WO2013013941A1 - Electroless nickel plating bath composition - Google Patents
Electroless nickel plating bath composition Download PDFInfo
- Publication number
- WO2013013941A1 WO2013013941A1 PCT/EP2012/062967 EP2012062967W WO2013013941A1 WO 2013013941 A1 WO2013013941 A1 WO 2013013941A1 EP 2012062967 W EP2012062967 W EP 2012062967W WO 2013013941 A1 WO2013013941 A1 WO 2013013941A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- plating bath
- nickel
- ranges
- concentration
- aqueous plating
- Prior art date
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- 238000007747 plating Methods 0.000 title claims abstract description 83
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 32
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 22
- 239000000956 alloy Substances 0.000 claims abstract description 22
- 239000003381 stabilizer Substances 0.000 claims abstract description 22
- 238000000151 deposition Methods 0.000 claims abstract 2
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 12
- 239000008139 complexing agent Substances 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 12
- 239000011591 potassium Substances 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 11
- -1 hypophosphite compound Chemical class 0.000 claims description 10
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 8
- 229910001453 nickel ion Inorganic materials 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 238000007772 electroless plating Methods 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 229910001385 heavy metal Inorganic materials 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- 150000003460 sulfonic acids Chemical class 0.000 claims description 3
- 229910052716 thallium Inorganic materials 0.000 claims description 3
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 2
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 2
- 229910052787 antimony Inorganic materials 0.000 claims 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000080 wetting agent Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 235000011090 malic acid Nutrition 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- OBDVFOBWBHMJDG-UHFFFAOYSA-N 3-mercapto-1-propanesulfonic acid Chemical compound OS(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-N 0.000 description 2
- QNAYBMKLOCPYGJ-UHFFFAOYSA-N Alanine Chemical compound CC([NH3+])C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910001439 antimony ion Inorganic materials 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical group O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 150000003628 tricarboxylic acids Chemical class 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- CEGRHPCDLKAHJD-UHFFFAOYSA-N 1,1,1-propanetricarboxylic acid Chemical compound CCC(C(O)=O)(C(O)=O)C(O)=O CEGRHPCDLKAHJD-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000004129 EU approved improving agent Substances 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229960002449 glycine Drugs 0.000 description 1
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 1
- 229960004275 glycolic acid Drugs 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 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 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
Definitions
- the present invention relates to an aqueous plating bath composition for the electroless deposition of nickel phosphorous alloys.
- Electroless plating of nickel-phosphorous alloys is used in various industries.
- the deposits derived are used e.g. as wear resistant coatings and barrier layers.
- Such plating bath compositions generally comprise a source of nickel ions, a hypophosphite compound as the reducing agent, at least one complexing agent and at least one stabilizing agent.
- the at least one stabilizing agent present is required in order to provide a sufficient bath lifetime, a reasonable deposition rate and to control the phosphorous content in the as deposited nickel phosphorous alloy.
- plating baths for deposition of nickel-phosphorous alloys known in the art comprise more than one stabilizing agent.
- Common stabilizing agents are selected from heavy metal ions such as cadmium, thallium, bismuth, lead and antimony ions, inorganic ions such as SCN " and various organic compounds such as thiourea.
- the patent document US 2,830,014 discloses plating bath compositions for electroplating of nickel which comprise thioalkane sulfonic acids or salts thereof such as mercaptopropane-1 -sodium sulfonate as brightening and ductility- improving agents.
- the patent application US 2005/0013928 A1 discloses an electroless plating pre-treatment solution which comprises 3-mercaptopropanesulfonic acid.
- the pre-treatment solution reduces the incubation time (time from the start of the supply of an electroless plating solution to the start of the plating reaction) of nickel plating from an electroless plating bath on a copper surface.
- the patent application US 2006/024043 A1 discloses an alkaline aqueous plating bath for deposition of nickel phosphorous alloys which optionally comprises further additives such as thiourea and/or 3-mercapto-1 -propane sulfonic acid. Such plating bath compositions are not acceptable for industrial applications (see Examples 2 to 5). Furthermore, thiourea is a carcinogenic substance.
- the main disadvantages of known stabilizing agents are a) the toxic behaviour of heavy metal ions such as cadmium, thallium, lead and antimony ions and b) in case more than one stabilizing agent is present in an electroless nickel plating bath, the control of the mixture of stabilizing agents during use of such a plating bath is complex.
- an aqueous plating bath composition for electro- less plating of a nickel phosphorous alloy comprising
- a stabilizing agent selected from the group consisting of compounds according to formulae (1 ) and (2):
- R 1 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, lithium, sodium, potassium and ammonium, n ranges from 1 to 6,
- R 2 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, lithium, sodium, potassium and ammonium,
- R 3 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, lithium, sodium, potassium and ammonium and m ranges from 1 to 6 and having a pH value in the range of 3.5 to 6.5. From such a plating bath composition, a nickel phosphorous alloy having a phosphorous content in the range of 5 to 2 wt.-% of phosphorous is derived by electroless plating.
- the aqueous plating bath composition according to the present invention comprises a water soluble source of nickel ions such as nickel sulfate, a reducing agent such as sodium hypophosphite, at least one complexing agent and a stabilizing agent selected from compounds according to formulae (1 ) and (2).
- the concentration of nickel ions ranges from 1 to 18 g/l, more preferably from 3 to 9 g/l.
- the reducing agent is selected from hypophosphite compounds such as hypo- phosphorous acid or a bath soluble salt thereof such as sodium hypophosphite, potassium hypophosphite and ammonium hypophosphite.
- the amount of the reducing agent employed in the plating bath ranges from 2 to 60 g/l, more preferably from 2 to 50 g/l and most preferably from 20 to 45 g/l. As a conventional practice the reducing agent is replenished during the reaction.
- the complexing agents are employed in amounts of 1 to 200 g/l, more preferably from 5 to 75 g/l.
- carboxylic acids, polyamines and sulfonic acids or mixtures thereof are selected as complexing agents.
- Useful carboxylic acids include mono-, di-, tri- and tetra-carboxylic acids.
- the carboxylic acids may be substituted with various substituent moieties such as hydroxy or amino groups and the acids may be introduced into the plating solutions as their sodium, potassium or ammonium salts.
- Some complexing agents such as acetic acid, for example, may also act as a buffering agent, and the appropriate concentration of such additive components can be optimised for any plating solution in consideration of their dual functionality.
- carboxylic acids which are useful as the complexing agents include: monocarboxylic acids such as acetic acid, hydroxyacetic acid, amino- acetic acid, 2-amino propanoic acid, 2-hydroxy propanoic acid, lactic acid; di- carboxylic acids such as succinic acid, amino succinic acid, hydroxy succinic acid, propanedioic acid, hydroxybutanedioic acid, tartaric acid, malic acid; tricarboxylic acids such as 2-hydroxy- ,2,3 propane tricarboxylic acid; and tetra- carboxylic acids such as ethylene diamine tetra acetic acid (EDTA).
- monocarboxylic acids such as acetic acid, hydroxyacetic acid, amino- acetic acid, 2-amino propanoic acid, 2-hydroxy propanoic acid, lactic acid
- di- carboxylic acids such as succinic acid, amino succinic acid, hydroxy succinic acid, propanedioic acid, hydroxy
- the most preferred complexing agents are selected from the group consisting of mono-carboxylic acids and di-carboxylic acids. In one embodiment, mixtures of two or more of the above complexing agents are utilized.
- the stabilizing agent is selected from compounds according to formulae (1 ) and
- R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, lithium, sodium, potassium and ammonium, n ranges from 1 to 6
- R 2 is selected from the group consisting of hydrogen, methyl, ethyl propyl, butyl, lithium, sodium, potassium and ammonium,
- R 3 is selected from the group consisting of hydrogen, methyl, ethyl propyl, butyl, lithium, sodium, potassium and ammonium and m ranges from 1 to 6. More preferably, R 1 is selected from the group consisting of hydrogen, sodium and potassium.
- n ranges from 2 to 4.
- R 2 is selected from the group consisting of hydrogen, sodium and potassium.
- R 3 is selected from the group consisting of hydrogen, sodium and potassium.
- m ranges from 2 to 4.
- the concentration of the stabilizing agent according to formulae (1 ) and (2) in the plating bath composition preferably ranges from 1 to 100 ppm, more preferably from 2 to 50 ppm and most preferably from 3 to 30 ppm.
- the pH may be periodically or continuously adjusted by adding bath-soluble and bath-compatible alkaline substances such as sodium, potassium or ammonium hydroxides, carbonates and bicar- bonates.
- bath-soluble and bath-compatible alkaline substances such as sodium, potassium or ammonium hydroxides, carbonates and bicar- bonates.
- the stability of the operating pH of the plating solutions can be improved by the addition of various buffer compounds such as acetic acid, propionic acid, boric acid, or the like, in amounts of up to 30 g/l, more preferably from 2 to 10 g/l.
- the pH value of the aqueous plating bath according to the present invention preferably ranges from 3.5 to 6.5, more preferably from 4 to 6.
- nickel plating solutions such as buffers and wetting agents. These materials are known in the art.
- the nickel plating solutions optionally may employ one or more wetting agents of any of the various types heretofore known which are soluble and compatible with the other bath constituents.
- wetting agents prevents or hinders pitting of the nickel phosphorous alloy deposit, and the wetting agents can be employed in amounts up to about 1 g/l.
- the substrate to be plated is contacted with the plating bath at a temperature of at least 40°C up to 95 °C.
- the electroless nickel plating baths according to the present invention are employed, in one embodiment, at a temperature of from 70°C to 95°C, and more often, at a temperature of from 80°C to 90°C.
- the duration of contact of the electroless nickel plating bath with the substrate being plated is a function which is dependent on the desired thickness of the nickel phosphorus alloy. Typically, a contact time can range from 1 to 30 min.
- the substrate to be coated with a nickel phosphorous alloy can be contacted with the plating bath according to the present invention by dipping the substrate into the plating bath or by spraying the plating bath onto the substrate.
- mild agitation may be employed. Agitation may be a mild air agitation, mechanical agitation, bath cir- culation by pumping, rotation of a barrel plating, etc.
- the plating solution may also be subjected to a periodic or continuous filtration treatment to reduce the level of contaminants therein. Replenishment of the constituents of the bath may also be performed, in some embodiments, on a periodic or continuous basis to maintain the concentration of constituents, and in particular, the concen- tration of nickel ions and hypophosphite ions, as well as the pH level within the desired limits.
- An electroless nickel plating bath comprising 6 g/l nickel ions as nickel sulfate, hypophosphite as reducing agent, a mixture of lactic acid and malic acid as complexing agents (overall concentration: 150 mmol/l) and lead ions as stabiliz- ing additive was tested.
- the pH value of this plating bath was 4.8.
- the plating results are summarised in Table 1 .
- the phosphorous concentration in the deposited nickel phosphorous alloys increases from 7.0 wt.-% at 1 MTO to 8.3 wt.-% at 3 MTO.
- the stabilizing agent according to the present invention shows the desired properties in respect to the stable phosphorous concentration in the deposited nickel phosphorous alloy layers when using the plating bath. Furthermore, the plating rate is sufficient for industrial application.
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
The present invention relates to an aqueous plating bath composition for depositing a nickel phosphorous alloy having a phosphorous content in the range of to 12 wt.-%. The plating bath comprises a sulfur-containing organic stabilizing agent.
Description
Electroless Nickel Plating Bath Composition
Field of the Invention
The present invention relates to an aqueous plating bath composition for the electroless deposition of nickel phosphorous alloys.
Background of the Invention
Electroless plating of nickel-phosphorous alloys is used in various industries. The deposits derived are used e.g. as wear resistant coatings and barrier layers.
Such plating bath compositions generally comprise a source of nickel ions, a hypophosphite compound as the reducing agent, at least one complexing agent and at least one stabilizing agent.
The at least one stabilizing agent present is required in order to provide a sufficient bath lifetime, a reasonable deposition rate and to control the phosphorous content in the as deposited nickel phosphorous alloy. Often, plating baths for deposition of nickel-phosphorous alloys known in the art comprise more than one stabilizing agent.
Common stabilizing agents are selected from heavy metal ions such as cadmium, thallium, bismuth, lead and antimony ions, inorganic ions such as SCN" and various organic compounds such as thiourea.
The patent document US 2,830,014 discloses plating bath compositions for electroplating of nickel which comprise thioalkane sulfonic acids or salts thereof
such as mercaptopropane-1 -sodium sulfonate as brightening and ductility- improving agents.
The patent application US 2005/0013928 A1 discloses an electroless plating pre-treatment solution which comprises 3-mercaptopropanesulfonic acid. The pre-treatment solution reduces the incubation time (time from the start of the supply of an electroless plating solution to the start of the plating reaction) of nickel plating from an electroless plating bath on a copper surface.
The patent application US 2006/024043 A1 discloses an alkaline aqueous plating bath for deposition of nickel phosphorous alloys which optionally comprises further additives such as thiourea and/or 3-mercapto-1 -propane sulfonic acid. Such plating bath compositions are not acceptable for industrial applications (see Examples 2 to 5). Furthermore, thiourea is a carcinogenic substance.
The main disadvantages of known stabilizing agents are a) the toxic behaviour of heavy metal ions such as cadmium, thallium, lead and antimony ions and b) in case more than one stabilizing agent is present in an electroless nickel plating bath, the control of the mixture of stabilizing agents during use of such a plating bath is complex.
Objective of the Invention
Therefore it is the objective of the present invention to provide a bath composition for electroless deposition of nickel phosphorous alloys which is free of toxic heavy metal ion based stabilizers.
It is a further objective of the present invention to provide a bath composition for electroless deposition of nickel phosphorous alloys which allows deposition of a nickel phosphorous alloy having a phosphorous concentration in the range of 5 to 12 wt.-%.
Summary of the Invention
These objectives are solved by an aqueous plating bath composition for electro- less plating of a nickel phosphorous alloy, the plating bath comprising
(i) a water soluble source of nickel ions
(ii) a hypophosphite compound
(iii) at least one complexing agent and
(iv) a stabilizing agent selected from the group consisting of compounds according to formulae (1 ) and (2):
R1S— (CH2)n— SO3R2 (1 )
R3SO3-(CH2)m-S-S-(CH2)m-SO3R3 (2) wherein
R1 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, lithium, sodium, potassium and ammonium, n ranges from 1 to 6,
R2 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, lithium, sodium, potassium and ammonium,
R3 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, lithium, sodium, potassium and ammonium and m ranges from 1 to 6 and having a pH value in the range of 3.5 to 6.5.
From such a plating bath composition, a nickel phosphorous alloy having a phosphorous content in the range of 5 to 2 wt.-% of phosphorous is derived by electroless plating.
Detailed Description of the Invention
The aqueous plating bath composition according to the present invention comprises a water soluble source of nickel ions such as nickel sulfate, a reducing agent such as sodium hypophosphite, at least one complexing agent and a stabilizing agent selected from compounds according to formulae (1 ) and (2).
The concentration of nickel ions ranges from 1 to 18 g/l, more preferably from 3 to 9 g/l.
The reducing agent is selected from hypophosphite compounds such as hypo- phosphorous acid or a bath soluble salt thereof such as sodium hypophosphite, potassium hypophosphite and ammonium hypophosphite. The amount of the reducing agent employed in the plating bath ranges from 2 to 60 g/l, more preferably from 2 to 50 g/l and most preferably from 20 to 45 g/l. As a conventional practice the reducing agent is replenished during the reaction.
The complexing agents are employed in amounts of 1 to 200 g/l, more preferably from 5 to 75 g/l.
In one embodiment of the present invention, carboxylic acids, polyamines and sulfonic acids or mixtures thereof are selected as complexing agents. Useful carboxylic acids include mono-, di-, tri- and tetra-carboxylic acids. The carboxylic acids may be substituted with various substituent moieties such as hydroxy or amino groups and the acids may be introduced into the plating solutions as their sodium, potassium or ammonium salts. Some complexing agents such as acetic acid, for example, may also act as a buffering agent, and the appropriate concentration of such additive components can be optimised for any plating solution in consideration of their dual functionality.
Examples of such carboxylic acids which are useful as the complexing agents include: monocarboxylic acids such as acetic acid, hydroxyacetic acid, amino- acetic acid, 2-amino propanoic acid, 2-hydroxy propanoic acid, lactic acid; di- carboxylic acids such as succinic acid, amino succinic acid, hydroxy succinic acid, propanedioic acid, hydroxybutanedioic acid, tartaric acid, malic acid; tricarboxylic acids such as 2-hydroxy- ,2,3 propane tricarboxylic acid; and tetra- carboxylic acids such as ethylene diamine tetra acetic acid (EDTA).
The most preferred complexing agents are selected from the group consisting of mono-carboxylic acids and di-carboxylic acids. In one embodiment, mixtures of two or more of the above complexing agents are utilized.
The stabilizing agent is selected from compounds according to formulae (1 ) and
(2):
R1S— (CH2)n— SO3R2 (1 )
R3SO3— (CH2)m— S— S— (CH2)m— SO3R3 (2) wherein
R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, lithium, sodium, potassium and ammonium, n ranges from 1 to 6
R2 is selected from the group consisting of hydrogen, methyl, ethyl propyl, butyl, lithium, sodium, potassium and ammonium,
R3 is selected from the group consisting of hydrogen, methyl, ethyl propyl, butyl, lithium, sodium, potassium and ammonium and m ranges from 1 to 6.
More preferably, R1 is selected from the group consisting of hydrogen, sodium and potassium.
More preferably, n ranges from 2 to 4.
More preferably, R2 is selected from the group consisting of hydrogen, sodium and potassium.
More preferably, R3 is selected from the group consisting of hydrogen, sodium and potassium.
More preferably, m ranges from 2 to 4.
The concentration of the stabilizing agent according to formulae (1 ) and (2) in the plating bath composition preferably ranges from 1 to 100 ppm, more preferably from 2 to 50 ppm and most preferably from 3 to 30 ppm.
Since the plating solution has a tendency to become more acidic during its operation due to the formation of H30+ ions, the pH may be periodically or continuously adjusted by adding bath-soluble and bath-compatible alkaline substances such as sodium, potassium or ammonium hydroxides, carbonates and bicar- bonates. The stability of the operating pH of the plating solutions can be improved by the addition of various buffer compounds such as acetic acid, propionic acid, boric acid, or the like, in amounts of up to 30 g/l, more preferably from 2 to 10 g/l.
The pH value of the aqueous plating bath according to the present invention preferably ranges from 3.5 to 6.5, more preferably from 4 to 6.
Other materials may be included in the nickel plating solutions such as buffers and wetting agents. These materials are known in the art.
The nickel plating solutions optionally may employ one or more wetting agents of any of the various types heretofore known which are soluble and compatible with the other bath constituents. In one embodiment, the use of such wetting
agents prevents or hinders pitting of the nickel phosphorous alloy deposit, and the wetting agents can be employed in amounts up to about 1 g/l.
The substrate to be plated is contacted with the plating bath at a temperature of at least 40°C up to 95 °C. The electroless nickel plating baths according to the present invention are employed, in one embodiment, at a temperature of from 70°C to 95°C, and more often, at a temperature of from 80°C to 90°C.
The duration of contact of the electroless nickel plating bath with the substrate being plated is a function which is dependent on the desired thickness of the nickel phosphorus alloy. Typically, a contact time can range from 1 to 30 min. The substrate to be coated with a nickel phosphorous alloy can be contacted with the plating bath according to the present invention by dipping the substrate into the plating bath or by spraying the plating bath onto the substrate.
During the deposition of the nickel phosphorous alloy, mild agitation may be employed. Agitation may be a mild air agitation, mechanical agitation, bath cir- culation by pumping, rotation of a barrel plating, etc. The plating solution may also be subjected to a periodic or continuous filtration treatment to reduce the level of contaminants therein. Replenishment of the constituents of the bath may also be performed, in some embodiments, on a periodic or continuous basis to maintain the concentration of constituents, and in particular, the concen- tration of nickel ions and hypophosphite ions, as well as the pH level within the desired limits.
Examples
The invention will now be illustrated by reference to the following non-limiting examples. Example 1 (comparative)
An electroless nickel plating bath comprising 6 g/l nickel ions as nickel sulfate, hypophosphite as reducing agent, a mixture of lactic acid and malic acid as complexing agents (overall concentration: 150 mmol/l) and lead ions as stabiliz-
ing additive was tested. The pH value of this plating bath was 4.8. The plating results are summarised in Table 1 .
Table 1 : plating results obtained for an electroless nickel plating bath known from prior art (MTO = metal turn over).
Sample MTO Lead concenP concentration in dePlating rate
No. tration / ppm posited layer / wt.-% / pm/h
1 1 0.9 7.0 1 1 .8
2 2 1 .2 7.7 1 1 .9
3 3 1 .3 8.3 1 1 .0
The phosphorous concentration in the deposited nickel phosphorous alloys increases from 7.0 wt.-% at 1 MTO to 8.3 wt.-% at 3 MTO.
Example 2 (comparative)
The same plating bath as described for example 1 was used. Instead of lead ions, 0.6 g/l of a stabilizing agent according to formula (1 ) with R1 = hydrogen, R2 = sodium and n = 3 (600 ppm, as disclosed in US 2006/0264043 A1 ) was added to said plating bath. The pH value of this plating bath composition was adjusted with an aqueous solution of ammonia to 9.25. The plating bath temperature was held at 85 °C in presence of the substrate.
No nickel phosphorous alloy layer was deposited onto the substrate. Accordingly, the plating rate of this plating bath is 0 pm/h.
Example 3 (comparative)
The same plating bath as described for example 1 was used. Instead of lead ions, 0.6 g/l of a stabilizing agent according to formula (1 ) with R1 = hydrogen, R2 = sodium and n = 3 (600 ppm, as disclosed in US 2006/0264043 A1 ) was added to said plating bath. The pH value of this plating bath composition was adjusted with an aqueous solution of ammonia to 4.8. The plating bath temperature was held at 85 °C in presence of the substrate.
No nickel phosphorous alloy layer was deposited onto the substrate. Accordingly, the plating rate of this plating bath is 0 m/h.
Example 4 (comparative)
The same plating bath as described for example 1 was used. Instead of lead ions, 0.6 g/l of thiourea (600 ppm, as disclosed in US 2006/0264043 A1 ) were added to the plating bath as stabilizing agent. The pH value of this plating bath composition was adjusted with an aqueous solution of ammonia to 9.25. The plating bath temperature was held at 85 °C in presence of the substrate.
No nickel phosphorous alloy layer was deposited onto the substrate. Accordingly, the plating rate of this plating bath is 0 pm/h.
Example 5 (comparative)
The same plating bath as described for example 1 was used. Instead of lead ions, 0.6 g/l of thiourea (600 ppm, as disclosed in US 2006/0264043 A1 ) were added to the plating bath as stabilizing agent. The pH value of this plating bath composition was adjusted with an aqueous solution of ammonia to 4.8. The plating bath temperature was held at 85 °C in presence of the substrate.
No nickel phosphorous alloy layer was deposited onto the substrate. Accordingly, the plating rate of this plating bath is 0 pm/h.
Example 6 (present invention)
The same plating bath as described for example 1 was used. Instead of lead ions, a stabilizing agent according to formula (1 ) with R1 = hydrogen, R2 = sodium and n = 3 was added to said plating bath. The pH value of this plating bath was 4.8. The plating results are summarized in Table 2.
Table 2: plating results obtained for an electroless nickel plating bath known from prior art (MTO = metal turn over).
Sample MTO Stabilising agent P concentration in dePlating rate
No. concentration posited layer / wt.-% / pm/h
/ ppm
1 1 5 8.2 12.3
2 2 5 7.9 12.3
3 3 5 8.2 1 1 .2
The stabilizing agent according to the present invention shows the desired properties in respect to the stable phosphorous concentration in the deposited nickel phosphorous alloy layers when using the plating bath. Furthermore, the plating rate is sufficient for industrial application.
Claims
1 . An aqueous plating bath composition for electroless plating of a nickel phosphorous alloy, the plating bath comprising
(i) a water soluble source of nickel ions
(ii) a hypophosphite compound
(iii) at least one complexing agent selected from the group comprising carboxylic acids, polyamines, sulfonic acids and mixtures thereof and
(iv) a stabilizing agent selected from the group consisting of compounds according to formulae (1 ) and (2):
R1S— (CH2)n— SO3R2 (1 )
R3SO3-(CH2)m-S-S-(CH2)m-SO3R3 (2) wherein
R1 , R2 and R3 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, lithium, sodium, potassium and ammonium, n ranges from 1 to 6 and m ranges from 1 to 6 and having a pH value in the range of 3.5 to 6.5.
2. The aqueous plating bath according to claim 1 wherein the concentration of nickel ions ranges from 1 to 8 g/l. The aqueous plating bath composition according to any of the foregoing claims wherein the hypophosphite compound is selected from the group comprising phosphorous acid, sodium hypophosphite, potassium hypophosphite and ammonium hypophosphite.
The aqueous plating bath according to any of the foregoing claims wherein the concentration of the hypophosphite compound ranges from 2 to 60 g/l.
The aqueous plating bath according to any of the foregoing claims wherein the concentration of the at least one complexing agent ranges from 1 to 200 g/l.
The aqueous plating bath according to any of the foregoing claims wherein the concentration of the stabilizing agent according to formulae (1 ) and (2) ranges from 1 to 100 ppm.
The aqueous plating bath according to any of the foregoing claims wherein the plating bath composition is essentially free of heavy metal ions selected from cadmium, thallium, lead and antimony.
The aqueous plating bath according to any of the foregoing claims having a pH value in the range of 4 to 6.
Method for depositing a nickel phosphorous alloy having a phosphorous concentration in the range of 5 to 12 wt.-%, the method comprising the steps of
(i) providing a substrate
(ii) contacting said substrate with an aqueous plating bath according to claims 1 to 8.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014522015A JP6053785B2 (en) | 2011-07-26 | 2012-07-04 | Electroless nickel plating bath composition |
| EP12743909.9A EP2737107B1 (en) | 2011-07-26 | 2012-07-04 | Electroless nickel plating bath composition |
| CN201280036718.5A CN103946420B (en) | 2011-07-26 | 2012-07-04 | Electroless nickel plating bath compositions |
| KR1020147001368A KR101936977B1 (en) | 2011-07-26 | 2012-07-04 | Electroless nickel plating bath composition |
| US14/131,949 US20140150689A1 (en) | 2011-07-26 | 2012-07-04 | Electroless nickel plating bath composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11175295A EP2551375A1 (en) | 2011-07-26 | 2011-07-26 | Electroless nickel plating bath composition |
| EP11175295.2 | 2011-07-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2013013941A1 true WO2013013941A1 (en) | 2013-01-31 |
Family
ID=44736123
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2012/062967 WO2013013941A1 (en) | 2011-07-26 | 2012-07-04 | Electroless nickel plating bath composition |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20140150689A1 (en) |
| EP (2) | EP2551375A1 (en) |
| JP (1) | JP6053785B2 (en) |
| KR (1) | KR101936977B1 (en) |
| CN (1) | CN103946420B (en) |
| TW (1) | TWI555878B (en) |
| WO (1) | WO2013013941A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3034650A1 (en) | 2014-12-16 | 2016-06-22 | ATOTECH Deutschland GmbH | Plating bath compositions for electroless plating of metals and metal alloys |
| WO2016150879A1 (en) | 2015-03-20 | 2016-09-29 | Atotech Deutschland Gmbh | Activation method for silicon substrates |
| EP3190208A1 (en) | 2016-01-06 | 2017-07-12 | ATOTECH Deutschland GmbH | Electroless nickel plating baths comprising aminonitriles and a method for deposition of nickel and nickel alloys |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2551375A1 (en) | 2011-07-26 | 2013-01-30 | Atotech Deutschland GmbH | Electroless nickel plating bath composition |
| US11685999B2 (en) | 2014-06-02 | 2023-06-27 | Macdermid Acumen, Inc. | Aqueous electroless nickel plating bath and method of using the same |
| CN104152877B (en) * | 2014-07-17 | 2017-02-15 | 广东致卓精密金属科技有限公司 | Chemical nickel-plating liquor |
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| PL2145986T3 (en) * | 2008-07-15 | 2010-09-30 | Atotech Deutschland Gmbh | Solution and method for electrochemically depositing a metal on a substrate |
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| EP2551375A1 (en) | 2011-07-26 | 2013-01-30 | Atotech Deutschland GmbH | Electroless nickel plating bath composition |
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- 2012-07-04 KR KR1020147001368A patent/KR101936977B1/en active Active
- 2012-07-04 US US14/131,949 patent/US20140150689A1/en not_active Abandoned
- 2012-07-04 JP JP2014522015A patent/JP6053785B2/en active Active
- 2012-07-04 WO PCT/EP2012/062967 patent/WO2013013941A1/en active Application Filing
- 2012-07-04 EP EP12743909.9A patent/EP2737107B1/en active Active
- 2012-07-04 CN CN201280036718.5A patent/CN103946420B/en active Active
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3034650A1 (en) | 2014-12-16 | 2016-06-22 | ATOTECH Deutschland GmbH | Plating bath compositions for electroless plating of metals and metal alloys |
| US9909216B2 (en) | 2014-12-16 | 2018-03-06 | Atotech Deutschland Gmbh | Plating bath compositions for electroless plating of metals and metal alloys |
| WO2016150879A1 (en) | 2015-03-20 | 2016-09-29 | Atotech Deutschland Gmbh | Activation method for silicon substrates |
| US9960051B2 (en) | 2015-03-20 | 2018-05-01 | Atotech Deutschland Gmbh | Activation method for silicon substrates comprising at least two aromatic acids |
| EP3190208A1 (en) | 2016-01-06 | 2017-07-12 | ATOTECH Deutschland GmbH | Electroless nickel plating baths comprising aminonitriles and a method for deposition of nickel and nickel alloys |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI555878B (en) | 2016-11-01 |
| KR20140041762A (en) | 2014-04-04 |
| TW201309844A (en) | 2013-03-01 |
| JP2014521834A (en) | 2014-08-28 |
| EP2737107A1 (en) | 2014-06-04 |
| CN103946420B (en) | 2015-11-25 |
| US20140150689A1 (en) | 2014-06-05 |
| JP6053785B2 (en) | 2016-12-27 |
| EP2737107B1 (en) | 2015-09-09 |
| KR101936977B1 (en) | 2019-01-09 |
| CN103946420A (en) | 2014-07-23 |
| EP2551375A1 (en) | 2013-01-30 |
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