CN116601338A - 用于沉积硬银层的银-铋电解液 - Google Patents
用于沉积硬银层的银-铋电解液 Download PDFInfo
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- CN116601338A CN116601338A CN202180082618.5A CN202180082618A CN116601338A CN 116601338 A CN116601338 A CN 116601338A CN 202180082618 A CN202180082618 A CN 202180082618A CN 116601338 A CN116601338 A CN 116601338A
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- Prior art keywords
- silver
- bismuth
- electrolyte
- iii
- method comprises
- Prior art date
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 71
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000004332 silver Substances 0.000 title claims abstract description 34
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 33
- 238000000151 deposition Methods 0.000 title claims abstract description 24
- CCXYPVYRAOXCHB-UHFFFAOYSA-N bismuth silver Chemical compound [Ag].[Bi] CCXYPVYRAOXCHB-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 26
- 229910001152 Bi alloy Inorganic materials 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 23
- 230000008021 deposition Effects 0.000 claims description 15
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 12
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000080 wetting agent Substances 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 239000007859 condensation product Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000012990 dithiocarbamate Substances 0.000 claims description 6
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 claims description 6
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 5
- 238000005282 brightening Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229940098221 silver cyanide Drugs 0.000 claims description 5
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 4
- PPNKDDZCLDMRHS-UHFFFAOYSA-N bismuth(III) nitrate Inorganic materials [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 3
- 150000001622 bismuth compounds Chemical class 0.000 claims description 3
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 3
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims description 3
- 229940100890 silver compound Drugs 0.000 claims description 3
- 150000003379 silver compounds Chemical class 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
- MSBGPEACXKBQSX-UHFFFAOYSA-N (4-fluorophenyl) carbonochloridate Chemical compound FC1=CC=C(OC(Cl)=O)C=C1 MSBGPEACXKBQSX-UHFFFAOYSA-N 0.000 claims description 2
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 2
- RYKLZUPYJFFNRR-UHFFFAOYSA-N 3-hydroxypiperidin-2-one Chemical compound OC1CCCNC1=O RYKLZUPYJFFNRR-UHFFFAOYSA-N 0.000 claims description 2
- ZSILVJLXKHGNPL-UHFFFAOYSA-L S(=S)(=O)([O-])[O-].[Ag+2] Chemical compound S(=S)(=O)([O-])[O-].[Ag+2] ZSILVJLXKHGNPL-UHFFFAOYSA-L 0.000 claims description 2
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 2
- 238000000137 annealing Methods 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- SULICOHAQXOMED-UHFFFAOYSA-H bis(5,6-dihydroxy-4,7-dioxo-1,3,2-dioxabismepan-2-yl) 2,3-dihydroxybutanedioate Chemical compound [Bi+3].[Bi+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O SULICOHAQXOMED-UHFFFAOYSA-H 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- ANERHPOLUMFRDC-UHFFFAOYSA-K bismuth citrate Chemical compound [Bi+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ANERHPOLUMFRDC-UHFFFAOYSA-K 0.000 claims description 2
- TXKAQZRUJUNDHI-UHFFFAOYSA-K bismuth tribromide Chemical compound Br[Bi](Br)Br TXKAQZRUJUNDHI-UHFFFAOYSA-K 0.000 claims description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 2
- MNMKEULGSNUTIA-UHFFFAOYSA-K bismuth;methanesulfonate Chemical compound [Bi+3].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O MNMKEULGSNUTIA-UHFFFAOYSA-K 0.000 claims description 2
- BRCWHGIUHLWZBK-UHFFFAOYSA-K bismuth;trifluoride Chemical compound F[Bi](F)F BRCWHGIUHLWZBK-UHFFFAOYSA-K 0.000 claims description 2
- IAQAJTTVJUUIQJ-UHFFFAOYSA-N bismuth;trihydrate Chemical compound O.O.O.[Bi] IAQAJTTVJUUIQJ-UHFFFAOYSA-N 0.000 claims description 2
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 claims description 2
- 229940091173 hydantoin Drugs 0.000 claims description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 2
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 2
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 2
- 229940096017 silver fluoride Drugs 0.000 claims description 2
- 229940045105 silver iodide Drugs 0.000 claims description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 2
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 229910001923 silver oxide Inorganic materials 0.000 claims description 2
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 claims description 2
- 229910000161 silver phosphate Inorganic materials 0.000 claims description 2
- 229940019931 silver phosphate Drugs 0.000 claims description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 2
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 2
- RHUVFRWZKMEWNS-UHFFFAOYSA-M silver thiocyanate Chemical compound [Ag+].[S-]C#N RHUVFRWZKMEWNS-UHFFFAOYSA-M 0.000 claims description 2
- LMEWRZSPCQHBOB-UHFFFAOYSA-M silver;2-hydroxypropanoate Chemical compound [Ag+].CC(O)C([O-])=O LMEWRZSPCQHBOB-UHFFFAOYSA-M 0.000 claims description 2
- VPKAOUKDMHJLAY-UHFFFAOYSA-J tetrasilver;phosphonato phosphate Chemical compound [Ag+].[Ag+].[Ag+].[Ag+].[O-]P([O-])(=O)OP([O-])([O-])=O VPKAOUKDMHJLAY-UHFFFAOYSA-J 0.000 claims description 2
- VZZHAYFWMLLWGG-UHFFFAOYSA-K triazanium;bismuth;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [NH4+].[NH4+].[NH4+].[Bi+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O VZZHAYFWMLLWGG-UHFFFAOYSA-K 0.000 claims description 2
- KOECRLKKXSXCPB-UHFFFAOYSA-K triiodobismuthane Chemical compound I[Bi](I)I KOECRLKKXSXCPB-UHFFFAOYSA-K 0.000 claims description 2
- 238000005363 electrowinning Methods 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 abstract description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- -1 aliphatic sulfides Chemical class 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000005275 alloying Methods 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- LGFYIAWZICUNLK-UHFFFAOYSA-N antimony silver Chemical compound [Ag].[Sb] LGFYIAWZICUNLK-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229910002065 alloy metal Inorganic materials 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- FJPGAMCQJNLTJC-UHFFFAOYSA-N 2,3-Heptanedione Chemical compound CCCCC(=O)C(C)=O FJPGAMCQJNLTJC-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- KVFQMAZOBTXCAZ-UHFFFAOYSA-N 3,4-Hexanedione Chemical compound CCC(=O)C(=O)CC KVFQMAZOBTXCAZ-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 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 description 2
- 241000920033 Eugenes Species 0.000 description 2
- BACYUWVYYTXETD-UHFFFAOYSA-N N-Lauroylsarcosine Chemical compound CCCCCCCCCCCC(=O)N(C)CC(O)=O BACYUWVYYTXETD-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 108010077895 Sarcosine Proteins 0.000 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 description 2
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- 230000032683 aging Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
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- 235000015165 citric acid Nutrition 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
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- 239000008367 deionised water Substances 0.000 description 2
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- 238000004870 electrical engineering Methods 0.000 description 2
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- 238000005323 electroforming Methods 0.000 description 2
- 239000003353 gold alloy Substances 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 2
- ILPNRWUGFSPGAA-UHFFFAOYSA-N heptane-2,4-dione Chemical compound CCCC(=O)CC(C)=O ILPNRWUGFSPGAA-UHFFFAOYSA-N 0.000 description 2
- MWVFCEVNXHTDNF-UHFFFAOYSA-N hexane-2,3-dione Chemical compound CCCC(=O)C(C)=O MWVFCEVNXHTDNF-UHFFFAOYSA-N 0.000 description 2
- XTEGVFVZDVNBPF-UHFFFAOYSA-N naphthalene-1,5-disulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1S(O)(=O)=O XTEGVFVZDVNBPF-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
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- MIAUJDCQDVWHEV-UHFFFAOYSA-N benzene-1,2-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1S(O)(=O)=O MIAUJDCQDVWHEV-UHFFFAOYSA-N 0.000 description 1
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- OATNQHYJXLHTEW-UHFFFAOYSA-N benzene-1,4-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(S(O)(=O)=O)C=C1 OATNQHYJXLHTEW-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
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- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- C25D3/64—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of silver
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/018—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of a noble metal or a noble metal alloy
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
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- 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
- C25D3/46—Electroplating: Baths therefor from solutions of silver
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- 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
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Abstract
本发明涉及一种用于沉积硬银层的电解液,其中将元素铋与银合金化。本发明还涉及一种用于从根据本发明的电解液沉积相应的银‑铋合金的方法以及相应沉积的层。
Description
描述
本发明涉及一种用于沉积硬银层的电解液,其中将元素铋与银合金化。本发明还涉及一种用于从根据本发明的电解液沉积相应的银-铋合金的方法以及相应沉积的层。
电接触件目前用于几乎所有电器中。电接触件在机动车工业或航空航天技术中的应用范围从简单的插头连接器到通信领域的安全相关的精密开关接触件。在此要求接触表面具有以下特性:良好的导电性、长期稳定的低接触电阻、良好的耐腐蚀性和具有尽可能低的插入力的耐磨性以及良好的耐热性。在电气工程中,常常用由金-钴、金-镍或金-铁组成的硬质金合金层来涂覆插头接触件。这些层具有良好的耐磨性、良好的可焊性、长期稳定的低接触电阻、以及良好的耐腐蚀性。由于金价上涨,正在寻求更廉价的替代品。
作为硬金镀层的替代品,具有富银的银合金(硬银)的涂层已被证明是有利的。银和银合金是电气工程中最重要的接触材料之一,这不仅仅是由于其较高的导电率和良好的氧化抗性。根椐添加到合金中的金属,这些银合金层具有与当前使用的硬金层和层组合(诸如具有金薄层的钯镍)的层特性类似的层特性。此外,银的价格相比于其它贵金属,特别是硬金合金相对较低。
对于硬银层的沉积,在工业中主要使用银-锑电解液。沉积的锑合金硬银层在沉积状态下具有约160-180HV的硬度。在于150℃的温度老化最高达1000h后的永久硬度为约120HV。对耐温性的要求变得越来越严格。还必须考虑电特性。纯银的特征在于非常低的接触电阻值。银合金层的接触电阻必须不会由于第二金属的合金化和所导致的硬度增加而增加太多。目标值是在50cN接触力下至多10mOhm的接触电阻。具有最多3%锑的银-锑涂层满足该要求。然而,如上所述,永久硬度被限制为最大120-140HV的值。此外,在电解液中使用的锑(lll)在操作期间被阳极地转化成其五价氧化态,因此不再有效作为硬化剂。这限制了电解液的使用寿命并且使得加工更加困难,因为需要高水平的分析努力来确定锑(ll)含量。
因此限制了在银-锑涂层中使用接触表面的可能性。在现代应用中,经常会出现最高达200℃的热负荷。这里重要的是甚至在高温下的永久硬度和由于磨耗导致的低磨损。在文献中描述了银-铋电解液,但其不能在宽电流密度范围内沉积足够均匀且有光泽的涂层。
在US7628903B1中,使用脂族硫化物在强酸性pH范围内从非氰化物电解液电解沉积银和具有Sn、Bi、In、Pb的银合金。铜或铜合金层的涂层在此出现问题,因为它们在强酸性pH范围内快速溶解。
JPH11279787A描述了同样处于强酸性pH范围内的银和使用氨基苯硫酚化合物以Sn、Bi、Zn、In、Cu、Sb、Ti、Fe、Ni或Co作为合金伴侣的银合金沉积物。这里也一样,当涂覆铜或铜合金基材时,强酸性电解液也存在问题。
通过循环伏安法的银-铋电解液的电解沉积描述于I.Valkova;I.Krastev,Transactions of the institute of metal finishing 80,(2002)21-24。在此,使用不含氰化物的碱性电解液,该碱性电解液仅具有低的可用电流密度和不足的稳定性。
DE1182014B描述了一种用于电沉积具有高硬度的银-锑或银-铋合金的方法。氰化银电解液使用多羟基氨基醇来络合合金金属,但仅允许最高达3A/dm2的电流密度,这对于连续系统中的涂覆是不够的。
DE2731595B1描述了酮-二硫化碳缩合产物的光亮剂组合在氰化物银浴中的用途。然而,在这种情况下没有提及与铋的合金化。
因此,基于这些发现,本发明旨在开发银-铋合金电解液,其目的是改善上述范围内的电解液或沉积层的特性。通过根据本发明权利要求1的电解液解决了此目的和此处未提及但对本领域技术人员显而易见的其它目的。本发明电解液的优选配置描述于从属于权利要求1的子权利要求中。权利要求4-9涉及一种根据本发明的用于沉积银-铋合金的方法。权利要求10和11分别涉及沉积层和层序列。
电镀液是电化学金属沉淀物(涂层)可从其沉积到基底(物体)上的包含金属盐的溶液。这类电镀液也通常称为“电解液”。因此,水性电镀液在下文中被称为“电解液”。
通过提供一种用于将银-铋合金电解沉积在导电基材上的水性电解液,获得了所述问题的解决方案,该电解液具有以下特征:
-基于金属为0.5g/l-200g/l的银化合物或包含银的可溶性阳极;
-基于金属为0.1g/l-50g/l的可溶性铋化合物;
-5g/l-200g/l的可溶性氰化物,特别是氰化钾;
-0.05mol/l-2mol/l的可溶性二羧酸、三羧酸或四羧酸;
->0g/l-5g/l的可溶性光亮剂A,其为酮或二硫代氨基甲酸酯与二硫化碳的反应产物;
->0g/l-5g/l的另一可溶性光亮剂B,其选自芳基磺酸与甲醛的缩合产物;
-1mg/l-1000mg/l的可溶性润湿剂;以及
-10-14的pH值。在此描述的银-铋电解液已经证明是非常稳定的。与锑(lll)相比,存在的铋(lll)经受显著更少的氧化。当沉积银-铋涂层时,获得了在永久硬度和电特性方面的上述优点。令人惊讶地,这些涂层具有非常高且温度稳定的硬度值,在初始状态下达到最高250HV的值,并且甚至在于150℃老化1000小时后仍超过200HV。相比之下,在文献中仅描述了在沉积状态下80HV至180HV的硬度值。当在本文中提及HV时,这是指维氏硬度(DINEN ISO 14577-1-申请日的最新版本)。
根据本发明的电解液中的银通过相应可溶性银盐提供。其优选地选自甲磺酸银、碳酸银、磷酸银、焦磷酸银、硝酸银、氧化银、乳酸银、氟化银、溴化银、氯化银、碘化银、硫氰酸银、硫代硫酸银、乙内酰脲银、硫酸银、氰化银和碱性氰化银。氰化银钾是非常优选的。本领域技术人员可针对其应用目的具体选择银的量。通常,银浓度基于金属为0.5g/l-200g/l。在优选的实施方案中,该值为1g/l-100g/l,并且特别优选10g/l-50g/l。另选地或另外地,银还可以以包含银的可溶性阳极的形式进入电解液中(Praktische Galvanotechnik,第5版,Eugen G.Leuze Verlag,p.342f,1997)。
根据本发明的电解液中的第二合金金属是铋。这同样可以通过本领域技术人员已知的化合物添加到电解液中。铋优选以(III)氧化态存在。在本文中有利的化合物是选自氧化铋(III)、氢氧化铋(III)、氟化铋(III)、氯化铋(III)、溴化铋(III)、碘化铋(III)、甲磺酸铋(III)、硝酸铋(III)、酒石酸铋(III)、柠檬酸铋(III),特别是柠檬酸铋铵的那些。金属的量可由本领域技术人员选择,但基于金属通常为0.1g/l-50g/l。在优选的实施方案中,该值为0.5g/l-10g/l,并且特别优选1g/l-5g/l。
游离氰化物也存在于根据本发明的电解液中。其以可溶性化合物的形式使用。本领域技术人员知道哪些化合物适于本发明的目的。在这种情况下优选使用氰化钠或特别是氰化钾。这也用作导电盐。其用量为5g/l-200g/l,优选10g/l-100g/l,并且非常优选20g/l-80g/l。
电解液含有某些具有一个或多个羧酸基团的有机化合物。具体地,这些有机化合物是二羧酸、三羧酸或四羧酸。它们为本领域技术人员熟知用于本发明目的,并且可以例如在文献(Beyer-Walter,Lehrbuch der Organ-ischen Chemie,第22版,S.Hirzel-Verlag,第324页及后续页)中找到。在本文中特别优选的是选自由以下组成的组的酸:草酸、柠檬酸、酒石酸、琥珀酸、马来酸、戊二酸、己二酸、丙二酸、苹果酸。草酸、丙二酸、柠檬酸和酒石酸是高度优选的。这些酸在待设定的pH值下以其阴离子形式天然存在于电解液中。这里提到的羧酸以0.05mol/l-2mol/l,优选0.1mol/l-1mol/l以及非常特别优选0.2mol/l-0.5mol/l的浓度添加到电解液中。
二硫化碳和酮或二硫代氨基甲酸酯的反应产物用作本发明电解液中的光亮剂A。本领域技术人员知道可在此使用的产物。其例如描述于专利DE885036C、DE2731595B1或DE959775C中。优选用于本发明的酮是选自丙酮、2-丁酮、2-戊酮、3-戊酮、2,3-己二酮、2,4-己二酮、2,5-己二酮、3,4-己二酮、2-庚酮、3-庚酮、4-庚酮、2,3-庚二酮、2,4-庚二酮、2,5-庚二酮、2,4-庚二酮、3,5-庚二酮、2,6-庚二酮、苯乙酮的那些。优选使用的二硫代氨基甲酸酯是选自碱金属二乙基二硫代氨基甲酸酯、碱金属二苯基二硫代氨基甲酸酯的那些。
这些反应产物在电解液中的用量为>0mg/l-5000mg/l,优选1mg/l-500mg/l,并且特别优选5mg/l-200mg/l。
同样用于电解液中的光亮剂B是一种或多种芳基磺酸和甲醛的缩合产物。此聚合重整是本领域技术人员已知的。例如,在DE2731595B1中,其与酮和二硫化碳的上述缩合产物一起用于银沉积中。在本文中特别优选使用1-萘磺酸和2-萘磺酸。然而,其它芳基磺酸也可用于此目的并且在本领域技术人员的能力范围内,例如酚磺酸、苯磺酸、1,2-苯二磺酸、1,3-苯二磺酸、1,4-苯二磺酸、1,5-萘二磺酸、吡啶-3-磺酸。该光亮剂B在根据本发明的电解液中以>0mg/l-5000mg/l,更优选5mg/l-2500mg/l,并且非常优选100mg/l-1000mg/l的浓度使用。
在本发明的电解液中,取决于应用,还通常可以使用阴离子和非离子表面活性剂作为润湿剂,例如聚乙二醇加合物、脂肪醇硫酸盐、烷基硫酸盐、烷基磺酸盐、芳基磺酸盐、烷基芳基磺酸盐、杂芳基硫酸盐、甜菜碱、含氟表面活性剂及其盐和衍生物(也参见:Kanani,N:Galvanotechnik;Hanser Verlag,Munich Vienna,2000;第84页及后续页)。润湿剂还可以是例如取代的甘氨酸衍生物,其在商业上被称为 由N-酰基肌氨酸盐组成,即脂肪酸酰基残基和N-甲基甘氨酸(肌氨酸)的缩合产物。用这些浴沉积的银涂层是白色且有光泽至高度有光泽的。润湿剂导致无孔层。其它有利的润湿剂是选自下组的那些:
-非离子润湿剂,例如β-萘酚乙氧基化物钾盐、脂肪醇聚乙二醇醚、聚乙烯亚胺、聚乙二醇、以及它们的混合物。分子量低于2,000g/mol的润湿剂是特别有利的。
-阴离子润湿剂,例如N-十二酰基-N-甲基甘氨酸、(N-月桂酰基肌氨酸)-Na盐、烷基胶原水解物、2-乙基己基硫酸-Na盐、月桂基醚硫酸-Na盐、1-萘磺酸-Na盐、1,5-萘二磺酸-Na盐、以及它们的混合物,
-阳离子润湿剂,例如1H-咪唑鎓-1-乙烯基(或3-甲基)-,甲基硫酸盐均聚物。
根据本发明的电解液在碱性pH范围内使用。最佳结果可在电解液中以10-14的pH值获得。本领域的技术人员将知道可如何调节电解液的pH值。这优选在强碱性范围内,更优选>11。高度有利的是选择极其强碱性的沉积条件,其中pH值高于12并且在例外情况下甚至可以达到13或甚至14。
原则上,pH值可以根据本领域技术人员的需要进行调节。然而,本领域技术人员将遵循的观念是将尽可能少的附加物质引入电解液中,所述附加物质可不利地影响所考虑合金的沉积。因此,在特别优选的实施方案中,仅通过添加碱来设定pH值。本领域技术人员可以将适于相应应用的所有化合物用作碱。优选地,他们将为此目的而使用碱金属氢氧化物,特别是氢氧化钾。
本发明的另一主题是一种用于从刚刚描述的电解液电解沉积银合金涂层的方法。在该方法中,将导电基材浸没在根据本发明的电解液中并且在与所述电解液接触的阳极和作为阴极的所述基材之间建立电流。
银和银合金涂层沉积期间的主要温度可根据本领域的技术人员所期望的那样进行选择。他们将受到的指导一方面是足够的沉积速率和可用的电流密度范围,另一方面是成本方面或电解液的稳定性。有利的是将温度设定为20℃至90℃,优选25℃至65℃,并且特别优选30℃至50℃。
在沉积过程中,在阴极和阳极之间的电解液中建立的电流密度可由本领域的技术人员根据沉积效率和质量进行选择。根据应用和涂覆设备类型,电解液中的电流密度有利地设定为0.2至150A/dm2。如果需要,可以通过调节系统参数,例如涂覆单元的设计、流速、阳极或阴极关系等来增加或减少电流密度。0.2A/dm2-100A/dm2的电流密度是有利的,0.2A/dm2-50A/dm2是优选的,并且0.5A/dm2-30A/dm2是特别优选的。
在本发明的上下文中,低、中等和高电流密度范围定义如下:
-低电流密度范围:0.1A/dm2至0.75A/dm2,
-中等电流密度范围:大于0.75A/dm2至5A/dm2,
-高电流密度范围:大于5A/dm2。
根据本发明的电解液和根据本发明的方法可以用于银-铋涂层的电解沉积,所述银-铋涂层用于技术应用,例如电插头连接器和印刷电路板,以及用于装饰应用,例如珠宝和手表。
如上文已指出的那样,根据本发明的电解液是碱性类型。在电解期间可能发生关于电解液的pH值的波动。在本方法的一个优选实施方案中,本领域的技术人员将因此继续进行,使得他们在电解期间监测pH值,并且必要时将其调节至设定值。氢氧化钾有利地用于设定pH值。
可在使用电解质时采用各种阳极。可溶性阳极或不溶性阳极正好与可溶性阳极和不溶性阳极的组合一样适合。如果使用可溶性阳极,则特别优选使用银阳极或银铋阳极或铋阳极(DE1228887,Praktische Galvanotechnik,第5版,Eugen G.Leuze Verlag,p.342f,1997)。
作为不溶性阳极优选的是由选自由镀铂钛、石墨、混合的金属氧化物、玻璃碳阳极和特定碳材料(“类金刚石碳(Diamond-Like Carbon)”DLC)的材料制成的不溶性阳极或这些阳极的组合。铂化钛或涂覆有混合金属氧化物的钛的不溶性阳极是有利的,其中混合金属氧化物优选地选自氧化铱、氧化钌、氧化钽以及它们的混合物。由铱-钌混合氧化物、铱-钌-钛混合氧化物或铱-钽混合氧化物组成的铱-过渡金属混合氧化物阳极也有利地用于实施本发明。更多信息可见于Cobley,A.J.等人(The use of insoluble anodes in acidsulphate copper electrodeposition solutions,Trans IMF,2001,79(3),第113页和第114页)。
通常,将0.1μm至0.3μm范围内的薄层厚度的银,例如,用于在台架操作中涂覆塑料盖。在此使用0.25μm至0.75A/dm2范围内的低电流密度。低电流密度的另一应用是用在滚筒技术或振动技术中,例如在接触销的涂层中。在此,在0.25A/dm2至0.75A/dm2的电流密度范围内施加约0.5μm至3μm的银合金。1μm至10μm范围内的层厚度通常在用于技术和装饰应用的台架操作中沉积,其中电流密度在1A/dm2至5A/dm2的范围内。对于技术应用,有时也沉积最高达25μm的层厚度。在连续系统中,在约0.5μm至约5μm的相对较大范围内的层厚度以最高可能的沉积速率沉积,并因此以5A/dm2至50A/dm2的最高可能的电流密度沉积。另外,还有特殊的应用,例如在电铸的情况下,沉积的层厚度相对较高,从几十μm直到几毫米。
也可以施加脉冲直流电流来代替直流电流。由此,电流被中断一段时间(脉冲电镀)。在反向脉冲电镀中,电极的极性被切换,使得涂层被阳极地部分分离。通过不断交替所述阳极脱离与阴极脉冲,从而控制层的堆起。在平均电流密度下施加简单的脉冲条件,例如1s电流(ton)和0.5s脉冲暂停(toff),产生均匀、有光泽且白色的涂层。
本发明还涉及一种通过根据本发明的方法产生的银-铋合金层,该银-铋合金层具有0.1μm-50μm的厚度并且在涂层在于150℃退火1000h后具有>200HV的硬度。硬度的上限在于金属层的技术上可获得的硬度。它可以是350HV或更优选甚至400HV(图1)。根据本发明的层的优选厚度在上述范围内,优选0.5μm-30μm,并且非常优选1μm-5μm。
优选地,根据本发明的合金层沉积在镍或镍合金层或者铜或铜合金层上。在此有利地使用的合适的基材材料是铜基材料如纯铜、黄铜、青铜(例如,CuSn、CuSnZn)或用于插头连接器的特种铜合金如与硅、铍、碲、磷的合金,或铁基材料如铁或不锈钢或者镍或镍合金如NiP、NiW、NiB、金或银。基材材料还可以是已经电镀涂覆或使用其他涂覆技术涂覆的多层系统。这包括例如已经镀镍或镀铜并且然后任选地镀金或涂覆有预银的含铁材料。另一种基材材料是用银导电漆预涂覆的蜡芯(电铸)。
本发明的电解液提供了一种有光泽的沉积物,从而给出了银色的印象。沉积的合金金属层有利地具有超过+97的L*值。根据Cielab色系(EN ISO 11664-4-申请日的最新版本),a*值优选地为-0.2至0.2,并且b*值介于+2和+4之间。这些值用Konica Minolta CM-700d来测定。
根据本发明的电解液具有长期稳定性。通过将针对银沉积和银与铋合金化描述的光亮剂组合,可以获得适于所描述应用的涂层。其具有足够低的接触电阻,此外,甚至在暴露于热后仍保持令人惊讶的高硬度。这在现有技术中是不可预料的。
实施例:
将1升的相应示例性实施方案中指定的电解液通过磁力搅拌器加热至示例性实施方案中指定的温度,同时用60mm长的圆柱形磁力搅拌棒以至少200rpm搅拌。在涂覆期间还保持这种搅拌和温度。
在达到期望的温度之后,使用KOH溶液(c=0.5g/ml)和合适的酸诸如硫酸(c=25%)将电解液的pH值设定为在示例性实施方案中指定的值。
使用银板或混合金属氧化物涂覆的钛作为阳极。
将表面积至少为0.2dm2的机械抛光的黄铜板用作阴极。这可以预先用至少5μm的来自电解液的镍进行涂覆,这产生高光泽层。也可以在镍层上沉积约0.1μm厚的金层。
在引入到电解液中之前,借助于电解脱脂(5-7V)和含硫酸(c=5%硫酸)的酸浸来清洁这些阴极。在每个清洁步骤之间和在引入电解液之前,用去离子水冲洗阴极。
阴极定位在电解液中,位于阳极之间,并以至少5cm/s平行于其移动。阳极和阴极之间的距离不应改变。
在电解液中,通过在阳极与阴极之间施加直流电流来涂覆阴极。电流密度被选择成使得在表面区域上实现至少0.5A/dm2。如果在应用实施例中指定的电解液旨在产生可用于技术和装饰目的的层,则可选择更高的电流密度。
电流的持续时间被选择成使得在表面区域上平均地实现对于至少0.5μm至1μm的层厚。如果在应用实施例中指定的电解液旨在产生可以用于技术和装饰目的的质量的层,则可以产生更高的层厚度。
涂覆后,将阴极从电解液中取出并用去离子水冲洗。阴极的干燥可通过压缩空气、热空气或离心来进行。
记录阴极的表面区域、施加电流的水平和持续时间以及涂覆之前和之后阴极的重量,并将其用于确定平均层厚度以及沉积的效率。
表1.示例性实施方案
a)根据DE2731595,2-丁酮与二硫化碳的反应产物
b)根据DE2731595,2,5-己二酮与二硫化碳的反应产物
c)根据DE959775,苯基二硫代氨基甲酸钾与二硫化碳的反应产物
d)根据DE2731595,萘磺酸-甲醛缩合产物
将由根据实施例编号3(表1)的电解液获得的涂层于150℃老化100小时和500小时,然后测定硬度值。结果在图1中示出。
Claims (11)
1.一种用于将银-铋合金电解沉积到导电基材上的水性电解液,所述电解液具有以下特征:
-基于金属为0.5g/l-200g/l的银化合物或包含银的可溶性阳极;
-基于金属为0.1g/l-50g/l的可溶性铋化合物;
-5g/l-200g/l的可溶性氰化物,特别是氰化钾;
-0.05mol/l-2mol/l的可溶性二羧酸、三羧酸或四羧酸;
->0g/l-5g/l的可溶性光亮剂A,其为酮或二硫代氨基甲酸酯与二硫化碳的反应产物;
->0g/l-5g/l的另一可溶性光亮剂B,其选自芳基磺酸与甲醛的缩合产物;
-1mg/l-1000mg/l的可溶性润湿剂;以及
-10-14的pH。
2.根据权利要求1所述的电解液,
其特征在于,
所述银化合物选自甲磺酸银、碳酸银、磷酸银、焦磷酸银、硝酸银、氧化银、乳酸银、氟化银、溴化银、氯化银、碘化银、硫氰酸银、硫代硫酸银、乙内酰脲银、硫酸银、氰化银和碱性氰化银。
3.根据权利要求1或2所述的电解液,
其特征在于,
所述铋化合物选自氧化铋(III)、氢氧化铋(III)、氟化铋(III)、氯化铋(III)、溴化铋(III)、碘化铋(III)、甲磺酸铋(III)、硝酸铋(III)、酒石酸铋(III)、柠檬酸铋(III),特别是柠檬酸铋铵。
4.一种用于从根据权利要求1至3所述的电解液电解沉积银和银合金涂层的方法,
其特征在于,
将导电基材浸没在所述电解液中并且在与所述电解液接触的阳极和作为阴极的所述基材之间建立电流。
5.根据权利要求4所述的方法,
其特征在于,
所述电解液的温度为20℃至90℃。
6.根据权利要求4至5中任一项所述的方法,
其特征在于,
电解期间的电流密度为0.2A/dm2至150A/dm2。
7.根据权利要求4至6中任一项所述的方法,
其特征在于,
将电解期间的pH值连续设定为在10和14之间的范围。
8.根据权利要求4至7中任一项所述的方法,
其特征在于,
沉积银-铋涂层,所述银-铋涂层具有0.1-50μm的厚度。
9.根据权利要求4至8中任一项所述的方法,
其特征在于,
将可溶性银阳极和/或不溶性阳极用作所述阳极。
10.一种根据权利要求4至9中任一项产生的银-铋合金层,所述银-铋合金层具有0.1μm-50μm的厚度并且在所述涂层于150℃退火1000h后具有>200HV的硬度。
11.根据权利要求10所述的合金层,
其特征在于,
将所述合金层沉积在镍或镍合金层或者铜或铜合金层上。
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EP (1) | EP4259856A1 (zh) |
JP (1) | JP2023553958A (zh) |
KR (1) | KR20230121097A (zh) |
CN (1) | CN116601338A (zh) |
DE (1) | DE102020133188A1 (zh) |
WO (1) | WO2022122989A1 (zh) |
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JP7490134B1 (ja) | 2023-11-30 | 2024-05-24 | 松田産業株式会社 | 銀めっき皮膜及び該銀めっき皮膜を備えた電気接点 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
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NL77004C (zh) | 1950-09-15 | |||
DE959775C (de) | 1954-09-18 | 1957-03-14 | Max Schloetter Fa Dr Ing | Cyankalisches Bad zur galvanischen Abscheidung glaenzender Silberniederschlaege |
DE1182014B (de) | 1960-04-12 | 1964-11-19 | Riedel & Co | Bad zum galvanischen Abscheiden von Silber-Antimon- oder Silber-Wismut-Legierungen hoher Haerte |
NL267282A (zh) * | 1960-04-12 | |||
DE1228887B (de) | 1961-10-26 | 1966-11-17 | Riedel & Co | Verfahren zum galvanischen Abscheiden von Silber-Antimon- oder Silber-Wismut-Legierungen hoher Haerte |
DE2731595C3 (de) | 1977-07-13 | 1984-06-28 | G. P. - Chemie GmbH, 5650 Solingen | Verwendung einer Glanzzusatz-Kombination in cyanidischen Silberbädern |
US7628903B1 (en) | 2000-05-02 | 2009-12-08 | Ishihara Chemical Co., Ltd. | Silver and silver alloy plating bath |
DE102018120357A1 (de) * | 2018-08-21 | 2020-02-27 | Umicore Galvanotechnik Gmbh | Elektrolyt zur Abscheidung von Silber und Silberlegierungsüberzügen |
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2020
- 2020-12-11 DE DE102020133188.6A patent/DE102020133188A1/de active Granted
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2021
- 2021-12-10 WO PCT/EP2021/085127 patent/WO2022122989A1/de active Application Filing
- 2021-12-10 EP EP21836441.2A patent/EP4259856A1/de active Pending
- 2021-12-10 KR KR1020237023357A patent/KR20230121097A/ko unknown
- 2021-12-10 CN CN202180082618.5A patent/CN116601338A/zh active Pending
- 2021-12-10 US US18/256,321 patent/US20240035184A1/en active Pending
- 2021-12-10 JP JP2023535548A patent/JP2023553958A/ja active Pending
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KR20230121097A (ko) | 2023-08-17 |
EP4259856A1 (de) | 2023-10-18 |
US20240035184A1 (en) | 2024-02-01 |
JP2023553958A (ja) | 2023-12-26 |
WO2022122989A1 (de) | 2022-06-16 |
DE102020133188A1 (de) | 2022-06-15 |
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