Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
• • 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
  • C23C18/18—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
  • C23C18/1834—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
• • 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
  • C23C18/1886—Multistep pretreatment
  • C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
• • 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
  • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
  • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
  • C23C18/2073—Multistep pretreatment
  • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
• • 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
  • C23C18/28—Sensitising or activating
  • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D7/00—Electroplating characterised by the article coated
  • C25D7/12—Semiconductors
  • C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
• • 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
  • 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

Definitions

• the epoxy resin carrier is first functionalized by a so-called polymerization initiator layer.
• the surface of the support covered with a first polymer layer is then contacted with a solution of monomers and a polymer with reactive functional groups in solution.
• This polymer initiates a polymerization reaction leading to the grafting of a film comprising a polyurethane bicomponent mixture on the surface of the epoxy support.
• the deposited film is then generally crosslinked by radiative or thermal treatment.
• Polyamines have already been used for coating various materials such as silicon or epoxy resin.
• Polyethyleneimines and polyvinylpyridines will be mentioned.
• This method offers several advantages over the grafting methods known in the state of the art.
• the layer perfectly follows the topography of the surface of the material.
• This method is particularly advantageous when it comes to coating substrates with a complex geometry, for example substrates having edges such as cubic or parallelepipedal geometries, or having a high form factor: this is the case in particular with substrates having a groove or a deep hole whose opening diameter is narrow, such as vias in microelectronics.
• the conformal character of the polymer layer obtained by this method leads to a thin metal coating, very good adhesion and very good compliance while using a low energy treatment, by example a low temperature heat treatment.
• this process is not specific to the substrate and makes it possible to coat organic or inorganic solid supports of various natures, without the application of an electric current, in particular metals, aramids, polyimides, or polymers which are very difficult to modify, such as, for example, polytetrafluoroethylene (PTFE).
• PTFE polytetrafluoroethylene
• step d) removal of the molecules of the polymer deposit which have not grafted onto the substrate, which elimination is carried out by dl) rinsing the substrate coating obtained in step c) with a solvent of the polymer, which solvent may or may not be identical to the solvent used in step a1), then by d2) drying said substrate so as to remove the solvent;
• non-electrochemical method a process such as step a2) of contacting the substrate with the solution is carried out without imposing an electric potential difference between the substrate and the solution.
• the substrate covered with a polymer film obtained at the end of step e) can then be used as a support in other processes comprising at least one metallization step carried out under electrochemical or non-electrochemical (electroless) conditions.
• grafting or “fixation” is meant in particular the creation of chemical bonds between the polymer and the surface of the solid support; it is preferred that the majority of the bonds are covalent bonds. Ion bonds or Van der Waals bonds can be created to a lesser extent. The covalent bonds are essentially created at the interface between the substrate and the polymer, but they may also result from cross-linking between the polymer chains in the thickness of the deposit. Heat treatment can indeed create radical chemical mechanisms at the interface of the polymer and the substrate, but also in the polymer mass. This grafting makes the polymer layer more cohesive, less soluble and mechanically more difficult to tear.
• the polymer film corresponds to the polymer mass obtained at the end of the rinsing step d). Consequently, the polymer film may correspond to a polymer mass whose structure and thickness are totally different from those of the previously defined polymer deposition.
• the polymer used in step a1) may be electrolyte or non-electrolyte.
• the polymer may be a saturated polymer without a double bond and without the possibility of intra-molecular recombination.
• the grafting method of the invention consists in creating bonds predominantly at the interface between the polymer deposition and the substrate, by limiting the crosslinking reactions in the deposition of the polymer. .,
• the weight or number of molecular weight of the polymer used in step a1) may vary in particular by 100 g. mol "1 to 1,000,000 g mol " 1 .
• the thickness of the polymer deposit obtained in step b) can be adjusted by two means: by varying the concentration of the polymer in the solution prepared in step a1) and / or by making successive depositions of several layers of polymer on the support surface (i.e. by repeating steps a2) to b).
• the removal of the solvent can be carried out by any suitable technique well known to those skilled in the art such as simple air drying, in particular for solutions based on alcoholic solvents, for example with ethanol, evaporation under reduced pressure, in particular for solutions based on hydroalcoholic solvents.
• Gamma rays are particularly suitable for complex surface supports which have, for example, cavities or "shaded” surfaces because they have a low absorption coefficient. This possibility is not offered by the VUV irradiation which remains more adapted to surfaces accessible to light.
• the method of the third subject of the invention comprises depositing a barrier layer based on nickel or cobalt on the surface of a graft polymer insulating film on a conductive or semiconductor substrate, which Insulating film is obtained by the method described above as the first subject of the present invention.
• the substrate comprises cavities and step B1) comprises the deposition of two metallic materials: the deposition of a first metal layer of nickel, cobalt or one of their alloys, which first layer serves a barrier function to the diffusion of copper, and the deposition of a second metallic layer of copper.
• the deposition of the copper layer on the barrier layer can be implemented by electrodeposition in pulsed galvano mode.
• the nitrogenous polymer is preferably a polyvinylpyridine or a polyethyleneimine.
• the heat treatment of step c) can advantageously be carried out at a temperature of between 100 and 400 ° C., preferably between 200 and 300 ° C., for a duration ranging from 10 seconds to 15 minutes.
• the process which has just been described will be followed by a step of filling the cavities with copper, possibly preceded by a step of forming a copper seed layer.
• the deposition of copper can be achieved by a conventional electroplating process. These methods are well known to those skilled in the art include the application of a wafer current previously covered with a barrier layer, which is immersed in an acid bath or basic copper ions.
• a complexing agent for copper consisting of at least one compound chosen from polyamines and carboxylic acids;
• aliphatic polyamines that may be used include ethylenediamine, diethylenediamine, triethylenetetramine and dipropylenetriamine and preferably ethylenediamine.
• Figure 7 shows the Kevlar fiber sample completely covered with the NiB metal layer.
• FIG. 11 reproduces the IR spectrum of the P4VP deposited on the surface of INOX but not grafted (high, blue), rinsed with ethanol (medium, red) and deposited on the surface and then grafted for 2 min at 400.degree. heat gun then rinsed with ethanol (low, pink).
• Example 1A Coating a substrate coated with a silicon oxide layer SiO z from a solution containing a polymer P4VP
• P4VP poly-4-vinylpiridine polymer coating
• the substrate used in this example was obtained at the end of step b3) of Example 1A.
• NiB metal layer intended to form a diffusion barrier with electroless The activated substrate c2) is immersed in a nickel-boron electroless bath (Aveni E460 commercial bath - A + B) regulated at a temperature of 65 ° C. The substrate is thus quenched for 3 minutes in order to obtain a complete and homogeneous metallization. Abundant rinsing with deionized water (18.2 MOhm / cm) and drying under a nitrogen sweep are carried out. The thickness of the nickel-boron film is typically 50 nm. The metal layer thus obtained was annealed at 250 ° C. for 10 minutes under a reducing atmosphere (N 2 + H 2 mixture (4% in H 2 )).
• the deposition of a copper seed layer on the substrate coated at the end of step d) was carried out using a commercial solution (Alchimer V201).
• the electroplating process used in this example included a copper growth step during which the treated substrate obtained at the end of step d) was cathodically polarized in galvano-pulsed mode and simultaneously rotated. at a speed of 60 rpm.
• the metal stack thus obtained was annealed at 250 ° C. for 10 minutes under a reducing atmosphere (N 2 + H 2 mixture (5% in H 2 )).
• Example 2A Coating of a Substrate Coated with a SiO Silicon Oxide Layer from a Solution Containing a P4VP Polymer and an Activator
• Example 1A the sample used and its cleaning are identical to a) of Example 1A.
• the application of the P4VP solution is made by soaking-removing (immersion-emersion) of the sample for 10 seconds.
• the evaporation of ethanol which can be facilitated by a compressed air flow, provides a film of P4VP and benzoyl peroxide covering but not homogeneous. Their deposition then occurs on both sides of the substrate.
• This step is identical to step e) of Example 1B.
• a substrate identical to that described in a) and having no benzoyl peroxide described in b1) but having undergone all the steps does not have a thin film grafted to the surface and not metallized in the step d).
• This sample has TSVs of dimensions 5 ⁇ 50 microns, themselves covered with a layer of silicon (SiO 2 ) thermal oxide with a thickness of less than 300 nm continuous with the layer present on the surface.
• the samples were placed in a solution containing 50 ml of concentrated sulfuric acid (H 2 SO 4 ) and 20 ml of hydrogen peroxide (H 2 O 2 ) for 10 minutes at 80 ° C.
• the sample was then rinsed abundantly with de-ionized water (18.2 MOhm / cm) and dried under a nitrogen sweep before being activated according to b).
• de-ionized water (18.2 MOhm / cm)
• isopropanol cleaning of the surface rinsing with isopropanol and drying under a nitrogen sweep.
• Adherent and uniform layers are obtained on the SiO 2 substrate as described in a).
• the images in profile view by scanning electron microscopy show, in FIG. 3, the succession of the Si-SiO 2 -NiB stack in the TSVs.
• a substrate identical to that described in a) and not having undergone the steps in b) but those in c) and d) shows no metallization of this substrate.
• Example 4A Flexible Polvimide Substrate (Kapton Type) Coated with Polymer P4VP
• a flexible polyimide coupon 4 cm square (4 * 4 cm) and 500 ⁇ m thick was used as the substrate.
• the coupon was cleaned with isopropanol by soaking and dried under a nitrogen sweep before being activated according to b).
• Example 4B electroless deposition of a layer of nickel and a layer of Copper on a substrate coated with a silicon oxide layer SiO z and polymer P4VP.
• the substrate used in this example was obtained at the end of step b3) of Example 4A.
• Electroless deposit of a conductive NiB metal layer The activated substrate in c2) is immersed in a nickel-boron electroless bath (Aveni E460 commercial bath - A + B) regulated at a temperature of 65 ° C. It then undergoes the same treatment as in d) of Example 1B.
• a nickel-boron electroless bath Aveni E460 commercial bath - A + B
• Example 5A Coating of a Flexible Polyimide Substrate (Kapton Type) from a Solution Containing a P4VP Polymer and a Palladium Salt
• a flexible polyimide coupon (Kapton type) 4 cm in length (4 * 4 cm) and 500 ⁇ m thick was used as the substrate.
• the coupon was cleaned with isopropanol by soaking and dried under a nitrogen sweep before being activated according to b).
• a solution comprising 10 mg of P4VP (Mn 60,000) and 15 mg of palladium acetate Pd (OAc) 2 dissolved in a mixture of 10 ml of water and 90 ml of propanoic acid is prepared by checking the total solubilization of components.
• coating of the P4VP and palladium solution is done by ink jet printing.
• the solution is introduced into the liquid cartridge supplying the ink jet needle.
• the surface is dried by a slight flow of nitrogen.
• a film of P4VP covering but not homogeneous, and following the pattern chosen by the user, is obtained. In this case it is the Alchimer logo.
• the coating is only on the chosen face and not on both sides as in the previous examples.
• the substrate coated with P4VP is treated as in b3) of Example 3A. Abundant rinsing with deionized water (18.2 MOhm / cm) and drying under nitrogen sweep are performed. The substrate becomes partially hydrophilic, which suggests the logo according to a visual appreciation.
• the substrate used in this example was obtained at the end of step b3) of Example 5A.
• Example 6A Coating of an Aramid Braided Substrate (Keylar) from a Solution Containing a P4VP Polymer
• the coating of the solution of P4VP is made by soaking for 2 minutes then by withdrawal (immersion-emersion) in order to obtain after evaporation of ethanol aided by a slight flow of nitrogen. P4VP film covering but not homogeneous. P4VP deposition then occurs on all sides of the substrate.
• P4VP ' poly-4-vinylpiridine polymer coating
• Example 6B Electroless deposition of a nickel layer on an aramid substrate coated with a P4VP polymer layer.
• the substrate used in this example was obtained at the end of step b3) of Example 6A.
• the substrates are immersed for two minutes in the solution of palladium complex prepared in Cl). Abundant rinsing with deionized water (18.2 MOhm / cm) and drying under a nitrogen sweep are carried out. The substrate then becomes hydrophilic again according to a visual assessment.
• Example 7A Coating a carbon fiber substrate in an epoxy matrix from a solution containing a polymer P4VP
• the coating of the solution of P4VP and benzoyl peroxide is made by soaking for 2 minutes then by withdrawal (immersion-emersion) to obtain after evaporation of the ethanol aided by a slight flow Nitrogen a P4VP film covering but not homogeneous. Deposition of P4VP and benzoyl peroxide occurs over the entire surface of the substrate.
• P4VP poly-4-vinylpiridine polymer coating
• Example 7B Electroless deposition of a layer of nickel and a layer of carbon on a carbon fiber substrate in an epoxy matrix coated with a P4VP polymer layer.
• the substrate used in this example was obtained at the end of step b3) of Example 7A.
• the substrates are immersed for two minutes in the palladium solution prepared in Cl). An abundant rinsing deionized water (18.2 MOhm / cm) and drying under a nitrogen sweep are carried out. The substrate then becomes hydrophilic again according to a visual assessment.
• Adherent and uniform layers are obtained on the carbon fiber substrate as described in a).
• the images show in FIG. 8, the succession of the C-NiB fiber stack, and in FIG. 9, the C-fiber stack. -NiB-Cu.
• a substrate identical to that described in a) and not having undergone the steps in b) but those in c) and d) shows no metallization of this substrate.
• a solution of P4VP as described in b) but not containing benzoyl peroxide does not allow after steps c) and d) to have a grafting and metallization of the substrate.
• Example 8A Coating of a substrate made of aluminum foil from a solution containing a polymer P4VP
• an aluminum foil of about 0.02 mm was used as the substrate.
• the sample was cleaned with isopropanol by soaking and dried under a nitrogen sweep before being activated according to b).
• the coating of the solution of P4VP and benzoyl peroxide is made by soaking for 2 minutes then by withdrawal (immersion-emersion) to obtain after evaporation of the ethanol aided by a slight flow of nitrogen. A film of P4VP covering but not homogeneous is obtained. Deposition of P4VP and benzoyl peroxide occurs over the entire surface of the substrate.
• Example 8B Electroless deposition of a nickel layer on an aluminum foil coated with a P4VP polymer layer.
• the substrate used in this example was obtained at the end of step b3) of Example 8A.
• the substrates are immersed for two minutes in the solution of palladium complex prepared in Cl). Abundant rinsing with deionized water (18.2 MOhm / cm) and drying under a nitrogen sweep are carried out. The substrate then becomes hydrophilic again according to a visual assessment.
• the activated substrate c2) is immersed in a nickel-boron electroless bath (Aveni E460-A + B commercial bath) regulated at a temperature of 65 ° C. It then undergoes the same treatment as in d) of Example 1.
• a nickel-boron electroless bath Aveni E460-A + B commercial bath
• Adherent and uniform layers are obtained on the aluminum substrate as described in a).
• a substrate identical to that described in a) and not having undergone the steps in b) but those in c) and d) shows no metallization of this substrate. 5
• Example 9A Coating of a substrate coated with a silicon oxide SiO 2 layer from a solution containing a branched polyethylene imine polymer (PEI)
• PEI polyethylene imine polymer
• the sample was placed in a solution containing 50 ml of concentrated sulfuric acid (H 2 SO 4 ) and 20 ml of hydrogen peroxide (H 2 O 2 ) for 10 minutes at 80 ° C.
• the sample was then was thoroughly rinsed with de-ionized water (18.2 MOhm / cm) and dried under a nitrogen sweep before being activated according to b).
• de-ionized water (18.2 MOhm / cm
• Another alternative is an isopropanol cleaning of the surface, rinsing with isopropanol and drying under a nitrogen sweep.
• PEI polyethyleneimine polymer
• Example 9B Electroless deposition of a layer of nickel and a layer of copper on a substrate coated with a layer of silicon oxide SiQ 2 and polymer PEI.
• the substrate used in this example was obtained at the end of step b3) of Example 9A.
• the substrates are immersed for two minutes in the palladium solution prepared in Cl). Abundant rinsing with deionized water (18.2 MOhm / cm) and drying under a nitrogen sweep are carried out. The substrate then becomes more hydrophilic according to a visual appreciation.
• the substrate activated in c2) is immersed in a nickel-boron electroless bath
• Adherent and uniform layers are obtained on the Si0 2 substrate as described in a)
• the images in profile by scanning electron microscopy show in Figure 10, the succession of the stack Si-Si0 2 -NiB.
• the adhesion of the metal stack is evaluated by applying the ASTM D3359 standardized scotch test.
• the result provides a 16/16 measurement for the Si-SiO2-NiB-Cu global stack.
• Example 10 Coating of a Polished Stainless Steel Substrate with a Solution Containing a P4VP Polymer
• a substrate of a polished INOX plate of approximately 1x4cm was used.
• the sample was cleaned with isopropanol by soaking, rinsing with isopropanol and dried under a nitrogen sweep before being activated according to b).
• the application of the P4VP solution is made by soaking-removing (immersion-emersion) of the sample for 10 seconds.
• the evaporation of ethanol which can be facilitated by a compressed air flow, provides a covering but not homogeneous P4VP film.
• the deposition of P4VP then occurs on both sides of the substrate.
• P4VP poly-4-vinylpiridine polymer coating
• Example 11A Coating of a substrate made of foam
• This step is performed as step b2) of Example 2A.
• Example 11 B Electroless deposition of a layer of nickel on polyurethane foam coated with an epoxy matrix and then coated with a P4VP polymer layer.
• the substrate used in this example was obtained at the end of step b3) of Example 11A.
• a substrate identical to that described in a) and not having undergone the steps in b) but those in c) and d) shows no metallization of this substrate.

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• 2015
  • 2015-10-08 FR FR1559596A patent/FR3042133B1/fr active Active
• 2016
  • 2016-10-07 WO PCT/FR2016/052605 patent/WO2017060656A2/fr not_active Ceased
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