EP2599896A2 - Procédé de séparation galvanique d'au moins un métal ou un semi-conducteur - Google Patents

Procédé de séparation galvanique d'au moins un métal ou un semi-conducteur Download PDF

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Publication number
EP2599896A2
EP2599896A2 EP12191555.7A EP12191555A EP2599896A2 EP 2599896 A2 EP2599896 A2 EP 2599896A2 EP 12191555 A EP12191555 A EP 12191555A EP 2599896 A2 EP2599896 A2 EP 2599896A2
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Prior art keywords
electrolyte
metal
semiconductor
organic liquid
substituted
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EP12191555.7A
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German (de)
English (en)
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EP2599896B1 (fr
EP2599896A3 (fr
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Volkmar Neubert
Ashraf Bakkar
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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
    • 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
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/11—Use of protective surface layers on electrolytic baths
    • 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
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/42—Electroplating: Baths therefor from solutions of light metals
    • C25D3/44—Aluminium

Definitions

  • the invention relates to a method for the electrodeposition of at least one metal or semiconductor on a substrate to be coated in a galvanic cell having an anode, a cathode and, if desired, a reference electrode immersed in an electrolyte, the metal or semiconductor used for the coating being the electrolyte is added and / or used in the form of the anode, the substrate to be coated is connected as a cathode and the electrolyte is selected from ionic liquids and wherein a potential is applied at a level such that the induced current through the metal or the semiconductor on the Substrate surface is electrodeposited.
  • the electrochemical metal deposition of base metals is known, that is such metals with a more negative normal potential than hydrogen.
  • the Hall-Heroult process is used for the electrodeposition of aluminum.
  • this method is unsuitable for coating materials with aluminum, since the aluminum reduction takes place at temperatures of about 1000 ° C, namely the bath temperature of the electrolyte cryolite (Na 2 AIF 6 ) / alumina (Al 2 O 3 ). In this case, aluminum is obtained in the liquid state.
  • PVD and CVD physical and chemical deposition used from the gas phase
  • PVD and CVD physical and chemical deposition used from the gas phase
  • a disadvantage of the aforementioned methods is that they sometimes require very high temperatures, so that they can not be used to coat any surface. Further, for example, dipping processes are not particularly well suited to producing thin aluminum layers.
  • the deposition methods on physical or chemical deposition from the gas phase have the disadvantage that they are technically complex and therefore relatively expensive.
  • nonaqueous electrolytes In the case of the abovementioned nonaqueous electrolytes, this problem does not occur because they do not contain water.
  • non-aqueous electrolytes are generally sensitive to air and moisture. Therefore, the electrochemical deposition process is carried out under an inert gas atmosphere, such as under an argon or nitrogen atmosphere. This is costly because you have to work in a closed system.
  • non-aqueous electrolyte baths contain organic solvents which are highly flammable and volatile.
  • electrolyte baths often hygroscopic and therefore difficult to handle.
  • the starting materials used for electroplating in the form of organic metal compounds are often pyrophoric, ie react in the air with auto-ignition and show extremely violent reaction on contact with water. This circumstance, in combination with the highly flammable solvents used, represents a high hazard potential.
  • aluminum can be deposited under an inert atmosphere from a binary aluminum chloride / alkali metal chloride mixture, the alkali metal chlorides being made from those of sodium, lithium or mixtures of potassium and sodium chlorides.
  • chlorides and bromides or iodides can be used.
  • Such a method is for example off J. Fransaer, E. Leunis, T. Herato, JP Celis, J. Appl. Electrochem. 32 (2002) 123-128 known. In this approach, however, it is sometimes considered disadvantageous that the above-described electrolytes are highly corrosive.
  • aluminum chloride has a comparatively high vapor pressure. At the required temperatures, this can easily lead to explosions.
  • a further disadvantage is that the high temperatures required by the method promote the formation of intermetallic compounds between the aluminum to be deposited and the substrate surface. These layers are often brittle and thus worsen the adhesion of the aluminum layer to the metal substrate.
  • the object of the present invention was therefore to provide an improved process for the electrochemical deposition of base metals such as aluminum and the like, which need not be carried out inert gas conditions and also leads to uniform and well-adherent electroplated layers.
  • This object is achieved in a method of the type mentioned in that the electrolyte is covered with an organic liquid is, wherein the layer thickness of the organic liquid is at least 2 mm.
  • the organic liquid is expediently chosen so that it does not undergo any electrochemical reactions under the electrolysis conditions or these are of secondary importance.
  • the layer thickness of organic liquid applied on the electrolyte is set to a thickness of at least 2 mm or more, preferably at least 5 mm, more preferably at least 10 mm. This can ensure that as little moisture or oxygen as possible diffuses through the organic liquid layer to the electrolyte during the duration of the electrochemical metal deposition process.
  • the electrolyte can also be subjected to agitation by stirring or pumping over, without there being any formation at the surface of openings through the protective layer of the organic liquid.
  • a mixing or movement of the electrolyte may be advantageous to counteract the formation of concentration inhomogeneities of dissolved metal ions in the electrolyte.
  • the metal layers which can be produced by the method according to the invention are further distinguished by good adhesion to a multiplicity of usable cathode materials.
  • metal layers which can be produced by the method according to the invention are further distinguished by good adhesion to a multiplicity of usable cathode materials.
  • high-gloss layers be produced without the need for additives such as brighteners or the like should be added to the electrolyte.
  • the electrolyte is covered with an organic liquid.
  • an organic liquid is liquid at 25 ° C, preferably at 20 ° C, more preferably at a temperature of ⁇ 15 ° C.
  • the metal used for the coating or the semiconductor can be added to the electrolyte and / or used in the form of the anode.
  • the use of metal salts is well known in galvanic processes.
  • all anhydrous salts of the metal to be coated can be used in the process according to the invention.
  • Corresponding organometallic compounds can also be used or else mixtures of anhydrous salts and organometallics.
  • the anode can consist of a passive electrode material, ie one which, under the chosen potential conditions, itself is not subject to any electrochemical reactions.
  • electrodes made of graphite or precious metals such as platinum or gold come into question.
  • the anode can also consist of or contain the metal to be coated.
  • the anode material takes on the electrochemical actively participating by the material of the anode is oxidized and passes into the electrolyte. In other words, the anode is consumed in this process, with the dissolved metal again being deposited on the cathode surface.
  • an anode of pure aluminum is subject to the following anodic partial reaction: Al 0 solid ⁇ Al 3+ dissolved + 3 e -
  • the organic liquid has a lower density than the electrolyte, so that the organic liquid floats on the electrolyte and thus can protect it from air and / or moisture access.
  • the density of the organic liquid at 25 ° C. is preferably at most 1 g / cm 3 , preferably at most 0.9 g / cm 3 , particularly preferably at most 0.85 g / cm 3 .
  • the organic liquid is selected from hydrocarbon compounds which do not have Zerewitinoff-active H atoms, the organic liquid being selected in particular from linear, branched or cyclic alkanes or alkenes, or aromatic hydrocarbon compounds.
  • a Zerewitinoff-active H atom is understood as meaning an acidic H atom or "active" H atom. Such can be determined in a conventional manner by reacting with a corresponding Grignard reagent.
  • the amount of Zerewitinoff-active H atoms is typically determined by the methane release released in a reaction of the substance under test with methylmagnesium bromide (CH 3 -MgBr) according to the following reaction equation: CH 3 -MgBr + ROH ⁇ CH 4 + Mg (OR) Br
  • Zerewitinoff-active H atoms are typically derived from CH acidic organic groups, -OH, -SH, -NH 2, or -NHR with R as the organic residue, and -COOH.
  • the organic liquid is selected from aromatic hydrocarbon compounds having from 6 to 30 carbon atoms, aliphatic hydrocarbon compounds having from 9 to 30 carbon atoms, in particular from alkanes or alkenes.
  • Particularly suitable are linear hydrocarbon compounds having 9 to 15 carbon atoms, in particular having 10 to 15 carbon atoms or mixtures thereof.
  • the aforementioned linear hydrocarbon compounds are saturated or monounsaturated. These are, for example, n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane and n-pentadecene. Of these, n-decane is particularly preferred.
  • Sinarol is a C 14 -C 19 hydrocarbon mixture with a boiling range of 250 ° C - 330 ° C.
  • the organic liquid mixes as little as possible with water. In this way it can be ensured that the organic liquid used for overcoating represents a particularly effective diffusion barrier to water.
  • the organic liquid has a Kow value (n-octanol-water partition coefficient) of> 1.0, in particular of ⁇ 2.0.
  • Solvents having a Kow value of ⁇ 5.0 are, for example, n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane and the corresponding alkenes, in particular n-pentadecene.
  • Ionic liquids are a group of solvents which, unlike traditional organic or aqueous solvents, are composed of anions and cations.
  • ionic liquids are typically composed of an organic cation, which is often obtained by alkylation of a compound.
  • These may be selected from imidazoles, pyrazoles, thiazoles, isothiazoles, azathiazoles, oxothiazoles, oxazines, oxazolines, oxazaboroles, dithiozoles, triazoles, selenozoles, oxaphospholes, pyrroles, borols, furans, thiophenes, phospholes, pentazoles, indoles, indolines, oxazoles, isoxazoles , Isotriazoles, tetrazoles, benzofurans, dibenzofurans, benzothiophenes, dibenzothiophenes, thiadiazoles, pyridines, pyrimidines, pyrazines, pyridazines, piperazines, piperidines, morpholones, pyrans, anolines, phthalazines, quinazolines, quinoxalines and combinations thereof.
  • the anionic portion of the ionic liquid may be composed of inorganic or organic anions. Typical examples are halides, BX 4 - , PF 6 - , AsF 6 - , SbF 6 - , NO 2 - , NO 3 - , SO 4 2- , BR 4 - , substituted or unsubstituted carboranes, substituted or unsubstituted metallocarboranes, phosphates, phosphites, polyoxometalates, substituted or unsubstituted carboxylates such as acetate, triflates and non-coordinating anions.
  • halides BX 4 - , PF 6 - , AsF 6 - , SbF 6 - , NO 2 - , NO 3 - , SO 4 2- , BR 4 - , substituted or unsubstituted carboranes, substituted or unsubstituted metallocarboranes, phosphates,
  • X independently of one another may stand for fluoride, chloride, bromide or iodide and R independently of one another hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy-aryloxy , Acyl, silyl, boryl, phosphino, amino, thio or seleno.
  • a suitable compound is, for example, 1-ethyl-3-methylimidazole chloride.
  • ionic liquids are particularly suitable in the context of the method according to the invention, since they have a good electrical conductivity.
  • compounds or salts of the metal or semiconductor to be deposited are well soluble in these ionic liquids.
  • metals, semiconductors or also any mixtures or alloys thereof can be deposited by chemical means.
  • the inventive method is basically not limited to base metals, but is just as suitable for precious metals such as copper, gold, silver, platinum, palladium o. The like. It is particularly advantageous, however, that the metal used for the coating, the semiconductor or the alloy may be selected from relatively base metals.
  • non-noble metals are understood in particular to mean those in the electrochemical series in acidic solution have a more negative normal potential than hydrogen, wherein the normal potential is in particular 1.0 V or less, preferably -1.1 V or less, particularly preferably -1.5 V or less.
  • the advantage of the method according to the invention is that the electrolyte used contains no protic solvent, so that no hydrogen ions can be reduced to hydrogen at the cathode. Hydrogen reduction would otherwise prevent the latter as a competing reaction to metal deposition if the normal potential of metal deposition is more negative than hydrogen deposition and this potential difference is not compensated for by potential underpotential deposition of the metal on the particular substrate or by hydrogen overvoltage.
  • the metal is aluminum or an aluminum alloy.
  • a substrate comes in the context of the method according to the invention a variety of possible substances in question. These can be selected from conductors, semiconductors and also insulators. Of course, it is necessary for insulators to provide them in advance with an electrically conductive surface in order to use them as a cathode can. For this purpose, in a conventional manner, a graphite or metal coating in question, for example with copper or zinc.
  • Applicable insulators are for example glasses such as borosilicate glasses, quartz glass u. like., But also Plastics such as polycarbonate (PC), polystyrene (PS), polyvinyl chloride (PVC) or polymethyl methacrylate (PMMA), to name just a few examples.
  • PC polycarbonate
  • PS polystyrene
  • PVC polyvinyl chloride
  • PMMA polymethyl methacrylate
  • the inventive method can be operated over a wide temperature range of the electrolyte.
  • the electrolyte temperature during the deposition for example, be maintained at a temperature of 0 to 100 ° C, in particular at a temperature of 20 to 80 ° C.
  • the electrolyte temperature and the organic liquid used for overlaying are coordinated so that the electrolyte temperature does not come too close to the boiling point of the organic liquid.
  • the electrolyte temperature in particular at least 60 ° C lower than the boiling point of the organic liquid.
  • this difference is at least 80 ° C, more preferably at least 100 ° C.
  • Another object of the present invention relates to a device for the electrodeposition of at least one metal or semiconductor on a substrate to be coated, comprising a galvanic cell with an anode, a cathode and, if desired, a reference electrode and an electrolyte container in which the electrodes can be immersed, and a voltage source with which a potential can be applied at such a level that the induced current makes it possible to electrodeposit the metal or the semiconductor on the substrate surface, the device being characterized in that the device comprises a device for covering the electrolyte with a includes organic liquid.
  • the means for overlaying comprises a metering device for the organic liquid.
  • a control device with which a uniform layer thickness of organic liquid can be ensured.
  • This control device can determine the layer thickness of the organic liquid by means of optical sensors and, if necessary, meter in additional organic liquid when it falls below a predefinable minimum layer thickness in order to restore the desired layer thickness.
  • Another object of the present invention is the use of an organic liquid for overcoating an ionic liquid-containing electrolyte in a process for the electrodeposition of at least one metal or semiconductor on a substrate to be coated in a galvanic cell.
  • the cathodes made of steel strips of an edge length of 100 ⁇ 20 ⁇ 2 mm were cut from low-carbon steel (grade A516).
  • the steel has the following composition (in% by weight): 0.21 C, 0.13 to 0.45 Si, 0.55 to 0.98 Mn, 0.035 P and 0.040 S.
  • the samples were coated with 2004 SiC. Paper and then ground with diamond paste until an optically smooth surface was obtained. Subsequently, the samples were subjected to etching treatment in 10% hydrochloric acid for 5 minutes each, followed by washing with distilled water. Finally, the samples were again cleaned in acetone and dried.
  • an electrolyte was prepared by mixing 0.6 mol of anhydrous aluminum chloride and 0.4 mol of 1-ethyl-3-methyl-imidazole chloride by mixing in a vessel inside an argon-filled glove box. The resulting in the mixture of exothermic formed within a few minutes of the liquid electrolyte. Subsequently, the electrolyte was overcoated with a 1 cm thick layer of n-decane. Thereafter, the container with the overcoated electrolyte could be removed from the glove box for further use.
  • an anode made of pure aluminum, a cathode made of steel and a wire of pure aluminum as a reference electrode were inserted in a 3-electrode arrangement and connected to a computer-controlled potentiostat (Wenking PGS 95).
  • the use of a protective gas atmosphere was not required due to the inventive coating of n-decane.
  • a cyclic voltammogram was taken in the aforementioned arrangement to determine the deposition potential.
  • This in Fig. 1 The cyclic voltammogram (CV) shown was in the range of -1.0 to +1.0 V vs. AI recorded at a feed rate of 10 mV / s in the forward and reverse.
  • the metal deposition begins at about -200 mV vs. Al, with the maximum current density set at -650mV.
  • a steel cathode was immersed in the above-described 3-electrode arrangement in the electrolyte as described above and subjected to cathodic aluminum deposition for a period of 3600 seconds at various static cathodic potentials.
  • Potentials of -400 mV and -600 mV vs. AI set at the potentiostat to investigate the potential dependence of the grain sizes of the deposited aluminum.
  • the aluminum layers produced by the method according to the invention adhere well to the substrate, whereby at lower deposition potentials high-gloss aluminum layers could be produced without further additions to the electrolyte.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Paints Or Removers (AREA)
  • Electroplating Methods And Accessories (AREA)
EP12191555.7A 2011-12-01 2012-11-07 Procédé de dépôt galvanique d'au moins un métal ou un semi-conducteur et dispositif à cet effet Active EP2599896B1 (fr)

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DE102011055911A DE102011055911B3 (de) 2011-12-01 2011-12-01 Verfahren zur galvanischen Abscheidung wenigstens eines Metalls oder Halbleiters

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EP2599896A2 true EP2599896A2 (fr) 2013-06-05
EP2599896A3 EP2599896A3 (fr) 2014-01-22
EP2599896B1 EP2599896B1 (fr) 2021-05-26

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2891730A4 (fr) * 2012-08-31 2016-05-18 Hitachi Ltd Procédé de dépôt électrolytique non aqueux et appareil de dépôt électrolytique non aqueux

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6050888B2 (ja) * 2013-03-07 2016-12-21 株式会社日立製作所 基材上へのアルミナイド皮膜の形成方法
EP2971267B1 (fr) * 2013-03-15 2020-10-14 United Technologies Corporation Traitement de revêtement de zinc bimétallique pour une adhérence améliorée d'aluminium sur des alliages en aluminium

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0339536A1 (fr) 1988-04-26 1989-11-02 Nisshin Steel Co., Ltd. Bain de placage pour le dépôt électrolytique d'aluminium et procédé de placage utilisant ce bain
WO2010106072A2 (fr) 2009-03-18 2010-09-23 Basf Se Électrolyte et additifs tensio-actifs pour le dépôt galvanique de couches d'aluminium lisses et compactes à partir de liquides ioniques
DE102011007559A1 (de) 2010-04-19 2011-10-20 Basf Se Verfahren zur Herstellung von Elektrolyten für die Aluminiumabscheidung

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Publication number Priority date Publication date Assignee Title
BE540052A (fr) * 1955-06-13
DE2260191C3 (de) * 1972-12-08 1979-04-19 Siemens Ag, 1000 Berlin Und 8000 Muenchen Verfahren zur Vorbereitung von Werkstücken aus elektrisch leitfähigen Materialien, insbesondere Metall für die galvanische Beschichtung
DE2901586A1 (de) * 1979-01-17 1980-07-31 Montblanc Simplo Gmbh Aluminierzelle
GB0920590D0 (en) * 2009-11-25 2010-01-06 Univ Leicester New ionic liquids

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0339536A1 (fr) 1988-04-26 1989-11-02 Nisshin Steel Co., Ltd. Bain de placage pour le dépôt électrolytique d'aluminium et procédé de placage utilisant ce bain
WO2010106072A2 (fr) 2009-03-18 2010-09-23 Basf Se Électrolyte et additifs tensio-actifs pour le dépôt galvanique de couches d'aluminium lisses et compactes à partir de liquides ioniques
DE102011007559A1 (de) 2010-04-19 2011-10-20 Basf Se Verfahren zur Herstellung von Elektrolyten für die Aluminiumabscheidung

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
F. H. HURLEY; T. P. WIER, J. ELECTROCHEM. SOC., vol. 98, 1951, pages 207
J. FRANSAER; E. LEUNIS; T. HERATO; J. P. CELIS, J. APPL. ELECTROCHEM., vol. 32, 2002, pages 123 - 128
T. ZUDA; C. L. HOSSEY; G. R. STAFFORD, 210TH ECS MEETING
T. ZUDA; C. L. HOSSEY; G. R. STAFFORD, J. ELECTROCHEM. SOC., vol. 151, 2004

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2891730A4 (fr) * 2012-08-31 2016-05-18 Hitachi Ltd Procédé de dépôt électrolytique non aqueux et appareil de dépôt électrolytique non aqueux

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EP2599896B1 (fr) 2021-05-26
EP2599896A3 (fr) 2014-01-22
DE102011055911B3 (de) 2012-11-29

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