EP0693579B1 - Palladium-silver alloys electroplating bath - Google Patents

Palladium-silver alloys electroplating bath Download PDF

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Publication number
EP0693579B1
EP0693579B1 EP95107534A EP95107534A EP0693579B1 EP 0693579 B1 EP0693579 B1 EP 0693579B1 EP 95107534 A EP95107534 A EP 95107534A EP 95107534 A EP95107534 A EP 95107534A EP 0693579 B1 EP0693579 B1 EP 0693579B1
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EP
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Prior art keywords
silver
palladium
bath according
acid
bath
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EP95107534A
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German (de)
French (fr)
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EP0693579A1 (en
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Günter Dr. Herklotz
Thomas Frey
Otto Camus
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WC Heraus GmbH and Co KG
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WC Heraus GmbH and Co KG
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Priority claimed from DE4444232A external-priority patent/DE4444232C1/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/567—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/64—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of silver

Definitions

  • the invention relates to an ammoniacal bath for the electrodeposition of palladium-silver alloys, which contains complex-bound palladium, a silver compound and a capto compound.
  • German patent 1 221 874 describes a method for the electrodeposition of pore-free palladium-silver alloy coatings (thickness approximately 5 to 100 micrometers) from ammoniacal palladium and silver nitrate solution with a pH of 7.5 to 11, a temperature of 35 to 90 ° C and a current density of 1 to 10 mA / cm 2 at a voltage of 0.5 to 7 volts. Good results are obtained when the solution contains about 0.5 to 10 g of the metal or metals per liter of solution. However, solutions with up to 150 g and more metal per liter can also be used.
  • the bath known from the Swiss patent specification 649 582 for the electroplating of substrates with palladium or palladium alloys at 20 to 75 ° C and a current density of 0.1 to 10 A / dm 2 is characterized in that it prevents unwanted precipitation of Palladium or the alloy metal (copper, cobalt, cadmium, gold, iron, indium, nickel, silver, tin, zinc) has a pH of 6.5 to 9.5 buffered by ammonium, amine or alkali metal borate during operation .
  • the bath contains 1 to 50 g / l palladium as a palladium-amine complex (palladium (II) di or tetrammine complex), 0 to 20 g / l of the alloy metal, 10 to 50 g / l borate and optionally to to 5 g / l of gloss agent aromatic sulfonated imide or amide, aromatic alkali metal sulfonate and / or aromatic sulfonic acid.
  • palladium (II) di or tetrammine complex palladium (II) di or tetrammine complex
  • 0 to 20 g / l of the alloy metal 10 to 50 g / l borate and optionally to to 5 g / l of gloss agent aromatic sulfonated imide or amide, aromatic alkali metal sulfonate and / or aromatic sulfonic acid.
  • a similar bath is known from Platinum Metals Review 1984, 28 (3), 117-124. It contains palladium and silver as amine complexes Pd (NH 3 ) 4 (NO 3 ) 2 and Ag (NH 3 ) 2 NO 3 and has a pH of 11.5.
  • EP 0 059 452 B1 and EP 0 073 236 B1 relate to processes for the electrodeposition of coatings made of palladium and its alloys with silver, copper and / or nickel from baths, which, as palladium source, use complexes of palladium with aliphatic polyamines (1,3-diaminopropane, N, N, N ', N'-tetramethylethylenediamine, 2-hydroxy-1,3-diaminopropane) and have a pH between 7.5 and 13.5.
  • a special aqueous bath for the galvanic deposition of the palladium-silver alloys consists of 69.6 g / l silver (I) oxide, 53.2 g / l palladium (II) chloride, 222 g / l 1.3 -Diaminopropane, 106.2 g / l K 3 PO 4 and 86.5 g / l K 2 HPO 4 together and has a pH of 11.3 adjusted with KOH or H 3 PO 4 .
  • the bath temperature is between 40 and 65 ° C, the current density between 1.1 and 538 mA / cm 2 .
  • the palladium-silver alloys are particularly suitable as surfaces for electrical contacts.
  • the bath contains 1 - 50 g / l of an aliphatic or aromatic mercapto compound (mercaptoacetic acid, mercaptopropionic acid, mercapto-succinic acid, thioglycerol, thiophenol, thiosalicylic acid) as a brightener and, if necessary, additionally that Amide of an aliphatic carboxylic acid, as a result of which black silver-containing precipitates that may occur in the bath can be largely avoided.
  • an aliphatic or aromatic mercapto compound mercaptoacetic acid, mercaptopropionic acid, mercapto-succinic acid, thioglycerol, thiophenol, thiosalicylic acid
  • Ammonium phosphate, acetate and / or nitrate can also be contained in the bath borate and as the conductive salt.
  • This bath can be used to deposit shiny, ductile, pore and crack-free coatings made of palladium-silver alloys with up to 40% by weight of silver, which are particularly suitable as contact layers for electrical contacts.
  • the object of the invention is to find a bath for depositing contact layers made of palladium-silver alloys suitable for electrical contacts, also with a higher silver content.
  • the bath should be able to be operated both at room temperature and at elevated temperature - then higher deposition rates are possible - and allow long operating times without the formation of black silver-containing precipitates. It should be able to be used in bell and drum systems as well as in continuous processes.
  • the bath of the type characterized at the outset, which is the solution to the problem, is characterized according to the invention by the preparation from water and 5 - 50 g / l Palladium as a palladium-amine complex, 2 - 40 g / l Silver as a silver compound, 30-150 g / l Leitsalz, 5 - 100 g / l Amine component from one or more aliphatic polyamines with 2 - 10 amino groups in the molecule and 2 - 50 g / l Mercaptoalkan carboxylic acid and / or mercaptoalkane sulfonic acid and / or their salts and a pH of 7.0-10.0 adjusted with ammonium hydroxide.
  • the bathroom has proven particularly useful when it consists of water and 5 - 20 g / l Palladium as a palladium-amine complex, 2 - 30 g / l Silver as a silver compound, 50-100 g / l Leitsalz, 5 - 100 g / l Amine component from one or more aliphatic polyamines with 2 - 10 amino groups in the molecule and 2 - 20 g / l Mercaptoalkan carboxylic acid and / or mercaptoalkane sulfonic acid and / or their salts prepared and its pH is adjusted to 7.0-10.0 with ammonium hydroxide.
  • Palladium diammine dichloride, palladium diammine dibromide or palladium diamine dinitrite as palladium amine complex and silver chloride, silver nitrate, silver sulfate or a silver diammine complex as silver compound are well suited for the preparation of the bath; palladium diammonitrite and silver nitrate are preferred.
  • the amine component can consist of one or more of the polyamines.
  • an increase in the silver content of the deposited palladium-silver alloys can be achieved by using a polyamine mixture (see examples).
  • the conductive salt are carboxylic acids, such as tartaric acid and citric acid, or their salts, boric acid and ammonium salts of inorganic acids, such as ammonium bromide, ammonium chloride, ammonium nitrate and ammonium sulfate, it being possible for the conductive salt to consist of one or more of these compounds.
  • carboxylic acids such as tartaric acid and citric acid
  • boric acid and ammonium salts of inorganic acids such as ammonium bromide, ammonium chloride, ammonium nitrate and ammonium sulfate
  • Preferred mercapto acids are 2- and 3-mercaptopropionic acid and 3-mercaptopropanesulfonic acid. They can be used individually or in a mixture with one another and as free acids and / or in the form of their salts, especially the alkali metal and ammonium salts, for the preparation of the bath.
  • the bath can be operated at temperatures of 20 - 80 ° C. Current densities up to about 20 A / dm 2 can be used; current densities of 0.5-10 A / dm 2 are preferably selected.
  • An increase in the pH value and / or the bath temperature enables - with a given palladium and silver concentration in the bath - the deposition of palladium-silver alloys with a higher silver content.
  • the bath can be supplemented by adding the palladium and silver compounds used for its preparation or - with regard to the silver concentration - also by using soluble silver anodes.
  • the bath according to the invention is very stable even if it is kept at a temperature higher than room temperature. If the components forming the bath are supplemented accordingly, it can be operated for several months without a black, silver-containing precipitate forming. These very good properties which are characteristic of the bath are based, as comparative experiments show, on the interaction (synergistic effect) of the amine component with the mercapto acid.
  • the bath can be used for electroplating small parts as well as tapes and wires and enables the deposition of alloys with a silver content of up to about 99% by weight.
  • the deposited palladium / silver coatings are shiny, ductile and free of pores and cracks and are therefore particularly suitable as contact layers for electrical contacts.
  • Table III shows the dependence of the silver content of the deposited palladium / silver layers on the pH and the temperature of the bath.
  • Table III PH value Bath temperature [° C] Pd / Ag [% by weight] Pd Ag 7.5 25th 85 15 8.5 25th 72 28 9.5 25th 59 41 7.5 50 75 25th 8.5 50 57 43 9.5 50 43 57
  • Table IV shows the dependency of the silver content of the deposited palladium / silver layers on the pH and the temperature of the bath.
  • Table IV PH value Bath temperature [° C] Pd / Ag [% by weight] Pd Ag 7.5 25th 80 20th 8.5 25th 60 40 9.5 25th 40 60 7.5 50 61 39 8.5 50 43 57 9.5 50 35 65
  • Example 12 (comparative example )

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Description

Die Erfindung betrifft ein ammoniakalisches Bad zum galvanischen Abscheiden von Palladium-Silber-Legierungen, das komplexgebundenes Palladium, eine Silberverbindung und eine captoverbindung enthält.The invention relates to an ammoniacal bath for the electrodeposition of palladium-silver alloys, which contains complex-bound palladium, a silver compound and a capto compound.

In der deutschen Patentschrift 1 221 874 wird ein Verfahren zum galvanischen Abscheiden von porenfreien Palladium-Silber-Legierungsüberzügen (Dicke etwa 5 bis 100 Mikrometer) aus ammoniakalischer Palladium- und Silbernitratlösung mit einem pH-Wert von 7,5 bis 11, einer Temperatur von 35 bis 90°C und einer Stromdichte von 1 bis 10 mA/cm2 bei einer Spannung von 0,5 bis 7 Volt beschrieben. Gute Ergebnisse werden erhalten, wenn die Lösung etwa 0,5 bis 10 g des Metalls oder der Metalle je Liter Lösung enthält. Es können aber auch Lösungen mit bis zu 150 g und mehr Metall je Liter verwendet werden.German patent 1 221 874 describes a method for the electrodeposition of pore-free palladium-silver alloy coatings (thickness approximately 5 to 100 micrometers) from ammoniacal palladium and silver nitrate solution with a pH of 7.5 to 11, a temperature of 35 to 90 ° C and a current density of 1 to 10 mA / cm 2 at a voltage of 0.5 to 7 volts. Good results are obtained when the solution contains about 0.5 to 10 g of the metal or metals per liter of solution. However, solutions with up to 150 g and more metal per liter can also be used.

Das aus der schweizerischen Patentschrift 649 582 bekannte Bad für die Elektroplattierung von Substraten mit Palladium oder Palladium-Legierungen bei 20 bis 75°C und einer Stromdichte von 0,1 bis 10 A/dm2 ist dadurch gekennzeichnet, daß es zur Verhinderung unerwünschter Ausfällung von Palladium oder des Legierungsmetalls (Kupfer, Kobalt, Cadmium, Gold, Eisen, Indium, Nickel, Silber, Zinn, Zink) während des Betriebs einen durch Ammonium-, Amin- oder Alkalimetallborat gepufferten pH-Wert von 6,5 bis 9,5 aufweist. Das Bad enthält 1 bis 50 g/l Palladium als Palladium-ammin-Komplex (Palladium(II)-di- oder -tetrammin-Komplex), 0 bis 20 g/l des Legierungsmetalls, 10 bis 50 g/l Borat und gegebenenfalls bis zu 5 g/l Glanzmittel aus aromatischem sulfoniertem Imid oder Amid, aromatischem Alkalimetallsulfonat und/oder aromatischer Sulfonsäure.The bath known from the Swiss patent specification 649 582 for the electroplating of substrates with palladium or palladium alloys at 20 to 75 ° C and a current density of 0.1 to 10 A / dm 2 is characterized in that it prevents unwanted precipitation of Palladium or the alloy metal (copper, cobalt, cadmium, gold, iron, indium, nickel, silver, tin, zinc) has a pH of 6.5 to 9.5 buffered by ammonium, amine or alkali metal borate during operation . The bath contains 1 to 50 g / l palladium as a palladium-amine complex (palladium (II) di or tetrammine complex), 0 to 20 g / l of the alloy metal, 10 to 50 g / l borate and optionally to to 5 g / l of gloss agent aromatic sulfonated imide or amide, aromatic alkali metal sulfonate and / or aromatic sulfonic acid.

Ein ähnliches Bad ist aus Platinum Metals Review 1984, 28(3), 117 - 124, bekannt. Es enthält Palladium und Silber als Amminkomplexe Pd(NH3)4(NO3)2 und Ag(NH3)2NO3 und besitzt einen pH-Wert von 11,5.A similar bath is known from Platinum Metals Review 1984, 28 (3), 117-124. It contains palladium and silver as amine complexes Pd (NH 3 ) 4 (NO 3 ) 2 and Ag (NH 3 ) 2 NO 3 and has a pH of 11.5.

EP 0 059 452 B1 und EP 0 073 236 B1 betreffen Verfahren zum galvanischen Abscheiden von Überzügen aus Palladium und seinen Legierungen mit Silber, Kupfer und/oder Nickel aus Bädern, die als Palladiumquelle Komplexe des Palladiums mit aliphatischen Polyaminen (1,3-Diaminopropan, N,N,N',N'-Tetramethylethylendiamin, 2-Hydroxy-1,3-diaminopropan) enthalten und einen pH-Wert zwischen 7,5 und 13,5 besitzen. Ein spezielles wässeriges Bad für die galvanische Abscheidung der Palladium-Silber-Legierungen setzt sich aus 69,6 g/l Silber(I)-oxid, 53,2 g/l Palladium(II)-chlorid, 222 g/l 1,3-Diaminopropan, 106,2 g/l K3PO4 und 86,5 g/l K2HPO4 zusammen und weist einen mit KOH oder H3PO4 eingestellten pH-Wert von 11,3 auf. Die Bad-Temperatur liegt zwischen 40 und 65°C, die Stromdichte zwischen 1,1 und 538 mA/cm2. Die Palladium-Silber-Legierungen eignen sich besonders als Oberflächen für elektrische Kontakte.EP 0 059 452 B1 and EP 0 073 236 B1 relate to processes for the electrodeposition of coatings made of palladium and its alloys with silver, copper and / or nickel from baths, which, as palladium source, use complexes of palladium with aliphatic polyamines (1,3-diaminopropane, N, N, N ', N'-tetramethylethylenediamine, 2-hydroxy-1,3-diaminopropane) and have a pH between 7.5 and 13.5. A special aqueous bath for the galvanic deposition of the palladium-silver alloys consists of 69.6 g / l silver (I) oxide, 53.2 g / l palladium (II) chloride, 222 g / l 1.3 -Diaminopropane, 106.2 g / l K 3 PO 4 and 86.5 g / l K 2 HPO 4 together and has a pH of 11.3 adjusted with KOH or H 3 PO 4 . The bath temperature is between 40 and 65 ° C, the current density between 1.1 and 538 mA / cm 2 . The palladium-silver alloys are particularly suitable as surfaces for electrical contacts.

In DE 39 35 664 C1 wird ein wässeriges ammoniakalisches Bad mit einem pH-Wert über 8 zum galvanischen Abscheiden von Palladium-Silber-Legierungen, in dem Palladium und Silber als Ammin-Komplexe vorliegen, beschrieben. Neben 5 - 50 g/l Palladium und 2 - 40 g/l Silber enthält das Bad als Glanzbildner 1 - 50 g/l einer aliphatischen oder aromatischen Mercaptoverbindung (Mercaptoessigsäure, Mercaptopropionsäure, Mercaptobernsteinsäure, Thioglycerin, Thiophenol, Thiosalicylsäure) und gegebenenfalls zusätzlich noch das Amid einer aliphatischen Carbonsäure, wodurch eventuell in dem Bad auftretende schwarze silberhaltige Niederschläge weitgehend vermieden werden können. Weiter können in dem Bad Borat und als Leitsalz Ammoniumphosphat, -acetat und/oder -nitrat enthalten sein. Aus diesem Bad können bei Raumtemperatur glänzende, duktile und poren- und rißfreie Überzüge aus Palladium-Silber-Legierungen mit bis zu 40 Gewichts-% Silber, die besonders als Kontaktschichten für elektrische Kontakte geeignet sind, abgeschieden werden.DE 39 35 664 C1 describes an aqueous ammoniacal bath with a pH value above 8 for the electrodeposition of palladium-silver alloys, in which palladium and silver are present as ammine complexes. In addition to 5 - 50 g / l palladium and 2 - 40 g / l silver, the bath contains 1 - 50 g / l of an aliphatic or aromatic mercapto compound (mercaptoacetic acid, mercaptopropionic acid, mercapto-succinic acid, thioglycerol, thiophenol, thiosalicylic acid) as a brightener and, if necessary, additionally that Amide of an aliphatic carboxylic acid, as a result of which black silver-containing precipitates that may occur in the bath can be largely avoided. Ammonium phosphate, acetate and / or nitrate can also be contained in the bath borate and as the conductive salt. This bath can be used to deposit shiny, ductile, pore and crack-free coatings made of palladium-silver alloys with up to 40% by weight of silver, which are particularly suitable as contact layers for electrical contacts.

Ausgehend von dem aus DE 39 35 664 C1 bekannten Bad, liegt der Erfindung die Aufgabe zugrunde, ein Bad zum Abscheiden von für elektrische Kontakte geeigneten Kontaktschichten aus Palladium-Silber-Legierungen auch mit einem höheren Silber-Anteil zu finden. Das Bad soll sowohl bei Raumtemperatur als auch bei erhöhter Temperatur - dann sind höhere Abscheidungsgeschwindigkeiten möglich - betrieben werden können und, ohne daß sich schwarze silberhaltige Niederschläge bilden, lange Betriebszeiten erlauben. Es soll sowohl in Glocken- und Trommelanlagen als auch für Durchlaufverfahren eingesetzt werden können.Starting from the bath known from DE 39 35 664 C1, the object of the invention is to find a bath for depositing contact layers made of palladium-silver alloys suitable for electrical contacts, also with a higher silver content. The bath should be able to be operated both at room temperature and at elevated temperature - then higher deposition rates are possible - and allow long operating times without the formation of black silver-containing precipitates. It should be able to be used in bell and drum systems as well as in continuous processes.

Das die Lösung der Aufgabe darstellende Bad der eingangs charakterisierten Art ist erfindungsgemäß gekennzeichnet durch die Zubereitung aus Wasser und 5 - 50 g/l Palladium als Palladium-ammin-Komplex, 2 - 40 g/l Silber als Silberverbindung, 30 - 150 g/l Leitsalz, 5 - 100 g/l Amin-Bestandteil aus einem oder mehreren aliphatischen Polyaminen mit 2 - 10 Amino-Gruppen im Molekül und 2 - 50 g/l Mercaptoalkancarbonsäure und/oder Mercaptoalkansulfonsäure und/oder deren Salze und durch einen mit Ammoniumhydroxid eingestellten pH-Wert von 7,0 - 10,0.The bath of the type characterized at the outset, which is the solution to the problem, is characterized according to the invention by the preparation from water and 5 - 50 g / l Palladium as a palladium-amine complex, 2 - 40 g / l Silver as a silver compound, 30-150 g / l Leitsalz, 5 - 100 g / l Amine component from one or more aliphatic polyamines with 2 - 10 amino groups in the molecule and 2 - 50 g / l Mercaptoalkan carboxylic acid and / or mercaptoalkane sulfonic acid and / or their salts and a pH of 7.0-10.0 adjusted with ammonium hydroxide.

Besonders bewährt hat sich das Bad, wenn es aus Wasser und 5 - 20 g/l Palladium als Palladium-ammin-Komplex, 2 - 30 g/l Silber als Silberverbindung, 50 - 100 g/l Leitsalz, 5 - 100 g/l Amin-Bestandteil aus einem oder mehreren aliphatischen Polyaminen mit 2 - 10 Amino-Gruppen im Molekül und 2 - 20 g/l Mercaptoalkancarbonsäure und/oder Mercaptoalkansulfonsäure und/oder deren Salze zubereitet und sein pH-Wert mit Ammoniumhydroxid auf 7,0 - 10,0 eingestellt wird.The bathroom has proven particularly useful when it consists of water and 5 - 20 g / l Palladium as a palladium-amine complex, 2 - 30 g / l Silver as a silver compound, 50-100 g / l Leitsalz, 5 - 100 g / l Amine component from one or more aliphatic polyamines with 2 - 10 amino groups in the molecule and 2 - 20 g / l Mercaptoalkan carboxylic acid and / or mercaptoalkane sulfonic acid and / or their salts prepared and its pH is adjusted to 7.0-10.0 with ammonium hydroxide.

Für die Zubereitung des Bades sind Palladiumdiammindichlorid, Palladiumdiammindibromid oder Palladiumdiammindinitrit als Palladium-ammin-Komplex und Silberchlorid, Silbernitrat, Silbersulfat oder ein Silber-diammin-Komplex als Silberverbindung gut geeignet; bevorzugt werden Palladiumdiammindinitrit und Silbernitrat.Palladium diammine dichloride, palladium diammine dibromide or palladium diamine dinitrite as palladium amine complex and silver chloride, silver nitrate, silver sulfate or a silver diammine complex as silver compound are well suited for the preparation of the bath; palladium diammonitrite and silver nitrate are preferred.

Der Amin-Bestandteil umfaßt Polyamine und Derivate der Polyamine, wie Hydroxy- und Carboxypolyamine. Bevorzugt werden

  • Alkylendiamine mit 2 - 6 C-Atomen in der Alkylen-Gruppe, besonders Ethylendiamin und Hexamethylendiamin,
  • Polyethylenamine der allgemeinen Formel NH2(CH2CH2NH)nH mit n = 2 - 5, besonders Diethylentriamin, Triethylentetramin und Pentaethylenhexamin, und
  • die Polyamin-Derivate Bis-(2-hydroxy-3-aminopropyl)-amin, N-(2-Aminoethyl)-1,3-diaminopropan und Ethylendiamintetraessigsäure.
The amine component includes polyamines and derivatives of the polyamines such as hydroxy and carboxypolyamines. To be favoured
  • Alkylenediamines with 2 - 6 carbon atoms in the alkylene group, especially ethylenediamine and hexamethylenediamine,
  • Polyethylene amines of the general formula NH 2 (CH 2 CH 2 NH) n H with n = 2 - 5, especially diethylenetriamine, triethylenetetramine and pentaethylene hexamine, and
  • the polyamine derivatives bis- (2-hydroxy-3-aminopropyl) amine, N- (2-aminoethyl) -1,3-diaminopropane and ethylenediaminetetraacetic acid.

Der Amin-Bestandteil kann aus einem oder mehreren der Polyamine bestehen. Überraschenderweise läßt sich durch die Verwendung eines Polyamin-Gemisches eine Erhöhung des Silber-Gehaltes der abgeschiedenen Palladium-Silber-Legierungen erreichen (siehe Beispiele).The amine component can consist of one or more of the polyamines. Surprisingly, an increase in the silver content of the deposited palladium-silver alloys can be achieved by using a polyamine mixture (see examples).

Als Leitsalz eignen sich besonders Carbonsäuren, wie Weinsäure und Zitronensäure, beziehungsweise deren Salze, Borsäure und Ammoniumsalze anorganischer Säuren, wie Ammoniumbromid, Ammoniumchlorid, Ammoniumnitrat und Ammoniumsulfat, wobei das Leitsalz aus einer oder mehreren dieser Verbindungen bestehen kann.Particularly suitable as the conductive salt are carboxylic acids, such as tartaric acid and citric acid, or their salts, boric acid and ammonium salts of inorganic acids, such as ammonium bromide, ammonium chloride, ammonium nitrate and ammonium sulfate, it being possible for the conductive salt to consist of one or more of these compounds.

Bevorzugte Mercaptosäuren sind die 2- und 3-Mercaptopropionsäure und die 3-Mercaptopropansulfonsäure. Sie können einzeln oder im Gemisch miteinander und als freie Säuren und/oder in Form ihrer Salze, speziell der Alkalimetall- und Ammoniumsalze, für die Zubereitung des Bades eingesetzt werden.Preferred mercapto acids are 2- and 3-mercaptopropionic acid and 3-mercaptopropanesulfonic acid. They can be used individually or in a mixture with one another and as free acids and / or in the form of their salts, especially the alkali metal and ammonium salts, for the preparation of the bath.

Das Bad kann bei Temperaturen von 20 - 80°C betrieben werden. Es können Stromdichten bis zu etwa 20 A/dm2 angewandt werden; vorzugsweise werden Stromdichten von 0,5 - 10 A/dm2 gewählt. Eine Erhöhung des pH-Wertes und/oder der Bad-Temperatur ermöglicht - bei gegebener Palladium- und Silber-Konzentration im Bad - die Abscheidung von Palladium-Silber-Legierungen mit höherem Silber-Gehalt.The bath can be operated at temperatures of 20 - 80 ° C. Current densities up to about 20 A / dm 2 can be used; current densities of 0.5-10 A / dm 2 are preferably selected. An increase in the pH value and / or the bath temperature enables - with a given palladium and silver concentration in the bath - the deposition of palladium-silver alloys with a higher silver content.

Das Bad läßt sich durch Zusatz der für seine Zubereitung eingesetzten Palladium- und Silberverbindungen bzw. - hinsichtlich der Silber-Konzentration - auch durch die Verwendung löslicher Silber-Anoden ergänzen.The bath can be supplemented by adding the palladium and silver compounds used for its preparation or - with regard to the silver concentration - also by using soluble silver anodes.

Überraschenderweise ist das Bad gemäß der Erfindung sehr stabil, auch wenn es bei einer höheren Temperatur als der Raumtemperatur gehalten wird. Es kann bei entsprechender Ergänzung der das Bad bildenden Bestandteile mehrere Monate lang betrieben werden, ohne daß sich ein schwarzer silberhaltiger Niederschlag bildet. Diese für das Bad charakteristischen sehr guten Eigenschaften beruhen, wie Vergleichsversuche zeigen, auf dem Zusammenwirken (synergistische Wirkung) des Amin-Bestandteils mit der Mercaptosäure.Surprisingly, the bath according to the invention is very stable even if it is kept at a temperature higher than room temperature. If the components forming the bath are supplemented accordingly, it can be operated for several months without a black, silver-containing precipitate forming. These very good properties which are characteristic of the bath are based, as comparative experiments show, on the interaction (synergistic effect) of the amine component with the mercapto acid.

Das Bad läßt sich für das Galvanisieren sowohl von Kleinteilen als auch von Bändern und Drähten einsetzen und ermöglicht die Abscheidung von Legierungen mit einem Silber-Gehalt bis zu etwa 99 Gewichts-%.The bath can be used for electroplating small parts as well as tapes and wires and enables the deposition of alloys with a silver content of up to about 99% by weight.

Die abgeschiedenen Palladium/Silber-Überzüge sind glänzend, duktil und poren- und rißfrei und eignen sich daher besonders als Kontaktschichten für elektrische Kontakte.The deposited palladium / silver coatings are shiny, ductile and free of pores and cracks and are therefore particularly suitable as contact layers for electrical contacts.

Zur näheren Erläuterung der Erfindung werden in den folgenden Beispielen 1 bis 10 Bäder gemäß der Erfindung und in den Beispielen 11 und 12 bekannte Bäder und die Abscheidung von Überzügen aus Palladium-Silber-Legierungen daraus beschrieben.To explain the invention in more detail, the following examples 1 to 10 baths according to the invention and in examples 11 and 12 known baths and the deposition of coatings from palladium-silver alloys therefrom are described.

Beispiel 1example 1

Es wird eine wässerige Lösung aus 20 g/l Palladium als Pd(NH3)2(NO2)2, 5 g/l Silber als AgNO3, 70 g/l Weinsäure, 22,5 g/l Ethylendiamin und 9,6 g/l 2-Mercaptopropionsäure zubereitet und durch Zugabe von Ammoniumhydroxid der pH-Wert der Lösung auf 8 eingestellt.It becomes an aqueous solution 20 g / l Palladium as Pd (NH 3 ) 2 (NO 2 ) 2 , 5 g / l Silver as AgNO 3 , 70 g / l Tartaric acid, 22.5 g / l Ethylenediamine and 9.6 g / l 2-mercaptopropionic acid prepared and the pH of the solution adjusted to 8 by adding ammonium hydroxide.

Beispiel 2Example 2

Der in Beispiel 1 beschriebenen wässerigen Lösung werden 7 g/l Triethylentetramin und Ammoniumhydroxid bis zu einem pH-Wert von 8 zugesetzt.7 g / l triethylenetetramine and ammonium hydroxide are added to the aqueous solution described in Example 1 up to a pH of 8.

Beispiel 3Example 3

Der in Beispiel 1 beschriebenen wässerigen Lösung werden 20 g/l Triethylentetramin und Ammoniumhydroxid bis zu einem pH-Wert von 8 zugesetzt.20 g / l triethylenetetramine and ammonium hydroxide are added to the aqueous solution described in Example 1 up to a pH of 8.

Aus den Bädern nach den Beispielen 1 - 3 werden bei einer Bad-Temperatur von 35°C und einer mittleren Stromdichte von 2 A/dm2 glänzende, duktile und poren- und rißfreie Palladium/Silber-Schichten unterschiedlicher Zusammensetzung abgeschieden (siehe Tabelle I). Tabelle I Beispiel Ethylendiamin/Triethylentetramin [g/g] pH-Wert Pd/Ag [Gewichts-%] Pd Ag 1 22,5: 0 8 81 19 2 22,5: 7 8 72 28 3 22,5: 20 8 55 45 From the baths according to Examples 1-3, at a bath temperature of 35 ° C and an average current density of 2 A / dm 2 shiny, ductile and non-porous and crack-free palladium / silver layers of different compositions are deposited (see Table I) . Table I example Ethylenediamine / triethylenetetramine [g / g] PH value Pd / Ag [% by weight] Pd Ag 1 22.5: 0 8th 81 19th 2nd 22.5: 7 8th 72 28 3rd 22.5: 20 8th 55 45

Beispiel 4Example 4

Es wird eine wässerige Lösung aus 10 g/l Palladium als Pd(NH3)2(NO2)2, 5 g/l Silber als AgNO3, 60 g/l NH4NO3, 18 g/l Ethylendiamin und 4,8 g/l 2-Mercaptopropionsäure zubereitet und durch Zugabe von Ammoniumhydroxid der pH-Wert der Lösung auf 7,5 eingestellt.It becomes an aqueous solution 10 g / l Palladium as Pd (NH 3 ) 2 (NO 2 ) 2 , 5 g / l Silver as AgNO 3 , 60 g / l NH 4 NO 3 , 18 g / l Ethylenediamine and 4.8 g / l 2-mercaptopropionic acid prepared and the pH of the solution adjusted to 7.5 by adding ammonium hydroxide.

Beispiel 5Example 5

Der in Beispiel 4 beschriebenen wässerigen Lösung werden 7 g Triethylentetramin und Ammoniumhydroxid bis zu einem pH-Wert von 7,5 zugesetzt.7 g of triethylenetetramine and ammonium hydroxide are added to the aqueous solution described in Example 4 up to a pH of 7.5.

Beispiel 6Example 6

Der in Beispiel 4 beschriebenen wässerigen Lösung werden 20 g Triethylentetramin und Ammoniumhydroxid bis zu einem pH-Wert von 7,5 zugesetzt.20 g of triethylenetetramine and ammonium hydroxide are added to the aqueous solution described in Example 4 up to a pH of 7.5.

Beispiel 7Example 7

Der in Beispiel 4 beschriebenen wässerigen Lösung werden 34 g Triethylentetramin und Ammoniumhydroxid bis zu einem pH-Wert von 7,5 zugesetzt.34 g of triethylenetetramine and ammonium hydroxide are added to the aqueous solution described in Example 4 up to a pH of 7.5.

Aus den in den Beispielen 4 - 7 beschriebenen Bädern werden bei einer Bad-Temperatur von 35°C und einer mittleren Stromdichte von 2 A/dm2 glänzende, duktile und poren- und rißfreie Palladium/Silber-Schichten unterschiedlicher Zusammensetzung abgeschieden (siehe Tabelle II). Tabelle II Beispiel Ethylendiamin/Triethylentetramin [g/g] pH-Wert Pd/Ag [Gewichts-%] Pd Ag 4 18: 0 7,5 75 25 5 18: 7 7,5 73 27 6 18: 20 7,5 70 30 7 18: 34 7,5 65 35 From the in Examples 4 - are described 7 bath at a bath temperature of 35 ° C and an average current density of 2 A / dm 2 bright, ductile and pore-free and crack-free palladium / silver layers of different composition is deposited (see Table II ). Table II example Ethylenediamine / triethylenetetramine [g / g] PH value Pd / Ag [% by weight] Pd Ag 4th 18: 0 7.5 75 25th 5 18: 7 7.5 73 27 6 18:20 7.5 70 30th 7 18:34 7.5 65 35

Beispiel 8Example 8

Es wird eine wässerige Lösung aus 10 g/l Palladium als Pd(NH3)2(NO2)2, 5 g/l Silber als AgNO3, 80 g/l NH4NO3, 20 g/l Triethylentetramin und 4,8 g/l 2-Mercaptopropionsäure zubereitet. Durch Zugabe von Ammoniumhydroxid wird der pH-Wert auf 7,5,8,5 beziehungsweise 9,5 eingestellt. Die Abscheidung von glänzenden, duktilen und poren- und rißfreien Palladium/Silber-Schichten erfolgt bei Bad-Temperaturen von 25°C und 50°C und einer mittleren Stromdichte von 2 A/dm2.It becomes an aqueous solution 10 g / l Palladium as Pd (NH 3 ) 2 (NO 2 ) 2 , 5 g / l Silver as AgNO 3 , 80 g / l NH 4 NO 3 , 20 g / l Triethylenetetramine and 4.8 g / l 2-mercaptopropionic acid prepared. The pH is adjusted to 7.5, 8.5 and 9.5 by adding ammonium hydroxide. The separation of shiny, ductile and non-porous and crack-free Palladium / silver layers occur at bath temperatures of 25 ° C and 50 ° C and an average current density of 2 A / dm 2 .

Die Abhängigkeit des Silber-Gehaltes der abgeschiedenen Palladium/Silber-Schichten von dem pH-Wert und der Temperatur des Bades zeigt die Tabelle III. Tabelle III pH-Wert Badtemperatur [°C] Pd/Ag [Gewichts-%] Pd Ag 7,5 25 85 15 8,5 25 72 28 9,5 25 59 41 7,5 50 75 25 8,5 50 57 43 9,5 50 43 57 Table III shows the dependence of the silver content of the deposited palladium / silver layers on the pH and the temperature of the bath. Table III PH value Bath temperature [° C] Pd / Ag [% by weight] Pd Ag 7.5 25th 85 15 8.5 25th 72 28 9.5 25th 59 41 7.5 50 75 25th 8.5 50 57 43 9.5 50 43 57

Beispiel 9Example 9

Es wird eine wässerige Lösung aus 10 g/l Palladium als Pd(NH3)2(NO2)2, 5 g/l Silber als AgNO3, 80 g/l NH4NO3, 28,5 g/l Diethylentriamin, 8,5 g/l Pentaethylenhexamin und 4,8 g/l 2-Mercaptopropionsäure zubereitet. Durch Zugabe von Ammoniumhydroxid wird der pH-Wert auf 7,5,8,5 beziehungsweise 9,5 eingestellt. Die Abscheidung von glänzenden, duktilen und poren- und rißfreien Palladium/Silber-Schichten erfolgt bei Bad-Temperaturen von 25°C und 50°C und einer mittleren Stromdichte von 2 A/dm2. Die Abhängigkeit des Silber-Gehaltes der abgeschiedenen Palladium/Silber-Schichten von dem pH-Wert und der Temperatur des Bades zeigt die Tabelle IV. Tabelle IV pH-Wert Badtemperatur [°C] Pd/Ag [Gewichts-%] Pd Ag 7,5 25 80 20 8,5 25 60 40 9,5 25 40 60 7,5 50 61 39 8,5 50 43 57 9,5 50 35 65 It becomes an aqueous solution 10 g / l Palladium as Pd (NH 3 ) 2 (NO 2 ) 2 , 5 g / l Silver as AgNO 3 , 80 g / l NH 4 NO 3 , 28.5 g / l Diethylene triamine, 8.5 g / l Pentaethylene hexamine and 4.8 g / l 2-mercaptopropionic acid prepared. The pH is adjusted to 7.5, 8.5 and 9.5 by adding ammonium hydroxide. The deposition of shiny, ductile and pore and crack-free palladium / silver layers takes place at bath temperatures of 25 ° C and 50 ° C and an average current density of 2 A / dm 2 . Table IV shows the dependency of the silver content of the deposited palladium / silver layers on the pH and the temperature of the bath. Table IV PH value Bath temperature [° C] Pd / Ag [% by weight] Pd Ag 7.5 25th 80 20th 8.5 25th 60 40 9.5 25th 40 60 7.5 50 61 39 8.5 50 43 57 9.5 50 35 65

Beispiel 10Example 10

Es wird eine wässerige Lösung aus 7 g/l Palladium als Pd(NH3)2(NO2)2, 20 g/l Silber als AgNO3, 30 g/l Ammoniumnitrat, 10 g/l Borsäure, 7 g/l Diethylentriamin und 20 g/l 3-Mercaptopropansulfonsäure zubereitet und durch Zugabe von Ammoniumhydroxid der pH-Wert der Lösung auf 8,7 eingestellt. Bei einer Bad-Temperatur von 25° C und einer mittleren Stromdichte von 1 A/dm2 werden seidenglänzende, duktile, poren- und rißfreie Palladium/Silber-Schichten mit 2 Gewichts-% Palladium abgeschieden.It becomes an aqueous solution 7 g / l Palladium as Pd (NH 3 ) 2 (NO 2 ) 2 , 20 g / l Silver as AgNO 3 , 30 g / l Ammonium nitrate, 10 g / l Boric acid, 7 g / l Diethylene triamine and 20 g / l 3-mercaptopropanesulfonic acid prepared and the pH of the solution adjusted to 8.7 by adding ammonium hydroxide. At a bath temperature of 25 ° C and an average current density of 1 A / dm 2 , silky, ductile, pore- and crack-free palladium / silver layers with 2% by weight palladium are deposited.

Beispiel 11 (Vergleichsbeispiel) Example 11 (comparative example )

Es wird eine wässerige Lösung aus 20 g/l Pd als PdCl2(NH3)2, 5 g/l Ag als AgNO3, 40 g/l Ammoniumphosphat, 30 g/l Borsäure und 12 g/l 2-Mercaptopropionsäure zubereitet und der pH-Wert mit Ammoniumhydroxid auf 9,5 eingestellt. Bei einer Bad-Temperatur von 25°C werden bei einer mittleren Stromdichte von 2 A/dm2 glänzende, duktile und poren- und rißfreie Palladium/Silber-Schichten abgeschieden. Nach einigen Stunden bildet sich in dem Bad ein schwarzer Niederschlag.It becomes an aqueous solution 20 g / l Pd as PdCl 2 (NH 3 ) 2 , 5 g / l Ag as AgNO 3 , 40 g / l Ammonium phosphate, 30 g / l Boric acid and 12 g / l 2-mercaptopropionic acid prepared and the pH adjusted to 9.5 with ammonium hydroxide. At a bath temperature of 25 ° C and a mean current density of 2 A / dm 2 shiny, ductile and pore and crack-free palladium / silver layers are deposited. After a few hours, a black precipitate forms in the bath.

Beispiel 12 (Vergleichsbeispiel) Example 12 (comparative example )

Es wird eine wässerige Lösung aus 20 g/l Pd als PdCl2(NH3)2, 5 g/l Ag als AgNO3, 40 g/l Ammoniumphosphat, 30 g/l Borsäure, 12 g/l 2-Mercaptopropionsäure und 10 g/l Bernsteinsäuremonoamid zubereitet und der pH-Wert mit Ammoniumhydroxid auf 9,5 eingestellt. Bei einer Bad-Temperatur von 25°C werden bei einer mittleren Stromdichte von 2 A/dm2 glänzende, duktile und poren- und rißfreie Palladium/Silber-Schichten abgeschieden. Ein schwarzer Niederschlag entsteht nicht. Bei einer Bad-Temperatur von 35°C werden bei einer mittleren Stromdichte von 2 A/dm2 ebenfalls glänzende, duktile und poren- und rißfreie Palladium/Silber-Schichten abgeschieden. Nach einigen Stunden bildet sich in dem Bad ein schwarzer Niederschlag.It becomes an aqueous solution 20 g / l Pd as PdCl 2 (NH 3 ) 2 , 5 g / l Ag as AgNO 3 , 40 g / l Ammonium phosphate, 30 g / l Boric acid, 12 g / l 2-mercaptopropionic acid and 10 g / l Succinic acid monoamide prepared and the pH adjusted to 9.5 with ammonium hydroxide. At a bath temperature of 25 ° C and a mean current density of 2 A / dm 2 shiny, ductile and pore and crack-free palladium / silver layers are deposited. There is no black precipitation. At a bath temperature of 35 ° C and a mean current density of 2 A / dm 2 , shiny, ductile and pore and crack-free palladium / silver layers are also deposited. After a few hours, a black precipitate forms in the bath.

Claims (13)

  1. Ammoniacal bath for the electrodeposition of palladium-silver alloys, which contains complexed palladium, a silver compound and a mercapto compound, characterized by formulation from water and 5 - 50 g/l of palladium as an ammine-palladium complex, 2 - 40 g/l of silver as a silver compound, 30 - 150 g/l of a conducting salt, 5 - 100 g/l of an amine component of one or more aliphatic polyamines having 2 - 10 amino groups in the molecule and 2 - 50 g/l of mercaptoalkanecarboxylic acid and/or mercaptoalkanesulphonic acid and/or salts thereof
    and by a pH of 7.0 - 10.0 established with ammonium hydroxide.
  2. Bath according to Claim 1, characterized by formulation from water and 5 - 20 g/l of palladium as an ammine-palladium complex, 2 - 30 g/l of silver as a silver compound, 50 - 100 g/l of a conducting salt, 5 - 100 g/l of an amine component of one or more aliphatic polyamines having 2 - 10 amino groups in the molecule and 2 - 20 g/l of mercaptoalkanecarboxylic acid and/or mercaptoalkanesulphonic acid and/or salts thereof
    and by a pH of 7.0 - 10.0 established with ammonium hydroxide.
  3. Bath according to Claim 1 or 2, characterized in that the ammine-palladium complex is diamminepalladium dichloride, diamminepalladium dibromide or diamminepalladium dinitrite.
  4. Bath according to any of Claims 1 to 3, characterized in that the silver compound is silver chloride, silver nitrate, silver sulphate or a diamminesilver complex.
  5. Bath according to any of Claims 1 to 4, characterized in that an alkylenediamine having 2 - 6 C atoms in the alkylene group is present as the polyamine.
  6. Bath according to Claim 5, characterized in that ethylenediamine and/or hexamethylenediamine are present as the alkylenediamine.
  7. Bath according to any of Claims 1 to 6, characterized in that a polyethyleneamine of the general formula NH2(CH2CH2NH)nH in which n = 2 - 5 is present as the polyamine.
  8. Bath according to Claim 7, characterized in that diethylenetriamine, triethylenetetramine and/or pentaethylenehexamine are present as the polyethyleneamine.
  9. Bath according to Claims 6 and 8, characterized in that a mixture of ethylenediamine and triethylenetetramine is present as the polyamine.
  10. Bath according to any of Claims 1 to 9, characterized by carboxylic acids or salts thereof as the conducting salt.
  11. Bath according to any of Claims 1 to 10, characterized by ammonium salts of inorganic acids as the conducting salt.
  12. Bath according to any of Claims 1 to 11, characterized by 2- or 3-mercaptopropionic acid as the mercaptoalkanecarboxylic acid.
  13. Bath according to any of Claims 1 to 12, characterized by 3-mercaptopropanesulphonic acid as the mercaptoalkanesulphonic acid.
EP95107534A 1994-07-21 1995-05-18 Palladium-silver alloys electroplating bath Expired - Lifetime EP0693579B1 (en)

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DE4444232A DE4444232C1 (en) 1994-07-21 1994-12-13 Bath for the galvanic deposition of palladium-silver alloys

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US5976344A (en) * 1996-05-10 1999-11-02 Lucent Technologies Inc. Composition for electroplating palladium alloys and electroplating process using that composition
DE19629658C2 (en) * 1996-07-23 1999-01-14 Degussa Cyanide-free galvanic bath for the deposition of gold and gold alloys
JP3301707B2 (en) * 1997-01-20 2002-07-15 ディップソール株式会社 Tin-silver alloy acid electroplating bath
JP2000212763A (en) * 1999-01-19 2000-08-02 Shipley Far East Ltd Silver alloy plating bath and formation of silver alloy coating film using it
US7537799B2 (en) * 2003-07-11 2009-05-26 Hewlett-Packard Development Company, L.P. Methods of forming electrically conductive pathways using palladium aliphatic amine complexes
EP3159435B1 (en) * 2015-10-21 2018-05-23 Umicore Galvanotechnik GmbH Additive for silver palladium alloy electrolytes

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NL276877A (en) * 1961-04-06
US4126524A (en) * 1975-03-12 1978-11-21 Technic, Inc. Silver complex, method of making said complex and method and electrolyte containing said complex for electroplating silver and silver alloys
US4066517A (en) * 1976-03-11 1978-01-03 Oxy Metal Industries Corporation Electrodeposition of palladium
GB2112018B (en) * 1981-02-27 1984-08-15 Western Electric Co Palladium and palladium alloys electroplating procedure
US4673472A (en) * 1986-02-28 1987-06-16 Technic Inc. Method and electroplating solution for deposition of palladium or alloys thereof
DE3935664C1 (en) * 1989-10-26 1991-03-28 W.C. Heraeus Gmbh, 6450 Hanau, De Palladium-silver alloys for electrical contacts - deposited from ammoniacal bath contg. palladium tetramine complex, silver di:amine complex and organic sulphur cpd.

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