EP0167949A1 - Medium for the electroless deposition of tin and/or lead - Google Patents

Medium for the electroless deposition of tin and/or lead 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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Prior art keywords
tin
lead
salt
mineral acid
acid
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German (de)
French (fr)
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EP0167949B1 (en
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Eugen Dr. Scholz
Hans-Jürgen Luttmann
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Honeywell Riedel de Haen AG
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Riedel de Haen AG
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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.

Abstract

1. Agent for the electroless deposition of tin and/or lead, consisting of an aqueous solution of a tin salt and/or lead salt, containing a mineral acid and a sulphur-containing complexing agent for tin and/or lead, characterised in that the tin salt and/or lead sald is a characterised 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.

Description

Die Erfindung bezieht sich auf ein Mittel für die stromlose Abscheidung von Zinn und/oder' Blei, das aus einer wäßrigen Lösung eines Zinnsalzes und/oder Bleisalzes besteht, die eine Mineralsäure und einen schwefelhaltigen Komplexbildner für Zinn und/oder Blei enthält, sowie auf ein Verfahren zur stromlosen Abscheidung von metallischem Zinn und/oder Blei aus einer solchen Lösung auf ein Substrat.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.

Es ist bereits bekannt, daß ein Metallsubstrat mit einer Zinn-Blei-Legierung durch Eintauchen des Substrats in ein Bad plattiert wird, das ein Zinnsalz, ein Blei(II)-salz und einen Schwefel enthaltenden Komplexbildner für das Zinn und das Blei enthält. Als Zinnsalz ist ausschließlich Zinn(II)-chlorid und als Bleisalz ausschließlich Blei(II)-chlorid erwähnt. Das Bad enthält als Komplexbildner vorzugsweise Thioharnstoff oder ein Thioharnstoffderivat. Als Substrat eignet sich insbesondere Kupfer oder eine Kupfer-Legierung; in diesem Fall soll das Bad einen pH-Wert von 0,5 bis 1,0 aufweisen. Die Abscheidung der Zinn-Blei-Legierung erfolgt bei einer Arbeitstemperatur von 38 bis 93°C (vgl. deutsche Offenlegungsschrift 26 16 409= britische Patentschrift 1 492 506).It is already known that 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. Only 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. The tin-lead alloy is deposited at a working temperature of 38 to 93 ° C (see German Offenlegungsschrift 26 16 409 = British Patent 1 492 506).

Ferner ist bekannt, daß sich zum elektrolytischen Niederschlagen eines Zinnüberzuges auf metallischen Unterlagen ein Verzinnungstauchbad eignet, das ein lösliches Zinn(II)-salz, eine schwefelhaltige Komponente, eine Mineralsäure und einen Benetzer enthält. Das Zinnsalz kann unter anderem ein Fluoborat sein, während die schwefelhaltige Komponente beispielsweise eine aliphatische Schwefel-Stickstoff-Verbindung wie Thioharnstoff, eine fünfgliedrige heterocyclische Verbindung wie Thiazol und Isothiazol oder ein Dithiol wie 1,2-Ethandithiol ist. Dabei enthält die schwefelhaltige Komponente vorzugsweise mindestens zwei Schwefelverbindungen, von denen eine ein Alkalimetallpolysulfid sein muß. Als Mineralsäure wird insbesondere eine starke anorganische Mineralsäure verwendet, nämlich Salzsäure, Schwefelsäure, Salpetersäure oder Phosphorsäure. Geeignete Benetzungsmittel sind organische oberflächenaktive Benetzungsmittel, vor allem aus der Reihe der fluorierten Carbonsäuren. Das Verzinnungsbad dient zum Aufbringen von Zinnüberzügen auf Kupfer und anderen Metallunterlagen; die Schichtdicke des Zinnüberzugs liegt im Bereich von 1,4 bis 8,4 um. Das Bad wird bei einer Temperatur von 50 bis 80°C betrieben (vgl. deutsche Offenlegungsschrift 24 33 820= US-Patentschrift 3 917 486).It is also known that 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, while 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. In particular, 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 tinning bath is used to apply tin coatings to copper and other metal substrates; the layer thickness of the tin coating is in the range from 1.4 to 8.4 μm. The bath is operated at a temperature of 50 to 80 ° C (see German Offenlegungsschrift 24 33 820 = US Patent 3,917,486).

Die bekannten Bäder haben den Nachteil, daß sie bei erhöhter Temperatur betrieben werden, da bei einer niedrigeren Temperatur die Gefahr des Aussalzens besteht. Bei höherer Temperatur wiederum ist eine Zersetzung der Schwefelkomponente zu befürchten.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.

Aufgabe der Erfindung ist die Bereitstellung eines Metallisierungsbades, das bei Raumtemperatur keine Aussalzerscheinungen zeigt und deswegen auch bei niederen Arbeitstemperaturen verwendbar ist.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.

Die Erfindung betrifft ein Mittel für die stromlose Abscheidung von Zinn und/oder Blei, bestehend aus einer wäßrigen Lösung eines Zinnsalzes und/oder Bleisalzes, die eine Mineralsäure und einen schwefelhaltigen Komplexbildner für Zinn und/oder Blei enthält, das dadurch gekennzeichnet ist, daß das Zinnsalz und/oder Bleisalz ein Salz einer fluorhaltigen Mineralsäure und die Mineralsäure eine fluorhaltige Mineralsäure ist und die Lösung einen pH-Wert von 0 bis 3 aufweist.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.

Weiterhin betrifft die Erfindung ein Verfahren zur stromlosen Abscheidung von metallischem Zinn und/oder Blei aus einer wäßrigen Lösung eines Zinnsalzes und/oder Bleisalzes, die eine Mineralsäure und einen schwefelhaltigen Komplexbildner für Zinn und/oder Blei enthält, auf ein Substrat, das dadurch gekennzeichnet ist, daß man das Substrat bei einer Temperatur von 10 bis 80°C mit einer wäßrigen Lösung eines Zinnsalzes und/oder Bleisalzes einer fluorhaltigen Mineralsäure, die eine fluorhaltige Mineralsäure und einen schwefelhaltigen Komplexbildner für Zinn und/oder Blei enthält und einen pH-Wert von 0 bis 3 aufweist, in Berührung bringt.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.

Das in dem erfindunggemäßen Mittel enthaltene Zinnsalz ist ein Zinnsalz einer fluorhaltigen Mineralsäure, vorzugsweise Zinn(II)-fluorid, Zinn(II)-fluoroborat oder Zinn(II)-fluorosilikat. Das Bleisalz ist ebenfalls ein Salz einer fluorhaltigen Mineralsäure, vorzugsweise Blei(II)-fluarid, Blei(II)-fluoroborat oder Blei(II)-fluorosilikat. Das Zinnsalz und das Bleisalz sind in dem Mittel jeweils in gelöster Form enthalten. Das Mittel kann jeweils ein Zinnsalz oder ein Bleisalz oder ein Gemisch aus einem Bleisalz und einem Zinnsalz enthalten, wobei im letzteren Fall die jeweiligen Anionen gleich oder verschieden sein können. Die Menge des Zinns beträgt 1 bis 50, vorzugsweise 5 bis 30 g/1 Lösung, und die Menge des Bleis liegt im Bereich von 1 bis 10, vorzugsweise 2 bis 5 g/l Lösung.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.

Der schwefelhaltige Komplexbildner für Zinn und/oder Blei ist eine aliphatische Verbindung, die Schwefel und Stickstoff enthält und mit Zinn und/oder Blei Chelate bilden kann; besonders geeignet ist Thioharnstoff oder ein Thioharnstoff, der mit niederen Alkylresten substituiert ist, z.B. Tetramethylthioharnstoff. Die Menge des Komplexbildners beträgt 10 bis 400, vorzugsweise 50 bis 150 g/1 Lösung.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.

Die Mineralsäure ist eine fluorhaltige Mineralsäure, insbesondere Flußsäure, Fluoroborsäure oder Fluorokieselsäure. Sie liegt in der Lösung in einer Konzentration von 1 bis 200, vorzugsweise 10 bis 150 g/1 vor.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.

Das erfindungsgemäße Mittel hat einen pH-Wert von 0 bis 3, vorzugsweise 0,1 bis 2 (gemessen mit der Wasserstoffelektrode).The agent according to the invention has a pH of 0 to 3, preferably 0.1 to 2 (measured with the hydrogen electrode).

Das Mittel wird dadurch hergestellt, daß das Salz oder Salzgemisch, die Mineralsäure und der Komplexbildner bei einer Temperatur von 15 bis 30°C in Wasser gelöst werden. Die Anwendung von demineralisiertem Wasser ist zweckmäßig. Das Mittel wird in Form einer klaren Lösung eingesetzt.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.

Das erfindungsgemäße Mittel eignet sich als Tauchbad oder Sprühflüssigkeit für die stromlose Abscheidung von metallischem Zinn und/oder Blei auf metallischen Substraten, insbesondere Kupfer, Kupferlegierungen, oxidiertem Zinn, oder oxidierten Zinn/Blei-Legierungen. Dabei wird das Substrat bei einer Temperatur von 10 bis 80°C, vorzugsweise 15 bis 30°C, mit dem Mittel in Berührung gebracht. Die Abscheidungsmenge des Zinns und/oder Bleis ist abhängig von der Temperatur und der Behandlungszeit; dies ist aus der Tabelle (Anwendungsbeispiel) und der Figur ersichtlich. Das Zinn und/oder Blei wird in dünner Schicht abgeschieden, die ab einer Schichtstärke von 1 µm porenfrei ist. Zur Bestimmung der Schichtstärke wird eine Kupferplatine (100 mm x 30 mm x 1,5 mm) als Substrat verwendet, und die Schichtstärke wird nach dem coulometrischen Ablöseverfahren ermittelt (DIN 50 955)..Derart plattierte Substrate werden beispielsweise in der Leiterplattentechnik verwendet; die Schichten dienen als Ätzschutz und als Löthilfe.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 µm. To determine the layer thickness, 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.

Bei Raumtemperatur, d.h. im Temperaturbereich von 15 bis 30°C, zeigen die erfindungsgemäßen Mittel keinerlei Aussalzerscheinungen. Ein weiterer Vorteil ist ihre geringe Empfindlichkeit gegen Oxidation durch Luftsauerstoff; die Mittel sind drei Monate lang stabil. Vorteilhaft ist ferner die hohe Abscheidungsgeschwindigkeit, und zwar auch bei Temperaturen unterhalb 30°C.At room temperature, ie in the temperature range from 15 to 30 ° C., 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.

Die nachstehenden Beispiele dienen zur näheren Erläuterung der Erfindung. Die Prozentangaben beziehen sich auf das Gewicht.The following examples serve to explain the invention in more detail. The percentages relate to the weight.

Beispiel 1example 1

10 g Zinn(II)-fluorid (= 7,5 g Sn), 80 g Thioharnstoff und 40 ml Flußsäure (50 Prozent HF) wurden in 1 Liter demineralisiertem Wasser zu einer klaren Lösung gelöst. Die Lösung hatte einen pH-Wert von 1,8.10 g of tin (II) fluoride (= 7.5 g of Sn), 80 g of thiourea and 40 ml of hydrofluoric acid (50 percent HF) were dissolved in 1 liter of demineralized water to give a clear solution. The solution had a pH of 1.8.

Beispiel 2Example 2

20 ml einer wäßrigen Zinn(II)-fluoroboratlösung (Sn-Gehalt 6,7 g), 5 ml einer wäßrigen Bleifluorosilikatlösung (Pb-Gehalt 3,3 g), 40 ml Fluoroborsäure (50 Prozent BBF4) und 80 g Thioharnstoff wurden in 1 Liter demineralisiertem Wasser gelöst. Die Lösung hatte einen pH-Wert von 0,45.20 ml of an aqueous tin (II) fluoroborate solution (Sn content 6.7 g), 5 ml of an aqueous lead fluorosilicate solution (Pb content 3.3 g), 40 ml of fluoroboric acid (50 percent BBF 4 ) and 80 g of thiourea were added 1 liter of demineralized water dissolved. The solution had a pH of 0.45.

Beispiel 3Example 3

100 ml einer wäßrigen Zinn(II)-fluoroboratlösung (Sn-Gehalt 33,5 g), 400 g Thioharnstoff und 250 ml Fluoroborsäure (50 Prozent HBF4) wurden in demineralisiertem Wasser zu einem Gesamtvolumen von 1 Liter gelöst. Die Lösung hatte einen pH-Wert von 0,2.100 ml of an aqueous tin (II) fluoroborate solution (Sn content 33.5 g), 400 g of thiourea and 250 ml of fluoroboric acid (50 percent HBF 4 ) were dissolved in demineralized water to a total volume of 1 liter. The solution had a pH of 0.2.

Beispiel 4Example 4

10 ml einer wäßrigen Bleifluoroboratlösung (Pb-Gehalt 5 g), 50 g Thioharnstoff und 20 ml Fluoroborsäure (50 Prozent HBF4) wurden in demineralisiertem Wasser zu einem Gesamtvolumen von 1 Liter gelöst. Die klare konzentrierte Lösung hatte einen pH-Wert von 0,95.10 ml of an aqueous lead fluoroborate solution (Pb content 5 g), 50 g thiourea and 20 ml fluoroboric acid (50 percent HBF 4 ) were dissolved in demineralized water to a total volume of 1 liter. The clear concentrated solution had a pH of 0.95.

Beispiel 5Example 5

30 ml einer wäßrigen Zinn(II)-fluoroboratlösung (Sn-Gehalt 10,05 g), 50 g Thioharnstoff und 50 ml Fluoroborsäure (50 Prozent HBF4) wurden in demineralisiertem Wasser zu einem Gesamtvolumen von 1 Liter gelöst. Die klare konzentrierte Lösung hatte einen pH-Wert von 0,55.30 ml of an aqueous tin (II) fluoroborate solution (Sn content 10.05 g), 50 g of thiourea and 50 ml of fluoroboric acid (50 percent HBF 4 ) were dissolved in demineralized water to a total volume of 1 liter. The clear concentrated solution had a pH of 0.55.

AnwendungsbeispielApplication example

Kupfer-Platinen mit den Abmessungen 100 mm x 30 mm x 1,5 mm wurden jeweils 60 min lang bei verschiedenen Temperaturen (20°C, 40°C, 60°C) in Lösungen gemäß Beispiel 5 getaucht. Die erhaltenen Schichtstärken wurden nach dem coulometrisehen Ablöseverfahren (DIN 50 955) bestimmt. Die Bestimmung der Schichtstärke im Abstand von jeweils 10 min ergab die in der Tabelle aufgeführten Werte. Der Verlauf der Zinn-Abscheidung ist auch aus der Figur ersichtlich.

Figure imgb0001
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.
Figure imgb0001

Claims (5)

1. Mittel für die stromlose Abscheidung von Zinn und/oder Blei, bestehend aus einer wäßrigen Lösung eines Zinnsalzes und/oder Bleisalzes, die eine Mineralsäure und einen schwefelhaltigen Komplexbildner für Zinn und/oder Blei enthält, dadurch gekennzeichnet, daß das Zinnsalz und/oder Bleisalz ein Salz einer fluorhaltigen Mineralsäure und die Mineralsäure eine fluorhaltige Mineralsäure ist und die Lösung einen pH-Wert von 0 bis 3 aufweist.1. 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, 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. 2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß die fluorhaltige Mineralsäure Flußsäure, Fluoroborsäure oder Fluorokieselsäure ist.2. Composition according to claim 1, characterized in that the fluorine-containing mineral acid is hydrofluoric acid, fluoroboric acid or fluorosilicic acid. 3. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß das Zinnsalz Zinnfluorid oder Zinnfluoroborat ist.3. Composition according to claim 1, characterized in that the tin salt is tin fluoride or tin fluoroborate. 4. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß das Bleisalz Bleifluorid oder Bleifluoroborat ist.4. Composition according to claim 1, characterized in that the lead salt is lead fluoride or lead fluoroborate. 5. Verfahren zur stromlosen Abscheidung von metallischem Zinn und/oder Blei aus einer wäßrigen Lösung eines Zinnsalzes und/oder Bleisalzes, die eine Mineralsäure und einen schwefelhaltigen Komplexbildner für Zinn und/oder Blei enthält, auf ein Substrat, dadurch gekennzeichnet, daß man das Substrat bei einer Temperatur von 10 bis 80°C mit einer wäßrigen Lösung eines Zinnsalzes und/oder Bleisalzes einer fluorhaltigen Mineralsäure, die eine fluorhaltige Mineralsäure und einen schwefelhaltigen Komplexbildner für Zinn und/oder Blei enthält und einen pH-Wert von 0 bis 3 aufweist, in Berührung bringt.5. A process 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, characterized in that the substrate at a temperature of 10 to 80 ° C with an 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, in Touches.
EP85108089A 1984-07-09 1985-06-29 Medium for the electroless deposition of tin and/or lead Expired EP0167949B1 (en)

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DE3425214 1984-07-09
DE19843425214 DE3425214A1 (en) 1984-07-09 1984-07-09 MEANS FOR THE DEFLECTIVE DEPOSITION OF TIN AND / OR LEAD

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EP0167949B1 EP0167949B1 (en) 1988-04-20

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EP0278752A1 (en) * 1987-02-10 1988-08-17 A.P.T. Advanced Plating Technologies, Ltd. A tin coating immersion solution and a coating process using the same
US5143544A (en) * 1990-06-04 1992-09-01 Shipley Company Inc. Tin lead plating solution
EP0524422A2 (en) * 1991-07-22 1993-01-27 Shipley Company Inc. Tin lead treatment

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JPH04363093A (en) * 1990-11-27 1992-12-15 Mitsubishi Electric Corp Manufacture of printed board

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DE2917019A1 (en) * 1978-04-28 1979-11-08 Gould Inc METHOD FOR METALLIZING COMPOSITE MATERIAL AND SUITABLE BATHROOM COMPOSITION

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0278752A1 (en) * 1987-02-10 1988-08-17 A.P.T. Advanced Plating Technologies, Ltd. A tin coating immersion solution and a coating process using the same
US5143544A (en) * 1990-06-04 1992-09-01 Shipley Company Inc. Tin lead plating solution
EP0524422A2 (en) * 1991-07-22 1993-01-27 Shipley Company Inc. Tin lead treatment
EP0524422A3 (en) * 1991-07-22 1994-04-13 Shipley Co

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EP0167949B1 (en) 1988-04-20
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