EP0542771B1 - Stable, electroless, aqueous, acid gold bath for the deposition of gold and its use - Google Patents

Stable, electroless, aqueous, acid gold bath for the deposition of gold and its use Download PDF

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Publication number
EP0542771B1
EP0542771B1 EP91913280A EP91913280A EP0542771B1 EP 0542771 B1 EP0542771 B1 EP 0542771B1 EP 91913280 A EP91913280 A EP 91913280A EP 91913280 A EP91913280 A EP 91913280A EP 0542771 B1 EP0542771 B1 EP 0542771B1
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Prior art keywords
gold
bath
stable
electroless
acid
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EP91913280A
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German (de)
French (fr)
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EP0542771A1 (en
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Manfred Dettke
Robert Ruether
Klaus Janotta
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Atotech Deutschland GmbH and Co KG
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Atotech Deutschland GmbH and Co KG
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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
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals 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
    • C23C18/42—Coating with noble metals

Definitions

  • the invention relates to a stable, currentless, aqueous, acidic gold bath for the deposition of gold and its use.
  • the bath according to the invention containing the anion tetracyano gold (III), a complexing agent or a mixture of several complexing agents, an acid or an acid mixture, is suitable for the electroless deposition of gold on metals that are less noble than gold, as well as on alloys of these metals.
  • Gold baths for electroless deposition of gold are already known, for example from the documents DE-PS 3640028, US Pat. No. 4,830,668 and GB-PS 20 99 460. These are gold baths which predominantly contain an alkali metal dicyanoaurate - (I) or alkali tetracyanoaurate (III ), contain a complexing agent and a reducing agent. All of these baths generally have an unsatisfactory stability and decompose with the deposition of metallic gold or gold (I) cyanide.
  • the object of the present invention is to deposit in the acidic range from the tetracyano gold (III) gold onto metals or their alloys and at the same time to provide a more stable gold bath.
  • complexing agents or mixtures of several complexing agents which contain different groups per molecule which have a complexing and reducing effect.
  • These are compounds which contain one or more carboxyl groups and one or more phosphonic acid groups per molecule.
  • they are compounds of the general formulas I and II, according to patent claims 2 and 3.
  • N, N-bis (carboxymethylene) -1-aminoethane-1,1-diphosphonic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid have proven particularly useful as complexing agents in the baths according to the invention.
  • a particular advantage of the bath according to the invention is that layers up to 0.5 »m are already obtained with gold contents in the bath of 1.0 g / l gold.
  • the bath thus enables the gold-plating of alloys that are common in the semiconductor industry, for example iron-nickel-cobalt alloys and chemically reductively deposited nickel alloys such as nickel-phosphorus, nickel-boron and pure nickel.
  • carboxymethylene-aminoalkyl-phosphenoic acids and / or phosphonalkylcarboxylic acids are used as complexing agents, which allow a substantial increase in the deposition rate and higher layer thicknesses, which was not foreseeable.
  • the acids used are, for example, sulfuric acid or phosphoric acid or mixtures thereof.
  • the basic composition of the bath according to the invention is, for example, as follows: Gold as metal 0.05 - 30 grams / liter Complexing agent 5.0 - 100 grams / liter acid 10 - 100 ml / liter
  • the working temperature of the bath is usually 70 to 90 o C. It has been found that even at higher temperatures there is no decomposition of the bath, for example the precipitation of elemental gold. Another advantage of the bath is that it can be used repeatedly and that the gold salt can be replenished as required.
  • the bath according to the invention has a constant deposition rate up to layer thicknesses of 0.5 ⁇ m, which is dependent on the gold content and the temperature.
  • the bath according to the invention can be used for gold layers of solder connections which are formed by crystal or wire bonding, which is of particular technical value.
  • the high deposition speed also enables use in decorative gilding. A uniform yellow layer can be observed after seconds.
  • the stable bath compositions listed below can be used to deposit very uniform and ductile coatings under the working conditions listed.
  • the invention also relates to the use of the gold baths according to the invention for the deposition of gold on metals which are less noble than gold or on alloys of these metals.
  • Potassium tetracyanoaurat-III 6.0 g / l Complex 2-phosphonobutane-1,2,4-tricarboxylic acid 40.0 ml / l Sulfuric acid / phosphoric acid 1: 1 50.0 ml / l PH value less than 1 temperature 60 o C Deposition speed particularly good adhesive strength 0.2 »m / 30 min.

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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)
  • Manufacture And Refinement Of Metals (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

PCT No. PCT/DE91/00624 Sec. 371 Date Apr. 2, 1993 Sec. 102(e) Date Apr. 2, 1993 PCT Filed Aug. 1, 1991 PCT Pub. No. WO92/02663 PCT Pub. Date Feb. 20, 1992.Stable, electroless, aqueous acidic gold bath, containing the tetracyano-(III) anion, a complexing agent, or a mixture of several complexing agents, and an acid, or a mixture of acids, and the use of these baths for the deposition of gold on metals which are less noble than gold or on alloys of these metals.

Description

Die Erfindung betrifft ein stabiles, stromloses, wässriges, saures Goldbad zur Abscheidung von Gold und dessen Verwendung. Das erfindungsgemäße Bad, enthaltend das Anion Tetracyanogold-(III), einen Komplexbildner oder ein Gemisch mehrerer Komplexbildner, eine Säure oder ein Säuregemisch eignet sich zur stromlosen Abscheidung von Gold auf Metallen, die unedler als Gold sind, sowie auf Legierungen dieser Metalle.The invention relates to a stable, currentless, aqueous, acidic gold bath for the deposition of gold and its use. The bath according to the invention, containing the anion tetracyano gold (III), a complexing agent or a mixture of several complexing agents, an acid or an acid mixture, is suitable for the electroless deposition of gold on metals that are less noble than gold, as well as on alloys of these metals.

Goldbäder zur stromlosesn Abscheidung von Gold sind bereits bekannt, beispielsweise aus den Schriften DE-PS 3640028, US-PS 4,830,668 und GB-PS 20 99 460. Es handelt sich um Goldbäder, die vorwiegend ein Alkalidicyanoaurat -(I) oder Alkalitetracyanoaurat-(III), einen Komplexbildner und ein Reduktionsmittel enthalten. Alle diese Bäder haben in der Regel eine unbefriedigende Stabilität und zersetzen sich unter Abscheidung von metallischem Gold oder Gold-(I)-cyanid.Gold baths for electroless deposition of gold are already known, for example from the documents DE-PS 3640028, US Pat. No. 4,830,668 and GB-PS 20 99 460. These are gold baths which predominantly contain an alkali metal dicyanoaurate - (I) or alkali tetracyanoaurate (III ), contain a complexing agent and a reducing agent. All of these baths generally have an unsatisfactory stability and decompose with the deposition of metallic gold or gold (I) cyanide.

Die vorliegende Erfindung hat die Aufgabe, im sauren Bereich aus dem Tetracyanogold-(III) Gold auf Metallen bzw. deren Legierungen abzuscheiden und gleichzeitig ein stabileres Goldbad bereitzustellen.The object of the present invention is to deposit in the acidic range from the tetracyano gold (III) gold onto metals or their alloys and at the same time to provide a more stable gold bath.

Diese Aufgabe wird durch das Goldbad gemäß den Patentansprüchen gelöst.This object is achieved by the gold bath according to the patent claims.

Es wurde gefunden, daß die Stabilität des Goldbades dadurch erhöht wird, daß Komplexbildner oder Gemische mehrerer Komplexbildner verwendet werden, die pro Molekül verschiedene Gruppen enthalten, die komplexierend und reduzierend wirken. Es handelt sich dabei um solche Verbindungen, die pro Molekül ein oder mehrere Carboxylgruppen und ein oder mehrere Phosphonsäuregruppen enthalten. Insbesondere sind es Verbindungen der allgemeinen Formeln I und II, gemäß den Patentansprüchen 2 und 3.It has been found that the stability of the gold bath is increased by using complexing agents or mixtures of several complexing agents which contain different groups per molecule which have a complexing and reducing effect. These are compounds which contain one or more carboxyl groups and one or more phosphonic acid groups per molecule. In particular, they are compounds of the general formulas I and II, according to patent claims 2 and 3.

Als Komplexbildner in den erfindungegemäßen Bädern haben sich besonders N,N-Bis(carboxymethylen)-1-aminoethan-1,1-diphosphonsäure und 2-Phosphonobutan-1,2,4-tricarbonsäure bewährt.N, N-bis (carboxymethylene) -1-aminoethane-1,1-diphosphonic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid have proven particularly useful as complexing agents in the baths according to the invention.

Ein besonderer Vorteil des erfindungsgemäßen Bades besteht darin, daß Schichten bis 0,5 »m bereits mit Goldgehalten im Bad von 1,0 g/l Gold erhalten werden. Das Bad ermöglicht somit die Vergoldung von Legierungen, wie sie in der Halbleiterindustrie üblich sind, zum Beispiel Eisen-Nickel-Cobalt-Legierungen und chemisch reduktiv abgeschiedene Nickellegierungen wie Nickel-Phosphor, Nickel-Bor und Reinstnickel.A particular advantage of the bath according to the invention is that layers up to 0.5 »m are already obtained with gold contents in the bath of 1.0 g / l gold. The bath thus enables the gold-plating of alloys that are common in the semiconductor industry, for example iron-nickel-cobalt alloys and chemically reductively deposited nickel alloys such as nickel-phosphorus, nickel-boron and pure nickel.

Überraschenderweise wurde außerdem gefunden, daß eine Direktbeschichtung von Wolfram ebenfalls möglich ist, was zu völlig neuen Schichtaufbauten in der Chipcarrier-Industrie führt.Surprisingly, it was also found that direct coating of tungsten is also possible, which leads to completely new layer structures in the chip carrier industry.

Als Komplexbildner dienen erfindungsgemäß Carboxymethylen-aminoalkyl-phosphensäuren und/oder Phosphonalkylcarbonsäuren, die eine wesentliche Erhöhung der Abscheidungsgeschwindigkeit und höhere Schichtdicken ermöglichen, was nicht vorhersehbar war.According to the invention, carboxymethylene-aminoalkyl-phosphenoic acids and / or phosphonalkylcarboxylic acids are used as complexing agents, which allow a substantial increase in the deposition rate and higher layer thicknesses, which was not foreseeable.

Bei den eingesetzten Säuren handelt es sich beispielsweise um Schwefelsäure oder Phosphorsäure oder deren Gemische.The acids used are, for example, sulfuric acid or phosphoric acid or mixtures thereof.

Die Grundzusammensetzung des erfindungsgemäßen Bades ist bespielsweise wie folgt: Gold als Metall 0,05 - 30 Gramm / Liter Komplexbildner 5,0 - 100 Gramm / Liter Säure 10 - 100 ml / Liter The basic composition of the bath according to the invention is, for example, as follows: Gold as metal 0.05 - 30 grams / liter Complexing agent 5.0 - 100 grams / liter acid 10 - 100 ml / liter

Die Arbeitstemperatur des Bades liegt in der Regel bei 70 bis 90o C. Festgestellt wurde, daß auch bei höheren Temperaturen es nicht zu einer Zersetzung des Bades kommt, z.B. zur Ausfällung von elementarem Gold. Ein weiterer Vorteil des Bades ist, daß es sich wiederholt verwenden läßt, und daß das Goldsalz beliebig nachdosiert werden kann.The working temperature of the bath is usually 70 to 90 o C. It has been found that even at higher temperatures there is no decomposition of the bath, for example the precipitation of elemental gold. Another advantage of the bath is that it can be used repeatedly and that the gold salt can be replenished as required.

Das erfindungsgemäße Bad hat bis zu Schichtstärken von 0,5 »m eine konstante Abscheidungsgeschwindigkeit, die abhängig vom Goldgehalt und von der Temperatur ist.The bath according to the invention has a constant deposition rate up to layer thicknesses of 0.5 μm, which is dependent on the gold content and the temperature.

Das erfindungsgemäße Bad läßt sich für Goldschichten von Lötverbindungen, die durch Kristall- oder Drahtbonden entstehen, einsetzen, was technisch von besonderem Wert ist.The bath according to the invention can be used for gold layers of solder connections which are formed by crystal or wire bonding, which is of particular technical value.

Die hohe Abscheidungsgeschwindigkeit ermöglicht auch den Einsatz bei der dekorativen Vergoldung. Eine gleichmäßig gelbe Schicht ist nach Sekunden zu beobachten.The high deposition speed also enables use in decorative gilding. A uniform yellow layer can be observed after seconds.

Aus den nachstehend aufgeführten stabilen Badzusammensetzungen lassen sich unter den aufgeführten Arbeitsbedingungen sehr gleichmäßige und duktile Überzüge abscheiden.The stable bath compositions listed below can be used to deposit very uniform and ductile coatings under the working conditions listed.

Die Erfindung betrifft auch die Verwendung der erfindungsgemäßen Goldbäder zur Abscheidung von Gold auf Metalle, die unedler als Gold sind, oder auf Legierungen dieser Metalle.The invention also relates to the use of the gold baths according to the invention for the deposition of gold on metals which are less noble than gold or on alloys of these metals.

BEISPIEL 1EXAMPLE 1

Kaliumtetracyanoaurat-IIIPotassium tetracyanoaurat-III 1,0 g/l1.0 g / l Komplex 2-Phosphonobutan-1,2,4-tricarbonsäureComplex 2-phosphonobutane-1,2,4-tricarboxylic acid 10 g/l10 g / l Schwefelsäure D 1,84Sulfuric acid D 1.84 20 ml/l20 ml / l pH-WertPH value kleiner 1less than 1 Temperaturtemperature 90o C90 o C AbscheidungsgeschwindigkeitDeposition rate 0,5 »m in 30 min0.5 »m in 30 min

BEISPIEL 2EXAMPLE 2

Kaliumtetracyanoaurat-IIIPotassium tetracyanoaurat-III 6,0 g/l6.0 g / l Komplex 2-Phosphonobutan-1,2,4-tricarbonsäureComplex 2-phosphonobutane-1,2,4-tricarboxylic acid 40,0 ml/l40.0 ml / l Schwefelsäure/Phosphorsäure 1 : 1Sulfuric acid / phosphoric acid 1: 1 50,0 ml/l50.0 ml / l pH-WertPH value kleiner 1less than 1 Temperaturtemperature 60o C60 o C Abscheidungsgeschwindigkeit besonders gute HaftfestigkeitDeposition speed particularly good adhesive strength 0,2 »m/30 min.0.2 »m / 30 min.

Claims (6)

  1. Stable, electroless, aqueous, acidic gold bath, containing the tetracyanogold(III) anion, a complexing agent or a mixture of complexing agents and an acid or a mixture of acids, characterized in that it contains compounds as complexing agents which contain, per molecule of complexing agent, one or more carboxyl groups and one or more phosphonic acid groups.
  2. Stable, electroless, aqueous, acidic gold bath, in accordance with claim 1, characterized in that it contains as complexing agent at least one compound of general formula I:
    Figure imgb0003
     whereby:
    A = H, -CH₃, -(CH₂)n―PO(OH)₂,
    B = H, -(CH₂)n―COOH,
    n = 0 or 1 - 5.
  3. Stable, electroless, aqueous, acidic gold bath, in accordance with claim 1, characterized in that it contains as complexing agent at least one compound of general formula II:
    Figure imgb0004
     whereby:
    B = H, -(CH₂)n-COOH and
    n = 0 or 1 - 5.
  4. Gold bath in accordance with claim 1, containing N,N-bis(carboxymethylene)-1-aminoethane-1,1-diphosphonic acid and/or 2-phosphonobutane-1,2,4-tricarboxylic acid as complexing agents.
  5. Stable, electroless, aqueous, acidic gold bath, in accordance with at least one of the claims 1 - 4, characterized in that the complexing agent or the mixture of complexing agents, as a whole is contained in a concentration of 5,0 - 100 g/l.
  6. Use of the gold bath in accordance with at least one of the claims 1 - 4 for the deposition of gold on metals or metal alloys which are less noble than gold.
EP91913280A 1990-08-02 1991-08-01 Stable, electroless, aqueous, acid gold bath for the deposition of gold and its use Expired - Lifetime EP0542771B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4024764A DE4024764C1 (en) 1990-08-02 1990-08-02
DE4024764 1990-08-02
PCT/DE1991/000624 WO1992002663A1 (en) 1990-08-02 1991-08-01 Stable, stationary aqueous acid gold bath for the deposition of gold and its use

Publications (2)

Publication Number Publication Date
EP0542771A1 EP0542771A1 (en) 1993-05-26
EP0542771B1 true EP0542771B1 (en) 1995-01-25

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US (1) US5322552A (en)
EP (1) EP0542771B1 (en)
JP (1) JPH05509360A (en)
AT (1) ATE117740T1 (en)
DE (2) DE4024764C1 (en)
TW (1) TW241312B (en)
WO (1) WO1992002663A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19745601C2 (en) * 1997-10-08 2001-07-12 Fraunhofer Ges Forschung Solution and method for the electroless deposition of gold layers and use of the solution
DE19745602C1 (en) * 1997-10-08 1999-07-15 Atotech Deutschland Gmbh Method and solution for the production of gold layers
US5935306A (en) * 1998-02-10 1999-08-10 Technic Inc. Electroless gold plating bath
JP4116718B2 (en) * 1998-11-05 2008-07-09 日本リーロナール有限会社 Electroless gold plating method and electroless gold plating solution used therefor
DE102009041264A1 (en) 2009-09-11 2011-03-24 IPHT Jena Institut für Photonische Technologien e.V. Method for producing optically active nano-structures that are utilized for e.g. surface enhanced Raman scattering spectroscopy, involves selecting characteristics by presetting position, size, shape and composition of nano-structures

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4374876A (en) * 1981-06-02 1983-02-22 Occidental Chemical Corporation Process for the immersion deposition of gold
US4474838A (en) * 1982-12-01 1984-10-02 Omi International Corporation Electroless direct deposition of gold on metallized ceramics
DE3614090C1 (en) * 1986-04-25 1987-04-30 Heraeus Gmbh W C Bath for the currentless deposition of gold layers
DE3640028C1 (en) * 1986-11-24 1987-10-01 Heraeus Gmbh W C Acid bath for the electroless deposition of gold layers
DE3707817A1 (en) * 1987-03-09 1988-09-22 Schering Ag STABILIZED ALKALINE GOLD BATH FOR ELECTRIC DEPOSIT OF GOLD
US4919720A (en) * 1988-06-30 1990-04-24 Learonal, Inc. Electroless gold plating solutions

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TW241312B (en) 1995-02-21
JPH05509360A (en) 1993-12-22
US5322552A (en) 1994-06-21
ATE117740T1 (en) 1995-02-15
WO1992002663A1 (en) 1992-02-20
EP0542771A1 (en) 1993-05-26
DE4024764C1 (en) 1991-10-10
DE59104436D1 (en) 1995-03-09

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