WO2017213866A1 - Utilisation de composés de lanthanide solubles dans l'eau en tant que stabilisant dans des électrolytes pour le dépôt chimique de métal - Google Patents

Utilisation de composés de lanthanide solubles dans l'eau en tant que stabilisant dans des électrolytes pour le dépôt chimique de métal Download PDF

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WO2017213866A1
WO2017213866A1 PCT/US2017/034380 US2017034380W WO2017213866A1 WO 2017213866 A1 WO2017213866 A1 WO 2017213866A1 US 2017034380 W US2017034380 W US 2017034380W WO 2017213866 A1 WO2017213866 A1 WO 2017213866A1
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metal
electrolyte
stabilizer
acid
aqueous electrolyte
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PCT/US2017/034380
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English (en)
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Holger Kirschbaum
Katrin SÖNTGERATH
Stefan Schäfer
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Macdermid Enthone Inc.
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Publication of WO2017213866A1 publication Critical patent/WO2017213866A1/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
    • C23C18/38—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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents

Definitions

  • the present invention relates to the use of water soluble lanthanide compounds 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 aluminum 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.
  • CN 101348927 A 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 eth
  • 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 as stabilizer a water-soluble lanthanide compound.
  • water-soluble lanthanide compounds 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.
  • Lanthanide compounds in the meaning of this invention shall refer to compounds of the elements of the lanthanide group of the periodic system, i.e. lanthanum, cerium, praeseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holroium, erbium, thulium, ytterbium, and lutetium.
  • Compounds in the meaning of this invention shall refer to salts, organic compounds, metal organic compounds or complexes. Examples for salts are, e.g.
  • halides like fluorides, chlorides, bromides, or iodides, sulfates, phosphates, or nitrates.
  • Examples for complexes may be (NH 4 ) 2 [Ln(N0 3 ) 6 ], (NH 4 ) 2 [Ln(S0 4 ) 3 ] or [Ln(N0 3 ) 4 (OPPh 3 ) 2 ].
  • Water soluble in the meaning of the invention shall mean that the Ln compound is soluble in an aqueous system to an extent of at least 0.007 mmol/L or 1 mg/L of Ln.
  • water-soluble lanthanide compounds 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.
  • 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.
  • this edge weakening effect can be avoided which significantly increases the overall outline accuracy of the plating especially when plating large substrates.
  • the use of a water-soluble lanthanide compounds as stabilizer results in a more even deposition having 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 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.
  • a stabilizer according to the present invention provides a deposit having significantly better corrosion resistance including excellent resistance vs. nitric acid; is more environmental friendly (less toxic additive); and lower plating temperatures can be used to achieve the same plating speed.
  • 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.
  • water-soluble lanthanide compounds according to the general formula preferably 2 to 4, like e.g. ( are found to be very effective as stabilizers in electroless plating electrolytes.
  • neodymium(III)acetate is a preferred embodiment of a water-soluble lanthanide compound.
  • the water-soluble lanthanide compounds 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 ⁇ 80 mg/L, most preferably between >1 mg/L and ⁇ 50 mg/L calculated on the lanthanide metal.
  • the inventive electrolyte 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/1, and even more preferably with a concentration of 12 to 30 g/1.
  • a metal ion source in the inventive electrolyte advantageously a metal compound of the group consisting metal chloride, metal sulfate, metal acetate, metal nitrate, metal propionate, metal forrniate, 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 forrniate 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,
  • the word volatile anion should be understood as anions of volatile compounds, i.e. compounds having an initial boiling point in the range of 50°C to 250°C at a standard atmospheric pressure of 101.3 kPa, This enables to extend the lifetime of the electrolyte significantly, which under normal conditions is only limited. For example, by the use of volatile anions also at a metal turnover rate of 22 metal layers having internal compressive stress can be deposited.
  • 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 deiivates.
  • 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, methane sulfonic acid, methane disulfonic acid or combinations of these.
  • electrolyte e.g. sulfuric acid, acetic acid, lactic acid, citric acid, hypophosphorus acid, sulfonic acids, methane sulfonic acid, methane disulfonic acid or combinations of these.
  • bases e.g. sodium carbonate, potassium carbonate, ammonium hydroxide, sodium hydroxide, potassium hydroxide, Hthiuni 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 B-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) and a carboxylic functional group as derived for the carboxylic acid or its salt, is a ⁇ -amide.
  • the condensation product is present in a monomelic, oHgomeric and/or polymeric form, i.e., as the N-teiminal 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 ⁇ -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 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 lanthanide compound, i.e. at least one compound of a metal selected from the group consisting of lanthanum, cerium, praeseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium, a second one being a ⁇ -amino acid, and a third one being an inorganic stabilizer, like e.g. antimony.
  • a lanthanide compound i.e. at least one compound of a metal selected from the group consisting of lanthanum, cerium, praeseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium
  • a further property of a metal layer deposited for an electrolyte according to the present invention is that it is very passive.
  • a further advantage of the metal layers deposited for an electrolyte according to the present invention is the good residual compressive stress. Furthermore, the metal layers exhibit an enhanced corrosion resistance.
  • 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, a complexing agent, an accelerator, and a stabilizer, characterized in that the electrolyte comprises as stabilizer a water-soluble lanthanide compound.
  • the substrate is contacted with the electiOlyte 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 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 electiOlyte 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, amino borane, or other organic boranes.
  • the reducing agent may be comprised in the electiOlyte 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, propanediol 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 water-soluble lanthanide compound.
  • Said lanthamde compound may be a least one compound selected from the group consisting of fluorides, chlorides, bromides, iodides, sulfates, phosphates, or nitrates, of at least on metal selected from the group consisting of lanthanum, cerium, praeseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
  • Said stabilizer may be comprised in the electrolyte in a concentration within a range of >0.05 mg/L and ⁇ 100 mg/L, preferably between >0.1 mg/L and ⁇ 80 mg/L, most preferably between >1 mg/L and ⁇ 50 mg/L calculated on the lanthanide metal.
  • 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 water-soluble lanthanide compound. Said lanthanide compound may be a least one.
  • compound selected from the group consisting of fluorides, chlorides, bromides, iodides, sulfates, phosphates, or nitrates, of at least on metal selected from the group consisting of lanthanum, cerium, praeseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
  • Said stabilizer may be comprised in the electrolyte in a concentration within a range of >0.05 mg/L and ⁇ 100 mg/L, preferably between >0.1 mg/L and ⁇ 80 mg/L, most preferably between >1 mg/L and ⁇ 50 mg/L calculated on the lanthanide metal.
  • 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- arninoethane-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/1, preferably 100 mg/L to 1 gfl, 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 water-soluble lanthanide compound
  • Said lanthanide compound may be a least one compound selected from the group consisting of fluorides, chlorides, bromides, iodides, sulfates, phosphates, or nitrates, of at least on metal selected from the group consisting of lanthanum, cerium, praeseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and Iutetium.
  • Said stabilizer may be comprised in the electrolyte in a concentration within a range of >0.05 mg/L and ⁇ 100 mg/L, preferably between >0.1 mg/L and ⁇ 80 mg/L, most preferably between >1 mg/L and ⁇ 50 mg/L calculated on the lanthanide metal.
  • the electrolyte comprises antimony as an inorganic stabilizer.
  • Antimony is comprised in a concentration of between 0.05 mg/L and 0,5 g/1, preferably 0.5 mg/L and 0.1 g/1.
  • 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, dimethyl aminoborane, aminoborane, or other organic boranes.
  • the reducing agent may be comprised in the electrolyte in a concentration of between 0.08 moI/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 rnol/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 water-soluble lanthanide compound
  • Said lanthanide compound may be a least one compound selected from the group consisting of fluorides, chlorides, bromides, iodides, sulfates, phosphates, or nitrates, of at least on metal selected from the group consisting of ' lanthanum, cerium, praeseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
  • Said stabilizer may be comprised in the electrolyte in a concentration within a range of >0.05 mg/L and ⁇ 100 mg/L, preferably between >0.1 mg/L and ⁇ 80 mg/L, most preferably between >1 mg/L and ⁇ 50 mg/L calculated on the lanthanide metal.
  • 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 (B-alanin), 3-aminobutyric acid, 3-amino-4-methyl valeric acid and 2- amino ethane-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/1, preferably 100 mg/L to 1 g/1, 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/1, preferably 0.5 mg/L and 0.1 g/1.
  • 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 Ci to C 4t ⁇ - ⁇ -unsaturated carboxylic acids, particularly C 1 to C 4 and especially acrylic,
  • pH is in a range of pH 4 to pH 7.
  • a substrate (steel sheet) was brought into contact with an electrolyte comprising:
  • ABS plaque 18 mg/L potassium antimony tartrate wherein the pH is in a range of pH 4.0 to pH 5 at a temperature between 80 °C and 94 °C 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 could be plated from this electrolyte with a plating speed of 8 - 10 ⁇ m/h with a composition of 90 - 91 % by weight nickel and 9 - 10 % by weight of phosphorous.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Mechanical Engineering (AREA)
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  • Chemically Coating (AREA)

Abstract

La présente invention concerne l'utilisation de composés de lanthanide solubles dans l'eau comme stabilisants dans des électrolytes pour le dépôt chimique de métal, un électrolyte ainsi qu'un procédé pour le dépôt chimique de métaux, en particulier des couches de nickel, de cuivre, de cobalt, de bore, d'argent, de palladium ou d'or, ainsi que des couches d'alliages comprenant au moins l'un des métaux susmentionnés en tant que métal d'alliage.
PCT/US2017/034380 2016-06-07 2017-05-25 Utilisation de composés de lanthanide solubles dans l'eau en tant que stabilisant dans des électrolytes pour le dépôt chimique de métal WO2017213866A1 (fr)

Applications Claiming Priority (2)

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EP16173403.3A EP3255175A1 (fr) 2016-06-07 2016-06-07 Utilisation de composés de lanthanide hydrosoluble en tant qu'agents de stabilisation dans des électrolytes de dépôt auto-catalytique de métal
EP16173403.3 2016-06-07

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3650777A (en) * 1971-02-11 1972-03-21 Kollmorgen Corp Electroless copper plating
US20040253450A1 (en) * 2001-05-24 2004-12-16 Shipley Company, L.L.C. Formaldehyde-free electroless copper plating process and solution for use in the process

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2178146C (fr) 1995-06-06 2002-01-15 Mark W. Zitko Depot autocatalytique d'un alliage de nickel-cobalt-phosphore
DE10246453A1 (de) 2002-10-04 2004-04-15 Enthone Inc., West Haven Verfahren zur stromlosen Abscheidung von Nickel
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
CN104846383B (zh) * 2015-05-11 2017-09-26 山东汇川汽车部件有限公司 一种汽车助力转向泵阀芯的生产方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3650777A (en) * 1971-02-11 1972-03-21 Kollmorgen Corp Electroless copper plating
US20040253450A1 (en) * 2001-05-24 2004-12-16 Shipley Company, L.L.C. Formaldehyde-free electroless copper plating process and solution for use in the process

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