EP2935659A2 - Procédé de métallisation d'une pièce à travailler et structure en couches à partir d'une pièce à travailler et d'une couche de métal - Google Patents

Procédé de métallisation d'une pièce à travailler et structure en couches à partir d'une pièce à travailler et d'une couche de métal

Info

Publication number
EP2935659A2
EP2935659A2 EP13828908.7A EP13828908A EP2935659A2 EP 2935659 A2 EP2935659 A2 EP 2935659A2 EP 13828908 A EP13828908 A EP 13828908A EP 2935659 A2 EP2935659 A2 EP 2935659A2
Authority
EP
European Patent Office
Prior art keywords
workpiece
microstructures
tool
metal layer
layer structure
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Withdrawn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
EP13828908.7A
Other languages
German (de)
English (en)
Inventor
Roman Ostholt
Robin Alexander Krüger
Bernd Rösener
Eugen Haumann
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.)
LPKF Laser and Electronics AG
Original Assignee
LPKF Laser and Electronics AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by LPKF Laser and Electronics AG filed Critical LPKF Laser and Electronics AG
Publication of EP2935659A2 publication Critical patent/EP2935659A2/fr
Withdrawn legal-status Critical Current

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44F—SPECIAL DESIGNS OR PICTURES
    • B44F3/00—Designs characterised by outlines
    • 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
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • 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
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2013—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by mechanical pretreatment, e.g. grinding, sanding
    • 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
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
    • C23C18/204—Radiation, e.g. UV, laser
    • 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
    • C23C18/31—Coating with metals
    • 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
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • 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
    • C25D5/02—Electroplating of selected surface areas
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0296—Conductive pattern lay-out details not covered by sub groups H05K1/02 - H05K1/0295
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0011—Working of insulating substrates or insulating layers
    • H05K3/0014—Shaping of the substrate, e.g. by moulding
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
    • 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
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1837—Multistep pretreatment
    • C23C18/1841—Multistep pretreatment with use of metal first
    • 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
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/208—Multistep pretreatment with use of metal first
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/20—Details of printed circuits not provided for in H05K2201/01 - H05K2201/10
    • H05K2201/2072—Anchoring, i.e. one structure gripping into another
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/01—Tools for processing; Objects used during processing
    • H05K2203/0104—Tools for processing; Objects used during processing for patterning or coating
    • H05K2203/0113—Female die used for patterning or transferring, e.g. temporary substrate having recessed pattern

Definitions

  • the invention relates to a method for the at least partial and adherent metallization of a non-conductive workpiece. Furthermore, the invention relates to a layer structure comprising a workpiece and an adherent metal layer connected thereto by means of structuring.
  • ABS acrylonitrile-butadiene-styrene
  • thermoplastics which can be thermally loaded even higher, such as, for example, Polyetherimide (PI), polyphenylene sulfide (PPS), polyetherether ketone (PEEK) or liquid crystal polymer (LCP), for the purpose of functional and / or decorative surface refinement adhesive metallize.
  • PI Polyetherimide
  • PPS polyphenylene sulfide
  • PEEK polyetherether ketone
  • LCP liquid crystal polymer
  • pretreatment of plastic surfaces prior to their metallization can be subdivided into the process steps of conditioning, germination and activation.
  • the process step of conditioning is of decisive importance for adherent metallization.
  • the literature describes a whole range of different chemical and physical methods for surface pretreatment of plastic surfaces.
  • the chemical processes are often tailored to the nature of the plastic surface.
  • Essential in all these methods is the unlocking of the plastic substrate surface in order to generate the necessary primer for the metal layer to be deposited.
  • the chemical process is achieved by pickling or swelling and dissolution of certain components of the plastic, the formation of caverns open to the surface, due to the undercuts for provide the so-called "push button effect" and thus lead to an adherent metallization.
  • patent application DE 100 54 544 A1 discloses a process for the chemical metalation of surfaces, in particular surfaces of acrylonitrile-butadiene-styrene copolymers (ABS) and their mixtures (blends) with other polymers, by dissolving their surfaces in highly concentrated solutions of Cr (VI) ions are pickled in sulfuric acid. It belongs to the general understanding of the skilled worker that the aggressive attack of these pickles oxidizes the butadiene component from the ABS substrate matrix superficially and removes the oxidation products selectively from the surface, thus giving rise to a porous, cavernous substrate surface suitable for the subsequent Edelmetallbekeimung and chemical metallization ensures good adhesion due to the "push button effect".
  • ABS acrylonitrile-butadiene-styrene copolymers
  • V Cr
  • ABS acrylonitrile-butadiene-styrene
  • EP 0 146 724 B1 discloses, for the pretreatment of the surface of polyamide moldings prior to electroless plating, treatment in a mixture of halides of group IA or IIA elements of the periodic table with sulfates, nitrates or chlorides of groups I NA, HIB, IVA , IVB, VIA and VIIA or of non-noble metals of group VIIIA of the periodic table in a non-corrosive, organic swelling or solvent and a metal-organic Komplexvoritati of elements of group IB or VIIIA of the Periodic Table.
  • the object of the pretreatment of plastics and especially of polyamides prior to chemical metallization is also the subject of document DE 10 2005 051632 B4 with a method in which the plastic surfaces are treated with a halide-containing and / or nitrate-containing solution of Na, Mg, Al, Si, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ca or Zn ions containing pickling solution, said solution containing a soluble fluoride in the form of a coordination compound of the general formula M1 (HF2) ,
  • HF2 general formula M1
  • a seeding, activation and subsequent electroless metallization of the surface without the above-described conditioning of the plastic surface although also forms a metal layer, but this is due to the low adhesion to the Substrate unusable for technical or decorative purposes.
  • Chromosulphuric acid is also a highly toxic, carcinogenic and fertility-damaging substance. The safe treatment of all surfaces to be metallized with chromosulfuric acid
  • microstructures mentioned arise in the laser irradiation of metals with high intensity and short pulse length ( ⁇ 100 ns) as a result of the photon-phonon interaction in a self-organizing process.
  • the exact surface topography can not be predicted or can not be predicted with reasonable effort before the laser irradiation.
  • the exact position of a survey or a valley can not currently or not predict at reasonable cost.
  • microstructures have the structural features described above. These structural features make it expedient for the person skilled in the art to make use of a description of the periodic self-organizing structures by means of-optionally medium-wavelength and amplitude.
  • microstructures In addition to the periodic repetition of specific surface topographies, all these microstructures share the characteristic that the mean wavelength of the microstructures is usually many times smaller than the dimensions commonly used for the interaction zone between laser radiation and material surface, so that it is clear to the person skilled in the art that the expression of the Microstructures can not influence by the choice of the beam diameter, but of course can limit to the irradiated area.
  • the nature of the microstructures is determined by the fluence present.
  • the self-organized laser-induced microstructures described are already being used in a number of applications. Thus, CLPs can be used to increase the absorption of electromagnetic radiation.
  • DE 10 2010 034 085 A1 describes a method for the production of embossing tools, which consist of a substrate, in the surface of which embossed structures are introduced for microstructure elements, such as holograms, nanostructures or the like.
  • the embossed structures are introduced into the surface of the substrate for the microstructure elements by means of ultrashort laser pulses of polarized electromagnetic waves or polarized electromagnetic radiation.
  • a method of surface structuring is used to produce embossing tools for microstructure elements.
  • US 2003/0135998 A1 discloses a method for producing an electrical connection element, characterized by the following method steps: a) providing a substrate made of a plastically deformable polymeric material, b) mechanical deformation of the substrate by an embossing tool, so that there substantially channel-like recesses are formed where tracks are to be formed, c) coating the substrate with an electrically conductive layer, d) plating the substrate until the recesses are filled, and e) removing conductor material until those locations of the substrate are free of a metal coating, which should have no conductive surface.
  • the channel-shaped depression describes the outer geometry of the later conductor track.
  • the invention has for its object to provide an economical and environmentally friendly way to particular selective and adherent metallization of a non-conductive workpiece surface. Furthermore, the object of the invention is to create a corresponding layer structure comprising a workpiece and a metal layer.
  • the first object is achieved by a method according to the features of claim 1.
  • the further embodiment of the invention can be found in the dependent claims.
  • the invention is based on the surprising finding that a firmly adhering metallization on non-conductive workpieces is also due to micromachined on the workpiece surface.
  • Roregalen which are free of undercuts, so without the so-called "push button effect” get done, can be achieved.
  • These undercut-free periodic microstructures can preferably be produced by an impression.
  • a method is provided for the at least partially adherent metallization of nonconductive workpieces, in which microstructures are introduced into the workpiece in the areas to be metallized by molding a microstructured tool, which are preferably free of undercuts and nevertheless lead to an increase in the adhesive strength.
  • microstructures required for adherent metallization are produced by molding microstructures of a tool.
  • the periodic microstructures refer to the surface to be metallized later. Accordingly, these are microstructured regions enclosed by metallization boundary lines.
  • the term "microstructures" does not define the absolute size of the metallized area but the properties within the metallized area.
  • the impression can be made by microstructuring both a forming and a forming tool. It is obvious to the person skilled in the art that such an impression of the microstructures can only produce structures which, according to the present invention, have substantially no undercuts.
  • the microstructure is generated in the tools by means of laser radiation.
  • Self-organizing laser-induced microstructures have proven to be particularly favorable microstructures in the tool.
  • Those skilled in the art are familiar with such structures as “Cone Like Protrusions” (CLP), “Spikes”, “Nanoripples” or “Nanospheres”.
  • CLPs are preferred according to the invention when a particularly high adhesive strength is required, nanoripples or nanospheres are preferred when decorative, so particularly smooth metal surfaces are sought.
  • the geometry of the CLPs is usually direction-independent, so that the wavelength of the structure is approximately constant in any two orthogonal spatial directions.
  • CLPs usually have a mean wavelength of about 5-30 ⁇ and a structural height ⁇ 100 ⁇ , in particular ⁇ 50 ⁇ on.
  • Nanoripples have an orientation that depends on the direction of polarization of the laser radiation, meaning that they are only meaningfully described in one spatial direction by one wavelength. This mean wavelength of nanoripples is ⁇ 5 ⁇ , typically ⁇ 1 ⁇ .
  • the amplitude of the nanoripples is usually ⁇ 5 ⁇ m, typically ⁇ 2 ⁇ m.
  • the nanospheres in turn result from irradiation with circularly polarized laser radiation and have a nearly spherical surface section with a diameter ⁇ 1 ⁇ m.
  • the microstructures (6) preferably have an average structure height (peak-to-valley) of less than 50 ⁇ m.
  • the ratio of the average structure height (peak-to-valley) of the microstructures (6) to the mean wavelength of the microstructures (6) is preferably more than 0.3, in particular more than 0.5, preferably more than 1.
  • the microstructured tool according to the invention preferably has a microstructured region, at least in a partial region of the surface which is intended for the molding of the workpiece. a region which has elevations or depressions as microstructures.
  • the entire surface of the microstructured tool, which is provided for the molding of the workpiece such a microstructured area.
  • this microstructured area only makes up at most 90%, more preferably at most 80%, of that surface of the microstructured tool which is intended for the impression of the workpiece.
  • a workpiece is then produced whose surface also has a microstructured (partial) region, but as a negative contour, i. Microstructural elevations in the tool surface are shaped as microstructural depressions in the workpiece surface and vice versa.
  • the preferred embodiments described below are defined such that the tool surface has depressions and corresponding elevations are formed in the workpiece surface.
  • a person skilled in the art will recognize that this preferred embodiment ments apply analogously to the reverse case, in which the tool surface has elevations, which are formed in the workpiece surface as depressions.
  • the microstructured (partial) region of the tool surface or the microstructured (partial) region of the molded workpiece surface has a main extension surface to which orthogonal recesses or elevations are arranged.
  • this main extension surface is essentially a planar plane. In another preferred embodiment, this main extension surface is curved, for example convex or concave.
  • the microstructures cause an increase in the surface area of the microstructured (partial) area of the tool surface or workpiece surface in comparison to the non-microstructured, i. essentially smooth surface.
  • this increase in surface area is at least 40% or at least 50%, more preferably at least 60% or at least 70%, even more preferably at least 80% or at least 100%, most preferably at least 150% or at least 200% and especially at least 250% or at least 300 %.
  • Methods for determining the surface are known to a person skilled in the art, for example by measuring the BET adsorption isotherm in accordance with DIN ISO 9277: 2003-05.
  • any non-conductive materials can be processed.
  • Particularly relevant to the metallization according to the present method are materials whose main component is a polymer or a polymer mixture. It is obvious to the person skilled in the art that the method according to the invention is not limited to certain plastics. Rather, in contrast to the prior art metallization processes, the process can process both thermoplastic and thermoset materials, which can be etchable or non-etchable.
  • the workpiece surface into which the microstructures according to the invention are introduced comprises a thermoplastic.
  • the thermoplastic is preferably selected from the group consisting of polyamide, polyester (eg, polylactate, polyethylene terephthalate, polybutylene terephthalate), polyurethane, polycarbonate, polyacrylonitrile, polymethyl methacrylate, polyolefin (eg polyethylene, polypropylene, polymethylphenyls, polybutene), polystyrene, Acrylonitrile butadiene styrene, polyvinyl chloride, polyetherimide, poly phenylene sulfide, polyether ether ketone, liquid crystal polymer and their copolymers and / or mixtures thereof.
  • the workpiece surface according to the invention into which the microstructures according to the invention are introduced, comprises acrylonitrile-butadiene-styrene (ABS), then the butadiene component is preferably still completely present since, according to the invention, the microstructures are not produced by etching the workpiece surface.
  • ABS acrylonitrile-butadiene-styrene
  • the workpiece surface into which the microstructures according to the invention are introduced comprises a duroplastic.
  • the thermoset is selected from the group consisting of aminoplasts, phenolic resins, polyurethanes, epoxy resins and crosslinked polyacrylates.
  • the method according to the invention allows the at least selective metallization of a non-conductive workpiece with locally different adhesive strengths, so that predetermined breaking points, etc. can be formed in this way.
  • the metal layer preferably has an adhesive strength according to ASTM D1876-08 of at least 3 N / cm, more preferably at least 5 N / cm, even more preferably at least 8 N / cm and in particular at least 11 N / cm.
  • microstructure is mapped multiple times by means of the tool on the workpiece surface of the same workpiece. Repeated use of the tool thus achieves a multiple imaging of the microstructures, which can be supplemented to a total metal structure during the subsequent metallization.
  • the effort for the production of the tool is reduced by only one tool has to be produced for matching microstructures.
  • several identical or different tools can be modularly added to a combination tool, so as to enable a flexible use and the possibility for reuse in other applications.
  • the workpiece surface is to be enriched either with catalytically active nuclei at least in the areas of later adherent metallization or provided with a thin conductive starting layer.
  • a thin conductive layer could be created by vaporization of metals or by chemical vapor deposition (CVD). More promising is the germination of the surface with, for example, palladium or silver, as in the Prior art is known, and a subsequent galvanic metallization, as is also known in the art.
  • a simple post-germination washing step can limit the enrichment of the catalytically active nuclei to the regions of the microstructures while efficiently and obviously removing them in non-microstructured regions.
  • the selective metallization according to the method of the invention could be used to produce MID (Molded Interconnect Devices) or to produce decorative metallic patterns.
  • the adherent metal layer is preferably applied to the workpiece surface in distinct patterns, in particular conductor tracks or decorative patterns.
  • the workpiece is thermally treated in the course of the process according to the invention.
  • the further object to provide a corresponding layer structure of a workpiece and a metal layer is inventively achieved in that the structuring is formed essentially by microstructures, which are introduced free of undercuts in the workpiece.
  • the invention is based on the knowledge, which is surprising for the person skilled in the art, that adherent metallization on non-conductive workpieces is possible in which the workpiece has microstructures in the metallized regions which are largely free from undercuts. With the method according to the invention, any non-conductive materials can be processed.
  • Particularly relevant to the metallization according to the present method are materials whose main component is a polymer, wherein the layer structure is not limited to certain plastics, but may include both thermoplastic and thermosetting constituents.
  • an injection molding tool made of tool steel 1.2343 is selectively structured with CLPs by means of picosecond laser radiation (laser power 12 W, wavelength 515 nm, scanning speed 50 mm / s, beam diameter in the alternating Effective zone 30 ⁇ ).
  • the structured tool is used to injection mold polyamide (PA) samples.
  • PA injection mold polyamide
  • the injection-molded samples are then immersed for one minute in a 50 ° C silver nitrate solution (10 g of silver nitrate dissolved in 800 ml of water). After washing with deionized water and drying the sample, the sample is thermally post-treated in a 120 ° C oven for 20 minutes. The sample is then metallized in an electroless plating bath.
  • the sample is galvanically post-amplified to a thickness of about 25 pm.
  • an adhesion strength of more than 10 N / cm is measured according to ASTM D1876-08.
  • an embossing stamp with the method mentioned in the first embodiment is selectively structured with CLP and molded onto a sample of PC + ABS blend. The sample is then steamed with gold. Due to the continuous conductive starting layer, this sample is metallized directly by electroplating. On the sample thus prepared, an adhesion strength of more than 15 N / cm is measured according to ASTM D1876-08.
  • a polybutylene terephthalate (PBT) workpiece structured according to the above procedure is etched for 10 minutes at 60 ° C. in an alkaline solution of 45 g sodium hydroxide and 45 g potassium permanganate in one liter of water to chemically functionalize the surface and thus for loading to prepare with palladium ions. Subsequently, the workpiece is washed with deionized water and incubated for 10 minutes in a solution of 200 mg of palladium chloride in 20 ml of water.
  • the surface is wetted directly with a solution of 1 g of the sodium salt of 9,10-anthraquinone-2,6-disulfonic acid in 10 ml of glycol and irradiated for 10 minutes with a commercial laboratory UV lamp. After washing with water, copper is deposited at the sites treated in a chemical metallization. An adhesion strength according to ASTM D1876-0B of greater than 12 N / cm is measured on the sample produced in this way.
  • FIGS. 4 to 12 show each in a schematic diagram in
  • FIG. 1 shows an example of the introduction of structures into a substrate according to the prior art
  • FIG. 2 shows the introduction of cavities into the substrate by means of an etching method according to the prior art
  • FIG. 3 shows a metal layer connected to the substrate by undercuts in the cavities in the prior art
  • 4 shows conical microstructures according to the invention without undercuts
  • 5 shows the introduction according to the invention of microstructures (depressions) into a tool surface of an embossing tool
  • FIG. 6 shows a negative contour introduced according to the invention into a workpiece surface by means of the embossing tool, relative to the microstructure shown in FIG. 5;
  • FIG. 7 shows the workpiece surface provided with metal nuclei according to the invention
  • FIG. 8 shows a workpiece surface provided with a metal layer according to the invention
  • 9 shows a scanning electron micrograph of a tool surface according to the invention, on which microstructures Cone Like Protrusions can be recognized;
  • FIG. 10 shows a scanning electron micrograph of a tool surface according to the invention, on which nanoripples can be recognized as microstructures;
  • FIG. 11 shows a scanning electron micrograph of a device according to the invention
  • Fig. 12 is a provided with microstructures workpiece.
  • FIGS. 1 to 3 the process sequence for introducing microstructures into a substrate by means of an etching process according to the prior art is shown in FIGS. 1 to 3.
  • certain constituents contained in the workpiece shown laterally in cross section
  • FIGS. 1 to 3 certain constituents contained in the workpiece are broken up by removing the workpiece surface and subsequently released chemically from the workpiece by means of the etching process.
  • Figure 4 shows a schematic representation of the different shape of the inventively produced microstructures and the metal layer applied thereto.
  • the microstructures have a tapered shape in the direction of the metal layer, as can be realized, for example, by conical or pyramidal shapes.
  • the invention is not limited to regular structures.
  • the microstructures can be introduced as a negative contour in such a way that the workpiece surface is removed only in the region of the microstructures to be produced.
  • the microstructures emerge from the surrounding workpiece surface. For this purpose, the workpiece surface recessed from the microstructures is removed over a large area.
  • microstructures 6 are introduced as substantially regular elevations and depressions in a first method step by means of a laser beam 5 into the tool surface 1.
  • the laser beam 5 carries material from the tool surface 1, resulting in depressions. Those areas of the tool surface 1 at which the laser beam 5 does not remove any material or less material remain as elevations relative to the depressions.
  • elevations and depressions are transferred to the workpiece surface 3 in a subsequent method step by partially transforming the workpiece surface 3 by means of the tool 2 designed as an embossing tool and the microstructures 6 as a negative contour 7 on the workpiece surface 3 within a surface enclosed by boundary lines and subsequently to be metallized be imaged.
  • This is followed by seeding of the negative contour 7 with metal nuclei 8, in particular palladium seeds, which adhere only in the region of the negative contour 7 and can be easily removed in the remaining regions.
  • the metal nuclei 8 penetrate into the workpiece surface 3, so that a flat or linear metal layer 9 is produced by a subsequent metallization starting from the metal nuclei 8.
  • FIGS. 9 to 11 different manifestations of the microstructures on the workpiece are illustrated by means of scanning electron micrographs of the tool surface.
  • FIG. 9 shows Cone Like Protrusions
  • FIG. 10 nanoripples shows nanospheres as microstructures according to the invention on the tool surface.
  • FIG. 11 shows nanospheres as microstructures according to the invention on the tool surface.
  • the workpiece 2 embodied as a printed circuit board is shown by way of example in a plan view, wherein a surface treatment of the tool surface 1 has taken place in the region of the printed conductors to be produced.
  • the microstructures 6 are to be seen as substantially regular elevations and depressions within a surface enclosed by boundary lines 10 and subsequently to be metallized, which have been introduced by molding the microstructured tool 2 shown in FIG.

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Abstract

L'invention concerne un procédé de métallisation d'une surface de pièce à travailler. La surface de pièce à travailler est dotée, dans les régions à métalliser, de microstructures périodiques (6) qui sont conférées, de préférence, par formage ou déformation d'un outil (2) microstructuré au moyen d'un rayonnement laser (5), à la surface de la pièce à travailler. Ensuite, au moins les zones microstructurées de la surface de la pièce à travailler sont métallisées avec une forte adhérence et la structure en couches est ainsi obtenue.
EP13828908.7A 2012-12-18 2013-12-03 Procédé de métallisation d'une pièce à travailler et structure en couches à partir d'une pièce à travailler et d'une couche de métal Withdrawn EP2935659A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012112550.3A DE102012112550A1 (de) 2012-12-18 2012-12-18 Verfahren zur Metallisierung eines Werkstücks sowie ein Schichtaufbau aus einem Werkstück und einer Metallschicht
PCT/DE2013/100405 WO2014094729A2 (fr) 2012-12-18 2013-12-03 Procédé de métallisation d'une pièce à travailler et structure en couches à partir d'une pièce à travailler et d'une couche de métal

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EP2935659A2 true EP2935659A2 (fr) 2015-10-28

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US (1) US9924601B2 (fr)
EP (1) EP2935659A2 (fr)
JP (1) JP2016507642A (fr)
KR (1) KR20150088893A (fr)
CN (1) CN104838046B (fr)
DE (1) DE102012112550A1 (fr)
WO (1) WO2014094729A2 (fr)

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DE102012112550A1 (de) 2014-06-18
KR20150088893A (ko) 2015-08-03
CN104838046B (zh) 2017-11-14
CN104838046A (zh) 2015-08-12
US9924601B2 (en) 2018-03-20
WO2014094729A3 (fr) 2014-08-14
US20160037650A1 (en) 2016-02-04
JP2016507642A (ja) 2016-03-10

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Ipc: C23C 18/38 20060101ALI20180111BHEP

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Ipc: C25D 5/00 20060101AFI20180111BHEP

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