EP0542771B1 - Bain d'or acide, aqueux, stable, sans courant pour le depot d'or et son utilisation - Google Patents

Bain d'or acide, aqueux, stable, sans courant pour le depot d'or et son utilisation 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
Authority
EP
European Patent Office
Prior art keywords
gold
bath
stable
electroless
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91913280A
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German (de)
English (en)
Other versions
EP0542771A1 (fr
Inventor
Manfred Dettke
Robert Ruether
Klaus Janotta
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Atotech Deutschland GmbH and Co KG
Original Assignee
Atotech Deutschland GmbH and Co KG
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Filing date
Publication date
Application filed by Atotech Deutschland GmbH and Co KG filed Critical Atotech Deutschland GmbH and Co KG
Publication of EP0542771A1 publication Critical patent/EP0542771A1/fr
Application granted granted Critical
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Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Claims (6)

  1. Bain d'or acide aqueux stable sans courant , contenant l'anion de tétracyanure d'or - (III), un agent complexant ou un mélange de plusieurs agents complexants et un acide ou un mélange d'acides, caractérisé en ce qu'il contient comme agent complexant des composés qui contiennent un ou plusieurs groupes carboxyle et un ou plusieurs groupes d'acide phosphonique par molécule d'agent complexant.
  2. Bain d'or acide aqueux stable sans courant , selon la revendication 1, caractérisé en ce qu'il contient comme agent complexant au moins un composé de la formule générale I,
    Figure imgb0005
     où
    A = H, -CH₃, -(CH₂)n―PO(OH)₂,
    B = H, ―(CH₂)n―COOH,
    n = 0 ou 1 - 5
  3. Bain d'or acide aqueux stable sans courant , selon la revendication 1, caractérisé en ce qu'il contient comme agent complexant au moins un composé de la formule générale II,
    Figure imgb0006
     où
    B = H, ―(CH₂)n―COOH et
    n = 0 ou 1 - 5
  4. Bain d'or selon la revendication 1, contenant de l'acide N, N-Bis (carboxyméthylène) - 1 - aminoéthane - 1, 1 - diphosphonique et/ou de l'acide 2 - phosphonobutane - 1, 2, 4 - tricarbonique comme agents complexants.
  5. Bain d'or acide aqueux stable sans courant , selon les revendications 1 à 4, caractérisé en ce que l'agent complexant ou le mélange des agents complexants sont en somme contenus dans une concentration de 5,0 - 100 g/l.
  6. Utilisation du bain d'or selon l'une au moins des revendications 1 à 4 pour le dépôt d'or sur des métaux ou des alliages métalliques moins nobles que l'or.
EP91913280A 1990-08-02 1991-08-01 Bain d'or acide, aqueux, stable, sans courant pour le depot d'or et son utilisation Expired - Lifetime EP0542771B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4024764A DE4024764C1 (fr) 1990-08-02 1990-08-02
DE4024764 1990-08-02
PCT/DE1991/000624 WO1992002663A1 (fr) 1990-08-02 1991-08-01 Bain d'or acide, aqueux, stable, sans courant pour le depot d'or et son utilisation

Publications (2)

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

Family

ID=6411638

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91913280A Expired - Lifetime EP0542771B1 (fr) 1990-08-02 1991-08-01 Bain d'or acide, aqueux, stable, sans courant pour le depot d'or et son utilisation

Country Status (7)

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

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19745601C2 (de) * 1997-10-08 2001-07-12 Fraunhofer Ges Forschung Lösung und Verfahren zum stromlosen Abscheiden von Goldschichten sowie Verwendung der Lösung
DE19745602C1 (de) * 1997-10-08 1999-07-15 Atotech Deutschland Gmbh Verfahren und Lösung zur Herstellung von Goldschichten
US5935306A (en) * 1998-02-10 1999-08-10 Technic Inc. Electroless gold plating bath
JP4116718B2 (ja) * 1998-11-05 2008-07-09 日本リーロナール有限会社 無電解金めっき方法及びそれに使用する無電解金めっき液
DE102009041264A1 (de) 2009-09-11 2011-03-24 IPHT Jena Institut für Photonische Technologien e.V. Verfahren zur Herstellung von optisch aktiven Nanostrukturen

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 (de) * 1986-11-24 1987-10-01 Heraeus Gmbh W C Saures Bad fuer das stromlose Abscheiden von Goldschichten
DE3707817A1 (de) * 1987-03-09 1988-09-22 Schering Ag Stabilisiertes alkalisches goldbad zur stromlosen abscheidung von gold
US4919720A (en) * 1988-06-30 1990-04-24 Learonal, Inc. Electroless gold plating solutions

Also Published As

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

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