EP3765658A1 - Elektroplattierte produkte und elektroplattierungsbad zur bereitstellung solcher produkte - Google Patents
Elektroplattierte produkte und elektroplattierungsbad zur bereitstellung solcher produkteInfo
- Publication number
- EP3765658A1 EP3765658A1 EP19709513.6A EP19709513A EP3765658A1 EP 3765658 A1 EP3765658 A1 EP 3765658A1 EP 19709513 A EP19709513 A EP 19709513A EP 3765658 A1 EP3765658 A1 EP 3765658A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- indium
- gold
- copper
- electroplated product
- 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
- 238000009713 electroplating Methods 0.000 title claims description 38
- 239000010949 copper Substances 0.000 claims abstract description 86
- 229910052802 copper Inorganic materials 0.000 claims abstract description 79
- 229910052738 indium Inorganic materials 0.000 claims abstract description 77
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 76
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 73
- 238000009792 diffusion process Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 230000004888 barrier function Effects 0.000 claims abstract description 26
- 239000010970 precious metal Substances 0.000 claims abstract description 22
- 229910000846 In alloy Inorganic materials 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000010931 gold Substances 0.000 claims description 63
- 229910052737 gold Inorganic materials 0.000 claims description 58
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 43
- 239000003792 electrolyte Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 20
- 229910052709 silver Inorganic materials 0.000 claims description 15
- 229910045601 alloy Inorganic materials 0.000 claims description 14
- 239000000956 alloy Substances 0.000 claims description 14
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 14
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 11
- 239000008139 complexing agent Substances 0.000 claims description 11
- 230000008021 deposition Effects 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 9
- -1 aminobetaine Chemical compound 0.000 claims description 8
- 229910001449 indium ion Inorganic materials 0.000 claims description 8
- 229960003237 betaine Drugs 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 5
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- 235000001014 amino acid Nutrition 0.000 claims description 4
- 150000001413 amino acids Chemical class 0.000 claims description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- 235000010356 sorbitol Nutrition 0.000 claims description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 229960003975 potassium Drugs 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- DIROHOMJLWMERM-UHFFFAOYSA-N 3-[dimethyl(octadecyl)azaniumyl]propane-1-sulfonate Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCS([O-])(=O)=O DIROHOMJLWMERM-UHFFFAOYSA-N 0.000 claims description 2
- BCSZNBYWPPFADT-UHFFFAOYSA-N 4-(1,2,4-triazol-4-ylmethyl)benzonitrile Chemical compound C1=CC(C#N)=CC=C1CN1C=NN=C1 BCSZNBYWPPFADT-UHFFFAOYSA-N 0.000 claims description 2
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 claims description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims description 2
- 229910003803 Gold(III) chloride Inorganic materials 0.000 claims description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
- HLCFGWHYROZGBI-JJKGCWMISA-M Potassium gluconate Chemical compound [K+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O HLCFGWHYROZGBI-JJKGCWMISA-M 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 2
- OBITVHZFHDIQGH-UHFFFAOYSA-N [Au].[K]C#N Chemical compound [Au].[K]C#N OBITVHZFHDIQGH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001720 carbohydrates Chemical class 0.000 claims description 2
- 235000014633 carbohydrates Nutrition 0.000 claims description 2
- 150000001860 citric acid derivatives Chemical class 0.000 claims description 2
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 claims description 2
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 2
- 235000018417 cysteine Nutrition 0.000 claims description 2
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 claims description 2
- 235000011180 diphosphates Nutrition 0.000 claims description 2
- 229940050410 gluconate Drugs 0.000 claims description 2
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 claims description 2
- ZBKIUFWVEIBQRT-UHFFFAOYSA-N gold(1+) Chemical compound [Au+] ZBKIUFWVEIBQRT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001469 hydantoins Chemical class 0.000 claims description 2
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 2
- IZWSFJTYBVKZNK-UHFFFAOYSA-N lauryl sulfobetaine Chemical compound CCCCCCCCCCCC[N+](C)(C)CCCS([O-])(=O)=O IZWSFJTYBVKZNK-UHFFFAOYSA-N 0.000 claims description 2
- 239000010985 leather Substances 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004224 potassium gluconate Substances 0.000 claims description 2
- 229960003189 potassium gluconate Drugs 0.000 claims description 2
- 235000013926 potassium gluconate Nutrition 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- 239000000176 sodium gluconate Substances 0.000 claims description 2
- 235000012207 sodium gluconate Nutrition 0.000 claims description 2
- 229940005574 sodium gluconate Drugs 0.000 claims description 2
- 150000005846 sugar alcohols Chemical class 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- 150000003464 sulfur compounds Chemical class 0.000 claims description 2
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 2
- 229940035024 thioglycerol Drugs 0.000 claims description 2
- 239000000811 xylitol Substances 0.000 claims description 2
- 235000010447 xylitol Nutrition 0.000 claims description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
- 229960002675 xylitol Drugs 0.000 claims description 2
- 229940024606 amino acid Drugs 0.000 claims 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims 1
- 229940073507 cocamidopropyl betaine Drugs 0.000 claims 1
- 229940000425 combination drug Drugs 0.000 claims 1
- 229960002433 cysteine Drugs 0.000 claims 1
- 229960001855 mannitol Drugs 0.000 claims 1
- 229920000136 polysorbate Polymers 0.000 claims 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims 1
- 229960001790 sodium citrate Drugs 0.000 claims 1
- 229960002920 sorbitol Drugs 0.000 claims 1
- 230000005012 migration Effects 0.000 abstract description 13
- 238000013508 migration Methods 0.000 abstract description 13
- 239000010410 layer Substances 0.000 description 99
- 229910001369 Brass Inorganic materials 0.000 description 19
- 239000010951 brass Substances 0.000 description 19
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 19
- 229910000906 Bronze Inorganic materials 0.000 description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 18
- 238000001336 glow discharge atomic emission spectroscopy Methods 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 239000010974 bronze Substances 0.000 description 17
- 238000000151 deposition Methods 0.000 description 12
- 238000007669 thermal treatment Methods 0.000 description 12
- 239000011135 tin Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 229910001297 Zn alloy Inorganic materials 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 8
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 8
- GPYPVKIFOKLUGD-UHFFFAOYSA-N gold indium Chemical compound [In].[Au] GPYPVKIFOKLUGD-UHFFFAOYSA-N 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- 229910052718 tin Inorganic materials 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- 239000010944 silver (metal) Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 229910001020 Au alloy Inorganic materials 0.000 description 3
- 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 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000004280 Sodium formate Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 3
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 description 3
- 239000001508 potassium citrate Substances 0.000 description 3
- 229960002635 potassium citrate Drugs 0.000 description 3
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 3
- 235000011082 potassium citrates Nutrition 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 235000019254 sodium formate Nutrition 0.000 description 3
- 229910002058 ternary alloy Inorganic materials 0.000 description 3
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000002009 allergenic effect Effects 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 239000006172 buffering agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 239000011532 electronic conductor Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- URRDJELAUALLFD-UHFFFAOYSA-N indium;3-sulfanylpropane-1,2-diol Chemical compound [In].OCC(O)CS URRDJELAUALLFD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- ZWNQSJPQMSUVSE-UHFFFAOYSA-N [Cu].[Sn].[In] Chemical compound [Cu].[Sn].[In] ZWNQSJPQMSUVSE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 229940077731 carbohydrate nutrients Drugs 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- PMIMPWOYEBUHAC-UHFFFAOYSA-N gold;3-sulfanylpropane-1,2-diol Chemical compound [Au].OCC(O)CS PMIMPWOYEBUHAC-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910000923 precious metal alloy Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000008521 reorganization Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 235000019592 roughness Nutrition 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 150000003751 zinc Chemical class 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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
- C25D5/611—Smooth layers
-
- 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
- C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
-
- 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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
-
- 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
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/005—Jewels; Clockworks; Coins
Definitions
- Electroplated products and electroplating bath for providing such products are Electroplated products and electroplating bath for providing such products
- the present invention relates to electroplated products having a combination of layers used to provide a diffusion barrier layer which prevents the interdi- fussion between the underlayer and the top layer under a precious metal top layer on a substrate comprising a copper based material and/or a copper based underlayer, such that the layer or combination of layers prevents or retards the migration of copper into the precious metal layer or the opposite.
- the diffusion barrier layer comprises indium or an indium alloy.
- the present invention refers a method for preparing such an electroplated product.
- the common electroplating sequence comprises electroplating on the substrate a first layer of acid copper to ensure a proper levelling of the substrate rough ness followed by a white bronze layer of 2 to 5 pm and by a thin palladium based layer of a thickness from 0.2 to 0.5 miti to stop the diffusion of the top precious metal layer, mainly gold or a gold alloy, into the copper or copper alloy underlayer, and most importantly to prevent the diffusion of copper into the precious metal layer.
- a first layer of acid copper to ensure a proper levelling of the substrate rough ness followed by a white bronze layer of 2 to 5 pm and by a thin palladium based layer of a thickness from 0.2 to 0.5 miti to stop the diffusion of the top precious metal layer, mainly gold or a gold alloy, into the copper or copper alloy underlayer, and most importantly to prevent the diffusion of copper into the precious metal layer.
- the present bronze technology mainly uses cyanide as a complexing agent to enable the co-deposition of a ternary alloy of copper, tin and zinc which is also efficient as a copper diffusion barrier.
- WO2016/166330 A1 describes an electroplated product with a precious metal finishing layer that has an improved corrosion and abrasion resistance.
- the electroplated product comprises two electroplated copper alloy layers having a different copper concentration (e.g. white bronze and yellow bronze).
- Another advantage of the electroplated product is that the use of allergenic nickel or expensive palladium intermediate layers against copper migration can be dispensed with.
- WO2017/055553 A1 describes an electroplating bath for electrochemical deposition of a novel Cu-Sn-Zn-Pd alloy on a substrate.
- the novel alloy is characterized by improved corrosion resistance but is based on cyanide media.
- the metal indium is nowadays used mainly for photovoltaic applications due to its high thermal conductivity ( ⁇ 82 W/mK ). It also has other unique physical properties which make it very useful in numerous industries. For example, it is sufficiently soft such that it is readily deformed and fills microstructures between two mating parts, has a low melting temperature (156° C). Such properties recommend indium for various uses in the electronics and related industries.
- the use of indium in electroplating has already been tested as a constituent of bronze layers. W02015/000010 A1 describes a bath for the cathodic deposi tion of ternary bronze alloys.
- the electrolyte composition comprises indium as a third metallic alloying constituent. A ternary copper-tin-indium alloy is deposited directly on an optional copper layer.
- EP 1 930 478 A1 teaches an electrolyte composition as well as a method for the deposition of another quaternary copper alloy on a substrate.
- the electrolyte composition comprises besides the alloying metals copper, tin and zinc, at least one metal from the group consisting of indium and gallium providing white bronze layers free of noxious heavy metals.
- the previously mentioned documents are based on baths containing cyanide. Cyanide based solutions have several disadvantages associated with the high toxicity of the electrolyte, difficulties associated with storage and transporta tion of the cyanide salts and solutions, and costs associated with the waste- water treatments.
- Several attempts have been made to formulate cyanide free ternary bronze to substitute the dangerous complexing agent but none of them fulfils the market requirements to prevent the gold and copper inter diffusion as well as to maintain a bright and shiny aspect of the electroplated layers.
- W02004/035875 A3 refers to a method for bronze galvanic coating which consists of metallizing a substrate to be coated by its immersion into an acidic electrolyte which contains at least tin and copper ions.
- the acidic electrolyte used for bronze coating is also disclosed.
- WO2013/092314 cites an aqueous alkaline electrolyte, which is cyanide-free, pyrophosphate-free and phosphonic acid-free for depositing a ternary alloy comprising copper and tin present in dissolved form and zinc present as a zinc salt.
- KR1168215 B1 teaches a copper-tin alloy plating film, a non- cyanide-based copper-tin alloy plating bath, and a plating method using the same.
- the deposit was not a barrier to copper diffusion.
- the US 2,458,839 A teaches a bath which comprises at least 20 g/L of indium. However, with such high concentrations that no thin bright layers can be provided.
- W02009/097360 A1 describes an electroplating solution for the deposition of a pure indium film on a conductive surface useful in fabricating electronic devices.
- the indium electroplating solutions are used to deposit indium films which are compositionally pure, uniform, substantially free of defects and smooth. Such films can be plated with almost 100% plating efficiency.
- sub-micron thick indium layers are described. Such indium layers are used in fabrication of electronic devices such as thin film solar cells.
- EP 2 123 799 B1 teaches a method to prevent silver from tarnishing by electroplating a thin indium metal layer onto a silver substrate.
- the indium and silver composite has high electrical conductivity.
- W02017/060216 A1 teaches a process for indium or indium alloy deposition and for the formation of very smooth and glossy indium or indium alloy layers and their use in electronic and semiconductor devices, in particular intercon nections used in electronic and semiconductor industries such as flip chips, tape automated bonding and the like.
- a method for preparing an electroplated product by electroplating a substrate comprising the following steps: a) Electroplating a substrate with an underlayer consisting of copper or an copper alloy with an electrolyte comprising at least one source of copper ions, at least one conductive salt, and, optionally, at least one ion source of an alloy former for copper, b) Electroplating of a barrier layer on the underlayer with an aqueous bath comprising at least one source of indium ions and at least one conductive salt, c) Electroplating of a top layer consisting of a precious metal selected from the group consisting of Ag, Au, Pd, Rh, Ru, Pt and its alloys with an electrolyte comprising at least one ion source for the precious metal and at least one conductive salt.
- indium has been found to be an efficient copper diffusion barrier, able with very low thickness to prevent copper migration to the top gold layer and thus preventing the article from undesirable change of colour.
- the indium in the diffusion barrier layer which is deposited between the copper or copper alloy underlayer and the precious metal or precious metal alloy top layer, can migrate into the precious metal top layer, but prevents the interdiffusion between the underlayer and the top layer.
- an underlayer consisting of copper or a copper alloy is obtained by electrodeposition from a copper electroplating solution.
- This copper electroplating solution is generally very acidic as it contains up to 60 g/L of 98% sulfuric acid. It produces a bright deposit with high levelling characteristics. The deposits are free of pits even at high thicknesses.
- the electroplated copper thicknesses can vary from 5 to 60 pm depending on the substrate and the targeted properties.
- the function of the top layer consisting of a precious metal selected from the group consisting of Au, Ag, Pd, Rh, Ru, Pt and its alloys is highly decorative, it must be of a constant colour and give a very uniform and generally bright aspect to the final item.
- the thickness is generally low due to the cost of the precious metals used. It typically varies between 0.05 pm up to 5 pm prefera bly between 0.1 and 1 pm. It is absolutely necessary that the top layer colour and aspects are not affected by the copper underlayer. In the absence of a proper diffusion barrier, the interdiffusion of the copper or copper rich underlayer and the top finishing layer will lead to a non-acceptable finish of the part upon ageing or storage. That is why it is so important to provide an intermediate layer that prevents the interdiffusion of the copper rich under layer and the precious metal top layer.
- the electroplating bath of step b) preferably has a pH in the range of 1 to 14, more preferably of 2 to 11, and most preferably of 4 to 10.
- the at least one source of indium ion in the electroplating bath of step b) is preferably selected from the group consisting of indium sulfate, indium chloride, indium acetate, indium sulfamate and its combinations or mixtures. Considering the cost of this valuable metal, the source of indium ion should be affordable.
- the bath has a concentration of indium as a metal of 0.1 to 20 g/L, preferably 0.2 to 15 g/L, more preferably 0.3 to 10 g/L, most prefera bly 0.5 to 7 g/L.
- a concentration in these ranges is sufficient to obtain the suitable aspect of the indium thin layer.
- a concentration of indium above 20 g/L was found to be detrimental to maintain brightness and thickness distribution.
- the electroplating bath contains conductive salts in order to spread the indium distribution throughout the required current density range.
- the conductive salts are selected and balanced to not only act as a conductive salt but also as a buffering agent.
- the conductive salts are selected and balanced to not only act as a conductive salt but also as a buffering agent.
- salts/buffering agents are preferably selected from the group consisting of citrates (e.g. sodium or potassium citrate or their corresponding acidic version), formiates (e.g. sodium formiate or the corresponding acidic version), pyrophosphates (e.g. tetrapotassium pyrophosphate) and gluconates (e.g. sodium or potassium gluconate) and combinations or mixtures thereof.
- citrates e.g. sodium or potassium citrate or their corresponding acidic version
- formiates e.g. sodium formiate or the corresponding acidic version
- pyrophosphates e.g. tetrapotassium pyrophosphate
- gluconates e.g. sodium or potassium gluconate
- the at least one conductive salt has a concentration of 30 to 500 g/L, more preferably 50 to 300 g/L, and most preferably 100 to 200 g/L.
- a concentration in this range is suitable for keeping the pH of the inventive electroplating solution constant for many turnovers (TOs) of the electroplat ing solution.
- the brightness of the indium deposit is controlled by the introduction of a surfactant.
- the surfactant acts as a wetting agent and reduces the surface tension to allow indium electroplating.
- the surfactants may belong to the amphoteric family and are selected from the group consisting of propionic amino acids, propionic imino acids, quaternary alkyl betaines or sulfo-betains.
- the surfactant is preferably selected from the group of betain, aminobetain, imidazoline, cocoamidopropyl betaine, N,N-dimethyl-N-(3-cocoamidopropyl)- N-(2-hydroxy-3-sulfopropyl) ammonium betain, N,N-dimethyl-N-octadecyl-N- (3-sulfopropyl)ammonium betaine, N,N-dimethyl-N-dodecyl-N-(3- sulfopropyl)ammonium betaine and combinations or mixtures thereof.
- the surfactant concentration according to the invention is preferably from 0.1 to 5 g/L, more preferably from 0.5 to 1.5 g/L.
- the indium ions may be complexed in solution by a complexing agent.
- the complexing agent is preferably selected from the group consisting of carbohy- drates, amino acids, imino acids, sulfur compounds, sugar alcohols, and combinations or mixtures thereof. More preferably, the complexing agent is selected from the group consisting of sorbitol, mannitol, gluconate, erithrytol, xylitol, nitrilotriacetic acid, cysteine, iminodiacetic acid, triethanolamine and combinations or mixtures thereof. Said complexing agents were found to be perfectly suited for complexing indium ions.
- the concentration of the complexing agent in the bath is preferably from 0.5 to 100 g/L, preferably from 1 to 75 g/L, most preferably from 2.5 to 50 g/L, and in particular from 5 to 35 g/L. A concentration in these ranges is sufficient for complexing the indium ions which are comprised in the inventive electro plating solution. A concentration of complexing agent under 0.5 g/L was found to be detrimental and not able to stabilize the bath at the required pH.
- the diffusion barrier layer consists of an alloy of indium with the material of the top layer, i.e. a precious metal like Au, Ag, Pd, Rh, Ru, and Pt.
- a precious metal like Au, Ag, Pd, Rh, Ru, and Pt.
- An alloy of indium und gold is particularly preferred.
- An alloy of indium with the men tioned precious metals is very easy to process and shows improved diffusion barrier properties compared to other metals as alloy former.
- a diffusion barrier layer of gold and indium allows to strongly reduce copper migration.
- it is preferred to select an indium alloy with the proviso that this indium alloy is not a ternary alloy of indium, copper and tin.
- the electroplating bath comprises at least one source of gold ions, preferably selected from the group consisting of potassium gold (I) cyanide , sodium gold(l) sulphite, potassium gold(lll) cyanide , gold (III) chloride and tetrachloroaurates(lll), gold(l) thioglycerol and gold( I) and gold(lll) hydantoin complexes, and combinations or mixtures thereof.
- the concentration of the at least one source of gold is preferably from 0.5 to 10 g/L, more preferably from 1 to 5 g/L and most preferably from 2.5 to 3.5 g/L.
- the concentration of indium in the electroplating bath is preferably from 0.1 to 20 g/L, more preferably from 0.2 to 15 g/L and most preferably from 0.25 to 0.75 g/L.
- steps a) to c) is not interrupted by further deposition steps with the consequence that the layers electroplated in step a) to c) abut to each other.
- an electroplated product which comprises a substrate which is coated with an underlayer consisting of copper or a copper alloy and a top layer consisting of a precious metal selected from the group consisting of Au, Ag, Pd, Rh, Ru, Pt and alloys thereof, more preferably a precious metal selected from the group consisting of Au, Ag and its alloys.
- the underlayer and the top layer are separated by a diffusion barrier layer consisting of indium or an alloy of indium with the material of the top layer.
- the diffusion barrier layer has preferably a thickness of 10 to 200 nm, more preferably 25 to 150 nm and most preferably 50 to 100 nm. It has been determined that a thickness of the indium intermediate layer of less than 50 nm does not prevent the diffusion of copper into the gold. A thickness above 200 nm leads to poor brightness and presents a powdering aspect.
- the diffusion barrier layer comprises an gold indium alloy, preferably with 90 to 95 % by weight of gold and 5 to 10 % by weight of indium.
- the electroplated products are preferably selected from the group consisting of jewelry, leather goods, spectacle frame, fashion, watch, trinkets and/or lock industry.
- the copper plated panels were then plated with various subsequent layers using different electrolytes.
- Minolta CM-503i spectrophotometer *measured with Minolta CM-503i spectrophotometer. Illuminant used was Daylight D65 (6500K) with reflective component included (sci). Observer was set at standard (10°) and the measurements were done in the Color space CIE L*a*b*.
- indium intermediate layer from 0 to 3 pm obtained via the method here above described (electrolyte 1)
- Gold top layer 0.5 pm (obtained via the method here above de scribed)
- Fig. 2 a* evolution over thermal treatment depending on indium thickness
- Figs. 1, 2 and 3 show that for example 1 where gold is plated directly on copper, there is a strong evolution of the Lab value after heat treatment indicating a reorganization of the two elements upon heating:
- Fig. 1 shows that from 0.05 pm to 2 pm of indium between copper and gold, the L* value does not change after heating at 180°C
- Fig. 2 and 3 show the evolution of a* and b* values versus thickness of the indium layer.
- the range of thicknesses where the evo lution of a* and b* values are acceptable is comprised between 0.05 and 0.1 pm.
- GDOES low discharge optical emission spectrometry
- the sample forms the cathode and a thin (4 mm diameter) copper tube forms the anode.
- a small O-ring separates the anode from the cathode.
- High-purity argon is pumped into the anode chamber.
- a high voltage (DC or RF) between sample and anode ionizes the argon to produce a glow discharge plasma.
- the excited argon ions bombard the electroplated product sample and cause uniform sputtering of the sample surface. Atoms ejected are then excited by the argon plasma, and finally relax to their fundamental energy level, emitting a characteristic X-ray photon.
- Emitted photons whose energy is characteristic of the energy level of a chemical element, are then collected by photomultipliers.
- the intensity of each emission depends on the concentration of the element in the sample.
- the recorded signals are processed to obtain the distribution of the elements according to the erosion time.
- GDOES provides a depth profiling analysis of solids like metals, powders, polymers, glasses and ceramics (in the present case: depth profiling of electroplated substrates).
- GDOES GDOES-like e.g . C, N and 0.
- the spectrum obtained represents the qualitative intensity of the metallic signal variation depending on time of sputtering in s.
- Figs. 4 to 9 give the GDOES depth profiles for the different electroplated products of Examples 1 to 6 before and after the heat treatment at 180°C for 24 hours.
- concentration of each chemical element Au, Cu, In and option ally Sn and Zn for reference is shown (y-axis for intensity) as a function of the distance from the surface of the finishing layer towards the base material of the electroplated product (x-axis for erosion time).
- Substrate brass (copper - zinc alloy)
- Fig. 5a is the profile of a sample reported in Example 2 before heat treatment. We can see that each layer is well-defined, and no copper is present in the gold layer.
- Example 3 according to the present invention the following sequence was used on the reference brass panels:
- Example 3 From Example 3 according to the invention, it can be seen from Fig. 6a that the thin intermediate layer of indium is located between the copper and the top gold top layer.
- the resulting top layer is an alloy of gold and indium that contains only very little if any copper. Obviously, copper migration to the surface was inhibited.
- the top layer is composed of an Au-ln alloy as a cover layer for the Cu under layer (and the substrate). It appears, therefore, that In can be employed as a copper diffusion barrier between a copper or copper alloy substrate and a gold surface layer in a way similar to the action of a nickel or palladium barrier commonly used until recently.
- Substrate brass (copper - zinc alloy)
- Example 5 according to the present invention the following sequence was used on the reference brass panels:
- Substrate brass (copper - zinc alloy)
- Example 5 according to the present invention the following sequence was used on the reference brass panels:
- Substrate brass (copper - zinc alloy)
- the gold-indium alloy (Au 90-95 % : In 5-10 %) layer can strongly reduce the copper migration during the thermal treatment procedure.
- the interface between the copper layer and the gold-indium alloys is well defined in both cases and no copper migration is observed from the bottom copper layer.
- Substrate brass (copper - zinc alloy)
- Example 8 according to the present invention the following sequence was used on the reference brass panels:
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- Chemical Kinetics & Catalysis (AREA)
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP18161575.8A EP3540097A1 (de) | 2018-03-13 | 2018-03-13 | Elektroplattierte produkte und elektroplattierungsbad zur bereitstellung solcher produkte |
PCT/EP2019/056328 WO2019175270A1 (en) | 2018-03-13 | 2019-03-13 | Electroplated products and electroplating bath for providing such products |
Publications (2)
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EP3765658A1 true EP3765658A1 (de) | 2021-01-20 |
EP3765658B1 EP3765658B1 (de) | 2023-06-14 |
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EP18161575.8A Withdrawn EP3540097A1 (de) | 2018-03-13 | 2018-03-13 | Elektroplattierte produkte und elektroplattierungsbad zur bereitstellung solcher produkte |
EP19709513.6A Active EP3765658B1 (de) | 2018-03-13 | 2019-03-13 | Elektroplattierte produkte und elektroplattierungsbad zur bereitstellung solcher produkte |
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EP18161575.8A Withdrawn EP3540097A1 (de) | 2018-03-13 | 2018-03-13 | Elektroplattierte produkte und elektroplattierungsbad zur bereitstellung solcher produkte |
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WO (1) | WO2019175270A1 (de) |
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EP4001472A1 (de) | 2020-11-16 | 2022-05-25 | COVENTYA S.p.A. | Verfahren zur herstellung eines elektroplattierten produktes durch abscheiden einer unterschicht, einer diffusionssperrschicht und einer deckschicht auf der oberfläche eines substrats und so hergestelltes elektroplattiertes produkt |
CN114540895B (zh) * | 2022-03-01 | 2023-05-30 | 九牧厨卫股份有限公司 | 一种杀菌灰色复合镀层及其制备方法和灰色杀菌产品 |
CN114525553B (zh) * | 2022-03-01 | 2023-05-30 | 九牧厨卫股份有限公司 | 一种蓝白色复合镀层及其制备方法和蓝白色杀菌产品 |
Family Cites Families (15)
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US2458839A (en) | 1944-04-19 | 1949-01-11 | Indium Corp America | Electrodeposition of indium and its alloys |
US3367754A (en) * | 1965-02-03 | 1968-02-06 | Gen Dynamics Corp | Electronic transmission material and method of fabrication |
ES2531163T3 (es) | 2002-10-11 | 2015-03-11 | Enthone | Procedimiento y electrolito para la deposición galvánica de bronces |
EP1930478B1 (de) | 2006-12-06 | 2013-06-19 | Enthone, Inc. | Zusammensetzung eines Elektrolyten und Verfahren zur Beschichtung von quaternären Kupferlegierungen |
JP4834022B2 (ja) * | 2007-03-27 | 2011-12-07 | 古河電気工業株式会社 | 可動接点部品用銀被覆材およびその製造方法 |
US20090188808A1 (en) | 2008-01-29 | 2009-07-30 | Jiaxiong Wang | Indium electroplating baths for thin layer deposition |
EP2123799B1 (de) | 2008-04-22 | 2015-04-22 | Rohm and Haas Electronic Materials LLC | Verfahren zum Nachfüllen von Indiumionen in Indium-Elektroplattierzusammensetzungen |
EP2383244A1 (de) * | 2010-04-23 | 2011-11-02 | Omega SA | Keramikelement mit mindestens einem Metalldekoreinsatz |
DE102011121798B4 (de) | 2011-12-21 | 2013-08-29 | Umicore Galvanotechnik Gmbh | Elektrolyt und Verfahren zur elektrolytischen Abscheidung von Cu-Zn-Sn-Legierungsschichten und Verfahren zur Herstellung einer Dünnschichtsolarzelle |
KR101168215B1 (ko) | 2012-01-20 | 2012-07-25 | 가부시끼가이샤시미즈 | 동-주석 합금 도금 피막, 비시안계 동-주석 합금 도금욕 및 그것을 이용한 도금 방법 |
AT514427B1 (de) | 2013-07-05 | 2015-01-15 | W Garhöfer Ges M B H Ing | Elektrolytbad sowie damit erhältliche Objekte bzw. Artikel |
JP2015045045A (ja) * | 2013-08-27 | 2015-03-12 | Jx日鉱日石金属株式会社 | 電子部品用金属材料及びその製造方法、それを用いたコネクタ端子、コネクタ及び電子部品 |
EP3081673A1 (de) | 2015-04-16 | 2016-10-19 | COVENTYA S.p.A. | Elektroplattiertes produkt mit einer edelmetalloberflächenschicht und verbesserter korrosionsbeständigkeit, verfahren zu dessen herstellung und verwendungen davon |
EP3150744B1 (de) | 2015-09-30 | 2020-02-12 | COVENTYA S.p.A. | Galvanikbad zur elektrochemischen abscheidung einer cu-sn-zn-pd legierungsschicht, verfahren zur elektrochemischen abscheidung der legierungsschicht, substrat mit der legierungsschicht und verwendungen des beschichteten substrats |
JP6813574B2 (ja) | 2015-10-06 | 2021-01-13 | アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングAtotech Deutschland GmbH | インジウムまたはインジウム合金の堆積方法および物品 |
-
2018
- 2018-03-13 EP EP18161575.8A patent/EP3540097A1/de not_active Withdrawn
-
2019
- 2019-03-13 WO PCT/EP2019/056328 patent/WO2019175270A1/en unknown
- 2019-03-13 EP EP19709513.6A patent/EP3765658B1/de active Active
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WO2019175270A1 (en) | 2019-09-19 |
EP3765658B1 (de) | 2023-06-14 |
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