EP0079975B1 - Kupferkolloid und Verfahren zur Aktivierung isolierender Oberflächen für die nachfolgende Galvanisierung - Google Patents

Kupferkolloid und Verfahren zur Aktivierung isolierender Oberflächen für die nachfolgende Galvanisierung Download PDF

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Publication number
EP0079975B1
EP0079975B1 EP19810109802 EP81109802A EP0079975B1 EP 0079975 B1 EP0079975 B1 EP 0079975B1 EP 19810109802 EP19810109802 EP 19810109802 EP 81109802 A EP81109802 A EP 81109802A EP 0079975 B1 EP0079975 B1 EP 0079975B1
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EP
European Patent Office
Prior art keywords
copper
colloid
palladium
ionizable
metallic
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
Application number
EP19810109802
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English (en)
French (fr)
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EP0079975A1 (de
Inventor
William Robert Brasch
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.)
Shipley Co Inc
Original Assignee
LeaRonal Inc
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Publication date
Application filed by LeaRonal Inc filed Critical LeaRonal Inc
Priority to EP19810109802 priority Critical patent/EP0079975B1/de
Priority to DE8181109802T priority patent/DE3177050D1/de
Publication of EP0079975A1 publication Critical patent/EP0079975A1/de
Application granted granted Critical
Publication of EP0079975B1 publication Critical patent/EP0079975B1/de
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Classifications

    • 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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating

Definitions

  • the invention relates to colloidal copper solutions containing palladium useful for activating non-conductive substrates for subsequent electroless plating, to a method for preparing said solutions, to methods for activating a non-conductive substrate for electroless metal plating and to a non-conductive substrate having activating sites thereon.
  • the process requires the activation of the non-conductive substrate since electroplating cannot be carried out on such a substrate and electroless plating will also not deposit on such nonconductive surfaces.
  • the activation is followed by an electroless plating which will carry a current for subsequent electroplating or which can alternatively be further electrolessly plated with the same or a different metal.
  • U.S. Patent No. 4,239,538 to Feldstein discloses solutions containing copper ions, stannous ions and a phenol or creosol as a so-called linking agent for treatment of non-conductive substrates for subsequent electroless plating
  • Feldstein's U.S. Patent No. 4,259,376 discloses an emulsion containing copper as the principal catalytic agent and a catalytic promoter consisting of a number of non-noble metals to yield an enhanced catalytic activity for electroless plating of non-conductive substrates.
  • this bath When operating this bath at about 48.9°C (120°F), it is considered to be a fast bath and will deposit about 254 x 10- s cm (100 micro inches) of copper onto a conductive or properly activated surface in about 30 minutes.
  • An example of a slow bath would be an aqueous solution containing about 20 ml/I of a 37% formaldehyde solution, 15 g/I of sodium hydroxide, and 3 g/I of copper metal; again supplied to the solution by means of a suitable salt.
  • All of these electroless copper baths also contain stabilizers and complexing agents for the copper.
  • These stabilizing and complexing agents are also well known in the art.
  • the applicant prefers to use divalent sulfur compounds as stabilizing agents, such as those disclosed in the Schenble U.S. Patent No. 3,361,580, plus a small amount of cyanide ion.
  • the amount and type of stabilizing agent can be varied in these baths depending upon whether the bath to be employed is a slow or fast bath. Generally it is advisable to increase the amount of stabilizing agent when a fast bath is being employed. This is also well known to those skilled in the art and regulation of the stabilizing agent to obtain optimum stability will depend upon the makeup of the particular bath being employed and the operating temperature of the bath.
  • palladium metal it is advantageous to add as little palladium metal as possible to the copper colloids for economic reasons.
  • a sufficient amount of palladium metal should be added to increase the coverage of the electroless copper deposit to that desired.
  • the most advantageous amount of palladium metal has been determined to date to be about 20 parts per million (ppm) although considerably lower amounts can be used.
  • the mimimum amount of palladium metal will also depend somewhat upon the speed of the electroless copper bath and the particular ionizable palladium compound employed.
  • the upper limit of palladium metal will depend upon the particular ionizable palladium compound added to the bath, the effect of the anion of the ionizable palladium metal on the stability of the bath, and the stability of the bath itself. Thus, one should add the palladium metal in an amount which will still retain the stability of the colloid.
  • the addition of palladium metal as palladium tetra-ammonium chloride in excess of about 80 ppm of palladium metal has been found to cause coagulation of the colloid and rendering it unstable.
  • the colloids which are less stable to begin with the colloids may coagulate or be rendered unstable when amounts of palladium metal are added thereto of less than about 80 ppm.
  • the maximum amount of palladium metal that is added is that which will retain sufficient stability of the colloid so that the non-conductive substrate can be adequately activated by the colloid for subsequent electroless plating.
  • the palladium is added to the colloid in the ionic state.
  • any palladium compounds or salts capable of ionization and reduction can be used, such as the palladium chloride acid salt and palladium tetra-ammonium chloride; the latter being presently preferred.
  • the addition of palladium metal from commercial colloidal palladium activating catalysts in the amount of 20 ppm of the palladium metal, causes precipitation or coagulation of the copper colloid, and when an attempt is made to use this copper colloid containing the palladium metal added from a palladium activating colloid, zero coverage is obtained when utilizing a slow electroless copper bath.
  • a palladium metal colloid containing 20 ppm of palladium alone without the presence of the copper colloid only 60% coverage is obtained from the slow electroless copper baths.
  • the ionic palladium added to the copper colloid is reduced at some stage to palladium metal prior to electroless plating.
  • the palladium compounds can be added directly to the copper colloid if it contains an excess of reducing agent or during the preparation of the colloid if the colloid is prepared by a reduction technique, such as disclosed in the above U.S. patent to Donovan.
  • the palladium can also be added to colloids prepared by a precipitation process, such as disclosed in the Feldstein Patent No. 3,993,799 and the ionic palladium reduced after the colloid has been coated on the non-conductive substrate by immersion of the coated substrate into a reducing agent.
  • a copper colloid was prepared in accordance with Example 2 of the Donovan Patent No. 3,958,048, and a glass filled epoxy panel was immersed in the colloid, and an attempt was made to electrolessly plate the treated panel with the above-noted slow electroless copper bath. No coverage or plating of copper was noted after 30 minutes immersion time. 20 ppm of palladium metal was then added to this same colloid as palladium tetra-ammonium chloride. The palladium ammonium chloride was added to the colloid after its preparation since the prepared colloid contained sufficient excess reducing agent capable of reducing the ionic palladium contained therein to palladium metal. The panel was activated by the copper colloid containing the palladium by immersion, and then electrolessly plated with the same copper bath. The coverage of the electroless deposit on the panel was found to be about 70% after 30 minutes.
  • a copper colloid was prepared in accordance with Example 4 of the Feldstein Patent No. 4,259,376 without the manganese chloride.
  • the standard glass epoxy panel was treated with this colloid and subjected to the standard electroless solution as described above.
  • the coverage of the electroless copper was found to be about 20%.
  • Example 4 of Feldstein was again repeated adding the manganese chloride and the coverage of the electroless copper deposition was found to be about 35%.
  • the coverage from the standard slow electroless copper bath was found to be approximately 75%.
  • non-conductive substrates that can be activated according to this invention are the same as those disclosed in the patents referred to above.
  • the colloids of the invention are particularly advantageous for activating plastics such as epoxy-glass, phenolic glass, ABS-glass, phenolic- paper, etc., and the non conductive portions of laminated circuit boards.
  • These circuit boards are generally composed of such plastic compositions having two thin sheets of copper foil laminated to both sides of the plastic and having appropriate holes drilled through both copper sheets and the plastic.
  • the plastic portions of the laminate such as that exposed by the drilled holes, must be electroplated to provide continuity of electric conductivity throughout the circuit board. Thus, the exposed plastic portion of the laminate must be activated for electroless metal plating and subsequent electro metal plating.
  • colloidal copper particles themselves do not have a zeta potential of between about +3 and +13 MV.
  • the particles are altered by treatment with the suspending or stabilizing agent to possess the desired zeta potential.
  • the suspending agent itself has a zeta potential of a sufficient value to form a composite particle which has the desired zeta potential or somehow alters the zeta potential of metallic copper and/or copper oxide particles to within the desired range.
  • a stabilizing agent may have a zeta potential of about +18 mV when combined with copper particles having a minus zeta potential causing the composite particles so formed to have a zeta potential within the desired range of +3 to +13 mV.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)

Claims (8)

1. Verfahren zur Herstellung eines stabilen wäßrigen Kupferoxidkolloid zum Aktivieren eines nichtleitfähigen Substrates, dadurch gekennzeichnet, daß man eine kleinere Menge einer ionisierbaren Palladiumverbindung, wie Palladium-tetra-Ammonium-Chlorid, zu einem wäßrigen Kupferoxidkolloid gibt und die Palladiumverbindung innerhalb des Kupferkolloids unter Ausbildung von metallischen Palladiumteilchen in einer Menge, die ausreicht, um die Kupferkolloidteilchen als primäre Aktivierungsmittel beizubehalten, reduziert, wobei die maximale Menge an Palladiummetall, zugegeben als ionisierbare Palladiumverbindung, derart ist, daß die Stabilität des Kolloids beibehalten wird.
2. Verfahren gemäß Anspruch 1, bei dem das Ausgangskupferkolloid nach seiner Herstellung einen Überschuß an Reduktionsmittel enthält, und die ionisierbare Palladiumverbindung, die anschließend dazugegeben wird, durch das überschüssige Reduktionsmittel reduziert wird.
3. Verfahren gemäß Anspruch 1, bei dem die ionisierbare Palladiumverbindung innerhalb des Kupferkolloids in Gegenwart eines Suspensionsmittels, wie Gelatine, zur Metallform reduziert wird.
4. Stabiles wäßriges Kupferoxidkolloid zur Aktivierung eines nicht-leitfähigen Substrates für eine anschließende stromlose Plattierung, umfassend Kolloidteilchen aus metallischem Kupfer und wenigstens 20 ppm Palladiummetall, welches durch Reduktion einer ionisierbaren Palladiumverbindung, wie Palladium-tetra-Ammonium-Chlorid, innerhalb des Kupferkolloids ausgebildet ist, um die Kupferkolloidteilchen als primäre Aktivierungsmittel und eine ausreichende Stabilität des Kolloids beizubehalten.
5. Stabiles wäßriges Kupferoxidkolloid zum Aktivieren eines nicht-leitenden Substrates für eine stromlose Plattierung, umfassend Teilchen aus metallischem Kupfer und/oder Kupferoxid mit einer Teilchengröße zwischen etwa 0,01 und 0,1 um, und mit einem Zeta-Potential zwischen etwa +3 und +13 Millivolt, wobei das Kolloid eine ausreichende Menge an Teilchen hat, um die Oberfläche eines Nichtleiters zu aktivieren, und wenigstens 20 ppm Palladiummetall, das durch Reduktion einer ionisierbaren Palladiumverbindung, wie Palladium-tetra-Ammonium-Chlorid, die innerhalb des Kupferkolloids während der Herstellung des Kupfers durchgeführt wurde, oder durch separate Reduktion einer ionisierbaren Palladiumverbindung in Gegenwart eines Suspensionsmittels, wie Gelatine, innerhalb des Kupferkolloids nach dessen Zubereitung durchgeführt wurde, zu erhalten.
6. Verfahren zum Aktivieren eines nicht-leitfähigen Substrates für eine stromlose Metallplattierung, welche das Behandelns des nicht-leitenden Substrates mit dem stabilen wäßrigen Kupferkolloid gemäß Anspruch 4 oder 5 umfaßt.
7. Verfahren zum Aktivieren eines nicht-leitfähigen Substrates für eine stromlose Metaliplattierung, welche das Behandeln des Substrates mit einer Zusammensetzung, enthaltend eine kleinere Menge einer ionisierbaren Palladiumverbindung, wie Palladium-tetra-Ammonium-Chlorid und eine größere Menge an Kupferkolloidteilchen, welche eine ausreichende Menge an Reduktionsmittel enthalten, um die ionisierbare Palladiumverbindung zu einer Menge an metallischem Palladium, welche die Stabilität des Kolloids beibehält, zu reduzieren, umfaßt, sowie die Reduktion von Kolloidteilchen und der ionisierbaren Palladiumverbindung, wobei man eine Mischung von metallischem Kupfer und metallischem Palladium erhält, und wobei die Mischung metallisches Kupfer als das primäre Aktivierungsmittel und metallisches Palladium enthält und an dem nicht-leitenden Substrat anhaftet.
8. Nicht-leitendes Substrat, auf dem aktivierende Stellen in einem solchen Ausmaß vorliegen, daß eine stromlose Plattierung darauf möglich ist, und wobei die aktivierten Stellen eine Mischung aus einer großen Menge an Kupfermetall und von 20 bis 80 ppm Palladiummetall umfassen.
EP19810109802 1981-11-20 1981-11-20 Kupferkolloid und Verfahren zur Aktivierung isolierender Oberflächen für die nachfolgende Galvanisierung Expired EP0079975B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP19810109802 EP0079975B1 (de) 1981-11-20 1981-11-20 Kupferkolloid und Verfahren zur Aktivierung isolierender Oberflächen für die nachfolgende Galvanisierung
DE8181109802T DE3177050D1 (en) 1981-11-20 1981-11-20 Copper colloid and method of activating insulating surfaces for subsequent electroplating

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19810109802 EP0079975B1 (de) 1981-11-20 1981-11-20 Kupferkolloid und Verfahren zur Aktivierung isolierender Oberflächen für die nachfolgende Galvanisierung

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EP0079975A1 EP0079975A1 (de) 1983-06-01
EP0079975B1 true EP0079975B1 (de) 1989-05-10

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Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8501086D0 (en) * 1985-01-16 1985-02-20 Canning W Materials Ltd Metal coating
FR2935713B1 (fr) 2008-09-08 2010-12-10 Alchimer Procede de reparation de couches barrieres a la diffusion du cuivre sur substrat solide semi-conducteur ; kit de reparation pour la mise en oeuvre de ce procede
CN104264137A (zh) * 2014-10-13 2015-01-07 无锡长辉机电科技有限公司 一种胶体铜活化液的制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3011920A (en) * 1959-06-08 1961-12-05 Shipley Co Method of electroless deposition on a substrate and catalyst solution therefor
US4008343A (en) * 1975-08-15 1977-02-15 Bell Telephone Laboratories, Incorporated Process for electroless plating using colloid sensitization and acid rinse
US4048354A (en) * 1975-10-23 1977-09-13 Nathan Feldstein Method of preparation and use of novel electroless plating catalysts
US4273804A (en) * 1975-10-23 1981-06-16 Nathan Feldstein Process using activated electroless plating catalysts
US4293591A (en) * 1975-10-23 1981-10-06 Nathan Feldstein Process using activated electroless plating catalysts
US4180600A (en) * 1975-10-23 1979-12-25 Nathan Feldstein Process using activated electroless plating catalysts
US4042730A (en) * 1976-03-29 1977-08-16 Bell Telephone Laboratories, Incorporated Process for electroless plating using separate sensitization and activation steps
DE2659680C2 (de) * 1976-12-30 1985-01-31 Ibm Deutschland Gmbh, 7000 Stuttgart Verfahren zum Aktivieren von Oberflächen

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EP0079975A1 (de) 1983-06-01
DE3177050D1 (en) 1989-06-15

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