DE102011055117A1 - Metallizing a surface of polymeric-substrates useful for producing conductive structures during laser direct structuring-method, comprises e.g. metallizing the substrate wetted with an alkaline solution by chemical deposition of a metal - Google Patents
Metallizing a surface of polymeric-substrates useful for producing conductive structures during laser direct structuring-method, comprises e.g. metallizing the substrate wetted with an alkaline solution by chemical deposition of a metal Download PDFInfo
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- DE102011055117A1 DE102011055117A1 DE201110055117 DE102011055117A DE102011055117A1 DE 102011055117 A1 DE102011055117 A1 DE 102011055117A1 DE 201110055117 DE201110055117 DE 201110055117 DE 102011055117 A DE102011055117 A DE 102011055117A DE 102011055117 A1 DE102011055117 A1 DE 102011055117A1
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- 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
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- 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
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- 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
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
- C23C18/1641—Organic substrates, e.g. resin, plastic
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- 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
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- 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
- C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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- 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
- C23C18/22—Roughening, e.g. by etching
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- 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
- H05K3/185—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 by making a catalytic pattern by photo-imaging
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- 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
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0236—Plating catalyst as filler in insulating material
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- 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
- H05K2201/09—Shape and layout
- H05K2201/09009—Substrate related
- H05K2201/09118—Moulded substrate
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- 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
- H05K2203/10—Using electric, magnetic and electromagnetic fields; Using laser light
- H05K2203/107—Using laser light
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
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- Toxicology (AREA)
- Physics & Mathematics (AREA)
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Abstract
Description
Die Erfindung betrifft ein Verfahren zur Metallisierung der Oberfläche eines Substrats, insbesondere zur Metallisierung der Oberfläche eines Polymer-Substrats, sowie einer chemische Lösung zur Durchführung des Verfahrens. The invention relates to a method for metallizing the surface of a substrate, in particular for metallizing the surface of a polymer substrate, and to a chemical solution for carrying out the method.
Ein derartiges Verfahren wird benötigt um im Spritzgußverfahren hergestellte Bauteile aus einem, vorzugsweise elektrisch nichtleitenden, Polymer-Substrat mit metallischen, elektrisch-leitenden Bahnen zu versehen. Dieses, als MID-Technologie (Moulded Interconnection Device) bekanntes Verfahren wird verwendet um komplexe, 3-dimensionale Leiterbahnstrukturen auf Bauteilen zu erzeugen, die konventionelle gedruckten Leiterplatten ersetzen. Such a method is required to provide components produced by injection molding from a, preferably electrically non-conductive, polymer substrate with metallic, electrically-conductive webs. This method, known as Molded Interconnection Device (MID) technology, is used to create complex, 3-dimensional trace structures on components that replace conventional printed circuit boards.
In der MID-Technologie sind verschiedene Verfahren bekannt, wobei diese Erfindung sich auf das LDS-Verfahren (Laserdirektstrukturierung) bezieht. Various methods are known in MID technology, and this invention relates to the LDS (laser direct structuring) method.
Das LDS-Verfahren ist in der Patentanmeldung
Um eine möglichst gute elektrische Leitfähigkeit zu erzielen werden je nach Anwendungsgebiet meist mehrere metallische Schichten abgeschieden. Eine typische Beschichtung wäre beispielsweise eine 4 bis 10 µm dicke Kupferschicht, gefolgt von einer 3 bis 8 µm dicken Nickelschicht und einer obersten Schicht aus 0,05 bis 0,1 µm Gold. In order to achieve the best possible electrical conductivity, depending on the field of application, usually several metallic layers are deposited. A typical coating would be, for example, a 4 to 10 μm thick copper layer, followed by a 3 to 8 μm thick nickel layer and a top layer of 0.05 to 0.1 μm gold.
Des Weiteren wird in der
Die zu metallisierenden Bereiche weisen durch die Bestrahlung mit einem Laser eine erhöhte Rauheit durch Ablationsprodukte des Polymers auf, welche zwar eine bessere Anhaftung von Metall im chemischen Verfahren bewirken, jedoch aber die Kontaktierung der entstandenen metallisierten Schichten durch Bonden erschweren. Die
Nachteilig dabei ist, dass für jedes Bauteil, eine eigene Stempelform zur Komprimierung der Bereiche erstellt werden muss. Da nur die metallisierten Bereiche komprimiert werden sollen, muss das jeweilige Werkzeug genau der 3-dimensionalen Struktur des beschichteten Bauteils angepasst sein. Daher ist dieses Verfahren nicht universal einsetzbar und dadurch teuer. The disadvantage here is that for each component, a separate stamp shape for compression of the areas must be created. Since only the metallized areas are to be compressed, the respective tool must be adapted exactly to the 3-dimensional structure of the coated component. Therefore, this method is not universally applicable and therefore expensive.
Ein weiterer Nachteil an den bisher beschriebenen Verfahren zur Metallisierung von Polymer-Substraten mit dem LDS-Verfahren ist, dass es bei der stromlosen, chemischen Abscheidung zu sogenannten Wildabscheidungen kommt. A further disadvantage of the previously described process for the metallization of polymer substrates with the LDS process is that so-called wild deposition occurs in the electroless, chemical deposition.
Bei der Bestrahlung des Polymer-Substrates mit einem Laser wird die oberste Schicht des Substrates abgetragen und verdampft. Dabei entstehende Ablationsprodukte. Das sind Partikel des abgetragenen Substrates die sich auf und um die bestrahlten Flächen des abgetragenen Substrats anlagern. Die Ablationsprodukte enthalten, ebenso wie die bestrahlten Bereiche, Metallkeime die zur stromlosen, chemischen Abscheidung von Metall geeignet sind. Upon irradiation of the polymer substrate with a laser, the uppermost layer of the substrate is removed and evaporated. Resulting ablation products. These are particles of the ablated substrate which accumulate on and around the irradiated areas of the ablated substrate. The ablation products contain, as well as the irradiated areas, metal nuclei suitable for the electroless, chemical deposition of metal.
Durch die stromlose Abscheidung in einem chemischen Bad wird somit auch an den Ablationsprodukten auf dem Polymer-Substrat Metall abgeschieden. Diese unerwünschten Abscheidungen zwischen den Leiterstrukturen führen zu einer Verkürzung der Leiterbahnabstände und somit zu einer Verkürzung der Kriechstrecken. Je nach Ausbildung dieser Wildabscheidungen kann es sogar zu Kurzschlüssen zwischen einzelnen Leiterbahnen kommen. As a result of the electroless deposition in a chemical bath, metal is also deposited on the ablation products on the polymer substrate. These unwanted deposits between the conductor structures lead to a shortening of the conductor track distances and thus to a shortening of the creepage distances. Depending on the formation of these wild depositions, it can even lead to short circuits between individual tracks.
Der Erfindung liegt daher die Aufgabe zugrunde, ein Verfahren vorzustellen, welches zur Erzeugung von Leiterstrukturen im LDS-Verfahren geeignet ist, jedoch eine geringere Rauheit der Leiterstrukturen bietet. Zudem soll die Generierung von Wildabscheidungen bei der stromlosen Abscheidung verringert werden. The invention is therefore based on the object to provide a method which is suitable for the production of conductor structures in the LDS method, but offers a lower roughness of the conductor structures. In addition, the generation of game deposits in the electroless deposition should be reduced.
Diese Aufgabe wird durch das im Anspruch 1 beschriebene Verfahren sowie die im/in Verbindung mit der in Anspruche 5 beschriebene chemische Lösung gelöst. This object is achieved by the method described in claim 1 and the in / in connection with the chemical solution described in claim 5.
Bei der vorliegenden Erfindung handelt es sich um ein Verfahren sowie eine in diesem Verfahren verwendete chemische Lösung zur stromlosen Metallabscheidung auf laserstrukturierten Kunststoffflächen. Dieses als LDS (Laserdirektstrukturierung) bekanntes Verfahren findet als Alternative zu konventionellen gedruckten Schaltungen zur Schaltungsgestaltung auf Spritzgießteilen Anwendung. The present invention relates to a method and a chemical solution for electroless metal deposition on laser-structured plastic surfaces used in this method. This process, known as LDS (Laser Direct Structuring), is used as an alternative to conventional printed circuits for circuit design on injection molded parts.
Als Substratmaterial sind insbesondere LCP (Liquid Crystal Polymer = Flüssigkristallpolymer) geeignet, da sich diese durch gute mechanische, chemische, elektrische und umwelttechnische Eigenschaften auszeichnet. As substrate material in particular LCP (liquid crystal polymer = liquid crystal polymer) are suitable, since this is characterized by good mechanical, chemical, electrical and environmental properties.
Für die erfindungsgemäße Anwendung des Verfahrens eignen sich bevorzugt die folgenden Polyamide als Substrat:
flüssigkristalline Kunststoffe (Vectra LCP von Ticona, Zenite® von DuPont), Polybutylenterephthalat (Pocan von LANXESS Deutschland GmbH), Polyethylenterephthalat (PET), Polyvinylchlorid, Polystyrol, Acril-Styrol-Acrylnitril-Copolymere (ABS), Epoxidharzen, Polyetheretherketon, Polyoxymethylen, Polyformaldehyd, Polyacetal, Polyurethan, Polyetherimid, Polyphenylsulfon, Polyphenylensulfid, Polyarylamid, Polyphthalamid (PPA) mit/ohne Glasfaserverstärkung, Polycarbonat PC, Polyethylen PE, Polypropylen PP, Polyimid, Fluorkunststoff PTFE, Textolit PT, Glastextolit. For the application of the method according to the invention, the following polyamides are preferably suitable as substrate:
liquid crystal polymers (Vectra LCP Ticona, Zenite ® from DuPont), polybutylene terephthalate (Pocan from LANXESS Germany GmbH), polyethylene terephthalate (PET), polyvinyl chloride, polystyrene, Acril-styrene-acrylonitrile copolymers (ABS), epoxy resins, polyether ether ketone, polyoxymethylene, polyformaldehyde , Polyacetal, polyurethane, polyetherimide, polyphenylsulfone, polyphenylene sulfide, polyarylamide, polyphthalamide (PPA) with / without glass fiber reinforcement, polycarbonate PC, polyethylene PE, polypropylene PP, polyimide, fluoroplastic PTFE, textolite PT, glass textolite.
Das zur Metallisierung vorgesehene, spritzgegossene, dreidimensionale Substrat wird mittels eines Lasers an den Bereichen strukturiert, die beschichtet werden sollen. Durch die Bestrahlung mit dem Laser werden chemisch im Substrat gebundene Metalle aktiviert und bilden Metallkeime an der Oberfläche der bestrahlten Bereiche. Die Metallkeime sind geeignet um an ihnen in einem chemischen Bad Metall abzuscheiden. Eine gängige Beschichtung der strukturierten Bereiche erfolgt zum Beispiele mit Kupfer, Nickel und Gold. The injection-molded, three-dimensional substrate intended for metallization is structured by means of a laser at the areas which are to be coated. Irradiation with the laser activates metals chemically bound in the substrate and forms metal nuclei on the surface of the irradiated areas. The metal nuclei are suitable for depositing metal in a chemical bath. A common coating of the structured areas takes place for example with copper, nickel and gold.
Durch die Strukturierung der Oberfläche des Substrates mit einem Laser, weißt diese nach der Strukturierung eine höhere Rauheit auf. By structuring the surface of the substrate with a laser, this has a higher roughness after structuring.
Ablationsprodukte die durch das Lasern entstehen, setzen sich sowohl auf den strukturierten Bereichen, als auch in der Umgebung der Bereiche ab. Dies führt nicht nur zu einer erhöhten Rauheit, sondern auch zu freiliegenden Metallpartikeln die sich neben den strukturierten Bereichen befinden die Beschichtung mit Metall vorgesehen sind. Ablation products that result from lasering settle on both the structured areas and the surroundings of the areas. This not only leads to an increased roughness, but also to exposed metal particles which are provided next to the structured areas, the coating with metal.
Das vorgeschlagene Verfahren sieht vor den weiteren, schon im Stand der Technik bekannten Verfahrensschritten der Reinigung und Metallabscheidung auf dem Substrat eine stark alkalische Ätzung der Oberfläche es Substrats vor. Durch dieses Ätzen findet eine gleichmäßige Abtragung der Oberfläche des Substrats statt. Die durch das Lasern entstandenen Ablationsprodukte werden entfernt, wodurch die Rauheit der Oberfläche reduziert wird. Die glattere Oberfläche des Substrates hat eine glattere Metalloberfläche nach der chemischen Abscheidung zur Folge. The proposed method provides for a strong alkaline etching of the surface of the substrate prior to the further, already known in the prior art process steps of cleaning and metal deposition on the substrate. By this etching takes place a uniform removal of the surface of the substrate. The ablation products produced by the laser are removed, whereby the roughness of the surface is reduced. The smoother surface of the substrate results in a smoother metal surface after chemical deposition.
Neben der Rauheit der Oberfläche werden auch die Ablationsprodukte und damit verbundenen Metallpartikel, die sich neben den strukturieren Bereichen abgesetzt haben entfernt. Dadurch sind die Bereiche zwischen den zu metallisierenden Leiterbahnen frei von Ablationsprodukten, wodurch die Qualität der Metallisierung in Hinblick auf unerwünschte Metallabscheidungen erhöht wird. In addition to the roughness of the surface, the ablation products and associated metal particles that have settled next to the structured areas are also removed. As a result, the areas between the tracks to be metallized are free of ablation products, which increases the quality of the metallization with regard to undesired metal deposits.
Die erfindungsgemäße Lösung wird aus einer Basis von KOH oder NaOH gebildet, mit oder ohne Zusatz von anionischen, nichtionischen oder amphoteren Tensiden. Auch eine Mischung der Tenside ist denkbar. Die Lösung sollte dabei eine 10 bis 40%ige Konzentration des Alkalihydroxid aufweisen. Die erfindungsgemäße Lösung wird mit vorzugsweise zwei verschiedenen Tensiden der erwähnten Tensidklassen versetzt. The solution according to the invention is formed from a base of KOH or NaOH, with or without the addition of anionic, nonionic or amphoteric surfactants. A mixture of surfactants is conceivable. The solution should have a 10 to 40% concentration of the alkali metal hydroxide. The solution according to the invention is mixed with preferably two different surfactants of the mentioned classes of surfactants.
Die Anreicherung der Lösung mit Tensiden dient vorrangig zur Reduzierung der Grenzflächenspannung. Zudem können nichtionische Tenside eine unerwünschte Schaumbildung vermeiden. Dies ist insbesondere bei chemischen Bädern von Vorteil, da eine schaumige Lösung den Druck von Umwälzpumpen reduziert, wodurch die Wirkung reduziert wird. Als erfindungsgemäß nichtionische Tenside wären beispielsweise Alkylpolyglukoside (z.B. Octylglucoside, Hexylglucoside), Fettalkoholalkoxylate mit einer Kettenlänge von 10-18 C-Atomen und 2–10 mol Ethylenoxid (EO)/Propylenoxid (PO) (z.B. HOESCH FA 42 LF, Ethylan CPG 660) geeignet. The enrichment of the solution with surfactants serves primarily to reduce the interfacial tension. In addition, nonionic surfactants can avoid unwanted foaming. This is particularly advantageous in chemical baths because a foamy solution reduces the pressure of circulating pumps, thereby reducing the effect. As non-ionic surfactants according to the invention would be, for example Alkylpolyglucosides (eg octylglucosides, hexylglucosides), fatty alcohol alkoxylates having a chain length of 10-18 C-atoms and 2-10 moles of ethylene oxide (EO) / propylene oxide (PO) (eg HOESCH FA 42 LF, Ethylan CPG 660) are suitable.
Als vorteilhaft hat sich eine Konzentration anionischer Tenside von 15 bis 500 ppm, vorzugsweise von 15 bis 50 ppm herausgestellt. Nichtionische Tenside sollten in einer Konzentration von 15 bis 500 ppm, vorzugsweise von 15 bis 100 ppm in der Lösung enthalten sein. A concentration of anionic surfactants of 15 to 500 ppm, preferably 15 to 50 ppm, has proved to be advantageous. Nonionic surfactants should be included in the solution at a concentration of 15 to 500 ppm, preferably 15 to 100 ppm.
In der Lösung für die Durchführung des Verfahrens sollte so durch den Zusatz von Tensiden eine Oberflächenspannung von weniger als 70 mN/m erziehlt werden. Als besonders vorteilhaft hat sich eine Oberflächenspannung der Lösung von weniger als 50 mN/m herausgestellt. In the solution for carrying out the process, a surface tension of less than 70 mN / m should be achieved by the addition of surfactants. A surface tension of the solution of less than 50 mN / m has proven particularly advantageous.
Die Behandlungsdauer des Substrates in der Lösung sollte zwischen 10 Sekunden und 6 Minuten liegen. Vorteilhaft hat sich eine Behandlung von 15 Sekunden bis 2 Minuten erwiesen. The treatment time of the substrate in the solution should be between 10 seconds and 6 minutes. Advantageously, a treatment of 15 seconds to 2 minutes has been found.
Nach der Behandlung des Substrates in der erfindungsgemäßen Lösung sind die weiteren, bereits im Stand der Technik bekannten Verfahrensschritte zur Metallisierung vorgesehen. Hier seien genannt die Reinigung des Substrats in ein oder mehreren Spülstationen, wobei sich eine Reinigung unter Einsatz von Ultraschall als besonders vorteilhaft erwiesen hat, und die stromlose Metallisierung der gelaserten Bereiche auf dem Substrat in Metallisierungsbädern. After the treatment of the substrate in the solution according to the invention, the further, already known in the prior art process steps for metallization are provided. Mention may be made here of the cleaning of the substrate in one or more rinsing stations, wherein cleaning using ultrasound has proven to be particularly advantageous, and the electroless metallization of the lasered areas on the substrate in metallization baths.
Die durch das erfindungsgemäße Verfahren in Verbindung mit der erfindungsgemäßen Lösung erzeugten, glatten, metallischen Leiterbahnen an der Oberfläche des Substrats weisen eine bessere Löt- und Bondbarkeit als auf unbehandelten Oberflächen auf. The smooth, metallic interconnects on the surface of the substrate produced by the method according to the invention in conjunction with the solution according to the invention have a better solderability and bondability than on untreated surfaces.
Die folgenden Beispiele dienen zur Erläuterung des erfindungsgemäßen Verfahrens sowie der erfindungsgemäßen Lösung. The following examples serve to illustrate the process according to the invention and the solution according to the invention.
In den Versuchsbeispielen wurde jeweils ein im Spritzgußverfahren hergestelltes LCP-Substrat in einer erfindungsgemäßen Lösung gehandelt. Neben Angaben über das verwendete Substrat enthalten die folgenden Beispiele Angaben über die Zusammensetzung der verwendeten Lösung, sowie Behandlungsdauer, Temperatur der Lösung, Art und Stärke der abgeschiedenen Metallschicht, die mittlere Rauheit (Ra) der zu beschichtenden Bereiche vor der metallischen Beschichtung und die gemittelte Rautiefe (Rz) der metallisierten Leiterbahn nach der Beschichtung. Ferner wird aufgeführt ob unerwünschte Metallabscheidungen zwischen den Leiterbahnen nach der Beschichtung vorhanden sind. In each of the experimental examples, an injection molded LCP substrate was traded in a solution according to the invention. In addition to information about the substrate used, the following examples contain information on the composition of the solution used, and treatment time, temperature of the solution, type and thickness of the deposited metal layer, the average roughness (R a ) of the areas to be coated before the metallic coating and the averaged Surface roughness (R z ) of the metallized conductor track after the coating. It is also listed whether there are unwanted metal deposits between the tracks after the coating.
Die mittlere Rauheit (Ra) ist dabei der arithmetische Mittelwert aller Ordinatenwerte des Rauheitsprofils innerhalb der Messstrecke. Sie stellt somit die mittlere Abweichung des Profils vom Mittelwert des Profils dar. Dahingegen ist die gemittelte Rautiefe (Rz) das arithmetische Mittel der Differenz zwischen der Höhe der größten Profilspitze und der Tiefe des größten Profiltals innerhalb von fünf Einzelmessstrecken. Beispiel 1
Ähnliche Ergebnisse wurden in analogen Versuchsreihen mit den Ätzlösungen 5, 6, 7 erzielt, wobei sich für die resultierenden Rauheiten (Rz) der Kupferschicht bei vergleichbarer Behandlung der strukturierten Oberfläche zwischen 10 und 15 µm ergaben. Beispiel 5
Vergleichbare Ergebnisse wurden in entsprechenden Versuchsreihen mit den Ätzlösungen 2, 3 und 4 erzielt, wobei sich für die resultierenden, gemittelten Rautiefen (Rz) bei vergleichbarer Behandlung Werte zwischen 10,9 und 15,1 µm ergaben. Beispiel 7
Mit den erfindungsgemäßen Ätzlösungen, die zur weiteren Vergleichmäßigung der Ätzung ferner bis zu 0,03 Vol.-% eines Netzmittels enthalten können, erfolgt das Ätzen der Oberfläche von LCP-Substraten mit geringeren mittleren Rauheiten als nicht erfindungsmässig behandelte Oberfläche. Mittlere Rauheiten (Ra) zwischen 1,0 und 1,5 µm können für die gebräuchlichsten LCP-Substratmaterialien als typisch angesehen werden. With the etching solutions according to the invention, which may further comprise up to 0.03% by volume of a wetting agent to further homogenize the etching, the surface of LCP substrates with lower mean roughnesses is etched than surface not treated according to the invention. Average roughnesses (Ra) between 1.0 and 1.5 μm may be considered typical for the most common LCP substrate materials.
ZITATE ENTHALTEN IN DER BESCHREIBUNG QUOTES INCLUDE IN THE DESCRIPTION
Diese Liste der vom Anmelder aufgeführten Dokumente wurde automatisiert erzeugt und ist ausschließlich zur besseren Information des Lesers aufgenommen. Die Liste ist nicht Bestandteil der deutschen Patent- bzw. Gebrauchsmusteranmeldung. Das DPMA übernimmt keinerlei Haftung für etwaige Fehler oder Auslassungen.This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.
Zitierte PatentliteraturCited patent literature
- DE 10132092 A1 [0004] DE 10132092 A1 [0004]
- DE 102006041610 B3 [0006, 0007] DE 102006041610 B3 [0006, 0007]
Claims (19)
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DE201110055117 DE102011055117A1 (en) | 2011-11-08 | 2011-11-08 | Metallizing a surface of polymeric-substrates useful for producing conductive structures during laser direct structuring-method, comprises e.g. metallizing the substrate wetted with an alkaline solution by chemical deposition of a metal |
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DE201110055117 DE102011055117A1 (en) | 2011-11-08 | 2011-11-08 | Metallizing a surface of polymeric-substrates useful for producing conductive structures during laser direct structuring-method, comprises e.g. metallizing the substrate wetted with an alkaline solution by chemical deposition of a metal |
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CN106283132A (en) * | 2016-08-26 | 2017-01-04 | 湖北吉和昌化工科技有限公司 | A kind of soft dispersant of subacidity system electroplating bright copper |
DE102016222943B3 (en) * | 2016-11-21 | 2017-12-28 | Leibniz-Institut Für Polymerforschung Dresden E.V. | Metallised surfaces and methods for their production |
DE102021129921B3 (en) | 2021-11-16 | 2022-03-24 | Leibniz-Institut Für Polymerforschung Dresden E.V. | Process for recycling composite materials or composite materials |
US11770896B2 (en) | 2020-02-05 | 2023-09-26 | Harting Ag | Component carrier for arranging electrical components on a circuit board |
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EP0311232B1 (en) * | 1987-10-02 | 1993-09-29 | Polyplastics Co. Ltd. | Process for surface treatment of moldings of liquid-crystalline polyester resin |
DE19718177A1 (en) * | 1997-04-29 | 1998-11-05 | Fraunhofer Ges Forschung | Process for roughening plastics |
DE10132092A1 (en) | 2001-07-05 | 2003-01-23 | Lpkf Laser & Electronics Ag | Track structures and processes for their manufacture |
DE102006041610B3 (en) | 2006-09-05 | 2008-05-08 | Harting Mitronics Ag | Metallised plastic surface and method of processing metallized plastic surfaces |
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EP0311232B1 (en) * | 1987-10-02 | 1993-09-29 | Polyplastics Co. Ltd. | Process for surface treatment of moldings of liquid-crystalline polyester resin |
US5192581A (en) * | 1989-08-10 | 1993-03-09 | Microelectronics And Computer Technology Corporation | Protective layer for preventing electroless deposition on a dielectric |
DE19718177A1 (en) * | 1997-04-29 | 1998-11-05 | Fraunhofer Ges Forschung | Process for roughening plastics |
DE10132092A1 (en) | 2001-07-05 | 2003-01-23 | Lpkf Laser & Electronics Ag | Track structures and processes for their manufacture |
DE102006041610B3 (en) | 2006-09-05 | 2008-05-08 | Harting Mitronics Ag | Metallised plastic surface and method of processing metallized plastic surfaces |
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CN106283132A (en) * | 2016-08-26 | 2017-01-04 | 湖北吉和昌化工科技有限公司 | A kind of soft dispersant of subacidity system electroplating bright copper |
CN106283132B (en) * | 2016-08-26 | 2018-07-10 | 湖北吉和昌化工科技有限公司 | A kind of soft dispersant of subacidity system electroplating bright copper |
DE102016222943B3 (en) * | 2016-11-21 | 2017-12-28 | Leibniz-Institut Für Polymerforschung Dresden E.V. | Metallised surfaces and methods for their production |
US11770896B2 (en) | 2020-02-05 | 2023-09-26 | Harting Ag | Component carrier for arranging electrical components on a circuit board |
DE102021129921B3 (en) | 2021-11-16 | 2022-03-24 | Leibniz-Institut Für Polymerforschung Dresden E.V. | Process for recycling composite materials or composite materials |
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