EP3156517B1 - 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 - Google Patents

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 Download PDF

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Publication number
EP3156517B1
EP3156517B1 EP15189465.6A EP15189465A EP3156517B1 EP 3156517 B1 EP3156517 B1 EP 3156517B1 EP 15189465 A EP15189465 A EP 15189465A EP 3156517 B1 EP3156517 B1 EP 3156517B1
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Prior art keywords
metal
group
electrolyte
acid
stabilizer
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EP15189465.6A
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German (de)
English (en)
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EP3156517A8 (fr
EP3156517A1 (fr
Inventor
Stefan Schäfer
Katrin SÖNTGERATH
Marlies Kleinfeld
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MacDermid Enthone Inc
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MacDermid Enthone Inc
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Priority to ES15189465T priority Critical patent/ES2712858T3/es
Application filed by MacDermid Enthone Inc filed Critical MacDermid Enthone Inc
Priority to EP15189465.6A priority patent/EP3156517B1/fr
Priority to CN201680059667.6A priority patent/CN108495952A/zh
Priority to PCT/US2016/055655 priority patent/WO2017066069A1/fr
Priority to US15/765,637 priority patent/US20190085461A1/en
Priority to KR1020187013527A priority patent/KR20180089398A/ko
Priority to TW105132884A priority patent/TW201718938A/zh
Publication of EP3156517A1 publication Critical patent/EP3156517A1/fr
Publication of EP3156517A8 publication Critical patent/EP3156517A8/fr
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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 stabilizer in electrolytes for electroless metal deposition, an electrolyte as well as a method for the electroless deposition of metals, particularly layers of nickel, copper, cobalt, boron, silver, palladium or gold, as well as layers of alloys comprising at least one of the aforementioned metals as alloying metal.
  • the present invention further relates to an organic stabilizer for electroless plating processes, and an 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, a stabilizer and preferably an accelerator, as well as a method for the electroless deposition of a metal layer on a surface from an electrolyte according to the invention.
  • electroless plating methods have long been known from the state of the art.
  • electroless plating also known as chemical plating
  • the coating of almost every metal and a huge number of non-conductive substrate surfaces is possible.
  • the electroless deposited metal layers differ from the galvanically deposited metal layers, i.e. those layers deposited by the use of an external current, in physical as well as mechanical aspects.
  • metal alloy layers with non-metal elements like for example cobalt/phosphor, nickel/phosphor, nickel/boron or boron carbide layers are deposited by means of electroless deposition methods.
  • electroless deposited layers in many cases differ also 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 methods are also used for the coating of other non-conductive substrates, like for example plastic substrates, to render the surface of such substrates conductive and/or to change the appearance of the substrate in aesthetic respect.
  • the material properties of the coated substrate can be improved or amended.
  • 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.
  • a reducing agent commonly used in the field of electroless deposition of metals on substrate surfaces is sodium hypophosphite. However, also other reducing agents are used in dependency of the metals to be deposited.
  • U.S. Pat. No. 6,146,702 discloses an electroless nickel cobalt phosphorus composition and plating process. The process is provided for enhancing the wear resistance of aluminium and other materials by depositing on the substrate a nickel, cobalt, phosphorus alloy coating 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, for example, an electrolyte for the electroless deposition of nickel layers having internal compressive stress.
  • the electrolyte disclosed in this 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 2009-149965A 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, and can form the silver-plated film having 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 subsequently to the step (B), (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 a 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, and 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: wherein R1, R2 and R3, are each the same or different, represent a monovalent aliphatic hydrocarbon group which may have a substituent group, an aryl group which may have a substituent group, or a heterocyclic group which may have a substituent group.
  • CN 101348927A discloses a cyanogen-free preplated copper solution.
  • the solution adopts a nontoxic organic phosphine compound to replace cyanide as a complexing agent for the preplated copper, and 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 consists of (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 ethoxy
  • EP1138803A2 Another way of achieving plating on plastics is for instance disclosed in EP1138803A2 .
  • This document disclose a process for metallizing of at least one insulating layer of an electronic or micromechanical element comprises applying at least one of the insulating layers to the substrate and activating by treating with an activator; applying the further insulating layer and structuring; and metallizing the first insulating layer.
  • 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 for reducing the metal ions, an accelerator, and a stabilizer, characterized in that the electrolyte comprises as stabilizer a phosphaadamantane according to the general formula I wherein the hydrogen atoms on carbon atom 1 to 6 may independently from each other substituted by a moiety of the group consisting of F, Cl, 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 atom.
  • phosphaadamantanes according to the general formula I are capable to replace heavy metal stabilizers, cyanides, selenium compounds as well as sulfur compounds comprising sulfur in an oxidation state between -2 and +5 in electrolytes for the electroless deposition of metal layers, totally.
  • 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. So the wild deposition of the metals can be avoided. Additionally, also the foreign ions comprised in the electrolyte which are responsible for the wild deposition, too, are inactivated by the used such phosphaadamantanes.
  • a further benefit of the inventive electrolyte is that an effect known as edge weakness can be avoided.
  • edge weakness When using electrolytes for the electroless deposition of metal layers which comprise heavy metal ions as stabilizers 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 which significantly increases the overall outline accuracy of the plating especially when plating large substrates.
  • phosphaadamantanes according to general formula I as stabilizers result in an improved deposition and a significant reduction of discard.
  • 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 equipment, occurs. By this the need for maintenance is significantly reduced which in turn results in a notable economic benefit to the plating shops due to less down time.
  • An electrolytic bath, with a single class of metal, containing the stabilizer of the present invention leads to deposited metal layers, having properties like an amorphous metal. These properties are, for example, that these layers have no edge weakness effect; they are very passive; have a good resistance against corrosion; wear-resistance; and good compressive stress properties.
  • the stabilizer according to the present invention is metal free; provides a deposit having significantly better corrosion resistance including excellent resistance vs. nitric acid; is environmental friendly (non-toxic additive); has a higher phosphorus concentration at given pH level; and lower plating temperatures can be used to achieve the same plating speed and phosphorus content.
  • 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 quit sensitive to foreign metals and therefore required intensive rinse steps after the activation, the inventive plating electrolytes does not show any significant deterioration even at Pd-concentrations » 2mg/L.
  • phosphaadamantanes according to general formula I having no hydrogene substituted are found to be very effective as stabilizers in electroless plating electrolytes.
  • 1,3,5-Triaza-7-phosphatricyclo[3.3.1.1]decane (PTA) is a preferred embodiment of the phosphaadamantanes according to general formula I.
  • PTA has a sufficiently high solubility in aqueous systems and has a high oxidations 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.
  • At least one reducing agent of the group consisting of sodium hypophosphite, formaldehyde, dimethylaminoborane, aminoborane, or other organic boranes can be comprised.
  • the reducing agent may be comprised 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/l, and even more preferably with a concentration of 12 to 30 g/l.
  • a metal compound of the group consisting metal chloride, metal sulfate, metal acetate, metal nitrate, metal propionate, metal formiate, metal oxalate, metal citrate, and metal ascorbinate can be used, i.e., the source of cations of the metal to be deposited may comprise the counter anion of any of such salts.
  • the metal compounds having volatile ions like for example metal acetate, metal nitrate, metal propionate, and metal formiate are preferred since the volatile character of the anion those anions leak out from the electrolyte in gaseous form which enables to reduce the amount of anions in the electrolyte.
  • Volatile ions in the sense of this invention are ions which form together with according counter ion moieties which are volatile at the temperature the electrolyte is commonly used at.
  • An example for such volatile ions 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 of the group consisting of 2-hydroxy propionic acid, propanedioic acid (malonic acid), EDTA, and amino acetic acid.
  • the complexing agent may be comprised in the electrolyte in a concentration of between 0.05 mol/L and 0.5 mol/L, preferably 0.2 mol/L and 0.4 mol/L.
  • the inventive electrolyte comprises an accelerator, which may preferably comprise a compound of the group consisting of saccharin, hydantoin, rhodanine, or carbamide and its derivates.
  • the accelerator may be comprised in the electrolyte in a concentration of between 0.05 mmol/L and 0.1 mol/L, preferably 0.005 mol/L and 0.025mol/L.
  • the inventive electrolyte may comprise a metal of the group consisting of nickel, copper, cobalt, boron, silver, palladium and gold.
  • the metal to be deposited also alloys like for example nickel/cobalt-alloys, nickel/phosphor-alloys, cobalt/phosphor-alloys nickel/boron or the like can be deposited.
  • the deposition of nickel/PTFE-layers or nickel/boron carbide/graphite-layers from dispersion bathes is possible by 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. Hence, it is preferred that the inventive electrolyte is slightly acidic.
  • the pH-value of the electrolyte it may comprise pH adjusting compounds, like e.g. acids, bases, and/or buffers.
  • organic and inorganic acids may be comprised in the electrolyte, e.g. sulfuric acid, acetic acid, lactic acid, citric acid, hypophosphorus acid, sulfonic acids or combinations of these.
  • bases e.g. sodium carbonate, ammonium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, or combination of these may be comprised in the electrolyte.
  • the electrolyte may comprise e.g. an acetic acid/ acetate buffer, or a citric acid / citrate buffer.
  • the electrolyte may comprise as an additional stabilizer a ⁇ -amino acid.
  • ⁇ -amino acids having a pK a -value within a range of 4 to 8, preferably within a range of 5 to 7 seems to be suitable in this respect.
  • 3-amino propionic acid ( ⁇ -alanin), 3-aminobutyric acid, 3-amino-4-methyl valeric acid and 2-aminoethane-sulfonic acid (Taurin) are usable as additional stabilizers.
  • the ⁇ -amino acid may be comprised 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 formulation of the invention may comprises an organic stabilizer for electroless plating processes comprising an organic molecule which is the condensation product (adduct) of at least one ⁇ .-amino acid and at least one carboxyl component which may be introduced into the aqueous medium as, e.g., the free carboxylic acid or a salt thereof.
  • the condensation product of the ⁇ -amino acid e.g. ⁇ -alanine
  • a carboxylic functional group as derived for the carboxylic acid or its salt
  • the condensation product is present in a monomeric, oligomeric and/or polymeric form, i.e., as the N-terminal amide of a ⁇ -amino acid monomer, dimer, trimer, oligopeptide and polypeptide.
  • the condensation product of the ⁇ -amino acid may be comprised 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, like e.g. ⁇ .-alanine, with a carboxylic acid, like e.g. lactic acid, glycine, or malic acid increases the stabilizing effect and can those beneficially be used as a second stabilizer in sense of the invention. 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 of 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 -RCO 2 - ) can be used.
  • the electrolyte according to this invention may additionally comprise an inorganic stabilizer, preferably antimony.
  • an inorganic stabilizer may be comprised in a concentration of between 0.05 mg/L and 0.5 g/L, preferably 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, like e.g. PTA, a second one being a ⁇ -amino acid, and a third one being an inorganic stabilizer, like e.g. antimony.
  • a phosphine according to the general formula I like e.g. PTA
  • a second one being a ⁇ -amino acid
  • an inorganic stabilizer like e.g. antimony.
  • a metal layer on a surface of a substrate is deposited, wherein the phosphorous content of the metal layer is 2-6%, 6-10% or >10.5%.
  • the amount of phosphorous 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 and a lower phosphorous content for example improved hardness of the metal layer.
  • a further property of a metal layer according to the present invention is that it is very passive.
  • a further advantage of the metal layers according to the present invention is the good residual compressive stress.
  • a stabilizer according to the present invention it is possible to yield metal layers having various phosphorus content: low phosphorus, 3-5% (crystalline); middle phosphorus, 5-7 (9) % (partially crystalline); high phosphorus, >10% (amorphous).
  • 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.
  • halogen and/or halogen oxygen compounds may be comprised 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 addition deposition of nickel on the heating elements or areas of local overheating is avoid.
  • Example for alkali metal halogenides and/or an alkali metal halogenates are, e.g. potassium iodite, potassium iodate, sodium iodite, sodium iodate, potassium chloride, potassium chlorate, sodium bromide, lithium chloride, lithium iodate or lithium chlorate.
  • the object of the invention is solved by a method for the electroless deposition of a metal layer on a substrate comprising 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 for reducing the metal ions, a complexing agent, an accelerator, and a stabilizer, characterized in that the electrolyte comprises as stabilizer a phosphaadamantane according to the general formula I wherein the hydrogen atoms on carbon atom 1 to 6 may independently from each other substituted by a moiety of the group consisting of F, Cl, 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 atom.
  • 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 ⁇ 1s and ⁇ 480 min, preferably between ⁇ 10s and ⁇ 240 min.
  • the formulation of the invention contains ions of at least one metal of the group consisting of nickel, copper, cobalt, boron, silver, palladium and gold.
  • salts of the metals are comprised in the electrolyte, e.g. metal chloride, metal sulfate, metal acetate, metal nitrate, metal propionate, metal formiate, metal oxalate, metal citrate, and metal ascorbinate of the respective metals.
  • the metal ions are comprised 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 of the group consisting of sodium hypophosphite, formaldehyde, dimethylaminoborane, aminoborane, or other organic boranes.
  • the reducing agent may be comprised 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 compound of the group consisting of 2-hydroxy propionic acid, propanedioic acid (malonic acid), EDTA, and amino acetic acid.
  • the complexing agent is comprised in the electrolyte in a concentration of between 0.05 mol/L and 0.5 mol/L, preferably 0.2 mol/L and 0.4mol/L.
  • the electrolyte comprises a compound of the group consisting of saccharin, hydantoin, rhodanine, or carbamide and its derivates.
  • the accelerator is comprised in the electrolyte in a concentration of between 0.05 mmol/L and 0.1 mol/L, preferably, 5 mmol/L and 0.25 mol/L.
  • the electrolyte comprises at least a phosphaadamantane according to the general formula I wherein the hydrogen atoms on carbon atom 1 to 6 may independently from each other substituted by a moiety of the group consisting of F, Cl, 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 atom.
  • Said phosphadamantne is comprised 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 use of a phosphaadamantane according to general formula I as stabilizer results in a more even deposition having less nodules.
  • the formulation of the invention contains ions of at least one metal of the group consisting of nickel, copper, cobalt, boron, silver, palladium and gold.
  • salts of the metals are comprised in the electrolyte, e.g. metal chloride, metal sulfate, metal acetate, metal nitrate, metal propionate, metal formiate, metal oxalate, metal citrate, and metal ascorbinate of the respective metals.
  • the metal ions are comprised in the electrolyte in a concentration between 0.01 mol/L and 2 mol/L, preferably between 0.02 mol/L and 0.5 mol/L.
  • the electrolyte comprises at least one reducing agent of the group consisting of sodium hypophosphite, formaldehyde, dimethylaminoborane, aminoborane, or other organic boranes.
  • the reducing agent may be comprised 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 compound of the group consisting of 2-hydroxy propionic acid, propanedioic acid (malonic acid), EDTA, and amino acetic acid.
  • the complexing agent is comprised in the electrolyte in a concentration of between 0.05 mol/L and 0.5 mol/L, preferably 0.2 mol/L and 0.4mol/L.
  • the electrolyte comprises a compound of the group consisting of saccharin, hydantoin, rhodanine, or carbamide and its derivates.
  • the accelerator is comprised in the electrolyte in a concentration of between 0.05 mmol/L and 0.1 mol/L, preferably, 5 mmol/L and 0.25 mol/L.
  • the electrolyte comprises at least a phosphaadamantane according to the general formula I wherein the hydrogen atoms on carbon atom 1 to 6 may independently from each other substituted by a moiety of the group consisting of F, Cl, 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 atom.
  • Said phosphadamantne is comprised 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 comprised in this embodiment of the inventive electrolyte within a range of 1 mg/L to 2 g/l, preferably 100 mg/L to 1 g/l, and even more preferred 200 mg/L to 400 mg/L.
  • the use of a combination of two stabilizers beneficially results in a further improvement of the deposition by reduction of nodules.
  • the formulation of the invention contains ions of at least one metal of the group consisting of nickel, copper, cobalt, boron, silver, palladium and gold.
  • salts of the metals are comprised in the electrolyte, e.g. metal chloride, metal sulfate, metal acetate, metal nitrate, metal propionate, metal formiate, metal oxalate, metal citrate, and metal ascorbinate of the respective metals.
  • the metal ions are comprised 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 of the group consisting of sodium hypophosphite, formaldehyde, dimethylaminoborane, aminoborane, or other organic boranes.
  • the reducing agent may be comprised 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 compound of the group consisting of 2-hydroxy propionic acid, propanedioic acid (malonic acid), EDTA, and amino acetic acid.
  • the complexing agent is comprised in the electrolyte in a concentration of between 0.05 mol/L and 0.5 mol/L, preferably 0.2 mol/L and 0.4mol/L.
  • the electrolyte comprises a compound of the group consisting of saccharin, hydantoin, rhodanine, or carbamide and its derivates.
  • the accelerator is comprised in the electrolyte in a concentration of between 0.05 mmol/L and 0.1 mol/L, preferably, 5 mmol/L and 0.25 mol/L.
  • the electrolyte comprises at least a phosphaadamantane according to the general formula I wherein the hydrogen atoms on carbon atom 1 to 6 may independently from each other substituted by a moiety of the group consisting of F, Cl, 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 atom.
  • Said phosphadamantne is comprised 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 antimony as an inorganic stabilizer.
  • Antimony is comprised in a concentration of between 0.05 mg/L and 0.5 g/l, preferably 0.5 mg/L and 0.1 g/l.
  • the antimony is added as water soluble salt, preferably as chloride, sulfate, acetate, nitrate, propionate, formiate, oxalate, citrate, ascorbinate, or a mixture of these.
  • the formulation of the invention contains ions of at least one metal of the group consisting of nickel, copper, cobalt, boron, silver, and gold.
  • salts of the metals are comprised in the electrolyte, e.g. metal chloride, metal sulfate, metal acetate, metal nitrate, metal propionate, metal formiate, metal oxalate, metal citrate, and metal ascorbinate of the respective metals.
  • the metal ions are comprised in the electrolyte in a concentration between 0.01 mol/L and 2 mol/L, preferably between 0.02 mol/L and 0.5 mol/L.
  • the electrolyte comprises at least one reducing agent of the group consisting of sodium hypophosphite, formaldehyde, dimethylaminoborane, aminoborane, or other organic boranes.
  • the reducing agent may be comprised 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 compound of the group consisting of 2-hydroxy propionic acid, propanedioic acid (malonic acid), EDTA, and amino acetic acid.
  • the complexing agent is comprised in the electrolyte in a concentration of between 0.05 mol/L and 0.5 mol/L, preferably 0.2 mol/L and 0.4mol/L.
  • the electrolyte comprises a compound of the group consisting of saccharin, hydantoin, rhodanine, or carbamide and its derivates.
  • the accelerator is comprised in the electrolyte in a concentration of between 0.05 mmol/L and 0.1 mol/L, preferably, 5 mmol/L and 0.25 mol/L.
  • the electrolyte comprises at least a phosphaadamantane according to the general formula I wherein the hydrogen atoms on carbon atom 1 to 6 may independently from each other substituted by a moiety of the group consisting of F, Cl, 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 atom.
  • Said phosphadamantne is comprised 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 comprised in this embodiment of the inventive electrolyte within a range of 1 mg/L to 2 g/l, preferably 100 mg/L to 1 g/l, and even more preferred 200 mg/L to 400 mg/L.
  • the electrolyte comprises antimony as an inorganic stabilizer.
  • Antimony is comprised in a concentration of between 0.05 mg/L and 0.5 g/l, preferably 0.5 mg/L and 0.1 g/l.
  • the antimony is added as water soluble salt, preferably as chloride, sulfate, acetate, nitrate, propionate, formiate, oxalate, citrate, ascorbinate, or a mixture of these.
  • the formulation of the invention contains a carboxyl component.
  • the electrolyte formulation may contain a monocarboxylic, dicarboxylic, 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, ⁇ -hydroxycarboxylic acids, including ⁇ -hydroxy dicarboxylic acids particularly C 1 to C 4 , ⁇ - ⁇ -unsaturated carboxylic acids, particularly C 1 to C 4 and especially acrylic.
  • the electrolyte comprises:
  • a substrate (steel sheet) was brought into contact with an electrolyte comprising:

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Claims (14)

  1. Composition aqueuse d'électrolyte destinée au dépôt sans électrode d'une couche de métal sur un substrat, comprenant une source d'ions de métal pour le métal devant être déposé, un agent de réduction pour réduire les ions de métal, un agent complexant, un accélérateur et un stabilisant, caractérisée en ce que l'électrolyte comprend un phospho adamantane en tant que stabilisant selon la formule générale I
    Figure imgb0012
     où les atomes d'hydrogène sur les atomes de carbone 1 à 6 peuvent être, indépendamment les uns des autres, substitués par une entité du groupe constitué de F, Cl, Br, d'un groupement alkyle ayant de 1 à 6 atomes de carbone, d'un groupement alcoxy ayant de 1 à 6 atomes de carbone et d'un groupement alcool ayant de 1 à 6 atomes de carbone.
  2. Composition aqueuse d'électrolyte selon la revendication 1, dans laquelle l'électrolyte comprend le phospho adamantane à une concentration entre ≥ 0,05 mg/l et ≤ 100 mg/l, de préférence entre ≥ 0,1 mg/l et ≤ 25 mg/l, plus préférentiellement entre ≥ 0,5 mg/l et ≤ 10 mg/l.
  3. Composition aqueuse d'électrolyte selon l'une quelconque des revendications précédentes, dans laquelle le métal devant être déposé est au moins un métal choisi dans le groupe constitué du nickel, du cuivre, du cobalt, du bore, de l'argent et de l'or.
  4. Composition aqueuse d'électrolyte selon l'une quelconque des revendications précédentes, dans laquelle un accélérateur est au moins un accélérateur du groupe constitué de la saccharine, de l'hydantoïne, de la rhodanine, du carbamide et de dérivés de carbamide.
  5. Composition aqueuse d'électrolyte selon l'une quelconque des revendications précédentes, dans laquelle l'électrolyte est exempt de stabilisants inorganiques, spécifiquement exempt de plomb, de bismuth, de zinc et/ou d'étain.
  6. Composition aqueuse d'électrolyte selon l'une quelconque des revendications précédentes, où la composition est exempte de cyanures, de composés de sélénium et de composés soufrés comprenant du soufre dans un degré d'oxydation entre -2 et +5.
  7. Composition aqueuse d'électrolyte selon l'une quelconque des revendications précédentes, comprenant en outre au moins un acide carboxylique supplémentaire et/ou au moins un sel d'un acide carboxylique.
  8. Composition aqueuse d'électrolyte selon la revendication 7, dans laquelle l'acide carboxylique est un composé du groupe constitué des acides acryliques, des acides carboxyliques aromatiques, des acides gras, des acides carboxyliques aliphatiques, des céto acides, des acides dicarboxyliques, des acide tricarboxyliques, des acides carboxyliques à chaîne linéaire, des acides carboxyliques hétérocycliques, des acides carboxyliques saturés, des acides carboxyliques insaturés et des α-hydroxy acides.
  9. Composition aqueuse d'électrolyte selon l'une quelconque des revendications précédentes, dans laquelle la valeur de pH de la composition est dans la plage entre pH 4 et pH 7.
  10. Composition aqueuse d'électrolyte selon l'une quelconque des revendications précédentes, dans laquelle l'agent de réduction est au moins un composé du groupe constitué de l'hypophosphite de sodium, du formaldéhyde, du diméthyl aminoborane, de l'amino borane et d'autres boranes organiques.
  11. Composition aqueuse d'électrolyte selon l'une quelconque des revendications précédentes, dans laquelle l'agent complexant est au moins un composé du groupe constitué de l'acide 2-hydroxy propionique, de l'acide propanedioïque (acide malonique), de l'EDTA et de l'acide amino acétique.
  12. Procédé de dépôt sans électrode d'une couche de métal sur un substrat comprenant les étapes de mise en contact du substrat devant être plaqué avec un électrolyte comprenant une source d'ions de métal pour le métal devant être déposé, un agent de réduction pour réduire les ions de métal, un agent complexant, un accélérateur et un stabilisant, caractérisée en ce que l'électrolyte comprend un phospho adamantane en tant que stabilisant selon la formule générale I
    Figure imgb0013
     où les atomes d'hydrogène sur les atomes de carbone 1 à 6 peuvent être, indépendamment les uns des autres, substitués par une entité du groupe constitué de F, Cl, Br, d'un groupement alkyle ayant de 1 à 6 atomes de carbone, d'un groupement alcoxy ayant de 1 à 6 atomes de carbone et d'un groupement alcool ayant de 1 à 6 atomes de carbone.
  13. Procédé selon la revendication 12, dans lequel le substrat est mis en contact avec l'électrolyte à une température dans la plage entre ≥ 20 °C et ≤ 85 °C, de préférence ≥ 25 °C et ≤ 70 °C.
  14. Procédé selon l'une quelconque des revendications 12 et 13, dans lequel le substrat est mis en contact avec l'électrolyte pendant une durée entre ≥ 1 s et ≤ 180 min, de préférence entre ≥ 10 s et ≤ 60 min.
EP15189465.6A 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 Active EP3156517B1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
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
ES15189465T ES2712858T3 (es) 2015-10-13 2015-10-13 Uso de fosfa-adamantanos solubles en agua y estables en aire como estabilizadores en electrolitos para deposición no electrolítica de metal
PCT/US2016/055655 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
US15/765,637 US20190085461A1 (en) 2015-10-13 2016-10-06 Water soluble and air stable phosphaadamantanes as stabilizers for electroless metal deposition
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
KR1020187013527A KR20180089398A (ko) 2015-10-13 2016-10-06 무전해 금속 도금용 안정제로서의 수용성이고 공기 안정성인 포스파아다만탄
TW105132884A TW201718938A (zh) 2015-10-13 2016-10-12 水溶性且空氣穩定的磷雜金剛烷用於無電金屬鍍敷之電解質中作為安定劑之用途

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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

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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
CN109457238B (zh) * 2018-08-30 2021-01-15 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
JP7228411B2 (ja) * 2019-03-06 2023-02-24 上村工業株式会社 無電解金めっき浴

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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
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ES2714824T3 (es) * 2009-07-03 2019-05-30 Macdermid Enthone Inc Electrolito que comprende beta-aminoácidos y método para la deposición de una capa de metal

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US20190085461A1 (en) 2019-03-21
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ES2712858T3 (es) 2019-05-16
WO2017066069A1 (fr) 2017-04-20
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EP3156517A1 (fr) 2017-04-19
TW201718938A (zh) 2017-06-01

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