EP1230034B1 - Verfahren zur stromlosen verzinnung von kupfer oder kupferlegierungen - Google Patents

Verfahren zur stromlosen verzinnung von kupfer oder kupferlegierungen Download PDF

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Publication number
EP1230034B1
EP1230034B1 EP00978519A EP00978519A EP1230034B1 EP 1230034 B1 EP1230034 B1 EP 1230034B1 EP 00978519 A EP00978519 A EP 00978519A EP 00978519 A EP00978519 A EP 00978519A EP 1230034 B1 EP1230034 B1 EP 1230034B1
Authority
EP
European Patent Office
Prior art keywords
tin
copper
use according
electrolyte
thiourea
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
Application number
EP00978519A
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English (en)
French (fr)
Other versions
EP1230034A4 (de
EP1230034A1 (de
Inventor
Jane Bell
Joachim Heyer
Jurgen Hupe
Ingo Kalker
Marlies Kleinfeld
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.)
MacDermid Enthone Inc
Original Assignee
Enthone Inc
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Publication date
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Application filed by Enthone Inc filed Critical Enthone Inc
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Publication of EP1230034A4 publication Critical patent/EP1230034A4/de
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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
    • 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
    • C23C18/48—Coating with alloys

Definitions

  • the invention deals with a use of a foreign metal as diffusion barrier.
  • Non-galvanic tin precipitation is known from the current state of the art and is commonly used, based both on acidic and alkaline electrolytes.
  • copper and copper alloys are tin plated in an ion exchange process, for example pipes, pipe sections and fittings for cold and hot water, battery posts, sanitary connectors as well as conductor frames.
  • bivalent tin salt is used, such as for example tin chloride, tin sulfate, tin tetrafluorborate or tin methanesulphonate.
  • non-galvanically precipitated tin layers on copper and copper alloys is effected by the exchange of copper for tin atoms, whereby the removal of the copper is made possible by a complexing agent.
  • the tin layers produced with the tin precipitation processes known heretofore only grow until no more surface copper can pass through the porous tin layer.
  • the achievable layer thickness is therefore limited to a maximum of 2 ⁇ m.
  • the disadvantage is that a diffusion of metals from the base material, especially of alloy components, can occur which may lead to undesirable effects.
  • copper of a potable water pipe may dissolve and diffuse through the tin and can enter the water, which may have effects detrimental to health.
  • the liberation of lead and zinc from brass base materials for example, can not be prevented by the precipitation of a generic tin layer.
  • difficulties with soldering of the surface of tin plated base materials due to the diffusion are a disadvantage.
  • US 5,435,838 discloses a method comprising the deposition of a tin-bismuth plate onto a surface formed of copper. Large amounts of bismuth, however, are required and the metal plate is prone to corrosion.
  • US 4,749,626 discloses a tin coating solution comprising an addition for inhibiting the growth of tin whiskers.
  • the addition is a metal salt of the group consisting of palladium chloride or silver sulfate.
  • JP H09-302476 discloses an electroless plating method of a tin-silver alloy onto a copper substrate in order to replace harmful tin-lead solder. Certain additions are necessary for the plating bath in order to dissolve stably the silver ions in the solution of the plating bath and the suppress preferential deposition of silver. A diffusion barrier is not used.
  • a tin bath is suggested for the formation of a tin layer by chemical precipitation, which contains at least one foreign metal.
  • the addition of foreign metals to the tin bath achieves an advantageous suppression of the diffusion processes, and thus a diffusion barrier is built which prevents the liberation of metals from the base material to a large extent.
  • the advantages thus gained are good soldering characteristics at the surface and good durability of the tin layer.
  • a metal of the group silver, bismuth, nickel, titanium, zirconium and indium is suggested as the foreign metal, whereby the use of indium has shown to be especially effective.
  • the foreign metal for the formation of a diffusion barrier within the tin layer, at least one of the above metals is added to the tin bath as a foreign metal.
  • thiourea and/or its derivative is used as the comlexing agent.
  • Thiourea as the complexing agent enables the liberation of positively charged copper ions.
  • a copper thiourea complex forms which is soluble in electrolytes at a temperature of >28°C.
  • As a result of the complexing of the copper its potential compared to that of tin is reduced.
  • the then more noble tin precipitates, forming a layer of tin on the copper.
  • the liberated copper ions concentrate in the electrolyte, whereby at a copper concentration above 7g/l economical working is no longer possible since at these concentrations tin is no longer precipitated at satisfactory rates.
  • the electrolytic bath further comprises an antioxidant.
  • a tin bath which preferably contains the following components:
  • the use described by the invention makes it possible to produce diffusion-stable tin layers by means of chemical precipitation, whereby the diffusion barrier generated by the addition of foreign metals prevents the liberation of metals from the base materials in an advantageous manner.
  • thiourea as complexing agent it becomes possible to remove the copper ions liberated from the copper from the electrolyte by filtration, and thus to achieve a substantially extended useful life. Furthermore, in this manner a substantial acceleration of the process is achieved.

Claims (14)

  1. Verwendung eines Fremdmetalls aus der Gruppe, die aus Ag, Bi, Ni, Ti, Zr und In besteht, als Diffusionsbarriere zur Unterdrückung der Diffusion eines Basisschichtmaterials durch eine Zinnschicht hindurch, wobei es sich bei der Basisschicht um eine Kupfer- oder Kupferlegierungsschicht handelt und die Zinnschicht stromlos auf der Basisschicht abgeschieden wird.
  2. Verwendung nach Anspruch 1, wobei die Zinnschicht aus einem Elektrolyt abgeschieden wird, der 5 bis 200 g/l Methansulfonsäure, wodurch das Zinnbad einen pH-Wert von 0 bis 3 annimmt, 1 bis 30 g/l Zinn und 1 bis 500 mg/l des Fremdmetalls umfasst, das als Diffusionsbarriere verwendet wird.
  3. Verwendung nach Anspruch 2, wobei der Elektrolyt ein Antioxidationsmittel umfasst.
  4. Verwendung nach Anspruch 2 oder 3, wobei der Elektrolyt Thioharnstoff und/oder ein Derivat desselben als Komplexbildner umfasst.
  5. Verwendung nach einem der Ansprüche 2 bis 4, wobei der Elektrolyt wiederaufbereitet wird, indem das in dem Elektrolyt gelöste Kupfer durch Ausfällen als Kupfer-Thioharnstoff-Verbindung entfernt wird.
  6. Verwendung nach Anspruch 5, wobei der Kupfer-Thioharnstoff-Niederschlag durch Filtration aus dem Elektrolyt entfernt wird, wodurch der Ausfällungsprozess beschleunigt wird.
  7. Verwendung nach einem der Ansprüche 1 bis 6, wobei das Fremdmetall Silber umfasst.
  8. Verwendung nach einem der Ansprüche 1 bis 6, wobei das Fremdmetall Bismut umfasst.
  9. Verwendung nach einem der Ansprüche 1 bis 6, wobei das Fremdmetall Indium umfasst.
  10. Verwendung nach einem der Ansprüche 2 bis 9, wobei der Elektrolyt ein zweiwertiges Zinnsalz umfasst.
  11. Verwendung nach Anspruch 10, wobei das zweiwertige Zinnsalz Zinnmethansulfonat umfasst.
  12. Verwendung nach einem der Ansprüche 2 bis 11, wobei der Elektrolyt 10 bis 200 g/l Thioharnstoff oder ein Thioharnstoff-Derivat umfasst.
  13. Verwendung nach einem der Ansprüche 2 bis 12, wobei der Elektrolyt 1 bis 10 g/l Benetzungsmittel umfasst.
  14. Verwendung nach einem der Ansprüche 2 bis 13, wobei die Temperatur des Elektrolyten während der Zinnabscheidung 35 °C bis 80 °C beträgt.
EP00978519A 1999-11-12 2000-11-09 Verfahren zur stromlosen verzinnung von kupfer oder kupferlegierungen Expired - Lifetime EP1230034B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19954613 1999-11-12
DE19954613A DE19954613A1 (de) 1999-11-12 1999-11-12 Verfahren zur stromlosen Verzinnung von Kupfer oder Kupferlegierungen
PCT/US2000/030983 WO2001034310A1 (en) 1999-11-12 2000-11-09 Process for the non-galvanic tin plating of copper or copper alloys

Publications (3)

Publication Number Publication Date
EP1230034A1 EP1230034A1 (de) 2002-08-14
EP1230034A4 EP1230034A4 (de) 2003-01-08
EP1230034B1 true EP1230034B1 (de) 2010-09-08

Family

ID=7928903

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00978519A Expired - Lifetime EP1230034B1 (de) 1999-11-12 2000-11-09 Verfahren zur stromlosen verzinnung von kupfer oder kupferlegierungen

Country Status (7)

Country Link
EP (1) EP1230034B1 (de)
JP (1) JP4084569B2 (de)
CN (1) CN1192125C (de)
AT (1) ATE480340T1 (de)
AU (1) AU1597501A (de)
DE (2) DE19954613A1 (de)
WO (1) WO2001034310A1 (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4998704B2 (ja) 2007-01-22 2012-08-15 上村工業株式会社 置換錫合金めっき皮膜の形成方法、置換錫合金めっき浴及びめっき性能の維持方法
US9175400B2 (en) * 2009-10-28 2015-11-03 Enthone Inc. Immersion tin silver plating in electronics manufacture
DE102010031181A1 (de) 2010-07-09 2012-01-12 Atotech Deutschland Gmbh Verfahren und Anordnung zum Abscheiden einer Metallschicht
JP5715411B2 (ja) * 2010-12-28 2015-05-07 ローム・アンド・ハース電子材料株式会社 めっき液中から不純物を除去する方法
JP5830242B2 (ja) * 2010-12-28 2015-12-09 ローム・アンド・ハース電子材料株式会社 めっき液中から不純物を除去する方法
JP5937320B2 (ja) * 2011-09-14 2016-06-22 ローム・アンド・ハース電子材料株式会社 めっき液中から不純物を除去する方法
MA37931A1 (fr) * 2012-08-13 2016-07-29 Teni Boulikas Procédés améliorés permettant de traiter un cancer avec une toxicité rénale réduite

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4749626A (en) 1985-08-05 1988-06-07 Olin Corporation Whisker resistant tin coatings and baths and methods for making such coatings
US5160422A (en) * 1989-05-29 1992-11-03 Shimizu Co., Ltd. Bath for immersion plating tin-lead alloys
JP2833026B2 (ja) 1989-07-05 1998-12-09 上村工業株式会社 無電解錫めっき方法
US5266103A (en) * 1991-07-04 1993-11-30 C. Uyemura & Co., Ltd. Bath and method for the electroless plating of tin and tin-lead alloy
US5211831A (en) 1991-11-27 1993-05-18 Mcgean-Rohco, Inc. Process for extending the life of a displacement plating bath
US5217751A (en) * 1991-11-27 1993-06-08 Mcgean-Rohco, Inc. Stabilized spray displacement plating process
JP3274232B2 (ja) * 1993-06-01 2002-04-15 ディップソール株式会社 錫−ビスマス合金めっき浴及びそれを使用するめっき方法
US5391402A (en) * 1993-12-03 1995-02-21 Motorola Immersion plating of tin-bismuth solder
JP3419995B2 (ja) 1996-05-10 2003-06-23 株式会社大和化成研究所 無電解錫−銀合金めっき浴
JP3660777B2 (ja) * 1997-03-06 2005-06-15 日本エレクトロプレイテイング・エンジニヤース株式会社 錫合金膜の形成方法およびその錫合金めっき浴

Also Published As

Publication number Publication date
DE60044943D1 (de) 2010-10-21
WO2001034310A1 (en) 2001-05-17
CN1192125C (zh) 2005-03-09
EP1230034A4 (de) 2003-01-08
DE19954613A1 (de) 2001-05-17
EP1230034A1 (de) 2002-08-14
AU1597501A (en) 2001-06-06
JP2003514120A (ja) 2003-04-15
JP4084569B2 (ja) 2008-04-30
CN1387465A (zh) 2002-12-25
ATE480340T1 (de) 2010-09-15

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