[go: up one dir, main page]

WO2017066069A1 - Phospha-adamantanes solubles dans l'eau et stables à l'air en tant que stabilisants pour le dépôt autocatalytique de métal - Google Patents

Phospha-adamantanes solubles dans l'eau et stables à l'air en tant que stabilisants pour le dépôt autocatalytique de métal Download PDF

Info

Publication number
WO2017066069A1
WO2017066069A1 PCT/US2016/055655 US2016055655W WO2017066069A1 WO 2017066069 A1 WO2017066069 A1 WO 2017066069A1 US 2016055655 W US2016055655 W US 2016055655W WO 2017066069 A1 WO2017066069 A1 WO 2017066069A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
electrolyte
group
aqueous electrolyte
electrolyte composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2016/055655
Other languages
English (en)
Other versions
WO2017066069A8 (fr
Inventor
Stefan Schafer
Katrin SOENTGERAT
Marlies Kleinfeld
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
MacDermid Enthone Inc
Original Assignee
Enthone Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Enthone Inc filed Critical Enthone Inc
Priority to CN201680059667.6A priority Critical patent/CN108495952A/zh
Priority to US15/765,637 priority patent/US20190085461A1/en
Priority to KR1020187013527A priority patent/KR20180089398A/ko
Publication of WO2017066069A1 publication Critical patent/WO2017066069A1/fr
Anticipated expiration legal-status Critical
Publication of WO2017066069A8 publication Critical patent/WO2017066069A8/fr
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—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
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper 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
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • C23C18/405—Formaldehyde
    • 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

Definitions

  • the present invention relates to the use of water soluble and air stable phosphaadamantanes as stabilizers in electrolytes for electroless metal deposition.
  • the invention provides an electrolyte, as well as a method, for the electroless deposition of metals.
  • the present invention further relates to an organic stabilizer for an electroless plating method, and an electrolyte for the electroless deposition of a metal layer on a substrate.
  • Electroless plating methods have long been known from the state of the art in the metal plating industry. By electroless plating, also known as chemical plating, the coating of almost every metal and a huge number of non-conductive substrate surfaces is possible. Electrolessly deposited metal layers differ from galvanically deposited metal layers, i.e. those layers deposited by the use of an external current, in physical as well as mechanical aspects. Often, metal alloy layers with non-metal elements, like cobalt/phosphorus, nickel/phosphorus, nickel/boron or boron carbide are deposited by means of electroless deposition methods. In this respect, electrolessly deposited layers in many cases differ in their chemical nature from the galvanically deposited layers.
  • One major advantage of the electroless deposited metal layer is the outline accuracy of the layer thickness of the deposited layer independent from the substrate geometry.
  • Electroless plating methods are also used for the coating of other non-conductive substrates, like plastic substrates, to render the surface of such substrates conductive and/or to change the aesthetic appearance of the substrate.
  • the material properties of the coated substrate can be improved or amended with electroless plating. Specifically, the corrosion resistance or the hardness of the surface and/or the wear resistance of the substrate can be improved, e.g. for gas and/or oil industry applications.
  • Electroless plating methods are based on an autocatalytic process, in which process the metal ions comprised in the electrolytes are reduced to the elemental metal by a reducing agent which is oxidized during this redox reaction.
  • Sodium hypophosphite is a commonly used reducing agent in the field of electroless deposition of metals on substrate surfaces. Other reducing agents are also used in dependency of the metals to be deposited.
  • cyanides are used as stabilizers. Like heavy metal ions, cyanides are subject to environmental regulations. The same is true for selenium compounds, which are also commonly used as stabilizers. In addition, some heavy metal stabilizers are difficult to analyze. Since analyzing of concentration of said heavy metal stabilizers is mandatory but difficult, bath control can also be difficult.
  • U.S. Pat. No. 6, 146,702 discloses an electroless nickel cobalt phosphorus composition and plating process. The process provides for enhancing the wear resistance of aluminium and other materials by depositing a nickel, cobalt, phosphorus alloy coating on the substrate using an electroless plating bath to provide a plated alloy having a cobalt content of at least about 20% by weight and a % Co / % P weight ratio of at least about 5.
  • European patent application EP 1 413 646 A2 discloses an electrolyte for the electroless deposition of nickel layers having internal compressive stress.
  • the electrolyte disclosed in the application comprises a metal salt of the metal to be deposited, a reducing agent, a complexing agent, an accelerator, and a stabilizer.
  • the accelerator is used to increase the deposition rate of the metal on the substrate surface.
  • JP 2009- 149965 A discloses a silver-plating method, which does not need to form an unnecessary layer of a nickel layer in between a substrate, which is difficult to be plated, and a silver-plated film.
  • the silver-plated film has sufficient adhesiveness directly on the substrate, which is difficult to be plated, with the use of a halide-free plating bath under a satisfactory working environment.
  • the silver-plating method disclosed is used for forming the silver-plated film on the substrate on which an oxide film is easily formed and the oxide film hinders the adhesiveness of a plated film, and comprises at least the steps of: (A) degreasing the substrate; (B) removing the oxide film with a strongly acidic solution; and then, (C) plating the substrate with silver by using a phosphine-containing acidic silver- plating bath which essentially does not contain a halide ion and a cyanide ion while skipping the step of nickel strike plating or nickel-alloy strike plating.
  • JP 2005-290415A discloses a stabilizing agent for electroless copper-plating electrolytes, which imparts adequate stability to an electroless copper-plating solution without lowering characteristics of an electroless copper-plated film.
  • the stabilizing agent is made of a highly safe material.
  • the electroless copper-plating solution includes a phosphine compound expressed by the following general Formula, as the stabilizing agent:
  • CN 101348927A discloses a cyanogen-free preplated copper solution.
  • the solution comprises a nontoxic organic phosphine compound to replace cyanide as a complexing agent for the preplated copper. This is particularly suitable for preplated copper used to electroplate steel, aluminum, magnesium, zinc, titanium and titanium alloy.
  • the cyanogen-free preplated copper solution has the following main technical characteristic that the solution comprises: (a) one sort of copper sulphate, basic cupric carbonate or copper nitrate with the volume concentration of between 30 and 60 g L; (b) one sort or two sorts of compounds selected from methylene diphosphonic acid, 1-hydroxyethylidene 1,1-diphosphonic acid and 1- hydroxybutyleneidene 1, 1-diphosphonic acid with the volume concentration of between 120 and 160 g/L; (c) one sort or two sorts of compounds selected from methylamino dimethylene diphosphonic acid, hexamethylene diamine tetramethylene phosphonic acid and ethylenediamine tetramethylene phosphonic acid, with the volume concentration of between 2 and 5 g L;; (d) one sort of potassium citrate, amine citrate or s pizzate salt, with the volume concentration of between 6 and 12 g L, and (e) polyethyleneimine alkyl slat or aliphatic amine
  • an aqueous electrolyte for the electroless deposition of a metal layer on a substrate comprising a metal ion source for the metal to be deposited, a reducing agent, a complexing agent, an accelerator, and a stabilizer, characterized in that the electrolyte comprises a phosphaadamantane, as a stabilizer, according to the general Formula I,
  • the invention is summarized as being an aqueous electrolyte composition for the electroless deposition of a metal layer on a substrate, comprising:
  • a stabilizer characterized in that the stabilizer is a phosphaadamantane according to the general Formula I:
  • hydrogen atoms on carbon atoms 1 to 6 may independently from each other be substituted by a moiety of the group consisting of F, CI, Br, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alcohol group having 1 to 6 carbon atoms.
  • the inventive method is summarized as a method for the electroless deposition of a metal layer on a substrate comprising the steps of:
  • an electrolyte comprising:
  • the electrolyte comprises phosphaadamantane, as a stabilizer, according to the general Formula I:
  • phosphaadamantanes are capable of completely replacing heavy metal stabilizers, cyanides, selenium compounds and sulfur compounds comprising sulfur in an oxidation state between -2 and +5 in electrolytes for the electroless deposition of metal layers.
  • the applicant believes that the phosphaadamantanes, according to general Formula I, due to their indirectly tertiary amino groups, as well as their tertiary phosphorus group are capable to at least temporarily jam the active centers on the substrate surface, which are responsible for the uncontrolled deposition. Wild deposition of the metals can now therefore be avoided. Additionally, the foreign ions present in the electrolyte, which are responsible for the wild deposition, are inactivated by the phosphaadamantanes.
  • a further benefit of the inventive electrolyte is that an effect known as edge weakness can be avoided.
  • electrolytes that comprise heavy metal ions as stabilizers for the electroless deposition of metal layers which at high convection of the electrolyte, a decreased deposition of metal at the edges of the substrate occurs. This is deemed to be related to an increased assembly of the heavy metal ions used as stabilizers in these areas. This effect deteriorates the outline accuracy of the plating.
  • phosphaadamantanes, according to general Formula I as stabilizers in electroless plating methods, this edge weakening effect can be avoided.
  • phosphaadamantanes as stabilizers significantly increases the overall outline accuracy of the plating, especially when plating large substrates.
  • phosphaadamantane as a stabilizer, according to general Formula I, results in a more even deposit with less nodules.
  • a further benefit of the inventive electrolyte is that a significant reduction of deposition on components of the plating equipment, especially on the heating systems used in the plating baths, occurs. This significantly reduces equipment maintenance, which in turn results in a notable economic benefit to the plating shops due to less down time.
  • plating electrolytes for the electroless deposition become less sensitive to foreign metal carry-over, like e.g. palladium ions resulting from the activation pretreatment of the substrate to be plated.
  • foreign metal carry-over like e.g. palladium ions resulting from the activation pretreatment of the substrate to be plated.
  • non-conductive substrates like e.g. plastics
  • noble metal colloids for seeding the surfaces.
  • the known plating electrolytes turned out to be quite sensitive to foreign metals and therefore required intensive rinse steps after the activation, the inventive plating electrolytes do not show any significant deterioration even at Pd- concentrations > 2mg L.
  • phosphaadamantanes having no substituted hydrogens, are found to be very effective as stabilizers in electroless plating electrolytes.
  • PTA l,3,5-triaza-7-phosphatricyclo[3,3,l, l]decane
  • PTA has a sufficiently high solubility in aqueous systems and has a high oxidation stability.
  • the phosphaadamantanes according to general Formula I can be comprised in the inventive electrolyte within a range of >0.05 mg/L and ⁇ 100 mg/L, preferably between >0.1 mg/L and ⁇ 25 mg L, most preferably between >0.5 mg L and ⁇ 10 mg/L.
  • the electrolyte comprises at least one reducing agent of the group consisting of sodium hypophosphite, formaldehyde, dimethyl aminoborane, aminoborane, or other organic boranes.
  • the reducing agent may be present in the electrolyte in a concentration of between 0.08 mol/L and 0.5 mol/L, preferably, 0.1 mol/L and 0.3 mol L.
  • the electrolyte may comprises e,g, sodium hypophosphite (mono hydrate) with a concentration of 10 to 40 g 1, and even more preferably with a concentration of 12 to 30 g 1.
  • Volatile ions in the sense of this invention, are ions which form together with counter ion moieties, which are volatile at the temperature the electrolyte is commonly used at.
  • An example of such a volatile ion is acetate, which forms under the plating conditions acetic acid. Since acetic acid has a vapor pressure of 16hPa at 20 °C, it will evaporate from the electrolyte under the plating conditions, and can be recovered from the exhaust air system.
  • the inventive electrolyte comprises a compound a complexing agent selected from the group consisting of 2-hydroxy propionic acid, propanedioic acid (malonic acid), EDTA, and amino acetic acid.
  • the complexing agent may be in the electrolyte in a concentration of between 0.05 mol/L and 0.5 moJ/L, preferably between 0.2 mol/L and 0.4 mol L.
  • the inventive electrolyte comprises an accelerator, which preferably is selected from the group consisting of saccharin, hydantoin, rhodanine, or carbamide and its derivates.
  • the accelerator can be in the electrolyte in a concentration of between 0.05 mmol L and 0.1 mol L, preferably between 0.005 mol/L and 0.025mol/L.
  • the metal to be deposited by the inventive electrolyte can be selected from the group consisting of nickel, copper, cobalt, boron, silver, palladium and gold.
  • the metal to be deposited may also be alloys such as nickel/cobalt, nickel/phosphorus, cobalt/phosphorus, nickel/boron or the like.
  • the deposition of nickel/PTFE-layers or nickel/boron carbide/graphite-layers from dispersion baths is also possible using the inventive electrolyte.
  • the inventive electrolyte can have a pH-value within a range of between pH 4 and pH 7, preferably within pH 4 and pH 6. It is preferred that the inventive electrolyte is slightly acidic.
  • the electrolyte may comprise pH adjusting compounds, like acids, bases, and/or buffers to control the pH of the electrolyte.
  • the electrolyte may comprise organic and inorganic acids. Examples of these acids are sulfuric acid, acetic acid, lactic acid, citric acid, hypophosphorus acid, sulfonic acids or combinations of these.
  • the electrolyte may also comprise bases such as sodium carbonate, ammonium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, or combinations thereof.
  • the electrolyte may comprise an acetic acid/ acetate buffer, or a citric acid / citrate buffer.
  • the electrolyte may comprise as an additional stabilizer, a ⁇ -amino acid.
  • a ⁇ -amino acid Preferably useful are, ⁇ -amino acids having a pK a - value within a range of 4 to 8, preferably within a range of 5 to 7.
  • 3-amino propionic acid ( ⁇ -alanin), 3-aminobutyric acid, 3-amino-4-methyI valeric acid and 2- aminoethane-sulfonic acid (Taurin) are useful as additional stabilizers.
  • the ⁇ -amino acid may be used in the inventive electrolyte within a range of 1 mg/L to 5 g L, preferably 100 mg/L to 2 g/L, and even more preferred 200 mg L to 1.5 g/L.
  • the electrolyte of the invention may comprise an organic stabilizer comprising an organic molecule, which is the condensation product (adduct) of at least one ⁇ .-amino acid and at least one carboxyl component. This may be introduced into the aqueous medium as the free carboxylic acid or a salt thereof.
  • the condensation product of the ⁇ -amino acid (e.g. ⁇ - alanine) and a carboxylic functional group derived from the carboxylic acid or its salt, is a ⁇ - amide.
  • the condensation product is a monomeric, oligomeric and/or polymeric form, i.e., as the N-terminal amide of a ⁇ -amino acid monomer, dimer, trimer, oligopeptide or polypeptide.
  • the condensation product of the ⁇ -amino acid can be present in the inventive electrolyte within a range of 1 mg L to 5 g/L, preferably 100 mg/L to 2 g L, and even more preferred 200 mg/L to 1.5 g/L.
  • a pre mixture of a ⁇ -amino acid in the inventive electrolyte, e.g. ⁇ .- alanine, with a carboxylic acid, e.g. lactic acid, glycine, or malic acid increases the stabilizing effect and can be beneficially used as a second stabilizer. It has been discovered that the carboxylic acid reacts with ⁇ -amino acids to form amide structures, which is deemed to be the reason for the enhanced stabilizing effect.
  • the carboxylic acid may be a compound selected from the group consisting of acrylic acids, aromatic carboxylic acids, fatty acids, aliphatic carboxylic acids, keto acids, dicarboxylic acids, tricarboxylic acids, straight chain carboxylic acids, heterocyclic carboxylic acids, saturated carboxylic acids, unsaturated carboxylic acids, and alpha-hydroxy acids. It is also possible to use other organic compounds having a carboxylic functional group. In particular, the salts of carboxylic acids (carboxylate anion -RC0 2 ⁇ ) can be used.
  • the electrolyte according to this invention may additionally comprise an inorganic stabilizer, preferably antimony.
  • an inorganic stabilizer can be present in a concentration of between 0.05 mg/L and 0.5 g/L, preferably between 0.5 mg/L and 0.1 g L.
  • the electrolyte may comprise three different stabilizers, one being a phosphine according to the general Formula I (e.g. PTA), a second one being a ⁇ -amino acid, and a third one being an inorganic stabilizer (e.g. antimony).
  • a phosphine according to the general Formula I e.g. PTA
  • a second one being a ⁇ -amino acid
  • an inorganic stabilizer e.g. antimony
  • the inventive electrolyte deposits a metal layer on a surface of a substrate, wherein the phosphorous content of the metal layer is 2-6%, 6-10% or >10.5%.
  • the amount of phosphorous in the deposit has a considerable effect on the properties of the metal layer.
  • a high phosphorous content of the metal layer leads to improved properties, for example improved corrosion resistance.
  • a lower phosphorous content in the metal layer has, for example, improved hardness.
  • a further property of a metal layer, according to the present invention is that it is very passive. Another further advantage is that the metal layers have good residual compressive stress.
  • the electrolyte may comprise an alkali metal halogenide and/or an alkali metal halogenate, i.e. a salt of an alkali metal with a halogen or a conjugated base of a halogen acid, wherein the halogen has an oxidation state of +5.
  • Such halogen and/or halogen oxygen compounds may be present in the inventive electrolyte in a concentration of between > 0.05 g L and ⁇ 5 g L, preferably between > 0.1 g L and ⁇ 2 g L. While not being bound to this theory, it is assumed that these compounds act as thermal stabilizers, by which deposition of nickel on the heating elements or areas of local overheating is avoided.
  • alkali metal halogenides and/or an alkali metal halogenates are potassium iodite, potassium iodate, sodium iodite, sodium iodate, potassium chloride, potassium chlorate, sodium bromide, lithium chloride, lithium iodate, lithium chlorate, or mixtures thereof.
  • the inventive method for the electroless deposition of a metal layer on a substrate comprises the steps of: contacting the substrate to be plated with an electrolyte comprising: a metal ion source for the metal to be deposited, a reducing agent, a complexing agent, an accelerator, and a stabilizer; characterized in that the electrolyte comprises phosphaadamantane, as a stabilizer according to the general Formula I:
  • the substrate is contacted with the electrolyte at a temperature within the range of between >20 °C and ⁇ 100 °C, preferably between >25 °C and ⁇ 95 °C, e.g. between >70 °C and ⁇ 91 °C.
  • the substrate is contacted with the electrolyte for a time between > Is and ⁇ 480 min, preferably between > 10s and ⁇ 240 min.
  • the electrolyte of the invention contains ions of at least one metal selected from the group consisting of nickel, copper, cobalt, boron, silver, palladium and gold.
  • Sources for these metal ions are salts of the metals, which are present in the electrolyte as metal chlorides, metai sulfates, metal acetates, metal nitrates, metal propionates, metal formates, metal oxalates, metal citrates, and metal ascorbinates of the respective metals.
  • the metal ions are present in the electrolyte in a concentration between 0.01 mol/L and 0.5 moI L, preferably between 0.02 mol/L and 0.2 mol/L.
  • the electrolyte comprises at least one reducing agent from the group consisting of sodium hypophosphite, formaldehyde, dimethylaminoborane, aminoborane, other organic boranes, or mixtures thereof.
  • the reducing agent may be present in the electrolyte in a concentration of between 0.08 mol L and 0.5 mol/L, preferably, 0.1 mol L and 0.3 mol/L.
  • the electrolyte comprises a complexing agent that is selected from the group consisting of 2-hydroxy propionic acid, propanedioic acid (malonic acid), EDTA, amino acetic acid, and mixtures thereof.
  • the complexing agent is present in the electrolyte in a concentration of between 0.05 mol/L and 0.5 mol/L, preferably between 0.2 mol/L and 0.4mol/L.
  • the electrolyte comprises an accelerator selected from the group consisting of saccharin, hydantoin, rhodanine, or carbamide and its derivates.
  • the accelerator is present in the electrolyte in a concentration of between 0.05 mmol/L and 0.1 mol L, preferably, between 5 mmol/L and 0.25 mol/L.
  • the electrolyte comprises at least a phosphaadamantane, as a stabilizer, according to general Formula I:
  • the electrolyte of the invention contains ions of at least one metal selected from the group consisting of nickel, copper, cobalt, boron, silver, palladium and gold.
  • Sources for these metal ions are salts of the metals, which are present in the electrolyte as metal chlorides, metal sulfates, metal acetates, metal nitrates, metal propionates, metal formates, metal oxalates, metal citrates, and metal ascorbinates of the respective metals.
  • the metal ions are present in the electrolyte in a concentration between 0.01 mol/L and 0.5 mol/L, preferably between 0.02 mol/L and 0.2 mol/L.
  • the electrolyte comprises at least one reducing agent from the group consisting of sodium hypophosphite, formaldehyde, dimethylaminoborane, aminoborane, other organic boranes, or mixtures thereof.
  • the reducing agent may be present in the electrolyte in a concentration of between 0.08 mol/L and 0.5 mol L, preferably, 0.1 mol L and 0.3 mol/L.
  • the electrolyte comprises a complexing agent that is selected from the group consisting of 2-hydroxy propionic acid, propanedioic acid (malonic acid), EDTA, amino acetic acid, and mixtures thereof.
  • the complexing agent is present in the electrolyte in a concentration of between 0.05 mol/L and 0.5 mol/L, preferably between 0.2 mol/L and 0.4mol L.
  • the electrolyte comprises an accelerator selected from the group consisting of saccharin, hydantoin, rhodanine, or carbamide and its derivates.
  • the accelerator is present in the electrolyte in a concentration of between 0.05 mmol/L and 0.1 mol L, preferably, between 5 mmol/L and 0.25 mol/L.
  • the electrolyte comprises at least a phosphaadamantane, as a stabilizer, according to general Formula I:
  • Forma I wherein the hydrogen atoms on carbon atoms 1 to 6 may independently from each other be substituted by a moiety of the group consisting of F, CI, Br, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alcohol group having 1 to 6 carbon atoms.
  • the phosphaadamantane is present within a range of >0.05 mg L and ⁇ 100 mg/L, preferably between >0.1 mg L and ⁇ 25 mg L, most preferably between >0.5 mg/L and ⁇ 10 mg/L.
  • the electrolyte comprises at least one ⁇ -amino acid having a pK a -value within a range of 4 to 8, preferably within a range of 5 to 7.
  • the electrolyte comprises at least one ⁇ -amino acid of the group consisting of 3- amino propionic acid ( ⁇ -alanin), 3-aminobutyric acid, 3-amino-4-methyl valeric acid and 2- aminoethane-sulfonic acid (Taurin).
  • the ⁇ -amino acid is present in this embodiment of the inventive electrolyte within a range of 1 mg L to 2 g/1, preferably 100 mg/L to 1 g/1, and even more preferred 200 mg/L to 400 mg L.
  • the electrolyte of the invention contains ions of at least one metal selected from the group consisting of nickel, copper, cobalt, boron, silver, palladium and gold.
  • Sources for these metal ions are salts of the metals, which are present in the electrolyte as metal chlorides, metal sulfates, metal acetates, metal nitrates, metal propionates, metal formates, metal oxalates, metal citrates, and metal ascorbinates of the respective metals.
  • the metal ions are present in the electrolyte in a concentration between 0.01 mol/L and 0.5 mol/L, preferably between 0.02 mol/L and 0.2 mol L.
  • the electrolyte comprises at least one reducing agent from the group consisting of sodium hypophosphite, formaldehyde, dim ethyl aminoborane, aminoborane, other organic boranes, or mixtures thereof.
  • the reducing agent may be present in the electrolyte in a concentration of between 0.08 mol L and 0.5 mol/L, preferably, 0.1 mol/L and 0.3 mol/L.
  • the electrolyte comprises a complexing agent that is selected from the group consisting of 2-hydroxy propionic acid, propanedioic acid (malonic acid), EDTA, amino acetic acid, and mixtures thereof.
  • the complexing agent is present in the electrolyte in a concentration of between 0.05 mol/L and 0.5 mol L, preferably between 0.2 mol/L and 0.4mol/L.
  • the electrolyte comprises an accelerator selected from the group consisting of saccharin, hydantoin, rhodanine, or carbamide and its derivates.
  • the accelerator is present in the electrolyte in a concentration of between 0.05 mmol/L and 0.1 mol L, preferably, between 5 mmol L and 0.25 mol/L.
  • the electrolyte comprises at least a phosphaadamantane, as a stabilizer, according to general Formula I:
  • Sources for these metal ions are salts of the metals, which are present in the electrolyte as metal chlorides, metal sulfates, metal acetates, metal nitrates, metal propionates, metal formates, metal oxalates, metal citrates, and metal ascorbinates of the respective metals.
  • the metal ions are present in the electrolyte in a concentration between 0.01 mol/L and 0.5 mol/L, preferably between 0.02 mol L and 0.2 mol/L.
  • the electrolyte comprises at least one reducing agent from the group consisting of sodium hypophosphite, formaldehyde, dimethyl aminoborane, aminoborane, other organic boranes, or mixtures thereof.
  • the reducing agent may be present in the electrolyte in a concentration of between 0.08 mol L and 0.5 mol L, preferably, 0.1 mol/L and 0.3 mol/L.
  • the electrolyte comprises a complexing agent that is selected from the group consisting of 2-hydroxy propionic acid, propanedioic acid (malonic acid), EDTA, amino acetic acid, and mixtures thereof.
  • the complexing agent is present in the electrolyte in a concentration of between 0.05 mol L and 0.5 mol L, preferably between 0.2 mol/L and 0.4mol L.
  • the electrolyte comprises an accelerator selected from the group consisting of saccharin, hydantoin, rhodanine, or carbamide and its derivates.
  • the accelerator is present in the electrolyte in a concentration of between 0.05 mmol/L and 0.1 mol/L, preferably, between 5 mmol/L and 0.25 mol/L.
  • the electrolyte comprises at least a phosphaadamantane, as a stabilizer, according to general Formula I:
  • the electrolyte comprises at least one ⁇ -amino acid having a p a -value within a range of 4 to 8, preferably within a range of 5 to 7.
  • the electrolyte comprises at least one ⁇ -amino acid selected from the group consisting of 3-amino propionic acid ( ⁇ -alanin), 3-aminobutyric acid, 3-amino-4-methyl valeric acid and 2-aminoethane-sulfonic acid (Taurin).
  • the ⁇ -amino acid is present in this embodiment of the inventive electrolyte within a range of 1 mg L to 2 g/l, preferably from 100 mg L to 1 g/l, and even more preferred from 200 mg L to 400 mg/L.
  • the electrolyte comprises antimony as an inorganic stabilizer.
  • Antimony is present in a concentration of between 0.05 mg/L and 0.5 g l, preferably between 0.5 mg L and 0.1 g/l.
  • the antimony is added as a water soluble salt, preferably as a chloride, sulfate, acetate, nitrate, propionate, formate, oxalate, citrate, ascorbinate, or a mixture of these.
  • the electrolyte contains a carboxyl component.
  • the electrolyte formulation may contain a monocarboxylic, dicarbox lic, or tricarboxylic organic acid.
  • This component can comprise an aryl carboxylic acid, an aliphatic carboxylic acid, or a heterocyclic carboxylic acid.
  • suitable aliphatic carboxylic acids are fatty acids, a-hydroxycarboxylic acids, including a-hydroxy dicarboxylic acids, particularly Ci to C 4 , ⁇ - ⁇ -unsaturated carboxylic acids, particularly Ci to C 4 and especially acrylic.
  • the inventive the electrolyte is essentially free of inorganic stabilizers, lead, bismuth, zinc and/or tin.
  • the electrolyte composition is also essentially free of cyanides, selenium compounds and sulfur compounds comprising sulfur in an oxidation state between -2 and +5. Essentially free means that these compounds cannot be detected by common and readily available analytical techniques used for electrolyte analysis.
  • the electrolyte according to the present invention comprises:
  • pH is in a range of pH 4 to pH 7.
  • a substrate (steel sheet) was brought into contact with an electrolyte, at a temperature between 80 °C and 94 °C, comprising:
  • the electrolyte according to the present invention comprises:
  • pH is in a range of pH 4.0 to pH 5 at a temperature between 80 °C and 94°C.
  • a steel panel was plated in an electrolyte with the above mentioned composition.
  • a glossy nickel deposit was plated from this electrolyte with a plating speed of 8 - 10 ⁇ / ⁇ , with a composition of 88 - 89 % by weight nickel, and 10 - 1 1.5 % by weight of phosphorous.
  • the electrolyte according to the present invention comprises:
  • An ABS plaque was plated in an electrolyte with the above mentioned composition.
  • the ABS plaque was pre-treated in a standard POP (plating-on-plastic) pretreatment cycle before plating.
  • a glossy nickel deposit was plated from this electrolyte with a plating speed of 8 - 10 ⁇ / ⁇ , with a composition of 90 - 91 % by weight nickel, and 9 - 10 % by weight of phosphorous.

Landscapes

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

Abstract

La présente invention concerne l'utilisation de phospha-adamantanes solubles dans l'eau et stables à l'air en tant que stabilisants dans des électrolytes de dépôt autocatalytique de métal. Un électrolyte et un procédé pour le dépôt autocatalytique de métaux sont décrits. Les couches de métal plaquées peuvent comprendre du nickel, du cuivre, du cobalt, du bore, de l'argent, du palladium ou de l'or, ainsi que des alliages comprenant au moins l'un des métaux mentionnés ci-dessus en tant que métal d'alliage. La présente invention concerne en outre un stabilisant organique pour des procédés de placage autocatalytique, et un électrolyte pour le dépôt autocatalytique d'une couche métallique sur un substrat, l'électrolyte comprenant une source d'ions métalliques du métal à déposer, un agent réducteur, un agent complexant, un stabilisant et, de préférence, un accélérateur. L'invention concerne également un procédé pour le dépôt autocatalytique d'une couche métallique sur une surface à partir d'un électrolyte selon l'invention.
PCT/US2016/055655 2015-10-13 2016-10-06 Phospha-adamantanes solubles dans l'eau et stables à l'air en tant que stabilisants pour le dépôt autocatalytique de métal Ceased WO2017066069A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201680059667.6A CN108495952A (zh) 2015-10-13 2016-10-06 作为无电金属沉积用稳定剂的水溶性且空气稳定的磷杂金刚烷
US15/765,637 US20190085461A1 (en) 2015-10-13 2016-10-06 Water soluble and air stable phosphaadamantanes as stabilizers for electroless metal deposition
KR1020187013527A KR20180089398A (ko) 2015-10-13 2016-10-06 무전해 금속 도금용 안정제로서의 수용성이고 공기 안정성인 포스파아다만탄

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB15189465.6 2015-10-13
EP15189465.6 2015-10-13
EP15189465.6A EP3156517B1 (fr) 2015-10-13 2015-10-13 Utilisation de phosphaadamantanes solubles dans l'eau et stables dans l'air en tant qu'agents de stabilisation dans des électrolytes pour dépôt de métal auto-catalytique

Publications (2)

Publication Number Publication Date
WO2017066069A1 true WO2017066069A1 (fr) 2017-04-20
WO2017066069A8 WO2017066069A8 (fr) 2018-07-19

Family

ID=54324851

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2016/055655 Ceased WO2017066069A1 (fr) 2015-10-13 2016-10-06 Phospha-adamantanes solubles dans l'eau et stables à l'air en tant que stabilisants pour le dépôt autocatalytique de métal

Country Status (7)

Country Link
US (1) US20190085461A1 (fr)
EP (1) EP3156517B1 (fr)
KR (1) KR20180089398A (fr)
CN (1) CN108495952A (fr)
ES (1) ES2712858T3 (fr)
TW (1) TW201718938A (fr)
WO (1) WO2017066069A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109457238A (zh) * 2018-08-30 2019-03-12 上海昕沐化学科技有限公司 高速稳定的化学镀铜液及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI646215B (zh) * 2017-11-03 2019-01-01 陳始明 無電極電鍍金屬的裝置及其方法
JP7228411B2 (ja) * 2019-03-06 2023-02-24 上村工業株式会社 無電解金めっき浴

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150167175A1 (en) * 2009-07-03 2015-06-18 Enthone Inc. Beta-amino acid comprising plating formulation

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0769572A1 (fr) 1995-06-06 1997-04-23 ENTHONE-OMI, Inc. Procédé et bain de dépÔt chimique d'un alliage nickel-cobalt-phosphore
JP3816241B2 (ja) * 1998-07-14 2006-08-30 株式会社大和化成研究所 金属を還元析出させるための水溶液
DE10015214C1 (de) * 2000-03-27 2002-03-21 Infineon Technologies Ag Verfahren zur Metallisierung eines Isolators und/oder eines Dielektrikums
DE10246453A1 (de) 2002-10-04 2004-04-15 Enthone Inc., West Haven Verfahren zur stromlosen Abscheidung von Nickel
JP2005290415A (ja) 2004-03-31 2005-10-20 Okuno Chem Ind Co Ltd 無電解銅めっき液
JP5247142B2 (ja) 2007-12-19 2013-07-24 株式会社大和化成研究所 銀めっき方法
CN101348927B (zh) 2008-09-05 2010-10-06 江南机器（集团）有限公司 无氰预镀铜溶液
GB2467163B (en) * 2009-01-26 2013-11-06 Rhodia Operations Ligands

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150167175A1 (en) * 2009-07-03 2015-06-18 Enthone Inc. Beta-amino acid comprising plating formulation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MOHR, F ET AL.: "Organometallic Gold(I) and Gold(III) Complexes Containing 1,3,5-Triaza-7-phosphaadamantane (TPA): Examples of Water-Soluble Organometallic Gold Compounds.", ORGANOMETALLICS, vol. 25, no. 3, 2006, pages 644 - 648, XP055375398 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109457238A (zh) * 2018-08-30 2019-03-12 上海昕沐化学科技有限公司 高速稳定的化学镀铜液及其制备方法

Also Published As

Publication number Publication date
EP3156517B1 (fr) 2018-12-05
ES2712858T3 (es) 2019-05-16
WO2017066069A8 (fr) 2018-07-19
TW201718938A (zh) 2017-06-01
CN108495952A (zh) 2018-09-04
KR20180089398A (ko) 2018-08-08
EP3156517A8 (fr) 2017-06-07
EP3156517A1 (fr) 2017-04-19
US20190085461A1 (en) 2019-03-21

Similar Documents

Publication Publication Date Title
EP2449148B1 (fr) Electrolyte contenant un acide bêta-aminé et procédé de dépôt d'une couche métallique
WO2013182489A2 (fr) Bain de placage pour dépôt autocatalytique de couches de nickel
EP3156517B1 (fr) Utilisation de phosphaadamantanes solubles dans l'eau et stables dans l'air en tant qu'agents de stabilisation dans des électrolytes pour dépôt de métal auto-catalytique
JP6449335B2 (ja) 水性無電解ニッケルめっき浴、及びその使用方法
TW201720955A (zh) 用於金之無電電鍍之鍍浴組合物及沉積金層之方法
EP3224388B1 (fr) Bain de placage et procédé de dépôt anélectrolytique de couches de nickel
KR20180064378A (ko) 무전해 은 도금욕 및 이를 이용하는 방법
JPH11269658A (ja) 無電解パラジウムメッキ液
KR102137300B1 (ko) 철 붕소 합금 코팅들 및 그것의 제조 방법
WO2023144003A1 (fr) Composition pour le dépôt d'un revêtement de palladium sur un substrat revêtu de cuivre activé
KR101507452B1 (ko) Pcb 제조를 위한 무전해 니켈-팔라듐-금 도금 방법
WO2017213866A1 (fr) Utilisation de composés de lanthanide solubles dans l'eau en tant que stabilisant dans des électrolytes pour le dépôt chimique de métal
US9708693B2 (en) High phosphorus electroless nickel
EP2270255A1 (fr) Electrolyte comprenant de l'acide bêta-aminé et procédé de dépôt d'une couche métallique
EP4061981A1 (fr) Bains de placage d'alliage de nickel autocatalytique, procédé de dépôt d'alliages de nickel, dépôts d'alliages de nickel et utilisations desdits dépôts d'alliages de nickel formés

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16855980

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20187013527

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1020187013527

Country of ref document: KR

122 Ep: pct application non-entry in european phase

Ref document number: 16855980

Country of ref document: EP

Kind code of ref document: A1