EP0167949A1 - Moyen pour le dépôt sans courant d'étain et/ou de plomb - Google Patents

Moyen pour le dépôt sans courant d'étain et/ou de plomb Download PDF

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Publication number
EP0167949A1
EP0167949A1 EP85108089A EP85108089A EP0167949A1 EP 0167949 A1 EP0167949 A1 EP 0167949A1 EP 85108089 A EP85108089 A EP 85108089A EP 85108089 A EP85108089 A EP 85108089A EP 0167949 A1 EP0167949 A1 EP 0167949A1
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EP
European Patent Office
Prior art keywords
tin
lead
salt
mineral acid
acid
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.)
Granted
Application number
EP85108089A
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German (de)
English (en)
Other versions
EP0167949B1 (fr
Inventor
Eugen Dr. Scholz
Hans-Jürgen Luttmann
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.)
Honeywell Riedel de Haen AG
Original Assignee
Riedel de Haen AG
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
Application filed by Riedel de Haen AG filed Critical Riedel de Haen AG
Publication of EP0167949A1 publication Critical patent/EP0167949A1/fr
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Publication of EP0167949B1 publication Critical patent/EP0167949B1/fr
Expired legal-status Critical Current

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    • 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
    • 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

Definitions

  • the invention relates to an agent for the currentless deposition of tin and / or 'lead, which consists of an aqueous solution of a tin salt and / or lead salt, which contains a mineral acid and a sulfur-containing complexing agent for tin and / or lead, and on Process for the electroless deposition of metallic tin and / or lead from such a solution onto a substrate.
  • a metal substrate with a tin-lead alloy is plated by immersing the substrate in a bath containing a tin salt, a lead (II) salt and a sulfur-containing complexing agent for the tin and the lead.
  • tin (II) chloride is mentioned as tin salt and only lead (II) chloride as lead salt.
  • the bath preferably contains thiourea or a thiourea derivative as a complexing agent. Copper or a copper alloy are particularly suitable as substrates; in this case the bath should have a pH of 0.5 to 1.0.
  • a tin plating bath which contains a soluble tin (II) salt, a sulfur-containing component, a mineral acid and a wetting agent is suitable for the electrolytic deposition of a tin coating on metallic substrates.
  • the tin salt can be, inter alia, a fluoborate
  • the sulfur-containing component is, for example, an aliphatic sulfur-nitrogen compound such as thiourea, a five-membered heterocyclic compound such as thiazole and isothiazole or a dithiol such as 1,2-ethanedithiol.
  • the sulfur-containing component preferably contains at least two Sulfur compounds, one of which must be an alkali metal polysulfide.
  • a strong inorganic mineral acid is used as the mineral acid, namely hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid.
  • Suitable wetting agents are organic surface-active wetting agents, especially from the fluorinated carboxylic acid series.
  • the known baths have the disadvantage that they are operated at an elevated temperature since there is a risk of salting out at a lower temperature. At higher temperatures, decomposition of the sulfur component is to be feared.
  • the object of the invention is to provide a metallization bath which shows no salting-out phenomena at room temperature and can therefore also be used at low working temperatures.
  • the invention relates to an agent for the currentless deposition of tin and / or lead, consisting of an aqueous solution of a tin salt and / or lead salt, which contains a mineral acid and a sulfur-containing complexing agent for tin and / or lead, which is characterized in that the Tin salt and / or lead salt is a salt of a fluorine-containing mineral acid and the mineral acid is a fluorine-containing mineral acid and the solution has a pH of 0 to 3.
  • the invention further relates to a method for the currentless deposition of metallic tin and / or lead from an aqueous solution of a tin salt and / or lead salt, which contains a mineral acid and a sulfur-containing complexing agent for tin and / or lead, on a substrate, which is characterized in that the substrate at a temperature of 10 to 80 ° C with a aqueous solution of a tin salt and / or lead salt of a fluorine-containing mineral acid which contains a fluorine-containing mineral acid and a sulfur-containing complexing agent for tin and / or lead and has a pH of 0 to 3.
  • the tin salt contained in the agent according to the invention is a tin salt of a fluorine-containing mineral acid, preferably tin (II) fluoride, tin (II) fluoroborate or tin (II) fluorosilicate.
  • the lead salt is also a salt of a fluorine-containing mineral acid, preferably lead (II) fluoride, lead (II) fluoroborate or lead (II) fluorosilicate.
  • the tin salt and the lead salt are each contained in the agent in dissolved form.
  • the agent can each contain a tin salt or a lead salt or a mixture of a lead salt and a tin salt, in which case the respective anions can be the same or different.
  • the amount of tin is 1 to 50, preferably 5 to 30 g / l of solution, and the amount of lead is in the range of 1 to 10, preferably 2 to 5 g / l of solution.
  • the sulfur-containing complexing agent for tin and / or lead is an aliphatic compound which contains sulfur and nitrogen and can form chelates with tin and / or lead; thiourea or a thiourea substituted with lower alkyl radicals is particularly suitable, e.g. Tetramethylthiourea.
  • the amount of the complexing agent is 10 to 400, preferably 50 to 150 g / 1 solution.
  • the mineral acid is a fluorine-containing mineral acid, in particular hydrofluoric acid, fluoroboric acid or fluorosilica acid. It is present in the solution in a concentration of 1 to 200, preferably 10 to 150 g / l.
  • the agent according to the invention has a pH of 0 to 3, preferably 0.1 to 2 (measured with the hydrogen electrode).
  • the agent is prepared by dissolving the salt or salt mixture, the mineral acid and the complexing agent in water at a temperature of 15 to 30 ° C.
  • the use of demineralized water is advisable.
  • the remedy is used in the form of a clear solution.
  • the agent according to the invention is suitable as an immersion bath or spray liquid for the electroless deposition of metallic tin and / or lead on metallic substrates, in particular copper, copper alloys, oxidized tin, or oxidized tin / lead alloys.
  • the substrate is brought into contact with the agent at a temperature of 10 to 80 ° C., preferably 15 to 30 ° C.
  • the amount of tin and / or lead deposited depends on the temperature and the treatment time; this can be seen from the table (application example) and the figure.
  • the tin and / or lead is deposited in a thin layer that is pore-free from a layer thickness of 1 ⁇ m.
  • a copper board (100 mm x 30 mm x 1.5 mm) is used as the substrate, and the layer thickness is determined by the coulometric detachment method (DIN 50 955).
  • Such plated substrates are used, for example, in printed circuit board technology; the layers serve as a protection against etching and as a soldering aid.
  • the agents according to the invention show no signs of salting out.
  • Another advantage is their low sensitivity to oxidation by atmospheric oxygen; the Means are stable for three months.
  • Another advantage is the high deposition rate, even at temperatures below 30 ° C.
  • Copper boards with the dimensions 100 mm x 30 mm x 1.5 mm were immersed for 60 minutes at different temperatures (20 ° C, 40 ° C, 60 ° C) in solutions according to Example 5.
  • the layer thicknesses obtained were determined by the coulometric peeling method (DIN 50 955). The determination of the layer thickness at intervals of 10 min each gave the values listed in the table. The course of the tin deposition can also be seen in the figure.

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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)
EP85108089A 1984-07-09 1985-06-29 Moyen pour le dépôt sans courant d'étain et/ou de plomb Expired EP0167949B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3425214 1984-07-09
DE19843425214 DE3425214A1 (de) 1984-07-09 1984-07-09 Mittel fuer die stromlose abscheidung von zinn und/oder blei

Publications (2)

Publication Number Publication Date
EP0167949A1 true EP0167949A1 (fr) 1986-01-15
EP0167949B1 EP0167949B1 (fr) 1988-04-20

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ID=6240176

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85108089A Expired EP0167949B1 (fr) 1984-07-09 1985-06-29 Moyen pour le dépôt sans courant d'étain et/ou de plomb

Country Status (2)

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EP (1) EP0167949B1 (fr)
DE (2) DE3425214A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0278752A1 (fr) * 1987-02-10 1988-08-17 A.P.T. Advanced Plating Technologies, Ltd. Solution d'immersion pour revêtir d'étain et procédé de revêtement l'utilisant
US5143544A (en) * 1990-06-04 1992-09-01 Shipley Company Inc. Tin lead plating solution
EP0524422A2 (fr) * 1991-07-22 1993-01-27 Shipley Company Inc. Traitement d'une surface en étain-plomb

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04363093A (ja) * 1990-11-27 1992-12-15 Mitsubishi Electric Corp プリント基板の製造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4027055A (en) * 1973-07-24 1977-05-31 Photocircuits Division Of Kollmorgan Corporation Process of tin plating by immersion
DE2917019A1 (de) * 1978-04-28 1979-11-08 Gould Inc Verfahren zur metallisierung von verbundmaterial und dazu geeignete badzusammensetzung

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4027055A (en) * 1973-07-24 1977-05-31 Photocircuits Division Of Kollmorgan Corporation Process of tin plating by immersion
DE2917019A1 (de) * 1978-04-28 1979-11-08 Gould Inc Verfahren zur metallisierung von verbundmaterial und dazu geeignete badzusammensetzung

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, unexamined applications, C Field, Vol. 8, No. 178, 16. August 1984 THE PATENT OFFICE JAPANESE GOVERNMENT Seite 85 (C-238); & JP-A-59 074 271 (SUWA SEIKOSHA K.K.) 26-04-1984 *
SOVIET INVENTIONS ILLUSTRATED, Sektion Ch, Woche C05, 12. Marz 1980 DERWENT PUBLICATIONS LTD., London M 11; & SU-A-662622 (KUZNETSOVA O M) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0278752A1 (fr) * 1987-02-10 1988-08-17 A.P.T. Advanced Plating Technologies, Ltd. Solution d'immersion pour revêtir d'étain et procédé de revêtement l'utilisant
US5143544A (en) * 1990-06-04 1992-09-01 Shipley Company Inc. Tin lead plating solution
EP0524422A2 (fr) * 1991-07-22 1993-01-27 Shipley Company Inc. Traitement d'une surface en étain-plomb
EP0524422A3 (fr) * 1991-07-22 1994-04-13 Shipley Co

Also Published As

Publication number Publication date
DE3425214A1 (de) 1986-02-06
DE3562278D1 (en) 1988-05-26
EP0167949B1 (fr) 1988-04-20

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