WO2022112379A1 - Couche d'alliage de ruthénium et ses combinaisons de couches - Google Patents
Couche d'alliage de ruthénium et ses combinaisons de couches Download PDFInfo
- Publication number
- WO2022112379A1 WO2022112379A1 PCT/EP2021/082914 EP2021082914W WO2022112379A1 WO 2022112379 A1 WO2022112379 A1 WO 2022112379A1 EP 2021082914 W EP2021082914 W EP 2021082914W WO 2022112379 A1 WO2022112379 A1 WO 2022112379A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrolyte
- ruthenium
- acid
- layer
- metal
- Prior art date
Links
- 229910000929 Ru alloy Inorganic materials 0.000 title claims abstract description 29
- 239000003792 electrolyte Substances 0.000 claims abstract description 73
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 230000008021 deposition Effects 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000010953 base metal Substances 0.000 claims abstract description 14
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 31
- 229910052707 ruthenium Inorganic materials 0.000 claims description 30
- 229910052763 palladium Inorganic materials 0.000 claims description 24
- 238000000151 deposition Methods 0.000 claims description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 16
- 229910002065 alloy metal Inorganic materials 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- -1 fatty alcohol sulfates Chemical class 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 238000005275 alloying Methods 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 238000005299 abrasion Methods 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 5
- 239000000872 buffer Substances 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000010970 precious metal Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 3
- 150000003628 tricarboxylic acids Chemical class 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 claims description 2
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 2
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 125000005228 aryl sulfonate group Chemical group 0.000 claims description 2
- 239000007853 buffer solution Substances 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 238000000576 coating method Methods 0.000 description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229910052737 gold Inorganic materials 0.000 description 8
- 239000010931 gold Substances 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 229910001252 Pd alloy Inorganic materials 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910001369 Brass Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000010944 silver (metal) Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-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
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910019017 PtRh Inorganic materials 0.000 description 1
- 229910002849 PtRu Inorganic materials 0.000 description 1
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HJPBEXZMTWFZHY-UHFFFAOYSA-N [Ti].[Ru].[Ir] Chemical compound [Ti].[Ru].[Ir] HJPBEXZMTWFZHY-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005323 electroforming Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 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
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- CJTCBBYSPFAVFL-UHFFFAOYSA-N iridium ruthenium Chemical compound [Ru].[Ir] CJTCBBYSPFAVFL-UHFFFAOYSA-N 0.000 description 1
- ULFQGKXWKFZMLH-UHFFFAOYSA-N iridium tantalum Chemical compound [Ta].[Ir] ULFQGKXWKFZMLH-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 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
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/007—Current directing devices
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/02—Heating or cooling
-
- 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
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
Definitions
- the present invention is directed to an aqueous electrolyte for depositing a ruthenium alloy layer onto metallic surfaces, particularly base metallic surfaces.
- Another subject of the present invention is the use of the electrolyte according to the invention for the production of ruthenium alloy layers on corresponding surfaces by an electrolytic process, which is also a subject of the invention.
- the invention also encompasses layer sequences which have a ruthenium alloy layer deposited in this way.
- palladium is often used as a coating for, for example, electrical connectors, printed circuit boards, decorative applications and many other industrial and commercial uses.
- palladium represents an economical, more cost-effective alternative, since palladium also has a wide range of possible uses. Alloys of palladium with base metals such as nickel or cobalt are less expensive than pure precious metals, so such alloys have been and are used for a long time. Coatings of such palladium alloys are often produced by electrodeposition from Palladiumle alloy electrolytes.
- the ruthenium baths and processes described in the prior art often relate to the deposition of black ruthenium and ruthenium alloy layers and may contain toxicologically questionable compounds such as thio compounds as blackening additives (e.g. DE102011105207B4 and the literature cited there). Due to their acidic character, these baths often only allow deposition on metals that are relatively noble in character (e.g. DE1959907A1).
- a nitridochloro complex of ruthenium can be used in an aqueous, non-acidic bath for the electrodeposition of ruthenium. Such a method is described in US4297178. It also contains oxalic acid or an oxalate anion. According to this, only pure ruthenium deposits are generated, which, however, cannot replace palladium and palladium alloy deposits in this form without disadvantages.
- Ruthenium deposits are mentioned, inter alia, in US3692641 or GB2101633. In the former, deposits of ruthenium with other precious metals, among others, are propagated. In the latter, ruthenium alloy deposits in an acidic environment are addressed.
- WO18142430A1 describes the production of differently colored ruthenium or ruthenium alloy deposits, inter alia, with metals such as Ni, Co, Cu, Sn, etc. It is mentioned that deposits on base metallic substrates are possible. However, only strongly acidic electrolytes are presented here, which is why direct deposition on these substrates is certainly not possible. A possibility is also being sought of successfully avoiding palladium-containing layers in electrolytic deposition practice. For this, the replacing layers should have properties that are as similar as possible to layers containing palladium. This should apply in particular with regard to, inter alia, appearance, corrosion resistance, abrasion resistance and cracking characteristics. It should also be possible to deposit corresponding layers on base metal surfaces in order to be able to replace the Pd strike depositions that are frequently used for this purpose. In addition, replacing the palladium should of course result in cost savings.
- Claims 2 to 7 are directed to preferred configurations of the electrolyte according to the invention.
- Claims 8, 12 and 15, respectively, are directed with the corresponding subclaims to the use of the electrolyte, a method for electrolytic deposition from the electrolyte and a layer sequence obtainable therewith.
- an aqueous electrolyte for the deposition of ruthenium alloys on base metal surfaces in particular, comprising: a) ruthenium as a binuclear, anionic ruthenium nitrido complex of the formula [RU 2 N(H 2 0) 2 X 8 ] 3 , where X is one or more simple or multiply negatively charged counterions, such as halide ions, hydroxide ions or other anionic ligands (eg sulfate, phosphate, oxalate, citrate), in a concentration of 0.5-20 g/l based on ruthenium as the metal; b) one or more alloying metals dissolved in ionic form, selected from the group consisting of: Cu, W, Fe, Co, Ni, In, Zn, Sn, Pd, Pt in a concentration of 0.5 - 10 g/l each related to the metal; c) one or more anions of a di-, tri- or tetracarboxy
- Ruthenium is preferably used in the form of a water-soluble compound known to those skilled in the art as a binuclear, anionic nitridohalogeno complex compound of the formula [RU 2 N(H 2 O) 2 X 8 ] 3 , where X is a halide ion.
- the chloro complex [Ru 2 N(H 2 O) 2 Cl 8 ] 3 is particularly preferred in this context.
- the amount of the complex compound in the electrolyte according to the invention can preferably be chosen such that the concentration of ruthenium after complete dissolution of the compound is between 1 and 20 grams per liter of electrolyte, calculated as ruthenium metal.
- the finished electrolyte particularly preferably contains 1 to 10 grams of ruthenium per liter of electrolyte, very particularly preferably 3 to 7 grams of ruthenium per liter of electrolyte.
- the electrolyte contains certain organic compounds that have one or more carboxylic acid groups.
- these are di-, tri-, or tetracarboxylic acids.
- these are well known to those skilled in the art and can be found, for example, in literature (Beyer-Walter, Textbook of Organic Chemistry, 22nd edition, S. Hirzel-Verlag, p. 324 ff). be removed.
- acids selected from the group consisting of oxalic acid, citric acid, tartaric acid, succinic acid, maleic acid, glutaric acid, adipic acid, malonic acid and malic acid.
- Oxalic acid is particularly preferred in this connection.
- the acids are naturally present in their anionic form in the electrolyte at the pH value to be set.
- the carboxylic acids mentioned here are added to the electrolyte in a concentration of 0.05-2 moles per liter, preferably 0.1-1 mole per liter and very particularly preferably between 0.2-0.5 mole per liter. This applies in particular to the use of oxalic acid, which is believed to also serve as a conducting salt in the electrolyte.
- anionic surfactants are used as wetting agents. These are, for example, those selected from the group consisting of fatty alcohol sulfates, alkyl sulfates, alkyl sulfonates, aryl sulfonates, alkylaryl sulfonates, heteroaryl sulfates and their salts and in particular their alkoxylated derivatives (see also: Kanani, N: Galvanotechnik; Hanser Verlag, Kunststoff Vienna, 2000; page 84 ff). Ethoxylated sodium fatty alcohol (C12-C14) ether sulfate or sodium fatty alcohol sulfate (C12-C14) are particularly preferred.
- the pH of the electrolyte is preferably in the only slightly acidic to slightly alkaline range. According to the invention, the pH is adjusted to a range between 5 and 10. More preferably, the pH of the electrolyte in use is between 6 and 9, most preferably between 7 and 8 pH adjusted to approx. 7.5.
- the pH value is kept constant during the electrolysis by adding buffer substances. These are well known to those skilled in the art (Handbook of Chemistry and Physics, CRC Press, 66th Edition, D-144 ff). Preferred buffer systems are borate, phosphate and carbonate buffers.
- Compounds for producing these buffer systems can be selected from the group consisting of boric acid, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium hydrogen carbonate or dipotassium carbonate.
- the buffer system comes in a concentration of 0.08-1.15 moles per liter, preferably 0.15-0.65 moles per liter and very particularly preferably 0.2-0.4 moles per liter (based on the anion) for use.
- conductive salts and brightening additives are those selected from the group consisting of alkali metal sulfates, ammonium sulfate, ammonium chloride and ammonium oxalate.
- dissolved metals are also present in the electrolyte. These are electrolytically deposited together with the ruthenium as a ruthenium alloy layer. There are those selected from the group consisting of: Cu, W, Fe, Co, Ni, In, Zn, Sn, Pd, Pt in question. These are usually dissolved as salts, in particular as sulfates in the electrolyte. In this context, it is particularly preferred if the alloying metal is selected from the group consisting of Ni, Sn, Zn, Co and Pd. It is extremely preferred to use Ni.
- the alloying metals are present in the electrolyte in a concentration of 0.1 - 10 g/l each.
- the concentration of the alloying metal is preferably 1-6 g/l and very particularly preferably 2-5 g/l. It has been found that the addition of the alloying metal to the electrolyte according to the invention in the specified concentration ranges helps in particular to improve the corrosion resistance and the tendency for the ruthenium layer to form cracks. Ni in particular has shown good results here.
- the present electrolyte can contain sulphur-containing compounds, such as the wetting agents or surfactants mentioned above. However, it is advantageous if the electrolyte does not contain any sulfur-containing compounds in which the sulfur is present in an oxidation state of ⁇ +4. In particular, blackening additives based on sulfur compounds are not present in the electrolyte according to the invention.
- the present electrolyte does not produce a black or dark anthracite-colored deposit, but rather a greyish, metallic-looking deposit. It is thus even similar in appearance to the Pd and Pd alloy deposits to be replaced.
- the a* value is preferably between -3 and +3 and the b* value between -7 and +7 according to the Cielab color system (EN ISO 11664-4 - latest version on the filing date).
- the present invention also relates to the use of the electrolyte just described for the production of articles with an electrolytically deposited alloy metal layer, in particular on base metal surfaces, containing the metals ruthenium and one or more of the alloy metals dissolved in ionic form, selected from the group consisting of: Cu, W, Fe, Co, Ni, In, Zn, Sn, Pd, Pt, where the alloy metal layer has a corrosion resistance similar to that of the corresponding palladium containing layers.
- the alloying of the listed metals also means that the tendency to form cracks during electrolytic deposition is significantly reduced compared to pure ruthenium deposits.
- the tendency to form cracks is preferably determined by optical assessment in a light microscope at 20x magnification.
- base metal surfaces include those which are unstable in an acidic or more basic environment and tend to dissolve.
- Preferred base metal sub-layers for the ruthenium alloy layer are those selected from the group consisting of copper, copper alloys, nickel or nickel alloys.
- the ruthenium alloy layer that can be obtained by using the electrolyte according to the invention can have a specific thickness as determined by a person skilled in the art.
- the thickness of the alloy metal layer is 0.05 - 5 ⁇ m, more preferably 0.05 - 2 ⁇ m, and most preferably 0.05 - 1 ⁇ m.
- the alloy metal layer is preferably used as a sub-layer for a further metal layer to be electrolytically deposited, just as is the case, for example, for Pd or Pd-Ni layers.
- the metal layer deposited on the ruthenium alloy layer can consist, for example, of noble metals such as Ag, Au, Pt, Rh or their alloys and generally has a thickness of 0.03-10 ⁇ m, preferably 0.05-3 ⁇ m and very preferably 0 ,1 - 1 p.m. It has been found that the metal deposits discussed here (for the ruthenium alloy layer itself and for the layer sequence) have a very high abrasion resistance, which is particularly advantageous both for jewelry and for technical applications (e.g. as a contact material).
- the metal deposits of the ruthenium alloy also achieve values below 0.25 ⁇ m/1000 strokes with the electrolyte according to the invention. Further advantageous are even less than 0.1 ⁇ m/1000 strokes and very advantageously less than 0.08 ⁇ m/1000 strokes in the realm of feasibility.
- the composition of the ruthenium alloy layer is very preferably 95:5 to 80:20, most preferably 90:10 to 80:20, based on the weight ratio of ruthenium to the other metal(s).
- the subject matter of the present invention is also a method for depositing an alloy metal layer on, in particular, base metal surfaces, in which: a) the metal surface as the cathode is contacted with an aqueous electrolyte as just described; b) contacting an anode with the electrolyte; c) and established a sufficient current flow between cathode and anode.
- the current density established during the deposition process in the electrolyte between the cathode and the anode can be chosen by those skilled in the art based on the efficiency and quality of the deposition.
- the current density in the electrolyte is advantageously set to 0.1 to 50 A/dm 2 depending on the application and the type of coating system. If necessary, the current densities can be increased or decreased by adjusting the system parameters such as the structure of the coating cell, flow rates, anode and cathode conditions, etc.
- a current density of 0.2-25 A/dm 2 , preferably 0.25-15 A/dm 2 and very particularly preferably 0.25-10 A/dm 2 is typically advantageous. Most preferably, the current density is 0.25-5 A/dm 2 .
- the selected current density value is also determined by the type of coating process. In a drum coating process lies the preferred current density between 0.25 to 5 A/dm2. In rack coating processes, a current density of 0.5 to 10 A/dm2 gives better results.
- thin layer thicknesses in the range from 0.1 to 0.3 ⁇ m are produced in rack operation.
- low current densities in the range from 0.25 to 5 A/dm 2 are advantageously used.
- Another application of low current densities is in drum or vibration technology, for example when coating contact pins.
- approx. 0.25 to 0.5 ⁇ m thick layers are applied in the current density range from 0.25 to 0.75 A/dm 2 .
- Layer thicknesses in the range from 0.1 to 1.0 ⁇ m are typically deposited in rack operation, primarily for decorative applications with current densities in the range from 0.25 to 5 A/dm 2 .
- Pulsed direct current can also be used instead of direct current.
- the current flow is interrupted for a certain period of time (pulse plating).
- pulse plating With reverse pulse plating, the polarity of the electrodes is reversed so that the coating is partially anodicly detached. In this way, the layer structure is controlled in constant alternation with cathodic pulses.
- simple pulse conditions such as 1 s current flow (t on ) and 0.5 s pulse pause ( ) with medium current densities leads to more homogeneous coatings (pulse plating, J.-C. Puippe, F. Leaman, Eugen G. Leu- zeverlag, Bad Saulgau, 1990).
- insoluble anodes can preferably be used.
- the insoluble anodes used are preferably those made from a material selected from the group consisting of platinized titanium, graphite, mixed metal oxides, glassy carbon anodes and special carbon material (“diamond-like carbon” DLC) or combinations of these anodes.
- Insoluble anodes made of platinized titanium or titanium coated with mixed metal oxides are advantageous, the mixed metal oxides preferably being selected from iridium oxide, ruthenium oxide, tantalum oxide and mixtures thereof.
- Iridium transition metal oxide mixed oxide anodes particularly preferably mixed oxide anodes made from iridium-ruthenium mixed oxide, iridium-ruthenium-titanium mixed oxide or iridium-tantalum mixed oxide, are also used advantageously for carrying out the invention. More can be found at Cobley, AJ et al. (The use of insoluble anodes in Acid Sulphate Copper Electrodeposition Solutions, Trans IMF, 2001, 79(3), p. 113 and 114). The deposition of the ruthenium alloy layers on, in particular, base metallic objects according to the present invention can be carried out as follows, taking into account the above:
- the pieces of jewelry, decorative goods, consumer goods or technical objects to be coated are immersed in the electrolytes according to the invention (collectively referred to as substrates). These form the cathode.
- An anode made of, for example, platinized titanium (product information PLATINODE ® from Umicore Galvanotechnik GmbH) is also immersed in the electrolyte. A corresponding current flow is then ensured between the anode and the cathode.
- a maximum current density of 10 amperes per square decimeter [A/dm 2 ] has proven advantageous in order to obtain adherent, uniform layers.
- the temperature which the electrolyte has during the deposition can be adjusted accordingly by a person skilled in the art.
- the temperature range to be set is advantageously a range of 20-80.degree.
- a temperature of 50° to 75° C. and particularly preferably 60° to 70° C. is preferably set. It can be advantageous if the electrolyte under consideration is stirred during the deposition.
- Suitable substrate materials that are advantageously used here are copper-based materials such as pure copper, brass or bronze, ferrous materials such as iron or stainless steel, nickel, gold and silver.
- the substrate materials can also be multi-layer systems that have been coated galvanically or with another coating technique. This applies, for example, to circuit board base material or iron materials that have been nickel- or copper-plated and then optionally gold-plated or coated with pre-silver.
- Another substrate material is, for example, a wax core that has been pre-coated with conductive silver lacquer (so-called electroforming).
- a further object of the present invention is a metallic layer sequence comprising a substrate equipped with a base metal surface in particular, an alloy metal layer electrolytically applied thereto produced by the method according to the invention with a thickness as described above and a metal layer of noble metals such as e.g. Ag, Au, Pt or Rh and their alloys with a thickness also as previously described.
- the thicknesses of the layers can be in the ranges given above preferred areas vary.
- the preferred embodiments described for the electrolyte, its use and the method according to the invention are also used mutatis mutandis for the layer sequence described here.
- the ruthenium alloy layer described here represents an adequate replacement for the expensive Pd or Pd alloy layers, in particular Pd-Ni layers. Wherever the latter are used advantageously, the ruthenium alloy layer described here can represent a more cost-effective alternative.
- a precious metal layer can be applied as a finish to the ruthenium alloy layer according to the invention, particularly in the case of items of jewelry. Rhodium, platinum, gold and silver are particularly suitable as noble metals. The person skilled in the art knows how to carry out such a finish.
- the ruthenium alloy layer can also be established as a Pd or Pd-Ni substitute in electronic articles.
- rhodium Rhodium alloys e.g. RhRu), platinum, platinum alloys (PtRh, PtRu) or gold preferred top layers.
- Thin palladium or palladium-nickel layers can also be applied as top layers. The top layer to be applied and its layer thickness depends on the application and is known to the person skilled in the art.
- the present invention can be preferably used in barrel and rack coating processes.
- electrolyte described here it is possible to achieve particularly crack-free, corrosion-resistant and abrasion-resistant deposits of ruthenium alloys on a corresponding substrate that are similar to Pd deposits.
- electrolyte in the neutral range which for the first time allows the deposition of ruthenium alloy coatings on base metals without having to provide them with a noble intermediate layer beforehand.
- 1 liter of the electrolyte specified in the respective exemplary embodiment is heated to the temperature specified in the exemplary embodiment using a magnetic stirrer while stirring with a 60 mm long cylindrical magnetic stirring rod at at least 200 rpm. This agitation and temperature is also maintained during coating.
- a mechanically polished brass sheet with a surface area of at least 0.2 dm 2 is used as the cathode.
- This can be coated beforehand with at least 5 ⁇ m of nickel from an electrolyte, which produces high-gloss layers.
- a gold layer approximately 0.1 ⁇ m thick can also be deposited on the nickel layer.
- the cathode is positioned in the electrolyte between the anodes and moved parallel to them at at least 5 cm/second. The distance between anode and cathode should not change.
- the cathode is coated by applying an electrical direct current between the anode and cathode.
- the amperage is chosen so that at least 0.5 A/dm 2 is reached on the surface. Higher current densities can be selected if the electrolyte mentioned in the application example is intended to be used to produce layers that can be used for technical and decorative purposes.
- the duration of the current flow is chosen so that at least a layer thickness of 0.5 to 1 ⁇ m is achieved on average over the area. Higher layer thicknesses can be produced if the electrolyte mentioned in the application example is intended to produce layers with a quality that can be used for technical and decorative purposes.
- the cathode is removed from the electrolyte and rinsed with deionized water.
- the cathodes can be dried by compressed air, hot air or centrifugation.
- the area of the cathode, the level and duration of the applied current and the weight of the cathode before and after coating are documented and used to calculate the average coating thickness and the efficiency of the deposition determine.
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Abstract
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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CN202180054837.2A CN116157557A (zh) | 2020-11-26 | 2021-11-25 | 钌合金层及其层组合 |
US18/253,065 US20240018679A1 (en) | 2020-11-26 | 2021-11-25 | Ruthenium Alloy Layer and Its Layer Combinations |
JP2023532198A JP2023550807A (ja) | 2020-11-26 | 2021-11-25 | ルテニウム合金層及び該層の組み合わせ |
EP21820188.7A EP4251792A1 (fr) | 2020-11-26 | 2021-11-25 | Couche d'alliage de ruthénium et ses combinaisons de couches |
KR1020237021452A KR20230113355A (ko) | 2020-11-26 | 2021-11-25 | 루테늄 합금 층 및 이의 층 조합 |
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DE102020131371.3A DE102020131371A1 (de) | 2020-11-26 | 2020-11-26 | Rutheniumlegierungsschicht und deren Schichtkombinationen |
DE102020131371.3 | 2020-11-26 |
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WO2022112379A1 true WO2022112379A1 (fr) | 2022-06-02 |
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PCT/EP2021/082914 WO2022112379A1 (fr) | 2020-11-26 | 2021-11-25 | Couche d'alliage de ruthénium et ses combinaisons de couches |
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US (1) | US20240018679A1 (fr) |
EP (1) | EP4251792A1 (fr) |
JP (1) | JP2023550807A (fr) |
KR (1) | KR20230113355A (fr) |
CN (1) | CN116157557A (fr) |
DE (1) | DE102020131371A1 (fr) |
WO (1) | WO2022112379A1 (fr) |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1959907A1 (de) | 1968-11-28 | 1970-06-18 | Johnson Matthey Co Ltd | Rutheniumkomplex und seine Verwendung bei der Elektroplattierung |
US3692641A (en) | 1970-03-20 | 1972-09-19 | Sel Rex Corp | Electrodeposition of low stress ruthenium alloy |
US4082625A (en) | 1976-06-08 | 1978-04-04 | The International Nickel Company, Inc. | Electrodeposition of ruthenium |
EP0018165A1 (fr) * | 1979-04-10 | 1980-10-29 | Inco Europe Limited | Bain et procédé pour le dépôt électrolytique de ruthénium, solution concentrée pour la fabrication de ce bain et objet revêtu de ruthénium |
GB2101633A (en) | 1981-06-02 | 1983-01-19 | Occidental Chem Co | Bath for the electrodeposition of ruthenium |
US6117301A (en) * | 1997-09-24 | 2000-09-12 | Degussa-Huls Aktiengesellschaft | Electrolyte for the galvanic deposition of low-stress, crack-resistant ruthenium layers |
EP2757180A1 (fr) * | 2013-01-18 | 2014-07-23 | Valmet S.p.A. | Procédé de dépôt électrolytique d'un alliage à base de ruthénium et d'étain, bain électrolytique qui permet le dépôt de l'alliage et alliage obtenu au moyen dudit procédé |
DE102011105207B4 (de) | 2011-06-17 | 2015-09-10 | Umicore Galvanotechnik Gmbh | Elektrolyt und seine Verwendung zur Abscheidung von Schwarz-Ruthenium-Überzügen und so erhaltene Überzüge und Artikel |
WO2018142430A1 (fr) | 2017-01-31 | 2018-08-09 | Valmet Plating S.R.L. | Procédé de dépôt galvanique permettant de former des dépôts de ruthénium colorés et/ou de ses alliages |
DE102019109188A1 (de) * | 2019-04-08 | 2020-10-08 | Umicore Galvanotechnik Gmbh | Elektrolyt zur Abscheidung von anthrazit/schwarzen Rhodium/Ruthenium Legierungsschichten |
AT523922B1 (de) * | 2020-09-08 | 2022-01-15 | Iwg Ing W Garhoefer Ges M B H | Elektrolytbad für Palladium-Ruthenium-Beschichtungen |
-
2020
- 2020-11-26 DE DE102020131371.3A patent/DE102020131371A1/de active Granted
-
2021
- 2021-11-25 KR KR1020237021452A patent/KR20230113355A/ko unknown
- 2021-11-25 EP EP21820188.7A patent/EP4251792A1/fr active Pending
- 2021-11-25 JP JP2023532198A patent/JP2023550807A/ja active Pending
- 2021-11-25 US US18/253,065 patent/US20240018679A1/en active Pending
- 2021-11-25 WO PCT/EP2021/082914 patent/WO2022112379A1/fr active Application Filing
- 2021-11-25 CN CN202180054837.2A patent/CN116157557A/zh active Pending
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1959907A1 (de) | 1968-11-28 | 1970-06-18 | Johnson Matthey Co Ltd | Rutheniumkomplex und seine Verwendung bei der Elektroplattierung |
US3692641A (en) | 1970-03-20 | 1972-09-19 | Sel Rex Corp | Electrodeposition of low stress ruthenium alloy |
US4082625A (en) | 1976-06-08 | 1978-04-04 | The International Nickel Company, Inc. | Electrodeposition of ruthenium |
EP0018165A1 (fr) * | 1979-04-10 | 1980-10-29 | Inco Europe Limited | Bain et procédé pour le dépôt électrolytique de ruthénium, solution concentrée pour la fabrication de ce bain et objet revêtu de ruthénium |
US4297178A (en) | 1979-04-10 | 1981-10-27 | The International Nickel Company, Inc. | Ruthenium electroplating and baths and compositions therefor |
GB2101633A (en) | 1981-06-02 | 1983-01-19 | Occidental Chem Co | Bath for the electrodeposition of ruthenium |
US6117301A (en) * | 1997-09-24 | 2000-09-12 | Degussa-Huls Aktiengesellschaft | Electrolyte for the galvanic deposition of low-stress, crack-resistant ruthenium layers |
DE102011105207B4 (de) | 2011-06-17 | 2015-09-10 | Umicore Galvanotechnik Gmbh | Elektrolyt und seine Verwendung zur Abscheidung von Schwarz-Ruthenium-Überzügen und so erhaltene Überzüge und Artikel |
EP2757180A1 (fr) * | 2013-01-18 | 2014-07-23 | Valmet S.p.A. | Procédé de dépôt électrolytique d'un alliage à base de ruthénium et d'étain, bain électrolytique qui permet le dépôt de l'alliage et alliage obtenu au moyen dudit procédé |
WO2018142430A1 (fr) | 2017-01-31 | 2018-08-09 | Valmet Plating S.R.L. | Procédé de dépôt galvanique permettant de former des dépôts de ruthénium colorés et/ou de ses alliages |
DE102019109188A1 (de) * | 2019-04-08 | 2020-10-08 | Umicore Galvanotechnik Gmbh | Elektrolyt zur Abscheidung von anthrazit/schwarzen Rhodium/Ruthenium Legierungsschichten |
AT523922B1 (de) * | 2020-09-08 | 2022-01-15 | Iwg Ing W Garhoefer Ges M B H | Elektrolytbad für Palladium-Ruthenium-Beschichtungen |
Non-Patent Citations (2)
Title |
---|
COBLEY, A.J. ET AL.: "The use uf insoluble Anodes in Acid Sulphate Copper Electrodeposition Solutions", TRANS IMF, vol. 79, no. 3, 2001, pages 113,114, XP001023283 |
KANANI, N: "Galvanotechnik", 2000, HANSER VERLAG, pages: 84 |
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CN116157557A (zh) | 2023-05-23 |
US20240018679A1 (en) | 2024-01-18 |
JP2023550807A (ja) | 2023-12-05 |
EP4251792A1 (fr) | 2023-10-04 |
KR20230113355A (ko) | 2023-07-28 |
DE102020131371A1 (de) | 2022-06-02 |
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