WO2004111299A2 - Solution and method for ultra thin, non-porous and highly adhesive gold coating - Google Patents

Solution and method for ultra thin, non-porous and highly adhesive gold coating Download PDF

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Publication number
WO2004111299A2
WO2004111299A2 PCT/IL2004/000513 IL2004000513W WO2004111299A2 WO 2004111299 A2 WO2004111299 A2 WO 2004111299A2 IL 2004000513 W IL2004000513 W IL 2004000513W WO 2004111299 A2 WO2004111299 A2 WO 2004111299A2
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WO
WIPO (PCT)
Prior art keywords
gold
coating
group
copper
substrate
Prior art date
Application number
PCT/IL2004/000513
Other languages
French (fr)
Other versions
WO2004111299A3 (en
Inventor
Felix Levin
Alexander Tarnopolsky
Gregory Kleiner
Iliya Baskin
Olga Greenshtein
Igor Shekhtman
Roman Gurfinkel
Original Assignee
Unifine Works, Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from IL15644203A external-priority patent/IL156442A0/en
Priority claimed from IL16244204A external-priority patent/IL162442A0/en
Application filed by Unifine Works, Ltd. filed Critical Unifine Works, Ltd.
Publication of WO2004111299A2 publication Critical patent/WO2004111299A2/en
Publication of WO2004111299A3 publication Critical patent/WO2004111299A3/en

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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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • 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
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/24—Reinforcing the conductive pattern
    • H05K3/244—Finish plating of conductors, especially of copper conductors, e.g. for pads or lands

Definitions

  • the present invention relates to new method for gold coating on metal surfaces. More particularly the present invention relates to a new composition for immersion coating of gold onto a metallic substrate, methods utilizing the same and products produced thereby.
  • the unique method of the present invention involves exposure of the metallic substrates to a solution that contains a soluble gold salt, a complexant and a special reducing agent.
  • a highly adhesive, non -porous gold coating with various thicknesses can be prepared by this new approach.
  • This new coating method can also be used for discrete coating of various metallic substrates having large surface areas such as ultra fine (nano- and micron scale) powders and thin wires.
  • the resulted coated powders and wires can be used as heterogeneous catalysts for CO oxidation and other chemical reactions. Description of the related art
  • Immersion gold deposition gives coatings of required quality.
  • gold adheres to the metal surface through electromotive potentials generated internally by chemical interaction and not by an external force generated by an electric current.
  • the coating of gold is as uniform as the surface.
  • the process continues as long as part of the metal surface remains uncovered, since metal cations are essentially liberated from this surface to the solution.
  • This method provides maximum coating density i.e. the coating is non-porous at the minimum coating thickness, and therefore gives a coating with the physical properties required for decorative purposes.
  • Typical thickness of immersion coatings is 0.05-1 ⁇ m.
  • composition for gold coating comprising: a) a water soluble gold salt; b) a complexation agent; and c) a tri-substituted reducing agent of the formula NX 3 wherein all of the x's are the same and are reducing moieties.
  • said moiety x is selected from the group consisting of CH 2 PO 3 H 2 , CSNH 2 and CH 2 CH 2 S 2 O 2 Na.
  • said gold is deposed on a substrate material selected from the group consisting of copper, nickel, silver, an alloy of copper-tin, an alloy of copper-zinc, an alloy of copper-nickel and stainless steel.
  • said gold is deposed on a substrate having a form selected from the group consisting of a plate, an ultra-thin wire, micro-particles and nano-particles.
  • said complexation agent is a compound of the formula 1
  • each of R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, aminoalkyl, and alkylcarboxylic acid.
  • a method for providing a non-porous gold coating having a thickness of about 0.03-1 O ⁇ m on a metallic substrate comprising immersing said substrate in an immersion solution at a temperature of between about 50-90 0 C in the presence of an immersion solution comprising a water soluble gold salt; a complexation agent; and a tri-substituted reducing agent of the formula NX 3 wherein all of the x's are the same and are reducing moieties for a period of between about 10 and 300 minutes.
  • the invention also provides a product whenever produced utilizing the coating method defined above wherein said product is selected from the group consisting of electronic board circuits and devices, jewelry, religious items, adorning items, decorative items, heterogeneous catalysts, sensor devices, and pharmaceutical and cosmetic formulations.
  • the present invention provides for the preparation of a heterogeneous catalyst produced by discrete coating of ultra fine powders and thin wires.
  • This catalyst is capable of oxidizing CO to CO 2 and may be used in other industrially important chemical processes.
  • Most economic methods for catalyst synthesis require co-precipitation of gold hydroxide with metal oxides followed by a calcination step to produce neutral gold particles deposited on a carrier.
  • the catalyst presented herein comprises gold particles produced directly in one step. Thus this catalyst is superior to prior art catalysts both with regard to cost and ease of preparation.
  • the present invention relates to a gold coating method that in effect performs both immersion and electroless plating directly in one bath.
  • Immersion benefits high surface coverage and electroless plating allows a large range of coating thicknesses to be achieved.
  • the combination of those techniques becomes possible due to the use of novel reducing agents together with complexing agents such as ethylene diamine derivatives.
  • a substrate material is placed into a coating bath preheated to 50-90 0 C for 10- 300 min as required for desirable coating thickness, then washed in water and dried.
  • a nickel substrate is inserted in hot (about 7O 0 C) solution that containing 3 g/l of EDTA, 1.25 g/l KAu(CN) 2 and 2 g/l of nitrilo tris(methylene) triphosphoric acid. The duration of the process is 15 minutes. There is produced a nickel substrate having a gold coating wherein the thickness of coating is 0.1 ⁇ m.
  • EXAMPLE 3 A silver substrate is inserted in hot (about 85-90 ⁇ C) solution that containing 3 g/l of EDTA, 5 g/l KAu(CN) 2 and 10 g/l of nitrilo tris(methylene) triphosphoric acid. The duration of the process is 120 minutes. There is produced a silver substrate having a gold coating wherein the thickness of coating is 2 ⁇ m.

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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)
  • Electrochemistry (AREA)
  • Paints Or Removers (AREA)
  • Chemically Coating (AREA)

Abstract

The invention provides a composition for gold coating comprising a water-soluble gold salt; a complexation agent; and a tri-substituted reducing agent of the formula NX3 wherein all of the x’s are the same and are reducing moieties.

Description

SOLUTION AND METHOD FOR ULTRA THIN5 NON-POROUS AND HIGHLY ADHESIVE GOLD COATING
The present invention relates to new method for gold coating on metal surfaces. More particularly the present invention relates to a new composition for immersion coating of gold onto a metallic substrate, methods utilizing the same and products produced thereby.
Existing methods allow coating to be made either by immersion technique or by electroless coating. In contradistinction the present invention combines both techniques in situ.
As will be described hereinafter, the unique method of the present invention involves exposure of the metallic substrates to a solution that contains a soluble gold salt, a complexant and a special reducing agent. A highly adhesive, non -porous gold coating with various thicknesses can be prepared by this new approach. This new coating method can also be used for discrete coating of various metallic substrates having large surface areas such as ultra fine (nano- and micron scale) powders and thin wires. The resulted coated powders and wires can be used as heterogeneous catalysts for CO oxidation and other chemical reactions. Description of the related art
Development of economical alternative to gold electroplating originally served two major industries, i.e. the electrical (electronic) industry and the decorative (jewelry) industry.
For decorative purposes high adhesion, hardness and uniform appearance is critical. For this industry the goal was to obtain the thinnest possible coating which never-the-less fulfilled those requirements in order to minimize cost. Immersion gold deposition gives coatings of required quality. During the immersion process gold adheres to the metal surface through electromotive potentials generated internally by chemical interaction and not by an external force generated by an electric current. The coating of gold is as uniform as the surface. The process continues as long as part of the metal surface remains uncovered, since metal cations are essentially liberated from this surface to the solution. When virtually all of the metal surface is coated, immersion terminates. This method provides maximum coating density i.e. the coating is non-porous at the minimum coating thickness, and therefore gives a coating with the physical properties required for decorative purposes. Typical thickness of immersion coatings is 0.05-1 μm.
In the electrical industry thick, i.e. a coating of about 2-15 μm, is required since the coated surface should have high electric and thermal conductivity. Known immersion procedures cannot provide a coating that thick, since immersion is a self- terminating process. Therefore electroless plating is a method of choice in this case. In this technique initially precipitated gold nuclei catalize reduction of cationic gold by a soluble reductant, i.e. the coating grows on the gold primer. Therefore electroless plating is an autocatalytic process which will continue once it has started and as long as the plating bath contains the proper components such as, metal ions, reducing agents, etc.. In theory, there is no limit to the thickness of metal that can be deposited by this process. However physical properties of the obtained plating are compromised compared to those of the immersion coating, i.e. pure adhesion and high porosivity
Recent development of electronic devices and competition in this field have created a need for coatings with better physical properties and good appearance. Existing solutions for this challenge comprise two stage processes, for example electroless nickel/ immersion gold. As will realized in light of the above state of the art, a one step, in situ, method would be superior to those solutions in terms of cost effectiveness and ease of implementation.
With this state of the art in mind there is now provided according to the present invention a composition for gold coating comprising: a) a water soluble gold salt; b) a complexation agent; and c) a tri-substituted reducing agent of the formula NX3 wherein all of the x's are the same and are reducing moieties.
In preferred embodiment of the present invention said moiety x is selected from the group consisting of CH2PO3H2, CSNH2 and CH2CH2S2O2Na. Preferably said gold is deposed on a substrate material selected from the group consisting of copper, nickel, silver, an alloy of copper-tin, an alloy of copper-zinc, an alloy of copper-nickel and stainless steel.
Preferable said gold is deposed on a substrate having a form selected from the group consisting of a plate, an ultra-thin wire, micro-particles and nano-particles.
In preferred embodiment of the present invention said complexation agent is a compound of the formula 1
Figure imgf000004_0001
wherein each of R1, R2, R3 and R4 are each independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, aminoalkyl, and alkylcarboxylic acid.
In another aspect of the present invention there is provided a method for providing a non-porous gold coating having a thickness of about 0.03-1 Oμm on a metallic substrate comprising immersing said substrate in an immersion solution at a temperature of between about 50-900C in the presence of an immersion solution comprising a water soluble gold salt; a complexation agent; and a tri-substituted reducing agent of the formula NX3 wherein all of the x's are the same and are reducing moieties for a period of between about 10 and 300 minutes.
The invention also provides a product whenever produced utilizing the coating method defined above wherein said product is selected from the group consisting of electronic board circuits and devices, jewelry, religious items, adorning items, decorative items, heterogeneous catalysts, sensor devices, and pharmaceutical and cosmetic formulations.
Thus as will be realized major application of the invention is in the coating of parts used in manufacturing of electronic devices. Additional applications are preparation of heterogeneous catalysts, gas sensory devices and components for cosmetic and pharmaceutical products. In addition the present invention provides for the preparation of a heterogeneous catalyst produced by discrete coating of ultra fine powders and thin wires. This catalyst is capable of oxidizing CO to CO2 and may be used in other industrially important chemical processes. Most economic methods for catalyst synthesis require co-precipitation of gold hydroxide with metal oxides followed by a calcination step to produce neutral gold particles deposited on a carrier. The catalyst presented herein comprises gold particles produced directly in one step. Thus this catalyst is superior to prior art catalysts both with regard to cost and ease of preparation.
As is known change in surface potential occurs when a substrate adsorbs to the surface of a heterogeneous catalyst. Preparation of a discrete gold coating on ultra thin, metal wire enables monitoring of this potential change, and this is a principle for development of gas sensory devices.
Several cosmetic and pharmaceutical applications of noble metals have been explored recently. Silver is added to skin care products and it is claimed that such formulations inhibit contamination and aging of the skin due to the antiseptic properties of silver. Gold is superior to silver in terms of antiseptic properties and therefore applicable in the above mentioned formulations. However final gold containing products will be significantly more expensive than silver analogues. This problem can be overcome by ultra thin gold coating of metal powders and use of those powders in ointments and other pharmaceutical formulations.
Thus the present invention relates to a gold coating method that in effect performs both immersion and electroless plating directly in one bath. Immersion benefits high surface coverage and electroless plating allows a large range of coating thicknesses to be achieved. The combination of those techniques becomes possible due to the use of novel reducing agents together with complexing agents such as ethylene diamine derivatives.
While the invention will now be described in connection with certain preferred embodiments in the following examples so that aspects thereof may be more fully understood and appreciated, it is not intended to limit the invention to these particular embodiments. On the contrary, it is intended to cover all alternatives, modifications and equivalents as may be included within the scope of the invention as defined by the appended claims. Thus, the following examples, which include preferred embodiments will serve to illustrate the practice of this invention, it being understood that the particulars shown are by way of example and for purposes of illustrative discussion of preferred embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of formulation procedures as well as of the principles and conceptual aspects of the invention. EXAMPLE 1 Preparation of coating solution:
Ingredients listed in Table 2 are dissolved in 900ml of distilled water, and then water is added to bring the final volume of the homogeneous solution to 1000ml.
Table 2 Ingredients and their amounts
Figure imgf000006_0001
Deposition procedure:
A substrate material is placed into a coating bath preheated to 50-900C for 10- 300 min as required for desirable coating thickness, then washed in water and dried. EXAMPLE 2
A nickel substrate is inserted in hot (about 7O0C) solution that containing 3 g/l of EDTA, 1.25 g/l KAu(CN)2 and 2 g/l of nitrilo tris(methylene) triphosphoric acid. The duration of the process is 15 minutes. There is produced a nickel substrate having a gold coating wherein the thickness of coating is 0.1 μm. EXAMPLE 3 A silver substrate is inserted in hot (about 85-90 α C) solution that containing 3 g/l of EDTA, 5 g/l KAu(CN)2 and 10 g/l of nitrilo tris(methylene) triphosphoric acid. The duration of the process is 120 minutes. There is produced a silver substrate having a gold coating wherein the thickness of coating is 2μm. EXAMPLE 4
The procedure of examples 1 and 2 is repeated to produce ultrathin coatings on different metals as set forth in table 3 hereinafter. Table 3 Substrate material, time of immersion and resulting thickness
Figure imgf000007_0001
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative examples and that the present invention may be embodied in other specific forms without departing from the essential attributes thereof, and it is therefore desired that the present embodiments and examples be considered in all respects as illustrative and not restrictive, reference being made to the appended claims, rather than to the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims

WHAT IS CLAIMED IS:
1. A composition for gold coating comprising: a) a water soluble gold salt; b) a complexation agent; and c) a tri-substituted reducing agent of the formula NX3 wherein all of the x's are the same and are reducing moieties.
2. A composition according to claim 1 wherein the moiety x is selected from the group consisting of CH2PO3H2, CSNH2 and CH2CH2S2O2Na.
3. A composition according to claim 1 wherein the gold is deposed on a substrate material selected from the group consisting of copper, nickel, silver, an alloy of copper-tin, an alloy of copper-zinc, an alloy of copper-nickel and stainless steel.
4. A composition according to claim 1 wherein the gold is deposed on a substrate having a form selected from the group consisting of a plate, an ultra-thin wire, micro-particles and nano-particles.
5 A composition according to claim 1 wherein said complexation agent is a compound of the formula 1
Figure imgf000008_0001
wherein each of R1, R2, R3 and R4 are each independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, aminoalkyl, and alkylcarboxylic acid.
6. A method for providing a non-porous gold coating having a thickness of about 0.03-1 Oμm on a metallic substrate comprising immersing said substrate in an immersion solution at a temperature of between about 50-900C in the presence of an immersion solution comprising a water soluble gold salt; a complexation agent; and a tri-substituted reducing agent of the formula NX3 wherein all of the x's are the same and are reducing moieties for a period of between about 10 and 300 minutes.
7. A product whenever produced utilizing the coating method of claim 6 wherein said product is selected from the group consisting of electronic board circuits and devices, jewelry, religious items, adorning items, decorative items, heterogeneous catalysts, sensor devices, and pharmaceutical and cosmetic formulations.
PCT/IL2004/000513 2003-06-15 2004-06-14 Solution and method for ultra thin, non-porous and highly adhesive gold coating WO2004111299A2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
IL15644203A IL156442A0 (en) 2003-06-15 2003-06-15 Novel solution and method for ultra thin, non-porous and highly adhesive gold coating
IL156,442 2003-06-15
IL16244204A IL162442A0 (en) 2004-06-10 2004-06-10 Solution and method for ultra thin, non-porous andhighly adhesive goldcoating
IL162,442 2004-06-10

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WO2004111299A2 true WO2004111299A2 (en) 2004-12-23
WO2004111299A3 WO2004111299A3 (en) 2005-02-10

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0618307A1 (en) * 1993-03-26 1994-10-05 C. Uyemura & Co, Ltd Electroless gold plating bath
US6287371B1 (en) * 1998-11-05 2001-09-11 Learonal Japan Inc. Non-electrolytic gold plating liquid and non-electrolytic gold plating method using same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0618307A1 (en) * 1993-03-26 1994-10-05 C. Uyemura & Co, Ltd Electroless gold plating bath
US6287371B1 (en) * 1998-11-05 2001-09-11 Learonal Japan Inc. Non-electrolytic gold plating liquid and non-electrolytic gold plating method using same

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