EP0666342B1 - Bad zum galvanischen Abscheiden von Silber-Zinn-Legierungen - Google Patents
Bad zum galvanischen Abscheiden von Silber-Zinn-Legierungen Download PDFInfo
- Publication number
- EP0666342B1 EP0666342B1 EP95100167A EP95100167A EP0666342B1 EP 0666342 B1 EP0666342 B1 EP 0666342B1 EP 95100167 A EP95100167 A EP 95100167A EP 95100167 A EP95100167 A EP 95100167A EP 0666342 B1 EP0666342 B1 EP 0666342B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- tin
- silver
- bath according
- compound
- 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.)
- Expired - Lifetime
Links
- 229910001128 Sn alloy Inorganic materials 0.000 title claims description 21
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 title claims description 19
- 238000009713 electroplating Methods 0.000 title description 2
- 229910052709 silver Inorganic materials 0.000 claims description 41
- 239000004332 silver Substances 0.000 claims description 41
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 34
- 229910052718 tin Inorganic materials 0.000 claims description 34
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 33
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 14
- -1 tin(II) compound Chemical class 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 12
- 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 11
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 10
- 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 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 235000012208 gluconic acid Nutrition 0.000 claims description 9
- 229940100890 silver compound Drugs 0.000 claims description 9
- 150000003379 silver compounds Chemical class 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 7
- 150000003606 tin compounds Chemical class 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052785 arsenic Inorganic materials 0.000 claims description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 238000004070 electrodeposition Methods 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229940071182 stannate Drugs 0.000 claims description 4
- OBDVFOBWBHMJDG-UHFFFAOYSA-N 3-mercapto-1-propanesulfonic acid Chemical compound OS(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 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 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001261 hydroxy acids Chemical class 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 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
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- DSLZVSRJTYRBFB-LLEIAEIESA-N D-glucaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O DSLZVSRJTYRBFB-LLEIAEIESA-N 0.000 claims description 2
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- IAJILQKETJEXLJ-QTBDOELSSA-N aldehydo-D-glucuronic acid Chemical compound O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)C(O)=O IAJILQKETJEXLJ-QTBDOELSSA-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
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 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
- ZNEWHQLOPFWXOF-UHFFFAOYSA-N coenzyme M Chemical compound OS(=O)(=O)CCS ZNEWHQLOPFWXOF-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 229940097043 glucuronic acid Drugs 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 2
- OBBXFSIWZVFYJR-UHFFFAOYSA-L tin(2+);sulfate Chemical compound [Sn+2].[O-]S([O-])(=O)=O OBBXFSIWZVFYJR-UHFFFAOYSA-L 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 claims 2
- 239000002184 metal Substances 0.000 claims 2
- 150000002739 metals Chemical class 0.000 claims 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 38
- 239000000243 solution Substances 0.000 description 28
- 238000001556 precipitation Methods 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 229950006191 gluconic acid Drugs 0.000 description 8
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 7
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 7
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 229910001316 Ag alloy Inorganic materials 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 230000001464 adherent effect Effects 0.000 description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- LDXUSCIEMIJYBX-UHFFFAOYSA-N [Ag].[As].[Sn] Chemical compound [Ag].[As].[Sn] LDXUSCIEMIJYBX-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 239000001508 potassium citrate Substances 0.000 description 2
- 229960002635 potassium citrate Drugs 0.000 description 2
- 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 2
- 235000011082 potassium citrates Nutrition 0.000 description 2
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 2
- 125000005402 stannate group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- GZNAASVAJNXPPW-UHFFFAOYSA-M tin(4+) chloride dihydrate Chemical compound O.O.[Cl-].[Sn+4] GZNAASVAJNXPPW-UHFFFAOYSA-M 0.000 description 2
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Substances O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- 229940006193 2-mercaptoethanesulfonic acid Drugs 0.000 description 1
- 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 description 1
- 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 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- ZSILVJLXKHGNPL-UHFFFAOYSA-L S(=S)(=O)([O-])[O-].[Ag+2] Chemical compound S(=S)(=O)([O-])[O-].[Ag+2] ZSILVJLXKHGNPL-UHFFFAOYSA-L 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- AOPCTAWIMYYTKA-UHFFFAOYSA-N [As].[Ag] Chemical compound [As].[Ag] AOPCTAWIMYYTKA-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- FBPFZTCFMRRESA-GUCUJZIJSA-N galactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-GUCUJZIJSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- HKSGQTYSSZOJOA-UHFFFAOYSA-N potassium argentocyanide Chemical compound [K+].[Ag+].N#[C-].N#[C-] HKSGQTYSSZOJOA-UHFFFAOYSA-N 0.000 description 1
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229940098221 silver cyanide Drugs 0.000 description 1
- HAAYBYDROVFKPU-UHFFFAOYSA-N silver;azane;nitrate Chemical compound N.N.[Ag+].[O-][N+]([O-])=O HAAYBYDROVFKPU-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- SYRHIZPPCHMRIT-UHFFFAOYSA-N tin(4+) Chemical class [Sn+4] SYRHIZPPCHMRIT-UHFFFAOYSA-N 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/64—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of silver
Definitions
- the invention relates to a bath for the electrodeposition of silver-tin alloys, the Silver as a soluble silver compound, tin as a soluble tin compound and a complexing agent contains.
- German patent specification 718 252 relates to a process for producing galvanic coatings from silver-tin alloys with a tin content of 5-20%, alkaline cyanide baths containing tin as stannate or tetrachloride and current densities of 0.1-1 A / dm 2 used.
- the baths can additionally contain potassium gold cyanide and / or palladium chloride; then silver-tin alloys with 2 - 20% gold and / or palladium are deposited.
- German patent specification 849 787 as for the galvanic deposition of alloys of silver with germanium, tin, arsenic or antimony from cyanide electrolytes Suitable complexing agents oxyacids, amino acids or salts of these acids are proposed.
- the deposited coatings are hard and are characterized by a high gloss Subsequent polishing is made easier even in heavy rainfall.
- Generally applicable Limit values for the additions of germanium, tin, arsenic or antimony must be specified not possible because they are strong with the composition of the baths and the working conditions Subject to fluctuations. Brilliant additives can also be added to the baths; however, the effect generally remains low.
- a cyanide bath for the electrodeposition of alloys of the silver present in the bath as potassium silver cyanide, which contains the alloy partners - especially tin, lead, antimony and bismuth - as complexes with an aromatic dihydroxy compound is known from German Auslegeschrift 1 153 587.
- the bath is operated at a current density of 0.5-1.5 A / dm 2 and at room temperature.
- the current density can be increased to over 2 A / dm 2 by adding gloss agents.
- aliphatic oxycarboxylic acids such as oxalic acid or tartaric acid
- aliphatic straight-chain polyoxy compounds such as sorbitol, dulcitol or glycerol
- U.S. Patent 4,399,006 relates to the electrodeposition of silver on metallic Substrates.
- Suitable mercaptans are mercapto derivatives of polyglycols and of organic acids such as thioglycerin, thio malic acid and thiolactic acid.
- the invention is based on the object of a bath of the type described above for galvanic Deposit silver-tin alloys to find the cyanide free and over one wide pH range is stable and both at room temperature and at elevated temperature can be operated.
- the bathroom should have even and adhesive layers of silver-tin alloys with a tin content of up to about 80% by weight, their composition given the silver and tin concentration of the bath should be relatively independent of the current density and the temperature.
- the bath representing the solution to the problem is characterized in that it is a preparation of water and 1 - 120 g / l Silver as a silver compound, 1 - 100 g / l Tin as tin compound, 5 - 450 g / l Mercaptoalkane carboxylic acid and / or mercaptoalkane sulfonic acid and / or its salt and 0-200 g / l Leitsalz contains, has a pH of 0 - 14 and is cyanide-free.
- the bathroom which is made up of water and water, has proven particularly useful 5 - 60 g / l Silver as a silver compound, 5 - 20 g / l Tin as tin compound, 5-200 g / l Mercaptoalkane carboxylic acid and / or mercaptoalkane sulfonic acid and / or its salt and 0-150 g / l Leitsalz contains and has a pH of 0 - 11.
- Tin (II) and tin (IV) compounds are particularly suitable as tin compounds Tin (II) halides, such as tin (II) chloride, and tin (II) sulfate, tin (IV) halides, such as tin (IV) chloride, and stannates such as alkali metal and ammonium stannate.
- Thioglycolic acid (2-mercaptoacetic acid) has proven particularly useful as mercaptoalkane carboxylic acid, Thio malic acid (mercaptosuccinic acid), thiolactic acid (2-mercaptopropionic acid) and thiohydracrylic acid (3-mercaptopropionic acid) as mercaptoalkanesulfonic acid 2-mercaptoethanesulfonic acid and 3-mercaptopropanesulfonic acid.
- the mercapto acids can individually or in a mixture with one another and as free acids or / and in the form of their salts, especially the alkali metal and ammonium salts used to prepare the bath.
- Conductive salts which are particularly suitable for the bath are boric acid, carboxylic acids, hydroxy acids and Salts of these acids insofar as they are water-soluble. Formic acid, acetic acid, Oxalic acid, citric acid, malic acid, tartaric acid, gluconic acid, glucaric acid, glucuronic acid and salts of these acids since these compounds also have a stabilizing effect.
- the bath can be operated at temperatures of 20-70 ° C. and at current densities of 0.1-10 A / dm 2 , preferably 1-6 A / dm 2 .
- the alloys can be deposited more quickly by increasing the current density and reach the bath temperature without - given the silver and tin content of the Bades - major fluctuations in the composition of the deposited alloys occur.
- the bath according to the invention is very stable, even when it is at temperatures is kept above room temperature so that long operating times are possible.
- the silver-tin alloys separated from the bath are characterized by a uniform Surface and good adhesive strength.
- gloss agents are desired, the additional use of gloss agents is required possible.
- Metallic Brighteners, such as from German patent 1 960 047 and the US patent 4,246,077 are also suitable and can be used in the bath in an amount of 50 mg / l - 5 g / l, preferably from 100 - 250 mg / l, can be added.
- Effective Brighteners are also polyethylene glycols and their derivatives, preferably the polyethylene glycol ethers, as far as they are soluble in water. You can use it as the sole brightener or also in a mixture with the metal compounds mentioned.
- the bath can be used for electroplating small parts as well as tapes and wires use and enables the deposition of silver alloys with a tin content up to about 80% by weight.
- the bath obtained in this way is used at a bath temperature of a) 20 ° C. and b) 45 ° C. with a current density of 5 A / dm 2 to form uniform, adhesive and glossy layers of a palladium-containing silver-tin alloy with 81% by weight. % Silver deposited.
- the bathroom is stable; There is no precipitation.
- the bath obtained in this way becomes uniform, adhesive and shiny layers made of a silver-tin alloy of 96% by weight silver and 4% by weight tin, deposited at a bath temperature of 30 ° C and a current density of 4 A / dm 2 uniform, adhesive and shiny layers made of a silver-tin alloy of 95% by weight silver and 5% by weight tin.
- the bathroom is stable; There is no precipitation.
- the bathroom is stable; There is no precipitation.
- a solution is prepared as described in Example 10 and with 100 mg / l arsenic trioxide offset; the pH of the solution is adjusted with a mixture of potassium hydroxide and ammonium hydroxide (Weight ratio 1: 1) set to 7.1.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4403601 | 1994-02-05 | ||
| DE4403601 | 1994-02-05 | ||
| DE4440176A DE4440176C2 (de) | 1994-02-05 | 1994-11-10 | Bad zum galvanischen Abscheiden von Silber-Zinn-Legierungen |
| DE4440176 | 1994-11-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0666342A1 EP0666342A1 (de) | 1995-08-09 |
| EP0666342B1 true EP0666342B1 (de) | 1998-05-06 |
Family
ID=25933579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP95100167A Expired - Lifetime EP0666342B1 (de) | 1994-02-05 | 1995-01-07 | Bad zum galvanischen Abscheiden von Silber-Zinn-Legierungen |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5514261A (ja) |
| EP (1) | EP0666342B1 (ja) |
| JP (1) | JPH07252684A (ja) |
| CA (1) | CA2141090A1 (ja) |
| ES (1) | ES2117995T3 (ja) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10014852A1 (de) * | 2000-03-24 | 2001-09-27 | Enthone Omi Deutschland Gmbh | Verfahren zur Abscheidung einer Silber-Zinn-Legierung |
| DE10158227A1 (de) * | 2001-11-15 | 2003-06-05 | Siemens Ag | Elektrolysebad zum galvanischen Abscheiden von Silber-Zinn-Legierungen |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3301707B2 (ja) * | 1997-01-20 | 2002-07-15 | ディップソール株式会社 | 錫−銀合金酸性電気めっき浴 |
| DE19752329A1 (de) | 1997-11-26 | 1999-05-27 | Stolberger Metallwerke Gmbh | Verfahren zur Herstellung eines metallischen Verbundbands |
| US6210556B1 (en) | 1998-02-12 | 2001-04-03 | Learonal, Inc. | Electrolyte and tin-silver electroplating process |
| JP3352422B2 (ja) | 1999-02-10 | 2002-12-03 | セントラル硝子株式会社 | 銀被膜形成用薬液および銀被膜形成方法 |
| JP3433291B2 (ja) * | 1999-09-27 | 2003-08-04 | 石原薬品株式会社 | スズ−銅含有合金メッキ浴、スズ−銅含有合金メッキ方法及びスズ−銅含有合金メッキ皮膜が形成された物品 |
| JP3266242B2 (ja) * | 1999-10-12 | 2002-03-18 | 理研電線株式会社 | 錫めっき線の熱酸化黄変防止法 |
| US6491806B1 (en) * | 2000-04-27 | 2002-12-10 | Intel Corporation | Electroplating bath composition |
| US7628903B1 (en) | 2000-05-02 | 2009-12-08 | Ishihara Chemical Co., Ltd. | Silver and silver alloy plating bath |
| US6924044B2 (en) * | 2001-08-14 | 2005-08-02 | Snag, Llc | Tin-silver coatings |
| US7122108B2 (en) | 2001-10-24 | 2006-10-17 | Shipley Company, L.L.C. | Tin-silver electrolyte |
| TW500836B (en) * | 2001-11-13 | 2002-09-01 | Jung-Huei Chen | Low-lead-content plating process |
| US20070037005A1 (en) * | 2003-04-11 | 2007-02-15 | Rohm And Haas Electronic Materials Llc | Tin-silver electrolyte |
| DE102005055742A1 (de) * | 2005-11-23 | 2007-05-24 | Robert Bosch Gmbh | Verfahren zum Herstellen einer kontaktgeeigneten Schicht auf einem Metallelement |
| US20070158199A1 (en) * | 2005-12-30 | 2007-07-12 | Haight Scott M | Method to modulate the surface roughness of a plated deposit and create fine-grained flat bumps |
| US20080308300A1 (en) * | 2007-06-18 | 2008-12-18 | Conti Mark A | Method of manufacturing electrically conductive strips |
| EP2085502A1 (en) * | 2008-01-29 | 2009-08-05 | Enthone, Incorporated | Electrolyte composition and method for the deposition of a tin-zinc alloy |
| DE102011088211A1 (de) * | 2011-12-12 | 2013-06-13 | Robert Bosch Gmbh | Kontaktelement und Verfahren zu seiner Herstellung |
| US9663667B2 (en) | 2013-01-22 | 2017-05-30 | Andre Reiss | Electroless silvering ink |
| US9512529B2 (en) | 2013-06-04 | 2016-12-06 | Rohm And Haas Electronic Materials Llc | Electroplating baths of silver and tin alloys |
| CN108517516B (zh) * | 2018-05-29 | 2020-10-23 | 电子科技大学 | 一种化学镀银液及其制备方法 |
| DE102018126174B3 (de) * | 2018-10-22 | 2019-08-29 | Umicore Galvanotechnik Gmbh | Thermisch stabile Silberlegierungsschichten, Verfahren zur Abscheidung und Verwendung |
| US11242609B2 (en) * | 2019-10-15 | 2022-02-08 | Rohm and Hass Electronic Materials LLC | Acidic aqueous silver-nickel alloy electroplating compositions and methods |
| US11434577B2 (en) * | 2019-10-17 | 2022-09-06 | Rohm And Haas Electronic Materials Llc | Acid aqueous binary silver-bismuth alloy electroplating compositions and methods |
| CN116134181A (zh) * | 2020-07-22 | 2023-05-16 | 三菱综合材料株式会社 | 连接器用端子材 |
| JP7119267B2 (ja) * | 2020-07-22 | 2022-08-17 | 三菱マテリアル株式会社 | コネクタ用端子材 |
| JP7353249B2 (ja) * | 2020-08-19 | 2023-09-29 | Ｅｅｊａ株式会社 | シアン系電解銀合金めっき液 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE718252C (de) * | 1939-06-01 | 1942-03-07 | Degussa | Verfahren zur Erzeugung schwefelwasserstoffbestaendiger galvanischer Silberueberzuege |
| DE849787C (de) * | 1949-11-15 | 1952-09-18 | Forsch | Verfahren zur Herstellung harter galvanischer Silber- und Goldueberzuege |
| NL263506A (ja) * | 1960-04-12 | |||
| CH494284A (fr) * | 1968-11-28 | 1970-07-31 | Sel Rex Corp | Procédé pour le dépôt électrolytique d'un alliage d'or avec au moins un autre métal commun et bain aqueux de placage pour la mise en oeuvre de ce procédé |
| US4246077A (en) * | 1975-03-12 | 1981-01-20 | Technic, Inc. | Non-cyanide bright silver electroplating bath therefor, silver compounds and method of making silver compounds |
| JPS54141346A (en) * | 1978-04-26 | 1979-11-02 | Matsushita Electric Ind Co Ltd | Silver-copper alloy plating method |
| JPS5512111A (en) * | 1978-07-11 | 1980-01-28 | Chugoku Toryo Kk | Seaweed-feeding coating composition |
| US4399006A (en) * | 1978-08-29 | 1983-08-16 | Learonal, Inc. | Silver plating |
| BR8001854A (pt) * | 1979-04-04 | 1980-11-18 | Engelhard Min & Chem | Banho de revestimento de prata ou liga da mesma e respectivo processo de estabilizacao |
| US4248375A (en) * | 1979-08-30 | 1981-02-03 | Honeywell Inc. | Clock thermostat apparatus having means for reducing the setback temperature when the normal temperature selection is turned down |
| JPS574715A (en) * | 1980-06-12 | 1982-01-11 | Matsushita Electric Works Ltd | Extrusion type granulator for synthetic resin molding material |
| JPS5782492A (en) * | 1980-11-11 | 1982-05-22 | Seiko Instr & Electronics Ltd | Copper-tin alloy plating bath |
| US4412965A (en) * | 1981-09-08 | 1983-11-01 | The Goodyear Tire & Rubber Company | Method of making an air spring |
| US4582576A (en) * | 1985-03-26 | 1986-04-15 | Mcgean-Rohco, Inc. | Plating bath and method for electroplating tin and/or lead |
| JPH0751630B2 (ja) * | 1989-06-20 | 1995-06-05 | 住友精化株式会社 | 硬化性組成物 |
| JP2676547B2 (ja) * | 1989-03-29 | 1997-11-17 | 株式会社大和化成研究所 | 中性すず又はすず―鉛合金電気めっき浴 |
-
1995
- 1995-01-07 ES ES95100167T patent/ES2117995T3/es not_active Expired - Lifetime
- 1995-01-07 EP EP95100167A patent/EP0666342B1/de not_active Expired - Lifetime
- 1995-01-25 CA CA002141090A patent/CA2141090A1/en not_active Abandoned
- 1995-01-30 US US08/380,066 patent/US5514261A/en not_active Expired - Fee Related
- 1995-01-31 JP JP7014285A patent/JPH07252684A/ja active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10014852A1 (de) * | 2000-03-24 | 2001-09-27 | Enthone Omi Deutschland Gmbh | Verfahren zur Abscheidung einer Silber-Zinn-Legierung |
| DE10158227A1 (de) * | 2001-11-15 | 2003-06-05 | Siemens Ag | Elektrolysebad zum galvanischen Abscheiden von Silber-Zinn-Legierungen |
Also Published As
| Publication number | Publication date |
|---|---|
| US5514261A (en) | 1996-05-07 |
| ES2117995T3 (es) | 1998-09-01 |
| JPH07252684A (ja) | 1995-10-03 |
| EP0666342A1 (de) | 1995-08-09 |
| CA2141090A1 (en) | 1995-08-06 |
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