EP2045365A1 - Électrolyte et procédé de dépôt de couches métalliques, en particulier de fer, cobalt, nickel, cuivre et zinc - Google Patents

Électrolyte et procédé de dépôt de couches métalliques, en particulier de fer, cobalt, nickel, cuivre et zinc Download PDF

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Publication number
EP2045365A1
EP2045365A1 EP08460009A EP08460009A EP2045365A1 EP 2045365 A1 EP2045365 A1 EP 2045365A1 EP 08460009 A EP08460009 A EP 08460009A EP 08460009 A EP08460009 A EP 08460009A EP 2045365 A1 EP2045365 A1 EP 2045365A1
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EP
European Patent Office
Prior art keywords
electrolyte
acetone
iron
water
cobalt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08460009A
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German (de)
English (en)
Inventor
Olszewski Wojciech
Krzysztof Rafal Szymanski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Uniwersytet W Bialymstoku
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Uniwersytet W Bialymstoku
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Filing date
Publication date
Application filed by Uniwersytet W Bialymstoku filed Critical Uniwersytet W Bialymstoku
Publication of EP2045365A1 publication Critical patent/EP2045365A1/fr
Withdrawn legal-status Critical Current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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • 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

Definitions

  • the subject of invention is the electrolyte and the method of depositing metal layers, especially of iron, cobalt, nickel, copper and zinc, used in electrotechnics and/or electroplating technology.
  • nonaqueous electrolytes are also known for deposition of metals, which cannot be deposited from water solutions - alkaline metals, magnesium, aluminium and rare earths.
  • nonaqueous electrolytes are composed of many substances and the compositions are set for the deposition of a particular ion.
  • Nonaqueous electrolytes are prepared from organic solvent, a dissociating compound providing the ionic transport, and the appropriate cation.
  • German patent DE 3411320 the method of separating tantalum from organic electrolytes is claimed where anodic dissolution of tantalum is applied. In this process nonaqueous electrolytes and an atmosphere of inert gas are used.
  • the method of depositing metal layers, especially of iron, cobalt, nickel, copper and zinc, according to the invention, by electrolytic deposition from the electrolyte being a mixture mainly of acetone, hydrochloric acid, positive ions of metal being deposited, is characterized in that at the initial stage of the process at least one anode is dissolved in an electrolyte containing 90-99% of acetone, 1-10 % of water and 0.5-3% of concentrated hydrochloric acid (36 % solution of HCl in water).
  • concentration of ions of the metal being deposited in the electrolyte is set automatically when the anode is being dissolved, and then on the surface of cathode the metallic layer is deposited.
  • metal layers especially of iron, cobalt, nickel, copper and zinc
  • metal layers especially of iron, cobalt, nickel, copper and zinc
  • Electrolyte used for production of metallic layers, especially iron, cobalt, nickel, copper and zinc, on different metallic substrates, according to the invention containing mainly acetone, hydrochloric acid positive ions of metal being deposited, is characterized in that it contains 90-99% of acetone, 1-10% of water and 0.5-3% of concentrated hydrochloric acid (36% solution of HCl in water).
  • the method of depositing metal layers, especially of iron, cobalt, nickel and zinc with the use of electrolyte, according to the invention, has attributes of universal applicability - a range of different metals can be deposited from the electrolyte of the same initial composition and the same current characteristics - what may be of great importance for applications. There is no need to prepare the electrolyte containing a particular cation. With the use of an appropriate anode, proper concentration of deposited metal is created automatically. Concentration of a positive ion in the electrolyte during the stage of deposition of metal is about 0.03 Mol/dm 3 , as was determined with the methods of optical spectroscopy.
  • the main constituent of the electrolyte (over 90%) is acetone, which is rather neutral for the natural environment.
  • the content of positive ions at the final stage of the process of the deposition of layers is about ten times lower than the concentration of positive ions in commercial, acid electrolytes.
  • the quantities of positive ion of metal being deposited are grams per litre, which helps to reduce costs connected with the preparation of the electrolyte.
  • Electrolytes based on acetone are of special importance in the case of radiochemistry, in processes of the preparation of radioactive sources.
  • the application of electrolyte based on acetone in a commercial process of Mössbauer sources preparation, in which a metallic layer of cobalt is being deposited would decrease the concentration of radioactive constituent of 57 Co in a solution by one order of magnitude, which would be important for radiation safety.
  • the electrolyte containing low concentration of hydrogen ions can easily be diluted by the inactive basic constituent which is acetone. It allows to control the process of taking the electrodes out with thin layers of metals. Therefore, it is possible to remove from the bath layers of thickness under 1 micrometer with ease. Low concentrations of ions enable simple replacement of a deposited ion. Hence, it is possible to obtain multi-layers by use of electrolysis processes based on acetone electrolytes. So it is possible to deposit layers containing more than one component simultaneously.
  • Anode 1, 2 is a metal, from which ions of metal are supplied to the electrolyte 4 and then a layer is being formed on the surface of cathode 5.
  • ions from anode 1, 2 go to the solution of electrolyte 4.
  • the process is performed at room temperature.
  • the power supply unit 3, 6 allows to keep constant current density ca. 5 mA/cm 2 . After a few or over a dozen minutes, a metallic layer is deposited on the surface of cathode 5.
  • the method of depositing layers and multi-layers of 3 d metals is of great practical importance for electronics and spintronics. Special importance for electronics and in particular for production lines manufacturing integrated circuits has the deposition of Cu (the so called Damascene process).
  • Layers of 3 d ferromagnetic metal alloys obtained by electrochemical methods are used on the industrial scale in production of magnetoresistive sensors. Because of low concentrations of ions in the electrolyte composed mainly of acetone with a small amount of hydrochloric acid and water, this method can be applied for radioactive sources preparation, e.g. sources with 57 Co isotope used in Mössbauer spectroscopy.

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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)
EP08460009A 2007-04-02 2008-03-28 Électrolyte et procédé de dépôt de couches métalliques, en particulier de fer, cobalt, nickel, cuivre et zinc Withdrawn EP2045365A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PL382115A PL207757B1 (pl) 2007-04-02 2007-04-02 Sposób nanoszenia warstw metali, zwłaszcza żelaza, kobaltu, niklu, miedzi i cynku oraz elektrolit do wytwarzania warstw metalicznych

Publications (1)

Publication Number Publication Date
EP2045365A1 true EP2045365A1 (fr) 2009-04-08

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EP08460009A Withdrawn EP2045365A1 (fr) 2007-04-02 2008-03-28 Électrolyte et procédé de dépôt de couches métalliques, en particulier de fer, cobalt, nickel, cuivre et zinc

Country Status (2)

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EP (1) EP2045365A1 (fr)
PL (1) PL207757B1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1811204A1 (de) * 1967-11-29 1969-08-21 Commissariat Energie Atomique Verfahren zur Herstellung duenner Schichten durch elektrolytische Abscheidung
SU420703A1 (ru) * 1972-05-23 1974-03-25 В. В. Кузнецов, В. П. Григорьев, Б. Н. Колесников, Электролит кобальтирования
DE3411320A1 (de) 1984-03-28 1985-10-10 W.C. Heraeus Gmbh, 6450 Hanau Bad und verfahren zur galvanischen abscheidung von ueberzuegen aus tantal
US4701244A (en) 1983-12-22 1987-10-20 Learonal, Inc. Bath and process for electroplating tin, lead and tin/alloys
DE19840842A1 (de) * 1998-09-07 2000-03-09 Henkel Kgaa Elektrochemische Herstellung amorpher oder kristalliner Metalloxide mit Teilchengrößen im Nanometerbereich
WO2004031449A2 (fr) 2002-09-27 2004-04-15 Sustech Gmbh & Co. Kg Procede electrochimique de regulation des dimensions des nanoparticules lors de la production d'oxydes metalliques

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1811204A1 (de) * 1967-11-29 1969-08-21 Commissariat Energie Atomique Verfahren zur Herstellung duenner Schichten durch elektrolytische Abscheidung
SU420703A1 (ru) * 1972-05-23 1974-03-25 В. В. Кузнецов, В. П. Григорьев, Б. Н. Колесников, Электролит кобальтирования
US4701244A (en) 1983-12-22 1987-10-20 Learonal, Inc. Bath and process for electroplating tin, lead and tin/alloys
DE3411320A1 (de) 1984-03-28 1985-10-10 W.C. Heraeus Gmbh, 6450 Hanau Bad und verfahren zur galvanischen abscheidung von ueberzuegen aus tantal
DE19840842A1 (de) * 1998-09-07 2000-03-09 Henkel Kgaa Elektrochemische Herstellung amorpher oder kristalliner Metalloxide mit Teilchengrößen im Nanometerbereich
WO2004031449A2 (fr) 2002-09-27 2004-04-15 Sustech Gmbh & Co. Kg Procede electrochimique de regulation des dimensions des nanoparticules lors de la production d'oxydes metalliques

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 197507, Derwent World Patents Index; AN 1975-12105W, XP002510210 *
ELECTROCHIMICA ACTA, vol. 49, 2004, pages 321
GUAN FU-YU; GAO XIAO-XIA: "Voltammetric study on the reduction of rare earths in acetone", J. CHIN. RE SOC., vol. 8, 1990, pages 166
KAMADA K ET AL: "Anodic dissolution of tantalum and niobium in acetone solvent with halogen additives for electrochemical synthesis of Ta2O5 and Nb2O5 thin films", ELECTROCHIMICA ACTA, ELSEVIER SCIENCE PUBLISHERS, BARKING, GB, vol. 49, no. 2, 15 January 2004 (2004-01-15), pages 321 - 327, XP004474653, ISSN: 0013-4686 *
S.G. VUL'FSON; A.N. VERESHCHAGIN; A. E. ARBUZOV: "Electrochemical reduction of rare-earth chelates with certain - diketones", JOURNAL RUSSIAN CHEMICAL BULLETIN, vol. 39, 1990, pages 2481
V.N. TITOVA ET AL.: "The influence of solvent on the kinetics of silver electrodeposition", JOURNAL OF ANALYTICAL CHEMISTRY, vol. 381, 1995, pages 227
YU.YA. FIALKOV; A.N. ZHITOMIRSKII; YU.A. TARASENKO: "Fizicheskaya Khimiya Nevodnykh Rastvorov", PHYSICAL CHEMISTRY OF NONAQUEOUS SOLUTIONS, 1973

Also Published As

Publication number Publication date
PL382115A1 (pl) 2008-10-13
PL207757B1 (pl) 2011-01-31

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