EP1983078A1 - Elektrolytische Abscheidung - Google Patents

Elektrolytische Abscheidung Download PDF

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Publication number
EP1983078A1
EP1983078A1 EP07106339A EP07106339A EP1983078A1 EP 1983078 A1 EP1983078 A1 EP 1983078A1 EP 07106339 A EP07106339 A EP 07106339A EP 07106339 A EP07106339 A EP 07106339A EP 1983078 A1 EP1983078 A1 EP 1983078A1
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EP
European Patent Office
Prior art keywords
metalloid
current
potential
substrate
metal
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Application number
EP07106339A
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English (en)
French (fr)
Inventor
Joost Van Erkel
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Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
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Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
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Priority to EP07106339A priority Critical patent/EP1983078A1/de
Priority to PCT/NL2008/050222 priority patent/WO2008127112A2/en
Publication of EP1983078A1 publication Critical patent/EP1983078A1/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/66—Electroplating: Baths therefor from melts
    • C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance

Definitions

  • the invention relates to a method wherein a metal or a metalloid is deposited on a substrate by electro-deposition.
  • the invention further relates to an article provided with such a metal or metalloid.
  • a substrate may be provided with a metallic or metalloid for several purposes, e.g. a metallic or metalloid layer may be applied to improve the corrosion resistance of the substrate, as an intermediate layer for facilitating or improving the adherence of a subsequent functional layer to be applied to the substrate as a functional layer, such as a catalytically active layer, a layer for reflective electromagnetic radiation - for instance light - or to impart the substrate with a desirable visual appearance.
  • a relatively thin functional layer may be applied on a substrate for economic and/or technical reasons. For instance a layer of a relatively expensive, lowly conductive and/or brittle functional metal (such as Ti) or metalloid may be applied to a substrate of a relatively cheap, highly conductive and/or stiff metal (e.g. steel or copper).
  • Corrosion resistance can be improved by providing a layer of a suitable metal, such as a valve metal.
  • a suitable metal such as a valve metal.
  • Valve metals are metals that - when oxidised - form a dense metal oxide layer that has a low permeability to oxygen and/or water, such that it protects the metal covered by the oxide layer against corrosion. Such layer may also be referred to as a passivating oxide film.
  • valve metals are titanium, hafnium, tantalum, aluminium, bismuth, zirconium, tungsten, niobum.
  • Well-known methods to provide a metal layer to a substrate include electro-deposition, cladding, welding or gluing of a metal layer to the substrate.
  • the layer thickness and/or to provide a uniform metal layer thickness in particular in case the layer to be applied should be thin and/or in case the surface of the substrate is three-dimensionally shaped (not flat).
  • the presence of one or more protrusions, protuberances, recesses (e.g. holes), curves and/or edges in/on a surface of a substrate to be coated may be detrimental to a property of the layer applied with such a technique.
  • Electrochemical deposition also called electro-deposition or electroplating
  • electro-deposition electroplating
  • electroplating involves the reduction of ions from an electrolyte solution.
  • the technique is well-known for deposition of many metal and metalloid layer.
  • electro-deposition the substrate is placed in a suitable electrolyte containing the ions of the metal or metalloid to be deposited.
  • the substrate must have an electron conductive layer which forms the cathode which is connected to the negative terminal of a power supply.
  • the positive terminal is connected to a suitable anode.
  • the thickness of the deposited layer is a function of the number of electrons (charge) used in the electro-deposition process.
  • Electro-deposition from aqueous solutions is only possible for providing a layer of a metal or metalloid having a sufficiently high standard potential (also known as Nernst potential).
  • the standard potential of the metal or metalloid should be higher than the standard potential of water to hydrogen, or the kinetic for the reduction of water to hydrogen at the surface of the metal or metalloid should be so slow that the metal can be plated even if its standard reduction potential is below 0 Volt.
  • the noble metals and copper are examples of the first category, while zinc, chromium and cadmium are within the second category of metals that can be plated from aqueous solutions.
  • an aqueous solution is in general not suitable or at least not practical for deposition of a metal or metalloid with a low reduction potential, e.g., an alkaline earth metal, such as barium.
  • a layer of a metal or metalloid having a substantially lower reduction potential than the reduction potential of water to hydrogen for instance a layer of a valve metal such as aluminium, electro-deposition from aqueous solution is not feasible.
  • Past attempts to form a (valve) metal layer making use of a nonaqueous plating solution have not lead to satisfactory protective layers.
  • the deposited layers were found to be insufficiently homogenous and/or the maximum thickness that could be realised was limited due to (chemical) inhibition. For instance, for titanium a thickness of up to only a few nanometers was feasible.
  • an intermediate metal layer is for instance relevant for the manufacture of devices which may be used in a chemical process, such as catalytic devices, electrodes, in particular electrodes for electrocatalytic processes or other electrochemical processes.
  • a chemical process such as catalytic devices, electrodes, in particular electrodes for electrocatalytic processes or other electrochemical processes.
  • one or more factors such as sufficient dimensionally stability, conductivity, chemical stability, physical stability, ability to withstand severe anodic attack, corrosion resistance, manufacture performance, electrochemical performance, catalytic activity and/or catalytic selectivity, are important.
  • Electrodes made by a known method in particular electrodes for electrochemical processes made by a known method, generally lack sufficient or desirable performance in one or more of the above factors, at least when used in an industrial setting.
  • composite electrodes comprising a catalytic coating on a metal base.
  • a metal base An example thereof is the dimensionally stable anode (DSA), described in US 3,632,498 .
  • DSA dimensionally stable anode
  • a specific electrically conductive base is described with a coating of a mixed crystal material comprising an oxide of a film-forming metal, such as titanium oxide, and an oxide of a platinum group metal.
  • a drawback of this electrode is the need to manufacture and operate the electrode under strictly controlled conditions in order to avoid the formation of an insulating oxide layer of the film-forming metal, which would result in electro-chemical passivation of the anode with an excessive rise of the cell voltage (the potential between the anode and cathode) during use.
  • an intermediate protective coating may be used to form a barrier against oxidation of an electrode base.
  • factors such as satisfactory adherence, conductivity, impermeability to water and/or oxygen, resistance to oxidation, physical stability and/or chemical stability are important.
  • valve metal electrodes can evolve hydrogen at reasonably low over potentials, but are badly effected by adsorbed hydrogen atoms which migrate into the valve metal and form hydrides, causing expansion of the valve metal lattice, weakening of its structure and falling or peeling off of the electrocatalytic coating. This effect is known in the art as hydrogen embrittlement.
  • US 4,331,528 describes a dimensionally stable electrode wherein a layer of a non-stoichiometric oxide of a passive metal is provided on the electrode substrate, to prolong the life-time of an electrode.
  • the metallic/metalloid is deposited as a layer, more in particular a protective layer, to protect the part of the article provided with the metallic/metalloid layer against corrosion, wherein the article preferably is an electrode, and/or wherein the metallic/metalloid layer is a (electro)catalytically active layer.
  • the present invention relates a method for preparing an article which comprises a metal and/or a metalloid deposition, applied by electro-deposition, the method comprising
  • At least one of the values A respectively B is equal to or higher than the standard potential of the metal/metalloid ion which is to be reduced and deposited to form the metal/metalloid layer.
  • a moiety e.g. a compound, an ion, an additive etc.
  • the plural is meant to be included.
  • the potential respectively current may changed from
  • a reducing respectively non-reducing potential is dependent upon the metal ions and/or metalloid ions which are to be deposited, and conditions such as the temperature.
  • a non-reducing/reducing potential respectively current can be routinely determined based on the reduction potential of the specific metal or metalloid, optionally in combination with some routine experimentation.
  • a suitable potential/ current for step A respectively B reducing respectively non-reducing potential is dependent upon the metal ions and/or metalloid ions from which the layer is formed, and conditions such as the temperature.
  • a non-reducing potential/current may be an oxidising potential/current, i.e. a potential/current sufficient to cause part of the deposited metal/metalloid to be oxidised.
  • An oxidising potential/current may be useful to etch or polish the surface of the deposited metal/metalloid. This may be beneficial to a property of the finally deposited material.
  • a metal/metalloid may in particular be deposited at a surface of the substrate.
  • the surface may be an outer surface or an inner surface, e.g. inside pores of a porous substrate or an inner surface of a substrate comprising another type of cavity.
  • the metal/metalloid may be deposited as a layer partially or fully covering an inner or an outer surface of a substrate.
  • a method of the invention is in particular advantageous for providing a particular smooth, homogenous and/or closed metallic or metalloid layer. It is possible to provide a layer which has a low number of gaps identifiable with (scanning electron) microscopy or is essentially free of such gaps.
  • one or more of such properties may be provided under relatively mild conditions, such as at a relatively low temperature.
  • An advantage of a method in accordance with the present invention is that a metal or metalloid (layer) can be applied onto a large surface by means of, for instance, a roll-to-roll deposition process. Moreover, the method generally does not require to be operated by highly skilled personnel. Further, a method of the invention may be carried out using relatively simple equipment, without needing a high investment, in particular compared to vacuum deposition technologies.
  • a layer to a substrate with satisfactory properties, in particular for the layer to be suitable as a corrosion resistant layer, and/or a (electro-)catalytically active layer.
  • one or more properties, such as continuity of the layer may be improved.
  • the inventions allows the formation of a layer with satisfactory properties within a wide thickness range.
  • the thickness may in particular be at least 1 nm, at least 10 nm, at least 100 nm, at least 1 ⁇ m, at least 10 ⁇ m or at least 100 ⁇ m.
  • the thickness may in particular be up to 10 mm, up to 1 mm, up to 400 ⁇ m, up to 100 ⁇ m, up to 10 ⁇ m, up to 1 ⁇ m up to 100 nm or up to 10 nm.
  • the invention allows the formation of a highly continuous metallic or metalloid layer, also in case the layer is relatively thick.
  • the invention further relates to an article comprising a metallic or a metalloid deposition (such as a metallic or a metalloid layer), obtainable by a method of the invention.
  • a metallic or a metalloid deposition such as a metallic or a metalloid layer
  • the invention further provides an article with a highly homogenous and/or smooth layer.
  • the invention relates to an article, and a method for preparing such article, wherein the number of crystal defects in the metallic layer or metalloid layer is 10 6 /m 2 or less, or 10 5 /m 2 or less.
  • the number of such defects can be determined by scanning electron microscopy (SEM).
  • the metallic or metalloid layer has a low permeability to a gaseous, vaporous or liquid component, such as water.
  • a gaseous, vaporous or liquid component such as water.
  • the permeability to water may be less than 10 -6 g water/m 2 /day.
  • the permeability may be determined as described in US2006/147346 .
  • the substrate usually is an article of which at least part of the surface is electrically conductive.
  • the substrate may comprise a metal surface, a metalloid surface, a (semi-)conductive inorganic oxide surface or an organic (semi-)conductive surface. At least when the electrical potential is applied, the substrate and anode are in electrical communication with each other, forming an electrochemical cell with the plating liquid.
  • the surface of the substrate upon which the metal or metalloid is deposited may comprise a metal selected from the group of titanium, iron, copper, aluminium, nickel, silver, zinc, molybdenum, chromium, lead, platinum, palladium, gold, including mixtures thereof, such as alloys thereof, in particular brass or steel.
  • the surface may comprise an electron conductive form of carbon (such as graphite).
  • the surface of the substrate may comprise another sufficiently electron conductive material, such as a semiconductor, a (semi-) conductive polymer, a metalloid or a conductive oxide, or a combination of two or more of these (semi-)conductors.
  • the conductive oxide may comprise one or more conductive oxides, selected from the group of zinc oxide, tin oxide and/or indium tin oxide. These are available in transparent forms.
  • the transparent conductive oxide layer comprises zinc oxide and/or tin oxide. More preferably, the transparent conductive oxide layer comprises tin oxide.
  • the substrate may be a substrate selected from the group of circuit boards, vessels (such as reactor vessels), plates, tubes, pipes, sheets, electrodes, foils, bars and bus-bars.
  • vessels such as reactor vessels
  • plates such as plates, tubes, pipes, sheets, electrodes, foils, bars and bus-bars.
  • a substrate of a relatively cheap material e.g. copper
  • a layer of a relatively expensive material such as titanium, tantalum, gold, silver or a metal from the platinum group is deposited.
  • the substrate comprises a material with one or more desirable mechanical properties for a specific purpose, for instance steel or brass, but undesirable (electro-)chemical stability or another undesirable property for use in a specific application.
  • the invention allows the provision of a protective metallic or metalloid layer on the substrate, to combine an advantageous mechanical property of the substrate, for instance a vessel or piping for use in a chemical process, with an advantageous chemical resistance (e.g . against corrosion) provided by the metallic or metalloid layer.
  • the substrate Prior to the plating, the substrate may be pre-treated in a manner known in the art for electro-plating. In particular contaminants and/or films may be removed from the substrate.
  • the pre-treatment may in particular comprise a chemical cleaning step, such as an electro-chemical cleaning step and or a physical cleaning step. Suitable pre-treatment steps are known in the art, and are, e.g, described in Dexter D. Snyder “Preparation for Deposition”, chapter 23 in M. Schlesinger, M. Paunovic (eds), “Modern Electroplating", Electrochemical Society Series, 4th Edition, 2000, John Wiley & Sons, New York .
  • the invention allows the preparation of an article comprising a metallic or metalloid deposition (such as a layer) wherein a property of the deposition, such as thickness, density, structure, continuity or the like can be adequately controlled by selecting the electro-deposition conditions, in particular with respect to the changing voltage or current.
  • the voltage/current during the electro-plating process may be performed at galvanostatic control (current control), potentiostatic (potential control, using the potential difference over the substrate and a reference electrode, or at cell voltage control (i.e. wherein the potential over the substrate and anode (counter electrode) is controlled.
  • Parameters that can be controlled to adjust properties of the deposition include cell voltage, cathode potential, and current conditions. More specifically, by choosing the duration of the electro-deposition and total charge (coulombs) applied for the duration of the electro-deposition, and in particular by choosing the plating conditions with respect to frequency by which the current/potential is changed, duration of the steps A respectively B, value of (absolute maximum of) "reducing voltage/current” respectively “non-reducing voltage/current", slope by which the voltage/current is changed.
  • the potential of the substrate is below the reduction potential of the metal ions and/or metalloid ions in the plating liquid which are to be deposited on the substrate.
  • a non-reducing voltage/current may be 0. Accordingly, the cell may be let at the open cell voltage, or at the rest potential for a period of time.
  • a non-reducing voltage/current may have the opposite sign of charge from the (current at the) reduction potential.
  • a part of the deposited metal/metalloid may be reoxidised and optionally dissolved.
  • voltage/current should be such that - on average - reduction and deposition is larger the oxidation and dissolution.
  • the ratio of the current in step B to the current in step A (wherein current and potential are taken as their absolute value) is less than 1.
  • said ratio is less than 0.9.
  • said ratio up to 0.8, in particular up to 0.6, more in particular up to 0.5.
  • the ratio of the current in step B to the current in step A (absolute values) is at least 0.
  • the current in step B may be an oxidising current (to redissolve part of the deposited metal or metalloid), as long as on average the amount of redissolved metal or metalloid is less than the amount of deposited metal or metalloid. It is also possible to change between a high reducing current and a low reducing current, wherein the low reducing current can be advantageous to allow growth of nuclei of the metal or metalloid.
  • the frequency of changing the potential/current can be chosen within wide limits.
  • the frequency may be essentially constant or varied.
  • the average frequency of the changing (to get from a first reducing potential/current to the next reducing potential/current) is at least 0.01 Hz, in particular at least 0.1 Hz or at least 1 Hz.
  • the average frequency of the changing is usually up to 10 KHz, in particular up to 1 KHz or up to 500 Hz.
  • the number of changes may be chosen within wide limits, depending upon factors, such as the desired amount of deposition (such as the desired layer thickness), the current density applied, the frequency, the deposition efficiency, the optional use of an etching potential/current.
  • the skilled person will be able to determine a suitable number, based upon the information disclosed herein, common general knowledge and optionally some routine testing.
  • the number of changes from A to B or B to A usually is more than 2, and in particular it may be at least 5, at least 10 or at least 25.
  • the upper limit is determined by reaching the target deposition (such as reaching a specific thickness of a metallic/metalloid layer). It may for instance be up to 1000, up to 100 000 or up to 1 000 000. However a higher number of changes is in principle allowed, in particular in case the changing frequency is high.
  • Level II is a reduction current/potential at which deposition takes place.
  • Level I can be a) a 0 current or rest potential (open circuit potential); b) an anodic current/potential at which a part of the previously deposited metal or metalloid may be (oxidised and) dissolved; c) a relatively low reduction current/potential (compared to Level II) which may be used to grow metal/metalloid nuclei, which are formed in a previous Level II current/potential.
  • t 1 is the cycle time from a first Level I to the next (the reciprocal of the frequency), t 2 the duration of the current/potential at level II, t 3 the duration at level I, and t 4 respectively t 5 the time to change from (an extreme) current/potential from one level to the other, in case the current/voltage change is effected with a specific slope.
  • the ratio of t 2 /t 1 may be chosen within wide limits. A relatively high ratio may be advantageous from a processing time of view.
  • the ratio t 2 /t 1 may in particular be at least 0.001, at least 0.01, or at least 1.
  • the ratio t 2 /t 1 may in particular be up to 1000, up to 100 or up to 10.
  • the changing comprises applying current/potential pulses, e.g . as shown in Figure 1A .
  • the current/potential is changed essentially instantaneously.
  • the change from a first current/potential to another takes places at a specific rate, e.g . as shown in Figure 1B .
  • the changing comprises applying current/potential in an undulating way, for instance by a sinusoidal change, e.g. as shown in Figure 1C .
  • the temperature may be controlled. Typically, the temperature is at least above the melting temperature of the ionic liquid / salt system. For practical reasons, the temperature is preferably at least ambient temperature, such as at least 20 °C or at least 25 °C. An elevated temperature, e.g . of at least 30 °C, at least 40 °C or at least 50 °C may be chosen in case a plating liquid to be used is not sufficiently liquid at ambient temperature. A relatively high temperature is usually advantageous for achieving a relatively low viscosity and/or a improved electrical conductance of the liquid.
  • Selecting a temperature within a specific range may be used for a (further) improved smoothness of the layer.
  • the temperature is up to 200 °C.
  • the temperature is up to 100 °C , up to 70 °C or up to 50 °C.
  • electro-deposition may be carried out with or without convection of the liquid, for instance with or without agitation. Convection is considered advantageous in order to avoid or at least reduce the occurrence of a possibly detrimental concentration gradient of the ions to be deposited at the cathode.
  • the plating liquid comprises an ionic liquid.
  • An ionic liquid is a liquid formed of a salt that is liquid under the process conditions, such as a melt of a salt.
  • an ionic liquid used in a method of the invention has a melting point below 200 °C, preferably of 100 °C or less, in particular of 50 °C or less. It is in particular preferred that the ionic liquid is liquid at about 20 °C or at about 25 °C. Such liquid may be referred to as a room temperature liquid salt.
  • Salts that form an ionic liquid are known in the art.
  • US-A 4,764,440 discloses a composition comprising a mixture of a metal halide and a hydrocarbyl-saturated onium salt, wherein at least one of the hydrocarbyl groups is an aromatic hydrocarbyl group.
  • US-A 5,731,101 discloses an ionic liquid composition
  • an ionic liquid composition comprising a mixture of a metal halide and an alkyl-containing amine hydrohalide salt of the formula R 3 N.HX, where at least one R is alkyl and X is halogen, which amine hydrohalide salt contains either one or two alkyl groups therein.
  • ionic liquid selected from the ionic liquids described in WO 02/26381 , of which the contents of this publication with respect to the description of suitable ionic liquids, in particular as specified in the claims thereof is incorporated herein by reference.
  • ionic compound can be formed by the reaction of at least one amine salt of the formula R 1 R 2 R 3 R 4 N + X - (I) with at least one hydrated salt, which is a chloride, nitrate, sulphate or acetate of Li, Mg, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb, Bi, La or Ce; wherein R 1 , R 2 and R 3 are each independently a C 1 to C 5 alkyl or a C 6 to C 10 cycloalkyl group, or wherein R 2 and R 3 taken together represent a C 4 to C 10 alkylene group, thereby forming with the N atom of formula I a 5 to 11 membered heterocyclic ring, and
  • the ionic liquid comprises a salt of the following cations and/or anions:
  • the plating liquid may comprise a solvent, solvents being materials other than the liquid salt which are liquid under the conditions at which the method is carried out.
  • the solvent may be chosen from inorganic solvents other than water and organic solvents, such as benzene or an alcohol.
  • the solvent concentration will usually be less than 25 wt. %, based on total liquid salt, in particular 20 wt. % or less, more in particular 15 wt. %wt or less.
  • the solvent concentration is up to 2 wt. % based on total liquid salt, more preferably less than 1 wt. %.
  • the plating liquid is essentially free of water and/or other solvents.
  • a plating liquid is in particular considered to be essentially free of a solvent if the concentration of that solvent is less than 0.5 wt. %, based on total liquid salt, more in particular less than 0.1wt. % of a solvent, or less than 0.01 wt. %.
  • the metal/metalloid ions for forming the metallic/metalloid deposition may in particular be any metal ion or metalloid ion that can be reduced from ionic state to non-ionic state (atomic state).
  • the ions may all be of the same metal or metalloid, or a combination of two or more ions selected from the group of metal ions and metalloid ions may be used.
  • a metallic deposition (such as a layer) as used herein is a deposition comprising one or more metals, thus the term includes depositions of a metallic alloy. In particular a deposition is considered metallic if it shows metallic electrical conductance.
  • the ions may be selected from valve metals and catalytically active metals, such as metals from the platinum group.
  • Preferred metal ions include ions selected from the group of titanium, tantalum, aluminium, hafnium, bismuth, zirconium, tungsten, niobum, chromium, manganese, zinc, silver, gold, platinum and palladium, ruthenium, including combinations thereof, in particular alloys thereof.
  • Particularly preferred is at least one metal ion selected from titanium, aluminium and tantalum.
  • Metalloids are elements that are generally not considered real metals, but that do show more or less metallic behaviour in one or more specific aspects.
  • metalloids are capable of conducting electricity, to the extent that they are semiconductors rather than metallic conductors.
  • Boron (B), Silicon (Si), Germanium (Ge), Arsenic (As), Antimony (Sb), Tellurium (Te) and Polonium (Po) are examples of metalloids.
  • silicon and/or germanium are preferred examples of metalloids, to be deposited on a substrate in accordance with the invention.
  • a metalloid deposition (such as a layer) as used herein is a deposition comprising one or more metalloids, thus the term includes depositions of a metalloid alloy.
  • a deposition is considered a metalloid deposition if it shows metalloid electrical conductance (i.e. showing semi-conductive properties, such as a semi-metal).
  • the counter ions of the metal ions or metalloid used for deposition may be the same or different from the cations of the ionic liquid.
  • the counter ions may be chosen from the group of chloride, bromide, iodide, nitrate, nitrite, fluoride, phosphate, imide, amide, borate, tosylate, tetrafluoroborate, hexafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, methylsulfate, bis(pentafluoroethyl)phosphinate, thiocynate, octylsulfate, hexylsulfate, buthylsulfate, ethylsulfate, dicyanamide, hexafluoroantimonate, bis-(pentafluoroethyl)phospinate, bis-(trifluoromethyl)imide, trifluor
  • a deposition (such as a layer) of an alloy is formed by using co-deposition, This may be achieved by using a single plating liquid comprising more than one type of ions to be deposited on the substrate, to allow co-deposition to take place in a single electro-deposition process.
  • the different ions to be deposited are dissolved in separate plating liquids, with which the substrate is sequentially contacted under plating conditions. This allows the formation of different layers on top of each other.
  • the total concentration of the salt comprising the ions for forming the metallic/metalloid layer preferably is at least 0,1 mol%, more preferably at least 1 mol%, even more preferably at least 5 mol%, or at least 10 mol%.
  • a relatively high concentration is in particular advantageous in order to allow a high deposition speed.
  • the upper limit is in particular determined by the maximum allowable concentration in order to maintain the plating liquid in a liquid state (the saturation level).
  • a relatively high concentration usually advantageous for a high deposition rate. Also, this allows for a relatively large amount of ions can usually to be reduced and deposited before depletion of the liquid may become noticeable. Also the presence of the ions to be deposited in a relatively high concentration may be advantageous for improved liquidity (reduced viscosity, reduced melting temperature of the liquid), and/or improved electrical conductance.
  • the total concentration of the salt of the metal/metalloid ions for forming the metallic/metalloid deposition preferably is up 70 mol %, more preferably up to 65 mol %, in particular up to 60 mol%.
  • a lower concentration may be chosen, e.g. up to 40 mol %, up to 20 mol °/, up to 10 mol %, or 5 mol % or less.
  • a "sacrificial electrode” is used as a counter electrode (anode). At least the surface of such an electrode comprises the same metal or metalloid as the metal or metalloid that is to be deposited on the substrate. While the metal or metalloid is deposited on the substrate during electro-deposition, metal/metalloid at a surface of the sacrificial electrode will be oxidised and dissolve in the plating liquid. Thus, the composition of the plating liquid can be maintained at about the same concentration for a prolonged timed, or at least depletion of the liquid with metal/metalloid ions can be postponed.
  • Such electrode may for instance be a plate, foil or thread of the metal/metalloid to be deposited, e.g. an aluminium counter electrode can be used when depositing aluminium on a substrate form a aluminium ions containing ionic liquid electrolyte.
  • the plating liquid may further comprise one or more additives, such as a brightener and/or a surface active agent.
  • additives such as a brightener and/or a surface active agent.
  • One or more additives are optionally also deposited. Suitable conditions for the additives are e.g. described in " Effect of additives", Chapter 10 in M. Schlesinger, M. Paunovic (eds), “Fundamentals of Electrochemical Deposition”, Electrochemical Society Series, 2nd Edition, 2006, John Wiley & Sons, New York , of which Chapter the contents are incorporated by reference.
  • the article may be subjected to one or more post-treatment steps. For instance, excess ionic liquid may be removed from the article.
  • the substrate properties were as follows: ⁇ 1cm 2 Si(100) crystal coated with ⁇ 5nm Chromium (adherence layer) and ⁇ 200nm gold (surface layer upon which aluminium is deposited).
  • Aluminium-wire diameter 0,5mm 99,99% Al was used as a reference electrode.
  • the ionic liquid was 1-Ethyl-3-methyl-imidazoliumchloride (EMImCl) (40 mol %) comprising Aluminium chloride (AlCl 3 ) (60mol%).
  • EMImCl 1-Ethyl-3-methyl-imidazoliumchloride
  • AlCl 3 Aluminium chloride
  • electro-deposition was carried out using a pulsed current, as schematically shown in Figure 1A .
  • I I 0 mA/cm 2
  • I II -100mA/cm 2
  • t 1 0,11s
  • t 2 0,01s
  • t 3 0,1s.
  • Deposition takes place during t 2 .
  • Example 2 was repeated, but with t 1 : 0,2s, t 2 : 0,1s, t 3 : 0,1s and a deposition time of 6 seconds to realise the same deposition charge (0,3 C/cm 2 )
  • the adherence of the layer was tested with the so called scotch tape test and found to be excellent.
  • a substrate of ⁇ 1cm 2 glass coated with ITO Indium tin oxide, a transparent conducting oxide layer
  • ITO Indium tin oxide, a transparent conducting oxide layer
  • PEDOT Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate)
  • the counter Electrode was aluminium-sheet 99,99% Al ⁇ 6 cm 2 .
  • the reference electrode was aluminium-wire diameter 0,5mm 99,99% Al.
  • Ionic liquid was 1-Ethyl-3-methyl-imidazoliumchloride (EMImCl, 40 mol%) comprising aluminiumchloride (AlCl 3 , 60mol%)
  • a pulsed current was used as schematically shown in Figure 1A , with I 1 : 0 mA/cm 2 , I 2 : -20mA/cm 2 , t 1 : 0,2s, t 2 : 0,1s, t 3 : 0,1s.
  • the deposited layer was mat to lustrous and homogenous, also at the edges.

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  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
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WO2009106269A1 (de) * 2008-02-26 2009-09-03 Ewald Dörken Ag Beschichtungsverfahren für ein werkstück
WO2010119018A1 (de) * 2009-04-16 2010-10-21 Basf Se Entfernung und recycling metallsalz-haltiger ionischer flüssigkeiten von oberflächenbehandelten werkstücken
CN101949044A (zh) * 2010-09-20 2011-01-19 大连海事大学 离子液体中钢表面电渗铌的方法
DE102009035660A1 (de) * 2009-07-30 2011-02-03 Ewald Dörken Ag Verfahren zur elektrochemischen Beschichtung eines Werkstücks
CN101985766A (zh) * 2010-11-26 2011-03-16 昆明理工大学 一种离子液体电镀Zn-Ti合金的方法
CN101724869B (zh) * 2009-12-18 2011-06-22 北京有色金属研究总院 一种离子液体添加剂在瓦特电镀镍溶液中的应用
WO2012099466A3 (en) * 2011-01-18 2013-01-03 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Method for manufacturing an electronic device by electrodeposition from an ionic liquid
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WO2015151099A1 (en) * 2014-03-31 2015-10-08 Technion Research & Development Foundation Limited A method for passive metal activation and uses thereof
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US8778164B2 (en) 2010-12-16 2014-07-15 Honeywell International Inc. Methods for producing a high temperature oxidation resistant coating on superalloy substrates and the coated superalloy substrates thereby produced
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WO2010119018A1 (de) * 2009-04-16 2010-10-21 Basf Se Entfernung und recycling metallsalz-haltiger ionischer flüssigkeiten von oberflächenbehandelten werkstücken
DE102009035660A1 (de) * 2009-07-30 2011-02-03 Ewald Dörken Ag Verfahren zur elektrochemischen Beschichtung eines Werkstücks
CN101724869B (zh) * 2009-12-18 2011-06-22 北京有色金属研究总院 一种离子液体添加剂在瓦特电镀镍溶液中的应用
CN101949044A (zh) * 2010-09-20 2011-01-19 大连海事大学 离子液体中钢表面电渗铌的方法
CN101949044B (zh) * 2010-09-20 2011-12-28 大连海事大学 离子液体中钢表面电渗铌的方法
CN101985766A (zh) * 2010-11-26 2011-03-16 昆明理工大学 一种离子液体电镀Zn-Ti合金的方法
CN101985766B (zh) * 2010-11-26 2012-09-05 昆明理工大学 一种离子液体电镀Zn-Ti合金的方法
WO2012099466A3 (en) * 2011-01-18 2013-01-03 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Method for manufacturing an electronic device by electrodeposition from an ionic liquid
WO2013173006A1 (en) * 2012-05-14 2013-11-21 United Technologies Corporation Method for making metal plated gas turbine engine components
WO2015151099A1 (en) * 2014-03-31 2015-10-08 Technion Research & Development Foundation Limited A method for passive metal activation and uses thereof
CN106415919A (zh) * 2014-03-31 2017-02-15 泰克年研究发展基金会公司 钝态金属活化方法和其用途
CN109524617A (zh) * 2014-03-31 2019-03-26 泰克年研究发展基金会公司 钝态金属活化方法和其用途
US10644304B2 (en) 2014-03-31 2020-05-05 Technion Research & Development Foundation Limited Method for passive metal activation and uses thereof
US11688845B2 (en) 2014-03-31 2023-06-27 Technion Research & Development Foundation Limited Method for passive metal activation and uses thereof
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CN109023454A (zh) * 2018-09-18 2018-12-18 惠州市碧欣环保科技有限公司 一种双阳离子离子液体电镀Cr-Ag合金镀层的方法
CN109023454B (zh) * 2018-09-18 2020-04-07 蒙城繁枫真空科技有限公司 一种双阳离子离子液体电镀Cr-Ag合金镀层的方法
CN114855231A (zh) * 2022-05-27 2022-08-05 江西思远再生资源有限公司 一种在镁及其合金上镀铌的方法

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