170A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrolyte
- palladium
- electrolyte according
- nickel
- group
- 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.)
- Granted
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 82
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 39
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 83
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 229910001252 Pd alloy Inorganic materials 0.000 claims abstract description 11
- 238000004070 electrodeposition Methods 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- 238000000151 deposition Methods 0.000 claims description 25
- 230000008021 deposition Effects 0.000 claims description 24
- -1 3-sulfopropyl Chemical group 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 239000002253 acid Chemical group 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- REEBJQTUIJTGAL-UHFFFAOYSA-N 3-pyridin-1-ium-1-ylpropane-1-sulfonate Chemical compound [O-]S(=O)(=O)CCC[N+]1=CC=CC=C1 REEBJQTUIJTGAL-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001449 anionic compounds Chemical class 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910001412 inorganic anion Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical class C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims 1
- 150000002940 palladium Chemical class 0.000 abstract description 5
- 238000009713 electroplating Methods 0.000 abstract 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 31
- 229940012017 ethylenediamine Drugs 0.000 description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 229960003237 betaine Drugs 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 239000000470 constituent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000080 wetting agent Substances 0.000 description 5
- DNHDSWZXBHTLDP-UHFFFAOYSA-N 3-(2-ethenylpyridin-1-ium-1-yl)propane-1-sulfonate Chemical compound [O-]S(=O)(=O)CCC[N+]1=CC=CC=C1C=C DNHDSWZXBHTLDP-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 4
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 4
- 230000001419 dependent effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- RJPRZHQPROLZRW-UHFFFAOYSA-N 2-hydroxy-3-pyridin-1-ium-1-ylpropane-1-sulfonate Chemical compound [O-]S(=O)(=O)CC(O)C[N+]1=CC=CC=C1 RJPRZHQPROLZRW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- QYYPTZGPXKUKRM-UHFFFAOYSA-L azane;hydrogen carbonate;palladium(2+) Chemical compound N.N.N.N.[Pd+2].OC([O-])=O.OC([O-])=O QYYPTZGPXKUKRM-UHFFFAOYSA-L 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- VUVORVXMOLQFMO-ONEGZZNKSA-N (e)-3-pyridin-3-ylprop-2-enoic acid Chemical compound OC(=O)\C=C\C1=CC=CN=C1 VUVORVXMOLQFMO-ONEGZZNKSA-N 0.000 description 1
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 description 1
- SHHKMWMIKILKQW-UHFFFAOYSA-N 2-formylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=O SHHKMWMIKILKQW-UHFFFAOYSA-N 0.000 description 1
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 108091034117 Oligonucleotide Proteins 0.000 description 1
- 229910002669 PdNi Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- WINXNKPZLFISPD-UHFFFAOYSA-M Saccharin sodium Chemical compound [Na+].C1=CC=C2C(=O)[N-]S(=O)(=O)C2=C1 WINXNKPZLFISPD-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- JLCPHMBAVCMARE-UHFFFAOYSA-N [3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[5-(2-amino-6-oxo-1H-purin-9-yl)-3-[[3-[[3-[[3-[[3-[[3-[[5-(2-amino-6-oxo-1H-purin-9-yl)-3-[[5-(2-amino-6-oxo-1H-purin-9-yl)-3-hydroxyoxolan-2-yl]methoxy-hydroxyphosphoryl]oxyoxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxyoxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methyl [5-(6-aminopurin-9-yl)-2-(hydroxymethyl)oxolan-3-yl] hydrogen phosphate Polymers Cc1cn(C2CC(OP(O)(=O)OCC3OC(CC3OP(O)(=O)OCC3OC(CC3O)n3cnc4c3nc(N)[nH]c4=O)n3cnc4c3nc(N)[nH]c4=O)C(COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3CO)n3cnc4c(N)ncnc34)n3ccc(N)nc3=O)n3cnc4c(N)ncnc34)n3ccc(N)nc3=O)n3ccc(N)nc3=O)n3ccc(N)nc3=O)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)n3cc(C)c(=O)[nH]c3=O)n3cc(C)c(=O)[nH]c3=O)n3ccc(N)nc3=O)n3cc(C)c(=O)[nH]c3=O)n3cnc4c3nc(N)[nH]c4=O)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)O2)c(=O)[nH]c1=O JLCPHMBAVCMARE-UHFFFAOYSA-N 0.000 description 1
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- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
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- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000005586 carbonic acid group Chemical group 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
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- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- KDOWHHULNTXTNS-UHFFFAOYSA-N hex-3-yne-2,5-diol Chemical compound CC(O)C#CC(C)O KDOWHHULNTXTNS-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-O hydron;pyrimidine Chemical compound C1=CN=C[NH+]=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-O 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- LPAGFVYQRIESJQ-UHFFFAOYSA-N indoline Chemical compound C1=CC=C2NCCC2=C1 LPAGFVYQRIESJQ-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- JZJXKEWVUBVOEH-UHFFFAOYSA-N n,n-diethylprop-2-yn-1-amine Chemical compound CCN(CC)CC#C JZJXKEWVUBVOEH-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- UOCCVDMCNJYVIW-UHFFFAOYSA-N prop-2-yne-1-sulfonic acid Chemical compound OS(=O)(=O)CC#C UOCCVDMCNJYVIW-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
- 238000010992 reflux Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 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
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-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
- C25D3/52—Electroplating: Baths therefor from solutions of platinum group metals characterised by the organic bath constituents used
-
- 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 relates to an electrolyte for the electrodeposition of palladium or palladium alloys on metallic or conductive substrates.
- this is a Pd electrolyte containing optionally further metals and an organic oligoamine as a complexing agent, with the alloy coatings with e.g. 80% Pd for technical and decorative applications can be deposited.
- the invention is directed to a corresponding galvanotechnisches method using this electrolyte and special, advantageously usable for this process palladium salts.
- the electrodeposition of palladium or palladium alloys on metallic substrates has a variety of decorative and technical applications.
- Galvanically deposited pure palladium and palladium-nickel layers, if appropriate each with gold flash, are recognized materials, e.g. for low-current contacts or plug contacts (for example on printed circuit boards) and can be considered as a replacement for hard gold [Galvanotechnik 5 (2002), 121 Off, Simon u. Yasumura: "Galvanic Palladium Layers for Technical Applications in Electronics”].
- palladium deposits with a very small layer thickness on so-called lead frames in semiconductor production can replace the silver used in the bond area [Galvanotechnik 6 (2002), 1473ff, Simon et al. Yasumura: "Galvanic Palladium Layers for Technical Applications in Electronics”].
- Patent DE 4428966 (US Pat. No. 5,415,685) describes a palladium bath in which, in addition to a palladium compound (namely palladium diaminodinitrite) and various ammonium salts (sulfate, citrate and phosphate), a combination of gloss additives is also mentioned.
- the described ammoniacal process operates in a pH range between 5 and 12.
- the claimed brighteners are a combination of a sulfonic acid and an aromatic N-heterocycle. Specifically named are, inter alia, o-formylbenzenesulfonic acid and 1- (3-sulfopropyl) -2-vinylpyridinium betaine.
- pyridines mentioned by name are 1- (3-sulfopropylpyridinium betaine and 1- (2-hydroxy-3-sulfopropylpyridinium betaine). The latter two substances have, according to the authors, a negative effect on the gloss of the resulting coatings.
- a process according to US6743346 also employs ethylenediamine as a complexing agent and incorporates the palladium in the form of the solid compound of palladium sulfate and ethylenediamine.
- the salt contains 31 to 41% palladium (mole ratios [SO 4 ]: [Pd] between 0.9 and 1.15 and [ethylene diamine]: [Pd] between 0.8 and 1.2). It is insoluble in water but dissolves in the electrolyte with excess ethylenediamine (Plating & Surface Finishing, (2007) 4, pp. 26-35, St. Burling "Precious Metal Plating and the Environment").
- As brighteners here are the substances 3- (3-pyridyl) acrylic acid or 3- ( It is mentioned that the brighteners based on sulfonates are not able to ensure the desired gloss, especially at current densities of 15 to 150 A / dm 2 , in galvanic electrolytes.
- Object of the present invention was in the context of the cited prior art, the indication of a further electrolyte and working with this electrolyte process, which help overcome the disadvantages mentioned.
- the specified electrolyte composition or the corresponding method should help to produce glossy surfaces even at high current densities and fast electrolysis processes, which would be particularly advantageous from an economic and ecological point of view.
- aqueous electrolyte for the electrodeposition of palladium or a palladium alloy on a metallic or conductive substrate, which to be deposited, complexed with organic oligoamines metal ions in the form of their salts with oxide hydroxide, hydroxide, bicarbonate and / or carbonate as Having counterions and a brightener based on an inner salt of a quaternary ammonium and a sulfonic acid group, one arrives in a surprisingly simple manner and successfully to solve the problem.
- the electrolyte according to the invention or by using the method according to the invention it is now possible to produce the desired shiny surfaces with qualitatively excellent results both at low and at high current densities.
- the electrolyte composition according to the invention is in no way suggested by the prior art.
- the electrolyte according to the invention makes it possible to deposit the palladium alone or in the form of an alloy associated with other metals.
- Other metals that can be used in the art for this purpose in question. These may be e.g. Nickel, cobalt, iron, indium, gold, silver or tin or mixtures thereof.
- the metal ions to be deposited are selected from the group consisting of nickel, cobalt, iron and mixtures thereof.
- the electrolyte contains these metals in the form of their soluble salts.
- Suitable salts are preferably those selected from the group of phosphates, carbonates, bicarbonates, hydroxides, oxides, sulfates, sulfamates, alkanesulfonates, pyrophosphates, phosphonates, nitrates, carboxylic acid salts and mixtures thereof.
- the person skilled in the art selects the concentrations of the metals to be used in the electrolyte on the basis of his general technical knowledge. It has been found that advantageous results can be obtained when palladium is used in concentrations of 1-100 g / L, preferably 2-70 g / L, and more preferably 4-50 g / L and most preferably 5-25 g / L is present based on the electrolyte.
- the further metal ions to be deposited can be present in concentrations of ⁇ 50 g / L based on the electrolyte. Preferably, the concentration of these ions in the electrolyte ⁇ 40 g / L, more preferably ⁇ 30 g / L based on the electrolyte.
- a uniform deposition of the metal ions under the conditions according to the invention is advantageous, inter alia, if they are complexed.
- Suitable oligonucleotides for these complexes have proven to be organic oligoamines.
- Advantageous is the use of polydentate, in particular ligands based on di-, tri- or tetraamines. Particularly preferred are those having 2 to 11 carbon atoms.
- Very particular preference is given to the use of ligands selected from the group consisting of ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,2-propylenediamine, trimethylenetetramine, hexamethylenetetramine.
- EDA ethylene diamine
- oligoamines used in the estimation of the amount. In the estimation of the amount, he will orientate himself by the fact that a sufficient amount must be present in order to obtain as even as possible a deposition of the palladium or of the palladium alloy. On the other hand, at least economic considerations limit the use of large quantities of oligoamines.
- An amount of 0.1-5 mol / L of oligoamines in the electrolyte is advantageous. More preferably, the concentration is in the range between 0.3-3 mol / L. Most preferably, the concentration of oligoamines at 0.5 - 2 mol / L electrolyte.
- the pH of the electrolyte according to the invention can be adjusted according to the skilled person for the particular application in the acidic to neutral range.
- a further preferred range is from pH 3.5 to pH 6.5, more preferably from pH 4 to pH 6, and most preferably around pH 5 to pH 5 ; 5.
- the electrolyte according to the invention has brighteners based on an internal salt of a quaternary ammonium and an acid group.
- a quaternary ammonium compound is preferably one in which the positively charged nitrogen atom is part of an aromatic ring system.
- Those skilled in the art are particularly suitable as such molecular constituents, which relate to a mononuclear or polynuclear aromatic systems, such as pyridinium, pyrimidinium, pyrazinium, pyrrolinium, imidazolinium, thiazolinium, indolinium, carbazolinium or such substituted systems in consideration.
- pyridinium- or alkyl- or alkenyl-substituted pyridinium derivatives used.
- a brightener having as a molecular constituent a quaternary ammonium compound based on a pyridinium derivative.
- the brightener contains an acid group, so that in the present case the brightener is an internal salt or a betaine.
- the term "acid group” refers to a group which, under the given conditions, is present predominantly in the deprotonated form in the electrolyte.
- the acid group may be derived from those selected from the group consisting of phosphoric acid, phosphonic acid, sulfuric acid, sulfonic acid, carboxylic acid. Particularly preferred is the sulfonic acid as part of the brightener.
- the acid group and the quaternary ammonium moiety of the brightener may be linked by (CrCsJ-alkylene-, (d-C ⁇ J-alkenylene-, (C 6 -C 18 ) -arylene, which may optionally be substituted, being highly preferred compounds in this
- those selected from the group consisting of 1- (3-sulfopropyl) -2-vinylpyridinium betaine), 1- (3-sulfopropylpyridinium betaine and 1- (2-hydroxy-3-sulfopropylpyridinium betaine have proven.
- the brightener can be used in quantities which are obvious to a person skilled in the art.
- An upper limit is the amount of brightener, in which the cost of its use is no longer justified by the effect achieved.
- the use of the brightener is thus advantageous in amounts of from 1 to 10000 mg / L of electrolyte.
- the brightener is used in a concentration of 5 to 5000 mg / L of electrolyte, most preferably in an amount of 10 to 1000 mg / L of electrolyte.
- the electrolyte according to the invention may contain further constituents which have a positive influence with regard to the bath stability, the deposition behavior of the metals, the quality of the deposited material and the electrolysis conditions.
- those skilled in the art in particular means for reducing the internal stresses of the coating, wetting agents, conductive salts, other brighteners and / or buffer substances, etc. into consideration.
- additives for reducing the surface tension of the electrolyte wetting agents can be selected from the following groups consisting of anionic wetting agents such as sodium lauryl sulfate, dodecylbenzenesulfonate sodium salt, sodium dioctylsulfosuccinate, nonionic wetting agents such as polyethylene glycol Fatty acid esters and / or cationic wetting agents such as cetyltrimethylammonium be used.
- anionic wetting agents such as sodium lauryl sulfate, dodecylbenzenesulfonate sodium salt, sodium dioctylsulfosuccinate
- nonionic wetting agents such as polyethylene glycol Fatty acid esters and / or cationic wetting agents such as cetyltrimethylammonium be used.
- Conducting salts selected from the group consisting of potassium sulfate or sodium sulfate, phosphate, nitrate, alkanesulfonate, sulfamate and mixtures thereof can advantageously be used to improve the conductivity and throwing power of the electrolyte.
- buffer substances are those selected from the group consisting of boric acid or phosphates or a carboxylic acid and / or salts thereof, such as e.g. Acetic acid, citric acid, tartaric acid, oxalic acid, succinic acid, malic acid, lactic acid, phthalic acid.
- brightener additives may advantageously those selected from the group consisting of N, N-diethyl-2-propyn-1-amine, 1,1-dimethyl-2-propynyl-1-amine, 2-butyne-1, 4-diol, 2-butyne-1,4-diol ethoxylate, 2-butyne-1,4-diol propoxylate, 3-hexyne-2,5-diol and sulfopropylated 2-butyne-1,4-diol or one of their salts.
- Other base gloss agents may be allylsulfonic acid and / or vinylsulfonic acid and / or
- Propargylsulfonklare or their alkali metal salts in amounts of 0.01 to 10 g / L electrolyte.
- those selected from the group consisting of iminodisuccinic acid and / or sulfamic acid and / or sodium saccharinate may be advantageously used.
- no further metal salts with inorganic anions except sulfate or nitrate, bicarbonate or carbonate ions or oxide, hydroxide or mixtures thereof are added to the electrolyte.
- Such an approach in turn has a positive effect on the service life of the electrolyte.
- Particularly advantageous is the embodiment in which only those deposition metal salts are used whose anions consist of bicarbonate or carbonate ions or oxide, hydroxide or mixtures thereof.
- the present invention also provides a process for the electrodeposition of palladium or a palladium alloy on a metallic or conductive substrate, wherein an electrolyte according to the invention is used.
- the palladium or palladium alloy may be electrodeposited on substrates well known to those skilled in the art for this purpose.
- the metallic or electrically conductive substrates are selected from the group consisting of nickel, nickel alloys, gold, silver, copper and copper alloys, iron, iron alloys. Particularly preferred is nickel or copper or
- the temperature in the electrolytic deposition can be chosen arbitrarily by the expert.
- the temperature is set at which a corresponding desired deposition can take place. This is the case at temperatures from 2O 0 C to 80 0 C.
- a temperature of 30 0 C to 70 0 C and most preferably from 40 ° C to 60 ° C is set.
- the current density to be set can be selected by the person skilled in the art according to the underlying electrolysis arrangement during the electrolysis according to the invention.
- the current densities are preferably between 0.1 and 150 A / dm 2 . Particularly preferred are 0.1-10.0 A / dm 2 for drum and rack applications and 5.0-100 A / dm 2 for high speed applications. Most preferably, 5.0-70 A / dm 2 is set for high-speed applications, and 0.2-5 A / dm 2 is most preferred in drum and rack applications.
- the inventive method is advantageously carried out so that the deposition is carried out using non-soluble anodes.
- non-soluble anodes particularly preferred is the use of insoluble anodes of platinized titanium or mixed oxide anodes. These are most preferably non-soluble anodes of platinized titanium or iridium / ruthenium / tantalum oxide coated titanium or niobium or tantalum.
- Anodes made of graphite or of durable stainless steel are also possible.
- the subject matter of the present invention is likewise a special palladium salt which can advantageously be used and adapted for the process according to the invention.
- These are a palladium complex compounds consisting of a divalent palladium cation, one or more di-, tri- or tetradentate organic amine ligands and carbonate or two bicarbonate or hydroxyl anions or a mixture thereof.
- the advantage here is the use of multidentate ligands based on di-, tri or tetraamines. Particularly preferred are those having 2 to 11 carbon atoms.
- ligands selected from the group consisting of ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,2-propylenediamine, trimethylenetetramine, hexamethylenetetramine.
- EDA ethylene diamine
- the reaction temperature is preferably between 20 and 95 0 C, more preferably between 40 and 90 0 C, most preferably between 60 and 80 0 C.
- an electrolyte of the invention described herein with, for example, 20 g / l of palladium as bis (ethylenediamino) -palladium (II) hydrogen carbonate, 16 g / l of nickel as nickel (II) sulfate and 50 g / l of ethylenediamine enable the brighteners 1- (3 - Sulfopropylpyridiniumbetain or 1- (2-hydroxy-3-sulfopropylpyridiniumbetain in amounts of 50 to 500 mg / l, especially in the low current density range the
- Ammonia and chloride are also avoided with the new palladium-nickel electrolyte based on ethylenediamine, which significantly reduces the risk potential and the unpleasant odor for humans and plant corrosion.
- the disadvantages of the previous, ammonium and chloride-free ethylene-diamine based processes are avoided.
- the use of carbonate or bicarbonate as counter ions to palladium and nickel allows an extension of the service life.
- the anions used are not stable in the applied pH range between, for example, 3 and 5.5 and decompose immediately upon addition of the metal salt to carbon dioxide and hydroxide. The volatile CO 2 escapes from the electrolyte and thus does not contribute to increasing the bath density.
- the indicated constituents of the electrolyte are dissolved in 4 L of deionized water. Subsequently, the palladium or the palladium alloy is deposited on a brass sheet under the given electrolysis conditions.
- An electrolyte for depositing PdNi layers with 80% by weight of palladium may be e.g. have the following composition:
- Electrolyte for high-speed deposition 20 g / l Pd as bis (ethylenediamino) palladium (II) bicarbonate
- Substrate Copper or copper alloy, possibly undepleted
- the resulting coatings (2 microns) are homogeneously shiny, bright, ductile, crack-free in the current density range mentioned and have a relatively constant Pd content of 80 to 83%.
- Substrate copper or copper alloy, possibly nickel-plated anodes: Pt / Ti
- the resulting coatings (2 microns) are homogeneously high gloss in the current density range mentioned, brilliant-bright, very ductile, crack-free and have a relatively constant Pd content of 80 to 83%.
- Tetraamminepalladium (II) bicarbonate (product # 45082) from Alfa Aesar Ethylene diamine 99% for synthesis (e.g., Merck # 800947)
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Abstract
Description
Claims
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PL08758401T PL2283170T3 (en) | 2008-05-07 | 2008-05-07 | Pd and pd-ni electrolyte baths |
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PCT/EP2008/003667 WO2009135505A1 (en) | 2008-05-07 | 2008-05-07 | Pd and pd-ni electrolyte baths |
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US (1) | US8900436B2 (en) |
EP (1) | EP2283170B1 (en) |
JP (1) | JP5586587B2 (en) |
KR (1) | KR101502804B1 (en) |
CN (1) | CN102037162B (en) |
AT (1) | ATE555235T1 (en) |
ES (1) | ES2387055T3 (en) |
PL (1) | PL2283170T3 (en) |
TW (1) | TWI475134B (en) |
WO (1) | WO2009135505A1 (en) |
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DE102009029558A1 (en) * | 2009-09-17 | 2011-03-31 | Schott Solar Ag | electrolyte composition |
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CN104885298B (en) * | 2012-12-12 | 2017-12-26 | Ls电线有限公司 | Wireless power antenna and the dual-mode antenna for possessing the wireless power antenna |
WO2016035645A1 (en) * | 2014-09-04 | 2016-03-10 | 日本高純度化学株式会社 | Palladium plating solution and palladium coating obtained using same |
JP6189878B2 (en) * | 2015-01-14 | 2017-08-30 | 松田産業株式会社 | Cyan resistance imparting agent for palladium or palladium alloy plating, plating solution, method for imparting cyan resistance to plating solution |
AT516876B1 (en) * | 2015-03-09 | 2016-11-15 | Ing W Garhöfer Ges M B H | Deposition of decorative palladium-iron alloy coatings on metallic substances |
US20180053714A1 (en) * | 2016-08-18 | 2018-02-22 | Rohm And Haas Electronic Materials Llc | Multi-layer electrical contact element |
JP6663335B2 (en) * | 2016-10-07 | 2020-03-11 | 松田産業株式会社 | Palladium-nickel alloy coating and method for producing the same |
KR101867733B1 (en) * | 2016-12-22 | 2018-06-14 | 주식회사 포스코 | Fe-Ni ALLOY ELECTROLYTES, Fe-Ni ALLOY FOIL HAVING EXCELLENT SURFACE ROUGHNESS AND METHOD FOR THE SAME |
CN107385481A (en) * | 2017-07-26 | 2017-11-24 | 苏州鑫旷新材料科技有限公司 | A kind of cyanide-free gold electroplating liquid |
EP3456870A1 (en) * | 2017-09-13 | 2019-03-20 | ATOTECH Deutschland GmbH | A bath and method for filling a vertical interconnect access or trench of a work piece with nickel or a nickel alloy |
CN108864200B (en) * | 2018-08-06 | 2020-12-11 | 金川集团股份有限公司 | One-step preparation method of ethylenediamine palladium sulfate for electroplating |
DE102018133244A1 (en) | 2018-12-20 | 2020-06-25 | Umicore Galvanotechnik Gmbh | Nickel-amine complex with a reduced tendency to form harmful degradation products |
CN110144729B (en) * | 2019-06-14 | 2020-07-07 | 中国科学院长春应用化学研究所 | Conductive gold-coated polyimide fiber and preparation method thereof |
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2008
- 2008-05-07 ES ES08758401T patent/ES2387055T3/en active Active
- 2008-05-07 US US12/990,864 patent/US8900436B2/en active Active
- 2008-05-07 JP JP2011507793A patent/JP5586587B2/en active Active
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- 2008-05-07 WO PCT/EP2008/003667 patent/WO2009135505A1/en active Application Filing
- 2008-05-07 KR KR1020107024801A patent/KR101502804B1/en active IP Right Grant
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JP5586587B2 (en) | 2014-09-10 |
WO2009135505A1 (en) | 2009-11-12 |
TW201006967A (en) | 2010-02-16 |
PL2283170T3 (en) | 2012-09-28 |
KR20110003519A (en) | 2011-01-12 |
US8900436B2 (en) | 2014-12-02 |
TWI475134B (en) | 2015-03-01 |
KR101502804B1 (en) | 2015-03-16 |
ES2387055T3 (en) | 2012-09-12 |
CN102037162A (en) | 2011-04-27 |
EP2283170B1 (en) | 2012-04-25 |
US20110168566A1 (en) | 2011-07-14 |
CN102037162B (en) | 2013-03-27 |
ATE555235T1 (en) | 2012-05-15 |
JP2011520036A (en) | 2011-07-14 |
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