WO2015017913A1 - Solution unique pour dépôt électrolytique et autocatalytique de métaux - Google Patents

Solution unique pour dépôt électrolytique et autocatalytique de métaux Download PDF

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Publication number
WO2015017913A1
WO2015017913A1 PCT/CA2014/000472 CA2014000472W WO2015017913A1 WO 2015017913 A1 WO2015017913 A1 WO 2015017913A1 CA 2014000472 W CA2014000472 W CA 2014000472W WO 2015017913 A1 WO2015017913 A1 WO 2015017913A1
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WO
WIPO (PCT)
Prior art keywords
plating
substrate
anode
ions
metal
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PCT/CA2014/000472
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English (en)
Inventor
Mordechay Schlesinger
Robert PETRO
Original Assignee
University Of Windsor
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Publication date
Application filed by University Of Windsor filed Critical University Of Windsor
Priority to CA2919877A priority Critical patent/CA2919877A1/fr
Priority to US14/909,552 priority patent/US20160177455A1/en
Priority to EP14833717.3A priority patent/EP3041975A1/fr
Publication of WO2015017913A1 publication Critical patent/WO2015017913A1/fr

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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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • 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
    • C23C18/1637—Composition of the substrate metallic 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
    • C23C18/16—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
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • 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
    • C23C18/1655—Process features
    • C23C18/1664—Process features with additional means during the plating process
    • C23C18/1671—Electric field
    • 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
    • C23C18/1675—Process conditions
    • C23C18/168—Control of temperature, e.g. temperature of bath, 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
    • C23C18/16—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
    • C23C18/32—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
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • 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
    • C23C18/48—Coating with alloys
    • C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
    • 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
    • C23C18/52—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 using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/02—Heating or cooling
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • 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
    • C23C18/1675—Process conditions
    • C23C18/1676—Heating of the solution
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode

Definitions

  • the present invention provides for a single solution for use in a combined process for electroplating and electroless deposition of metal coatings as part of a hybrid deposition process.
  • Electroless deposition processes have been combined with the deposit of other non- conductive and semi-conductive materials such as TeflonTM, diamond dust and sulfur suspended as a powder in the electroless solutions, and which carried with the metal to the surface being coated to provide unique properties to the coating process.
  • the present invention provides a hybrid deposition process which uses both electroplating and electroless deposition to co-deposit metals, or deposit metal coatings or layers, and most preferably differing metal coatings on layers, on a substrate. More preferably, in one non-limiting embodiment, the process is used to deposit metallic gold layers using a sulfite bath without any breakdown, in place of a cyanide bath. This is environmentally beneficial, and minimizes cost for waste treatment/removal.
  • simple electro-electroless deposition baths are provided for the deposition of different metal layers including, for example, nickel and Ni-Zn-P coatings, and Cu and Ni coatings. More preferably, the electro-electroless deposition baths are used in a multi metal hybrid electro-electroless coating process to selectively coat one metal using an electro-plating process, then turning off the electroplating process and activating the plating of a second different metal which then coats the article using the electroless process.
  • the electro-electroless deposition is provided a hybrid deposition process, whereby multiple layers of thin metal films, or multi-layers, are deposited from a single solution by interspacing electroplated layers of a first metal or alloy, within a constant electroless deposition of a second different metal or alloy.
  • the electro-electroless deposition process may provide a range of possible deposits characterized by two or more streams, multi-layers and, optionally, alloying. Most preferably, the process allows for control over the degree of alloying of electro-deposited layer, and/or even electro-doping of the electroless deposit for alloy creation.
  • multi-layer deposition is performed using a plating bath solution having an electroless plating ion metal source, and either an anion or electroplating metal ion source in solution.
  • the electroplated metal ions are selected not to interfere with, and act purely as 'spectators', to the electroless deposition process.
  • copper/nickel [Cu/Ni] multi-layer metal thin films are deposited from a single solution.
  • Cu is present at a lower concentration and deposited at a lower potential around 0.17V, whilst Ni is typically present at a higher concentration, several thousand times higher, and deposited at the higher potential, around 1.19V.
  • Ni is typically present at a higher concentration, several thousand times higher, and deposited at the higher potential, around 1.19V.
  • Cu is present at 0.17V Cu alone is deposited, while at 1.19V a small amount of Cu is included in the Ni deposit.
  • the higher concentration of the Ni salt is so that during Ni phase of the deposit, minimal Cu is co- deposited. Additionally, the Ni phase is deposited faster, using shorter pulses than the Cu phase.
  • a hybrid deposit technique further has the possibility of being further combined with existing electroplated multi-layers to provide more complex alloys of multiple, or even three or more, components.
  • the process temperatures, for such hybrid deposition process using aqueous deposition baths, are primarily those needed for the electroless deposition bath. In most cases this will be anywhere from room temperature to just below the boiling point, generally around 95-98°C.
  • temperatures below 60°C may be less preferred.
  • the lower temperatures may slow or hinder deposition as the Zn interferes with the deposition (the presence of Zn contaminates and slows the deposit) however, in such cases the maximum temperature would remain the same.
  • the process temperature range may tend to become narrower in the case of electroless deposition.
  • the deposition temperature is based on the stability of the electroless process.
  • the present resides in a process for the deposition of multiple layers of thin metal films on a substrate comprising: preparing a plating bath comprising an electroless plating metal component and electroplating metal component; and immersing the substrate in a plating bath to effect electroless plating of the electroless plating metal component; and with said substrate remaining immersed in said bath, selectively apply a selected voltage over a predetermined interval or series of intervals to effect electroplating of the electroplating metal component thereon.
  • the present invention also resides in various further non-limiting aspects, and which include: 1. A process for deposition of a multi-layer metal coating on a metal substrate to be plated, the process comprising, at least partially immersing said substrate into a plating bath, the plating bath comprising a reducing agent, and a source of metal plating ions, the plating ions comprising one or more from the grouping consisting of copper ions, gold ions, nickel ions, zinc ions, silver ions, boron ions, cobalt ions and phosphorous ions, providing a sacrificial metal anode and cathode in said plating bath, and electrically connecting said anode and cathode, selectively supplying power to said anode, wherein said power is supplied in a pulsed time-wise manner to alternately effect anode oxidation and the formation of an electro- deposition plating layer of metal ions from the anode on the substrate, and the formation of an electroless deposition plating layer of the plating
  • a process for alternatively depositing metal coatings on a substrate comprising, immersing a portion of the substrates to be plated in a plating bath, the plating bath including a least one source of plating ions selected from the group consisting of sodium tetrachloroaurate, nickel sulfate heptahydrate, zinc sulfate heptahydrate, boric acid, cobalt chloride heptahydrate, nickel chloride hexahydrate, providing a metal anode and a cathode in said plating bath, said anode being in electrical communication with said cathode, selectively supplying power to said anode in a pulsed time-wise manner to form on the portion of the substrate to be plated, alternating electro-deposited metal layers and electroless deposited metal layers.
  • the plating bath including a least one source of plating ions selected from the group consisting of sodium tetrachloroaurate, nickel sulfate heptahydrate, zinc sulfate
  • a process for the deposition of multiple layers of thin metal films on a substrate comprising: preparing a plating bath comprising an electroless plating metal component and electroplating metal component; and immersing the substrate in a plating bath to effect electroless plating of the electroless plating metal component; and with said substrate remaining immersed in said bath, selectively apply a selected voltage over a predetermined interval or series of intervals to effect electroplating of the electroplating metal component thereon.
  • An aspect according to any of the foregoing 1 to 3 further comprising maintaining the plating bath at a temperature of upto 120°C, preferably between about 40°C to less than about 99°C, and more preferably from about 95°C to about 98°C.
  • plating ions are gold ions
  • said anode comprises a metal selected from the group consisting of nickel, and cobalt.
  • said substrate comprises magnesium or a magnesium alloy
  • said anode comprises zinc
  • said plating ions comprise nickel, zinc and phosphorous ions in relative amounts selected to form an electroless Ni-Zn-P plating layer.
  • the plating bath solution is a two part solution comprising, a first part comprising: 1 to 4 grams, and preferably about 2 grams per litre sodium tetrachloroaurate as an electroless plating metal component; 5 to 15 grams, and preferably about 10 grams per litre boric acid; and upto 2 grams and preferably about 1 gram per litre sodium hydroxide; and a second part comprising: 7 to 12 grams, and preferably about 9.5 grams per litre sodium thiosulfate; 2 to 5 grams, and preferably about 3.75 grams per liter sodium sulfite; and 7.5 to 15 grams, and preferably about 10 grams per liter of boric acid.
  • plating bath further comprises a dopant solution comprising: upto 70 grams and preferably 25 to 50 grams per litre cobalt chloride heptahydrate; and upto 75 grams, and preferably 25 to 50 grams per litre nickel chloride hexahydrate.
  • Figures 1, 2a, and 2b show macroscopic photographs showing plating samples formed by the electroless gold-electroplated nickel deposition process, illustrating the alternate deposition of gold and nickel layers on test substrates;
  • Figure 3 shows a macroscopic photograph showing the further formation of sulfur/oxide complexes on the plating samples in accordance with Figures 2a and 2b;
  • Figures 4a and 4b show photographs illustrating the anode used in electrodeposition of the coatings of Figure 1 ;
  • Figures 5a to 5b illustrate photographs of a plating sample and EDS analysis after electroless Ni-Zn-P and electro-Zn deposition on a substrate according to the invention thereon;
  • Figures 6a and 6b show macroscopic photographs of an electroless gold and electroplated cobalt/nickel deposition on sample nickel substrate;
  • Figures 7a, 7b and 7c illustrate microscopic (SEM) image and electron diffraction x- ray spectroscopy (EDS) results showing the electroless gold deposition on the nickel substrate of Figure 5 and the co-deposition of nickel/cobalt at the plating boundary regions;
  • SEM microscopic
  • EDS electron diffraction x- ray spectroscopy
  • Figure 8 shows a macroscopic scanned image of a gold/nickel deposited nickel substrate sample illustrating the electroless gold and electroplated-Ni deposition of a four layer test strip in accordance with the present invention
  • FIGS 9a, 9b and 9c illustrate SEM microscopic image and electron diffraction x-ray spectroscopy (EDS) results showing the electroless gold deposition on the nickel substrate of Figure 8 and the co-deposition of nickel at the plating boundary regions;
  • EDS electron diffraction x-ray spectroscopy
  • FIGS 10a, 10b and 10c shows SEM microscopic image and electron diffraction x- ray spectroscopy (EDS) results showing the electroless gold deposition on a copper substrate and the co-deposition of electroplated nickel thereon; and
  • EDS electron diffraction x- ray spectroscopy
  • Figure 11 shows a macroscopic scan illustrating a copper substrate showing an electroless gold deposited layer thereon as a gold/nickel electroless-electro deposition.
  • An electro-electroless deposition is provided as a hybrid deposition process, whereby multiple layers of metal films are deposited from a single plating solution having both electroless and electroplating components.
  • An article to be plated is immersed in the solution.
  • Electric current is then selectively applied at fixed or variable voltages. The current is supplied for predetermined times, and at selected intervals depending on the desired electroplated layer thickness.
  • the application of the current effects electroplating to thereby form interspaced electroplated layers of a first metal or alloy, and electroless deposited layers and/or alternatively with the constant electroless deposition of a second different metal and alloy.
  • the electro-electroless deposition process provides a range of possible deposits characterized by two or more streams, multi-layers and, optionally, alloying.
  • the process allows for control over the degree of alloying of electro- deposited layer, and/or even electro-doping of the electroless deposit for alloy creation.
  • the solution chemistry and/or plating temperature may be tailored, whereby the initiation of electroplating by the application of current effects the electrodeposition of the electroplating component to the substantially relative exclusion of the electroless bath component, and whereby the bath chemistry allows for electroplating to effectively be turned on or off.
  • co-depositing Co with Au coating layers may provide increased strength to electronic components by mixing face centered cubic (fee) and hexagonal close packed (hep) crystal structures of Au and Co, respectively.
  • multilayers which are traditionally harder than either constituent metal, may be used to achieve a comparatively hardened gold deposit or layer on a suitable substrate.
  • the electroless/electro hybrid deposits may be used to provide corrosion resistance to Mg alloys or substrates.
  • the electroless/electro hybrid deposits may be used to provide corrosion resistance to Mg alloys or substrates.
  • Figure 1 shows an example test strip showing an electro-electroless deposition coating which is formed as a multiple layer structure of alternating gold and nickel films.
  • the alternating metal layers illustrated in Figure 1 were formed using a plating solution providing a suitable deposit source of gold ions for electroless deposition, such as sodium tetrachloroaurate.
  • a suitable deposit source of gold ions for electroless deposition such as sodium tetrachloroaurate.
  • the metal, gold and nickel layer were alternately deposited as sample strips, and are first shown in Figures 2a and 2b.
  • the alternating layering shown in Figures 1 , 2a and 2b was achieved by raising the sample substrate in the plating bath a short distance after each stage, in an effort to show the alternating layers provided by the process and deposition bath. Shedding in the first two layers is due to rising of the sample to see each layer. The exposure of the gasses of the bath and heat of the sample coupled with the smoothness of the polishing and stresses in the deposit are believed the cause of the shedding. The last two layers of the test strips have no shedding, as the exposure to the environment was minimal. The thick gold layers were deposited over 45 minutes each, while the electroplated nickel was deposited over 5 minutes using pulse plating. A cross-sectional view is difficult as the gold is soft and care must be taken to ensure minimal delamination.
  • Zn (or Ni) layers were electrodeposited formation with electroless formed layers Ni-Zn-P on Mg/Mg Alloy
  • HEED hybrid electro-electroless deposit
  • the application of the present hybrid electro-electroless deposit (HEED) coating process allows for improvement of corrosion protecting properties of Ni-Zn-P coating on Mg or Mg alloys.
  • the application of an electroplating step to deposit Zn or (Ni) after initial coating formation allows for the deposition of Ni or Zn rich layers on top of the electroless deposited Ni-Zn-P layers.
  • Initial electroless deposition of Ni-Zn-P is performed to provide a continuous coating over the substrate surface, accessing recessed areas.
  • the coating of recessed areas which is difficult using standard electroplating techniques, prevents the formation of a galvanic cell between uncoated and coated regions of the coated part.
  • Secondary or pulsed electroplating then may provide for a reinforcement or outer cladding layers of Ni or Zn.
  • the electroplated reinforcing layers thus allow for greater corrosion protection, and in the case of multi-layers, greater wear protection of the Mg/Mg alloy substrate.
  • Ni-Zn-P coatings and multi-layers produced therein With the formation of electroless Ni-Zn-P coatings and multi-layers produced therein, Zn enrichment of the coatings provides a more anodic layer, relative to the remainder of the coating.
  • the arrangement of such layers produces a sacrificial multi-layer structure which protects the coating from corrosion by forming corrosion to propagate along the coating surface, rather than through the coating to the substrate.
  • the formation of sacrificial multilayer coatings has previously been suggested for Ni/Zn layers, with layers deposited from separate electrolytes. Using the current process, electroplating in place of a two bath system produces some alloying of the Zn layer, as would be expected when depositing the less noble metal of a binary multi-layer electrolyte.
  • Ni-Zn-P and Zn are likely to provide increased corrosion protection at a level robust enough so that the coating not only resists galvanic corrosion but also overall, normal corrosion.
  • This scheme can be adjusted to provide a low Zn Ni-Zn-P layer, -2-5% Zn, followed by an electroplated-Zn layer essentially making Ni-P/Zn multilayer coatings.
  • Zn is more anodic than Ni and would act as a sacrificial layer, provided the coating is not severely damaged, to the point of exposing the Mg substrate.
  • test Sample - Electroless Au-Electroplated Co-Ni Deposition In a further example, electroless gold-electro-cobalt nickel hybrid deposition was achieved using a two-component plating bath, in combination with a dopant solution as follows:
  • pH of Bath A should be adjusted to around 7
  • Bath A was added to B slowly at room temperature, mixed, then let stand for 24 hours. After 24 hours, the additives and dopant metal were added to the solution, with the creation of a dopant solution as follows.
  • the pH of the deposition was adjusted with NaOH to be above 8.
  • the pH of the 60mL deposition bath was adjusted with 0.25g of NaOH and 0.8mL of NH 4 OH to a final pH of 10.23.
  • Both electrodeposition and electroless deposition were performed at 60°C. Nickel electrodes measuring 25mmx90mmx3mm were used as both the anode and cathode.
  • the electroless gold deposition from the borohydride system may be achieved on a number of noble metals such as Pd, Rh, Ag, and Au itself; as well as on substrates comprising active metals such as Cu, Ni, Co, Fe, and their alloys.
  • noble metals such as Pd, Rh, Ag, and Au itself
  • substrates comprising active metals such as Cu, Ni, Co, Fe, and their alloys.
  • active metals such as Cu, Ni, Co, Fe, and their alloys.
  • the initial reactions on these two classes of metals are understood as different. On noble metals the reaction is catalytic from the very beginning, whereas the gold deposition on the active metals is initiated by galvanic displacement, which results in accumulation of ions of those metals in the bath.
  • Electron Diffraction X-ray Spectroscopy provides a means of analysis that penetrates the coating; hence the Au signal remains visible in the electroplated Ni-Co region. Beam spread is believed the reason for Cobalt appearing in the upper, electroless Au region.
  • Figure 8 shows a scan of nickel substrate illustrating electroless deposition of gold and electrodeposition of Ni as deposits thereon. In the illustrated figure, shedding is due to prolonged deposition on a smooth surface and resulting stress of the deposit. Again, in exemplary testing, four layers were successfully deposited from a single deposition bath.
  • Figures 10a, 10b and 10c illustrate scans showing the electroless deposition gold and electro-Ni deposition on a copper substrate.
  • the present invention provides for a variety of non- limiting possible applications in coating and plating processes.
  • the hybrid deposition process of the present application may prove highly suitable for use in the coating medical implants with biomerit materials.
  • gold and tin may be recognized as metals which are suitable for deposition and which are bio-compatible.
  • other possible alloys which may be suitable for possible deposition could include, without restriction, titanium as well as cobalt and chromium, depending on the implant composition.
  • the hybrid deposition process of the present invention could be used to effect the application of conducting coatings on plastics as either a final layer or an intermediate layer for subsequent metal plating.
  • the coatings of the present application may be effected in a single deposition bath.
  • certain "additives" may be used to increase deposition rates, and which in accordance with preferred aspects would include nickel/gold deposition systems, as well as Ni-Zn-P deposition systems.
  • a further application of the present system may include, without restriction, the manufacture of magnets; and most preferably magnets using electroless Ni-Fe-P deposition which may contain upto 25% Fe.
  • the hybrid deposition process of the present invention may be used in the manufacture of high-wear conductive contact points, as for example, are used in electronics and electronic systems.
  • the applicant has appreciated that early experimental results have shown the successful formation of multi-layer nickel- gold deposits. It is further envisions that the deposition of alloys could equally be achieved by slowing the electroplating rate. Further, as the gold bath in questions is initiated by tandem electroless deposit and simple displacement reaction, nickel may be electroplated to achieve an Au/Ni hardened alloy.
  • the hybrid deposition process of the present invention further may advantageously provide enhanced adhesive surfaces for metal adhesive bonding or welding in combination or tandem with the deposition of different metals.

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Abstract

Cette invention concerne un procédé hybride de dépôt électrolytique et autocatalytique, consistant à déposer une pluralité de couches de film métallique provenant d'une seule solution de placage qui comprend à la fois des composants de dépôt électrolytique et des composants de dépôt autocatalytique. L'article à plaquer est immergé dans la solution et un courant électrique est sélectivement appliqué à des tensions déterminées pendant des laps de temps prédéterminés et à des intervalles sélectionnés, de sorte à réaliser un dépôt électrolytique conjointement avec un dépôt autocatalytique. Des couches de métal déposées par dépôt électrolytique sont intercalées parmi des couches de métal déposées par dépôt autocatalytique.
PCT/CA2014/000472 2013-08-09 2014-06-02 Solution unique pour dépôt électrolytique et autocatalytique de métaux WO2015017913A1 (fr)

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US14/909,552 US20160177455A1 (en) 2013-08-09 2014-06-02 Single Solution for Electro-Electroless Deposition of Metals
EP14833717.3A EP3041975A1 (fr) 2013-08-09 2014-06-02 Solution unique pour dépôt électrolytique et autocatalytique de métaux

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