EP0152601A1 - Aqueous alcaline bath for chemically plating copper or nickel - Google Patents

Aqueous alcaline bath for chemically plating copper or nickel Download PDF

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Publication number
EP0152601A1
EP0152601A1 EP84115513A EP84115513A EP0152601A1 EP 0152601 A1 EP0152601 A1 EP 0152601A1 EP 84115513 A EP84115513 A EP 84115513A EP 84115513 A EP84115513 A EP 84115513A EP 0152601 A1 EP0152601 A1 EP 0152601A1
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Prior art keywords
aqueous alkaline
compounds
alkaline bath
bath according
bath
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EP84115513A
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German (de)
French (fr)
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EP0152601B1 (en
Inventor
Josif Dr. Culjkovic
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Bayer Pharma AG
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Schering 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
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • 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
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents

Definitions

  • the invention relates to an aqueous alkaline bath for the chemical deposition of copper, nickel, cobalt or their alloys according to the preamble of claim 1 and a method for the adhesive chemical deposition of these metals and alloys according to the preamble of claim 11.
  • Baths of the type described in the introduction are generally known. They usually contain considerable amounts of complexing agents to prevent the precipitation of metal hydroxides. This inevitably leads to an unsatisfactory quality of the coatings deposited from these baths, which, depending on the bath type, contain considerable amounts of impurities such as carbon, nitrogen, hydrogen and others. can contain, which have a decisive influence on the crystal structure and thus on technologically important properties, such as specific electrical conductivity, internal tension, adhesive strength and ductility. For example, this has a particularly disruptive effect in the production of printed circuit boards in which undesired bubbles, lifts and cracks can form, and the more so the thicker the deposited metal layer.
  • the concentrates or rinsing water produced during the operation of the known baths are moreover usually obtained in the form of solutions which can only be disposed of with great technical effort since their direct return to the working process is not readily possible.
  • the object of the present invention is to provide a bath and a method which permit a highly adhesive chemical deposition of copper, nickel, cobalt and their alloys with the greatest purity and at the same time technically problem-free recovery of the metals used.
  • metal coatings of the highest purity can be deposited from the bath according to the invention, which is not possible with the known chemical baths.
  • the sum of impurities in carbon, hydrogen and nitrogen in copper coatings deposited according to the invention is 0.03%, while in conventional coatings, impurities are in the order of 0.07 to 0.37%.
  • the quality of the metal coatings deposited according to the invention therefore corresponds to that which is otherwise only achieved with electrolytic metal deposition. Purity and the properties of the coatings deposited according to the invention, such as average residual stress, average lattice distortion and the crystallite size, are therefore equal to the electroplated coatings.
  • the bath according to the invention therefore enables in particular the production of printed circuit boards with adhesive layers which are extremely ductile and easy to solder and which are characterized by the lowest internal stresses, which means a breakthrough in technology.
  • the complexing agents to be scrapped according to the invention also have the particular advantage of being readily biodegradable and thus, in contrast to the known complexing agents, to be particularly environmentally friendly.
  • the glycerol to be used according to the invention has not been shown to have any damaging effect on organisms, so that, taking further account of its classification as a highly biodegradable substance, it exhibits favorable ecological properties.
  • metals copper, nickel and cobalt their sulfates, nitrates, chlorides, bromides, rhodanides, oxides, hydroxides, carbonates, basic carbonates, acetates and others can be used, specifically in metal concentrations of 10 -4 to 2 mol / liter, preferably of 10 - 2 to 1 mole / liter.
  • These metal compounds form complex compounds with the complexing agents according to the invention in the bath solution, which develop the desired effect.
  • these complex compounds can also be prepared per se in a manner known per se and can only be added to the bath solution before they are used.
  • the complex compound Schiff's potassium cupri biuret according to the invention can be prepared by adding 1 mol of copper acetate to an aqueous solution of 1 mol of biuret and 4 mol of potassium hydroxide by precipitation with a 2% alcoholic potassium hydroxide solution.
  • the molar ratio of metal to complexing agent is at least -1: 0.8, preferably from 1: 1 to 1: 6.
  • the labeled polyols which also have the general formula, are suitable as complexing agents according to the invention with R in the meaning of hydrogen or C 1 -C 6 alkyl and n the numbers 2 to 8 can be described.
  • Biuret-type compounds are understood to mean those which have at least two in the molecule Contain groups that are connected in an open chain and directly to one another or by a C or N atom.
  • the stability of the metal complexes formed from these complexing agents is extremely high, but can, if desired, be influenced immediately if the pH changes by acidification, which leads to the complete precipitation of the metal hydroxide, which can then be returned to the working process.
  • the pH of the bath according to the invention should be greater than 10, preferably from 12 to 14, and is kept at the desired value by adding customary pH-regulating substances or mixtures of substances.
  • Particularly suitable reducing agents are formaldehyde, sodium borohydride, dimethylaminoborane, diethylaminoborane, sodium hypophosphite, hydrazine, glyceraldehyde, dihydroxyacetone and other customary reducing agents.
  • the bath is operated at temperatures from 5 ° C to the boiling point, preferably from 20 ° to 80 ° C.
  • the bath can additionally contain stabilizers known per se based on polyamines, N-containing compounds, reaction products of N-containing compounds with epihalohydrins, sulfur or selenium compounds with the oxidation state minus one or minus two, mercury compounds or lead compounds, to ensure a sufficient lifespan of the bath.
  • the basic composition of the bath according to the invention is as follows:
  • the bath according to the invention is suitable for the full and partial metallization of conductors and non-conductors after corresponding customary pretreatment, such as degreasing, pickling, cleaning, conditioning, activating and reducing.
  • customary pretreatment such as degreasing, pickling, cleaning, conditioning, activating and reducing.
  • a preferred field of application is the production of printed circuits.
  • the conductors that had been plated through in this bath were, according to the transmitted light method, flawless.
  • the deposition rate was approx. 2 fm / h, so that a treatment time of 15-20 minutes is completely sufficient.
  • This bath deposits ductile copper coatings at a speed of approx. 5 ⁇ m / h, which are particularly suitable for semi or additive technology.
  • Copper-phosphorus alloys with 0.3 to 0.5% phosphorus were deposited from this bath.
  • the deposition rate was 1.2 ⁇ m / h.
  • Adhesive layers of Cu 2 O on Al 2 0 3 ceramic could be deposited from this bath. After an annealing process at 400 to 600 ° C, within 10 minutes the layers were strengthened to 30 ⁇ m / in an acidic galvanic copper bath. Tempering and spinel formation resulted in an increase in adhesive strength of up to 2 N / mm in a peel test. With conventional techniques, without spinel formation, an adhesive strength of only 0.7 N / mm is achieved.
  • Ductile nickel coatings with a boron content of approximately 0.2 to 0.4% could be deposited from this bath.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

Die Erfindung betrifft ein wäßriges alkalisches Bad zur haftfesten chemischen Abscheidung von Kupfer, Nickel, Kobalt oder deren Legierungen mit größter Reinheit, enthaltend Verbindungen dieser Metalle, Reduktionsmittel, Netzmittel, pH-regulierende Stoffe, Stabilisatoren, Inhibitoren und Komplexbildner, dadurch gekennzeichnet, daß es als Komplexbildner Polyole und/oder Verbindungen vom Biuret-Typ enthält, sowie ein Verfahren unter Verwendung dieses Bades, insbesondere zur Herstellung von gedruckten Schaltungen.The invention relates to an aqueous alkaline bath for the adhesive chemical deposition of copper, nickel, cobalt or their alloys with the greatest purity, containing compounds of these metals, reducing agents, wetting agents, pH regulators, stabilizers, inhibitors and complexing agents, characterized in that it is as Contains complexing agents polyols and / or compounds of the biuret type, and a method using this bath, in particular for the production of printed circuits.

Description

Die Erfindung betrifft ein wäßriges alkalisches Bad zur chemischen Abscheidung von Kupfer, Nickel, Kobalt oder deren Legierungen gemäß Oberbegriff des Anspruchs 1 sowie ein Verfahren zur haftfesten chemischen Abscheidung dieser Metalle und Legierungen gemäß Oberbegriff des Anspruchs 11.The invention relates to an aqueous alkaline bath for the chemical deposition of copper, nickel, cobalt or their alloys according to the preamble of claim 1 and a method for the adhesive chemical deposition of these metals and alloys according to the preamble of claim 11.

Bäder der eingangs bezeichneten Art sind allgemein bekannt. Sie enthalten in der Regel beträchtliche Mengen an Komplexbildnern, um das Ausfällen von Metallhydroxiden zu verhindern. Das führt zwangsläufig zu einer unbefriedigenden Qualität der aus diesen Bädern abgeschiedenen Überzüge, die, je nach Badtyp, erhebliche Mengen an Verunreinigungen, wie Kohlenstoff, Stickstoff, Wasserstoff u.a. enthalten können, welche einen entscheidenden Einfluß auf die Kristallstruktur und somit auf technologisch wichtige Eigenschaften, wie spezifische elektrische Leitfähigkeit, innere Spannung, Haftfestigkeit und Dehnbarkeit beziehungsweise Duktilität, ausüben. Dies wirkt sich zum Beispiel besonders störend bei der Herstellung von Leiterplatten aus, bei denen sich unerwünschte Blasen, Abhebungen und Risse bilden können, und zwar um so mehr, je dicker die abgeschiedene Metallschicht ist.Baths of the type described in the introduction are generally known. They usually contain considerable amounts of complexing agents to prevent the precipitation of metal hydroxides. This inevitably leads to an unsatisfactory quality of the coatings deposited from these baths, which, depending on the bath type, contain considerable amounts of impurities such as carbon, nitrogen, hydrogen and others. can contain, which have a decisive influence on the crystal structure and thus on technologically important properties, such as specific electrical conductivity, internal tension, adhesive strength and ductility. For example, this has a particularly disruptive effect in the production of printed circuit boards in which undesired bubbles, lifts and cracks can form, and the more so the thicker the deposited metal layer.

Die beim Betrieb der bekannten Bäder anfallenden Konzentrate beziehungsweise Spülwässer fallen überdies meist in Form von Lösungen an, die nur mit großem technischen Aufwand entsorgt werden können, da ihre direkte Zurückführung in den Arbeitsprozess nicht ohne weiteres möglich ist.The concentrates or rinsing water produced during the operation of the known baths are moreover usually obtained in the form of solutions which can only be disposed of with great technical effort since their direct return to the working process is not readily possible.

Aufgabe der vorliegenden Erfindung ist die Schaffung eines Bades und eines Verfahrens, welche eine haftfeste chemische Abscheidung von Kupfer, Nickel, Kobalt und deren Legierungen mit größter Reinheit bei gleichzeitig technisch problemloser Rückgewinnung der eingesetzten Metalle erlauben.The object of the present invention is to provide a bath and a method which permit a highly adhesive chemical deposition of copper, nickel, cobalt and their alloys with the greatest purity and at the same time technically problem-free recovery of the metals used.

Diese Aufgabe wird erfindungsgemäß durch den in den Ansprüchen gekennzeichneten Gegenstand gelöst.This object is achieved according to the invention by the subject matter characterized in the claims.

Vorteilhafte Weiterbildungen sind in den Unteransprüchen beschrieben.Advantageous further developments are described in the subclaims.

Aus dem erfindungsgemäßen Bad können überraschenderweise Metallüberzüge von höchster Reinheit abgeschieden werden, was mit den bekannten chemischen Bädern nicht möglich ist.Surprisingly, metal coatings of the highest purity can be deposited from the bath according to the invention, which is not possible with the known chemical baths.

So ist zum Beispiel die Summe der Verunreinigungen an Kohlenstoff, Wasserstoff und Stickstoff in erfindungsgemäß abgeschiedenen Kupferüberzügen 0,03 %, während in konventionell abgeschiedenen Überzügen Verunreinigungen in der Größenordnung von 0,07 bis 0,37 % enthalten sind.For example, the sum of impurities in carbon, hydrogen and nitrogen in copper coatings deposited according to the invention is 0.03%, while in conventional coatings, impurities are in the order of 0.07 to 0.37%.

Die Qualität der erfindungsgemäß abgeschiedenen Metallüberzüge entspricht daher derjenigen, die sonst nur bei elektrolytischer Metallabscheidung erreicht wird. Reinheit und die hierdurch bestimmten Eigenschaften der erfindungsgemäß abgeschiedenen Überzüge, wie mittlere Eigenspannung, mittlere Gitterverzerrung sowie die Kristallitgröße sind demzufolge den galvanisch abgeschiedenen Überzügen ebenbürtig.The quality of the metal coatings deposited according to the invention therefore corresponds to that which is otherwise only achieved with electrolytic metal deposition. Purity and the properties of the coatings deposited according to the invention, such as average residual stress, average lattice distortion and the crystallite size, are therefore equal to the electroplated coatings.

Das erfindungsgemäße Bad ermöglicht daher insbesondere die Herstellung von Leiterplatten mit haftfesten Schichten, die äußerst duktil und lötfreudig sind und sich durch geringste innere Spannungen auszeichnen, was technologisch einen Durch--bruch bedeutet.The bath according to the invention therefore enables in particular the production of printed circuit boards with adhesive layers which are extremely ductile and easy to solder and which are characterized by the lowest internal stresses, which means a breakthrough in technology.

Die erfindungsgemäß zu verwrertenden Komplexbildner haben außerdem den besonderen Vorteil, biologisch leicht abbaubar und damit im Gegensatz zu den bekannten Komplexbildnern besonders umwelfreundlich zu sein. So ist zum Beispiel bei dem erfindungsgemäß zu verwendenden Glycerin keine schädigende Wirkung auf Organismen bekannt geworden, so daß es unter weiterer Berücksichtigung seiner Zuordnung als hoch biologischabbaubar einzustufender Stoff günstige ökologische Eigenschaften entfaltet.The complexing agents to be scrapped according to the invention also have the particular advantage of being readily biodegradable and thus, in contrast to the known complexing agents, to be particularly environmentally friendly. For example, the glycerol to be used according to the invention has not been shown to have any damaging effect on organisms, so that, taking further account of its classification as a highly biodegradable substance, it exhibits favorable ecological properties.

Als Verbindungen der Metalle Kupfer, Nickel und Kobalt können deren Sulfate, Nitrate, Chloride, Bromide, Rhodanide, Oxide, Hydroxide Carbonate, basische Carbonate, Acetate u.a. verwendet werden, und zwar in Metallkonzentrationen von 10-4 bis 2 Mol/Liter, vorzugsweise von 10-2 bis 1 Mol/Liter. Diese Metallverbindungen bilden mit den erfindungsgemäßen Komplexbildnern in der Badlösung Komplexverbindungen, welche die gewünschte Wirkung entfalten. Es versteht sich jedoch, daß diese Komplexverbindungen auch für sich in an sich bekannter Weise hergestellt und erst vor ihrer Verwendung der Badlösung zugefügt werden können.As compounds of the metals copper, nickel and cobalt, their sulfates, nitrates, chlorides, bromides, rhodanides, oxides, hydroxides, carbonates, basic carbonates, acetates and others can be used, specifically in metal concentrations of 10 -4 to 2 mol / liter, preferably of 10 - 2 to 1 mole / liter. These metal compounds form complex compounds with the complexing agents according to the invention in the bath solution, which develop the desired effect. However, it goes without saying that these complex compounds can also be prepared per se in a manner known per se and can only be added to the bath solution before they are used.

Beispielsweise läßt sich die erfindungsgemäße Komplexverbindung Schiffsches Kaliumkupri-Biuret durch Zugabe von 1 Mol Kupferacetat zu einer wäßrigen Lösung von 1 Mol Biuret und 4 Mol Kaliumhydroxid durch Fällen mit 2 %iger alkoholischer Kaliumhydroxidlösung herstellen.For example, the complex compound Schiff's potassium cupri biuret according to the invention can be prepared by adding 1 mol of copper acetate to an aqueous solution of 1 mol of biuret and 4 mol of potassium hydroxide by precipitation with a 2% alcoholic potassium hydroxide solution.

Es hat sich als besonders vorteilhaft erwiesen, wenn das molare Verhältnis von Metall zu Komplexbildner mindestens -1 : 0,8, vorzugsweise von 1 : 1 bis 1 : 6, beträgt.It has proven to be particularly advantageous if the molar ratio of metal to complexing agent is at least -1: 0.8, preferably from 1: 1 to 1: 6.

Als erfindungsgemäße Komplexbildner eignen sich die gekennzeichneten Polyole, die auch durch die allgemeine Formel

Figure imgb0001
mit R in der Bedeutung von Wasserstoff oder C1-C6-Alkyl und n die Zahlen 2 bis 8 beschrieben werden können.The labeled polyols, which also have the general formula, are suitable as complexing agents according to the invention
Figure imgb0001
 with R in the meaning of hydrogen or C 1 -C 6 alkyl and n the numbers 2 to 8 can be described.

Unter Verbindungen vom Biuret-Typ werden solche verstanden, die im Molekül mindestens zwei

Figure imgb0002
Gruppen enthalten, die in offener Kette und direkt miteinander oder durch ein C- oder N-Atom verbunden sind.Biuret-type compounds are understood to mean those which have at least two in the molecule
Figure imgb0002
 Contain groups that are connected in an open chain and directly to one another or by a C or N atom.

Die Stabilität der aus diesen Komplexbildnern gebildeten Metallkomplexe ist außerordentlich groß, kann jedoch bei Veränderung des pH-Wertes durch Ansäuern gewünschtenfalls sofort beeinflußt werden, wodurch es zur vollständigen Fällung des Metallhydroxids kommt, daß dann dem Arbeitsprozess wieder zurückgeführt werden kann.The stability of the metal complexes formed from these complexing agents is extremely high, but can, if desired, be influenced immediately if the pH changes by acidification, which leads to the complete precipitation of the metal hydroxide, which can then be returned to the working process.

Der pH-Wert des erfindungsgemäßen Bades soll größer als 10, vorzugsweise von 12 bis 14, betragen, und wird durch Zusatz üblicher pH-regulierender Stoffe oder Stoffgemische auf dem gewünschten Wert gehalten.The pH of the bath according to the invention should be greater than 10, preferably from 12 to 14, and is kept at the desired value by adding customary pH-regulating substances or mixtures of substances.

Als Reduktionsmittel eignen sich insbesondere Formaldehyd, Natriumborhydrid, Dimethylaminoboran, Diäthylaminoboran, Natriumhypophosphit, Hydrazin, Glycerinaldehyd, Dihydroxyaceton sowie andere übliche Reduktionsmittel.Particularly suitable reducing agents are formaldehyde, sodium borohydride, dimethylaminoborane, diethylaminoborane, sodium hypophosphite, hydrazine, glyceraldehyde, dihydroxyacetone and other customary reducing agents.

Das Bad wird bei Temperaturen von 5° C bis zum Siedepunkt, vorzugsweise von 20° bis 80° C, betrieben.The bath is operated at temperatures from 5 ° C to the boiling point, preferably from 20 ° to 80 ° C.

Sofern gewünscht, kann das Bad zusätzlich an sich bekannte Stabilisatoren auf Basis von Polyaminen, N-haltige Verbindungen, Umsetzungsprodukten von N-haltigen Verbindungen mit Epihalohydrinen, Schwefel- oder Selenverbindungen mit der Oxydationsstufe minus eins oder minus zwei, Quecksilber-Verbindungen oder Bleiverbindungen enthalten, um eine ausreichende Lebensdauer des. Bades zu gewährleisten.If desired, the bath can additionally contain stabilizers known per se based on polyamines, N-containing compounds, reaction products of N-containing compounds with epihalohydrins, sulfur or selenium compounds with the oxidation state minus one or minus two, mercury compounds or lead compounds, to ensure a sufficient lifespan of the bath.

Als Netzmittel eignen sich alle für diesen Zweck bekannten Produkte.All products known for this purpose are suitable as wetting agents.

Die Grundzusammensetzung des erfindungsgemäßen Bades ist wie folgt:

Figure imgb0003
The basic composition of the bath according to the invention is as follows:
Figure imgb0003

Das erfindungsgemäße Bad eignet sich für die Voll- und Partiellmetallisierung von Leitern und Nichtleitern nach entsprechender üblicher Vorbehandlung, wie Entfetten, Beizen, Reinigen, Konditionieren, Aktivieren und Reduzieren. Ein bevorzugtes Anwendungsgebiet ist die Herstellung von gedruckten Schaltungen.The bath according to the invention is suitable for the full and partial metallization of conductors and non-conductors after corresponding customary pretreatment, such as degreasing, pickling, cleaning, conditioning, activating and reducing. A preferred field of application is the production of printed circuits.

Die folgenden Beispiele dienen zur Erläuterung der Erfindung.The following examples serve to illustrate the invention.

B e i s p i e 1 1Example: 1 1

Figure imgb0004
Die in diesem Bad durchkontaktierten Leiter waren, nach der Durchlichtmethode beurteilt, einwandfrei. Die Abscheidungsgeschwindigkeit betrug ca. 2fm/h, so daß eine Behandlungszeit von 15-20 Minuten vollkommen ausreichend ist. Nach Absenkung des pH-Wertes, mit einer Säure, auf pH 7-10, fiel praktisch das gesammte Kupfer als Kupferhydroxid aus. Nach der Filtration kann es direkt im Bad wieder gelöst werden.
Figure imgb0004
 The conductors that had been plated through in this bath were, according to the transmitted light method, flawless. The deposition rate was approx. 2 fm / h, so that a treatment time of 15-20 minutes is completely sufficient. After lowering the pH with an acid to pH 7-10, practically all of the copper precipitated out as copper hydroxide. After filtration, it can be dissolved again in the bathroom.

Bei s p i e 1 2With s p i e 1 2

Figure imgb0005
Dieses Bad scheidet mit einer Geschwindigkeit von ca. 5 µm/h duktile Kupferüberzüge ab, die besonders für die Semi- oder Additivtechnik geeignet sind.
Figure imgb0005
 This bath deposits ductile copper coatings at a speed of approx. 5 µm / h, which are particularly suitable for semi or additive technology.

B i s p i e 1 3B i s p i e 1 3

Figure imgb0006
Aus diesem Bad wurden Kupfer-Phosphorlegierungen mit 0,3 bis 0,5 % Phosphor abgeschieden. Die Abscheidungsgeschwindigkeit betrug 1,2 µm/h.
Figure imgb0006
 Copper-phosphorus alloys with 0.3 to 0.5% phosphorus were deposited from this bath. The deposition rate was 1.2 µm / h.

B e i s p i e l 4Example 4

Figure imgb0007
Aus diesem Bad konnte man haftfeste Schichten von Cu2O auf Al203-Keramik abscheiden. Nach einem Temperprozeß bei 400 bis 600° C, innerhalb 10 Minuten wurden die Schichten auf 30 µm/in einem sauren galvanischen Kupferbad verstärkt. Durch die Temperung und Spinellbildung ergab sich eine Haftfestigkeitssteigerung von bis zu 2 N/mm in einem Schältest. Bei den herkömmlichen Techniken, ohne Spinellbildung, erzielt man lediglich eine Haftfestigkeit von 0,7 N/mm.
Figure imgb0007
 Adhesive layers of Cu 2 O on Al 2 0 3 ceramic could be deposited from this bath. After an annealing process at 400 to 600 ° C, within 10 minutes the layers were strengthened to 30 µm / in an acidic galvanic copper bath. Tempering and spinel formation resulted in an increase in adhesive strength of up to 2 N / mm in a peel test. With conventional techniques, without spinel formation, an adhesive strength of only 0.7 N / mm is achieved.

B e i s p i e 1 5Example: 1 5

Figure imgb0008
Aus diesem Bad konnte man duktile Nickelüberzüge mit einem Gehalt an Bor von ca. 0,2 bis 0,4 % abscheiden.
Figure imgb0008
 Ductile nickel coatings with a boron content of approximately 0.2 to 0.4% could be deposited from this bath.

Claims (12)

1. Wäßriges alkalisches Bad zur haftfesten chemischen Abscheidung von Kupfer, Nickel, Kobalt oder deren Legierungen mit größter Reinheit, enthaltend Verbindungen dieser Metalle, Reduktionsmittel, Netzmittel, pH-regulierende Stoffe, Stabilisatoren, Inhibitoren und Komplexbildner, dadurch gekennzeichnet, daß es als Komplexbildner Polyole und/oder Verbindungen vom Biuret-Typ enthält.1. Aqueous alkaline bath for the adhesive chemical deposition of copper, nickel, cobalt or their alloys with the greatest purity, containing compounds of these metals, reducing agents, wetting agents, pH-regulating substances, stabilizers, inhibitors and complexing agents, characterized in that it is a complexing agent polyols and / or contains compounds of the biuret type. 2. Wäßriges alkalisches Bad gemäß Anspruch 1, dadurch gekennzeichnet, daß es als Polyole aliphatische Kohlenwasserstoffe enthält, die mindestens zwei Hydroxygruppen aufweisen.2. Aqueous alkaline bath according to claim 1, characterized in that it contains, as polyols, aliphatic hydrocarbons which have at least two hydroxyl groups. 3. Wäßriges alkalisches Bad gemäß Ansprüchen 1 und 2, dadurch gekennzeichnet, daß es als Polyole Äthylenglykol, Glycerin, Erythrit, Arabit, Mannit, Dulcit, Sorbit, Polyvinylalkohol, Inosit, 3,4-Dihydroxytetrahydrofuran oder Maltit enthält.3. Aqueous alkaline bath according to claims 1 and 2, characterized in that it contains, as polyols, ethylene glycol, glycerol, erythritol, arabitol, mannitol, dulcitol, sorbitol, polyvinyl alcohol, inositol, 3,4-dihydroxytetrahydrofuran or maltitol. 4. Wäßriges alkalisches Bad gemäß Anspruch 1, dadurch gekennzeichnet, daß es als Verbindungen vom Biuret-Typ solche Verbindungen enthält, die im Molekül mindestens zwei
Figure imgb0009
Gruppen enthalten.4. Aqueous alkaline bath according to claim 1, characterized in that it contains as compounds of the biuret type those compounds which have at least two in the molecule
Figure imgb0009
 Groups included. 5. Wäßriges alkalisches Bad gemäß Ansprüchen 1 und 4, dadurch gekennzeichnet, daß es als Verbindungen vom Biuret-Typ Biuret, Malonamid, Oxamid, Aminoessigsäureamid, Guanylharnstoff oder Biguanid enthält.5. Aqueous alkaline bath according to claims 1 and 4, characterized in that it contains as compounds of the biuret type biuret, malonamide, oxamide, aminoacetic acid amide, guanylurea or biguanide. 6. Wäßriges alkalisches Bad gemäß Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß es die Komplexbildner in Konzentrationen von 10-4 bis 10 Mol /Liter, vorzugsweise von 10-2 bis 1 Mol /Liter, enthält.6. Aqueous alkaline bath according to claims 1 to 5, characterized in that it contains the complexing agents in concentrations of 10 -4 to 10 mol / liter, preferably from 10 - 2 to 1 mol / liter. 7. Wäßriges alkalisches Bad gemäß Ansprüchen 1 und 6, dadurch gekennzeichnet, daß das molare Verhältnis von Metall zu Komplexbildner mindestens 1 : 0,8, vorzugsweise von 1 : 1 bis 1 : 6, beträgt.7. Aqueous alkaline bath according to claims 1 and 6, characterized in that the molar ratio of metal to complexing agent is at least 1: 0.8, preferably from 1: 1 to 1: 6. 8. Wäßriges alkalisches Bad gemäß Anspruch 1, dadurch gekennzeichnet, daß es als Reduktionsmittel Formaldehyd, Natriumborhydrid, Dimethylaminoboran, Diäthylaminoboran, Natriumhypophosphit, Hydrazin, Glycerinaldehyd oder Dihydroxyaceton enthält.8. Aqueous alkaline bath according to claim 1, characterized in that it contains formaldehyde, sodium borohydride, dimethylaminoborane, diethylaminoborane, sodium hypophosphite, hydrazine, glyceraldehyde or dihydroxyacetone as a reducing agent. 9. Wäßriges alkalisches Bad gemäß Anspruch 1, gekennzeichnet durch einen pH-Wert größer als 10, vorzugsweise von 12 bis 14.9. Aqueous alkaline bath according to claim 1, characterized by a pH greater than 10, preferably from 12 to 14. 10. Wäßriges alkalisches Bad gemäß Anspruch 1, dadurch gekennzeichnet, daß es als Stabilisatoren zusätzlich Polyamine, N-haltige Verbindungen, Umsetzungsprodukte von N-haltigen Verbindungen mit Epihalohydrinen, Schwefel- oder Selenverbindungen mit der Oxydationsstufe minus eins oder minus zwei, Quecksilber-Verbindungen oder Bleiverbindungen enthält. (Cyanide, Komplexe-Cyanide)10. Aqueous alkaline bath according to claim 1, characterized in that it additionally contains polyamines, N-containing compounds, reaction products of N-containing compounds with epihalohydrins, sulfur or selenium compounds with the oxidation state minus one or minus two, mercury compounds or as stabilizers Contains lead compounds. (Cyanides, complex cyanides) 11. Verfahren zur haftfesten chemischen Abscheidung von Kupfer, Nickel, Kobalt oder deren Legierungen mit größter Reinheit, dadurch gekennzeichnet, daß Bäder gemäß den Ansprüchen 1 bis 10 bei Temperaturen von 5° C bis zum Siedepunkt, vorzugsweise von 20 bis 80° C, verwendet werden.11. A method for the adhesive chemical deposition of copper, nickel, cobalt or their alloys with the greatest purity, characterized in that baths according to claims 1 to 10 at temperatures from 5 ° C to the boiling point, preferably from 20 to 80 ° C, used will. 12. Verfahren gemäß Anspruch 11 zur Voll- oder Partiellmetallisierung von Leitern und Nichtleitern, insbesondere gedruckten Schaltungen.12. The method according to claim 11 for full or partial metallization of conductors and non-conductors, in particular printed circuits.
EP84115513A 1984-02-04 1984-12-15 Aqueous alcaline bath for chemically plating copper or nickel Expired EP0152601B1 (en)

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DE3404270 1984-02-04
DE19843404270 DE3404270A1 (en) 1984-02-04 1984-02-04 AQUEOUS ALKALINE BATH FOR CHEMICAL DEPOSITION OF COPPER, NICKEL, COBALT AND THEIR ALLOYS

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EP3190209A1 (en) 2016-01-06 2017-07-12 ATOTECH Deutschland GmbH 1-acylguanidine compounds and the use of said compounds in electroless deposition of nickel and nickel alloy coatings

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US20060141281A1 (en) * 2004-12-24 2006-06-29 Tdk Corporation R-T-B system permanent magnet and plating film
KR101681116B1 (en) * 2016-05-26 2016-12-09 (주)오알켐 Method for electroless copper plating through-hole of printed circuit board and method for preparing a catalytic solution used in method thereof

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ATA27385A (en) 1987-06-15
JPS60204885A (en) 1985-10-16
AT384829B (en) 1988-01-11
EP0152601B1 (en) 1988-12-07
US4720404A (en) 1988-01-19
DE3475535D1 (en) 1989-01-12
CA1254353A (en) 1989-05-23

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