CN113818053A - 含三价铬的电镀槽液和沉积铬的方法 - Google Patents
含三价铬的电镀槽液和沉积铬的方法 Download PDFInfo
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- CN113818053A CN113818053A CN202111217662.0A CN202111217662A CN113818053A CN 113818053 A CN113818053 A CN 113818053A CN 202111217662 A CN202111217662 A CN 202111217662A CN 113818053 A CN113818053 A CN 113818053A
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- China
- Prior art keywords
- chromium
- plating bath
- acid
- iii
- complexing agent
- Prior art date
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- 239000011651 chromium Substances 0.000 title claims abstract description 45
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 44
- 238000009713 electroplating Methods 0.000 title claims abstract description 31
- 238000000151 deposition Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000008139 complexing agent Substances 0.000 claims abstract description 19
- -1 halogen salt Chemical class 0.000 claims abstract description 19
- 150000001844 chromium Chemical class 0.000 claims abstract description 18
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 7
- 238000007747 plating Methods 0.000 claims description 45
- 239000012528 membrane Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 9
- 239000011696 chromium(III) sulphate Substances 0.000 claims description 9
- 235000015217 chromium(III) sulphate Nutrition 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 8
- 229910000356 chromium(III) sulfate Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 5
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 4
- 239000000080 wetting agent Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 3
- QYHKPQCMTYXLIA-UHFFFAOYSA-K chromium(3+);2-hydroxyacetate Chemical compound [Cr+3].OCC([O-])=O.OCC([O-])=O.OCC([O-])=O QYHKPQCMTYXLIA-UHFFFAOYSA-K 0.000 claims description 3
- 239000011636 chromium(III) chloride Substances 0.000 claims description 3
- 235000007831 chromium(III) chloride Nutrition 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 229910000599 Cr alloy Inorganic materials 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 claims description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 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
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002280 amphoteric surfactant Substances 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 235000003704 aspartic acid Nutrition 0.000 claims description 2
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- 239000000788 chromium alloy Substances 0.000 claims description 2
- MURRHPKQJKICNT-UHFFFAOYSA-K chromium(3+) methanesulfonate Chemical compound [Cr+3].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O MURRHPKQJKICNT-UHFFFAOYSA-K 0.000 claims description 2
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 2
- QOWZHEWZFLTYQP-UHFFFAOYSA-K chromium(3+);triformate Chemical compound [Cr+3].[O-]C=O.[O-]C=O.[O-]C=O QOWZHEWZFLTYQP-UHFFFAOYSA-K 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 2
- 150000003464 sulfur compounds Chemical class 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 150000001734 carboxylic acid salts Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- DSHWASKZZBZKOE-UHFFFAOYSA-K chromium(3+);hydroxide;sulfate Chemical compound [OH-].[Cr+3].[O-]S([O-])(=O)=O DSHWASKZZBZKOE-UHFFFAOYSA-K 0.000 claims 1
- XHFVDZNDZCNTLT-UHFFFAOYSA-H chromium(3+);tricarbonate Chemical compound [Cr+3].[Cr+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O XHFVDZNDZCNTLT-UHFFFAOYSA-H 0.000 claims 1
- 230000002087 whitening effect Effects 0.000 claims 1
- 239000000243 solution Substances 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 7
- 238000004070 electrodeposition Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 6
- 238000005341 cation exchange Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910021653 sulphate ion Inorganic materials 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
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- 238000000576 coating method Methods 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
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- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
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- 229920000557 Nafion® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- YJZATOSJMRIRIW-UHFFFAOYSA-N [Ir]=O Chemical class [Ir]=O YJZATOSJMRIRIW-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
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- FXNGWBDIVIGISM-UHFFFAOYSA-N methylidynechromium Chemical compound [Cr]#[C] FXNGWBDIVIGISM-UHFFFAOYSA-N 0.000 description 1
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- 150000007522 mineralic acids Chemical class 0.000 description 1
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- MKWYFZFMAMBPQK-UHFFFAOYSA-J sodium feredetate Chemical compound [Na+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O MKWYFZFMAMBPQK-UHFFFAOYSA-J 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
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- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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Images
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
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
-
- 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
- C25D17/002—Cell separation, e.g. membranes, diaphragms
-
- 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
- C25D17/02—Tanks; Installations therefor
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及到一种用于沉积铬的电镀槽液，所述电镀槽液包括至少一种三价铬盐、至少一种络合剂、至少一种卤素盐和任选的额外添加剂。另外，本发明还涉及到用所述电镀槽液在基材上沉积铬的方法。
Description
本申请是申请号为201580004384.7，申请日为2015年1月26日，发明名称为“含三价铬的电镀槽液和沉积铬的方法”的发明专利申请的分案申请。
本发明涉及一种用于沉积铬的电镀槽液，所述电镀槽液包括至少一种三价铬盐，至少一种络合剂，至少一种卤素盐和任选的其它的添加剂。另外，本发明涉及用所述电镀槽液在基材上沉积铬的方法。
多年前就已知，可以用三价镀铬槽液进行三价镀铬，在现有技术中，许多文件提到了，用三价镀铬槽液能够形成铬沉积物。
目前已经非常确定，可以用三价铬电解液来制备厚度0.1-1μm的铬均一镀层。这些厚度对于所谓的装饰性应用非常合适。
然而，还有很多应用，在这些应用中需要更厚的铬层，即高耐磨和/或抗腐蚀性的应用，例如卫生设施上的镀铬、外部的汽车零件的镀铬，而且还有用于在杆、活塞或起落架组件进行电镀的功能性应用。这些应用所需要的厚度在0.1-300μm之间。
US 4,804,446描述了一种电沉积形成坚硬的光滑的铬层的方法。所述槽液包括：作为铬源的氯化铬(III)、用于络合铬的柠檬酸、以及润湿剂(优选Triton X100)。还被添加溴化物，以防止在阳极产生六价铬。所述槽液的pH维持在4.0，温度大约在35℃。另外，电解液还包含用于提高反应动力学的硼酸。然而，由于硼酸具有毒性和潜在的危险性，避免其存在于电镀池中将是有利的。
WO 2009/046181公开了纳米颗粒的晶态的或无定形的功能化铬合金的沉积物，所述沉积物获自三价铬槽液，其中所述槽液含有羧酸并包含二价硫源以及碳源、氮源和氧源，它们是用于形成合金的组分。所述沉积物包含0.05-20wt％的硫，用于电镀这些沉积物的所述电镀槽液包含在大约0.0001M到0.05M的浓度范围的二价硫源。
US2013/0220819描述了一种用三价铬电镀槽液生产致密坚硬的铬层的方法。所述镀层的显微硬度值在804KHN-1067KHN之间。这些性能是通过使用一种三价铬电解液和采用特定周期的波形的脉冲镀法而得到的。必须指出的是，为了在复杂的和大表面积的部件上电镀坚硬的铬而使用脉冲电流，需要对电镀设备进行某些重大的改动。然而，不使用脉冲电流来沉积所述的厚的铬层将是有利的。
一些出版物描述了，对于硬铬的应用场合，使用脉冲以及脉冲反向电流及其效果。
出版物:脉冲和脉冲反向电镀－概念、优势和应用(Pulse and pulse reverseplating-Conceptual,advantages and applications),M.S.Chandrasekar,MalathyPushpavanam中央电化学研究院,Karaikudi 630006,TN,India Electrochimica Acta 53(2008)3313-3322，是关于脉冲和脉冲反向电镀技术应用于电沉积的综述，其中报道了某些金属和合金的脉冲电沉积(PED)。提出了质量传递、双电层脉冲参数和电流分布对于表面粗糙度和形态的影响。脉冲电流PC和脉冲反向电流PRC技术的应用、优势和劣势，结合理论部分和机理一起进行了讨论。
在出版物“用脉冲电沉积提高从铬(III)电镀槽液得到的纳米晶体铬-碳膜的硬度和摩擦特性”(Improving hardness and tribological characteristics ofnanocrystalline Cr-C films obtained from Cr(III)plating bath using pulsedelectrodeposition),Int.Journal of Refractory Metals and Hard Materials 31(2012)281-283中，对于获自三价铬槽液的Cr－C沉积物，研究了脉冲电沉积对纳米晶尺寸、成分、硬度、摩擦系数、和耐磨性的影响。已表明，所述电沉积含有约9％的碳。脉冲电沉积没有明显地影响碳含量。同时，脉冲关闭时段(off-time duration)的增加会导致了纳米晶尺寸的下降。当使用脉冲电流时，所述电沉积物的硬度和磨损参数会充分提高。例如，在ton＝toff＝1s时，硬度达到了约1200÷1300HV(而在稳态电解下，硬度接近于850÷950HV)。
虽然有一些关于三价铬沉积的出版物，但仍需要一种商用体系，该体系能够电镀厚度为0.1-300μm的均一厚度的铬沉积物，其致密均匀，表现出与基于CrO3的电解液所制备的沉积物相当的耐腐蚀性、硬度和耐磨性。
因此本发明的目的是提供一种电镀槽液，所述电镀槽液可提供具有致密、和均一厚度结构的铬镀层，从而使所述镀层具有高耐磨和/或高耐腐蚀性。
该目的已经通过具有权利要求1的特征的电镀槽液和具有权利要求24的特征的沉积铬层的方法而被解决。
根据本发明，提供了一种用于沉积铬的电镀槽液，它包含以下部分：
a)50-400g/L(即0.164M-1.314M)，较佳地为100-400g/L(即0.328M-1.314M)的至少一种三价铬盐
b)100-400g/L(2.17M-8.68M)的至少一种络合剂，
c)1-50g/L(0.0085M-0.425M)的至少一种卤素盐,
d)0-10g/L的添加剂,
另外，所述电镀槽液的pH值为4-7。对本发明至关重要的是，电镀槽液基本不含二价硫化合物和硼酸和/或其盐及衍生物。
已出乎意料地发现，采用本发明的电镀槽液，可以提供具有致密的均一结构的镀层。因为提供的层具有10-400μm的厚度，因此可用于高耐磨和/或高耐腐蚀的应用场合。
所述三价铬盐优选地选自下组：硫酸铬(III)(酸式或碱式)、氯化铬(III)、乙酸铬(III)、羟基乙酸铬(III)、甲酸铬(III)、羟基甲酸铬(III)、碳酸铬(III)、甲磺酸铬(III)、硫酸钾铬(III)、及其混合物。
较佳地，三价铬盐的含量为100-400g/L(优选为100-300g/L，即0.328M-0.984M)，更佳地为120-160g/L(即0.3936M-0.5248M)。
与现有技术中所描述的电解液相关的一个主要缺点，涉及到三价铬盐的抗衡离子的累积。在这样的电镀槽液中，铬(III)的消耗会非常高，特别是如果所需厚度为>10μm的上限范围。与三价铬阳离子有关的抗衡离子将会在电解液中积聚，造成一些缺点，例如增加槽液的密度和沉淀的风险。槽液的干组分含量可上升到某一限制点，此时因为溶解度的限制已不可能进一步溶解三价铬盐。
因此，本发明的一个优选实例是选择三价铬盐的抗衡离子，它包括一种“临时性的”即电解可消耗的阴离子，所述阴离子不会同“永久性的”阴离子(例如硫酸根)一样积聚在电解液中。在这些暂时性的阴离子中，优选的是甲酸根、乙酸根、丙酸根、羟基乙酸根、草酸根、碳酸根、柠檬酸根、及其组合。
本发明的电镀槽液优选含有合金形成物，所述合金形成物选自下组：钒、锰、铁、钴、镍、钼、钨和铟。所述槽液的有机组分和氨是在沉积过程中被合金所吸纳的碳、氮和氧的来源。尿素作为添加剂也是特别有效的。优选地，所述电镀槽液包括氨，特别是其的摩尔浓度小于或等于至少一种络合剂的摩尔浓度。最佳地，氨的浓度为70g/L-100g/L。
不在合金中共沉积的金属(例如铝和/或镓)的盐，其存在也是有利的，因为可以在槽液中与铬形成混合金属的复合物，所述复合物会影响沉积的动力学和机理。然而，所述电镀槽液也可能不含所述的金属的盐(例如没有铝盐)。
根据本发明，所述络合剂较佳地选自下组：包括羧酸和羧酸盐，优选甲酸、乙酸、丙酸、羟基乙酸、乳酸、草酸、苹果酸、柠檬酸、酒石酸、琥珀酸、葡糖酸、甘氨酸、天冬氨酸、谷氨酸、及其混合物，或其盐及其混合物。
所述络合剂的含量，较佳地为100-300g/L(2.17M-6.61M)，更佳地为150-250g/L(3.26M-5.51M)。络合剂与三价铬盐的摩尔比为8:1-15:1，优选地是10:1-13:1，，这使得槽液在所述的pH的范围内工作，并且保证沉积的是铬，而不是亚铬酸盐。
存在于所述的电镀槽液中的所述卤素盐，作为在槽液中抑制六价铬产生的抑制剂。所述卤素盐较佳地选自下组：溴化物、氯化物、碘化物、氟化物盐及其混合物。所述溴化盐是更优选的，特别是溴化钾、溴化钠、溴化铵及其混合物。所述卤素盐优选以5-50g/L(即0.0425M-0.425M)的量存在。
所述电镀槽液的添加剂可选自下组：增白剂，例如聚氨或聚氨的混合物，包括季铵化合物(它们是优选的用于这种应用的增白剂，例如在专利US 7964083中引用的种类)，和润湿剂，如电中性的、阳离子型和两性的表面活性剂。
特别优选的是，所述的电镀槽液是(基本上)不含氯离子和/或(基本上)不含铝离子，但是所述槽液可含有氟化物，其作为至少一种额外的络合剂(配体)和/或作为至少一种额外的卤素盐，在槽液中协助铬(III)复合物的配体交换。
根据本发明，还提供了一种在基材上沉积铬的方法，包括以下步骤：
·提供上述的电镀槽液
·将一基材浸入所述电镀槽液；和
·施加电流，使得铬沉积在所述基材上。
在沉积中的温度，优选为20-60℃，更优选为30-50℃。
可以用膜，将所述电镀槽液与阳极分开，优选阳离子型或阴离子型交换膜或多孔膜，更优选的是阳离子交换膜。阳离子交换膜的优点是可抑制阴极电解液中的硫酸根的迁移。
用于执行沉积的阳极由不溶性的材料制成，如石墨或混合氧化物材料，例如包覆钽和铱的氧化物的钛。
在本发明的一种具体实例中，所述阳极可以被合适的材料所包围，从而界定阳极电解液和阴极电解液，以便防止电镀槽液中某些组分接触阳极，以及便于对不利的氧化分解产物加以限制。
不利种类可以是例如来自于阳极的Cr(III)氧化的铬(VI)，也可以是在阳极处络合剂的氧化产物。
与使用屏蔽材料将阳极区与槽池隔开有关的另一种好处，是避免了一些物质的累积，而这些物质是非电沉积的并且会累积在阴极电解液中，例如硫酸盐，比如在补充硫酸盐的时候。
所述屏蔽材料可以是选自离子交换膜类的任意材料。它们可以是阴离子交换膜，例如Sybron IONAC材料MA3470。也可以使用阳离子交换膜，例如杜邦的全氟磺酸膜(Nafionmembrane)。一种优选的阳离子交换膜是N424膜。另外，多孔膜，如EP1702090中所述的多孔膜，可以作为合适的材料来界定阳极室，以便将阳极室与其他的电解液分隔开。
所述阳极室可以填充有任何与电解液相兼容的导电物质。它可以是酸性的或碱性的。由于母阴极电解液的弱酸性pH，阳极电解液也优选酸性的。不仅甲酸、乙酸、丙酸、羟基乙酸、柠檬酸，而且无机酸如H2SO4、H3PO4也可以使用。硫酸铬(III)的液体溶液也可以用作阳极电解液。或者，氢氧化钠、氢氧化钾、氢氧化锂或任何种类的没有CMR特性的碱性溶液，都可以在本发明的方法中用作阳极电解液。
施加于电解液的电流可以是直流电或者是脉冲电流。使用脉冲电流序列，提供了一种电镀沉积物的能力，由于氢积聚在界面，因此所述沉积物对裂缝的形成较不敏感。
所述脉冲序列可以由阳极相以及一种T断开(T off)相构成，以便帮助从界面去除氢，或者最后可以施加阳极相，以便氧化界面上的氢。
本发明还通过以下附图和实施例进行阐述。然而，本发明不限于这些具体的实施例。
图1显示了本发明的一种实例中阳极的设置的示意图。
图2显示了用于说明不同的电镀系统的硫酸盐浓度的编号的图表。
如图1中所示的本发明实施例1，使用了阳极电解液7，其作为铬(III)离子的储存液。在图1中，三价铬盐(例如硫酸铬或任何其他铬盐)的溶液,被用作电镀槽液7的成分，其中所述溶液含有10-50g/L的三价铬和30-140g/L的硫酸根离子或其他阴离子。离子交换膜3可以包含于或结合于载体2，并且优先选择阳离子交换膜，如上面提到的全氟磺酸膜N424。所述阴极电解液5由本发明的三价铬电解液组成，如下面实施例2中描述。阳极6由石墨材料制成。待电镀的样本工件被放置，作为阴极4。以硫酸铬(III)的形式补充铬盐，是在阳极电解液中进行。
在图2中，图表说明了在不同电解液系统中硫酸盐浓度与时间的相关性。尽管基于硫酸铬(III)的槽液的电镀系统且在没有膜的情况下，硫酸盐浓度迅速增加，但是在本发明使用“临时性的”阴离子的第一个实例中的浓度和在本发明使用膜分离的第二个实例中的浓度，在测量阶段基本上保持不变。
表1中显示了本发明的实施例1-4和基于铬(VI)的对比例的电镀槽液的组成，以及用于各电镀槽液的操作参数。
表1
DC:直流
PRC：脉冲反向电流
从表1中电镀槽液所制备的沉积物，其获得的性质示于表2。
表2
Claims (28)
1.一种用于沉积铬或铬合金的电镀槽液，其特征在于，包括：
a)50-400g/L(0.164-1.314M)的至少一种三价铬盐，
b)100-400g/L(2.17-8.68M)的至少一种络合剂，
c)1-50g/L(0.0085-0.425M)的至少一种卤素盐，
d)0-10g/L的添加剂，
其中，所述电镀槽液的pH值在4-7之间，并且基本上不含二价硫化合物和硼酸、它们的盐和/或衍生物，并且其中，所述络合剂与三价铬盐的摩尔比为10:1-15:1。
2.如权利要求1所述的电镀槽液，其特征在于，所述的三价铬盐选自下组：硫酸铬(III)，包括酸式或碱式硫酸铬、氯化铬(III)、乙酸铬(III)、羟基乙酸铬(III)、甲酸铬(III)、羟基甲酸铬(III)、碳酸铬(III)、甲磺酸铬(III)、硫酸钾铬(III)、及其混合物。
3.如权利要求1或2所述的电镀槽液，其特征在于，所述的三价铬盐的含量为100-300g/L(0.328-0.984M)。
4.如权利要求1或2所述的电镀槽液，其特征在于，所述的三价铬盐的含量为120-160g/L(0.3936-0.5248M)。
5.如权利要求1或2所述的电镀槽液，其特征在于，所述的三价铬盐的阴离子是挥发性的或电化学可消耗的酸的阴离子。
6.如权利要求1或2所述的电镀槽液，其特征在于，所述的选自下组：甲酸根、乙酸根、丙酸根、羟基乙酸根、草酸根、碳酸根、柠檬酸根、或其混合物。
7.如权利要求1或2所述的电镀槽液，其特征在于，所述的电镀槽液包含合金形成物，所述合金形成物选自下组：钒、锰、铁、钴、镍、钼、钨、及其混合物。
8.如权利要求1或2所述的电镀槽液，其特征在于，所述的电镀槽液还包含碳、氧、和氮，它们由电镀槽液中的有机组分或氨所提供。
9.如权利要求1或2所述的电镀槽液，其特征在于，所述的电镀槽液包含氨。
10.如权利要求8所述的电镀槽液，其特征在于，所述的氨的摩尔浓度是小于或等于至少一种络合剂的摩尔浓度。
11.如权利要求8所述的电镀槽液，其特征在于，所述的氨的浓度是70g/L-110g/L。
12.如权利要求1或2所述的电镀槽液，其特征在于，所述的络合剂选自下组：羧酸和羧酸盐。
13.如权利要求1或2所述的电镀槽液，其特征在于，所述的络合剂甲酸、乙酸、丙酸、羟基乙酸、乳酸、草酸、苹果酸、柠檬酸、酒石酸、琥珀酸、葡糖酸、甘氨酸、天冬氨酸、丙二酸、丁二酸、及其混合物、或它们的盐及其混合物。
14.如权利要求1或2所述的电镀槽液，其特征在于，所述的络合剂的含量是100-300g/L(2.17-6.61M)。
15.如权利要求1或2所述的电镀槽液，其特征在于，所述的络合剂的含量是150-250g/L(3.26-5.51M)。
16.如权利要求1或2所述的电镀槽液，其特征在于，所述的络合剂的含量是所述络合剂与三价铬盐的摩尔比为10:1-13:1。
17.如权利要求1或2所述的电镀槽液，其特征在于，所述的卤素盐选自下组：溴化钾、溴化钠、溴化铵及其混合物。
18.如权利要求1或2所述的电镀槽液，其特征在于，所述的卤素盐的含量为5-50g/L(0.0425-0.425M)。
19.如权利要求1或2所述的电镀槽液，其特征在于，所述的电镀槽液还包含氟化物作为至少一种额外的络合剂和/或至少一种额外的卤素盐。
20.如权利要求1或2所述的电镀槽液，其特征在于，所述的添加剂选自下组：增白剂。
21.如权利要求19所述的电镀槽液，其特征在于，所述的增白剂为聚氨或聚氨类的混合物，所述混合物包括季铵化合物，和润湿剂。
22.如权利要求20所述的电镀槽液，其特征在于，所述的润湿剂选自下组：电中性的、阳离子型和两性的表面活性剂。
23.如权利要求1或2所述的电镀槽液，其特征在于，所述的电镀槽液基本上不含氯离子和/或铝离子。
24.一种在基材上沉积铬的方法，其特征在于，包括以下步骤：
·提供上述任一权利要求所述的电镀槽液；
·将一基材浸入所述电镀槽液；和
·施加电流，使得三价铬沉积在所述基材上。
25.如权利要求23所述的方法，其特征在于，所述的电镀槽液与阳极被通过膜分开，以界定阳极电解液和阴极电解液。
26.如权利要求23所述的方法，其特征在于，所述膜为阳离子型或阴离子型交换膜或多孔膜。
27.如权利要求23所述的方法，其特征在于，所述膜为阳离子型交换膜。
28.如权利要求24所述的方法，其特征在于，所述的阳极电解液包括硫酸铬(III)。
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| EP14152463.7A EP2899299A1 (en) | 2014-01-24 | 2014-01-24 | Electroplating bath containing trivalent chromium and process for depositing chromium |
| CN201580004384.7A CN105917031B (zh) | 2014-01-24 | 2015-01-26 | 含三价铬的电镀槽液和沉积铬的方法 |
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| CN114875459A (zh) * | 2022-05-10 | 2022-08-09 | 成立航空股份有限公司 | 一种三价铬镀液及黑铬镀层 |
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| GB2534883A (en) * | 2015-02-03 | 2016-08-10 | Univ Leicester | Electrolyte for electroplating |
| WO2017042420A1 (en) * | 2015-09-09 | 2017-03-16 | Savroc Ltd | Chromium-based coating, a method for producing a chromium-based coating and a coated object |
| US10270691B2 (en) * | 2016-02-29 | 2019-04-23 | Cisco Technology, Inc. | System and method for dataplane-signaled packet capture in a segment routing environment |
| FR3051806B1 (fr) * | 2016-05-31 | 2018-06-01 | Safran Aircraft Engines | Procede de chromage par voie electrolytique d'un substrat a partir d'un bain de chrome trivalent |
| EP3382062A1 (en) | 2017-03-31 | 2018-10-03 | COVENTYA S.p.A. | Method for increasing the corrosion resistance of a chrome-plated substrate |
| PL3607115T3 (pl) * | 2017-04-04 | 2022-10-03 | Atotech Deutschland GmbH & Co. KG | Kontrolowany sposób osadzania warstwy chromu albo stopu chromu na co najmniej jednym podłożu |
| CN110446802B (zh) * | 2017-04-04 | 2023-02-28 | 安美特德国有限公司 | 在至少一个基底上电解沉积铬或铬合金层的方法 |
| CN108130570A (zh) * | 2017-12-15 | 2018-06-08 | 北京科技大学 | 一种复合三价电镀铬工艺 |
| CN109056005A (zh) * | 2018-09-11 | 2018-12-21 | 沈阳飞机工业（集团）有限公司 | 一种应用电沉积技术制备铬硼合金的方法 |
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- 2015-01-26 JP JP2016548141A patent/JP6534391B2/ja active Active
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| WO2015110627A1 (en) | 2015-07-30 |
| US10619258B2 (en) | 2020-04-14 |
| BR112016016834A2 (zh) | 2017-08-08 |
| CN105917031B (zh) | 2021-11-02 |
| JP6534391B2 (ja) | 2019-06-26 |
| EP2899299A1 (en) | 2015-07-29 |
| BR112016016834B1 (pt) | 2022-02-08 |
| MX2016009533A (es) | 2016-10-28 |
| EP3097222A1 (en) | 2016-11-30 |
| CN105917031A (zh) | 2016-08-31 |
| CA2935934C (en) | 2022-03-01 |
| KR102430755B1 (ko) | 2022-08-10 |
| KR20210147081A (ko) | 2021-12-06 |
| EP3097222B1 (en) | 2023-03-29 |
| CA2935934A1 (en) | 2015-07-30 |
| US20170009361A1 (en) | 2017-01-12 |
| HUE061836T2 (hu) | 2023-08-28 |
| KR20160113610A (ko) | 2016-09-30 |
| ES2944135T3 (es) | 2023-06-19 |
| PL3097222T3 (pl) | 2023-05-29 |
| JP2017503926A (ja) | 2017-02-02 |
| US20200308723A1 (en) | 2020-10-01 |
| US11905613B2 (en) | 2024-02-20 |
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