EP3601642A1 - Method for producing electrically conductive structures on a carrier material - Google Patents
Method for producing electrically conductive structures on a carrier materialInfo
- Publication number
- EP3601642A1 EP3601642A1 EP18714226.0A EP18714226A EP3601642A1 EP 3601642 A1 EP3601642 A1 EP 3601642A1 EP 18714226 A EP18714226 A EP 18714226A EP 3601642 A1 EP3601642 A1 EP 3601642A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- phosphate
- metal
- support material
- acids
- 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.)
- Pending
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
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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
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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
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1862—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by radiant energy
- C23C18/1868—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
- C23C18/2026—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
- 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
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
- G03F7/2053—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser
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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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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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
- H05K3/105—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 by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
- C08K2003/3081—Aluminum sulfate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/329—Phosphorus containing acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0703—Plating
- H05K2203/0716—Metallic plating catalysts, e.g. for direct electroplating of through holes; Sensitising or activating metallic plating catalysts
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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
Definitions
- the present invention relates to a process for the production of electrically conductive metal structures, preferably interconnect structures, by means of laser light on a non-conductive substrate and the use of a combination of at least one inorganic metal-phosphate compound and a stabilizer in such a process.
- MID molded interconnect devices
- additive techniques the conductor metal, usually copper, is applied only to the required locations such as conductor tracks, pads, etc.
- subtractive technique on the other hand, the entire surface of the carrier material is laminated with the conductor metal and then applied an etching resist.
- the Atzresist is either applied already structured, for example by screen printing, or it is applied over the entire surface and then z. B.
- a more modern additive process for the production of interconnect structures which is widely used due to its advantageous properties, is laser direct structuring (LDS).
- the method comprises applying or introducing non-conductive metal complexes or metal salts which release metallization nuclei upon laser irradiation, onto or into a thermoplastic dielectric and subsequent irradiation of the desired structures by means of laser light for initiating metal nucleation. After subsequent chemical metallization, it is possible to obtain such fine, firmly adhering printed conductor structures.
- the metal complexes described for this purpose in the prior art often have low stability in the processing processes for the preparation of the thermoplastic carrier materials such as extrusion or injection molding, resulting in deposits on the metal surfaces of the processing tools.
- complexes containing heavy metals are also accompanied by environmental and toxicological concerns.
- the complexes used can lead to undesirable side reactions in the materials used, such as plastic degradation, or they have a strong intrinsic color, whereby the carrier material is given an undesirable color.
- EP 0 917 597 B1 relates, for example, to a process for producing printed conductor structures in which a nonconductive organic heavy metal complex, in particular a Pd-containing heavy metal complex, is applied as a coating to a non-conductive carrier material.
- this component is broken up by UV radiation with the release of heavy metal nuclei and then chemically reductively metallized.
- the support material for this process must either have per se a microporous structure or the heavy metal component must be fixed with the aid of a binder on the support material.
- EP 1 191 127 B1 discloses a method for the selective metallization of dielectric materials, in which the dielectric is firmly adhered to an activating layer of conductive material and structuring is achieved by laser irradiation without a mask. This is subsequently metallized electrolytically or electrolessly.
- the conductive materials used are Pd or Cu nuclei coated conductive polymers, metal sulfides or metal polysulfides.
- Significant disadvantages of this method are the relatively high cost of the electrically conductive materials, such as the conductive polymers, as well as the toxicological and ecological concern of the heavy metal compounds. In addition, these can lead to undesirable degradation and side reactions in the dielectric.
- EP 1 274 288 B1 discloses a process which uses non-conductive, thermally highly stable complexes of heavy metals of the d and f blocks as a nucleating component, which can remain unchanged on the surface of the support material even after laser structuring in the vicinity of the conductor track structures. These are stable even after the action of the soldering temperatures and in the acidic or alkaline metallizing baths used for the metallization.
- Significant disadvantages of this process are the high costs of the transition metal compounds and their toxicological and ecological concern as well as possible side reactions by the transition metal compounds in the course of the processing.
- the object of the present invention was to provide a comparison with the prior art improved method for producing electrically conductive metal structures, preferably interconnect structures, on a non-conductive support material, which avoids the use of heavy metal complexes in particular or at least reduced and thus toxicologically and ecologically less questionable as known processes, causing no or less deposits on the processing tools and is comparatively easy and inexpensive.
- This object is achieved by a method for producing electrically conductive structures, preferably interconnect structures, by means of laser light on a non-conductive substrate (LDS method), characterized in that
- non-conductive support material which finely distributes or dissolves therein at least one inorganic metal-phosphate compound and at least one
- Stabilizer contains, the carrier material in areas irradiated by laser light to form the electrically conductive structures in the irradiated areas, wherein the at least one inorganic metal-phosphate compound is selected from the group consisting of
- the electrically conductive structures produced by means of laser irradiation may be elemental metal, electrically conductive metal oxide, electrically conductive carbon, electrically conductive carbon compound or a combination of the aforementioned. It has surprisingly been found that the use of the stabilizer according to the invention in combination with the at least one inorganic metal-phosphate compound creates particularly favorable reaction conditions for the generation of electrically conductive structures under the action of lasers. In addition, it has been found that the stabilizer prevents or at least reduces decomposition reactions due to thermal and mechanical action, which in the course of processing can lead to metal deposits on the processing equipment (extrusion screw, injection mold, etc.).
- Bronsted acid in the context of the present invention denotes a compound which acts as a proton donor and can transfer protons to a second reaction partner, the so-called Bronsted base.
- the Brönsted acid is defined as the compound whose pKa value is smaller than that of the reactant.
- the pKa of the Bronsted acid is less than the pKa of the water, which is 14.
- Lewis acid in the context of the present invention denotes a compound which acts as an electrophilic electron pair acceptor and thus receives a pair of electrons partially or completely from a second reaction partner, the so-called Lewis base, to form an adduct.
- the Lewis acids include compounds i) with incomplete electron octets, such as: B (CH 3) 3, BF 3, AlCl 3, FeC, (ii) metal cations as central atoms in chemical complexes, iii) molecules with polarized multiple bonds, iv) Unsaturated coordination halides such as SiCu or PF5, v) other electron pair acceptors, for example condensed phosphates.
- a carrier material may comprise any organic or inorganic material which may contain the metal-phosphate compound and stabilizer combination of the method according to the invention in finely divided or dissolved form.
- the metal-phosphate compound and the stabilizer can be distributed homogeneously in the carrier material in one embodiment of the invention. This has manufacturing advantages, because a homogeneous distribution is by means of common processing methods, such as melt, extrusion, extrusion, etc., very easy to implement.
- the metal-phosphate compounds and the stabilizer are more concentrated in certain areas of the support material than in other areas.
- the metal-phosphate compound and the stabilizer on the surface of the support material on which the metal structures are produced up to a certain penetration depth of preferably 10 ⁇ to 5 mm, more preferably from 50 ⁇ to 3 mm, particularly preferred from 100 ⁇ to 1 mm, higher concentrated than in deeper areas.
- a targeted enrichment in the near-surface region of the support material can lead to improved material properties and to better interconnect structures, since the metal-phosphate compound is needed there just for the production of the electrically conductive structures.
- the generation of electrically conductive material in deeper areas in the interior of the carrier material is reduced or completely prevented and thereby less adversely affects the structural integrity of the carrier material.
- the inorganic metal-phosphate compounds used in the process according to the invention are temperature-resistant in such a way that they remain stable in the processing process and under the effect of the soldering temperatures used in the processing of printed conductor structures, that is to say in this context that they are at elevated temperatures do not become electrically conductive and do not decompose. They remain unchanged during the manufacturing process of the conductor structures and also thereafter in the carrier material and in the environment of the conductor tracks. An additional process step to remove these compounds is not necessary.
- the at least one metal-phosphate compound used is or comprises water-free iron (II) orthophosphate of the general formula Fe 3 (PO 4 ) 2 and / or water-free iron (II) metal orthophosphate, iron (II) Metal phosphonate, iron (II) metal pyrophosphate or iron (II) metal metaphosphate of the general formula Fe a Metb (PO c ) d.
- iron compounds offer a number of advantages over metal compounds used to date in known LDS processes. They are more economical and cheaper to produce, which has an advantageous effect on the manufacturing cost of substrates with electrically conductive structures, in particular printed circuit boards according to the inventive method.
- NIR near infrared
- the Bronsted acids and / or Lewis acids used according to the invention as a stabilizer are expediently selected from those acids which are so temperature-resistant that they remain stable during the processing and after exposure to the soldering temperatures and do not decompose under these and other conditions used.
- Bronsted acids suitable and preferred as stabilizer according to the present invention include phosphorus oxy acids with phosphorus in the oxidation state + V, + IV, + III, + II or + l, sulfuric acid, nitric acid, hydrofluoric acid, silicic acid, aliphatic and aromatic carboxylic acids and salts of the aforementioned acids ,
- the oxygen acids of the phosphorus and salts thereof are selected from phosphoric acid, diphosphoric acid, polyphosphoric acids, hypodiphosphoric acid, phosphonic acid, diphosphonic acid, hypodiphosphonic acid, phosphinic acid and salts of the aforementioned acids.
- the aliphatic and aromatic carboxylic acids and their salts are preferably selected from acetic acid, formic acid, oxalic acid, phthalic acid, sulfonic acids, benzoic acid and salts of the abovementioned acids.
- Advantageous are acids which are readily miscible with the support material, do not decompose during the incorporation of the stabilizer in the support material and not or only slightly affect the material properties.
- Suitable Lewis acids suitable as stabilizer according to the invention include sodium aluminum sulfate (SAS), monocalcium phosphate monohydrate (MCPM), dicalcium phosphate dihydrate (DCPD), sodium aluminum phosphate (SALP), calcium magnesium aluminum phosphate, Calcium polyphosphate, aluminum chloride, boron trifluoride, magnesium polyphosphate, aluminum hydroxide, boric acid, alkylboranes, aluminum alkyls, ferrous salts, and mixtures of the foregoing.
- Lewis acids have the advantage over Brönsted acids that they do not split off and release water during the processing and structuring process, which could lead to foaming, cracking or ablation of the support material or to oxidation reactions of the metal-phosphate compound.
- the stabilizer comprises a combination of at least one Bronsted acid and at least one Lewis acid.
- a combination has the advantage that very easily advantageous conditions for the production of electrically conductive structures and increased stability of the metal-phosphate compound in the processing step can be achieved by the usually very high stability of the widely available Brönsted acids.
- the at least one Lewis acid optionally liberated water, which could adversely affect the Laser Modelltechniksbuch be intercepted.
- the process according to the invention has the advantage that good conductor structures can be obtained even without additional chemically reductive or electrolytic metal deposition. The production of carrier materials with electrically conductive structures can thereby be substantially simplified and carried out more cheaply.
- the method according to the invention also opens up very flexible production possibilities and changes to the interconnect structures produced since masks, such as screen printing masks or photomasks, are not required and additional metallization steps can be dispensed with depending on the requirements. It is also possible to dispense with the use of resist substances, as a result of which additional chemicals and process steps can be considerably saved. Complex and difficult-to-handle etching and stripping steps are not needed. In the case of laser structuring according to the method according to the invention, the reject rate is low in comparison with other methods, as a result of which considerable costs can be saved.
- metal is deposited chemically reductively or electrolytically on the electrically conductive structures produced by means of laser light.
- the chemically reductive metallization can advantageously be carried out wet-chemically in a metal bath, preferably in a copper, nickel, silver or gold bath, particularly preferably in a copper bath. Corresponding techniques and methods are known to those skilled in the art.
- the chemically reductive metallization has the advantage over the electrolytic metallization, that in this process the often required auxiliary conductors, which serve as current bridges between isolated conductor track areas, are not required and, unlike electrolytic metallization, not subsequently in a further process step, for example by laser treatment, must be removed again.
- the carrier material with the electrically conductive structures produced thereon is suitable, for example, for use as printed circuit boards for electrical circuits.
- the electrically conductive structures can also be embodied as antenna structures which serve as antennas for electromagnetic radiation, for example in mobile devices, can be used. In both cases, the generated electrically conductive structures can be used with or without additional chemically reductive or electrolytic metal deposition.
- the non-conductive support material contains the at least one inorganic metal-phosphate compound in an amount of 0.01% by weight to 45% by weight, preferably in an amount of 0.1% by weight 20 wt .-%, particularly preferably in an amount of 1 wt .-% to 10 wt .-%, based on the total mass of the composition of the sum of the mass of the non-conductive support material and the added substances.
- Too low a proportion ensures too low a density of metal-phosphate compound, which may result in poorly formed tracks, whereas too high a proportion of metal-phosphate compound can lead to a deterioration of the material properties of the non-conductive substrate.
- the non-conductive carrier material contains the at least one stabilizer in an amount of 0.01% by weight to 25% by weight, preferably in an amount of 0.1% by weight to 20% by weight. %, more preferably in an amount of 1 wt .-% to 10 wt .-%, based on the total mass of the composition of the sum of the mass of the nonconductive support material and the added substances.
- Too low a proportion provides too low a density of stabilizer, whereby the positive effect of the stabilizer with respect to the formation of the conductor structures in the laser structuring process and the stability in the processing process can be reduced, whereas too high a proportion of stabilizer to a deterioration of the material properties of the can lead to non-conductive substrate.
- the non-conductive support material additionally contains at least one synergist selected from metal phosphates, metal oxides or mixtures thereof.
- the metal atoms of the metal phosphates, metal oxides or mixtures thereof are selected from the group consisting of Cu, Au, Ag, Pd, Pt, Fe, Zn, Sn, Ti, Al. It has surprisingly been found that the synergist supports the process of metal complex decomposition and metal deposition on the surface of the support material.
- synergists selected from the group consisting of copper phosphate, Trikupferdiphosphat, copper pyrophosphate, tin phosphate, zinc phosphate, titanium oxide, zinc oxide, tin oxide and iron oxide.
- the synergists used are expediently selected in terms of their temperature resistance so that they remain stable in the processing process and after exposure to the soldering temperatures and do not decompose in the baths used for an optionally carried out metallization.
- the nonconductive carrier material contains the at least one synergist in an amount of 0.01% by weight to 15% by weight, preferably in an amount of 0.1% by weight to 10% by weight, more preferably in one Amount of 1 wt .-% to 5 wt .-%, based on the total mass of the composition of the sum of the mass of the nonconductive support material and the added substances.
- Too low a proportion results in too low a density of synergist, which can reduce the positive effect of the synergist with respect to the formation of the conductor structures in the laser structuring process, whereas too high a proportion of synergist can lead to a deterioration of the material properties of the nonconductive support material.
- Suitable amounts and a suitable ratio of metal-phosphate compound, stabilizer and optionally synergist can be determined by a person skilled in the art for a given carrier material with knowledge of the invention by simple experiments and u. a. depend on the carrier material used and the desired interconnect patterning, taking into account the process conditions to be used and the laser to be used.
- the non-conductive support material according to the invention is expediently selected from the group consisting of thermoplastics, thermosets, elastomers, glasses, ceramics, natural or synthetic paints, natural or synthetic resins, silicones or combinations or mixtures thereof.
- the non-conductive support material is a thermoplastic or a thermosetting plastic.
- the non-conductive support material is selected from the group consisting of polyvinyl butyral (PVB), polypropylene (PP), polyethylene (PE), polyamide (PA), polyesters such as polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyphenylene oxide, polyacetal, polymethacrylate , Polyoxymethylene, polyvinyl acetal, polystyrene, acryl-butadiene-styrene (ABS), acrylonitrile-styrene-acrylic ester (ASA), polycarbonate (PC), polyethersulfone, polysulfonate, polytetrafluoroethylene, polyurea, formaldehyde resin, melamine resin, polyether ketone, polyvinyl chloride, polylactide, polysiloxane, Phenol resin, epoxy resin, poly (imide), bismaleimide-triazine, thermoplastic polyurethane, copolymers and /
- the non-conductive support material may contain further additives or additives, for example fillers, such as silica and / or derivatives thereof, flame retardants, glass fibers, process aids, color pigments, etc., wherein these additives are to be selected so that they have the material properties of the support material and the inventive production of do not adversely affect electrically conductive structures as possible.
- fillers such as silica and / or derivatives thereof, flame retardants, glass fibers, process aids, color pigments, etc.
- a masterbatch is a polymer matrix in the form of granules or powder which contains the further substances in concentrations which are higher than in the end use.
- the masterbatch or various masterbatches are combined to produce the carrier material according to the invention with further polymer material without the other substances contained in the masterbatch in such quantities or ratios which correspond to the desired concentrations of the further substances in the final product.
- Masterbatches have the advantage over the addition of various substances in the form of pastes, powders or liquids that they ensure high process reliability and are very easy to process and dose.
- the nonconductive support material is a lacquer
- one-component lacquers (1-component lacquer) or two-component lacquers (2-component lacquer) are suitable according to the invention.
- One-component paints (1K paints) contain binders as a dispersion in aqueous solution or dissolved in organic solvent.
- the binder consists of resin and hardener. These are stored separately and mixed together just before processing. They react chemically and harden (without drying). Some 2K paints do not contain solvents.
- Binders include natural resins and oils (oil color), plant components (Chinese lacquer, Japanese lacquer), egg (egg tempera), gum arabic (watercolor), lime (lime), glue (glue color), tar or bitumen.
- Lacquers suitable according to the invention include oil varnishes, cellulose nitrate lacquers, alkyd resin lacquers, polyvinyl ester lacquers, such as dispersions of polyvinyl acetate, acrylic resin lacquers, such as polyacrylate lacquers and polymethacrylate lacquers, silicone resin lacquers, epoxy resin lacquers and polyurethane lacquers.
- the laser light for carrying out the method according to the invention may have a wavelength in the range of 200 nm to 12,000 nm.
- Suitable is the use of excimer lasers, as they are known from photolithography.
- Suitable excimer lasers are ArF, KrF, XeCl, XeF and KrCl lasers. The use of excimer lasers allows the formation of very sharp contours of the structures.
- a KrF excimer laser with a wavelength of 248 nm, in particular if the carrier material is a thermoplastic polymer material.
- the laser allows the structuring without significant heating and possibly with minimal melting of the material in the area of action of the laser. In addition, a very high limiting sharpness is achieved.
- Nd: YAG lasers are known from medical technology. Particularly suitable are Nd: YAG lasers with wavelengths of 1064 nm, 946 nm, 532 nm or 473 nm, with an Nd: YAG laser having a wavelength of 1064 nm being particularly preferred, since the laser structuring can thus take place particularly gently and little charring or similar degradation reactions of the carrier material occur.
- VCSEL lasers Very Cavity Surface Emitting Lasers
- semiconductor lasers in particular surface emitters, in which the light is emitted perpendicular to the plane of the semiconductor chip, in contrast to the conventional edge emitter, in which the light emerges on one or two flanks of the chip.
- Advantages of such surface emitter are firstly the low production costs and the low power consumption.
- the radiation profile with lower output power is better over edge emitters.
- the VCSEL is characterized by the fact that it is single-mode available and the wavelength is tunable.
- the invention further comprises the use of a combination of at least one inorganic metal-phosphate compound and a stabilizer and optionally at least one synergist as described and defined herein for the production of electrically conductive structures, preferably interconnect structures, by means of laser light on a non-conductive support material ,
- the invention also encompasses a support material having electrically conductive structures, preferably conductor track structures, on its surface, wherein the support material finely distributed or dissolved therein contains at least one inorganic metal phosphate compound and at least one stabilizer and optionally at least one synergist, as described herein are described and defined.
- metal-phosphate compounds water-free iron (II) - orthophosphate of the general formula Fe3 (P0 4 ) 2 and crystal water-free iron (II) metal orthophosphate, iron (II) Metal phosphonate, iron (II) metal pyrophosphate or iron (II) metal metaphosphate of the general formula Fe a Metb (PO c ) d.
- the attached figures show X-ray diffractograms of the metal phosphate compounds prepared according to the preparation examples.
- FIG. 1 shows the X-ray diffractogram of the invention according to the production example
- X-ray diffraction (XRD) measurements were made on a D8 Advance A25 diffractometer (Bruker) using CuKa radiation.
- Elemental analyzes were performed by X-ray fluorescence analysis (XRF) using the Axios FAST spectrometer (PANalytical) to determine and confirm the stoichiometries of the products produced.
- XRF X-ray fluorescence analysis
- PANalytical Axios FAST spectrometer
- the plates were irradiated with a Nd: YAG laser (Trumpf) with a wavelength of 1064 nm and structures were generated. There was a uniform metal deposition (metal nuclei), which was suitable as tracks or precursor of interconnects.
- Iron (II) magnesium phosphate of the formula Fe 2 Mg (PO 4) 2 was dry mixed with 1% by weight of disodium dihydrogen phosphate, Na 2 H 2 P 2 O 7. 5% by weight of the mixture were incorporated by means of an extruder (type ZSK18 from Coperion GmbH) into a polyamide 6,6 (Ultramid TM from BASF) and granules were produced. The granules were further processed into plates of size 3 cm ⁇ 4 cm ⁇ 3 mm. The plates were irradiated with a Nd: YAG laser (Trumpf) with a wavelength of 1064 nm and produced electrically conductive structures.
- Nd: YAG laser Trumpf
- LDPE Lipolen TM 1800 S from LyondellBasell
- the granules were further processed into plates of size 3 cm ⁇ 4 cm ⁇ 3 mm. There was a slight gray coloration in the plastic, but no deposition on the shaft of the extruder.
- the plates were irradiated with a Nd: YAG laser (Trumpf) with a wavelength of 1064 nm and structures were generated. There was a uniform formation of conductive structures, which were suitable as tracks or precursor of interconnects.
Abstract
Description
Claims
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DE102017106913.5A DE102017106913A1 (en) | 2017-03-30 | 2017-03-30 | Process for the production of electrically conductive structures on a carrier material |
PCT/EP2018/057662 WO2018178022A1 (en) | 2017-03-30 | 2018-03-26 | Method for producing electrically conductive structures on a carrier material |
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US (1) | US11718727B2 (en) |
EP (1) | EP3601642A1 (en) |
JP (2) | JP7213823B2 (en) |
KR (1) | KR20190133683A (en) |
CN (1) | CN110475911A (en) |
DE (1) | DE102017106913A1 (en) |
EA (1) | EA201991999A1 (en) |
MX (1) | MX2019011516A (en) |
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2018
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WO2018178022A1 (en) | 2018-10-04 |
JP7213823B2 (en) | 2023-01-27 |
DE102017106913A1 (en) | 2018-10-04 |
TW201843029A (en) | 2018-12-16 |
CN110475911A (en) | 2019-11-19 |
MX2019011516A (en) | 2020-02-05 |
JP7376667B2 (en) | 2023-11-08 |
EA201991999A1 (en) | 2020-02-28 |
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US20200032028A1 (en) | 2020-01-30 |
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