US20130209698A1 - Process for Electroless Deposition of Metals Using Highly Alkaline Plating Bath - Google Patents
Process for Electroless Deposition of Metals Using Highly Alkaline Plating Bath Download PDFInfo
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- US20130209698A1 US20130209698A1 US13/878,916 US201113878916A US2013209698A1 US 20130209698 A1 US20130209698 A1 US 20130209698A1 US 201113878916 A US201113878916 A US 201113878916A US 2013209698 A1 US2013209698 A1 US 2013209698A1
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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
- C23C18/54—Contact plating, i.e. electroless electrochemical plating
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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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1637—Composition of the substrate metallic substrate
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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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
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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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1658—Process features with two steps starting with metal deposition followed by addition of reducing agent
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- C—CHEMISTRY; METALLURGY
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- 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
- C23C18/166—Process features with two steps starting with addition of reducing agent followed by metal deposition
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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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1806—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by mechanical pretreatment, e.g. grinding, sanding
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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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
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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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1855—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by mechanical pretreatment, e.g. grinding, sanding
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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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
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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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
- C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
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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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
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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
- C23C18/38—Coating with copper
Definitions
- the present invention relates to a process for the electroless deposition or plating of metals on substrates, and more particularly a process for coating metals and metal alloys soluble at high pH levels greater than 11.5, and most preferably which are soluble at a pH of between 13.5 and 14.
- magnesium is a very light metal readily available material with good structural and mechanical properties, making it an ideal replacement for other heavier metals.
- a major issue with magnesium plating is that when it is mechanically attached to other metals an electrical conductivity exists between the two metals and the resulting galvanic effect may result in rapid oxidation corrosion of the magnesium.
- conventional electroless deposition solutions are susceptible to produce coatings which are intermittent due to surface oxidization and/or corrosion of the substrate surface disrupting the electroless deposition process.
- conventional electroless plating solution baths suffer disadvantages in that they permit and even facilitate the oxidation and/or corrosion of the reactive metal substrate surfaces, resulting in at most, spotty depositions of the desired coating.
- the present invention contemplates a plating process which uses an electroless plating bath formed from two separate prepared component solutions.
- the component solutions are preferably separately formed, and thereafter mixed shortly before and preferably within about five days prior to plating operations, to provide a highly alkaline plating bath solution which has a pH greater than about 11.5, preferably greater than about 13, and most preferably between about 13.5 to 14.
- One component solution of the two-part plating bath is provided with a metal salt or source of plating ions, and which is initially kept in a separate solution from the second other prepared component solution containing a formaldehyde, and paraformaldehyde, used to reduce the metal salts into the metal to be deposited on a substrate.
- Each component solution further includes sodium hydroxide in concentrations selected so that when the two solutions are mixed in a ratio of about 0.5:1 to 1.5:1, and preferably 0.7:1 to 1:1 the mixture provides an alkaline final plating bath solution having a pH greater than 11.5, preferably greater than 13, and most preferably of between about 13.5 to 14.
- the individual component solutions are prepared as pre-prepared solutions which are physically separated from each other until upto seven days, and preferably upto at least 3.5 days prior to plating operations.
- the applicant has appreciated by a process in which the plating bath solution is prepared by mixing two pre-prepared component solutions, it is possible to extend the shelf life of the individual bath components, increasing their stability, enabling their use in larger scales commercial electroless plating processes.
- the applicant has appreciated that with conventional highly alkaline plating solutions having pH levels in excess of 11.5, the sodium hydroxide in the plating bath may result in precipitation of the plating metal, shortening the bath shelf life.
- both component solutions may be pre-prepared for later mixture to provide a high pH plating bath in either a batch or as part of a continuous commercial plating process.
- magnesium may advantageously be plated with a selected plating metal in a highly alkaline plating bath having a pH of about 13.5 to 14, thereby avoiding any galvanic effect on the magnesium when mechanically attached to other metals.
- a highly alkaline plating bath having a pH of about 13.5 to 14, thereby avoiding any galvanic effect on the magnesium when mechanically attached to other metals.
- the present electroless deposition process contemplates that magnesium could therefore be used in a variety of structures and assemblies where dissimilar materials are mechanically fastened together.
- electroless cladding of plating metals such as copper in a highly alkaline deposition bath established for magnesium, magnesium alloys and other reactive metals is not limited.
- the present process is also suitable for use in plating metals such as copper on silicon substrates.
- the electroless deposition of metals ON silicon does not require a highly alkaline bath to mitigate corrosion. Rather, the higher alkalinity achieves improved electroless copper deposition at pH levels in excess of 11.5, and more preferably at a pH level of around 13.5, in an environment containing an excess of formaldehyde derivative reducing agent, such as paraformaldehyde.
- the high pH electroless coating bath of the present invention advantageously can also be used to apply coating of other metals and alloys to a variety of different substrates.
- Further substrates include, but are not limited to: beryllium, vanadium, and titanium.
- the high pH electroless coating process is useful with a range of plating or coating metals and alloys including but not limited to: silver, copper, nickel/tungsten, nickel, boron and any other metals and alloys that are soluble at higher pH levels greater than 11.5, preferably greater than 13, and most preferably at between 13.5 to 14.
- electroless coating systems using the two-part plating bath of the present invention can also include doped hybrid solutions containing non-metallic particles such as but not limited to, diamond, TeflonTM, ceramics, and/or molybdenum.
- doped hybrid solutions containing non-metallic particles such as but not limited to, diamond, TeflonTM, ceramics, and/or molybdenum.
- the present invention reside in a process for electroless plating a plating metal on a substrate comprising: preparing a first bath solution comprising: 10 to 50 g/L sodium hydroxide, 40 to 120 g/l potassium sodium tartrate, and a metal salt, preparing a second bath solution physically separates from the first bath solution comprising: 40 to 75 g/L paraformaldehyde, and 30 to 50 g/L sodium hydroxide, mixing the first and second bath solutions to form a mixed plating bath solution having a pH greater than 11.5, and immersing a substrate to be plated in the mixed solution, wherein the metal salt comprises a plating metal selected from the group consisting of Cu, Al, Ni, Au, Ag and their alloys.
- the present invention resides in a process for electroless plating nickel or a nickel alloy plating metal on a magnesium metal substrate comprising: preparing a first bath solution comprising: 25 to 60 g/L nickel chloride hexahydrate, preparing a second bath solution physically separate from the first solution comprising: 40 to 75 ml/L ethylenediamine, 30 to 50 g/L sodium hydroxide, and 3 to 8 g/L sodium borohydride, mixing the first and second bath solutions to form a mixed plating bath solution having a pH of at least 12, and immersing a substrate in the mixed solution
- the present invention resides in a process for electroless plating a plating copper on a substrate comprising: preparing a first bath solution comprising: 15 to 25 g/L sodium hydroxide, 60 to 100 g/L potassium sodium tartrate, and 35 to 40 g/L CuSO 4 .5H 2 O, preparing a second bath solution component physically separated from the first bath solution component comprising: 50 to 65 g/L paraformaldehyde, and 20 to 45 g/L sodium hydroxide, mixing the first and second bath solutions in a ratio selected at between about 0.5:1 to 1.5:1 to form a mixed plating bath solution having a pH greater than about 13, and with said bath having an operating temperature between about 17° C. and 32° C., immersing a substrate to be plated in the mixed solution.
- the present invention resides in a process for electroless copper plating on a substrate comprising: preparing a first bath component solution comprising: 10 to 30 g/L sodium hydroxide, 40 to 120 g/l potassium sodium tartrate, and 20 to 45 g/L copper sulfate pentahydrate, preparing a second bath component solution physically separates from the first bath solution comprising: 40 to 75 g/L paraformaldehyde, and 20 to 50 g/L sodium hydroxide, mixing the first and second bath solutions to form a mixed plating bath solution having a pH greater than 13, and immersing a substrate to be plated in the mixed solution, wherein the substrate comprising, a metal selected from the group consisting of magnesium, aluminum and their alloys.
- the present invention resides in a process for electroless plating Nickel-boron plating metal on a magnesium substrate comprising: preparing a first bath solution comprising: 25 to 50 g/L nickel chloride hexahydrate, preparing a second bath solution component physically separate from the first bath solution component comprising: 50 to 75 ml/L ethylenediamine, 30 to 50 g/L sodium hydroxide, and 3 to 8 g/L sodium borohydride, mixing the first and second bath solution components in a ratio selected to form a mixed plating bath solution having a pH of at least 13, and preferably about 14 immersing the magnesium substrate in the mixed solution.
- a highly alkaline plating bath solution for use in metal deposition is prepared in two component parts: the first component part being the metal-salt solution (solution A); and the second component part being the solvent part (solution B) of the final bath solution.
- Each of the component solutions include sodium hydroxide in concentrations selected to maintain the stability of each component while allowing their mixture to provide a final highly alkaline plating bath suitable for substrate use in plating both reactive metals, as well as silicon-based.
- the two component solutions are prepared and stored separately until shortly before they are to be used in the process. In particular, preferably within 84, and more preferably within 72 hours prior to plating operations, the component solutions are mixed at the desired ratios to form the final electroless metal deposition bath for processing parts.
- the present process is believed to achieve various advantages, particularly in, although not limited to, the plating of magnesium and magnesium alloys.
- the total encapsulation of a magnesium substrate in another metal that is not subject to galvanic oxidation will prevent galvanic oxidation of the magnesium core of the part.
- the two-part component solutions that combine to form plating the bath for high pH electroless plating processes maintain individual stability and permit long-term storage.
- high pH deposition bath prevents highly reactive metal substrates to be plated from oxidizing prior to the desired metal deposition being placed on the surface.
- the high pH of the plating bath provides an environment where complete surface coverage of a highly reactive material may take place prior to any significant oxidation of surfaces which could otherwise prevent the formation of the desired coating.
- experimental highly alkaline electroless plating baths were prepared as follows:
- a deposition bath was prepared by mixing a component metal-salt solution and solvent solutions prepared generally as follows:
- the substrates used were AZ91D and AM50 magnesium alloys (their composition is given in Table 2) that were cut into coupons of 2 cm ⁇ 3 cm ⁇ 0.5 cm.
- the samples had a hole drilled at the top on the 2 ⁇ 3 cm face so that they could be hung in the deposition bath via non-conducting nylon wire.
- samples were wet-polished smooth using 240 grit SiC emery paper and rinsed in distilled water.
- a highly alkaline deposition baths used for sample electroless deposition of Cu was prepared according to Table 3.
- Table 2 The compositions of AZ91D and AM50 magnesium alloys (in wt. %) Alloy Al Zn Mn Ni Cu Si Fe Magnesium AZ91D 8.3-9.7 0.35-1.0 0.15 ⁇ 0.002 ⁇ 0.03 ⁇ 0.10 ⁇ 0.005 Balance AM50 4.9 0.2 0.45 ⁇ 0.01 ⁇ 0.008 ⁇ 0.05 ⁇ 0.004 Balance
- Each of component solutions A and B exhibited high stability and an extended shelf life at room temperature. Following their preparations, component solutions A and B were mixed, the resulting mixed electroless plating solution was found to have both a high pH of between about 13.5 and 14; and a useful working life of at least 48 hours at room temperature.
- the shelf life of the mixed plating solution to be used was however found to depend on the temperature of the solution; the amount of processing through the solution; and the ratio of solution A to B.
- Samples were dry polished in open atmosphere using 240 grit SiC emery paper to remove the quick forming oxide/hydroxide layer. The polishing was done such that minimal heating of the sample occurred as to not further promote the formation of the insulating oxide layer. The samples were then placed into the electroless deposition bath (made of a 1:1 mixture of baths A and B) at temperatures prescribed in Table 1.
- the samples were removed and rinsed with distilled water before being hung dry. To increase the rate of drying, it was found beneficial to have the base of the samples in contact with a non-conducting wire as to allow for the flow of adsorbed water away from the sample.
- the first sets of deposits performed on the AZ91D Mg alloy were conducted to isolate the role of the oxides. Two samples were placed parallel in identical room temperature electroless Cu plating baths. First, however, both samples were wet polished, using 240 grit SiC paper, and let dry open to the atmosphere for 3 weeks. One of the samples then underwent polishing and was placed into the deposition bath as quickly as possible, as per our procedure, while the other was left untreated. Finally, both samples were left in the deposition bath for 20 minutes before removal. Deposition on the oxidized sample was essentially non-existent, while the deposit on the coated sample was of better quality being more continuous both macroscopically and as seen by EDS.
- acid etching is preformed on the substrate as a pretreatment to provide enhanced electroless copper deposition and bonding. It has been previously documented that acidic etching is capable of removing insulating oxides for the surface of a variety of metals including aluminum [Al] and magnesium [Mg]. Additionally, it has also been documented that the use of some acids are not conducive for oxide removal in the face of secondary deposition, as they result in corrosion of the substrate.
- tartaric acid [C 4 H 6 O 6 ] Table 5 and sulfuric acid [H 2 SO 4 ] (Table 6) were tested for the removal of oxides from Mg alloy surfaces. Test samples were dry polished with 240 grit SiC emery cloth and allowed to oxidize in open air over 48 hours prior to exposure to the de-oxidation treatments. In both cases, it was found that the acid was able to remove the oxide layer and allow for better deposition. In test examples, acidic exposure was limited to only a few seconds, and no rinse bath was conducted between the oxide removal and deposition steps, as the distilled water bath would result in re-oxidation of the surface.
- cupric sulfate pentahydrate [CuSO 4 .5H 2 O] was attempted in the C 4 H 6 O 6 bath in accordance with Table 7. In this case it was found that a simple displacement reaction appeared to occur with a black, discontinuous copper film appearing to form on the Mg-based substrate. Though the black deposit from the treatment was not very well adhered, subsequent copper deposition appeared to be very well adhered, though at a cost of bath life.
- the baths used in pre-treatment with acidic removal of oxide layer and subsequent electroless copper plating were prepared as follows according to Table 4:
- Tartaric acid has some solubility issues at the concentration of 53 g/L precipitating a white substance at the bottom of the vessel when paired with 30 g/L CuSO 4 •5H 2 O.
- metal coating can thereafter itself serve as the basis for the application and deposition of subsequent coatings. Selection of the initial coating is predicated on the subsequent coatings desired. Further, metal encapsulated magnesium maintains its electrical conductivity and may be fastened mechanically to dissimilar metals without galvanic effect or corrosion at the point of fastening.
- nickel-boron metal coating on magnesium substrates was prepared from a two-part solution (component solution A and component solution B) shown in Table 8 that was mixed just prior to substrate coating. As nickel itself is not soluble at high pH, a nickel-boron salt solution was prepared in a separate batch solution A maintained at a much lower pH than the final bath which forms part A which is shown in the table below.
- the nickel-boron deposition solution is prepared as a two-part system mixed with de-ionized water as follows:
- the solvent component solution B included the borohydride which is highly susceptible to oxidation in neutral pH or acidic pH solutions.
- solution A is added to solution B to advantageously prevent the oxidation of the borohydride.
- the ethylenediamine in compound solution B further facilitates the solubility of the nickel in the high pH solution and the nickel deposition on the magnesium surface; while the boron is deposited on the surface by means of the anodic reaction.
- ethylenediamine is highly reactive with copper.
- copper is preferably avoided during nickel-boron coating.
- the nickel-boron coating may however, be subsequently coated with copper by way of the electroless coating process described herein.
- the electroless deposition of nickel-boron as a plating on a magnesium substrate is performed as follows:
- Ni—B Deposition of a secondary electroless Cu thin film coating on Ni—B was observed to provide a nearly continuous coating both macroscopically as well as seen by SEM.
- the initial Ni—B deposit was produced on AZ91D Mg alloy over 5 minutes at around 87° C., resulting in a deposit with some expected discontinuity.
- the sample was placed in a room temperature electroless copper bath for 5 minutes after which the sample was rinsed in distilled water and again hung to dry open to atmosphere. Observations of the sample after the secondary deposition process suggest that the Ni—B coating was indeed somewhat discontinuous as some limited corrosion has occurred on the sample. This is confirmed by SEM which indicates an initially discontinuous coating that has only begun to build on the Ni—B ‘nucleation’ sites.
- a sample was produced such that only the lower half was exposed to secondary Cu deposition bath.
- the initial electroless Ni—B deposit was produced on a polished sample of AZ91D alloy at 89° C. over 5 minutes. As seen by SEM, the deposit was continuous with few defects only, even though EDS continued to show a small peak of Mg.
- the sample was then rinsed in distilled water and hung to dry for 25 minutes in open air. After the drying period, the lower part of the sample was exposed to a room temperature electroless Cu bath for another 5 minutes then rinsed and dried. During the secondary deposition process the coating hydrated above the bottom third exposed to the deposition bath.
- the electroless deposition process in highly alkaline environments provides well formed, well adhered deposits, especially in the case of the deposition of a secondary layer.
- secondary deposition baths are also highly alkaline in order to ensure any pinholes, gaps, or defects in the otherwise continuous coating do not readily form galvanic cells and begin corrosion.
- Gaps in the initial cladding of magnesium may be attributed, especially in the case of copper, to the formation of insulating surface oxides by means of one, or both, of the following likely processes.
- the process of the present invention may be used in the electroless deposition of metal coating layers such as copper or an aluminum or aluminum alloy substrate.
- the copper deposition plating bath is prepared on a two-part bath from component solutions A and B as follows:
- electroless deposition of copper is reported to be at a maximum pH of 13.5 for electroless copper baths, with a high concentration of formaldehyde reducing agent on an AlN substrate.
- electroless copper procedures which may provide suitable for Al plating include a copper immersion coating on 3003-Al alloy, prior to electroless Ni—P deposition.
- the copper immersion coating is formed in a bath with CuSO 4 5H 2 O (30 g/l), and C 4 H 6 O 6 (tartaric acid) (53 g/l) at 25° C. for 3 min. This coating is done to prevent direct contact of Al with a subsequent electroless nickel deposition solution, thereby increasing the stability of the electroless deposition bath.
- the immersion coating may be a way to expand the electroless copper deposition to a wider range of aluminum alloys.
- a subsequent electroless copper layer could be acidic or alkaline, as subsequent electroless Ni—P coating layers may be provided at conventional pH levels of about 4.5.
- Example experiments achieve and show an adhered electroless copper cladding on an Al alloy sample.
- the Al was a highly recycled metal with any number of impurities entering the mix.
- Test conducted on 12% Si and 6061 Al alloys have resulted in powdered, poorly adhering deposits on the surface of the sample. As such the nature of the alloy itself may be a contributing factor which allows a high degree of deposition to take place.
- electroless deposition of copper may be achieved at lower pH values, depending on the specific composition of the aluminum alloy and whether adhesion may be lacking. Lower pH electroless Cu would also be effective, possibly on those alloys upon which adhesion is lacking.
- the electroless copper process may be applied to form the conductive backing used to reunite ‘electrons’ with the ‘holes’.
- Conventionally conductive backing is currently made from an aluminum paste.
- the electroless deposition process of the present invention may be used to apply a copper layer to form the electrode gridding contacts on the front surface of the cell.
- the electrodes are formed by screen printing silver paste on both the front and back of the solar cell.
- the use of an electroless copper plating process may be both less expensive than using silver paste, instead of conventional printing processes could further increase solar cell efficiency by reducing the surface area currently covered by the gridding.
- the present electroless technique also shows promise in to integrated circuit manufacture, and in particular the assembly of processors.
- the deposition of copper using the process of the present invention has also been verified on n-type silicon substrates, as well as on another silicon sample believed to be essentially pure silicon. Given that the silicon is doped to form n- and p-types of silicon it is expected that the deposition technique will work on all silicon substrates used in the construction of electronic devices. Additionally, it should be noted that copper deposition was observed on the substrate edge where the sample was broken off from a bulk sheet indicating that it is the lack of oxide, and not some anomaly from the polishing method, that results in deposit formation.
- Measurement of the coating deposit thickness, and whether the deposition bath promoted oxide growth, forming an oxide interlayer between the silicon substrate and the copper cladding, will further allow for the adjustment of optimum bath conditions. Preliminary measurements appear to indicate that there is some degree of ohmic contact between the cladding and the substrate measurement using the 4-probe method of thin films is however required to verify accuracy.
- coating layers will allow a variety of silicon or metal substrates to be used in a great number of areas and applications which are not considered to be viable to date.
- these include but are not limited to the use of coated magnesium/magnesium alloy substrates, computer hard drives, naval vessels, aircraft and aerospace applications, internal combustion engine heads and blocks, transmission and gear housings, automobile frame assemblies, and the like.
- the amount of metal deposited on the surface of a given substrate should not affect its recycling.
- surface coatings may be applied in such controlled volume to remain within the limits of acceptable “impurities”.
- high wear resistant or hardened coatings may be applied on softer metal substrates such as magnesium, which will allow the metals to be used in areas where good surface wear qualities are required.
- the process of the present invention as used in copper and Nickel-Boron coating of magnesium, aluminium and silicon substrates, the invention is not limited. It is to be appreciated that the two-part coating process of the present invention may be used to apply a variety of different coating layers which are soluble in highly alkaline plating baths.
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US13/878,916 US20130209698A1 (en) | 2010-10-13 | 2011-10-12 | Process for Electroless Deposition of Metals Using Highly Alkaline Plating Bath |
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US34480010P | 2010-10-13 | 2010-10-13 | |
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US201161457590P | 2011-04-26 | 2011-04-26 | |
PCT/CA2011/001146 WO2012048412A1 (en) | 2010-10-13 | 2011-10-12 | Process for electroless deposition of metals using highly alkaline plating bath |
US13/878,916 US20130209698A1 (en) | 2010-10-13 | 2011-10-12 | Process for Electroless Deposition of Metals Using Highly Alkaline Plating Bath |
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EP (1) | EP2627798A1 (pt) |
JP (1) | JP5937086B2 (pt) |
KR (1) | KR20140020829A (pt) |
CN (1) | CN103221579B (pt) |
BR (1) | BR112013008950A2 (pt) |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8900998B2 (en) | 2012-11-21 | 2014-12-02 | University Of Windsor | Process for electroless deposition of gold and gold alloys on silicon |
US20160323992A1 (en) * | 2014-04-09 | 2016-11-03 | Finisar Corporation | Aluminum nitride substrate |
US11167375B2 (en) | 2018-08-10 | 2021-11-09 | The Research Foundation For The State University Of New York | Additive manufacturing processes and additively manufactured products |
Families Citing this family (3)
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EP3200955A4 (en) * | 2015-04-07 | 2018-08-29 | Hewlett-Packard Development Company, L.P. | Methods of polishing |
CN108531895A (zh) * | 2018-03-29 | 2018-09-14 | 西安理工大学 | 一种在氧化铝薄膜上无电沉积铜的方法 |
CN111455359A (zh) * | 2020-04-28 | 2020-07-28 | 中国科学院兰州化学物理研究所 | 一种铜表面金石墨烯复合镀层的制备方法 |
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US3886166A (en) * | 1972-12-22 | 1975-05-27 | Siphar Sa | Method for the synthesis of ({35 )-glaziovine |
US5017410A (en) * | 1988-05-23 | 1991-05-21 | United Technologies Corporation | Wear resistant electroless nickel-boron coating compositions |
US5269838A (en) * | 1992-04-20 | 1993-12-14 | Dipsol Chemicals Co., Ltd. | Electroless plating solution and plating method with it |
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US3033703A (en) * | 1958-12-08 | 1962-05-08 | Photocircuits Corp | Electroless plating of copper |
DE2445319B2 (de) * | 1974-09-23 | 1980-10-30 | Robert Bosch Gmbh, 7000 Stuttgart | Alkalisches Bad zum stromlosen Abscheiden von Kupfer |
US4983428A (en) * | 1988-06-09 | 1991-01-08 | United Technologies Corporation | Ethylenethiourea wear resistant electroless nickel-boron coating compositions |
JPH0734254A (ja) * | 1993-07-19 | 1995-02-03 | Okuno Chem Ind Co Ltd | アルミニウム系材料への無電解めっき方法 |
JP4521947B2 (ja) * | 2000-08-07 | 2010-08-11 | イビデン株式会社 | 無電解めっき用前処理液、無電解めっき用処理液、および、多層プリント配線板の製造方法 |
CN1890401A (zh) * | 2003-10-17 | 2007-01-03 | 应用材料公司 | 用含钴合金对铜进行选择性自引发无电镀覆 |
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2011
- 2011-10-12 WO PCT/CA2011/001146 patent/WO2012048412A1/en active Application Filing
- 2011-10-12 CN CN201180049557.9A patent/CN103221579B/zh not_active Expired - Fee Related
- 2011-10-12 JP JP2013533061A patent/JP5937086B2/ja not_active Expired - Fee Related
- 2011-10-12 KR KR1020137012294A patent/KR20140020829A/ko not_active Application Discontinuation
- 2011-10-12 CA CA2813818A patent/CA2813818A1/en not_active Abandoned
- 2011-10-12 BR BR112013008950A patent/BR112013008950A2/pt not_active IP Right Cessation
- 2011-10-12 EP EP11831881.5A patent/EP2627798A1/en not_active Withdrawn
- 2011-10-12 MX MX2013003935A patent/MX339242B/es active IP Right Grant
- 2011-10-12 US US13/878,916 patent/US20130209698A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3886166A (en) * | 1972-12-22 | 1975-05-27 | Siphar Sa | Method for the synthesis of ({35 )-glaziovine |
US5017410A (en) * | 1988-05-23 | 1991-05-21 | United Technologies Corporation | Wear resistant electroless nickel-boron coating compositions |
US5269838A (en) * | 1992-04-20 | 1993-12-14 | Dipsol Chemicals Co., Ltd. | Electroless plating solution and plating method with it |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8900998B2 (en) | 2012-11-21 | 2014-12-02 | University Of Windsor | Process for electroless deposition of gold and gold alloys on silicon |
US20160323992A1 (en) * | 2014-04-09 | 2016-11-03 | Finisar Corporation | Aluminum nitride substrate |
US10470302B2 (en) * | 2014-04-09 | 2019-11-05 | Finisar Corporation | Aluminum nitride substrate with graphite foil |
US10667388B2 (en) * | 2014-04-09 | 2020-05-26 | Ii-Vi Delaware Inc. | Optical waveguide having aluminum nitride thin film |
US11167375B2 (en) | 2018-08-10 | 2021-11-09 | The Research Foundation For The State University Of New York | Additive manufacturing processes and additively manufactured products |
US11426818B2 (en) | 2018-08-10 | 2022-08-30 | The Research Foundation for the State University | Additive manufacturing processes and additively manufactured products |
Also Published As
Publication number | Publication date |
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JP5937086B2 (ja) | 2016-06-22 |
JP2013540205A (ja) | 2013-10-31 |
CN103221579B (zh) | 2015-04-29 |
MX2013003935A (es) | 2013-10-17 |
BR112013008950A2 (pt) | 2019-09-24 |
EP2627798A1 (en) | 2013-08-21 |
MX339242B (es) | 2016-05-18 |
CN103221579A (zh) | 2013-07-24 |
KR20140020829A (ko) | 2014-02-19 |
CA2813818A1 (en) | 2012-04-19 |
WO2012048412A1 (en) | 2012-04-19 |
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