EP0926262B1 - Verfahren zur selektiven Abscheidung einer Metallschicht - Google Patents
Verfahren zur selektiven Abscheidung einer Metallschicht Download PDFInfo
- Publication number
- EP0926262B1 EP0926262B1 EP98121020A EP98121020A EP0926262B1 EP 0926262 B1 EP0926262 B1 EP 0926262B1 EP 98121020 A EP98121020 A EP 98121020A EP 98121020 A EP98121020 A EP 98121020A EP 0926262 B1 EP0926262 B1 EP 0926262B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- solution
- subjected
- noble metal
- complex compound
- metal layer
- 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
Links
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
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1605—Process or apparatus coating on selected surface areas by masking
-
- 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
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
- C23C18/1608—Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
-
- 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
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
- C23C18/1612—Process or apparatus coating on selected surface areas by direct patterning through irradiation means
-
- 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
- C23C18/30—Activating 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 claim 1
- 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.
- ionic baths palladium ions are deposited on the surface and then reduced.
- Other methods of metal deposition from baths are based on the contact of the plastic surface with a reducing medium. The reduced surface area of the plastic can then even reduce metal ions from another bath. In principle, this process is also not location-selective and it requires further intermediate steps in order to achieve a 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, part 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 site-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.
- EP 0 182 379 A2 discloses a method for electroless deposition of a metal layer a plastic such as polyacrylic sulfide. As a result, the plastic surface is laser-impacted has that the metal adheres better in the radiation-exposed areas. After Known methods of metal deposition can be used to laser pretreatment to ensure location-selective metallization.
- DD 228 835 also describes a method for depositing a metal layer on a dielectric surface known.
- the dielectric surface is made with IR laser radiation applied.
- a metal layer by chemical reductive metal deposition for example nickel phosphide 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 with UV 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. Since 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 are electrostatic interactions, but also formation of complex or Hydrogen bonds.
- groups listed above also form complexes with phenyl radicals or derivatives (sandwich complexes or Metallocenes).
- a deposition for example, by better 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 further compounds can in turn be bound covalently.
- 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 you can on the 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.
- SEM scanning electron microscope
- AFM Atomic force microscope
- 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.
- 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 radiation 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 of dimethylamine borane in 100 ml of 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).
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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)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemically Coating (AREA)
Description
- man beaufschlagt die zu beschichtenden Bereiche der Oberfläche mit elektromagnetischer Strahlung
- man erzeugt durch die Beaufschlagung der Oberfläche mit UV-Strahlung reaktive Zentren
- man fixiert durch Kontaktierung der Oberfläche mit einer Lösung einer oder mehrerer Edelmetallverbindungen die Edelmetallverbindung an den reaktiven funktionellen Gruppen der Oberfläche
- man scheidet in einem stromlosen Metallisierungsbad die Metallschicht ab
- man beaufschlagt die Oberfläche eines Kunststoffsubstrats aus Polybutylenterephthalat mit Ultraviolettstrahlung
- man erzeugt durch die Beaufschlagung der Oberfläche mit der Ultraviolettstrahlung reaktive Zentren
- man quillt das Kunststoffsubstrat nach der Bestrahlung in einer Lösung an
- man fixiert durch Kontaktierung der Oberfläche mit einer wässrigen Lösung einer Palladiumkomplexverbindung die Palladiumkomplexverbindung an den reaktiven Zentren der Oberfläche
- nach der Fixierung reduziert man das Kunststoffsubstrat mit einer Lösung von Dimethylaminboran
- man scheidet in einem stromlosen Metallisierungsbad die Metallschicht ab
Claims (9)
- Verfahren zur selektiven Abscheidung einer Metallschicht auf der Oberfläche eines Kunststoffsubstrats, bei dem die zu beschichteten Bereiche der Oberfläche mit elektromagnetischer Strahlung beaufschlagt werden,
dadurch gekennzeichnet, dass man durch die Beaufschlagung der Oberfläche mit UV-Strahlung reaktive Zentren erzeugt, dass man durch Kontaktierung der Oberfläche mit einer Lösung einer oder mehrerer Edelmetallverbindungen die Edelmetallverbindung an den reaktiven funktionellen Gruppen der Oberfläche fixiert, und man in einem stromlosen Metallisierungsbad die Metallschicht abscheidet. - Verfahren nach Anspruch 1,
dadurch gekennzeichnet, dass man die Oberfläche unter Zuhilfenahme einer Maske oder mittels eines schreibenden Laserstrahls mit elektromagnetischer Strahlung beaufschlagt, - Verfahren nach einem der Ansprüche bis 1 bis 2,
dadurch gekennzeichnet, dass man die Oberfläche eines aromatischen Kohlenwasserstoff enthaltenden Kunststoffs, und bevorzugt eines Polycarbonats oder eines Copolymers aus Acrylnitril-Butadien-Styrols mit elektromagnetischer Strahlung beaufschlagt. - Verfahren nach einem der Ansprüche 1 bis 2,
dadurch gekennzeichnet, dass man die Oberfläche eines Polyesters und bevorzugt eines Polybutylenterephthalats mit elektromagnetischer Strahlung beaufschlagt. - Verfahren nach einem der Ansprüche 1 bis 4,
dadurch gekennzeichnet, dass man die Oberfläche mit einer oder mehreren wasserlöslichen Edelmetallverbindungen kontaktiert, welche sich in einer bevorzugt wässrigen Lösung befinden. - Verfahren nach einem der Ansprüche 1 bis 5,
dadurch gekennzeichnet, dass man eine Edelmetallkomplexverbindung an die reaktiven Zentren der Oberfläche fixiert. - Verfahren nach Anspruch 6,
dadurch gekennzeichnet, dass man eine palladiumhaltige Edelmetallkomplexverbindung und bevorzugt Dinatriumtetrachloropalladat an die reaktiven Zentren der Oberfläche fixiert. - Verfahren nach einem der Ansprüche 1 bis 7,
dadurch gekennzeichnet, dass man die flüssige Lösung durch Zugabe von Eriochromschwarz T stabilisiert. - Verfahren nach einem oder mehreren der Ansprüche 1 bis 8,
dadurch gekennzeichnet,dass man die Oberfläche eines Kunststoffsubstrats aus Polybutylenterephthalat mit Ultraviolettstrahlung beaufschlagt, so dass reaktive Zentren entstehen,dass man das Kunststoffsubstrat nach der Bestrahlung in einer Lösung anquillt,dass man durch Kontaktierung der Oberfläche mit einer wässrigen Lösung einer Palladiumkomplexverbindung die Palladiumkomplexverbindung an den reaktiven Zentren der Oberfläche fixiert,dass man nach der Fixierung die Palladiumkomplexverbindung mit einer Lösung aus Dimethylaminboran reduziert,und dass man in einem stromlosen Metallisierungsbad die Metallschicht abscheidet.
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 EP0926262A1 (de) | 1999-06-30 |
EP0926262B1 true EP0926262B1 (de) | 2003-03-26 |
Family
ID=7847699
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98121020A Expired - Lifetime EP0926262B1 (de) | 1997-11-05 | 1998-11-05 | Verfahren zur selektiven Abscheidung einer Metallschicht |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0926262B1 (de) |
DE (2) | DE59807643D1 (de) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19957130A1 (de) * | 1999-11-26 | 2001-05-31 | Infineon Technologies Ag | Metallisierungsverfahren für Dielektrika |
DE10015213C1 (de) * | 2000-03-27 | 2001-09-27 | Infineon Technologies Ag | Verfahren zur Metallisierung zumindest einer Isolierschicht eines Bauelements |
DE10015214C1 (de) | 2000-03-27 | 2002-03-21 | Infineon Technologies Ag | Verfahren zur Metallisierung eines Isolators und/oder eines Dielektrikums |
EP1253217A4 (de) * | 2000-07-06 | 2006-11-29 | Nat Inst Of Advanced Ind Scien | Vorbehandlungsverfahren von stromlos zu beschichtendes material |
DE102004017440A1 (de) * | 2004-04-08 | 2005-11-03 | Enthone Inc., West Haven | Verfahren zur Behandlung von laserstrukturierten Kunststoffoberflächen |
EP2581469B1 (de) | 2011-10-10 | 2015-04-15 | Enthone, Inc. | Wässrige Aktivierungslösung und Verfahren zur stromlosen Kupferabscheidung auf direkt laserstrukturierten Substraten |
DE102013216745B4 (de) | 2013-08-23 | 2015-10-22 | Schaeffler Technologies AG & Co. KG | Wälzlagerkäfig |
Family Cites Families (2)
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 |
US4615907A (en) * | 1984-11-23 | 1986-10-07 | Phillips Petroleum Company | Plating poly(arylene sulfide) surfaces |
-
1998
- 1998-11-05 DE DE59807643T patent/DE59807643D1/de not_active Expired - Fee Related
- 1998-11-05 DE DE19851101A patent/DE19851101A1/de not_active Ceased
- 1998-11-05 EP EP98121020A patent/EP0926262B1/de not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
DE19851101A1 (de) | 1999-05-06 |
DE59807643D1 (de) | 2003-04-30 |
EP0926262A1 (de) | 1999-06-30 |
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