EP0926262A1 - Verfahren zur selektiven Abscheidung einer Metallschicht - Google Patents

Verfahren zur selektiven Abscheidung einer Metallschicht Download PDF

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Publication number
EP0926262A1
EP0926262A1 EP98121020A EP98121020A EP0926262A1 EP 0926262 A1 EP0926262 A1 EP 0926262A1 EP 98121020 A EP98121020 A EP 98121020A EP 98121020 A EP98121020 A EP 98121020A EP 0926262 A1 EP0926262 A1 EP 0926262A1
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EP
European Patent Office
Prior art keywords
compound
plastic substrate
reactive centers
electromagnetic radiation
solution
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.)
Granted
Application number
EP98121020A
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German (de)
English (en)
French (fr)
Other versions
EP0926262B1 (de
Inventor
Sebastian Dipl-Phys. Beil
Christoph Dipl-Chem. Hilgers
Herbert Dipl-Ing. Horn
Klaus Dipl-Phys. Pochner
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Publication of EP0926262A1 publication Critical patent/EP0926262A1/de
Application granted granted Critical
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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/1601Process or apparatus
    • C23C18/1603Process or apparatus coating on selected surface areas
    • C23C18/1605Process or apparatus coating on selected surface areas by masking
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/1601Process or apparatus
    • C23C18/1603Process or apparatus coating on selected surface areas
    • C23C18/1607Process or apparatus coating on selected surface areas by direct patterning
    • C23C18/1608Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/1601Process or apparatus
    • C23C18/1603Process or apparatus coating on selected surface areas
    • C23C18/1607Process or apparatus coating on selected surface areas by direct patterning
    • C23C18/1612Process or apparatus coating on selected surface areas by direct patterning through irradiation means
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/18Pretreatment of the material to be coated
    • C23C18/20Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28Sensitising or activating
    • C23C18/30Activating or accelerating or sensitising with palladium or other noble metal

Definitions

  • the invention relates to methods for the selective deposition of a metal layer on the Surface of a plastic substrate according to claims 1 and 10 and a Process for the site-selective coupling of a polyatomic polar compound to the Surface of a plastic substrate according to claim 11.
  • Preferred The field of application is the electroless metallization of plastic substrates.
  • colloidal and ionogenic processes are primarily used to deposit palladium on plastic surfaces.
  • colloidal baths small particles of atomic palladum, protected by an SnCl 4 2- shell (colloid), adhere to the plastic surface.
  • ionogenic baths palladium ions are deposited on the surface and then reduced.
  • both processes are not location-selective and require chemical modification of the plastic through aggressive etching steps.
  • Other methods of metal deposition from baths are based on the contact of the plastic surface with a reducing medium. The reduced surface of the plastic can then even reduce metal ions from another bath. In principle, this method is also not location-selective and it requires further intermediate steps in order to achieve structured metal deposition.
  • Location-selective or partial coatings can be by additive or Subtractive processes can be implemented. In the latter case, the entire Provide the surface with the coating and then the ones that are not required Partial areas freed from the layer again. Any, full-surface processes. The location selectivity becomes partial over a previously applied separating layer or a subsequently applied, parts of the surface covering etching mask. This process brings a very high consumption Material for separating layers and etching agents, but also with metallization baths, that the metal layer is applied over the entire area before structuring. Problematic is still the treatment of the waste of the etching or removal processes.
  • a Palladium-containing precursor substance is applied to the plastic, which is then is selectively decomposed so that metallic palladium is formed on the surface.
  • the precursor can be decomposed thermally or by irradiation. After that the non-decomposed precursor substance must be removed from the untreated areas are removed without the palladium deposited at the treated sites remove.
  • the precursor to be applied must be thin and even mostly dissolved in harmful solvents. Furthermore, is also by Irradiation of gaseous precursors enables decomposition near the surface.
  • Plastic surfaces usually show a hydrophobic and chemically inert Behavior. This makes the deposition of substances on plastic surfaces difficult to impossible using liquid solutions.
  • a thin layer must be used as a catalyst for the electroless metallization bath or evenly distributed island atoms made of a precious metal such as Palladium can be applied.
  • the invention has for its object to provide a method which the above avoids disadvantages mentioned and with which the germination of a plastic surface can be made selectively.
  • Location-selective irradiation can be done with the help a mask or by means of a writing light beam and preferably one writing laser beam.
  • the surface to be treated is electromagnetic Radiation applied.
  • the energy of the radiation must be sufficient to be thin Layer on the plastic surface to cause chemical changes.
  • the fat this modified layer depends on the penetration depth of the ultraviolet radiation and is a maximum of about 200 nm. It has been shown that these chemical Adjust changes preferred when using ultraviolet radiation, whereby the chemical changes at a wavelength below 320 nm and preferred 222 nm are particularly good.
  • aromatic hydrocarbons come into question containing plastics, preferably polycarbonate or copolymers of acrylonitrile-butadiene-styrene.
  • plastics made of polyester and preferably made of are also suitable Polybutylene terephthalate.
  • the treated plastic part is either still in one Swelling solution dipped to increase the deposition of the substances to be separated, or immediately contacted with the solution containing the substances to be separated or their Contains precursors.
  • the substances are passed on to the reactive centers fixed. Because the reactive centers only on the previously irradiated Areas have been created, selective separation takes place in this way the previously irradiated areas.
  • noble metal compounds and preferably noble metal complex compounds
  • the compounds mentioned can specifically be palladium-containing compounds. Good results were achieved in particular with disodium tetrachloropalladate (Na 2 Cl 4 Pd). It is advantageous to stabilize the liquid solution by adding eriochrome black T.
  • Conceivable are polar functional groups such as carbonyl, carboxyl, hydroxyl, peroxo, Hydroperoxo, amino, imino, thiol or sulfonic acid groups.
  • Conceivable mechanisms here are electrostatic interactions, but also formation of complex or Hydrogen bonds.
  • complexes with phenyl radicals or derivatives also form complexes with phenyl radicals or derivatives (sandwich complexes or Metallocenes).
  • a deposition for example, by a better one Wetting the surface with the solvent or interactions with the hydrated shell of the solute.
  • a covalent one Coupling is possible, for example from reactive hydrazines to carbonyl groups, to the again further compounds can be covalently bound.
  • the solution containing the substance to be separated is removed from the previous one irradiated plastic part, for example by dripping, by rinsing with a Solvent or simple evaporation of the solvent, so it can be no deposition of the substance can be detected in unirradiated areas.
  • the plastic part can then be fed to further reactions, for example in the case a palladium deposition of a metallization in an electroless nickel bath.
  • the invention enables the selective metallization of Plastic surfaces without the use of vacuum equipment, photoresists or harmful solvents.
  • the order of a precursor or of Intermediate layers are not necessary.
  • the samples only need to be selectively irradiated and then be contacted with a preferably aqueous solution.
  • the Germination result with the precious metal, e.g. with palladium, is particularly good if the precious metal compound is water soluble. This makes it very easy complex and finely structured coatings on two or three-dimensional components produce.
  • the germination according to the invention works in a location-selective manner even on smooth substrates or single-phase polymers.
  • Even with a very thorough investigation of the Plastic surface through a scanning electron microscope (SEM) or a Atomic force microscope (AFM) could not be topographical or morphological changes in the polymer base material can be found.
  • SEM scanning electron microscope
  • AFM Atomic force microscope
  • the adhesive strength can be improved if a rough substrate is used instead of a smooth surface.
  • examples are ceramics with and without organic binder or metals.
  • Sufficient energy i.e. from the vacuum UV range, can also be used inorganic materials Bonds of the base material or the native oxide layer broken up and thus chemically active sites are generated.
  • Similar to Plastic workpieces can also be used for coated metallic workpieces Bonds in the organic surface layer, for example a color layer, be activated photochemically.
  • others can wet chemical coating process of a locally selectively applied germination be initiated. Examples are the application of paints, inks or adhesives.
  • the method according to the invention can also be used for the location-selective coupling of a polyatomic polar compound to the surface of a plastic substrate, in which areas of the surface are exposed to electromagnetic radiation, in which components of the base material of the plastic substrate are converted into reactive centers in the irradiated areas which the plastic substrate is brought into contact with after exposure to a liquid solution of the polar compound, and in which the polyatomic polar compound couples exclusively to the reactive centers.
  • Good results have been achieved with organic dyes, especially with rhodamine B, but inorganic compounds can also be fixed to the reactive centers in the manner described above. It is possible that the compound in liquid solution reacts at the irradiated areas and forms the compound to be deposited there. If potassium permanganate (KMnO 4 ) is selected as the polar compound, manganese dioxide (MnO 2 ) is present on the plastic surface after the treatment in aqueous solution.
  • a sample of polybutylene terephthalate (PBT) in a 1% solution of Mucasol in water is cleaned for the selective deposition of palladium.
  • This is followed by selective irradiation with 222 nm UV radiation (for example using an excimer UV lamp from the manufacturer Heraeus-Noblelight GmbH) with an output of 0.68 mW / cm 2 at a distance of 10 cm from the lamp.
  • the irradiation lasts 5 minutes.
  • the masking can be done either by putting on a mask or by applying an opaque, water-soluble ink.
  • the sample is then swollen in a 5 molar solution of NaOH in water for 5 minutes. The solution is at room temperature and is stirred.
  • the sample After rinsing in distilled water, the sample is immersed in a solution of 0.03 g Na 2 Cl 4 Pd and 0.01 g eriochrome black T in 100 ml water. The treatment is carried out at room temperature with stirring and takes 5 minutes. The palladium complexes present in the solution selectively couple to the irradiated areas of the sample. After rinsing, the sample is immersed for a further 3 minutes in a solution of 0.4 g dimethylamine borane in 100 ml water. The coupled palladium complexes are reduced in the solution at approx. 40 ° C. for 3 minutes. In the subsequent electroless nickel bath, this leads to faster deposition of the nickel bath and prevents carryover of liquid residues with dissolved, uncoupled palladium complexes into the nickel bath.
  • the PBT sample is irradiated as in Example 1.
  • the sample is then immersed in a solution of 0.5 g KMnO 4 in 100 ml water at approx. 60 degrees Celsius. After 5 minutes, a clearly visible layer of MnO 2 was deposited on the irradiated areas.
  • Braunstein (MnO 2 ) is a common catalyst for redox reactions. Therefore, a location-selective coating with manganese dioxide is interesting with regard to alternative deposition mechanisms (eg polymerization).
  • the PBT sample is irradiated as in Example 1. Then it is immersed in a solution of 0.02 g rhodamine B in 30 ml ethanol.
EP98121020A 1997-11-05 1998-11-05 Verfahren zur selektiven Abscheidung einer Metallschicht Expired - Lifetime EP0926262B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19748888 1997-11-05
DE19748888 1997-11-05

Publications (2)

Publication Number Publication Date
EP0926262A1 true EP0926262A1 (de) 1999-06-30
EP0926262B1 EP0926262B1 (de) 2003-03-26

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EP98121020A Expired - Lifetime EP0926262B1 (de) 1997-11-05 1998-11-05 Verfahren zur selektiven Abscheidung einer Metallschicht

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EP (1) EP0926262B1 (es)
DE (2) DE59807643D1 (es)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2581469A1 (en) * 2011-10-10 2013-04-17 Enthone, Inc. Aqueous activator solution and process for electroless copper deposition on laser-direct structured substrates

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002004705A1 (fr) * 1999-01-20 2002-01-17 National Institute Of Advanced Industrial Science And Technology Procede de traitement preliminaire d'un materiau devant etre soumis a un depot autocatalytique
DE19957130A1 (de) 1999-11-26 2001-05-31 Infineon Technologies Ag Metallisierungsverfahren für Dielektrika
DE10015214C1 (de) 2000-03-27 2002-03-21 Infineon Technologies Ag Verfahren zur Metallisierung eines Isolators und/oder eines Dielektrikums
DE10015213C1 (de) * 2000-03-27 2001-09-27 Infineon Technologies Ag Verfahren zur Metallisierung zumindest einer Isolierschicht eines Bauelements
DE102004017440A1 (de) 2004-04-08 2005-11-03 Enthone Inc., West Haven Verfahren zur Behandlung von laserstrukturierten Kunststoffoberflächen
DE102013216745B4 (de) 2013-08-23 2015-10-22 Schaeffler Technologies AG & Co. KG Wälzlagerkäfig

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD228835A1 (de) * 1984-09-14 1985-10-23 Mittweida Ing Hochschule Laseraktivierung von dielektrischen oberflaechen zur partiellen chemischreduktiven metallabscheidung
EP0182379A2 (en) * 1984-11-23 1986-05-28 Phillips Petroleum Company Plating poly(arylene sulfide) surfaces

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD228835A1 (de) * 1984-09-14 1985-10-23 Mittweida Ing Hochschule Laseraktivierung von dielektrischen oberflaechen zur partiellen chemischreduktiven metallabscheidung
EP0182379A2 (en) * 1984-11-23 1986-05-28 Phillips Petroleum Company Plating poly(arylene sulfide) surfaces

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2581469A1 (en) * 2011-10-10 2013-04-17 Enthone, Inc. Aqueous activator solution and process for electroless copper deposition on laser-direct structured substrates
WO2013055786A1 (en) * 2011-10-10 2013-04-18 Enthone Inc Aqueous activator solution and process for electroless copper deposition on laser-direct structured substrates
US9538665B2 (en) 2011-10-10 2017-01-03 Enthone Inc. Process for electroless copper deposition on laser-direct structured substrates

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Publication number Publication date
DE59807643D1 (de) 2003-04-30
EP0926262B1 (de) 2003-03-26
DE19851101A1 (de) 1999-05-06

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