EP1228266B1 - Verfahren zur elektrochemischen metallisierung eines isolierenden substrats - Google Patents

Verfahren zur elektrochemischen metallisierung eines isolierenden substrats Download PDF

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Publication number
EP1228266B1
EP1228266B1 EP00966282A EP00966282A EP1228266B1 EP 1228266 B1 EP1228266 B1 EP 1228266B1 EP 00966282 A EP00966282 A EP 00966282A EP 00966282 A EP00966282 A EP 00966282A EP 1228266 B1 EP1228266 B1 EP 1228266B1
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EP
European Patent Office
Prior art keywords
metal
substrate
film
electrochemical cell
cathode
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.)
Expired - Lifetime
Application number
EP00966282A
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English (en)
French (fr)
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EP1228266A1 (de
Inventor
Vincent Fleury
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Centre National de la Recherche Scientifique CNRS
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Centre National de la Recherche Scientifique CNRS
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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
    • C25D5/54—Electroplating of non-metallic surfaces
    • 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
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics

Definitions

  • the present invention relates to a method of metallization of an insulating substrate electrochemically.
  • the oldest processes consist in putting the insulating plate to be metallized in contact with a solution of a salt of the metal and a reducing solution which causes a precipitation.
  • the contacting can be done by watering or by immersion. These methods require the use a mixture of salts and optionally additives. In addition, they do not allow to control neither the speed of deposit, nor the texture, that is to say the quality of the deposit obtained.
  • V. Fleury "Branched fractal patterns in non-equilibrium electrochemical deposition from oscillatory nucleation and growth", Nature, Vol. 390, Nov. 1997, 145-148] discloses a method for depositing a copper film on a galvanically insulating substrate. The surface to be metallized of the insulating substrate is covered with a thin film of gold.
  • the substrate is then placed in a solution of a copper salt and is connected to an anode constituted by copper and a cathode constituted by a gold film, the two electrodes being connected to a current generator.
  • the deposit on the surface of the insulating substrate is obtained by reducing the copper at the cathode.
  • the reduced metal begins to settle at the cathode, then the deposit continues on the surface to be metallized covered with the thin non-conductive gold film. But in this case too, it leads to a dendritic growth that does not form a regular thin film completely covering.
  • the structure of the deposit is extremely arborescent and tortuous.
  • the research carried out by the inventor made it possible show that when an electrochemical process is used to grow powders along the surface of a substrate, by applying to the electrochemical cell a density much higher current than the densities of current beyond which it could not, according to the art previous, obtain that three-dimensional powders, one obtained on the substrate a deposit in which the grains arrange to form a uniform film covering and not more dendrites.
  • the subject of the present invention is a electrochemical process for deposition on a substrate insulation, a continuous thin metal film.
  • the current can vary within the above range. It is however preferable to operate in galvanostatic mode by imposing a current constant to improve the homogeneity of the deposited film.
  • the method of the invention can be implemented to metallize a wide variety of insulating substrates, such as examples of plates or glass fibers, plates or Teflon® threads, filter paper, ceramic.
  • the solvent of the electrolyte may be aqueous or non-aqueous. Aqueous solutions are particularly preferred for the simplicity of their implementation.
  • the salt concentration of the electrolyte is preferably between 0.02 and 0.05 mol.l -1 .
  • the device comprises an electrochemical cell 1 connected to a generator 2.
  • Cell 1 is constituted by two rectangular glass slides 3 and 4 placed vertically and parallel to each other, one of the sides (of length L) of the blades being placed horizontally.
  • the substrate to be metallized is the face of the oriented blade 3 towards the inside of the cell.
  • Blades 3 and 4 are maintained spaced at a distance h by a separator 5.
  • the separator 5 may be a blade or a wire of the metal M or a another stable metal with respect to the electrolyte, that is to say a metal that has a higher oxidation potential than that of the metal M, so as to avoid the deposit of type electroless.
  • the distance h is preferably between about 50 ⁇ m and a few mm.
  • a cathode 6, located at the upper part of the blade 3, can be constituted by a simple painting of metal (type "silver lacquer") filed on the upper edge of the blade 3.
  • An anode 7, located at the lower part of the blade 3, can be constituted by a wire or sheet of metal M.
  • the separator 5 is also used contact between the generator 2 and the electrode 6.
  • the anode 7 also serves as a separator.
  • the anode is directly connected to the substrate. Islands of metal M 'in layer 8 sufficiently thin to be non-percolating, are deposited on the face to be metallized of the blade 3.
  • the intensity of the current applied to the cell which makes it possible to obtain a uniform and covering film of metal M is between 100. and 2000 ⁇ A, when the salt concentration C of the metal M in the electrolyte is of the order of 0.05 mol / liter.
  • This intensity of current applied to the electrochemical cell causes a current density between 2.5 and 50 mA per cm 2 of surface in the horizontal section of the cell at the level of the growth front of the deposit.
  • e 2h x C / C M.
  • the thickness e of the film can be varied by altering the concentration of metal salt M in the electrolyte.
  • the electrochemical cell can be adapted from in a way that the deposition of the metal M takes place continuously. we then pulls the substrate vertically upwards through the cell, as the part immersed in the electrolyte is covered with metal.
  • the cell consists of a glass tube segment capillary, inner diameter 1 mm and length 3 cm, curved U-shaped, so that both openings are located in the upper position, to prevent the electrolyte from disperses by gravity.
  • the tube was filled with a solution of silver nitrate.
  • Fiberglass which has a diameter 200 ⁇ m, was coated with a silver lacquer primer and vertically into one of the openings, up to that the cathodic portion serving as a primer is immersed in the electrolyte to a depth of about 2 mm.
  • a wire counter electrode anode
  • the current was circulated through the tube by imposing a constant current of 100 ⁇ A between the primer on the fiber and the anode. We thus obtained a uniform deposit of a metal film on the fiber. The fiber has then removed by pulling it upwards, making sure to do not scrape the metallized fiber on the edges of the tube glass.

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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)
  • Electroplating Methods And Accessories (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Insulated Metal Substrates For Printed Circuits (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Chemically Coating (AREA)

Claims (9)

  1. Verfahren zum Metallisieren eines isolierenden Substrats durch Auftragen eines gleichmäßigen dünnen Films aus einem Metall M auf dem isolierenden Substrat, wobei das Metall M aus Kupfer, Silber, Kobalt, Eisen oder Zinn ausgewählt ist, wobei das Verfahren darin besteht, das isolierende Substrat in einer elektrochemischen Zelle anzuordnen, die als Elektrolyt eine Lösung eines Salzes von Metall M in einem Lösungsmittel enthält und die eine Anode, die aus dem Metall M besteht, und eine Kathode umfasst, die in direktem Kontakt mit dem isolierenden Substrat steht, und dann eine Elektrolyse bei konstantem Strom durchzuführen, wobei das Verfahren dadurch gekennzeichnet ist, dass
    zunächst auf ein Ende des Substrates ein leitender Film aufgebracht wird, der die Kathode bildet;
    das Substrat so in der elektrochemischen Zelle angeordnet wird, dass die zu metallisierende Oberfläche vertikal verläuft und sich die Kathode im oberen Abschnitt befindet;
    an die elektrochemische Zelle ein Strom mit einer solchen Intensität eingeprägt wird, dass sie eine Stromdichte zwischen 1 und 50 mA/cm2 im horizontalen Abschnitt der elektrochemischen Zelle auf Höhe der Wachstumsfläche des sich ablagernden Films erzeugt.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das isolierende Substrat eine Glasplatte oder -faden, eine Platte oder ein Faden aus Teflon®, Filterpapier oder eine Keramikplatte ist.
  3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass der Elektrolyt eine wässrige Kupfersulfat-, Kupferchlorid-, Silbernitrat-, Zinnchlorid- oder Eisenchloridlösung mit einer Salzkonzentration über 10-3 Mol.l-1 ist.
  4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass die Salzkonzentration zwischen 0,02 und 0,05 Mol.l-1 liegt.
  5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Oberfläche des zu metallisierenden Substrats mit einem Niederschlag eines nicht perkolierenden und somit nicht leitenden dünnen metallischen Films aus einem gegenüber Luft stabilen Metall in der metallischen Form vorbehandelt wird.
  6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass der nicht perkolierende dünne metallische Film aus Gold oder Palladium besteht.
  7. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Intensität des an die elektrochemische Zelle angelegten Stroms zwischen 2,5 und 50 mA bei einem Zellenquerschnitt von 1 cm2 liegt.
  8. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Substrat eine rechteckige Platte ist, die vertikal in der elektrochemischen Zelle angeordnet ist, wobei der obere Abschnitt der Platte den als Kathode dienenden leitenden Film trägt, wobei der gegenüberliegende Abschnitt der Platte mit der Anode aus Metall M verbunden ist.
  9. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Substrat ein Faden ist, dessen eines Ende mit einem leitenden Film bedeckt ist und die Kathode bildet, während das andere Ende entweder frei oder direkt mit einer Anode aus Metall M verbunden ist.
EP00966282A 1999-10-11 2000-10-04 Verfahren zur elektrochemischen metallisierung eines isolierenden substrats Expired - Lifetime EP1228266B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9912644 1999-10-11
FR9912644A FR2799475B1 (fr) 1999-10-11 1999-10-11 Procede de metallisation d'un substrat isolant par voie electrochimique
PCT/FR2000/002757 WO2001027356A1 (fr) 1999-10-11 2000-10-04 Procédé de métallisation d'un substrat isolant par voie électrochimique

Publications (2)

Publication Number Publication Date
EP1228266A1 EP1228266A1 (de) 2002-08-07
EP1228266B1 true EP1228266B1 (de) 2004-02-04

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EP00966282A Expired - Lifetime EP1228266B1 (de) 1999-10-11 2000-10-04 Verfahren zur elektrochemischen metallisierung eines isolierenden substrats

Country Status (10)

Country Link
US (1) US6764586B1 (de)
EP (1) EP1228266B1 (de)
JP (1) JP4637429B2 (de)
AT (1) ATE259006T1 (de)
AU (1) AU7672900A (de)
CA (1) CA2387109C (de)
DE (1) DE60008134T2 (de)
ES (1) ES2213047T3 (de)
FR (1) FR2799475B1 (de)
WO (1) WO2001027356A1 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2812723B1 (fr) * 2000-08-01 2002-11-15 Centre Nat Rech Scient Capteur de molecules gazeuses reductrices
DE10240921B4 (de) * 2002-09-02 2007-12-13 Qimonda Ag Verfahren und Anordnung zum selektiven Metallisieren von 3-D-Strukturen
US20170105287A1 (en) * 2015-10-12 2017-04-13 Tyco Electronics Corporation Process of Producing Electronic Component and an Electronic Component
US10184189B2 (en) 2016-07-18 2019-01-22 ECSI Fibrotools, Inc. Apparatus and method of contact electroplating of isolated structures

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2596515A (en) * 1946-03-14 1952-05-13 Libbey Owens Ford Glass Co Coating vitreous substances
JP2829304B2 (ja) * 1992-11-05 1998-11-25 誠 河瀬 セラミック上へのＺｒ合金めっき方法
FR2707673B1 (fr) * 1993-07-16 1995-08-18 Trefimetaux Procédé de métallisation de substrats non-conducteurs.
FR2746116B1 (fr) * 1996-03-15 1998-06-05 Galvanoplastie sous champ
US6572743B2 (en) * 2001-08-23 2003-06-03 3M Innovative Properties Company Electroplating assembly for metal plated optical fibers

Also Published As

Publication number Publication date
DE60008134D1 (de) 2004-03-11
EP1228266A1 (de) 2002-08-07
CA2387109A1 (fr) 2001-04-19
CA2387109C (fr) 2011-05-24
JP4637429B2 (ja) 2011-02-23
ES2213047T3 (es) 2004-08-16
FR2799475B1 (fr) 2002-02-01
AU7672900A (en) 2001-04-23
DE60008134T2 (de) 2004-09-02
US6764586B1 (en) 2004-07-20
JP2003511564A (ja) 2003-03-25
WO2001027356A1 (fr) 2001-04-19
FR2799475A1 (fr) 2001-04-13
ATE259006T1 (de) 2004-02-15

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