EP0180265B1 - Verfahren zur autokatalytischen Verzinnung von Kupfer- und Kupferlegierungsgegenständen - Google Patents

Verfahren zur autokatalytischen Verzinnung von Kupfer- und Kupferlegierungsgegenständen Download PDF

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Publication number
EP0180265B1
EP0180265B1 EP85201585A EP85201585A EP0180265B1 EP 0180265 B1 EP0180265 B1 EP 0180265B1 EP 85201585 A EP85201585 A EP 85201585A EP 85201585 A EP85201585 A EP 85201585A EP 0180265 B1 EP0180265 B1 EP 0180265B1
Authority
EP
European Patent Office
Prior art keywords
mol
tin
copper
solution
ions
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
Application number
EP85201585A
Other languages
English (en)
French (fr)
Other versions
EP0180265A1 (de
Inventor
Arian Molenaar
Jacobus Johannes Chretien Coumans
Brigitta Christina Maria Meenderink
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.)
Koninklijke Philips NV
Original Assignee
Philips Gloeilampenfabrieken NV
Koninklijke Philips Electronics NV
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 Philips Gloeilampenfabrieken NV, Koninklijke Philips Electronics NV filed Critical Philips Gloeilampenfabrieken NV
Publication of EP0180265A1 publication Critical patent/EP0180265A1/de
Application granted granted Critical
Publication of EP0180265B1 publication Critical patent/EP0180265B1/de
Expired 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
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating
    • 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 a method of autocatalytically tin-plating articles of copper or of a copper alloy.
  • GB-PS-2 039 534 discloses an electrolessly operating tin-plating solution which consists of a strongly alkaline aqueous solution containing at least 0.20 mol/litre of bivalent tin ions.
  • the operating temperature of said solution is between 60 and 95°C and it contains at least 1 mol/litre of alkali hydroxide.
  • a strong reduction agent for example hypophosphite or a borazane
  • soldering properties of tin deposited electrolessly directly on a copper surface are insufficient in practice without additions. Even with an addition of hypophosphite, which for practical reasons is rather to be avoided, the desired soldering properties are often not obtained.
  • the exchanged layer which is obtained from the alkaline solution has the structure of (3-tin, the same modification which is also obtained from the autocatalytic solution. In spite of the fact that the same modification is deposited, often no optimum soldering properties are obtained.
  • the exchanged layer also comprises the alloy Cu 6 Sn 5 , better soldering properties are nevertheless obtained after growing said layer by means of the autocatalytic method which deposits tin in the form of the ⁇ -modification, than when an alkaline exchanging solution has been used for the pre-treatment.
  • Various acids may be used in the exchanging solution, for example, hydrochloric acid, sulphuric acid or citric acid, but the very best results are obtained by means of a sulphuric acid solution.
  • This aqueous solution is preferably used at a temperature between 20 and 30°C, the articles being kept immersed in it for 10 minutes.
  • the best result as regards the quality and the adhesion of the tin deposit is obtained when the surface of copper or the copper alloy is previously cleaned.
  • This cleaning may be done mechanically or chemically.
  • the chemical method may be a cleaning, polishing or etching method but the surface is preferably treated by means of a chemical polishing solution.
  • the articles are kept immersed at room temperature for 30-60 seconds.
  • the electroless tinplating solution comprises an aqueous solution containing at least 0.20 mol/I of a salt of bivalent tin and at least 1 mol/I of alkalihydroxide, works with these bath-constituents only.
  • the solution contains also a complex-forming agent for bivalent tin-ions, such as citrate or tartrate.
  • citrate or tartrate The presence of tartrate is to be preferred as higher tin-concentrations are then attainable.
  • the presence of citrate or tartrate moreover produces a tin-deposit of further improved solderability.
  • hypophosphite In certain cases it may be advantageous to nevertheless add hypophosphite to the autocatalytic solution.
  • the reliability of the soldered joint is further increased by the combination of pre-treatment and addition of hypophosphite to the autocatalytic solution.
  • US-A-2 369 620 discloses an acid tin immersion bath containing SnCl 2 , H 2 SO 4 and thiourea. With this bath only thin layers are obtained after a long time, e.g. 2.3 mg Sn/cm 2 after 24 hours.
  • the process according to US-A-2 369 620 is based on the principle of metal exchange. It is possible to continue deposition, but the increase in the amount of deposited Sn vs time is due to the fact that the obtained tin coating is not dense, but porous. In that case tin growth continues as long as parts of the copper surface are still uncoated. The solderability of these layers is poor. There is no suggestion to use such an acid immersion bath as a pre-treatment solution for an autocatalytic tin bath.
  • Copper plates having dimensions 3xl cm 2 were subjected to the following treatments.
  • a dull Cu layer of 15 ⁇ m was electro-deposited on said plates by means of an acid copper sulphate bath. They were then rinsed in water and polished in the solution of the following composition for 1 minute:
  • connection wires of glow discharge lamps consisting of copper-clad wire having a diameter of 3 and 4 millimetres were subjected to the following treatment. First of all they were immersed for 10 seconds in H 2 SO 4 (48% by weight) at 90°C, then rinsed with demineralized water for 10 seconds and polished in the following solution for 30 seconds:
  • connection wires were dipped at 30°C in the following aqueous solution for 15 minutes:
  • connection wires were immersed at 75°C for 15 minutes in the following aqueous solution:
  • Copper plates having dimensions of 3x1 cm 2 were subjected to the following treatments. First of all they were coated by electrodeposition with a dull copper layer of 15 ⁇ m by means of an acid copper sulphate bath, rinsed in water and subjected to one of the following cleaning treatments:
  • the etching rates of the said cleaning treatments are as follows:
  • the solderability was evaluated as follows:
  • Copper plates having dimensions 3x1 cm 2 were subjected to the following treatments.
  • a dull copper layer of 15 ⁇ m was electrodeposited on them by means of an acid coppersulphate bath. They were subsequently rinsed in water and during one minute polished in the solution of the following composition:
  • This solution was prepared by dissolving the Na-citrate in about half of the volume of water and adding the SnCl 2 ⁇ 2H 2 0 (soin. 1), dissolving NaOH in about half of the volume of water (soln. 2) and combine solutions 1 and 2 while stirring vigorously.
  • the plates were electrolessly tin-plated at 75°C during 3 hours in an aqueous solution of the following composition:
  • This solution was prepared by dissolving the Na-K-tartrate in about half of the volume of water, dissolving the NaOH in the remaining volume of water, combining the two solutions and adding thereto the SnCl 2 ⁇ 2H 2 0.

Landscapes

  • 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)
  • Electrochemistry (AREA)
  • Chemically Coating (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Claims (7)

1. Verfahren zur autokatalytischen Verzinnung von Gegenständen aus Kupfer oder Kupferlegierung, wobei die Gegenstände zunächst mit einer wässrigen Lösung eines zweiwertigen Zinnsalzes und eines Komplexformers für Cu++- und/oder Cu+-lonen vorbehandelt werden, wodurch eine Kupferschicht gegen eine Zinnschicht ausgewechselt wird, wonach der Gegenstand in eine stark alkalische wässrige Lösung getaucht wird, die wenigstens 0,20 mol/1 zweiwertige Zinnionen und wenigstens 1 mol/I Alkalihydroxide aufweist bei einer Temperatur zwischen 60 und 95°C, dadurch gekennzeichnet, dass die Vorbehandlungslösung eine saure Lösung ist mit Thioharnstoff als Komplexformer.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Vorbehandlung in einer schwefelsäurehaltigen Lösung durchgeführt wird.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Vorbehandlung in einer wässrigen Lösung mit
0,02 mol/I SnCl2 · 2H20
0,2 mol/I H2SO4 und
0,6 mol/I Thioharnstoff

durchgeführt wird.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Gegenstände aus Kupfer oder einer Kupferlegierung mechanisch oder chemisch gereinigt werden, bevor sie der Auswechsellösung ausgesetzt werden.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die stark alkalische, zweiwertige Zinnionen enthaltende wässrige Lösung ebenfalls ein Komlexformmittel für zweiwertige Zinnionen aufweist.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass das Komplexformmittel Zitrat oder Tartrat ist.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die stark alkalische, zweiwertige Zinnionen enthaltende wässrige Lösung ebenfalls ein lösliches Hypophosphit aufweist.
EP85201585A 1984-10-05 1985-10-02 Verfahren zur autokatalytischen Verzinnung von Kupfer- und Kupferlegierungsgegenständen Expired EP0180265B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL8403033 1984-10-05
NL8403033A NL8403033A (nl) 1984-10-05 1984-10-05 Werkwijze voor het autokatalytisch vertinnen van voorwerpen van koper of een koperlegering.

Publications (2)

Publication Number Publication Date
EP0180265A1 EP0180265A1 (de) 1986-05-07
EP0180265B1 true EP0180265B1 (de) 1989-04-19

Family

ID=19844566

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85201585A Expired EP0180265B1 (de) 1984-10-05 1985-10-02 Verfahren zur autokatalytischen Verzinnung von Kupfer- und Kupferlegierungsgegenständen

Country Status (5)

Country Link
EP (1) EP0180265B1 (de)
JP (1) JPS6191362A (de)
KR (1) KR860003362A (de)
DE (1) DE3569580D1 (de)
NL (1) NL8403033A (de)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5104688A (en) * 1990-06-04 1992-04-14 Macdermid, Incorporated Pretreatment composition and process for tin-lead immersion plating
US5173109A (en) * 1990-06-04 1992-12-22 Shipley Company Inc. Process for forming reflowable immersion tin lead deposit
US5334240A (en) * 1990-06-04 1994-08-02 Macdermid, Incorporated Aqueous acidic tin-lead immersion plating bath containing weak acid and weak base
US5143544A (en) * 1990-06-04 1992-09-01 Shipley Company Inc. Tin lead plating solution
US5296268A (en) * 1991-09-03 1994-03-22 Shipley Company Inc. Pretreatment process of tin lead plating
US5169692A (en) * 1991-11-19 1992-12-08 Shipley Company Inc. Tin lead process
DE4238242C2 (de) * 1992-09-17 2003-04-24 Rieger Franz Metallveredelung Verfahren zur Vorbehandlung von Leichtmetallen nach Patent DE 4231052 C2
DE69716222T2 (de) * 1996-06-05 2004-09-16 Sumitomo Light Metal Industries Ltd. Herstellungsverfahren zum zinnplattieren einer kupferröhre von innen
DE19653765A1 (de) * 1996-12-23 1998-06-25 Km Europa Metal Ag Innen verzinntes Kupferrohr und Verfahren zur Beschichtung eines Kupferrohrs
KR101012815B1 (ko) * 2010-07-21 2011-02-08 주식회사 에이엔씨코리아 칩 도금용 약산성 주석 도금액

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2369620A (en) * 1941-03-07 1945-02-13 Battelle Development Corp Method of coating cupreous metal with tin
NL184695C (nl) * 1978-12-04 1989-10-02 Philips Nv Bad voor het stroomloos neerslaan van tin op substraten.

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Autocatalytic tin deposition", A. Molenaar, J.J.C. Coumans *
Surface Technology, 16(1982), pp. 265-275 *

Also Published As

Publication number Publication date
NL8403033A (nl) 1986-05-01
DE3569580D1 (en) 1989-05-24
JPS6191362A (ja) 1986-05-09
EP0180265A1 (de) 1986-05-07
KR860003362A (ko) 1986-05-23

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