EP2551375A1 - Stromlose Vernickelungsbadzusammensetzung - Google Patents

Stromlose Vernickelungsbadzusammensetzung Download PDF

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Publication number
EP2551375A1
EP2551375A1 EP11175295A EP11175295A EP2551375A1 EP 2551375 A1 EP2551375 A1 EP 2551375A1 EP 11175295 A EP11175295 A EP 11175295A EP 11175295 A EP11175295 A EP 11175295A EP 2551375 A1 EP2551375 A1 EP 2551375A1
Authority
EP
European Patent Office
Prior art keywords
plating bath
ranges
nickel
concentration
aqueous plating
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.)
Withdrawn
Application number
EP11175295A
Other languages
English (en)
French (fr)
Inventor
Boris Alexander Janssen
Dr. Holger Bera
Sebastian Weißbrod
Dr. Britta Schafsteller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Atotech Deutschland GmbH and Co KG
Original Assignee
Atotech Deutschland GmbH and Co KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=44736123&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2551375(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Atotech Deutschland GmbH and Co KG filed Critical Atotech Deutschland GmbH and Co KG
Priority to EP11175295A priority Critical patent/EP2551375A1/de
Priority to JP2014522015A priority patent/JP6053785B2/ja
Priority to EP12743909.9A priority patent/EP2737107B1/de
Priority to CN201280036718.5A priority patent/CN103946420B/zh
Priority to US14/131,949 priority patent/US20140150689A1/en
Priority to PCT/EP2012/062967 priority patent/WO2013013941A1/en
Priority to KR1020147001368A priority patent/KR101936977B1/ko
Priority to TW101127003A priority patent/TWI555878B/zh
Publication of EP2551375A1 publication Critical patent/EP2551375A1/de
Withdrawn legal-status Critical Current

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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 is related 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 stabilising agent.
  • the at least one stabilising 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 stabilising agent.
  • Common stabilising 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.
  • an aqueous plating bath composition for electroless plating of a nickel phosphorous alloy comprising
  • a nickel phosphorous alloy having a phosphorous content in the range of 5 to 12 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 stabilising 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 hypophosphorous 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 12 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 15 to 75 g/l.
  • carboxylic acids, polyamines or 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, aminoacetic acid, 2-amino propanoic acid, 2-hydroxy propanoic acid, lactic acid; dicarboxylic acids such as succinic acid, amino succinic acid, hydroxy succinic acid, propanedioic acid, tartaric acid, malic acid; tricarboxylic acids such as 2-hydroxy-1,2,3 propane tricarboxylic acid; and tetracarboxylic acids such as ethylene diamine tetra acetic acid (EDTA).
  • monocarboxylic acids such as acetic acid, hydroxyacetic acid, aminoacetic acid, 2-amino propanoic acid, 2-hydroxy propanoic acid, lactic acid
  • dicarboxylic acids such as succinic acid, amino succinic acid, hydroxy succinic acid, propanedioic acid, tartaric acid, malic acid
  • tricarboxylic acids such
  • the most preferred complexing agents are selected from the group consisting of mono-carboxylic acids, and di-carboxylic acids.
  • mixtures of two or more of the above complexing agents are utilised.
  • the stabilising agent is selected from compounds according to formulae (1) and (2): R 1 S-(CH 2 ) n -SO 3 R 2 (1) R 3 SO 3 -(CH 2 ) m -S-S-(CH 2 ) m -SO 3 R 3 (2) wherein
  • 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 stabilising agent according to formulae (1) and (2) in the plating bath composition 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 bicarbonates.
  • bath-soluble and bath-compatible alkaline substances such as sodium, potassium or ammonium hydroxides, carbonates and bicarbonates.
  • 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.
  • 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.
  • 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 circulation 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 concentration of nickel ions and hypophosphite ions, as well as the pH level within the desired limits.
  • a electroless nickel plating bath comprising 6 g/l nickel ions as nickel sulphate, hypophosphite as reducing agent, a mixture of lactic acid and malic acid as complexing agents and lead ions as stabilising additive was tested.
  • the plating results are summarised in Table 1.
  • MTO metal turn over.
  • 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 stabilising 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)
EP11175295A 2011-07-26 2011-07-26 Stromlose Vernickelungsbadzusammensetzung Withdrawn EP2551375A1 (de)

Priority Applications (8)

Application Number Priority Date Filing Date Title
EP11175295A EP2551375A1 (de) 2011-07-26 2011-07-26 Stromlose Vernickelungsbadzusammensetzung
JP2014522015A JP6053785B2 (ja) 2011-07-26 2012-07-04 無電解ニッケルめっき浴組成物
EP12743909.9A EP2737107B1 (de) 2011-07-26 2012-07-04 Stromlose vernickelungsbadzusammensetzung
CN201280036718.5A CN103946420B (zh) 2011-07-26 2012-07-04 无电镀镍镀浴组合物
US14/131,949 US20140150689A1 (en) 2011-07-26 2012-07-04 Electroless nickel plating bath composition
PCT/EP2012/062967 WO2013013941A1 (en) 2011-07-26 2012-07-04 Electroless nickel plating bath composition
KR1020147001368A KR101936977B1 (ko) 2011-07-26 2012-07-04 무전해 니켈 도금욕 조성물
TW101127003A TWI555878B (zh) 2011-07-26 2012-07-26 無電鎳鍍浴組合物

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP11175295A EP2551375A1 (de) 2011-07-26 2011-07-26 Stromlose Vernickelungsbadzusammensetzung

Publications (1)

Publication Number Publication Date
EP2551375A1 true EP2551375A1 (de) 2013-01-30

Family

ID=44736123

Family Applications (2)

Application Number Title Priority Date Filing Date
EP11175295A Withdrawn EP2551375A1 (de) 2011-07-26 2011-07-26 Stromlose Vernickelungsbadzusammensetzung
EP12743909.9A Active EP2737107B1 (de) 2011-07-26 2012-07-04 Stromlose vernickelungsbadzusammensetzung

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP12743909.9A Active EP2737107B1 (de) 2011-07-26 2012-07-04 Stromlose vernickelungsbadzusammensetzung

Country Status (7)

Country Link
US (1) US20140150689A1 (de)
EP (2) EP2551375A1 (de)
JP (1) JP6053785B2 (de)
KR (1) KR101936977B1 (de)
CN (1) CN103946420B (de)
TW (1) TWI555878B (de)
WO (1) WO2013013941A1 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2737107B1 (de) 2011-07-26 2015-09-09 Atotech Deutschland GmbH Stromlose vernickelungsbadzusammensetzung
EP3190208A1 (de) * 2016-01-06 2017-07-12 ATOTECH Deutschland GmbH Stromlose nickelplattierungsbäder mit aminonitrilen und verfahren zur abscheidung von nickel und nickellegierungen
US11685999B2 (en) 2014-06-02 2023-06-27 Macdermid Acumen, Inc. Aqueous electroless nickel plating bath and method of using the same

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104152877B (zh) * 2014-07-17 2017-02-15 广东致卓精密金属科技有限公司 一种化学镀镍液
EP3034650B1 (de) 2014-12-16 2017-06-21 ATOTECH Deutschland GmbH Plattierungsbadzusammensetzungen zur stromlosen Abscheidung von Metallen und Metalllegierungen
CN107429399B (zh) 2015-03-20 2020-02-07 埃托特克德国有限公司 用于硅基材的活化方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2830014A (en) 1954-03-22 1958-04-08 Dehydag Gmbh Electroplating process
JPS502861B1 (de) * 1970-05-09 1975-01-29
CH620710A5 (en) * 1975-10-06 1980-12-15 Fedor Petrovich Potapov Process for chemical nickel-plating of workpieces having a catalytic surface, and installation for carrying out the process
GB2155041A (en) * 1984-03-05 1985-09-18 Omi Int Corp Aqueous electroless nickel plating
US20050013928A1 (en) 2003-07-15 2005-01-20 Tokyo Electron Limited Electroless plating pre-treatment solution and electroles plating method
US20060264043A1 (en) * 2005-03-18 2006-11-23 Stewart Michael P Electroless deposition process on a silicon contact

Family Cites Families (13)

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US4150180A (en) * 1975-12-08 1979-04-17 Potapov Fedor P Method for chemical nickel-plating of parts having a catalytic surface employing a vessel having an upper heated zone and a lower cooled zone
US4483711A (en) * 1983-06-17 1984-11-20 Omi International Corporation Aqueous electroless nickel plating bath and process
TW390915B (en) * 1995-10-23 2000-05-21 Uyemura C & Co Ltd Electroless nickel plating solution and method
JP3594894B2 (ja) * 2000-02-01 2004-12-02 新光電気工業株式会社 ビアフィリングめっき方法
DE10327374B4 (de) 2003-06-18 2006-07-06 Raschig Gmbh Verwendung von propansulfonierten und 2-Hydroxy-propansulfonierten Alkylaminaloxylaten als Hilfsmittel zur elektrolytischen Abscheidung von metallischen Schichten und galvanische Bäder enthaltend diese
JP4731851B2 (ja) 2004-07-28 2011-07-27 キヤノン株式会社 画像転送システム
US20060026043A1 (en) * 2004-07-30 2006-02-02 Schneider John K Medical records system and method
US8182594B2 (en) * 2005-10-07 2012-05-22 Nippon Mining & Metals Co., Ltd. Electroless nickel plating liquid
TWI348499B (en) * 2006-07-07 2011-09-11 Rohm & Haas Elect Mat Electroless copper and redox couples
EP2145986B1 (de) * 2008-07-15 2010-03-24 Atotech Deutschland Gmbh Lösung und Verfahren zur elektrochemischen Abscheidung eines Metalls auf ein Substrat
EP2177646B1 (de) * 2008-10-17 2011-03-23 ATOTECH Deutschland GmbH Spannungsreduzierte Ni-P/Pd-Stapel für Waferoberfläche
EP2199315B1 (de) 2008-12-19 2013-12-11 Basf Se Egalisierungswirkstoff enthaltende Galvanisierzusammensetzung
EP2551375A1 (de) 2011-07-26 2013-01-30 Atotech Deutschland GmbH Stromlose Vernickelungsbadzusammensetzung

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2830014A (en) 1954-03-22 1958-04-08 Dehydag Gmbh Electroplating process
JPS502861B1 (de) * 1970-05-09 1975-01-29
CH620710A5 (en) * 1975-10-06 1980-12-15 Fedor Petrovich Potapov Process for chemical nickel-plating of workpieces having a catalytic surface, and installation for carrying out the process
GB2155041A (en) * 1984-03-05 1985-09-18 Omi Int Corp Aqueous electroless nickel plating
US20050013928A1 (en) 2003-07-15 2005-01-20 Tokyo Electron Limited Electroless plating pre-treatment solution and electroles plating method
US20060264043A1 (en) * 2005-03-18 2006-11-23 Stewart Michael P Electroless deposition process on a silicon contact

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 197508, Derwent World Patents Index; AN 1975-13728W, XP002661625 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2737107B1 (de) 2011-07-26 2015-09-09 Atotech Deutschland GmbH Stromlose vernickelungsbadzusammensetzung
US11685999B2 (en) 2014-06-02 2023-06-27 Macdermid Acumen, Inc. Aqueous electroless nickel plating bath and method of using the same
EP3190208A1 (de) * 2016-01-06 2017-07-12 ATOTECH Deutschland GmbH Stromlose nickelplattierungsbäder mit aminonitrilen und verfahren zur abscheidung von nickel und nickellegierungen
WO2017118655A1 (en) * 2016-01-06 2017-07-13 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
JP6053785B2 (ja) 2016-12-27
KR20140041762A (ko) 2014-04-04
CN103946420A (zh) 2014-07-23
US20140150689A1 (en) 2014-06-05
EP2737107B1 (de) 2015-09-09
TW201309844A (zh) 2013-03-01
TWI555878B (zh) 2016-11-01
EP2737107A1 (de) 2014-06-04
CN103946420B (zh) 2015-11-25
JP2014521834A (ja) 2014-08-28
KR101936977B1 (ko) 2019-01-09
WO2013013941A1 (en) 2013-01-31

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